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  • bicomponent networks  (2)
  • carbocationic polymerization  (1)
  • extractables  (1)
  • 1
    Electronic Resource
    Electronic Resource
    Living carbocationic polymerization of isobutyl vinyl ether and the synthesis of poly[isobutylene-b-(isobutyl vinyl ether)] (1993)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 2825-2834 
    Details
    ISSN: 0887-624X
    Keywords: carbocationic polymerization ; living polymerization ; poly(isobutyl vinyl ether) ; polyisobutylene ; block copolymers ; titanium tetrachloride ; common ion salt ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The MeCH(O-i-Bu)Cl/TiCl4/MeCONMe2 initiating system was found to induce the rapid living carbocationic polymerization (LC⊕Pzn) of isobutyl vinyl ether (IBuVE) at -100°C. Degradation by dealcoholation which usually accompanies the polymerization of alkyl vinyl ethers by strong Lewis acids is “frozen out” at this low temperature and poly(isobutyl vinyl ether)s (PIBuVEs) with theoretical molecular weights up to ca. 40,000 g/mol (calculated from the initiator/monomer input) and narrow molecular weight distributions (M̄w/M̄n ≤ 1.2) are readily obtained. According to 13C-NMR spectroscopy, PIBuVEs prepared by living polymerization at -100°C are not stereoregular. The MeCH(O-i-Bu)Cl/TiCl4 combination induces the rapid LC⊕Pzn of IBuVE even in the absence of N,N-dimethylacetamide (DMA). The addition of the common ion salt, n-Bu4NCl to the latter system retards the polymerization and meaningful kinetic information can be obtained. The kinetic findings have been explained in terms of TiCl4. IBuVE and TiCl4 · IBuVE and TiCl4 · PIBuVE complexes. The HCl (formal initiator)/TiCl4/DMA combination is the first initiating system that can be regarded to induce the LC⊕Pzn of both isobutylene (IB) and IBuVE. Polyisobutylene (PIB)-PIBuVE diblocks were prepared by sequential monomer addition in “one pot” by the 2-chloro-2,4,4-trimethylpentane (TMP-Cl)/TiCl4/DMA initiating system. Crossover efficiencies are, however, below 35% because the PIB⊕ + IBuVE → PIB-b-PIBuVE⊕ crossover is slow. © 1993 John Wiley & Sons, Inc.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1993.080311120
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    Paper (German National Licenses)
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  • 2
    Electronic Resource
    Electronic Resource
    Novel polyisobutylene/poly(dimethylsiloxane) bicomponent networks. I. Synthesis and characterization (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1891-1899 
    Details
    ISSN: 0887-624X
    Keywords: polyisobutylene ; poly(dimethylsiloxane) ; hydrosilation ; bicomponent networks ; molecular weight between crosslinks ; network functionality ; sol fraction ; extractables ; model networks ; end-linking ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of novel polyisobutylene (PIB)/poly(dimethylsiloxane) (PDMS) bicomponent networks is described. The synthesis strategy (see Figure 1) was to prepare well-defined and -characterized allyl-tritelechelic polyisobutylenes [φ(PIB - C - C=C)3] and SiH-ditelechelic poly(dimethylsiloxanes) (HSi-PDMS-SiH) and then crosslink these moieties by hydrosilation. The φ(PIB - C - C=C)3 was prepared by living isobutylene polymerization followed by end-quenching with allyltrimethylsilane, whereas the HSi-PDMS-SiH was obtained by equilibrium polymerization of octamethylcyclotetrasiloxane and tetramethyldisiloxane. The detailed structures of the starting polymers were characterized by GPC and 1H-NMR spectroscopy. A series of PIB/PDMS bicomponent networks of varying compositions and average molecular weights between crosslinks (Mc) of ∼ 20,000 g/mol were assembled. Optimum crosslinking conditions were defined in terms of H2PtCl6 catalyst concentration, nature of solvent, time, temperature, and stoichiometry of ∼ CH2CH=CH2/∼SiH groups, allowing for the convenient synthesis of well-defined model bicomponent networks. Swelling studies and elemental analysis confirm the correctness of the synthetic strategy. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1891-1899, 1998
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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    Paper (German National Licenses)
  • 3
    Electronic Resource
    Electronic Resource
    Novel polyisobutylene/poly(dimethylsiloxane) bicomponent networks. II. Network structure and property characterization (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1901-1910 
    Details
    ISSN: 0887-624X
    Keywords: polyisobutylene ; poly(dimethylsiloxane) ; bicomponent networks ; network structure ; molecular weight between crosslinks ; network properties ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The first part of this series concerned the synthesis of novel polyisobutylene (PIB)/poly(dimethylsiloxane) (PDMS) bicomponent networks; the present paper concerns the structure and property characterization of a series of bicomponent networks of varying compositions (PIB wt %/PDMS wt % = 92/8, 70/30, 50/50, 35/65) having average molecular weights between crosslinks (Mc) of ˜ 20,000 g/mol. According to network structure analysis by uniaxial equilibrium stress-strain measurements, the experimental Mc's are in excellent agreement with theoretical values. Hydrosilation end-linking efficiency was quantitated by the amount of sol and functional group analysis by 1H-NMR spectroscopy. NMR evidence indicates double-bond isomerization during hydrosilation. Network compositions by elemental analysis together with the low sol fractions indicate efficient crosslinking. These data suggest highly efficient network formation and well-defined bicomponent network structures. While PIB and PDMS showed Tg's at -72 and -124°C, respectively, the bicomponent network did not exhibit clearly discernible phase transitions. The heat stability of bicomponent networks increased slightly with increasing PDMS content showing initial (10%) degradation temperatures at ˜ 380°C in nitrogen and ˜ 320°C in air. Tensile strengths and elongations were dependent on composition and varied in the 0.6-3.8 MPa and 600-1100% ranges, respectively. The swelling behavior was not much affected by composition. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1901-1910, 1998
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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    Paper (German National Licenses)
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