Preparation of Polyolefin Elastomers by Neutral Nickel Catalysts: Synergistic Effect of Steric Hindrance and Secondary Interaction

doi:10.6023/cjoc202403034

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (11): 3399-3408.DOI: 10.6023/cjoc202403034 Previous Articles Next Articles

ARTICLE

中性镍催化制备聚烯烃弹性体: 位阻与次级配位协同作用

李乾坤^a^,^b, 穆红亮^a^,^*(), 简忠保^a^,^b^,^*()

a 中国科学院长春应用化学研究所高分子物理与化学国家重点实验室长春 130022
b 中国科学技术大学应用化学与工程学院合肥 230026

收稿日期:2024-05-07 修回日期:2024-06-12 发布日期:2024-07-02
基金资助:
国家自然科学基金(22122110); 国家自然科学基金(U23B6011); 吉林省科技厅(20230101347JC)

Preparation of Polyolefin Elastomers by Neutral Nickel Catalysts: Synergistic Effect of Steric Hindrance and Secondary Interaction

Qiankun Li^a^,^b, Hongliang Mu^a,*(), Zhongbao Jian^a^,^b,*()

a State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022
b School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026

Received:2024-05-07 Revised:2024-06-12 Published:2024-07-02
Contact: *E-mail:muhongliang@ciac.ac.cn;zbjian@ciac.ac.cn
Supported by:
National Natural Science Foundation of China(22122110); National Natural Science Foundation of China(U23B6011); Jilin Provincial Science and Technology Department Program(20230101347JC)

Salicylaldiminato neutral nickel catalysts is a family of classic ethylene polymerization catalysts. Through elabrate modulation of the structures, various polyethylene materials with different characteristics can be prepared, such as highly branched polyethylene oil and ultra-high molecular weight polyethylene with low branching. However, these catalysts face certain challenges in the preparation of elastomeric materials. In this study, two arylamines containing both sterically hindered groups and adjacent heteroatom groups were designed and synthesized for the synthesis of salicylaldiminato ligands and the corresponding neutral nickel catalysts ({N-[2,4-bis(dibenzosuberyl)-6-phenoxy]phenyl-3-tert-butylsalicylideneiminato}-nickel(II)-(phenyl)(triphenylphosphine) (Ni2) and {N-[2,4-bis(dibenzosuberyl)-6-benzenesulfonyl]phenyl-3-tert-butylsalicyli- deneiminato}-nickel(II)-(phenyl)(triphenylphosphine) (Ni3)). The effects of temperature and ethylene pressure on catalytic performance were systematically investigated, revealing the variation patterns of catalyst thermal stability, catalytic activity, polymer molecular weight and branching density. The combination of the secondary coordination effect of the heteroatom groups and the steric effect of the arylamine allowed catalyst Ni3 containing SO₂Ph group to achieve a balance between branching density (61 brs/1000C) and polymer molecular weight (M_n=15.29×10⁴), providing strong support for the preparation of polyethylene elastomer with excellent mechanical properties. The synergistic effect of steric hindrance and secondary interaction provides new ideas for the development of novel salicylaldiminato neutral nickel catalysts and the design and optimization of related catalysts.

Key words: secondary interaction, steric hindrance, neutral nickel catalyst, salicylaldimine, polyolefin elastomer

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Qiankun Li, Hongliang Mu, Zhongbao Jian. Preparation of Polyolefin Elastomers by Neutral Nickel Catalysts: Synergistic Effect of Steric Hindrance and Secondary Interaction[J]. Chinese Journal of Organic Chemistry, 2024, 44(11): 3399-3408.

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Entry	Cat.	T/℃	Acitivity/(10⁵ g•mol^－1• h^－1)	M_n^b/10⁴	M_w/M_n^b	Branching density^c/(brs/1000C)	T_m^d/℃
1	Ni-1	30	0.60	22.03	1.7	16.5	117.9
2	Ni-1	50	3.80	7.20	1.9	46.3	81.7
3	Ni-1	70	8.20	2.79	2.2	73.0	—
4	Ni-1	90	3.40	1.48	2.0	94.2	—
5	Ni-2	30	0.20	1.66	2.0	60.5	85.9
6	Ni-2	50	2.20	1.00	2.2	69.6	70.9
7	Ni-2	70	5.68	0.39^f	—	92.0	—
8	Ni-2	90	2.88	0.13^f	—	103.7	—
9	Ni-3	30	1.08	17.69	1.8	63.3	—
10	Ni-3	50	5.44	16.33	1.5	85.7	—
11	Ni-3	70	3.68	7.61	1.6	110.7	—
12	Ni-3	90	1.84	2.65	1.7	119.2	—
13^e	Ni-3	30	3.92	28.92	1.4	35.5	83.6
14^e	Ni-3	50	20.80	15.29	1.7	61.0	—
15^e	Ni-3	70	10.32	8.38	1.7	85.8	—
16^e	Ni-3	90	4.84	4.80	1.5	99.1	—

Entry	Cat.	T/℃	Acitivity/(10⁵ g•mol^－1• h^－1)	M_n^b/10⁴	M_w/M_n^b	Branching density^c/(brs/1000C)	T_m^d/℃
1	Ni-1	30	0.60	22.03	1.7	16.5	117.9
2	Ni-1	50	3.80	7.20	1.9	46.3	81.7
3	Ni-1	70	8.20	2.79	2.2	73.0	—
4	Ni-1	90	3.40	1.48	2.0	94.2	—
5	Ni-2	30	0.20	1.66	2.0	60.5	85.9
6	Ni-2	50	2.20	1.00	2.2	69.6	70.9
7	Ni-2	70	5.68	0.39^f	—	92.0	—
8	Ni-2	90	2.88	0.13^f	—	103.7	—
9	Ni-3	30	1.08	17.69	1.8	63.3	—
10	Ni-3	50	5.44	16.33	1.5	85.7	—
11	Ni-3	70	3.68	7.61	1.6	110.7	—
12	Ni-3	90	1.84	2.65	1.7	119.2	—
13^e	Ni-3	30	3.92	28.92	1.4	35.5	83.6
14^e	Ni-3	50	20.80	15.29	1.7	61.0	—
15^e	Ni-3	70	10.32	8.38	1.7	85.8	—
16^e	Ni-3	90	4.84	4.80	1.5	99.1	—

中性镍催化制备聚烯烃弹性体: 位阻与次级配位协同作用

Preparation of Polyolefin Elastomers by Neutral Nickel Catalysts: Synergistic Effect of Steric Hindrance and Secondary Interaction

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