固相力化学方法制备聚合物微粉及其对硅橡胶的补强作用
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摘要
本文利用磨盘形力化学反应器常温粉碎聚碳酸酯(PC)、聚醚醚酮(PEEK)和废旧轮胎橡胶，制备聚合物超细微粉和力化学活化胶粉。通过GPC、DSC、WXRD等方法研究了非晶聚合物PC、结晶聚合物PEEK在剪切、挤压等三维应力场下的力化学变化和微观结构变化。根据二甲苯抽提精细轮胎胶粉的可溶物含量变化，研究了废旧轮胎胶粉在磨盘碾磨过程中的力化学脱硫和力化学降解现象。用碾磨制备的PC超细微粉填充硅橡胶以部分代替白炭黑，考察PC超细微粉／气相白炭黑对硅橡胶的杂化增强效果。利用精细活化胶粉填充硅橡胶，研究了活化胶粉对硅橡胶的补强机理。
非晶聚合物PC在磨盘碾磨过程中发生轻微力化学降解，分子量降低，分子量分布变窄，碾磨20遍后PC数均分子量仅降低1500左右。磨盘碾磨还可能造成PC自由体积增加。PC玻璃化转变温度随碾磨时间增加持续降低，碾磨20遍后，其玻璃化转变温度降低了5℃。
结晶聚合物PEEK在剪切、挤压等三维应力场下不但发生力化学降解，而且部分晶体遭到破坏发生无定形转变，碾磨前其结晶度为46.19％，碾磨50遍后其结晶度降到35.69％。经磨盘碾磨后，PEEK的熔融焓减小但熔融峰值温度略有升高，可能是在应力场作用下PEEK晶体中结晶不完善的次片晶相更容易遭到破坏。
在硅橡胶常规补强体系中引入PC超细微粉以部分代替白炭黑，PC超细微粉／气相白炭黑杂化对硅橡胶具有杂化增强作用，能在一定程
Polycarbonate (PC), Poly (ether ether ketone) (PEEK) micron-sized powders and mechanochemically activated waste tire powder (WTP) were prepared through pan-type milling equipment at ambient temperature. Stress-induced mechanochemical change and microstructure change of PC and PEEK were studied using GPC, DSC, and WXRD etc. Mechanochemical devulcanization and degradation of waste tire rubber were analyzed, based on the increase in the content of the soluble or sol components extracted by xylene. PC powder were introduced into silicone rubber matrix as a filler to replace part of fumed silica, and the mechanical properties and thermal stability of the resultant composite were studied. The reinforcement of WTP in silicone rubber was also studied.
PC experienced slight mechanochemical degradation caused by pan-milling, resulting in decrease in molecular weight and down-narrowing of molecular weight distribution. Long milling time possibly increased the free volume, which was attributed to chain-end defects resulting from scission of macromolecular chain. Pan milling caused decrease in glass transition temperature.
PEEK, during pan milling, experienced not only mechanochemical degradation, but also amorphorization of crystallite due to collapse of crystal structure. Crystallinity of PEEK dropped sharply from 46.19% before milling to 35.69% after
非晶聚合物PC在磨盘碾磨过程中发生轻微力化学降解，分子量降低，分子量分布变窄，碾磨20遍后PC数均分子量仅降低1500左右。磨盘碾磨还可能造成PC自由体积增加。PC玻璃化转变温度随碾磨时间增加持续降低，碾磨20遍后，其玻璃化转变温度降低了5℃。
结晶聚合物PEEK在剪切、挤压等三维应力场下不但发生力化学降解，而且部分晶体遭到破坏发生无定形转变，碾磨前其结晶度为46.19％，碾磨50遍后其结晶度降到35.69％。经磨盘碾磨后，PEEK的熔融焓减小但熔融峰值温度略有升高，可能是在应力场作用下PEEK晶体中结晶不完善的次片晶相更容易遭到破坏。
在硅橡胶常规补强体系中引入PC超细微粉以部分代替白炭黑，PC超细微粉／气相白炭黑杂化对硅橡胶具有杂化增强作用，能在一定程
Polycarbonate (PC), Poly (ether ether ketone) (PEEK) micron-sized powders and mechanochemically activated waste tire powder (WTP) were prepared through pan-type milling equipment at ambient temperature. Stress-induced mechanochemical change and microstructure change of PC and PEEK were studied using GPC, DSC, and WXRD etc. Mechanochemical devulcanization and degradation of waste tire rubber were analyzed, based on the increase in the content of the soluble or sol components extracted by xylene. PC powder were introduced into silicone rubber matrix as a filler to replace part of fumed silica, and the mechanical properties and thermal stability of the resultant composite were studied. The reinforcement of WTP in silicone rubber was also studied.
PC experienced slight mechanochemical degradation caused by pan-milling, resulting in decrease in molecular weight and down-narrowing of molecular weight distribution. Long milling time possibly increased the free volume, which was attributed to chain-end defects resulting from scission of macromolecular chain. Pan milling caused decrease in glass transition temperature.
PEEK, during pan milling, experienced not only mechanochemical degradation, but also amorphorization of crystallite due to collapse of crystal structure. Crystallinity of PEEK dropped sharply from 46.19% before milling to 35.69% after
引文
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2．姜宏，大有作为的有机硅产业，今日科技，2003，4：40
3．郭守学，橡胶工业1998，(3)：183-190
4．刘爱堂编译，硅橡胶的最新进展，2006，36(1)：10-13
5．周宇琳编著，有机硅聚合物导论，科学出版社，2000，114-116
6．幸松民等编著，有机硅合成工艺及产品应用，化学工业出版社，2000，604
7．朱玉俊编著，弹性体的力学改性—填充补强及共混，北京科学技术出版社，1992，
8．柯扬船，(美)皮特·斯壮主编，聚合物—无机纳米复合材料，化学工业出版社，2003，24，34
9．漆宗能，尚文宇著，聚合物／层状硅酸盐纳米复合材料理论与实践，化学工业出版社，2002，9
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11. Z. Wang, T. J. Pinnavaia, Chemical Material, 1998, 10:1769-3771
12. M. Song et al, Journal of Applied Polymer Science, 2003, 90:3239-3243
13. Y. Kojima, et al, Material Science Letter, 1993, 12:889
14. www.chemat.com/html/solgel.html
15. L. Bokobza, Journal of Applied Polymer Science, 2004, 93:2095-2104
16．杜建科，杨荣杰，宇航材料工艺，2005，3：1-6
17. Guirong Pan, Reinforcement of Siloxane Elastomer with POSS based Fillers, Thesis for Master Degree, University of Cincinnati, 2003
18. Shuhong Wang, Ping Xu, J. E. Mark. Macromolucules, 1991, 24:6037-6039
19. Shuhong Wang, J. E. Mark, Macromolucules, 1990, 23:4288-4291
20. Morgan Richard et al, Rubber World, 1991, 204(2): 25-28
21．徐僖，王琪，力化学反应器，中国专利，1995，CN221463
22. Senna M. Materials Science Forum, 1999, 312-314:1672172
23. Smith A P, et al, Advanced Materials, 1999. 11(15):127721281
24．卢灿辉，聚丙烯-铁-废旧橡胶的碾磨粉碎应力诱导效应及复合材料的研究， 四川大学博士学位论文，2002
25. K.GUNTHER-SCHADE, et a, POLYMER ENGINEERING AND SCIENCE, 2004, 44 (7): 1351-1359
26. C. Suryanarayana, Progress in Materials Science, 2001, 46: 1±184
27. Hay J. N., Kemmidh D. j., Polymmer Communication, 1984, 25:195
28．柯扬船，郑玉斌，吴忠文，材料研究学报，1996，10(2)：205-209
29. Cheng S Z D, Cao MY, Wunderlich B.Macromolecules, 1986, 19:1868
30. Bassett D C, etal.Polymer, 1988, 29:1745
31. Wang M, Wolff S, Rubber Chem Technol 1991; 64:714
32．杜振霞，饶国瑛，南爱玲，宋善朋，高分子材料科学与工程，2003，19(3)：164-167
33. N. Nugay,. Ennan, Macromol. Sympl, 2001, 169, 69-274
34. D.J. Kohls, G.Beaucage. Current Opinion in Solid State and Materials Science 6 (2002) 183-194
35．张殿荣，辛振祥编著，现代橡胶配方设计(第二版)，化学工业出版社，2001，369
36．藤本邦彦，日本协会志，1964，37(8)：602
37. K. Ogawa, T. Vogt, M. Uilmsnn, S. Johnson, Journal of Applied Physics, 2000, 87:63
38．何颖，华南理工大学学报(自然科学版)，2006，32(1)：51-54
39．董诚春编，废橡胶资料综合利用，化学工业出版社，2003，2，87
40. Bilgili E, Arastoopour H, Berstein B. Rubber Chem. Tech. 2000, 73:340
41. K. Kircher, Chemical Reactions in Plastics Processing, Hanser Publishers, New York, 1987
42．何颖，李春忠，程起林，胡彦杰，功能材料2005，36(12)：1915-1918
43. Dale W. Schaefer et al, Physica A, 2002, 314:686-695
2．姜宏，大有作为的有机硅产业，今日科技，2003，4：40
3．郭守学，橡胶工业1998，(3)：183-190
4．刘爱堂编译，硅橡胶的最新进展，2006，36(1)：10-13
5．周宇琳编著，有机硅聚合物导论，科学出版社，2000，114-116
6．幸松民等编著，有机硅合成工艺及产品应用，化学工业出版社，2000，604
7．朱玉俊编著，弹性体的力学改性—填充补强及共混，北京科学技术出版社，1992，
8．柯扬船，(美)皮特·斯壮主编，聚合物—无机纳米复合材料，化学工业出版社，2003，24，34
9．漆宗能，尚文宇著，聚合物／层状硅酸盐纳米复合材料理论与实践，化学工业出版社，2002，9
10. M. Alexandre, P. Dubois, Materials Science and Engineering, 2000, 28, 1-63
11. Z. Wang, T. J. Pinnavaia, Chemical Material, 1998, 10:1769-3771
12. M. Song et al, Journal of Applied Polymer Science, 2003, 90:3239-3243
13. Y. Kojima, et al, Material Science Letter, 1993, 12:889
14. www.chemat.com/html/solgel.html
15. L. Bokobza, Journal of Applied Polymer Science, 2004, 93:2095-2104
16．杜建科，杨荣杰，宇航材料工艺，2005，3：1-6
17. Guirong Pan, Reinforcement of Siloxane Elastomer with POSS based Fillers, Thesis for Master Degree, University of Cincinnati, 2003
18. Shuhong Wang, Ping Xu, J. E. Mark. Macromolucules, 1991, 24:6037-6039
19. Shuhong Wang, J. E. Mark, Macromolucules, 1990, 23:4288-4291
20. Morgan Richard et al, Rubber World, 1991, 204(2): 25-28
21．徐僖，王琪，力化学反应器，中国专利，1995，CN221463
22. Senna M. Materials Science Forum, 1999, 312-314:1672172
23. Smith A P, et al, Advanced Materials, 1999. 11(15):127721281
24．卢灿辉，聚丙烯-铁-废旧橡胶的碾磨粉碎应力诱导效应及复合材料的研究， 四川大学博士学位论文，2002
25. K.GUNTHER-SCHADE, et a, POLYMER ENGINEERING AND SCIENCE, 2004, 44 (7): 1351-1359
26. C. Suryanarayana, Progress in Materials Science, 2001, 46: 1±184
27. Hay J. N., Kemmidh D. j., Polymmer Communication, 1984, 25:195
28．柯扬船，郑玉斌，吴忠文，材料研究学报，1996，10(2)：205-209
29. Cheng S Z D, Cao MY, Wunderlich B.Macromolecules, 1986, 19:1868
30. Bassett D C, etal.Polymer, 1988, 29:1745
31. Wang M, Wolff S, Rubber Chem Technol 1991; 64:714
32．杜振霞，饶国瑛，南爱玲，宋善朋，高分子材料科学与工程，2003，19(3)：164-167
33. N. Nugay,. Ennan, Macromol. Sympl, 2001, 169, 69-274
34. D.J. Kohls, G.Beaucage. Current Opinion in Solid State and Materials Science 6 (2002) 183-194
35．张殿荣，辛振祥编著，现代橡胶配方设计(第二版)，化学工业出版社，2001，369
36．藤本邦彦，日本协会志，1964，37(8)：602
37. K. Ogawa, T. Vogt, M. Uilmsnn, S. Johnson, Journal of Applied Physics, 2000, 87:63
38．何颖，华南理工大学学报(自然科学版)，2006，32(1)：51-54
39．董诚春编，废橡胶资料综合利用，化学工业出版社，2003，2，87
40. Bilgili E, Arastoopour H, Berstein B. Rubber Chem. Tech. 2000, 73:340
41. K. Kircher, Chemical Reactions in Plastics Processing, Hanser Publishers, New York, 1987
42．何颖，李春忠，程起林，胡彦杰，功能材料2005，36(12)：1915-1918
43. Dale W. Schaefer et al, Physica A, 2002, 314:686-695