以含磷单体、三聚氰胺、苯酚和甲醛为原料, 合成了一种含磷含氮酚醛树脂(NP-PF).将NP-PF与F51环氧树脂复配并固化, 并对其固化特征进行了研究, 同时考察了固化物的耐热性能和阻燃性能. 研究结果表明: 高含量的NP-PF能够提高NP-PF/F51体系的固化速率;NP-PF/F51固化物具有良好的耐热性能; 在NP-PF/F51固化体系中加入少量Al(OH)3, 能够达到UL94V-0级阻燃的效果.
The phosphorus-nitrogen containing phenolic resins (NP-PF) were synthesized from formaldehyde, melamine, phenol and phosphorus-containing monomer. The effect of NP-PF in NP-PF/F51 was investigated. The results show that (1) the curing rate of NPPF/ F51 accelerates with the increase of NP-PF contents; (2) the epoxy resin thermosets had good thermal stability; and (3) UL94V-0 rating is achieved with a lower Al(OH)3 content for the NP-PF/F51 system.
[1] 陈平, 刘胜平. 环氧树脂[M]. 北京: 化学工业出版社, 1999: 1-10.
[2] 祝大同. 环氧-玻纤布基板材料和薄型化技术[J]. 印刷电路信息, 2008(1): 12-16, 38.
[3] Wang C S, Zeng K L. Synthesis of high purity o-cresol formaldehyde novolac epoxy resins [J].Polymer Bulletin, 1991, 25: 559-565.
[4] Nakamura Y, Yamaguchi M, Okubo M, et al. Effects of particle size on mechanical and impact properties of epoxy resin filled with spherical silica [J]. Journal of Applied Polymer
Science, 1992, 45(7): 1281-1289.
[5] 苗森, 余若冰, 焦扬声, 等. 磷酸改性水溶性酚醛树脂的成炭性能[J]. 上海大学学报: 自然科学版,2010, 16(5): 508-512.
[6] Chen-Yang Y W, Lee H F, Yuan C Y. A flame-retardant phosphate and cyclotriphosphazenecontaining epoxy resin: synthesis and properties [J]. Journal of Polymer Science Part A: Polymer Chemistry, 2000, 38(6): 972-981.
[7] Levchik S V, Weil E D. Flame retardancy of thermoplastic polyesters-a review of the recent literature [J]. Polymer International, 2005, 54(1): 11-35.
[8] Qu H Q,WuWH, Jiao Y H, et al. Thermal behavior and flame retardancy of flexible poly (vinyl chloride) treated with Al(OH)3 and ZnO [J]. Polymer International, 2005, 54(11): 1469-1473.
[9] Wu Q, L¨u J P, Qu B J. Preparation and characterization of micro-capsulated red phosphorus and its flame-retardant mechanism in halogen-free flame retardant poly-olefins [J]. Polymer international, 2003, 52(8): 1326-1331.
[10] 陈红, 吴良义. 磷系阻燃环氧树脂与固化剂[J]. 热固性树脂, 2002, 17(1): 39-43.
[11] Zhang Z Y, Yu R B, Wang F, et al. Synthesis and properties of novel 4,4’-biphenylene-bridged flame-retardant cyanate ester resin [J]. Journal of Applied Polymer Science, 2011, 122: 2609-2615.
[12] 袁才登, 许涌深, 王艳君, 等. 含氮酚醛树脂及其对环氧树脂的阻燃改性[J]. 热固性树脂, 2000,15(2): 12-14.
[13] 缪爱花, 袁才登, 姜东峰. 双酚A型含氮酚醛树脂的合成及应用研究[J]. 热固性树脂, 2003, 18(1):18-20.
[14] Xia X N, Xiong Y Q, Zhang X H, et al. Synthesis and characterization of epoxy film cured with phosphorous-containing phenolic resin [J]. Journal of Applied Polymer Science, 2007, 104(6):3813-3817.
[15] Shieh J Y, Wang C S. Synthesis of novel flame retardant epoxy hardeners and properties of cured products [J]. Polymer, 2001, 42(18): 7617-7625.
[16] Flory P J. Principles of polymer chemistry [M]. New York: Cornell University Press, 1953.
[17] 王海军. 环氧树脂/含氮阻燃固化剂体系的研究[D]. 西安: 西北工业大学, 2006: 47.
[18] 马志领, 赵文革, 郝凤春, 等. 磷氮协同阻燃作用机理研究[J]. 河北大学学报: 自然科学版, 2000,20(4): 400-404.
[19] Kay M, Price A F. Fire test behaviour of various crystal types of melamine phosphate in intumescent formulations [J]. Fire and Materials, 1982, 6(3/4): 119-121.
