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  • 1
    Electronic Resource
    Electronic Resource
    Preparation of poly(vinyl chloride-g-isobutylene) by BCl3 (1979)
    Springer
    Polymer bulletin 1 (1979), S. 253-258 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Poly(vinyl chloride-g-isobutylene) has been synthesized using mildly dehydrochlorinated (NaOH treated) PVC in conjunction with BCl3 coinitiator. Treatment of PVC with NaOH increases initial thermal dehydrochlorination rate and renders the polymer suitable for efficient grafting. Untreated PVC produces negligible grafting.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00254333
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  • 2
    Electronic Resource
    Electronic Resource
    Olefin-Polymerisation und -Copolymerisation mit Al-Alkyl-Initiator-Systemen. 7. Mitt. Initüerung mit elektrophilen Halogenen (1975)
    Springer
    Colloid & polymer science 253 (1975), S. 351-351 
    Details
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02352229
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  • 3
    Electronic Resource
    Electronic Resource
    Ein Versuch zur Anwendung der Übersäure-Chemie auf Living-Carboniumionen-Polymerisationen (1977)
    Springer
    Colloid & polymer science 255 (1977), S. 101-101 
    Details
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01449730
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  • 4
    Electronic Resource
    Electronic Resource
    Analyse der Sequenzverteilung in Isobutylen/Styrol- und Isobutylen/Isopren-Copolymeren (1978)
    Springer
    Colloid & polymer science 256 (1978), S. 716-716 
    Details
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01784513
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  • 5
    Electronic Resource
    Electronic Resource
    Sequential copolymers by ionic polymerizations (1979)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 3 (1979), S. 1-16 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: While many well defined sequential copolymers have been synthesized by anionic and some by coordination polymerization techniques, cationic methods have not been exploited in this regard. This lecture focuses on “macromolecular engineering” by cationic techniques and summarizes the many recently developed and largely unpublished methods by which a great variety of sequential copolymers and modified polymers can readily be prepared. A new scheme for macromolecular engineering by carbocationic mechanism is proposed. Controlled initiation as a means of introducing head-groups into polymers or of graft-copolymer syntheses is described. Control of chain transfer to monomer became possible by the use of bifunctional initiator-chain transfer agents (inifers) or by proton sponges. The synthesis of telechelic α,ω-dichlorides, and -diolefins is outlined. α,ω-(Di-tert-chloro) polyisobutylene, a new symmetrical telechelic prepolymer has been used to prepare poly(α-methylstyrene-isobutylene-α-methylstyrene) thermoplastic elastomeric triblocks. Consequences of controlled termination are illustrated by the synthesis of diblock copolymers. Finally, by a combination of mechanistic elements, a system for macromolecular engineering by cationic techniques is outlined.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1979.020031979101
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  • 6
    Electronic Resource
    Electronic Resource
    Cationic polymerization with boron halides. IV. Elucidation and control of initiation and termination by the help of model experiments (1977)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2869-2892 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The proposition that BCl3-coinitiated olefin (isobutylene, styrene) polymerizations terminate by chlorination has been corroborated by model experiments. Key experiments showed that under simulated polymerization conditions neither tert-butyl chloride nor 2-chloro-2,4,4-trimethylpentane reacts with BCl3; that H2O/BCl3 + 2,4,4-trimethyl-1-pentene (TMP) produce 2-chloro-2,4,4-trimethylpentane; and that H2O/BCl3 + isobutylene gives rise to tert-butyl chloride. Extended model studies demonstrated that certain alkyl and benzyl chlorides produce carbenium ions in the presence of BCl3 and that TMP can readily be alkenylated by using 1-substituted allyl chlorides in conjunction with BCl3. These experiments led to the discovery that olefin polymerizations may be initiated by suitable allyl or benzyl chlorides and BCl3. Accordingly, polymerizations of isobutylene have been carried out with RCl/BCl3, where R is allyl or benzyl. These experiments suggest that both controlled initiation and termination, i.e., initiation by alkenylation and termination by chlorination, can be achieved with the allyl chloride/BCl3 initiator system opening new avenues toward the synthesis of asymmetric telechelic polymers.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1977.170151205
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  • 7
    Electronic Resource
    Electronic Resource
    Poly(vinyl chloride-g-butyl rubber) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 153-157 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of poly(vinyl chloride-g-butyl rubber) and some of its physical properties are described. The key to the synthesis involves copolymerization initiation of an isobutylene-isoprene charge by a PVC/Et2AlCl initiator system with 1,2-dichloroethane as solvent. The graft is a thermoplastic; cast films are flexible and optically clear. Proof of grafting is the crosslinking with S2Cl2 of the pentane-extracted product in THF solution. Crosslinking the butyl rubber moiety in the graft reduces overall stress properties.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140115
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  • 8
    Electronic Resource
    Electronic Resource
    Cationic polymerization with boron halides. V. Synthesis of poly(isobutylene-b-styrene) and poly(styrene-b-isobutylene) (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 243-259 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Block copolymers of isobutylene and styrene, PIB-b-PSt and PSt-b-PIB, have been prepared by a two-step synthesis involving (1) preparation of terminally chlorinated (telechelic) polyisobutylene or polystyrene “prepolymers” by using the H2O/BCl3 initiator system and (2) blocking from these telechelic prepolymers a second polymer segment by using an alkyaluminum, e.g., Et2AlCl coinitiator. The telechelic polyisobutylene and polystyrene contain tertiary and benzylic chlorine termini, respectively. Block copolymer characterization included detailed selective solvent extraction procedures, coupled with GPC determinations, PMR, solubility, and intrinsic viscosity studies. The synthesis of PIB-b-PSt and PSt-b-PIB provides direct chemical evidence for the presence and position of active chlorine termini in BCl3-coinitiated olefin polymerizations.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1978.170160123
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  • 9
    Electronic Resource
    Electronic Resource
    Cationic polymerization with boron halides. VI. Polymerization of styrene with BF3, BCl3, and BBr3Presented in part at the 172nd A.C.S. National Meeting, San Francisco, CA, as Part II of this series (ref. 1). (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 2191-2197 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of styrene with BF3, BCI3, and BBr3 coinitiators and CH2Cl2 solvent has been investigated. The effects of temperature, monomer concentration, and the nature of the boron halide on molecular weights, molecular weight distribution, and conversion were determined. Molecular weights were found to decrease in the order BCl3 〉BF3 〉BBr3. This sequence was discussed in terms of system ionicity and counterion stability. The overall energies of activation for polymerization (ΔEDPn) were -1.6 ± 0.3, -1.9 ± 0.8, and -0.9 ± 0.5 kcal/mole for BF3, BCI3, and BBr3, respectively, which indicated similar overall polymerization mechanisms in the range of -20 to -80°C. The predominant molecular-weight-governing event in polymerizations with BCl3, and BBr3 was chain transfer to monomer, whereas with BF3 chain transfer and termination were nearly equal. Chain termination in BCl3-coinitiated polymerizations involves chlorination of the growing polystyryl cation by BCl3OH⊖ and leads to benzylic chlorine termini.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1978.170160909
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  • 10
    Electronic Resource
    Electronic Resource
    Cationic polymerization with boron halides. III. BCl3 coinitiator for olefin polymerizationFor previous papers in this series, see Kennedy et al. and Feinberg and Kennedy. (1977)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2801-2819 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of isobutylene with BF3, BCl3, and BBr3 coinitiators has been investigated. The polymerization with BCl3 requires the presence of a cationogen, e.g., H2O. The presence of a polar solvent is also necessary. Surprisingly, large quantities of polar solvent are required for effective polymerization. To obtain high conversions, the mixing sequence of the reagents is critical: BCI3 must be added last to charges containing the monomer and H2O in a polar solvent. Ultimate conversions increase by decreasing the temperature. Kinetic termination exists. Experiments with BF3 and BBr3 revealed that polymerizations induced with BF3 proceed in nonpolar and/or polar media. Polymerization stops with BF3 at less than complete conversion (termination exists). In contrast to findings with BCl3, polymer yields with BF3 increase with increasing temperatures. BBr3 is a very inefficient coinitiator, even in the presence of polar solvent, over the -10 to -90°C temperature range. A hypothesis which explains these observations has been developed.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1977.170151201
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