Synthesis of Polymers with Adamantane Amino Derivatives as Pendant Groups

Yoshida, Eri; Tsuchiya, Takashi; Katayama, Koji

doi:10.1295/polymj.31.32

Cited by 10 publications

(3 citation statements)

References 6 publications

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“…We prepared a block copolymer consisting of two different kinds of random copolymers of poly(4-tert-butoxystyrene-ran-styrene) and poly(4-methoxystyreneran-styrene) through living radical polymerization mediated by 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO). 12 4-Vinyl phenol (VPh) units generated by the hydrolysis of t BOS units promote microphase segregation because of the hydrogen bonding in the polymers. Fukuda et al 10 demonstrated microphase separation for poly(4-vinyl phenol)-block-polystyrene (PVPh-b-PSt) diblock copolymers with transmission electron microscopy.…”

Section: Introductionmentioning

confidence: 99%

Micelle formation of poly(vinyl phenol)‐block‐polystyrene by α,ω‐diamines

Yoshida

Kunugi

2002

J. Polym. Sci. A Polym. Chem.

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Section: Introductionmentioning

confidence: 99%

Micelle formation of poly(vinyl phenol)‐block‐polystyrene by α,ω‐diamines

Yoshida

Kunugi

2002

J. Polym. Sci. A Polym. Chem.

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“…These T g values of the adamantyl‐substituted polystyrenes are significantly higher than that of the parent polystyrene ( T g = 100 °C). The highly symmetrical alicyclic adamantyl group has a negligible reactivity toward various chemical reagents, but it shows the drastic effect on enhancing the thermal properties of the resulting polymers …”

Section: Introductionmentioning

confidence: 99%

“…The highly symmetrical alicyclic adamantyl group has a negligible reactivity toward various chemical reagents, but it shows the drastic effect on enhancing the thermal properties of the resulting polymers. [29][30][31][32][33][34][35][36][37][38][39][40][41][42] Recently, the living anionic polymerizations of styrenes carrying reactive moieties, N-(1-adamantyl)-N-4-vinylbenzylideneamine, [41] and 1-adamantyl 4-vinylphenyl ketone [42] are also achieved. The rigid and bulky adamantyl substituents effectively hindered any serious side reactions of the nucleophilic initiators and the propagating carbanion with the electrophilic CO and CHN groups and realized the living anionic polymerizations.…”

mentioning

confidence: 99%

Living Anionic Polymerization of 4‐(1‐Adamantyl)‐α‐Methylstyrene

Kobayashi

Kataoka

Goseki

et al. 2017

Macro Chemistry & Physics

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the living fashions to give the polymers of well-defined chain structures. It is noteworthy that the glass transition temperatures (T g s) of poly(AdS) and poly(Ad2S) are 234 and 232 °C. These T g values of the adamantyl-substituted polystyrenes are significantly higher than that of the parent polystyrene (T g = 100 °C). The highly symmetrical alicyclic adamantyl group has a negligible reactivity toward various chemical reagents, but it shows the drastic effect on enhancing the thermal properties of the resulting polymers. [29][30][31][32][33][34][35][36][37][38][39][40][41][42] Recently, the living anionic polymerizations of styrenes carrying reactive moieties, [41] and 1-adamantyl 4-vinylphenyl ketone [42] are also achieved. The rigid and bulky adamantyl substituents effectively hindered any serious side reactions of the nucleophilic initiators and the propagating carbanion with the electrophilic CO and CHN groups and realized the living anionic polymerizations. The high T g values of these polymers are respectively observed at 193 and 257 °C. Thus, the adamantyl substituents play very important roles to increase the T g s of the substituted polymers and to sterically protect the reactive functional groups from the serious side reactions.In this study, we newly designed and anionically polymerized an adamantyl-substituted α-methylstyrene derivative, 4-(1-adamantyl)-α-methylstyrene (AdαMS), in order to check the polymerizability of the monomer and the thermal properties of the resulting polymer. It is well known that α-methylstyrene derivatives usually undergo the equilibrium polymerization under the anionic conditions due to the low ceiling temperatures. [43][44][45][46][47][48][49][50][51][52][53][54][55][56][57][58] The polymerization and depolymerization of α-methylstyrene derivatives reversibly occur under the equilibrium conditions. In addition, the poly(α-methylstyrene)s generally show higher T g values than those of the corresponding polystyrene derivatives and the ease of the chain degradation on heating. Results and DiscussionThe monomer, AdαMS, was synthesized from 1-bromoadamantane by the four-step reactions as shown in Scheme 1. In the final two steps, the Grignard reagent of 1-(4-bromophenyl) adamantane and acetone was reacted to give a corresponding tertiary alcohol. The following dehydration of the resulting alcohol in the presence of p-toluenesulfonic acid afforded

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Living Anionic Polymerization of 1‐Adamantyl 4‐vinylphenyl ketone

Matsuoka

Goseki

Uchida

et al. 2017

Macro Chemistry & Physics

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The anionic polymerization of 1-adamantyl 4-vinylphenyl ketone (1), a styrene derivative carrying an electrophilic carbonyl group, is carried out in tetrahydrofuran (THF). Although no polymerization of 1 occurs with sec-BuLi at −78 °C for 48 h, a polymeric product of 1 is obtained with diphenylmethyllithium in 10% yield under similar conditions. The resulting poly(1) has a very broad molar-mass dispersity (Đ M = M w /M n = 1.72) and a molecular weight higher than the calculated value based on the molar ratio of the monomer and initiator and the conversion. On the other hand, the polymerization of 1 with diphenylmethylpotassium or diphenylmethylcesium quantitatively proceeds in THF at −78 °C within 48 h to form the polymers with predicted molecular weights and narrow molecular weight distributions (M w /M n < 1.1). The stability of the propagating carbanion derived from 1 is demonstrated by the quantitative efficiency of the postpolymerization (sequential monomer addition). The reaction of the adamantyl ketone moieties of poly (1) with methylmagnesium iodide quantitatively proceeds in THF/diethyl ether at room temperature, indicating the high electrophilicity of ketone groups. The resulting poly(1) has a high glass transition temperature at 193 °C, indicating the effect of the bulky adamantyl substituent.

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Synthesis of Polymers with Adamantane Amino Derivatives as Pendant Groups

Cited by 10 publications

References 6 publications

Micelle formation of poly(vinyl phenol)‐block‐polystyrene by α,ω‐diamines

Micelle formation of poly(vinyl phenol)‐block‐polystyrene by α,ω‐diamines

Living Anionic Polymerization of 4‐(1‐Adamantyl)‐α‐Methylstyrene

Living Anionic Polymerization of 1‐Adamantyl 4‐vinylphenyl ketone

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