<i>α</i>-二亚胺镍(Ⅱ)催化乙烯与乙烯基三甲氧基硅烷共聚

张丹枫; 张文杰; 牛犇; 仝鑫

doi:10.14135/j.cnki.1006-3080.20220531001

α-二亚胺镍(Ⅱ)催化乙烯与乙烯基三甲氧基硅烷共聚

doi: 10.14135/j.cnki.1006-3080.20220531001

华东理工大学材料科学与工程学院, 上海市先进聚合物材料重点实验室, 上海200237

基金项目: 上海市重点学科和重点实验室项目（08DZ2230500）

详细信息

作者简介:
张丹枫（1965—），女，江苏宜兴人，副教授，博士，从事烯烃配位聚合研究。zdf93102@ecust.edu.cn

中图分类号: O631;O614.81
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- 文章访问数: 99
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出版历程
- 收稿日期: 2022-05-31
- 网络出版日期: 2022-09-14

Copolymerization of Ethylene and Vinyl Trimethoxysilane with α-diimine Nickel (II) Catalysts

Shanghai Key Laboratory of Advanced Polymeric Materials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China

摘要

摘要: 采用一系列不同结构的α-二亚胺镍(Ⅱ)催化剂，在倍半乙基氯化铝（EASC）作用下，催化乙烯和乙烯基三甲氧基硅烷（VTMoS）共聚。研究了催化剂结构、VTMoS浓度、催化剂用量、Al/Ni摩尔比、乙烯压力、聚合时间和溶剂等对共聚的影响，得到了最优化的催化工艺条件。采用高温核磁（NMR）、傅利叶红外光谱（FTIR）和差示扫描量热分析（DSC）表征了共聚物的微观结构和熔点，等离子体发射光谱测定了共聚物中的硅含量，平衡溶胀法分析了共聚物的交联程度以及共聚物交联网络的均匀性。研究结果表明，以 C4 为催化剂，乙烯压力为2~3 MPa，催化活性高达10⁶ g/(mol_Ni·h)，共聚物中硅含量在0.8%~2.1%。
- α-二亚胺镍催化剂 /
- 乙烯 /
- 乙烯基三甲氧基硅烷 /
- 共聚 /
- 功能化聚烯烃
Abstract: A series of α-diimine nickel (Ⅱ) catalysts [(2,6-C₆H₃R₂)-N=C(R₁)-C(R₁)=N-(2,6-C₆H₃R₂)]NiBr₂ ( C1 : R₁ = H, R₂ = CH₃, C2 : R₁ = H, R₂ = iPr, C3 : R₁ = CH₃, R₂ = CH₃, C4 : R₁ = CH₃, R₂ = iPr, C5 : R₁ = acenaphthyl, R₂ = iPr), in the presence of ethylaluminum sesquichloride (EASC) as cocatalyst, were applied in the copolymerization of ethylene and vinyl trimethoxysilane (VTMoS). The effects of polymerization parameters, in which VTMoS concentration, catalyst dosage, molar ration of Al/Ni (n_Al/n_Ni), ethylene pressure, reaction time and solvents were varied on the copolymerization were investigated with C4 as a model catalyst. The optimized catalytic reaction conditions, in which ([VTMoS] = 0.5 mol/L, 5 μmol catalyst, n_Al/n_Ni = 400, 1 MPa pressure, 25 ℃, for 0.5 h, toluene as solvent were obtained. The influence of the catalyst structures on the copolymerization were explored under the optimized conditions. High temperature ¹H, ¹³C-NMR, Fourier infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) were used to characterize the microstructure of the copolymers. Inductively coupled plasma (ICP) was applied to determine the silicon content of the copolymers. Equilibrium swelling method was used to study the crosslinking degree of copolymers. The results show that the catalytic activity of C4 reaches to 10⁶ g/(mol_Ni·h) in toluene and ethylene pressure of 2~3 MPa. With the increase of steric hindrance of α-diimine skeleton structure, the crosslinking degree of copolymer increases and the crosslinking network become more uniform. The contents of silicon in copolymer are in the range of 0.8% ~ 2.1%.
- α-diimine nickel catalyst /
- ethylene /
- vinyl trimethoxysilane /
- copolymerization /
- functional polyolefin

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1. α-diimine nickel(II) complexes （C1-C5）

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图 1 乙烯/VTMoS共聚物的¹H NMR谱图（表2中Entry 4）

Figure 1. ¹H NMR of ethylene/VTMoS copolymer (entry 4 in Table 2)

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图 2 乙烯/VTMoS共聚物的¹³C NMR谱图（表2中Entry 4）

Figure 2. ¹³C-NMR of ethylene/VTMoS copolymer (entry 4 in Table 2)

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图 3 乙烯/VTMoS共聚物的红外谱图（表2中Entry 5）

Figure 3. FTIR spectrum of ethylene/VTMoS copolymer (entry 5 in Table 2)

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图 4 乙烯/VTMoS共聚物的DSC图（表2中Entry 3~5）

Figure 4. DSC curve of ethylene/VTMoS copolymers (entry 3~5 in Table 2)

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表 1 反应条件对催化剂C4催化乙烯/VTMoS共聚合的影响

Table 1. Influence of reaction parameters on copolymerization of ethylene/VTMoS by catalyst C4

Entry	[Si]/ (mol/L)	[Cat]/ μmol	n_Al/n_Ni	P_C2H2 /MPa	t/ h	Activity/ (10⁵g/mol _Ni·h)	f ^a	% gel^a	M_c ^a g/mol
1	0	5	400	1	1	7.89	-	-	-
2	0.50	5	400	1	1	6.53	11.39	96.95	2902.25
3	1.00	5	400	1	1	3.24	10.26	65.48	2382.63
4	1.50	5	400	1	1	0.02	-	-	-
5	0.50	2.5	400	1	1	2.12	9.49	98.68	2048.10
6	0.50	10	400	1	1	3.26	7.01	96.34	1126.44
7	0.50	5	200	1	1	4.33	6.90	98.92	1092.69
8	0.50	5	800	1	1	6.51	10.15	89.93	2332.06
9	0.50	5	1000	1	1	9.01	6.48	89.47	961.30
10	0.50	5	400	0.5	1	1.19	5.13	95.91	589.23
11	0.50	5	400	2	1	10.41	12.37	91.46	3394.02
12	0.50	5	400	3	1	10.00	22.18	90.06	9858.99
13	0.50	5	400	1	0.5	7.50	6.90	97.33	1093.48
14	0.50	5	400	1	2	3.18	7.14	80.92	1169.58
15	0.50	5	400	1	4	2.04	8.34	81.75	1593.30
16	0.50	5	400	1	1	trance	-	-	-
17	0.50	5	400	1	1	11.63	23.38	84.66	10829.44
Co-catalyst: AlEt₂Cl; Entries 1-15, solvent: toluene, entry 16, solvent: hexane; entry 17, solvent: dichloromethane. Temperature: 25°C; V (toluene)=50 mL; a. f, % gel and M_c were determined by solvent swelling and extraction of the sample under refluxing p-xylene (139 °C).

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表 2 催化剂结构对乙烯/VTMoS共聚的影响

Table 2. Influence of catalyst structures on ethylene/VTMoS copolymerization

Entry	Catalyst structure	Activity/ (10⁵g·mol⁻¹_Ni·h⁻¹)	f ^a	gel^a/%	M_c^a/(g·mol⁻¹)	Si^b/%
1	C1	0.14	-	-	-	-
2	C2	0.72	13.85	70.76	4188.20	1.7
3	C3	0.70	6.90	47.97	1091.62	1.2
4	C4	6.53	11.39	96.95	2902.25	2.1
5	C5	0.84	9.94	73.42	2240.58	0.82
Catalyst dosage: 5 μmol; [VTMoS] = 0.50 mol/L; n_Al/n_Ni = 400, Ethylene pressure: 1 MPa; Temperature: 25 °C; Time: 1 h; V (total) = 50 mL; Solvent: toluene; a. f, % gel and M_c were determined by solvent swelling and extraction of the sample under refluxing p-xylene (139 °C). b. Si % was determined by inductively coupled plasma (ICP).

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