CN109370353A - 一种冬季使用的环保型氟改性苯丙乳液涂料及其制备方法 - Google Patents
一种冬季使用的环保型氟改性苯丙乳液涂料及其制备方法 Download PDFInfo
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- CN109370353A CN109370353A CN201811282966.3A CN201811282966A CN109370353A CN 109370353 A CN109370353 A CN 109370353A CN 201811282966 A CN201811282966 A CN 201811282966A CN 109370353 A CN109370353 A CN 109370353A
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Abstract
本发明涉及一种冬季使用的环保型氟改性苯丙乳液涂料及其制备方法,该涂料含有氟改性苯丙乳液、成膜树脂、环糊精、碳酸氢钠、羟乙基纤维素、硅藻土、滑石粉、重质碳酸钙、乳化剂、流平剂、催干剂、分散剂、消泡剂、稳定剂、水。该涂料具有较低的最低成膜温度,稳定性高,适于在冬季施工中使用。
Description
技术领域
本发明涉及涂料及制备技术领域,尤其涉及一种冬季使用的环保型氟改性苯丙乳液涂料及其制备方法。
背景技术
苯丙乳液(苯乙烯-丙烯酸酯乳液)是由苯乙烯和丙烯酸酯单体经乳液共聚而得,其在我国经过几十年的发展,由于具有优良的黏附性、耐氧化性和耐油性,现已广泛应用于建筑、涂料及胶黏剂等领域。但是其耐水性和耐候性较差,且易于形变,限制了它的应用。
目前使用有机硅或有机氟对苯丙乳液进行改性。有机硅具有优良的耐高低温、耐紫外线和耐红外辐射、耐氧化降解等性能,用有机硅对苯丙乳液进行改性,可以明显提高其耐候性、保光性、弹性和耐久性等。有机氟改性的苯丙乳液涂料,具有优异的耐候性、耐久性、耐化学品性和防腐性、耐磨性、绝缘性、非豁附性及耐污染性等性能,广泛地应用于建筑、航空、电子、电气、机械及家庭日用品、木器家具等领域,是一种集高、新、特于一身的性能优异的涂料,在涂料工业中占有十分重要的地位。
中国专利CN106675412A公开了一种有机硅改性的内墙涂料及其制备方法,包含遮盖性乳液、石灰、玻璃粉、润湿分散剂、有机硅改性丙烯酸乳液、陶瓷纤维、金刚石粉、助溶剂、水泥、红土、塑料、苯丙乳液、金红石型钛白粉、白漆、滑石粉,该涂料冻结温度低、防冻性好、抗拉及抗剪切强度高;具有拒水和透气性,杀菌灭菌;耐碱性好,遮盖力强,可用水洗抹,成本较低。
中国专利CN107227057A公开了一种建筑屋顶用防水浆料及制备方法,所述浆料包括如下组分:苯丙乳液、改性有机硅树脂、环氧树脂、季戊四醇三丙烯酸酯、氯化石蜡、高岭土、重质碳酸钙、蛭石粉、石墨烯、凹凸棒土、硫酸钡、云母粉、消泡剂、填料。该涂料所述浆料应用于屋顶建设中,不仅能够提高屋顶的防水、防开裂性能,还具有一定的耐腐蚀、耐老化的特点,具有较好的应用价值。
中国专利CN104789057A公开了有机氟改性苯丙防水涂料,由乳液、增塑剂、添加剂、重钙、色浆所组成,其中乳液为有机氟改性苯丙乳液,增塑剂为环保增塑剂ECOD-FLEX50,重钙为重质碳酸钙,添加剂由防腐剂、消泡剂、分散剂和肽白粉所组成。该涂料具有良好的耐老化性、延伸性、弹性、粘结性和成膜性。
上述现有技术中公开的涂料以及市售的涂料虽然性能已经很好,但这些涂料仅能在温度较高的情况下进行施工。在温度较低特别是冬季进行施工的时候,这些涂料的稳定性以及成膜性均会出现较大的问题。
发明内容
针对现有技术中的缺陷,本发明提供一种冬季使用的环保型氟改性苯丙乳液涂料及其制备方法,使用该方法制备得到的涂料环保健康,具有较低的最低成膜温度,稳定性高,适于在冬季施工中使用。
本发明的第一个目的是提供一种冬季使用的环保型氟改性苯丙乳液涂料,其特征在于,包括按照重量份计的以下组分:氟改性苯丙乳液50-100份、成膜树脂10-40份、环糊精0.1-10份、碳酸氢钠1-5份、羟乙基纤维素5-15份、硅藻土1-10份、滑石粉1-10份、重质碳酸钙1-10份、乳化剂1-5份、流平剂1-5份、催干剂1-5份、分散剂1-5份、消泡剂1-5份、稳定剂1-5份、水20-40份。
所述氟改性苯丙乳液是由重量比为(1-3):(2-5):(0.5-2)苯乙烯、丙烯酸酯和全氟辛基乙基丙烯酸酯经乳液共聚而得。
进一步地,包括按照重量份计的以下组分:氟改性苯丙乳液60-80份、成膜树脂20-30份、环糊精0.5-5份、碳酸氢钠1-3份、羟乙基纤维素10-15份、硅藻土1-5份、滑石粉1-5份、重质碳酸钙1-5份、乳化剂1-3份、流平剂1-3份、催干剂1-3份、分散剂1-3份、消泡剂1-3份、稳定剂1-3份、水25-35份。
所述氟改性苯丙乳液是由重量比为(1.5-2):(2.5-4):(0.5-1)苯乙烯、丙烯酸酯和全氟辛基乙基丙烯酸酯经乳液共聚而得。
进一步地,所述成膜树脂选自环氧树脂、聚酯树脂、有机硅树脂、丙烯酸树脂或氟碳树脂的一种或几种,优选为丙烯酸树脂。
进一步地,所述环糊精的重量为成膜树脂的0.5-20wt%,优选为3-15wt%,更优选为5-12wt%。
进一步地,所述乳化剂选自泊洛沙姆188、月桂山梨坦、油酸山梨坦、聚山梨酯80、鲸蜡硬脂醇、聚二甲基硅氧烷、脂肪酸单甘油脂、山嵛醇聚醚-25、季戊四醇二硬脂酸酯以及硬脂醇聚醚-21中的一种或多种。
进一步地,所述流平剂选自BYK358、BYK354、BYK333、PV88、EFKA3522中的一种或几种。
进一步地,所述催干剂为甲基二乙醇胺、乙二醇乙醚、乙二醇乙醚乙酯、二月桂酸二丁基锡、辛酸亚锡、异辛酸锌中的一种或几种。
进一步地,所述分散剂为乙烯基双硬脂酰胺、三硬脂酸甘油酯、月桂醇硫酸钠、硬脂酸钡、二辛基琥珀酸磺酸钠和甘胆酸钠中的一种或几种。
进一步地,所述消泡剂为聚氧丙烯氧化乙烯甘油醚、聚氧乙烯聚氧丙烯季戊四醇醚、苯乙醇油酸酯、乙氧基氨丙基聚二甲基硅氧烷和苯乙酸月桂醇酯中的一种或几种。
进一步地,所述稳定剂选自聚乙烯醇、羟基甲基纤维素、聚氧乙烯醚、聚丙烯酸钠、聚丙烯酰胺和淀粉中的一种或几种。
本发明的第二个目的是提供一种冬季使用的环保型氟改性苯丙乳液涂料的制备方法,其特征在于,包括以下步骤:
(1)在1000-1200转/分的搅拌条件下,向水中加入成乳化剂、流平剂、催干剂、分散剂、消泡剂、稳定剂,搅拌20-30分钟后降低搅拌速度得浆液,备用;
(2)在800-1000转/分的搅拌条件下向步骤(1)得到的浆液中依次加入氟改性苯丙乳液、成膜树脂、环糊精、碳酸氢钠、羟乙基纤维素,加pH调节剂调节pH值至8-9,得到浆料;
所述氟改性苯丙乳液是由重量比为(1-3):(2-5):(0.5-2)苯乙烯、丙烯酸酯和全氟辛基乙基丙烯酸酯经乳液共聚而得;
(3)将步骤(2)所得浆料在300-600转/分搅拌条件下,加入硅藻土、滑石粉、重质碳酸钙,搅拌10-20分钟,得到冬季使用的氟改性苯丙涂料。
最低成膜温度(MFT)是乳液颗粒相互聚集成连续薄膜的最低温度,是表征聚合物乳液成膜特性的常用方法,是涂料的使用极限值。当施工温度超过MFT时,乳液形成连续、透明的薄膜;反之,当施工温度低于MFT时,将会形成白色粉状有裂痕的薄膜。因此,为了满足使用的要求,涂料的施工温度应超过MFT。
涂料的成膜剂又称聚结剂,目前常用的为成膜树脂,其通过降低聚合物表面积,降低表面能,控制水的蒸发以促进聚合物成膜。在成膜剂的作用下乳液离子之间的界面消失,形成连续均匀的膜。加入成膜剂,能够在一定程度上降低最低成膜温度。现有市售的涂料的MFT一般都在20℃以上。在春夏秋季施工时,温度一般都高于涂料的MFT,但一旦到了冬季,特别是北方的冬季,施工温度一般会降低到5-10℃左右,那么现有市售涂料难以满足要求。本发明发现在涂料中加入环糊精,可提高乳胶粒的流动性、高分子弹性变形和聚结性能,同时增强聚合物塑性,促使分子的融合,帮助成膜剂更好地成膜,明显降低涂料的最低成膜温度。
环糊精(Cyclodextrin,简称CD)是直链淀粉在由芽孢杆菌产生的环糊精葡萄糖基转移酶作用下生成的一系列环状低聚糖的总称,通常含有6~12个D-吡喃葡萄糖单元。环糊精分子具有略呈锥形的中空圆筒立体环状结构,在其空洞结构中,外侧上端(较大开口端)由C2和C3的仲羟基构成,下端(较小开口端)由C6的伯羟基构成,具有亲水性,而空腔内由于受到C-H键的屏蔽作用形成了疏水区。环糊精具有的特殊结构与成膜剂特别是成膜树脂相互作用,使得成膜树脂的成膜性更好,降低涂料整体的最低成膜温度。在使涂料成膜性更好的同时,还能够提高涂料的稳定性。
附图说明
图1.环糊精的加入量对最低成膜温度的影响。
具体实施方式
实施例1-4
按照如下步骤制备实施例1-4的氟改性苯丙涂料。
(1)在1000转/分的搅拌条件下,向水中加入成乳化剂、流平剂、催干剂、分散剂、消泡剂、稳定剂,搅拌20-30分钟后降低搅拌速度得浆液,备用;
(2)在1000转/分的搅拌条件下向步骤(1)得到的浆液依次加入氟改性苯丙乳液,成膜树脂、环糊精、碳酸氢钠、羟乙基纤维素、加pH调节剂调节pH值至8-9,得到浆料;
所述氟改性苯丙乳液是由重量比为(1-3):(2-5):(0.5-2)苯乙烯、丙烯酸酯和全氟辛基乙基丙烯酸酯经乳液共聚而得;
(3)将步骤(2)所得浆料在500转/分搅拌条件下,加入硅藻土、滑石粉、重质碳酸钙,搅拌10-20分钟,得到冬季使用的氟改性苯丙涂料。
测试例:
分别取实施例1-4所获取的氟改性苯丙乳液涂料,对预定内墙进行涂刷,相关性能的测定方法和评价指标以GB/T 9756-2009《合成树脂乳液内墙涂料》为依据,测试结果如下。
如上表所示,实施例1-4所提供的氟改性苯丙乳液涂料各项性能均达到或优于GB/T 9756-2009《合成树脂乳液内墙涂料》的规定,涂料施工性能好,干燥时间短,无起泡、剥落、掉粉等现象,耐碱、耐水,耐洗刷,拉伸强度高、断裂伸长率高,因此本发明的涂料性能较优,具有很好地应用前景。
分别取实施例1-4所获取的环保型苯丙乳液涂料,对预定内墙进行涂刷,相关性能的测定方法和评价指标以GB18528-2001《室内装饰装修材料内墙涂料中有害物质限量》为依据,测试结果如下。
分别取实施例1-4所获取的环保型苯丙乳液涂料,对预定内墙进行涂刷,相关性能的测定方法和评价指标以JC/T1074-2008《室内空气净化材料功能涂覆材料净化性能》为依据,通过测定日光灯下密闭空间实验前和24小时后的甲醛浓度而计算得出最终的甲醛清除率,具体计算如下:甲醛清除率(%)=(初始甲醛浓度-24小时后甲醛浓度)/初始甲醛浓度×100%,测试结果如下。
项目 | 实施例1 | 实施例2 | 实施例3 | 实施例4 |
甲醛清除率 | 99.3% | 98.7% | 99.1% | 98.6% |
从上两张表中的数据可以得出,本发明实施例1-4的涂料中挥发性有机物和游离甲醛均符合环保要求,并且均具有较强的甲醛清除效果,可见本发明的涂料具有环保性。
环糊精的加入量对最低成膜温度的影响
采用RHOPOINT公司的最低成膜温度仪MFFT-90测试,按照实施例1的方法进行涂料制备,其中丙烯酸树脂为20份,环糊精与丙烯酸树脂的重量比如下表所示,其它成分和含量与实施例1一致。所得到的涂料用仪器自带的涂抹器均匀涂布在温度梯度板上,干燥后观察判定,结果如下:
环糊精与成膜树脂重量比wt/% | 最低成膜温度/℃ |
0.0 | 23.3 |
0.5 | 19.7 |
1.0 | 17.8 |
2.0 | 15.1 |
3.0 | 13.8 |
4.5 | 11.7 |
5.0 | 9.8 |
6.0 | 7.3 |
7.5 | 5.3 |
8.0 | 4.4 |
10.0 | 5.5 |
12.0 | 7.9 |
12.5 | 10.5 |
13.5 | 10.8 |
15.0 | 12.3 |
18.0 | 12.4 |
20.0 | 12.7 |
从上表和附图1中可以看出,没有加入环糊精时,最低成膜温度高于20℃,高于一般涂料的温度。随着环糊精加入量的增加,涂料的粘度会增大,最低成膜温度显著降低,降至10℃以下,能够在冬季施工时使用。但是用量过大则会取代乳胶粒表面的表面活性剂从而导致乳液凝结过早,最低成膜温度会又提升至10℃以上。因此,如果冬季施工的话,环糊精的用量控制在成膜树脂用量的5.0%-12.0%之间。
以上,对本发明的实施方式进行了说明。但是,本发明不限定于上述实施方式。凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种冬季使用的环保型氟改性苯丙乳液涂料,其特征在于,包括按照重量份计的以下组分:氟改性苯丙乳液50-100份、成膜树脂10-40份、环糊精0.1-10份、碳酸氢钠1-5份、羟乙基纤维素5-15份、硅藻土1-10份、滑石粉1-10份、重质碳酸钙1-10份、乳化剂1-5份、流平剂1-5份、催干剂1-5份、分散剂1-5份、消泡剂1-5份、稳定剂1-5份、水20-40份;
所述氟改性苯丙乳液是由重量比为(1-3):(2-5):(0.5-2)苯乙烯、丙烯酸酯和全氟辛基乙基丙烯酸酯经乳液共聚而得。
2.根据权利要求1的冬季使用的环保型氟改性苯丙乳液涂料,其特征在于,包括按照重量份计的以下组分:氟改性苯丙乳液60-80份、成膜树脂20-30份、环糊精0.5-5份、碳酸氢钠1-3份、羟乙基纤维素10-15份、硅藻土1-5份、滑石粉1-5份、重质碳酸钙1-5份、乳化剂1-3份、流平剂1-3份、催干剂1-3份、分散剂1-3份、消泡剂1-3份、稳定剂1-3份、水25-35份;
所述氟改性苯丙乳液是由重量比为(1.5-2):(2.5-4):(0.5-1)苯乙烯、丙烯酸酯和全氟辛基乙基丙烯酸酯经乳液共聚而得。
3.根据权利要求1或2的冬季使用的环保型氟改性苯丙乳液涂料,所述成膜树脂选自环氧树脂、聚酯树脂、有机硅树脂、丙烯酸树脂或氟碳树脂的一种或几种,优选为丙烯酸树脂。
4.根据权利要求1或2的冬季使用的环保型氟改性苯丙乳液涂料,所述环糊精的重量为成膜树脂的0.5-20wt%,优选为3-15wt%,更优选为5-12wt%。
5.根据权利要求1或2的冬季使用的环保型氟改性苯丙乳液涂料,所述乳化剂选自泊洛沙姆188、月桂山梨坦、油酸山梨坦、聚山梨酯80、鲸蜡硬脂醇、聚二甲基硅氧烷、脂肪酸单甘油脂、山嵛醇聚醚-25、季戊四醇二硬脂酸酯以及硬脂醇聚醚-21中的一种或多种。
6.根据权利要求1或2的冬季使用的环保型氟改性苯丙乳液涂料,所述流平剂选自BYK358、BYK354、BYK333、PV88、EFKA3522中的一种或几种。
7.根据权利要求1或2的冬季使用的环保型氟改性苯丙乳液涂料,所述催干剂为甲基二乙醇胺、乙二醇乙醚、乙二醇乙醚乙酯、二月桂酸二丁基锡、辛酸亚锡、异辛酸锌中的一种或几种。
8.根据权利要求1或2的冬季使用的环保型氟改性苯丙乳液涂料,所述分散剂为乙烯基双硬脂酰胺、三硬脂酸甘油酯、月桂醇硫酸钠、硬脂酸钡、二辛基琥珀酸磺酸钠和甘胆酸钠中的一种或几种。
9.根据权利要求1或2的冬季使用的环保型氟改性苯丙乳液涂料,所述消泡剂为聚氧丙烯氧化乙烯甘油醚、聚氧乙烯聚氧丙烯季戊四醇醚、苯乙醇油酸酯、乙氧基。
10.根据权利要求1的一种冬季使用的环保型氟改性苯丙乳液涂料的制备方法,其特征在于,包括以下步骤:
(1)在1000-1200转/分的搅拌条件下,向水中加入成乳化剂、流平剂、催干剂、分散剂、消泡剂、稳定剂,搅拌20-30分钟后降低搅拌速度得浆液,备用;
(2)在800-1000转/分的搅拌条件下向步骤(1)得到的浆液中依次加入氟改性苯丙乳液、成膜树脂、环糊精、碳酸氢钠、羟乙基纤维素,加pH调节剂调节pH值至8-9,得到浆料;
所述氟改性苯丙乳液是由重量比为(1-3):(2-5):(0.5-2)苯乙烯、丙烯酸酯和全氟辛基乙基丙烯酸酯经乳液共聚而得;
(3)将步骤(2)所得浆料在300-600转/分搅拌条件下,加入硅藻土、滑石粉、重质碳酸钙,搅拌10-20分钟,得到冬季使用的氟改性苯丙涂料。
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