有机催化二氧化碳、环氧化物和环状酸酐共聚制备高透明光学树脂

吕彦兵; 黄威; 邹俞民; 章伊欣; 刘雄; 李享; 张成建; 张兴宏

doi:10.11777/j.issn1000-3304.2026.26058

您当前的位置：

首页 >

文章列表页 >

有机催化二氧化碳、环氧化物和环状酸酐共聚制备高透明光学树脂

研究论文 | 更新时间：2026-06-15

- 有机催化二氧化碳、环氧化物和环状酸酐共聚制备高透明光学树脂
- Organocatalytic Copolymerization of CO₂, Epoxides, and Tricyclic Anhydrides for High-transparency Optical Resins
- 高分子学报 2026年页码：1-12
- 作者机构：
  
  浙江大学高分子科学与工程学系生物基运输燃料技术全国重点实验室浙江省全省高值化学品低碳合成重点实验室杭州 310058
- 作者简介：
  
  E-mail: chengjian.zhang@zju.edu.cn;； E-mail: xhzhang@zju.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 U23A2083)
- DOI：10.11777/j.issn1000-3304.2026.26058
  中图分类号：
- CSTR：32057.14.GFZXB.2026.7602
- 收稿：2026-02-26，
  
  录用：2026-04-03，
  
  网络首发：2026-06-15，
- 稿件说明：
移动端阅览
吕彦兵, 黄威, 邹俞民, 章伊欣, 刘雄, 李享, 张成建, 张兴宏. 有机催化二氧化碳、环氧化物和环状酸酐共聚制备高透明光学树脂. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26058.

Lu, Y. B.; Huang W.; Zou, Y. M.; Zhang, Y. X.; Liu, X.; Li, X.; Zhang, C. J.; Zhang, X. H. Organocatalytic copolymerization of CO₂, epoxides, and tricyclic anhydrides for high-transparency optical resins. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26058. CSTR: 32057.14.GFZXB.2026.7602.
吕彦兵, 黄威, 邹俞民, 章伊欣, 刘雄, 李享, 张成建, 张兴宏. 有机催化二氧化碳、环氧化物和环状酸酐共聚制备高透明光学树脂. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26058. DOI： CSTR： 32057.14.GFZXB.2026.7602.

Lu, Y. B.; Huang W.; Zou, Y. M.; Zhang, Y. X.; Liu, X.; Li, X.; Zhang, C. J.; Zhang, X. H. Organocatalytic copolymerization of CO₂, epoxides, and tricyclic anhydrides for high-transparency optical resins. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26058. CSTR: 32057.14.GFZXB.2026.7602. DOI：

摘要

具有优异光学功能的高性能树脂在高端镜片、高清成像等光学领域有重要应用. 本研究以CO

、环氧化物和生物源的大位阻三元环状酸酐为单体，采用无金属催化的途径制备得到无规结构的聚(酯-碳酸酯)，其数均分子量高达148.6 kg/mol. 通过改变环氧化物/环酸酐的投料比，所得产物的玻璃化转变温度范围为114~142 ℃，热分解温度范围219~284 ℃，为耐热性高的聚合物材料. 滴铸法所得该聚合物膜的透光率达91%，折光指数为1.50~1.52，阿贝数为46~57. 本研究结果为制备无金属残留的高性能有机光学材料提供了新途径.

Abstract

High-performance optical resins are increasingly vital for advanced applications such as high-definition lenses and optoelectronic devices

yet simultaneously achieving high refractive index and high Abbe number remains a significant challenge. This study presents a metal-free

one-pot terpolymerization strategy to synthesize random poly(ester-carbonate)s from CO

epoxides (cyclohexene oxide or vinyl cyclohexene oxide)

and bio-based tricyclic anhydrides using a triethylborane (TEB)/bis(triphenylphosphine) iminium chloride (PPNCl) Lewis pair catalyst system. The resulting copolymers exhibit a high number-average molecular weight (

) of up to 148.6 kg/mol. By adjusting the epoxide/anhydride feed ratio

the glass transition temperature (

) can be tuned from 114 ℃ to 142 ℃

with thermal decomposition temperatures exceeding 219 ℃. Notably

the incorporation of the rigid

saturated tricyclic skeleton enables the resins to achieve a high refractive index (

=1.50-1.52) while maintaining a high Abbe number (

=46-57)

overcoming the trade-off typically found in organic optical materials. The films prepared

via

drop-casting demonstrate excellent transparency (

91%). This work provides a green

efficient pathway for developing high-performance

metal-free optical materials with superior thermal and optical properties.

关键词

Keywords

references

Luo C. Y. ; Zuo J. D. ; Yuan Y. C. ; Lin X. C. ; Lin F. ; Zhao J. Q. Preparation and properties of a high refractive index optical resin prepared via click chemistry method . Opt. Mater. Express , 2015 , 5 ( 3 ), 462 . doi: 10.1364/ome.5.000462 http://dx.doi.org/10.1364/ome.5.000462

Higashihara T. ; Ueda M. Recent progress in high refractive index polymers . Macromolecules , 2015 , 48 ( 7 ), 1915 - 1929 . doi: 10.1021/ma502569r http://dx.doi.org/10.1021/ma502569r

Malallah R. ; Li H. Y. ; Kelly D. P. ; Healy J. J. ; Sheridan J. T. A review of hologram storage and self-written waveguides formation in photopolymer media . Polymers , 2017 , 9 ( 8 ), 337 . doi: 10.3390/polym9080337 http://dx.doi.org/10.3390/polym9080337

Camposeo A. ; Persano L. ; Farsari M. ; Pisignano D. Additive manufacturing: applications and directions in photonics and optoelectronics . Adv. Opt. Mater. , 2019 , 7 ( 1 ), 1800419 . doi: 10.1002/adom.201800419 http://dx.doi.org/10.1002/adom.201800419

Kozhevnikov V. S. ; Ponomarev R. S. ; Shmyrova A. I. The technology for manufacturing a lensed optical fiber using optical resin . Instrum. Exp. Technol. , 2022 , 65 ( 6 ), 924 - 933 . doi: 10.1134/s0020441222050256 http://dx.doi.org/10.1134/s0020441222050256

Inoue S. ; Koinuma H. ; Tsuruta T. Copolymerization of carbon dioxide and epoxide . J. Polym. Sci. Part B Polym. Lett. , 1969 , 7 ( 4 ), 287 - 292 . doi: 10.1002/pol.1969.110070408 http://dx.doi.org/10.1002/pol.1969.110070408

Zhang X. H. ; Chen S. ; Wu X. M. ; Sun X. K. ; Liu F. ; Qi G. R. Highly active double metal cyanide complexes: effect of central metal and ligand on reaction of epoxide/CO 2 . Chin. Chem. Lett. , 2007 , 18 ( 7 ), 887 - 890 . doi: 10.1016/j.cclet.2007.05.017 http://dx.doi.org/10.1016/j.cclet.2007.05.017

Huang Y. J. ; Zhang X. H. ; Hua Z. J. ; Qi G. R. Calcium chloride doped zinc-cobalt metal-cyanide complex: unexpected highly activity towards ring-opening polymerization of propylene oxide . Chin. Chem. Lett. , 2010 , 21 ( 8 ), 897 - 901 . doi: 10.1016/j.cclet.2010.02.009 http://dx.doi.org/10.1016/j.cclet.2010.02.009

Darensbourg, D. J.; Wilson, S. J. What's new wit h CO 2 ? Recent advances in its copolymerization with oxiranes . Green Chem. , 2012 , 14 ( 10 ), 2665 . doi: 10.1039/c2gc35928f http://dx.doi.org/10.1039/c2gc35928f

Wei R. J. ; Zhang X. H. ; Du B. Y. ; Fan Z. Q. ; Qi G. R. Synthesis of bis(cyclic carbonate) and propylene carbonate via a one-pot coupling reaction of CO 2 , bisepoxide and propylene oxide . RSC Adv., 2013, 3 ( 38 ), 17307 - 17313 . doi: 10.1039/c3ra42570c http://dx.doi.org/10.1039/c3ra42570c

Wei R. J. ; Zhang X. H. ; Du B. Y. ; Fan Z. Q. ; Qi G. R. Selective production of poly(carbonate- co -ether) over cyclic carbonate for epichlorohydrin and CO 2 copolymerization via heterogeneous catalysis of Zn-Co (III) double metal cyanide complex . Polymer , 2013 , 54 ( 23 ), 6357 - 6362 . doi: 10.1016/j.polymer.2013.09.040 http://dx.doi.org/10.1016/j.polymer.2013.09.040

Zhang D. Y. ; Boopathi S. K. ; Hadjichristidis N. ; Gnanou Y. ; Feng X. S. Metal-free alternating copolymerization of CO 2 epoxideswith: fulfilling "green" synthesis and activity. J. Am. Chem. Soc. , 2016 , 138 ( 35 ), 11117 - 11120 . doi: 10.1021/jacs.6b06679 http://dx.doi.org/10.1021/jacs.6b06679

Trott G. ; Saini P. K. ; Williams C. K. Catalysts for CO 2 /epoxide ring-opening copolymerizatio n . Phil. Trans. R. Soc. A. , 2016 , 374 ( 2061 ), 20150085 . doi: 10.1098/rsta.2015.0085 http://dx.doi.org/10.1098/rsta.2015.0085

Li Y. ; Zhang Y. Y. ; Hu L. F. ; Zhang X. H. ; Du B. Y. ; Xu J. T. Carbon dioxide-based copolymers with various architectures . Prog. Polym. Sci. , 2018 , 82 , 120 - 157 . doi: 10.1016/j.progpolymsci.2018.02.001 http://dx.doi.org/10.1016/j.progpolymsci.2018.02.001

Wang Y. ; Zhang J. Y. ; Yang J. L. ; Zhang H. K. ; Kiriratnikom J. ; Zhang C. J. ; Chen K. L. ; Cao X. H. ; Hu L. F. ; Zhang X. H. ; Tang B. Z. Highly selective and productive synthesis of a carbon dioxide-based copolymer upon zwitterionic growth . Macromolecules , 2021 , 54 ( 5 ), 2178 - 2186 . doi: 10.1021/acs.macromol.0c02377 http://dx.doi.org/10.1021/acs.macromol.0c02377

Zhang C. J. ; Geng X. W. ; Zhang X. H. ; Gnanou Y. ; Feng X. S. Alkyl borane-mediated metal-free ring-opening (co)polymerizations of oxygenated monomers . Prog. Polym. Sci. , 2023 , 136 , 101644 . doi: 10.1016/j.progpolymsci.2022.101644 http://dx.doi.org/10.1016/j.progpolymsci.2022.101644

Xia Y. N. ; Zhang C. J. ; Wang Y. ; Liu S. J. ; Zhang X. H. From oxygenated monomers to well-defined low-carbon polymers . Chin. Chem. Lett. , 2024 , 35 ( 1 ), 108860 . doi: 10.1016/j.cclet.2023.108860 http://dx.doi.org/10.1016/j.cclet.2023.108860

Liu Y. F. ; Huang K. L. ; Peng D. M. ; Wu H. Synthesis , characterization and hydrolysis of an aliphatic polycarbonate by terpolymerization of carbon dioxide, propylene oxide and maleic anhydride. Polymer, 2006 , 47 ( 26 ), 8453 - 8461 . doi: 10.1016/j.polymer.2006.10.024 http://dx.doi.org/10.1016/j.polymer.2006.10.024

Jeske R. ; Rowley J. ; Coates G. Pre-rate-determining selectivity in the terpolymerization of epoxides , cyclic anhydrides, and CO 2 : a one-step route to diblock copolymers . Angew. Chem. Int. Ed., 2008, 47 ( 32 ), 6041 - 6044 . doi: 10.1002/anie.200801415 http://dx.doi.org/10.1002/anie.200801415

Huijser S. ; HosseiniNejad E. ; Sablong R. ; de Jong C. ; Koning C. E. ; Duchateau R. Ring-opening co- and terpolymerization of an alicyclic oxirane with carboxylic acid anhydrides and CO 2 in the presence of chromium porphyrinato and salen catalysts . Macromolecules , 2011 , 44 ( 5 ), 1132 - 1139 . doi: 10.1021/ma102238u http://dx.doi.org/10.1021/ma102238u

Darensbourg D. J. ; Poland R. R. ; Escobedo C. Kinetic studies of the alternating copolymerization of cyclic acid anhydrides and epoxides , and the terpolymerization of cyclic acid anhydrides, epoxides, and CO 2 catalyzed by (salen)CrIIICl . Macromolecules, 2012, 45 ( 5 ), 2242 - 2248 . doi: 10.1021/ma2026385 http://dx.doi.org/10.1021/ma2026385

Jeon J. Y. ; Eo S. C. ; Varghese J. K. ; Lee B. Y. Copolymerization and terpolymerization of carbon dioxide/propylene oxide/phthalic anhydride using a (salen)Co(III) complex tethering four quaternary ammonium salts . Beilstein J. Org. Chem. , 2014 , 10 , 1787 - 1795 . doi: 10.3762/bjoc.10.187 http://dx.doi.org/10.3762/bjoc.10.187

Duan Z. Y. ; Wang X. Y. ; Gao Q. ; Zhang L. ; Liu B. Y. ; Kim I. Highly active bifunctional cobalt-salen complexes for the synthesis of poly(ester-block-carbonate) copolymer via terpolymerization of carbon dioxide, propylene oxide, and norbornene anhydride isomer: roles of anhydride conformation consideration . J. Polym. Sci. Part A Polym. Chem. , 2014 , 52 ( 6 ), 789 - 795 . doi: 10.1002/pola.27057 http://dx.doi.org/10.1002/pola.27057

Thevenon A. ; Garden J. A. ; White A. J. P. ; Williams C. K. Dinuclear zinc salen catalysts for the ring opening copolymerization of epoxides and carbon dioxide or anhydrides . Inorg. Chem. , 2015 , 54 ( 24 ), 11906 - 11915 . doi: 10.1021/acs.inorgchem.5b02233 http://dx.doi.org/10.1021/acs.inorgchem.5b02233

Han B. ; Liu B. Y. ; Ding H. N. ; Duan Z. Y. ; Wang X. H. ; Theato P. CO 2-tuned sequential synthesis of stereoblock copolymers comprising a stereoregularity-adjustable polyester block and an atactic CO2-based polycarbonate block. Macromolecules , 2017 , 50 ( 23 ), 9207 - 9215 . doi: 10.1021/acs.macromol.7b01905 http://dx.doi.org/10.1021/acs.macromol.7b01905

Lamparelli, D. H.; Capacchione, C. Terpolymerization of CO 2 with epoxides and cyclic organic anhydrides or cyclic esters . Catalysts , 2021 , 11 ( 8 ), 961 . doi: 10.3390/catal11080961 http://dx.doi.org/10.3390/catal11080961

Niknam F. ; Buonerba A. ; Grassi A. ; Capacchione C. Ring opening copolymerization of epoxides with CO 2 and organic anhydrides promoted by dinuclear [OSSO ] -type metal complexes. ChemCatChem , 2024 , 16 ( 13 ), e 202400011 . doi: 10.1002/cctc.202400011 http://dx.doi.org/10.1002/cctc.202400011

Suresh L. ; Zwettler K. ; Törnroos K. W. ; Le W. ; Marcolini B. ; Frache G. ; Le Roux E. N-heterocyclic carbene-based group 4 catalysts for the terpolymerization of cyclohexene oxide and cyclic anhydrides with CO 2 . ACS Org. Inorg. Au, 2025, 5 ( 3 ), 171 - 180 . doi: 10.1021/acsorginorgau.5c00002 http://dx.doi.org/10.1021/acsorginorgau.5c00002

Hu L. F. ; Zhang C. J. ; Wu H. L. ; Yang J. L. ; Liu B. ; Duan H. Y. ; Zhang X. H. Highly active organic lewis pairs for the copolymerization of epoxides with cyclic anhydrides: metal-free access to well-defined aliphatic polyesters . Macromolecules , 2018 , 51 ( 8 ), 3126 - 3134 . doi: 10.1021/acs.macromol.8b00499 http://dx.doi.org/10.1021/acs.macromol.8b00499

Zhang J. B. ; Wang L. B. ; Liu S. F. ; Kang X. H. ; Li Z. B. A lewis pair as organocatalyst for one-pot synthesis of block copolymers from a mixture of epoxide , anhydride, and CO 2 . Macromolecules, 2021, 54 ( 2 ), 763 - 772 . doi: 10.1021/acs.macromol.0c02647 http://dx.doi.org/10.1021/acs.macromol.0c02647

Ye S. X. ; Wang W. J. ; Liang J. X. ; Wang S. J. ; Xiao M. ; Meng Y. Z. Metal-free approach for a one-pot construction of biodegradable block copolymers from epoxides , phthalic anhydride, and CO 2 . ACS Sustainable Chem. Eng., 2020, 8 ( 48 ), 17860 - 17867 . doi: 10.1021/acssuschemeng.0c07283 http://dx.doi.org/10.1021/acssuschemeng.0c07283

Chidara V. K. ; Boopathi S. K. ; Hadjichristidis N. ; Gnanou Y. ; Feng X. S. Triethylborane-assisted synthesis of random and block poly(ester-carbonate)s through one-pot terpolymerization of epoxides , CO 2 , and cyclic anhydrides . Macromolecules, 2021, 54 ( 6 ), 2711 - 2719 . doi: 10.1021/acs.macromol.0c02825 http://dx.doi.org/10.1021/acs.macromol.0c02825

Liu S. F. ; Ren C. L. ; Zhao N. ; Shen Y. ; Li Z. B. Phosphazene bases as organocatalysts for ring-opening polymerization of cyclic esters . Macromol. Rapid Commun. , 2018 , 39 ( 24 ), 1800485 . doi: 10.1002/marc.201800485 http://dx.doi.org/10.1002/marc.201800485

Liang J. X. ; Ye S. X. ; Wang S. Y. ; Wang S. J. ; Han D. M. ; Huang S. ; Huang Z. H. ; Liu W. ; Xiao M. ; Sun L. Y. ; Meng Y. Z. Biodegradable copolymers from CO 2 , epoxides, and anhydrides catalyzed by organoborane/tertiary amine pairs : high selectivity and productivity . Macromolecules, 2022, 55 ( 14 ), 6120 - 6130 . doi: 10.1039/c7cy01295k http://dx.doi.org/10.1039/c7cy01295k

Zhao M. J. ; Zhu S. S. ; Zhang G. C. ; Wang Y. ; Liao Y. G. ; Xu J. ; Zhou X. P. ; Xie X. L. One-step synthesis of linear and hyperbranched CO 2 -based block copolymers via organocatalytic switchable polymerization . Macromolecules , 2023 , 56 ( 6 ), 2379 - 2387 . doi: 10.1021/acs.macromol.3c00213 http://dx.doi.org/10.1021/acs.macromol.3c00213

Huang Q. ; Wang W. Z. ; Liu S. ; Jia X. G. ; Xia L. ; Qin F. L. ; Wang Q. ; Liu Y. ; Li H. J. Green fabrication of carbon dioxide-based polycarbonates with durable antimicrobial properties and UV resistance . Chem. Eng. J. , 2023 , 477 , 147107 . doi: 10.1016/j.cej.2023.147107 http://dx.doi.org/10.1016/j.cej.2023.147107

Ma Y. K. ; Wang Z. H. ; Jiang L. H. ; Zhang J. B. ; Ren C. L. ; Kou X. H. ; Liu S. F. ; Li Z. B. Bulky phosphazenium salt controlling chemoselective terpolymerization of epoxide , anhydride and CO 2 : from well-defined block to truly random copolymers . Angew. Chem., 2025, 137 ( 4 ), e 202416104 . doi: 10.1002/ange.202416104 http://dx.doi.org/10.1002/ange.202416104

Wang Z. H. ; Ma Y. K. ; Zhang J. B. ; Liu S. F. ; Li Z. B. Binary catalyst manipulating the sequences of poly(ester-carbonate) copolymers in metal-free terpolymerization of epoxide , anhydride, and CO 2 . Precis. Chem., 2025, 3 ( 1 ), 35 - 42 . doi: 10.1021/prechem.4c00062 http://dx.doi.org/10.1021/prechem.4c00062

Zhang J. B. ; Wang Z. H. ; Liu S. F. ; Li Z. B. Terpolymerization of epoxides , anhydrides, and CO 2 Using binary metal-free catalysts . Acc. Mater. Res., 2026, 7 ( 1 ), 100 - 116 . doi: 10.1021/accountsmr.5c00321 http://dx.doi.org/10.1021/accountsmr.5c00321

Sanford M. J. ; Peña Carrodeguas L. ; Van Zee N. J. ; Kleij A. W. ; Coates G. W. Alternating copolymerization of propylene oxide and cyclohexene oxide with tricyclic anhydrides: access to partially renewable aliphatic polyesters with high glass transition temperatures . Macromolecules , 2016 , 49 ( 17 ), 6394 - 6400 . doi: 10.1021/acs.macromol.6b01425 http://dx.doi.org/10.1021/acs.macromol.6b01425

Kummari A. ; Pappuru S. ; Chakraborty D. Fully alternating and regioselective ring-opening copolymerization of phthalic anhydride with epoxides using highly active metal-free Lewis pairs as a catalyst . Polym. Chem. , 2018 , 9 ( 29 ), 4052 - 4062 . doi: 10.1039/c8py00715b http://dx.doi.org/10.1039/c8py00715b

Ji H. Y. ; Chen X. L. ; Wang B. ; Pan L. ; Li Y. S. Metal-free, regioselective and stereoregular alternating copolymerization of monosubstituted epoxides and tricyclic anhydrides . Green Chem. , 2018 , 20 ( 17 ), 3963 - 3973 . doi: 10.1039/C8GC01641K http://dx.doi.org/10.1039/C8GC01641K

Khanarian G. Optical properties of cyclic olefin copolymers . Opt. Eng , 2001 , 40 ( 6 ), 1024 . doi: 10.1117/1.1369411 http://dx.doi.org/10.1117/1.1369411

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

氮丙啶衍生物与环状酸酐共聚合成聚酯酰胺

有机Lewis酸碱对催化氧硫化碳和环氧氯丙烷交替共聚

紫外光照亲水性聚碳酸酯的合成及性能

聚合物自由表面效应物理机制的研究进展

动态微界面聚合：二维聚合物片层制备的新策略及高性能准固态电解质应用