Skip to main content

Advertisement

SpringerLink
Log in

A trifunctional active ester for curing DGEBA: synthesis, curing behavior, and properties of its cured product

  • Original Paper
  • Published:
Journal of Polymer Research Aims and scope Submit manuscript

Abstract

A trifunctional active ester curing agent, triacetoxytriphenylmethane (TATPM), which was dissolvable in diglycidyl ether of bisphenol A (DGEBA), was prepared and characterized. Though TATPM/DGEBA mixture was too viscous to flow at room temperature, its viscosity rapidly declined to a very low level when heating above 120 °C, showing great processability. Accelerators 4-dimethylaminopyridine (DMAP), 2-methylimidazole (2MI), and tetrabutylammonium bromide (TBAB) were used to catalyze the reactions between TATPM and DGEBA. DMAP-catalyzed one reached Tpeak and Tendset earlier, and showed higher conversion than 2MI and TBAB-catalyzed one, exhibiting superior accelerating effect. Ea and A of DMAP-catalyzed system were higher than that of 2MI-catalyzed system. Moreover, the properties of cured products depended on accelerator type, and DMAP-catalyzed one had the highest Tg, Td5%, and Td10%, lowest Df, EQUATION and saturated water uptake, making DMAP a better accelerator than 2MI and TBAB. Meanwhile, TATPM cured epoxies showed higher Td, lower Dk and Df than that of phenolic compound THTPM cured epoxies, despite of its lower Tg.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12
Fig. 13
Fig. 14

Similar content being viewed by others

Data availability

Data will be made available on request.

References

  1. Lee M, Paria S, Mondal S, Lee GB, Shin B, Kim S, Park S, Nah C (2022) Amphiphilic block co-polymer and silica reinforced epoxy composite with excellent toughness and delamination resistance for durable electronic packaging application. Polymer 245:124679

    Article  CAS  Google Scholar 

  2. Li X, Zhou Y, Bao Y, Wei W, Fei X, Li X, Liu X (2022) Bismaleimide/phenolic/epoxy ternary resin system for molding compounds in high-temperature electronic packaging applications. Ind Eng Chem Res 61:4191–4201

    Article  CAS  Google Scholar 

  3. Hou J, Fang L, Huang G, Dai M, Liu F, Wang C, Li M, Zhang H, Sun J, Fang Q (2021) Low-dielectric polymers derived from biomass. ACS Appl Polym Mater 3:2835–2848

    Article  CAS  Google Scholar 

  4. Fu F, Shen M, Wang D, Liu H, Shang S, Hu F, Song Z, Song J (2021) A rosin-based dielectric polymer with intrinsic low dielectric constant and comprehensively excellent properties. J Mater Chem C 9:13144–13156

    Article  CAS  Google Scholar 

  5. Maier G (2001) Low dielectric constant polymers for microelectronics. Prog Polym Sci 26:3–65

    Article  CAS  Google Scholar 

  6. Chen CH, Lin CM, Juang TY, Abu-Omar MM, Lin CH (2019) The reaction of activated esters with epoxides for self-curable, highly flexible, A2B2- and A3B3-type epoxy compounds. Polym Chem 10:3983–3995

    Article  CAS  Google Scholar 

  7. Nakamura S, Saegusa Y, Yanagisawa H, Touse M, Shirai T, Nishikubo T (1991) Thermal analysis of epoxy curing using polyfunctional active esters as curing agents. Thermochim Acta 183:269–277

    Article  CAS  Google Scholar 

  8. Ogura I (1999) In: Nalwa HS (ed) Handbook of low and high dielectric constant materials and their applications. Academic Press, San Diego

  9. Nakamura S, Arima M (1995) Characterization of the network structure of epoxy resins cured with active esters. Int J Polym Anal Ch 1:75–86

    Article  CAS  Google Scholar 

  10. Nishikubo T, Kameyama A (1993) Addition reactions of cyclic ethers with various carbonyl compounds and their application for polymer synthesis. Prog Polym Sci 18:963–995

    Article  CAS  Google Scholar 

  11. Chen CH, Lee KW, Lin CH, Ho MJ, Hsu MF, Hsiang SJ, Huang NK, Juang TY (2018) High-Tg, low-dielectric epoxy thermosets derived from methacrylate-containing polyimides. Polymers (Basel) 10:27

    Article  Google Scholar 

  12. Liu J, Liu X, Cui X, Qin J, Wu M, Fu L, Shi M, Wang D, Liang L (2023) Investigation on the properties and structures of resveratrol-derived epoxy thermosets cured with an active ester. Polym Chem 14:1665–1679

    Article  CAS  Google Scholar 

  13. Cao Q, Li J, Qi Y, Zhang S, Wang J, Wei Z, Pang H, Jian X, Weng Z (2022) Engineering double load-sharing network in thermosetting: much more than just toughening. Macromolecules 55:9502–9512

    Article  CAS  Google Scholar 

  14. Funahashi K (1978) New ring opening reactions of three membered heterocycles, oxiranes, aziridines, and thiiranes, with phenyl acetate. Chem Lett 7:1043–1044

    Article  Google Scholar 

  15. Funahashi K (1979) New preparation of polyethers with pendant ester groups and a poly(ether-carbonate). Die Makromol Chem 180:501–503

    Article  CAS  Google Scholar 

  16. Funahashi K (1979) New ring opening reactions of oxiranes with aryl carboxylates. B Chem Soc Jpn 52:1488–1492

    Article  CAS  Google Scholar 

  17. Nishikubo T, Iizawa T, Takahashi E, Nono F (1985) Study of photopolymers. 26. Novel synthesis of self-sensitized photosensitive polymers by addition reactions of poly(glycidyl methacrylate) with nitroaryl cinnamate. Macromolecules 18:2131–2135

    Article  CAS  Google Scholar 

  18. Nishikubo T, Iizawa T, Saita S (1986) Addition reactions of pendant epoxide group in poly(glycidyl methacrylate) with various active esters. J Polym Sci Pol Chem 24:1685–1695

    Article  CAS  Google Scholar 

  19. Nishikubo T, Shimokawa T (1986) A novel insertion reaction of epoxy compounds into the pendant ester linkage of poly[4-(4-nitrobenzoyloxy)styrene]. Die Makromol Chem, Rapid Commun 7:179–181

    Article  CAS  Google Scholar 

  20. Nishikubo T, Saita S, Fujii T (1987) New thermo-crosslinking reactions of polymers containing pendant epoxide groups with various polyfunctional active esters. J Polym Sci Pol Chem 25:1339–1351

    Article  CAS  Google Scholar 

  21. Nishikubo T, Tanaka K (1987) A novel reaction of epoxy resins with polyfunctional active esters. J Appl Polym Sci 33:2821–2831

    Article  CAS  Google Scholar 

  22. Nishikubo T, Saita S (1987) New thermo-crosslinking reactions of copolymers of phenyl methacrylates by use of polyfunctional epoxy compounds. Die Makromol Chem 188:799–809

    Article  CAS  Google Scholar 

  23. Nishikubo T, Shiina A, Isobe N (1988) New addition reaction of active ester or cyclic ester with epoxy compounds catalyzed by insoluble polystyrene-bound quaternary phosphonium or ammonium salts. Chem Lett 17:1605–1608

    Article  Google Scholar 

  24. Nishikubo T, Shimokawa T, Hirano T, Shiina A (1989) A novel insertion reaction of epoxy compounds into phenyl ester linkages in polymer chains. J Polym Sci Pol Chem 27:2519–2530

    Article  CAS  Google Scholar 

  25. Nishikubo T, Kameyama A, Maejima C, Yamamoto Y (1994) Soluble polymer-supported catalysts containing pendant quaternary onium salt residues for regioselective addition reaction of epoxy compound with active ester. Macromolecules 27:7240–7247

    Article  CAS  Google Scholar 

  26. Nishikubo T, Kameyama A, Kudo H (2003) Novel high performance materials. Calixarene derivatives containing protective groups and polymerizable groups for photolithography, and calixarene derivatives containing active ester groups for thermal curing of epoxy resins. Polym J 35:213–229

    Article  CAS  Google Scholar 

  27. Nakamura S, Arima M (1993) Network structure and glass transition of epoxy resins cured with active ester. J Therm Anal 40:613–619

    Article  CAS  Google Scholar 

  28. Chen CH, Gu ZC, Tsai YL, Jeng RJ, Lin CH (2018) Identification of the reaction mechanism between phenyl methacrylate and epoxy and its application in preparing low-dielectric epoxy thermosets with flexibility. Polymer 140:225–232

    Article  CAS  Google Scholar 

  29. Chen CH, Liu CH, Ariraman M, Lin CH, Juang TY (2018) Phosphinated poly(aryl ether)s with acetic/phenyl methacrylic/vinylbenzyl ether moieties for high-Tg and low-dielectric thermosets. ACS Omega 3:6031–6038

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  30. Lin CM, Chen CH, Lin CH, Su WC, Juang TY (2018) Using dicyclopentadiene- derived polyarylates as epoxy curing agents to achieve high Tg and low dielectric epoxy thermosets. ACS Omega 3:4295–4305

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  31. Meng H, Zhang Q, Lu M, Qu Z, Chen B, Xu C, Lu M (2021) Cure kinetics and properties of high-performance epoxy thermosets cured with active ester-terminated poly (aryl ether ketone). High Perform Polym 33:1047–1060

    Article  CAS  Google Scholar 

  32. Heise MS, Martin GC (1989) Curing mechanism and thermal properties of epoxy-imidazole systems. Macromolecules 22:99–104

    Article  CAS  Google Scholar 

  33. Dell’Erba IE, Williams RJJ (2006) Homopolymerization of epoxy monomers initiated by 4-(dimethylamino)pyridine. Polym Eng Sci 46:351–359

    Article  CAS  Google Scholar 

  34. Vyazovkin S, Burnham AK, Criado JM, Pérez-Maqueda LA, Popescu C, Sbirrazzuoli N (2011) ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data. Thermochim Acta 520:1–19

    Article  CAS  Google Scholar 

  35. Vyazovkin S, Sbirrazzuoli N (2006) Isoconversional kinetic analysis of thermally stimulated processes in polymers. Macromol Rapid Comm 27:1515–1532

    Article  CAS  Google Scholar 

  36. Starink MJ (2003) The determination of activation energy from linear heating rate experiments: a comparison of the accuracy of isoconversion methods. Thermochim Acta 404:163–176

    Article  CAS  Google Scholar 

  37. Criado JM, Perez-Maqueda LA, Gotor FJ, Malek J, Koga N (2003) A unified theory for the kinetic analysis of solid state reactions under any thermal pathway. J Therm Anal Calorim 72:901–906

    Article  CAS  Google Scholar 

  38. Luo XW, Ping ZH, Ding JP, Ding YD, Li SJ (1997) Mechanism studies on water sorption and permeation in epoxy resin by impedance spectroscopy. II. Cure kinetics of o-cresol novolac resin with esterfied phenol novolac resin. J Macromol Sci A 34:2279–2291

    Article  Google Scholar 

  39. Zhang P, Ali Shah SA, Gao F, Sun H, Cui Z, Cheng J, Zhang J (2019) Latent curing epoxy systems with reduced curing temperature and improved stability. Thermochim Acta 676:130–138

    Article  CAS  Google Scholar 

  40. Li J, Ren C, An D, Ren Y, Moon K, Wong C (2020) Systematic evaluation of cyanate ester/epoxidized cresol novolac copolymer resin system for high temperature power electronic packaging applications. Polymer 195:122454

    Article  CAS  Google Scholar 

  41. Liu Z, Huo J, Yu Y (2017) Water absorption behavior and thermal-mechanical properties of epoxy resins cured with cardanol-based novolac resins and their esterified ramifications. Mater Today Commun 10:80–94

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was financially supported by National Key Research and Development Program of China (Grant # 2020YFE0100300).

Funding

National Key Research and Development Program of China, 2020YFE0100300, Longhai Guo.

Author information

Authors and Affiliations

  1. Beijing Advanced Innovation Centre for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing, 100029, People’s Republic of China

    An Xing & Wantai Yang

  2. State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, 100029, People’s Republic of China

    Chenchen Gao, Peichen Yuan, Yajing Qiao & Xiaoyu Li

  3. Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of Education, Beijing University of Chemical Technology, Beijing, 100029, People’s Republic of China

    Longhai Guo

Authors
  1. An Xing
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Chenchen Gao
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Peichen Yuan
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yajing Qiao
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Longhai Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Xiaoyu Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Wantai Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Xiaoyu Li.

Ethics declarations

Conflicts of interest

The authors declare that there is no conflict of interest.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Xing, A., Gao, C., Yuan, P. et al. A trifunctional active ester for curing DGEBA: synthesis, curing behavior, and properties of its cured product. J Polym Res 31, 66 (2024). https://doi.org/10.1007/s10965-024-03899-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s10965-024-03899-4

Keywords

Search

Navigation