Enzyme‐Catalyzed Preparation of Aliphatic Polythioester by Direct Polycondensation of Diacid Diester and Dithiol

Summary: Aliphatic dithiol‐diacid type polythioesters were first enzymatically prepared by the direct polycondensation of hexane‐1,6‐dithiol and diacid diesters using the immobilized lipase from Candida antarctica (lipase CA). As a typical example, diethyl sebacate and hexane‐1,6‐dithiol were polymerized using lipase CA in bulk in the presence of molecular sieves 4A to produce the corresponding polythioester with an of 10 200 in 90% yield. Both the melting and crystallization temperatures of the produced polythioesters were higher when compared to those of the corresponding polyoxyesters. A higher molecular weight polythioester was produced using lipase in a two‐step procedure, i.e., cyclization with subsequent ring‐opening polymerization.

Preparation of polythioester and melting temperature of various polythioesters and polyoxyesters.     

Enzyme‐Catalyzed Synthesis of Hyperbranched Aliphatic Polyesters

Hyperbranched aliphatic copolyesters have been prepared by copolymerization of ε‐caprolactone with 2,2‐bis(hydroxymethyl)butyric acid, catalyzed by immobilized Lipase B from Candida antarctica (Novozyme 435) under mild conditions. Via this novel combination of ring‐opening AB polymerization and AB₂ polycondensation, the degree of branching (DB) and, consequently, the density of functional end groups can be controlled by the comonomer ratio in the feed (0 < DB < 0.33).     

Enzyme‐Catalyzed Synthesis and Chemical Recycling of Polyesters

This article summarizes the enzyme‐catalyzed synthesis and chemical recycling of biodegradable aliphatic polyesters and poly(carbonate ester)s directed towards establishing green polymer chemistry. Lipase catalyzes the condensation polymerization of a hydroxy acid, diacid with diol, diacid anhydride with oxirane, and polyanhydride with diol, or the ring‐opening polymerization of lactones of small to large rings, and a cyclic diester to produce the corresponding polyesters. Also, lipase catalyzes the condensation polymerization of a dialkyl carbonate with diol, and the ring‐opening polymerization of a cyclic carbonate to produce the corresponding polycarbonates. These polyesters and polycarbonates were selectively degraded by lipase to produce repolymerizable oligomers. These chemical recycling systems using an enzyme will establish a novel methodology for sustainable polymer recycling. Finally, current trends in green polymer production using enzymes are discussed.     

酶催化脂肪族聚酯的合成

脂肪族聚酯是一种可生物降解的新型高聚物,可通过化学催化、发酵和酶催化来合成.酶催化合成聚酯是一种新型的环境友好绿色化学技术,可以在温和条件下高效的合成聚酯,有着传统聚合方法难以比拟的优势.尤其是特种酶的应用,为传统方法难以合成的聚酯,开辟了一条新的合成途径.本文综述了脂肪酶催化缩聚、酯交换、内酯开环聚合等聚酯合成方法,并讨论了反应参数(如溶剂、温度、酶和单体的浓度)对反应的影响.     

New Strategy for Controlling Biodegradability of Biodegradable Polyesters by Enzyme‐Catalyzed Surface Grafting

A novel preparation method for the core‐shell type biodegradable polyesters or biodegradable materials grafted with biodegradable polyesters was developed by alkaline surface treatment of biodegradable polyester films and subsequent enzymatic polymerization of aliphatic lactones, one example of which is shown in this study, i.e., the preparation of poly(L ‐lactide) (PLLA) film grafted with poly(ε‐caprolactone). It is revealed that only alkaline surface treatment or the combination of alkaline surface treatment and enzyme‐catalyzed grafting, the former and the latter, respectively accelerating and delaying the enzymatic degradation of PLLA, will give PLLA materials having a wide variety of biodegradability. Also, the specificity of the enzyme used for hydrolysis could be used to confirm the grafted chain species.

     

Enzyme‐Catalyzed Ring‐Opening Polymerization of Unsubstituted β‐Lactam

The synthesis of poly(β‐alanine) by Candida antarctica lipase B immobilized as novozyme 435 catalyzed ring‐opening of 2‐azetidinone is reported. After removal of cyclic side products and low molecular weight species pure linear poly(β‐alanine) is obtained. The formation of the polymer is confirmed with ¹H NMR spectroscopy and MALDI‐TOF mass spectrometry. The average degree of polymerization of the obtained polymer is limited to = 8 by its solubility in the reaction medium. Control experiments with β‐alanine as a substrate confirmed that the ring structure of the 2‐azetidinone is necessary to obtain the polymer.

     

Novel Aliphatic Polyesters Based on Functional Cyclic (Di)Esters

Recent progress in the chemical synthesis of novel aliphatic polyesters via ring‐opening polymerization of functional cyclic (di)esters are reviewed in this article. Syntheses of these functional aliphatic polyesters are being classified into three groups according to the structure of the cyclic monomers: (i) cyclic diesters, (ii) morpholine‐2,5‐dione derivatives, and (iii) cyclic esters. Progress in the synthesis and polymerization of monomers in each category is reported with an emphasis on controlled synthesis. The recent achievements have enabled the synthesis of a variety of novel aliphatic polyesters, including hydrophilic, halogenated, and unsaturated polyesters.

Structure of the most common R‐functionalized cyclic precursors of aliphatic polyesters.     

One‐Pot Difunctionalization of Poly(ω‐pentadecalactone) with Thiol‐Thiol or Thiol‐Acrylate Groups,Catalyzed by Candida antarctica Lipase B

Summary: An enzymatic one‐pot procedure has been developed for the synthesis of difunctional polyesters containing terminal thiols and acrylates. Candida antarctica lipase B was used as a catalyst for the ring‐opening polymerization of ω‐pentadecalactone. The polymerization was initiated with 6‐mercaptohexanol, then terminated with γ‐thiobutyrolactone or vinyl acrylate to create two types of difunctional polyesters with a very high content of thiol‐thiol or thiol‐acrylate end‐groups.

Difunctionalization of poly‐PDL.     

开环可控聚合制备脂肪族聚酯的最新研究进展

近年来,作为生物降解高分子材料,脂肪族聚酯由于良好的生物降解性及生物相容性受到人们的广泛关注。脂肪族聚酯在环境友好材料和生物医用材料领域都具有极大的应用价值,目前,部分聚酯材料已经商品化。与此同时,脂肪族聚酯的合成方法尤其是活性开环聚合也成为学术界及工业领域的研究热点。采用开环聚合法得到的聚合产物化学组成精确、分子量分...     

Cationic copolymerization of racemic‐β‐butyrolactone with L,L‐lactide: One‐pot synthesis of block copolymers

Cationic copolymerization of racemic‐β‐butyrolactone (β‐BL) with l,l ‐lactide (LA) initiated by alcohol and catalyzed by trifluoromethanesulfonic acid proceeding by activated monomer (AM) mechanism was investigated. Although both comonomers were present from the beginning in the reaction mixture, polymerization proceeded in sequential manner, with poly‐BL formed at the first stage acting as a macroinitiator for the subsequent polymerization of LA. Such course of copolymerization was confirmed by following the consumption of both comonomers throughout the process as well as by observing the changes of growing chain‐end structure using ¹H NMR. ¹³C NMR analysis and thermogravimetry revealed the block structure of resulting copolymers. The proposed mechanism of copolymerization was confirmed by the studies of changes of ¹H NMR chemical shift of acidic proton in the course of copolymerization, providing an indication that indeed protonated species and hydroxyl groups are present throughout the process, as required for AM mechanism. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4873–4884     

RIS Models and Unperturbed Chain Properties of Polyesters Containing 1,3‐Cyclobutylene and 1,4‐Cyclohexylene Linkages

Polyesters containing 1,3‐cyclobutylene and 1,4‐cyclohexylene linkages in the main chain are investigated using conformational energy calculations. Rotational isomeric state (RIS) models are developed for poly(1,4‐cyclohexylenedimethylene terephthalate) (PCT), poly(1,4‐cyclohexylenedimethylene 2,5‐dimethylterephthalate) (DMPCT), poly(1,4‐cyclohexylenedimethylene 1,4‐cyclohexylenedicarboxylate) (PCC), and poly(2,2,4,4‐tetramethyl‐1,3‐cyclobutylene terephthalate) (CBDO). In DMPCT, the ester linkage prefers skewed conformations with respect to the phenyl group to relieve the steric strain caused by the methyl groups. The methyl groups on the cyclobutanediol moiety in CBDO restrict the rotational freedom about the oxycyclobutylene linkage. The unperturbed dimensions as described by characteristic ratio and persistence length are calculated for the trans and cis configurations of these polyesters. CBDO shows highly extended chain conformations among these polyesters indicating relative chain rigidity of the backbone. For DMPCT and PCC, in their trans configuration, the chain dimensions decrease with an increase in temperature while for their cis configurations, the chain dimensions increase with temperature, arising from basic differences in the fragment structures that control the competition of the relative populations as affected by temperature. Temperature has negligible influence on the unperturbed dimensions of both isomeric linkages of CBDO, while this is true for the trans configuration of PCT. The study shows that induction of cyclobutylene groups in the main chain results in a greater rigidity for homopolyesters than for chains with cyclohexylene groups.

Structure of the repeat units of polyesters in the planar trans configuration and the schematic of the RIS models with definition of geometrical parameters.     

Anionic alternating copolymerization of epoxide and six‐membered lactone bearing naphthyl moiety

This article describes the anionic copolymerization of glycidyl phenyl ether (GPE) and 1,2‐dihydro‐3H‐naphtho[2,1‐b]pyran‐3‐one (DHNP), a six‐membered aromatic lactone bearing naphthyl moiety. The copolymerization proceeded in a 1:1 alternating manner, to afford the corresponding polyester. The ester linkage in the main chain was cleavable by reduction with lithium aluminum hydride to give the corresponding diol that inherited the structure of the alternating sequence. The copolymerization ability of DHNP permitted its addition as a comonomer to an imidazole‐initiated polymerization of bisphenol A diglycidyl ether. The resulting networked polymer, of which main chain was endowed with the DHNP‐derived rigid naphthalene moieties, showed a higher glass transition temperature than that obtained similarly with using 3,4‐dihydrocoumarin (DHCM) as a comonomer, an analogous aromatic lactone bearing phenylene moiety instead of naphthalene moiety of DHNP. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and Ring Opening Polymerization of a New Functional Lactone, α‐Iodo‐ε‐caprolactone: A Novel Route to Functionalized Aliphatic Polyesters

A new functional lactone, α‐iodo‐ε‐caprolactone (αIεCL), was synthesized from ε‐caprolactone by anionic activation using a non‐nucleophilic strong base (lithium diisopropylamide) followed by an electrophilic substitution with iodine chloride. Ring‐opening (co)polymerizations of the resulting monomer with ε‐caprolactone were carried out using tin 2‐ethylhexanoate as a catalyst in toluene at 100 °C. Homopolymerization of αIεCL was achieved, and poly(αIεCL) was fully characterized by SEC, ¹H NMR and elemental analysis. Random copolymerizations of αIεCL with εCL were controlled with experimental molecular weights close to the theoretical values, narrow molecular weight distributions and a good agreement between experimental and theoretical molar compositions of αIεCL.

     

Enzymatic Synthesis of Chitin‐ and Chitosan‐graft‐Aliphatic Polyesters

Summary: The title polymers, in which both the stem and the graft are biodegradable, have been synthesized for the first time in a one‐pot, lipase‐catalyzed, graft‐polymerization reaction (in bulk, at 70 °C) of β‐butyrolactone (β‐BL) and ε‐caprolactone (ε‐CL) onto chitin and chitosan. The reactivity order of the lactones was found to be ε‐CL > β‐BL ≫ γ‐BL (no reaction). All the graft polymers prepared are insoluble in common organic solvents.

Synthesis of chitin‐ or chitosan‐graft‐aliphatic polyesters.     

Polyester oligodiols by cationic AM copolymerization of L,L‐lactide and ε‐caprolactone initiated by diols

Cationic copolymerization of L,L ‐lactide (LA) and ε‐caprolactone (CL) initiated by low molecular weight diols in the presence of acid catalyst gives corresponding copolyesters terminated at both ends with hydroxyl groups in practically quantitative yield. Copolymerization proceeds by Activated Monomer mechanism. LA is consumed preferentially and at the later stages of copolymerization the reaction mixture is enriched with CL. In spite of that, random distribution of both units is observed and end‐groups are mainly ? LA‐OH groups and not ? CL‐OH groups. This is explained by the fact that to reach high conversion of both comonomers the relatively long reaction times are required and at those conditions transesterification reaction becomes significant. Thus the microstructure of copolymers and the nature of the end‐groups is governed by transesterification rather then by the kinetics of comonomers incorporation. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3090–3097, 2007     

Precision synthesis of microstructures in star‐shaped copolymers of ϵ‐caprolactone,L‐lactide,and 1,5‐dioxepan‐2‐one

Star‐shaped homo‐ and copolymers were synthesized in a controlled fashion using two different initiating systems. Homopolymers of ε‐caprolactone, L ‐lactide, and 1,5‐dioxepan‐2‐one were firstly polymerized using (I) a spirocyclic tin initiator and (II) stannous octoate (cocatalyst) together with pentaerythritol ethoxylate 15/4 EO/OH (coinitiator), to give polymers with identical core moieties. Our gained understanding of the versatile and controllable initiator systems kinetics, the transesterification reactions occurring, and the role which the reaction conditions play on the material outcome, made it possible to tailor the copolymer microstructure. Two strategies were used to successfully synthesize copolymers of different microstructures with the two initiator systems, i.e., a more multiblock‐ or a block‐structure. The correct choice of the monomer addition order enabled two distinct blocks to be created for the copolymers of poly(DXO‐co‐LLA) and poly(CL‐co‐LLA). In the case of poly(CL‐co‐DXO), multiblock copolymers were created using both systems whereas longer blocks were created with the spirocyclic tin initiator. © 2008 Wiley Periodicals, Inc. JPolym Sci Part A: Polym Chem 46: 1249–1264, 2008     

Proton‐Transfer Polymerization (HTP): Converting Methacrylates to Polyesters by an N‐Heterocyclic Carbene

A new polymerization termed proton (H)‐transfer polymerization (HTP) has been developed to convert dimethacrylates to unsaturated polyesters. HTP is catalyzed by a selective N‐heterocyclic carbene capable of promoting intermolecular Umpolung condensation through proton transfer and proceeds through the step‐growth propagation cycles via enamine intermediates. The role of the added suitable phenol, which is critical for achieving an effective HTP, is twofold: shutting down the radically induced chain‐growth addition polymerization under HTP conditions (typically at 80–120 °C) and facilitating proton transfer after each monomer enchainment. The resulting unsaturated polyesters have a high thermal stability and can be readily cross‐linked to robust polyester materials.     

Antimicrobial Hydantoin‐Containing Polyesters

A new N‐hydantoin‐containing biocompatible and enzymatically degradable polyester with antibacterial properties is presented. Different polyesters of dimethyl succinate, 1,4‐butanediol, and 3‐[N,N‐di(β‐hydroxyethyl)aminoethyl]‐5,5‐dimethylhydantoin in varying molar ratios are prepared via two‐step melt polycondensation. The antibacterially active N‐halamine form is obtained by subsequent chlorination of the polyesters with sodium hypochlorite. Chemical structures, thermal properties, and spherulitic morphologies of the copolymers are studied adopting FT‐IR, NMR, TGA, DSC, WAXD, and POM. The polyesters exhibit antibacterial activity against Escherichia coli. The adopted synthetic approach can be transferred to other polyesters in a straightforward manner.

     

Lipase‐Catalyzed Transformation of Unnatural‐Type Poly(3‐hydroxybutanoate) into Reactive Cyclic Oligomer

Unnatural‐type syndiotactic and atactic poly[(R,S)‐3‐hydroxybutanoate]s [P(3HB)s] were enzymatically transformed into a reactive cyclic 3HB oligomer of molecular weight ca. 500 in an organic solvent, such as toluene, using immobilized lipase from Candida antarctica at 40°C for 24 h. It was confirmed that similar results were obtained for both syndiotactic and atactic P(3HB)s. On the other hand, the acidic degradation of these polymers using a protonic acid, such as p‐toluenesulfonic acid, exclusively produced the linear 3HB oligomer instead of the cyclic oligomer. The formation of the cyclic oligomer was regarded as the characteristic feature of the lipase‐catalyzed degradation in organic media. The cyclic oligomer obtained readily reacted with alcohol as a nucleophile, and using lipase, to produce the alkyl ester of the 3HB oligomer.     

Renewable Polyethers via GaBr3‐Catalyzed Reduction of Polyesters

Herein, a novel approach is reported for the synthesis of medium‐ and long‐chain aliphatic polyethers 2 based on the GaBr₃‐catalysed reduction of polyesters 1 with TMDS as the reducing agent. Thus, various linear and branched aliphatic polyesters 1 were prepared and systematically investigated for this reduction strategy, demonstrating the applicability and versatility of this new polyether synthesis protocol. Medium‐ and long‐chain chain polyethers were obtained from the respective polyesters without or with minor chain degradation, whereas short‐chain polyesters, such as poly‐l ‐lactide 1 i and poly[(R)‐3‐hydroxybutanoate] 1 j , showed major chain degradation. In this way, previously unavailable and uncommon polyethers were obtained and studied.