Novel Biodegradable Aliphatic Poly(butylene succinate-co-cyclic carbonate)s with Functionalizable Carbonate Building Blocks. 1. Chemical Synthesis and Their Structural and Physical Characteriza
详细信息 查看全文
- 作者：Jing Yang ; Qinghui Hao ; Xiaoyun Liu ; Chaoyi Ba ; and Amin Cao
- 刊名：Biomacromolecules
- 出版年：2004
- 出版时间：January 2004
- 年：2004
- 卷：5
- 期：1
- 页码：209 - 218
- 全文大小：186K
- 年卷期：v.5,no.1(January 2004)
- ISSN：1526-4602
文摘
This study presents chemical synthesis, structural, and physical characterization of novel biodegradablealiphatic poly(butylene succinate-co-cyclic carbonate)s P(BS-co-CC) bearing functionalizable carbonatebuilding blocks. First, five kinds of six-membered cyclic carbonate monomers, namely, trimethylene carbonate(TMC), 1-methyl-1,3-trimethylene carbonate (MTMC), 2,2-dimethyl-1,3-trimethylene carbonate (DMTMC),5-benzyloxytrimethylene carbonate (BTMC), and 5-ethyl-5-benzyloxymethyl trimethylene carbonate(EBTMC), were well prepared from ethyl chloroformate and corresponding diols at 0 
C in THF solutionwith our modified synthetic strategies. Then, a series of new P(BS-co-CC)s were synthesized at 210 Cthrough a simple combination of polycondensation and ring-opening-polymerization (ROP) of hydroxylcapped PBS macromers and the prepared carbonate monomers, and titanium tetraisopropoxide Ti(i-OPr)4was used as a more suitable catalyst of 5 candidate catalysts which could concurrently catalyzepolycondensation and ROP. By means of NMR, GPC, FTIR, and thermal analytical instruments,macromolecular structures and physical properties have been characterized for these aliphatic poly(estercarbonate)s. The experimental results indicated that novel biodegradable P(BS-co-CC)s were successfullysynthesized with number average molecular weight 
ranging from 24.3 to 99.6 KDa and various CCmolar contents without any detectable decarboxylation and that the more bulky side group was attached toa cyclic carbonate monomer, the lower reactivity for its copolymerization would be observed. The occurrencesof 13C NMR signal splitting of succinyl carbonyl attributed to the BS building blocks could be proposeddue to the randomized sequences of BS and CC building blocks. FTIR characterization indicated two distinctabsorption bands at 1716 and 1733~1735 cm-1, respectively, stemming from carbonyl stretching modesfor corresponding BS and CC units. With regard to their thermal properties, it is seen that the synthesizedP(BS-co-CC)s exhibited thermal degradation temperatures 10~20 C higher than that of PBS. On the basisof the synthesized P(BS-co-BTMC)s, new aliphatic poly(butylene succinate-co-5-hydroxy trimethylenecarbonate)s were further synthesized, bearing hydrophilic hydroxyl pendant functional groups through anoptimized Pd/C catalyzed hydrogenation. These semicrystalline new biodegradable aliphatic copolymerswith tunable physical properties and functionalizable carbonate building blocks might be expected as potentialnew biomaterials.
C in THF solutionwith our modified synthetic strategies. Then, a series of new P(BS-co-CC)s were synthesized at 210 Cthrough a simple combination of polycondensation and ring-opening-polymerization (ROP) of hydroxylcapped PBS macromers and the prepared carbonate monomers, and titanium tetraisopropoxide Ti(i-OPr)4was used as a more suitable catalyst of 5 candidate catalysts which could concurrently catalyzepolycondensation and ROP. By means of NMR, GPC, FTIR, and thermal analytical instruments,macromolecular structures and physical properties have been characterized for these aliphatic poly(estercarbonate)s. The experimental results indicated that novel biodegradable P(BS-co-CC)s were successfullysynthesized with number average molecular weight ranging from 24.3 to 99.6 KDa and various CCmolar contents without any detectable decarboxylation and that the more bulky side group was attached toa cyclic carbonate monomer, the lower reactivity for its copolymerization would be observed. The occurrencesof 13C NMR signal splitting of succinyl carbonyl attributed to the BS building blocks could be proposeddue to the randomized sequences of BS and CC building blocks. FTIR characterization indicated two distinctabsorption bands at 1716 and 1733~1735 cm-1, respectively, stemming from carbonyl stretching modesfor corresponding BS and CC units. With regard to their thermal properties, it is seen that the synthesizedP(BS-co-CC)s exhibited thermal degradation temperatures 10~20 C higher than that of PBS. On the basisof the synthesized P(BS-co-BTMC)s, new aliphatic poly(butylene succinate-co-5-hydroxy trimethylenecarbonate)s were further synthesized, bearing hydrophilic hydroxyl pendant functional groups through anoptimized Pd/C catalyzed hydrogenation. These semicrystalline new biodegradable aliphatic copolymerswith tunable physical properties and functionalizable carbonate building blocks might be expected as potentialnew biomaterials.