Synthesis of Branched Polyethylene Wax using Bulky Iminopyridyl Nickel-Catalyzed Ethylene Chain-Walking Polymerization★

doi:10.6023/A25080288

Acta Chimica Sinica ›› 2025, Vol. 83 ›› Issue (12): 1480-1487.DOI: 10.6023/A25080288 Previous Articles Next Articles

Special Issue: “中国青年化学家”合辑

Article

大位阻亚胺吡啶镍催化乙烯链行走聚合制备支化聚乙烯蜡^★

薛虎^a, 徐姗^a, 王福周^a^,^*(), 陈昶乐^b^,^*()

^a 安徽大学物质科学与信息技术研究院合肥 230601
^b 中国科学技术大学高分子科学与工程系合肥 230026

投稿日期:2025-08-25 发布日期:2025-10-10
作者简介:
^★ “中国青年化学家”专辑.
基金资助:
中国科学院战略性先导科技专项(XDA0540000); 国家自然科学基金(52025031); 国家自然科学基金(22261142664); 中科院稳定支持基础研究领域青年团队计划(YSBR-094)

Synthesis of Branched Polyethylene Wax using Bulky Iminopyridyl Nickel-Catalyzed Ethylene Chain-Walking Polymerization^★

Hu Xue^a, Shan Xu^a, Fuzhou Wang^a^,^*(), Changle Chen^b^,^*()

^a Institutes of Physical Science and Information Technology, Anhui University, Hefei 230601
^b Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026

Received:2025-08-25 Published:2025-10-10
Contact: * E-mail: wangfuzhou@ahu.edu.cn;changle@ustc.edu.cn
About author:
^★For the VSI "Rising Stars in Chemistry".
Supported by:
the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA0540000); the National Natural Science Foundation of China(52025031); the National Natural Science Foundation of China(22261142664); the Chinese Academy of Sciences Project for Young Scientists in Basic Research(YSBR-094)

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Abstract

Polyethylene wax has the physical properties of ethylene oligomer, and can be used as lubricant, stabilizer and adhesive. It is widely used in plastics, rubber, ink, cosmetics and other fields. Its preparation technology has been upgraded from the traditional thermal cracking process to catalytic ethylene polymerization technology. In this work, we synthesized three iminopyridyl nickel catalysts Ni1~Ni3 with different steric effects and bulky 2,4,6-tris(4-fluorophenyl)methyl substituents, and investigated their catalytic performance in ethylene chain-walking polymerization processes. Results demonstrated that catalyst structure and polymerization conditions directly influence ethylene catalytic activity, as well as the molecular weight and branching degree of the resulting polyethylene wax. All catalysts successfully produced branched polyethylene waxes with methyl groups and long side chains, exhibiting narrow dispersion. By adjusting polymerization temperature (0~75 ℃), the branching structure of polyethylene wax could be effectively controlled (15~61/1000C). A solid powder of polyethylene was obtained at lower temperatures, primarily composed of methyl branches. These catalysts exhibited nearly identical superior performance to toluene in industrial solvent n-heptane. The Ph-substituted Ni2 showed high catalytic activity of 4.55×10⁶ g•mol^－1•h^－1 in n-heptane versus 4.72×10⁶ g•mol^－1•h^－1 in toluene. This technology enables direct synthesis of branched polyethylene wax materials through chain-walk polymerization, featuring simple preparation, cost-effectiveness, high catalytic efficiency, and excellent solvent tolerance. It paves new pathways for high-value production of polyethylene waxes in industrial applications.

Key words: branch polyethylene wax, ethylene polymerization, iminopyridyl nickel, chain-walking, catalyst design

Cite this article

Hu Xue, Shan Xu, Fuzhou Wang, Changle Chen. Synthesis of Branched Polyethylene Wax using Bulky Iminopyridyl Nickel-Catalyzed Ethylene Chain-Walking Polymerization^★[J]. Acta Chimica Sinica, 2025, 83(12): 1480-1487.

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References 26

[27]	Falivene L.; Wiedemann T.; Göttker-Schnetmann I.; Caporaso L.; Cavallo L.; Mecking S. J. Am. Chem. Soc. 2018, 140, 1305. doi: 10.1021/jacs.7b08975 pmid: 29261306
[28]	Ito S.; Ota Y.; Nozaki K. Dalton Trans. 2012, 41, 13807. doi: 10.1039/c2dt31771k
[29]	Liao Y. D.; Cai Q.; Dai S. Y. Chin. J. Polym. Sci. 2023, 41, 233. doi: 10.1007/s10118-022-2847-5
[30]	Wang Z.; Zhang Y. F.; Ma Y. P.; Hu X. Q.; Solan G. A.; Sun Y.; Sun W. H. J. Polym. Sci. Pol. Chem. 2017, 55, 3494. doi: 10.1002/pola.v55.20
[31]	Wiedemann T.; Voit G.; Tchernook A.; Roesle P.; Göttker-Schnetmann I.; Mecking S. J. Am. Chem. Soc. 2014, 136, 2078. doi: 10.1021/ja411945n pmid: 24450458
[32]	Zhu C. G.; Ding B. H.; Dai S. Y. J. Organomet. Chem. 2023, 1001, 5.
[33]	Dai S. Y.; Chen C. L. Angew. Chem. Int. Ed. 2016, 55, 13281. doi: 10.1002/anie.v55.42
[34]	Dai S. Y.; Sui X. L.; Chen C. L. Angew. Chem. Int. Ed. 2015, 54, 9948. doi: 10.1002/anie.v54.34
[35]	Guo L. H.; Zou C.; Dai S. Y.; Chen C. L. Polymers 2017, 9, 10. doi: 10.3390/polym9010010
[36]	Li M.; Wang X. B.; Luo Y.; Chen C. L. Angew. Chem. Int. Ed. 2017, 56, 11604. doi: 10.1002/anie.v56.38
[37]	Lian K. B.; Zhu Y.; Li W. M.; Dai S. Y.; Chen C. L. Macromolecules 2017, 50, 6074. doi: 10.1021/acs.macromol.7b01087
[38]	Long B. K.; Eagan J. M.; Mulzer M.; Coates G. W. Angew. Chem. Int. Ed. 2016, 55, 7106. doi: 10.1002/anie.v55.25
[39]	Na Y. N.; Dai S. Y.; Chen C. L. Macromolecules 2018, 51, 4040. doi: 10.1021/acs.macromol.8b00467
[40]	Wang F. Z.; Tanaka R.; Cai Z. G.; Nakayama Y.; Shiono T. Polymer 2017, 127, 88. doi: 10.1016/j.polymer.2017.08.050
[41]	Wang F. Z.; Tanaka R.; Li Q. S.; Nakayama Y.; Yuan J. C.; Shiono T. J. Mol. Catal. A-Chem. 2015, 398, 231. doi: 10.1016/j.molcata.2014.11.004
[42]	Zhang D. F.; Nadres E. T.; Brookhart M.; Daugulis O. Organometallics 2013, 32, 5136. doi: 10.1021/om400704h
[1]	Chen M.; Chen C.-L. Chin. Sci. Bull. 2022, 67, 1881 (in Chinese). doi: 10.1360/TB-2021-1187
	(陈敏, 陈昶乐, 科学通报, 2022, 67, 1881.)
[2]	Wang Y.; Yan J.-L. Acta Chim. Sinica 2023, 81, 275 (in Chinese). doi: 10.6023/A23010004
	(汪阳, 阎敬灵, 化学学报, 2023, 81, 275.) doi: 10.6023/A23010004
[3]	Wang Z.-H.; Chen M.; Chen C.-L. Acta Chim. Sinica 2023, 81, 559 (in Chinese). doi: 10.6023/A23040162
	(王子豪, 陈敏, 陈昶乐, 化学学报, 2023, 81, 559.) doi: 10.6023/A23040162
[4]	Zhuang Y.-J. Scientia Sinica (Chimica) 2025, 55, 1917 (in Chinese).
	(庄严俊, 中国科学:化学, 2025, 55, 1917.)
[5]	Stürzel M.; Mihan S.; Mülhaupt R. Chem. Rev. 2016, 116, 1398. doi: 10.1021/acs.chemrev.5b00310 pmid: 26375718
[6]	Ciesinska W.; Liszynska B.; Zielinski J. J. Therm. Anal. Calorim. 2016, 125, 1439. doi: 10.1007/s10973-016-5706-1
[7]	El-Nahas H. H.; Gad Y. H.; El-Hady M. A.; Ramadan A. B. Defects Solids 2012, 167, 367.
[8]	Khoshsefat M.; Ahmadjo S.; Zohuri G. H.; Ma Y. P.; Sun W. H. Appl. Organomet. Chem. 2023, 37, e7226.
[9]	Peng L. M.; Xu Z.; Wang W. Y.; Zhao X.; Bao R. Y.; Bai L.; Ke K.; Liu Z. Y.; Yang M. B.; Yang W. ACS Appl. Energy Mater. 2021, 4, 11173. doi: 10.1021/acsaem.1c02052
[43]	Gan J.; Dai S. Y. Polym. Chem. 2025, 16, 3172. doi: 10.1039/D5PY00083A
[44]	Laine T. V.; Piironen U.; Lappalainen K.; Klinga M.; Aitola E.; Leskelä M. J. Organomet. Chem. 2000, 606, 112. doi: 10.1016/S0022-328X(00)00291-6
[45]	Rauf H. S.; Liu Y. S.; Arslan M.; Solanki S. P. S.; Deydier E.; Poli R.; Grabow L. C.; Harth E. ACS Catal. 2024, 14, 13136. doi: 10.1021/acscatal.4c02708
[46]	Yan Z. P.; Xu G. Y.; Wang H.; Dai S. Y. Eur. Polym. J. 2022, 168, 7.
[47]	Figueira C. A.; Lopes P. S.; Gomes C. S. B.; Gomes J. C. S.; Lemos F.; Gomes P. T. Dalton Trans. 2018, 47, 15857. doi: 10.1039/c8dt02824a pmid: 30358779
[48]	Figueira C. A.; Lopes P. S.; Gomes C. S. B.; Gomes J. C. S.; Veiros L. F.; Lemos F.; Gomes P. T. Organometallics 2019, 38, 614. doi: 10.1021/acs.organomet.8b00669
[49]	Lu L. P.; Mu J. S.; Li Y. S. Chin. J. Polym. Sci. 2014, 32, 603. doi: 10.1007/s10118-014-1436-7
[50]	Mashima K.; Tsurugi H. J. Organomet. Chem. 2005, 690, 4414. doi: 10.1016/j.jorganchem.2004.12.035
[51]	Su B. Y.; Ta H. B.; Zhang Q. Z. Chin. J. Catal. 2011, 32, 1439.
[52]	Sun W. H.; Song S. J.; Li B. X.; Redshaw C; Hao X; Li Y. S.; Wang F. S. Dalton Trans. 2012, 41, 11999. doi: 10.1039/c2dt30989k
[53]	Chen Z.; Allen K. E.; White P. S.; Daugulis O.; Brookhart M. Organometallics 2016, 35, 1756. doi: 10.1021/acs.organomet.6b00165
[54]	Dai S. Y.; Sui X. L.; Chen C. L. Chem. Commun. 2016, 52, 9113. doi: 10.1039/C6CC00457A
[55]	Rong C. Y.; Wang F. Z.; Li W. M.; Chen M. Organometallics 2017, 36, 4458. doi: 10.1021/acs.organomet.7b00698
[56]	Li R.; Sun J.; Tian S.; Zhang Y.; Guo D.; Li W.; Wang F. Z. J. Organomet. Chem. 2019, 880, 26.
[57]	Khan M. A.; Gui F.; Liao D. H.; Chen M.; Chen A. Polymer 2024, 308, 6.
[10]	Xu X.; Zheng A. N.; Zhou X. D.; Guan Y.; Pan Y. F.; Xiao H. N. J. Appl. Polym. Sci. 2015, 132, 42214.
[11]	Qu L.; Li X.-F.; Li R.-X.; Liu J.-W. Guangdong Chem. Ind. 2025, 52, 77 (in Chinese).
	(曲琳, 李肖夫, 李汝贤, 刘金伟, 广东化工, 2025, 52, 77.)
[12]	Wu J.; Li Y.-P.; Fu Y.-M.; Li Y.-G. Ind. Miner. Process. 2024, 53, 1 (in Chinese).
	(吴杰, 李阳培, 付延明, 李有桂, 化工矿物与加工, 2024, 53, 1.)
[13]	Xu K. Petrochem. Technol. 2025, 54, 954 (in Chinese).
	(徐珂, 石油化工, 2025, 54, 954.)
[14]	Dayyoub T.; Olifirov L. K.; Chukov D. I.; Kaloshkin S. D.; Kolesnikov E.; Nematulloev S. Materials 2020, 13, 18. doi: 10.3390/ma13010018
[15]	Krupa I.; Miková G.; Luyt A. S. Eur. Polym. J. 2007, 43, 4695. doi: 10.1016/j.eurpolymj.2007.08.022
[16]	Pan X. L.; Schenning A. H. P. J.; Shen L. H.; Bastiaansen C. W. M. Macromolecules 2020, 53, 5599. doi: 10.1021/acs.macromol.9b02647
[17]	Li Y.; Wang X.-Y.; Tang Y. Acta Chim. Sinica 2021, 79, 1320 (in Chinese). doi: 10.6023/A21080377
	(李勇, 王晓艳, 唐勇, 化学学报, 2021, 79, 1320.) doi: 10.6023/A21080377
[58]	Wang Y. F.; Vignesh A.; Qu M. N.; Wang Z.; Sun Y.; Sun W. H. Eur. Polym. J. 2019, 117, 254. doi: 10.1016/j.eurpolymj.2019.05.015
[59]	Gibson V. C.; Redshaw C.; Solan G. A. Chem. Rev. 2007, 107, 1745. doi: 10.1021/cr068437y
[18]	Wang Y.-Y.; Hu X.-Q.; Mu H.-L.; Xia Y.; Chi Y.; Jian Z.-B. Acta Chim. Sinica 2022, 80, 741 (in Chinese). doi: 10.6023/A22020066
	(王玉银, 胡小强, 穆红亮, 夏艳, 迟悦, 简忠保, 化学学报, 2022, 80, 741.) doi: 10.6023/A22020066
[19]	Terao H.; Ishii S. I.; Saito J.; Matsuura S.; Mitani M.; Nagai N.; Tanaka H.; Fujita T. Macromolecules 2006, 39, 8584. doi: 10.1021/ma062214s
[20]	Umare P. S.; Tiwari A. J.; Antony R.; Tembe G. L.; Trivedi B. Appl. Organomet. Chem. 2007, 21, 652. doi: 10.1002/aoc.v21:8
[21]	Baur M.; Lin F.; Morgen T. O.; Odenwald L.; Mecking S. Science 2021, 374, 604. doi: 10.1126/science.abi8183
[22]	Fan H. J.; Kang X. H.; Dai S. Y. ACS Catal. 2024, 14, 13531. doi: 10.1021/acscatal.4c02385
[23]	Johnson L. K.; Killian C. M.; Brookhart M. J. Am. Chem. Soc. 1995, 117, 6414. doi: 10.1021/ja00128a054
[24]	Mu H. L.; Zhou G. L.; Hu X. Q.; Jian Z. B. Coord. Chem. Rev. 2021, 435, 213802. doi: 10.1016/j.ccr.2021.213802
[25]	Tan C.; Chen C. L. Angew. Chem. Int. Ed. 2019, 58, 7192. doi: 10.1002/anie.201814634 pmid: 30719812
[26]	Chen M.; Chen C. ACS Catal. 2017, 7, 1308. doi: 10.1021/acscatal.6b03394

Entry	Cat.	T/℃	Yield^b/g	Act.^b	M_n^c	PDI^c	B^d	T_m^e/℃
1	Ni1	0	0.67	0.80	4600	1.93	26	121.1
2	Ni1	25	2.15	2.58	9800	1.98	45	111.7
3	Ni1	50	1.26	1.51	6100	2.17	50	92.1
4	Ni1	75	0.88	1.06	3200	2.30	61	—
5	Ni2	0	1.36	1.63	5600	2.46	25	121.6
6	Ni2	25	3.93	4.72	22900	2.07	27	112.6
7	Ni2	50	2.18	2.62	11300	2.12	48	94.6
8	Ni2	75	1.07	1.28	4500	2.42	53	—
9	Ni3	0	0.92	1.10	6100	1.85	17	123.3
10	Ni3	25	3.01	3.61	52100	2.33	26	119.2
11	Ni3	50	1.87	2.24	13900	2.45	39	99.7
12	Ni3	75	0.99	1.19	5100	2.61	51	—

Entry	Cat.	T/℃	Yield^b/g	Act.^b	M_n^c	PDI^c	B^d	T_m^e/℃
1	Ni1	0	0.67	0.80	4600	1.93	26	121.1
2	Ni1	25	2.15	2.58	9800	1.98	45	111.7
3	Ni1	50	1.26	1.51	6100	2.17	50	92.1
4	Ni1	75	0.88	1.06	3200	2.30	61	—
5	Ni2	0	1.36	1.63	5600	2.46	25	121.6
6	Ni2	25	3.93	4.72	22900	2.07	27	112.6
7	Ni2	50	2.18	2.62	11300	2.12	48	94.6
8	Ni2	75	1.07	1.28	4500	2.42	53	—
9	Ni3	0	0.92	1.10	6100	1.85	17	123.3
10	Ni3	25	3.01	3.61	52100	2.33	26	119.2
11	Ni3	50	1.87	2.24	13900	2.45	39	99.7
12	Ni3	75	0.99	1.19	5100	2.61	51	—

Entry	Cat.	T/℃	Yield^b/g	Act.^b	M_n^c	PDI^c	B^d	T_m^e/℃
1	Ni1	0	0.55	0.66	4300	1.96	26	121.8
2	Ni1	25	2.01	2.41	8700	2.05	33	112.9
3	Ni1	50	1.13	1.36	5300	2.13	48	88.4
4	Ni1	75	0.76	0.91	3100	2.32	60	—
5	Ni2	0	1.14	1.37	5200	2.01	21	122.0
6	Ni2	25	3.79	4.55	21000	2.11	26	114.7
7	Ni2	50	2.03	2.44	9800	2.30	45	94.1
8	Ni2	75	0.95	1.14	3700	2.49	52	—
9	Ni3	0	0.82	0.98	5800	1.91	15	123.5
10	Ni3	25	2.81	3.37	43700	2.03	21	120.1
11	Ni3	50	1.70	2.04	12100	2.38	35	113.0
12	Ni3	75	0.86	1.03	4700	2.56	50	—

Entry	Cat.	T/℃	Yield^b/g	Act.^b	M_n^c	PDI^c	B^d	T_m^e/℃
1	Ni1	0	0.55	0.66	4300	1.96	26	121.8
2	Ni1	25	2.01	2.41	8700	2.05	33	112.9
3	Ni1	50	1.13	1.36	5300	2.13	48	88.4
4	Ni1	75	0.76	0.91	3100	2.32	60	—
5	Ni2	0	1.14	1.37	5200	2.01	21	122.0
6	Ni2	25	3.79	4.55	21000	2.11	26	114.7
7	Ni2	50	2.03	2.44	9800	2.30	45	94.1
8	Ni2	75	0.95	1.14	3700	2.49	52	—
9	Ni3	0	0.82	0.98	5800	1.91	15	123.5
10	Ni3	25	2.81	3.37	43700	2.03	21	120.1
11	Ni3	50	1.70	2.04	12100	2.38	35	113.0
12	Ni3	75	0.86	1.03	4700	2.56	50	—

大位阻亚胺吡啶镍催化乙烯链行走聚合制备支化聚乙烯蜡^★

Synthesis of Branched Polyethylene Wax using Bulky Iminopyridyl Nickel-Catalyzed Ethylene Chain-Walking Polymerization^★

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[2]	Wang Xinke, Sit Met-Met, Sun Jiea, Tang Yong, Xie Zuowei. Synthesis, Structure and Ethylene Polymerization Behavior of Group 4 Metal Complexes Bearing Salicylaldaminato Ligands with Appended Donor Functionality [J]. Acta Chimica Sinica, 2012, 70(18): 1909-1916.
[3]	YUAN Jian-Chao, LIU Yu-Feng, MEI Tong-Jian, WANG Xue-Hu. High Active a-Diimine Nickel(II)/DEAC Catalyst System for Ethylene Polymerization [J]. Acta Chimica Sinica, 2011, 69(07): 798-802.

大位阻亚胺吡啶镍催化乙烯链行走聚合制备支化聚乙烯蜡★

Synthesis of Branched Polyethylene Wax using Bulky Iminopyridyl Nickel-Catalyzed Ethylene Chain-Walking Polymerization★

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大位阻亚胺吡啶镍催化乙烯链行走聚合制备支化聚乙烯蜡^★

Synthesis of Branched Polyethylene Wax using Bulky Iminopyridyl Nickel-Catalyzed Ethylene Chain-Walking Polymerization^★