环境友好型生物基材料聚乳酸的合成进展
|
摘要
综述了近些年来关于聚乳酸的合成方法,主要有直接缩聚和开环聚合,对各种聚合方法比较了优缺点,并对其前景进行了展望。针对直接缩聚存在的问题,研发了新的丙交酯开环聚合制备聚乳酸,初步实现了聚乳酸工业化,使聚乳酸走进了市场,但由于原料来源的昂贵和工艺的复杂性,聚乳酸成本居高不下,难以大规模推广使用,因此对于该工艺的优化一直是近些年来研究的热点,其中关键的是开环聚合催化剂的选择,从无机金属催化剂到有机功能催化,使开环聚合工艺有巨大的推进。
In this paper, the synthesis methods of polylactic acid in recent years, such as direct polycondensation and ring-opening polymerization, are reviewed. The advantages and disadvantages of the polymerization method are expounded accordingly, and the prospects are prospected. Due to the inevitable problems of direct polycondensation, new synthetic processes have to be developed. Therefore, there is a synthetic method for the preparation of polylactic acid by ring-opening polymerization of lactide, and the initial industrialization of polylactic acid has been successfully realized. Polylactic acid has entered the market, but due to the high cost of raw materials and the complexity of the process, the cost price of polylactic acid is high, and it is difficult to achieve large-scale popularization. Therefore, the optimization of the process has been studied in recent years.Among which the selection of ring-opening polymerization catalysts is a key step. The development of inorganic metal catalysts to organic functional catalysis has greatly promoted the process optimization of ring-opening polymerization.
In this paper, the synthesis methods of polylactic acid in recent years, such as direct polycondensation and ring-opening polymerization, are reviewed. The advantages and disadvantages of the polymerization method are expounded accordingly, and the prospects are prospected. Due to the inevitable problems of direct polycondensation, new synthetic processes have to be developed. Therefore, there is a synthetic method for the preparation of polylactic acid by ring-opening polymerization of lactide, and the initial industrialization of polylactic acid has been successfully realized. Polylactic acid has entered the market, but due to the high cost of raw materials and the complexity of the process, the cost price of polylactic acid is high, and it is difficult to achieve large-scale popularization. Therefore, the optimization of the process has been studied in recent years.Among which the selection of ring-opening polymerization catalysts is a key step. The development of inorganic metal catalysts to organic functional catalysis has greatly promoted the process optimization of ring-opening polymerization.
引文
[1]Madhavan Nampoothiri K,Nair N R,John R P.An overview of the recent developments in polylactide(PLA)research[J].Bioresource Technology,2010,101(22):8493-8501.
[2]Lim L T,Auras R,Rubino M.Processing technologies for poly(lactic acid)[J].Progress in Polymer Science,2008,33(8):820-852.
[3]Ayd?n R S T,Akyol E,Hazer B.Soybean oil based polylactic acid membranes:Synthesis and degradation characteristics[J].Journal of Polymers&the Environment,2017,26(13):1-10.
[4]Tsuji H,Kondo F.Synthesis of meso-lactide by thermal configurational inversion and depolymerization of poly(l-lactide)and thermal configurational inversion of lactides[J].Polymer Degradation&Stability,2017(141):77-83.
[5]Carrasco F,Pagès P,Gámez-Pérez J,et al.Processing of poly(lactic acid):Characterization of chemical structure,thermal stability and mechanical properties[J].Polymer Degradation&Stability,2010,95(2):116-125.
[6]Chen V J,Ma P X.The effect of surface area on the degradation rate of nano-fibrous poly(L-lactic acid)foams[J].Biomaterials,2006,27(20):3708-3715.
[7]Schliecker G,Schmidt C,Fuchs S,et al.Characterization of a homologous series of D,L-lactic acid oligomers;A mechanistic study on the degradation kinetics in vitro[J].Biomaterials,2003,24(21):3835-3844.
[8]Lopes M S,Jardini A L,Filho R M.Poly(lactic acid)production for tissue engineering applications[J].Procedia Engineering,2012,42(4):1402-1413.
[9]Achmad F,Yamane K,Shi Q,et al.Synthesis of polylactic acid by direct polycondensation under vacuum without catalysts,solvents and initiators[J].Chemical Engineering Journal,2009,151(1):342-350.
[10]Otera J,Kawada K,Yano T.Direct condensation polymerization of L-lactic acid catalyzed by distannoxane[J].Chemistry Letters,1996,25(3):225-226.
[11]Nagahata R,Sano D,Suzuki H,et al.Microwave-assisted single-step synthesis of poly(lactic acid)by direct polycondensation of lactic acid[J].Macromolecular Rapid Communications,2007,28(4):437-442.
[12]Ajioka M,Enomoto K,Suzuki K,et al.The basic properties of poly(lactic acid)produced by the direct condensation polymerization of lactic acid[J].Journal of Environmental Polymer Degradation,1995,3(4):225-234.
[13]Chen G X,Kim H S,Kim E S,et al.Synthesis of high-molecular-weight poly(L-lactic acid)through the direct condensation polymerization of L-lactic acid in bulk state[J].European Polymer Journal,2006,42(2):468-472.
[14]Singh V M,Koo D,Palmese G R,et al.Synthesis of polylactide with varying molecular weight and aliphatic content:Effect on moisture sorption[J].Journal of Applied Polymer Science,2015,120(5):2543-2549.
[15]Carothers W H,Dorough G L,Van Natta F J.Studies of polymerization and ring formation.Ⅹ.The reversible polymerization of six-membered cyclic esters[J].J Amer Chem Soc,1932,54(2):761-772.
[16]Park H W,Chang Y K.Economically efficient synthesis of lactide using solid catalyst[J].Organic Process Research&Development,2017(21):1980-1984.
[17]Thomas C M.Stereocontrolled ring-opening polymerization of cyclic esters:Synthesis of new polyester microstructures[J].Chemical Society Reviews,2010,41(20):165.
[18]赵耀明,汪朝阳,麦杭珍,等.熔融-固相聚合法直接合成聚乳酸的研究[J].华南理工大学学报(自然科学版),2002,30(11):155-159.
[19]Coady D J,Engler A C,Horn H W,et al.Catalyst chelation effects in organocatalyzed ring-opening polymerization of lactide[J].Acs Macro Letters,2012,1(1):19-22.
[20]Icart L P,Fernandes E,Agüero L,et al.End functionalization by ring opening polymerization:Influence of reaction conditions on the synthesis of end functionalized poly(lactic acid)[J].J braz chem soc,2018,29(1):99-108.
[21]Averianov I V,Korzhikov-Vlakh V A,Moskalenko Y E,et al.One-pot synthesis of poly(lactic acid)with terminal methacrylate groups for the adjustment of mechanical properties of biomaterials[J].Mendeleev Communications,2017,27(6):574-576.
[22]Kohn F E,Ommen J G V,Feijen J.The mechanism of the ring-opening polymerization of lactide and glycolide[J].European Polymer Journal,1983,19(12):1081-1088.
[23]Zhen W,Zheng Y.Synthesis,characterization and thermal stability of poly(lactic acid)/zinc oxide pillared organic saponite nanocomposites via ring-opening polymerization of d,l-lactide[J].Polymers for Advanced Technologies,2016,27(5):606-614.
[24]潘虹,石军,张树林.丙交酯开环聚合反应的新型有机催化剂[J].化学通报,2015,78(2):125-131.
[25]Tang Zhaohui,Chen Xuesi,Liang Qizhi.Strontium-based initiator system for ring-opening polymerization of cyclic esters[J].Journal of Polymer Science Part A Polymer Chemistry,2010,41(13):1934-1941.
[26]Grignard B,Winter J D,Gerbaux P,et al.Merging supercritical carbon dioxide and organocatalysis for the precision and green synthesis of poly(lactide)-based(co)polymers[J].European Polymer Journal,2017(95):635-649.
[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]Goldys A M,Dixon D J.Organocatalytic ring-opening polymerization of cyclic esters mediated by highly active bifunctional iminophosphorane catalysts[J].Macromolecules,2014,47(4):1277-1284.
[29]Kricheldorf H R,Kreiser-Saunders I.Polylactones,19.Anionic polymerization of L-lactide in solution[J].Die Makromolekulare Chemie,1990,191(5):1057-1066.
[30]Li X,Chen C,Wu J.Lewis pair catalysts in the polymerization of lactide and related cyclic esters[J].Molecules,2018,23(1):189-192.
[31]Kricheldorf H R.Syntheses and application of polylactides[J].Chemosphere,2001,43(1):49-54.
[32]And M S,S?derg?rd?A.Use of monocarboxylic iron derivatives in the ring-opening polymerization of L-lactide[J].Macromolecules,2013,32(20):6412-6417.
[2]Lim L T,Auras R,Rubino M.Processing technologies for poly(lactic acid)[J].Progress in Polymer Science,2008,33(8):820-852.
[3]Ayd?n R S T,Akyol E,Hazer B.Soybean oil based polylactic acid membranes:Synthesis and degradation characteristics[J].Journal of Polymers&the Environment,2017,26(13):1-10.
[4]Tsuji H,Kondo F.Synthesis of meso-lactide by thermal configurational inversion and depolymerization of poly(l-lactide)and thermal configurational inversion of lactides[J].Polymer Degradation&Stability,2017(141):77-83.
[5]Carrasco F,Pagès P,Gámez-Pérez J,et al.Processing of poly(lactic acid):Characterization of chemical structure,thermal stability and mechanical properties[J].Polymer Degradation&Stability,2010,95(2):116-125.
[6]Chen V J,Ma P X.The effect of surface area on the degradation rate of nano-fibrous poly(L-lactic acid)foams[J].Biomaterials,2006,27(20):3708-3715.
[7]Schliecker G,Schmidt C,Fuchs S,et al.Characterization of a homologous series of D,L-lactic acid oligomers;A mechanistic study on the degradation kinetics in vitro[J].Biomaterials,2003,24(21):3835-3844.
[8]Lopes M S,Jardini A L,Filho R M.Poly(lactic acid)production for tissue engineering applications[J].Procedia Engineering,2012,42(4):1402-1413.
[9]Achmad F,Yamane K,Shi Q,et al.Synthesis of polylactic acid by direct polycondensation under vacuum without catalysts,solvents and initiators[J].Chemical Engineering Journal,2009,151(1):342-350.
[10]Otera J,Kawada K,Yano T.Direct condensation polymerization of L-lactic acid catalyzed by distannoxane[J].Chemistry Letters,1996,25(3):225-226.
[11]Nagahata R,Sano D,Suzuki H,et al.Microwave-assisted single-step synthesis of poly(lactic acid)by direct polycondensation of lactic acid[J].Macromolecular Rapid Communications,2007,28(4):437-442.
[12]Ajioka M,Enomoto K,Suzuki K,et al.The basic properties of poly(lactic acid)produced by the direct condensation polymerization of lactic acid[J].Journal of Environmental Polymer Degradation,1995,3(4):225-234.
[13]Chen G X,Kim H S,Kim E S,et al.Synthesis of high-molecular-weight poly(L-lactic acid)through the direct condensation polymerization of L-lactic acid in bulk state[J].European Polymer Journal,2006,42(2):468-472.
[14]Singh V M,Koo D,Palmese G R,et al.Synthesis of polylactide with varying molecular weight and aliphatic content:Effect on moisture sorption[J].Journal of Applied Polymer Science,2015,120(5):2543-2549.
[15]Carothers W H,Dorough G L,Van Natta F J.Studies of polymerization and ring formation.Ⅹ.The reversible polymerization of six-membered cyclic esters[J].J Amer Chem Soc,1932,54(2):761-772.
[16]Park H W,Chang Y K.Economically efficient synthesis of lactide using solid catalyst[J].Organic Process Research&Development,2017(21):1980-1984.
[17]Thomas C M.Stereocontrolled ring-opening polymerization of cyclic esters:Synthesis of new polyester microstructures[J].Chemical Society Reviews,2010,41(20):165.
[18]赵耀明,汪朝阳,麦杭珍,等.熔融-固相聚合法直接合成聚乳酸的研究[J].华南理工大学学报(自然科学版),2002,30(11):155-159.
[19]Coady D J,Engler A C,Horn H W,et al.Catalyst chelation effects in organocatalyzed ring-opening polymerization of lactide[J].Acs Macro Letters,2012,1(1):19-22.
[20]Icart L P,Fernandes E,Agüero L,et al.End functionalization by ring opening polymerization:Influence of reaction conditions on the synthesis of end functionalized poly(lactic acid)[J].J braz chem soc,2018,29(1):99-108.
[21]Averianov I V,Korzhikov-Vlakh V A,Moskalenko Y E,et al.One-pot synthesis of poly(lactic acid)with terminal methacrylate groups for the adjustment of mechanical properties of biomaterials[J].Mendeleev Communications,2017,27(6):574-576.
[22]Kohn F E,Ommen J G V,Feijen J.The mechanism of the ring-opening polymerization of lactide and glycolide[J].European Polymer Journal,1983,19(12):1081-1088.
[23]Zhen W,Zheng Y.Synthesis,characterization and thermal stability of poly(lactic acid)/zinc oxide pillared organic saponite nanocomposites via ring-opening polymerization of d,l-lactide[J].Polymers for Advanced Technologies,2016,27(5):606-614.
[24]潘虹,石军,张树林.丙交酯开环聚合反应的新型有机催化剂[J].化学通报,2015,78(2):125-131.
[25]Tang Zhaohui,Chen Xuesi,Liang Qizhi.Strontium-based initiator system for ring-opening polymerization of cyclic esters[J].Journal of Polymer Science Part A Polymer Chemistry,2010,41(13):1934-1941.
[26]Grignard B,Winter J D,Gerbaux P,et al.Merging supercritical carbon dioxide and organocatalysis for the precision and green synthesis of poly(lactide)-based(co)polymers[J].European Polymer Journal,2017(95):635-649.
[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]Goldys A M,Dixon D J.Organocatalytic ring-opening polymerization of cyclic esters mediated by highly active bifunctional iminophosphorane catalysts[J].Macromolecules,2014,47(4):1277-1284.
[29]Kricheldorf H R,Kreiser-Saunders I.Polylactones,19.Anionic polymerization of L-lactide in solution[J].Die Makromolekulare Chemie,1990,191(5):1057-1066.
[30]Li X,Chen C,Wu J.Lewis pair catalysts in the polymerization of lactide and related cyclic esters[J].Molecules,2018,23(1):189-192.
[31]Kricheldorf H R.Syntheses and application of polylactides[J].Chemosphere,2001,43(1):49-54.
[32]And M S,S?derg?rd?A.Use of monocarboxylic iron derivatives in the ring-opening polymerization of L-lactide[J].Macromolecules,2013,32(20):6412-6417.