ω-Pentandecalactone Polymerization and ω-Pentadecalactone/ε-Caprolactone Copolymerization Reactions Using Organic Catalysts

Bouyahyi, Miloud; Pepels, Mpf Mark; Heise, Andreas; Duchateau, Robbert

doi:10.1021/ma3001675

Cited by 134 publications

(175 citation statements)

References 48 publications

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“…Although there are some reports about the bulk ROP of cyclic esters using organocatalysts, the advantages of bulk conditions have not been investigated in detail. [12][13][14]25,26,37,[60][61][62][63][64][65][66][67][68][69][70][71][72][73] We now describe the organophosphate-catalyzed bulk ROP of various cyclic esters, such as ε-CL,…”

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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“…16 Furthermore, poly(CL-ran-PDL) copolymers were reported to exhibit isomorphism over the whole composition range, resulting in a steady decrease of the melting temperature upon increased CL content. 17,18 In this work, we investigated the influence of the main chain configuration in poly(CL-ran-PDL) copolymers on the crystalline morphology and its effect on the mechanical properties, in particular the yield stress. Furthermore, the origin of this behavior has been studied and related to the molecular structure.…”

Section: ■ Introductionmentioning

confidence: 99%

Influence of the Main-Chain Configuration on the Mechanical Properties of Linear Aliphatic Polyesters

2015

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Linear aliphatic polyesters have been investigated extensively over the last decades. However, the relation between the configuration of the ester groups in the main chain and the mechanical properties is only poorly understood. Therefore, in this work the influence of the composition of these polymers on the morphology, mechanical properties and relaxation processes for a set of random copolymers of ε-caprolactone (CL) and ω-pentadecalactone (PDL) is explored. For these isomorphic copolymers, the crystallinity and lamellar thickness was shown to be independent of the composition over the largest part of the composition range. However, the yield stress does decrease significantly when comonomers were introduced in either of the homopolymer chains. Dynamic mechanical analysis revealed an additional high-temperature relaxation process for the copolymers, which was attributed to mobility of the crystalline phase (α c -mobility) and is responsible for the decrease in yield stress relative to the homopolymers. The origin of this mobility was related to the stacking of the ester groups in the crystal lamellae, which occurs less regular in copolymers and therefore gives rise to lower energy barriers for defect propagation (responsible for α c -mobility). Furthermore, the yield-kinetics of polypentadecalactone and two copolymers were accurately captured using the Ree−Eyring theory, showing the relation between α c -mobility and the contribution of both interlamellar and intralamellar shear to the yield stress. ■ INTRODUCTIONAliphatic long-chain polyesters (ALCPEs) are interesting alternatives for polyethylenes in high-end applications, since their structure can be tuned to include additional functionalities, such as degradability, which is difficult to achieve for polyethylene. 1−3 The "PE-like" character of this class of polymers originates from their long linear methylene backbone dominating the crystallization behavior and crystal structure, as well as the resulting mechanical properties. 4−6 An example is polypentadecalactone, which crystallizes in an orthorhombic unit cell with dimensions very similar as for PE. 7 The ester groups fit well in the orthorhombic unit cell, leading to the inclusion of these groups with only a minor associated expansion of the unit cell dimensions compared to PE. 7 The most profound effect of the inclusion of ester groups is an enthalpic penalty reducing the heat of fusion of the crystal, which simultaneously decreases the melting temperature. 8,9 Nevertheless, the crystallinity remains high (>50%) independent of the amount of ester groups in the backbone of the polymer.Even though there are many reports on the synthesis and thermal properties of ALCPEs, 10−15 a systematic investigation into the influence of the amount and configuration of the ester groups on the mechanical properties has to our knowledge not been performed. Copolymers of ω-pentadecalactone (PDL) and ε-caprolactone (CL) are ideal candidates for such an investigation, since the random copolymers are easily synthesized in ...

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“…Macrolactones are an interesting alternative class of renewable monomers for the synthesis of aliphatic polyesters with enhanced physical properties compared to polymers from small and medium size lactones . Polyesters from macrolactones are readily accessible by enzyme catalyzed ring‐opening polymerization or, more recently, using (organo)catalytic approaches . We have lately focused on polymers from unsaturated macrolactones as the double bond offers perfect anchor points for further polymer functionalization or cross‐linking .…”

Section: Introductionmentioning

confidence: 99%

Functional Brush-Decorated Poly(globalide) Films by ARGET-ATRP for Bioconjugation

et al. 2014

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Formation of hydroxyl functionalized poly(macrolactone) films was achieved by a combination of enzymatic ring opening polymerization of globalide and thiol-ene coupling reactions. Reaction with α-bromoisobutyryl bromide yielded ATRP initiator functional films. Efficient activator regeneration by electron transfer (ARGET) ATRP was employed for the polymerization of tert-butyl acrylate (tBA) and NIPAM from the initiator decorated surfaces. Deprotection of the tert-butyl ester decorated polymer films yielded carboxylic acid groups for convenient attachment of biomolecule. The successful conjugation of green fluorescent protein (eGFP) and active enzyme chitobiase (Chb) on densely poly(acrylic acid)-functionalized polyester films is demonstrated.

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ω-Pentandecalactone Polymerization and ω-Pentadecalactone/ε-Caprolactone Copolymerization Reactions Using Organic Catalysts

Cited by 134 publications

References 48 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

Influence of the Main-Chain Configuration on the Mechanical Properties of Linear Aliphatic Polyesters

Functional Brush-Decorated Poly(globalide) Films by ARGET-ATRP for Bioconjugation

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