丝氨酸衍生环酯的合成及其开环聚合/共聚研究

doi:10.6023/A26040141

摘要/Abstract

丝氨酸是一种天然氨基酸, 其衍生的聚酯高分子兼具可再生性与可降解性, 是一种环境友好型高分子. 本工作分别以丝氨酸甲酯盐酸盐与丝氨醇为原料, 合成了新型环内酯单体L-和D-3-(二苄基氨基)丙内酯(L-M1、D-M1)以及环碳酸酯单体5-(二苄基氨基)-1,3-二氧杂环己烷-2-酮(M2), 单体合成步骤短、总产率较高(40%~53%). 通过核磁对两类单体进行了鉴定, 并通过X-Ray单晶衍射确定了D-M1的绝对构型. 以稀土配合物La1为催化剂, 成功实现单体M1开环聚合(ROP), 所得聚合物数均分子量接近其理论值、且分子量分布窄(PDI=1.02~1.08), 分子量最高可达1.28×10⁵ g/mol. 热分析实验表明P(D-M1)熔点为210 ℃, 但熔融过程伴随着分解, 且存在两个分解阶段. 以外消旋M1 (rac-M1)为单体时, 得到全同序列为主的聚合物P(rac-M1). 以碱金属配合物Na1为催化剂、N,N-二苄基丝氨醇(IV)为引发剂, 成功实现单体M2开环聚合, 所得聚合物P(M2)熔点最高可达T_m=170.1 ℃, 热失重过程仅呈现一个分解阶段. 碱金属配合物Na1~Na3均能有效催化1,3-二氧杂环己烷-2-酮(TMC)与M2共聚, 并最终得到无规共聚物, 其热分解分三个阶段进行. 以单体M2为原料所得均聚物以及M2与TMC的共聚物的数均分子量均接近相应理论值, 但分子量分布较宽(PDI=1.11~1.74).

关键词: 丝氨酸衍生物, 环内酯, 环碳酸酯, 开环聚合, 共聚, 聚酯

Serine is a naturally occurring amino acid; polyesters derived from serine exhibit inherent renewability and biodegradability, rendering them a promising class of eco-friendly polymers. In this work, two kinds of novel serine-derived cyclic ester monomers were synthesized, and their ring-opening polymerization (ROP) was systematically investigated. The four-membered cyclic lactones L- and D-3-(dibenzylamino)oxetan-2-one (L-M1, D-M1) were synthesized via three steps from serine methyl ester hydrochloride, benzyl bromide and 2-(1H-benzotriazole-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate (HBTU) in an overall yield of ca. 40%. The structure of M1 was further confirmed by NMR and X-ray single crystal diffraction studies. The cyclic carbonate monomer 5-(dibenzylamino)-1,3-dioxan-2-one (M2) was prepared from serinol, benzyl bromide and N,N'-carbonyldiimidazole (CDI) via a two-step procedure in an overall yield of ca. 53%. The ring-opening polymerization (ROP) of M1 was catalyzed by lanthanum complex La1, affording poly(M1)s (P(M1)s) with narrow polydispersities (PDI=1.02~1.08). The experimentally determined number-average molecular weights of the resulting polymers closely match the corresponding theoretical values, with the highest molecular weight reaching 1.28×10⁵ g/mol. The polymer P(D-M1) has a melting point of 210 ℃ and the melting process is accompanied by partial decomposition; moreover, two thermal decomposition stages are observed. The polymerization of racemic M1 (rac-M1) yielded a polymer predominantly with isotactic sequences. Using N,N-dibenzylserinol (IV) as the initiator, the ROP of M2 could be initiated by sodium complex Na1 efficiently to afford poly(M2)s (P(M2)s) with number-average molecular weights close to the theoretical values and relatively broad polydispersities (PDI=1.35~1.69). P(M2) possesses one thermal decomposition stage and a melting point of T_m=170.1 ℃. The copolymerization of M2 with 1,3-dioxan-2-one (TMC) was also realized successfully by using sodium complexes Na1~Na3 as catalysts, wherein TMC exhibited slightly faster initiation kinetics than M2. Regardless of the variations in polymerization time, monomer feed ratio, or catalyst structures, the number-average molecular weights of the resulting polymers consistently approached the theoretical values. Analysis of the average number of units per chain segment and assessment of sequence distribution characteristics revealed that the resulting copolymers are predominantly random. The typical copolymer possesses three thermal decomposition stages and a melting temperature of T_m=168.6 ℃.

Key words: serine derivative, cyclic lactone, cyclic carbonate, ring-opening polymerization, copolymerization, polyester

引用此文

黄洋, 马海燕. 丝氨酸衍生环酯的合成及其开环聚合/共聚研究[J]. 化学学报, 2026, 84(7): 1077-1086.

Yang Huang, Haiyan Ma. Synthesis and Ring-Opening Polymerization/Copolymerization of Serine-Derived Cyclic Esters[J]. Acta Chimica Sinica, 2026, 84(7): 1077-1086.

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图/表 18

图1. L-和D-3-(二苄基氨基)丙内酯(L-M1, D-M1)、5-(二苄基氨基)-1,3-二氧杂环己烷-2-酮(M2)的结构

Figure 1. The structures of L- and D-3-(dibenzylamino)oxetan-2-one (L-M1, D-M1) and 5-(dibenzylamino)-1,3-dioxan-2-one (M2)

图式1. 单体3-(二苄基氨基)-丙内酯(M1)合成路径

Scheme 1. Synthetic route of 3-(dibenzylamino)oxetan-2-one (M1)

图2. 单体D-M1的分子结构

Figure 2. The molecular structure of D-M1 Thermal ellipsoids are drawn at the 50% probability level. Selected bond lengths (nm) and angles (°): O(1)—C(1), 0.1188(2); O(2)—C(1), 0.1355(2); O(2)—C(2), 0.1477(2); C(1)—C(3), 0.1515(2); C(2)—C(3), 0.1549(3); N(1)—C(3), 0.1438(2); C(1)-O(2)-C(2), 91.82(13); O(2)-C(1)-C(3), 95.34(13); O(2)-C(2)-C(3), 89.19(13); C(1)-C(3)-C(2), 83.30(13)

图式2. 单体5-(二苄基氨基)-1,3-二氧杂环己烷-2-酮(M2)的合成路线

Scheme 2. Synthetic route of 5-(dibenzylamino)-1,3-dioxan-2-one (M2)

Run	Monomer	[M1]₀/[La]₀	Time /min	Conv.^b	M_n,cacld^c /(×10⁴)	M_n^d /(×10⁴)	PDI^d
Run	Monomer	[M1]₀/[La]₀	Time /min	/%	M_n,cacld^c /(×10⁴)	M_n^d /(×10⁴)	PDI^d
1	D-M1	50/1	20	>99	1.34	1.16	1.08
2	D-M1	500/1	55	>99	13.3	12.8	1.02
3	L-M1	500/1	53	>99	13.3	12.4	1.03
4	rac-M1	500/1	60	>99	13.3	9.40	1.03
5	rac-M1	1000/1	240	38	10.2	6.39	1.08
6^e	L-M1+ D-M1	500/1	32+31	>99	13.3	8.33	1.03
7^f	D-M1	50/1	4	>99	1.34	8.90	2.43
8^f	D-M1	500/1	20	>99	13.3	20.5	2.06

表1. 配合物La1催化单体M1开环聚合a

Table 1. ROP of M1 catalyzed by complex La1a

图3. 聚合物P(D-M1)的DSC和TG曲线: [D-M1]0/[La1]0=500/1, Conv.>99%

Figure 3. The DSC and TG curves of polymer P(D-M1): [D-M1]0/[La1]0=500/1, Conv.>99%

图4. 聚合物P(D-M1)的DTG曲线: [D-M1]0/[La1]0=500/1, Conv.>99%

Figure 4. The DTG curve of polymer P(D-M1): [D-M1]0/[La1]0=500/1, Conv.>99%

图5. 聚合物P(rac-M1)与P(L-M1)的核磁氢谱(局部)

Figure 5. The 1H NMR spectra of P(rac-M1) and P(L-M1) (Partial)

Run	[M2]₀/[Na1]₀	Time	Conv.^b	M_n,cacld^c	M_n^d	PDI^d
Run	/[IV]₀	/s	/%	/(×10⁴)	/(×10⁴)
1	250/1/2	90	>99	3.71	3.40	1.61
2^e	250/1/2	90	96	3.56	1.45	1.35
3	500/1/2	40	59	4.38	3.17	1.45
4	500/1/2	61	>99	7.42	6.69	1.69
5^f	500/1/2	55	95	7.05	4.45	1.59

表2. 配合物Na1催化M2开环聚合a

Table 2. ROP of M2 catalyzed by complex Na1 a

图6. 聚合物P(M2)的DSC曲线: [M2]0/[Na1]0/[IV]0=500/1/2, Conv.>99%

Figure 6. The DSC curve of polymer P(M2): [M2]0/[Na1]0/[IV]0= 500/1/2, Conv.>99%

图7. 聚合物P(M2)的TG曲线: [M2]0/[Na1]0/[IV]0=500/1/2, Conv.>99%

Figure 7. The TG curve of polymer P(M2): [M2]0/[Na1]0/[IV]0= 500/1/2, Conv.>99%

图8. 聚合物P(M2)的DTG曲线: [M2]0/[Na1]0/[IV]0=500/1/2, Conv.>99%

Figure 8. The DTG curve of polymer P(M2): [M2]0/[Na1]0/[IV]0= 500/1/2, Conv.>99%

图式3. 钠配合物催化M2和TMC共聚

Scheme 3. Copolymerization of M2 with TMC catalyzed by sodium complexes

Run	Cat.	[M2]₀/[TMC]₀	Time	Conv./%^b	M_n,cacld^c	M_n^d	PDI^d
Run		/[Cat.]₀/[IV]₀	/s	M2, TMC	/(×10⁴)	/(×10⁴)
1	Na1	250/250/1/2	10	45, 67	2.52	3.37	1.41
2	Na1	250/250/1/2	25	95, >99	4.79	3.43	1.74
3	Na1	250/250/1/2	61	>99, >99	4.99	3.61	1.76
4	Na1	375/125/1/2	30	83, >99	5.25	4.55	1.47
5	Na1	125/375/1/2	20	96, 98	3.66	3.37	1.40
6	Na2	250/250/1/2	26	95, >99	4.79	3.88	1.49
7	Na3	250/250/1/2	21	78, 87	3.82	2.18	1.11

表3. 配合物Na1~Na3催化M2和TMC共聚a

Table 3. Copolymerization of M2 with TMC catalyzed by complexes Na1~Na3a

图9. M2和TMC的共聚物定量碳谱羰基区域(CDCl3, 125 MHz): [M2]0/[TMC]0/[Na1]0/[IV]0=250/250/1/2, Conv.M2=95%, Conv.TMC>99%

Figure 9. The carbonyl region of quantitative 13C NMR spectrum of copolymer of M2 and TMC (CDCl3, 125 MHz): [M2]0/[TMC]0/[Na1]0/ [IV]0=250/250/1/2, Conv.M2=95%, Conv.TMC>99%

图10. M2和TMC的共聚物的DSC曲线: [M2]0/[TMC]0/[Na1]0/[IV]0= 250/250/1/2, Conv.M2=95%, Conv.TMC>99%

Figure 10. The DSC curve of copolymer of M2 and TMC: [M2]0/[TMC]0/[Na1]0/[IV]0=250/250/1/2, Conv.M2=95%, Conv.TMC>99%

图11. M2和TMC的共聚物的TG曲线: [M2]0/[TMC]0/[Na1]0/[IV]0= 250/250/1/2, Conv.M2=95%, Conv.TMC>99%

Figure 11. The TG curve of copolymer of M2 and TMC: [M2]0/[TMC]0/[Na1]0/[IV]0=250/250/1/2, Conv.M2=95%, Conv.TMC>99%

图12. M2和TMC的共聚物的DTG曲线: [M2]0/[TMC]0/[Na1]0/[IV]0= 250/250/1/2, Conv.M2=95%, Conv.TMC>99%

Figure 12. The DTG curve of copolymer of M2 and TMC: [M2]0/[TMC]0/[Na1]0/[IV]0=250/250/1/2, Conv.M2=95%, Conv.TMC>99%

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