锌掺杂聚吡咯催化乳酸缩合制备高光纯L-丙交酯

doi:10.6023/cjoc202204045

摘要/Abstract

聚乳酸作为生物可降解的聚合物材料, 有着广泛的应用前景. 目前, 高质量聚乳酸主要通过丙交酯缩合来制备. 其中, 丙交酯的光学纯度是影响聚乳酸材料力学性能的关键因素. 因此, 开发高光纯丙交酯的合成技术, 是有着很好应用价值的挑战性课题. 在本工作中设计制备了锌掺杂聚吡咯催化剂. 该材料可以很好地催化乳酸缩合, 合成高光纯丙交酯. 值得一提的是, 该材料可以多次套用, 并保持产物的光学纯度在98%以上.

关键词: 聚吡咯, 催化, 锌, 丙交酯, 聚乳酸

As a biodegradable polymer, poly-lactic acid (PLA) has a wide application prospect. At present, high quality PLA is mainly produced via lactide condensation. In the technique, the optical purity of lactide is the key factor affecting the mechanical properties of produced PLA. Thus, developing the synthesis technology of lactide with high optical purity is a challenging subject with good application value. In this work, zinc-doped polypyrrole (Zn@PPy) catalyst was designed and prepared. The material could catalyze the condensation of lactic acid to synthesize lactide with high optical purity. Notably, the material could be reused for many times with the optical purity of the produced lactide over 98%.

Key words: polypyrrole, catalyst, zinc, lactide, poly-lactic acid

引用此文

崔旭东, 孟祥坤, 陈颖, 刘永红, 俞磊. 锌掺杂聚吡咯催化乳酸缩合制备高光纯L-丙交酯[J]. 有机化学, 2022, 42(9): 2954-2960.

Xudong Cui, Xiangkun Meng, Ying Chen, Yonghong Liu, Lei Yu. Preparation of L-Lactide with High Optical Purity via the Zinc-Doped Polypyrrole-Catalyzed Lactic Acid Condensation[J]. Chinese Journal of Organic Chemistry, 2022, 42(9): 2954-2960.

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图/表 4

图1. (a) L-乳酸缩合制备L-丙交酯步骤(聚合反应温度150 ℃, 压力变化依次为101.3 kPa下3 h, 48.0 kPa下0.5 h, 1.3 kPa下0.5 h; 裂解步骤在220 ℃/1.3 kPa下反应3 h); (b)催化剂再利用对应产物产率与光学纯度

Figure 1. (a) Processes for the synthesis of L-lactide from L-lactic acid (polymerization at 150 ℃ under 101.3 kPa pressure for 3 h, 48.0 kPa pressure for 0.5 h, and 1.3 kPa pressure for 0.5 h subsequently; splitting at 220 ℃ under 1.3 kPa pressure for 3 h); (b) Product yield and optical purity corresponding to catalyst reuse

图2. Zn@PPy的XPS光谱图

Figure 2. XPS spectra of Zn@PPy

图3. Zn@PPy的表征谱图

Figure 3. Characterization Zn@PPy (a, b) SEM images; (c, d) TEM images; (e) Electron diffraction pattern; (f) HAADF-STEM image; (g, h, i) Element mapping image; (j) EDX spectral image

图式1. Zn@PPy催化L-乳酸缩合制备L-丙交酯的机理

Scheme 1. Mechanisms of the Zn@PPy-catalyzed condensation of L-LA to L-lactide

参考文献 26

[1]	(a) Xie, W.; Jiang, C.; Yu, X.; Shi, X.; Wang, S.; Sun, Y.; Yin, M.; Wu, D. ACS Appl. Polym. Mater. 2021, 3, 6078. doi: 10.1021/acsapm.1c00879
	(b) Li, J.; Wang, Y.; Wang, Z.; Wu, D. Carbohydr. Polym. 2021, 273, 118594. doi: 10.1016/j.carbpol.2021.118594
	(c) Ji, L.; Gong, M.; Qiao, W.; Zhang, W.; Liu, Q.; Dunham, R. E.; Gu, J. J. Polym. Res. 2018, 25, 210. doi: 10.1007/s10965-018-1600-9
	(d) Xu, C.; Lv, Q.; Wu, D.; Wang, Z. Cellulose 2017, 24, 2163. doi: 10.1007/s10570-017-1233-x
	(e) Lv, Q.; Wu, D.; Xie, H.; Peng, S.; Chen, Y.; Xu, C. RSC Adv. 2016, 6, 37721. doi: 10.1039/C6RA07752H
	(f) Song, X.; You, J.; Wang, J.; Zhu, A.; Ji, L.; Guo, R. Chem. Res. Chin. Univ. 2014, 30, 326. doi: 10.1007/s40242-014-3306-9
	(g) Wu, D.; Cheng, Y.; Feng, S., Yao, Z.; Zhang, M. Ind. Eng. Chem. Res. 2013, 52, 6731. doi: 10.1021/ie4004199
	(h) Lu, L.; Wu, D.; Zhang, M.; Zhou, W. Ind. Eng. Chem. Res. 2012, 51, 3682. doi: 10.1021/ie2028969
[2]	(a) Li, J.; Wu, D. Int. J. Biol. Macromol. 2022, 205, 587. doi: 10.1016/j.ijbiomac.2022.02.123
	(b) Zhang, Y.; Chen, Z.; Zhao, R. Wang, K.; Wu, D.; Wang, C.; Zhang, M. J. Appl. Polym. Sci. 2022, 139, 51545 doi: 10.1002/app.51545
	(c) Zhang, G.; Xie, W.; Wu, D. Carbohydr. Polym. 2020, 227, 115341. doi: 10.1016/j.carbpol.2019.115341
	(d) Wang, Y.; Ying, Z.; Xie, W.; Wu, D. Carbohydr. Polym. 2020, 233, 115845. doi: 10.1016/j.carbpol.2020.115845
	(e) Wanyan, Q.; Qiu, Y.; Xi, J.; Yin, S.; Zhang, W.; Wu, D. ACS Appl. Polym. Mater. 2020, 2, 5889. doi: 10.1021/acsapm.0c01107
	(f) Qiu, Y.; Wanyan, Q.; Xie, W.; Wang, Z.; Chen, M.; Wu, D. Polymer 2019, 180, 121733. doi: 10.1016/j.polymer.2019.121733
	(g) Xu, C.; Chen, C.; Wu, D. Carbohydr. Polym. 2018, 182, 115. doi: 10.1016/j.carbpol.2017.11.001
	(h) Lu, Y.; Huang, J.; Ge, L.; Xie, W.; Wu, D. Polymer 2018, 156, 136. doi: 10.1016/j.polymer.2018.10.005
	(i) Zhang, G.; Wu, D.; Xie, W.; Wang, Z.; Xu, C. Carbohydr. Polym. 2018, 195, 79. doi: 10.1016/j.carbpol.2018.04.079
[3]	Pu, X.; Zhou, X.; Huang, Z.; Yin, G.; Chen, X. Chin. Chem. Lett. 2020, 31, 1141. doi: 10.1016/j.cclet.2019.07.002
[4]	(a) Kim, S. H.; Kim, Y. H. Macromol. Symp. 1999, 144, 277. doi: 10.1002/masy.19991440125
	(b) Ajioka, M.; Enomoto, K.; Suzuki, K.; Yamaguchi, A. J. Environ. Polym. Degrad. 1995, 3, 225.
[5]	Jiang, X.; Zhao, N.; Li, Z. Chin. J. Chem. 2021, 39, 2403. doi: 10.1002/cjoc.202100230
[6]	(a) Poryvaeva, E. A.; Egiazaryan, T. A.; Makarov, V. M.; Moskalev, M. V.; Razborov, D. A.; Fedyushkin, I. L. Russ. J. Org. Chem. 2017, 53, 344. doi: 10.1134/S1070428017030058
	(b) De Clercq, R.; Dusselier, M.; Makshina, E.; Sels, B. F. Angew. Chem., Int. Ed. Engl. 2018, 57, 3074. doi: 10.1002/anie.201711446
	(c) Ishijima, Y.; Maruta, Y.; Abiko, A. Chem. Lett. 2012, 41, 1456. doi: 10.1246/cl.2012.1456
	(d) Upare, P. P.; Lee, M.; Hwang, D. W.; Hwang, Y. K.; Chang, J.-S. Catal. Commun. 2014, 56, 179. doi: 10.1016/j.catcom.2014.07.026
	(e) Meng, X. K.; Yu, L.; Cao, Y.-T.; Zhang, X.; Zhang, Y.-Y. Org. Biomol. Chem. 2021, 19, 10288. doi: 10.1039/D1OB01918J
[7]	Botvin, V.; Karaseva, S.; Khasanov, V. Polym. Degrad. Stab. 2020, 182, 109382. doi: 10.1016/j.polymdegradstab.2020.109382
[8]	(a) Tsukegi, T.; Motoyama, T.; Shirai, Y.; Nishida, H.; Endo, T. Polym. Degrad. Stab. 2007, 92, 552. doi: 10.1016/j.polymdegradstab.2007.01.009
	(b) Wang, G.; Tang, S.; Cao, F.; Wu, H.; Jia, H.; Wei, P.; Ouyang, P. Ind. Eng. Chem. Res. 2018, 57, 7711. doi: 10.1021/acs.iecr.8b01088
	(c) Jiang, B.; Tantai, X.; Zhang, L.; Hao, L.; Sun, Y.; Deng, L.; Shi, Z. RSC Adv. 2015, 5, 50747. doi: 10.1039/C5RA05073A
[9]	(a) Sun, H.; Shi, Y.; Fu, W.; Yu, L. ChemistrySelect 2021, 6, 7599. doi: 10.1002/slct.202101934
	(b) Gao, G.; Han, J.; Yu, L.; Xu, Q. Synlett 2019, 30, 1703. doi: 10.1055/s-0037-1612088
	(c) Liu, Y.; Tang, D.; Cao, K.; Yu, L.; Han, J.; Xu, Q. J. Catal. 2018, 360, 250. doi: 10.1016/j.jcat.2018.01.026
	(d) Yu, L.; Han, Z.; Ding, Y. Org. Process Res. Dev. 2016, 20, 2124. doi: 10.1021/acs.oprd.6b00322
	(e) Yu, L.; Huang, Y.; Wei, Z.; Ding, Y.; Su, C.; Xu, Q. J. Org. Chem. 2015, 80, 8677. doi: 10.1021/acs.joc.5b01358
[10]	Arnold, P. L.; Casely, I. J.; Turner, Z. R.; Bellabarba, R.; Tooze, R. B. Dalton Trans. 2009, 35, 7236.
[11]	Darensbourg, D. J.; Rainey, P.; Yarbrough. J. Inorg. Chem. 2001, 40, 986. doi: 10.1021/ic0006403
[12]	Abufarag, A.; Vahrenkamp, H. Inorg. Chem. 1995, 34, 2207. doi: 10.1021/ic00112a038
[13]	Wang, G.; Tang, S.; Cao, F.; Wu, H.; Jia, H.; Wei, P.; Ouyang, P. Ind. Eng. Chem. Res. 2018, 57, 7711. doi: 10.1021/acs.iecr.8b01088
[14]	Louette, P.; Bodino, F.; Pireaux, J. J. Surf. Sci. Spectra 2005, 12, 84. doi: 10.1116/11.20050918
[15]	Malitesta, C.; Losito, I.; Sabbatini, L.; Zambonin, P. G. J. Electron Spectrosc. Relat. Phenom. 1995, 76, 629. doi: 10.1016/0368-2048(95)02438-7
[16]	Sarno, D. M.; Matienzo, L. J.; Jones, W. E. Inorg. Chem. 2001, 40, 6308. pmid: 11703135
[17]	Hsieh, P.-T.; Chen, Y.-C.; Kao, K.-S.; Wang, C.-M. Appl. Phys. A: Mater. Sci. Process. 2008, 90, 317. doi: 10.1007/s00339-007-4275-3
[18]	Chen, X.; Mao, J.; Liu, C.; Chen, C.; Cao, H.; Yu, L. Chin. Chem. Lett. 2020, 31, 3205 doi: 10.1016/j.cclet.2020.07.031
[19]	(a) Zhang, J.; Cao, K.; Zhang, X.; Zhang, Q. Appl. Organomet. Chem. 2020, 34, e5377. pmid: 27580374
	(b) Fan, X.; Yao, Y.; Xu, Y.; Yu, L.; Qiu, C. ChemCatChem 2019, 11, 2596. doi: 10.1002/cctc.201900262 pmid: 27580374
	(c) Ebrahimi, T.; Mamleeva, E.; Yu, I.; Hatzikiriakos, S. G.; Mehrkhodavandi, P. Inorg. Chem. 2016, 55, 9445. doi: 10.1021/acs.inorgchem.6b01722 pmid: 27580374
[20]	Ajioka, M.; Enomoto, K.; Suzuki, K.; Yamaguchi, A. J. Environ. Polym. Degrad. 1995, 3, 225. doi: 10.1007/BF02068677
[21]	(a) Kovalchukova, O. V.; Anh, V. T. N.; Utenyshev, A. N.; Stash, A. I.; Ryabov, M. A.; Abbas, A. T. R. A.; Voronkova, V. K.; Bazan, L. V. Polyhedron 2020, 184, 114557. doi: 10.1016/j.poly.2020.114557 pmid: 30410851
	(b) Shaabani, A.; Mahyari, M.; Seyyedhamzeh, M.; Keshipour, S.; Ng, S. W. Tetrahedron Lett. 2011, 52, 4388. doi: 10.1016/j.tetlet.2011.06.017 pmid: 30410851
	(c) Karmakar, A.; Rubio, G. M. D. M.; Guedes, D. S. M. F. C.; Pombeiro, A. J. L. ChemistryOpen 2018, 7, 865. doi: 10.1002/open.201800170 pmid: 30410851
[22]	(a) Kricheldorf, H. R.; Damrau, D. O. Macromol. Chem. Phys. 1997, 198, 1753. doi: 10.1002/macp.1997.021980605
	(b) Kricheldorf, H. R.; Damrau, D. O. Macromol. Chem. Phys. 1998, 199, 1747. doi: 10.1002/(SICI)1521-3935(19980801)199:8【-逻辑与-】#x00026;lt;1747::AID-MACP1747【-逻辑与-】#x00026;gt;3.0.CO;2-2
	(c) Zhang, Y.-K.; Qi, Y.-B.; Yin, Y.; Sun, P.; Li, A.-M.; Zhang, Q.-X.; Jiang, W. ACS Sustainable Chem. Eng. 2020, 8, 2865. doi: 10.1021/acssuschemeng.9b06987
	(d) Ejfler, J.; Szafert, S.; Mierzwicki, K.; Jerzykiewicz, L. B.; Sobota, P. Dalton Trans. 2008, 46, 6556.
[23]	(a) Zhang, H.; Han, M.; Yang, C.; Yu, L.; Xu, Q. Chin. Chem. Lett. 2019, 30, 263. doi: 10.1016/j.cclet.2018.01.035
	(b) Zhang, H.; Han, M.; Chen, T.; Xu, L.; Yu, L. RSC Adv. 2017, 7, 48214. doi: 10.1039/C7RA09412D
	(c) Xu, L.; Wang, F.; Huang, J.; Yang, C.; Yu, L.; Fan, Y. Tetrahedron 2016, 72, 4076. doi: 10.1016/j.tet.2016.05.039
[24]	(a) Liu, M.; Zhang, X.; Chu, S.; Ge, Y.; Huang, T.; Liu, Y.; Yu, L. Chin. Chem. Lett. 2022, 33, 205. doi: 10.1016/j.cclet.2021.05.061
	(b) Xiao, X.; Shao, Z.; Yu, L. Chin. Chem. Lett. 2021, 32, 2933. doi: 10.1016/j.cclet.2021.03.047
	(c) Cao, H.; Ma, R.; Chu, S.; Xi, J.; Yu, L.; Guo, R. Chin. Chem. Lett. 2021, 32, 2761. doi: 10.1016/j.cclet.2021.03.029
	(d) Chen, C.; Cao, Y.; Wu, X.; Cai, Y.; Liu, J.; Xu, L.; Ding, K.; Yu, L. Chin. Chem. Lett. 2020, 31, 1078. doi: 10.1016/j.cclet.2019.12.019
	(e) Zheng, Y.; Wu, A.; Ke, Y.; Cao, H.; Yu, L. Chin. Chem. Lett. 2019, 30, 937. doi: 10.1016/j.cclet.2019.01.012
[25]	(a) Deng, X.; Qian, R.; Zhou, H.; Yu, L. Chin. Chem. Lett. 2021, 32, 1029. doi: 10.1016/j.cclet.2020.09.012
	(b) Jing, X.; Wang, T.; Ding, Y.; Yu, L. Appl. Catal., A 2017, 541, 107. doi: 10.1016/j.apcata.2017.05.007
	(c) Yu, L.; Bai, Z.; Zhang, X.; Zhang, X.; Ding, Y.; Xu, Q. Catal. Sci. Technol. 2016, 6, 1804. doi: 10.1039/C5CY01395J
	(d) Yu, L.; Ye, J.; Zhang, X.; Ding, Y.; Xu, Q. Catal. Sci. Technol. 2015, 5, 4830. doi: 10.1039/C5CY01030F
	(e) Yu, L.; Li, H.; Zhang, X.; Ye, J.; Liu, J.; Xu, Q.; Lautens, M. Org. Lett. 2014, 16, 1346. doi: 10.1021/ol500075h
[26]	Casarano, R.; Bentini, R.; Bueno, V. B.; Lacovella, T.; Monteiro, F. B. F.; Iha, F. A. S.; Campa, A.; Petri, D. F. S.; Jaffe, M.; Catalani, L. H. Polymer 2009, 50, 6218. doi: 10.1016/j.polymer.2009.10.048