[1]兰 莹,张华强,董 静,等.用溶液型磷酸酯钕催化合成高顺式丁戊橡胶[J].合成橡胶工业,2024,5:373-377.
LAN Ying,ZHANG Hua-qiang,DONG Jing,et al.Synthesis of high cis-1,4-butadiene-isoprene rubber catalyzed by solubilized neodymium phosphate ester catalyst[J].China synthetic rubber industy,2024,5:373-377.
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《合成橡胶工业》[ISSN:1000-1255/CN:62-1036/TQ]
- 期数:
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2024年5期
- 页码:
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373-377
- 栏目:
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- 出版日期:
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1900-01-01
文章信息/Info
- Title:
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Synthesis of high cis-1,4-butadiene-isoprene rubber catalyzed by solubilized neodymium phosphate ester catalyst
- 文章编号:
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1000-1255(2024)05-0373-05
- 作者:
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兰 莹1; 张华强2; 董 静2; 张松波1; 刘丕博1?鄢; 胡雁鸣1?鄢; 周光远1
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(1. 中国科学院大连化学物理研究所 能源材料研究部,辽宁 大连 116023; 2. 中国石油石油化工研究院 兰州化工研究中心,兰州 730060)
- Author(s):
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LAN Ying1; ZHANG Hua-qiang2; DONG Jing2; ZHANG Song-bo1; LIU Pi-bo1; HU Yan-ming1; ZHOU Guang-yuan1
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(1. Division of Energy Materials, Dalian Institute of Chemical Physics of the Chinese Academy of Sciences, Dalian 116023, China; 2. Lanzhou Petrochemical Research Center, Petrochemical Research Institute, PetroChina, Lanzhou 730060, China)
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- 关键词:
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丁戊橡胶; 磷酸酯钕; 顺式-1; 4-结构含量; 可逆配位链转移; 丁二烯; 异戊二烯; 分子量及其分布
- Keywords:
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butadiene-isoprene rubber; neodymium phosphate ester; cis-1; 4-unit content; reversible coordination chain transfer; butadiene; isoprene; molecular weight and its distribution
- 分类号:
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TQ 333.99
- DOI:
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DOI:10.19908/j.cnki.ISSN1000-1255.2024.05.0373
- 文献标识码:
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A
- 摘要:
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使用溶液型磷酸二(2-乙基己基)酯钕为主催化剂、烷基铝为助催化剂、氯化铝为第3组分,构建了均相磷酸酯稀土催化体系并用于催化丁二烯和异戊二烯进行共聚合,研究了烷基铝和氯化铝的组成及用量、催化剂用量和单体投料配比对共聚物性能的影响。结果表明,该催化体系可以高效催化丁二烯和异戊二烯的共聚合反应,所得聚合物为具有立构规整性、窄分子量分布的高顺式无规丁戊橡胶;当烷基铝为二异丁基氢化铝时,催化体系表现出可逆配位链转移聚合特征,每一个钕原子可产生高达10.3条聚合物分子链。
- Abstract:
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A homogeneous phosphate ester rare earth catalytic system was constructed with solubilized neodymium di(2-ethylhexyl) phosphate eater as the main catalyst, alkyl aluminum and aluminum chloride as co-catalyst and the third component, respectively. The copolymerization of butadiene and isoprene was catalyzed by this catalytic system. The effects of the composition and dosage of alkyl aluminum and aluminum chloride, catalyst dosage, and monomer feeding ratio on the properties of the copolymer were studied. The results showed that the catalytic system could efficiently catalyze the copolymerization of butadiene and isoprene, and the resulting polymer was a random butadiene-isoprene rubber with high cis-1,4-unit stereoregularity and narrow molecular weight distribution. When diisobutylaluminum hydride was chosen as the alkyl aluminum, the catalytic system exhibited reversible coordination chain transfer polymerization characteristics with 10.3 polymer molecular chains gene-rated per neodymium atom.
参考文献/References
[1] 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, 36(6): 422-426.[2] 马海芳, 孙保德, 张宏, 等. 溶液型磷酸酯钕催化体系合成cis-1,4-聚异戊橡胶[J]. 高分子材料科学与工程, 2016, 32(7): 47-50.[3] 郭俊, 闫蓉, 杨广明, 等. 用脂肪烃溶液型磷酸酯稀土催化剂合成高顺式聚异戊二烯[J]. 合成橡胶工业, 2020, 43(1): 22-26.[4] 朱寒, 白志欣, 赵姜维, 等. 稀土催化制备窄分子量分布高顺式聚异戊二烯及聚合反应动力学[J]. 高分子学报, 2012(5): 571-579.[5] Liang Shanshan, Zhang Huaqiang, Liu Heng, et al. Coordinative chain transfer copolymerization of 1,3-butadiene and isoprene by neodymium precatalyst[J]. 合成橡胶工业, 2020, 43(3): 250.[6] Wang Feng, Zhang Mingming, Liu Heng, et al. Randomly coordinative chain transfer copolymerization of 1,3-butadiene and isoprene: A highly atom-economic way for accessing butadiene/isoprene rubber[J]. Industrial & Engineering Chemistry Research, 2020, 59(23): 10754-10762.[7] Hu Yanming, Dong Weimin, Masuda T. Novel methylaluminoxane-activated neodymium isopropoxide catalysts for 1,3-butadiene polymerization and 1,3-butadiene/isoprene copolymerization[J]. Macromolecular Chemistry and Physics, 2013, 214(19): 2172-2180. [8] Fan Changliang, Bai Chenxi, Cai Hongguang, et al. Preparation of high cis-1,4 polyisoprene with narrow molecular weight distribution via coordinative chain transfer polymerization[J]. Journal of Polymer Science (Part A): Polymer Chemistry, 2010, 48(21): 4768-4774. [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 and Physics, 2002, 203(8): 1055-1064.[10] Guerra G, Cavallo L, Corradini P, et al. Molecular mechanics and stereospecificity in Ziegler-Natta 1,2 and cis-1,4 polyme-rizations of conjugated dienes[J]. Macromolecules, 1997, 30(4): 677-684.[11] Barton J M. Relation of glass transition temperature to molecular structure of addition copolymers[J]. Journal of Polymer Science (Part C): Polymer Symposia, 2007, 30(1): 573-597.
备注/Memo
- 备注/Memo:
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国家重点研发计划项目(2022 YFB 3704704)。
更新日期/Last Update:
1900-01-01