Synthesis of various end‐functionalized polyesters by controlled/living ring‐opening polymerization of lactones using pentafluorophenylbis(triflyl)methane

Makiguchi, Kosuke; Satoh, Toshifumi; Kakuchi, Toyoji

doi:10.1002/pola.24815

Cited by 23 publications

(13 citation statements)

References 40 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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“…In parallel, a variety of Brønsted acids including hydrochloric acid (HCl‐OEt 2 ), carboxylic acids, organic sulfonic acid, and organic phosphoric acids have been shown to catalyze the controlled/living ROPs with alcohols as initiators. Among the acid catalysts, phosphoric acids are nowadays attracting increasing attention as organocatalysts in the ROPs due to their moderate acidity.…”

Section: Introductionmentioning

confidence: 99%

Bifunctional imidodiphosphoric acid-catalyzed controlled/living ring-opening polymerization of trimethylene carbonate resulting block, α,ω-dihydroxy telechelic, and star-shaped polycarbonates

et al. 2013

J. Polym. Sci. Part A: Polym. Chem.

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The ring-opening polymerization (ROP) of trimethylene carbonate (TMC) using imidodiphosphoric acid (IDPA) as the organocatalyst and benzyl alcohol (BnOH) as the initiator has been investigated. The polymerization proceeded without decarboxylation to afford poly(trimethylene carbonate) (PTMiC) with controlled molecular weight and narrow polydispersity. 1 H NMR, SEC, and MALDI-TOF MS measurements of the obtained PTMC clearly indicated the quantitative incorporation of the initiator at the chain end. The controlled/living nature for the IDPA-catalyzed ROP of TMC was confirmed by the kinetic and chain extension experiments. A bifunctional activation mechanism was proposed for IDPA catalysis based on NMR and FTIR studies. Additionally, 1,3-propanediol, 1,1,1-trimethy-lolpropane, and pentaerythritol were used as di-ol, tri-, and tetra-ol initiators, producing the telechelic or star-shaped polycarbonates with narrow polydispersity indices. The welldefined diblock copolymers, poly(trimethylene carbonate)block-poly(d-valerolactone) and poly(trimethylene carbonate)block-poly(e-caprolactone), have been successfully synthesized by using the IDPA catalysis system.

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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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Synthesis of various end‐functionalized polyesters by controlled/living ring‐opening polymerization of lactones using pentafluorophenylbis(triflyl)methane

Cited by 23 publications

References 40 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

Bifunctional imidodiphosphoric acid-catalyzed controlled/living ring-opening polymerization of trimethylene carbonate resulting block, α,ω-dihydroxy telechelic, and star-shaped polycarbonates

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

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