Research progress in latent curing agent for one⁃component epoxy resin

doi:10.19491/j.issn.1001-9278.2021.12.024

Abstract

Abstract:

Based on the above advantages， single?component epoxy materials have become the current research hotspot in the field of epoxy resins. In view of this situation， this article summarized the curing agents for one?component epoxy resins at home and abroad and introduced the curing agents for the latent one?component epoxy resins， including the heating?type， wet?type， light?type， and microcapsule?type epoxy resins. A detailed overview of its preparation and synthesis methods and curing mechanism was performed， and the problems of the curing agent for one?component epoxy resin were pointed out. These can further clarify the research ideas at the next stage.

Key words: one?component epoxy resin, latent curing agent, microencapsulation technology, preparation, curing mechanism

CLC Number:

TQ323.5

FANG Yunfeng, MA Biao, WANG Xiaoqing, KANG Xingxiang, TANG Yuting. Research progress in latent curing agent for one⁃component epoxy resin[J]. China Plastics, 2021, 35(12): 154-165.

Figures/Tables 22

Fig.1. Principle of DICY curing epoxy resin［18］

Fig.2. DSC heat flow curves for DICY?cured Epiran 06 accelerated by 2 phr of three different accelerators［21］

反应体系	环氧树脂/份	DICY/ 份	促进剂/ 份	反应起始温度/℃	反应峰值温度/℃
ED	100	8	0.15	192	199
EDP	100	8	0.15	154	176
EDM	100	8	0.15	145	170
EDA	100	8	0.15	135	167
EDY	100	8	0.15	131	161

Tab. 1. Sample composition and curing temperature of epoxy/DICY/accelerator system［22］

Fig.3. Viscosity increase of epoxy resin/DICY system using 2MI as the accelerator with or without microsphere system［11］

Fig.4. The synthesis process of curing agent LB?A［25］

Fig.5. Reaction mechanism of organic acid hydrazide and epoxy resin

酰肼	熔点/ ℃	储存时间/月	DTA
酰肼	熔点/ ℃	储存时间/月	反应起始温度/℃	反应峰值温度/℃
丁二酸二酰肼（SuADH）	163	4	161	165
己二酸二酰肼（AADH）	180	4	161	167
间苯二甲酸二酰肼（IPADH）	212	4~5	154	160
对羟基苯甲酸酰肼（POBH）	248	4	153	161
水杨酸酰肼（SaAH）	151~2	（4 d）	96（175）	130（196）
苯基氨基丙酸酰肼（PAPAH）	93~5	（2 d）	75（115）	150

Tab. 2. Curing characteristics and latent time of commonly used hydrazide curing agents［30］

Fig.6. Conversion degree against temperature for the curing of DGEBA/dihydrazide formulations at a heating rate of 10 ℃/min［32］

Fig.7. DSC curves for DGEBA/AH formulations without any catalyst or catalyzed by 1 phr of BDMA or Yb（OTf）3 at a heating rate of 10 ℃/min［32］

Fig.8. The curing reaction mechanism of imidazole and epoxy resin

Fig.9. Chemical structures of liquid?type thermal latent curing agents 1a~1c， and their thermal decomposition reaction to generate imidazole［40］

Fig.10. Synthesis routes of EMI derivatives［41］

Fig.11. The onset temperature and latency of EMI and its three derivatives and epoxy resin［41］

Fig.12. Synthesis route of maleimide modified imidazole derivatives［42］

Fig.13. Storage time of four modified imidazole curing agents and epoxy resin［42］

Fig.14. Synthesis and thermal decomposition of DMMPZ［43］

Fig.15. Structures of chemicals used and synthetic route［46］

Fig.16. Illustration of synthesis of 2MICN?T［47］

Fig.17. The reaction process of polyethylene oxide imine and epoxy resin［50］

Fig.18. Photolysis reaction process of general structural formulas of three sulfur hexafluoroantimony salts

Fig.19. Weight loss of the microcapsules as a function of time at room temperature［69］

Fig.20. Manufacturing process of the double?layer microcapsules［70］

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