聚乳酸合成催化体系: 机遇与挑战

doi:10.6023/cjoc202206051

摘要/Abstract

随着国家减塑令的发布, 开发聚乳酸(PLA)等生物可降解材料逐渐成为热门话题. 对合成聚乳酸的不同方法进行了讨论. 丙交酯开环聚合法已成为获得高分子量聚乳酸的最常用方法. 因此, 重点介绍了用于丙交酯开环聚合的催化剂设计, 并阐述了聚合的机理, 希望能为设计开发低毒性、高选择性的催化体系指明方向.

关键词: 减塑令, 聚乳酸, 生物可降解, 催化剂, 聚合

With the national plastic reduction order issued, the development of biodegradable materials such as poly(lactic acid) (PLA) has gradually become a hot topic. The different methods for synthesizing polylactic acid are discussed. Since the ring-opening polymerization of lactide has become the major method for preparing PLA, we focused on the catalyst design for the process, and clarified the related mechanisms. This short review may point out the direction for the design and development of low-toxicity and high-selectivity catalyst systems for application.

Key words: plastic reduction order, polylactic acid, biodegradable, catalysts, polymerization

引用此文

孟祥坤, 祁正源, 俞磊, 张亦旸. 聚乳酸合成催化体系: 机遇与挑战[J]. 有机化学, 2023, 43(1): 112-119.

Xiangkun Meng, Zhengyuan Qi, Lei Yu, Yiyang Zhang. Catalytic System for Poly(lactic acid) Synthesis: Opportunities and Challenges[J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 112-119.

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图/表 13

图式1. 聚乳酸的合成方法

Scheme 1. Synthetic method of poly(lactic acid)

图式2. ZnLA2/A-15催化L-LA缩聚的可能机理

Scheme 2. Possible mechanism for L-LA polycondensation catalyzed by ZnLA2/A-15

图式3. 生物肌酐催化合成聚乳酸

Scheme 3. Catalytic synthesis of PLA by biological creatinine

Entry	Catalyst	Conv./%	M_n^a	PDI^b
1	16	95	37900	1.10
2	19	100	14300	1.08
3	20	100	14400	1.07
4	21	66	95000	1.60
5	22	56	80600	1.70
6	23	60	86000	1.30
7	24	54	77700	1.30
8	25	92	26700	1.63
9	26	84	12200	1.23
10	27	94	27100	1.16
11	28	81	23300	1.09
12	29	95	27400	1.20
13	30	94	115200	1.40
14	31	91	105300	1.20
15	32	92	106400	1.18
16	33	99	29310	1.57
17	34	99	51910	1.52
18	Co₃O₄	94	144300	1.17
19	MnO₂	93	138100	1.19
20	35	95	62600	1.19
21	36	99	55300	1.10
22	37	98	85000	1.08
23	42	99	38700	1.40
24	43	99	7300	1.30
25	44	—	3300	1.25

表1. 催化剂种类

Table 1. Type of catalyst

图式4. 辛酸亚锡聚合机理

Scheme 4. The polymerization mechanism of stannous octoate

图式5. 异丙醇铝聚合机理

Scheme 5. Polymerization mechanism of aluminium isopro- poxide

图式6. 醇锌络合物聚合机理

Scheme 6. Polymerization mechanism of zinc alkoxide complex

图1. 主要金属配合物

Figure 1. Major metal complexes

图式7. 25~27催化的丙交酯ROP

Scheme 7. ROP of lactide catalysed by 25~27

图2. 其他金属配合物

Figure 2. Other metal complexes

图3. 用于丙交酯开环聚合的有机催化剂

Figure 3. Organocatalysts for ring-opening polymerization of lactide

图式8. IHBD/HBA二元催化体系

Scheme 8. IHBD/HBA binary catalytic system

图4. 三种手性脲催化剂

Figure 4. Three types of chiral ureas catalysts

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