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  • Articles  (1,847)
  • Polymer and Materials Science  (1,608)
  • Chemical Engineering  (189)
  • Amino Acid Sequence  (50)
  • 1985-1989  (1,847)
  • 1950-1954
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  • 1985  (1,847)
  • Physics  (1,847)
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  • Articles  (1,847)
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  • 1985-1989  (1,847)
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  • 1
    Electronic Resource
    Electronic Resource
    Surface grafting of heparin-complexing poly(aminoamide) on poly( ethylene terephthalate) (dacron) (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 9 (1985), S. 233-238 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Surface grafting of low-molecular weight polyamines and poly(amino-amides) onto Dacron fabrics was performed by two different methods. The first one involves chlorosulfonation followed by a reaction with a polyamine such as triethylenetetramine, and finally with a vinyl-terminated poly(amino-amide). The latter involves the use of poly(1-acryloylbenzotriazole) in an intermediate step. The surfaces of the poly(amino-amide) - grafted materials showed a good heparin adsorbing capacity. Most of the adsorbed heparin was released only by elution with aqueous NaOH of pH 〉 10, thus confirming the strong interaction between polymer and heparin.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020091985134
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  • 2
    Electronic Resource
    Electronic Resource
    On the prediction of the rate of emulsion copolymerization and copolymer composition (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 10 (1985), S. 25-42 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The derivation of simple kinetic equations will be briefly reviewed which are applicable not only to the predictions of the rate of emulsion copolymerization and copolymer composition, but also to the quantitative analyses of the chemical and physical rate processes involved in an emulsion copolymerization system and to the evaluation of their rate constants. The validity of these kinetic equations for predicting the rate of emulsion copolymerization and copolymer composition is demonstrated by comparing the theoretical predictions with the experimental data for the emulsion copolymerization of styrene and methyl methacrylate. The utility of these kinetic equations for evaluating the rate constants in an emulsion copolymerization system is also shown by using the experimental data for the emulsion copolymerization of vinyl acetate and methyl methacrylate.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020101985105
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  • 3
    Electronic Resource
    Electronic Resource
    Copolymérisation en émulsion styrène-acrylate de butyle en réacteur fermé (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 10 (1985), S. 87-103 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The emulsion copolymerization kinetics of styrene-butyl acrylate was studied in a batch process. The effect of the initiator, emulsifier, chain transfer agent and monomer concentration on copolymerization rate and molecular weight distribution is discussed. Thermal and viscoelastic properties of copolymers were measured. It was found that the n-dodecylthiol introduced into the reactor with the monomers did not affect the copolymerization rate (no redox reaction with the initiator) but the molecular weight was strongly dependent upon its concentration. These two kinetic parameters increase with increasing the butyl acrylate concentration.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020101985109
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  • 4
    Electronic Resource
    Electronic Resource
    Experimental and modelling study of semi-continuous emulsion copolymerization of styrene and acrylonitrile (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 10 (1985), S. 149-158 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An experimental study of semi-continuous emulsion copolymerization of acrylonitrile (AN) and styrene (ST) was carried cut with an isothermal stirred vessel. Continuous addition of monomer emulsion (ME) was inserted between preliminary and finishing batch operations. A mathematical model to simulate the experimental results was also developed with a particular attention on the partition of hydrophilic AN between the aqueous and organic phases. The result of simulation was quite satisfactory even though the approximate rate expressions proposed by Szabo and Nauman (1) were employed.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020101985112
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  • 5
    Electronic Resource
    Electronic Resource
    Some aspects of inverse emulsion copolymerization of acrylamide with methacrylic acid (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 10 (1985), S. 199-214 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Inverse emulsion copolymerization studies of acrylamide (Am) with methacrylic acid (MAA) are reported. Aqueous monomer emulsions in toluene were prepared with a blend of two surfactants (sorbitan sesquioleate - Cl8 - terminated acrylamide oligomers). Polymerization kinetics in presence of an oil soluble initiator (AIBN) were determined at 40°C as function of MAA content and aqueous phase pH : monomer reactivity ratios have been derived as rAm = 0.58 ± 0.02, rMAA = 4.40 ± 0.10 at pH 4 and rAm = 0.56 ± 0.005, rMAA = 0.15 ± 0.03 at pH 10. Particle size and stability of inverse monomer emulsions and final latexes were found to depend upon the aqueous phase pH, as well as the intrinsic viscosities of the copolymers; this suggests differences in polymerization mechanism versus the pH.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020101985116
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  • 6
    Electronic Resource
    Electronic Resource
    Some thermodynamic aspects in emulsion copolymerization (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 10 (1985), S. 235-264 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Emulsion polymerization proceeds in a heterogeneous medium; in copolymerization, due to discrepancy in water solubility and interactions with the resulting copolymers, monomers are partitioned in a complex way between droplet, water and particle phases. As monomer swollen polymer particles are the main loci of polymerization, it is of great interest to know the monomer feed within the particle phase to understand the behaviour of this copolymerization whatever may be the process and the experimental conditions. Two approaches are examined in this lecture to investigate emulsion copolymer and colloid properties of the latexes. A first, simple one is based on experimental partition coefficients and a second one is based on more theoretical thermodynamic considerations (volume fractions, interaction χ parameters …). The latter gives a more general insight of emulsion processes and allows to investigate influence of many parameters like monomer-monomer, monomer-polymer, monomer-emulsifier interactions, interfacial tension, particle size, surface charge density… Computer programs are derived which give predictions in rather good agreement with experiments. The thermodynamic approach allows to study crosslinking effect as well as competition between polymerization rate and monomer diffusion rate if some control by diffusion does occur. Owing to these computer programs it becomes possible to correlate many experimental parameters. Most of experimental date are relative to styrene-acrylonitrile copolymerization.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020101985118
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  • 7
    Electronic Resource
    Electronic Resource
    Characterisation of acrylate latices by potentiometry and spectrophotometry (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 10 (1985), S. 297-303 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the characterisation of latices conductometry is the technique most commonly used. In this paper it is shown that a thorough characterisation of latices is possible based mainly on potentiometric titrations in aqueous and non-aqueous media and on spectrophotometry. Results obtained with these techniques in the study of acrylate latices prepared with nonylphenolpolyethyleneoxidesulphate as the emulsifier are presented. It is shown that this type of emulsifier is subjected to considerable hydrolysis during the emulsion polymerisation process.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020101985121
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  • 8
    Electronic Resource
    Electronic Resource
    Kinetics of quaternization of vinylbenzyl chloride copolymer latexes (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 10 (1985), S. 319-333 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the reaction of tertiary amines with vinylbenzyl chloride (VBC) copolymer latexes have been investigated. In this reaction, benzyl chloride groups on the latex particles are converted in high yield to quaternary ammonium groups. The course of the reaction is determined by amine reactivity rather than solubility. The kinetics are complicated by a severe retardation effect developing at conversions in excess of 30%. The limiting conversion appears to be associated with the maximum charge density that can be tolerated on a hydrophobic particle. A surface reaction model is invoked to explain the results.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020101985124
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  • 9
    Electronic Resource
    Electronic Resource
    Syntheses et caracteristiques structurelles de latex reactifs (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 10 (1985), S. 419-433 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The polymer particles with an heterogeneous structure are synthesised in emulsion using the method of the continued addition of monomers in two successive stages. The last fraction contains a mixture with an excess of reactive monomer. The core structure is made with a copolymer of n-butylacrylate (BuA) and butylmethacrylate (BuMA), the shell structure with a terpolymer of BuA, BuMA and glycidylmethacrylate (MAG).The classical epoxy group titrations which have been carried out have allowed the appraisal of the particle's superficial reactivity which is weak (about 5 to 10%) and the total concentration of oxirane functions, which is about 90%. This means the initiator redox system and the general polymerisation conditions are favorable for the epoxy function preservation.A gas chromatography essay of sampling was used for the kinetic tracing studies of polymerisation which gives an interesting schematic representation of the particle microstructure. The radial display of glycidylmethacrylate (MAG) in the particle will be examined in detail.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020101985129
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  • 10
    Electronic Resource
    Electronic Resource
    Approches cinetiques du mecanisme de la copolymerisation styrene acrylate de butyle (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 10 (1985), S. 69-86 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Batch emulsion copolymerizations of n-butyl acrylate (B) and styrene (S) have been carried out, using either potassium persulfate or “azocarboxy” as initiators and sodium dodecyl sulfate as emulsifier. Particle size vs conversion studies, within a broad range of initiator (0,37 to 3,3.10-3 mol. 1-1) and emulsifier (0,6 to 18.10-3 mol. 1-1) concentrations, 1/1 comonomer ratio and for two solid contents (20 and 50 %), have been investigated through dynamic light scattering and transmission electron microscopy methods. Molecular weight and surface characteristics of the emulsion copolymers were also estimated. From the results, it is suggested that, due to the water solubility of the n-butyl acrylate, the particle formation in this system follows a homogeneous nucleation mechanism where the limited flocculation step is strongly dependent upon the stabilizing properties of the latex.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020101985108
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  • 11
    Electronic Resource
    Electronic Resource
    Dynamic modelling of the batch, semi-batch and continuous production of styrene/butadiene copolymers by emulsion polymerization (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 10 (1985), S. 105-128 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A dynamic computer model which can predict polymer and polymer particle properties such as molecular weight averages (MN and MW) and (long chain branching frequency) and particle size distribution for the emulsion copolymerization of styrene/butadiene has been developed. Heat balances about the latex reactor and cooling jacket with proportional/integral control are included. This model can be used to design, optimize and control emulsion copolymerization in well-mixed stirred tank reactors operated in batch, semi-batch and continuous modes for transient and steady-state operation.Details of modelling are described and then applications of the model are shown to illustrate the range of operational conditions of various production systems that can be investigated.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020101985110
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  • 12
    Electronic Resource
    Electronic Resource
    Some aspects of semi-continuous emulsion copolymerization (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 10 (1985), S. 129-148 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A semi-continuous emulsion copolymerization of acrylic monomers was investigated. Under the conditions used, the polymerization rate was equal to the rate of feeding of monomers and a steady state with a constant ratio of free monomers was reached. “Effective” reactivity ratios were calculated for several couples of monomers. Significant differences in the particle size distribution were found with monomers of different polarity. The extent of particle flocculation during the process was affected by the emulsifier distribution between the initial reactor charge and the monomer emulsion as well as by the electrolyte concentration. The tendency of particles to flocculate decreased with the increasing concentration of carboxylic groups on the particle surface. A different extent of acid hydrolysis of ester groups was observed by emulsion polymerization of various acrylic monomers.
    Additional Material: 18 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020101985111
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  • 13
    Electronic Resource
    Electronic Resource
    Behavior of the complexes embedded in oriented molecular assembly layers (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 12 (1985), S. 239-249 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Behavior of the porphinato iron (heme) complexes embedded in phospholipid bilayer was described. Novel and finely modified heme derivatives were synthesized by expecting that compatibility of the heme with lipid bilayer and oxygen-binding ability of the heme are improved. The heme was oriented in parallel and molecularly dispersed to and in the bilayer, and reinforced the assemble bilayer structure. Oxygen-binding reaction was much influenced by fluidity of phase state of the environmental bilayer.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020121985120
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  • 14
    Electronic Resource
    Electronic Resource
    Donor - acceptor and ionic complexation in macromolecular systems - syntheses and properties - (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 12 (1985), S. 251-253 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020121985121
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  • 15
    Electronic Resource
    Electronic Resource
    Magnetic properties of polymers containing paramagnetic species (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 12 (1985), S. 255-263 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The magnetic properties of polymers containing nitroxyl, tetraphenylporphin (TPP)-Cu(II), -Ag(II), or -Co(II) in the side chains were studied by ESR and magnetic susceptibility(χM) measurements. The values of χM for the polymers containing nitroxyl, TPP-Cu(II), and -Co(II) were found to obey the Curie-Weiss law, and their magnetic moments showed the occurrence of a weak antiferromagnetic interaction between paramagnetic species. The value of χM for the polymer containing TPP-Ag(II) showed the presence of strongly interacting sites. This strong interaction possibly arises from a hyperexchange interaction through the C—O group situated among the Ag(II) ions. Polymers containing TPP-Co(II) adsorb oxygen below 180 K and the ratio of O2:Co(II) was found to be 1:1 at 77 K.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020121985122
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  • 16
    Electronic Resource
    Electronic Resource
    Nucleic acid base grafted poly(ethylenimine): Polynucleotide analog and therapeutic agent (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 13 (1985), S. 13-32 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(N-acyl ethylenimine) of various molecular weights was synthesized by the cationic ring-opening polymerization of 2-H-2-oxazoline and 2-methyl-2-oxazoline. Acid hydrolysis afforded the linear poly(ethylenimine) which was used in the following grafting reactions. Vapor pressure osmometry, gel permeation chromatography and viscosity measurements were used to characterize the polymers synthesized. Potassium 2-(cytos-l-yl) propanoate and potassium 3-(cytos-l-yl) butanoate were synthesized in good yield from thenucleic acid base. These cytosyl pendant groups were grafted onto the poly(ethylenimine) using 4-chloro-1-(4-chlorobenzenesulfonyl) benzotriazole, 90% graft, and norborn-5-ene-2,3-carboximido diphenyl phosphate, 70% graft. Grafting of the t-butoxycarbonyl and n-butoxycarbonyl protected cytosyl pendant groups resulted in a 47% graft. Hypochromicity studies indicated an ordered structure at the local level. The secondary structure is a base-stacked conformation. Light scattering results gave insight into the tertiary structure of the macromolecule. The polymer exists in solution as stiff chains, rod-like in nature. Continuous mixing experiments were carried out with polyribonucleotides. The Job plots indicated increased level of ordered conformation with either an increase in the molecular weight or an increase of the base to base distance in the analog. Enhancement in the base-stacked conformation was higher in the polyinosinic acid complex than that of the polyguanylic acid complex.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020131985103
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  • 17
    Electronic Resource
    Electronic Resource
    Molecular design of functional polymers having amino groups (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 13 (1985), S. 33-46 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three topics on molecular design of functional polymers having amino groups will be discussed. The first topic is on the synthesis of functional isoprene oligomers with one amino end group. The best condition for the synthesis is to seed a small amount of the amino-ended oligomer into a reaction system where isoprene was polymerized with lithium diisopropylamide as initiator. The highly active behavior of the amino-ended oligomer as chain transfer agent was ascribed to a “macromolecular effect”. The second topic is concerned with a study on the soluble poly(1,4-divinylbenzene) which was formed by polymerizing 1,4-divinylbenzene with lithium diisopropylamide in the presence of excess diisopropylamine in THF. Structural analyses with 400MHz1H NMR and 25 MHz13C NMR showed that there were 2 or 3 branchings per 100 monomeric units along the main chain. Population of the triad tacticities suggested the steric course of polymerization to proceed according to the Bernoulli statistics with respect to diad placements, m and r. Third topic is on a polyamine macromer which was prepared by allowing an ethylenediamine homologue, N,N′-diethylethylene-diamine (DEDA), to react with 1,4-divinylbenzene in the presence of lithium diisopropylamide as catalyst. Results on syntheses and properties of polystyrene-polyamine (SA) and poly(2-hydroxyethyl methacrylate)-polyamine (HA) graft copolymers will be presented with the emphasis on their biomedical behavior.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020131985104
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  • 18
    Electronic Resource
    Electronic Resource
    Cooperative interpolyelectrolyte reactions (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 13 (1985), S. 137-155 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Water-soluble nonstoichiometric polyelectrolyte complexes (NPEC) are formed as a result of interaction of opposite charged polyelectrolytes used in nonequivalent ratios. One of the most important properties of NPEC is their ability to participate in intermacromolecular exchange and substitution reactions in aqueous solutions. The kinetics of exchange and substitution reactions has been studied by the method of luminescence quenching. It has been found that such reactions proceed by the contact mechanism and that addition of low molecular electrolytes to the reaction mixtures results in a dramatic increase in the rates of the reactions. The kinetics of the reactions is well described by the equation q = 1-exp(- kt∝) (here q is the degree of conversion and ∝ 〈 1), deduced under the assumption that exchange and substitution occur by the nucleation mechanism and the development of nuclei is inhibited in time. The studied reactions represent a new class of interpolymer reactions and they can be very important, in particular, for understanding the mechanism of functioning of biologically important macromolecules and for the interpretation of the physiological activity of polyelectrolytes.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020131985111
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  • 19
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    Electronic Resource
    Foreword (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 14 (1985), S. 1-1 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020141985101
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  • 20
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    Electronic Resource
    POLYMER BONDED EXCITED COMPLEXES-A POWERFUL APPROACH TO STUDY POLYMER EFFECTS (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 14 (1985), S. 145-159 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Exciplex and excimer in polymers were investigated and compared with monomer and dimer model systems. Many condensation polymers(mostly polyesters) and a methacrylate polymer having excimer- or exciplex forming chromophores were prepared. Exciplex (or excimer) intensity, wavelength, and rise and decay of emission were discussed as functions of polymer structure, degree of polymerization, concentration, solvent, and temperature. Polymer effects on excimer and exciplex formation were always positive and it was not possible to explain them by local concentration effects. Specific intra- and interpolymer interactions and relaxation processes in polymers were also discussed.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020141985113
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  • 21
    Electronic Resource
    Electronic Resource
    Bilayer membranes of fluorocarbon amphiphiles (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 14 (1985), S. 81-90 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Bilayer membranes are formed spontaneously from single-chain, double-chain, and triple-chain amphiphiles which possess fluorocarbon tails. Their aggregation behavior is similar to those of the corresponding hydrocarbon amphiphiles. However, the bilayer characteristics are quite different between the two classes. Flurocarbon bilayers display limited miscibilities with hydrocarbon bilayers, and enhanced barrier capacities against permeation of ions and molecules. Membrane-bound fluorocarbon species show peculiar reactivities.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020141985108
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  • 22
    Electronic Resource
    Electronic Resource
    Polymer effects in photoinduced charge separation (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 14 (1985), S. 119-130 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reverse electron transfer between photogenerated redox pair in bulk aqueous solutions can be efficiently suppressed by collecting the photoliberated electron to the positively charged surface of molecular assemblies such as micelles, bilayers and polymers. Zwitterionic viologen molecules serve as efficient electron carriers, which shuttle between the bulk phase and the surface of molecular assemblies. The molecular assemblies with aligned viologen units at the surface are particularly useful as molecular device for the electron enrichment and storage. Quantitative charge separation of the cage-escaped redox pair can be achieved by the use of the amphiphilic viologen molecular assemblies in combination with the zwitterionic viologen. The lifetime of charge-separated state can be extremely extended in these systems : ca 30 ms for the viologen bilayer and above 1 s for the polymer with pendant viologen. Amphiphilic viologen molecular assemblies also help to increase charge-separation of the photoinduced, intramolecular electron transfer in sensitizeracceptor linked system incorporated into the molecular assemblies. All of these phenomena are ascribed to cooperativity effects of aligned viologen units, which induce electron hopping a long the surface via successive electron exchange between viologen molecules.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1985.020141985111
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    Water-insoluble dextrans by grafting, 2Part 1: cf.3.. Reaction of dextrans with n-alkyl chloroformates. Chemical and enzymatic hydrolysis (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 17-29 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This work deals with the modification reaction of dextran with ethyl and butyl chloroformate using tertiary amines as catalyst/acceptor systems and the DMF/LiCl system as solvent. The structure of the resulting polymers was determined by means of IR, 1H and 13C NMR spectroscopy as well as by chemical analyses. The reaction rate was found to increase in the following order: N,N′-dimethylaniline 〈 pyridine 〈 triethylamine. The presence of cyclic carbonates was observed when triethylamine was used as catalyst. A linear dependence of the reaction rate on polymer and pyridine concentrations and a more complex dependence on the n-alkyl chloroformate concentration were found. Reaction rate and yield decrease with increasing amount of LiCl in the solvent medium and increase with increasing chain length of the n-alkyl chloroformate. The activation energy was found to be 64 kJ/mol (15,3 kcal/mol). The equilibrium water content (EWC) values decreases progressively when either the content of carbonate groups or the side chain length increases. The hydrolysis in the heterogeneous phase showed that the time required for the polymer solubilization is dependent upon the nature of the carbonate groups, the temperature as well as the pH value of the medium. Dextranase was found to be inactive in the hydrolysis of water-insoluble modified dextrans. However, the hydrolysis takes place when water-soluble modified dextrans were used.
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    URL: http://dx.doi.org/10.1002/macp.1985.021860103
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    Interaction of poly(diallyldimethylammonium chloride) with ferro- and ferricyanide anions (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 71-75 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The interaction of poly(1,1-dimethylpyrrolidinium-3,4-diylethylene chloride) [poly(diallyldimethylammonium chloride)] (1) with ferro- and ferricyanide anions was investigated by conductometric titration, viscometry, IR and Raman spectroscopy. It could be shown that the binding of ferro- and ferricyanide anions with 1 proceeds by means of an ionic mechanism and is accompanied by a spectral shift of the cyanide bands.
    Additional Material: 4 Ill.
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    Conformational transition in poly(methacrylic acid)NCL Communication Number: 3483. (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 123-129 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The potentiometric behaviour of poly(methacrylic acid) was examined in water/1,4-dioxane mixtures at 25°C. Conformational transitions were observed in about the same range of apparent ionization in the 1,4-dioxane concentration range 0 to 15 vol.-%. Transitions were not observed in the 1,4-dioxane concentration range 20 to 35% and the corresponding Henderson-Hasselbalch plots were found to be linear. Phase separations were observed to occur beyond 40 vol.-% 1,4-dioxane. The free energy of the conformational transition decreased very rapidly with the initial incorporation of 1,4-dioxane but slowly at higher concentrations. Van der Waals methyl-methyl interactions as the cause of the compact form has been inferred. The large increase in intrinsic viscosity observed for the unneutralized poly(methacrylic acid) in a relatively narrow range of composition of the 1,4-dioxane/water mixtures has been ascribed to a solvent induced conformational transition.
    Additional Material: 4 Ill.
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    Precursors of hydrophilic polymers, 3Part 2: cf.1.. The potentiometric behaviour of isotactic and atactic poly(2-dimethylaminoethyl methacrylate) in water/ethanol solutionsTo Dr. M. Bohdanecký on the occasion of his 60th birthday (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 111-121 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dissociation constants of partially ionized isotactic and atactic poly(2-dimethylaminoethyl methacrylate) in water/ethanol solutions were measured. The strong dependence of the apparent dissociation constant on the degree of ionization of the macromolecule is discussed using viscometric data and compared with the properties of low-molecular-weight model compounds. The values of the internal dissociation constants at various ionic strength in various water/ethanol solutions were obtained by extrapolation of the apparent dissociation constants to zero ionization degree of the macromolecule. The conformational structures of macromolecules in solution are discussed.
    Additional Material: 4 Ill.
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    The thermodynamics of polyether sulfone-poly(ethylene oxide) mixtures (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 145-158 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mixtures of poly(ethylene oxide) and polyether sulfone have previously been shown to be miscible and undergo phase separation on heating, the minimum in the cloud point occurring at about 80°C and at 10:90 w/w PES:PEO composition. This paper describes an attempt to understand the thermodynamics of this system and to simulate the spinodal curves of the phase diagram using a modified form of the equation-of-state theory of Flory et al. Two methods were used to gain information about the interactional energy of the polymers. Heat of mixing measurements at 90°C on low molecular weight analogues were used to obtain a value of X12 of -40 J. cm-3. A modified form of the equations for the melting point depression of PEO in the blend was used to obtain values of X̄12 in the range of -35 to -50 J. cm-3 at 52°C, the melting point of PEO. In order to adjust the location of the simulated spinodal, using a value of X12 = -40 J. cm-3, it was necessary to assume an unfavourable non-combinatorial entropy contribution of Q12 = -0,048 J. cm-3 · K-1. If the spinodals were simulated assuming Q12 = 0 and hence X12 ≡ X̄12 then a value of X12 = -18 J · cm-3 must be used. This is not inconsistent with the melting point depression result considering the large uncertainties in this method and the fact that the results are obtained at a lower temperature. The simulated spinodals are not very molar mass dependent which corresponds to the similar findings of the cloud point. The shape of the spinodal is dominated by the value of the surface area to unit volume ratio S2/S1 through its effect on the interactional terms in the spinodal equation.
    Additional Material: 4 Ill.
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    Studies on the water induced plasticization behavior of nylon 4. The influence of crystallinity and radiation crosslinking (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 191-201 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of crystallinity and radiation crosslinking on the water induced depression of the glass transition temperature in Nylon 4 [poly(2-pyrrolidone)] has been investigated by differential scanning calorimetry. Radiation crosslinking was effective in preventing exothermic events associated with crystallization during the measurement of the incremental change in heat capacity (ΔCp); a parameter necessary for the theoretical evaluation of the depressed glass transition temperature. ΔCp, when normalized to account for fractional crystallinity, was found to deviate substantially from a linear two phase relation. A simple three phase representation of morphology is proposed to account for this deviation, and assumptions have been made regarding the distribution of plasticizer, leading to good agreement between the theoretical and experimentally observed depressions of the glass transition temperature.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1985.021860118
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  • 29
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    Synthesis and characterization of bisacrylamide microgels containing sulfo groups (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 273-281 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reactive microgels containing sulfo groups were prepared by copolymerization of N,N′-methylenediacrylamide (1) and 2-acrylamido-2-methylpropanesulfonic acid (2) in water. The composition of the microgels, their structure, density, molecular weight and viscosity in solution were examined depending on the composition of the monomer mixture and the reaction conditions.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1985.021860207
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    Cationic degradation of poly(thio-1,1-dimethylethylene) [poly(isobutylene sulfide)]Dedicated to Prof Dr. T. Tsuruta on the occasion of his 65th birthday (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 317-324 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: High molecular weight poly(thio-1,1-dimethylethylene) [poly(isobutylene sulfide)] obtained by anionic polymerization of 2,2-dimethylthiirane (isobutylene sulfide) was degraded to a mixture of low molecular weight compounds when treated with a catalytic amount of methyl trifluoromethanesulfonate. The following degradation products were found: 2,2,5,5-tetramethyl-1,4-dithiane (3), 2,2,6,6-tetramethyl-1,4-dithiane (4), 2-isopropyl-4,4-dimethyl-1,3-dithiolane (2), and an equimolar mixture of 3,3,6,6-tetramethyl-1,2,5-trithiepane (5) and 2-methylpropene (isobutylene). The formation of dithiolane 2 is explained by a hydride transfer to a transient carbenium ion.
    Additional Material: 4 Ill.
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    Dimethylsiloxane-ethylene oxide block copolymers, 2Part 1: cf.1.. Preliminary results on dilute solution properties (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 357-366 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dilute solution properties of poly(ethylene oxide)-polydimethylsiloxane-poly(ethylene oxide) (POE-PDMS-POE) triblock copolymers, of a POE-PDMS segmented block copolymer and of a grafted PDMS-g-(POE-co-POP) copolymer are investigated by means of viscosity, light scattering and small angle neutron scattering. The experiments indicate that the copolymers are molecularly dispersed or aggregated, depending on the properties of the solvents. A rather compact conformation is deduced from the viscosity measurements. Negative A2-values are observed in preferential solvents for one of the segments, a positiv A2-value in a common solvent for both segments forming the block copolymer.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1985.021860215
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    Free radical crosslinking copolymerization in the post-gel state, 3Part 2: cf.2.. Swelling and mechanical properties of polystyrene networks (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 407-422 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The free radical crosslinking copolymerization of styrene with a bi-unsaturated comonomer (divinylbenzene, ethylene dimethacrylate), present in small proportions, yields three-dimensional polymer networks. The gelation time tc is generally longer than expected if all double bonds originating from the bi-unsaturated monomer (including the pendent double bonds) were isoreactive. This delay in gelation has been attributed to the formation of intramolecular cyclizations, or to the lower reactivity of the pendent double bonds with respect to growing radicals. This paper, devoted to an investigation of the network forming reaction after gelation, presents some additional evidences in favor of the latter assumption, resulting from the variation of the fraction of extractable polymer, of the swelling degree and of the modulus of the swollen networks as a function of the overall degree of conversion. Furthermore, a direct proof of the role of the pendent double bonds is given by the “two-step” crosslinking experiments carried out.
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    URL: http://dx.doi.org/10.1002/macp.1985.021860219
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    Synthesis of water-soluble branched polysaccharides and their antitumor activity, 1. Branched polysaccharides from cellulose acetate (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 449-456 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Branched polysaccharides of cellulose having β-glycosidically linked D-glucose branches were synthesized by condensation of 3,4,6-tri-O-acetyl-(1,2-O-ethylorthoacetyl)-α-D-glucopyranose with activated cellulose acetates (DS ≈ 2) in boiling chlorobenzene in the presence of a catalytic amount of 2,6-dimethylpyridinium perchlorate. The branched polysaccharides were converted into water-soluble polysaccharides by saponification and then tested for their antitumor activity. Synthetic, branched polysaccharides with 30% or more branching were found to be completely soluble in water. The structure of branched polysaccharides was determined by methylation analysis, and it was found that branching occurred preferentially at the Cxyh6 positions by β-glucosidic linkages. The antitumor activity for Sarcoma 180 transplanted to mice was high for polysaccharides with a high DP. Cellulose did not react with acetyl glucose orthoester even after activation.
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    Soluble cyclopentadienylated polymers (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 473-481 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Copolymers from styrene and a mixture of p- and m-chloromethylstyrene were reacted with sodium cyclopentadienide in THF and precipitated in methanol at temperatures lower than -20°C to obtain soluble cyclopentadienylated polymers. Due to extensive gelation, the content of cyclopentadienyl groups could not be increased to more than 4 mol-% except with extremely low molecular weight polymers. An improved method, in which the copolymer was cyclopentadienylated in the presence of metallic sodium, gave soluble polymers with up to 29 mol-% cyclopentadienyl groups. Pendant cyclopentadienyl groups undergo Diels-Alder/retro-Diels-Alder addition to give thermoreversible cross-linked polymers. The amount of gel fraction of a 4 mol-% cyclopentadienylated polymer as a function of the heating time was examined in the temperature range of 40-80°C. The DSC curve of a 29 mol-% cyclopentadienylated polymer showed an exothermic peak due to the Diels-Alder reaction and an endothermic peak starting around 390°C, a temperature higher than that found for the degradation of polystyrene.
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    Graph theory of configurational and viscoelastic properties of polymers (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 513-525 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simple method for calculating the moments of the radius of gyration of polymers is developed. It can be applied to any molecule which does or does not possess close circuits in its structure. In the Rouse theory of viscoelastic behaviour, various functions such as the zero-shear-rate viscosity, η0, and the steady-state recoverable compliance, Je0, are directly related to the moments of the radius of gyration and hence the results obtained may prove useful for interpreting rheological data.
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    Dégradation du poly(carbonate de bisphénol-A) en phase liquide en présence de sels alcalins. Etude cinétique (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 573-582 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The degradation of poly(oxycarbonyloxy-1,4-phenyleneisopropylidene-1,4-phenylene) [poly-(bisphenol-A carbonate)] in cyclohexanone is shown to be efficiently catalyzed by organic salts and metal carbonates. The catalysis is of homogeneous type. More precisely, only the associated fraction of the dissolved salt is active. The apparent activation energy of the degradation ranges between 113 and 130 kJ · mol-1 (27 and 31 kcal · mol-1), being similar to energies usually observed for hydrolysis or alcoholysis of esters. A reaction mechanism based on the ketoenolic equilibirum in cyclohexanone is proposed to explain the fast degradation observed. The influence of the nature of ions is also assessed: the reactivity increases with decreasing cation diameter, whereas the nature of the anion is of no matter.
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    Poly(vinyl acetate) as a test of the roedel mechanism for short branch formation (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 633-640 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Probabilities of configurations conducive to the intramolecular back-biting abstraction of a hydrogen atom have been evaluated for growing unperturbed poly(vinyl acetate) chains. A realistic rotational isomeric state model was used for the chain statistics. Probabilities are found to be smaller than those seen in an earlier treatment of the polyethylene chain. The smaller probabilities of poly(vinyl acetate) contribute to the virtual absence of short branches. The present study therefore provides support for the validity of the Roedel mechanism for the formation of short branches in the free radical initiated polymerization of ethylene.
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    Phase transitions in polyphosphazene films: Poly[bis(trifluoroethoxy)phosphazene]Paper presented at the American Physical Society (D.H.P.P.), Session MT4, p. 561, March 26-30, 1984, Detroit, Michigan. (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 649-663 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The morphology of cast and annealed films from poly[bis(trifluoroethoxy)phosphazene] \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm \{ PBFP,\rlap{--} [(CF}_{\rm 3} {\rm CH}_{\rm 2} {\rm O)}_{\rm 2} {\rm P = N\rlap{--} ]}_{\rm n} {\rm \} } $\end{document} has been studied by electron, scanning electron and optical microscopy. Several polymorphic forms and one mesophase (hexatic) have been established. From THF solution, PBFP has a chain folded morphology (α-orthorhombic) which transforms into a chain extended 2D hexagonal mesophase at T(1). It remains in this state until final melting occurs at Tm = 245°C approximately. Upon cooling the melt, it quickly reverts to the hexagonal mesophase again, but then passes into a chain extended (3D) γ-orthorhombic modification. This material is much more stable thermodynamically than the α-form, which is friable or brittle. PBFP cannot be quenched to a glassy form from the molten state, but it can be disordered as assessed by its reduced T(1) enthalpy and less well defined morphology assessed by electron microscopy. Another crystal modification (β-monoclinic) has been found in solution cast low molecular weight PBFP films.
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    The chemical dehydrochlorination of poly(vinyl chloride), 2Part 1: cf.1. Studies on N,N-dimethylformamide solutions (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 707-714 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The chemical dehydrochlorination of poly(vinyl chloride) was studied in solution in N,N-dimethylformamide. By comparison with solutions in tetrahydrofuran, examined previously, the reaction was found to occur at a significantly enhanced rate for the four systems studied, a mass polymer of 55% syndiotacticity and a low temperature polymer of 63% syndiotacticity, dehydrochlorinated with potassium hydroxide or with potassium tert-butoxide. Furthermore, at dehydrochlorination levels up to about 60%, markedly longer polyene sequences are formed, the more so in the case of potassium tert-butoxide., where they reach values of at least 65, as assessed by Raman spectroscopy. For levels of 80%, and greater, there is a significant decrease in the sequence lengths, the result of cross-linking, which is facilitated by the substantial loss of the \documentclass{article}\pagestyle{empty}\begin{document}$\rlap{--} ({\rm CHCl \hbox{---} CH}_{\rm 2} \rlap{--} )_n$\end{document} sequences that sterically protect the long polyenes in the les heavily dehydrochlorinated materials. Limited results are also presented for chemically dehydrochlorinated PVC prepared by the urea clathrate method; the insolubility of this polymer probably leads to degradation on the surface of the particles only.
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    The chemical dehydrochlorination of poly(vinyl chloride), 1. Studies on tetrahydrofuran solutions (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 695-705 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The chemical dehydrochlorination of poly(vinyl chloride) was studied in solution in tetrahydrofuran. Two materials, a mass polymer of 55% syndiotacticity and a low temperature polymer of 63% syndiotacticity, were dehydrochlorinated with potassium hydroxide and with potassium tert-butoxide. The dehydrochlorination products were characterised by their chlorine contents and by UV/visible, IR and Raman spectroscopy, as a function of reaction time. The course of the reaction was found to be substantially independent of tacticity and the dehydrochlorinating reagent. Initially, the reaction follows a similar path to that occurring during photo- and thermal degradation, but as the dehydrochlorination continues, longer conjugated polyenes are formed than by these two latter processes. Sequences of 60 double bonds occur at the dehydrochlorination levels of about 55% that are attained after reaction times of 24 h. These sequences are sterically protected from cross-linking reactions by the presence of longish sequences of unreacted —CHCl—CH2— units.
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    Continuous fractionation and solution properties of PVC, 3Part 1, 2: cf. 1,2. Pressure dependence of the solubility in single solventsIn memoriam of Professor G. Rehage (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 769-776 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: From the break-down in the viscosity and from the increase of the intensity of the scattered light, associated with the entrance into the two-phase region, the pressure dependence of the demixing temperature of solutions of PVC 37 000, PVC 75 000 and PVC 100 000 in phenetole and PVC 75 000 in o-xylene was measured up to 1 000 bar. (The numbers in the codes of the PVC specimens are their approximate molecular weights.) The application of pressure increases the demixing temperatures of PVC in both solvents by about 1 K/100 bar. For a qualitative forecast of the pressure effects, the solubility parameter theory in combination with the corresponding states principle, and an empirical correlation to the relative distance of the critical demixing temperature to the melting point of the pure solvent were used. The results of both concepts are in accord with the experimental findings.
    Additional Material: 4 Ill.
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    Continuous fractionation and solution properties of PVC, 2Part 1: cf. 1. Scrutiny of solvents, intrinsic viscosityDedicated to Professor H. Inagaki in honour of his 60th birthday (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 753-767 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Investigations with ca. 100 organic liquids in a temperature range from -20°C to 90°C result in a survey of the solubility behaviour of PVC. The experimental results were compared with the predictions of the solubility parameter theory: Accepting δ = 9,75 (cal/cm3)1/2 as the solubility parameter for PVC, all solvents (except ketones in which PVC is soluble independent of their solubility parameters) are located within the range of δPVC ± 0,75. Only three of the 100 liquids examined turned out to be (endothermal) theta-solvents, namely the aromatic solvents o-xylene, phenetole and dimethyl phthalate. The theta-temperatures in o-xylene and phenetole were determined viscometrically by means of the temperature dependence of the Mark-Houwink exponent to be 84 and 88°C, respectively. Viscosity measurements were also performed in the temperature range of 25 to 60°C with solutions of PVC 75 000 in 10 thermodynamically good solvents used for rheological investigations. In all cases the intrinsic viscosities decrease slightly with increasing temperature, i.e., all solutions are weakly exothermal. The binary cluster integral, β, was determined (taking the monomeric unit as the statistical segment) and the polar contribution, βe, was calculated from Yamakawa's theory. The correlations between the non-polar part of (βn = β - βe) and the solubility parameter of the solvent, found by Utracki, were tested and found to be valid for the present systems, too.
    Additional Material: 4 Ill.
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    Cinétique de télomérisation, 3Partie 2: cf.2.. Détermination des constantes de tranfert en catalyse rédox (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 831-836 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three methods were used for the determination of transfer constants to the metallic complex in the telomerization reaction with redox catalysis. The first one consists in the determination of DPn as a function of the mole ratio of telogen to monomer at the beginning of the reaction. The second one is based on the variation of the conversion degree of telogen to monomer. The last one requires the knowledge of the cumulated DPn and the conversion degree of monomer samples during the reaction. The proposed laws were checked following the methyl acrylate telomerisation with CCl4 as a telogen and CuCl2 as a catalyst at 120°C. The transfer constant to CuCl2 was found to be about 600 according to the three methods.
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    Studies on methoxycarbonylcellulose: Conductivity measurements of solutions, 1 (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 837-846 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conductivity behaviour of a partially neutralized methoxycarbonylcellulose (carboxymethylcellulose, CMC) solution was investigated at different frequencies using a home made conductance bridge. The equivalent conductance of CMC solutions has very poor dependence on frequency contrary to the behaviour of simple ionic compounds. The effect of concentration on the polyelectrolyte behaviour was investigated conductometrically and it was observed that the polymer concentration has little effect on polymer charge fraction and polymer counterion fraction. Sodium ion-binding on the polymer molecule was also investigated.
    Additional Material: 8 Ill.
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    Influence de la température de cristallisation sur la morphologie du polypropylène isotactique (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 881-892 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The isothermal crystallization of isotactic polypropene samples cooled from the melt is studied. Particular emphasis is given to the morphology which develops depending on the melting and crystallizing conditions. Thus, the evolution of birefringence for samples crystallized between -20°C and +150°C is explained in terms of a quadritic arrangement of lamellae. The evolution of the relative amounts of radial and tangential lamellae is followed by differential thermal analysis, small angle light scattering and optical polarization microscopy.
    Additional Material: 7 Ill.
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    Poly(p-hydroxycinnamic acid)Poly(p-coumaric acid); systematic structure-based IUPAC name: poly(oxy-1,4-phenylene-3-oxopropenylene).Dedicated to Professor Dr. T. Tsuruta on the occasion of his 65th birthday (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 893-905 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(p-hydroxycinnamic acid) was synthesized by thionyl chloride activated polycondensation of p-hydroxycinnamic acid at ambient temperatures and by polycondensation of its various monomeric esters at elevated temperatures. The thionyl chloride activated polycondensation proceeds as a 2-stage process, yielding reduced viscosities of up to 102 mL/g. 360 MHz proton NMR spectra indicate an all-trans structure and the absence of side reactions. The polymer with a melting temperature of 313°C can be pressed into films.
    Additional Material: 6 Ill.
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    Polymerization by phase transfer catalysis, 2Part 1: cf.18. Polythiocarbonates by polymerization of Bisphenol A with thiophosgene (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 915-921 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Poly(oxythiocarbonyloxy-1,4-phenyleneisopropylidene-1,4-phenylene) (1) was obtained from 4,4′-isopropylidenediphenol (Bisphenol A) and thiophosgene under phase transfer conditions, using quaternary ammonium and phosphonium salts and crown ethers as catalysts. The polymer was identified by IR and 1H NMR spectroscopy, and the molecular weights were estimated from inherent viscosity measurements. The influence of catalysts, solvent and thiophosgene addition was studied in order to find the best conditions. It was found that tetrabutylammonium bromide, dichloromethane and the addition of thiophosgene at once gives the highest yields and inherent viscosities. Other catalysts and solvents were less efficient or unefficient for this reaction.
    Additional Material: 3 Tab.
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    Syntheses and polymerizations of dialkyldiallylammonium bromides as vesicles in solution (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 923-931 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Dialkyldiallylammonium salts 1a-c were prepared by quaternization of diallylamine with alkyl bromides and their polymerizability as oriented molecular assemblies in aqueous solution is discussed. Thin films of those ammonium salts on the glass wall were incubated by adding a phosphate buffer solution to yield giant spherical vesicles with diameters ranging from 10 to 100 μm. When large amounts of the ammonium salt were applied, it was necessary to add more than 5 mol-% of cholesterol in order to stabilize the resulting giant vesicles. By ultrasonication of the film-aqueous solution system, much smaller vesicles with diameters ranging from 0,03 to 0,2 μm were obtained. The stabilizing effect of cholesterol addition to the system of the small vesicles is similar to that observed for the giant vesicles. Under an inert atmosphere, the vesicles in aqueous solution were polymerized by ultraviolet irradiation. From the results of TEM and NMR spectroscopy, it was concluded that the molecules were polymerized in the vesicles without changing the profile of molecular assembly during an irradiation of 6 h. However, when the ammonium salts were dissolved homogeneously in degassed benzene, the ultraviolet irradiation polymerization did not proceed beyond a conversion of 5% under the same conditions.
    Additional Material: 8 Ill.
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    Extent of reaction, monomer conversion, and polymer yield in polycondensationsDedicated to Professor Dr. H. Inagaki on the occasion of his 60th birthday (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 865-879 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The extent of reaction of functional groups (pA), the extent of conversion of monomer molecules (qM), the true relative polymer yield (yp), the constitutional repeating unit-based apparent relative polymer yield (yPU), and the monomer-based apparent relative polymer yield (yPM) are defined and their interrelationships given. The use of yPU instead of yp overestimates the true yield, except in the limit of high degrees of polymerization. Use of yPM, on the other hand, always underestimates the true yield, especially at infinite degrees of polymerization. The correct expression for the calculation of the mass fraction of i-mers in reactants with a Schulz-Flory “most probable” distribution is given and shown to become identical with the usual approximation in the limit of vanishingly small mass of the leaving molecule.
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    Kinetics of irreversible, stoichiometric polycondensationsDedicated to Professor Ronald Koningsveld on the occasion of his 60th birthday (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 847-864 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Equations are derived for the time dependence of the extent of functional group reaction, pA, for catalyzed and uncatalyzed, irreversible, stoichiometric polycondensations of the AB and AA/BB type following pseudo-second-order and third-order chemical kinetics, resp., based on amount-of-substance concentrations. The resulting functions 1/(1 - pA) - f(t) for pseudo-second-order polycondensations and 1/(1 - pA)2 - f(t) for third-order polycondensations are predicted to be non-linear for low extents of reaction and practically linear for higher ones which agree with previous, hitherto unexplained experimental observations. The slope of the linear part does not give the true rate constant, contrary to traditional assumptions. The extent of non-linearity at small conversions and the deviation of the apparent rate constant from the true one depends on the initial amount of A groups, the molar mass of the leaving molecules, and the initial mass of the reaction mixture, if the molar concentrations are based on masses (“molalities”). The density of the leaving molecules enters, in addition, if the molar concentrations are volume related (“molarities”). The equations predict, for a given system, that the range of the non-linear region increases with decreasing rate constants, i.e., with decreasing temperature, in accordance with experimental observations.
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    Ziegler-natta catalysis by Mg-Ti complexes, 2Part 1, cf.15. Ethylene polymerization by MgTiCl6·4CH3COOC2H5 and triisobutylaluminium (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 907-913 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The reaction between the MgTiCl6·4CH3COOC2H5 complex and alkylaluminium compounds was studied. The solid samples, recovered after increasing reaction times, were analysed. Elemental analyses, X-ray diffraction patterns, and IR spectra clearly indicated the formation of activated, high-surface MgCl2. Polymerizations of ethylene were carried out employing, as the solid component of the catalyst system, both MgTiCl6·4CH3COOC2H5 and the recovered samples. The lower induction time in the latter case was related to the extent of MgCl2 formation and its degree of activation.
    Additional Material: 4 Ill.
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    Polybutadiène hydroxytéléchélique, 7Partie 6: cf.1. Cinétique de polycondensation en solution et en masse du polybutadiène hydroxytéléchélique avec le méthylène-4,4′ di(isocyanate de phényle) en l'absence de catalyseur. Etude par 1H NMR et 13C NMR (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 527-548 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Quantitative determinations by 13C NMR performed with insoluble polyurethanes allow to study the kinetics of the polymerization in bulk between hydroxytelechelic polybutadiene G 1000 and 4,4′-methylene diphenylisocyanate (MDI). Comparisons have been made with (G 1000 + MDI) polymerization and (monoalcohol or G 1000 + phenyl isocyanate) model reactions in toluene. With [NCO]/[OH] = 1 and T ≤ 60°C, in solution as well as in bulk, conversions are not complete. Because of the presence of gels, part of the reactive functions have been found to be trapped. For kinetic tests, only the first stage of the polymerization (conversion 〈 70%) may be taken into account. In bulk, the two alcohol functions are equally reactive, whereas in toluene, the hydroxylated 1,4 ends of the polybutadiene chains are more reactive. As evidenced for model reactions in the foregoing paper of this series, the kinetics fit better with the 3rd order than with the 2nd order equation. Nevertheless, at higher temperatures, the 2nd order may be used. The autocatalysis phenomenon found effective for model reactions is negligible in polymerization. All kinetic constants and activation parameters calculated must be considered to be apparent ones only.
    Additional Material: 13 Ill.
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    Etude de nouvelles membranes asymétriques à base de copolymère à blocs styrène-isoprène-styrène, 1. Synthèse, modification chimique et caractérisation (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 559-571 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A styrene-isoprene-styrene block copolymer was selected for the preparation of new asymmetric membranes which have blood compatibility properties after chemical modification by addition of gazeous N-chlorosulfonyl isocyanate to the double bonds of the polyisoprene sequences. The membranes were examined with a scanning electron microscope. The permeability of the membrane was studied as a function of time, pressure and viscosity.
    Additional Material: 9 Ill.
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    Equilibrium copolymerization, 1. Random model (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 597-608 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three cases of equilibrium copolymerization are re-treated theoretically. The expression of the molecular weight distribution of the copolymer is a two-dimensional distribution function with two random variables m and n, where m and n are the numbers of two different monomeric units, respectively. The molecular parameters of the copolymer, such as the number- and weight-average molecular weights, number-average degree of polymerization, copolymer composition and equilibrium conversions of comonomers, are derived. The relation between the parametric variables in the formulae and the equilibrium copolymerization conditions are determined from two binary cubic equations.
    Additional Material: 2 Ill.
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    Spin probe study of relaxation in poly(oxytetramethylene) (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 665-669 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using the spin probe method, the rotational mobility of two probes in poly(oxytetramethylene) (POT) in the region of rapid and slow rotation was investigated. Based on the relaxation diagram the obtained ESR results are compared and discussed in connection with other literature data. It was found that the behaviour of the probes corresponds to the α + β relaxation in the range of high frequencies. Differences in mobility of the probes as well as anisotropy effects of rotations are also discussed.
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    Cinétiques de télomérisation, 6Partie 5: cf.11.. Détermination des degrés de polymérisation a partir de la répartition moléculaire (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1467-1475 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is shown that the kinetic laws established for polymerization reactions can be applied for telomerization reactions provided the number-average degrees of polymerization DPn are greater than ten. For DPn 〉 10 it is necessary to calculate the molecular distributions. Values of DPn obtained with the method of Mayo and the molecular distribution method are compared and an experimental application is given by the radical-initiated telomerization of glycidyl methacrylate (2,3-epoxypropyl methacrylate) with bromotrichloromethane.
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    Mechanism of ring-opening polymerization of 1-methylbicyclo[2.2.1]hept-2-ene using metathesis catalysts (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1477-1494 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Polymers of the title monomer have been made using 24 different metathesis catalysts, based on Nb, Mo, W, Re, Ru, Os and Ir compounds. Their structure, determined by 13C NMR spectroscopy, varies from all-cis (ReCl5) to all-trans (RuCl3, OsCl3) and from fully biased (head-tail) to unbiased. The bias stems partly from an inability to from head-head dyads containing cis double bonds and partly from the dipolar interaction between the propagating metal-carbene complex and the monomer in forming the [2 + 2] transition state. Arguments are presented to show that the formation of biased polymers proceeds largely through a metal carbene species in which the last-added monomeric unit has its methyl group adjacent to the metal centre (PH). In high-cis polymers the sequences of three double bonds are such as to indicate that a kinetic distinction must be made between species in which the previous double bond formed was cis or trans (PHc or PHt), consistent with the observation that high-cis polymers of related monomers have a blocky cis/trans distribution.
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    Ion-conducting grafted polypropylene film, 2Part 1: cf.8.. Volume grafting of polypropylene and gradient composition of poly(propylene-g-acrylic acid) (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1425-1434 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Grafting of acrylic acid onto a pre-activated polypropylene film was investigated, varying the concentrations of monomer and Fe2+ -ions, the polymerization time and temperature. Experiments were planned according to a scheme of a latin square, and statistical analyses were performed for the optimization of the grafting variables. The concentration of ferrous ions was found to be the most significant variable for the graft level. At low concentration, ferrous ions act as activator of grafting but no grafting takes place at relatively high concentrations. The distribution of grafted poly(acrylic acid) within a PP film was examined by microphotometry of the coloured slides of the film. The grafted layer of PP reaches the center only at about 30% of grafted poly(acrylic acid) and up to 70% the distribution of grafted poly(acrylic acid) is still non-uniform with a decreasing amount of the polyacid from the surface to the center. The film samples containing 30% of grafted poly(acrylic acid) already show conductivity in alkaline media and are interesting ion conducting materials.
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    Cinétiques de télomérisation, 4Partie 3: cf.3.. Nouvelle méthode de détermination des constantes de transfert en catalyse radicalaire (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1445-1455 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: For the determination of transfer constants CT to the telogen in telomerization reactions started with free radicals we used three methods. The first one is the method of Mayo, the second one is based on the variation of the conversion degree of telogen to monomer and the last method requires the knowledge of the cumulated number-average degree of polymerization DPn and monomer conversion αM of the samples during the reaction. Verifications of the proposed laws are made for methacrylic acid telomerization with CCl3Br and methyl methacrylate telomerization with benzenethiol as a telogen and 2,2′-azoisobutyronitrile as the initiator at 70°C. The transfer constant to CCl3Br is ca. 0,03 and that to C6H5SH ca. 1,5.
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    Cinétiques de télomérisation, 5Partie 4: cf.: G. Bauduin, B. Boutevin, J.-P. Mistral, L. Sarraf, Makromol. Chem. 186, 1445 (1985).. Détermination des degrés de polymérisation moyens cumulés dans les réactions de télomérisation et de polymérisation radicalaires (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1457-1465 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Two principal methods are described for the determination of the cumulative number-average and weight-average degrees of polymerization in polymerization and telomerization reactions. The first method for the calculation of both quantities uses the ratio of monomer concentration and concentration of radicals created. In the second the instantaneous number-average degrees of polymerization of short intervals of monomer conversion are added up. A comparison of the two methods is given and an application is studied for redox telomerization of ethyl acrylate with carbon tetrachloride.
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    Use of the DEPT pulse sequence to facilitate the 13C NMR structural analysis of lignins (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1495-1504 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: One of the multipulse sequences in FT 13C NMR, the DEPT pulse sequence, was used to decrease the complexity and to improve the information content of 13C NMR spectra of macromolecules such as milled wood lignins (MWL) extracted from hardwoods (Birch and Aspen MWL). This sequence gives the possibility to edit subspectra selectively for CH, CH2 and CH3 carbons, and benefits from a large intensity enhancement for the carbon atom signals, due to polarization transfer. Thus, it is possible to discriminate precisely between quaternary and tertiary aromatic carbon atoms and to show unambiguously the presence of p-hydroxybenzoate structures in Aspen MWL and their absence in Birch MWL. In addition, the DEPT sequence has made possible the observation of signals which, with classical experiments, are overlapped by others signals, either partially, like the C-γ signal of syringaresinol units or completely like the C-α signal in cinnamaldehyde units. Preliminary results indicate that quantitative data might be obtained from the edited spectra.
    Additional Material: 3 Ill.
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    Reversible oxygen-binding to poly(ethyleneimine)-cobalt complexes in aqueous solution (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1513-1518 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cobalt(II) complexes of poly(ethyleneimine)s 1 in aqueous solution are able to form with oxygen a μ-peroxo adduct as is evidenced from stoichiometry and spectral properties. The oxygen adduct of Co/1 is characterized by its higher rate constant and activation entropy of the oxygen dissociation step, in comparison with those of the low-molecular-weight analogue Co/tetraethylenepentamine (2). This is related with the smaller affinity of Co/1 to oxygen and the reversibility in oxygen-binding. The dissociation of the oxygen molecule coordinated to and bridged with Co/1 is facilitated by a distortion of its μ-peroxo structure due to electrostatic repulsion of polycationic 1.
    Additional Material: 6 Ill.
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    Biocide polymere, 12Teil 11 : cf.1. Synthese und hydrolyseverhalten von copolymeren aus methacryl- und acrylsäure sowie 1-methacryloyl- und 1-acryloyl-3-methylpyrazol (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1605-1611 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The radical copolymerization of 1-acryloyl- and 1-methacryloyl-3-methylpyrazole (1a and 1b) with acrylic acid or methacrylic acid in solution was studied. Copolymers containing carboxyl as well as 3-methyl-1-pyrazolylcarbonyl groups as side chains were prepared via the reaction of 3(5)-methylpyrazole with activated poly(acrylic acid)s of various molecular weights. The hydrolysis data suggest that the release rates of the biocide 3(5)-methylpyrazole from the investigated copolymers vary significantly depending on the content of carboxyl groups and their change during the hydrolysis.
    Additional Material: 1 Ill.
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    Changes of the polymerization mechanism depending on the monomer and solvent for a homogeneous Ziegler-type initiating system (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1613-1623 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The homogeneous system resulting from the reaction between tetrabenzylzirconium and triethylaluminium is an active catalyst for the polymerization of styrene, and p-methyl-, α-methyl and p-chlorostyrenes. The molecular weights and the structures of the resulting polymers are highly dependent on the nature of the monomer and on the reaction medium. In toluene, styrene and p-methylstyrene give essentially linear unsaturated dimers, whereas p-chlorostyrene leads to a polymer with a high molecular weight. In methylene dichloride higher oligomers and a polymer are obtained simultaneously from all the monomers. The comparative behaviour of the styrene derivatives was examined in copolymerization experiments under various experimental conditions. The ratios of monomer incorporation were compared with those reported in the literature for related systems. The results show that, according to the monomer and the reacting medium, the same catalytic system is able to induce polymerizations of the “coordinated anionic”, radical and cationic type.
    Additional Material: 6 Ill.
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    Zur Bestimmung der Porenstruktur wassergequollener CellulosefasernHerrn Prof. Dr. J. Schurz zum 60. Geburtstag gewidmet (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1643-1655 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The pore structure of various water-swollen fibers of cotton and regenerated cellulose was investigated by means of fiber penetration studies with saccharides and dextrans. From the data the volumes of the pores were obtained and average pore diameters and surface areas calculated assuming a slit pore geometry. There are difficulties in interpreting the results with respect to pore-size distribution. It is shown that the surface areas are suitable parameters of the fiber structure for describing equilibrium dye adsorption of direct dyes in cellulose fibers. From this a simple dying method results for characterizing the pore structure of cellulose materials.
    Additional Material: 5 Ill.
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    Infrared spectroscopic studies on polyethylene, 6Part 5: cf. C. Baker, P. David, W. F. Maddams, Makromol. Chem. 180, 975 (1979).. Linear low density polymers (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1665-1670 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The infrared spectra of five linear low density polyethylenes, containing methyl, ethyl, butyl, isobutyl and hexyl branches, respectively, were measured. Particular interest attaches to the region 800-1200 cm-1 where the spectra, although weak, show significant differences. The findings of an earlier study on the methyl rocking mode, in the vicinity of 900 cm-1, are confirmed and extended. In particular, no band was detected for the ethyl branched polymer and it must be an order of magnitude weaker than for methyl, butyl and hexyl branches. Conversely, it is displaced in frequency and is markedly stronger for isobutyl branches. The methyl wagging mode band is at about 1 150 cm-1 with the methyl branched polymer. It is relatively broad and probably consists of two overlapping components, specific for methyl branches in crystalline and amorphous regions. This mode is not of detectable intensity for ethyl, butyl and hexyl branches but, as with the rocking mode, it is anomalously strong for isobutyl branches.
    Additional Material: 1 Ill.
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    Relaxation processes in a block copoly(ether-ester) elastomer investigated by the spin probe method (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1679-1683 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Relaxation processes in the soft segment phase of a block copoly(ether-ester) elastomer were investigated using the spin probe method. Rotational mobility of the two probes, differing in sizes, were analysed and the results were interpreted based on the relaxation diagram. It was found that the change in mobility of the probes, as detected by the change in ESR line shape, in the slow rotation region corresponds to the β-relaxation, whereas that in the rapid rotation region corresponds to the α + β-relaxation. The analysis of probe mobilities, including the way they rotate, indicates the necessity of inclusion of rotational anisotropy in the interpretation of the behaviour of probes of different size.
    Additional Material: 1 Ill.
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    The influence of molecular interaction on polymerization, 10Part 9: Boudevska, V. Sinigersky, Makromol. Chem. 185, 531 (1984).. On the copolymerization of methacrylic acid with styrene (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1711-1720 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Free radical copolymerization of methacrylic acid (MA) with styrene (St) at 60°C, initiated by 2,2′-azoisobutyronitrile (AIBN) is carried out in hydrogen-bond forming solvents and in solvents not capable of forming hydrogen bonds but exhibiting different dielectric constants. The influence of the solvent on copolymerization reactivity ratios, rate of polymerization, composition, molecular weight and polydispersity of the copolymers obtained is shown. The reactivity ratios of methacrylic acid rMA and of styrene rSt are determined by two different methods with good agreement. The values obtained by the Kelen-Tüdös method are as follows: in carbon tetrachloride: rMA = 0,54 ± 0,01; rSt = 0,06 ± 0,03;in chloroform: rMA = 0,51 ± 0,01; rSt = 0,08 ± 0,03;in acetone: rMA = 0,43 ± 0,00; rSt = 0,65 ± 0,02;in 1,4-dioxane: rMA = 0,41 ± 0,02; rSt = 0,59 ± 0,05;in acetonitrile: rMA = 0,06 ± 0,02; rSt = 0,29 ± 0,00.Changes of reactivity ratios depending on the medium are explained on the basis of the results from IR and 1H NMR spectroscopy and gel permeation chromatography (GPC).
    Additional Material: 3 Ill.
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    Polymorphism in poly(3,3-dimethyloxetane) (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1731-1737 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A detailed study of the polymorphism of poly(3,3-dimethyloxetane) was carried out by differential scanning calorimetry and X-ray diffraction. From the relaxed melt state, two modifications, Form II (monoclinic) and Form III (orthorhombic), are separately obtained depending on crystallization temperature. When the crystallization is accomplished for a given modification, this one is stable at any temperature below its melting temperature. However, if the crystallization of a given modification is not complete, the other modification can be crystallized from the amorphous phase. Thus, a possibility of obtaining both forms exists. The kinetic and thermodynamic factors which govern this process are analyzed. The free energies were calculated and the conclusion is that modification II is thermodynamically the most stable one at all temperatures below its melting point.
    Additional Material: 8 Ill.
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    NMR study of poly(phthalidylidenearylene)s (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1747-1753 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure of poly(phthalidylidenearylene)s, synthesized by electrophilic substitution reactions, was studied using 1H and 13C NMR spectroscopy. Homopolycondensation of 3-aryl-3-chlorophthalides 1a - d in nitrobenzene leads to para-substituted linear polymers 2a - d, whereas polycondensation of phthaloyl dichloride and bis[4-(3-chloro-3-phthalidyl)phenyl] ether (6) with diphenyl ether results in polymers 5 containing irregular units.
    Additional Material: 1 Ill.
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    Asymmetric addition of hydrogen cyanide to aliphatic aldehydes catalyzed by a synthetic cyclic peptide, cyclo[(S)-phenylalanyl-(S)-histidyl]Dedicated to Prof. T. Tsuruta on the occasion of his 65th birthday (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1755-1762 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The asymmetric addition of hydrogen cyanide to an aliphatic aldehyde, catalyzed by a synthetic dipeptide, cyclo[(S)-phenylalanyl-(S)-histidyl] (1), leads to a product having a higher optical yield than that reported for the reaction using an enzyme (D-oxynitrilase) as catalyst.
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    Influence of electron-donor-acceptor complex formation on the melt viscosity of some poly(dimethylsiloxane)sDedicated to Ernst Trommsdorff on the occasion of his 80th birthday (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1763-1772 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of poly(dimethylsiloxane)s was synthesized containing either electron donor or electron acceptor groups, statistically arranged along the polymer chain or only at the chain ends (telechelic polymers). Blending of the donor and acceptor modified statistical copolymers led to a strong increase of the melt viscosity as a consequence of complex formation. In contrast to this, complex formation had no significant influence on the viscosity in blends from telechelic polymers. This different behaviour seems to be caused by the different molecular architecture favouring crosslinking by complex formation for the statistical copolymers and a linear chain extension for the telechelic polymers.
    Additional Material: 3 Ill.
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    Copolymerization of styrene with α-chloromaleic anhydride, 2Part 1: cf.5.. Spontaneous copolymerization in 1,4-dioxane (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1863-1869 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: α-Chloromaleic anhydride (CMA) copolymerizes spontaneously with styrene (ST) at a higher rate than maleic anhydride (MA), and α,α′ -dichloromaleic anhydride (DCMA) does not copolymerize, even in the presence of a radical initiator. The results obtained from the copolymerization of ST with CMA in 1,4-dioxane in the absence of a radical initiator are as follows: the copolymerization is strongly accelerated by UV-irradiation; the monomer reactivity ratios of ST and CMA at 60°C are 0,06 and 0,00, respectively; the over-all activation energy of the copolymerization is 77,4 kJ · mol-1 (18,5 kcal · mol-1); the maximum rate of copolymerization at a constant total monomer concentration is observed at a mole fraction of ST of 0,4 to 0,5. The rate of copolymerization at equimolar feed composition is of second order with respect to the total monomer concentration. From the results obtained here and shown in the preceding paper, it was inferred that initiating radicals for the spontaneous copolymerization are formed through a charge transfer (CT) complex between the comonomers.
    Additional Material: 7 Ill.
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    Use of organophosphorus(V) sulfides for the modification of propene polymerization catalysts (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1871-1879 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Studies of various organophosphorus(V) sulfides, including esters of thiophosphoric acid and triorganophosphine sulfides, were evaluated as propene polymerization catalyst modifiers. Among these, triethyl thiophosphate (1a) leads to the best activity-stereospecificity combinations. Higher alkyl or aryl esters of thiophosphoric acid lead to higher catalyst activities but significantly poorer stereospecificities, relative to 1a, while the latter modifier is advantageous over triaryl- or tris(diakylamino)phosphorus sulfides, as far as both activity and stereospecificity are concerned. Organophosphorus(V) sulfides appear to be better modifiers in general than the corresponding oxides. No straightforward correlations of the modifying effects of the preceding compounds to the inductive and steric effects of the substituents on phosphorus were possible, as some of these compounds (namely the thiophosphoryl or phosphoryl alkyl esters) may undergo dealkylation reactions with the components of the catalyst system, yielding alkyl chloride, traces of HCl and alkene, and polymeric metal (Ti3+ or Al3+) complexes with anionic R2POS- ligands. A number of binary modifier (1a plus an additional modifier) packages with attractive performance characteristics were developed. Evaluations of these systems in 2 h bulk propylene polymerizations showed that use of triphenylantimony oxide (8) as additional modifier leads to the best overall catalyst performance (yield: 2636 g/g AA TiCl3; hexane extractables: 0,80%). With the 1a-collidine (9) modifier package, comparable stereospecificity but substantially lower catalyst activity were realized, while use of bis(tributylin) sulfide (6), tributyl phosphite (7) or 2,5-dimethyltetrahydrofuran (10) as additional modifiers led to good yields (2650-3000 g/g AA TiCl3) but more than double (1,70-2,00%) the hexane extractables, relative to the 1a-8 modifier system.
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    Polymerizable monolayers derived from crown ether surfactantsDedicated to Prof. Dr. Dr. h. c. mult. G. V. Schulz on the occasion of his 80th birthday (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1979-1986 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Starting from dibenzo-18-crown-6, 1,10-diaza-18-crown-6 and 1,7-diaza-15-crown-5, several crown ether surfactants were synthesized. They all form stable monolayers on water. The methacryloyloxy derivative of 1,10-bis(3-dodecyloxy-2-hydroxypropyl)-1,10-diaza-18-crown-6, 2c, could be polymerized in the monolayer by UV irradiation. This polymerizable crown ether surfactant also forms synthetic vesicles by sonication in water.
    Additional Material: 3 Ill.
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    Polymerization of lactams, 74.Part 73: cf.15. Behaviour of the polymerization mixture prepared by the non-activated polymerization of 2-pyrrolidone above the limit polymerization temperature, 1 (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1995-2004 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymerization mixtures of 2-pyrrolidone, i.e. the mixtures of monomer, polymer and their potassium salts, prepared by non-activated polymerization under optimal conditions (45°C), exhibit in the temperature interval between the ceiling temperature (70°C) and 110°C an increase in the polymer yield, whereas the yield and intrinsic viscosity [η] of the polymer decrease at higher temperatures (up to 160°C). The polymerization mixtures, heat stressed in this way, have an increased polymerization activity in comparison with the non-activated polymerization, if exposed again to the optimal polymerization temperature. A controlling effect of the present semicrystalline poly(2-pyrrolidone) and the stability of a part of growth centres, even at high temperature, are concluded from the investigated behaviour.
    Additional Material: 7 Ill.
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    Bifunctional anionic initiators: A critical study and overviewDedicated with best wishes to Prof. Dr. R. Kerber on the occasion of his 60th birthday (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 2017-2024 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The suitability of several dilithio compounds as initiators for the anionic polymerization of dienes was tested in view of the following criteria: quantitative reaction of diolefins with sec-butyllithium within reasonable periods of time, precipitation of dilithio compounds in a heptane/toluene mixture, sufficient solubility of the dilithio compounds in toluene, rapid initiation of polymerization and small dispersion index of the polymer, low cost of the preparation of the diolefins and the dilithio initiators. The results show that with respect to the diolefins investigated the bifunctional initiator derived from 1,4-bis(4-(1-phenylvinyl)phenyl)-butane is most suited for the preparation of diene blocks in ABA-triblock copolymers.
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    The structure and time evolution of a cellulose sheet in the nascent fibril produced by acetobacter xylinum (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 2609-2614 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Structure and time evolution of a nascent cellulose sheet, produced by Acetobacter xylinum, were examined regarding the resistance of the nascent fibrils to alkali. It became clear that the never-air-dried cellulose, obtained after an incubation period of 5 min, changes its morphology after an alkali treatment at very low concentrations (ranging from 1,0 · 10-3 to 1,0 · 10-2 wt.-%). It is subsequently transformed into cellulose II. On the other hand, although the fibril after an incubation period of 30 min seems to be in a stainable state toward sodium tungstophosphate when it was treated with 4,6 wt.-% alkali, 70-80% of it maintains the fibrous shape. Electron diffraction experiments, involving the fibrils, indicate a cellulose I structure. Even when the sample after an incubation period of 30 min was treated with 9,6 wt.-% alkali, about 30% of it still maintains the fibrous shape. Electron diffraction experiments, involving the fibrils, also indicate a cellulose I structure. The shape of a cellulose sheet, just after its extrusion from a cell, seems to be maintained by hydrophobic bonds. The enhancement of the resistance of cellulose toward alkali with time must be due to the development of inter-and intramolecular hydrogen bonds in each cellulose sheet.
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    Dilute solution properties of imogolite (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 2623-2638 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Imogolite, a natural product in the clay fraction of Japanese soil, was characterized through its dilute solution properties. Various methods were employed for this characterization, including viscosity, sedimentation, static/dynamic light scattering, and small angle X-ray scattering. All these measurements have revealed consistently that imogolite is represented by a rigid thin rod within the accuracy of available theories, where its repeat unit is composed of twelve gibbsite units. Since the evaluation of the chain length from the observed quantities depends on the molecular weight distribution, its effect was also considered where Mw/Mn ≈ 1,2 was estimated from the sedimentation profile.
    Additional Material: 11 Ill.
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    Influence of an external magnetic field on the cross-linking reaction of 1,4-polybutadiene with bis(2,4-dichlorobenzoyl) peroxideDedicated to Prof. R. Kerber on the occasion of his 60th birthday (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 2615-2622 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The cross-linking of (Z)-1,4-polybutadiene with bis(2,4-dichlorobenzoyl) peroxide was investigated between 80 and 100°C under the influence of an external magnetic field (flux density: 1 Tesla) and also without magnetic field. The cross-linking density was determined by measuring the equilibrium swelling in toluene at 25°C. The statistical evaluation showed that the magnetic field causes a decrease in the cross-link density. No influence of the magnetic field on the kinetics of the reaction was observed. The results are discussed in terms of the radical pair theory.
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    DSC studies of linear low density polyethylene. Insights into the disrupting effect of different comonomers and the minimum fold chain length of the polyethylene lamallae (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 2657-2662 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper reports a DSC examination of a series of linear low density polyethylenes (LLDPE) prepared variously with propylene, 1-butene or 4-methyl-1-pentene comonomers. The enthalpy of fusion of the crystalline regions of the LLDPE decreases progressively with increasing comonomer content and is effectively independent of the comonomer type. Disruption of polymer crystallinity is thus determined principally by the number and distribution of the chain irregularities. A sequence length of n = 14 was calculated as the critical chain dimension below which polyethylene segments cannot be readily packed into a stable crystal lattice.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.021861226
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    Preface (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 9 (1985), S. 1-1 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020091985101
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  • 83
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    Soluble polymers as hemoglobin carriers in blood substitutes (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 9 (1985), S. 43-46 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hemoglobin (Hb) in solution is capable of transporting oxygen and could thus be considered as an ideal red cell substitute. However, it presents two important drawbacks : a short vascular retention time and a high oxygen affinity. Chemical modifications of Hb by polymeric reagents could overcome these limitations, but generally, polymer-linked Hb exhibits too high an oxygen affinity. Covalent coupling of monomethoxypolyoxyethylene with Hb in conditions where the amines, essential for oxygen transport, are protected, gives rise to conjugates with good oxygen-binding properties.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1985.020091985106
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  • 84
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    Immunogenicity of N-(2-hydroxypropyl) methacrylamide copolymers (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 9 (1985), S. 13-24 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The homopolymer of N-(2-hydroxypropyl)methacrylamide (HPMA) and copolymers of HPMA differing in oligopeptide side chains (-Gly-Gly-OH;-Acap-Phe-OH;-Acap-Leu-HMDA and -Gly-Phe-Tyr-OH) or in their content (1.0, 3.5 and 8.4 mol. % of -Gly-Gly-OH side chains)Abbreviations see appropriate Tables and Figures. were investigated with respect to their ability to induce antibody formation in inbred strains of mice. The dependence on the antigen dose on structure of the side chains and on the genetic background of the immunized organism was defined. It was demonstrated that the specificity of the antibody formed is predominantly directed against oligopeptide side chains though some part of the produced antibody is against hydroxypropyl groups. Haptens, such as arsanilic acid and fluorescein isothiocyanate, modifying the side chains, were used as drug models, and their influence on immunogenicity of HPMA copolymers was tested.The HPMA copolymers can be considered as a possible targetable drug delivery system as conditions were found under which the specific antibodies attached to them can damage the target site.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1985.020091985103
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  • 85
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    Methods of targeting N-(2-hydroxypropyl) methacrylamide copolymers to particular cell types (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 9 (1985), S. 3-12 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Soluble synthetic polymers will only be useful as drug carriers, if methods can be devised for targeting them to specific cell types. Two approaches are currently being investigated. Firstly, the incorporation of specific residues such as galactosamine into N-(2-hydroxypropyl) methacrylamide copolymers has been shown to enhance greatly pinocytic capture by liver cells. Secondly, antibodies have been evaluated as a more universal address system. Binding rat IgG to N-(2-hydroxypropyl) methacrylamide copolymers increased their rate of uptake by rat visceral yolk sacs cultured in vitro and simultaneously enhanced their rate of exocytosis.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1985.020091985102
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  • 86
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    Synthesis of model biopolymers by reactions in polyphosphite chains (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 9 (1985), S. 47-51 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A possibility of obtaining high molecular weight analogues of natural polynucleotides based on poly(trimethylenephosphite) by the attachment of nucleotide fragments to the phosphite group of the chain of the initial polymer has been shown. Various methods of attachment were used to obtain imidazole-, uracil-, cytosine-, adenine- and inosine-containing analogues capable of undergoing hydrolytic decomposition and soluble in water and some organic solvents.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/macp.1985.020091985107
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  • 87
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    Composition of the protein layers adsorbed from blood or plasma to solid surfaces: A perspective (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 9 (1985), S. 69-80 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The protein layers deposited from blood onto contacting surfaces are believed to be a strong determinant of ultimate thrombogenesis. Recent research on the composition of these layers is reviewed. The layers are complex and contain a multiplicity of components, most of which are not yet identified. The abundant plasma proteins albumin, IgG and fibrinogen are found on most surfaces but in relatively small amounts. Other proteins found are hemoglobin, IgA, IgD, plasminogen, fibronectin, α- and β- lipoproteins, and von Willebrand factor. Considerable differences in composition have been found from surface to surface. The composition has also been found to vary with time. For example initially adsorbed fibrinogen is largely replaced by high molecular weight kininogen (HMWK). There is strong involvement of proteins of the contact phase of blood coagulation in the layer, and factor XII, factor XI and HMWK have been shown to be present on various surfaces. Protein alterations such as activation of factor XII and reactions such as degradation of fibrinogen by plasmin have also been shown to occur in the adsorbed layer.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1985.020091985109
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  • 88
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    Dynamic adsorption and desorption of proteins (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 9 (1985), S. 85-98 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To study the dynamics of adsorption and desorption of plasma proteins, bovine serum albumin(BSA), γ-globulin, fibrinogen, and plasma fibronectin(FN) were labeled with131 I and phosphate buffered solutions of the single proteins and of the mixed proteins were used for the in vitro adsorption and desorption study. When the proteins in single concentration were first adsorbed onto a polyethylene tube and desorbed after 60 min adsorption by changing the flowing liquid from the protein solution to a buffered saline without any protein, FN molecules were found to remain adsorbed so strongly on the tube surface that their desorption did not take place even after washing with the flowing buffer. On the contrary, BSA was rather readily desorbed from the tube surface upon continued washing. A similar result was obtained when the protein pre-adsorbed on a polyethylene film was exposed to the solution of the same but unlabeled protein; the adsorbed FN was not replaced, while the BSA solution expelled the adsorbed BSA molecules from the polyethylene surface. Adsorption and desorption behaviors of γ-globulin and fibrinogen were intermediate between those of BSA and FN. When a mixture of BSA and FN was allowed to flow into the polyethylene tube at a concentration of 0.05 mg ml-1 for each protein, BSA adsorption took place more rapidly and significantly than FN in the initial stage of adsorption but was decreased after passing a maximum, whereas FN was increasingly adsorbed onto the polyethylene surface with time and finally surpassed BSA in the adsorption amount.
    Additional Material: 16 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1985.020091985111
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  • 89
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    Blood compatibility of heparinized polyurethanes (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 9 (1985), S. 119-124 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Heparin - immobilized polyurethane (HI-PU) catheters implanted in canine femoral and jugular veins for one hour periods exhibited significant reduction in thrombus formation compared with untreated PU contralateral controls. PU catheters coated with a 9% heparin dispersion in PU, capable of releasing active heparin for several hours, provided even greater improvement in antithrombogenicity. Both types of heparinized surface displayed reduced platelet aggregation and fibrin formation, although platelet adhesion was somewhat higher on the HI material than on the heparin-releasing (HR) surface.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1985.020091985115
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  • 90
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    Polyglutamines-versatile biodegradable carriers (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 9 (1985), S. 129-135 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Biodegradation of homopolymers, poly-α-[Nγ-(2-hydroxyethyl)-L-glutamine] and poly-α-[Nγ-(2-hydroxypropyl)-L-glutamine], and of copolymers, poly-α-[Nγ-(2-hydroxyethyl)-L-glutamine-co-L-phenylalanine] with 3.7, 5.6, and 10.2 mol-% of Phe units was studied in vitro using pronase E, chymotrypsin A4 and extracts from native tissues. Gel permeation chromatography was used for evaluating the molecular-weight distribution of the original and partially degraded polymers. Homopolymers of Nγ-(2-hydroxyalkyl)-L-glutamines are biodegradable in the main chain by pronase as well as by native tissue extracts, yielding low-molecular-weight products. Although chymotrypsin does not catalyze hydrolysis of peptide bonds in the homopolymers, incorporation of phenylalanine units in the main chain by copolymerization renders the copolymer degradable by this enzyme, most probably in phenylalanyl-glutamine bonds.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1985.020091985117
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  • 91
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    Delivery of gonadotropin releasing hormone from polymer solutions - influence of viscosity (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 9 (1985), S. 163-168 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1985.020091985123
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  • 92
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    Development of macromolecular prodrugs of the antitumor antibiotic adriamycin (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 9 (1985), S. 175-178 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020091985125
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  • 93
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    Preparation and performance of symplex capsules (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 9 (1985), S. 203-210 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new process of encapsulation based on the formation of polyelectrolyte complexes is reported. By some examples of entrapping sensitive biological material its versatility in application is demonstrated.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1985.020091985129
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  • 94
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    Aspects of film formation with emulsion copolymers (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 10 (1985), S. 447-461 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: For homogeneous emulsion copolymers the process of film formation is correlated qualitatively with the viscoelastic properties of the polymer as is predicted by the theories of film formation. With highly water-soluble comonomers heterogeneous core-shell particles may be obtained with a shell of hydrophilic polymer which influences the structure and the properties of the films significantly. Heterogeneous polymer particles with a multi-phase morphology due to the presence of incompatible polymers of different glass transition temperature show a further stage of film formation with a distinct change in film morphology.
    Additional Material: 13 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1985.020101985131
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    Batch and semicontinuous emulsion copolymerization styrene/methyl methacrylate: Kinetics and viscoelastic propertiesPresented in part at the Colloque International sur les Copolymerisations et Copolymeres en Emulsion, Lyon, France, 6 - 9 March 1984. (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 10 (1985), S. 477-488 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Styrene (S)-Methyl methacrylate (MMA) copolymers have been synthesized via batch and semicontinuous processes. The copolymers obtained in both processes were richer in styrene than the initial monomers composition. This fact is strongly influenced by the solubility of MMA in water. The experimental results also showed the existence of an inverse relationship between initiator concentration and molecular weight and consequently in the flow properties of the materials. Furthermore, the molecular weight and flow properties did not show an important dependence on emulsifier content. It was found that the rate of copolymerization was an inverse function of the electrolyte present in the reaction medium. Comparison between copolymers made via batch and semicontinuously pointed out that in general the materials made in a batch process have lower viscosity and elasticity than its semicontinuous counterparts.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1985.020101985133
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  • 96
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    Caracterisation viscometrique des latex a partir d'une relation derivee de la loi de mooney (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 10 (1985), S. 511-536 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The method proposed uses the relation of viscosity versus concentration and gives characteristic parameters of aqueous acrylic dispersions.It allows characterization of lattices by four values representing hydrodynamic volume and crowding factor of particles. It gives also the contribution of the surface layer and serum to the rheological behaviour.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1985.020101985136
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    Some aspects of molecular weight determination in acrylic emulsion copolymersPart of this work was presented at the COLLOQUE INTERNATIONAL SUR LES COPOLYMÉRISATION ET LES COPOLYMÈRES EN EMULSION, Lyon, 7-9 Mars 1984 (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 10 (1985), S. 311-317 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three types of ethylacrylate (EA) and methyl methacrylate (MMA) copolymers and both homopolymers were synthesized by batch emulsion polymerization.The quantification of the influence of the low-molecular-weight compounds, originating also from the presence of emulsifiers, on molecular weight determination was the main purpose of this work.Therefore molecular weights and molecular weight distribution were determined for samples as synthesized (uncleaned samples) and for samples freed of low-molecular-weight compounds (cleaned samples).It was found that data on molecular weight averages and molecular weight distribution of cleaned samples do not provide sufficient information on the applicability of the emulsions concerning molecular weights.In this work the nonhomogeneity due to copolymer composition was neglected.With increasing the proportion of the more reactive monomer in monomer composition the molecular weight averages are increasing.
    Additional Material: 5 Ill.
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  • 98
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    Latex de particules structurees (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 10 (1985), S. 359-390 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A survey of the literature concerning the preparation and the characterization of structured latex particles is presented. The main features of the various processing techniques are discussed; the mechanisms and also the various parameters which shape the polymeric phase arrangement throughout the volume of the particles are emphasized.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1985.020101985126
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  • 99
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    Structure/properties of emulsion copolymers (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 10 (1985), S. 403-418 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Starting the polymerization in the water phase favours the concentration of hydrophilic comonomers in the oligomer radical formed there. The more hydrophilic molecular parts show the tendency to concentrate in the latex particle in the direction of the interface with the water, which promotes the formation of a particular morphological structure.Special feed processes allow one controlled composition of core-shell-type latex particles with specific property combinations that cannot be achieved in any other way.Voluntarily or involuntarily performed agglomerations during or after the polymerization also lead to favourable property combinations.Examples are given to illustrate the relationship between the morphological structure and certain physical and application properties.
    Additional Material: 23 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1985.020101985128
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  • 100
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    Permeability of heterogeneous films cast from core-shell polymer latices (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 10 (1985), S. 435-446 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Techniques have previously been developed for the preparation of thin (10-100 μm) polymer latex films, and the measurement of their gas permeabilities. These methods have been used to study heterogeneous polymer films cast from core-shell polymer latices. Such films comprise a regular dispersion of core particles in a continuum of coalesced shell polymer. The behaviour of these films is compared with heterogeneous films cast from mixtures of two homopolymer latices, and homogeneous films cast from homopolymer and copolymer latices and from polymer solutions.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1985.020101985130
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