Living carbocationic polymerization

Si, Jiaoshi; Kennedy, Joseph P.

doi:10.1007/bf00296078

Cited by 8 publications

(2 citation statements)

References 7 publications

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“…Since initiation from adventitious moisture is minimal in this system, we investigated the role of an added electron donor, dimethyl phthalate . For these experiments, we used methyl chloride as the polar solvent and 5- tert -butyl-1,3-bis(1-chloro-1-methylethyl)benzene as the initiator to better match the conditions desired for triblock copolymer preparation.…”

Section: Resultsmentioning

confidence: 99%

Dimethylaluminum Chloride Catalyzed Living Isobutylene Polymerization

2000

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The first examples of dimethylaluminum chloride catalyzed living isobutylene polymerizations are presented. The polymerizations are carried out with conventional tertiary alkyl chloride initiators and 60/40 v/v nonpolar/polar solvent mixtures, the most common solvent systems used for isobutylene triblock synthesis. Additives like proton traps and electron donors are not required. The "living" nature of these polymerizations is demonstrated at -75 to -80 °C in both 60/40 v/v hexane/methylene chloride and hexane/methyl chloride solvent systems using first-order rate plots, trends in M n and Mw/Mn versus conversion, and delayed incremental-monomer-addition experiments. Polyisobutylenes are prepared with Mn ) 150 kDa and Mw/Mn ) 1.2. Since initiation from adventitious moisture is of minor concern in this system, experiments were also run in the presence of dimethyl phthalate. "Livingness" was preserved though polymerization rates are slower with dimethyl phthalate than in its absence.

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Section: Resultsmentioning

confidence: 99%

Dimethylaluminum Chloride Catalyzed Living Isobutylene Polymerization

2000

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“…On the other hand, a catalytic amount of some strong bases such as amides and dimethyl sulfoxide (DMSO) induces living cationic polymerization of isobutene using BCl 3 or TiCl 4 , as reported by Kennedy and coworkers 6. However, these base‐stabilized living polymerization systems were limited to some combinations containing a monomer, an added base, and a Lewis acid 4–14. Recently, we found that SnCl 4 induces living cationic polymerization of amide‐containing vinyl ethers in the presence of an ester.…”

Section: Introductionmentioning

confidence: 91%

Living cationic polymerization of vinyl ethers in the presence of a strong base: Poisonous or helpful?

Yonezumi

Takano

Kanaoka

et al. 2008

J. Polym. Sci. A Polym. Chem.

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A quite small dose of a poisonous species was found to induce living cationic polymerization of isobutyl vinyl ether (IBVE) in toluene at 0 C. In the presence of a small amount of N,N-dimethylacetamide, living cationic polymerization of IBVE was achieved using SnCl 4 , producing a low polydispersity polymer (weight-average molecular weight/number-average molecular weight (M w /M n ) 1.1), whereas the polymerization was terminated at its higher concentration. In addition, amine derivatives (common terminators) as stronger bases allow living polymerization when a catalytic quantity was used. On the other hand, EtAlCl 2 produced polymers with comparatively broad MWDs (M w /M n $ 2), although the polymerization was slightly retarded. The systems with a strong base required much less quantity of bases than weak base systems such as ethers or esters for living polymerization. The strong base system exhibited Lewis acid preference: living polymerization proceeded only with SnCl 4 , TiCl 4 , or ZnCl 2 , whereas a range of Lewis acids are effective for achieving living polymerization in the conventional weak base system such as an ester and an ether. V V C 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6746-6753, 2008

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Cationic Polymerization

Cramail

Deffieux

2013

Materials Science and Technology

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The sections in this article are Introduction Carbocationic Polymerization of Ethylenic Monomers General Features Chemistry of Initiation Propagation Transfer Reactions Termination Reactions Principles and Methods of Controlled Cationic Alkene Polymerization General Features Vinyl Ethers Functional Vinyl Ethers Isobutene Styrene and Derivatives Macromolecular Engineering by Carbocationic Polymerization Synthesis of End‐Functionalized Polymers Synthesis of Block Copolymers Star‐Shaped and Macrocyclic Polymers Cationic Polymerization of Heterocyclic Monomers General Features of Cationic Ring‐Opening Polymerization Chemistry of Initiation Propagation Reaction Chain Transfer to Polymer Other Main Transfer and Termination Processes Main Families of Heterocyclic Monomers Cyclic Ethers Cyclic Acetals Cyclic Sulfides Cyclic Amines Cyclic Esters Cyclic Amides Cyclic Iminoesters Cyclic Phosphorous‐Containing Compounds Cyclic Silicone‐Containing Compounds

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Living carbocationic polymerization

Cited by 8 publications

References 7 publications

Dimethylaluminum Chloride Catalyzed Living Isobutylene Polymerization

Dimethylaluminum Chloride Catalyzed Living Isobutylene Polymerization

Living cationic polymerization of vinyl ethers in the presence of a strong base: Poisonous or helpful?

Cationic Polymerization

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