吡啶双亚胺酰氯Ni(Ⅱ)配合物的合成、 表征及催化合成液体聚丁二烯

doi:10.7503/cjcu20131246

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (6): 1336.doi: 10.7503/cjcu20131246

吡啶双亚胺酰氯Ni(Ⅱ)配合物的合成、表征及催化合成液体聚丁二烯

刘恒^1,², 刘李^1,³, 王凤^1,², 贾翔宇^1,², 白晨曦¹, 张春雨¹(), 张学全¹()

1. 中国科学院长春应用化学研究所高性能合成橡胶工程技术中心, 长春 130022
2. 中国科学院大学, 北京 100049
3. 吉林大学材料科学与工程学院, 长春 130022

收稿日期:2013-12-18 出版日期:2014-06-10 发布日期:2014-01-23
作者简介:联系人简介: 张学全, 男, 研究员, 博士生导师, 主要从事新型结构聚烯烃、聚双烯烃材料的合成研究. E-mail:xqzhang@ciac.ac.cn;张春雨, 男, 博士, 副研究员, 主要从事新型结构聚烯烃、聚双烯烃材料的合成研究. E-mail:cyzhang@ciac.ac.cn
基金资助:
中国科学院“百人计划”项目(批准号: Y220011001)、国家自然科学基金(批准号: 51203147)和吉林省基础研究计划基金(批准号: 20130102007JC)资助

Synthesis,Characterization of Bis(arylcarboximidoylchloride)pyridine Ni(Ⅱ) Complexes and Their Catalytic Behavior for the Synthesis of Liquid Polybutadiene^†

LIU Heng^1,², LIU Li^1,³, WANG Feng^1,², JIA Xiangyu^1,², BAI Chenxi¹, ZHANG Chunyu^1,^*(), ZHANG Xuequan^1,^*()

1. R & D Centre of High-performance Synthetic Rubber, Changchun Institute of Applied Chemistry,Chinese Academy of Sciences, Changchun 130022, China
2. University of Chinese Academy of Sciences, Beijing 100049, China
3. College of Material Science and Engineering, Jilin University, Changchun 130022, China

Received:2013-12-18 Online:2014-06-10 Published:2014-01-23
Contact: ZHANG Chunyu,ZHANG Xuequan E-mail:cyzhang@ciac.ac.cn;xqzhang@ciac.ac.cn
Supported by:
† Supported by the “100 Talents Project” of Chinese Academy of Sciences, China(No.Y220011001), the National Natural Science Foundation of China(No.51203147) and the Jilin Provincial Research Foundation for Basic Research, China(No.20130102007JC)

摘要/Abstract

摘要：

合成了一系列吡啶双亚胺酰氯三齿Ni(Ⅱ) 配合物(1a~1c, 2a~2c), 通过傅里叶变换红外光谱和元素分析对配合物进行表征, 测定了配合物1a~1c的晶体结构. 3个化合物同属于单斜晶系, 且都具有以Ni原子为中心的近似于C_s对称的扭曲三角双锥构型. 该系列配合物通过倍半乙基氯化铝(EASC)活化, 在20 ℃下对丁二烯聚合表现出良好的催化活性, 得到分子量为4700~5200、 cis-1,4含量为74.8%~77.2%(摩尔分数)的液体聚丁二烯. 通过改变配体的结构和聚合条件, 可在一定范围内调控聚丁二烯的结构和分子量.

关键词: 吡啶双亚胺酰氯, 镍配合物, 1, 3-丁二烯聚合

Abstract:

A series of bis(arylcarboximidoylchloride)pyridine Ni(Ⅱ) complexes with the general formula [2,6-(ArN═CCl)₂C₅H₃N]NiX₂[Ar=2,6-Me₂C₆H₃, X=Br(1a) or Cl(2a); Ar=2,4,6-Me₃C₆H₂, X=Br(1b) or Cl(2b); Ar=4-Cl-2,6-Me₂C₆H₂, X=Br(1c) or Cl(2c)] were synthesized and characterized by FTIR and elemental analysis. The molecular structures of 1a—1c were further characterized by X-ray single crystal diffraction, and the geometry at the metal centre for all the three complexes can be best described as distorted trigonal bipyramidal. At the presence of ethylaluminum sesquichloride(EASC), all the Ni(Ⅱ)-based complexes performed high activities towards butadiene polymerization at 20 ℃, liquid polybutadienes(PB) with molecular weight of 4700—5200 and medium cis-1,4-PB content(74.8%—77.2%) was obtained. Catalytic activities of the catalysts and the microstructures of the resulting polymers were little depen-dent on the ligand environment and highly dependent on polymerization conditions.

Key words: Bis(arylcarboximidoylchloride)pyridine, Ni(Ⅱ) complex, 1, 3-Butadiene polymerization

中图分类号:

O632.14

TrendMD:

刘恒, 刘李, 王凤, 贾翔宇, 白晨曦, 张春雨, 张学全. 吡啶双亚胺酰氯Ni(Ⅱ)配合物的合成、表征及催化合成液体聚丁二烯. 高等学校化学学报, 2014, 35(6): 1336.

LIU Heng, LIU Li, WANG Feng, JIA Xiangyu, BAI Chenxi, ZHANG Chunyu, ZHANG Xuequan. Synthesis,Characterization of Bis(arylcarboximidoylchloride)pyridine Ni(Ⅱ) Complexes and Their Catalytic Behavior for the Synthesis of Liquid Polybutadiene^†. Chem. J. Chinese Universities, 2014, 35(6): 1336.

图/表 11

Scheme 1 Synthetic process of Ni-based catalysts

Fig.1 Crystal structure of complex 1aMethylene dichloride molecules were omitted for clarity.

Fig.2 Crystal structure of complex 1bMethylene dichloride molecules were omitted for clarity.

Fig.3 Crystal structure of complex 1cMethylene dichloride were omitted for clarity.

Table 1 Crystal data and collection parameters of complexes 1a—1c

Complex	1a	1b·CH₂Cl₂	1c·CH₂Cl₂
Fomula	C₂₃H₂₁Br₂Cl₂N₃Ni	C₂₆H₂₇Br₂Cl₄N₃Ni	C₂₄H₂₁Br₂Cl₆N₃Ni
Molecular weight	628.86	741.84	782.67
Crystal system	Monoclinic	Monoclinic	Monoclinic
Space group	P2₁/c	P2₁/n	P2₁/n
a/nm	1.2328(2)	0.84209(9)	0.82406(5)
b/nm	1.8917(3)	2.2750(2)	2.28681(13)
c/nm	1.2291(1)	1.63727(16)	1.62322(9)
α/(°)	90.0	90.0	90.0
β/(°)	117.610(1)	102.488(2)	101.624(1)
γ/(°)	90.0	90.0	90.0
V/nm³	2.5400(6)	3.0624(5)	2.9962(3)
Z	4	4	4
T/K	188	293	188
D_c/(g·cm³)	1.645	1.609	1.735
μ(Mo Kα)/mm^-1	4.14	3.61	3.87
F(000)	1248	1480	1544
θ_range/(°)	2.2—23.4	2.2—23.1	2.2—25.6
Number of reflections collected	14280(R_int=0.069)	17609(R_int=0.032)	19049(R_int=0.035)
Number of independent reflections	4517	5399	5878
Number of data/restraints/parameters	4517/0/284	5399/0/331	5878/0/329
Goodness of fit	1.002	1.040	1.053
R₁[I>2σ(I)]	0.068	0.065	0.058
wR₂	0.185	0.223	0.189

Table 2 Selected bond distances(nm) and bond angles(°) of complexes 1a—1c

Bond	1a	1b·CH₂Cl₂	1c·CH₂Cl₂
Ni1—N1	0.2191(6)	0.2232(5)	0.2216(5)
Ni1—N2	0.1995(6)	0.1982(5)	0.1981(5)
Ni1—N3	0.2182(6)	0.2257(5)	0.2236(5)
Ni1—Br1	0.24233(16)	0.23226(12)	0.23843(10)
Ni1—Br2	0.23487(14)	0.23845(12)	0.23343(10)
N1—C1	0.1252(11)	0.1252(8)	0.1253(8)
N1—C14	0.1445(9)	0.1447(9)	0.1439(8)
N2—C6	0.1319(10)	0.1315(9)	0.1333(8)
N2—C2	0.1332(10)	0.1350(8)	0.1341(7)
N3—C7	0.1274(10)	0.1249(9)	0.1261(8)
N3—C8	0.1458(10)	0.1455(8)	0.1440(8)
N1—Ni1—N2	76.70(2)	77.40(2)	77.58(19)
N1—Ni1—Br1	96.45(19)	99.78(14)	94.37(13)
N1—Ni1—Br2	99.16(17)	94.49(14)	99.38(13)
N2—Ni1—N3	77.10(2)	75.90(2)	76.40(2)
N2—Ni1—Br1	155.00(2)	141.87(16)	144.06(15)
N2—Ni1—Br2	90.60(19)	98.29(16)	97.07(14)
N3—Ni1—Br1	96.74(19)	97.39(15)	94.25(14)
N3—Ni1—Br2	99.05(17)	95.34(15)	98.33(14)
N1—Ni1—N3	150.6(2)	152.6(2)	153.43(19)
Ni1—N1—C14	127.7(5)	128.2(4)	127.7(4)
Ni1—N3—C8	127.1(5)	127.9(4)	127.3(4)
C1—N1—C14	120.9(7)	121.4(6)	127.7(4)
C7—N3—C8	120.8(6)	122.1(6)	127.3(4)

Table 3 Butadiene polymerizatioin results using complexes 1a—1d, 2b—2d as catalystsa

Entry	Cat.	Al agent^b	T/℃	Yield(%)	10^-3 $M n c$	M_w/ $M n c$	Microstructure fraction^d(%)
Entry	Cat.	Al agent^b	T/℃	Yield(%)	10^-3 $M n c$	M_w/ $M n c$	Cis-1,4-PB	1,2-PB	Trans-1,4-PB
1	1a	EASC	20	94.2	5.1	3.2	77.2	0.9	21.9
2	1b	EASC	20	94.0	4.7	3.0	74.8	1.1	24.1
3	1c	EASC	20	92.7	5.0	3.0	75.8	1.1	23.2
4	2a	EASC	20	97.8	5.2	3.1	77.2	1.0	21.8
5	2b	EASC	20	96.0	4.8	3.1	75.4	1.0	23.7
6	2c	EASC	20	96.5	5.2	3.0	76.0	1.2	22.8
7	1b	EASC	-5	23.3	18.6	2.2	89.2	3.3	7.5
8	1b	EASC	50	61.0	4.5	4.0	69.5	1.5	29.0
9	1b	TEA	20	1.8
10	1b	TIBA	20

Table 3 Butadiene polymerizatioin results using complexes 1a—1d, 2b—2d as catalystsa

Entry	Cat.	Al agent^b	T/℃	Yield(%)	10^-3 $M n c$	M_w/ $M n c$	Microstructure fraction^d(%)
Entry	Cat.	Al agent^b	T/℃	Yield(%)	10^-3 $M n c$	M_w/ $M n c$	Cis-1,4-PB	1,2-PB	Trans-1,4-PB
1	1a	EASC	20	94.2	5.1	3.2	77.2	0.9	21.9
2	1b	EASC	20	94.0	4.7	3.0	74.8	1.1	24.1
3	1c	EASC	20	92.7	5.0	3.0	75.8	1.1	23.2
4	2a	EASC	20	97.8	5.2	3.1	77.2	1.0	21.8
5	2b	EASC	20	96.0	4.8	3.1	75.4	1.0	23.7
6	2c	EASC	20	96.5	5.2	3.0	76.0	1.2	22.8
7	1b	EASC	-5	23.3	18.6	2.2	89.2	3.3	7.5
8	1b	EASC	50	61.0	4.5	4.0	69.5	1.5	29.0
9	1b	TEA	20	1.8
10	1b	TIBA	20

Fig.4 Influence of temperature on the microstructures of polybutadienes obtained from 1b/EASC system

Fig.5 FTIR spectrum of polybutadiene obtained in Entry 2, Table 3

Fig.6 1H NMR spectrum of polybutadiene obtained in Entry 2, Table 3

Fig.7 13C NMR spectrum of polybutadiene obtained in Entry 2, Table 3

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吡啶双亚胺酰氯Ni(Ⅱ)配合物的合成、表征及催化合成液体聚丁二烯

Synthesis,Characterization of Bis(arylcarboximidoylchloride)pyridine Ni(Ⅱ) Complexes and Their Catalytic Behavior for the Synthesis of Liquid Polybutadiene^†

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吡啶双亚胺酰氯Ni(Ⅱ)配合物的合成、 表征及催化合成液体聚丁二烯

Synthesis,Characterization of Bis(arylcarboximidoylchloride)pyridine Ni(Ⅱ) Complexes and Their Catalytic Behavior for the Synthesis of Liquid Polybutadiene†

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吡啶双亚胺酰氯Ni(Ⅱ)配合物的合成、表征及催化合成液体聚丁二烯

Synthesis,Characterization of Bis(arylcarboximidoylchloride)pyridine Ni(Ⅱ) Complexes and Their Catalytic Behavior for the Synthesis of Liquid Polybutadiene^†