吡咯亚胺钒络合物催化制备含功能性乙氧基硅烷聚乙烯

doi:10.11949/j.issn.0438-1157.20160906

摘要/Abstract

摘要：

通过二甲基乙氧基硅烷与1，7-辛二烯的硅氢加成反应，制备出一种含功能性基团的极性单体——7-辛烯基乙氧基二甲基硅烷（OEMS），在吡咯亚胺钒络合物（VCIP）的催化作用下，该单体可与乙烯配位共聚制备含功能性乙氧基硅烷的乙烯共聚物（PE-co-OEMS）。通过高温核磁共振氢谱及碳谱（¹H NMR和¹³C NMR）、高温凝胶渗透色谱（HT-GPC）和热分析（DSC）等测试方法对共聚物的结构和热性能进行了表征。结果显示，当共单体OEMS的投料量增大至60 mmol·L^-1时，共聚反应活性仍可保持在1.2 kg·mmol^-1·h^-1，OEMS单体插入率为1.3%（摩尔分数）；此外，OEMS投料量对于共聚物的分子量（M_w）和分子量分布（PDI）均具有较大的影响，当OEMS投料量为30 mmol·L^-1时，共聚物M_w为16900，PDI为2.1；若继续增大共单体的投料量，共聚物分子量增大且分子量分布变宽。熔点（T_m）和结晶焓（ΔH_c）随着OEMS插入率的增大而降低。在三氟甲磺酸作用下，PE-co-OEMS交联后凝胶含量接近100%。

关键词: 聚乙烯, 有机硅, 交联, 聚合物, 制备, 合成

Abstract:

A well-defined silane-functionalized comonomer, 7-octenylethoxydimethylsilane (OEMS), was synthesized through hydrosilylation reaction of dimethylethoxysilane with 1,7-octadiene. Catalyzed by a vanadium complex bearing iminopyrrolide ligands (VCIP), the functional ethoxysilane-containing polyethylenes (PE-co-OEMS) were synthesized by copolymerization of ethylene with OEMS. The structure and properties of PE-co-OEMSs were characterized with ¹H NMR, ¹³C NMR, HT-GPC and DSC. It was found that catalytic activity still remained 1.2 kg·mmol^-1·h^-1 when OEMS feeding reached to 60 mmol·L^-1, and the OEMS incorporating in the copolymer was 1.3%(mol). Besides, the OEMS feeding had a great influence on the average molecular weight (M_w) and distribution (PDI) of copolymers. The Mw and PDI of PE-co-OEMS were 16900 and 2.1 when OEMS feeding was 30 mmol·L^-1. With further increasing the OEMS feeding, M_w increased and PDI became wider. The melting temperature (T_m) and crystallization enthalpy (ΔH_c) decreased with the increase of OEMS incorporation. The ethoxysilane-containing copolymers were easily crosslinked under the catalysis of trifluoromethanesulfonic acid, and the copolymer gel contents after crosslinking were nearly 100%.

Key words: polyethylene, silicone, crosslinking, polymer, preparation, synthesis

中图分类号:

TQ325.1

刘智颖, 范宏. 吡咯亚胺钒络合物催化制备含功能性乙氧基硅烷聚乙烯[J]. 化工学报, 2017, 68(2): 774-780.

LIU Zhiying, FAN Hong. Preparation of functional ethoxysilane-containing polyethylene through ethylene coordination copolymerization catalyzed by iminopyrrolide vanadium complex[J]. CIESC Journal, 2017, 68(2): 774-780.

参考文献 31

[1]	CHUM P S, SWOGGER K W. Olefin polymer technologies-history and recent progress at the dow chemical company[J]. Progress in Polymer Science, 2008, 33(8):797-819.
[2]	LOPEZ R G, D'AGOSTO F, BOISSON C. Synthesis of well-defined polymer architectures by successive catalytic olefin polymerization and living/controlled polymerization reactions[J]. Progress in Polymer Science, 2007, 32(4):419-454.
[3]	DONG J, HU Y. Design and synthesis of structurally well-defined functional polyolefins via transition metal-mediated olefin polymerization chemistry[J]. Coordination Chemistry Reviews, 2006, 250(1/2):47-65.
[4]	NAQVI M K, CHOUDHARY M S. Chemically modified polyolefins and their blends[J]. Journal of Macromolecular Science, Part C, 1996, 36(3):601-629.
[5]	YANJARAPPA M J, SIVARAM S. Recent developments in the synthesis of functional poly(olefin)s[J]. Progress in Polymer Science, 2002, 27(7):1347-1398.
[6]	徐志贤, 介素云, 李伯耿. 聚烯烃与极性聚合物的嵌段与接枝[J]. 化学反应工程与工艺, 2015, 31(6):522-529. XU Z X, JIE S Y, LI B G. Progress in blocking and grafting of polyolefin and polar polymer[J]. Chemical Reaction Engineering and Technology, 2015, 31(6):522-529.
[7]	潘博. 我国聚烯烃技术的现状及趋势研究[J]. 中国化工贸易, 2013, 12(12):25. PAN B. Study on the status and trends of polyolefin technology in China[J]. China Chemical Trade, 2013, 12(12):25.
[8]	汪焕心. 我国高分子材料未来发展的方向[J]. 广州化工, 2012, 40(3):1-3. WANG H X. The future direction of China's development of polymer materials[J]. Guangzhou Chemical Industry, 2012, 40(3):1-4.
[9]	胡友良, 乔金梁, 吕立新. 聚烯烃功能化及改性:科学与技术[M].北京:化学工业出版社, 2006:1-10. HU Y L, QIAO J L, LÜ L X. Functionalization and Modification of Polyolefins:Science and Technology[M]. Beijing:Chemical Industry Press, 2006:1-10.
[10]	FRANSSEN N M G, REEK J N H, BAS D B. ChemInform abstract:synthesis of functional ‘polyolefins’:state of the art and remaining challenges[J]. ChemInform, 2013, 42(37):193-210.
[11]	PURGETT M D, VOGL O. Functional polymers. XLVIII. Polymerization of ω-alkenoate derivatives[J]. Journal of Polymer Science Part A:Polymer Chemistry, 1988, 26(3):677-700.
[12]	CARRICK W L. Mechanism of ethylene polymerization with vanadium catalysts[J]. Journal of the American Chemical Society, 1958, 80(23):6455-6456.
[13]	CARRICK W L, KLUIBER R W, BONNER E F, et al. Transition metal catalysts(Ⅰ):Ethylene polymerization with a soluble catalyst formed from an aluminum halide, tetraphenyltin and a vanadium halide[J]. Journal of the American Chemical Society, 1960, 82(15):3883-3887.
[14]	LEHR M H. The active oxidation state of vanadium in soluble monoolefin polymerization catalysts[J]. Macromolecules, 1968, 1(2):178-184.
[15]	LEHR M H, CARMAN C J. Electron spin resonance evidence of inactive Ⅴ(Ⅲ) precursor to catalytically active Ⅴ(Ⅲ) in vanadium tetrachloride Ziegler catalysts[J]. Macromolecules, 1969, 2(2):217-219.
[16]	TANG L M, WU J Q, DUAN Y Q, et al. Ethylene polymerizations, and the copolymerizations of ethylene with hexene or norbornene with highly active mono(β-enaminoketonato) vanadium(III) catalysts[J]. Journal of Polymer Science Part A:Polymer Chemistry, 2008, 46(6):2038-2048.
[17]	WU J Q, PAN L, LIU S R, et al. Ethylene polymerization and ethylene/hexene copolymerization with vanadium(Ⅲ) catalysts bearing heteroatom-containing salicylaldiminato ligands[J]. Journal of Polymer Science Part A:Polymer Chemistry, 2009, 47(14):3573-3582.
[18]	NOMURA K, SAGARA A, IMANISHI Y. Olefin polymerization and ring-opening metathesis polymerization of norbornene by (Arylimido)(aryloxo)vanadium(Ⅴ) complexes of the type VX2(NAr) (Oar1). Remarkable effect of aluminum cocatalyst for the coordination and insertion and ring-opening metathesis polymerization[J]. Macromolecules, 2002, 35(5):1583-1590.
[19]	XU B C, HU T, WU J Q, et al. Novel vanadium(Ⅲ) complexes with bidentate N,N-chelating iminopyrrolide ligands:synthesis, characterization and catalytic behaviour of ethylene polymerization and copolymerization with 10-undecen-1-ol[J]. Dalton Transactions, 2009, 41:8854-8863.
[20]	YILG R E, YILG R I. Silicone containing copolymers:synthesis, properties and applications[J]. Progress in Polymer Science, 2014, 39(6):1165-1195.
[21]	ERBIL H Y, YASAR B, S ZER S, et al. Surface characterization of the hydroxy-terminated poly(ε-caprolactone)/poly(dimethylsiloxane) triblock copolymers by electron spectroscopy for chemical analysis and contact angle measurements[J]. Langmuir, 1997, 13(20):5484-5493.
[22]	CLARSON S J, SEMLYEN J A. Siloxane Polymers[M]. Englewood Cliffs, NJ:Prentice Hall, 1993:1-10.
[23]	VASILE C. Handbook of Polyolefins[M]. New York:Marcel Dekker, Inc., 2000:532.
[24]	UOZUMI T, TIAN G, AHN C H, et al. Synthesis of functionalized alternating olefin copolymer and modification to graft copolymer by hydrosilylation[J]. Journal of Polymer Science Part A:Polymer Chemistry, 2000, 38(10):1844-1847.
[25]	LI W, HUANG B. Synthesis of a polydimethylsiloxane macromonomer and its copolymerization with ethylene[J]. Die Makromolekulare Chemie, 1989, 190(10):2373-2380.
[26]	MUKBANIANI O, TITVINIDZE G, TATRISHVILI T, et al. Formation of polymethylsiloxanes with alkyl side groups[J]. Journal of Applied Polymer Science, 2007, 104(2):1176-1183.
[27]	GALL B T, THOMANN R, M LHAUPT R. Synthesis and characterization of semicrystalline triblockcopolymers of isotactic polystyrene and polydimethylsiloxane[J]. Journal of Polymer Science Part A:Polymer Chemistry, 2011, 49(11):2339-2345.
[28]	金震, 范宏. 长支链型PDMS-g-PE共聚物的制备及其增塑润滑作用[J]. 化工学报, 2016, 67(2):672-678. JIN Z, FAN H. Synthesis, characterization and lubricating effect of long chain branched polydimethylsiloxane-g-polyethylene (PDMS-g-PE) copolymers[J]. CIESC Journal, 2016, 67(2):672-678.
[29]	CIOLINO A E, BARRERA GALLAND G, VILLAR M A. Novel synthesis of polyethylene-poly(dimethylsiloxane) copolymers with a metallocene catalyst[J]. Journal of Polymer Science Part A:Polymer Chemistry, 2004, 42(10):2462-2473.
[30]	JIN Z, FAN H, LI B G, et al. Synthesis of a novel type of octyltetramethyldisiloxane-containing olefinic macromonomer and its copolymerization with ethylene[J]. Polymer, 2016, 83:20-26.
[31]	ZIMMER S, SCH BEL A, HALBACH T, et al. New curable propylene copolymers containing tert-butoxysilane side groups[J]. Macromolecular Rapid Communications, 2013, 34(3):221-226.