CN107474223B - 一种含硅氮苯并咪唑型环氧树脂固化剂及其制备方法 - Google Patents
一种含硅氮苯并咪唑型环氧树脂固化剂及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种含硅氮苯并咪唑型环氧树脂固化剂及其制备方法。本发明通过2‑氨基苯并咪唑与二氯硅烷的取代反应,一步法合成得到目标产物,该方法具有快速简便,无需高温高压操作、反应周期短、后处理简单、产率高等优点。制备方法如下:在惰性气体保护下,以四氢呋喃为溶剂,三乙胺为缚酸剂,2‑氨基苯并咪唑与二氯硅烷通过取代反应制备而得,其中2‑氨基苯并咪唑与二氯硅烷的摩尔比为(2~4):1。所制备的固化剂结构中含有Si‑NH和苯并咪唑环等结构,可用作耐热型环氧树脂固化剂,用该固化剂制备的环氧树脂固化产物具有优异的热稳定性,可以广泛应用于航空航天、耐高温结构涂层和耐热复合材料树脂基体等领域。
Description
技术领域
本发明涉及一种含硅氮苯并咪唑型环氧树脂固化剂及其制备方法,属于环氧树脂固化剂合成技术领域。
背景技术
环氧树脂一般是指结构含有两个或两个以上环氧基团的聚合物,具有加工性好、收缩率小、配方灵活多样,其固化产物的耐腐蚀性、化学稳定性、电绝缘性优异等特性,在涂料、复合材料、胶黏剂、电子电容材料和工程塑料等领域广泛的应用。随着电子产业和航空航天技术的迅速发展,对环氧树脂材料的热稳定性能提出更高的要求,因此如何提高环氧树脂的热稳定性一直是科研工作者研究环氧树脂的热点之一。
环氧树脂的热稳定性取决于本身的分子空间结构、固化剂的结构和固化的工艺,通过选用合适的固化剂提高树脂的耐热性能是研究的热点之一。Chandramohan等通过一种新型固化剂(BMEPC)固化N,N,N',N'-四缩水甘油基-4,4'-二氨基二苯基甲烷(TGDDM),其固化物的玻璃化转变温度(T g )由162 ℃提高到230 ℃,800 ℃的质量保留率为36.6 % (HighPerformance Polymers, 2011, 23(3):197-211.)。Meenakshi等采用(3-氨基苯基)苯基氧化膦(BAPPO)与POSS-NH2作为混合固化剂与TGDDM固化,所得固化物的分解温度达到290℃,1200 ℃的残余量为20 % (Arabian Journal of Chemistry, 2016, 9(1):79-85.)。Bhuvan等利用酰亚胺和DDM混合物作为环氧树脂固化剂,所得固化物的T g 由134 ℃提高到156 ℃(Journal of Applied Polymer Science, 2010, 108(3):2001-2009.)。Saito等合成一种全氢化含氮硅烷固化剂(PHPS),该固化剂与双酚A型环氧树脂(DGEBA)固化,固化物第一次分解的温度为255 ℃,第二次分解的温度为500 ℃,展示出优异的热稳定性(Journal of Applied Polymer Science, 2014, 127(3):2074-2081.)。Yang等合成一种新型固化剂(BNP),用该固化剂与DGEBA固化后可以提高固化物的热稳定性,T g 为205 ℃,失重5 %和最大失重所对应的温度分别为344 ℃和420 ℃,800 ℃的质量保留率为32.6 %,而用9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)固化DGEBA,固化物的T g 为170 ℃,失重5 %和最大失重所对应的温度分别为342 ℃和368 ℃,800 ℃的质量保留率为26.5 %(Journal of Applied Polymer Science, 2017, 13(4): 45291-45299.)。You 等合成一种新型固化剂4,4',4''- (1,3,5-六氢-三嗪-1,3,5-三基)三(N-(2-氨基乙基)苯甲酰胺)(HT-A),用该固化剂与DGEBA固化,所得固化物失重5 %和30 %时所对应的温度分别为316℃和363 ℃,耐热指数(T s )为168,而用商业化的4,4'-二氨基二苯基甲烷(DDM)固化DGEBA,所得固化物失重5 %和30 %时所对应温度分别为359 ℃和388 ℃,T s 为184(AcsSustainable Chemistry and Engineering, 2017,5 (6):4683-4689.)。研究表明:固化剂的结构对环氧树脂的性能具有较大的影响,向环氧树脂固化物结构中引入苯环、稠环、联苯等刚性基团以及含酰亚胺结构,可以提高固化物的T g 和分解温度,使其热性能得到很好的提升。
基于以上研究背景,本发明通过2-氨基苯并咪唑与二氯硅烷的取代反应合成一种含硅氮苯并咪唑型环氧树脂固化剂,所制备的固化剂结构中含有Si-NH和苯并咪唑环等结构,可用作耐热环氧树脂固化剂,用该固化剂制备的环氧树脂固化产物具有优异的热稳定性能,可以广泛应用于航空航天、耐高温结构涂层和耐热复合材料树脂基体等领域。
发明内容
本发明合成一种含硅氮苯并咪唑型环氧树脂固化剂,所述固化剂的结构式如下:
其中R1、R2为氢、C1~C5烷烃基、C2~C4烯烃基、C2~C4炔烃基、C6~C10芳基、苄基。
本发明的目的之一是提供一种含有Si-NH和苯并咪唑环等结构的耐热环氧树脂固化剂,用该固化剂制备的环氧树脂固化产物具有优异的热稳定性能,可以广泛应用于航空航天、耐高温结构涂层和耐热复合材料树脂基体等领域。
本发明的目的之二是提供一种含硅氮苯并咪唑型环氧树脂固化剂的合成方法。该方法是在惰性气体保护下,通过2-氨基苯并咪唑与二氯硅烷的取代反应,一步法合成而得。反应方程式为:
其中R1、R2为氢、C1~C5烷烃基、C2~C4烯烃基、C2~C4炔烃基、C6~C10芳基、苄基。
本发明的制备方法如下:
在高纯氮气保护下,将2-氨基苯并咪唑、四氢呋喃和三乙胺加入到三口烧瓶中,并搅拌溶解后,通过恒压滴液漏斗加入二氯硅烷和四氢呋喃的混合溶液,反应一段时间后,经抽滤除去三乙胺盐酸盐,收集滤液并用无水乙醚进行洗涤提纯、旋转蒸发除去溶剂、真空干燥得到目标产物。
所述的一种含硅氮苯并咪唑型环氧树脂固化剂的制备方法,其反应温度为-20 ℃~40 ℃,反应时间为2 h~8 h。
本发明合成一种含硅氮苯并咪唑型环氧树脂固化剂具有下列优点和积极效果:
1)本发明采用一步合成法、快速简便、无需高温高压操作、反应周期短、后处理简单、产率高。
2)本发明在惰性气体保护下,以四氢呋喃为溶剂,三乙胺为缚酸剂,2-氨基苯并咪唑与二氯硅烷通过取代反应制备而得,其中2-氨基苯并咪唑与二氯硅烷的摩尔比为(2 ~4):1。制备的固化剂中含有Si-NH和苯并咪唑环等结构,可用作耐热环氧树脂固化剂,用该固化剂制备的环氧树脂固化产物具有优异的热稳定性能,可以广泛应用于航空航天、耐高温结构涂层和耐热复合材料树脂基体等领域,克服了传统固化剂制备的环氧树脂固化物耐热性不足的缺点。
附图说明
图1为本发明专利实施例1所得固化物在氮气(a)和空气(b)条件的TGA曲线;
图2为本发明专利实施例2所得固化物在氮气(a)和空气(b)条件的TGA曲线;
图3为本发明专利实施例3所得固化物在氮气条件的TGA曲线。
具体实施方式
为了更好、准确了解本发明,下面结合具体实施方案进一步说明本发明的内容,但是本发明的内容远远不止下列实例。
实施例1
在高纯氮气保护下,向装有恒压滴液漏斗、冷凝管的三口烧瓶中依次加入2-氨基苯并咪唑(1.33 g,10 mmol),四氢呋喃(20 mL)和三乙胺(1.5 mL,10 mmol),搅拌溶解后,通过恒压滴液漏斗加入二苯基二氯硅烷(1 mL,5 mmol)和四氢呋喃(20 mL)的混合溶液,滴加完毕后在-20 ℃下继续反应3 h,反应结束后,静置沉降、经抽滤除去三乙胺盐酸盐,收集滤液并用无水乙醚洗涤、旋转蒸发除去溶剂、真空干燥得到目标产物。所述目标产物的结构为:
FTIR:3424 cm-1(N-H),3068 cm-1 、1589 cm-1(Ph-H),1123 cm-1(Si-C),992 cm-1(Si-N);1H-NMR:3.53 ppm(N-H),5.33 ppm(Si-NH),7.03~7.76 ppm(Ph-H)。
用合成的产物固化三缩水甘油基对氨基苯酚型环氧树脂(TGPAP),所得固化产物在N2气氛中的TGA(升温速率为10 ℃/min)曲线如图1中(a)所示,曲线表明:失重5 %(T d5 )和失重10 %(T d10 )所对应的温度分别为318 ℃和338 ℃,最大热失重速率对应的温度(T dmax )为 370 ℃,600 ℃的质量保留率为28. 3 %。
用合成的产物固化TGPAP,所得固化产物在空气中的TGA曲线(升温速率为10 ℃/min)如图1中(b)所示,曲线表明:T d5 和T d10 所对应的温度分别为274 ℃和294 ℃,T dmax 为352 ℃,600 ℃的质量保留率为9.71 %。
实施例2
在高纯氮气保护下,向装有恒压滴液漏斗、冷凝管的三口烧瓶中依次加入2-氨基苯并咪唑(1.33 g,10 mmol),四氢呋喃(20 mL)和三乙胺(1.5 mL,10 mmol),搅拌溶解后,通过恒压滴液漏斗加入甲基二氯硅烷(0.54 mL,5 mmol)和四氢呋喃(20 mL)的混合溶液,滴加完毕后在0 ℃下继续反应3 h,反应结束后,静置沉降、经抽滤除去三乙胺盐酸盐,收集滤液并用无水乙醚洗涤、旋转蒸发除去溶剂、真空干燥得到目标产物。所述目标产物的结构为:
FTIR:3387 cm-1(N-H),2968 cm-1、1266 cm-1(CH3),2170 cm-1(Si-H),1104 cm-1(Si-C),907cm-1(Si-N); 1H-NMR:7.10~7.15 ppm(Ph-H),5.33 ppm(Si-NH),3.71 ppm(Si-H),0.83 ppm(CH3)。
用合成的产物固化TGPAP,所得固化产物在N2气氛中的TGA(升温速率为10 ℃/min)曲线如图2中(a)所示,曲线表明:T d5 和T d10 所对应的温度分别为330 ℃和351 ℃,T dmax 为 374 ℃,600 ℃的质量保留率为39.9 %。
用合成的产物固化TGPAP,所得固化产物在空气中的TGA曲线(升温速率为10 ℃/min)如图2中(b)所示,曲线表明:T d5 和T d10 所对应的温度分别为291 ℃和320 ℃,T dmax 为368 ℃,600 ℃的质量保留率为28.8 %。
实施例3
在高纯氮气保护下,向装有恒压滴液漏斗、冷凝管的三口烧瓶中依次加入2-氨基苯并咪唑(2.66 g,20 mmol),四氢呋喃(40 mL)和三乙胺(3 mL,20 mmol),搅拌溶解后,通过恒压滴液漏斗加入二苯基二氯硅烷(2 mL,10 mmol)和四氢呋喃(40 mL)的混合溶液,滴加完毕后在10 ℃下继续反应6 h,反应结束后,静置沉降、经抽滤除去三乙胺盐酸盐,收集滤液并用无水乙醚洗涤、旋转蒸发除去溶剂、真空干燥得到目标产物。所述目标产物的结构为:
FTIR:3385 cm-1(N-H),3069 cm-1、1590 cm-1(Ph-H),1119 cm-1(Si-C),994 cm-1 (Si-N);1HNMR:3.54 ppm(N-H),5.30 ppm(Si-NH),7.12~7.81 ppm(Ph-H)。
用合成的产物固化N,N,N',N'-四缩水甘油基-4,4'-二氨基二苯基甲烷(TGDDM),所得固化产物在N2气氛中的TGA曲线(升温速率为10 ℃/min)如图3所示,曲线表明:T d5 和T d10 所对应的温度分别为337 ℃和354 ℃,T dmax 为 390 ℃,600 ℃的质量保留率为22.4 %。
以上所述仅为本发明的较佳实施案例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (5)
1.一种含硅氮苯并咪唑型环氧树脂固化剂,其特征在于,所述含硅氮苯并咪唑型环氧树脂固化剂的结构式为:
其中R1、R2为氢、C1~C5烷烃基、C2~C4烯烃基、C2~C4炔烃基、C6~C10芳基、苄基。
2.一种如权利要求1所述的含硅氮苯并咪唑型环氧树脂固化剂的制备方法,其特征在于,所述制备方法包括如下步骤:
在惰性气体保护下,依次将2-氨基苯并咪唑、四氢呋喃和三乙胺加入到三口烧瓶中,搅拌溶解后,通过恒压滴液漏斗加入二氯硅烷和四氢呋喃的混合溶液,反应一段时间后,经抽滤除去三乙胺盐酸盐,收集滤液并用无水乙醚洗涤、旋转蒸发除去溶剂、真空干燥得到目标产物。
3.根据权利要求2所述一种含硅氮苯并咪唑型环氧树脂固化剂的制备方法,其特征在于,2-氨基苯并咪唑与二氯硅烷的摩尔比为(2~4):1。
4.根据权利要求2所述一种含硅氮苯并咪唑型环氧树脂固化剂的制备方法,其特征在于,反应温度为 -20 ℃~40 ℃,反应时间为2 h~8 h。
5.根据权利要求2所述一种含硅氮苯并咪唑型环氧树脂固化剂的制备方法,其特征在于,所述惰性气体为氮气、氩气或氦气。
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