交联聚乙烯的实验研究
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摘要
本文通过硅烷交联和过氧化物交联两种方法实验研究了交联聚乙烯。研究了交联剂对硅烷交联聚乙烯拉伸强度、断裂伸长率及凝胶含量的影响，并比较了不同的硅烷对交联反应的影响。讨论了催化剂、抗氧剂、引发剂对硅烷交联聚乙烯性能的影响，对比了不同催化剂、不同水温对硅烷交联反应速率的影响。对不同交联剂的聚乙烯交联体系进行了对比分析。同时运用HAAKE流变仪对交联聚乙烯的流变性能进行了研究。采用了多种聚乙烯共混技术获得了一种流动性相对较好的共混基料，在此基础上又加入了流变剂进一步改善其流动性。通过大量的流变实验得到了较为满意的结果。介绍了过氧化物交联聚乙烯的工艺、材料用量对交联料性能的影响，探讨了温度对凝胶含量的影响、过氧化物用量对材料力学性能及交联度的影响，以及交联度与材料力学性能的关系，阐述了过氧化物交联反应机理。还对交联聚乙烯的耐油性能、应变应力曲线、硅烷交联反应动力学等进行了讨论，并通过电镜考查了PEX的微观形态。最后在小试的基础上进行了中试和工业化实验，取得了较好的结果，产品的各项性能均达到了国外同类产品的性能指标。并批量生产了硅烷交联聚乙烯材料供给了多家生产企业，生产出的管材拿到国家化学建材测试中心进行测试，各项指标都达到了美国ASTM标准。
In this paper crosslinkable PE is studied by silane crosslinking and peroxide crosslinking . Effects of silane on gel fraction are discussed. And effects of different types silane on crosslinking reaction are compared. Effects of catalyst> antioxdantN evocator on properties of PEX are compared. At the same time the flow behaviour of graft PE is studied by HAAKE rheoriscometer and reaction mechanism of grefting and crosslink are tested and verified. Then the oil resistance^ the strain/stress curve and the microstate are introduced. The kinetics of grafting and crosslinking are studied. The results show that grafting reaction follow first order kinetics with respect to silane concentration, and crosslinking reactions follow first order kinetics with respect to both catalyst and moisture concentration. The manufacturing technology of peroxide crosslinking PE as well as effects of raw materials and their amount on the compound properties are introduced. And the electric behaviour and ageing property of peroxide
crosslinking PE are studied. Lastly, the commercial process of silane crosslinking PE is studied. The suitable process and formula are found. PEX has been mass-produced for many factories. The pipe made by the PEX had been tested by the national testing center of chemical building
materials, every behaviour has come up to American standard ASTM. It can replace the imported PEX.
In this paper crosslinkable PE is studied by silane crosslinking and peroxide crosslinking . Effects of silane on gel fraction are discussed. And effects of different types silane on crosslinking reaction are compared. Effects of catalyst> antioxdantN evocator on properties of PEX are compared. At the same time the flow behaviour of graft PE is studied by HAAKE rheoriscometer and reaction mechanism of grefting and crosslink are tested and verified. Then the oil resistance^ the strain/stress curve and the microstate are introduced. The kinetics of grafting and crosslinking are studied. The results show that grafting reaction follow first order kinetics with respect to silane concentration, and crosslinking reactions follow first order kinetics with respect to both catalyst and moisture concentration. The manufacturing technology of peroxide crosslinking PE as well as effects of raw materials and their amount on the compound properties are introduced. And the electric behaviour and ageing property of peroxide
crosslinking PE are studied. Lastly, the commercial process of silane crosslinking PE is studied. The suitable process and formula are found. PEX has been mass-produced for many factories. The pipe made by the PEX had been tested by the national testing center of chemical building
materials, every behaviour has come up to American standard ASTM. It can replace the imported PEX.
引文
[1] 葛铁军，徐桂秋，郭峰，王志滨．硅烷交联 HDPE 配方的二次回归设计．现代塑料加工应用，1997(6)：13-16
[2] Bernt-Ake Sultan. Plastics. Rubbers and Composites Processing and Applications 21(1994)65-73
[3] Lawton EJ. Bueche A M. Balwit J S. Nature, 1953.172:76.
[4] 马以正，侯海林．交联 PE 绝缘电缆料的性能研究．阻燃材料与技术，1997．(3)；1-4
[5] Greig J M, plastic, Rubber and Composites Processing and Applications, 1994,21;133
[6] RANBY, B. and RABEK, J.F., ESR Spectroscopy in Polymer Research. Springer Verlag, Berlin, 1977, 12; 88-91
[7] FLEMMING, I., Frontier Qrbitals and Organic Chemical Reactions. John Wiley and Sons, London, 1978, 8; 15-19
[8] Becker R C, Electron Beam Processing of Rubber and Plastics, Dynamitron,(30)1980, 121-125
[9] BECKER, R.C., Electier Beam Processing of Rubber and Plastics, Dynamitron, Nov18(1980)57-62.
[10] BERNT-AKE SULTAN, Plastic, Rubber and Composites Processing and Applications 221(1994)65-73
[11] Oster G. J. Polym. Sci., 1956.22:185-187
[12] Oster G, Oster G K, Moroson H. J. Polym. Sci.,1959,34:671
[13] Ranby B, Hilborn J, Chen YL, et al. Polym. Prepr., 1988,29:526
[14] Qu B J, Ranby B.J. Photopolym. Sci. Teehnol., 1989,2:269
[15] Qu B J, Ranby B.J. Appl. Polym. Sci., 1993,48:701
[16] Qu b j, XuYH, Shi W F, et al. Macromolecules, 1992,25:5220.
[17] Qu b j, Qu X Xu YH, Shi W F, et al. Macromolecules, 1997,30:1408
[18] Qu B J, Ranby B.J. Appl. Polym. Sci., 1993,48:711;1993,49:1799
[19] Ranby B. Eur. Patent. 490 854(1992)
[20] 瞿保钧，梁任又，施文芳．中国专利 No.91208158．9(1991)
[21] Zamotaev PV, Litsov. N I, Kachan AA. Polym. Photochem., 1986.7:139
[22] MENGES, G., KIRCHER, K., FRANZKOCH, B. AND HOFFZCKER, W., Vernetzen von polyethylene im UHF-yeld unter miterwendung von UHF-aktiven hilfsstoffen. Kunststoffe, 69(1979)430-4
[23] MENGES, G. and STRAUCH, T., Rohrextrusion-vernetzung von rohren aus polyethylene mittels mikrowellenergie. Plastverarbeiter, 36(1985)126-37
[24] Crosslinking Peroxides and Coagents. Product survey, Brochure by Akzo Chemicals, The Netherlands, Xl.01/10-89.
[25] 黄德骏．交联聚乙烯管的应用及评价方法．现代塑料加工应用[J]，1993，(2)：45-48
[26] Cross LH. Novel[J], 1978, 911):21
[27] 仇武林，方鲲，麦堪成，曾汉民．聚烯烃的硅烷交联技术．高分子材料科学与工程[J]，1998，(4)：136-139
[28] 曹胜先，郝振军，吴林美，张德英．塑料科技[J]，1996，(3)：10-14
[29] 刘秉志．硅烷交联聚乙烯电缆绝缘料的研究．中国塑料[J]，1995，(5)：26-29
[30] 龙文保，吴大鸣，刘颖，徐绍宏．反应挤出硅烷交联热收缩管坯的研究．塑料科技[J]，1996(3)：3-6
[31] 何宏伟 西北工业大学毕业论文[D] 1998
[32] 许晓秋，唐德敏，冯建新，张爽男，杨桦．LLDPE／HDPE共混体系的结晶动力学及力学性能研究．高分子材料科学与工程[J]，1999，(2)：86-89
[33] 蒋涛．材料导报[J]，1998，(4)：53
[34] 葛铁军，徐桂秋，郭峰，王志滨．硅烷交联 HDPE 配方的二次回归设计(续后)．现代塑料加工应用[J]，1997，(3)：13-16
[35] 刘伯元，徐凌秀．硅烷交联聚乙烯，现代塑料加工应用[J]，1997，(4)：57
[36] 苏文艺．聚乙烯熔融接枝硅烷动力学及在线测量技术的应用．塑料科技[J]，1995，(1)：23-28
[37] 龚方红，LDPE交联物结构的研究．高分子材料科学与工程[J]，2000，(2)：140-143
[38] 蒋涛，曾邦禄．硅烷接枝聚乙烯水解交联反应的研究．塑料工业[J]，1996，(1)：56-58
[39] 冯绍华，黄兆革，韩立慧，李兴胜 硅烷交联 LDPE 配方正交设计．塑料[J]，1998，(1)：34-37
[40] 刘震，黄兆革，冯绍华，马玉，孙英侠．硅烷交联聚乙烯的制备及性能．工程塑料应用[J]，2000，(3)：4-6
[41] Peter Suarbrick, Willian John Green U.S. 4117 195.
[42] Jeffrey D. Umpleby. E.P. 207 627
[43] Zamotaev PV,,Luzgarev S V. Die Angew. Makromol. Chem., 1989,173:47
[44] M. narkis polymer engineering and science, September 1985. Vol. 25.NO. 13:857
[45] ACHINTYA Kumar polymer engineering and science NOVER 1989.Vol29. no. 22 5-9
[46] 吕世光．《塑料助剂手册》．轻工业出版社 1998，426
[47] 北京大学数学力学系数学专业概率统计组，《正交设计》人民教育出版社，1976：101-148
[48] 张殿荣，马占兴，杨清芝．现代橡胶配方设计师 化学工业出版社 1994：135-147
[49] 马德柱，何平笙，徐种德等．高聚物的结构和性能．北京：科学出版社，1995：25-28
[50] Mateev M, et al.J of Mater Pro Tech, 1995, 10(3～6): 389
[51] Achintya Kumar sen, Bibha Mukherjee, A.s. Bhattacharyya, P.P. DE. Journal of Applied Polymer Science, Vol. 44, 1153-1164(1992)
[52] H. J. Borchardt and F. Daniels, j. Am. Chem. Soc., 79,41(1957)
[53] B. Thomas and M. Bowrey, Wire J., 88(May 1977)
[2] Bernt-Ake Sultan. Plastics. Rubbers and Composites Processing and Applications 21(1994)65-73
[3] Lawton EJ. Bueche A M. Balwit J S. Nature, 1953.172:76.
[4] 马以正，侯海林．交联 PE 绝缘电缆料的性能研究．阻燃材料与技术，1997．(3)；1-4
[5] Greig J M, plastic, Rubber and Composites Processing and Applications, 1994,21;133
[6] RANBY, B. and RABEK, J.F., ESR Spectroscopy in Polymer Research. Springer Verlag, Berlin, 1977, 12; 88-91
[7] FLEMMING, I., Frontier Qrbitals and Organic Chemical Reactions. John Wiley and Sons, London, 1978, 8; 15-19
[8] Becker R C, Electron Beam Processing of Rubber and Plastics, Dynamitron,(30)1980, 121-125
[9] BECKER, R.C., Electier Beam Processing of Rubber and Plastics, Dynamitron, Nov18(1980)57-62.
[10] BERNT-AKE SULTAN, Plastic, Rubber and Composites Processing and Applications 221(1994)65-73
[11] Oster G. J. Polym. Sci., 1956.22:185-187
[12] Oster G, Oster G K, Moroson H. J. Polym. Sci.,1959,34:671
[13] Ranby B, Hilborn J, Chen YL, et al. Polym. Prepr., 1988,29:526
[14] Qu B J, Ranby B.J. Photopolym. Sci. Teehnol., 1989,2:269
[15] Qu B J, Ranby B.J. Appl. Polym. Sci., 1993,48:701
[16] Qu b j, XuYH, Shi W F, et al. Macromolecules, 1992,25:5220.
[17] Qu b j, Qu X Xu YH, Shi W F, et al. Macromolecules, 1997,30:1408
[18] Qu B J, Ranby B.J. Appl. Polym. Sci., 1993,48:711;1993,49:1799
[19] Ranby B. Eur. Patent. 490 854(1992)
[20] 瞿保钧，梁任又，施文芳．中国专利 No.91208158．9(1991)
[21] Zamotaev PV, Litsov. N I, Kachan AA. Polym. Photochem., 1986.7:139
[22] MENGES, G., KIRCHER, K., FRANZKOCH, B. AND HOFFZCKER, W., Vernetzen von polyethylene im UHF-yeld unter miterwendung von UHF-aktiven hilfsstoffen. Kunststoffe, 69(1979)430-4
[23] MENGES, G. and STRAUCH, T., Rohrextrusion-vernetzung von rohren aus polyethylene mittels mikrowellenergie. Plastverarbeiter, 36(1985)126-37
[24] Crosslinking Peroxides and Coagents. Product survey, Brochure by Akzo Chemicals, The Netherlands, Xl.01/10-89.
[25] 黄德骏．交联聚乙烯管的应用及评价方法．现代塑料加工应用[J]，1993，(2)：45-48
[26] Cross LH. Novel[J], 1978, 911):21
[27] 仇武林，方鲲，麦堪成，曾汉民．聚烯烃的硅烷交联技术．高分子材料科学与工程[J]，1998，(4)：136-139
[28] 曹胜先，郝振军，吴林美，张德英．塑料科技[J]，1996，(3)：10-14
[29] 刘秉志．硅烷交联聚乙烯电缆绝缘料的研究．中国塑料[J]，1995，(5)：26-29
[30] 龙文保，吴大鸣，刘颖，徐绍宏．反应挤出硅烷交联热收缩管坯的研究．塑料科技[J]，1996(3)：3-6
[31] 何宏伟 西北工业大学毕业论文[D] 1998
[32] 许晓秋，唐德敏，冯建新，张爽男，杨桦．LLDPE／HDPE共混体系的结晶动力学及力学性能研究．高分子材料科学与工程[J]，1999，(2)：86-89
[33] 蒋涛．材料导报[J]，1998，(4)：53
[34] 葛铁军，徐桂秋，郭峰，王志滨．硅烷交联 HDPE 配方的二次回归设计(续后)．现代塑料加工应用[J]，1997，(3)：13-16
[35] 刘伯元，徐凌秀．硅烷交联聚乙烯，现代塑料加工应用[J]，1997，(4)：57
[36] 苏文艺．聚乙烯熔融接枝硅烷动力学及在线测量技术的应用．塑料科技[J]，1995，(1)：23-28
[37] 龚方红，LDPE交联物结构的研究．高分子材料科学与工程[J]，2000，(2)：140-143
[38] 蒋涛，曾邦禄．硅烷接枝聚乙烯水解交联反应的研究．塑料工业[J]，1996，(1)：56-58
[39] 冯绍华，黄兆革，韩立慧，李兴胜 硅烷交联 LDPE 配方正交设计．塑料[J]，1998，(1)：34-37
[40] 刘震，黄兆革，冯绍华，马玉，孙英侠．硅烷交联聚乙烯的制备及性能．工程塑料应用[J]，2000，(3)：4-6
[41] Peter Suarbrick, Willian John Green U.S. 4117 195.
[42] Jeffrey D. Umpleby. E.P. 207 627
[43] Zamotaev PV,,Luzgarev S V. Die Angew. Makromol. Chem., 1989,173:47
[44] M. narkis polymer engineering and science, September 1985. Vol. 25.NO. 13:857
[45] ACHINTYA Kumar polymer engineering and science NOVER 1989.Vol29. no. 22 5-9
[46] 吕世光．《塑料助剂手册》．轻工业出版社 1998，426
[47] 北京大学数学力学系数学专业概率统计组，《正交设计》人民教育出版社，1976：101-148
[48] 张殿荣，马占兴，杨清芝．现代橡胶配方设计师 化学工业出版社 1994：135-147
[49] 马德柱，何平笙，徐种德等．高聚物的结构和性能．北京：科学出版社，1995：25-28
[50] Mateev M, et al.J of Mater Pro Tech, 1995, 10(3～6): 389
[51] Achintya Kumar sen, Bibha Mukherjee, A.s. Bhattacharyya, P.P. DE. Journal of Applied Polymer Science, Vol. 44, 1153-1164(1992)
[52] H. J. Borchardt and F. Daniels, j. Am. Chem. Soc., 79,41(1957)
[53] B. Thomas and M. Bowrey, Wire J., 88(May 1977)