<i>o</i>-Benzenedisulfonimide as a recyclable cationic organocatalyst for the controlled/living ring-opening polymerization of δ-valerolactone and ε-caprolactone

Yu, Jie‐Hui; Ji, Yufeng; He, Xiaojiang; Kan, Suli; Xia, Haidong; Liang, Binqi; Jia, Chen; Wu, Hao; Guo, Kai; Li, Zhenjiang

doi:10.1039/c3py01613g

Cited by 35 publications

(26 citation statements)

References 44 publications

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“…[1][2][3][4][5] Ring-opening polymerization (ROP) of epoxides 6,7 and cyclic esters (lactones or lactides) [8][9][10][11] has been a commonly used method to synthesize, respectively, polyethers and polyesters with controlled molecular weights, low dispersities and tailored macromolecular structures. [26][27][28][29][30][31][32][33][34] Although neither can act as an ideal single catalyst for both types of monomers, [35][36][37] the combination (sequential performance) of t-BuP 4 -promoted ROP of epoxides and acidcatalyzed ROP of lactones, i.e. However, it has remained a major challenge as the monomers are suited to different initiating/catalytic systems, i.e.…”

Section: Introductionmentioning

confidence: 99%

Polymerization of 5-alkyl δ-lactones catalyzed by diphenyl phosphate and their sequential organocatalytic polymerization with monosubstituted epoxides

Zhao

Hadjichristidis

2015

Polym. Chem.

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ARTICLE This journal isOrganocatalytic ring-opening polymerization (ROP) of three renewable 5-alkyl δ-lactones, namely, δ-hexalactone (HL), δ-nonalactone (NL) and δ-decalactone (DL), using diphenyl phosphate (DPP) was investigated. Room temperature together with a relatively high monomer concentration (≥ 3 M) was demonstrated to be suited for the achievement of a living manner of the ROP, a high conversion of the lactone, a controlled molecular weight and a low dispersity of the polyester. HL, carrying a 5-methyl substituent, showed a much higher reactivity (polymerization rate) and a slightly higher equilibrium conversion than the ones with longer alkyl substituents (NL and DL). The effectiveness of DPP-catalyzed ROP of 5-alkyl δ-lactones facilitated the one-pot performance following the t-BuP 4 -promoted ROP of monosubstituted epoxides. It has been shown in an earlier study that substituted polyethers acted as "slow initiators" for non-substituted lactones. However, efficient initiations were observed in the present study as substituted lactones were polymerized from the substituted polyethers, which therefore has reinforced the previously developed "catalyst switch" strategy making it a more versatile tool for the synthesis of well-defined polyether-polyester block copolymers involving a large variety of epoxide and lactone monomers. ARTICLEThis journal is ARTICLE This journal is ARTICLE This journal is ARTICLE This journal is ARTICLEThis journal is Scheme 2. Reaction scheme toward the synthesis of polyether-polyester diblock copolymer via sequential organocatalytic ROP of a monosubstituted epoxide and a 5alkyl δ-lactone using the base→acid "catalyst switch" strategy. ARTICLE This journal is ARTICLE This journal is ARTICLEThis journal is

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Section: Introductionmentioning

confidence: 99%

Polymerization of 5-alkyl δ-lactones catalyzed by diphenyl phosphate and their sequential organocatalytic polymerization with monosubstituted epoxides

Zhao

Hadjichristidis

2015

Polym. Chem.

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“…7 Considerable effort has been directed toward the evaluation of various types of both organic acids/bases for the ROP of cyclic esters, 7-37 cyclic carbonates, [38][39][40][41][42][43] epoxides, [44][45][46][47] lactams, 48 cyclic (carbo)siloxanes, 49 cyclic phosphates, [50][51][52][53][54] etc. Regarding the ROP of cyclic esters, organic Brønsted acids, e.g., methane sulfonic acid (MSA) and triflimide, were found to be suited for the polymerization of lactones, [8][9][10][11][12][13][14][15][16][17][18][19] whereas organic bases, e.g., 1,8-diazadicyclo [5.4.0]undec-7-ene (DBU) and 4-dimethylaminopyridine (DMAP), were effective for the ROP of the lactide (LA). 7,[20][21][22][23][24]26 In addition, the bifunctional catalytic system possessing two activation sites for the monomer and propagating chain end also turned out to be effective for the ROP of ε-caprolactone (ε-CL) and LA.…”

Section: Introductionmentioning

confidence: 99%

Organophosphate-catalyzed bulk ring-opening polymerization as an environmentally benign route leading to block copolyesters, end-functionalized polyesters, and polyester-based polyurethane

et al. 2015

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Abstract. The ring-opening polymerizations (ROPs) of ε-caprolactone (ε-CL), -varelolactone, 1,5-dioxepan-2-one, trimethylene carbonate, and L-lactide were performed in the bulk using an organophosphate, such as diphenyl phosphate, bis(4-nitrophenyl)phosphate, and di(2,6-xylyl)phosphate, as the catalyst. The ROPs proceeded in a well-controlled manner even in the bulk condition to afford well-defined aliphatic polyesters, polyester-ether, and polycarbonate with relatively low dispersities. Notably, the amount of the loaded catalyst was successfully reduced when compared to the conventional organophosphate-catalyzed ROP in solution. A kinetic study revealed the controlled/living nature of the present bulk ROP system, which allowed us to produce the block copolymers composed of polyesters, polyester-ether, and polycarbonate in one-pot. Syntheses of the end-functionalized poly(ε-caprolactone)s (PCLs) and poly(trimethylene carbonate) were successfully demonstrated using alcohol initiators possessing highly reactive functional groups. Furthermore, the α,ω-dihydroxy telechelic PCL-diol as well as the three-and four-armed star-shaped PCL-polyols were also easily obtained by using the polyols as an initiator. Finally, the one-pot synthesis of polyurethane via the ROP of ε-CL and subsequent urethane forming reaction was demonstrated by taking advantage of the dual catalytic abilities of the organophosphate for both the ROP and polyurethane synthesis.

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“…Three strategies of 5 hydrogen-bonding activation existed in the ROP of cyclic carbonyl-containing monomers: (i) the simultaneous activation of an alcohol group and a carbonyl function by a unique bifunctional catalyst provided with a hydrogen bond donor and an acceptor, for example thiourea-amine catalysts were used to catalyze the ROP of lactide by Waymouth and Hedrick in 2005 [33]; (ii) the catalytic system consisted of two separate species with one of them acted as hydrogen bond 10 donor and the other as hydrogen bond acceptor, which was demonstrated by thiourea/amine [34][35][36]; (iii) the single activation of an alcohol group by a hydrogen bond acceptor, such as phosphazene [37,38]. In continuation of our interest in organocatalysis in ROPs [36, [39][40][41][42], we envisioned the concept of multicatalysis [43] should pioneer in an HBD cooperating with BA model in polymerizations. 15…”

Section: Accepted Manuscriptmentioning

confidence: 98%

o-Benzenedisulfonimide as a recyclable cationic organocatalyst for the controlled/living ring-opening polymerization of δ-valerolactone and ε-caprolactone

Abstract: A safe, recyclable, and water-tolerant Brønsted acid o-benzenedisulfonimide (OBS) catalyzed ROP of lactones in a living/controlled manner.

Cited by 35 publications

References 44 publications

Polymerization of 5-alkyl δ-lactones catalyzed by diphenyl phosphate and their sequential organocatalytic polymerization with monosubstituted epoxides

Polymerization of 5-alkyl δ-lactones catalyzed by diphenyl phosphate and their sequential organocatalytic polymerization with monosubstituted epoxides

Organophosphate-catalyzed bulk ring-opening polymerization as an environmentally benign route leading to block copolyesters, end-functionalized polyesters, and polyester-based polyurethane

Thiourea binding with carboxylic acid promoted cationic ring-opening polymerization

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