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  • Chemistry  (50,842)
  • SPACE SCIENCES
  • 1990-1994  (50,842)
  • 101
    Electronic Resource
    Electronic Resource
    Macromolecular engineering of polylactones and polylactides. XV. Poly(D,L)-lactide macromonomers as precursors of biocompatible graft copolymers and bioerodible gels (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2099-2110 
    Details
    ISSN: 0887-624X
    Keywords: polylactide ; macromonomer ; ring-opening polymerization ; graft copolymers ; amphiphilic gel ; biocompatible ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The functional aluminum alkoxide, Et2Al—O—(CH2)2—O-C(O)—C(CH3)=CH2, is a very effective initiator for the (D,L)-lactide (LA) polymerization in toluene at 707deg;C. The coordination-insertion type of polymerization is living and exclusively yields linear P (D,L)-lactide macromonomers of a predictable molecular weight and a narrow molecular weight distribution. IR and 1H-NMR studies show that the methacryloyl group of the initiator is selectively and quantitatively attached to one chain end, whereas the second extremity is systematically a hydroxyl function resulting from the hydrolysis of the living growing site. α,ω-Dimethacryloyl-P(D,L)-lactides, i.e., α,ω-macromonomers, have also been successfully synthesized by the additional control of the termination step, i.e., by reaction of Al alkoxide end groups with methacryloyl chloride. α-Macromonomer and α,ω-macromonomer P(D,L)-lactides are easily free-radical copolymerized with 2-hydroxyethyl methacrylate (HEMA), resulting in a hydrophilic poly (HEMA) backbone grafted with hydrophobic P(D,L)-lactide subchains and a biodegradable amphiphilic network, respectively. © 1994 John Wiley & Sons, Inc.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321112
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  • 102
    Electronic Resource
    Electronic Resource
    Molecular composite. II. Novel block copolymer and semi-interpenetrating polymer network of rigid polyamide and flexible polyimide (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2629-2639 
    Details
    ISSN: 0887-624X
    Keywords: molecular composite ; liquid-crystalline polymer ; lyotropic polyamide ; polyimide ; semi-interpenetrating polymer network ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2,2'-Dimethyl-4,4'-diamino-biphenyl was used to prepare a lyotropic amine-terminated polyamide (PBTA) prepolymer with terephthaloyl dichloride, and an amide oligomer with reactive endcaps of maleimide, respectively. The former was employed in an attempt to increase the solubility of PA/PI block copolymers, and the latter to produce a three-dimensional (isotropic) reinforced molecular composite through the technology of a semiinterpenetrating polymer network (semi-IPN). PBTA prepolymer was copolymerized with an amine-terminated polyimide via a coupling reaction using terephthaloyl dichloride. The resultant block copolymers were characterized by IR, NMR, ηinh and GPC to confirm that the copolymerization reaction was precisely accomplished, as well as to determine their composition and molecular weight. Thermal analysis and lyotropic behavior were also studied for these copolymers. Rigid-rod amide oligomer was crosslinked in the presence of another flexible polyimide. Five sets of semi-IPN films were prepared under varying compositions. The curing conditions were investigated by DSC; in addition, the cured semi-IPNs exhibited a single phase (1 Tg) according to examination by an instrument for thermally stimulated current (TSC). No large-scale phase separation was observed in SEM images of the fractured surfaces. © 1994 John Wiley & Sons, Inc.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321404
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  • 103
    Electronic Resource
    Electronic Resource
    Reactivity and catalytic activity of cationic lonomers for the nucleophilic substitution reactions (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2677-2686 
    Details
    ISSN: 0887-624X
    Keywords: polystyrene-based ionomers ; cationic ionomers ; nucleophilicity ; phasetransfer catalysts ; quaternary salts ; triphase catalysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polystyrene-based crosslinked cationic ionomers containing ammonium or phosphonium chlorides (AxRCI and PxBuCI) were reacted with decyl methanesulfonate. The kinetic data were correlated with the swelling behavior of the ionomers and the solution viscosity of the corresponding linear ionomers. The reactivity of the ionomers was independent of the particle size of the ionomer beads, indicating no diffusion control of the reaction. The solvent and the ion content of the ionomers greatly affect the reactivity. In nonpolar solvents with a low acceptor number, AN, such as toluene, the aggregation of ionic groups with an increasing ion content reduces the reactivity. A solvent with a high value of AN, such as chloroform, led a very low reactivity independent of the ion content. Aprotic polar solvent, such as acetonitrila, promoted the dissociation of the ionic groups and furnished a relatively high reactivity independent of the ion content. Several catalytic substitution reactions were carried out under liquid-solid-solid triphase conditions. The kinetic results were accounted for in terms of slow nucleophile transport and fast chemical reaction within the ionomer particles. © 1994 John Wiley & Sons, Inc.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321408
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  • 104
    Electronic Resource
    Electronic Resource
    Acid catalyzed fullerenation of carbazole polymer (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2727-2737 
    Details
    ISSN: 0887-624X
    Keywords: fullerenes ; carbazole ; acid catalyzed alkylation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new homogeneous fullerenated carbazole polymer has been synthesized, revealing a new substitution pattern for carbazole and a new photodecomposition-resistant substitution pattern for fullerenes. The synthetic method may be accomplished in one pot via acid catalyzed alkylation. The new polymer has several unusual photovoltaic, charge storage, and photoconductivity capabilities. © 1994 John Wiley & Sons, Inc.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321413
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  • 105
    Electronic Resource
    Electronic Resource
    Synthesis and photoinitiated cationic polymerization of 1,2,3-tris(1-propenoxy) propane (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2755-2763 
    Details
    ISSN: 0887-624X
    Keywords: photopolymerization ; propenyl ethers ; cationic polymerization ; diaryliodonium salt ; triarylsulfonium salt ; free radicals ; inhibition ; 1,2,3-tris (1-propenoxy) propane ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of 1,2,3-tris (1-propenoxy) propane (GTPE) was carried out by the rearrangement of 1,2,3-tris(2-propenoxy) propane (glycerol triallyl ether, GTAE) and the Z: E isomer composition of the GTPE was determined using gas chromatography and 1HNMR. The photoinitiated cationic polymerization of the GTPE was studied using realtime infrared spectroscopy (RTIR). Employing the data from these studies, rates of polymerization for the respective E and Z propenyl ether double bonds were calculated. The rate of incorporation of Z-double bonds of GTPE into the crosslinked polymer matrix is 1.6 times that of E-double bonds. The effects of oxygen and several other free radical polymerization inhibitors were investigated. An increase in the photogel time and decrease of the gel-content in the presence of these inhibitors implicates the involvement of free radicals in the process of the generation of propagating cationic centers when diaryliodonium salt cationic photoinitiators are used. © 1994 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321416
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  • 106
    Electronic Resource
    Electronic Resource
    Hydrolyzable poly(ester-urethane) networks from L-lysine diisocyanate and D,L-lactide/∊-caprolactone homo- and copolyester triols (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2345-2363 
    Details
    ISSN: 0887-624X
    Keywords: biomedical ; poly(D,L-lactide) ; poly(∊-caprolactone) ; poly (ester-urethane) ; L-Lysine diisocyanate ; absorbable ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bioabsorbable poly(ester-urethane) networks were synthesized from ethyl 2,6-diisocyanatohexanoate (L-lysine diisocyanate) (LDI) and a series of polyester triols. LDI was synthesized by refluxing L-lysine monohydrochloride with ethanol to form the ester, which was subsequently refluxed with 1,1,1,3,3,3-hexamethyldisilazane to yield a silazane-protected intermediate. This product was then phosgenated using triphosgene. Polyester triols were synthesized from D,L-lactide, ∊-caprolactone, or comonomer mixtures thereof, using glycerol as initiator and stannous octoate as catalyst. Polyurethane networks were cured using [NCO]/[OH] = 1.05 and stannous octoate (0.05 wt %) for 24 h at room temperature and pressure and 24 h at 50°C and 0.1 mm Hg. LDI-based polyurethane networks were totally amorphous and possessed very low sol contents. Networks based on poly (D,L-lactide) triols were rigid (Tg ∽ 60°C) with ultimate tensile strengths of ∼ 40-70 MPa, tensile moduli of ∼ 1.2-2.0 GPa, and ultimate elongations of ∼ 4-10%. Networks based on ∊-caprolactone triols were low-modulus elastomers with tensile strengths and moduli of ∼ 1-4 MPa and ∼ 3-6 GPa, respectively, and ultimate elongations of ∼ 50-300%. Networks based on copolymers displayed physical properties consistent with monomer composition and were tougher than the networks based on the homopolymers. Tensile strengths for the copolymers were ∼ 3-25 MPa with ultimate elongations up to 600%. Hydrolytic degradation under simulated physiological conditions showed that D,L-lactide homopolymer networks were the most resistant to degradation, undergoing virtually no change in mass or physical properties for 60 days. ∊-Caprolactone-based networks were resistant to degradation for 40 days, and high-lactide copolymer-based networks suffered substantial losses in physical properties after only 3 days. © 1994 John Wiley & Sons, Inc.
    Additional Material: 18 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321216
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  • 107
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    Electrically conductive pseudo IPNs of linear poly(carbonate-urethane) and crosslinked polychloroprene (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2395-2400 
    Details
    ISSN: 0887-624X
    Keywords: pseudo IPNs ; PCU ; CR ; conducting polymer ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A number of pseudo IPNs of poly(carbonate-urethane) (PCU) and crosslinked polychloroprene (CR) have been synthesized and characterized. The single phase morphology of these novel pseudo IPNs has been confirmed by DSC measurements and electron microscopy. The room temperature electrical conductives of homopolymers and pseudo IPNs have been investigated for both undoped and iodine-doped samples. © 1994 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321220
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  • 108
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    Hindered lithium dialkylamide initiators for the living anionic polymerization of methacrylic esters (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2425-2430 
    Details
    ISSN: 0887-624X
    Keywords: anionic ; polymerization ; living ; methyl methacrylate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Lithium diisopropylamide is an efficient initiator for the anionic polymerization of methyl methacrylate in polar solvents at -78°C. Predictable molecular weights based on the initiator concentration were obtained, yields were quantitative, and molecular weight distributions were relatively narrow (〈1.30). The presence of an amino end group and confirmation of the initiation mechanism were confirmed by potentiometric titration using HClO4. Number-average molecular weights determined by titration agreed well with values determined by SEC. Other lithium dialkylamides that contain larger alkyl groups such as lithium diisobutylamide were less efficient initiators. This was attributed to the more nucleophilic anion due to less steric hindrance near the nitrogen atom. Molecular weight distributions were significantly broadened (〉2.0), and molecular weight control was not achieved. However, polymer yields were quantitative. In all cases, PMMA stereochemistry was indicative of a solvent-separated lithium counterion, and triad compositions were identical to organolithium initiated homopolymers, i.e., 78% syndiotactic, 20% heterotactic, and 2% isotactic. © 1994 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321303
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  • 109
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    Acyclic diene metathesis (ADMET) depolymerization of functionalized furan-based polymers (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2469-2477 
    Details
    ISSN: 0887-624X
    Keywords: acyclic dience metathesis ; ADMET ; depolymerization ; aqueous ring-opening metathesis polymerization ; ROMP ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acyclic dience metathesis (ADMET) depolymerization of functionalized furan-based polymers prepared via aqueous ring-opening polymerization of 7-oxanobornenes has been investigated. Results indicate that while very high molecular weight poly [exo-N-methyl-7-oxabicyclo [2.2.1] hept-2,5-diene-2,3-dicarboximide] can be depolymerized to oligomers with ease, poly [2,3-dicarbomethoxy-7-oxabicyclo [2.2.1] hept-2,5-diene] is more resistant to depolymerization under similar conditions. This difference may be due to differential interaction of the carbonyls in the side chains with the metal atom of the catalyst in the proposed metallacyclobutane intermediate. ADMET depolymerization of poly [2,3-bis (trifluoromethyl)-7-oxabicyclo [2.2.1] hept-2,5-diene] was feasible, however, the extent of depolymerization was decreased due to the use of a coordinating solvent (THF) used during the depolymerization process. © 1994 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321308
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  • 110
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    Thermoreversible reaction of diels - alder polymer composed of difurufuryladipate with bismaleimidodiphenylmethane (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2501-2504 
    Details
    ISSN: 0887-624X
    Keywords: thermoreversible polymer ; Diels-Alder polymerization ; retro-Diels-Alder degradation ; difurufuryladipate ; bismaleimidodiphenylmethane ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermoreversible reaction of Diels-Alder polymer composed of difurufuryladipate with bismaleimidodiphenylmethane was studied in dimethylformamide solution. The retro-Diels-Alder degradation occurred gradually at 90°C and Diels-Alder polymerization proceeded quickly at 60°C. © 1994 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321312
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  • 111
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    Annealing effects on the thermal properties of liquid crystalline polyurethanes (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2559-2563 
    Details
    ISSN: 0887-624X
    Keywords: main-chain liquid crystalline polymers ; thermotropic polyurethane ; annealing effect ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This work is a continuation of our earlier investigations of liquid crystalline polyurethanes prepared from 4,4′-bis(2-hydroxyethoxy) biphenyl (BHBP), 2,4-tolylene diisocyanate (TDI), and poly (oxytetramethylene) diols (PTMO). The annealing effects on the thermal properties of the investigation polyurethanes are presented for three samples with the same BHBP content, different flexible spacer length, and different molecular weight of the polyurethanes. The annealed polyurethanes were investigated by means of DSC, and polarizing microscopy. The results of the thermal analysis show that the temperatures of phase transitions depend on the annealing temperature and time. These dependences are different for different molecular weights. © 1994 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321319
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  • 112
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    Synthesis and dielectric analysis of aliphatic poly(carbonate-sulfone)s based on 1,4-bis(3-hydroxypropylsulfonyl) butane (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2809-2816 
    Details
    ISSN: 0887-624X
    Keywords: 1,4-bis((3-hydroxypropylsulfonyl)butane ; polycarbonate ; poly(carbonatesulfone) ; liquid crystalline ; dipole-dipole interaction ; dielectric constant ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High molecular weight aliphatic poly(carbonate-sulfone) homopolymer (PC-343) and random copolymer (PC-343-10) were synthesized from 1,4-bis(3-hydroxypropylsulfonyl)butane (Diol-343) and a 1/1 molar mixture of Diol-343 and 1,10-decanediol, respectively. As a comparison, an aliphatic polycarbonate homopolymer (PC-10) was prepared from 1,10-decanediol. While PC-10 exhibited a single melting peak during its DSC heating scan, both PC-343 and PC-343-10 exhibited multiple reproducible first-order transitions during DSC heating scans. Both PC-343 and PC-343-10 showed broad reflections in their WAXD diagrams; the crystalline order of PC-343 is higher than that of PC-343-10. Based on the DSC and WAXD results and our discovery on the liquid crystalline behavior of aliphatic poly(carbonate-sulfone)s from 1,3-bis(hydroxypropylsulfonyl)propane, we suggest PC-343 and PC-343-10 are liquid crystalline and the liquid crystalline phase formation is directed by the dipole-dipole interactions between sulfone groups. Films were obtained from these polymers by compression molding and dielectric analyses were conducted on them. One glass transition related dielectric relaxation was observed in PC-343-10. One glass transition related dielectric relaxation and one sub-glass transition related dielectric relaxation were observed in PC-343. The glass transition temperature increases with the increase of sulfone content in the polymers. A dramatic rise in dielectric constant with temperature was observed in PC-343 and PC-343-10 at low frequencies, which is probably due to the sulfone dipole interaction with the electrical field. © 1994 John Wiley & Sons, Inc.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321502
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  • 113
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    New results of the free radical ring-opening polymerization (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2867-2871 
    Details
    ISSN: 0887-624X
    Keywords: radical ring-opening polymerization ; keten-O, N-acetal ; cyclic esteramide ; benzoyl peroxide ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of 5-ring ketene-O, N-acetals with peroxides was investigated. It was shown that benzoyl peroxide adds to monomers 5a and 5b by ring opening, giving the corresponding linear diester amides 6a and 6b, respectively. The ketene-O,N-acetal 5c adds benzoyl peroxide, without ring opening, by addition to the exomethylene group, giving the cyclic-O,N-acetal diester 6c. With phthaloyl peroxide cyclic esteramides 7 and oligomeric products are formed. The chemical structures of the addition products were confirmed by NMR spectra and elemental analysis. © 1994 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321508
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  • 114
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    Synthesis, characterization, and polymerization of propenyl ether analogues (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2895-2909 
    Details
    ISSN: 0887-624X
    Keywords: propenyl ether analogues ; cationic photopolymerization ; monomer synthesis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of aromatic monomers bearing cationically polymerizable propenyl groups were prepared and characterized using the readily available starting materials: isoeugenol and o-allyl phenol. Monomers with both propenyl and vinyl ether functional groups were also synthesized by the reaction of these starting materials with chloroethyl vinyl ether. The reactivity of the resulting monomers in photoinitiated cationic polymerization was studied using differential scanning photocalorimetry and photogel point measurements. Their thermal properties were determined using thermogravimetric analysis. © 1994 John Wiley & Sons, Inc.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321511
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  • 115
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    A facile synthesis of aliphatic polybenzoxazoles from a bis(o-aminophenol) or its hydrochloride and aliphatic dinitriles (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2947-2951 
    Details
    ISSN: 0887-624X
    Keywords: aliphatic polybenzoxazoles ; melt polycondensation ; dinitrile monomers ; crystalline polybenzoxazoles ; thermal behavior ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A facile one-step method for the synthesis of aliphatic polybenzoxazoles has been developed. Thus, a series of aliphatic polybenzoxazoles having inherent viscosities of 0.2-0.7 dL/g in concentrated sulfuric acid were successfully synthesized by the melt polycondensation of alipatic dinitriles with 4,4′-diamino-3,3′-dihydroxybiphenyl (AHB) or its hydrochloride (AHB-HCl) with the elimination of ammonia or ammonium chloride, respectively. Monomer AHB-HCl was more reactive than the parent AHB, thereby affording higher molecular weight polybenzoxazoles in a shorter reaction time. The aliphatic polybenzoxazoles having 6-10 methylene units were highly crystalline with melting temperatures in the range of 187-308°C, which were stable up to 400°C in a melt state in nitrogen. © 1994 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pola.1994.080321516
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  • 116
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    Copolymerization of ethylene and 1-butene with highly active Ticl4/THF/Mgcl2, Ticl4/THF/Mgcl2/SiO2, and TiCl3.1/3AlCl3 catalysts (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2979-2987 
    Details
    ISSN: 0887-624X
    Keywords: ethylene/1-butene copolymerization ; Mg/Ti bimetallic catalyst ; copolymer sequence distribution ; solvent fractionation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Highly active catalysts for copolymerization have been prepared by the precipitation of MgCl2/ToCl4 complex with or without high surface area silica. Copolymerization of ethylene and 1-butene has been tested by using the prepared catalysts at various concentrations of 1-butene. The catalytic activities are 20-80 kg/g Ti h. The rate of copolymerization is strongly affected by the addition of 1-butene. The decay rate of copolymerization is first order with respect to time. Analyses of copolymers with solvent extraction, DSC, IR, XRD, and NMR were performed. Ethylene reactivity ratio (k11) for TiCl4/MgCl2/THF catalyst is calculated to be about 26 by NMR spectrum. © 1994 John Wiley & Sons, Inc.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pola.1994.080321521
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  • 117
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    Structural study of methyl methacrylate-α-trifluoromethacrylic acid copolymer by 1H-NMR (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2803-2807 
    Details
    ISSN: 0887-624X
    Keywords: copolymer sequence ; NMR ; methyl methacrylate ; styrene ; α-trifluorome-thacrylic acid ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: [no Abstrat]
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321501
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  • 118
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    A comparison of thermoreactive water-soluble poly-N,N-diethylacrylamide prepared by anionic and by group transfer polymerization (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 3019-3030 
    Details
    ISSN: 0887-624X
    Keywords: LCST ; thermoprecipitation ; poly-N,N-diethylacrylamide ; group transfer polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several batches of poly-N,N-diethylacrylamide were synthesized by anionic and by group transfer polymerization (GTP). A radical poly-N,N-diethylacrylamide prepared from the same monomer was also included in the comparison. According to matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) both types of living polymerization resulted in narrow molecular weight distributions with Mw/Mn values below 1.5. Average molecular weights (Mn) between 888 and 4678 g/mol were calculated in these cases. The radical polymer had an average molecular weight (Mn) of approximately 130,000 g/mol. The dry anionic and GTP polymers were investigated by differential scanning calorimetry (DSC) and x-ray diffraction spectrometry. Evidence for partial crystallinity in the solid state was found. The conformation of all polymers was examined by high resolution (600 MHz) NMR. According to these measurements, 75% of the —CHR— groups of the anionic poly-N,N-diethylacrylamide were located in an isotactic triade. The remaining 25% had heterotactic structure, while no indication for the presence of syndiotactic protons was found. Poly-N,N-diethylacrylamide prepared by GTP, on the other hand, had mainly syndiotactic structure. The aqueous solutions of the polymers showed phase separation upon heating. Whereas the lower critical solution temperature (LCST) was approximately 30°C in the case of the poly-N,N-diethylacrylamide prepared by GTP and by radical polymerization, uncommonly high LCSTs of more than 40°C were observed for the anionic poly-N,N-diethylacrylamide. © 1994 John Wiley & Sons, Inc.
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    Palladium- and platinum-catalyzed coupling reactions of allyloxy aromatics with hydridosilanes and hydridosiloxanes: Novel liquid crystalline/organosilane materials (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 3069-3089 
    Details
    ISSN: 0887-624X
    Keywords: hydrosilylation ; silsesquioxane ; oxysilylation ; allyloxyaromatic ; hydridosilane ; hydridosiloxane ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pt-and Pd-catalyzed reactions of a set of allyloxyaromatic mono-and diesters with selected silanes were examined to develop simple, mild methods of forming liquid crystal (LC)/ siloxane and LC/silsesquioxane polymers. Pt complexes catalyze hydrosilylation to give primarily (≤ 80% selectivity at 100% conversion) terminal silylation of the allyloxys. The catalyst, platinum-1,3-divinyltetramethyldisiloxane [Pt (dvs), gives the cleanest reactions, fewest side products, under the mildest conditions. Model studies of Pt(dvs) catalyzed hydrosilylation of 4-allyloxy methylbenzoate gave relative reactivities (HSiO1.5)8 ≫ Et3SiH 〉 HMe2Si—O—SiMe2H 〉 Ph2SiH2. The cubic silsesquioxane, (HSiO1.5)8, is so reactive hydrosilylation is over in 1-3 h at 0°C. All other reactions required 〉 40°C and longer reaction times. Initial efforts to form high polymers by Pt-catalyzed reactions of bis-allyloxy aromatics with Ph2SiH2 provide polymers with bimodal MW distributions (polystyrene), Mws ≈ 30 kDa, and PDIs ≈ 5. Pd catalysis gives quite different products resulting from loss of propene with coincident formation of Si—O bonds, “oxysilylation.” The same products appear (10-15%) in some Pt catalyzed reactions. Palladium dibenzylideneacetone/ Ph3P[Pd(dba)2/Ph3P], gives the cleanest oxysilylation reactions. Relative oxysilylation activities are: Ph2SiH2 〉 HMe2SiOSiMe2H 〉 Et3SiH. Polymerization with Pd catalysts provides polymers with Mws ≈ 11 kDa, and PDIs ≈ 2. Reaction of 1 equiv. of (HSiO1.5)8 with 4 equiv. of 4-(4-allyloxy-benzoyloxy) biphenyl gives relatively pure tetrasubstituted LC/silsesquioxane [Mn ≈ 1860 Da, PDI ≈ 1.09 (styrene equiv.) vs. 1746 Da caled.] A detailed analysis of the products formed, the catalytic reactivity patterns of the his (allyloxy) aromatic diesters and their LC transitions is presented. © 1994 John Wiley & Sons, Inc.
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    Solution polymerization of vinyl monomers in the presence of poly(N-acetyliminoethylene) macroazoinitiators (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 3123-3132 
    Details
    ISSN: 0887-624X
    Keywords: vinyl monomers ; solution polymerization ; poly(N-acetyliminoethylene) ; macroazoinitiator ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New block copolymers with poly(N-acetyliminoethylene) and vinyl sequences were obtained by a two-step synthetic approach. In the first stage macroinitiators of poly(N-acetyliminoethylene) type, with azo groups inserted in the main chain, were prepared. They were latter used in the radical polymerization of some vinyl monomers [styrene, methacrylic acid, methyl methacrylate, butyl methacrylate, β-(N-carbazolyl)ethyl acrylate, β-(methacryloyfoxy)ethyl 3,5-dinitrobenzoate]. The resulting block copolymers were characterized by spectral methods, elemental analysis, gel permeation chromatography, and electron microscopy. The kinetic study of the thermal and photochemical decomposition of the synthesized macroazoinitiators, as well as the polymerization data, suggest a dependence of their initiating efficiency on the length of the poly(N-acetyliminoethylene) segments. © 1994 John Wiley & Sons, Inc.
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    Amphiphilic networks. VII. Synthesis and characterization of pH-sensitive poly(sulfoethyl methacrylate)-1-polyisobutylene networksFor Part VI of this series, see REFERENCE 22. (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 3153-3160 
    Details
    ISSN: 0887-624X
    Keywords: polyisobutylene ; 2-sulfoethyl methacrylate ; copolymer ; network ; synthesis ; characterization ; swelling ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of environmentally sensitive amphiphilic networks consisting of 2-sulfoethyl methacrylate (SEMA) chains linked by methacrylate-ditelechelic polyisobutylene (MA-PIB-MA) chains have been prepared and characterized. Network composition was determined after sequential solvent extraction by elemental analysis. These networks are two-phase microheterogeneous systems containing hydrophobic rubbery PIB domains (Tg ∼ -60°C) and hydrophilic poly(2-sulfoethyl methacrylate) domains (Tg ∼ -15°C). They exhibit large contact-angle hysteresis in water which is due to surface segmental mobility and microheterogeneity. By increasing the SEMA content of the networks the contact-angle hysteresis increases. This phenomenon is due to an increase in the advancing contact angle most likely caused by the migration of the nonpolar PIB domains toward the surface and concomitant decrease of the receding contact angle. These amphiphilic networks exhibit non-Fickian swelling in n-heptane, as well as in water, and show pH-sensitive swelling in aqueous media. They rapidly and reversibly swell and deswell in response to increasing or decreasing the pH of the media (cycling between pH = 2 and 12). © 1994 John Wiley & Sons, Inc.
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    Synthesis of polyallylamine derivatives with N-carbamoylguanidine groups (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 3189-3191 
    Details
    ISSN: 0887-624X
    Keywords: polycationic polymer ; poly(allyl-N-carbamoylguanidino-co-allylamine) ; poly(allylguanidino-co-allylamine) ; potentiometric titration ; thermogravimetric analysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
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    Thermotropic liquid crystalline main-chain viologen polymers: Homopolymer-of 4,4′-bipyridyl with ditosylate of trans-1,4-cyclohexanedimethanol and its copolymers with ditosylate of 1,8-octanediol (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 3205-3209 
    Details
    ISSN: 0887-624X
    Keywords: viologen polymer ; thermotropic ; smectic ; synthesis ; characterization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
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    Diary (1994)
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 8 (1994), S. i 
    Details
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/cem.1180080402
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    Editorial (1994)
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 8 (1994), S. 243-243 
    Details
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/cem.1180080403
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    Direct distance measures in factor analysis spectral resolution (1994)
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 8 (1994), S. 245-261 
    Details
    ISSN: 0886-9383
    Keywords: Factor analysis ; Spectral resolution ; Two-dimensional luminescence ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A factor analysis algorithm that estimates the spectra of mixture components using the set of most dissimilar rows and/or columns is described and illustrated. This algorithm uses the distance as a measure of spectral similarity and is suitable for application to a variety of the bilinear matrix-formatted data types produced by hyphenated and multidimensional analytical techniqes. The algorithm requires that the data matrix contain at least one row or column that corresponds to the pure spectrum of each component to effect accurate spectral resolution. The performance of the method is illustrated using the resolution of excitation and emission spectra of up to four components from experimental fluorescence excitation-emission matrices (EEMs). In the case of the EEM, characteristic bands in an emission spectrum effect resolution of the excitation spectrum of the corresponding component, while characteristic bands in an excitation spectrum lead to resolution of the corresponding emission spectrum. The use of the set of most dissimilar rows and columns to evaluate the degree of overlap in the component spectra and compare the quality of row and column solutions is also described.
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    Methods for experimental design, Jacques L. Goupy, Elsevier, Amsterdam, 1993, ISBN 0-444-89529-9, 465 pp., 325 fl (1994)
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 8 (1994), S. 293-294 
    Details
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cem.1180080408
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    Correction (1994)
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 8 (1994), S. 303-303 
    Details
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cem.1180080413
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    Quantitative analysis of latex in paper coatings by ATR-FTIR spectroscopy (1994)
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 8 (1994), S. 333-347 
    Details
    ISSN: 0886-9383
    Keywords: PLS ; ATR ; Paper ; Resolution ; Infrared ; FTIR ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Attenuated total reflectance Fourier transform infrared spectrometry (ATR-FTIR) has been used to determine the amount of styrene-butadiene latex on the surface of coated papers and to predict the composition of the polymer. Spectrum recording was performed on the sample in its usual form without any modification.For quantitative analysis, partial least squares (PLS) regression, principal component regression (PCR) and multi-linear regression (MLR) were used to calculate models for prediction. The best result is obtained with PLS.We analysed two series of paper samples. The first analysis concerns the measurement of the quantity of latex of a constant quality on the coating surface. For 15 samples the concentration varied between 5 and 25 parts (grams per 100g of mineral pigments). We compared the predictive results at various resolutions. We obtained a relative error of 0.15 parts in latex at 4 cm-1 resolution. The second analysis concerns the measurement of the styrene/butadiene ratio in various types of latex. We obtained a relative error of 0.156 parts for styrene determination and 0.161 parts for butadiene determination.
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    PCB method applied to material design - computer-aided synthesis of BiPbSrCaCuOF superconductor (1994)
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 8 (1994), S. 439-443 
    Details
    ISSN: 0886-9383
    Keywords: Pattern recognition ; Principal component analysis ; Inverse mapping ; Optimization ; Material design ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An inverse mapping method called PCB (principal component backing), in which the point representing an unknown sample from a low-dimensional principal component subspace is back-projected to the high-dimensional original feature space, is proposed. Two sorts of boundary conditions, non-linear inverse mapping and linear inverse mapping, are used to obtain an accurate solution in the PCB method. The method is applied to the material design of high-Tc superconductors, predicting the composition and process conditions for the synthesis of F-doped Bi-based materials. Samples in the ‘optimal’ region with the highest Tc of the Bi-based ceramics have been predicted.
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    On the formation and properties of a high-temperature resin from a bisphthalonitrile (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1-8 
    Details
    ISSN: 0887-624X
    Keywords: bisphthalonitrile ; cure catalysis ; polymerization mechanism ; polymer properties ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When 4,4'-bis (3,4-dicyanophenoxy) biphenyl is heated with small amounts of aromatic amine or amidine salts, a highly crosslinked polytriazine is obtained. This polymer has been shown to be the same as that reported when bisphthalonitriles are heated with amines. Salts promote this reaction more readily and the glass transition temperature of the polymer after post-cure at 315°C is generally 30°C higher than when free bases are used. The fracture properties and elasticity of the salt-cured polymer have been measured at temperatures up to 250°C. As a model system, the self reaction of phthalonitrile promoted by amines and their salts has been studied. In both cases, poly[4-(2-cyanophenyl)-1,3,5-triazine-2,6-diyl-1,2-phenylene] is produced, and more efficiently using the salts. A reaction mechanism for this polymerization has been proposed. © 1994 John Wiley & Sons, Inc.
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    The synthesis and characterization of amine-terminated poly(aryl ether ketone)s as a function of side group and molecular weight (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 73-87 
    Details
    ISSN: 0887-624X
    Keywords: reactive thermoplastic oligomers ; amine-terminated poly(aryl ether ketone)s ; side group interactions ; controlled molecular weight ; characterization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown that amine-terminated poly(aryl ether ketone)s based on the reaction of 4,4'-difluorobenzophenone, and a substituted hydroquinone [either methylhydroquinone (MePK), t-butylhydroquinone (tBPK), or phenylhydroquinone (PhPK)] of controlled molecular weight and high amine-termination efficiency can be synthesized by a two-step reaction technique. Attempts to synthesize analogous materials by a one-step method were shown to be unsuccessful. The side groups are shown to have a large influence on the aromatic proton chemical shifts and this effect is characterized. The side groups and molecular weight are also shown to influence the thermal transitions of the respective polymers. The tBPK polymer possessed the highest glass transition temperature, while the MePK polymer was found to be the only semi-crystalline polymer; a unit cell is proposed. The side groups and molecular weight effects are also characterized as a function of thermal stability and mechanical properties. © 1994 John Wiley & Sons, Inc.
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    The effect of supporting electrolyte on the electrochemical synthesis, morphology, and conductivity of polyaniline (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 105-111 
    Details
    ISSN: 0887-624X
    Keywords: polyaniline ; conducting polymers ; morphology ; conductivity ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electrochemical synthesis of polyaniline (PANI) was carried out under cyclovoltammetric conditions using H2SO4, HCl, HNO3, and HClO4 as supporting electrolytes. The observed different rate of PANI deposit growth depending on the acid in the solution has been explained on the grounds of a different degree of specific adsorption for particular anion. It has been found that morphology of the deposit depends greatly upon the anion present in the solution. Thus, PANI synthesized from the solution of oxyacids results in a dense sponge-like structure while PANI from the hydrochloric acid solution results in a spaghetti-like structure. The structure of the deposit influences the conductivity, being higher for a dense deposit from oxyacid solutions and three orders of magnitude lower in case of a deposit from hydrochloric acid solution. © 1994 John Wiley & Sons, Inc.
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    NMR study of PMR-15 prepolymerization steps (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 203-217 
    Details
    ISSN: 0887-624X
    Keywords: PMR-15 ; polyimides ; PMR-15 NMR-analyses ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Variations in PMR-15 composites properties could be due to differences in their chemical compositions occurring during the curing cycle. Variations in the composition of the PMR-15 resin were studied for four different curing cycles, to determine the influences of parameters such as the heating rate or the presence of a temperature stage. The resin mixture was sampled at the same four different temperature points in each cycle and analyzed mainly by 1H- and 13C-NMR. Quantitative analysis of the different chemical species were realized by deconvolution of NMR spectra. At a given temperature, the resin contains the same molecules but in proportions which depend on the curing conditions and which reflect differences in the chemical reactivity of the monomeric species. We have precisely defined the temperature ranges at which each of the key reactions (amidization, imidization, exoendo isomerization) occurs. An imine condensation product of NE and MDA has been identified and shown to be present in the resin mixture even at low temperature. As a result of this study, two possible causes of resin alteration during ageing can be put forward: the presence of nonimidized BTDE moieties and the endo-exo isomerization reaction which will result in deformation and, possibly, microcracking, if reticulation of the end-capped nadimides is not total. © 1994 John Wiley & Sons, Inc.
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    Template polymerization of multiacrylate (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 295-300 
    Details
    ISSN: 0887-624X
    Keywords: multiacrylate ; template polymerization ; ladder polymer ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By reacting poly (2-hydroxyethyl methacrylate) with acryloyl chloride, multiacrylate connected through a covalent bond with polymethacrylate chain (template) has been obtained. The free-radical polymerization of multiacrylate in dilute dioxane solutions at 75°C and 85°C was examined by IR spectrophotometry and the distribution of molecular weights of the resultant products was evaluated by gel permeation chromatography. The findings show that under selected conditions the polymerization proceeds along ordered acrylic double bonds on the template and results in a ladder-type polymer. At a temperature of 85°C, in addition to the intramolecular cyclopolymerization, intermolecular reactions proceed to a minor extent. © 1994 John Wiley & Sons, Inc.
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    Quantification of end groups in polystyrenes by pyrolysis-gas chromatography (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 383-388 
    Details
    ISSN: 0887-624X
    Keywords: polystyrene ; pyrolysis-gas chromatography ; end groups ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The determination of end groups in polystyrenes (PSts) polymerized anionically with n-butyllithium as the initiator was carried out by pyrolysis-gas chromatography (Py-GC). The relative proportions of the end groups decrease with increasing molecular weight (MW). Consequently, the peaks which reflect the structure of the end groups can be distinguished by comparing pyrograms of samples with different MW. By comparing the intensities of these peaks relative to total intensities of all the peaks in the pyrogram, the numberaverage molecular weight (Mn) of the polymer can be estimated. The observed Mn values of PSts estimated by this method are compared with those determined by size exclusion chromatography (SEC). By this method it was possible to make direct determination of Mn values of PSts with MWs between 1000 and ca. 1 million. Furthermore, the calibration curve produced by the relative intensity of one of the most characteristic peaks (2-phenyl-1-heptene; C4H9—CH2C (Ph) = CH2) for the end group to total intensity of all the peaks in the pyrogram, gave rapid and highly reproducible Mn values. © 1994 John Wiley & Sons, Inc.
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    Preparation and properties of aromatic polyamides and polyimides derived from 3,3-bis [4-(4-aminophenoxy) phenyl] phthalide (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 423-433 
    Details
    ISSN: 0887-624X
    Keywords: 3,3-bis[4-(4-aminophenoxy)phenyl]phthalide ; aromatic polyamides ; soluble aromatic polyimides ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3,3-Bis[4-(4-aminophenoxy)phenyl]phthalide (II) was used as a monomer with various aromatic dicarboxylic acids and dianhydrides to synthesize polyamides and polyimides, respectively. The diamine II was derived by a nucleophilic substitution of phenolphthalein with p-chloronitrobenzene in the presence of K2CO3. Polyamides IVa-g having inherent viscosities of 0.77-2.46 dL/g were prepared by the direct polycondensation of diamine II with diacids IIIa-g using triphenyl phosphite and pyridine as condensing agents. The polyamides were readily soluble in a variety of solvents such as N, N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidinone (NMP) and afforded transparent and flexible films from the polymer solutions. These polymers had glass transition temperatures (Tgs) in the 227-307°C range and 10% weight loss temperatures occurred up to 450°C. Polyimides VIa-e based on diamine II and various aromatic dianhydrides Va-e were synthesized by the two-stage procedure that included ring-opening, followed by thermal or chemical conversion to polyimides. Most of the polyimides obtained by chemical cyclodehydration procedure were found to soluble in DMF, NMP, o-chlorophenol, and m-cresol. The Tgs of these polyimides were in the 260-328°C range and showed almost no weight loss up to 500°C under air and nitrogen atmosphere. © 1994 John Wiley & Sons, Inc.
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    New poly(amide-imide)s syntheses. VIII. Preparation and properties of poly (amide-imide)s derived from 2,3-bis(4-aminophenoxy)naphthalene, trimellitic anhydride, and various aromatic diamines (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 435-444 
    Details
    ISSN: 0887-624X
    Keywords: poly(amide-imide)s ; direct polycondensation ; 2,3-bis (4-aminophenoxy) naphthalene ; 2,3-bis (4-trimellitimidophenoxy) naphthalene ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The new polymer-forming diimide-diacid, 2,3-bis(4-trimellitimidophenoxy) naphthalene (I), was readily obtained by the condensation reaction of 2,3-bis (4-aminophenoxy) naphthalene with trimellitic anhydride. A series of novel aromatic poly (amide-imide)s were prepared by the direct polycondensation of diimide-diacid I with various aromatic diamines using triphenyl phosphite in N-methyl-2-pyrrolidone (NMP)/pyridine solution containing dissolved calcium chloride. The resultant polymers have inherent viscosities in the range of 0.65-1.02 dL/g at 30°C in N, N-dimethylacetamide. These polymers were readily soluble in various organic solvents and could be cast into transparent, tough, and flexible films. Their casting films showed tensile strength at break up to 86 MPa, elongation to break of 5-9%, and initial moduli up to 2.35 GPa. The wide-angle X-ray diffraction revealed that those polymers containing p-phenylene or p-oxyphenylene group are partially crystalline, and the other polymers are evidenced as amorphous patterns. These polymers show a glass transition in the range of 213-290°C in their differential scanning calorimetry (DSC) traces. The thermal stability of the polymers was evaluated by thermogravimetry analysis, which showed the 10% weight-loss temperatures in the range of 508-565°C in nitrogen and 480-529°C in air atmosphere. © 1994 John Wiley & Sons, Inc.
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    Novel preparation of electrically conducting poly (vinyl chloride) by photo-dehydrochlorination from poly (vinyl chloride)/polypyrrole composite film (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 33-38 
    Details
    ISSN: 0887-624X
    Keywords: electrical conductivity ; poly (vinyl chloride) ; photo-dehydrochlorination ; composite film ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polypyrrole (PPy) was deposited electrochemically on a platinum plate from a nitric acid solution of pyrrole. The PVC/PPy composite film was finally obtained by casting poly(vinyl chloride) (PVC) onto the PPy electrode from a tetrahydrofuran solution of PVC. The prepared composite film was irradiated at 90°C with a low-pressure mercury lamp in the stream of hydrogen gas saturated with steam, and the PVC film was dehydrochlorinated, leading to the formation of conjugated polyene. The electrical conductivity (σ) of the PVC film in the irradiated composite film was reveled: σ=2.51 × 10-5S cm-1. By iodine doping, σ was further enhanced up to 5.04 X 10-3 S cm-1. The tensile strength of the irradiated composite film became larger than that of the original PVC film; i.e., the stress at break was: 461 (composite film); 401 kg cm-2 (PVC). These results were brought about by the doping of radical species to the conjugated polyene. The anion, NO-3, doped during the electrodeposition of PPy was photodecomposed to generate radical NO2 and this species was doped to the polyene, resulting in the formation of electrically conductive PVC and mechanically improved composite film. © 1994 John Wiley & Sons, Inc.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pola.1994.080320104
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    Chemical preparation of conductive elastomeric blends: Polypyrrole/EPDM. I. Oxidant particle-size effect (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1001-1008 
    Details
    ISSN: 0887-624X
    Keywords: conductive rubber ; polypyrrole/EPDM blend ; chemical preparation ; electrical conductivity ; mechanical properties ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This work describes the preparation of polypyrrole and EPDM rubber blends, PPy/EPDM, by the sorption of pyrrole (vapor phase) in an EPDM matrix containing CuCl2. We investigated the effect of the oxidant particle-size on the sorption and polymerization equilibrium, electrical conductivity, and mechanical properties of the blends. Independently of the CuCl2 concentration and polymerization time, the polypyrrole weight fraction in the blend, Xppy, increases when the oxidant particle-size in changed from 150-250 μm to smaller than 106 μm. For blends containing 50 phr of CuCl2, obtained following 72 h of exposure to pyrrole, an increase in the Young's Modulus (from 2.2 ± 0.2 to 3.9 ± 0.6 MPa) and an increase in the electrical conductivity (from 10-9 to 10-7 S cm-1) was observed when the oxidant particle-size was decreased. Infrared spectroscopy, thermogravimetric analysis, scanning differential calorimetry, and scanning electron microscopy were used in sample characterization. © 1994 John Wiley & Sons, Inc.
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    Preparation of polyalkylviologen-polyanion complexes and their applications to the debromination of diphenyl bromomethane under heterophase condition (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1043-1048 
    Details
    ISSN: 0887-624X
    Keywords: polyalkylviologen - polyanion complex ; electron-transfer catalysis (ETC) ; diphenyl bromomethane (Ph2CHBr) ; debromination ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several polyelectrolyte complexes were prepared by the reaction of polyalkylviologens [polyethylviologen (PEV2+), polypropylviologen (PPrV2+), and polybutylviologen (PBV2+)] with polyanions [sodium alginic (ALG), sodium polyacrylate (PAA), or sodium polystyrenesulfonate (PSS)]. These complexes were used as electron-transfer catalysts (ETC) on the debromination of diphenyl bromomethane (Ph2CHBr) under heterophase condition [reductant: Na2S2O4, in H2O (liquid)-polyelectrolyte complex(S) - Ph2CHBr in CH2Cl2]. The work showed that these complexes could induce the debromination of Ph2CHBr to afford tetraphenyl ethane, and different polyanions in the complexes also affected the mediating abilities. © 1994 John Wiley & Sons, Inc.
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    Synthesis and characterization of new fluorescent poly(arylene ether)s (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1071-1076 
    Details
    ISSN: 0887-624X
    Keywords: functional aromatic polyethers ; fluorescent polymers ; aromatic nucleophillic substitution polymerization ; thermal behavior ; electron spin resonance ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The poly(arylene ether)s were prepared by the nucleophillic aromatic substitution polymerization of phenolphthalin and its derivatives with activated aromatic difluorides. The polymers had glass transition temperatures ranging from 210 to 240°C. Though the monomers have no fluorescence, the resulting polymers fluoresced a light green color in solid and solution states. The maximum excitation and emission wavelengths are 420 nm and 470 nm, respectively. In the polymer solutions, the fluorescence intensity decreased gradually, but the intensity was recovered by heating the polymer at 220°C for a few minutes. The fluorescent polymer had a stable radical. A model compound having the same repeating unit of the polymer was also prepared. The fluorescence properties of this model were almost the same as those of the polymers. © 1994 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pola.1994.080320609
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    1H-NMR and UV studies of Rh complexes as a stereoregular polymerization catalysts for phenylacetylenes: Effects of ligands and solvents on its catalyst activity (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1113-1120 
    Details
    ISSN: 0887-624X
    Keywords: phenylacetylene ; stereoregular polymerization ; Rh complex catalyst ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Phenylacetylene and its homologues bearing methoxy or chloro groups in the para position of the phenyl ring were stereoregularly polymerized by Rh complex catalysts, e.g., [Rh (norbornadiene) Cl]2, in the presence of various solvents. The 1H-NMR and UV study of the Rh complex showed that the activity of the Rh catalysts greatly depends upon not only the ligand in the Rh catalyst but also on the solvent used, e.g., polyphenylacetylene with a highly cis-transoidal content was quantitatively obtained when norbornadiene was coordinated as the ligand, and triethylamine (TEA) was used as solvent, whereas tetrahydrofuran (THF) and benzene reduced the cis content. It was also found that the Rh catalyst as a dimer complex dissociates into the monomeric species not only when TEA was used but also when alcohol, benzene, and THF were used. The resulting monomeric species was considered as the important propagation species in this polymerization. The sharp line width observed in the 1H-NMR spectrum of polyphenylacetylene and its homologues which were prepared in ethanol or TEA was interpreted by the narrow chemical shift distribution arising from the high cis content. © 1994 John Wiley & Sons, Inc.
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    Comparative characterization of MgCl2/ethyl benzoate/TiCl4 and MgCl2/2,2,6,6 tetramethylpiperidine/TiCl4 Ziegler-Natta precatalysts (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1137-1147 
    Details
    ISSN: 0887-624X
    Keywords: Ziegler-Natta catalysts ; propylene polymerization ; catalysts characterization ; supported catalysts ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this article we present the results of the preparation and characterization of two Ziegler-Natta precatalysts: MgCl2/Ethyl benzoate (EB)/TiCl4 and MgCl2/2,2,6,6 tetramethylpiperidine (TMPiP)/TiCl4 by means of FTIR, X-ray diffraction, SEM, BET surface area measurements, and other techniques applied at different steps of their preparation procedures.The precatalysts were prepared by impregnating with TiCl4 a given amount of MgCl2, which was previously ball-milled with the electron donor chosen.Prior to impregnation, the ball-milled material presented different surface compounds depending on the electron donor used: [(MgCl2)2] · 2EB, MgCl2 · EB, or a salt of the amine. The solid milled with EB is more homogeneous than the one milled with the TMPiP.Titanium is better retained in the solid milled with EB. This precatalyst has better morphological properties and larger BET surface area. By means of FTIR, we found evidences that an adequate surface structure for the formation of stereospecific sites in MgCl2/TMPiP/TiCl4 was formed. © 1994 John Wiley & Sons, Inc.
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    A comparison of models for hydrogen bonding in polymer blends (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1189-1193 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pola.1994.080320622
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    Swelling kinetics and release characteristic of crosslinked chitosan: Polyether polymer network (semi-IPN) hydrogels (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1213-1223 
    Details
    ISSN: 0887-624X
    Keywords: chitosan ; semi-IPN hydrogel ; swelling kinetics ; pH-sensitivity ; controlled release ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The aqueous swelling kinetics of a series of crosslinked chitosan (cr-CS) with glutaraldehyde (GA) interpenetrating polyether hydrogels have been studied as functions of pH, the N-deacetylation degree of chitosan, the amount of crosslinking agent, the electrolyte composition in solution, temperature, and gel composition. Based on these results, the swelling mechanism of the hydrogels was discussed. The release profiles of chlorhexidini acetas from the semi-IPN were also investigated. © 1994 John Wiley & Sons, Inc.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/pola.1994.080320702
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    Fully aromatic thermotropic liquid crystalline homopolyesters of 3,4′-benzophenone dicarboxylic acid (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 333-342 
    Details
    ISSN: 0887-624X
    Keywords: liquid crystalline polymer ; thermotropic homopolyester ; nematic ; X-ray diffraction ; synthesis ; characterization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of fully aromatic, thermotropic homopolyesters, derived from 3,4′-benzophenone dicarboxylic acid and various aromatic diols, was prepared by the melt polycondensation method and examined for thermotropic behavior by a variety of experimental techniques. The aromatic diols used in the study were hydroquinone, 2,6-, 1,4-, 1,5-, 2,3-, and 2,7-naphthalenediol isomers. All of the homopolyesters of 3,4′-benzophenone dicarboxylic acid with aromatic diols (except that with 2,7-naphthalenediol) formed a nematic LC phase in the melt. They had the glass transition temperatures (Tg) in the range of 133-164°C, the melting transitions (Tm) in the range 305-360°C and the high thermal stabilities (Td) in the range of 410-483°C. The 2,6-naphthalenediol based homopolymer had the highest Tm (360°C) and the 2,3-naphthalenediol based homopolymer had the lowest Tm (305°C) among all of the homopolymers of naphthalenediol isomers. © 1994 John Wiley & Sons, Inc.
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    Synthesis and characterization of poly (2-vinylpridine)-b-poly (t-butyl methacrylate) (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 363-368 
    Details
    ISSN: 0887-624X
    Keywords: 2-vinylpyridine ; t-butyl methacrylate ; anionic polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of well defined and monodisperse (Mw/Mn ≤ 1.2) narrow molecular weight distribution poly (2-vinylpyridine)-poly (t-butyl methacrylate) (P2VP-PTBMA) AB block copolymers is carried out by initiation of 2-vinylpyridine polymerization by 1,1-diphenylhexyllithium in THF at-78°C, followed by addition of TBMA and termination at -78°C using MeOH. The formation of the BAB block copolymer is carried out in a similar fashion except that 1,4-dilithio-1,1,4,4-tetraphenylbutane is used as initiator. The corresponding synthesis of P2VP-PMMA block copolymers is carried in a similar manner, except that 1-2 equivalents of TBMA is used to end-functionalize the living P2VP before the addition of MMA. Without the addition of TBMA, trimodal molecular weight distributions in P2VP-b-PMMA are obtained. All the block copolymers are characterized by Size Exclusion Chromatography (SEC), Nuclear Magnetic Resonance (NMR), and Differential Scanning Calorimetry (DSC). © 1994 John Wiley & Sons, Inc.
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    Molecular composites from sulfonated poly(p-phenylene terephthalamide) (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 397-400 
    Details
    ISSN: 0887-624X
    Keywords: molecular composites ; rigid polymers ; sulfonated poly(p-phenylene terephthalamide) ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pola.1994.080320223
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    Polymerization of surface-active monomers. VIII. Tacticity of polymers prepared by radical polymerization of quaternary salts of dimethylaminoethyl methacrylate in micellar and isotropic media (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 445-449 
    Details
    ISSN: 0887-624X
    Keywords: radical polymerization ; surface-active monomer ; quaternary salt ; dimethylaminoethyl methacrylate ; stereochemistry ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of monomer micellization on the polymerization was studied from the standpoint of stereochemistry in the polymerization. Quaternary salts (CnBr) of dimethylaminoethyl methacrylate with n-alkyl bromide having N (=4, 8 and 12) carbon atoms were polymerized with radical initiators in isotropic and anisotropic media and the resulting polymers were converted to poly (methyl methacrylate) (PMMA) to determine their tacticity. Tacticities of poly (C12Br)s were little affected by initiators and solvents used for their preparations. There was little dependence of the tacticities on alkyl chain length (N) for poly (CnBr)s prepared in water and dimethylformamide (DMF). Most of polymers produced here conformed to Bernoullian propagation statistics and a definite difference was not found in the tacticities between the polymers prepared in isotropic and anisotropic media. From the results obtained here it was deduced that the micellar aggregation has little influence upon the stereochemistry in the polymerization of the quaternary monomers. © 1994 John Wiley & Sons, Inc.
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    Synthesis and characterization of poly(ester-sulfone)s (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1351-1360 
    Details
    ISSN: 0887-624X
    Keywords: 1,3-bis(3-hydroxypropylsulfonyl)propane ; 1,4-bis(3-hydroxysulfonyl)butane ; polyesters ; poly(ester-sulfone) ; liquid crystalline ; glass transition ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aliphatic and aromatic-aliphatic poly(ester-sulfone)s were synthesized by the transesterifications of diphenyl adipate and diphenyl phthalates (ortho, meta, para) with two sulfonecontaining diols, 1,3-bis (3-hydroxypropylsulfonyl) propane (Diol-333) and 1,4-bis(3-hydroxypropylsulfonyl) butane (Diol-343). Based on DSC and WAXD studies, the aliphatic homopoly(ester-sulfone)s are semicrystalline at room temperature and liquid crystalline at elevated temperature, while their copolymers with alkanediols are liquid crystalline. The liquid crystalline phase formation in aliphatic poly(ester-sulfone)s is attributed to the strong dipole-dipole interactions between sulfone groups. The aromatic-aliphatic poly(estersulfone)s from diphenyl phthalate (ortho) and isophthalate (meta) are amorphous. They are soluble in trifluoroacetic acid and m-cresol at room temperature, and DMF, DMAC, and DMSO at elevated temperature. The aromatic-aliphatic poly(ester-sulfone)s from diphenyl terephthalate are semicrystalline and are soluble only in trifluoroacetic acid. For a given diol, the glass transition temperatures of aromatic-aliphatic poly(ester-sulfone)s increase from phthalate to isophthalate to terephthalate. This is because the flexibility of the benzene ring in the polymer backbone decreases from ortho to meta to para substitution. As a comparison, polyesters without sulfone groups were synthesized from two alkanediols, 1,9-nonanediol and 1,10-decanediol, and the diphenyl esters. The poly(ester-sulfone)s have glass transition temperatures 60-80°C higher than the corresponding polyesters without sulfone groups, due to the strong dipolar interactions between sulfone groups. © 1994 John Wiley & Sons, Inc.
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    Facile synthesis of a semicrystalline aromatic fluoroaliphatic poly (ether sulfone) (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 389-392 
    Details
    ISSN: 0887-624X
    Keywords: fluorinated poly (ether sulfone) ; semicrystalline polymer ; aromatic nucleophilic substitution ; trimethylsilyl ether ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pola.1994.080320221
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    Synthesis of crosslinked poly(styrene-co-sodium styrenesulfonate) latexes (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1431-1435 
    Details
    ISSN: 0887-624X
    Keywords: polystyrene ; latex ; sodium styrenesulfonate ; crosslinked ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Latexes of 100 nm diameter were synthesized by emulsifier-free copolymerization of styrene, sodium styrenesulfonate, and 1-5 wt% divinylbenzene using persulfate initiator at 91°C. A shot growth method was used to incorporate a high density of sulfonate groups. Coefficients of variation of particle size were 0.04-0.08 without resort to seed growth polymerization. Redox initiation at 40-50°C produced larger, more polydisperse, and less colloidally stable crosslinked latexes. © 1994 John Wiley & Sons, Inc.
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    Role of N,N-dimethyl-para-toluidine and saccharin in the radical polymerization of methyl methacrylate initiated by a redox system. I. Cumene hydroperoxide/copper saccharinate (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1459-1469 
    Details
    ISSN: 0887-624X
    Keywords: methyl methacrylate ; redox polymerization ; kinetics ; mechanism ; additives ; copper saccharinate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of methyl methacrylate polymerization initiated by a redox system [cumene hydroperoxide (CHP)/copper saccharinate] were studied in bulk at 20°C in the presence of accelerators such as N,N-dimethyl-p-toluidine (DMPT) and o-benzoic sulphimide (saccharin). Assuming a steady-state concentration of propagating radicals, the polymerization rate depends on the square root of the initiation rate and the kinetic orders with respect to each compound in the initiation step may be deduced. Initiation is first-order in CHP, copper saccharinate, and saccharin and second-order in DMPT. A reaction scheme consistent with these orders is proposed. The main features are the following: (1) CHP reduces rapidly Cu(II) to Cu(I); (2) a small fraction of Cu(I) is complexed with DMPT; (3) the complexed ions (Cu+, DMPT2) are strong reductants with respect to CHP whereas uncomplexed Cu+ are almost inactive; (4) the decomposition of CHP is strongly catalyzed by saccharin (protonated CHP is 13000 times more reactive than free CHP). Thus both accelerators are necessary to get high polymerization rates. © 1994 John Wiley & Sons, Inc.
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    Self-Crosslinkable poly(arylene ether)s containing pendent phenylenetriazene groups (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1507-1521 
    Details
    ISSN: 0887-624X
    Keywords: crosslinkable ; poly(arylene ether) ; triazene ; gel content ; dielectric constant ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Self-crosslinkable poly(arylene ether)s 6, and 8, containing pendent triazene groups were prepared by nucleophilic substitution reaction of poly(arylene ether)s 5, and 7, respectively, with 1-[4-(4-hydroxyphenoxy)phenylene]triazenes, 4, in the presence of potassium carbonate in N,N-dimethylacetamide. A series of triazenes 4 containing various substituents have been synthesized. Self-crosslinkable polymer 6e containing phenyl-substituted triazene pendants can be crosslinked at 215°C, which is about 40°C lower than the glass transition temperature of the virgin base polymer 5. The degree of crosslinking can be tailored by varying the concentration of the pendent phenylenetriazene groups in the polymer. After curing, the flexible polymer films (ca. 10 μm thick) exhibit high gel contents, increased glass transition temperatures, improved resistance to organic solvents, and little change in dielectric constant and thermal stability. These self-crosslinkable poly(arylene ether)s are potential candidates for electronic applications. © 1994 John Wiley & Sons, Inc.
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    Synthesis and characterization of poly(urethane-sulfone)s (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1531-1537 
    Details
    ISSN: 0887-624X
    Keywords: 1,3-bis(3 hydroxy propyl sulfonyl)propane ; 1,4-bis(3-hydroxypropyl sulfonyl)butane ; 1,3-propane dithiol ; 1,4-butane dithiol ; poly(urethane) ; poly sulfone ; methylene diphenyl diisocyanate (MDI) ; toluene diisocyanate (TDI) ; hexamethylene diisocyanate (HMDI) ; melt temperature ; glass transition temperature ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Eight poly(urethane-sulfone)s were synthesized from two sulfone-containing diols, 1,3-bis(3-hydroxypropylsulfonyl)propane (Diol-333) and 1,4-bis(3-hydroxypropylsulfonyl)butane (Diol-343), and three diisocyanates, 1,6-hexamethylene diisocyanate (HMDI), 4,4′-diphenylmethane diisocyanate (MDI), and tolylene diisocyanate (TDI, 2,4- 80%; 2,6-20%). As a comparison, eight polyurethanes were also synthesized from two alkanediols, 1,9-nonanediol and 1,10-decanediol, and three diisocyanates. Diol-333 and Diol-343 were prepared by the addition of 1,3-propanedithiol or 1,4-butanedithiol to allyl alcohol and subsequent oxidation of the resulting sulfide-containing diols. The homopoly(urethanesulfone)s from HMDI and MDI are semicrystalline, and are soluble in m-cresol and hot DMF, DMAC, and DMSO. The copoly(urethane-sulfone)s from a 1/1 molar ratio mixture of Diol-333 and Diol-343 with HMDI or MDI have lower crystallinity and better solubility than the corresponding homopoly(urethane-sulfone)s. The poly(urethane-sulfone)s from TDI are amorphous, and are readily soluble in m-cresol, DMF, DMAC, and DMSO at room temperature. Differential scanning calorimetry data showed that poly(urethane-sulfone)s have higher glass transition temperatures and melting points than the corresponding polyurethanes without sulfone groups. The rise in glass transition temperature is 20-25°C while the rise in melting temperature is 46-71°C. © 1994 John Wiley & Sons, Inc.
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    URL: http://dx.doi.org/10.1002/pola.1994.080320813
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    Pyrazoles - A novel class of blocking agents for isocyanates (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 753-765 
    Details
    ISSN: 0887-624X
    Keywords: pyrazole blocked isocyanate ; pyrazole masked isocyanate ; blocking group ; blocking agent ; synthesis ; deblocking reaction ; reactivity ; gelation time ; latency ; stability ; adhesion ; primer ; polymer ; bis (pyrazole) ; EPIC-systems ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrazoles were found as a novel class of blocking groups for isocyanates. Adhesive mixtures of pyrazole blocked isocyanates and amine terminated prepolymers like Jeffamines® (Texaco Chem. Co.) combine excellent reactivities (gelation times within minutes at 100-120°C), good latencies (more than 170 days at 40°C), and good adhesion properties on many substrates. The reactivity of pyrazole blocked isocyanates toward nucleophiles increases with the number of electron donor substituents on the pyrazole nucleus and, thus, can be fine tuned by the appropriate substitution pattern. This behavior contrasts sharply with that of phenolic blocked isocyanates, where reactivities with the same nucleophiles decrease with more and stronger electron donor substituents on the phenol nucleus. Therefore, different deblocking reaction mechanisms were proposed for pyrazole vs. phenol blocked isocyanates. The excellent latency of pyrazole blocked isocyanate/Jeffamine® mixtures is due to the insolubility of the two components at ambient temperature and the slow endothermic dissolution process at higher temperature. The good adhesion of formulations with pyrazole blocked isocyanates as reactive components on most plastic and metal substrates is ascribed to the primer action of the released blocking group. © 1994 John Wiley & Sons, Inc.
    Additional Material: 13 Ill.
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    URL: http://dx.doi.org/10.1002/pola.1994.080320414
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    Biodegradable and pH-sensitive hydrogels: Synthesis by crosslinking of N,N-dimethylacrylamide copolymer precursors (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1627-1637 
    Details
    ISSN: 0887-624X
    Keywords: degradable hydrogels ; crosslinking of polymeric precursors ; colon-specific polymer ; pH-dependent swelling ; azoaromatic crosslinks ; N,N-dimethylacrylamide copolymer ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Novel pH-sensitive hydrogels containing azoaromatic crosslinks were synthesized by the crosslinking of polymeric precursors. First, a reactive polymeric precursor was synthesized by copolymerization of N,N-dimethylacrylamide, N-tert-butylacrylamide, acrylic acid, and N-methacryloylglycylglycine p-nitrophenyl ester. The hydrogel was prepared in the second step by the reaction of the polymeric precursor with N,N′-(ω-aminocaproyl)-4,4′-diaminoazobenzene. The hydrogels were characterized by the network structure, (that is, content of crosslinks, unreacted pendent groups, and cycles), the equilibrium swelling ratio as a function of pH, modulus of elasticity in compression, and the degradability in vitro. The results obtained indicated that the hydrogel network structure strongly depends on the reaction conditions such as polymer concentration, and the ratio of the reactive groups during the crosslinking reaction. The swelling and mechanical properties of hydrogels can be controlled by the modification of polymer backbone structure and/or the crosslinking density. The rates of hydrogel degradation depended on their degree of swelling. The higher the degree of swelling, the higher the degradability. The properties of the hydrogels suggest that they have a potential as carriers for colon-specific drug delivery. © 1994 John Wiley & Sons, Inc.
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    URL: http://dx.doi.org/10.1002/pola.1994.080320904
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    Synthesis and characterization of bismaleimides derived from polyurethanes (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1665-1672 
    Details
    ISSN: 0887-624X
    Keywords: polyurethane ; bismaleimide ; crosslinking reaction ; mechanical property ; thermal property ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of novel bismaleimides (BMIs) were prepared from maleic anhydride and polyurethane prepolymers based on MDI (4,4′-diphenylmethane diisocyanate) and polyether and polyester diols with various chain lengths. All the BMIs were characterized by IR, 1H-NMR, and elemental analysis. DSC studies indicated that the thermal polymerization of the BMIs could be carried out in the temperature range of 102-245°C, and that curing behavior was significantly affected by the molecular weight of the BMIs. The crosslinked BMI elastomers showed good mechanical properties and much better thermal stability than that of the traditional polyurethane elastomers. The glass transition temperatures, mechanical, and dynamic mechanical properties were dependent on the types of polyols used and the resultant crosslink densities due to various chain lengths of the BMIs. © 1994 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pola.1994.080320908
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    Cationic polymerization of vinyl monomers initiated by 10-methylphenothiazine cation radicals (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1703-1710 
    Details
    ISSN: 0887-624X
    Keywords: cationic polymerization ; 10-methylphenothiazine ; cation radical ; electron transfer ; initiation mechanism ; vinyl ethers ; electrochemical oxidation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A small quantity of 10-methylphenothiazine cation radical (MPT.+), electrochemically prepared and stocked in acetonitrile solution, initiated cationic polymerizations of n-butyl, t-butyl, and 2-methoxyethyl vinyl ethers and p-methoxystyrene, while no initiation occurred for phenyl vinyl ether, styrene, methyl methacrylate, and phenyl glycidyl ether. 1H-NMR studies of oligomers and low molecular weight compounds isolated from the reaction mixture for the polymerization of t-butyl vinyl ether in the presence of a small amount of D2O indicated that electron transfer from the monomer to MPT.+ was involved in the initiation step. 1H- and 13C-NMR and MO calculation implied that monomers with higher electron densities on the vinyl groups and with lower ionization potentials were more susceptible to the initiation of MPT.+. © 1994 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
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    Acyloin condensation in aqueous system by durable polymer-supported thiazolium salt catalysts (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1711-1717 
    Details
    ISSN: 0887-624X
    Keywords: durable catalyst ; thiazolium salt ; aqueous system ; acyloin condensation ; enzyme model ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We characterized three low-molecular-weight thiazolium salt analogues: N-methyl-5-(2′-benzyloxyethyl)-4-methylthiazolium iodide (MBMTI), N-methyl-4-phenylthiazolium iodide (MPTI), and N-methylbenzothiazolium iodide (MBTI). MBMTI, having high-electron density on the thiezolium ring, was found to be a durable thiazolium salt in buffer solution. Then, the polymer-supported thiazolium salt catalyst having MBMTI structure as a catalytic site for acyloin condensation was prepared by the polymerization of the corresponding thiazole monomer and the following quaternization. The polymer catalyst had excellent catalytic activity even in buffer solution, while the corresponding low molecular weight catalyst did not show any activity in aqueous system. Furthermore, the durable polymer catalyst could be reused under the aqueous condition. © 1994 John Wiley & Sons, Inc.
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    Living cationic polymerization of isobutyl vinyl ether by EtAlCl2 in the presence of ether additives: Cyclic ethers, cyclic formals, and acyclic ethers with oxyethylene units (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1719-1728 
    Details
    ISSN: 0887-624X
    Keywords: living cationic polymerization ; isobutyl vinyl ether ; cyclic ether additives ; cyclic formal additives ; acyclic ether additives with oxyethylene units ; EtAlCl2 ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The living cationic polymerization of isobutyl vinyl ether (IBVE) was investigated in the presence of various cyclic and acyclic ethers with 1-(isobutoxy)ethyl acetate [CH3CH(OiBu)OCOCH3, 1]/EtAlCl2 initiating system in hexane at 0°C. In particular, the effect of the basicity and steric hindrance of the ethers on the living nature and the polymerization rate was studied. The polymerization in the presence of a wide variety of cyclic ethers [tetrahydrofuran (THF), tetrahydropyran (THP), oxepane, 1,4-dioxane] and cyclic formals (1,3-dioxolane, 1,3-dioxane) gave living polymers with a very narrow molecular weight distribution (MWD) (M̄ω/M̄n ≤ 1.1). On the other hand, propylene oxide and oxetane additives resulted in no polymerization, whereas 1,3,5-trioxane gave the nonliving polymer with a broader MWD. The polymerization rates were dependent on the number of oxygen and ring sizes, which were related to the basicity and the steric hindrance. The order of the apparent polymerization rates in the presence of cyclic ether and formal additives was as follows: nonadditive ∼ 1,3,5-trioxane ≫ 1,3-dioxane 〉 1,3-dioxolane ≫ 1,4-dioxane ≫ THP 〉 oxepane ≫ THF ≫ oxetane, propylene oxide ≫ 0. The polymerization in the presence of the cyclic formals was much faster than that of the cyclic ethers: for example, the apparent propagation rate constant k in the presence of 1,3-dioxolane was 103 times larger than that in the presence of THF. Another series of experiments showed that acyclic ethers with oxyethylene units were effective as additives for the living polymerization with 1/EtAlCl2 initiating system in hexane at 0°C. The polymers obtained in the presence of ethylene glycol diethyl ether and diethylene glycol diethyle ether had very narrow molecular weight distribution (M̄ω/M̄n ≤ 1.1), and the M̄n was directly proportional to the monomer conversion. The polymerization behavior was quite different in the polymerization rates and the MWD of the obtained polymers from that in the presence of diethyl ether. These results suggested the polydentate-type interaction or the alternate interaction of two or three ether oxygens in oxyethylene units with the propagating carbocation, to permit the living polymerization of IBVE. © 1994 John Wiley & Sons, Inc.
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    Preparation and properties of polyborosiloxanes as precursors for borosilicate formation of SiO2-B2O3 gel fibers and oxides by the sol-gel method using tetraacetoxysilane and boron tri-n-butoxide (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1049-1056 
    Details
    ISSN: 0887-624X
    Keywords: tetraacetoxysilane ; boron tri-n-butoxide ; sol-gel method ; condensation ; SiO2 - B2O3 gel fibers ; borosilicates ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Formation of SiO2-B2O3 gel fibers and oxides was investigated by the sol-gel method using tetraacetoxysilane (TAS) and boron tri-n-butoxide (BTB). Low molecular weight borosiloxanes (BS) were formed by the reaction of TAS with BTB in THF. Partial alkoxylation and hydrolysis of BS followed by further condensation of the resulting polymer (PBS) solutions led to the formation of highly polymerized polyborosiloxanes (HPBS) with good spinnability. Gel fibers were obtained by dry spinning of HPBS. The compositions of PBS and gels were not consistent with that in feed. Heat treatment of the gels, however, provided SiO2-B2O3 oxides with compositions almost compatible with those of the gels. © 1994 John Wiley & Sons, Inc.
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    Synthesis and thermal behavior of side-chain liquid crystalline polymethacrylates containing tolane-based mesogenic side groups (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1077-1085 
    Details
    ISSN: 0887-624X
    Keywords: liquid crystal polymer ; polymethacrylate ; tolane ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and characterization of nine polymethacrylates containing 4-alkoxy-4′-trifluoromethyltolane, 4-alkoxy-4′-cyanotolane, and 4-alkoxy-4′-nitrotolane side groups were described in this study. The phase behavior of the prepared monomers and polymers was characterized by differential scanning calorimetry, optical polarizing microscopy, and x-ray diffraction. All of the obtained monomers exhibit no mesophase, while most of the synthesized polymers reveal enantiotropic mesomorphism. The polymethacrylate containing 4-propanyloxy-4′-nitrotolane side groups was the only one which shows no mesomorphic behavior. Both the spacer length and the nature of terminal groups have profound influence on the phase transition temperatures and thermal stability of the mesophase. The polymers with longer spacers tend to form a more ordered mesophase with a wider temperature range. Among three polymers with the same spacer length, the polymer with a trifluoromethyl terminal end group is inclined to form a more ordered mesophase than the other two polymers. No side chain crystallization occurred for all obtained polymers. © 1994 John Wiley & Sons, Inc.
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    Anionic polymerization of propylene oxide: Isomerization of allyl ether to propenyl ether end groups (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1131-1135 
    Details
    ISSN: 0887-624X
    Keywords: poly(propylene oxide) ; allyl, propenyl ; isomerization ; 1H NMR ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The isomerization of allyl ether to propenyl ether end group in anionically-polymerized poly (propylene oxide) was monitored by 1H NMR spectroscopy. It was confirmed that the reaction followed a simple second-order rate law: -d[allyl]dt = k2[allyl] [O-]. Values of k2 determined over the 90-130°C temperature range, indicated an activation energy of 116 kJ mol-1. © 1994 John Wiley & Sons, Inc.
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    Dimethyltitanocene-induced surface chemical degradation of synthetic biodegradable polyesters (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 949-960 
    Details
    ISSN: 0887-624X
    Keywords: dimethyltitanocene ; biodegradable polymers ; poly(glycolic acid) ; surface degradation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The purpose of this research was to selectively alter the rate of surface degradation of linear aliphatic polyesters without adversely affecting their bulk properties by way of functional group transformation, where the surface ester linkages would be converted to vinyl ether functionalities with dimethyltitanocene. It has been observed that dimethyl titanocene causes surface degradation of poly (glycolic acid) without adversely affecting its bulk properties, such as Mv, bursting strength, and thermal properties The vinvl ether resulting from the conversion of the PGA ester groups was unstable under ambient conditions, and further reacted by polymer chain scissioning, as was observed from measurements of molecular weight. © 1994 John Wiley & Sons, Inc.
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    Laser-Induced generation of thin silicone layers with high chemical and spectral purity (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1893-1898 
    Details
    ISSN: 0887-624X
    Keywords: excimer laser ; organosilicon compounds ; additive-free polymers ; high chemical and spectral purity ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Excimer lasers (ArF, λ = 193 nm, and KrF, λ = 248 nm) were used to generate polymers free of additives such as catalysts, initiators, or sensitizers. The layers obtained are of potential interest for medical applications and future molecular electronics. Dimethylpolysiloxanes and dimethylsiloxane copolymers that contain phenyl-, n-hexyl- or 3.3.3-trifluoropropyl groups or silicon-bound hydrogen atoms were crosslinked in the liquid phase, whereby layer thicknesses in the range from 1-300 μm were obtained. Disiloxanes and alkoxysilanes were deposited from the gas phase (LCVD, laser chemical vapor deposition) resulting in layer thicknesses below 1 μm. In almost all cases, organic layers with a smooth surface, transparency, and good adhesion were obtained on silicon as well as quartz substrates. © 1994 John Wiley & Sons, Inc.
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    Phase-Transfer catalyzed free-radical polymerization of acrylonitrile (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1909-1914 
    Details
    ISSN: 0887-624X
    Keywords: phase transfer catalyst ; free-radical polymerization ; kinetics of polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of phase-transfer catalyzed free-radical polymerization of acrylonitrile (AN) was carried out with water-soluble initiator peroxomonosulphate (PMS) with phase-transfer catalysts (tetrabutylammonium chloride and benzyltributylammonium chloride (TBAC and BTBAC) in tolune/water two-phase systems in the temperature range of 45-55°C at fixed pH (4) and ionic strength. The rates of polymerization (Rp) were evaluated at various values of [PMS], [PTC], and [AN]. It has been observed that the rates of polymerization increase with an increase of [AN], [PMS], and [PTC]. A kinetic scheme has been proposed to account for the experimental observations. © 1994 John Wiley & Sons, Inc.
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    Study on chain transfer to acetic anhydride of THF polymerization (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1939-1947 
    Details
    ISSN: 0887-624X
    Keywords: polytetrahydrofuran ; acetylhexachloro-antimonate ; chain transfer ; THF ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the presence of acetic anhydride, the catalyst containing protons makes the polymerization complex.1,2 Thus, whether the living center, during the polymerization process of THF, transfers to the acetic anhydride is a difficult problem to answer. In this article, CH3COSbCl6 is used as the catalyst to avoid the interference of the protons. It is found that acetic anhydride is an effective chain transfer agent, by the experiment at different temperatures for two systems in the presence or absence of acetic anhydride, and by the comparison of kinetic behavior. In the system without acetic anhydride at the temperature of 7, 15, and 22°C, the propagation rate constants of THF, kp are 7.90, 14.23, and 23.35 10-3L/Mol.S, respectively. In the presence of acetic anhydride, kp are 1.51, 2.85, and 4.98 10-3L/Mol.S; and ktr are 2.04, 3.59, and 6.49 10-4L/Mol.S, respectively. © 1994 John Wiley & Sons, Inc.
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    Styrene polymerization with some new macro or macromonomeric azoinitiators having peg units (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1739-1746 
    Details
    ISSN: 0887-624X
    Keywords: macromerinitiator (macroinimer) ; crosslinked block copolymer ; macroinitiator ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several new macroinitiators and macromerinitiators (macroinimers) were synthesized and evaluated for the bulk polymerization of sytrene at 60°C. Macroinitiators were prepared from the reaction of 4,4′-dicyano-4,4′ azovaleryl chloride (1) with poly(ethylene glycol) (PEG) with a Mω of 400 and with either benzoyl chloride, acetyl chloride, phenyl isocyanate, or poly(ethylene glycol) oleyl ether. Macromer initiators were also prepared from the reaction of 1 with PEG having Mω values of 200, 400, 600, 1000, or 1500 and with 4-vinylbenzyl chloride. The bulk polymerization of styrene by macroinimers gave crosslinked styrene-PEG block copolymers, while the polymerization by macroinitiators gave soluble copolymers. The molecular weights of the styrene-PEG block copolymers obtained with macroinitiators having either oleyl, benzoyl, or phenyl urethane end groups were 22000-29000 g/mol. DSC measurements showed that the crosslinked block copolymers had crystalline PEG units with melting transitions ranging from 11-37°C. © 1994 John Wiley & Sons, Inc.
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    Studies on the formation of PEN. II. Polymerization of bis(hydroxyethyl) naphthalate by various metallic catalysts (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1305-1315 
    Details
    ISSN: 0887-624X
    Keywords: polyethylenenaphthalate ; bis(hydroxyethyl)naphthalate ; molecular weight ; polycondensation kinetics ; intrinsic viscosity ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis(hydroxyethyl) naphthalate (BHEN) was polymerized to polyethylenenaphthalate (PEN) in the presence of various metallic catalysts. The influence of the nature and concentration of these catalysts on the rate of polymerization has been investigated. The order of decreasing catalytic influence of various metal ions on the polymerization of BHEN was found to be: Ti 〉 Sb 〉 Zn 〉 Co 〉 Pb 〉 Ni(Mg). The effect of the reaction temperature has also been studied. The optimal concentration of these catalyst and reaction temperature were found to be 30 × 10-5 (mol/mol BHEN) and 285-293°C, respectively. Because of its insolubility in ordinary solvent, the molecular weight of PEN was measured using the light scattering method. © 1994 John Wiley & Sons, Inc.
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    Primary thermal degradation processes occurring in poly(phenylenesulfide) investigated by direct pyrolysis-mass spectrometry (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1807-1815 
    Details
    ISSN: 0887-624X
    Keywords: poly(phenylenesulfide) ; thermal degradation ; direct pyrolysis-mass spectrometry ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal degradation Processes which occur in poly(phenylenesulfide) (PPS) have been studied by direct pyrolysis-mass spectrometry (DPMS). The structure of the compounds evolved in the overall temperature range of PPS decomposition (400-700°C) suggests the occurrence of several thermal decomposition steps. At the onset of the thermal degradation (430-450°C) this polymer decomposes with the formation of cyclic oligomers, generated by a simple cylization mechanism either initiated at the - SH end groups or by the exchange between the inner sulfur atoms along the polymer chain. At higher temperature (〉 500°C) another decomposition reaction takes over with the formation of aromatic linear thiols. The formation of thiodibenzofuran units by a subsequent dehydrogenation reaction occurs in the temperature range of 550-650°C; in fact, pyrolysis products with a quasi-ladder structure have also been detected. Ultimately, above 600°C, extrusion of sulfur from the pyrolysis residue occurs with the maximum evolution at the end of decomposition (about 700°C). It appears, therefore, that the residue obtained at high temperature tends to have a crosslinked graphite-like structure from which the bonded sulfur is extruded. © 1994 John Wiley & Sons, Inc.
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    Effects of chain end group composition and concentration on the properties of bisphenol A-tetrabromobisphenol A copolycarbonates (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1885-1891 
    Details
    ISSN: 0887-624X
    Keywords: copolycarbonate ; bisphenol A ; tetrabromobisphenol A ; end group ; analysis ; properties ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The types and concentrations of end groups present in bisphenol A-tetrabromobisphenol A copolycarbonates (BA-TBBA coPCs) have major effects on the copolymer solution washability and thermal stability. Six types of coPC end groups are possible: two by monophenol capping of each comonomer, two phenolics (BA-OH and TBBA-OH), and two carbamates (one from each comonomer). BA-TBBA coPCs were prepared by typical solution and interfacial methods and their phenolic and carbamate end group concentrations were correlated with their solution washability and thermal discoloration. Both phenolic and carbamate end groups proved deleterious to these two copolymer properties. An improved interfacial process that employs 4-N,N-dimethylaminopyridine as the coupling catalyst provides coPCs having low concentrations of phenolic and carbamate end groups and that, therefore, wash without emulsification and are thermally stable. © 1994 John Wiley & Sons, Inc.
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    Synthesis and thermal stability of the resins prepared from the reactions of 1,4-bis(2,2-dicyanovinyl)benzene with aromatic diamines and electrical conductivity of the resulting materials following pyrolysis (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1915-1921 
    Details
    ISSN: 0887-624X
    Keywords: 1,4-bis(2,2-dicyanovinyl)benzene ; thermally stable polymers ; thermosetting resins ; conductive polymers ; electrical resistivity ; cyano-substituted polymers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New thermosetting resins were prepared from the reaction of 1,4-bis(2,2-dicyanovinyl)benzene with aromatic diamines in varying molar ratios. The thermal stability of these resins was correlated with their composition and the curing conditions. They were stable in N2 up to 370-448°C and afforded anaerobic char yields of 73-84% at 800°C after curing at 300°C for 20-60 h. The temperature dependence of the electrical resistivity of all resins pyrolyzed at 700°C for 15 h was studied in the temperature range from -173-327°C (100-600 K). The results showed that at room temperature the unpyrolyzed polymers have insulating properties, whereas a dramatic decrease in the electrical resistivity is observed following pyrolysis. The temperature dependence of the electrical resistivity suggests that all of the materials studied have semiconducting properties. The observed electrical conductivity is thermally activated with activation energies ranging from 0.03-0.06 eV. © 1994 John Wiley & Sons, Inc.
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    Synthesis of poly(γ-methoxypropylmethylsilylene) and poly(γ-methoxypropylmethylsilylene-co-di-n-hexylsilylene) (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1949-1956 
    Details
    ISSN: 0887-624X
    Keywords: polysilanes ; polysilylenes ; copolysilane ; alkoxy-substituted polysilane ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of γ;-methoxypropylmethyldichlorosilane, and its subsequent polymerization and copolymerization with di;-n;-hexyldichlorosilane through the reductive coupling with sodium has been accomplished. The resulting polymers contain methyl ether side groups that allow further synthetic transformations on the polysilane backbone. For poly (γ;-methoxypropylmethylsilylene) these groups impart solubility characteristics different than typical alkyl and aryl substituted polysilanes. These new polymers and copolymers have been characterized by GPC and 1H-, 13C-, and 29Si-NMR. © 1994 John Wiley & Sons, Inc.
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    Basic structure-property behavior of polyurethane cationomers (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1983-1989 
    Details
    ISSN: 0887-624X
    Keywords: polyurethane cationomer ; PTAd ; IPDI ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyurethane (PU) cationomers were synthesized from polytetramethylene adipate glycol (PTAd), isophorone diisocyanate (IPDI), and N-methyl diethanolamine (MDEA) according to a prepolymer mixing process. Basic structure-property behavior of the emulsion (obtained by adding water to the ionomer solution) and emulsion cast film was studied with regard to the molecular weight (Mn) of PTAd, MDEA content, degree of neutralization, and extender functionality. Particle size decreased asymptotically with increasing Mn of PTAd due to the increased chain flexibility, and with the degree of neutralization due to the increased hydrophilicity of the PU. Emulsion viscosity generally showed the opposite tendency with particle size dependence. The major transition temperature, corresponding to the glass transition (Tg) of phase mixed PU or hard segment-rich phase of the PU monotonically increased with MDEA content, degree of neutralization, and with increasing extender functionality. However, with increasing Mn of PTAd, Tg first decreased (Mn = 1000) and then increased (Mn = 1500, 2000), due respectively to the increased hard fraction of phase mixed PU, and soft segment crystallization. Tensile strength increased and elongation at break decreased with MDEA content, degree of neutralization, and extender functionality. © 1994 John Wiley & Sons, Inc.
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    Analysis of 1H-NMR spectra of various end-functionalized polyisobutylenes (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2011-2021 
    Details
    ISSN: 0887-624X
    Keywords: polyisobutylene ; living carbocationic polymerization ; proton NMR analysis ; hydroxyl-ended, chlorine-ended, olefin-ended, phenyl-ended polyisobutylenes ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1H-NMR spectra of various telechelic (i.e., ∼ CH2C(CH3)2Cl, ∼ CH2C(CH3)=CH2, ∼ CH=C(CH3)2, and ∼ CH2CH(CH3)CH2OH capped) polyisobutylenes (PIB) have been analyzed. The products were prepared by living carbocationic polymerization followed by end-group functionalization. Shielding and deshielding effects strongly influence the 1H-NMR spectra of these products. Inductive effects (chlorine-ended PIBs), magnetically anisotropic end-groups (olefin groups and phenyl rings), allylic coupling (olefin end-groups), chirality (hydroxyl end-groups), and the interaction of these effects on the 1H-NMR spectra are discussed. Numerous heretofore unidentified resonances have been assigned and better insight into the detailed structure of end-functionalized PIBs has been obtained. © 1994 John Wiley & Sons, Inc.
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    Effect of polarity of the medium on the stereospecific polymerization of propylene by ansa-zirconocene catalyst (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2049-2056 
    Details
    ISSN: 0887-624X
    Keywords: metallocenes ; olefin polymerizations ; Ziegler-Natta catalysts ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Propylene was polymerized with rac-ethylene-bis (1-η5-indenyl)dichlorozirconium/methylaluminoxane in solvents of different polarity. The poly (propylene) formed was separated by solvent extraction; 13C-NMR and DSC measurements were made on the polymer fractions. The poly(propylene) in each solvent fraction has its characteristic molecular weight steric pentad distributions, melting transition temperature, and enthalpy for fusion irrespective of the polymerization medium. The results suggest that the medium dielectric constant does not affect the polymerization rate or the intrinsic stereoselectivity, propagation and chain transfer rates a given catalytic species but can alter the occurrence of steric insertion errors through shifting of distributions of the propagating species producing poly(propylenes) of different stereoregularities. © 1994 John Wiley & Sons, Inc.
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    Radical polymerization of N-substituted itaconamic esters and itaconamides (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2085-2091 
    Details
    ISSN: 0887-624X
    Keywords: radical polymerization ; 1,1-disubstituted ethylene itaconamate ; itaconamide ; thermal property ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two kinds of itaconamic esters, α-substituted acrylate derivatives (IAE-I) and α-substituted acrylamide derivatives (IAE-II), as well as itaconamides (IAm) were prepared and polymerized with a radical initiator. It has been revealed that N,N-disubstituted IAE-I as an acrylate is more reactive in polymerization than N,N-disubstituted IAE-II as an acrylamide and that N,N′-dialkyl substituted IAm homopolymerizes but N,N,N′,N′;-tetraalkyl substituted one does not. In radical copolymerization with styrene, IAE-I showed a higher polymerization reactivity than IAE-II. The effects of the N-substituents on the polymerization reactivity were discussed on the basis of conformation of the monomers. The polymers obtained were also characterized. © 1994 John Wiley & Sons, Inc.
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    Polymer-supported Ziegler-Natta catalysts. I. A preliminary study of catalyst synthesis (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2127-2134 
    Details
    ISSN: 0887-624X
    Keywords: Ziegler-Natta catalyst ; polymer support ; ethylene ; polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymer-supported Ziegler-Natta catalysts based on various polymer carriers were synthesized by different methods, including (1) loading TiCl4 directly onto the polymer supports; (2) loading TiCl4 onto the polymer supports modified by magnesium chloride (MgCl2); (3) loading TiCl4 onto the polymer supports modified by Grignard reagent (RMgCl); and (4) loading TiCl4 onto the polymer supports modified by magnesium alkyls (MgR2). The activity and kinetic features of the catalysts for ethylene polymerization were examined. Among the combinations tested, the best was found to be TiCl4/n-Bu2Mg.Et3Al/poly(ethylene-co-acrylic acid) (92:8), which produced a catalyst of very high activity for ethylene polymerization. © 1994 John Wiley & Sons, Inc.
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    Triblock copolymers based on cyclic ethers: Preparation and properties of tetrahydrofuran and 3,3-bis(azidomethyl) oxetane triblock copolymers (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2155-2159 
    Details
    ISSN: 0887-624X
    Keywords: block copolymer ; tetrahydrofuran ; oxetanc ; ring opening ; cationic polymerization ; energetic ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Novel energetic thermoplastic elastomers (TPEs) based on tetrahydrofuran (THF) and 3,3-bis (azidomethyl) oxetane (BAMO) were prepared in this present study by cationic living polymerization. A bifunctional catalyst, triflic anhydride [(CF3SO2)2)O] was selected to be an initiator for the polymerization THF and BAMO. The resulting polymers were characterized by IR, NMR, and DSC, which demonstrated that triblock copolymers with A-B-A type were formed. The polymers were indicated from thermogravimetric analysis (TGA) to have decomposed at approximately 243°C. The decomposition enthalpies were determined by DSC. These enthalpies were varied with the poly-BAMO contents of the copolymers. The synthesized polymers exhibited relatively good mechanical properties and thermoplastic characteristics at room temperature. © 1994 John Wiley & Sons, Inc.
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    New fluorinated oxazoline block copolymer lowers the adhesion of platelets on polyurethane surfaces (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2187-2192 
    Details
    ISSN: 0887-624X
    Keywords: polyurethane ; poly (oxazoline) ; fluoropolymer ; biomaterial ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have prepared an amphiphilic oxazoline block copolymer of hydrophilic poly(2-methyl-2-oxazoline) and hydrophobic poly[2-(2-perfluorooctyl)ethyl-2-oxazoline] chains. By controlling the length and composition of polymer chains, we found that this fluorinated block copolymer can be readily dissolved in water. Furthermore, we can achieve a stable surface coating of the fluorinated block copolymer by dissolving the copolymer in water, then coating the aqueous copolymer solution onto surfaces of nonwater-soluble polymers. This is a simple and useful method of modifying the surface character of polymer substrates. We have found that the polyether urethane (PEU) coated by block copolymer has a different surface chemistry and biological reactivity than the uncoated PEU. From XPS analysis, we found the fluorinated copolymer was coated on PEU (atomic % of F: 31.3 on coated PEU, 0.3 on uncoated). The two surfaces have different affinities for biological molecules. Specifically, the fibrinogen adsorption on the fluorinated copolymer-coated PEU was 62 ± 39 ng/cm2, compared to a value of 156 ± 99 ng/cm2 for uncoated PEU. In an ex vivo evaluation of platelet adhesion, the surface of coated PEU attached a few white cells while uncoated PEU was covered with activated platelets. © 1994 John Wiley & Sons, Inc.
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    Quantitative theory of iniferter polymerization. I. Kinetics (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1557-1568 
    Details
    ISSN: 0887-624X
    Keywords: free-radical polymerization ; mechanism and kinetics ; nontraditional initiators ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On the basis of a rather general scheme of elementary reactions of radical polymerization conducted in the presence of iniferters, kinetic equations have been derived describing this process over the whole range of monomer conversion. Proceeding from thorough analysis of these equations, different regimes of polymerization have been found that differ in values of order with respect to the iniferter and monomer of the initial rate of polymerization. Conditions for kinetic parameters have been formulated whose fulfillment predetermines that radical polymerization occurs according to the iniferter mechanism. © 1994 John Wiley & Sons. Inc.
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    Whiskers. VIII. A convenient synthesis of poly(4-hydroxybenzoate) whiskers and their application in composites of nylon-6 (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1601-1607 
    Details
    ISSN: 0887-624X
    Keywords: poly(4-hydroxybenzoate) ; whiskers ; crystal growth ; nylon-6 composites ; mechanical properties ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Whiskers of poly(4-hydroxybenzoate) [poly(4-HBA)] were prepared by polycondensation of free 4-hydroxybenzoic acid with acetic anhydride and pyridine in a high boiling inert solvent. The purity of the monomer is decisive for the success of the synthesis. For a less pure 4-hydroxybenzoic acid, the preparation of acetylated oligomers with acetylchloride, followed by polycondensation of the isolated oligomers is a suitable alternative. Whiskers, with a solid-solid phase transition at 364°C were obtained, which is the highest temperature reported for this transition so far. Two batches of composites were prepared from nylon-6 using polyester whiskers with an alkaline or an acidic surface treatment. A third batch was prepared using poly(ester-amide) whiskers. The mechanical properties of these composites indicate that the surface treatment does not play any role, and that the poly(esteramide)s are inferior to the polyester whiskers, because they are not single crystals. © 1994 John Wiley & Sons, Inc.
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    Hydroquinone oxidation catalyzed by pyridine-Cu(II) complexes attached to polyorganosiloxane. II.For Part I, see: Reference 40. Elucidation of factors related to catalytic activity (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2457-2467 
    Details
    ISSN: 0887-624X
    Keywords: polyorganosiloxane ; pyridine-Cu(II) complex ; catalysis ; hydroquinone oxidation ; copolymerization ; hydrophobicity ; flexibility ; equilibrium dialysis ; ESR spectroscopy ; cyclic voltammetry ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of hydroquinone catalyzed by pyridine-Cu(II) complexes attached to polyorganosiloxane was investigated in the mixed solvent of methanol/water (vol. ratio 2/1). The catalytic oxidation followed Michaelis-Menten-like kinetics. The large k2 term related to a turnover number indicated that the present polymeric catalysts have a remarkable effect on the activation process. The methylene number between the side-chain acid amido and pyridyl groups of the polymeric ligand was shown to be closely related to the appearance of hydrophobic effects in both the substrate-binding and the activation processes as deduced from the Michaelis constant and the thermodynamic and activation parameters. The binding parameters for 4-methoxyphenol with pyridyl-functionalized polyorganosiloxanes supported that the flexible backbone is also effective in the oxidation of hydroquinone. The Cu(II) complexes with pyridyl-functionalized polyorganosiloxane would have the structures distorted from square planar formation, which would promote the reduction of Cu(II) to Cu(I), as concluded from ESR spectroscopy and electrochemical measurement. © 1994 John Wiley & Sons, Inc.
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    Ion-Free latex films as dual-phase electrolytes: Styrene-butadiene rubber and nitrile-butadiene rubber synthesized by emulsion polymerization with poly-(vinyl pyrrolidone) stabilizer (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2505-2515 
    Details
    ISSN: 0887-624X
    Keywords: polymer electrolyte ; latex ; battery ; styrene-butadiene ; acrylonitrile-butadiene ; dual-phase ; emulsion polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ion-free latices of styrene-butadiene rubber (SBR) and nitrile-butadiene rubber (NBR) were synthesized by emulsion polymerization with use of poly (vinyl pyrrolidone) (PVP) stabilizer. The goal was to prepare ion-free latex films, possessing dual-phase latex particle morphology, and swell the films with liquid electrolyte to yield dual-phase polymer electrolytes (DPE). SBR/PVP latex was prepared readily, but NBR/PVP latex was sensitive to coagulation. Differential scanning calorimetric (DSC) and scanning electron microscopic (SEM) analyses of latex films provided morphological evidence concerning particle structure and phase separation. Blends of NBR/PVP and PB/PVP latices (PB = polybutadiene) were also investigated, but particle structure was not present in the blended latex film, even though particle structure was present in the individual NBR/PVP and PB/PVP latex films. After extensive swelling of SBR/PVP latex films, PVP was extracted from the films, and ionic conductivities greater than 10-3 S/cm were achieved. © 1994-John Wiley & Sons, Inc.
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    Synthesis of hydroxyl-containing polyimides derived from 4,6-diamino-resorcinol dihydrochloride and aromatic tetracarboxylic dianhydrides (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1903-1908 
    Details
    ISSN: 0887-624X
    Keywords: polyimides ; pendant hydroxyl ; hydrophilic ; amine hydrochloride ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High Tg polyimides containing pendant phenolic hydroxyl groups were synthesized in high molecular weight via one-step solution polymerization of the dihydrochloride salt of 4,6-diaminoresorcinol with various commercially available dianhydrides. Polymerization proceeds via initial dissociation of diaminoresorcinol dihydrochloride to hydrogen chloride gas and diaminoresorcinol, followed by rapid dissolution of diaminoresorcinol and polymerization with the dianhydride monomer to afford soluble, fully-cyclized polyimide. The resulting poly(hydroxy-imide)s, which contain two phenolic hydroxyl groups per repeat unit, were soluble in amide solvents and dilute aqueous bases, displayed reasonably high glass transition temperatures and a high degree of water uptake. © 1994 John Wiley & Sons, Inc.
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    Cation exchange membranes by pre-irradiation grafting of styrene into FEP films. I. Influence of synthesis conditions (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1931-1938 
    Details
    ISSN: 0887-624X
    Keywords: FEP ; styrene ; radiation grafting ; synthesis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Gamma radiation-induced grafting of styrene into FEP films was investigated by the pre-irradiation method. The degree of grafting was found to be strongly dependent on the synthesis conditions, such as radiation dose, monomer concentration, crosslinker, temperature, and film thickness. The order of dependence of the rate of grafting on pre-irradiation dose and monomer concentration was found to be 0.64 and 1.90, respectively. The activation energy for the grafting in the temperature range of 50-80°C was determined to be 27.9 kJ/mol. A negative first order dependence of grafting on film thickness was observed. The results suggest that the initial grafting takes place at the film surface and proceeds to the middle by progressive diffusion of monomer through the polystyrene grafted layers. © 1994 John Wiley & Sons, Inc.
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    Synthesis and properties of poly(arylene ether imide ketone)s (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1969-1975 
    Details
    ISSN: 0887-624X
    Keywords: high-performance aromatic polyethers ; aromatic nucleophilic substitution polymerization ; aromatic polyether ketone containing imide ; thermal behavior ; high-temperature polymers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(arylene ether ketone)s containing imide units were prepared by the aromatic nucleophilic displacement reaction of the potassium salts of bisphenols with bis(4-fluorobenzoyl)phthalimides in N-methyl-2-pyrrolidone at elevated temperature. The polymers having inherent viscosities of 0.34-0.77 dL/g were obtained in 2 h. The polymers exhibited glass transition temperatures ranging from 216 to 268°C and decomposition temperatures (5% weight loss under air atmosphere) ranging from 450-570°C mainly depending on the bisphenols used in the polymer synthesis. The isothermal TGA measurements (400°C under air or nitrogen atmosphere) revealed that the 4,4'-biphenol- and hydroquinone-based poly(arylene ether ketone imide)s belong to a superior class of heat resistant polymers. The mechanical properties of these polymers are also described. © 1994 John Wiley & Sons, Inc.
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    Polymeric networks by the cationic crosslinking reaction of poly(allenyl ether)s having oligo(oxyethylene) moieties in the side chain (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1991-1995 
    Details
    ISSN: 0887-624X
    Keywords: allenyl ethers ; oligo(oxyethylene)s ; crosslinking ; nonionic hydrogel ; cationic catalyst ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cationic crosslinking reactions of poly(allenyl ether)s having oligo(oxyethylene) moieties prepared by the radical polymerization of the corresponding allenyl ethers were carried out under some varied reaction conditions. For instance, a crosslinked polymer was obtained in 82% yield by the treatment of poly(ethylene glycol methyl allenyl ether) (1a) with 1.2 mol% of BF3·OEt2 (2) under high concentration in dichloromethane (46 wt %). The gels obtained showed good swelling properties in water, alcohols, and polar organic solvents such as dichloromethane. In particular, the degrees of swelling of these gels in aqueous sodium chloride (1M) were quite similar to those in ion-free water, indicating that these gels served as nonionic hydrogels. © 1994 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321023
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    A highly conductive and crystalline graphite-like polymer from 2,4-hexadiyn-1,6-diol (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2437-2441 
    Details
    ISSN: 0887-624X
    Keywords: metathesis ; graphite-like crystal ; pyrolysis ; conductivity ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-(2,4-hexadiyn-1,6-diol) (PHDO), prepared by NbCl5/(n-Bu)4Sn catalyzed metathesis of HDO, was pyrolyzed at various temperatures and electrical and structural properties of resulting polymers were investigated by FT-IR, Laser Raman, CP/MAS 13C-NMR and X-ray diffraction methods. The polymer obtained by pyrolysis of PHDO at 800°C showed a conductivity of about 10 S/cm at room temperature. The structure of the polymer seems to be a graphite-like crystal consisting of condensed aromatic layers. © 1994 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pola.1994.080321305
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    A comparative study of the silent discharge treatment of saturated and unsaturated hydrocarbon polymers (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2479-2486 
    Details
    ISSN: 0887-624X
    Keywords: surface treatment ; silent discharge ; plasma ; polyethylene ; polypropylene ; polyisobutylene ; polystyrene ; polyisoprene ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dielectric barrier air discharge treatment of polyethylene, polypropylene, polyisobutylene, polystyrene, and polyisoprene substrates has been characterized by x-ray photoelectron spectroscopy (XPS). The relative reactivities of these polymers towards silent discharge oxidation are rationalized in terms of ozone molecules interacting with an excited surface. © 1994 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pola.1994.080321309
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  • 193
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    Synthesis of poly(biphenylene ketone)s via palladium catalyzed cross-coupling reactions with ketone diacetals (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2493-2500 
    Details
    ISSN: 0887-624X
    Keywords: aromatic polyketone ; palladium catalysis ; diacetal ; cross-coupling condensation ; zinc reagent ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dibromobenzophenone diacetals (BrC6H4)2C(OR)2 undergo cross-coupling reactions with (Bu3SnC6H4)2O in the presence of palladium catalysts to give poly (diacetal ether)s whose molecular weights reflect the solubility changes of the growing polymer chains as a function of the diacetal precursors, R = Me 〈 1/2 CH2CH2 〈 1/2 CH2CHMe and are significantly higher than those of polymers derived from dibromobenzophenone. New di-zinc reagents based on diacetal derivatives were synthesized and used as organometallic coupling reagents with a range of dibromoarenes, resulting in a series of previously inaccessible poly (biphenylene ketone)s and poly (biphenylene ketone sulfone)s. While poly (biphenylene ether ketone)s are insoluble, poly (biphenylene ketone)s readily dissolve in concentrated sulfuric acid. The effects of reaction parameters on the molecular weight of poly (biphenylene ketone) were determined. © 1994 John Wiley & Sons, Inc.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/pola.1994.080321311
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    Synthesis of end-functionalized polystyrenes with organosilicon end-capping reagents via living cationic polymerizationThis work was presented in part at the 41st Annual Meeting of the Society of Polymer Science, Japan, Yokohama, May 1992; Paper I-D-11: see Ref. 1. (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2531-2542 
    Details
    ISSN: 0887-624X
    Keywords: living polymerization ; cationic polymerization ; styrene ; end-functionalized polymer ; macromonomer ; organosilicon compounds ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The end-functionalization of living polymers with bases (methanol, benzylamine, diethyl sodiomalonate, and sodium methoxide) and organosilicon compounds [X — Si(CH3)3;X —: CH2=C(CH3)COO—, CH3COO—, CH2=CHCH2—, C6H5—] was investigated in the living cationic polymerization of styrene initiated with the 1-phenylethyl chloride/SnCl4/nBu4NCl system in CH2Cl2 at -15°C. The four bases and C6H5SiMe3, independent of their structures, were apparently incapable of reacting with the living end and invariably led to polystyrenes with the ω-end chlorine [∼ ∼ ∼ CH2CH(Ph)Cl] originated from the initiating system. The number-average end-functionality (F̄n) of the chloride, determined by 1H-NMR, was close to unity (F̄n 〉 0.9). The presence of chlorine in the polymer was also confirmed by elemental analysis. In contrast, the quenching by the trimethylsilyl compounds with X = methacryloxy, acetoxy, and allyl gave ω-end-functionalized polystyrenes with the corresponding terminal groups (X) for which the F̄n values were close to unity (F̄n 〉 0.9). The effects of the structure of silyl compounds on end-capping are also discussed. © 1994 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pola.1994.080321316
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  • 195
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    Polymerization of N-alkyl-substituted itaconimides and N-(alkyl-substituted phenyl)itaconimides and characterization of the resulting polymers (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2073-2083 
    Details
    ISSN: 0887-624X
    Keywords: radical polymerization ; anionic polymerization ; polyimide ; thermal stability ; itaconic derivatives ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-alkyl-substituted itaconimides (RII) and N-(alkyl-substituted phenyl)itaconimides (RPhII) with various alkyl substituents were prepared and polymerized in the presence of a radical or anionic initiator to give high molecular weight polymers in high yields. The effects of the alkyl substituents on the polymerization reactivities were investigated. It has been revealed that RII and RPhII have the highest polymerization reactivity compared with other itaconic and citraconic derivatives including dialkyl itaconates and citraconimides. The structure and some properties of poly(RII) and poly(RPhII) were examined. These polymers were found to have excellent thermal stability, better than poly (dialkyl itaconate)s. © 1994 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pola.1994.080321109
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  • 196
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    Influence of the morphology of polypropylene films on the formation and evolution of irradiation-induced peroxy-radicals (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2193-2198 
    Details
    ISSN: 0887-624X
    Keywords: ESR ; polypropylene ; radical ; morphology ; diffusion ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To gain some knowledge on the influence of a substrate morphology upon radiochemical grafting efficiency, the formation and the evolution of irradiation induced peroxy-radicals were measured by ESR in two polypropylene (PP) films of different origins. The creation rate of peroxy-radicals was found to be almost proportional to the irradiation dose in the film presenting the best crystallinity, the bi-oriented PP, while it saturates in the unoriented one. The recombination kinetics of the radicals appeared to be controlled by their diffusion in the matrix and the corresponding diffusion coefficients are dependent on the matrix itself and on its evolution under irradiation. It is suggested that the crystalline order of the matrix is the parameter governing the mobility and thus the lifetime of the radicals. © 1994 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pola.1994.080321123
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  • 197
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    Determining the chromophore in the amylopectin-iodine complex by theoretical and experimental studies (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2257-2265 
    Details
    ISSN: 0887-624X
    Keywords: helix in amylopectin-iodine complex ; I4 unit in amylopectin-iodine complex ; spectra of amylopectin-iodine complex ; amylopectin-iodine chromophore composition ; amylopectin fine structures and complex formation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A partial hydrolysis of amylose followed by the addition of iodine provides a spectrum almost identical to that of the amylopectin-iodine (API) complex suggesting the involvement of smaller “amylose-like” units in the API complex. Our theoretical studies on different polyiodine and polyiodide species suggest that a nearly linear I4 unit stabilized within the cavity of a small “amylose-like” helix is responsible for the characteristic API spectrum. Since there are 2.75 anhydroglucose residues (AGU) for every iodine atom in the amylose-iodine (AI) complex and a structural similarity exists between the API and the AI (amylose-iodine) complexes, we identify (C6H10O5)11I4 to be the chromophore in the API complex. © 1994 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pola.1994.080321207
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    Cationic ring-opening polymerization of bicyclic amide acetals (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2283-2290 
    Details
    ISSN: 0887-624X
    Keywords: epoxide ; bicyclic amide acetal ; 2-oxazoline ; ring-opening polymerization ; zwitterion polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Various bicyclic amide acetals were synthesized from the cycloaddition reactions of 2-substituted-2-oxazolines with styrene oxide. Ring-opening polymerization of the bicyclic amide acetals occurred upon heating in the presence of methyl tosylate. Characterization of the bicyclic amide acetals and their polymers was accomplished by NMR and elemental analysis. Vapor pressure osmometry showed the highest polymer molecular weight was only 2,400. The mechanisms for cycloaddition and polymerization are discussed. © 1994 John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pola.1994.080321210
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    Photografting of vinyl polymers onto ultrafine inorganic particles: Photopolymerization of vinyl monomers initiated by AZO groups introduced onto these surfaces (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2327-2332 
    Details
    ISSN: 0887-624X
    Keywords: surface grafting of polymers ; ultrafine silica ; titanium oxide ; photografting ; azo groups ; vinyl polymer ; dispersibility ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photografting of polymers onto ultrafine inorganic particles, such as silica and titanium oxide, initiated by azo groups introduced onto these surfaces was investigated. The introduction of azo groups onto the particles was achieved by the reaction of 4,4′-azobis(4-cyanopentanoic acid) with surface isocyanate groups, which were introduced by the treatment with tolylene 2,4-diisocyanate. It was found that the photopolymerization of vinyl monomers, such as methyl methacrylate (MMA), styrene, and N-vinylcarbazole, is initiated by ultrafine particles having azo groups. The corresponding polymers were effectively grafted onto these surfaces through the propagation of the polymer from the surface radicals formed by the photodecomposition of the azo groups: e.g., the percentage of grafting of PMMA and polystyrene onto silica was reached to 112 and 176%, respectively. The percentage of grafting onto silica in the graft polymerization initiated by photodecomposition of surface azo groups was much larger than that initiated by thermal decomposition. Polymer-grafted ultrafine particles thus obtained gave a stable colloidal dispersion in good solvents for the grafted chain. © 1994 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321214
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    Synthesis of soluble, thermosetting polymides derived from 1,4-phenylenebis(phenylmaleic anhydride) and aromatic diamines (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2377-2385 
    Details
    ISSN: 0887-624X
    Keywords: thermosetting imides ; 1,4-phenylenebis(phenylmaleic anhydride) ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dianhydride monomer 1,4-phenylenebis(phenylmaleic anhydride) was polymerized with various aromatic diamines in a one-step solution polymerization to afford high molecular weight, soluble polyimides containing backbone phenylmaleimide structures. The polymides were soluble in amide solvents, chlorinated hydrocarbons, and tetrahydrofuran at 25°C at a concentration of 15% (w/v), displayed molecular weight distributions (Mw/Mn) of 2.0-2.2 as determined by absolute GPC and showed Tg values of 240°C and above as measured by differential scanning calorimetry. In addition, polyimide thermosets were prepared from these materials by thermal cure at 350-360°C. The crosslinked polyimides displayed Tgs 20-25°C higher than their soluble precursors, and chloroform extraction indicated gel fractions ranging from 74-100% after cure. © 1994 John Wiley & Sons, Inc.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321218
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