高乙烯基聚丁二烯橡胶.pptVIP

* * 高乙烯基聚丁二烯橡胶 中国科学院长春应用化学研究所 张学全 xqzhang@ciac.jl.cn 高乙烯基聚丁二烯橡胶 通用轮胎橡胶中以顺丁橡胶滚动阻力最低（顺丁橡胶中稀土顺丁滚动阻力最低，抗湿滑性能也稍好），但其抗湿滑性差（主要作为胎侧胶使用）；丁苯橡胶（胎面和胎体）抗湿滑性虽好，但其滚动阻力大，生热高。乙烯基橡胶是集低滚动阻力、低生热和良好的抗湿滑性于一身的理想轮胎胎面胶。 Vinyl PB 抗湿滑性 生热性 Fe-based Catalyst Problems Relatively low activity and stereoselectivity Microstructure sensitive to polym. conditions Low polym. Temp. required Potentialities Versatility in polymer chain structure Continuous RD on new electron donors Still highlighted in both olefin and diene polym. Fe3+ + Al(R)3 → Fe0 (inactive) Fe3+ + Al(R)3 + Donor → ? Bidentated Nitrogen-containing Compounds CIAC in 1980s, by Wang, F. S. et. al. PB with ca. 40-50% cis-1,4 and 40-45% 1,2-units with good cured properties Allyl-Cl as effective Mw agent PI with up to 70% 3,4-units, crystalline difficulty to indus. Appl. Phosphites as donors — Recent work in CIAC S. Luo first reported dialkyl phosphite (DAP) as ED in 2001. We have studied DAPs in different structure in details. Our own phosphits as ED (patented). 189.0 5.0 95.0 82.8 (C6H5O)3P(O) Triphenyl phosphate ? ? ? oligomer (C4H9O)3P(O) Tributyl phosphate ? ? ? oligomer (C2H5O)3P(O) Triethyl phosphate ? ? ? oligomer (C2H5O)2P(O)C2H5 Diethylethyl phosphonate 180.1 15.2 84.8 75.0 (C6H5O)2P(O)H Diphenyl phosphite 177.4 9.1 90.9 85.0 (C2H5O)2P(O)H Diethyl phosphite ? ? ? oligomer (C6H5O)3P Triphenyl phosphite ? ? ? oligomer (C2H5O)3P Triethyl phosphite ? ? ? oligomer (C6H5)3P Triphenyl phosphine oC (mol%) (mol%) (wt%) Tm 1,4 1,2 Yield Phosphorus compound Different phosphorus compounds on the 1,3-butadiene polymerization with Fe(2-EHA)3-Al(i-Bu)3 catalyst (OR)2 4.8 95.2 76.5 BD+(Fe+P)+Al ---- ---- NP BD+(Fe+Al)+P 5.0 95.0 71.0 BD+Al+P+Fe 5.0 95.0 82.8 BD+Fe+P+Al 1,4(%) 1,2(%) Yield (%) Addition order Bd polymerization with different addition order of catalyst component Al/Fe = 10 (a), 20 (b) and 30 (c) (mol/mol). Syn- PB with medium crystallinity (mp: 90-150℃) Syn- PB with hig