溶聚体系制备集成橡胶SIBR的基础研究
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摘要
集成橡胶SIBR（苯乙烯-异戊二烯-丁二烯橡胶）具有优异的综合性能，本论文
研究了TMEDA/n-BuLi体系下的丁二烯（Bd）、苯乙烯（St）、异戊二烯（I）三元
共聚合反应。鉴于此三元共聚合体系的复杂性（由多种活性链端和多种单体组
成），本论文采用了一种新的方法，对此共聚体系进行了研究，即将Bd、I、St先
分别进行均聚合，后将Bd、St、I两两共聚合，最后将Bd、I、St进行三元共聚合，
并利用均聚合和二元共聚合中的规律以及测得的动力学组成和结构数据对三元共聚
合体系的规律进行了研究和解释，取得了较为满意的结果。
在I均聚合中，无调节剂存在时I均聚合引发反应缓慢，TMEDA可加速引发。
TMEDA/Li增加，I均聚速率降低；当TMEDA/Li≥1.0时，聚合速率基本不再变化。
在二元共聚合体系中，TMEDA/Li增加，I-St共聚合速率降低；I-Bd共聚合速
率增加；Bd-St共聚合速率先增加，TMEDA/Li=1.0时达最大值，后又降低。利用改
进的曲线拟合法 (TM法），求取了各共聚体系中各单体的竞聚率r_(Bd)，r_I，r_(St)。
TMEDA/Li增加；在I-St共聚体系中，r_I降低、r_(St)增加，并在TMEDA/Li=0.8后r_(St)
超过了r_I；在I-Bd共聚体系中，r_(Bd)增加、r_I降低，但TMEDA/Li≥0.8后，TMEDA
用量对r_(Bd)、r_I基本无影响；在Bd-St共聚体系中，r_(Bd)降低、r_(St)增加。推算了各共聚
物的组成，发现：在I-St共聚体系中，当0.5≤TMEDA/Li≤1.0时，共聚物的无规
性较好；在I-Bd共聚体系中，无调节剂存在时，r_I＜r_(Bd)；TMEDA/Li增加，共聚物无
规性降低；TMEDA/Li≥0.8后，TMEDA用量对无规性基本无影响；在Bd-St共聚
体系中，随着TMEDA/Li值的增加，共聚物无规性提高，当TMEDA/Li≥20后，
TMEDA/Li对组成基本无影响。
在Bd-St-I三元共聚合体系中，TMEDA/Li增加，共聚合速率增加；TMEDA/Li
=1.0时达最大值，后又降低。无调节剂存在时，St在初始共聚物中的结合量远低于
配料组成。TMEDA/Li增加，St结合量迅速增加，并超过了I结合量；温度变化对
共聚物组成影响不大。结合St、I、Bd均聚合获得的速率常数Kp和St-I、Bd-I、Bd-
St共聚合求得的竞聚率数据对三元共聚合体系的动力学进行了模拟，发现实验值与
计算值拟合良好。
在聚合物的微观结构研究中，首次采用了相同温度、相同TMEDA/Li下均聚物
的微观结构含量表征共聚物微观结构含量的方法，解决了Bd-I和St-I-Bd共聚物中
各微观结构特征吸收峰相互干扰的矛盾。通过将相同反应条件下，St-Bd共聚物与
Bd均聚物对比发现，St单体的引入使共聚物中1，2-结构聚丁二烯含量降低。
The integral rubber SEBR has excellent comprehensive,the anionic solution terpolymerizations of Styrene(St),Isoprene(I) and Butadiene(Bd) with TMEDA/n-BuLi are investigated by batch reactor operation. Because of the complication of terpolymerization, a new method was adopted to study it that is Bd, I and St were homopolymerizated separately,and then Bd, I and St were dipolymerizated with each other ;at last Bd, I and St were terpolymerizated ,the laws and data of polymerization rate ,composition and microstructure were used to study and explain terpolymerization, and the results are satisfactory.
In the homopolymerization ofI,without additive the initiation rate of the polymerization is slow, and the introduction of additive can accelerate it With the increasing of TMEDA/Li, polyme-rization rate of I decreases. Beyond the ratio of 1.0, the reaction rate of I changes very little..
In the dipolymerization, with the increasing of TMEDA/Li, the dipolymerization rate of I and St decreases; the dipolymerization rate of I and Bd increases; the dipolymerization rate of Bd and St increases and approaches a maximum value when TMEDA/Li is around 1.0 then decreases Each monomer reactivity ratio (rB )dipolymerization is obtained by advanced TM method. With the increasing of TMEDA/Li: In dipolymerization of I and St, rI decreases; rSt increases ;after TMEDA/Li 0.8, rSt overflows rI. In the dipolymerization of I and Bd, rBd increases; rI decreases; TMEDA/Li has no effect on rBd and rI after TMEDA/Li 0.8.In the dipolymerization of Bd and St, rBd decreases; rSt increases. The composition of each dipotymer was calculated and shows:In the dipolymerization of St and I, randomness is better when TMEDA/Li is between 0.5 and 1.0; in the dipolymerization of I and Bd, when there is no additive, rI, tle. In Ihe dipolyme-rization of Bd and St, with the increasing of TMEDA/Li ,randomness increases; after TMEDA/Li 2.0, randomness changes very little.
In terpolymerization of St, I and Bd, with the increasing of TMEDA/Li, the rate of terpoly-merization increases and approaches a maximum value when the TMEDA/Li is around 1.0 then decreases. Without TMEDA,St uptake in initial terpolymer is much lower than monomer compo-sition ; with the increasing of TMEDA/Li, St uptake in initial polymer increases steeply and overflows that of I. Temperature has small effects on the terpolymer's composition. The terpoly-merization rate was deduced by the homopolymerization rate constant Kp and the monomer reactivity ratio of dipolymerization.
In the study on polymer microstructure ,the microstructure content of homopolymer at the same temperature and TMEDA/Li was used to characterize microstructure content of I-Bd and I-St-Bd copolymer for the first time. It eliminates the disturbances of infrared spectroscopy characteristic absorption peaks mutually The comparison between copolymer of St,Bd and homopolymer of Bd shows the introduction of St leads to decreasing of l,2-PBd% in copolymer of St and Bd
研究了TMEDA/n-BuLi体系下的丁二烯（Bd）、苯乙烯（St）、异戊二烯（I）三元
共聚合反应。鉴于此三元共聚合体系的复杂性（由多种活性链端和多种单体组
成），本论文采用了一种新的方法，对此共聚体系进行了研究，即将Bd、I、St先
分别进行均聚合，后将Bd、St、I两两共聚合，最后将Bd、I、St进行三元共聚合，
并利用均聚合和二元共聚合中的规律以及测得的动力学组成和结构数据对三元共聚
合体系的规律进行了研究和解释，取得了较为满意的结果。
在I均聚合中，无调节剂存在时I均聚合引发反应缓慢，TMEDA可加速引发。
TMEDA/Li增加，I均聚速率降低；当TMEDA/Li≥1.0时，聚合速率基本不再变化。
在二元共聚合体系中，TMEDA/Li增加，I-St共聚合速率降低；I-Bd共聚合速
率增加；Bd-St共聚合速率先增加，TMEDA/Li=1.0时达最大值，后又降低。利用改
进的曲线拟合法 (TM法），求取了各共聚体系中各单体的竞聚率r_(Bd)，r_I，r_(St)。
TMEDA/Li增加；在I-St共聚体系中，r_I降低、r_(St)增加，并在TMEDA/Li=0.8后r_(St)
超过了r_I；在I-Bd共聚体系中，r_(Bd)增加、r_I降低，但TMEDA/Li≥0.8后，TMEDA
用量对r_(Bd)、r_I基本无影响；在Bd-St共聚体系中，r_(Bd)降低、r_(St)增加。推算了各共聚
物的组成，发现：在I-St共聚体系中，当0.5≤TMEDA/Li≤1.0时，共聚物的无规
性较好；在I-Bd共聚体系中，无调节剂存在时，r_I＜r_(Bd)；TMEDA/Li增加，共聚物无
规性降低；TMEDA/Li≥0.8后，TMEDA用量对无规性基本无影响；在Bd-St共聚
体系中，随着TMEDA/Li值的增加，共聚物无规性提高，当TMEDA/Li≥20后，
TMEDA/Li对组成基本无影响。
在Bd-St-I三元共聚合体系中，TMEDA/Li增加，共聚合速率增加；TMEDA/Li
=1.0时达最大值，后又降低。无调节剂存在时，St在初始共聚物中的结合量远低于
配料组成。TMEDA/Li增加，St结合量迅速增加，并超过了I结合量；温度变化对
共聚物组成影响不大。结合St、I、Bd均聚合获得的速率常数Kp和St-I、Bd-I、Bd-
St共聚合求得的竞聚率数据对三元共聚合体系的动力学进行了模拟，发现实验值与
计算值拟合良好。
在聚合物的微观结构研究中，首次采用了相同温度、相同TMEDA/Li下均聚物
的微观结构含量表征共聚物微观结构含量的方法，解决了Bd-I和St-I-Bd共聚物中
各微观结构特征吸收峰相互干扰的矛盾。通过将相同反应条件下，St-Bd共聚物与
Bd均聚物对比发现，St单体的引入使共聚物中1，2-结构聚丁二烯含量降低。
The integral rubber SEBR has excellent comprehensive,the anionic solution terpolymerizations of Styrene(St),Isoprene(I) and Butadiene(Bd) with TMEDA/n-BuLi are investigated by batch reactor operation. Because of the complication of terpolymerization, a new method was adopted to study it that is Bd, I and St were homopolymerizated separately,and then Bd, I and St were dipolymerizated with each other ;at last Bd, I and St were terpolymerizated ,the laws and data of polymerization rate ,composition and microstructure were used to study and explain terpolymerization, and the results are satisfactory.
In the homopolymerization ofI,without additive the initiation rate of the polymerization is slow, and the introduction of additive can accelerate it With the increasing of TMEDA/Li, polyme-rization rate of I decreases. Beyond the ratio of 1.0, the reaction rate of I changes very little..
In the dipolymerization, with the increasing of TMEDA/Li, the dipolymerization rate of I and St decreases; the dipolymerization rate of I and Bd increases; the dipolymerization rate of Bd and St increases and approaches a maximum value when TMEDA/Li is around 1.0 then decreases Each monomer reactivity ratio (rB )dipolymerization is obtained by advanced TM method. With the increasing of TMEDA/Li: In dipolymerization of I and St, rI decreases; rSt increases ;after TMEDA/Li 0.8, rSt overflows rI. In the dipolymerization of I and Bd, rBd increases; rI decreases; TMEDA/Li has no effect on rBd and rI after TMEDA/Li 0.8.In the dipolymerization of Bd and St, rBd decreases; rSt increases. The composition of each dipotymer was calculated and shows:In the dipolymerization of St and I, randomness is better when TMEDA/Li is between 0.5 and 1.0; in the dipolymerization of I and Bd, when there is no additive, rI,
In terpolymerization of St, I and Bd, with the increasing of TMEDA/Li, the rate of terpoly-merization increases and approaches a maximum value when the TMEDA/Li is around 1.0 then decreases. Without TMEDA,St uptake in initial terpolymer is much lower than monomer compo-sition ; with the increasing of TMEDA/Li, St uptake in initial polymer increases steeply and overflows that of I. Temperature has small effects on the terpolymer's composition. The terpoly-merization rate was deduced by the homopolymerization rate constant Kp and the monomer reactivity ratio of dipolymerization.
In the study on polymer microstructure ,the microstructure content of homopolymer at the same temperature and TMEDA/Li was used to characterize microstructure content of I-Bd and I-St-Bd copolymer for the first time. It eliminates the disturbances of infrared spectroscopy characteristic absorption peaks mutually The comparison between copolymer of St,Bd and homopolymer of Bd shows the introduction of St leads to decreasing of l,2-PBd% in copolymer of St and Bd
引文
1．合成橡胶工业，1998，21(1)：7；
2．化工新型材料，1992，8：27；
3. Europeane Rubber Journal, 1990, 172 (6): 35;
4. Rubber Chemistry and Technology, 1997, 70 (3): 295;
5．弹性体，1997，7(1)：34；
6．弹性体，1997，7(4)：44；
7. Macromolecules, 1992, 25: 4649;
8．弹性体，1994，4(4)：15；
9．高分子材料科学与工程，1997，13(6)：45；
10．弹性体，1994，4(4)：35；
11．合成橡胶工业，1997，20(1)：6；
12．合成橡胶工业，1999，22(2)：116；
13. Ploymer, 1988, 29 (10): 1801;
14. (KGK) Kautschuk Gummi Kunststoffe, 1984, 37 (8): 683;
15. KGK, 1993, 46 (5): 380;
16. Europeane Rubber Journal, 1989, 171 (11): 29;
17. Tyres Accessories, 1989 (8): 56;
18. Polymer International, 1994, 33: 151;
19．弹性体，1999，9(2)：35；
20. Polymer International, 1994, 33: 151;
21．阴离子聚合的理论和应用，中国友谊出版社，1990；
22．合成橡胶工业手册，化学工业出版社，1991；
23．合成橡胶工业，1999，22(5)：257；
24. US: 5, 047, 483;
25. US: 5, 254, 653;
26. EP: 438, 966A_1;
27. DE: 3, 724, 876;
28. EP: 438, 966B_1;
29. EP: 439, 342;
30. US: 4, 981, 911;
31. US: 5, 070, 148;
32. US: 4, 843, 120;
33. US: 5, 239, 009;
34. US: 4, 530, 985;
35. DE: 4, 234, 827;
36. DE: 3, 833, 759;
37. DE: 3, 905, 269;
38. DE: 3, 724, 871;
39. EP: 384, 033A_2;
40. EP: 344, 441A_2;
41. EP: 645, 407;
42. EP: 438, 967B_1;
43. EP: 438, 967A_1;
44. EP: 302, 196A_2;
45. EP: 302, 196B_1;
46. US: 5, 137, 998;
47. US: 5, 284, 927;
48. EP: 483, 046A_1;
49. JP: 59, 646, 45;
50. EP: 483, 046B_1;
51. US: 4, 814, 386;
52. DE: 3, 804, 547;
53. DE: 3, 710, 002;
54. US: 4, 673, 709;
55. US: 5, 272, 220;
56. US: 5, 008, 343;
57. JP: 01, 488, 04;
58. DE: 3, 833, 760;
59. EP: 384, 033B_1;
60. EP: 344, 441B_1;
61．石化技术，1998，5(4) 237；
62．兰化科技，98，2(12) 88；
63. EP: 005,440;
64. J Amer Chem Soc. 1944, 66:1515
65．王军．大连理工大学硕士学位论文．1999
66．共聚合原理．化学工业出版社．1984：167
67. J Polym Sci. 1965, A3:369
68. J Polym Sci. 1965, A3:2843
59. J Am Chem Soc. 1946, 68:1781
70. Polymer Preprints. 1967, 8(1) :209
71．合成橡胶工业，1982(4)：299
72．工业化学志，1962，65：2074
73．青岛化工学院学报，1998，19(3)：217
74．稀土催化合成橡胶文集，科学出版社，1980
2．化工新型材料，1992，8：27；
3. Europeane Rubber Journal, 1990, 172 (6): 35;
4. Rubber Chemistry and Technology, 1997, 70 (3): 295;
5．弹性体，1997，7(1)：34；
6．弹性体，1997，7(4)：44；
7. Macromolecules, 1992, 25: 4649;
8．弹性体，1994，4(4)：15；
9．高分子材料科学与工程，1997，13(6)：45；
10．弹性体，1994，4(4)：35；
11．合成橡胶工业，1997，20(1)：6；
12．合成橡胶工业，1999，22(2)：116；
13. Ploymer, 1988, 29 (10): 1801;
14. (KGK) Kautschuk Gummi Kunststoffe, 1984, 37 (8): 683;
15. KGK, 1993, 46 (5): 380;
16. Europeane Rubber Journal, 1989, 171 (11): 29;
17. Tyres Accessories, 1989 (8): 56;
18. Polymer International, 1994, 33: 151;
19．弹性体，1999，9(2)：35；
20. Polymer International, 1994, 33: 151;
21．阴离子聚合的理论和应用，中国友谊出版社，1990；
22．合成橡胶工业手册，化学工业出版社，1991；
23．合成橡胶工业，1999，22(5)：257；
24. US: 5, 047, 483;
25. US: 5, 254, 653;
26. EP: 438, 966A_1;
27. DE: 3, 724, 876;
28. EP: 438, 966B_1;
29. EP: 439, 342;
30. US: 4, 981, 911;
31. US: 5, 070, 148;
32. US: 4, 843, 120;
33. US: 5, 239, 009;
34. US: 4, 530, 985;
35. DE: 4, 234, 827;
36. DE: 3, 833, 759;
37. DE: 3, 905, 269;
38. DE: 3, 724, 871;
39. EP: 384, 033A_2;
40. EP: 344, 441A_2;
41. EP: 645, 407;
42. EP: 438, 967B_1;
43. EP: 438, 967A_1;
44. EP: 302, 196A_2;
45. EP: 302, 196B_1;
46. US: 5, 137, 998;
47. US: 5, 284, 927;
48. EP: 483, 046A_1;
49. JP: 59, 646, 45;
50. EP: 483, 046B_1;
51. US: 4, 814, 386;
52. DE: 3, 804, 547;
53. DE: 3, 710, 002;
54. US: 4, 673, 709;
55. US: 5, 272, 220;
56. US: 5, 008, 343;
57. JP: 01, 488, 04;
58. DE: 3, 833, 760;
59. EP: 384, 033B_1;
60. EP: 344, 441B_1;
61．石化技术，1998，5(4) 237；
62．兰化科技，98，2(12) 88；
63. EP: 005,440;
64. J Amer Chem Soc. 1944, 66:1515
65．王军．大连理工大学硕士学位论文．1999
66．共聚合原理．化学工业出版社．1984：167
67. J Polym Sci. 1965, A3:369
68. J Polym Sci. 1965, A3:2843
59. J Am Chem Soc. 1946, 68:1781
70. Polymer Preprints. 1967, 8(1) :209
71．合成橡胶工业，1982(4)：299
72．工业化学志，1962，65：2074
73．青岛化工学院学报，1998，19(3)：217
74．稀土催化合成橡胶文集，科学出版社，1980