Effect of the Polymerization Temperature on the Copolymerization of Butadiene and Isoprene Catalyzed by Supported Ziegler-Natta Catalyst

doi:10.7503/cjcu20200163

Abstract

Abstract: As the most important catalysts in polyolefin industry, heterogeneous TiCl₄/MgCl₂ Ziegler-Natta(Heterogeneous Z-N) catalysts activated by alkylaluminium show complex active center structures, which are sensitive to polymerization temperature, polymerization time, type and concentration of alkylaluminium. In this paper, the copolymerization kinetics of butadiene(Bd) and isoprene(Ip) catalyzed by TiCl₄/MgCl₂-AlEt₃(triethylaluminium) at different polymerization temperatures were studied. It was found that the activity of the copolymerization increased firstly and then decreased with the increase in the polymerization time, and the highest activity was observed at 50℃. The microstructure, the number of active centers, molecular weight and molecular weight distribution of the copolymers studied by proton nuclear magnetic resonance(¹H NMR), microcoulometric sulfur spectrometer and gel permeation chromatography(GPC) changed in different ways with the increase in polymerization temperature and polymerization time. The results of this study is helpful for further understanding the kinetics and its key influencing factors of conjugated diolefin polymerization catalyzed by heterogeneous Z-N catalysts under different polymerization temperatures.

Key words: Ziegler-Natta catalyst, Isoprene, Butadiene, Copolymerization, Temperature, Coordination polymerization

CLC Number:

O631

TrendMD:

ZHANG Junying, PENG Wei, CHEN Ziwei, HE Aihua. Effect of the Polymerization Temperature on the Copolymerization of Butadiene and Isoprene Catalyzed by Supported Ziegler-Natta Catalyst[J]. Chem. J. Chinese Universities, 2020, 41(8): 1873.

References 42

[1]	Niu Q. T., Jiang X. B., He A. H., Polymer, 2014, 55(9), 2146-2152
[2]	He A. H., Huang B. C., Jiao S. K., Hu Y. L., J. Appl. Polym. Sci., 2003, 89(7), 1800-1807
[3]	Jiang X. B., Zhang Q. F., He A. H., Chin. J. Polym. Sci., 2015, 33(6), 815-822
[4]	He A. H., Yao W., Jia Z. F., Huang B. C., Acta Polym. Sin., 2002, 83(1), 19-24
[5]	Song J. S., Huang B. C., Yu D. S., J. Appl. Polym. Sci., 2001, 82(1), 81-89
[6]	He A. H., Yao W., Huang B. C., Huang Y. Q., Jiao S. K., J. Appl. Polym. Sci., 2004, 92, 2941-2948
[7]	He A. H., Yao W., Huang G. X., Huang B. C., Jiao S. K., Hu Y. L., China Elastomerics, 2002, 12(1), 1-6(贺爱华, 姚薇, 黄光兴, 黄宝琛, 焦书科, 胡友良. 弹性体, 2002, 12(1), 1-6)
[8]	He A. H., Yao W., Jia Z. F., Huang B. C., Jiao S. K., China Synthetic Rubber Industry, 2002, 25(2), 75-79(贺爱华, 姚薇, 贾志峰, 黄宝琛, 焦书科. 合成橡胶工业, 2002, 25(2), 75-79)
[9]	He A. H., Yao W., Huang B. C., Jiao S. K., Acta Chimica Sinica, 2001, 59(10), 1793-1797(贺爱华, 姚薇, 黄宝琛, 焦书科. 化学学报, 2001, 59(10), 1793-1797)
[10]	Du K., Yao W., Guo C. Q., He A. H., Huang B. C., China Synthetic Rubber Industry, 2011, 34(1), 29-33(杜凯, 姚薇, 郭常青, 贺爱华, 黄宝琛. 合成橡胶工业, 2011, 34(1), 29-33)
[11]	Bahri-Laleh N., Correa A., Mehdipour-Ataei S.,Arabi H., Haghighi M. N., Zohuri G., Cavallo L., Macromolecules, 2011, 44(4), 778-783
[12]	Yang H. R., Zhang L. T., Zang D. D., Fu Z. S., Fan Z. Q., Catalysis Communications, 2015, 62, 104-106
[13]	Liu B. P., Nitta T., Nakatani H., Terano M., Macromolecular Chemistry & Physics, 2002, 203(17), 2412-2421
[14]	Al-arifi A. S. N., J. Appl. Polym. Sci., 2004, 93, 56-62
[15]	Hu J., Han B., Shen X. R., Fu Z. S., Fan Z. Q., Chin. J. Polym. Sci., 2013, 31(4), 583-590
[16]	Zhang H. X., Lee Y. J., Park J. R., Lee D. H., Yoon K. B., J. Appl. Polym. Sci., 2011, 120, 101-108
[17]	Rishina L. A., Vizen E. I., Dyachkovsky F. S., European Polymer Journal, 1979, 15(1), 93-97
[18]	Chadwick J. C., Morini G., Balbontin G., Sudrnezjer O., Macromolecular Chemistry and Physics, 1998, 199(9), 1873-1878
[19]	Gao M. Z., Liu H. T., Wang J., Li C. X., Ma J., Wei G. S., Polymer, 2004, 45(7), 2175-2180
[20]	Fregonese D., Mortara S., Bresadola S., Journal of Molecular Catalysis A Chemical, 2001, 172(1), 89-95
[21]	Druz N. N., Zak A. V., Lobach M. I., Vasiliev V. A., Kormer V. A., European Polymer Journal, 1978, 14, 21-24
[22]	Durand J. P., Dawans F., Journal of Polymer Science, Part B, Polymer Letters, 1970, 8, 743-747
[23]	Appukuttan V., Zhang L., Ha C. S., Kim I., Polymer, 2009, 50, 1150-1158
[24]	Ricci G., Italia S., Porri L., Macromol. Chem. Phys., 1994, 195, 1389-1397
[25]	Wang H., Cui H. H., Ma Y. S., Zhang J. P., Song L. Y., He A. H., Polymer Bulletin, 2016, 10, 61-67(王浩, 崔虹虹, 马韵升, 张剑平, 宋丽媛, 贺爱华, 高分子通报, 2016, 10, 61-67)
[26]	Zhang X. P., Cui H. H., Song L. Y., Ren H. C., Wang R. G., He A. H., Composites Science and Technology, 2018, 158, 156-163
[27]	Wang H., Zou C., He A. H., Acta Polym. Sin., 2015, 12, 1387-1395(王浩, 邹陈, 贺爱华. 高分子学报, 2015, 12, 1387-1395)
[28]	Wang H., Song L.Y., Ma Y. S., Wang R. G., He A. H., Acta Polym. Sin., 2018, 3, 419-428
[29]	Li W. T., Peng W., Ren S. T., He A. H., Ind. Eng. Chem. Res., 2019, 58, 10609-10617
[30]	Wang H., Zhang J. P., Ma Y. S., Wang R. G., He A. H., Chem. J. Chinese Universities, 2017, 38(11), 2095-2101(王浩, 张剑平, 马韵升, 王日国, 贺爱华, 高等学校化学学报, 2017, 38(11), 2095-2101)
[31]	Niu Q. T., Zou C., Wang R. G., Li L. G., He A. H., Chem. J. Chinese Universities, 2018, 39(10), 2312-2319(牛庆涛, 邹陈, 王日国, 李兰阁, 贺爱华. 高等学校化学学报, 2018, 39(10), 2312-2319)
[32]	Zhang Q. F., Jiang X. B., He A. H., Chin. J. Polym. Sci., 2014, 32(8), 1068-1076
[33]	Liu X. Y., Li W. T., Niu Q. T., Wang R. G., He A. H., Polymer, 2018, 140, 255-268
[34]	Sato H., Tanaka Y., Journal of Polymer Science Polymer Chemistry Edition, 1979, 17, 3551-3558
[35]	Wang Z. H., Qian Y. Q., Zhang W. J., Wang J. Y., He L. X., Lin Q. J., Sun W. H., Polymer International, 2015, 64, 1030-1036
[36]	Wang B. L., Cui D. M., Lv K., Macromolecules, 2008, 41(6), 1983-1988
[37]	Niu Q. T., Zou C., Liu X. Y., Wang R. G., He A. H., Polymer, 2016, 109, 197-204
[38]	Niu Q. T., Li W. T., Liu X. Y., Wang R. G., He A. H., Polymer, 2018, 143, 173-183
[39]	Shen X. R., Hu J., Fu Z. S., Lou J. Q., Fan Z. Q., Catalysis Communications, 2013, 30, 66-69
[40]	Shen X. R., Fu Z. S., Hu J., Wang Q., Fan Z. Q., Journal of Physical Chemistry C, 2013, 117(29), 15174-15182
[41]	Jiang B. Y., Liu X. Y., Weng Y. H., Fu Z. S., He A. H., Fan Z. Q., Journal of Catalysis, 2019, 369, 324-334
[42]	Niu Q. T., Zhang J. Y., Peng W., Fan Z. Q., He A. H., Molecular Catalysis, 2019, 471, 1-8