Synthesis of Well-Defined (AB)<sub><i>n</i></sub>Multiblock Copolymers Composed of Polystyrene and Poly(methyl methacrylate) Segments Using Specially Designed Living AB Diblock Copolymer Anion

Sugiyama, Kenji; Oie, Toshiyuki; El-Magd, Ahmed Abou; Hirao, Akira

doi:10.1021/ma902473t

Cited by 48 publications

(57 citation statements)

References 54 publications

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“…4a, two signals appeared at 3.6-3.7 ppm (due to O-CH 3 groups) and 6.55-7.05 ppm (due to C 6 H 5 ) could be related to the being of PMMA and PS, respectively. This spectrum is similar to the spectrum obtained from the mixture of PS and PMMA except for some additional signals appeared due to the formation of PMMA chains grafted on PS (the signals occurred at 2.8-3.0 ppm) [18][19][20]. The 1 H-NMR spectrum shown in The signal occurring at 3.6 ppm in Fig.…”

Section: Copolymer Formationsupporting

confidence: 71%

Synthesis of core-shell PS/PMMA expandable particles via seeded suspension polymerization

et al. 2015

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Expandable core-shell beads were synthesized by dosing methyl methacrylate (and styrene) in a constant rate and polymerizing in the presence of polystyrene seeds and pentane. The morphological studies of beads indicated that there were larger poly(methyl methacrylate)-rich domains near the shell. The sizes of these domains were decreased towards the core of the particles. For better surveying the likely structures of domains and the extent of expansion agent diffusion, the beads having the shells formed with copolymerization of styrene and methyl methacrylate in the presence of polystyrene seeds were studied. From the morphological studies, the parallel regular and the onion-like structures were recognizable. In addition, another shell was formed around the dispersed phase showing a complex core/shell structure both in particle and in domain scales. The pentane content in the beads with copolymerized styrene and methyl methacrylate monomers on the polystyrene seeds was increased compared to the beads having the shells of pure poly(methyl methacrylate). This was because the onset of gel effect was longer with adding the styrene to methyl methacrylate monomer hence there was more time for expansion agent to diffuse into the beads. The different amounts of pentane distributed in polystyrene-and poly(methyl methacrylate)-rich phases were discussed in terms of the changes in glass transition temperature of two phases.

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Section: Copolymer Formationsupporting

confidence: 71%

Synthesis of core-shell PS/PMMA expandable particles via seeded suspension polymerization

et al. 2015

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“…This methodology was extended to the synthesis of a series of alternate multiblock copolymers of (PS-b-PMMA) n [61]. The synthetic outline is shown in Scheme 7.…”

Section: Triblock Copolymers and Alternate Multiblock Copolymersmentioning

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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“…1 A living PS-b-PMMA (1.51 g, M n,RALLS = 15 800 g/mol, 0.0956 mmol) was prepared at À78°C in the same manner reported by our previous paper. 48 A small amount (ca. 10% in volume) was taken for analytical purposes, and the residual living polymer (0.0872 mmol) solution was mixed with the R-terminal PA-functionalized P2VP (0.413 g, M n = 18 800 g/mol, 0.0220 mmol for PA R-terminus) prepared above.…”

Section: ' Introductionmentioning

confidence: 99%

Facile Synthesis of Triblock Co- and Terpolymers of Styrene, 2-Vinylpyridine, and Methyl Methacrylate by a New Methodology Combining Living Anionic Diblock Copolymers with a Specially Designed Linking Reaction

et al. 2011

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Triblock co-and terpolymers with orders of blocks synthetically difficult to be obtained by means of sequential living anionic polymerization were successfully synthesized by developing a new methodology combining living anionic block copolymers with a specially designed linking reaction. The synthesized polymers involve ACB and BAC triblock terpolymers and ABA 0 , ACA 0 , and BCB 0 triblock copolymers, where A, B, and C are polystyrene, poly(2-vinylpyridine), and poly(methyl methacrylate) segments, respectively. The A 0 , A as well as B, B 0 are identical in polymer structure but different in molecular weight. All of them are new type triblock ter-and copolymers with well-defined structures, i.e., predictable molecular weights, compositions, and narrow molecular weight distributions. Transmission electron microscopic studies were performed on bulk morphologies of ACB and BAC triblock terpolymers to exemplarily investigate the influence of changing block sequence and thus changing interfaces. Although both terpolymers showed the tendency to form a lamellaÀlamella morphology, ACB revealed unusually strongly curved lamellae and BAC even undulated lamellae. ' INTRODUCTIONBlock polymers with a high degree of molecular and compositional homogeneity have attracted increasing interest as model polymers to elucidate interesting properties and behavior in combination with morphologies and molecular assemblies. 1À9 Such welldefined block polymers are usually synthesized by means of living anionic polymerization where two or more monomers are sequentially added to appropriate anionic initiators. 10 In fact, well-defined AB diblock copolymers, ABC triblock terpolymers, and (AB) n multiblock copolymers have been successfully synthesized.In order to achieve further design and synthesis of well-defined block polymers by using living anionic polymerization, it is

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Synthesis of Well-Defined (AB)_nMultiblock Copolymers Composed of Polystyrene and Poly(methyl methacrylate) Segments Using Specially Designed Living AB Diblock Copolymer Anion

Cited by 48 publications

References 54 publications

Synthesis of core-shell PS/PMMA expandable particles via seeded suspension polymerization

Synthesis of core-shell PS/PMMA expandable particles via seeded suspension polymerization

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

Facile Synthesis of Triblock Co- and Terpolymers of Styrene, 2-Vinylpyridine, and Methyl Methacrylate by a New Methodology Combining Living Anionic Diblock Copolymers with a Specially Designed Linking Reaction

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Synthesis of Well-Defined (AB)nMultiblock Copolymers Composed of Polystyrene and Poly(methyl methacrylate) Segments Using Specially Designed Living AB Diblock Copolymer Anion

Cited by 48 publications

References 54 publications

Synthesis of core-shell PS/PMMA expandable particles via seeded suspension polymerization

Synthesis of core-shell PS/PMMA expandable particles via seeded suspension polymerization

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

Facile Synthesis of Triblock Co- and Terpolymers of Styrene, 2-Vinylpyridine, and Methyl Methacrylate by a New Methodology Combining Living Anionic Diblock Copolymers with a Specially Designed Linking Reaction

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Synthesis of Well-Defined (AB)_nMultiblock Copolymers Composed of Polystyrene and Poly(methyl methacrylate) Segments Using Specially Designed Living AB Diblock Copolymer Anion