茂金属聚乙烯的结构与性能研究
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摘要
本论文以六种茂金属聚乙烯和LDPE、LLDPE、HDPE三种传统聚乙烯树脂作为研究对象，借助GPC、FTIR、WAXD、DSC、ARES、密度梯度仪以及万能试验机等现代化测试手段，系统研究了茂金属聚乙烯的结构与性能，同时对于茂金属聚乙烯的加工应用也作了初步探索。
通过对茂金属聚乙烯和传统聚乙烯的分子链结构(分子量及其分布、相对支化度)、结晶结构、力学性能以及流变性能的深入研究，发现茂金属聚乙烯结构规整，分子量分布窄，这一方面使茂金属聚乙烯的力学性能明显优于传统聚乙烯，另一方面亦使其加工性能远不如传统聚乙烯，其中mPE-5的加工性能较差，而mPE-3由于分子中引入部分长支链结构，使其剪切粘度对频率和温度的敏感性得到显著提高，故其加工性能较好；另外，通过将茂金属聚乙烯与传统低密度聚乙烯共混吹膜实验，发现少量低密度聚乙烯的掺入，不仅能够在一定程度上改善茂金属聚乙烯的加工性能，而且所得薄膜力学性能亦较好。这些结果对于茂金属聚乙烯的分子设计和应用研究提供了重要的基础数据。
The Structure and properties of six metallocene polyethylenes and three traditional polyethylenes were studied by means of GPC, FTIR, WAXD, DSC, ARES, density and tensile tests respectively, while the processing application of metallocene polyethylenes was also investigated primarily.Based on the intensive study of chain structure ( molecular weight and its distribution, branching degree, etc. ), crystalline structure, mechanical properties and rheological properties of polyethylenes, it was found that the uniform structure and narrow molecular weight contribute a lot to the excellent mechanical properties and the poor processibility of metallocene polyethylenes. Among the six metallocene polyethylenes, mPE-5 exhibit poor processibility, while the melt viscosity of mPE-3 was sensitive to both frequence and temperature, which primarily due to the introduction of long chain branches ( LCBs ) to its main chain and do good to its processibility. By addition, the processibility of metallocene polyethylenes could be improved through blending them with a little part of traditional LDPE, and the mechanical properties of result films were also well. All the above results would provide important database to the molecular design and application study of metallocene polyethylenes.
通过对茂金属聚乙烯和传统聚乙烯的分子链结构(分子量及其分布、相对支化度)、结晶结构、力学性能以及流变性能的深入研究，发现茂金属聚乙烯结构规整，分子量分布窄，这一方面使茂金属聚乙烯的力学性能明显优于传统聚乙烯，另一方面亦使其加工性能远不如传统聚乙烯，其中mPE-5的加工性能较差，而mPE-3由于分子中引入部分长支链结构，使其剪切粘度对频率和温度的敏感性得到显著提高，故其加工性能较好；另外，通过将茂金属聚乙烯与传统低密度聚乙烯共混吹膜实验，发现少量低密度聚乙烯的掺入，不仅能够在一定程度上改善茂金属聚乙烯的加工性能，而且所得薄膜力学性能亦较好。这些结果对于茂金属聚乙烯的分子设计和应用研究提供了重要的基础数据。
The Structure and properties of six metallocene polyethylenes and three traditional polyethylenes were studied by means of GPC, FTIR, WAXD, DSC, ARES, density and tensile tests respectively, while the processing application of metallocene polyethylenes was also investigated primarily.Based on the intensive study of chain structure ( molecular weight and its distribution, branching degree, etc. ), crystalline structure, mechanical properties and rheological properties of polyethylenes, it was found that the uniform structure and narrow molecular weight contribute a lot to the excellent mechanical properties and the poor processibility of metallocene polyethylenes. Among the six metallocene polyethylenes, mPE-5 exhibit poor processibility, while the melt viscosity of mPE-3 was sensitive to both frequence and temperature, which primarily due to the introduction of long chain branches ( LCBs ) to its main chain and do good to its processibility. By addition, the processibility of metallocene polyethylenes could be improved through blending them with a little part of traditional LDPE, and the mechanical properties of result films were also well. All the above results would provide important database to the molecular design and application study of metallocene polyethylenes.
引文
[1]. Sinn H, Kaminsky W. Adv Orgnnoment Chem, 1980, 18:990
[2]. F Garbassi, et al. Polymer Nwes, 1994, 19 (12): 367
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[8]．王海华，萧维，王峻沂，烯烃聚合反应茂金属催化剂的进展，合成树脂及塑料，1997：14(3)：5-9
[9]．陈伟，景振华，金属茂催化剂及其聚烯烃的研究发展，高分子通报，1997；35：54-58
[10] Ewen JA, et al, J Am Chem Soc, 1998; 110:6255
[11] Pasgola, et al, Macromol Chen, 1990:191:2387
[12] Kaminsky W, et al, Polym Int , 1993: 28:251
[13] Sago K, et al , Macromolecules , 1994:27:7938
[14] Cly de F, Payn, Opening Remarks, Metcon'95, 1995: Houston
[15] 唐伟家，茂金属聚乙烯工业化前景及市场预测，石油化工动态，2000；8(1)：45-49
[16] K. W. Swogger, Enhanced Polythylene llising Insite Process Technology, Metcon'96, Houston, June 12-13
[17] Hsieh ET, TsoCC, Byers JD et al, J Macromole Sci Phys, 1997:B36:615
[18] Kskugo M, Miyatake T, Mizumumn K, Macromolecules, 1991:24:1469
[19] 徐君庭，范志强，王齐，封麟先，均相催化剂制备的乙丙共聚物的组成均相性研究，高分子学报，1997；(5)：624-628
[20] 吕立新，用茂金属催化剂进行烯烃聚合进展近况，化工科技动态，1995；112：21-23
[21] 邹盛欧，茂金属聚乙烯开发近况，化工新型材料，1997；(5)：3-7
[22] 关肇基，姜斌，国外聚乙烯开发近况，化工新型材料，1997：13(1)：1-6
[23] Anon, Plastics Technology, 1995:41(2):74
[24] 陈伟，郑刚，孙春燕等，茂金属催化剂淤浆法聚乙烯中试评价，石油化工，1999；28(7)：455-459
[25] 王立，袁幼菱，潘杰，叶朝阳，封麟先，茂金属双峰聚乙烯的研究进展，合成树脂及塑料，1999；16(6)：37-40
[26] 陈伟，景振华，王涛，茂金属加合物催化剂及其聚乙烯的研究开发，合成树脂及塑料，1998：15(2)：6-10
[27] 邹筑华，国外单反应器生产双峰HDPE的工艺技术，合成树脂及塑料，1999；16(5)：45-47
[28] Marigo A, Zannetti R, Milani F, Eur Polym J, 1997:33(5):595
[29] Miri VG, Elkoun S, Deguela R, Polym Eng Sci, 1997:37(10):1672
[30] Blum HR, Metcon'97 Worldwide Metallocene Conference, Houston, USA,1997
[31] Wilfong DL, Knight G W , J Polym Sci Polym Phys, 1990:28:861
[32] Bassett DC Principle of Polymer Morphology, Cambridge University Press, New York: 1981
[33] Defoor F, Groeninckx G, Reynaers H et al, J Appl Polym Sci, 1993:47:1839
[34] Ueda M, Register R A. J Macromol Sci Phys, 1996:B35 (1):23
[35] Lww S Y, J hoJ Y, LeeYC. Polym Mater Sci Eng, 1997:76:325
[36] Brianl Turtle. Advances in Innovoene With Insite Technology, Metallocene Technology '97 Conference, Chicago:1997
[37] Wheeler A A. Metallecenes in Blown films: A Machine Manufacturer's Perspective, Met Con'96, Houston:1996
[38] 张宏炎，茂金属催化剂的应用开发，石油炼制与化工，1998；29(8)：54-57
[39] Polymer Hmldbook
[40] 沈德言，红外光谱法在高分子研究中的应用，科学出版社，1982；169
[41] 金日光，华幼卿，高分子物理(第三版)；化学工业出版社，2000
[42] Antonio Marigo, Roberto Zannetti and Federico Milani. Eur. Polym. J,1997:33 (5):595
[43] 刘彦昌，分子量分布对聚乙烯的影响及控制方法，合成树脂及塑料，1999；16(6)：31-33
[44] 马德柱，何平笙等，高聚物的结构与性能，科学出版社，2000，第二版
[45] 何曼君，陈维孝，董西侠，高分子物理，复旦大学出版社，1990．10．12
[46] D．w．范克雷维伦著[荷兰]，聚合物的性质(性质的估算及其与化学结构的关系)，科学出版社，1981
[47] 徐旭荣，徐君庭，封麟先，石油化工，1999；28：784-788
[48] Adriane G Simanke etc, Influence of the comonomer content on the thermal and dynamic mechanical properties of metallocene ethylene/1-octene copolymers: Polymers 40 (1999):5489-5495.
[49] J. J. Janimak, G. C'. Stevens, Polymer, 2000: 41:4233
[50] 傅强，杜荣昵，和天白，茂金属聚乙烯的支化非均匀性与结晶形态，高分子学报，2000；2：142-146
[51] 曾继军，李育英，何嘉松，茂金属聚乙烯的非等温结晶动力学，高分子学报，1996(6)，N03：280-285
[52] T. Ozawa, Polymer, 1971: 12:150
[53] PAK RANA, KYUCHEOL CHO, et al. Journal of Applied Polymer Science , 1999: Vol. 74:1169
[54] 祝景云，丁艳芬，刘芳，周春蓉，mLLDPE及mLLDPE／LDPE共混物挤出加工性能的研究，中国塑料，2000；14(2)：34-37
[55] N. KUKALEVA, M. JOLLANDS, F. CSER, E. KOSIOR. Joumal of Applied Polymer Science, 2000: Vol. 76:1011-1018
[56] D. Yan, W. J. Wang, S. Zhu: Polymer, 1999:40:1737-1744
[57] 曾继军，李育英，何嘉松，茂金属聚乙烯的流变性与加工性，高分子学报，2000；1：69-73
[58] 廖家志，陈伟，许歆，茂金属PE LH-113的纺丝流变行为，合成树脂及塑料，1999；16(1)：39-41
[59] Adriane G. Simanke, Griselda B. Galland, Liane Freitas, et al. Polymer,1999:40:5489-5495
[60] P. Starck, P. Lehmus, and J.V. Soppala, Polymer Engineering and Science, 1999. 8: 39(1):1444-1455
[61] P . RANA , C. H. LEE, K. CHO , B. H. LEE, S. CHOE. Journal of Applied Polymer Science , 1998: 69:2441-2450
[62] MASAYUKI YAMAGUCHI , SHIGEHIKO ABE . Journal of Applied Polymer Science ,1999: 74:3160-3164
[2]. F Garbassi, et al. Polymer Nwes, 1994, 19 (12): 367
[3]. Michacl P, et al. Plastics Engineering, 1997, 53 (5): 25
[4]．于德禧，李蕴能，李兰，孟丽萍，茂金属聚合物进展，中国塑料，2000；14(2)：12-17
[5]．陈杰 金属茂聚乙烯的发展及我们的对策，现代塑料加工应用，1996；8(5)：55-58
[6]．崔春明，陈伟，景振华，金属茂催化剂的结构和催化活性，石油炼制与加工，1996：27(2)：28-32
[7]．王金梅，吕兵，洪晓宇，景振华，乙烯二聚共聚双功能均相催化体系的研究，石油炼制与加工，1995；26(12)：26-28
[8]．王海华，萧维，王峻沂，烯烃聚合反应茂金属催化剂的进展，合成树脂及塑料，1997：14(3)：5-9
[9]．陈伟，景振华，金属茂催化剂及其聚烯烃的研究发展，高分子通报，1997；35：54-58
[10] Ewen JA, et al, J Am Chem Soc, 1998; 110:6255
[11] Pasgola, et al, Macromol Chen, 1990:191:2387
[12] Kaminsky W, et al, Polym Int , 1993: 28:251
[13] Sago K, et al , Macromolecules , 1994:27:7938
[14] Cly de F, Payn, Opening Remarks, Metcon'95, 1995: Houston
[15] 唐伟家，茂金属聚乙烯工业化前景及市场预测，石油化工动态，2000；8(1)：45-49
[16] K. W. Swogger, Enhanced Polythylene llising Insite Process Technology, Metcon'96, Houston, June 12-13
[17] Hsieh ET, TsoCC, Byers JD et al, J Macromole Sci Phys, 1997:B36:615
[18] Kskugo M, Miyatake T, Mizumumn K, Macromolecules, 1991:24:1469
[19] 徐君庭，范志强，王齐，封麟先，均相催化剂制备的乙丙共聚物的组成均相性研究，高分子学报，1997；(5)：624-628
[20] 吕立新，用茂金属催化剂进行烯烃聚合进展近况，化工科技动态，1995；112：21-23
[21] 邹盛欧，茂金属聚乙烯开发近况，化工新型材料，1997；(5)：3-7
[22] 关肇基，姜斌，国外聚乙烯开发近况，化工新型材料，1997：13(1)：1-6
[23] Anon, Plastics Technology, 1995:41(2):74
[24] 陈伟，郑刚，孙春燕等，茂金属催化剂淤浆法聚乙烯中试评价，石油化工，1999；28(7)：455-459
[25] 王立，袁幼菱，潘杰，叶朝阳，封麟先，茂金属双峰聚乙烯的研究进展，合成树脂及塑料，1999；16(6)：37-40
[26] 陈伟，景振华，王涛，茂金属加合物催化剂及其聚乙烯的研究开发，合成树脂及塑料，1998：15(2)：6-10
[27] 邹筑华，国外单反应器生产双峰HDPE的工艺技术，合成树脂及塑料，1999；16(5)：45-47
[28] Marigo A, Zannetti R, Milani F, Eur Polym J, 1997:33(5):595
[29] Miri VG, Elkoun S, Deguela R, Polym Eng Sci, 1997:37(10):1672
[30] Blum HR, Metcon'97 Worldwide Metallocene Conference, Houston, USA,1997
[31] Wilfong DL, Knight G W , J Polym Sci Polym Phys, 1990:28:861
[32] Bassett DC Principle of Polymer Morphology, Cambridge University Press, New York: 1981
[33] Defoor F, Groeninckx G, Reynaers H et al, J Appl Polym Sci, 1993:47:1839
[34] Ueda M, Register R A. J Macromol Sci Phys, 1996:B35 (1):23
[35] Lww S Y, J hoJ Y, LeeYC. Polym Mater Sci Eng, 1997:76:325
[36] Brianl Turtle. Advances in Innovoene With Insite Technology, Metallocene Technology '97 Conference, Chicago:1997
[37] Wheeler A A. Metallecenes in Blown films: A Machine Manufacturer's Perspective, Met Con'96, Houston:1996
[38] 张宏炎，茂金属催化剂的应用开发，石油炼制与化工，1998；29(8)：54-57
[39] Polymer Hmldbook
[40] 沈德言，红外光谱法在高分子研究中的应用，科学出版社，1982；169
[41] 金日光，华幼卿，高分子物理(第三版)；化学工业出版社，2000
[42] Antonio Marigo, Roberto Zannetti and Federico Milani. Eur. Polym. J,1997:33 (5):595
[43] 刘彦昌，分子量分布对聚乙烯的影响及控制方法，合成树脂及塑料，1999；16(6)：31-33
[44] 马德柱，何平笙等，高聚物的结构与性能，科学出版社，2000，第二版
[45] 何曼君，陈维孝，董西侠，高分子物理，复旦大学出版社，1990．10．12
[46] D．w．范克雷维伦著[荷兰]，聚合物的性质(性质的估算及其与化学结构的关系)，科学出版社，1981
[47] 徐旭荣，徐君庭，封麟先，石油化工，1999；28：784-788
[48] Adriane G Simanke etc, Influence of the comonomer content on the thermal and dynamic mechanical properties of metallocene ethylene/1-octene copolymers: Polymers 40 (1999):5489-5495.
[49] J. J. Janimak, G. C'. Stevens, Polymer, 2000: 41:4233
[50] 傅强，杜荣昵，和天白，茂金属聚乙烯的支化非均匀性与结晶形态，高分子学报，2000；2：142-146
[51] 曾继军，李育英，何嘉松，茂金属聚乙烯的非等温结晶动力学，高分子学报，1996(6)，N03：280-285
[52] T. Ozawa, Polymer, 1971: 12:150
[53] PAK RANA, KYUCHEOL CHO, et al. Journal of Applied Polymer Science , 1999: Vol. 74:1169
[54] 祝景云，丁艳芬，刘芳，周春蓉，mLLDPE及mLLDPE／LDPE共混物挤出加工性能的研究，中国塑料，2000；14(2)：34-37
[55] N. KUKALEVA, M. JOLLANDS, F. CSER, E. KOSIOR. Joumal of Applied Polymer Science, 2000: Vol. 76:1011-1018
[56] D. Yan, W. J. Wang, S. Zhu: Polymer, 1999:40:1737-1744
[57] 曾继军，李育英，何嘉松，茂金属聚乙烯的流变性与加工性，高分子学报，2000；1：69-73
[58] 廖家志，陈伟，许歆，茂金属PE LH-113的纺丝流变行为，合成树脂及塑料，1999；16(1)：39-41
[59] Adriane G. Simanke, Griselda B. Galland, Liane Freitas, et al. Polymer,1999:40:5489-5495
[60] P. Starck, P. Lehmus, and J.V. Soppala, Polymer Engineering and Science, 1999. 8: 39(1):1444-1455
[61] P . RANA , C. H. LEE, K. CHO , B. H. LEE, S. CHOE. Journal of Applied Polymer Science , 1998: 69:2441-2450
[62] MASAYUKI YAMAGUCHI , SHIGEHIKO ABE . Journal of Applied Polymer Science ,1999: 74:3160-3164