CN110698810A - 一种高韧性、抗紫外吸收且阻燃的环氧树脂组合物及其制备 - Google Patents
一种高韧性、抗紫外吸收且阻燃的环氧树脂组合物及其制备 Download PDFInfo
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- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
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Abstract
本发明属于环氧树脂材料技术领域,具体涉及一种高韧性、抗紫外吸收且阻燃的环氧树脂组合物,所述组合物制备的环氧树脂材料韧性、抗紫外及阻燃性能均有提高,综合性能好,冲击强度可达25KJ/m2以上,阻燃性能可达UL94‑V0级别,紫外长时间照射后未黄变或轻微黄变,拉伸强度变化小。
Description
技术领域
本发明属于环氧树脂材料技术领域,具体涉及一种高韧性、抗紫外吸收且阻燃的环氧树脂组合物及其制备。
技术背景
环氧树脂是一种重要的热固性树脂,以优异的力学性能,电性能和粘结性能著称,广泛的应用于电子电器、化工防腐、航空航天、玻璃钢复合材料制备等领域,并越来越受到人们的重视。但是,一方面,环氧树脂的疲劳强度和冲击韧性难以满足现代工业技术的发展要求,其增韧研究一直是本领域技术人员的研究热点;另一方面,环氧树脂光环境下易老化、易燃性等缺点也成为了限制其广泛应用的主要瓶颈。因此,增加环氧树脂的韧性,提高环氧树脂的抗紫外性能、阻燃性能具有十分重要的意义。
发明内容
本发明的一个目的是提供一种高韧性、抗紫外吸收且阻燃的环氧树脂组合物,所述组合物制备的环氧树脂材料韧性、抗紫外及阻燃性能均有提高,综合性能好,冲击强度可达25KJ/m2以上,阻燃性能可达UL94-V0级别,紫外长时间照射后未黄变或轻微黄变,拉伸强度变化小。
本发明的另一个目的是提供上述环氧树脂组合物制备环氧树脂复合材料的制备方法。
为实现上述发明目的,本发明提供以下技术方案:
一方面,本发明提供一种高韧性、抗紫外吸收且阻燃的环氧树脂组合物,按重量计,包括以下组分:双酚A型环氧树脂100~120重量份,式(I)所示固化剂20~35重量份,硅橡胶核壳增韧纳米粒子18~25重量份,促进剂0.5~1.2 重量份,
在一些优选的实施方案中,本发明的高韧性、抗紫外吸收且阻燃的环氧树脂组合物,按重量计,包括以下组分:双酚A型环氧树脂100重量份,式(I)所示固化剂20~30重量份,硅橡胶核壳增韧纳米粒子20~22重量份,促进剂0.8 ~1.0重量份。
在一些更为优选的实施方案中,本发明的高韧性、抗紫外吸收且阻燃的环氧树脂组合物,按重量计,包括以下组分:双酚A型环氧树脂100重量份,式(I) 所示固化剂28重量份,硅橡胶核壳增韧纳米粒子20~22重量份,促进剂1.0重量份。
其中,所述双酚A型环氧树脂选自E-44、E-51和E55中的至少一种。
其中,所述式(I)所示固化剂的制备方法包括如下步骤:
步骤(1):对硝基苯甲醛与乙酸酐反应制得对硝基肉桂酸;
步骤(2):对硝基肉桂酸酰化制得对硝基肉桂酰氯;
步骤(3):对硝基肉桂酰氯与2,4-二羟基二苯甲酮反应制得式(a)化合物,即2-羟基-4-(2-对硝基苯基丙烯酸酯基)二苯甲酮;
步骤(4):式(a)化合物还原得到式(b)化合物,即2-羟基-4-(2-对氨基苯基丙烯酸酯基)二苯甲酮;
步骤(5):式(b)化合物与DOPO反应得到式(I)化合物;反应方程式如下:
其中,所述步骤(5)中式(b)化合物与DOPO是在惰性气体保护下反应得到,所用惰性气体为氮气、氩气或氦气中的一种;
所述步骤(5)中所得式(I)化合物在甲醇-丙酮混合溶剂中重结晶纯化,所述甲醇-丙酮混合溶剂的体积比为3:1。
其中,所述硅橡胶核壳增韧复合纳米粒子中所述复合纳米粒子硅橡胶核的平均粒径为200~500nm,硅橡胶含量为45%~60%,所述的硅橡胶选自甲基乙烯基硅橡胶和甲基乙烯基苯基硅橡胶中的一种。
其中,所述硅橡胶核壳增韧复合纳米粒子是由硅橡胶与双酚A环氧树脂制备得到,外层壳结构由加成反应嫁接到硅胶核表面,具体地,所述硅橡胶核壳增韧复合纳米粒子将双酚环氧树脂加入反应装置中,在80℃下按比例加入硅橡胶粒子,搅拌0.5小时后升温至100℃,高速搅拌3h后,120℃真空脱泡处理即得,所述硅橡胶重量占硅橡胶与双酚A环氧树脂质量总和的45%~60%。
其中,所述的促进剂选自2-甲基咪唑、1-甲基咪唑、2-乙基-4-甲基咪唑、2- 苯基咪唑和2-苯基-4-甲基咪唑中的一种或几种。
第二方面,本发明提供上述高韧性、抗紫外吸收且阻燃的环氧树脂组合物制备环氧树脂复合材料的方法,所述方法包括如下步骤:
步骤a:按比例将双酚A型环氧树脂,硅橡胶核壳增韧纳米粒子搅拌分散在丙酮中,超声0.5-1h;
步骤b:减压蒸除步骤a所得混合物中的丙酮,按比例加入固化剂和促进剂, 120-130℃搅拌混合均匀;
步骤c:将步骤b所得物倒入100-120℃预热好的涂有环氧树脂脱模剂的不锈钢模具中,抽真空0.5-1h,脱泡;
步骤d:脱泡后,在160℃固化5h,200℃固化4h,自然冷却后脱模,得到环氧树脂复合材料。
具体实施方式
实施例1式I所示固化剂的制备
步骤1:对硝基肉桂酸的制备
称取15g对硝基苯甲醛、6g乙酸钠于反应瓶中,加入乙酸酐30mL,180℃回流反应8h,反应结束后,加水50mL,饱和碳酸钾溶解调pH至8,活性炭脱色,趁热过滤,盐酸调节pH至4左右,过滤,即得。
ES:M/Z 181[M+H]+。
步骤2:对硝基肉桂酰氯的制备
称取5g步骤1所得物对硝基肉桂酸于反应瓶中,加入二氯亚砜30mL,DMF 2mL,升温回流2h,减压蒸除溶剂,直接用于下一步。
步骤3:2-羟基-4-(2-对硝基苯基丙烯酸酯基)二苯甲酮的制备
称取2,4-二羟基二苯甲酮3.4g于反应瓶中,加入三乙胺3mL,四氢呋喃20mL,0-5℃下缓慢滴加10mL溶解有步骤2所得物的四氢呋喃溶液,滴毕,0-10℃下继续搅拌4h,反应结束后,加入水30mL,二氯甲烷萃取(3*50mL),无水硫酸钠干燥,柱层析纯化即得标题化合物。
ES:M/Z 390[M+H]+。
1H NMR(600MHz,CDCl3)(δ,ppm):8.51~8.50(m,2H),8.02~8.00(m,2H), 7.82~7.81(m,2H),7.55~7.53(m,2H),7.40~7.39(m,2H),6.98~6.95(m,2H), 6.50(s,1H),6.37(s,1H),5.00(s,1H).
步骤4:2-羟基-4-(2-对氨基苯基丙烯酸酯基)二苯甲酮的制备
称取1g步骤3所得物2-羟基-4-(2-对硝基苯基丙烯酸酯基)二苯甲酮于反应瓶中,加入30ml甲醇溶解,溶解有0.6g硫氢化钠的甲醇溶液10ml,回流反应 10h,反应结束,减压旋除甲醇,加入冷水30ml,过滤,所得固体柱层析混合的标题化合物。
ES:M/Z 360[M+H]+。
1H NMR(600MHz,CDCl3)(δ,ppm):8.03~8.01(m,2H),7.82~7.81(m,2H), 7.54~7.53(m,2H),7.19~7.17(m,2H),6.42~6.39(m,3H),6.19(s,1H),6.10(s, 1H),5.00(s,1H).
步骤5:式I化合物的制备
称取10gDOPO于反应瓶中,加入8.6g步骤4所得物2-羟基-4-(2-对氨基苯基丙烯酸酯基)二苯甲酮,150ml二氧六环,氮气保护下回流反应10h,反应结束后,冷却至室温,减压蒸除溶剂,甲醇/丙酮(体积比3:1)重结晶即得标题化合物。
ES:M/Z 360[M+H]+。
1H NMR(600MHz,CDCl3)(δ,ppm):8.11(m,1H),8.02~7.98(m,3H),7.82~7.78 (m,4H),7.56~7.54(m,2H),7.51(m,1H),7.39~7.37(m,1H),7.13~7.14(m,4H), 7.06~7.04(m,2H),6.58~6.56(m,2H),6.32(s,2H),5.05(s,1H),4.01~3.99(m,1H), 3.21~3.19(m,1H),3.03~3.02(m,1H).
实施例2环氧树脂复合材料的制备
按表1中的重量比将双酚A型环氧树脂,硅橡胶核壳增韧纳米粒子搅拌分散在丙酮中,超声1h,然后减压蒸除丙酮,按表1中的重量比加入固化剂和促进剂,120℃搅拌混合1h,倒入120℃预热好的涂有环氧树脂脱模剂的不锈钢模具中,抽真空1h,然后160℃固化5h,200℃固化4h,自然冷却后脱模,得到环氧树脂复合材料。
表1
将实施例2a-2e的环氧树脂复合材料进行力学性能测试和垂直燃烧测试,拉伸、冲击试验样条为浇筑体,100mm×50mm×50mm,垂直燃烧试验样条为浇筑体, 100mm×10mm×10mm,测试结果见表2.
表2
将实施例2a-2e的环氧树脂复合材料紫外照射试验样条为薄膜,100mm×10mm×3mm,在紫外波长为340nm,强度为0.76W/m2,60℃下辐照暴露3个月,其拉伸强度降低不到10%,黄变值低于15。
Claims (9)
2.如权利要求1所述的环氧树脂组合物,其特征在于:按重量计,包括以下组分:双酚A型环氧树脂100重量份,式(I)所示固化剂20~30重量份,硅橡胶核壳增韧纳米粒子20~22重量份,促进剂0.8~1.0重量份。
3.如权利要求1所述的环氧树脂组合物,其特征在于:按重量计,包括以下组分:双酚A型环氧树脂100重量份,式(I)所示固化剂28重量份,硅橡胶核壳增韧纳米粒子20~22重量份,促进剂1.0重量份。
4.如权利要求1-3任一项所述的环氧树脂组合物,其特征在于:所述双酚A型环氧树脂选自E-44、E-51和E55中的至少一种。
6.如权利要求1-3任一项所述的环氧树脂组合物,其特征在于:所述硅橡胶核壳增韧复合纳米粒子中复合纳米粒子硅橡胶核的平均粒径为200~500nm,硅橡胶含量为45%~60%,所述的硅橡胶选自甲基乙烯基硅橡胶和甲基乙烯基苯基硅橡胶中的一种。
7.如权利要求1-3任一项所述的环氧树脂组合物,其特征在于:所述硅橡胶核壳增韧复合纳米粒子是由硅橡胶与双酚A环氧树脂制备得到,外层壳结构由加成反应嫁接到硅胶核表面,具体地,所述硅橡胶核壳增韧复合纳米粒子将双酚环氧树脂加入反应装置中,在80℃下按比例加入硅橡胶粒子,搅拌0.5小时后升温至100℃,高速搅拌3h后,120℃真空脱泡处理即得,所述硅橡胶重量占硅橡胶与双酚A环氧树脂质量总和的45%~60%。
8.如权利要求1-3任一项所述的环氧树脂组合物,其特征在于:所述的促进剂选自2-甲基咪唑、1-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑和2-苯基-4-甲基咪唑中的一种或几种。
9.权利要求1-3任一项所述的环氧树脂组合物制备环氧树脂复合材料的方法,所述方法包括如下步骤:
步骤a:按比例将双酚A型环氧树脂,硅橡胶核壳增韧纳米粒子搅拌分散在丙酮中,超声0.5-1h;
步骤b:减压蒸除步骤a所得混合物中的丙酮,按比例加入固化剂和促进剂,120-130℃搅拌混合均匀;
步骤c:将步骤b所得物倒入100-120℃预热好的涂有环氧树脂脱模剂的不锈钢模具中,抽真空0.5-1h,脱泡;
步骤d:脱泡后,在160℃固化5h,200℃固化4h,自然冷却后脱模,得到环氧树脂复合材料。
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