Anionic Polymerization: Recent Advances

Ishizone, Takashi; Hirao, Akira

doi:10.1002/9783527603978.mst0415

Cited by 12 publications

(15 citation statements)

References 293 publications

(225 reference statements)

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“…Second, extremely narrow molecular weight distributions are attained, M w /M n values being 1.05 or even smaller. Third, the tolerance of various functional groups, much more than the numbers that one can consider, can be realized, although some of them are required to be protected during polymerization [28][29][30][31][32][33]. Finally, the resulting living anionic polymers have active chain-end anions that are highly reactive, but stable under appropriate conditions.…”

Section: Introductionmentioning

confidence: 99%

Precise Synthesis of Block Polymers Composed of Three or More Blocks by Specially Designed Linking Methodologies in Conjunction with Living Anionic Polymerization System

et al. 2013

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This article reviews the successful development of two specially designed linking methodologies in conjunction with a living anionic polymerization system for the synthesis of novel multiblock polymers, composed of three or more blocks, difficult to be synthesized by sequential polymerization. The first methodology with the use of a new heterofunctional linking agent, 2-(4-chloromethylphenyl)ethyldimethylchlorosilane (1), was developed for the synthesis of multiblock polymers containing poly(dimethylsiloxane) (PDMS) blocks. This methodology is based on the selective reaction of the chain-end silanolate anion of living PDMS, with the silyl chloride function of 1, and subsequent linking reaction of the resulting ω-chain-end-benzyl chloride-functionalized polymer with either a living anionic polymer or living anionic block copolymer. With this methodology, various multiblock polymers containing PDMS blocks, up to the pentablock quintopolymer, were successfully synthesized. The second methodology using an α-phenylacrylate (PA) reaction site was developed for the synthesis of multiblock polymers composed of all-vinyl polymer blocks. In this methodology, an α-chain-end-PA-functionalized polymer or block copolymer, via the living anionic polymerization, was first prepared and, then, reacted with appropriate living anionic polymer or block copolymer to link the two polymer chains. As OPEN ACCESSPolymers 2013, 5 1013 a result, ACB (BCA), BAC (CAB), (AB) n , (AC) n , ABA, ACA, BCB, and ABCA multiblock polymers, where A, B, and C were polystyrene, poly(2-vinylpyridine), and poly(methyl methacrylate) segments, could be successfully synthesized. The synthesis of triblock copolymers, BAB, CAC, and CBC, having molecular asymmetry in both side blocks, was also achieved. Furthermore, the use of living anionic polymers, derived from many other monomers, categorized as either of styrene, 2-vinylpyridine, or methyl methacrylate in monomer reactivity, in the linking methodology enabled the number of synthetically possible block polymers to be greatly increased. Once again, all of the block polymers synthesized by these methodologies are new and cannot be synthesized at all by sequential polymerization. They were well-defined in block architecture and precisely controlled in block segment.

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Section: Introductionmentioning

confidence: 99%

Precise Synthesis of Block Polymers Composed of Three or More Blocks by Specially Designed Linking Methodologies in Conjunction with Living Anionic Polymerization System

et al. 2013

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“…In fact, the relative anionic polymerizability (electrophilicity) of the above vinyl monomers, categories (i) and (ii), is well related to the relative reactivity (nucleophilicity or basicity) of anionic initiators. It has been reported that vinyl monomers are categorized into four classes, (A)-(D) ( Table 1) [2]. Conjugated hydrocarbons, such as styrene and 1,3-diene monomers, correspond to the least reactive monomers under the anionic conditions in class (A).…”

Section: Fundamentals Of Anionic Addition Polymerization Monomersmentioning

confidence: 99%

“…Among these living polymerization systems, this living anionic addition polymerization of hydrocarbon monomers, such as styrene and 1,3-dienes, is still a most established system and allows a synthesis of well-defined polymers possessing predicted molecular weights and narrow molecular weight distributions. Furthermore, the living character of the propagating carbanion enables to prepare the tailored block copolymers by the sequential copolymerization and the end-functionalized polymers by the suitable termination reactions [1][2][3] (Fig. 10).…”

Section: Living Anionic Polymerizationmentioning

confidence: 99%

“…Anionic polymerization has contributed to the precise polymer synthesis from both academic and industrial viewpoints and is still in progress [1][2][3]. For instance, the anionic polymerization plays a very important role in producing a number of industrial polymeric materials, such as solutionpolymerized styrene-butadiene rubber (S-SBR) and thermoplastic elastomers (TPEs).…”

Section: Introductionmentioning

confidence: 99%

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Anionic Addition Polymerization (Fundamental)

Ishizone

Goseki

2014

Encyclopedia of Polymeric Nanomaterials

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SynonymsAddition polymerization; Anionic polymerization; Ionic polymerization; Vinyl polymerization Definition Anionic addition polymerization is an ionic polymerization of vinyl monomers and can be categorized as a chain polymerization initiated with nucleophilic reagents, such as organolithiums, Grignard reagents, and metal alkoxides. Anionic addition polymerization proceeds with the growing chain end carrying negative charge and counter cation. The typical monomers capable of anionic addition polymerization involve vinyl monomers having electron-withdrawing groups, such as methyl methacrylate, acrylonitrile, and 2-vinylpyridine, as well as conjugated hydrocarbon monomers, such as styrene and 1,3-butadiene.

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“…Living anionic polymerization provides the best and the most elegant method for preparing block copolymers by the sequential addition of different monomers because it can produce block copolymers in which each block has a predictable molecular weight in a wide range and a very narrow molecular weight distribution under the adequate reaction conditions [1,2]. A variety of vinyl monomers, such as styrene derivatives, 1,3-dienes, alkyl methacrylates, and acrylamides, are capable of living anionic polymerization.…”

Section: Synthesis Of Block Copolymers By Sequential Living Polymerizmentioning

confidence: 99%

Block Copolymer Synthesis

Sugiyama

2014

Encyclopedia of Polymeric Nanomaterials

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SynonymsDiblock copolymer; Multiblock copolymer; Triblock copolymer; Triblock terpolymer DefinitionSummarizing the recent advances in a wide variety of block copolymer synthesis, including the following strategies: living polymerization of different monomers by sequential additions, the use of end-functional groups on an original polymer chain to initiate another living polymerization, and end-linking reaction of different polymers through highly reactive functional groups. StrategySynthesis of block copolymers has always attracted great interest since Szwarc prepared a block copolymer of styrene and isoprene by means of living anionic polymerization in the 1950s. Particularly, the preparation of well-defined block copolymers by living polymerization provides many advantages from both theoretical and practical viewpoints. Thermodynamic incompatibility between each polymer segments leads to a micro-phase separation. Segment ratio and block lengths of each polymer segment play an important role on such ordered structures. Therefore, the welldefined architectures of the block copolymers, such as controlled compositions, predictable molecular weights, and narrow molecular weight distributions, are of essential importance. Recent great advance of living polymerization systems allows a diversity of chemical structures on block copolymer. In addition, the following two topics attract recent attention: the creative combination of different mechanistic polymerization techniques and the linking reaction of end-functionalized polymers incorporated as building blocks.There are three principal methodologies for synthesis of block copolymers with well-defined structures:

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Anionic Polymerization: Recent Advances

Cited by 12 publications

References 293 publications

Precise Synthesis of Block Polymers Composed of Three or More Blocks by Specially Designed Linking Methodologies in Conjunction with Living Anionic Polymerization System

Precise Synthesis of Block Polymers Composed of Three or More Blocks by Specially Designed Linking Methodologies in Conjunction with Living Anionic Polymerization System

Anionic Addition Polymerization (Fundamental)

Block Copolymer Synthesis

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