爪形氨基酚氧基锌氯化物催化环氧化物和酸酐共聚研究

doi:10.6023/A24040122

摘要/Abstract

本工作合成了一系列基于爪形氨基酚氧基配体的新型锌氯化物, 均通过¹H NMR、¹³C NMR以及元素分析等进行了表征, 且典型络合物通过X-ray单晶衍射分析确定了其空间配位结构. 利用上述络合物实现了催化环氧环己烷、外消旋环氧氯丙烷和邻苯二甲酸酐的共聚反应. 在共聚过程中均表现出较高催化活性以及高酯链节选择性(>99%), 得到分子量分布较窄的交替共聚物. 典型络合物Zn1在80 ℃下催化环氧环己烷和邻苯二甲酸酐共聚时, TOF_PA值可达到490 h^-1, 在相同条件下催化外消旋环氧氯丙烷和邻苯二甲酸酐共聚时, TOF_PA值可达到848 h^-1. 研究表明, 共聚反应可能通过环氧化物在亲核试剂进攻下开环引发, 经后续重复的酸酐和环氧化物交替插入得到高酯链节含量共聚物.

关键词: 爪形氨基酚氧基锌氯化物, 环氧化物, 酸酐, 共聚, 酯链节选择性

A series of novel claw-type aminophenolate zinc chlorides Zn1~Zn8 were synthesized via the reactions of the corresponding sodium salts of the proligands H^1-8L with one equiv. of zinc dichloride at room temperature respectively. All the complexes were characterized by ¹H NMR, ¹³C NMR spectroscopy and elemental analyses. The X-ray diffraction analysis of complex Zn2 showed that, being obtained as a pair of racemic isomers (with configurations of S_NS_Zn and R_NR_Zn), the complex possesses a mononuclear structure and the zinc center is four-coordinated by the tridentate aminophenolate ligand and one chloride ligand in the solid state. When bis(triphenylphosphine)iminium chloride (PPNCl) was used as a co-catalyst, all of these zinc complexes showed high catalytic activities and high selectivities for the formation of polyesters (>99%) in the ring-opening copolymerization (ROCOP) of cyclohexene oxide (CHO) and phthalic anhydride (PA), giving alternative copolymers with narrow molecular weight distributions (PDI=1.14~1.24). The steric hindrance of the substituents on the ligand has an important influence on the catalytic activity of the complex. Zn4 with cumyl groups on the ligand that make the metal center more crowded showed a lower activity than Zn3 at 80 ℃ (Zn3, TOF_PA=400 h^-1, Zn4, TOF_PA=384 h^-1). Moreover, the electron-withdrawing effect of the substituents increased the catalytic activity of the catalyst. For example, under the same conditions, Zn1 with electron-withdrawing substituents took only 22 min to achieve 90% conversion of PA, while Zn2 took 26 min to achieve 87% conversion of PA. Complex Zn1 showed the highest catalytic activity in the copolymerization of CHO and PA (TOF=490 h^-1). In addition, with the increase of the amount of PPNCl, the selectivity of complexes for ester linkages gradually increased. For instance, when one equiv. of PPNCl was added, the selectivity of Zn2 for ester linkages was 96%, while a selectivity of 99% was achieved with the addition of 5 equiv. of PPNCl. All the complexes were also applied in the ROCOP of rac-epichlorohydrin (rac-ECH) and PA, and showed high catalytic activities and high selectivities for polyesters (>99%), but with somewhat wide molecular weight distributions (PDI=1.36~1.49). Complex Zn1 also proved to be the most active one (TOF=848 h^-1). Compared with those for CHO and PA copolymerization, the catalytic activities of the complexes toward the ROCOP of rac-ECH and PA were higher (e.g. Zn2, TOF=402 h^-1, CHO/PA; TOF=745 h^-1, ECH/PA). Further studies suggested that the ROCOP was likely initiated through the ring-opening of epoxides upon the attack of an nucleophilic reagent, for instance, Cl^-.

Key words: claw-type aminophenolate zinc chlorides, epoxide, anhydride, copolymerization, selectivity for ester linkage

引用此文

王海成, 马海燕. 爪形氨基酚氧基锌氯化物催化环氧化物和酸酐共聚研究[J]. 化学学报, 2024, 82(6): 577-588.

Haicheng Wang, Haiyan Ma. Ring-opening Copolymerization of Epoxides and Anhydride Mediated by Claw-type Aminophenolate Zinc Chlorides[J]. Acta Chimica Sinica, 2024, 82(6): 577-588.

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图/表 8

图式1. 锌氯化物Zn1~Zn8的合成路线及PPNCl的结构式

Scheme 1. Synthetic route of zinc chlorides Zn1~Zn8 and the structure of PPNCl

图1. 锌氯化物Zn2的分子结构

Figure 1. The molecular structure of zinc chloride Zn2

Entry	Cat.	Temp/℃	Time/min	Conv.^b/%	TOF_PA^c/h^-1	Ester^d/%	M_n,calcd^e/×10³	M_n^f/×10³	M_w/M_n^f
1	Zn1	80	22	90	490	99	8.9	5.5	1.16
2	Zn2	25	31 h	85	5	99	8.4	4.9	1.21
3^g		80	10 h	20	4	12	—	—	—
4^h		80	125	89	85	96	43.8	6.5	1.17
5		80	26	87	402	99	8.6	5.0	1.22
6	Zn3	80	28	91	400	99	9.0	5.6	1.23
7	Zn4	80	29	93	384	99	9.2	5.7	1.14
8	Zn5	80	34	87	307	99	8.6	4.9	1.23
9	Zn6	80	21	82	468	99	8.1	4.3	1.24
10	Zn7	80	26	84	388	99	8.3	4.7	1.24
11	Zn8	80	27	82	364	99	8.1	4.3	1.23

表1. 锌氯化物Zn1~Zn8催化环氧环己烷和邻苯二甲酸酐开环共聚a

Table 1. ROCOP of CHO and PA catalyzed by zinc chlorides Zn1~Zn8a

图2. Zn1催化环氧环己烷和邻苯二甲酸酐开环共聚所得聚合物的1H NMR谱图(CDCl3, 400 MHz; 表1, Entry 1; *: CH2Cl2; **: CHO; #: CDCl3) 催化环氧环己烷和邻苯二甲酸酐开环共聚所得聚合物的1H NMR谱图(CDCl3, 400 MHz; 表1, Entry 1; *: CH2Cl2; **: CHO; #: CDCl3)

Figure 2. 1H NMR spectrum of the copolymer obtained by ROCOP of CHO and PA catalyzed by Zn1 (CDCl3, 400 MHz; Table 1, Entry 1; *: CH2Cl2; **: CHO; #: CDCl3)

图3. 络合物Zn2催化环氧环己烷和邻苯二甲酸酐共聚所得到聚合物的MALDI-TOF质谱图(80 ℃, [CHO]0∶[PA]0∶[Zn2]0∶[PPNCl]0=1000∶100∶1∶5, 转化率: 59%)

Figure 3. MALDI-TOF mass spectrum of the copolymer obtained by ROCOP of CHO and PA catalyzed by complex Zn2 (80 ℃, [CHO]0∶[PA]0∶[Zn2]0∶[PPNCl]0=1000∶100∶1∶5, conv: 59%)

图式2. 锌氯化物催化环氧环己烷和邻苯二甲酸酐(含邻苯二甲酸)交替共聚的机理假设([Zn]-Cl代表锌氯化物)

Scheme 2. Proposed mechanism for the ROCOP of cyclohexene oxide and phthalic anhydride (containing phthalic acid) catalyzed by zinc chloride complex ([Zn]-Cl represents zinc chloride complex)

Run	Cat.	Temp/℃	Time/min	Conv.^b/%	TOF_PA^c/h^-1	Ester^d/%	M_n,calcd^e/×10³	M_n^f/×10³	M_w/M_n^f
1	Zn1	80	14	99	848	99	9.5	2.9	1.49
2	Zn2	25	24 h	87	7	99	8.4	2.1	1.37
3		80	14	87	745	99	8.4	2.3	1.44
4	Zn3	80	15	89	710	99	8.5	2.3	1.37
5	Zn4	80	16	89	668	99	8.5	2.5	1.48
6	Zn5	80	17	85	600	99	8.4	2.1	1.39
7	Zn6	80	12	80	800	99	7.7	1.9	1.45
8	Zn7	80	15	90	720	99	8.6	2.2	1.43
9	Zn8	80	18	90	640	99	8.6	2.3	1.36

表2. 锌氯化物Zn1~Zn8催化外消旋环氧氯丙烷和邻苯二甲酸酐开环共聚a

Table 2. ROCOP of rac-ECH and PA catalyzed by zinc chlorides Zn1~Zn8a

图4. Zn1催化外消旋环氧氯丙烷和邻苯二甲酸酐开环共聚所得聚合物的1H NMR谱图(CDCl3, 400 MHz; 表2, Entry 1; *: CH2Cl2; #: CDCl3) 催化外消旋环氧氯丙烷和邻苯二甲酸酐开环共聚所得聚合物的1H NMR谱图(CDCl3, 400 MHz; 表2, Entry 1; *: CH2Cl2; #: CDCl3)

Figure 4. 1H NMR spectrum of the copolymer obtained by ROCOP of rac-ECH and PA catalyzed by Zn1 (CDCl3, 400 MHz; Table 2, Entry 1; *: CH2Cl2; #: CDCl3)

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