双助催Ziegler-Natta体系用于混合癸烯制备润滑油基础油
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摘要
以自制混合癸烯为原料,采用AlEt_2Cl和AlEt_3两种助催化剂与TiCl_4形成双助催Ziegler-Natta体系,制备出高黏度指数的聚α-烯烃合成润滑油基础油(PAO)。利用GC表征和黏度测定的方法研究了反应条件对PAO收率和黏温特性的影响。实验结果表明,采用AlEt_2Cl-AlEt_3双组分助催化剂制备PAO,PAO的收率和黏度指数较高。适宜的PAO制备条件为:TiCl_4用量2%(w)(基于混合癸烯的质量)、反应温度80℃、铝钛摩尔比为1.4∶1,在该条件下,所得PAO的100℃运动黏度为30 mm2/s,黏度指数135。推测了该催化体系催化癸烯合成PAO的反应机理。双助催Ziegler-Natta体系催化混合癸烯得到的PAO具有中等黏度和高黏度指数的特点,在润滑油领域具有很大的发展潜力。
Poly-α-olefin(PAO) which can be used as lube base oil with high viscosity index was synthesized from mixed decene with a Ziegler-Natta catalyst system consisting of TiCl_4,AlEt_2Cl and AlEt_3. The effects of reaction conditions on the yield and viscosity-temperature characteristics of PAO were investigated by means of GC and viscosity determination. The results showed that both the yield and the viscosity-temperature characteristics of PAO synthesized were relatively high. Under the optimum reaction conditions of 80 ℃,Al/Ti mole ratio 1.4 ∶1 and TiCl_4 dosage of 2%(w)(based on the mass of mixed decene),the kinematic viscosity at 100 ℃ and the viscosity index of PAO were 30 mm~2/s and 135,respectively. The reaction mechanism for the synthesis of PAO from decene with the catalyst system was proposed. PAO obtained with moderate viscosity and high viscosity index has great potential in the lubricant field.
Poly-α-olefin(PAO) which can be used as lube base oil with high viscosity index was synthesized from mixed decene with a Ziegler-Natta catalyst system consisting of TiCl_4,AlEt_2Cl and AlEt_3. The effects of reaction conditions on the yield and viscosity-temperature characteristics of PAO were investigated by means of GC and viscosity determination. The results showed that both the yield and the viscosity-temperature characteristics of PAO synthesized were relatively high. Under the optimum reaction conditions of 80 ℃,Al/Ti mole ratio 1.4 ∶1 and TiCl_4 dosage of 2%(w)(based on the mass of mixed decene),the kinematic viscosity at 100 ℃ and the viscosity index of PAO were 30 mm~2/s and 135,respectively. The reaction mechanism for the synthesis of PAO from decene with the catalyst system was proposed. PAO obtained with moderate viscosity and high viscosity index has great potential in the lubricant field.
引文
[1]吕春胜,许云飞,颜子龙,等.1-C12烯烃齐聚制备高性能润滑油基础油[J].石油学报:石油加工,2014,30(3):446-452.
[2]李红平,冯乐刚,张海忠,等.不同黏度聚α-烯烃合成润滑油基础油的制备[J].石油化工,2013,42(4):384-387.
[3]申志明.1-癸烯齐聚制备聚烯烃合成油[D].大连:大连理工大学,2009.
[4]于小桥.煤蜡裂解α-烯烃合成润滑油基础油新技术研究[D].上海:华东理工大学,2013.
[5]王秀绘,高飞,王亚丽,等.聚α-烯烃润滑油催化剂的发展[J].化工科技市场,2010,33(4):4-6.
[6]高宇新,孙淑坤,曹婷婷,等.混合癸烯齐聚制备α-烯烃合成油的研究[C]//全国工业催化技术及应用年会.西安:工业催化杂志社,2013.
[7]江玲.1-癸烯齐聚物润滑油基础油的合成研究[D].上海:华东理工大学,2011.
[8]中国石油化工集团公司.GB/T 265-1988石油产品运动粘度测定法[S].北京:中国标准出版社,1989.
[9]崔立娟,任合刚,王路海.烷基铝对齐格勒-纳塔催化剂催化1-丁烯聚合性能的影响[J].工业催化,2013,21(11):49-52.
[10]申志明,蒋山,郝策,等.(C2H5)2Al Cl/Ti Cl4催化1-癸烯聚合制备高黏度指数润滑油[J].工业催化,2009,17(12):32-36.
[11]黄启谷,陈立国,付志峰,等.负载型Ziegler-Natta催化剂催化1-癸烯齐聚[J].石油化工,2004,33(10):928-931.
[12]沈国良,唐丽华.Ti Cl4/(C2H5)2Al Cl/(C2H5)Al Cl2催化体系中异戊二烯低聚的研究[J].精细石油化工,2004,5(1):17-20.
[13]Huang Qigu,Chen Liguo,Ma Li,et al.Synthesis and characterization of oligomer from 1-decene catalyzed by supported Ziegler-Natta catalyst[J].Eur Polym J,2005,41(12):2909-2915.
[14]吴浩,李惠萍,胡子昭,等.合成PAO的过程中各因素对粘均分子量的影响[J].当代化工,2011,40(11):1140-1142.
[15]吕春胜,赵俊峰.限制几何构型茂金属/硼化物催化1-癸烯齐聚及其产物表征[J].化工进展,2009,28(8):1371-1375.
[16]蒋岩,孙恩浩,刘通,等.Al Cl3催化剂催化1-癸烯齐聚及其黏温性与低温性的研究[J].精细石油化工进展,2016,17(1):41-44.
[17]董诚,牛慧,董金勇.三乙基铝调控的Ziegler-Natta/茂金属复合催化剂制备聚丙烯催化合金[J].高分子学报,2014(8):1143-1152.
[18]Senso N,Praserthdam P,Jongsomjit B,et al.Effects of Ti oxidation state on ethylene,1-hexene co-monomer polymerization by Mg Cl2-supported Ziegler-Natta catalysts[J].Polym Bull,2011,67(9):1979-1989.
[19]Nayeri H H,Taromi F A,Hemmati M,et al.Preparation method of superactive Ziegler-Natta catalysts to produce ultra-high molecular weight amorphous poly(1-octene),poly(1-decene),and their copolymers[J].J Coord Chem,2014,67(19):3270-3278.
[20]曲敏.Ti Cl4/Al(C2H5)2Cl催化剂催化烯烃齐聚制备润滑油基础油的研究[D].大连:大连海事大学,2008.
[21]Huang Qigu,Chen Liguo,Sheng Yaping,et al.Synthesis and characterization of oligomer from 1-decene catalyzed by Al Cl3/Ti Cl4/Si O2/Et2Al Cl[J].J Appl Polym Sci,2006,101(1):584-590.
[2]李红平,冯乐刚,张海忠,等.不同黏度聚α-烯烃合成润滑油基础油的制备[J].石油化工,2013,42(4):384-387.
[3]申志明.1-癸烯齐聚制备聚烯烃合成油[D].大连:大连理工大学,2009.
[4]于小桥.煤蜡裂解α-烯烃合成润滑油基础油新技术研究[D].上海:华东理工大学,2013.
[5]王秀绘,高飞,王亚丽,等.聚α-烯烃润滑油催化剂的发展[J].化工科技市场,2010,33(4):4-6.
[6]高宇新,孙淑坤,曹婷婷,等.混合癸烯齐聚制备α-烯烃合成油的研究[C]//全国工业催化技术及应用年会.西安:工业催化杂志社,2013.
[7]江玲.1-癸烯齐聚物润滑油基础油的合成研究[D].上海:华东理工大学,2011.
[8]中国石油化工集团公司.GB/T 265-1988石油产品运动粘度测定法[S].北京:中国标准出版社,1989.
[9]崔立娟,任合刚,王路海.烷基铝对齐格勒-纳塔催化剂催化1-丁烯聚合性能的影响[J].工业催化,2013,21(11):49-52.
[10]申志明,蒋山,郝策,等.(C2H5)2Al Cl/Ti Cl4催化1-癸烯聚合制备高黏度指数润滑油[J].工业催化,2009,17(12):32-36.
[11]黄启谷,陈立国,付志峰,等.负载型Ziegler-Natta催化剂催化1-癸烯齐聚[J].石油化工,2004,33(10):928-931.
[12]沈国良,唐丽华.Ti Cl4/(C2H5)2Al Cl/(C2H5)Al Cl2催化体系中异戊二烯低聚的研究[J].精细石油化工,2004,5(1):17-20.
[13]Huang Qigu,Chen Liguo,Ma Li,et al.Synthesis and characterization of oligomer from 1-decene catalyzed by supported Ziegler-Natta catalyst[J].Eur Polym J,2005,41(12):2909-2915.
[14]吴浩,李惠萍,胡子昭,等.合成PAO的过程中各因素对粘均分子量的影响[J].当代化工,2011,40(11):1140-1142.
[15]吕春胜,赵俊峰.限制几何构型茂金属/硼化物催化1-癸烯齐聚及其产物表征[J].化工进展,2009,28(8):1371-1375.
[16]蒋岩,孙恩浩,刘通,等.Al Cl3催化剂催化1-癸烯齐聚及其黏温性与低温性的研究[J].精细石油化工进展,2016,17(1):41-44.
[17]董诚,牛慧,董金勇.三乙基铝调控的Ziegler-Natta/茂金属复合催化剂制备聚丙烯催化合金[J].高分子学报,2014(8):1143-1152.
[18]Senso N,Praserthdam P,Jongsomjit B,et al.Effects of Ti oxidation state on ethylene,1-hexene co-monomer polymerization by Mg Cl2-supported Ziegler-Natta catalysts[J].Polym Bull,2011,67(9):1979-1989.
[19]Nayeri H H,Taromi F A,Hemmati M,et al.Preparation method of superactive Ziegler-Natta catalysts to produce ultra-high molecular weight amorphous poly(1-octene),poly(1-decene),and their copolymers[J].J Coord Chem,2014,67(19):3270-3278.
[20]曲敏.Ti Cl4/Al(C2H5)2Cl催化剂催化烯烃齐聚制备润滑油基础油的研究[D].大连:大连海事大学,2008.
[21]Huang Qigu,Chen Liguo,Sheng Yaping,et al.Synthesis and characterization of oligomer from 1-decene catalyzed by Al Cl3/Ti Cl4/Si O2/Et2Al Cl[J].J Appl Polym Sci,2006,101(1):584-590.