Citation: Yue-chao Xu, Hui Zhou, Xiao-bing Lu. Regioselective Polymerization of α-Methylene β-Butyrolactone: Synthesis of Linear and Cyclic Polyesters[J]. Acta Polymerica Sinica, ;2020, 51(1): 91-97. doi: 10.11777/j.issn1000-3304.2020.19145 shu

Regioselective Polymerization of α-Methylene β-Butyrolactone: Synthesis of Linear and Cyclic Polyesters

State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024

Corresponding author: Xiao-bing Lu, xblu@dlut.edu.cn
Received Date: 2 August 2019
Revised Date: 20 August 2019
Available Online: 27 September 2019

Regioselective polymerization of α-methylene β-butyrolactone (M_βBL) to afford polyesters with various topological structures was achieved by the use of different catalysts or initiators. With azodiisobutyronitrile (AIBN) as initiator, polymerization selectively occurred at the C＝C bond to produce linear poly(α-methylene-β-butyrolactone) (PM_βBL) with the remain of β-butyrolactone unit. Achiral Salen aluminum complexes afforded linear syndiotactic-enriched polyesters with controllable molecular weight and a narrow polydispersity, in which ring-opening polymerization selectively occurred at the acyl C―O bond of M_βBL and the C＝C bond was remained. Strong organic bases, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), exhibited high activity for ring-opening polymerization of M_βBL under mild condition, affording linear polyesters. Simple sodium iodide mediated M_βBL polymerization predominately produced crystalline cyclic polyesters with a melting point of 145.4 °C, in which the ring-opening mainly concerned the alkyl C_β―O bond cleavage. This study demonstrates that the synthesis of various topological materials with different properties can be achieved by regioselective polymerization of functional monomers with the exquisite choice of catalyst or initiator.
- α-Methylene β-butyrolactone,
- Polyester,
- Ring-opening polymerization,
- Regioselectivity,
- Cyclic polymer
1. [1]
  Williams C K. Chem Soc Rev, 2007, 36: 1573 − 1580 doi: 10.1039/b614342n
2. [2]
  Pang X, Zhuang X L, Tang Z H, Chen X S. Biotech J, 2010, 5: 1125 − 1136 doi: 10.1002/biot.201000135
3. [3]
  Yuan Pengjun(袁鹏俊), Hong Miao(洪缪). Acta Polymerica Sinica(高分子学报), 2019, 50(4): 327 − 337 doi: 10.11777/j.issn1000-3304.2018.18232
4. [4]
  Huang Yu(黄玉), Wang Siteng(王斯滕), Zhu Xinyuan(朱新远). Acta Polymerica Sinica(高分子学报), 2017, (2): 245 − 258 doi: 10.11777/j.issn1000-3304.2017.16309
5. [5]
  Li M S, Tao Y, Tang J D, Wang Y C, Zhang X Y, Tao Y H, Wang X H. J Am Chem Soc, 2019, 141: 281 − 289 doi: 10.1021/jacs.8b09739
6. [6]
  Liang Xiaolin(梁孝林), Wen Jie(闻杰), Yang Wendi(杨雯迪), Liu Wenyi(刘文毅), Shi Dongjian(施冬健), Chen Mingqing(陈明清). Acta Polymerica Sinica(高分子学报), 2019, 50(2): 147 − 159 doi: 10.11777/j.issn1000-3304.2018.18176
7. [7]
  Cui Shuquan(崔书铨), Yu Lin(俞麟), Ding Jiandong(丁建东). Acta Polymerica Sinica(高分子学报), 2018, (8): 997 − 1015 doi: 10.11777/j.issn1000-3304.2018.18084
8. [8]
  Zhou Y C, Hu C Y, Zhang T H, Xu X W, Duan R L, Luo Y, Sun Z Q, Pang X, Chen X S. Macromolecules, 2019, 52: 3462 − 3470 doi: 10.1021/acs.macromol.9b00001
9. [9]
  Sun X Y, Ren W M, Liu S J, Jia Y B, Wang Y M, Lu X B. Molecules, 2018, 23: 468 doi: 10.3390/molecules23020468
10. [10]
  Liu Y, Ma H. J Polym Sci Part A: Polym Chem, 2014, 52: 3096 − 3106 doi: 10.1002/pola.27359
11. [11]
  Liu J, Ren W, Lu X. Sci China Chem, 2015, 58: 999 − 1004 doi: 10.1007/s11426-014-5263-z
12. [12]
  Müller H M, Seebach D. Angew Chem Int Ed, 1993, 32: 477 − 502 doi: 10.1002/anie.199304771
13. [13]
  Hiki S, Miyamoto M, Kimura Y. Polymer, 2000, 41: 7369 − 7379 doi: 10.1016/S0032-3861(00)00086-0
14. [14]
  Wu L P, Chen S T, Li Z B, Xu K T, Chen G Q. Polym Int, 2008, 57: 939 − 949 doi: 10.1002/pi.2431
15. [15]
  Xu Y C, Zhou H, Sun X Y, Ren W M, Lu X B. Macromolecules, 2016, 49: 5782 − 5787 doi: 10.1021/acs.macromol.6b01372
16. [16]
  Xu Y C, Ren W M, Zhou H, Gu G G, Lu X B. Macromolecules, 2017, 50: 3131 − 3142 doi: 10.1021/acs.macromol.7b00239
1. [1]
  Shihui Shi , Haoyu Li , Shaojie Han , Yifan Yao , Siqi Liu . Regioselectively Synthesis of Halogenated Arenes via Self-Assembly and Synergistic Catalysis Strategy. University Chemistry, 2024, 39(5): 336-344. doi: 10.3866/PKU.DXHX202312002
2. [2]
  Danqing Wu , Jiajun Liu , Tianyu Li , Dazhen Xu , Zhiwei Miao . Research Progress on the Simultaneous Construction of C—O and C—X Bonds via 1,2-Difunctionalization of Olefins through Radical Pathways. University Chemistry, 2024, 39(11): 146-157. doi: 10.12461/PKU.DXHX202403087
3. [3]
  Yaqin Zheng , Lian Zhuo , Meng Li , Chunying Rong . Enhancing Understanding of the Electronic Effect of Substituents on Benzene Rings Using Quantum Chemistry Calculations. University Chemistry, 2025, 40(3): 193-198. doi: 10.12461/PKU.DXHX202406119
4. [4]
  Junjie Zhang , Yue Wang , Qiuhan Wu , Ruquan Shen , Han Liu , Xinhua Duan . Preparation and Selective Separation of Lightweight Magnetic Molecularly Imprinted Polymers for Trace Tetracycline Detection in Milk. University Chemistry, 2024, 39(5): 251-257. doi: 10.3866/PKU.DXHX202311084
5. [5]
  Ruiying WANG , Hui WANG , Fenglan CHAI , Zhinan ZUO , Benlai WU . Three-dimensional homochiral Eu(Ⅲ) coordination polymer and its amino acid configuration recognition. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 877-884. doi: 10.11862/CJIC.20250052
6. [6]
  Yuxia Luo , Xiaoyu Xie , Fangfang Chen . 药物递送魔法师——分子印迹聚合物. University Chemistry, 2025, 40(8): 202-210. doi: 10.12461/PKU.DXHX202409129
7. [7]
  Zhongxin YU , Wei SONG , Yang LIU , Yuxue DING , Fanhao MENG , Shuju WANG , Lixin YOU . Fluorescence sensing on chlortetracycline of a Zn-coordination polymer based on mixed ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2415-2421. doi: 10.11862/CJIC.20240304
8. [8]
  Bao Jia , Yunzhe Ke , Shiyue Sun , Dongxue Yu , Ying Liu , Shuaishuai Ding . Innovative Experimental Teaching for the Preparation and Modification of Conductive Organic Polymer Thin Films in Undergraduate Courses. University Chemistry, 2024, 39(10): 271-282. doi: 10.12461/PKU.DXHX202404121
9. [9]
  Xiao SANG , Qi LIU , Jianping LANG . Synthesis, structure, and fluorescence properties of Zn(Ⅱ) coordination polymers containing tetra-alkenylpyridine ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2124-2132. doi: 10.11862/CJIC.20240158
10. [10]
  Xuefei Leng , Yanshai Wang , Hai Wang , Shengyang Tao . The In-Depth integration of “Industry-University-Research” in the Exploration and Practice of “Comprehensive Training in Polymer Engineering”. University Chemistry, 2025, 40(4): 66-71. doi: 10.12461/PKU.DXHX202405105
11. [11]
  Ke Qiu , Fengmei Wang , Mochou Liao , Kerun Zhu , Jiawei Chen , Wei Zhang , Yongyao Xia , Xiaoli Dong , Fei Wang . A Fumed SiO₂-based Composite Hydrogel Polymer Electrolyte for Near-Neutral Zinc-Air Batteries. Acta Physico-Chimica Sinica, 2024, 40(3): 2304036-0. doi: 10.3866/PKU.WHXB202304036
12. [12]
  Minghui Wu , Markus Mühlinghaus , Xuechao Li , Chaojie Xu , Qiang Chen , Haiming Zhang , Klaus Müllen , Lifeng Chi . On-Surface Synthesis of Chevron-Shaped Conjugated Ladder Polymers Consisting of Benzo[a]azulene Units. Acta Physico-Chimica Sinica, 2024, 40(8): 2307024-0. doi: 10.3866/PKU.WHXB202307024
13. [13]
  Chunyuan Kang , Xiaoyu Li , Fan Yang , Bai Yang . Ionic-bond crosslinked carbonized polymer dots for tunable and enhanced room temperature phosphorescence. Acta Physico-Chimica Sinica, 2026, 42(1): 100156-0. doi: 10.1016/j.actphy.2025.100156
14. [14]
  Xilin Zhao , Xingyu Tu , Zongxuan Li , Rui Dong , Bo Jiang , Zhiwei Miao . Research Progress in Enantioselective Synthesis of Axial Chiral Compounds. University Chemistry, 2024, 39(11): 158-173. doi: 10.12461/PKU.DXHX202403106
15. [15]
  Anqiu LIU , Long LIN , Dezhi ZHANG , Junyu LEI , Kefeng WANG , Wei ZHANG , Junpeng ZHUANG , Haijun HAO . Synthesis, structures, and catalytic activity of aluminum and zinc complexes chelated by 2-((2,6-dimethylphenyl)amino)ethanolate. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 791-798. doi: 10.11862/CJIC.20230424
16. [16]
  Fanpeng Meng , Fei Zhao , Jingkai Lin , Jinsheng Zhao , Huayang Zhang , Shaobin Wang . Optimizing interfacial electric fields in carbon nitride nanosheet/spherical conjugated polymer S-scheme heterojunction for hydrogen evolution. Acta Physico-Chimica Sinica, 2025, 41(8): 100095-0. doi: 10.1016/j.actphy.2025.100095
17. [17]
  Xingchao Zhao , Xiaoming Li , Ming Liu , Zijin Zhao , Kaixuan Yang , Pengtian Liu , Haolan Zhang , Jintai Li , Xiaoling Ma , Qi Yao , Yanming Sun , Fujun Zhang . Photomultiplication-Type All-Polymer Photodetectors and Their Applications in Photoplethysmography Sensor. Acta Physico-Chimica Sinica, 2025, 41(1): 100007-0. doi: 10.3866/PKU.WHXB202311021
18. [18]
  Hanmei Lü , Xin Chen , Qifu Sun , Ning Zhao , Xiangxin Guo . Uniform Garnet Nanoparticle Dispersion in Composite Polymer Electrolytes. Acta Physico-Chimica Sinica, 2024, 40(3): 2305016-0. doi: 10.3866/PKU.WHXB202305016
19. [19]
  Gengjia Chen , Junjie Ou . Application of the van Deemter Equation in Instrumental Analysis Teaching: A Case of Organic Polymer Monolithic Columns. University Chemistry, 2025, 40(11): 362-368. doi: 10.12461/PKU.DXHX202502003
20. [20]
  Dongdong Yao , JunweiGu , Yi Yan , Junliang Zhang , Yaping Zheng . Teaching Phase Separation Mechanism in Polymer Blends Using Process Representation Teaching Method: A Teaching Design for Challenging Theoretical Concepts in “Polymer Structure and Properties” Course. University Chemistry, 2025, 40(4): 131-137. doi: 10.12461/PKU.DXHX202408125

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(3991)
HTML views(443)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142