MECHANISM OF LACTIDE POLYMERIZATION IN THE PRESENCE OF STANNOUS OCTOATE - THE EFFECT OF HYDROXY AND CARBOXYLIC-ACID SUBSTANCES

被引:195
作者
ZHANG, XC [1 ]
MACDONALD, DA [1 ]
GOOSEN, MFA [1 ]
MCAULEY, KB [1 ]
机构
[1] QUEENS UNIV,DEPT CHEM ENGN,KINGSTON K7L 3N6,ON,CANADA
关键词
LACTIDE; POLYMERIZATION; MECHANISM; ALCOHOL; CARBOXYLIC ACID;
D O I
10.1002/pola.1994.080321519
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
The effect of hydroxy and carboxylic acid substances on lactide polymerization in the presence of stannous octoate was investigated. A polymerization mechanism was postulated to attempt to explain the controversies existing in the literature and also to explain our experimental observations. Stannous alkoxide, a reaction product between stannous octoate and alcohol, is proposed as the substance initiating the polymerization through coordinative insertion of lactide. Alcohol can affect the polymerization through the reactions of initiator formation, chain transfer, and transesterfication. Carboxylic acid affects the polymerization through a deactivation reaction. Experiments showed that alcohol increased PLLA production rate while carboxylic acid decreased it. Both alcohol and carboxylic acid reduced PLLA final molecular weight. The higher the alcohol concentration, the lower the polymer molecular weight. However, the final molecular weight of PLLA was not sensitive to the carboxylic acid concentration. A polymerization induction period was observed at high carboxylic acid concentration, due to the deactivation reaction caused by carboxylic acid. (C) 1994 John Wiley and Sons, Inc.
引用
收藏
页码:2965 / 2970
页数:6
相关论文
共 22 条
[1]  
ASANO M, 1985, MAKROMOL CHEM-RAPID, V6, P509
[2]   MACROMOLECULAR ENGINEERING OF POLYLACTONES AND POLYLACTIDES .10. SELECTIVE END-FUNCTIONALIZATION OF POLY(D,L)-LACTIDE [J].
BARAKAT, I ;
DUBOIS, P ;
JEROME, R ;
TEYSSIE, P .
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 1993, 31 (02) :505-514
[3]   LACTONE POLYMERIZATION AND POLYMER PROPERTIES [J].
BRODE, GL ;
KOLESKE, JV .
JOURNAL OF MACROMOLECULAR SCIENCE-CHEMISTRY, 1972, A 6 (06) :1109-1144
[4]   BIODEGRADABLE POLYMERS .7. ON THE MECHANISM OF RING-OPENING POLYMERIZATION OF CYCLIC ESTERS OF ALIPHATIC HYDROXYCARBOXYLIC ACIDS BY MEANS OF DIFFERENT TIN-COMPOUNDS [J].
DAHLMANN, J ;
RAFLER, G .
ACTA POLYMERICA, 1993, 44 (02) :103-107
[5]   EFFECT OF THE OPERATING-CONDITIONS ON THE PREPARATION OF STANNOUS OCTANOATE FROM STANNOUS OXIDE [J].
DIEZ, FV ;
SASTRE, H ;
COCA, J .
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 1988, 27 (05) :845-847
[6]  
DUB M, 1967, ORGANOMETALLIC COMPO, V2, P395
[7]  
EENINK MJD, 1987, THESIS TWENTE U
[8]  
KIM SH, 1992, MAKROMOL CHEM, V193, P1623
[9]  
KRICHELDORF HR, 1986, MAKROMOL CHEM, V187, P1611
[10]   POLY(LACTONES) .9. POLYMERIZATION MECHANISM OF METAL ALKOXIDE INITIATED POLYMERIZATIONS OF LACTIDE AND VARIOUS LACTONES [J].
KRICHELDORF, HR ;
BERL, M ;
SCHARNAGL, N .
MACROMOLECULES, 1988, 21 (02) :286-293