AlEt_(1.5)Cl_(1.5)与Al(OPhCH_3)(i-Bu)_2复配对钼系催化丁二烯聚合和产物微观结构的影响
|
摘要
采用MoCl_5·磷酸三丁酯(TBP)/Al(OPhCH_3)(i-Bu)_2和MoCl_5·TBP/AlEt_(1.5)Cl_(1.5)钼系催化体系催化丁二烯(Bd)配位聚合可分别制备高1,2含量的聚丁二烯橡胶(HVPB)和含反式(trans)-1,4-结构的部分结晶的聚丁二烯橡胶。在同一反应器中先加入Al(i-Bu)_2(OPhCH_3)/MoCl_5·TBP催化丁二烯聚合,然后单独加入AlEt_(1.5)Cl_(1.5)或同时加入AlEt_(1.5)Cl_(1.5)/MoCl_5·TBP,制备1,2-结构和trans-1,4结构在一定范围内可调的聚丁二烯的立构共混物。文中研究了催化剂的加入方式、第二组分加入时间和聚合温度等对聚合活性和产物结构的影响。实验结果表明,通过2种Al加入量的调节和反应条件的改变可实现1,2-结构含量和trans-1,4-结构含量分别在30%～80%和15%～60%范围内的调节,从而制得含一定结晶微区的无定形1,2-PB,有望提高1,2-PB的力学强度。
Polybutadiene rubbers with high 1,2-structure contents(HVBR) and partially crystallized trans-1,4 structures were prepared by the coordination polymerization of butadiene(Bd) catalyzed by two types of catalyst systems of MoCl_5·tributyl phosphate(TBP)/Al(OPhCH_3)(i-Bu)_2 and MoCl_5·TBP/AlEt_(1.5)Cl_(1.5), respectively. The Al(i-Bu)_2(OPhCH_3)/MoCl_5·TBP catalyst system was firstly added into the reactor to initiate the polymerization of butadiene, and then AlEt_(1.5)Cl_(1.5) was added alone or AlEt_(1.5)Cl_(1.5)/MoCl_5·TBP was joined at the same time to prepare the polymerization blends, of which 1,2-struceres and trans-1,4 structures could be adjusted at a certain range. The effects of the adding way of catalyst, adding time of second components and reaction temperature on the polymerization reactivity and microstructures were investigated. The experimental results show that the contents of 1,2-structure and trans-1,4-structure could be adjusted from 30% to 80% and from 15% to 60% through control of the adding amounts of two kinds of Al and reaction conditions, which is beneficial to prepare amorphous 1,2-polybutadiene(1,2-PB) with a certain crystalline region and is expected to improve the tensile strength of 1,2-PB.
Polybutadiene rubbers with high 1,2-structure contents(HVBR) and partially crystallized trans-1,4 structures were prepared by the coordination polymerization of butadiene(Bd) catalyzed by two types of catalyst systems of MoCl_5·tributyl phosphate(TBP)/Al(OPhCH_3)(i-Bu)_2 and MoCl_5·TBP/AlEt_(1.5)Cl_(1.5), respectively. The Al(i-Bu)_2(OPhCH_3)/MoCl_5·TBP catalyst system was firstly added into the reactor to initiate the polymerization of butadiene, and then AlEt_(1.5)Cl_(1.5) was added alone or AlEt_(1.5)Cl_(1.5)/MoCl_5·TBP was joined at the same time to prepare the polymerization blends, of which 1,2-struceres and trans-1,4 structures could be adjusted at a certain range. The effects of the adding way of catalyst, adding time of second components and reaction temperature on the polymerization reactivity and microstructures were investigated. The experimental results show that the contents of 1,2-structure and trans-1,4-structure could be adjusted from 30% to 80% and from 15% to 60% through control of the adding amounts of two kinds of Al and reaction conditions, which is beneficial to prepare amorphous 1,2-polybutadiene(1,2-PB) with a certain crystalline region and is expected to improve the tensile strength of 1,2-PB.
引文
[1] 唐月.铁系催化剂聚合1,3-丁二烯的研究[D]. 长春:长春工业大学, 2012. Tang Y. Study on polymerization of 1,3-butadiene by iron catalyst[D]. Changchun: Changchun University of Technology, 2012.
[2] Hu Y M, Yu Q Z, Jiang L S, et al. Iron-based catalysts for conjugated diene polymerization and the polymer properties[J]. Chin. Sci. Bull., 2015, 61: 3315-3325.
[3] 李勇, 易建军, 胡少坤,等. 溶聚丁苯橡胶生产技术现状及发展建议[J]. 弹性体, 2014, 24(1): 78-82. Li Y, Yi J J, Hu S K, et al.Current status and development suggestions of dissolved polystyrene butadiene rubber production technology[J]. China Elastomerics, 2014, 24(1): 78-82.
[4] Buonerba A, Cuomo C, Speranza V, et al. Crystalline syndiotactic polystyrene as reinforcing agent of cis-1,4-polybutadiene rubber[J]. Macromolecules, 2010, 43: 367-374.
[5] Luo S. Process for producing blends of syndiotactic 1,2-polybutiene and rubber elastomers with a chromium-based catalyst system: US, 6291591B1[P]. 2003-03-04.
[6] Luo S. Process for producing blends of syndiotactic 1,2-polybutadiene and rubbery elastomers: US,6528588 B2[P]. 2001-09-18.
[7] Pan W, Chen H, Mu J, et al. Synthesis of high crystalline syndiotactic 1,2-polybutadienes and study on their reinforcing effect on cis -1,4 polybutadiene[J]. Polymer, 2017, 111: 20-26.
[8] Pan W, Chen H, Mu J, et al. Synthesis of high crystalline syndiotactic 1,2-polybutadienes and study on their reinforcing effect on cis-1,4 polybutadiene[J]. Polymer, 2017, 111: 20-26.
[9] Gong D, Pan W, Zhu T, et al. Polymerization of 1,3-butadiene catalyzed by a thermal robust, high selective and active iron catalyst: an applicable recipe for producing syndiotactic 1,2-polybutadiene[J]. Polymer, 2016, 98: 136-142.
[10] 杨小牛, 孔晓华, 周恩乐,等. 聚反式1,4-丁二烯的稀溶液结晶[J]. 电子显微学报, 2000, 19(4): 497-498. Yang X N, Kong X H, Zhou E L, et al. Dilute solution crystallization of poly-trans 1,4-butadiene[J]. Journal of Chinese Electron Microscopy Society, 2000, 19(4): 497-498.
[11] 倪少儒, 高绪国, 唐学明. 钼体系催化丁二烯聚合动力学——聚合速度及有关动力学参数的测定[J]. 高分子学报, 1983(4): 241-246. Ni S R, Gao X G, Tang X M. Kinetics of butadiene polymerization with molybdenum catalyst system Ⅰ. The polymerization rate and kinetic parameters[J]. Acta Polymerica Sinica, 1983(4): 241-246.
[12] Siesler H W. Fourier transform infrared (FT-IR) spectroscopy in polymer research[J]. J. Mol. Struct., 1980, 59: 15-37.
[13] 鲁红. 凝胶渗透色谱仪及其使用[J]. 分析仪器, 2010(3): 65-69. Lu H. Gel permeation chromatography and its use[J]. Analytical Instrumentation, 2010(3): 65-69.
[14] 利帕托夫. 聚合物物理化学手册[M]. 北京: 中国石化出版社, 1994.
[15] 丛悦鑫, 李迎, 华静. 钼系高乙烯基聚丁二烯橡胶硫化配方研究[J]. 齐鲁石油化工, 2014, 42(1): 9-12.Cong Y, Li Y, Hua J. Vulcanization formula study on high vinyl polybutadiene rubber synthesized by molybdenum catalyst system[J]. Qilu Petrochemical Technology, 2014, 42(1): 9-12.
[2] Hu Y M, Yu Q Z, Jiang L S, et al. Iron-based catalysts for conjugated diene polymerization and the polymer properties[J]. Chin. Sci. Bull., 2015, 61: 3315-3325.
[3] 李勇, 易建军, 胡少坤,等. 溶聚丁苯橡胶生产技术现状及发展建议[J]. 弹性体, 2014, 24(1): 78-82. Li Y, Yi J J, Hu S K, et al.Current status and development suggestions of dissolved polystyrene butadiene rubber production technology[J]. China Elastomerics, 2014, 24(1): 78-82.
[4] Buonerba A, Cuomo C, Speranza V, et al. Crystalline syndiotactic polystyrene as reinforcing agent of cis-1,4-polybutadiene rubber[J]. Macromolecules, 2010, 43: 367-374.
[5] Luo S. Process for producing blends of syndiotactic 1,2-polybutiene and rubber elastomers with a chromium-based catalyst system: US, 6291591B1[P]. 2003-03-04.
[6] Luo S. Process for producing blends of syndiotactic 1,2-polybutadiene and rubbery elastomers: US,6528588 B2[P]. 2001-09-18.
[7] Pan W, Chen H, Mu J, et al. Synthesis of high crystalline syndiotactic 1,2-polybutadienes and study on their reinforcing effect on cis -1,4 polybutadiene[J]. Polymer, 2017, 111: 20-26.
[8] Pan W, Chen H, Mu J, et al. Synthesis of high crystalline syndiotactic 1,2-polybutadienes and study on their reinforcing effect on cis-1,4 polybutadiene[J]. Polymer, 2017, 111: 20-26.
[9] Gong D, Pan W, Zhu T, et al. Polymerization of 1,3-butadiene catalyzed by a thermal robust, high selective and active iron catalyst: an applicable recipe for producing syndiotactic 1,2-polybutadiene[J]. Polymer, 2016, 98: 136-142.
[10] 杨小牛, 孔晓华, 周恩乐,等. 聚反式1,4-丁二烯的稀溶液结晶[J]. 电子显微学报, 2000, 19(4): 497-498. Yang X N, Kong X H, Zhou E L, et al. Dilute solution crystallization of poly-trans 1,4-butadiene[J]. Journal of Chinese Electron Microscopy Society, 2000, 19(4): 497-498.
[11] 倪少儒, 高绪国, 唐学明. 钼体系催化丁二烯聚合动力学——聚合速度及有关动力学参数的测定[J]. 高分子学报, 1983(4): 241-246. Ni S R, Gao X G, Tang X M. Kinetics of butadiene polymerization with molybdenum catalyst system Ⅰ. The polymerization rate and kinetic parameters[J]. Acta Polymerica Sinica, 1983(4): 241-246.
[12] Siesler H W. Fourier transform infrared (FT-IR) spectroscopy in polymer research[J]. J. Mol. Struct., 1980, 59: 15-37.
[13] 鲁红. 凝胶渗透色谱仪及其使用[J]. 分析仪器, 2010(3): 65-69. Lu H. Gel permeation chromatography and its use[J]. Analytical Instrumentation, 2010(3): 65-69.
[14] 利帕托夫. 聚合物物理化学手册[M]. 北京: 中国石化出版社, 1994.
[15] 丛悦鑫, 李迎, 华静. 钼系高乙烯基聚丁二烯橡胶硫化配方研究[J]. 齐鲁石油化工, 2014, 42(1): 9-12.Cong Y, Li Y, Hua J. Vulcanization formula study on high vinyl polybutadiene rubber synthesized by molybdenum catalyst system[J]. Qilu Petrochemical Technology, 2014, 42(1): 9-12.