Synthesis of Stereoregular and Functional Polyhydroxyalkanoates via Ring-Opening Polymerization Mediated by Spiro-salen Complexes★

doi:10.6023/A25050150

Abstract

Polyhydroxyalkanoates (PHAs) are a class of biodegradable materials produced by bacterial fermentation. They are considered as potential alternatives for traditional plastics because their material properties are comparable to those of commercial polyolefins. However, the high cost of fermentation production has seriously restricted their large-scale application. Although PHAs produced by natural bacterial fermentation show rich structural diversity, the products are mostly limited to alkyl side-substituted derivatives and are mainly used as thermoplastics. Consequently, the development of cost-effective and efficient chemical synthesis routes to produce PHAs with enhanced structural diversity and broader potential applications is of considerable importance. In this study, functionalized four-membered cyclic lactone monomers, BPL^CH2OR (R=Bu, Bn), substituted with alkoxy and benzyloxy groups, were synthesized via carbonylation of commercially available epoxides with carbon monoxide. These monomers undergo stereoselective ring-opening polymerization (ROP) to yield polymers with structures distinct from those of natural PHAs. A stereoselective polymerization system for rac- BPL^CH2OR was developed using a spiro-salen yttrium complex Y2 as the catalyst. The resulting PHAs with high syndiotacticity (P_r>0.95) exhibit significant differences in stereoregularity and thermal performance compared to their natural counterparts. It was observed that rac-Y2 and its corresponding chiral (R)-Y2 exhibit distinct catalytic behaviors: while both catalysts enable good molecular weight control, producing P(BPL^CH2OR) with low dispersity (Đ<1.15), polymerization catalyzed by (R)-Y2 yielded atactic P(BPL^CH2OR) in the form of oily liquids, whereas rac-Y2-catalyzed polymerization produced semicrystalline syndiotactic P(BPL^CH2OR) (P_r>0.95). The glass transition temperatures (T_g) and melting temperatures (T_m) range from －61 ℃ to 74 ℃. P(BPL^CH2OBn) illustrates potential for post-polymerization modification. Upon debenzylation, it is expected to generate hydrophilic, stereoregular and biodegradable materials, thus demonstrating promising application prospects in the biomedical field.

Key words: ring-opening polymerization, polyhydroxyalkanoates, stereoselective polymerization, sustainable polymers, metal complexes

Cite this article

Haoyi Huang, Min Xie, Yuting Huang, Jiahao Cui, Zhongzheng Cai, Jianbo Zhu. Synthesis of Stereoregular and Functional Polyhydroxyalkanoates via Ring-Opening Polymerization Mediated by Spiro-salen Complexes^★[J]. Acta Chimica Sinica, 2025, 83(8): 810-815.

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Entry	Monomer	Catalyst	Time^b	Conv.^c/%	M_n^d/kDa	Đ^d (M_w/M_n)	P_r^e
1	rac-BPL^CH2OBu	rac-Y1	10 min 12 h	17 51	n.d.^f 1.24	n.d.^f 1.27	n.d.^f 0.50
2	rac-BPL^CH2OBu	(R)-Y2	3.5 h	73	7.59	1.07	0.66
3	rac-BPL^CH2OBu	rac-Y2	1 h	>99	8.26	1.12	>0.95
4	rac-BPL^CH2OBn	rac-Y1	10 min 12 h	n.d.^f 85	n.d.^f 1.06	n.d.^f 1.05	n.d.^f 0.65
5	rac-BPL^CH2OBn	(R)-Y1	6 h	30	n.d.^f	n.d.^f	0.60
6	rac-BPL^CH2OBn	(R)-Y2	3.5 h	79	8.50	1.15	0.49
7	rac-BPL^CH2OBn	rac-Y2	20 s	>99	10.7	1.13	>0.95

Entry	Monomer	Catalyst	Time^b	Conv.^c/%	M_n^d/kDa	Đ^d (M_w/M_n)	P_r^e
1	rac-BPL^CH2OBu	rac-Y1	10 min 12 h	17 51	n.d.^f 1.24	n.d.^f 1.27	n.d.^f 0.50
2	rac-BPL^CH2OBu	(R)-Y2	3.5 h	73	7.59	1.07	0.66
3	rac-BPL^CH2OBu	rac-Y2	1 h	>99	8.26	1.12	>0.95
4	rac-BPL^CH2OBn	rac-Y1	10 min 12 h	n.d.^f 85	n.d.^f 1.06	n.d.^f 1.05	n.d.^f 0.65
5	rac-BPL^CH2OBn	(R)-Y1	6 h	30	n.d.^f	n.d.^f	0.60
6	rac-BPL^CH2OBn	(R)-Y2	3.5 h	79	8.50	1.15	0.49
7	rac-BPL^CH2OBn	rac-Y2	20 s	>99	10.7	1.13	>0.95

螺环-salen配合物催化开环聚合制备立构规整、功能化聚羟基脂肪酸酯^★