[ONSN]-Type Fe(III) Complexes Catalyzed the Ring Opening Copolymerization of Epoxides and Anhydrides

doi:10.6023/cjoc202502002

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (8): 2854-2866.DOI: 10.6023/cjoc202502002 Previous Articles Next Articles

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[ONSN]-型Fe(III)配合物催化环氧化物和酸酐的开环共聚反应

周永博^a^,^†, 徐东晓^a^,^†, 赵晓静^b^,^†, 李志彬^b, 白世涛^b, 刘宁^a^,^*()

^a 石河子大学化学化工学院化工绿色过程省部共建国家重点实验室培育基地新疆石河子 832003
^b 晨光生物科技集团克拉玛依有限公司新疆胡杨河 834034

收稿日期:2025-02-03 修回日期:2025-03-30 发布日期:2025-04-24
作者简介:
†共同第一作者.
基金资助:
国家自然科学基金(22168034); 兵团英才; 第七师胡杨河市科技计划(QS2024013); 兵团研究生科研创新(BTYJXM-2024-K26)

[ONSN]-Type Fe(III) Complexes Catalyzed the Ring Opening Copolymerization of Epoxides and Anhydrides

Yongbo Zhou^a, Dongxiao Xu^a, Xiaojing Zhao^b, Zhibin Li^b, Shitao Bai^b, Ning Liu^a^,^*()

^a State Key Laboratory Incubation Base for Green Processing of Chemical Engineering, School of Chemistry and Chemical Engineering, Shihezi University, Shihezi, Xinjiang 832003
^b Chenguang Biotechnology Group Karamay Co., Ltd., Huyanghe, Xinjiang 834034

Received:2025-02-03 Revised:2025-03-30 Published:2025-04-24
Contact: *E-mail:ningliu@shzu.edu.cn
About author:
†The authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22168034); Bingtuan Talents; Science and Technology Project of 7th Division Huyanghe City(QS2024013); Bingtuan Graduate Research Innovation Project of Production and Construction(BTYJXM-2024-K26)

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Abstract

Four [ONSN]-type iron(III) complexes were synthesized, and applied in the ring opening copolymerization (ROCOP) reaction of epoxides and anhydrides. The reaction conditions were optimized using cyclohexene oxide (CHO) and phthalic anhydride (PA) as benchmark substrate. It was found that the binary catalytic system incombination of iron complexes Cat 1 with 4-dimethylaminopyridine (DMAP) had high catalytic activity at 100 ℃. A series of polyesters prepared under optimization conditions had a number-average molecular weight (M_n) of up to 13.1 kg/mol and a molecular weight distribution (PDI) of only 1.19, turnover frequency (TOF) value is 99 h^－1. The catalytic system was suitable or the ROCOP reaction of different epoxides and anhydrides to prepare polyesters with high yields and excellent M_n and PDI. The catalytic system was suitable for ROCOP reaction of castor oil-derived epoxide monomer (OYU) with PA, and the obtained polymer has a number average molecular weight (M_n) of 16.5 kg/mol

Key words: Fe complex, ring opening copolymerization, polyesters, bio-based polymer

Cite this article

Yongbo Zhou, Dongxiao Xu, Xiaojing Zhao, Zhibin Li, Shitao Bai, Ning Liu. [ONSN]-Type Fe(III) Complexes Catalyzed the Ring Opening Copolymerization of Epoxides and Anhydrides[J]. Chinese Journal of Organic Chemistry, 2025, 45(8): 2854-2866.

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Fig. & Tab. 19

Entry^a	Catalyst/mol%	Cocatalyst/mol%	Epoxide	Anhydride	T/℃	Time/h	Yield^b/%	M_n^c/(kg•mol^－1)	PDI^c
1^[22]	卟啉-Al [4.0]	EtPh₃PBr [4.0]	EO	PA	r.t.	168	100	3.0	1.10
2^[23]	β-二亚胺-Zn [0.5]	—	CHO	DGA	50	60	91	31.0	1.20
3^[24]	Salen-CrCl [0.5]	PPNCl [0.5]	PO	CA	30	24	100	16.9	1.20
4^[25]	Salen-Fe [0.4]	PPNCl [0.4]	CHO	PA	100	1	100	12.3	1.26
5^[26]	氨基三酚-Fe [0.4]	DMAP [0.5]	LO	PA	65	48	92	10.7	1.24
6^[27]	Fe/K异双核 [0.1]	—	CHO	PA	100	1	95	19.1	1.09

Table 1. Ring opening copolymerization of epoxides and anhydrides

Scheme 1. Synthesis roadmap of catalysts Cat 1~Cat 4

Figure 1. X-ray single crystal crystals structure of complexes Cat 1 and Cat 3

Entry	Catalyst	Cocatalyst	Yield^b/%	M_n^c/(kg•mol^－1)	PDI^c
1	Cat 1	PPNCl	90	3.0	1.22
2	Cat 2	PPNCl	88	2.9	1.19
3	Cat 3	PPNCl	88	3.3	1.14
4	Cat 4	PPNCl	87	2.7	1.20
5	Cat 1	TBAB	88	2.3	1.22
6	Cat 1	TBAC	92	2.6	1.23
7	Cat 1	TBAI	88	2.5	1.26
8	Cat 1	DMAP	92	3.7	1.20
9	Cat 1	Py	72	2.3	1.23
10	Cat 1	4-PPy	86	3.6	1.16
11	Cat 1	4-AP	89	2.6	1.26
12	Cat 1	DBU	90	3.0	1.33

Table 2. Effects of different catalysts on ROCOP reaction

Entry	n(CHO)∶n(PA)∶n(Cat 1)∶n(DMAP)	Yield^b/%	Ester linkage/%^c	M_n^d/(kg•mol^－1)	PDI ^d
1	200∶200∶1∶1	99	82	3.6	1.23
2	300∶200∶1∶1	99	79	4.5	1.27
3	500∶500∶1∶1	96	83	5.1	1.28
4	1000∶500∶1∶1	99	85	7.0	1.16
5	1000∶500∶2∶1	99	76	9.8	1.55
6	1000∶500∶1∶2	99	82	9.5	1.37
7	2000∶1000∶1∶1	80	90	12.3	1.41
8^e	2000∶1000∶1∶1	99	92	13.1	1.19
9^f	2000∶1000∶1∶1	99	90	9.5	1.29
10^g	2000∶1000∶1∶1	99	78	7.7	1.46

Table 3. Optimization of catalyst conditions

Figure 2. NMR spectrum of the PA/CHO polyester

Table 4. Expansion of substrates for acid anhydrides and epoxides

Figure 3. NMR spectra of the NBA/CHO polyester

Figure 4. In situ IR observation reaction process: (a) ROCOP reaction between CHO and PA, (b) ROCOP reaction between CHO and NBA

Scheme 2. Preparation of vegetable oil-based polymers

Figure 5. GPC curve of PA/OYU polyesters

Figure 6. NMR spectra of the PA/OYU polyesters

Figure 7. 1H NMR of crude reaction solution between CHO and PA

Figure 8. Mechanism exploration of copolymerization of epoxides and anhydrides: (a) FT-IR spectra with addition of DMAP to a solution of complex Cat 1 in dichloromethane; (b) UV-vis spectra with addition of DMAP to a solution of complex Cat 1 in dichloromethane; (c) electrochemical impedance spectroscopy (EIS) of DMAP added to dichloromethane solution of Cat 1

Scheme 3. Two reaction pathways for epoxide ring opening

Figure 9. Conversion curves of Cat 1 and Cat 5

Scheme 4. ROCOP reaction of CHO and PA catalyzed by Cat 1 and Cat 5

Scheme 5. Mechanism of ROCOP of epoxides and anhydrides

Figure 10. Two-step synthesis of oxiran-2-ylmethyl 10-unde- cenoate

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[ONSN]-型Fe(III)配合物催化环氧化物和酸酐的开环共聚反应

[ONSN]-Type Fe(III) Complexes Catalyzed the Ring Opening Copolymerization of Epoxides and Anhydrides

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