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★

doi:10.6023/A25050150

摘要/Abstract

聚羟基脂肪酸酯(polyhydroxyalkanoates, PHAs)作为一类由细菌发酵制备的生物可降解材料, 因其性能可媲美商业聚烯烃, 被视为传统塑料的潜在替代品. 然而, 高昂的生产成本严重制约了其规模化应用. 尽管天然细菌发酵PHAs呈现丰富的结构多样性, 但产物多局限于烷基侧基取代衍生物. 本研究通过开发外消旋杂原子取代四元环内酯单体的立体选择性聚合体系, 成功合成了具有高间同立构结构的PHAs (P_r>0.95), 其分子结构显著区别于微生物合成PHAs, 突破了传统发酵法在结构调控上的局限性, 拓展了PHAs的结构多样性及潜在应用范围.

关键词: 开环聚合, 聚羟基脂肪酸酯, 立体选择性聚合, 可持续聚合物, 金属配合物

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

引用此文

黄皓毅, 谢敏, 黄玉婷, 崔嘉豪, 蔡中正, 朱剑波. 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^★[J]. 化学学报, 2025, 83(8): 810-815.

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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图/表 4

图1. 开环聚合制备结构多样的PHAs

Figure 1. PHAs with diverse structures via ring-opening polymerization

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

表1. 螺环-salen配合物催化的取代丙内酯立体选择性开环聚合a

Table 1. Stereoselective ROP of substituted propiolactones mediated by spiro-salen complexes

图2. 间同和无规PHAs的13C NMR谱图

Figure 2. 13C NMR spectra of syndiotactic and atactic PHAs

图3. 间同和无规PHAs的DSC曲线

Figure 3. DSC curves of syndiotactic and atactic PHAs

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