高端基烯烃聚异丁烯催化剂研究
摘要
以异丁烯为原料，用VPO方法分析数均分子量，用核磁共振分析α烯烃含量，用釜式反应器进行聚异丁烯合成。同时，进行了连续聚合实验，催化剂是以BF_3为主催化剂，MTBE为助催化剂氯代烃为溶剂配制聚合催化剂。
在低于常温下进行了催化剂组成，助催化剂的种类和含量、溶剂的种类对聚异丁烯的分子量和α烯烃含量的影响，同时，进行了主催化剂/助催化剂比例，催化剂制备温度，催化剂保存温度室温放置时间的考察，研究了原料的种类、原料的预处理的条件、反应时间、反应温度、催化剂的加入量以及终止剂的种类和其配比的影响、考察了终止时间的影响。确定了催化剂制备的最佳工艺条件和聚合反应的最佳工艺条件。在间歇反应的基础上，进行了连续聚合工艺条件的研究，考察了连续聚合的反应时间、温度影响。
通过实验，发现影响催化剂活性的因素有：主催化剂的纯度、助催化剂的种类，用MTBE为助催化剂制备的络合催化剂体系，聚合物颜色较好、催化剂活性和α烯烃含量都高。主催化剂的纯度在99.6％可以满足催化剂活性要求，从溶剂的种类和量影响实验中可知，溶剂对改变BF_3-MTBE催化剂粘度，使催化剂在体系中分散性方面有显著的作用。CHCl_3为溶剂催化活性高，加入CHCl_3、CH_2Cl_2溶剂后，可以延长催化剂的放置时间。溶剂加入次序对络合催化剂性能有影响，先加入溶剂制备的络合催化剂高于催化剂制备完，再加溶剂的络合催化剂。反应原料对聚合条件及结果的影响是用丁二烯抽余液、重油催化加氢碳四及蜡油催化碳四为原料进行聚合，同一原料，催化剂和异丁烯比不同，对聚合物的收率和α烯烃的含量影响较大，催化剂和异丁烯比大，聚合物收率和α烯烃的含量都高，丁二烯含量低，聚合物的收率和α烯烃含量二项指标都好，原料中丁二烯含量影响催化剂的活性，消耗催化剂的量。反应时间对分子量的影响不大，但收率却随着反应时间的延长而增加。随着反应温度的提高，聚合物分子量逐渐降低，收率变化不大。催化剂与原料中异丁烯的比例也影响着产品分子量和收率，当催化剂/异丁烯的量小于1.2‰时，聚异丁烯收率较低。催化剂滴加时间长使聚合物分子量增加，收率下降。用乙醇做终止剂时，随着催化剂/乙醇的比增加，聚合物的收率增加，α烯烃含量增加。终止温度的升高，α烯烃含量减少。最佳工艺条件确定采用正交设计法。
在连续装置中，考察了反应温度的变化规律，但在相同的工艺条件下，得到产品的分子量和收率却比间歇反应的低，在连续反应中，反应时间的变化对分子量的影响比间歇的大。终止聚合反应后，各种低聚物却需要通过减压蒸馏除去。在真空度一定的条件下，提高蒸馏温度，蒸馏出的低聚物虽然变化不大，但却能较大地提高产品分子量。
The properties of different catalysts for polyisobutylene with a terminal double bond in isobutylene were studied. The Mn of polyisobutylene was measured using VOP method and the amount of a-olefins was determined by NMR. Polyisobutylene was prepared in the kettle reactor. Besides, the experiment of polymerization had gotten together in succession , the catalyst comprising BF3 as the main catalyst , MTBE for catalyst-accelerators compound and hydrocarbon chloridized for the solvent.
The effect of the composition of catalyst, the kind and content of the catalyst-accelerators and the kinds of solvents in lower than ambient temperature on the molecular weight of polyisobutylene and the amount of a-olefins was discussed. Besides, the proportion of main catalysts /catalyst-accelerators, the temperature catalysts prepared, the store temperature and the period kept in ambient temperature also were considered This text involved the effect of raw materials kinds, and the conditions of raw materials pretreated, and the temperature and time, and the total amount of catalyst used and the kinds and the proportion of halts. The best process conditions for the preparation of catalysts and for the reaction of polymerization were defined. The process conditions for the polymerization in succession were studied on the basis of reaction in batches, and the temperature and time for the reaction of polymerization in succession were discussed.
The results of the experiment show that the activation of catalyst was affected by the purity of the main catalyst and the kind of the catalyst-accelerators. The activation of catalyst comprising MTBE for catalyst-accelerators and the amount of a-olefins were both high and the color of the polymer is better. The purity of the main catalyst requested by the active of catalyst can be satisfied with 99.6%. Solvent have remarkable function on changing viscidity and dispersibility of BF3-MTBE catalyst, which can be found in experiment. The activation catalyst comprising CHCl3 for the solvent was high, The shelf life of catalyst can be extended by adding solvents of CHCls, CH2Cl2- The order adding solvent influenced the performance of complexing catalyst, which is higher before than after finishing preparing catalysts. The conditions and results of polymerization also were affected by raw materials. Butadiene remainder, C4 of catalytic hydrogenation of heavy oil and C4 of wax oil catalysis for raw material for pol
ymerization, the yield of polymer and the amount of alpha-olefins were heavily affected by the different ratio catalyst to isobutylene. The yield of polymer and the amount of a-olefins were both high when the ratio catalyst to isobutylene was large, and the two targets were both gratifying when the content of isobutylene is low. The activation of catalyst was affected by the content of butadiene in raw materials, and the quantity of the catalyst consumed and the time for reaction had a little effect on the molecular weight, but the yield increased with extending reaction time. With heightening temperature, the molecular weight of the polymer was reduced gradually, and the yield changed little. The molecular weight and yield of product also influenced by the proportion of catalyst/isobutylene in raw materials. The yield of polyisobutylene was lower at catalyst/isobutylene lower than 1.2‰ . The molecular weight of the polymer increased and the yield reduced when catalyst dropping time became long. With the pr
oportion of catalyst/ethanol increasing, alcohol as the halt, the yield of product increased and the amount of a-olefins also increased but the amount reduced with halt temperature increasing. The best process conditions were defined by method of perpendicularity designing.
The changing rule of reaction temperature in fitting in succession was discussed. Under the same process
conditions, it was lower than intermittent reaction to get the molecular weight and the yield of the products ,and the molecular weight was influenced by the changing of time in succession greater t
在低于常温下进行了催化剂组成，助催化剂的种类和含量、溶剂的种类对聚异丁烯的分子量和α烯烃含量的影响，同时，进行了主催化剂/助催化剂比例，催化剂制备温度，催化剂保存温度室温放置时间的考察，研究了原料的种类、原料的预处理的条件、反应时间、反应温度、催化剂的加入量以及终止剂的种类和其配比的影响、考察了终止时间的影响。确定了催化剂制备的最佳工艺条件和聚合反应的最佳工艺条件。在间歇反应的基础上，进行了连续聚合工艺条件的研究，考察了连续聚合的反应时间、温度影响。
通过实验，发现影响催化剂活性的因素有：主催化剂的纯度、助催化剂的种类，用MTBE为助催化剂制备的络合催化剂体系，聚合物颜色较好、催化剂活性和α烯烃含量都高。主催化剂的纯度在99.6％可以满足催化剂活性要求，从溶剂的种类和量影响实验中可知，溶剂对改变BF_3-MTBE催化剂粘度，使催化剂在体系中分散性方面有显著的作用。CHCl_3为溶剂催化活性高，加入CHCl_3、CH_2Cl_2溶剂后，可以延长催化剂的放置时间。溶剂加入次序对络合催化剂性能有影响，先加入溶剂制备的络合催化剂高于催化剂制备完，再加溶剂的络合催化剂。反应原料对聚合条件及结果的影响是用丁二烯抽余液、重油催化加氢碳四及蜡油催化碳四为原料进行聚合，同一原料，催化剂和异丁烯比不同，对聚合物的收率和α烯烃的含量影响较大，催化剂和异丁烯比大，聚合物收率和α烯烃的含量都高，丁二烯含量低，聚合物的收率和α烯烃含量二项指标都好，原料中丁二烯含量影响催化剂的活性，消耗催化剂的量。反应时间对分子量的影响不大，但收率却随着反应时间的延长而增加。随着反应温度的提高，聚合物分子量逐渐降低，收率变化不大。催化剂与原料中异丁烯的比例也影响着产品分子量和收率，当催化剂/异丁烯的量小于1.2‰时，聚异丁烯收率较低。催化剂滴加时间长使聚合物分子量增加，收率下降。用乙醇做终止剂时，随着催化剂/乙醇的比增加，聚合物的收率增加，α烯烃含量增加。终止温度的升高，α烯烃含量减少。最佳工艺条件确定采用正交设计法。
在连续装置中，考察了反应温度的变化规律，但在相同的工艺条件下，得到产品的分子量和收率却比间歇反应的低，在连续反应中，反应时间的变化对分子量的影响比间歇的大。终止聚合反应后，各种低聚物却需要通过减压蒸馏除去。在真空度一定的条件下，提高蒸馏温度，蒸馏出的低聚物虽然变化不大，但却能较大地提高产品分子量。
The properties of different catalysts for polyisobutylene with a terminal double bond in isobutylene were studied. The Mn of polyisobutylene was measured using VOP method and the amount of a-olefins was determined by NMR. Polyisobutylene was prepared in the kettle reactor. Besides, the experiment of polymerization had gotten together in succession , the catalyst comprising BF3 as the main catalyst , MTBE for catalyst-accelerators compound and hydrocarbon chloridized for the solvent.
The effect of the composition of catalyst, the kind and content of the catalyst-accelerators and the kinds of solvents in lower than ambient temperature on the molecular weight of polyisobutylene and the amount of a-olefins was discussed. Besides, the proportion of main catalysts /catalyst-accelerators, the temperature catalysts prepared, the store temperature and the period kept in ambient temperature also were considered This text involved the effect of raw materials kinds, and the conditions of raw materials pretreated, and the temperature and time, and the total amount of catalyst used and the kinds and the proportion of halts. The best process conditions for the preparation of catalysts and for the reaction of polymerization were defined. The process conditions for the polymerization in succession were studied on the basis of reaction in batches, and the temperature and time for the reaction of polymerization in succession were discussed.
The results of the experiment show that the activation of catalyst was affected by the purity of the main catalyst and the kind of the catalyst-accelerators. The activation of catalyst comprising MTBE for catalyst-accelerators and the amount of a-olefins were both high and the color of the polymer is better. The purity of the main catalyst requested by the active of catalyst can be satisfied with 99.6%. Solvent have remarkable function on changing viscidity and dispersibility of BF3-MTBE catalyst, which can be found in experiment. The activation catalyst comprising CHCl3 for the solvent was high, The shelf life of catalyst can be extended by adding solvents of CHCls, CH2Cl2- The order adding solvent influenced the performance of complexing catalyst, which is higher before than after finishing preparing catalysts. The conditions and results of polymerization also were affected by raw materials. Butadiene remainder, C4 of catalytic hydrogenation of heavy oil and C4 of wax oil catalysis for raw material for pol
ymerization, the yield of polymer and the amount of alpha-olefins were heavily affected by the different ratio catalyst to isobutylene. The yield of polymer and the amount of a-olefins were both high when the ratio catalyst to isobutylene was large, and the two targets were both gratifying when the content of isobutylene is low. The activation of catalyst was affected by the content of butadiene in raw materials, and the quantity of the catalyst consumed and the time for reaction had a little effect on the molecular weight, but the yield increased with extending reaction time. With heightening temperature, the molecular weight of the polymer was reduced gradually, and the yield changed little. The molecular weight and yield of product also influenced by the proportion of catalyst/isobutylene in raw materials. The yield of polyisobutylene was lower at catalyst/isobutylene lower than 1.2‰ . The molecular weight of the polymer increased and the yield reduced when catalyst dropping time became long. With the pr
oportion of catalyst/ethanol increasing, alcohol as the halt, the yield of product increased and the amount of a-olefins also increased but the amount reduced with halt temperature increasing. The best process conditions were defined by method of perpendicularity designing.
The changing rule of reaction temperature in fitting in succession was discussed. Under the same process
conditions, it was lower than intermittent reaction to get the molecular weight and the yield of the products ,and the molecular weight was influenced by the changing of time in succession greater t
引文
1． 金山译．应用广泛的低聚异丁烯．WorldPlastics，2000，18(4)：25～26
2． 汪多仁．聚异丁烯(聚丁烯)的合成应用进展．润滑油，1999，14(5)：57～58
3． 晨曦．聚异丁烯的开发应用．弹性体，1999，9(1)：23
4． 韩秀山．低聚异丁烯的应用及遥爪低聚物．弹性体，1997，7(3)：36～42
5. Pol.PL,120331(1983)
6. Pol.PL120342(1983)
7. U.S.S.RSU747870(1980)
8． 沃文英．科研与开发纯异丁烯的开发利用．当代化工，2001，30(1)
9． 张威．异丁烯的利用．精细石油化工，1992，(2)：57～63
10． 蔡杰．MMA生产技术及市场前景分析．化工商品科技，1999，(3)：8～1142
11． 李万宝．聚异丁烯制各技术进展及开发建议．兰化科技，1999，15(3)：193～197
12. StoreyRobsonF.etc,J.Macromol.Sci,PureAppl.Chem. 1992,A29(11),1017～30
13. LajosBaloghandRudolfFaust,PolymerBulletin. 1992,(28):367～374
14. Ludas,Rudolfetc.,MacromolChem.,MacromolSymp., 1992,(60):37～45
15. LudekToman.,PolymerBulletin.1992,(28): 175～180
16. GullapalliPratap,HellerJ.P.JChemCommun,1993,(18):1384～13856 Hu. 59706. 1992
17. WO. 9302110. 1993
18. US. 5219948. 1993
19. CS. 266684. 1990
20. SU. 1659424.1991
21. Chung,TC.PolymerBull, 1993,30(4);385～391
22. Chung,TC.PolymerBull,1992,(28):123～128
23. Gy,Peak,etc.PolymerBull, 1992(29):239～246
24. Wo. 9203484. 1992
25． 巴斯福股份公司．无卤素的反应活性的聚异丁烯的制备方法CN，1246870A
26． 巴斯福股份公司．无卤素的反应活性的聚异丁烯的制各方法，CN，1192753A
27． 韩秀山．高活性低分子量聚异丁烯．化工生产与技术，2001，8(3)：14～17
2． 汪多仁．聚异丁烯(聚丁烯)的合成应用进展．润滑油，1999，14(5)：57～58
3． 晨曦．聚异丁烯的开发应用．弹性体，1999，9(1)：23
4． 韩秀山．低聚异丁烯的应用及遥爪低聚物．弹性体，1997，7(3)：36～42
5. Pol.PL,120331(1983)
6. Pol.PL120342(1983)
7. U.S.S.RSU747870(1980)
8． 沃文英．科研与开发纯异丁烯的开发利用．当代化工，2001，30(1)
9． 张威．异丁烯的利用．精细石油化工，1992，(2)：57～63
10． 蔡杰．MMA生产技术及市场前景分析．化工商品科技，1999，(3)：8～1142
11． 李万宝．聚异丁烯制各技术进展及开发建议．兰化科技，1999，15(3)：193～197
12. StoreyRobsonF.etc,J.Macromol.Sci,PureAppl.Chem. 1992,A29(11),1017～30
13. LajosBaloghandRudolfFaust,PolymerBulletin. 1992,(28):367～374
14. Ludas,Rudolfetc.,MacromolChem.,MacromolSymp., 1992,(60):37～45
15. LudekToman.,PolymerBulletin.1992,(28): 175～180
16. GullapalliPratap,HellerJ.P.JChemCommun,1993,(18):1384～13856 Hu. 59706. 1992
17. WO. 9302110. 1993
18. US. 5219948. 1993
19. CS. 266684. 1990
20. SU. 1659424.1991
21. Chung,TC.PolymerBull, 1993,30(4);385～391
22. Chung,TC.PolymerBull,1992,(28):123～128
23. Gy,Peak,etc.PolymerBull, 1992(29):239～246
24. Wo. 9203484. 1992
25． 巴斯福股份公司．无卤素的反应活性的聚异丁烯的制备方法CN，1246870A
26． 巴斯福股份公司．无卤素的反应活性的聚异丁烯的制各方法，CN，1192753A
27． 韩秀山．高活性低分子量聚异丁烯．化工生产与技术，2001，8(3)：14～17