三氟化硼催化体系聚异丁烯合成工艺技术研究
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摘要
高活性聚异丁烯(Polyisobuty lene)是纯异丁烯经过阳离子溶液聚合制得的高分子均聚物,是一种无色、无味、无毒的粘稠状物质。因其末端α-双键含量大于80%,使其具有反应活性高,合成的下游产品(如聚异丁烯胺)中不含氯,分散性能和低温性能俱佳等独特优势,主要应用于润滑油添加剂和燃料油添加剂行业,以及乳化炸药、表面活性剂、清洁剂及防锈剂等领域,市场前景广阔。
本文通过研究三氟化硼络合催化剂配制工艺及异丁烯聚合规律,开展小试及中试技术研究,确定了催化剂配制的工艺参数、包括用量、加入方式、聚合温度和原料中杂质含量等对聚合转化率及选择性的影响。
本论文通过对比采用气相三氟化硼催化剂及液相三氟化硼络合催化剂对聚合反应的影响,确定生产中低分子量高活性聚异丁烯的最佳工艺路线及聚合反应条件。研究影响聚合转化率及聚合物分子量的关键因素,并建立了在连续聚合反应时分子量与反应温度及单体与催化剂质量流量比间的经验关系式,成功开发出了三氟化硼催化体系制备高活性聚异丁烯工艺技术路线。
针对生产运行过程中暴露的瓶颈问题,进行了技术优化及改进,开展了必要的补充实验,进一步完善工艺技术,提高了装置的抗风险能力及产品的竞争力。
Highly reactive polyisobutylene is a kind of macromolecule homopolymer, which is got through pure isobutene being polymerized by cation solution. It is colorless, odourless innoxious and viscous substance, and characterized by high reactivity, good dispersibility and low-temperature performance because of 80% over a end double bond content. There is no chlorine in its downstream products, such as polyisobutene amine. It is mainly used in lubricant and fuel oil additive industries, as well as emulsion explosives, surfactants, cleansers and antirusts etc. It has broad market prospects.
In this paper, based on the studies boron trifluoride catalyst preparation process and polyisobutene polymerization laws, at small scales and pilot sscales and determines the affects on polymerization conversion and selectivity by process parameters, such as dosage, filling method, polymerization temperature and impurity content in the raw materials for catalyst preparation was investigated.
By comparing of the polymerization reaction by boron trifluoride in gas and liquid phases, an optimum process routine and polymerization reaction conditions for LMW highly reactive polyisobutylene were studied. This paper studies key factors for polymerization conversion and polymer MW, establishes empirical relations for MW and reactive temperature as well as monomer and catalyst mass flow ratio and develops a technical routine for boron trifluoride system to prepare Highly Reactive Polyisobutylene.
PetroChemical Jilin Corporation has built the first highly reactive polyisobutylene industrialization plant in China using his self-developed know-hows. Magnified process flow is feasible. Each performance index of the product has reached world level of similar products. Once the product put into markets, it has got much good reputations from the customers. Now market share has got to 90% over. It has filled up technique and product blanks in this field in China. With developing in several years, Highly Reactive Polyisobutylene technique and its product has been improved a lot, but some gaps still exist in process techniques and product quality.
For bottleneck problems revealed in production, they have been optimized and improved technically. Necessary make-up tests have been carried out in order to perfect process technology and risk resistance capacity and product competitiveness of the plant has been improved.
本文通过研究三氟化硼络合催化剂配制工艺及异丁烯聚合规律,开展小试及中试技术研究,确定了催化剂配制的工艺参数、包括用量、加入方式、聚合温度和原料中杂质含量等对聚合转化率及选择性的影响。
本论文通过对比采用气相三氟化硼催化剂及液相三氟化硼络合催化剂对聚合反应的影响,确定生产中低分子量高活性聚异丁烯的最佳工艺路线及聚合反应条件。研究影响聚合转化率及聚合物分子量的关键因素,并建立了在连续聚合反应时分子量与反应温度及单体与催化剂质量流量比间的经验关系式,成功开发出了三氟化硼催化体系制备高活性聚异丁烯工艺技术路线。
针对生产运行过程中暴露的瓶颈问题,进行了技术优化及改进,开展了必要的补充实验,进一步完善工艺技术,提高了装置的抗风险能力及产品的竞争力。
Highly reactive polyisobutylene is a kind of macromolecule homopolymer, which is got through pure isobutene being polymerized by cation solution. It is colorless, odourless innoxious and viscous substance, and characterized by high reactivity, good dispersibility and low-temperature performance because of 80% over a end double bond content. There is no chlorine in its downstream products, such as polyisobutene amine. It is mainly used in lubricant and fuel oil additive industries, as well as emulsion explosives, surfactants, cleansers and antirusts etc. It has broad market prospects.
In this paper, based on the studies boron trifluoride catalyst preparation process and polyisobutene polymerization laws, at small scales and pilot sscales and determines the affects on polymerization conversion and selectivity by process parameters, such as dosage, filling method, polymerization temperature and impurity content in the raw materials for catalyst preparation was investigated.
By comparing of the polymerization reaction by boron trifluoride in gas and liquid phases, an optimum process routine and polymerization reaction conditions for LMW highly reactive polyisobutylene were studied. This paper studies key factors for polymerization conversion and polymer MW, establishes empirical relations for MW and reactive temperature as well as monomer and catalyst mass flow ratio and develops a technical routine for boron trifluoride system to prepare Highly Reactive Polyisobutylene.
PetroChemical Jilin Corporation has built the first highly reactive polyisobutylene industrialization plant in China using his self-developed know-hows. Magnified process flow is feasible. Each performance index of the product has reached world level of similar products. Once the product put into markets, it has got much good reputations from the customers. Now market share has got to 90% over. It has filled up technique and product blanks in this field in China. With developing in several years, Highly Reactive Polyisobutylene technique and its product has been improved a lot, but some gaps still exist in process techniques and product quality.
For bottleneck problems revealed in production, they have been optimized and improved technically. Necessary make-up tests have been carried out in order to perfect process technology and risk resistance capacity and product competitiveness of the plant has been improved.
引文
[1]蔡平.高活性聚异丁烯的生产技术概况及其市场前景[J].弹性体.2004,14(3)：72-76.
[2]Prokof'ev Ya., Orlova A., Kopylov E., et al., Study of the Synthesis of high-molecular Polyisobutylene(PIB) in A Medium of Methyl Chloride [J], Promyshlennost Sinteticheskogo Kauchuka.1982,7:5-12.
[3]韩秀山.高活性低分子量聚异丁烯[J].化工生产与技术.2001,8(3)：14-17.
[4]陈娟,张伟.聚异丁烯的应用[J].河北化工,2011,34(8)：57-59,75.
[5]孟玉良.聚异丁烯在高聚物中的应用[J].上海化工.2010,5：33-35.
[6]得克萨斯石化公司聚异丁烯产能翻翻[J].精细石油化工进展.2009,9(1)：56-57.
[7]汉继程,马常胜.聚异丁烯项目调查报告[J].润滑油与燃料.2005,15(73)：9-12,21.
[8]远山.中分子量聚异丁烯的生产与应用[J].精细化工原料及中间体.2008,(1)：7,15.
[9]杨明哲.我国中分子量聚异丁烯产业现状[J].中国胶粘剂.2010,19(3)：63-63.
[10]韩秀山.聚异丁烯国内外市场分析.上海化工.2009,34(11)：32-35.
[11]韩秀山,孙振民,鞠炳仁,等.高活性聚异丁烯发展前景[J].广东橡胶.2009,3：15-16.
[12]管浩,王媛.高活性聚异丁烯的生产技术概况及其市场前景[J].甘肃石油和化工.2011,25(2)：1-5,48.
[13]郭和军,王煊军,刘治中.汽油清净剂聚异丁烯胺类的研究进展[J].精细石油化工2001,(3)：43-45.
[14]韩秀山,许家亮.中分子量聚异丁烯生产现状及发展前景[J].化学工程师.2008,159(12)：38-40.
[15]关颖.聚异丁烯产业发展分析[J].化学工业.2009,27(8)：25-30.
[16]王宏革,崔华,董德,等.聚异丁烯研究进展及其工艺优化[J].弹性体.2007,17(1)：78-83.
[17]张晓君.吉林石化精细化学品厂高活性聚异丁烯打入国际市场[J].弹性体.2007,17(5)：9.
[18]三氟化硼引发体系生产高品质中分子量聚异丁烯通过验收[J].上海化工.2010,(3)：47.
[19]Kennedy J. P., Huang S. Y., Feinberg S. C., Cationic polymeri-zation with boron halides. Ⅲ BCl3 coinitator for olefin poly-merization [J]. J. Polym. Ses. Polym.1997,15: 2801-2819.
[20]拉思H.P..低分子量高活性聚异丁烯的制备[P].CN1187208.1998.
[21]拉思H.P.,堪尼U.,范德克F..低分子量、高反应活性聚异丁烯的制备工艺[P].CN1281473.2001.
[22]奥尔H.,坎内U.,德福斯A..高活性聚异丁烯的生产方法[P].CN1484653.2004.
[23]盛金田.异丁烯的聚合方法[P].CN101386656.2009.
[24]林涛,吴一弦,叶晓林,等.TiCl4共引发异丁烯正离子聚合合成反应活性聚异丁烯[J].高分子学报.2008,(2)：129-135.
[25]关颖,王旭辉.混合C4制备高活性聚异丁烯技术进展[J].化工新型材料.2011,39(7)：14-16,28.
[26]吴一弦,刘刚.高反应活性聚异丁烯的制备方法[P].CN101033275.2007.
[27]吴一弦.一种用于合成高反应活法性聚异丁烯的引发体系[P].CN101613423.2009.
[28]吴一炫,黄强.可控/活性正离子聚合的研究与发展[J].高分子通报.2008,7：35-55.
[29]Volkis, Victoria. LICB11(CH3)12-Catalyzed Radical Polymerization of Isobutylene:Highly Branched Polyisobutylene and an Isobutylene-Ethyl Acrylate Copolymer [J]. Journal of the American Chemical Society.2009,131(9):3132-3133.
[30]李树新,郭文莉,商育伟.四臂星型聚异丁烯的制备及应用[J].石油化工高等学校学报.2005,18(2)：11-14.
[31]韩飞.聚异丁烯(Ⅰ)[J].甘肃石油和化工.2008,1：9-14.
[32]韩飞.聚异丁烯(Ⅲ)[J].甘肃石油和化工.2008.1：12-17.
[33]齐泮仑,西晓丽.高活性聚异丁烯的合成[J].石油炼制与化工.2006,37(3)：19-23.
[34]Magagnini P.L., Cesea S., Giusli P.. Studies on Polyroerizations Initiated Syncataly Compounds [J]. Mahromol. Chem.1977,178:2235-2248.
[35]Ghanem N.A.,Marek M.. The Role and of Water as Co-catalyst in Catiomc Polymenzation [J]. EurPolym.J.1972,8:999-1008.
[36]西晓丽,齐泮仑,王刚,等.高反应活性聚异丁烯的制备方法[P].CN1353122.2002.
[37]吉文苏,崔华.低分子量、高活性聚异丁烯的制备方法[P].CN1412210.2003.
[38]金建浩,姜盟,刘伟明.吉林石化分公司精细化学品厂高活性聚异丁烯装置分析规程.2008.
[39]李鹤春,王桂英,南春模,等.合成聚异丁烯所用的三氟化硼络合物催化剂及其制备方法[P].ZL 02 1 44631.8.2007.
[40]李鹤春.无色聚异丁烯合成鉴定报告.中试聚合研究.1997.
[41]李鹤春,南春模,王桂英.一种聚异丁烯聚合釜[P].ZL 2006 1 0016937.3.2008.
[42]李鹤春,南春模,王桂英.一种聚合釜[P].CN2920389.2007.
[43]李坤,曲亮,郭琳,等.吉林石化分公司精细化学品厂高活性聚异丁烯装置操作规程.2008.
[44]李鹤春,南春模,史春岩.高活性聚异丁烯产业化示范装置高新技术产业科技货款报告.2008.
[45]李鹤春,史春岩.吉林石化分公司精细化学品厂中分子量聚异丁烯工艺优化项目技术报告.2009.
[46]孙英,王宏丽.一万吨／年高活性聚异丁烯可行性研究报告.2008.
[47]金文.聚异丁烯及其下游产品的生产和应用[J].精细化工原料及中间体.2005,5：20-23.
[48]聚异丁烯胺国内外市场调研报告.中国化工信息.2007.
[49]金晶哲,刘立红,郭阳.汽油清净剂的发展历程及现状简述[J].化工科技.2010,18(2)：74-77,84.
[2]Prokof'ev Ya., Orlova A., Kopylov E., et al., Study of the Synthesis of high-molecular Polyisobutylene(PIB) in A Medium of Methyl Chloride [J], Promyshlennost Sinteticheskogo Kauchuka.1982,7:5-12.
[3]韩秀山.高活性低分子量聚异丁烯[J].化工生产与技术.2001,8(3)：14-17.
[4]陈娟,张伟.聚异丁烯的应用[J].河北化工,2011,34(8)：57-59,75.
[5]孟玉良.聚异丁烯在高聚物中的应用[J].上海化工.2010,5：33-35.
[6]得克萨斯石化公司聚异丁烯产能翻翻[J].精细石油化工进展.2009,9(1)：56-57.
[7]汉继程,马常胜.聚异丁烯项目调查报告[J].润滑油与燃料.2005,15(73)：9-12,21.
[8]远山.中分子量聚异丁烯的生产与应用[J].精细化工原料及中间体.2008,(1)：7,15.
[9]杨明哲.我国中分子量聚异丁烯产业现状[J].中国胶粘剂.2010,19(3)：63-63.
[10]韩秀山.聚异丁烯国内外市场分析.上海化工.2009,34(11)：32-35.
[11]韩秀山,孙振民,鞠炳仁,等.高活性聚异丁烯发展前景[J].广东橡胶.2009,3：15-16.
[12]管浩,王媛.高活性聚异丁烯的生产技术概况及其市场前景[J].甘肃石油和化工.2011,25(2)：1-5,48.
[13]郭和军,王煊军,刘治中.汽油清净剂聚异丁烯胺类的研究进展[J].精细石油化工2001,(3)：43-45.
[14]韩秀山,许家亮.中分子量聚异丁烯生产现状及发展前景[J].化学工程师.2008,159(12)：38-40.
[15]关颖.聚异丁烯产业发展分析[J].化学工业.2009,27(8)：25-30.
[16]王宏革,崔华,董德,等.聚异丁烯研究进展及其工艺优化[J].弹性体.2007,17(1)：78-83.
[17]张晓君.吉林石化精细化学品厂高活性聚异丁烯打入国际市场[J].弹性体.2007,17(5)：9.
[18]三氟化硼引发体系生产高品质中分子量聚异丁烯通过验收[J].上海化工.2010,(3)：47.
[19]Kennedy J. P., Huang S. Y., Feinberg S. C., Cationic polymeri-zation with boron halides. Ⅲ BCl3 coinitator for olefin poly-merization [J]. J. Polym. Ses. Polym.1997,15: 2801-2819.
[20]拉思H.P..低分子量高活性聚异丁烯的制备[P].CN1187208.1998.
[21]拉思H.P.,堪尼U.,范德克F..低分子量、高反应活性聚异丁烯的制备工艺[P].CN1281473.2001.
[22]奥尔H.,坎内U.,德福斯A..高活性聚异丁烯的生产方法[P].CN1484653.2004.
[23]盛金田.异丁烯的聚合方法[P].CN101386656.2009.
[24]林涛,吴一弦,叶晓林,等.TiCl4共引发异丁烯正离子聚合合成反应活性聚异丁烯[J].高分子学报.2008,(2)：129-135.
[25]关颖,王旭辉.混合C4制备高活性聚异丁烯技术进展[J].化工新型材料.2011,39(7)：14-16,28.
[26]吴一弦,刘刚.高反应活性聚异丁烯的制备方法[P].CN101033275.2007.
[27]吴一弦.一种用于合成高反应活法性聚异丁烯的引发体系[P].CN101613423.2009.
[28]吴一炫,黄强.可控/活性正离子聚合的研究与发展[J].高分子通报.2008,7：35-55.
[29]Volkis, Victoria. LICB11(CH3)12-Catalyzed Radical Polymerization of Isobutylene:Highly Branched Polyisobutylene and an Isobutylene-Ethyl Acrylate Copolymer [J]. Journal of the American Chemical Society.2009,131(9):3132-3133.
[30]李树新,郭文莉,商育伟.四臂星型聚异丁烯的制备及应用[J].石油化工高等学校学报.2005,18(2)：11-14.
[31]韩飞.聚异丁烯(Ⅰ)[J].甘肃石油和化工.2008,1：9-14.
[32]韩飞.聚异丁烯(Ⅲ)[J].甘肃石油和化工.2008.1：12-17.
[33]齐泮仑,西晓丽.高活性聚异丁烯的合成[J].石油炼制与化工.2006,37(3)：19-23.
[34]Magagnini P.L., Cesea S., Giusli P.. Studies on Polyroerizations Initiated Syncataly Compounds [J]. Mahromol. Chem.1977,178:2235-2248.
[35]Ghanem N.A.,Marek M.. The Role and of Water as Co-catalyst in Catiomc Polymenzation [J]. EurPolym.J.1972,8:999-1008.
[36]西晓丽,齐泮仑,王刚,等.高反应活性聚异丁烯的制备方法[P].CN1353122.2002.
[37]吉文苏,崔华.低分子量、高活性聚异丁烯的制备方法[P].CN1412210.2003.
[38]金建浩,姜盟,刘伟明.吉林石化分公司精细化学品厂高活性聚异丁烯装置分析规程.2008.
[39]李鹤春,王桂英,南春模,等.合成聚异丁烯所用的三氟化硼络合物催化剂及其制备方法[P].ZL 02 1 44631.8.2007.
[40]李鹤春.无色聚异丁烯合成鉴定报告.中试聚合研究.1997.
[41]李鹤春,南春模,王桂英.一种聚异丁烯聚合釜[P].ZL 2006 1 0016937.3.2008.
[42]李鹤春,南春模,王桂英.一种聚合釜[P].CN2920389.2007.
[43]李坤,曲亮,郭琳,等.吉林石化分公司精细化学品厂高活性聚异丁烯装置操作规程.2008.
[44]李鹤春,南春模,史春岩.高活性聚异丁烯产业化示范装置高新技术产业科技货款报告.2008.
[45]李鹤春,史春岩.吉林石化分公司精细化学品厂中分子量聚异丁烯工艺优化项目技术报告.2009.
[46]孙英,王宏丽.一万吨／年高活性聚异丁烯可行性研究报告.2008.
[47]金文.聚异丁烯及其下游产品的生产和应用[J].精细化工原料及中间体.2005,5：20-23.
[48]聚异丁烯胺国内外市场调研报告.中国化工信息.2007.
[49]金晶哲,刘立红,郭阳.汽油清净剂的发展历程及现状简述[J].化工科技.2010,18(2)：74-77,84.