氧桥联双核钛、 镍配合物的合成及催化制备双峰聚乙烯

doi:10.7503/cjcu20180216

摘要/Abstract

摘要：

从2种氧原子桥联双膦化合物双(2-二苯基膦苯基)醚(1a)和4,5-双(二苯基膦)-9,9-二甲基氧杂蒽(1b)出发, 合成氧原子桥联双膦亚胺钛、镍配合物. 在甲苯中回流条件下首先将化合物1a和1b与叠氮三甲基硅烷发生Staudinger反应, 分别生成单和双膦亚胺前驱体2a和2b. 然后再与环戊二烯基三氯化钛反应, 脱去三甲基氯硅烷后得到相应膦亚胺过渡金属钛配合物3a和3b. 单钛中心配合物3b进一步与乙二醇二甲醚溴化镍反应生成钛-镍异核双中心配合物4b. 通过 ¹H NMR, ¹³C NMR, ³¹P NMR, FTIR及元素分析对产物进行了表征, 并利用X射线单晶衍射分析确定了配合物3a和3b的分子结构. 在助催化剂甲基铝氧烷(MAO)作用下, 配合物3a和4b对乙烯聚合均表现出较高的催化活性, 其中双钛中心配合物3a催化得到较宽分子量的聚乙烯产物, 而异核双中心配合物4b催化得到呈双峰分布的聚乙烯产物.

关键词: 桥联化合物, 膦亚胺, 双金属中心配合物, 双峰聚乙烯

Abstract:

To explore the potential of oxygen-bridged bisphosphinimine titanium and nickel complexes possessing bimetallic centers as catalysts for olefin polymerization, two oxygen-bridged diphosphorus compounds, named bis-(2-diphenylphosphino) phenylether(1a) and 9,9-dimethyl-4,6-bis(diphenylphosphino)xanthene(1b), were synthesized. After Staudinger reaction with Me₃SiN₃ in toluene under reflux, compound 1a with a flexible diphenyl ether bridge was converted into the bisphosphinimine precusor, while compound 1b with a rigid xanthene bridge was transformed into the monophosphinimine one. Subsequently, the dehalosilylation with CpTiCl₃ afforded the corresponding phosphinimine titanium complexes 3a and 3b, respectively. Single titanium center complex 3b further reacts with NiBr₂(DME) to translate into titaniumnickel heteronuclear bimetallic complex 4b. The structures of the complexes were characterized by ¹H, ¹³C, ³¹P NMR and elemental analyses. And the molecular structures of complexes 3a and 4b were further determined by single-crystal X-ray diffraction analysis. When activated by the methylaluminoxane(MAO), complexes 3a and 4b displayed high catalytic activity for ethylene polymerization. The bimetallic titanium complex 3a produced a wide molecular weight distribution polyethylene product, while the titanium-nickel heteronuclear bimetallic complex 4b gave rise to the bimodal polyethylene product.

Key words: Bridged compound, Phosphinimine, Bimetallic complex, Bimodal polyethylene

中图分类号:

O631
O627

TrendMD:

王铁石, 陈建军, 叶霖, 张爱英, 冯增国. 氧桥联双核钛、镍配合物的合成及催化制备双峰聚乙烯. 高等学校化学学报, 2018, 39(11): 2586.

WANG Tieshi, CHEN Jianjun, YE Lin, ZHANG Aiying, FENG Zengguo. Synthesis of Oxygen-bridged Binuclear Titanium and Nickel Complexes and Application in Catalysis of Bimodal Polyethylene^†. Chem. J. Chinese Universities, 2018, 39(11): 2586.

图/表 6

参考文献 31

[1]	Zhong F., Schwabe J., Hofmann D., Meier J., Thomann R., Enders M., Mülhaupt R., Polymer, 2018, 140, 107—116
[2]	Li L. D., Wang Q., Fan Z. Q., Chem. J. Chinese Universities, 2004, 25(9), 1777—1779
	(李利东, 王齐, 范志强. 高等学校化学学报, 2004, 25(9), 1777—1779)
[3]	Ban Q., Sun J. Q., Chem. J. Chinese Universities, 2003, 24(12), 2304—2307
	(班青, 孙俊全. 高等学校化学学报, 2003, 24(12), 2304—2307)
[4]	Jin Y. L., Zhao N., Cheng R. H., Liu B. P., CIESC Journal, 2017, 68(2), 485—495
	(金玉龙, 赵柠, 程瑞华, 刘柏平. 化工学报, 2017, 68(2), 485—495)
[5]	Cheng R. H., Xue X., Liu W. W., Zhao N., He X. L., Liu Z., Liu B. P., Macromol. React. Eng., 2015, 9(5), 462—472
[6]	Takeuchi D., Chiba Y., Takano S., Kurihara H., Kobayashi M., Osakada K., Polym. Chem., 2017, 8, 5112—5119
[7]	Wang Z., Solan G. A., Mahmood O., Liu Q. B., Ma Y. P., Hao X., Sun W. H., Organometallics, 2018, 37, 380—389
[8]	Makio H., Terao H., Iwashita A., Fujita T., Chem. Rev., 2011, 111, 2363—2449
[9]	Su B. Y., Jia P. Y., Wang Y. Z., Li Y. N., Huang H., Li Q. D., Chin. J. Org. Chem., 2016, 36(10), 2344—2352
	(苏碧云, 郏佩瑜, 王彦昭, 李亚宁, 黄鹤, 李谦定. 有机化学, 2016, 36(10), 2344—2352)
[10]	Zhu B. L., Wang B. Q., Xu S. S., Zhou X. Z., Chin. J. Org. Chem., 2003, 23(10), 1049—1057
	(朱柏林, 王佰全, 徐善生, 周秀中. 有机化学, 2003, 23(10), 1049—1057)
[11]	Li M. Y., Shu X., Cai Z. G., Eisen M. S., Organometallics, 2018, 37(7), 1172—1180
[12]	Delferro M., Marks T. J., Chem. Rev., 2011, 111, 2450—2485
[13]	Weberski M .P., Chen C. L., Delferro M., Marks T. J., Chem. Eur. J., 2012, 18, 10715—10732
[14]	Xu S., Jia J. J., Huang J. L., J. Polym. Sci., Part A: Polym. Chem., 2007, 45, 4901—4913
[15]	Xu S., Liang C. C., Lv Z. W., Zhu Y. L., Zhang C., Mi P. K., Chin. J. Org. Chem., 2017, 37(5), 1284—1289
	(许胜, 梁春超, 吕中文, 朱玉玲, 张翠, 米普科. 有机化学, 2017, 37(5), 1284—1289)
[16]	Mi P. K., Xu S., Qu L. D., Zhang D. S., Qian C., Wang S. H., J. Appl. Polym. Sci., 2011, 121, 21—26
[17]	Xu S., Huang J. L., J. Appl. Polym. Sci., 2013, 130, 2891—2900
[18]	Xu S. S., Wu T., Cui H. L., Dai X. L., Wang B. Q., Zhou X. Z., Zou F. L., Li Y., Chem. J. Chinese Universities, 2002, 23(10), 1891—1895
	(徐善生, 吴涛, 崔慧玲, 代徐良, 王佰全, 周秀中, 邹丰楼, 李杨. 高等学校化学学报, 2002, 23(10), 1891—1895)
[19]	Haak R. M., Wezenberg S. J., Kleij A. W., Chem. Commun., 2010, 46, 2713—2723
[20]	Siemeling U., Kölling L., Stammler A., Stammler H. G., J. Chem. Soc., Dalton Trans., 2002, 3277—3279
[21]	Sarsfield M. J., Said M., Thornton-Pett M., Gerrard L. A., Bochmann M., J. Chem. Soc., Dalton Trans., 2001, 822—827
[22]	Hollink E., Stewart J. C., Wei P. R., Stephan D. W., J. Chem. Soc., Dalton Trans., 2003, 3968—3974
[23]	Hollink E., Stewart J. C., Wei P. R., Stephan D. W., Can. J. Chem., 2004, 82, 1304—1311
[24]	McInnis J. P., Delferro M., Marks T. J., Acc. Chem. Res., 2014, 47, 2545—2557
[25]	Deng X. B., Xu S. S., Wang B. Q., Zhou X. Z., Yang L., Li Y. F., Hu Y. L., Chem. J. Chinese Universities, 2002, 23(11), 2089—2092
	(邓小斌, 徐善生, 王佰全, 周秀中, 杨玲, 李于飞, 胡友良. 高等学校化学学报, 2002, 23(11), 2089—2092)
[26]	Salata M. R., Marks T. J., Macromolecules, 2009, 42(6), 1920—1933
[27]	Liu S., Motta A., Mouat A. R., Delferro M., Marks T. J., J. Am. Chem. Soc., 2014, 136, 10460—10469
[28]	Guo N., Stern C. L., Marks T. J., J. Am. Chem. Soc., 2008, 130, 2246—2261
[29]	Amin S. B., Marks T. J., J. Am. Chem. Soc., 2007, 129, 2938—2953
[30]	Kranenburg M., Burgt Y. E. M., Kamer P. C. J., Leeuwen P. W. N. M., Goubitz K., Fraanje J., Organometallics, 1995, 14, 3081—3089
[31]	Veen L. A., Keeven P. H., Schoemaker G. C., Reek J. N. H., Kamer P. C. J., Leeuwen P. W. N. M., Lutz M., Spek A. L., Organometallics, 2000, 19, 872—883

3a				3b
Ti1—Cl1	0.23011(17)	Cl2—Ti1—Cl1	101.79(5)	Ti1—Cl1	0.23161(19)	Cl1—Ti1—Cl2	104.25(7)
Ti1—N1	0.1766(3)	C24—O1—C23	115.9(3)	Ti1—N1	0.1769(4)	N1—P2—C26	108.0(2)
Ti2—N2	0.1764(3)	N1—Ti1—Cl1	102.67(12)	P1—C1	0.1834(6)	N1—Ti1—Cl1	102.23(16)
P1—N1	0.1593(3)	N2—Ti2—Cl3	103.38(12)	P2—N1	0.1602(4)	C25—C26—P2	115.2(4)
P1—C6	0.1799(4)	C18—P1—N1	109.44(18)	P2—C26	0.1808(5)	C27—O1—C18	118.8(4)
P2—N2	0.1579(3)	C29—P2—N2	112.29(18)	O1—C18	0.1389(6)	C27—C26—P2	125.3(4)
O1—C23	0.1398(5)	P1—N1—Ti1	163.2(2)	O1—C27	0.1380(6)	P2—N1—Ti1	164.7(3)
O1—C24	0.1392(5)	P2—N2—Ti2	158.0(2)

3a				3b
Ti1—Cl1	0.23011(17)	Cl2—Ti1—Cl1	101.79(5)	Ti1—Cl1	0.23161(19)	Cl1—Ti1—Cl2	104.25(7)
Ti1—N1	0.1766(3)	C24—O1—C23	115.9(3)	Ti1—N1	0.1769(4)	N1—P2—C26	108.0(2)
Ti2—N2	0.1764(3)	N1—Ti1—Cl1	102.67(12)	P1—C1	0.1834(6)	N1—Ti1—Cl1	102.23(16)
P1—N1	0.1593(3)	N2—Ti2—Cl3	103.38(12)	P2—N1	0.1602(4)	C25—C26—P2	115.2(4)
P1—C6	0.1799(4)	C18—P1—N1	109.44(18)	P2—C26	0.1808(5)	C27—O1—C18	118.8(4)
P2—N2	0.1579(3)	C29—P2—N2	112.29(18)	O1—C18	0.1389(6)	C27—C26—P2	125.3(4)
O1—C23	0.1398(5)	P1—N1—Ti1	163.2(2)	O1—C27	0.1380(6)	P2—N1—Ti1	164.7(3)
O1—C24	0.1392(5)	P2—N2—Ti2	158.0(2)

Entry	Cat.	Molar ratio of Al/Cat. ^a	Time/min	Temperature/℃	Pressure/MPa	Yield/g	Activity^b	10^-5M_w(GPC)	PDI
1	3a	1600	15	40	0.5	3.25	13.00	5.82	8.3
2	4b	1600	15	40	0.5	1.93	7.72	8.16	22.6
3	4b	400	15	40	0.5	0.64	2.56	3.88	11.4
4	4b	800	15	40	0.5	1.27	5.08	6.73	18.4
5	4b	3200	15	40	0.5	1.78	7.12	6.15	18.6
6	4b	1600	5	40	0.5	0.89	10.68	6.31	12.1
7	4b	1600	10	40	0.5	1.45	8.70	7.55	17.1
8	4b	1600	30	40	0.5	2.31	4.62	8.32	24.5
9	4b	1600	15	20	0.5	1.33	5.32	8.34	23.3
10	4b	1600	15	60	0.5	2.17	8.68	7.38	21.2
11	4b	1600	15	80	0.5	1.84	7.36	4.94	22.2
12	4b	1600	15	40	0.3	1.21	4.84	5.01	19.9
13	4b	1600	15	40	0.7	2.76	11.04	9.93	25.3

Entry	Cat.	Molar ratio of Al/Cat. ^a	Time/min	Temperature/℃	Pressure/MPa	Yield/g	Activity^b	10^-5M_w(GPC)	PDI
1	3a	1600	15	40	0.5	3.25	13.00	5.82	8.3
2	4b	1600	15	40	0.5	1.93	7.72	8.16	22.6
3	4b	400	15	40	0.5	0.64	2.56	3.88	11.4
4	4b	800	15	40	0.5	1.27	5.08	6.73	18.4
5	4b	3200	15	40	0.5	1.78	7.12	6.15	18.6
6	4b	1600	5	40	0.5	0.89	10.68	6.31	12.1
7	4b	1600	10	40	0.5	1.45	8.70	7.55	17.1
8	4b	1600	30	40	0.5	2.31	4.62	8.32	24.5
9	4b	1600	15	20	0.5	1.33	5.32	8.34	23.3
10	4b	1600	15	60	0.5	2.17	8.68	7.38	21.2
11	4b	1600	15	80	0.5	1.84	7.36	4.94	22.2
12	4b	1600	15	40	0.3	1.21	4.84	5.01	19.9
13	4b	1600	15	40	0.7	2.76	11.04	9.93	25.3