Synthesis of polymers with carboxy end groups by reaction of polystyryl anions with 4-bromo-1,1,1-trimethoxybutane

Hirao, Akira; Nagahama, Hiroyuki; Ishizone, Takashi; Nakahama, Seiichi

doi:10.1021/ma00061a001

Cited by 43 publications

(28 citation statements)

References 7 publications

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“…The stability of the ortho ester function and its usefulness as a protecting group for a COOH moiety through the reaction of anionic living polystyrene and 4,4,4-trimethoxy-1-bromobutane were demonstrated earlier (Chart 3). 22 The nucleophilic attack of terminal carbanion selectively occurred with the CH 2 Br bond but not with the ortho ester moiety. After the S N 2 functionalization and the hydrolysis of the ortho ester, the polystyrenes possessing the terminal (CH 2 ) 3 COOH group were produced in nearly quantitative yields.…”

Section: Resultsmentioning

confidence: 99%

Protection and Polymerization of Functional Monomers. 29. Syntheses of Well-Defined Poly[(4-vinylphenyl)acetic acid], Poly[3-(4-vinylphenyl)propionic acid], and Poly(3-vinylbenzoic acid) by Means of Anionic Living Polymerizations of Protected Monomers Bearing Bicyclic Ortho Ester Moieties

et al. 1999

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Anionic polymerizations of four styrenes protected with bicyclic ortho ester moieties, 1-(4-vinylphenyl)methyl-4-methyl-2,6,7-trioxabicyclo[2.2.2]octane (1), 1-[2-(4-vinylphenyl)ethyl]-4-methyl-2,6,7-trioxabicyclo[2.2.2]octane (2), 1-(3-vinylphenyl)-4-methyl-2,6,7-trioxabicyclo[2.2.2]octane (3), and 1-(4-vinylphenyl)-4-methyl-2,6,7-trioxabicyclo[2.2.2]octane (4), were carried out in THF at -78°C for 0.5 h with oligo(R-methylstyryl)lithium and -dipotassium and potassium naphthalenide. Poly(1)-(3) were quantitatively obtained, and the resulting polymers possessed the predicted molecular weights based on the molar ratios of monomers to initiators and narrow molecular weight distributions (MWDs, M w/Mn < 1.1). By contrast, polymerization of 4 did not go to completion and gave insoluble polymeric product in low yield due to the side reactions under the similar conditions. The substituent position in the monomer was very important for the success of the polymerization, although the bicyclic ortho ester was found to be stable under the polymerization conditions of 1-3. Well-defined block copolymers of 1 and 2 with styrene were synthesized by the sequential block copolymerizations regardless of the order of addition of the monomers. Hydrolyses of bicyclic ortho ester moieties of the resulting polymers were performed at room temperature by treating with 6 N HCl in THF/MeOH for 1 h and subsequently with 10% NaOH-(aq) in THF/MeOH for 12 h. Deprotections of poly(1), poly(2), and poly(3) quantitatively proceeded to afford poly [(4-vinylphenyl)acetic acid], poly [3-(4-vinylphenyl)propionic acid], and poly(3-vinylbenzoic acid) having tailored chain structures, respectively.

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Section: Resultsmentioning

confidence: 99%

Protection and Polymerization of Functional Monomers. 29. Syntheses of Well-Defined Poly[(4-vinylphenyl)acetic acid], Poly[3-(4-vinylphenyl)propionic acid], and Poly(3-vinylbenzoic acid) by Means of Anionic Living Polymerizations of Protected Monomers Bearing Bicyclic Ortho Ester Moieties

et al. 1999

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“…In fact, these reactions have been utilized as the classical approach to the synthesis of chain-end-functionalized polymers. In this case, some of the functional groups were protected prior to the post-polymerization reactions, such that well-defined, chain-end-functionalized PSs and PIs with COOH, OH, SH, NH 2 , (CH 2 ) n X, perfluoroalkyl, d-glucose, aziridinyl, 4-vinylphenyl, 1,1-diphenylethenyl, and 1,3-butadienyl (>95%) could be successfully obtained [175][176][177][178][179][180][181]. Unfortunately, however, many of these reactions were inadequately characterized or optimized for general utility.…”

Section: Reaction Of Living Anionic Polymers With Electrophiles: Syntmentioning

confidence: 99%

Anionic Polymerization: Recent Advances

Ishizone

Hirao

2012

Materials Science and Technology

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polymerize the monomers in classes B, C, and D, but they cannot initiate the polymerization of monomers in class A. The initiators in class c can polymerize both C and D class monomers, while they are inert for the monomers in classes A and B. The least-reactive initiators in class d, such as amines and phosphines, undergo anionic polymerization of the most-reactive D class monomers Among the monomers, α-cyanoacrylate is polymerized, even with water.The relationship between a monomer and its growing chain-end anion is also important in order to understand anionic polymerization behavior. In general, the most-reactive chain-end anions derive from the least-reactive monomers and vice-versa, because they are conjugated bases and acids with each other. For example, when considering styrene (class A) and methyl methacrylate (MMA) (class B), the latter is more reactive than the former because the electron density on the C=C bond of MMA is considerably reduced by the electron-withdrawing ester carbonyl group, whereas that on the styrene C=C bond is influenced much less by the phenyl group. On the other hand, the chain-end anion derived from MMA is also reduced in electron density by the same electron-withdrawing effect, and becomes less reactive than that derived from styrene. In practice, the chain-end anion from MMA has no ability to polymerize styrene, whilst the chain-end anion from styrene can polymerize styrene and, of course, the more-reactive MMA. Thus, the monomers in class A will always produce the most reactive growing chain-end anions that can polymerize all monomers in classes A, B, C, and D. In contrast, the least-reactive chain-end anions derived from the most-reactive monomers in class D can polymerize only the monomers in class D. These relationships are very important -even critical -for selecting the correct anionic initiator in polymerization, as well as when synthesizing block copolymers.

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“…Hirao et al successfully prepared well-defined polystyrenes with terminal carboxy groups by the reaction of living polystyryl anions with 4-bromo-1,1,1-trimethoxybutane, followed by treatment with 0.1 N HCl at first and then with 0.2 N LiOH. 10 Preliminary experiments showed that the lithium-halogen exchange reactions of 4-chloro-1,1,1-trimethoxybutane or 4-chloro-1,1,1-triethoxybutane in ether at Ϫ30°C were unsuccessful. We found that cyclic orthoester, 1-(3-chloropropyl)-4-methyl-2,6,7-trioxabicyclo[2.2.2]octane (11) is effective for lithium-halogen exchange reaction.…”

Section: Synthetic Strategy For ␣-Carboxyl -Amino Heterodifunctionalmentioning

confidence: 99%

Synthesis of a well-defined cyclic polystyrene via ?-carboxyl, ?-amino heterodifunctional polystyrene

Kubo

Takeuchi

Ohara

et al. 1999

J. Polym. Sci. A Polym. Chem.

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Synthesis of polymers with carboxy end groups by reaction of polystyryl anions with 4-bromo-1,1,1-trimethoxybutane

Cited by 43 publications

References 7 publications

Protection and Polymerization of Functional Monomers. 29. Syntheses of Well-Defined Poly[(4-vinylphenyl)acetic acid], Poly[3-(4-vinylphenyl)propionic acid], and Poly(3-vinylbenzoic acid) by Means of Anionic Living Polymerizations of Protected Monomers Bearing Bicyclic Ortho Ester Moieties

Protection and Polymerization of Functional Monomers. 29. Syntheses of Well-Defined Poly[(4-vinylphenyl)acetic acid], Poly[3-(4-vinylphenyl)propionic acid], and Poly(3-vinylbenzoic acid) by Means of Anionic Living Polymerizations of Protected Monomers Bearing Bicyclic Ortho Ester Moieties

Anionic Polymerization: Recent Advances

Synthesis of a well-defined cyclic polystyrene via ?-carboxyl, ?-amino heterodifunctional polystyrene

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