doi:10.11777/j.issn1000-3304.2019.19128

引用本文: 卢令攀, 王凯悌, 刘翼, 吴佳骏. 三齿β-酮亚胺钒(III)配合物的合成及其催化乙烯(共)聚合行为研究[J]. 高分子学报. doi: 10.11777/j.issn1000-3304.2019.19128 shu

Citation: Ling-pan Lu, Kai-ti Wang, Yi Liu and Jia-jun Wu. Systheisis of Vanadium Complexes Bearing Tridentate β-Ketoimine Ligands and Their Catalytic Capabilities towards Ethylene (Co)polymerization[J]. Acta Polymerica Sinica. doi: 10.11777/j.issn1000-3304.2019.19128 shu

三齿β-酮亚胺钒(III)配合物的合成及其催化乙烯(共)聚合行为研究

卢令攀 ¹ ,
王凯悌 ^{2
,
,} ,
刘翼 ² ,
吴佳骏 ²

1.
郑州工业应用技术学院药学与化学工程学院　郑州 451199
2.
重庆理工大学材料科学与工程学院　重庆 400054

通讯作者: 王凯悌, E-mail: ktwang@cqut.edu.cn

摘要: 合成了6种三齿β-酮亚胺钒(III)配合物{[(R)X(C₆H₄)N＝CH(C₆H₅)C₁₀H₇O]VCl₂(THF): 2a , R = CH₃, X = S; 2b , R = CF₃, X = S; 2c , R = Ph, X = S; 2d , R = ^tBu, X = S; 2e , R = Ph₂, X = P; 2f , R = Ph, X = O}，并对其结构进行了表征和证明. 2a ~ 2f 在催化乙烯均聚及其与环烯烃共聚时表现出了较高的催化活性和较为优异的稳定性，所得聚合物的分子量均呈单峰分布. 在催化乙烯与降冰片烯(NBE)共聚以及乙烯与外型-1,4,4a,9,9a,10-六氢-9,10(1 ′,2′)-桥苯亚基-1,4-桥亚甲基蒽(HBM)共聚时，部分催化剂表现出了“正共单体效应”. 催化所得乙烯/NBE共聚物的分子量为43.1 ~ 66.4 kg/mol，NBE单元含量为30.9 mol% ~ 42.1 mol%，玻璃化转变温度为84 ~ 105 °C；乙烯/HBM共聚物的分子量为90.2 ~ 138 kg/mol，HBM单元含量为14.7 mol% ~ 25.0 mol%，玻璃化转变温度为173 ~ 188 °C.

关键词:

English

Systheisis of Vanadium Complexes Bearing Tridentate β-Ketoimine Ligands and Their Catalytic Capabilities towards Ethylene (Co)polymerization

1.
School of Pharmacy and Chemical Engineering, Zhengzhou University of Industrial Technology, Zhengzhou 451199
2.
School of Materials Science and Engineering, Chongqing University of Technology, Chongqing 400054

Corresponding author: Kai-ti Wang, E-mail: ktwang@cqut.edu.cn

Received Date: 2019-07-03
Accepted Date: 2019-07-25
Available Online: 2019-01-01

Abstract: Vanadium catalysts always show outstanding catalytic properties towards ethylene (co)polymeriztaion, while the high-valent vanadium species would be deactivated because of the generation of inactive or less active low-valent species at elevated temperature and/or in prolonged time. As proved, introducing of bulky groups into the ligands is benefit to improving the catalytic properties of vanadium complexes. Herein, in order to well control the oxidation state of vanadium species, a series of tridentate β-ketoimine type vanadium(III) complexes bearing cyclic skeleton {[(R)X(C₆H₄)N＝CH(C₆H₅)C₁₀H₇O]VCl₂(THF): 2a , R = CH₃, X = S; 2b , R = CF₃, X = S; 2c , R = Ph, X = S; 2d , R = ^tBu, X = S; 2e , R = Ph₂, X = P; 2f , R = Ph, X = O}, were synthesized and characterized. Because of the constrained effects of the cyclic skeleton and the stabilizing effects of the bi-chelating ring, these synthesized catalysts showed high activities and improved stabilities in ethylene (co)polymerization. In the presences of Et₂AlCl and ethyl trichloroacetate, catalysts 2a − 2f showed 8.16 − 19.9 kg_polymer/(mmol_V·h), 7.68 − 26.9 kg_polymer/(mmol_V·h) and 4.80 − 42.2 kg_polymer/(mmol_V·h) of catalytic activities towards ethylene polymerization, ethylene/norbornene (NBE) copolymerization and ethylene/exo-1,4,4a,9,9a,10-hexahy-dro-9,10(1′,2′)-benzeno-1,4-methanoanthracene (HBM) copolymerization, respectively. All of the resultant polymers exhibited a unimodal distribution, indicating that these vanadium catalysts showed single-site catalytic behaviour, even at elevated temperatures (50 − 70 °C). Catalysts 2b , 2d , 2e and 2f showed "positive" comonomer effects in both ethylene/NBE copolymerization and ethylene/HBM copolymerization. Besides, 2a and 2c also exhibited positive comonomer effects in ethylene/HBM copolymerization. Cyclic olefin copolymers possessing high molecular weights (NBE: 43.1 − 66.4 kg/mol; HBM: 90.2 − 138 kg/mol) and high comonomer incorporations (NBE: 30.9 mol% − 42.1 mol%; HBM: 14.7 mol% − 25.0 mol%) were obtained facilely via direct copolymerization. The glass transition temperature is dominantly affected by the cyclic olefin incorporations and the steric hindrance of the cyclic olefin. Compared with the ethylene/NBE copolymers, the obtained ethylene/HBM copolymers showed much higher glass transition temperatures (NBE: 84 − 105 °C versus HBM: 173 − 188 °C).

Key words:

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Figure 1. Structures of the vanadium(III) catalysts

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Figure 2. The synthetic route to the ligands and complexes

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Figure 3. The GPC curves of the polyethylenes produced by 2e under different temperatures

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Figure 4. Evaluation of the lifetime of catalyst 2e

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Figure 5. The influences of Et₂AlCl on the ethylene polymerization catalyzed by 2e

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Figure 6. ¹³C-NMR spectra of ethylene/NBE copolymers produced by 2e (Top, NBE incorporation is 36.9 mol%; Bottom, BE incorporation is 30.9 mol%.)

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Figure 7. ¹³C-NMR spectra of ethylene/NBE copolymers produced by 2e (Top, NBE incorporation is 23.7 mol%; Bottom, BE incorporation is 14.7 mol%.)

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Table 1. Typical ethylene polymerization results ^a

Entry	Cat.	Temp. (°C)	Yield (g)	Activity (kg_PE/(mmol_V·h))	M_w ^b (kg/mol)	PDI ^b	T_m/T_c^c (°C)
1	2a	50	0.75	18.0	53.3	1.7	133/119
2	2b	50	0.79	19.0	58.2	1.7	133/118
3	2c	50	0.76	18.2	59.3	1.8	133/119
4	2d	50	0.40	9.60	67.8	1.8	133/119
5	2e	50	0.83	19.9	62.2	1.8	133/119
6	2f	50	0.50	12.0	58.9	1.9	133/119
7	2e	30	0.34	8.16	141	1.6	135/117
8	2e	70	0.54	13.0	32.6	1.4	131/120
^a Conditions: The feedstock of vanadium catalyst is 0.5 μmol; Et₂AlCl, 2.0 mmol; ETA, 0.15 mmol; solvent, toluene; total volume, 50 mL; polymerization time, 5 min; ethylene pressure, 0.1 MPa; ^b Determined by HT-GPC at 150 °C; ^c Measured on DSC

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Table 2. Typical ethylene/NBE copolymerization results ^a


Entry	Cat.	NBE (mol/L)	Yield (g)	Activity (kg_polymer/(mmol_V·h))	Comonomer incorp. ^b (mol%)	M_w ^c (kg/mol)	PDI ^c	T_g ^d (°C)
1	2a	0.5	0.66	15.8	33.2	58.1	1.3	84
2	2a	1.0	0.40	9.60	40.6	43.1	1.4	103
3	2b	0.5	0.81	19.4	34.3	63.7	1.3	89
4	2b	1.0	0.51	12.2	42.1	48.9	1.3	105
5	2c	0.5	0.74	17.8	32.1	64.0	1.3	87
6	2c	1.0	0.45	10.8	39.6	49.6	1.3	103
7	2d	0.5	0.58	13.9	31.4	64.5	1.4	88
8	2d	1.0	0.36	8.64	38.4	49.6	1.3	102
9	2e	0.5	1.12	26.9	30.9	66.4	1.3	86
10	2e	1.0	0.70	16.8	36.9	51.0	1.4	99
11	2f	0.5	0.51	12.2	34.0	52.9	1.4	84
12	2f	1.0	0.32	7.68	40.6	39.2	1.4	103
^a Conditions: The feedstock of vanadium catalyst is 0.5 μmol; Et₂AlCl, 2.0 mmol; ETA, 0.15 mmol; solvent, toluene; total volume, 50 mL; polymerization time, 5 min; ethylene pressure, 0.1 MPa; ^b Calculated according to the ¹³C NMR; ^cDetermined by GPC; ^d Measured by DSC

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Table 3. Typical ethylene/HBM copolymerization results ^a


Entry	Cat.	HBM (mmol)	Yield (g)	Activity (kg_polymer/(mmol_V·h))	Comonomer incorp.^b (mol%)	M_w ^c (kg/mol)	PDI ^c	T_g ^d (°C)
1	2a	0.2	0.84	20.2	15.5	90.2	1.7	135
2	2a	0.4	0.65	15.6	23.4	94.2	1.6	183
3	2b	0.2	0.86	20.6	16.9	99.6	1.6	137
4	2b	0.4	1.27	30.5	25.0	104	1.6	188
5	2c	0.2	1.13	27.1	16.4	110	1.6	137
6	2c	0.4	0.85	20.4	24.8	121	1.5	188
7	2d	0.2	0.43	10.3	14.7	104	1.6	131
8	2d	0.4	0.20	4.80	21.8	111	1.6	173
9	2e	0.2	0.93	22.3	14.7	116	1.6	131
10	2e	0.4	1.76	42.2	23.7	138	1.6	183
11	2f	0.2	0.60	14.4	15.6	91.6	1.6	133
12	2f	0.4	0.89	21.3	24.9	95.5	1.5	186
^a Conditions: The feedstock of vanadium catalyst is 0.5 μmol; Et₂AlCl, 2.0 mmol; ETA, 0.15 mmol; solvent, toluene; total volume, 50 mL; polymerization time, 5 min; ethylene pressure, 0.1 MPa; ^b Calculated according to the ¹³C NMR; ^cDetermined by GPC; ^d Measured by DSC

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

三齿β-酮亚胺钒(III)配合物的合成及其催化乙烯(共)聚合行为研究

通讯作者: 王凯悌, E-mail: ktwang@cqut.edu.cn

English

Systheisis of Vanadium Complexes Bearing Tridentate β-Ketoimine Ligands and Their Catalytic Capabilities towards Ethylene (Co)polymerization

Corresponding author: Kai-ti Wang, E-mail: ktwang@cqut.edu.cn

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