Preparation of an ester-terminated telechelic polybutadiene by a two-step olefin metathesis process

被引:13
作者
Nubel, PO
Yokelson, HB
Lutman, CA
Bouslog, WG
Behrends, RT
Runge, KD
机构
关键词
olefin metathesis; ring-opening metathesis polymerization; telechelic; polybutadiene;
D O I
10.1016/S1381-1169(96)00082-9
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A two-step olefin metathesis process was devised and utilized to prepare an ester-terminated telechelic 1,4-polybutadiene of high difunctional purity using readily available olefin reactants (methyl undecylenate and 1,5-cyclooctadiene or 1,5,9-cyclododecatriene). In the first step of this process, methyl undecyclenate was self-metathesized in the presence of WCl6-SnMe(4) catalyst to yield an acyclic olefinic diester, dimethyl 10-eicosene-1,20-dioate (DMED), plus ethylene. In the second step, ring-opening metathesis polymerization (ROMP) of 1,5-cyclooctadiene or 1,5,9-cyclododecatriene with DMED as a chain transfer agent was carried out using WCl6-SnMe(4) catalyst to afford the polybutadiene product. The methanol-insoluble fraction of the product, which was isolated in yields of 70-80%, consisted primarily of acyclic ester-terminated 1,4-polybutadiene species. The use of highly pure I,5-cyclooctadiene and a low catalyst charge in the ROMP reaction yielded product in which the acyclic component was determined to be purely ester-terminated (F-n = 2.0) telechelic 1,4-polybutadiene by high-sensitivity C-13-NMR analysis. Further evidence of the high difunctional purity was obtained through chain extension of the telechelic polybutadiene to a high molecular weight polyester material by transesterification with 1,6-hexanediol.
引用
收藏
页码:43 / 50
页数:8
相关论文
共 24 条
[1]  
[Anonymous], POLYM PREPR 34
[2]   THE UV-VIS SPECTROSCOPIC STUDY OF THE INTERACTION BETWEEN WCL6 AND ESTERS OF CARBOXYLIC-ACIDS [J].
BALCAR, H ;
DYBAL, J .
REACTION KINETICS AND CATALYSIS LETTERS, 1986, 30 (01) :17-22
[3]   TELECHELIC POLYISOBUTYLENE - A FACILE SYNTHESIS VIA THE CROSS-METATHESIS REACTION AND TRIALKYLBORANE-CONTAINING OLEFINS [J].
CHASMAWALA, M ;
CHUNG, TC .
MACROMOLECULES, 1995, 28 (05) :1333-1339
[4]   SYNTHESIS OF TELECHELIC 1,4-POLYBUTADIENE BY METATHESIS REACTIONS AND BORANE MONOMERS [J].
CHUNG, TC ;
CHASMAWALA, M .
MACROMOLECULES, 1992, 25 (20) :5137-5144
[5]   SYNTHESIS OF FUNCTIONAL POLYMERS VIA BORANE MONOMERS AND METATHESIS CATALYSTS [J].
CHUNG, TC .
JOURNAL OF MOLECULAR CATALYSIS, 1992, 76 (1-3) :15-31
[6]   FUNCTIONAL OLIGOMERS OF NORBORNENE .1. OLIGOMERIZATION BY RING-OPENING METATHESIS POLYMERIZATION IN THE PRESENCE OF UNSATURATED DIESTERS [J].
CRAMAIL, H ;
FONTANILLE, M ;
SOUM, A .
JOURNAL OF MOLECULAR CATALYSIS, 1991, 65 (1-2) :193-203
[7]   FUNCTIONAL OLIGOMERS OF NORBORNENE .2. KINETICS AND MECHANISM OF THE OLIGOMERIZATION REACTION [J].
CRAMAIL, H ;
FONTANILLE, M ;
SOUM, A .
MAKROMOLEKULARE CHEMIE-MACROMOLECULAR SYMPOSIA, 1991, 42-3 :281-292
[8]  
Goethals E.J., 1989, Telechelic Polymers: Synthesis and Applications
[9]   INITIATION OF OLEFIN METATHESIS - REACTION OF DECA-2,8-DIENE WITH CATALYSTS FORMED FROM ME4SN-WCL6 AND ME3AL2CL3-(PH3P)2(NO)2CL2MO [J].
GRUBBS, RH ;
HOPPIN, CR .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1977, (18) :634-635
[10]   PREPARATION OF HYDROXYTELECHELIC POLY(BUTADIENE) VIA RING-OPENING METATHESIS POLYMERIZATION EMPLOYING A WELL-DEFINED METATHESIS CATALYST [J].
HILLMYER, MA ;
GRUBBS, RH .
MACROMOLECULES, 1993, 26 (04) :872-874