磷酸酯钕催化剂合成高顺式液体聚丁二烯的研究
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摘要
以二(2-乙基己基)膦酸酯钕(Nd)/二异丁基氢化铝(Al)/乙基倍半氯化铝(Cl)/丁二烯(Bdcat)为催化体系进行了液体丁二烯的聚合,制备了高顺式含量的聚丁二烯(LPB),考察了各种因素对聚合的影响,并采用红外光谱和核磁波谱表征了聚合物的微观结构及序列结构。结果表明,本催化体系下进行高顺式LPB的聚合条件范围为:Al/Nd(摩尔比,下同)为20～30、Cl/Nd为1.5～2.0、Bdcat/Nd为10～50、催化剂用量为3.3×10~(-4)。所制得的LPB样品顺式含量高于92%,以顺式-1,4-长序列结构为主。
The high cis liquid polybutadiene was synthesized by polymerization of 1,3-butadiene(Bd)with neodymium tris[bis(2-ethylhexyl)phosphate](Nd)/diisobutyl aluminium hydride(Al)/sesquiethylaluminum chloride(Cl)/Bdcatcatalyst system.The effect factors of polymerization of Bd were investigated,and the microstructure and sequence structure of polymer was characterized by infrared spectroscopy and~(13) C-nuclear magnetic resonance.The results showed that the optimum polymerization conditions of high cis LPB were Al/Nd(mole ratio)20～30,Cl/Nd(mole ratio)1.5～2.0,Bdcat/Nd 10～50,and the amount of catalyst was 3.3×10~(-4).The cis content of samples was higher than 92%,most of which were long cis-1,4-sequence structure.
The high cis liquid polybutadiene was synthesized by polymerization of 1,3-butadiene(Bd)with neodymium tris[bis(2-ethylhexyl)phosphate](Nd)/diisobutyl aluminium hydride(Al)/sesquiethylaluminum chloride(Cl)/Bdcatcatalyst system.The effect factors of polymerization of Bd were investigated,and the microstructure and sequence structure of polymer was characterized by infrared spectroscopy and~(13) C-nuclear magnetic resonance.The results showed that the optimum polymerization conditions of high cis LPB were Al/Nd(mole ratio)20～30,Cl/Nd(mole ratio)1.5～2.0,Bdcat/Nd 10～50,and the amount of catalyst was 3.3×10~(-4).The cis content of samples was higher than 92%,most of which were long cis-1,4-sequence structure.
引文
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[4]Wang F,Liu H,Zheng W,et al.Fully-reversible and semi-reversible coordinative chain transfer polymerizations of 1,3-butadiene with neodymium-based catalytic systems[J].Polymer,2013,54(25):6716-6724.
[5]胡尊燕,代全权,刘海燕,等.二元三氟甲磺酸稀土催化体系合成高顺式-1,4-聚丁二烯橡胶[J].合成橡胶工业,2014,37(2):96-100.
[6]唐正伟,赵姜维,徐林,等.均相稀土催化剂及其组合物和聚丁二烯及其制备方法:中国,201810235018.8[P].2018.
[7]唐正伟,梁汉东,徐林,等.凝胶渗透色谱内标法测定聚合物的相对分子质量及其分布[J].石油化工,2018,47(3):291-294.
[8]Shen Z Q,Song X Y,Xiao S H,et al.Coordination copolymerization of butadiene and isoprene with rare-earth chloride-alcohol-aluminum trialkyl catalytic systems[J].Scientia Sinica Series B,1982,28(2):124-136.
[9]Friebe L,Nuyken O,Windisch H,et al.Polymerization of 1,3-butadiene initiated by neodymium versatate/diisobutylaluminium hydride/ethylaluminium sesquichloride:kinetics and conclusions about the reaction mechanism[J].Macromolecular Chemistry &Physics,2002,203(8):1055-1064.
[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]Dai Q,Zhang X,Hu Y,et al.Regulation of the cis-1,4-and trans-1,4-polybutadiene multiblock copolymers via chain shuttling polymerization using a ternary neodymium organic sulfonate catalyst[J].Macromolecules 2017,50(20):7887-7894.
[12]Gao Y,Wu Y,Liu J,et al.Effect of chain structure on the glass transition temperature and viscoelastic property of cis-1,4-polybutadiene via molecular simulation[J].Journal of Polymer Science Part B Polymer Physics,2017,55(4)1005-1016.
[13]胡尊燕,刘海燕,袁本福,等.有机磷酸稀土催化体系合成超高顺-1,4-聚丁二烯橡胶[J].合成橡胶工业,2016,39(3):182-186.
[14]赵姜维,朱寒,吴一弦,等.原位ATR-FTIR法研究丁二烯配位聚合反应动力学[J].高分子学报,2010(2):211-216.
[15]赵芳儒,苏会文,苏邦瑛,等.13C-NMR研究聚丁二烯长支链支化[J].高分子学报,1982(3):67-72.