Your email was sent successfully. Check your inbox.

An error occurred while sending the email. Please try again.

Proceed reservation?

Export
  • 1
    ISSN: 0887-624X
    Keywords: thermoplastic elastomer ; carbocationic polymerization ; polyisobutylene ; living polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New linear triblock thermoplastic elastomers (TPEs) comprising a rubbery polyisobutylene (PIB) midblock flanked by two glassy endblocks of various styrenic polymers have been synthesized by living carbocationic polymerization by sequential monomer addition. First isobutylene (IB) was polymerized by a bifunctional tert-ether (dicumyl methyl ether) initiator in conjunction with TiCl4 coinitiator in CH3Cl/methylcyclohexane (MeCHx) (40/60 v/v) solvent mixtures at -80°C. After the living narrow molecular weight distribution PIB midblock ($\[\bar M_n\]$ = 1.1-1.2) has reached the desired molecular weight, the styrenic monomers together with an electron pair donor (ED) and a proton trap (di-tert-butylpyridine, DtBP) were added to start the blocking of the glassy segments from the living ⊕PIB⊕ chain ends. While p-methylstyrene (pMeSt), p-t-butylstyrene (ptBuSt) and indene (In) gave essentially 100% blocking to the corresponding glassy endblocks, the blocking of 2,4,6-trimethylstyrene (TMeSt) and α-methylstyrene (αMeSt) were ineffective. Uncontrolled initiation by protic impurities was prevented by the use of DtBP. In the simultaneous presence of DtBP and the strong ED N,N-dimethylacetamide (DMA), TPEs with good mechanical properties (10-20 MPa tensile strength, 300-600% elongation) were prepared. The products exhibit a low and a high temperature Tg characteristic of phase separated rubbery and glassy domains. The service temperature of these new TPEs exceeds that of PSt-PIB-PSt triblock copolymers due to the higher Tgs (PpMeSt = 108, PptBuSt = 142 and PIn = 220-240°C) of the outer blocks. The Tg of the glassy blocks can be regulated by copolymerizing two styrene derivatives; a triblock copolymer with outer blocks of poly(pt-butylstyrene-co-indene) showed a single glassy transition Tg = +165°C, i.e., in between that of PptBuSt and PIn. Virgin TPEs have been repeatedly compression molded without deterioration of physical properties. The high melt flow index obtained with a TPE containing PptBuSt endblocks suggests superior processability relative to those with PSt end-blocks. The tensile strength retention at 60°C of the former TPE is far superior to that of a PSt-PIB-PSt triblock of similar composition.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Signatur Availability
    BibTip Others were also interested in ...
  • 2
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New linear and three-arm star thermoplastic elastomers (TPEs) comprising a rubbery polysobutylene (PIB) midblock flanked by glass polystyrene (PSt) blocks have been synthesized by living carbocationic polymerization in the presence of select additives by sequential monomer addition. First, isobutylene (IB) was polymerized by bi- and trifunctional tert-ether (dicumyl- and tricumyl methoxy) initiators in conjunction with TiCl4 conintiator in CH3Cl/methylcyclohexane (MeCHx) (40/60 v/v) solvent mixtures at -80°C. After the living, narrow molecular weight, distribution PIB (M̄w/M̄n = 1.1-1.2) has reached the desired molecular weight, styrene (St) together with an electron pair donor (ED) and a proton trap (di-tert-butylpyridine, DtBP) were added to block PSt from the living chain ends. Uncontrolled initiation by protic impurities that produces PSt contamination is prevented by the use of DtBP. PSt-PIB-PSt blocks obtained in the absence of additives are contaminated by homopolymer and /or diblocks due to inefficient blocking and initiation by protic impurities, and exhibit poor physical properties. In contrast in the presence of the strong ED N,N-dimethylacetamide (DMA) and DtBP the blocking of St from living PIB chain occurs efficiently and block copolymers exhibiting good mechanical properties can be prepared. Virgin TPEs can be repeatedly compression molded without deterioration of physical properties. The products exhibit a low and a high temperature Tg characteristic of phase separated PIB and PSt domains. Transmission electron microscopy of linear triblocks containing ∼ 34 wt % PSt also indicates microphase separation and suggests PSt rods dispersed in a PIB matrix.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Signatur Availability
    BibTip Others were also interested in ...
  • 3
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The living carbocationic polymerisation of styrene (St) has been investigated by the 2-chloro-2,4,4-trimethylpentane (TMPCI)/TiCl4 initiating system in the presence of various additives such as electron pair donors (EDs) and the proton trap 2,6-di-tert-butylpyridine (DtBP) by the use of the mixed solvent CH3Cl/methyl-cyclohexane (MCHx) (40/60 v/v) at -80°C under conventional laboratory conditions. The TMPCl/TiCl4 system in the absence of additives produces ill-defined bimodal molecular weight distribution (MWD) polymers. Much better defined polystyrenes (PSt) can be obtained in the presence of EDs, such as N,N-dimethylacetamide (DMA) and hexamethylphosphoramide (HMPA). Monomer depletion should be avoided to prevent intra- or intermolecular alkylation yielding indanyl end groups or branched polymers, respectively. In the combined presence of an ED and the proton trap, i.e., DMA + DtBP, the living polymerization of St has been achieved and thus the foundations for the carbocationic synthesis of PSt block polymers by sequential monomer addition have been laid.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Signatur Availability
    BibTip Others were also interested in ...
Close ⊗
This website uses cookies and the analysis tool Matomo. More information can be found here...