Photocontrolled Solution [2+2] Polymerization of <italic style="font-style: italic">p</italic>-Phenylenediacrylate and Depolymerization

Miao-Yan Yi; Yu Jiang; Sai-Hu Liao

doi:10.1007/s10118-025-3431-6

Your Location：

Home >

Browse articles >

Photocontrolled Solution [2+2] Polymerization of p-Phenylenediacrylate and Depolymerization

RESEARCH ARTICLE | Updated：2025-10-30

- Photocontrolled Solution [2+2] Polymerization of p-Phenylenediacrylate and Depolymerization
- Photocontrolled Solution [2+2] Polymerization of p-Phenylenediacrylate and Depolymerization
- 高分子科学（英文） 2025年43卷第11期页码：1973-1980
- Affiliations：
  
  State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Research Center of Chemicals for Electronics Manufacturing (Reconstruction), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
- Author bio：
  
  shliao@xmu.edu.cn
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (Nos. 22371240 and 22361132535) and Xiamen University for the financial support.;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-025-3431-6.
- DOI：10.1007/s10118-025-3431-6
  中图分类号：
- 收稿：2025-05-22，
  
  录用：2025-08-08，
  
  网络首发：2025-10-16，
  
  纸质出版：2025-11-05
- Accepted：
Scan QR Code
Yi, M. Y.; Jiang, Y.; Liao, S. H. Photocontrolled solution [2+2] polymerization of p-phenylenediacrylate and depolymerization. Chinese J. Polym. Sci. 2025, 43, 1973–1980

Miao-Yan Yi, Yu Jiang, Sai-Hu Liao. Photocontrolled Solution [2+2] Polymerization of p-Phenylenediacrylate and Depolymerization[J]. Chinese Journal of Polymer Science, 2025, 43(11): 1973-1980. DOI: 10.1007/s10118-025-3431-6.
Yi, M. Y.; Jiang, Y.; Liao, S. H. Photocontrolled solution [2+2] polymerization of p-phenylenediacrylate and depolymerization. Chinese J. Polym. Sci. 2025, 43, 1973–1980 DOI： 10.1007/s10118-025-3431-6.

Miao-Yan Yi, Yu Jiang, Sai-Hu Liao. Photocontrolled Solution [2+2] Polymerization of p-Phenylenediacrylate and Depolymerization[J]. Chinese Journal of Polymer Science, 2025, 43(11): 1973-1980. DOI: 10.1007/s10118-025-3431-6. DOI：

摘要

We achieved visible-light-driven [2+2] solution polymerization of phenylenediacrylate monomers via energy transfer photocatalysis. This method yields cyclobutane-containing polymers with good thermal stability and processability

which are depolymerizable

showing potential for closed-loop recycling.

Abstract

The [2+2

]

photopolymerization of bisolefinic monomers is an important method for the synthesis of polymeric materials. However

these processes are usually carried out in solid states under the irradiation of high-energy UV light

while the corresponding [2+2

]

polymerization in solution has proved to be inefficient due to the lack of preassembly of the monomers. Herein

we demonstrate that the [2+2

]

polymerization of

-phenylenediacrylate monomers can be achieved in solution under visible light by employing energy transfer catalysis with 2

2’-methoxythioxanthone as a photocatalyst. Because no preassembly is required

this solution polymerization is applicable to

-phenylenediacrylate monomers with different ester groups

affording a series of cyclobutane-imbedded full-carbon chain polymers with high thermal stability

good solubility

and processibility. In addition

by virtue of the reversibility of the photo [2+2

]

cycloaddition

this [2+2

]

photopolymerization product can also undergo depolymerization to lower molecular weight polymers

suggesting the potential of this class of photopolymerization in the development of closed-loop chemical recyclable polymers.

关键词

Keywords

references

Yilmaz, G.; Yagci, Y. Light-induced step-growth polymerization. Prog. Polym. Sci. 2020 , 100 , 101178..

[Addadi, L.; Cohen, M. D.; Lahav, M. The synthesis of optically active dimers and polymers by reaction in crystals of chiral structure. J. Chem. Soc., Chem. Commun . 1975 , 471−473..

Kaur, G.; Johnston, P.; Saito, K. Photo-reversible dimerisation reactions and their applications in polymeric systems. Polym. Chem. 2014 , 5 , 2171−2186..

Kabb, C. P.; O’Bryan, C. S.; Deng, C. C.; Angelini, T. E.; Sumerlin, B. S. Photoreversible covalent hydrogels for soft-matter additive manufacturing. ACS Appl. Mater. Interfaces 2018 , 10 , 16793−16801..

Rath, B. B.; Vittal, J. J. Photoreactive crystals exhibiting [2+2 ] photocycloaddition reaction and dynamic effects. Acc. Chem. Res. 2022 , 55 , 1445−1455..

Ishige, R.; Tokita, M.; Naito, Y.; Zhang, C. Y.; Watanabe, J. Unusual formation of smectic a structure in cross-linked monodomain elastomer of main-chain lc polyester with 3-methylpentane spacer. Macromolecules 2008 , 41 , 2671−2676..

Goodall, G. W.; Hayes, W. Advances in cycloaddition polymerizations. Chem. Soc. Rev. 2006 , 35 , 280−312..

Herkstroeter, W. G.; Farid, S. Photodimerization—relevant triplet state parameters of methyl cinnamate, diethyl 1, 4-phenylenediacrylate and methyl 1-naphthylacrylate. J. Photochem. 1986 , 35 , 71−85..

Ding, L.; Liu, L.; Chen, Y.; Du, Y.; Guan, S.; Bai, Y.; Huang, Y. Modification of poly(ethylene terephthalate) by copolymerization of plant-derived α-truxillic acid with excellent ultraviolet shielding and mechanical properties. Chem. Eng. J. 2019 , 374 , 1317−1325..

Truong, V. X.; Bachmann, J.; Unterreiner, A. N.; Blinco, J. P.; Barner-Kowollik, C. Wavelength-orthogonal stiffening of hydrogel networks with visible light. Angew. Chem. Int. Ed. 2022 , 61 , e202113076..

Hasegawa, M.; Yurugi, T.; Namiki, S.; Shiobara, T.; Nakanishi, H.; Nakanishi, F. Preparation and thermal behavior of poly-p-phenylene diacrylic acid dimethyl ester. J. Polym. Sci. Pol. Chem. 1981 , 19 , 1291−1299..

Kanetsuna, H.; Hasegawa, M.; Mitsuhashi, S.; Kurita, T.; Sasaki, K.; Maeda, K.; Obata, H.; Hatakeyama, T. Structure and properties of poly-2, 5-distyrylpyrazine. J. Polym. Sci. Part A-2: Polym. Phys. 1970 , 8 , 1027−1037..

Hema, K.; Ravi, A.; Raju, C.; Pathan, J. R.; Rai, R.; Sureshan, K. M. Topochemical polymerizations for the solid-state synthesis of organic polymers. Chem. Soc. Rev. 2021 , 50 , 4062−4099..

Chakrabarti, S.; Maity, A. K.; Misra, T. Spectroscopic study of solid-state photoreaction in organic crystal: Photopolymerization of dimethyl ester of α, α′-dicyano-p-phenylenediacrylic acid and diethyl ester of p-phenylenediacrylic acid. J. Polym. Sci. Part A: Polym. Chem. 1992 , 30 , 1625−1631..

Nakanishi, H.; Hasegawa, M.; Sasada, Y. Four-center photopolymerization in the crystalline state. Viii. X-ray crystallographic study of the polymerization of some diolefinic compounds. J. Polym. Sci: Polym. Phys 1977 , 15 , 173−191..

Addadi, L.; Van Mil, J.; Lahav, M. Photopolymerization in chiral crystals. 4. Engineering of chiral crystals for asymmetric (2. Pi.+ 2. Pi.) photopolymerization. Execution of an" absolute" asymmetric synthesis with quantitative enantiomeric yield. J. Am. Chem. Soc. 1982 , 104 , 3422−3429..

Ramamurthy, V.; Sivaguru, J. Supramolecular photochemistry as a potential synthetic tool: photocycloaddition. Chem. Rev. 2016 , 116 , 9914−9993..

Coates, G. W.; Dunn, A. R.; Henling, L. M.; Ziller, J. W.; Lobkovsky, E. B.; Grubbs, R. H. Phenyl−perfluorophenyl stacking interactions: topochemical [2+2 ] photodimerization and photopolymerization of olefinic compounds. J. Am. Chem. Soc. 1998 , 120 , 3641−3649..

Dalrymple, D. L.; Russo, W. B. Thermal isomerizations of dimethyl 3, 4-diphenylmuconates. J. Org. Chem. 1975 , 40 , 492−495..

Addadi, L.; Lahav, M. Photopolymerization of chiral crystals. 1. The planning and execution of a topochemical solid-state asymmetric synthesis with quantitative asymmetric induction. J. Am. Chem. Soc. 1978 , 100 , 2838−2844..

MacGillivray, L. R.; Papaefstathiou, G. S.; Friščić, T.; Hamilton, T. D.; Bučar, D.-K.; Chu, Q.; Varshney, D. B.; Georgiev, I. G. Supramolecular control of reactivity in the solid state: From templates to ladderanes to metal-organic frameworks. Acc. Chem. Res. 2008 , 41 , 280−291..

Johnston, P.; Braybrook, C.; Saito, K. Topochemical photo-reversible polymerization of a bioinspired monomer and its recovery and repolymerization after photo-depolymerization. Chem. Sci. 2012 , 3 , 2301−2306..

El-Arid, S.; Lenihan, J. M.; Beeler, A. B.; Grinstaff, M. W. Truxinates and truxillates: Building blocks for architecturally complex polymers and advanced materials. Polym. Chem. 2024 , 15 , 3935−3953..

Suzuki, F.; Suzuki, Y.; Nakani shi, H.; Hasegawa, M. Four-center type photopolymerization in the solid state. Iii. Polymerization of phenylene diacrylic acid and its derivatives. J. Polym. Sci. Part A-1: Polym. Chem. 1969 , 7 , 2319−2331..

Schmidt, G. Photodimerization in the solid state. Pure Appl. Chem. 1971 , 27 , 647−678..

Guney-Altay, O.; Pestov, D.; Tepper, G. Organic zeolites from a diolefinic monomer. J. Am. Chem. Soc. 2007 , 129 , 13957−13962..

Levit, N.; Guney-Altay, O.; Pestov, D.; Tepper, G. Development of layered polymer nanocomposites using supercritical fluid technology. Macromolecules 2005 , 38 , 6528−6532..

Pestov, D.; Levit, N.; Maniscalco, V.; Deveney, B.; Tepper, G. Molecular imprinting using monomers with solid-state polymerization. Anal. Chim. Acta 2004 , 504 , 31−35..

Green, B. S.; Rejto, M. µ -Truxinic acid. J. Org. Chem. 1974 , 39 , 3284−3285..

Takahashi, S.; Miura, H.; Kasai, H.; Okada, S.; Oikawa, H.; Nakanishi, H. Single-crystal-to-single-crystal transformation of diolefin derivatives in nanocrystals. J. Am. Chem. Soc. 2002 , 124 , 10944−10945..

Marschner, D. E.; Frisch, H.; Offenloch, J. T.; Tuten, B. T.; Becer, C. R.; Walther, A.; Goldmann, A. S.; Tzvetkova, P.; Barner-Kowollik, C. Visible light [2+2 ] cycloadditions for reversible polymer ligation. Macromolecules 2018 , 51 , 3802−3807..

Kalayci, K.; Frisch, H.; Barner-Kowollik, C.; Truong, V. X. Wavelength-dependent stiffening of hydrogel matrices via redshifted [2+2 ] photocycloadditions. Adv. Funct. Mater. 2020 , 30 , 1908171..

Irshadeen, I. M.; De Bruycker, K.; Micallef, A. S.; Walden, S. L.; Frisch, H.; Barner-Kowollik, C. Green light led activated ligation of a scalable, versatile chalcone chromophore. Polym. Chem. 2021 , 12 , 4903−4909..

Jiang, Y.; Zhu, H.; Chen, J.; Ma, Q.; Liao, S. Linear cyclobutane-containing polymer synthesis via [2+2 ] photopolymerization in an unconfined environment under visible light. ACS Macro Lett. 2022 , 11 , 1336−1342..

Green, B. S.; Rabinsohn, Y.; Rejtö, M. Sugar alcohols as templates for photochemical asymmetric synthesis. Carbohydr. Res. 1975 , 45 , 115−126..

Woolley, J. M.; Peters, J. S.; Turner, M. A. P.; Clarkson, G. J.; Horbury, M. D.; Stavros, V. G. The role of symmetric functionalisation on photoisomerisation of a UV commercial chemical filter. Phys. Chem. Chem. Phys. 2019 , 21 , 14350−14356..

Lewis, F. D.; Quillen, S. L.; Hale, P. D.; Oxman, J. D. Lewis acid catalysis of photochemical reactions. 7. Photodimerization and cross-cycloaddition of cinnamic esters. J. Am. Chem. Soc. 1988 , 110 , 1261−1267..

Wang, J. S.; Wu, K.; Yin, C.; Li, K.; Huang, Y.; Ruan, J.; Feng, X.; Hu, P.; Su, C. Y. Cage-confined photocatalysis for wide-scope unusually selective [2+2 ] cycloaddition through visible-light triplet sensitization. Nat. Commun. 2020 , 11 , 4675..

Ikezawa, H.; Kutal, C.; Yasufuku, K.; Yamazaki, H. Direct and sensitized valence photoisomerization of a substituted norbornadiene. Examination of the disparity b etween singlet-and triplet-state reactivities. J. Am. Chem. Soc. 1986 , 108 , 1589−1594..

Zou, Y. Q.; Duan, S. W.; Meng, X. G.; Hu, X. Q.; Gao, S.; Chen, J. R.; Xiao, W. J. Visible light induced intermolecular [2+2 ] -cycloaddition reactions of 3-ylideneoxindoles through energy transfer pathway. Tetrahedron 2012 , 68 , 6914−6919..

Jiang, Y.; Ma, Q.; Zhang, X.; Li, J. f.; Liao, S. h. Solution [2+2 ] photopolymerization of biomass-derived nonrigid biscinnamate monomers enabled by energy transfer catalysis. Polym. Chem. 2022 , 13 , 2538−2544..

Nomoto, A.; Inai, N.; Yanai, T.; Okuno, Y. Substituent and solvent effects on the photoisomerization of cinnamate derivatives: an xms-caspt2 study. J. Phys. Chem. A 2022 , 126 , 497−505..

Shirai, M.; Tanaka, M. Cation binding properties of polyesters with photodimerizable groups and oxyethylene units. Effect of photocrosslinking with template cations. Eur. Polym. J. 1985 , 21 , 999−1003..

Hasegawa, M. Photopolymerization of diolefin crystals. Chem. Rev. 1983 , 83 , 507−518..

Wang, Z.; Kastern, B.; Randazzo, K.; Ugrinov, A.; Butz, J.; Seals, D. W.; Sibi, M. P.; Chu, Q. R. Linear polyester synthesized from furfural-based monomer by photoreaction in sunlight. Green Chem. 2015 , 17 , 4720−4724..

Fan, H. Z.; Yang, X.; Wu, Y. C.; Cao, Q.; Cai, Z.; Zhu, J. B. Leveraging the monomer structure for high-performance chemically recyclable semiaromatic polyesters. Polym. Chem. 2023 , 14 , 747−753..

Truong, V. X.; Li, F.; Ercole, F.; Forsythe, J. S. Wavelength-selective coupling and decoupling of polymer chains via reversible [2+2 ] photocycloaddition of styrylpyrene for construction of cytocompatible photodynamic hydrogels. ACS Macro Lett. 2018 , 7 , 464−469..

Mohadjer Beromi, M.; Kennedy, C. R.; Younker, J. M.; Carpenter, A. E.; Mattler, S. J.; Throckmorton, J. A.; Chirik, P. J. Iron-catalysed synthesis and chemical recycling of telechelic 1,3-enchained oligocyclobutanes. Nat. Chem. 2021 , 13 , 156−162..

Zhao, L. M. Construction of gel networks via [2+2 ] photocycloaddition. J. Mater. Chem. C 2023 , 11 , 2826−2830..

Shi, C.; Reilly, L. T.; Phani Kumar, V. S.; Coile, M. W.; Nicholson, S. R.; Broadbelt, L. J.; Beckham, G. T.; Chen, E. Y. X. Design principles for intrinsically circular polymers with tunable properties. Chem 2021 , 7 , 2896−2912..

浏览量

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

From Waste to Coatings: Acidolysis of Polyurethane Elastomers with Itaconic Acid for Polyurethane Coating

3D Printing of Biocompatible Nanocellulose-reinforced Hydrogels via Polymerizable Ternary Deep Eutectic Solvent Assistance

Backbone Degradable Polymers via Chain-growth Radical Polymerization

Depolymerization and Functionalization of Super Engineering Plastics

Manipulating Hierarchical Aggregation Structure via Film-forming Kinetics Enables Organic Photovoltaics over 20% Efficiency

Photocontrolled Solution [2+2] Polymerization of p-Phenylenediacrylate and Depolymerization

Photocontrolled Solution [2+2] Polymerization of p-Phenylenediacrylate and Depolymerization

DOI：10.1007/s10118-025-3431-6

摘要

Abstract

关键词

Keywords

references