發(fā)布時間：2018-07-16 17:10

【摘要】：環(huán)氧樹脂(EP)具有很好的絕緣性、防潮性、化學(xué)穩(wěn)定性、耐腐蝕性以及機械加工性能等,其在涂料、粘合劑和家電設(shè)備等領(lǐng)域都有廣泛的應(yīng)用。然而,常用的環(huán)氧樹脂是易燃材料,生煙量大,難以滿足某些特定應(yīng)用領(lǐng)域的防火性能要求。因此,新型的無鹵阻燃環(huán)氧樹脂則成為了阻燃高分子材料領(lǐng)域中的一個重要研究方向。本文針對以上問題,開展了以下研究工作:1.首先,以二茂鐵、乙酰氯和次氯酸鈉為原料合成了單體1,1′-二乙�；F(DAF)和1,1′-二茂鐵二甲酸(Fc(COOH)2);其次,以三聚氯氰、甲醇和氨水為原料合成了單體2-甲氧基-4,6-二氯均三嗪(MDCT)和2,4-二氨基-6-甲氧基均三嗪(DAMT);最后,將Fc(COOH)2和DAMT作為原料,通過溶液聚合的方法合成了二茂鐵-三嗪環(huán)雙基阻燃齊聚物(PFCTR)。探索了DAF和Fc(COOH)2的反應(yīng)條件,并利用FTIR和1H NMR對單體結(jié)構(gòu)進(jìn)行了表征。此外,摸索了阻燃劑PFCTR的合成條件,通過FTIR和1H NMR對其結(jié)構(gòu)與聚合度進(jìn)行了表征,估算聚合度為13。采用熱重-紅外(TG-IR)聯(lián)用技術(shù)、熱裂解氣相色譜-質(zhì)譜聯(lián)用(Py-GC/MS)技術(shù)以及SEM研究了PFCTR的熱穩(wěn)定性和熱分解機理。結(jié)果表明,阻燃劑在高溫下分解形成了CO2、CO、NH3、H2O以及鐵的氧化物等物質(zhì),在700 ℃時的殘余量僅為9.2 wt%。2.探討了阻燃劑PFCTR、聚磷酸銨(APP)以及APP-PFCTR體系對EP的阻燃作用。研究表明,當(dāng)PFCTR添加量為5 wt%時,阻燃EP的極限氧指數(shù)(LOI)為28.3,通過UL-94 V-1級別�？刂浦鷦┑目偺砑恿繛�4 wt%,分別研究APP與APP-PFCTR對EP的阻燃效果。結(jié)果表明,只添加APP對EP基本沒有阻燃效果。然而,當(dāng)PFCTR添加0.5 wt%,APP添加3.5 wt%時,LOI可達(dá)到30.5,且通過UL-94V-0級別。利用錐形量熱儀(CONE)對每個體系中的最佳樣品(EP、FR-3、FR-7以及FR-10)進(jìn)行燃燒性能測試,結(jié)果表明,阻燃劑的加入使得EP的熱釋放、煙釋放以及燃燒時尾氣中CO的釋放速率和濃度都有大幅度的降低,大大提高了EP的阻燃性能,其中以FR-10最為顯著。同時,也證實了PFCTR與APP之間確實存在著很好的協(xié)效阻燃效果。3.利用TG-IR方法研究了阻燃EP體系的熱降解歷程,并探討了阻燃EP在氣相和凝聚相中的阻燃機理。結(jié)果表明,PFCTR與APP的結(jié)合不僅大大提高了殘?zhí)柯?而且產(chǎn)生了CO2、CO、NH3以及H2C=NH等不燃?xì)怏w和芳烴化合物,起到了氣相阻燃的作用,從而改善了EP的阻燃性能。此外,通過SEM測試更為直觀的觀察了阻燃EP體系的成炭情況,結(jié)果表明,FR-10體系炭層外表面最為致密、光滑,可有效阻隔熱和氧氣的傳遞。
[Abstract]:Epoxy resin (EP) has good insulation, moisture resistance, chemical stability, corrosion resistance and mechanical properties. It is widely used in coatings, adhesives and household appliances. However, the commonly used epoxy resin is flammable material, which is difficult to meet the requirements of fire resistance in some specific application fields because of the large amount of smoke. Therefore, new halogen-free flame retardant epoxy resin has become an important research direction in the field of flame retardant polymer materials. In order to solve the above problems, this paper has carried out the following research work: 1. First, the monomers of 1hlO1-diacetylferrocene (DAF) and 1kirmono-ferrocene dicarboxylic acid (FC (COOH) _ 2) were synthesized from ferrocene, acetyl chloride and sodium hypochlorite. The monomers 2-methoxy-6-dichloro-3-triazine (MDCT) and 2-diamino-6-methoxy-3-triazine (DAMT) were synthesized from methanol and ammonia. Finally, ferrocene-triazine cyclic flame retardant oligomer (PFCTR) was synthesized by solution polymerization using FC (COOH) 2 and DAMT as raw materials. The reaction conditions of DAF and FC (COOH) 2 were investigated and the monomer structure was characterized by FTIR and 1H NMR. The structure and degree of polymerization of PFCTR were characterized by FTIR and 1H NMR, and the degree of polymerization was estimated to be 13.3%. The thermal stability and thermal decomposition mechanism of PFCTR were studied by thermogravimetric infrared (TG-IR), pyrolysis gas chromatography-mass spectrometry (Py-GC / MS) and SEM. The results show that the flame retardant decomposes at high temperature to form CO _ 2C _ 2O NH _ 3H _ 2O and iron oxides, and the residual amount at 700 鈩，

本文編號：2127053