硫代羧基环内酸酐与丙交酯的可切换共聚

黄月洲; 胡晨阳; 王天昶; 庞烜; 陈学思

doi:10.11777/j.issn1000-3304.2022.22355

您当前的位置：

首页 >

文章列表页 >

硫代羧基环内酸酐与丙交酯的可切换共聚

研究论文 | 更新时间：2023-03-08

- 硫代羧基环内酸酐与丙交酯的可切换共聚
- Switchable Polymerization of Sulfur-containing Carboxyanhydride and Lactide
- 高分子学报 2023年54卷第4期页码：467-475
- 作者机构：
  
  1.中国科学院长春应用化学研究所中科院生态环境高分子材料重点实验室长春 130022
  2.中国科学技术大学应用化学与工程学院合肥 230026
- 作者简介：
  
  E-mail: xpang@ciac.ac.cn
  xschen@ciac.ac.cn
- 基金信息：
  
  科技部国家重点研发计划(2021YFB3801901);国家自然科学基金面上项目(基金号 52073272)
- DOI：10.11777/j.issn1000-3304.2022.22355
  中图分类号：
- 纸质出版日期：2023-04-20，
  
  网络出版日期：2023-01-10，
  
  收稿日期：2022-10-19，
  
  录用日期：2022-11-23
扫描看全文
黄月洲,胡晨阳,王天昶等.硫代羧基环内酸酐与丙交酯的可切换共聚[J].高分子学报,2023,54(04):467-475.

Huang Yue-zhou,Hu Chen-yang,Wang Tian-chang,et al.Switchable Polymerization of Sulfur-containing Carboxyanhydride and Lactide[J].ACTA POLYMERICA SINICA,2023,54(04):467-475.
黄月洲,胡晨阳,王天昶等.硫代羧基环内酸酐与丙交酯的可切换共聚[J].高分子学报,2023,54(04):467-475. DOI： 10.11777/j.issn1000-3304.2022.22355.

Huang Yue-zhou,Hu Chen-yang,Wang Tian-chang,et al.Switchable Polymerization of Sulfur-containing Carboxyanhydride and Lactide[J].ACTA POLYMERICA SINICA,2023,54(04):467-475. DOI： 10.11777/j.issn1000-3304.2022.22355.

摘要

硫代聚酯是一种兼具聚酯材料的优点(降解性、生物相容性和热稳定性等)与含硫聚合物材料的优点 (光学性能和金属吸附性能等)的新型材料. 本文合成了含硫单体硫代羧基环内酸酐(MDTD)，以希夫碱锰(Salen-Mn)为催化剂，在低投料比(50:1)较低温度(60 ℃)的情况下，抑制了小分子副产物的生成，实现了MDTD的活性聚合. 在此基础上，利用Salen-Mn可逆插入氧硫化碳(COS)的性质，设计开发出了一条新的硫代单体控制的自切换共聚路线. 通过在丙交酯(LA)聚合的过程中添加MDTD单体以及改变聚合反应气氛的手段实现了MDTD与LA的可切换共聚，并应用核磁、凝胶渗透色谱等方法跟踪反应进程表征反应产物，证实了多嵌段聚酯/聚硫酯(p(LA-

-MDTD-

-LA))的生成. 通过该方法最终得到了五嵌段的聚酯/聚硫酯(

=12.4 kg/mol，

=1.20)的嵌段共聚物. 该方法可以通过改变相应的单体结构合成相应的多嵌段聚酯/聚硫酯，为改善含硫聚酯的物理化学性质打下了基础.

Abstract

Thiopolyesters is a new type of materials that combine the advantages of polyester materials (degradability

biocompatibility

thermal stability

etc

.) and sulfur-containing polymer materials (optical properties

metal adsorption properties

etc

.). In this study

the sulfur-containing carboxyanhydride (5-methyl dithiolane-2

4-dione

MDTD) was synthesized and polymerized by Schiff base-manganese (Salen-Mn). The formation of small-molecule by-products was inhibited and the active homopolymerization of MDTD was realized under the condition of low feed ratio (50:1) using 4-dimethylaminopyridine (DMAP) as cocatalyst

at lower temperature (60 ℃). Based on the reversible insertion of carbon oxysulfide (COS) by Salen-Mn

a new monomer controlled self-switchable polymerization route was developed by sequentially addition of the MDTD and the removal of COS. Chemoselective ring opening between MDTD and lactide (LA) was explored with DMAP as cocatalyst. The monomer controlled switchable copolymerization reaction process and the formation of polyblock polyester/polythioester (p(LA-

-MDTD-

-LA)) were confirmed by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). Eventually

a two-step switchable copolymerization was realized by sequential addition of MDTD and degassing

a five-block polyester/polythioester (

= 12.4 kg/mol

=1.20) copolymer was obtained. This emerging polymerization strategy could synthesize the corresponding multi-block polyester/polythioester by changing the structure of the Sulfur-containing carboxyanhydride monomer

which lays a foundation for improving physical and chemcial properties of the thiopolyesters.

关键词

可切换共聚聚硫酯硫代羧基环内酸酐开环聚合多嵌段共聚物

Keywords

Switchable copolymerizationSulfur-containing carboxyanhydridePolythiosetersRing-opening copolymerization (ROCOP)Multi-block copolymer

references

Walsh C. T. The Chemical Biology of Sulfur. Cambridge: RSC Publishing. 2020. 5-22. doi:10.1039/9781839161841http://dx.doi.org/10.1039/9781839161841

Wang M.; Jiang X. Sulfur-sulfur bond construction. Topics Curr. Chem., 2018, 376, 14. doi:10.1007/s41061-018-0192-5http://dx.doi.org/10.1007/s41061-018-0192-5

Lee T.; Dirlam P. T.; Njardarson J. T.; Glass R. S.; Pyun J. Polymerizations with elemental sulfur: from petroleum refining to polymeric materials. J. Am. Chem. Soc., 2022, 144(1), 5-22. doi:10.1021/jacs.1c09329http://dx.doi.org/10.1021/jacs.1c09329

Xiao X.; Xue J.; Jiang X. Polysulfurating reagent design for unsymmetrical polysulfide construction. Nat. Commun., 2018, 9(1), 1-9. doi:10.1038/s41467-018-04306-5http://dx.doi.org/10.1038/s41467-018-04306-5

Mutlu H.; Ceper E. B.; Li X.; Yang J.; Dong W.; Ozmen M. M.; Theato P. Sulfur chemistry in polymer and materials science. Macromol. Rapid Commun., 2019, 40(1), 1800650. doi:10.1002/marc.201800650http://dx.doi.org/10.1002/marc.201800650

Lowe A. B.; Hoyle C. E.; Bowman C. N. Thiol-yne click chemistry: a powerful and versatile methodology for materials synthesis. J. Mater. Chem., 2010, 20(23), 4745-4750. doi:10.1039/b917102ahttp://dx.doi.org/10.1039/b917102a

朱忆诺, 陶友华. 基于氨基酸基交硫酯单体的闭环回收高分子. 高分子学报, 2022, 53(9), 1023-1031. doi:10.11777/j.issn1000-3304.2022.22102http://dx.doi.org/10.11777/j.issn1000-3304.2022.22102

Zhang C. J.; Zhu T. C.; Cao X. H.; Hong X.; Zhang X. H. Poly(thioether)s from closed-system one-pot reaction of carbonyl sulfide and epoxides by organic bases. J. Am. Chem. Soc., 2019, 141(13), 5490-5496. doi:10.1021/jacs.9b00544http://dx.doi.org/10.1021/jacs.9b00544

王莹, 杨嘉良, 张成建, 张兴宏. 有机催化含硫一碳单体与环氧化物共聚. 高分子学报, 2020, 51(10), 1092-1103. doi:10.11777/j.issn1000-3304.2020.20096http://dx.doi.org/10.11777/j.issn1000-3304.2020.20096

Fairbanks B. D.; Singh S. P.; Bowman C. N.; Anseth K. S. Photodegradable, photoadaptable hydrogels via radical-mediated disulfide fragmentation reaction. Macromolecules, 2011, 44(8), 2444-2450. doi:10.1021/ma200202whttp://dx.doi.org/10.1021/ma200202w

Kricheldorf H. R.; Schwarz, G. Poly(thioester)s. J. Macromol. Sci. A, 2007, 44(6), 625-649. doi:10.1080/10601320701285094http://dx.doi.org/10.1080/10601320701285094

Yue T. J.; Ren W. M.; Chen L.; Gu G. G.; Liu Y.; Lu X. B. Synthesis of chiral sulfur-containing polymers: asymmetric copolymerization of meso‐epoxides and carbonyl sulfide. Angew. Chem. Int. Ed., 2018, 130(39), 12852-12856. doi:10.1002/ange.201805200http://dx.doi.org/10.1002/ange.201805200

Datta P. P.; Kiesewetter M. K. Controlled organocatalytic ring-opening polymerization of epsilon-thionocaprolactone. Macromolecules, 2016, 49(3), 774-780. doi:10.1021/acs.macromol.6b00136http://dx.doi.org/10.1021/acs.macromol.6b00136

Chen X. L.; Wang B.; Song D. P.; Pan L.; Li Y. S. One-step synthesis of sequence-controlled polyester-block-poly(ester-alt-thioester) by chemoselective multicomponent polymerization. Macromolecules, 2022, 55(4), 1153-1164. doi:10.1021/acs.macromol.1c02303http://dx.doi.org/10.1021/acs.macromol.1c02303

Teator A. J.; Lastovickova D. N.; Bielawski C. W. Switchable polymerization catalysts. Chem. Rev., 2016, 116(4), 1969-1992. doi:10.1021/acs.chemrev.5b00426http://dx.doi.org/10.1021/acs.chemrev.5b00426

Coulembier O.; Dove A. P.; Pratt R. C.; Sentman A. C.; Culkin D. A.; Mespouille L.; Dubois P.; Waymouth R. M.; Hedrick J. L. Latent, thermally activated organic catalysts for the on‐demand living polymerization of lactide. Angew. Chem. Int. Ed., 2005, 44(31), 4964-4968. doi:10.1002/anie.200500723http://dx.doi.org/10.1002/anie.200500723

Hu C.; Duan R.; Yang S.; Pang X.; Chen X. CO2 catalysiscontrolled: switchable homopolymerization and copolymerization. Macromolecules, 2018, 51(12), 4699-4704. doi:10.1021/acs.macromol.8b00696http://dx.doi.org/10.1021/acs.macromol.8b00696

Osaki M.; Takashima Y.; Yamaguchi H.; Harada A. Switching of polymerization activity of cinnamoyl-‍α‍-cyclodextrin. Org. Biomol. Chem., 2009, 7(8), 1646-1651. doi:10.1039/b818241hhttp://dx.doi.org/10.1039/b818241h

Wang X.; Thevenon A.; Brosmer J. L.; Yu I.; Khan S. I.; Mehrkhodavandi P.; Diaconescu P. L. Redox control of group 4 metal ring-opening polymerization activity toward L-lactide and ε-caprolactone. J. Am. Chem. Soc., 2014, 136(32), 11264-11267. doi:10.1021/ja505883uhttp://dx.doi.org/10.1021/ja505883u

Huang Y.; Hu C.; Pang X.; Zhou Y.; Duan R.; Sun Z.; Chen X. Electrochemically controlled switchable copolymerization of lactide, dioxidecarbon, and epoxides. Angew. Chem. Int. Ed., 2022, 61(20), 202202660. doi:10.1002/anie.202202660http://dx.doi.org/10.1002/anie.202202660

Biernesser A. B.; Delle Chiaie K. R.; Curley J. B.; Byers J. A. Block copolymerization of lactide and an epoxide facilitated by a redox switchable iron‐based catalyst. Angew. Chem. Int. Ed., 2016, 55(17), 5251-5254. doi:10.1002/anie.201511793http://dx.doi.org/10.1002/anie.201511793

Yoon H. J.; Kuwabara J.; Kim J. H.; Mirkin C. A. Allosteric supramolecular triple-layer catalysts. Science, 2010, 330(6000), 66-69. doi:10.1126/science.1193928http://dx.doi.org/10.1126/science.1193928

Raman S. K.; Raja R.; Arnold P. L.; Davidson M. G.; Williams C. K. notWaste, notwant: CO2 (re)cycling into block polymers. Chem. Commun., 2019, 55(51), 7315-7318. doi:10.1039/c9cc02459jhttp://dx.doi.org/10.1039/c9cc02459j

Stoesser T.; Mulryan D.; Williams C. K. Switch catalysis to deliver multi-block polyesters from mixtures of propene oxide, lactide, and phthalic anhydride. Angew. Chem. Int. Ed., 2018, 57(51), 16893-16897. doi:10.1002/anie.201810245http://dx.doi.org/10.1002/anie.201810245

Stosser T.; Sulley G. S.; Gregory G. L.; Williams C. K. Easy access to oxygenated block polymers via switchable catalysis. Nat. Commun., 2019, 10, 2668. doi:10.1038/s41467-019-10481-whttp://dx.doi.org/10.1038/s41467-019-10481-w

Huang Y.; Hu C.; Zhou Y.; Duan R.; Sun Z.; Wan P.; Xiao C.; Pang X.; Chen X. Monomer controlled switchable copolymerization: a feasible route for the functionalization of poly(lactide). Angew. Chem. Int. Ed., 2021, 60(17), 9274-9278. doi:10.1002/anie.202017088http://dx.doi.org/10.1002/anie.202017088

Kricheldorf H. R.; Lomadze N.; Schwarz G. Cyclic poly(thioglycolide) and poly(D,‍L-thiolactide) by zwitterionic polymerization of dithiolane-2,4-diones. Macromolecules, 2007, 40(14), 4859-4864. doi:10.1021/ma0705467http://dx.doi.org/10.1021/ma0705467

Yang Z. J.; Hu C. Y.; Duan R. L.; Sun Z. Q.; Zhang H.; Pang X.; Li L. L. Salen-manganese complexes and their application in the ring-opening polymerization of lactide and epsilon-caprolactone. Asian J. Org. Chem., 2019, 8(3), 376-384. doi:10.1002/ajoc.201800695http://dx.doi.org/10.1002/ajoc.201800695

Wang R. B.; Zhang J. W.; Yin Q.; Xu Y. X.; Cheng J. J.; Tong R. Controlled ring-opening polymerization of O-carboxyanhydrides using a beta-diiminate zinc catalyst. Angew. Chem. Int. Ed., 2016, 55(42), 13010-13014. doi:10.1002/anie.201605508http://dx.doi.org/10.1002/anie.201605508

Hayman G. D.; Hodge J.; Howard B. J.; Muenter J. S.; Dyke T. R. Infrared absorption and microwave-infrared double resonance studies of Ne·OCS molecular beams. J. Chem. Phys., 1987, 86(4), 1670-1678. ArticleResearch. doi:10.1063/1.452758http://dx.doi.org/10.1063/1.452758

更多指标>

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

暂无数据