无规共聚聚丙烯流延膜专用料的工程化研究
摘要
流延法是利用热塑性材料生产塑料薄膜的方法之一。聚丙烯流延膜(CPP)是塑料工业中一种未拉伸的平模挤出聚丙烯(CPP)薄膜，与聚丙烯双向拉伸薄膜(BOPP)、OPP、吹胀膜(IPP)共同作为聚丙烯包装薄膜的三大品种，广泛应用于食品、纺织品、日用品的包装。
CPP的产品类型主要有金属化(镀铝)型、普通复合型、蒸煮型、特殊用途类等，多采用多层复合共挤方式。多层复合共挤流延膜一般可分为热封层、支撑层，电晕层三层，其中热封层、电晕层采用无规共聚聚丙烯树脂为原料。
本文针对无规共聚聚丙烯流延膜热封层专用料的工业化开发与规模化生产所涉及的多方面因素进行了探讨研究，通过对国内外同类原料进行剖析比较，确定了共聚合工艺中乙烯的加入量、MFR等关键控制指标；对聚丙烯无规共聚工艺进行深入的研究，评价、筛选了适宜的催化剂体系，对影响装置长周期运行的因素进行了摸索，避免因环管易堵所导致的装置停工；并针对专用料添加剂体系结合产品的应用性能要求进行了设计和优化。
通过本文所开展的研究工作，为专用料的工程化开发提供了指导，并成功实现了专用料的工业规模化开发。
Cast is a method of preparing plastic films with thermoplasticmaterials. Cast polypropylene (CPP) film is of a kind of thin film extrudedfrom flat mold in the plastics industry. The PP packing films such asCPP, BOPP, OPP and IPP are widely used in the packings of the food, textileproduct and daily necessity.
The types of CPP products mainly includes plating(aluminum)type, common type, steam to cooking type, special use etc., much adoptionmany layer compound total crowded way, cast film can is divided into heatsealing layer, propup layer, electricity dizzy layer, among them heatsealing layer, electricity dizzy layer adoption random propylene-ethylenecopolymer as raw material.
The factors of industrial development and scaled production of CPPare discussed in this paper. By analyzing and comparing the raw materialsof domestic and overseas, the crucial index such as the dosage of ethylenein copolymerization technics and MFR are confirmed. To polypropylenepolyaddtion to carry on thorough of research, evaluating catalyzersystem, limit factors that affect stable long term safe running of theco-polymerization unit and relevant solutions has been research, avoidbecause of loop reactor easy cause of equip cease work; according to thedemand of cast film combine to appropriation anticipate additive systemto carried on a design with excellent turn.
The industrialization passing the research of this work, the characterparameter and production technics condition are confirmed, and the specialresin was successfully industrializing developed.
CPP的产品类型主要有金属化(镀铝)型、普通复合型、蒸煮型、特殊用途类等，多采用多层复合共挤方式。多层复合共挤流延膜一般可分为热封层、支撑层，电晕层三层，其中热封层、电晕层采用无规共聚聚丙烯树脂为原料。
本文针对无规共聚聚丙烯流延膜热封层专用料的工业化开发与规模化生产所涉及的多方面因素进行了探讨研究，通过对国内外同类原料进行剖析比较，确定了共聚合工艺中乙烯的加入量、MFR等关键控制指标；对聚丙烯无规共聚工艺进行深入的研究，评价、筛选了适宜的催化剂体系，对影响装置长周期运行的因素进行了摸索，避免因环管易堵所导致的装置停工；并针对专用料添加剂体系结合产品的应用性能要求进行了设计和优化。
通过本文所开展的研究工作，为专用料的工程化开发提供了指导，并成功实现了专用料的工业规模化开发。
Cast is a method of preparing plastic films with thermoplasticmaterials. Cast polypropylene (CPP) film is of a kind of thin film extrudedfrom flat mold in the plastics industry. The PP packing films such asCPP, BOPP, OPP and IPP are widely used in the packings of the food, textileproduct and daily necessity.
The types of CPP products mainly includes plating(aluminum)type, common type, steam to cooking type, special use etc., much adoptionmany layer compound total crowded way, cast film can is divided into heatsealing layer, propup layer, electricity dizzy layer, among them heatsealing layer, electricity dizzy layer adoption random propylene-ethylenecopolymer as raw material.
The factors of industrial development and scaled production of CPPare discussed in this paper. By analyzing and comparing the raw materialsof domestic and overseas, the crucial index such as the dosage of ethylenein copolymerization technics and MFR are confirmed. To polypropylenepolyaddtion to carry on thorough of research, evaluating catalyzersystem, limit factors that affect stable long term safe running of theco-polymerization unit and relevant solutions has been research, avoidbecause of loop reactor easy cause of equip cease work; according to thedemand of cast film combine to appropriation anticipate additive systemto carried on a design with excellent turn.
The industrialization passing the research of this work, the characterparameter and production technics condition are confirmed, and the specialresin was successfully industrializing developed.
引文
[1] 张旭之主编．丙烯衍生物工学．北京：化学工业出版社，1995
[2] 关肇基．国内外聚丙烯技术市场概况．塑料加工应用．1996，1
[3] 崔小明．我国聚丙烯生产现状及市场前景分析．中国石油和化工经济分析，2005，(10)，32-37
[4] Galli P., Haylock J. C. Advances in Ziegler-Natta Polymerization-Unique Polyolefin Copolymers, Alloys and Blends Made Directly in the Reactor. Die Makromolekulare Chemie Macromolecular Symposia, 1992, 63, 19-25.
[5] Erik Tornqvist, Langer JR Arthur W, Polymerization catalyst. US3032510 to Exxon Research Engineering Co., 1962.
[6] Catalytic complexes FR2130231 to SOLVAY, 1972.
[7] 黄葆同，沈之荃．烯烃双烯烃配位聚合进展，科学出版社，1998．
[8] Soga K., Shiono T. Ziegler-Natta catalysts for olefin polymerizations. Progress in Polymer Science, 1997, 22 (7), 1503-1546.
[9] Mayr A.; Galli P., Polymerization of olefins GB1286867 to Montedison Spa, Italy, 1972.
[10] Mayr A.; Susa E., Polymerization of olefins GB1292853 to Montedison Spa, Italy, 1972.
[11] Galli P., Barbe P. C., Noristi L. High yield catalysts in olefin polymerization. Die Angewandte Makromolekulare Chemic. 1984, 120, 73-90.
[12] Galli P., Luciani L., Cechin G. Advances in the polymerization of polyolefins with coordination catalysts. Die Angewandte Makromolekulare Chemic. 1981, 94, 63-89.
[13] Xie Yuyu, McAuley K B. Gas phase ethylene polymerization: production processes, polymer properties, and reactor modeling. Industrial & Engineering Chemistry Research, 1994, 33(3): 449-479.
[14] Barbe, P.C.; Cecchin, G.; Noristi, L. Adv. Polym. Sci. 1987, 81, 1～81.
[15] 肖士镜．CS-1型和CS-2型高效催化剂的研制、生产和应用．高分子通报，2005，(4)，95-99
[16] 毛炳权，杨霭春，郑莹，杨菊秀，李珠兰．用于烯烃聚合和共聚合的催化剂体系CN100607lB to化学工业部北京化工研究院 中国石油化工总公司，1989
[17] Mao Bingquan, Yang Aichun, Zheng Ying, Yang Juxiou, Li Zhulan. Catalyst system for use in olefinic polymerization. US4784983 to Beijing Research Institute of Chemical Industry. 1988
[18] Mao Bingquan, Yang Aichun, Zheng Ying, Yang Juxiou, Li Zhulan. Catalyst system for use in olefinic polymerization. US4861847 to Beijing Research Institute of Chemical Industry, China Petrochemical Corp. 1989
[19] 李玉贵．CS-1型聚丙烯高效载体催化剂工业应用试验．合成树脂及塑料，1990，7(4)，9-14
[20] 王一轩．CS-1型高效催化剂在间歇液相本体法聚丙烯装置上的应用．合成树脂及塑料，1991，8(1)，10-13
[21] 周爱武，谢丹．CS-1型高效催化剂应用于液相本体聚丙烯生产过程中几个问题的探讨．石油炼制与化工，1995，26(8)，32-36
[22] 陈涓．CS-1型高效催化剂的试用．炼油设计，1995，25(6)，35-36
[23] 白文玉．CS-1型高效载体催化剂在间歇式液相本体法聚丙烯生产装置上的应用．精细石油化工进展．2002，3(7)，10-12
[24] 钱新华，唐治钫，胡雅芝，李鑫．国产高效催化剂在抚顺乙烯工业的应用．辽宁化工，2001，30(8)．-330-334
[25] 郭晓军．国产N催化剂在环管工艺聚丙烯装置上的应用．金山油化纤，1999，18(4)，14-18
[26] 郭万青，佘贤万，徐浩．丙烯环管聚合催化剂的应用比较．工业催化．1999，7(5)，54-58
[27] 战立秋．HDC聚丙烯球形高效催化剂通过鉴定．合成树脂及塑料，2005，22(4)，66-66
[28] 黄葆同，陈伟．茂金属催化剂及其烯烃聚合物，化学工业出版社，2000．
[29] European Chemical News, April 6, 1992, p27.
[30] European Chemical News, July 13, 1992, p19.
[31] Chemical Week, Sept. 10, 1992, p1.
[32] 洪定一．塑料工业手册 聚烯烃，化学工业出版社，1999．
[33] Zacca J. J.,Debling J.A.,Ray W. H. Reactor residence-time distribution effects on the multistage polymerization of olefins—Ⅰ. Basic Principles and illustrative Examples, Polypropylene. Chemical Engineering Science, 1997,51, 4859-4886.
[34] 王凯，孙建中．工业聚合反应装置，中国石化出版社，1997
[35] Debling J.A., Zacca J. J., and Ray W. H. Reactor residence-time distribution effects on the multistage polymerization of olefins—Ⅲ. Multi-layered products: impact polypropylene, Chemical Engineering Science, 1997, 52 (12), 1969-2001
[36] Debling J.A.,Ray W.H. Heat and Mass Transfer Effects in Multistage Polymerization Processes: Impact Polypropylene, Ind. Eng. Chem. Res. 1995, 34, 3466-3480
[37] Collina G., Dall' occo. T., Galimberti M., Albizzati E., Noristi L. Process for the (Co)polymerization of olefins, WO9611218 to Motell Technology Company BV (the Netherlands), 1996.
[38] Govoni G., Sacchetti M.,Pasquali S. Multistage Process for the (Co)polymerization of olefins, WO9602583 to Motell Technology Company BV (the Netherlands),1996.
[39] Resconi L., Piemontesi F., Galimberti M. Elastomeric copolymers of ethylene with at least one alpha-olefin. US5886123 to Motell Technology Company BV (Italy), 1999.
[40] Spherizone launched. Focus on Catalysts, 2003, (1), 6.
[41] Basell launches Spherizone process for PP. Focus on Catalysts, 2003, (2),5.
[41] Galli P, Luciani L, Cechin G. Advances in the polymerization of polyolefins with coordination catalysts. Die Angewandte Makromolekulare Chemie. 1981,94, 63-89.
[42] Hutchinson R. A, Ray W. H. Polymerization of olefins through heterogeneous catalysis Ⅷ: Monomer sorption effects. Journal of Applied Polymer Science, 1990, 41 (1-2),51-81
[43] Operation manual. Himont 公司(内部资料)
[44] 钱伯章．中国PP膜市场谁领风骚．中国化工报．2006年．6月．30日．第007版
[45] 祖国红．我国流延聚丙烯薄膜的现状及发展前景[J]．塑料加工应用，2000，22(1)：44．
[46] 于庆顺等．聚丙烯流延膜的加工与应用．工程塑料应用2002年，第30卷，27
[47] CPP薄膜的分类．第19卷 第4期2001年8月．石化技术与应用
[48] Andrew W C. et al. The efects of crystallisation in polypropylene film casting. British Plastics & Rubber. 1 994(1): 4
[49] 孙彤彤．我国流延聚丙烯薄膜的生产和发展趋势．中国包装工业，2000，68(2)
[50] 邱丽萍．包装薄膜材料的开发与创新 中国包装工业2000 57(9)：32。
[51] 郭玉海等．电晕放电处理．中国塑料．1999，13(9)：58
[52] 陈杰．多层共挤复合膜的生产与应用[J]．合成树脂及塑料，1996，13(2)：45．
[53] 欧洲市场上透气膜生产的领航者．纺织导报．2000 6：46
[54] 赵幸，胡声威，周澜．CPP薄膜及专用料的生产发展[J]．塑料加工，2000，28(1)：20．
[55] 唐伟家．流延聚丙烯薄膜[J]．塑料加工应用，2000，22(3)：55．
[56] 吴培熙，王祖玉等著．塑料制品生产工业手册北京：化学工业出版社，1998．5
[2] 关肇基．国内外聚丙烯技术市场概况．塑料加工应用．1996，1
[3] 崔小明．我国聚丙烯生产现状及市场前景分析．中国石油和化工经济分析，2005，(10)，32-37
[4] Galli P., Haylock J. C. Advances in Ziegler-Natta Polymerization-Unique Polyolefin Copolymers, Alloys and Blends Made Directly in the Reactor. Die Makromolekulare Chemie Macromolecular Symposia, 1992, 63, 19-25.
[5] Erik Tornqvist, Langer JR Arthur W, Polymerization catalyst. US3032510 to Exxon Research Engineering Co., 1962.
[6] Catalytic complexes FR2130231 to SOLVAY, 1972.
[7] 黄葆同，沈之荃．烯烃双烯烃配位聚合进展，科学出版社，1998．
[8] Soga K., Shiono T. Ziegler-Natta catalysts for olefin polymerizations. Progress in Polymer Science, 1997, 22 (7), 1503-1546.
[9] Mayr A.; Galli P., Polymerization of olefins GB1286867 to Montedison Spa, Italy, 1972.
[10] Mayr A.; Susa E., Polymerization of olefins GB1292853 to Montedison Spa, Italy, 1972.
[11] Galli P., Barbe P. C., Noristi L. High yield catalysts in olefin polymerization. Die Angewandte Makromolekulare Chemic. 1984, 120, 73-90.
[12] Galli P., Luciani L., Cechin G. Advances in the polymerization of polyolefins with coordination catalysts. Die Angewandte Makromolekulare Chemic. 1981, 94, 63-89.
[13] Xie Yuyu, McAuley K B. Gas phase ethylene polymerization: production processes, polymer properties, and reactor modeling. Industrial & Engineering Chemistry Research, 1994, 33(3): 449-479.
[14] Barbe, P.C.; Cecchin, G.; Noristi, L. Adv. Polym. Sci. 1987, 81, 1～81.
[15] 肖士镜．CS-1型和CS-2型高效催化剂的研制、生产和应用．高分子通报，2005，(4)，95-99
[16] 毛炳权，杨霭春，郑莹，杨菊秀，李珠兰．用于烯烃聚合和共聚合的催化剂体系CN100607lB to化学工业部北京化工研究院 中国石油化工总公司，1989
[17] Mao Bingquan, Yang Aichun, Zheng Ying, Yang Juxiou, Li Zhulan. Catalyst system for use in olefinic polymerization. US4784983 to Beijing Research Institute of Chemical Industry. 1988
[18] Mao Bingquan, Yang Aichun, Zheng Ying, Yang Juxiou, Li Zhulan. Catalyst system for use in olefinic polymerization. US4861847 to Beijing Research Institute of Chemical Industry, China Petrochemical Corp. 1989
[19] 李玉贵．CS-1型聚丙烯高效载体催化剂工业应用试验．合成树脂及塑料，1990，7(4)，9-14
[20] 王一轩．CS-1型高效催化剂在间歇液相本体法聚丙烯装置上的应用．合成树脂及塑料，1991，8(1)，10-13
[21] 周爱武，谢丹．CS-1型高效催化剂应用于液相本体聚丙烯生产过程中几个问题的探讨．石油炼制与化工，1995，26(8)，32-36
[22] 陈涓．CS-1型高效催化剂的试用．炼油设计，1995，25(6)，35-36
[23] 白文玉．CS-1型高效载体催化剂在间歇式液相本体法聚丙烯生产装置上的应用．精细石油化工进展．2002，3(7)，10-12
[24] 钱新华，唐治钫，胡雅芝，李鑫．国产高效催化剂在抚顺乙烯工业的应用．辽宁化工，2001，30(8)．-330-334
[25] 郭晓军．国产N催化剂在环管工艺聚丙烯装置上的应用．金山油化纤，1999，18(4)，14-18
[26] 郭万青，佘贤万，徐浩．丙烯环管聚合催化剂的应用比较．工业催化．1999，7(5)，54-58
[27] 战立秋．HDC聚丙烯球形高效催化剂通过鉴定．合成树脂及塑料，2005，22(4)，66-66
[28] 黄葆同，陈伟．茂金属催化剂及其烯烃聚合物，化学工业出版社，2000．
[29] European Chemical News, April 6, 1992, p27.
[30] European Chemical News, July 13, 1992, p19.
[31] Chemical Week, Sept. 10, 1992, p1.
[32] 洪定一．塑料工业手册 聚烯烃，化学工业出版社，1999．
[33] Zacca J. J.,Debling J.A.,Ray W. H. Reactor residence-time distribution effects on the multistage polymerization of olefins—Ⅰ. Basic Principles and illustrative Examples, Polypropylene. Chemical Engineering Science, 1997,51, 4859-4886.
[34] 王凯，孙建中．工业聚合反应装置，中国石化出版社，1997
[35] Debling J.A., Zacca J. J., and Ray W. H. Reactor residence-time distribution effects on the multistage polymerization of olefins—Ⅲ. Multi-layered products: impact polypropylene, Chemical Engineering Science, 1997, 52 (12), 1969-2001
[36] Debling J.A.,Ray W.H. Heat and Mass Transfer Effects in Multistage Polymerization Processes: Impact Polypropylene, Ind. Eng. Chem. Res. 1995, 34, 3466-3480
[37] Collina G., Dall' occo. T., Galimberti M., Albizzati E., Noristi L. Process for the (Co)polymerization of olefins, WO9611218 to Motell Technology Company BV (the Netherlands), 1996.
[38] Govoni G., Sacchetti M.,Pasquali S. Multistage Process for the (Co)polymerization of olefins, WO9602583 to Motell Technology Company BV (the Netherlands),1996.
[39] Resconi L., Piemontesi F., Galimberti M. Elastomeric copolymers of ethylene with at least one alpha-olefin. US5886123 to Motell Technology Company BV (Italy), 1999.
[40] Spherizone launched. Focus on Catalysts, 2003, (1), 6.
[41] Basell launches Spherizone process for PP. Focus on Catalysts, 2003, (2),5.
[41] Galli P, Luciani L, Cechin G. Advances in the polymerization of polyolefins with coordination catalysts. Die Angewandte Makromolekulare Chemie. 1981,94, 63-89.
[42] Hutchinson R. A, Ray W. H. Polymerization of olefins through heterogeneous catalysis Ⅷ: Monomer sorption effects. Journal of Applied Polymer Science, 1990, 41 (1-2),51-81
[43] Operation manual. Himont 公司(内部资料)
[44] 钱伯章．中国PP膜市场谁领风骚．中国化工报．2006年．6月．30日．第007版
[45] 祖国红．我国流延聚丙烯薄膜的现状及发展前景[J]．塑料加工应用，2000，22(1)：44．
[46] 于庆顺等．聚丙烯流延膜的加工与应用．工程塑料应用2002年，第30卷，27
[47] CPP薄膜的分类．第19卷 第4期2001年8月．石化技术与应用
[48] Andrew W C. et al. The efects of crystallisation in polypropylene film casting. British Plastics & Rubber. 1 994(1): 4
[49] 孙彤彤．我国流延聚丙烯薄膜的生产和发展趋势．中国包装工业，2000，68(2)
[50] 邱丽萍．包装薄膜材料的开发与创新 中国包装工业2000 57(9)：32。
[51] 郭玉海等．电晕放电处理．中国塑料．1999，13(9)：58
[52] 陈杰．多层共挤复合膜的生产与应用[J]．合成树脂及塑料，1996，13(2)：45．
[53] 欧洲市场上透气膜生产的领航者．纺织导报．2000 6：46
[54] 赵幸，胡声威，周澜．CPP薄膜及专用料的生产发展[J]．塑料加工，2000，28(1)：20．
[55] 唐伟家．流延聚丙烯薄膜[J]．塑料加工应用，2000，22(3)：55．
[56] 吴培熙，王祖玉等著．塑料制品生产工业手册北京：化学工业出版社，1998．5
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