偶联型S-SBR共混胶料结构设计及性能最优化研究
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摘要
本论文研究工作可分三个部分：
第一部分：对北京化工大学自制的锡偶联S-SBR、燕化研究院的S-SBR以及日本JSR公司的SL552进行了全面的性能对比研究，系统地考察了这几种偶联型S-SBR的加工性能、物机性能、动态性能等。
第二部分：深入研究了偶联效率对S-SBR性能的影响、Sn-C键接转移机理以及补强剂对S-SBR、S-SBR／BR体系的补强作用。
第三部分：在前两部分工作的基础上，用数学方法对以S-SBR为基料的胎面配方进行优化及设计。用三元二次通用旋转正交设计法研究了变量SSBR／BR、DM／D、C．B／SiO_2与硫化胶物理机械性能的关系，得到一系列变量与性能的等高图，揭示了诸因素之间的内在规律，优选出二元共混胎面配方。引入均匀设计这一先进的配方设计方法，对SSBR／NR／BR三元共混胎面配方进行了预测和优选，用三角座标图表征了三元共混胶的相互配比与性能，尤其是生热性能关系，找出了最佳配方，取得良好的效果。
研究结果表明：日本JSR公司的锡偶联型溶聚丁苯S-SBR SL552的综合性能较优。燕化研究院的锡偶联型SSBR2305的物机性能与S-SBR SL552相差不多，其60℃的tan δ与S-SBR SL552很接近。北化自合成产品的性能研究表明，随偶联效率的增加，S-SBR的物机性能略有提高，动态生热呈降低趋势，即60℃的tan δ明显降低。为保证偶联型SSBR的综合性能，偶联效率40-80％较佳。SSBR之所以生热低的原因是因其端点键接转移机理。均匀设计方法在橡胶配方设计中能发挥很好的作用，不仅大大减小实验次数，而且能准确地揭示出性能与变量之间的定量关系，从而达到调整配方、优选配方的目的。
The research of the thesis can be divided into three parts:Firstly, there is a comprehensive research of properties for SSBR of BUCT, Yanhua academe and JSR company. We investigated the processing performance, physical mechanic properties and dynamic properties of coupled SSBR.Secondly, we researched the change of properties of SSBR with the increasing coupling efficiency, the mechanism of Sn-C transfering and the effect of C.B reinforcing to SSBR and SSBR/BR blending system.Thirdly, on the basis of the former research, we optimized the formula of trend based on SSBR by means of math, the relations between variables SSBR/BR, DM/D C.B/SiO2 and sulfured Rubber's physical properties had been studied by means of three elements quadratic general revolving compound design. The results disclosed the inner regulars among many factors by a series of contours of variable and property. Moreover, we intorduce a advanced design method of formula to anticipate and optimize the tread formula of SSBR/NR/BR blending system. The relations between compounding ratio and properties are showed by triangle graph.The results of experiments show that the SSBR SL552 of Japan JSR company has a better comprehensive properties, the physical mechanic properties of Yanhua SSBR 2305 approaches that of SSBR SL552 and its tan 6 (60℃) is closed to SSBR SL552. The research of BUCT SSBR indicates that the physical mechanic properties are increased with the coupling efficiency and the dynamic heating is declined. In order to guarantee the comprehensive properties of coupled SSBR, the coupling efficiency
between 40% and 80% is better. The reson of low heating is the mechanism of Sn-C transfering. The method of uniformity design showed a good effect in formula design of rubber. It not noly decreases the experiment number but also discloses the quantitative relation between properties and variables accurately. Furthermore, we can achieve the purpose of adjusting formula and optimizing formula through it.
第一部分：对北京化工大学自制的锡偶联S-SBR、燕化研究院的S-SBR以及日本JSR公司的SL552进行了全面的性能对比研究，系统地考察了这几种偶联型S-SBR的加工性能、物机性能、动态性能等。
第二部分：深入研究了偶联效率对S-SBR性能的影响、Sn-C键接转移机理以及补强剂对S-SBR、S-SBR／BR体系的补强作用。
第三部分：在前两部分工作的基础上，用数学方法对以S-SBR为基料的胎面配方进行优化及设计。用三元二次通用旋转正交设计法研究了变量SSBR／BR、DM／D、C．B／SiO_2与硫化胶物理机械性能的关系，得到一系列变量与性能的等高图，揭示了诸因素之间的内在规律，优选出二元共混胎面配方。引入均匀设计这一先进的配方设计方法，对SSBR／NR／BR三元共混胎面配方进行了预测和优选，用三角座标图表征了三元共混胶的相互配比与性能，尤其是生热性能关系，找出了最佳配方，取得良好的效果。
研究结果表明：日本JSR公司的锡偶联型溶聚丁苯S-SBR SL552的综合性能较优。燕化研究院的锡偶联型SSBR2305的物机性能与S-SBR SL552相差不多，其60℃的tan δ与S-SBR SL552很接近。北化自合成产品的性能研究表明，随偶联效率的增加，S-SBR的物机性能略有提高，动态生热呈降低趋势，即60℃的tan δ明显降低。为保证偶联型SSBR的综合性能，偶联效率40-80％较佳。SSBR之所以生热低的原因是因其端点键接转移机理。均匀设计方法在橡胶配方设计中能发挥很好的作用，不仅大大减小实验次数，而且能准确地揭示出性能与变量之间的定量关系，从而达到调整配方、优选配方的目的。
The research of the thesis can be divided into three parts:Firstly, there is a comprehensive research of properties for SSBR of BUCT, Yanhua academe and JSR company. We investigated the processing performance, physical mechanic properties and dynamic properties of coupled SSBR.Secondly, we researched the change of properties of SSBR with the increasing coupling efficiency, the mechanism of Sn-C transfering and the effect of C.B reinforcing to SSBR and SSBR/BR blending system.Thirdly, on the basis of the former research, we optimized the formula of trend based on SSBR by means of math, the relations between variables SSBR/BR, DM/D C.B/SiO2 and sulfured Rubber's physical properties had been studied by means of three elements quadratic general revolving compound design. The results disclosed the inner regulars among many factors by a series of contours of variable and property. Moreover, we intorduce a advanced design method of formula to anticipate and optimize the tread formula of SSBR/NR/BR blending system. The relations between compounding ratio and properties are showed by triangle graph.The results of experiments show that the SSBR SL552 of Japan JSR company has a better comprehensive properties, the physical mechanic properties of Yanhua SSBR 2305 approaches that of SSBR SL552 and its tan 6 (60℃) is closed to SSBR SL552. The research of BUCT SSBR indicates that the physical mechanic properties are increased with the coupling efficiency and the dynamic heating is declined. In order to guarantee the comprehensive properties of coupled SSBR, the coupling efficiency
between 40% and 80% is better. The reson of low heating is the mechanism of Sn-C transfering. The method of uniformity design showed a good effect in formula design of rubber. It not noly decreases the experiment number but also discloses the quantitative relation between properties and variables accurately. Furthermore, we can achieve the purpose of adjusting formula and optimizing formula through it.
引文
1. Karen Manly&Mitch Barry, Benefits of solution Polymerized SBR, Tire Technology international 98,78-82
2．服部岩和，溶液聚合丁苯橡胶，日本协会志，1993，66(8)，605-611
3. W. H. Sung, A. B. Dean, Paper No15, Evaluation of Various SBR in Tread Compounds, 135th Meeting of the Rubber Division ACS, 1990
4．JSR公司技术资料
5．赵素合，张兴英等，胎面材料锡偶联型溶聚丁苯橡胶的研究，合成橡胶工业，1995，vol 18(4)，212-215
6．辛振祥，橡胶配合加工技术讲座 第二讲 丁苯橡胶(SBR)(继一)，橡胶工业，1997，44(10)，633-635
7．陈士朝，溶聚丁苯橡胶的性能研究，合成橡胶工业，1997，20(1)，6-9
8．罗志河，关于发展溶聚丁苯橡胶的探讨，合成橡胶工业，1988，11(3)，191-195
9．橡胶工业手册第一分册，化工出版社，1993
10．A. J. M. Sumner, Bayer公司技术手册
11．张兴英，金关泰，节能型溶聚丁苯橡胶的合成，合成橡胶工业，1991，14(6)，391-394
12. H.L. Brantley, Improved Tire Performance with Solution SBR Type Polymers, Kautschuk+Gummi+Kunststoffe, 1987,40(2), 122-125
13．李扬，张淑芬，我国锂系聚合物发展的前景展望，合成橡胶工业，1995，18(3)，266-270
14. Fumitoshi Suzuki, Rubber for low Rolling Resistance, Tire Technology International 1997,87-90
15．赵素合，张兴英，胎面材料锡偶联型溶聚丁苯橡胶的研究，合成橡胶工业，1995，18(4)，212-215
16．赵素合，张兴英，锡偶联型溶聚丁苯胶的性能研究，弹性体，1995，5(3)，25-28
17．梁修源，发展溶聚丁苯橡胶诌议，合成橡胶工业，1989，12(6)，359-360
18．林裔珍，陈鼎希等，溶聚丁苯橡胶在轮胎中的应用研究，轮胎工业，1989，18(9)，535-538
19．鲍爱华，八十年代世界橡胶市场供需动向和技术开发重点，合成橡胶工业，1989，10(1)，50—56
20. M. Bortolotti, S. Busette, etc, Dynamic Properties of Batch Polymerized S-SBR Based Compounds, Kautschuk+Gummi+Kunststoffe, 1988, vol51(5), 331-335
21. Manfred Hensel, Karl-Hans meeting, Green Tire Additives in an S-SBR -Silica-PC Tread Compound, Tire Technology International 97,124-127
22．小林直一著，李汉堂译，胎面胶中炭黑与白炭黑的比较，轮胎研究与开发，1998：3 44-50
23．李鹤松，王剑波等，国产溶聚丁苯橡胶在轿车轮胎胎冠中的应用，轮胎工业，1989，18(9)，543-544
24. J. EStamhuis, W.M. Groenwoud, Two type of S-SBR Blends for Tire Tread Application, Plastics and Rubber Processing and Application, 1989, 1889, 11(2),93-98
25. William J. Patterson,Meng-jiao wang, Carbon-Silica Dual-Phase filler-A New-Generation Reinforcing Agent, Tire Technology International 98, 33-40
26．服部岩和，锡联接物溶液聚合丁二烯—苯乙烯橡胶的开发，日本JSR公司技术交流会使用资料，1997．5．22-33
27. H. Parttls, M. Hensel等，Tire Technology International, 1996:54-56
28．候金香，林裔真，国产溶聚丁苯橡胶(SSBR)的性能研究，弹性体，1997，7(4)：49-55
29．梁俐，天然橡胶／溶聚丁苯橡胶胎面载重轮胎的研制，橡胶工业，1991，38(5)：273-278
30. T. Ohgama, A. Veda etc, Vibration Isolation Characteristics, Fatigue properties of Chemically Modified Solution Polymerized Rubber Blended with NR, Rubber word, 1992,205(3):22-26
31．王真 北京化工大学硕士生毕业论文 1999
32．F．Tsutsumi等著 江畹兰译 锡偶联溶聚丁苯橡胶的结构及动态性能 橡胶译丛 1992 15-22
33. Hamada, Tatsure,Yokoyama. Rubber compositions for tire treads with low hysteresis loss and excellent abrasion and wet skid resistance. JPn, JP0707,188,462.25 Jul 1995.
34. Scriver, Richard. M. Rubber blends for skid-resistant tire treads. Goodyear Tire and Rubber Co.U.S.,US4894420.18 Jun 1996.
35. Araki, Shunji. Abrasion-resistant pneumatic tires for radial tires of tracks and buses. Jpn, JP 06,263,920.10 Sep 1994.
36．张华，张兴英，金关泰．理想的胎面材料-集成橡胶SIBR(Ⅰ)．弹性体，1997，7(7)：34
37. Thise, Ghislain, Adolphe Lean. Butadiene-isoprene rubber in tread compositions for truck tires. Eur, EP 654,499.24 May 1995.
38. Kikuchi, Yasushi, Shiro kawa. SBR blend compositions for tire trends. Jpn, JP 06,278,405.04 Oct 1994.
39. Tokamatsu, Hideo, Yamada. Rubber compositions with good workability for tires. Jpn, JP 06,220,256.09 Aug 1994.
40. Aolyama, Masanori,Yomanaka. All-season pneumatic tires with good braking proerties and abrasion resistance. Jpn, JP 06,306,207.01 Nov 1994.
41. Misono, Shinji. Carbon black for rubber compositions for tires. U.S. US 5,321,072.14 Jun 1994.
42. Segatta, Thomos Joseph, Sandstrom. Sulfur-cured rubber composition containing epoxidized natural rubber and silica filler. Eur, EP 644, 235.22 Mar 1995.
43. Wideman, Lawson, Gibson. Silica-reinforced rubber compositions for tire treads. Eur, EP 682,067.15 Nov 1995.
44. S. wolff, U. Grl, M.J Wang..Silica-based tread compounds. European Rubber Journal, 1994,176:10
45．项可风、吴启光，试验设计与数学分析，上海科学出版社，上海，(1989)．
46．中国科学院数学研究所统计组(方开泰执笔)，方差分析，科学出版社 北京，(1997，1981)
47．中国科学院数学研究所数理通计所，正交试验法，人民教育出版社，北京，(1975)．
48．王元，均匀设计—一种试验设计方法均匀设计论文选，第二集，p1-4(1997．5)
49．徐洪泉、沈世镒，基于计算机试验的均匀设计均匀设计论文选，第二集，p16-21(1997．5)
50．Fang, K. T. (方开泰)and Zhang J. T. (张金廷), Criteria for uniform design, Technical Report Math - 002, Hong Kong Baptist College, (1992).
51. Cornell, J.A., Experiments with Mixtures, Designs, Models, and the Analysis of Mixture Data, Wiley, New York, (1981).
52．方开泰，均匀设计，中国科学院数学研究所或中国科学院应用数学研究所印，(1979，1983，1984)
53．方开泰、全辉、陈庆云，实用回归分析，科学出版社，北京，(1988)．
54．田国粱，多项式回归和正交多项式回归的比较均匀设计论文选，第二集，p5-15(1997．5)
55．张学中均匀设计及其应用，内部资料，北京军事医学科学院，(1992)．
56．方开泰，均匀设计与均匀设计表 科学出版社，1994
57．纪奎江，范汝良 21世纪的计算机辅助橡胶配方设计 合成橡胶工业 1998- 11-15，21(6)：321-324
58
58. Urbanik D. Computer Aided Compound Design-Compounding in the 21st Century. 97'IRC. Nuremberg, Germany, June 30-July 3,1997,227
59. Strothenk H, Hannover. Compounding-Ingenious or statistical Design of Experiments. Kautsch+Gummi+Kunstst, 1995, 48(11):806
60. Claxton W. E, Pearson D, Clarke R E, et al. Role of Computers in Elastomer Research. Rubber Chem and Technol, 1968,41(1):86
61．蔡常丰，数学模型建模分析，北京：科学出版社，1995
62. A. I. Medalia, Effects of Carbon Black on Abrasion and Tread Wear, Kautschuk+Gummi+Kunststoffe, 1994, vol 47(5),364-368
63．李秀贞译，曹元礼校，轮胎的磨擦和粘弹性能，橡胶参考资料，1997，vol27(11)，58-64
64．茆诗松，回归分析及其试验设计，华东师范大学出版社，1981
2．服部岩和，溶液聚合丁苯橡胶，日本协会志，1993，66(8)，605-611
3. W. H. Sung, A. B. Dean, Paper No15, Evaluation of Various SBR in Tread Compounds, 135th Meeting of the Rubber Division ACS, 1990
4．JSR公司技术资料
5．赵素合，张兴英等，胎面材料锡偶联型溶聚丁苯橡胶的研究，合成橡胶工业，1995，vol 18(4)，212-215
6．辛振祥，橡胶配合加工技术讲座 第二讲 丁苯橡胶(SBR)(继一)，橡胶工业，1997，44(10)，633-635
7．陈士朝，溶聚丁苯橡胶的性能研究，合成橡胶工业，1997，20(1)，6-9
8．罗志河，关于发展溶聚丁苯橡胶的探讨，合成橡胶工业，1988，11(3)，191-195
9．橡胶工业手册第一分册，化工出版社，1993
10．A. J. M. Sumner, Bayer公司技术手册
11．张兴英，金关泰，节能型溶聚丁苯橡胶的合成，合成橡胶工业，1991，14(6)，391-394
12. H.L. Brantley, Improved Tire Performance with Solution SBR Type Polymers, Kautschuk+Gummi+Kunststoffe, 1987,40(2), 122-125
13．李扬，张淑芬，我国锂系聚合物发展的前景展望，合成橡胶工业，1995，18(3)，266-270
14. Fumitoshi Suzuki, Rubber for low Rolling Resistance, Tire Technology International 1997,87-90
15．赵素合，张兴英，胎面材料锡偶联型溶聚丁苯橡胶的研究，合成橡胶工业，1995，18(4)，212-215
16．赵素合，张兴英，锡偶联型溶聚丁苯胶的性能研究，弹性体，1995，5(3)，25-28
17．梁修源，发展溶聚丁苯橡胶诌议，合成橡胶工业，1989，12(6)，359-360
18．林裔珍，陈鼎希等，溶聚丁苯橡胶在轮胎中的应用研究，轮胎工业，1989，18(9)，535-538
19．鲍爱华，八十年代世界橡胶市场供需动向和技术开发重点，合成橡胶工业，1989，10(1)，50—56
20. M. Bortolotti, S. Busette, etc, Dynamic Properties of Batch Polymerized S-SBR Based Compounds, Kautschuk+Gummi+Kunststoffe, 1988, vol51(5), 331-335
21. Manfred Hensel, Karl-Hans meeting, Green Tire Additives in an S-SBR -Silica-PC Tread Compound, Tire Technology International 97,124-127
22．小林直一著，李汉堂译，胎面胶中炭黑与白炭黑的比较，轮胎研究与开发，1998：3 44-50
23．李鹤松，王剑波等，国产溶聚丁苯橡胶在轿车轮胎胎冠中的应用，轮胎工业，1989，18(9)，543-544
24. J. EStamhuis, W.M. Groenwoud, Two type of S-SBR Blends for Tire Tread Application, Plastics and Rubber Processing and Application, 1989, 1889, 11(2),93-98
25. William J. Patterson,Meng-jiao wang, Carbon-Silica Dual-Phase filler-A New-Generation Reinforcing Agent, Tire Technology International 98, 33-40
26．服部岩和，锡联接物溶液聚合丁二烯—苯乙烯橡胶的开发，日本JSR公司技术交流会使用资料，1997．5．22-33
27. H. Parttls, M. Hensel等，Tire Technology International, 1996:54-56
28．候金香，林裔真，国产溶聚丁苯橡胶(SSBR)的性能研究，弹性体，1997，7(4)：49-55
29．梁俐，天然橡胶／溶聚丁苯橡胶胎面载重轮胎的研制，橡胶工业，1991，38(5)：273-278
30. T. Ohgama, A. Veda etc, Vibration Isolation Characteristics, Fatigue properties of Chemically Modified Solution Polymerized Rubber Blended with NR, Rubber word, 1992,205(3):22-26
31．王真 北京化工大学硕士生毕业论文 1999
32．F．Tsutsumi等著 江畹兰译 锡偶联溶聚丁苯橡胶的结构及动态性能 橡胶译丛 1992 15-22
33. Hamada, Tatsure,Yokoyama. Rubber compositions for tire treads with low hysteresis loss and excellent abrasion and wet skid resistance. JPn, JP0707,188,462.25 Jul 1995.
34. Scriver, Richard. M. Rubber blends for skid-resistant tire treads. Goodyear Tire and Rubber Co.U.S.,US4894420.18 Jun 1996.
35. Araki, Shunji. Abrasion-resistant pneumatic tires for radial tires of tracks and buses. Jpn, JP 06,263,920.10 Sep 1994.
36．张华，张兴英，金关泰．理想的胎面材料-集成橡胶SIBR(Ⅰ)．弹性体，1997，7(7)：34
37. Thise, Ghislain, Adolphe Lean. Butadiene-isoprene rubber in tread compositions for truck tires. Eur, EP 654,499.24 May 1995.
38. Kikuchi, Yasushi, Shiro kawa. SBR blend compositions for tire trends. Jpn, JP 06,278,405.04 Oct 1994.
39. Tokamatsu, Hideo, Yamada. Rubber compositions with good workability for tires. Jpn, JP 06,220,256.09 Aug 1994.
40. Aolyama, Masanori,Yomanaka. All-season pneumatic tires with good braking proerties and abrasion resistance. Jpn, JP 06,306,207.01 Nov 1994.
41. Misono, Shinji. Carbon black for rubber compositions for tires. U.S. US 5,321,072.14 Jun 1994.
42. Segatta, Thomos Joseph, Sandstrom. Sulfur-cured rubber composition containing epoxidized natural rubber and silica filler. Eur, EP 644, 235.22 Mar 1995.
43. Wideman, Lawson, Gibson. Silica-reinforced rubber compositions for tire treads. Eur, EP 682,067.15 Nov 1995.
44. S. wolff, U. Grl, M.J Wang..Silica-based tread compounds. European Rubber Journal, 1994,176:10
45．项可风、吴启光，试验设计与数学分析，上海科学出版社，上海，(1989)．
46．中国科学院数学研究所统计组(方开泰执笔)，方差分析，科学出版社 北京，(1997，1981)
47．中国科学院数学研究所数理通计所，正交试验法，人民教育出版社，北京，(1975)．
48．王元，均匀设计—一种试验设计方法均匀设计论文选，第二集，p1-4(1997．5)
49．徐洪泉、沈世镒，基于计算机试验的均匀设计均匀设计论文选，第二集，p16-21(1997．5)
50．Fang, K. T. (方开泰)and Zhang J. T. (张金廷), Criteria for uniform design, Technical Report Math - 002, Hong Kong Baptist College, (1992).
51. Cornell, J.A., Experiments with Mixtures, Designs, Models, and the Analysis of Mixture Data, Wiley, New York, (1981).
52．方开泰，均匀设计，中国科学院数学研究所或中国科学院应用数学研究所印，(1979，1983，1984)
53．方开泰、全辉、陈庆云，实用回归分析，科学出版社，北京，(1988)．
54．田国粱，多项式回归和正交多项式回归的比较均匀设计论文选，第二集，p5-15(1997．5)
55．张学中均匀设计及其应用，内部资料，北京军事医学科学院，(1992)．
56．方开泰，均匀设计与均匀设计表 科学出版社，1994
57．纪奎江，范汝良 21世纪的计算机辅助橡胶配方设计 合成橡胶工业 1998- 11-15，21(6)：321-324
58
58. Urbanik D. Computer Aided Compound Design-Compounding in the 21st Century. 97'IRC. Nuremberg, Germany, June 30-July 3,1997,227
59. Strothenk H, Hannover. Compounding-Ingenious or statistical Design of Experiments. Kautsch+Gummi+Kunstst, 1995, 48(11):806
60. Claxton W. E, Pearson D, Clarke R E, et al. Role of Computers in Elastomer Research. Rubber Chem and Technol, 1968,41(1):86
61．蔡常丰，数学模型建模分析，北京：科学出版社，1995
62. A. I. Medalia, Effects of Carbon Black on Abrasion and Tread Wear, Kautschuk+Gummi+Kunststoffe, 1994, vol 47(5),364-368
63．李秀贞译，曹元礼校，轮胎的磨擦和粘弹性能，橡胶参考资料，1997，vol27(11)，58-64
64．茆诗松，回归分析及其试验设计，华东师范大学出版社，1981
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