环酯的开环聚合——催化体系与原理
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摘要
所述环酯泛指具有内酯(lactone)特征的环状单体,即单体中包括酯基结构。利用不同催化/引发体系,实现环酯的开环聚合制备的生物降解聚酯,具有可循环、可降解等特性,可解决塑料应用的白色污染问题,在生物医药、组织工程等领域均有巨大应用潜力。以开环聚合机理区分,应用于环酯开环聚合的催化剂主要是遵循配位-插入机理的金属催化剂,可分为以下类型:1)通过亲核加成或者亲电加成而活化单体;2)活化引发剂以及增长中的聚合物链末端,通过活性末端实现对单体的再引发与链增长;3)对单体与引发剂/增长链的双官能团活化。
Cyclic ester described in this paper is cyclic monomer with characteristics of lactone(lactone),monomers include the structure of ester base.Using different initiator/catalyst system,it can realize ring opening polymerization of cyclic ester to produce biodegradable polyester,it is renewable,biodegradable,and it can solve the white pollution problems of the application of plastic,and have huge potential application in the field of biological medicine,tissue engineering and so on.Using ring opening polymerization mechanism to distinguish,catalyst applied to ring opening polymerization of cyclic ester is mainly metal catalysts which following coordination-insertion mechanism.It can be divided into the following types:1)Through nucleophilic addition or electrophilic addition to active monomer.2)To activatethe initiator and the end of the polymer chain,through active end to realise re-initiation and chain growth of monomer.3)Toactivate double functional groups of monomer and initiator/growing chain.
Cyclic ester described in this paper is cyclic monomer with characteristics of lactone(lactone),monomers include the structure of ester base.Using different initiator/catalyst system,it can realize ring opening polymerization of cyclic ester to produce biodegradable polyester,it is renewable,biodegradable,and it can solve the white pollution problems of the application of plastic,and have huge potential application in the field of biological medicine,tissue engineering and so on.Using ring opening polymerization mechanism to distinguish,catalyst applied to ring opening polymerization of cyclic ester is mainly metal catalysts which following coordination-insertion mechanism.It can be divided into the following types:1)Through nucleophilic addition or electrophilic addition to active monomer.2)To activatethe initiator and the end of the polymer chain,through active end to realise re-initiation and chain growth of monomer.3)Toactivate double functional groups of monomer and initiator/growing chain.
引文
[1]Kricheldorf H,Stricker A.Polymers of carbonic acid29.Bu2SnOct2-initiated polymerizations of trimethylene carbonate(TMC,1,3-dioxanone-2)[J].Polymer,2000,41(20):7311-7320.
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[3]Koller,Bergman R G.Highly efficient aluminum-catalyzed ring-opening polymerization of cyclic carbonates,lactones,and lactides,including a unique crystallographic snapshot of an intermediate[J].Organometallics,2011,30(11):3217-3224.
[4]Shen Y,Shen Z,Zhang Y,et al.A comparison of polymerization characteristics and mechanisms ofε-caprolactone and trimethylene-carbonate with rare earth halides[J].Journal of Polymer Science:Part A:Polymer Chemistry,1997,35(8):1339-1352.
[5]Takeuchi D,Nakamura T,Aida T.Bulky titanium bis(phenolate)complexes as novel initiators for living anionic polymerization ofε-caprolactone[J].Macromolecules,2000,33(3):725-729.
[6]Zhong Z,Schneiderbauer S,Dijkstra P J,et al.Singlesite calcium initiators for the controlled ring-opening polymerization of lactides and lactones[J].Polymer Bulletin,2003,51(3):175-182.
[7]Darensbourg D J,Choi W,Ganguly P,et al.Biometal derivatives as catalysts for the ring-opening polymerization of trimethylene carbonate:Optimization of the Ca(Ⅱ)salen catalyst system[J].Macromolecules,2006,39(13):4374-4379.
[8]Chamberlain B M,Cheng M,Moore D R,et al.Polymerization of lactide with zinc and magnesiumβ-diiminate complexes:Stereocontrol and mechanism[J].Journal of the American Chemical Society,2001,123(14):3229-3238.
[9]Cheng M,Attygalle A B,Lobkovsky E B,et al.Singlesite catalysts for ring-opening polymerization:Synthesis of heterotactic poly(lactic acid)from rac-lactide[J].Journal of the American Chemical Society,1999,121(49):11583-11584.
[10]Dobrzynski P,Pastusiak M,Bero M.Less toxic acetylacetonates as initiators of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate ring opening polymerization[J].Journal of Polymer Science:Part A:Polymer Chemistry,2005,43(9):1913-1922.
[11]Müller A J,Keul H,Hcker H.Lithium and potassium alcoholates of poly(ethylene glycol)s as initiators for the anionic polymerization of 2,2-dimethyltrimethylene carbonate:Synthesis of AB and ABA block copolymers[J].European Polymer Journal,1991,27(12):1323-1330.
[12]Müller A J,Keul H,Hcker H.Synthesis and thermal properties of poly(2,2-dimethyltrimethylene carbonate)-block-poly(tetrahydrofuran)-block-poly(2,2-dimethyltrimethylene carbonate)[J].European Polymer Journal,1993,29(9):1171-1178.
[13]Matsuo J,Aoki K,Sanda F,et al.Substituent effect on the anionic equilibrium polymerization of six-membered cyclic carbonates[J].Macromolecules,1998,31(14):4432-4438.
[14]Kricheldorf H R,Kreiser-Saunders I,Boettcher C.Polylactones:31:Sn(Ⅱ)octoate-initiated polymerization of L-Lactide:A mechanistic study[J].Polymer,1995,36(6):1253-1259.
[15]Kricheldorf H R,Kreiser-Saunders I,Stricker A.Polylactones:48:SnOct2-initiated polymerizations of lactide:A mechanistic study[J].Macromolecules,2000,33(3):702-709.
[16]Kricheldorf H R,Serra A.Polylactones[J].Polymer Bulletin,1985,14(6):497-502.
[17]Albertsson A C,Varma I K.Recent developments in ring opening polymerization of lactones for biomedical applications[J].Biomacromolecules,2003,4(6):1466-1486.
[18]Brignou P,Priebe Gil M,Casagrande O,et al.Polycarbonates derived from green acids:ring-opening polymerization of seven-membered cyclic carbonates[J].Macromolecules,2010,43(19):8007-8017.
[19]Bourissou D,Martin-Vaca B,Dumitrescu A,et al.Controlled cationic polymerization of lactide[J].Macromolecules,2005,38(24):9993-9998.
[20]Delcroix D,Martín-Vaca B,Bourissou D,et al.Ring-opening polymerization of trimethylene carbonate catalyzed by methanesulfonic acid:Activated monomer versus active chain end mechanisms[J].Macromolecules,2010,43(21):8828-8835.
[21]Shibasaki Y,Sanda F,Endo T.Cationic ring-opening polymerization of seven-membered cyclic carbonate with water-hydrogen chloride through activated monomer process[J].Macromolecules,2000,33(10):3590-3593.
[22]Kakuchi R,Tsuji Y,Chiba K,et al.Controlled/living ring-opening polymerization ofδ-valerolactone using triflylimide as an efficient cationic organocatalyst[J].Macromolecules,2010,43(17):7090-7094.
[23]Oshimura M,Tang T,Takasu A.Ring-opening polymerization ofε-caprolactone using perfluoroalkanesulfonates and perfluoroalkanesulfonimides as organic catalysts[J].Journal of Polymer Science:Part A:Polymer Chemistry,2011,49(5):1210-1218.
[24]Dove A P,Li H,Pratt R C,et al.Stereoselective polymerization of rac-and meso-lactide catalyzed by sterically encumbered N-heterocyclic carbenes[J].Chemical Communications,2006(27):2881-2883.
[25]Zhang L,Pratt R C,Nederberg F,et al.Acyclic guanidines as organic catalysts for living polymerization of lactide[J].Macromolecules,2010,43(3):1660-1664.
[26]Lohmeijer B G,Pratt R C,Leibfarth F,et al.Guanidine and amidine organocatalysts for ring-opening polymerization of cyclic esters[J].Macromolecules,2006,39(25):8574-8583.
[27]Zhang L,Nederberg F,Messman J M,et al.Organocatalytic stereoselective ring-opening polymerization of lactide with dimeric phosphazene bases[J].Journal of the American Chemical Society,2007,129(42):12610-12611.
[28]Kanai M,Kato N,Ichikawa E,et al.Power of cooperativity:Lewis acid-Lewis base bifunctional asymmetric catalysis[J].Synlett,2005,2005(10):1491-1508.
[29]Paull D H,Abraham C J,Scerba M T,et al.Bifunctional asymmetric catalysis:Cooperative Lewis acid/base systems[J].Accounts of Chemical Research,2008,41(5):655-663.
[30]Noyori R,Yamakawa M,Hashiguchi S.Metal-ligand bifunctional catalysis:A nonclassical mechanism for asymmetric hydrogen transfer between alcohols and carbonyl compounds[J].The Journal of Organic Chemistry,2001,66(24):7931-7944.
[31]Ikariya T,Murata K,Noyori R.Bifunctional transition metal-based molecular catalysts for asymmetric syntheses[J].Organic&Biomolecular Chemistry,2006,4(3):393-406.
[32]Cole A C,Jensen J L,Ntai I,et al.Novel brnsted acidic ionic liquids and their use as dual solvent-catalysts[J].Journal of the American Chemical Society,2002,124(21):5962-5963.
[33]Inokuma T,Hoashi Y,Takemoto Y.Thiourea-catalyzed asymmetric michael addition of activated methylene compounds toα,β-unsaturated imides:Dual activation of imide by intra-and intermolecular hydrogen bonding[J].Journal of the American Chemical Society,2006,128(29):9413-9419.
[34]Dove A P,Pratt R C,Lohmeijer B G,et al.Thioureabased bifunctional organocatalysis:Supramolecular recognition for living polymerization[J].Journal of the American Chemical Society,2005,127(40):13798-13799.
[35]Alba A,Schopp A,De Sousa Delgado A P,et al.Controlled ring-opening polymerization of lactide by bissulfonamide/amine associations:Cooperative hydrogen-bonding catalysis[J].Journal of Polymer Science:Part A:Polymer Chemistry,2010,48(4):959-965.
[36]Simón L,Goodman J M.The mechanism of TBD-catalyzed ring-opening polymerization of cyclic esters[J].The Journal of Organic Chemistry,2007,72(25):9656-9662.
[2]Bhaw-Luximon A,Jhurry D,Motala-Timol S,et al.Polymerization ofε-caprolactone and its copolymerization withγ-butyrolactone using metal complexes:proceedings of the macromolecular symposia[C].Wiley Online Library,2005.
[3]Koller,Bergman R G.Highly efficient aluminum-catalyzed ring-opening polymerization of cyclic carbonates,lactones,and lactides,including a unique crystallographic snapshot of an intermediate[J].Organometallics,2011,30(11):3217-3224.
[4]Shen Y,Shen Z,Zhang Y,et al.A comparison of polymerization characteristics and mechanisms ofε-caprolactone and trimethylene-carbonate with rare earth halides[J].Journal of Polymer Science:Part A:Polymer Chemistry,1997,35(8):1339-1352.
[5]Takeuchi D,Nakamura T,Aida T.Bulky titanium bis(phenolate)complexes as novel initiators for living anionic polymerization ofε-caprolactone[J].Macromolecules,2000,33(3):725-729.
[6]Zhong Z,Schneiderbauer S,Dijkstra P J,et al.Singlesite calcium initiators for the controlled ring-opening polymerization of lactides and lactones[J].Polymer Bulletin,2003,51(3):175-182.
[7]Darensbourg D J,Choi W,Ganguly P,et al.Biometal derivatives as catalysts for the ring-opening polymerization of trimethylene carbonate:Optimization of the Ca(Ⅱ)salen catalyst system[J].Macromolecules,2006,39(13):4374-4379.
[8]Chamberlain B M,Cheng M,Moore D R,et al.Polymerization of lactide with zinc and magnesiumβ-diiminate complexes:Stereocontrol and mechanism[J].Journal of the American Chemical Society,2001,123(14):3229-3238.
[9]Cheng M,Attygalle A B,Lobkovsky E B,et al.Singlesite catalysts for ring-opening polymerization:Synthesis of heterotactic poly(lactic acid)from rac-lactide[J].Journal of the American Chemical Society,1999,121(49):11583-11584.
[10]Dobrzynski P,Pastusiak M,Bero M.Less toxic acetylacetonates as initiators of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate ring opening polymerization[J].Journal of Polymer Science:Part A:Polymer Chemistry,2005,43(9):1913-1922.
[11]Müller A J,Keul H,Hcker H.Lithium and potassium alcoholates of poly(ethylene glycol)s as initiators for the anionic polymerization of 2,2-dimethyltrimethylene carbonate:Synthesis of AB and ABA block copolymers[J].European Polymer Journal,1991,27(12):1323-1330.
[12]Müller A J,Keul H,Hcker H.Synthesis and thermal properties of poly(2,2-dimethyltrimethylene carbonate)-block-poly(tetrahydrofuran)-block-poly(2,2-dimethyltrimethylene carbonate)[J].European Polymer Journal,1993,29(9):1171-1178.
[13]Matsuo J,Aoki K,Sanda F,et al.Substituent effect on the anionic equilibrium polymerization of six-membered cyclic carbonates[J].Macromolecules,1998,31(14):4432-4438.
[14]Kricheldorf H R,Kreiser-Saunders I,Boettcher C.Polylactones:31:Sn(Ⅱ)octoate-initiated polymerization of L-Lactide:A mechanistic study[J].Polymer,1995,36(6):1253-1259.
[15]Kricheldorf H R,Kreiser-Saunders I,Stricker A.Polylactones:48:SnOct2-initiated polymerizations of lactide:A mechanistic study[J].Macromolecules,2000,33(3):702-709.
[16]Kricheldorf H R,Serra A.Polylactones[J].Polymer Bulletin,1985,14(6):497-502.
[17]Albertsson A C,Varma I K.Recent developments in ring opening polymerization of lactones for biomedical applications[J].Biomacromolecules,2003,4(6):1466-1486.
[18]Brignou P,Priebe Gil M,Casagrande O,et al.Polycarbonates derived from green acids:ring-opening polymerization of seven-membered cyclic carbonates[J].Macromolecules,2010,43(19):8007-8017.
[19]Bourissou D,Martin-Vaca B,Dumitrescu A,et al.Controlled cationic polymerization of lactide[J].Macromolecules,2005,38(24):9993-9998.
[20]Delcroix D,Martín-Vaca B,Bourissou D,et al.Ring-opening polymerization of trimethylene carbonate catalyzed by methanesulfonic acid:Activated monomer versus active chain end mechanisms[J].Macromolecules,2010,43(21):8828-8835.
[21]Shibasaki Y,Sanda F,Endo T.Cationic ring-opening polymerization of seven-membered cyclic carbonate with water-hydrogen chloride through activated monomer process[J].Macromolecules,2000,33(10):3590-3593.
[22]Kakuchi R,Tsuji Y,Chiba K,et al.Controlled/living ring-opening polymerization ofδ-valerolactone using triflylimide as an efficient cationic organocatalyst[J].Macromolecules,2010,43(17):7090-7094.
[23]Oshimura M,Tang T,Takasu A.Ring-opening polymerization ofε-caprolactone using perfluoroalkanesulfonates and perfluoroalkanesulfonimides as organic catalysts[J].Journal of Polymer Science:Part A:Polymer Chemistry,2011,49(5):1210-1218.
[24]Dove A P,Li H,Pratt R C,et al.Stereoselective polymerization of rac-and meso-lactide catalyzed by sterically encumbered N-heterocyclic carbenes[J].Chemical Communications,2006(27):2881-2883.
[25]Zhang L,Pratt R C,Nederberg F,et al.Acyclic guanidines as organic catalysts for living polymerization of lactide[J].Macromolecules,2010,43(3):1660-1664.
[26]Lohmeijer B G,Pratt R C,Leibfarth F,et al.Guanidine and amidine organocatalysts for ring-opening polymerization of cyclic esters[J].Macromolecules,2006,39(25):8574-8583.
[27]Zhang L,Nederberg F,Messman J M,et al.Organocatalytic stereoselective ring-opening polymerization of lactide with dimeric phosphazene bases[J].Journal of the American Chemical Society,2007,129(42):12610-12611.
[28]Kanai M,Kato N,Ichikawa E,et al.Power of cooperativity:Lewis acid-Lewis base bifunctional asymmetric catalysis[J].Synlett,2005,2005(10):1491-1508.
[29]Paull D H,Abraham C J,Scerba M T,et al.Bifunctional asymmetric catalysis:Cooperative Lewis acid/base systems[J].Accounts of Chemical Research,2008,41(5):655-663.
[30]Noyori R,Yamakawa M,Hashiguchi S.Metal-ligand bifunctional catalysis:A nonclassical mechanism for asymmetric hydrogen transfer between alcohols and carbonyl compounds[J].The Journal of Organic Chemistry,2001,66(24):7931-7944.
[31]Ikariya T,Murata K,Noyori R.Bifunctional transition metal-based molecular catalysts for asymmetric syntheses[J].Organic&Biomolecular Chemistry,2006,4(3):393-406.
[32]Cole A C,Jensen J L,Ntai I,et al.Novel brnsted acidic ionic liquids and their use as dual solvent-catalysts[J].Journal of the American Chemical Society,2002,124(21):5962-5963.
[33]Inokuma T,Hoashi Y,Takemoto Y.Thiourea-catalyzed asymmetric michael addition of activated methylene compounds toα,β-unsaturated imides:Dual activation of imide by intra-and intermolecular hydrogen bonding[J].Journal of the American Chemical Society,2006,128(29):9413-9419.
[34]Dove A P,Pratt R C,Lohmeijer B G,et al.Thioureabased bifunctional organocatalysis:Supramolecular recognition for living polymerization[J].Journal of the American Chemical Society,2005,127(40):13798-13799.
[35]Alba A,Schopp A,De Sousa Delgado A P,et al.Controlled ring-opening polymerization of lactide by bissulfonamide/amine associations:Cooperative hydrogen-bonding catalysis[J].Journal of Polymer Science:Part A:Polymer Chemistry,2010,48(4):959-965.
[36]Simón L,Goodman J M.The mechanism of TBD-catalyzed ring-opening polymerization of cyclic esters[J].The Journal of Organic Chemistry,2007,72(25):9656-9662.