Reaction to effect the transformation of anionic polymerization into cationic polymerization: 1. Synthesis and reactivities of anionically generated bromine terminated polymers

Burgess, F.J.; Cûnliffe, A.V.; MacCallum, J.R.; Richards, D. H.

doi:10.1016/0032-3861(77)90240-3

Cited by 86 publications

(23 citation statements)

References 10 publications

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“…The transformation of an active chain end into another type of initiating site has been extensively used in the synthesis of block copolymers [90]. Well-defined block copolymers have been prepared by the transformation of initiating sites from living anionic to living cationic [91][92][93][94], from living cationic to living anionic [95][96][97], and from living coordination to living cationic polymerization [98]. Here we describe the recent advances in the synthesis of block copolymers via combination of controlled radical polymerizations with other living polymerizations.…”

Section: Other Mono-and Difunctional Polymersmentioning

confidence: 99%

Syntheses and Characterizations of Block Copolymers Prepared via Controlled Radical Polymerization Methods

Pan

2004

Developments in Block Copolymer Science and Technology

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Section: Other Mono-and Difunctional Polymersmentioning

confidence: 99%

Syntheses and Characterizations of Block Copolymers Prepared via Controlled Radical Polymerization Methods

Pan

2004

Developments in Block Copolymer Science and Technology

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“…In the case of the synthesis of triblock, reduced blocking efficiency would result in homopolymer and/or diblock with an attendant reduction in mechanical properties. A notable example of chainend transformation of living anionic to living cationic polymerization yielded poly(styrene-i?-tetramethylene oxide); the synthesis was performed by terminating the living anionic polymerization of styrene with an excess of bromine or xylene dibromide to yield the bromide or benzylbromide chainend, respectively, which upon treatment with AgPF6 in the presence of THF initiated the living cationic polymerization of THF to yield the target block copolymer (21,22,23).…”

Section: Kennedy and Price Block Copolymer Thermoplastic Elastomers 259mentioning

confidence: 99%

Poly(methyl methacrylate)-block-polyisobutylene-block-poly(methyl methacrylate) Thermoplastic Elastomers

Kennedy

Price²

1992

ACS Symposium Series

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Poly(methyl methacrylate-b-isobutylene-b-methyl meth acrylate) (PMMA-PIB-PMMA) triblock copolymers have been synthesized by a combination of living cationic and living anionic polymerizations. The total synthesis invol ved five steps: 1.) The living cationic polymerization of isobutylene (IB) leading to well defined, narrow molecular weight distribution, α,ω-dichloropolyisobutylenes ( t Cl-ΡΙΒ -t Cl). 2.) The alkylation of toluene with t Cl-ΡΙΒ-t Cl using AlCl3 at -78°C which yields α,ω-p-ditolylpolyisobutylene (CH3-Ø-PIB-Ø-CH3).3.) The quantitative lithiation of the latter to α,ω-dibenzyllithiumpolyisobutylene (LiCH2-Ø-PIB--Ø-CH2Li) by using a complex of s-butyllithium (s-BuLi) and N,N,N',N'-tetramethylethyldiamine (TMEDA) (TMEDA/s--BuLi = 2) in n-hexane at 0°C for 48 hrs. 4.) The reaction of LiCH2-Ø-PIB-Ø-CH2Li with 1,1-diphenylethylene. 5.) The living anionic polymerization of methyl methacrylate (MMA) with the latter intermediate. An inventory of various PMMA-PIB-PMMA have been prepared, characterized, and some of their mechanical properties studied. The molecular weight distribution of the triblocks was nearly identical to the PIB center block which indicates good blocking efficiency. DSC and DMTA showed two transitions (-61 and 105°C for PIB and PMMA, respectively) which indicates a two phase microarchitecture. Stress--strain measurements were performed on clear cast sheets and the data analyzed in terms of compositional information of these new thermoplastic elastomers.

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“…1 Essentially, two kinds of methods can be used to synthesize block copolymers: One is living polymerization systems, including the well-known anionic polymerization, cationic polymerization, 2 group-transfer polymerization, 3 and "living" controlled radical polymerization. 4,5 The other is to combine different polymerization techniques together, such as anionic polymerization with cationic, 6 anionic with Ziegler-Natta 7 coordinate polymerization, and anionic with radical 8 polymerization. By means of the latter method, some special block copolymers which are impossible to prepare by a single polymerization method can be obtained.…”

Section: Introductionmentioning

confidence: 99%

Preparation of PMMA-PS-PMMA via combination of anionic and photoinduced charge-transfer polymerization

Wan

Huang

1999

J. Appl. Polym. Sci.

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PMMA-PS-PMMA triblock copolymers were prepared by the combination of an anionic mechanism with charge-transfer polymerization. Polystyrene with aromatic tertiary amino groups at both ends (PS ba ) was synthesized first by the reaction of a living polystyrene macrodianion with excess p-(dimethylamino)benzaldehyde; then, the PS ba was constituted into a binary system with benzophenone (BP) to initiate the polymerization of methyl methacrylate (MMA) under UV irradiation. The intermediate and resulting block copolymers were characterized by GPC, IR, and 1 H-NMR.

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Reaction to effect the transformation of anionic polymerization into cationic polymerization: 1. Synthesis and reactivities of anionically generated bromine terminated polymers

Cited by 86 publications

References 10 publications

Syntheses and Characterizations of Block Copolymers Prepared via Controlled Radical Polymerization Methods

Syntheses and Characterizations of Block Copolymers Prepared via Controlled Radical Polymerization Methods

Poly(methyl methacrylate)-block-polyisobutylene-block-poly(methyl methacrylate) Thermoplastic Elastomers

Preparation of PMMA-PS-PMMA via combination of anionic and photoinduced charge-transfer polymerization

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