Phenols and Tertiary Amines: An Amazingly Simple Hydrogen‐Bonding Organocatalytic System Promoting Ring Opening Polymerization

Thomas, Coralie; Peruch, Frédéric; Deffieux, Alain; Milet, Anne; Desvergne, Jean‐Pierre; Bibal, Brigitte

doi:10.1002/adsc.201100013

Cited by 43 publications

(48 citation statements)

References 34 publications

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“…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. [27][28][29][30][31][32][33][34][35][36][37] For example, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as a bifunctional catalytic system promotes the ROP of the ε-CL, whereas DBU is ineffective, 20 and the MSA/DMAP bifunctional 4 catalytic system promotes the ROP of the LA, whereas MSA alone does not work. 31 Despite such numerous efforts, there are still many problems to be overcome for the industrial scale production of aliphatic polyesters using an organocatalytic system.…”

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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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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“…The catalyst 2MP had a lower rate constant than phenol. This was not surprising as previous theoretical calculations showed that an intramolecular hydrogen bond is formed between the OH and o‐OMe substituent . Nonetheless, 2MP enhanced the reaction rate as compared to an uncatalyzed reaction.…”

Section: Resultsmentioning

confidence: 55%

“…Crosslinking and gelation was previously observed at elevated temperatures for fatty acid based 6CC monomers . Given the potential for ROP and crosslinking when using TBD, DBU, and TU, we also surveyed a range of weaker alcohol‐based hydrogen bond donors whose catalytic activity can be tuned via structural modifications …”

Section: Resultsmentioning

confidence: 99%

Nonisocyanate polyurethanes from six‐membered cyclic carbonates: Catalysis and side reactions

Lambeth

Mathew

Baranoski

et al. 2017

J of Applied Polymer Sci

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We present a detailed investigation of the aminolysis of six‐membered cyclic carbonates to form (poly)hydroxyurethanes. Model reactions between hexyl amine and trimethylene carbonate were performed under different conditions where we surveyed the effects of temperature and the presence of catalyst on the rate of reaction. Increased temperatures and the presence of catalyst lead to significant increases in the rate of reaction and overall conversion depending on the structure of the catalyst. Similar observations were also made in model polymerization between a carbonate derivative of di(trimethylolpropane) and diaminopentane. However, the increased rates of reaction and conversion only lead to modest gains in molecular weight. In addition, gelation of the polymerization mixture often occurred as well. Nominal and high‐resolution mass spectrometry were used to identify side products that formed during the reaction between trimethylene carbonate and hexyl amine, which explained the gelation of polymerization mixture and lower than expected molecular weights. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44941.

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“…Instruments NMR Spectra were recorded in CDCl 3 or C 6 D 6 on BRUKER Avance 300, 400, and 500 MHz spectrometers at room temperature and chemical shifts are reported in ppm relative to Me 4 Si as an external standard. 1 H measurements were used to determine the monomer conversion, the NMR degree of polymerization (DP NMR ), and the end group fidelity.…”

Section: Methodsmentioning

confidence: 99%

“…Various H-bond donor moieties with one, two or three binding sites have been used. 1b The most common are thioureas, 2 perfluorinated alcohols, 3 phenols, 4 squaramides, 5 sulfonamides, 6 amido-indoles.…”

mentioning

confidence: 99%

Ring-opening polymerization of ε-caprolactone catalyzed by ionic hydrogen bond activation with bis-pyridiniums

Gontard

Amgoune

Bourissou

2016

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

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Phenols and Tertiary Amines: An Amazingly Simple Hydrogen‐Bonding Organocatalytic System Promoting Ring Opening Polymerization

Cited by 43 publications

References 34 publications

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

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

Nonisocyanate polyurethanes from six‐membered cyclic carbonates: Catalysis and side reactions

Ring-opening polymerization of ε-caprolactone catalyzed by ionic hydrogen bond activation with bis-pyridiniums

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