用二[二(2-乙基己基)磷酸]异辛酸钕盐/氢化二异丁基铝/一氯二乙基铝催化体系制备高顺式丁二烯-异戊二烯共聚物
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摘要
以二[二(2-乙基己基)磷酸]异辛酸钕盐[Nd(P_(204))_2EHA,简称Nd]/氢化二异丁基铝(简称Al)/一氯二乙基铝催化体系催化丁二烯-异戊二烯共聚合,考察了催化剂用量、n(Al)/n(Nd)和共聚单体比对聚合的影响。结果表明,该催化体系在n(Al)/n(Nd)为10时即具有高活性,且所得共聚物具有高的分子量(数均分子量大于10×10~4)和窄分子量分布(分布指数小于2.0),特别是其中的丁二烯和异戊二烯链节的顺式-1,4-结构摩尔分数均超过了97%。随n(Al)/n(Nd)增大,聚合物的收率增加,同时由于链转移反应增强导致聚合物的分子量降低、分子量分布变宽。随着共聚单体中丁二烯用量的增加,共聚物中异戊二烯链节的顺式-1,4-结构含量增加,而丁二烯链节基本不变,顺式-1,4-结构摩尔分数保持在约99.4%。
Copolymerization of butadiene and isoprene was conducted with neodymium di[bis( 2-ethylhexyl) phosphate] 2-ethylhexanoate(Nd( P_(204))_2 EHA,simplified as Nd)/diisobutylaluminum hydride( Al(i-Bu)_2 H,simplified as Al)/diethylaluminum chloride( AlEt_2 Cl,simplified as Cl) catalyst,and the effects of catalyst loading level,n( Al)/n( Nd),and monomer feed ratio on the polymerization were studied. The results showed that catalyst was highly effective in the copolymerization even at low n( Al)/n( Nd) of 10. The yielding copolymers had high molecular weight(M_n more than 10 × 10~4),quite narrow molecular weight distribution( M_w/M_n less than 2.0),and most importantly,high cis-1,4-unit contents of butadiene and isoprene segments( mole fraction more than 97%). The increase of n( Al)/n( Nd) led to an increase of the polymer yield,while the molecular weight of the resulted polymer decreased and the molecular weight distribution became broad due to the enhanced chain transfer reaction. With increasing the butadiene content in the monomer feed,the cis-1,4-unit content of isoprene segment in the copolymer increased,meanwhile the cis-1,4-unit content of butadiene segment was almost unchanged and stayed around 99. 4%( mole fraction).
Copolymerization of butadiene and isoprene was conducted with neodymium di[bis( 2-ethylhexyl) phosphate] 2-ethylhexanoate(Nd( P_(204))_2 EHA,simplified as Nd)/diisobutylaluminum hydride( Al(i-Bu)_2 H,simplified as Al)/diethylaluminum chloride( AlEt_2 Cl,simplified as Cl) catalyst,and the effects of catalyst loading level,n( Al)/n( Nd),and monomer feed ratio on the polymerization were studied. The results showed that catalyst was highly effective in the copolymerization even at low n( Al)/n( Nd) of 10. The yielding copolymers had high molecular weight(M_n more than 10 × 10~4),quite narrow molecular weight distribution( M_w/M_n less than 2.0),and most importantly,high cis-1,4-unit contents of butadiene and isoprene segments( mole fraction more than 97%). The increase of n( Al)/n( Nd) led to an increase of the polymer yield,while the molecular weight of the resulted polymer decreased and the molecular weight distribution became broad due to the enhanced chain transfer reaction. With increasing the butadiene content in the monomer feed,the cis-1,4-unit content of isoprene segment in the copolymer increased,meanwhile the cis-1,4-unit content of butadiene segment was almost unchanged and stayed around 99. 4%( mole fraction).
引文
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[8]Oehme A,Gebauer U,Gehrke K,et al.The influence of the catalyst preparation on the homo and copolymerization of butadiene and isoprene[J].Macromol Chem Phys,1994,195(12):3773-3781.
[9]代全权,胡雁鸣,白晨曦,等.新癸酸钕/烷基铝/二异丁基氯化铝催化丁二烯/异戊二烯共聚合[J].合成橡胶工业,2015,38(6):422-426.
[10]孔春丽,胡雁鸣,李杨,等.磷酸酯钕系催化剂合成高顺式丁二烯-异戊二烯共聚物[J].合成橡胶工业,2012,35(5):356-360.
[11]张志强,林曙光,张凯,等.用混合配体稀土催化剂制备窄分子量分布高顺式聚丁二烯[J].合成橡胶工业,2018,41(1):2-5.
[12]张志强,林曙光,李潇,等.含混合配体的稀土催化剂及其制备方法和应用:中国,106905458 A[P].2017-06-30.
[13]Zhao J,Ghebremeskel G N.A review of some of the factors affecting fracture and fatigue in SBR and BR vulcanizates[J].Rubb Chem Tech,2001,74(3):409-427.
[2]杜凯,姚薇,李旭东,等.高顺式丁二烯-异戊二烯共聚橡胶研究进展[J].特种橡胶制品,2005,26(2):37-41.
[3]李柏林,张新惠,蔡洪光.中门尼粘度稀土催化丁二烯-异戊二烯共聚橡胶的性能[J].合成橡胶工业,1999,22(5):263-265.
[4]张洪林,孙峰,崔立强,等.丁二烯-异戊二烯共聚橡胶的流变性能[J].合成橡胶工业,2003,26(1):25-27.
[5]Friebe L,Nuyken O,Obrecht W.Neodymium based Ziegler/Natta catalysts and their application in diene polymerization[J].Adv Polym Sci,2006,204(11):1-154.
[6]方天茹,沈琪,杨国洁.分子量及其分布对稀土丁-异戊橡胶硫化胶性质的影响[J].应用化学,1980:16-21.
[7]Shen Zhiquan,Song Xiangyu,Xiao Shuxiu,et al.Coordination copolymerization of butadiene and isoprene with rare earth chloride-alcohol-aluminum trialkyl catalytic systems[J].J Appl Polym Sci,1983,28(5):1585-1597.
[8]Oehme A,Gebauer U,Gehrke K,et al.The influence of the catalyst preparation on the homo and copolymerization of butadiene and isoprene[J].Macromol Chem Phys,1994,195(12):3773-3781.
[9]代全权,胡雁鸣,白晨曦,等.新癸酸钕/烷基铝/二异丁基氯化铝催化丁二烯/异戊二烯共聚合[J].合成橡胶工业,2015,38(6):422-426.
[10]孔春丽,胡雁鸣,李杨,等.磷酸酯钕系催化剂合成高顺式丁二烯-异戊二烯共聚物[J].合成橡胶工业,2012,35(5):356-360.
[11]张志强,林曙光,张凯,等.用混合配体稀土催化剂制备窄分子量分布高顺式聚丁二烯[J].合成橡胶工业,2018,41(1):2-5.
[12]张志强,林曙光,李潇,等.含混合配体的稀土催化剂及其制备方法和应用:中国,106905458 A[P].2017-06-30.
[13]Zhao J,Ghebremeskel G N.A review of some of the factors affecting fracture and fatigue in SBR and BR vulcanizates[J].Rubb Chem Tech,2001,74(3):409-427.