CN110819196A - 一种超低voc高固含水性环氧涂料及其制备方法与应用 - Google Patents
一种超低voc高固含水性环氧涂料及其制备方法与应用 Download PDFInfo
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Abstract
本发明提供的一种超低VOC高固含水性环氧涂料,包括以下重量份的组份:水性环氧树脂20‑30份,固化剂20‑30份,乳化剂4‑6份,颜填料1‑10份。本发明提供的超低VOC高固含水性环氧涂料配方简单、成本低;具有耐水性、耐油性、耐酸碱性、耐盐雾腐蚀性等化学特性;耐磨性、耐冲压性、耐洗刷性等优异;表面光亮、平整、美观、无接缝、易清洗、易维修保养、经久耐用。
Description
技术领域
本发明涉及涂料材料领域,特别涉及一种超低VOC高固含水性环氧涂料及其制备方法与应用。
背景技术
随着国家环保政策的相继出台和法律监管的日益严格,涂料企业纷纷投入大量人力、物力开发包括环氧涂料在内的环保型低VOC的涂料。
环保型环氧涂料的技术路线有很多种,例如超低VOC高固含水性环氧涂料、溶剂型高固体份涂料、无溶剂、粉末等等。这些不同种类的涂料有其各自独特的性能和特点,可以满足不同场合的应用需求。其中无溶剂和粉末涂料等技术路线几乎可以实现零VOC,虽然其对施工的环境条件要求高,但是技术是相对成熟的,所以它们需要的不是技术的创新而是应用的创新和推广。故而,含有VOC的溶剂型环氧涂料将是未来涂料VOC减排的重点针对对象。
环氧涂料有以下三个降低VOC可能的方向:
1)高VOC的低固体份含量的溶剂型涂料(VOC>420g/L)转向低VOC的低固体份含量的水性涂料(VOC<420g/L),该方向是“油转水”的范畴。
2)高VOC的低固体份含量的溶剂型涂料(VOC>420g/L)转向低VOC的高固体份的溶剂型涂料(VOC<420g/L),该方向是“油转油”的范畴。
3)低VOC的高固体份的溶剂型(VOC<420g/L)转向超低VOC高固体份水性涂料,该方向是“油转水”的范畴。
为进一步降低生产过程中的能耗和有害物质排放,提升超低VOC高固含水性环氧涂料品质,实现绿色生产,亟需对涂料生产工艺进行改进。
发明内容
技术问题:为了解决现有技术的缺陷,本发明提供了一种超低VOC高固含水性环氧涂料及其制备方法与应用。
技术方案:本发明提供的一种超低VOC高固含水性环氧涂料,包括以下重量份的组份:水性环氧树脂20-30份,固化剂20-30份,乳化剂4-6份,颜填料1-10份;
所述水性环氧树脂,其结构式如下:
R1-R10分别独立的为H、卤素、烷基、环烷基、芳基、羟基;n为自然数;
所述固化剂,包括以下重量份的组份:式(I)所示的化合物1份、三羟甲基丙烷三缩水甘油醚2-3重量份、二甲基乙醇胺2-3重量份、壳聚糖1-2重量份;
式(I)所示的化合物为
所述乳化剂,其结构式如下:
其中,R11、R12分别独立的为烷基;m为自然数。
本发明还提供了一种超低VOC高固含水性环氧涂料,包括以下重量份的组份:水性环氧树脂20-30份,固化剂20-30份,乳化剂4-6份,颜填料1-10份;
所述水性环氧树脂,其结构式如下:
所述固化剂,包括以下重量份的组份:式(I)所示的化合物1份、三羟甲基丙烷三缩水甘油醚2-3重量份、二甲基乙醇胺2-3重量份、壳聚糖1-2重量份;
式(I)所示的化合物为
所述乳化剂,其结构式如下:
m为自然数。
其中,所述水性环氧树脂的制备方法,包括以下步骤:
(1)在氢氧化钠存在下,式I所示的化合物与过量的环氧丙醇聚合反应,得式II所示的化合物;
(2)式II所示的化合物与甲基丙烯酸、苯乙烯反应,即得;
反应式如下:
n为自然数。
优选地,步骤(1),将式II所示的化合物溶于甲苯中,加入氢氧化钠水溶液,边搅拌边加热,当温度升到60-70℃时恒温搅拌并滴加环氧丙醇,于2小时内滴加完毕;提高温度,于80-90℃保持1-2h;加入蒸馏水,搅拌,静止分层除去水层,甲苯层减压蒸干即得;式II所示的化合物与环氧丙醇的摩尔比为n:(2n+2至2n+4);氢氧化钠水溶液中氢氧化钠的含量为0.5n-1.5n摩尔;蒸馏水和甲苯的体积比为(2-4):1;步骤(2),式II所示的化合物与溶解于混合溶剂中,氮气保护下,缓慢滴加甲基丙烯酸、苯乙烯,再加入引发剂,升温至110-120℃,恒温反应1-2h,冷却至40-50℃,调pH至7-8,恒温反应1-2h,即得。
其中,所述固化剂的制备方法,包括以下步骤:
(1)制备式(I)所示的化合物:
(1.1):对硝基苯甲醛与乙酸酐反应制得对硝基肉桂酸;
(1.2):对硝基肉桂酸酰化制得对硝基肉桂酰氯;
(1.3):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;
(1.4):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;
(1.5):式(b)化合物与反应得到式(I)化合物;
反应方程式如下:
(2)将式(I)所示的化合物溶于二氯甲烷中,加热至50-60℃恒温,边搅拌编滴入三羟甲基丙烷三缩水甘油醚,在2h内滴完,再加入二甲基乙醇胺,恒温搅拌1-2h;
(3)升温至70-80℃,搅拌同时再加入壳聚糖,恒温搅拌1-2h;降至室温,即得。
优选地,所述步骤(1.5)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。
优选地,所述步骤(1.5)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。
优选地,各原料的用量为:式(I)所示的化合物1份、三羟甲基丙烷三缩水甘油醚2-3重量份、二甲基乙醇胺2-3重量份、壳聚糖1-2重量份。
其中,所述乳化剂的制备方法,包括以下步骤:
(1)在90-100℃下,式(IV)所示的化合物与环氧丙醇回流反应,得式(V)所示化合物;
(2)降温至40-50℃,式(V)所示化合物中加入丁二酸,搅拌,即得;
优选地,步骤(1)中,反应时间为1-2h,式(IV)所示的化合物与环氧丙醇的用量比为1:(2-3);步骤(2)中,反应时间为0.4-0.6h,式(IV)所示的化合物与丁二酸的用量比为1:(0.8-1.0)。
有益效果:本发明提供的超低VOC高固含水性环氧涂料配方简单、成本低;具有耐水性、耐油性、耐酸碱性、耐盐雾腐蚀性等化学特性;耐磨性、耐冲压性、耐洗刷性等优异;表面光亮、平整、美观、无接缝、易清洗、易维修保养、经久耐用。
附图说明
图1为本发明制得的水性环氧树脂的氢谱图。
图2为机械性能测试结果图。
图3为湿碰湿效果图
图4为耐盐雾性能测试结果图。
具体实施方式
下面对本发明作出进一步说明。
实施例1水性环氧树脂的制备
将式I所示的化合物溶于甲苯中,加入氢氧化钠水溶液,边搅拌边加热,当温度升到65℃时恒温搅拌并滴加环氧丙醇,于2小时内滴加完毕;提高温度,于85℃保持1.5h;加入蒸馏水,搅拌,静止分层除去水层,甲苯层减压蒸干得式I所示化合物;式I所示的化合物与环氧丙醇的摩尔比为n:(2n+2至2n+4);氢氧化钠水溶液中氢氧化钠的含量为0.5n-1.5n摩尔;蒸馏水和甲苯的体积比为3:1。
式II所示的化合物与溶解于混合溶剂中,氮气保护下,缓慢滴加甲基丙烯酸、苯乙烯,再加入引发剂,升温至115℃,恒温反应1.5h,冷却至45℃,调pH至7-8,恒温反应1.5h,即得。
得反应产物1126.3g,氢谱见图1。
实施例2固化剂的制备
2.1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]+。
2.2对硝基肉桂酰氯的制备
称取5g实施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。
2.3 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溶解有实施例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).
2.4 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实施例3化合物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).
2.5式(I)化合物的制备
称取10gDOPO于反应瓶中,加入8.6g实施例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).
2.6高固含水性涂料用固化剂的制备,包括以下重量份的组份:式(I)所示的化合物1份、三羟甲基丙烷三缩水甘油醚2.5重量份、二甲基乙醇胺2.5重量份、壳聚糖1.5重量份。
其制备方法,包括以下步骤:
(1)将式(I)所示的化合物溶于二氯甲烷中,加热至55℃恒温,边搅拌编滴入三羟甲基丙烷三缩水甘油醚,在2h内滴完,再加入二甲基乙醇胺,恒温搅拌1.5h;
(2)升温至75℃,搅拌同时再加入壳聚糖,恒温搅拌1.5h;降至室温,即得。
实施例3水性环氧树脂用乳化剂的制备
水性环氧树脂用乳化剂的制备方法,包括以下步骤:
(1)在95℃下,式(IV)所示的化合物与环氧丙醇回流反应,得式(V)所示化合物;反应时间为1.5h,式(IV)所示的化合物与环氧丙醇的用量比为1:2.5。
(2)降温至45℃,式(V)所示化合物中加入丁二酸,搅拌,即得;反应时间为0.5h,式(IV)所示的化合物与丁二酸的用量比为1∶1。
实施例4超低VOC高固含水性环氧涂料的制备
制备一批超低VOC高固含水性环氧涂料,其配方如下表。
实验例测试实施例4的超低VOC高固含水性环氧涂料性能
(1)干燥时间及硬度:表干时间10min,硬干时间1.5h,实干时间2.5h。
(2)硬度:见下表:
干燥时间 | 4h | 1d | 7d | 14d |
硬度(底漆,马口板) | 可打磨 | 2H | 2H | 3H |
4h可打磨,可满足快速修补(如汽车修补漆),刮腻子等领域的工艺需求。
(3)优良的机械性能,结果见图2。
(4)“湿碰湿”的效果
湿碰湿制板过程:喷完底漆,通风处放置20min,复涂聚氨酯面漆,后置于通风处20min,80℃烘烤30min。
湿碰湿效果图见图3,聚氨酯面漆表面无痱子、起泡等缺陷,60°光泽大于90。
(5)耐盐雾性能,见图4。
Claims (8)
4.根据权利要求3所述的一种超低VOC高固含水性环氧涂料,其特征在于:步骤(1),将式II所示的化合物溶于甲苯中,加入氢氧化钠水溶液,边搅拌边加热,当温度升到60-70℃时恒温搅拌并滴加环氧丙醇,于2小时内滴加完毕;提高温度,于80-90℃保持1-2h;加入蒸馏水,搅拌,静止分层除去水层,甲苯层减压蒸干即得;式II所示的化合物与环氧丙醇的摩尔比为n:(2n+2至2n+4);氢氧化钠水溶液中氢氧化钠的含量为0.5n-1.5n摩尔;蒸馏水和甲苯的体积比为(2-4):1;步骤(2),式II所示的化合物与溶解于混合溶剂中,氮气保护下,缓慢滴加甲基丙烯酸、苯乙烯,再加入引发剂,升温至110-120℃,恒温反应1-2h,冷却至40-50℃,调pH至7-8,恒温反应1-2h,即得。
5.根据权利要求1所述的一种超低VOC高固含水性环氧涂料,其特征在于:所述固化剂的制备方法,包括以下步骤:
(1)制备式(III)所示的化合物:
(1.1):乙烯基二甲基氯硅烷与2-氨基-5-硝基苯甲酸甲酯反应制得式a的化合物;
(1.2):式a的化合物与DOPO反应制得式b的化合物;
(1.3):式b的化合物水解制得式c的化合物;
(1.4):式c的化合物与2,4-二羟基二苯甲酮反应制得式d的化合物;
(1.5):式d的化合物还原制得式III的化合物,
反应方程式如下:
(2)将式(III)所示的化合物溶于二氯甲烷中,加热至50-60℃恒温,边搅拌编滴入三羟甲基丙烷三缩水甘油醚,在2h内滴完,再加入二甲基乙醇胺,恒温搅拌1-2h;
(3)升温至70-80℃,搅拌同时再加入壳聚糖,恒温搅拌1-2h;降至室温,即得。
6.根据权利要求5所述的一种超低VOC高固含水性环氧涂料,其特征在于:各原料的用量为:式(I)所示的化合物1份、三羟甲基丙烷三缩水甘油醚2-3重量份、二甲基乙醇胺2-3重量份、壳聚糖1-2重量份。
7.根据权利要求1所述的一种超低VOC高固含水性环氧涂料,其特征在于:所述乳化剂的制备方法,包括以下步骤:
(1)在90-100℃下,式(IV)所示的化合物与环氧丙醇回流反应,得式(V)所示化合物;
(2)降温至40-50℃,式(V)所示化合物中加入丁二酸,搅拌,即得;
k为自然数。
8.根据权利要求7所述的一种超低VOC高固含水性环氧涂料,其特征在于:步骤(1)中,反应时间为1-2h,式(IV)所示的化合物与环氧丙醇的用量比为1:(2-3);步骤(2)中,反应时间为0.4-0.6h,式(IV)所示的化合物与丁二酸的用量比为1:(0.8-1.0)。
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