Block Copolymer Synthesis by Styrene Polymerization Initiated with Nitroxy-Functionalized Polybutadiene

Kobatake, Seiya; Harwood, H. James; Quirk, Roderic P.; Priddy, Duane B.

doi:10.1021/ma9718154

Cited by 43 publications

(32 citation statements)

References 55 publications

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“…The reverse process was also successful because of the high tolerance of cationic polymerization of vinyl ethers to impurities [277]. Living carbanions were quenched by species serving as initiators for NMP and also for ATRP, and subsequently chain extended via CRP [278,279].…”

Section: Crp and Living Carbocationic And Carbanionic Polymerizationmentioning

confidence: 99%

Radical Polymerization

Matyjaszewski

2009

Controlled and Living Polymerizations

158

218

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Approximately 50% of all synthetic polymers are currently made via radical polymerization (RP) processes. The commercial success of RP can be attributed to the large range of radically polymerizable monomers, their facile copolymerization, the convenient reaction conditions employed (typically room temperature to 100 • C, ambient pressure), and very minimal requirements for purification of monomers and solvents. RP is not affected by water and protic impurities and can be carried out in bulk, solution, aqueous suspension, emulsion, dispersion, etc. The range of monomers is larger for RP than for any other chain polymerization because radicals are tolerant to many functionalities, including acidic, hydroxy, and amino groups. In conventional RP, high molecular weight (MW) polymers are formed at the early stages of the polymerization, and neither long reaction times nor high conversions are required, in sharp contrast to step-growth polymerization.However, RP has some limitations, especially in comparison with ionic processes that provide facile routes to living polymers. For a polymerization to be considered ''living,'' the contribution of chain breaking reactions such as termination and transfer should be negligible. While transfer is not a major issue in RP when the appropriate conditions are applied, termination is much less avoidable and is a major limitation of RP. In contrast to ionic reactions, in which cations or anions do not react via bimolecular termination, radicals terminate with a diffusion controlled rate. To form high MW polymers, the relative probability of such termination must be minimized. This is accomplished by running RP at very low concentrations (from ppb to ppm) of propagating radicals. The concentrations of growing species are thus much lower in RP than in carbanionic or ring-opening polymerizations. In RP, a steady concentration of radicals is established by balancing the rate of termination with that of initiation. The rate of propagation is much faster than the rate of initiation/termination (as required to keep radical concentration low). Therefore, Controlled and Living Polymerizations. Edited a Measurements in bulk at 40 • C and ambient pressure, unless otherwise stated. b k t reported at 1000 bar. c Solvent = chlorobenzene. E p and A p represent the Arrhenius activation energy for propagation and frequency factor for propagation, respectively. Typical Features of Radical Polymerization 107coefficients of termination depend on chain length and conversion (viscosity), the values in Table 3.1 are given for low conversion and DP ≈ 100. CopolymerizationFacile statistical copolymerization is one of the main advantages of RP. In contrast to ionic polymerization, the reactivities of many monomers are relatively similar, which makes them easy to copolymerize statistically. For monomers with opposite polarities, there is a tendency for alternation (r A r B < 1, where r A = k AA /k AB and r B = k BB /k BA ). Electrophilic radicals (i.e., those with -CN, -C(O)OR, or Cl groups) prefer to react ...

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Section: Crp and Living Carbocationic And Carbanionic Polymerizationmentioning

confidence: 99%

Radical Polymerization

Matyjaszewski

2009

Controlled and Living Polymerizations

158

218

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“…The synthesis of Styrene-Butadiene block copolymers by radical polymerization has already been achieved using nitroxyle-functionalized poly(BD), by Kobatake et al [40][41][42][43] It has also been already attempted in one pot via the RAFT process using phenylethyl dithiobenzoate, and led to a low polydispersed styrene/butadiene statistical copolymer (30 : 70). [21] Also, controlled radical polymerization of 1,3-butadiene in the presence of Tempo was studied.…”

Section: Radical Polymerization Of 13-butadienementioning

confidence: 99%

Use of Originalω-Perfluorinated Dithioesters for the Synthesis of Well-Controlled Polymers by Reversible Addition-Fragmentation Chain Transfer (RAFT)

Lebreton¹,

Améduri²,

Boutevin³

et al. 2002

Macromol. Chem. Phys.

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“…As each living mechanism is only applicable to a limited number of monomers, it is highly desirable to combine at least two living polymerization techniques in order to prepare novel polymeric materials. Recent publications have dealt with the combination of living anionic polymerization with cationic [52**,53*.54,55,56*,57], controlled radical [58], and group transfer [59] polymerizations.…”

Section: Combination Of Anionic With Other Living Polymerizationsmentioning

confidence: 99%

Recent developments in anionic polymerization

Jérôme

Tong

1998

Current Opinion in Solid State and Materials Science

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The past year witnessed very significant advances in the living anionic polymerization of (meth)acrylate monomers, particularly in hydrocarbons at or below 0°C. Block polymerization of alkyl methacrylates with primary alkyl acrylates, although somewhat improved, remains a challenge. Anionic polymerization of styrene, diene and its derivatives was carried out with the aim of synthesizing functional polymers and block copolymers of various architectures. There has been a trend towards combining different living techniques in order to design polymers of unique architectures and properties. AbbreviationsDBTMGLi di-tert-butyl 2-lithio-2,4,4'-trimethylglutarate

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Block Copolymer Synthesis by Styrene Polymerization Initiated with Nitroxy-Functionalized Polybutadiene

Cited by 43 publications

References 55 publications

Radical Polymerization

Radical Polymerization

Use of Originalω-Perfluorinated Dithioesters for the Synthesis of Well-Controlled Polymers by Reversible Addition-Fragmentation Chain Transfer (RAFT)

Recent developments in anionic polymerization

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