CN114853982A - 水性uv固化环氧丙烯酸酯树脂及其制备方法和应用 - Google Patents
水性uv固化环氧丙烯酸酯树脂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种水性UV固化环氧丙烯酸酯树脂及其制备方法和应用,树脂由包含以下重量份的原料制成:环氧树脂29‑36份、乳化剂2.8‑5份、丙烯酸20‑26份、催化剂、阻聚剂、水,其中乳化剂由聚乙二醇与脂肪族酸酐反应得到,环氧树脂为异氰脲酸三缩水甘油酯或二缩水甘油基异氰尿酸酯中的至少一种。本发明的乳化剂中含有亲水性非离子型聚乙二醇链段,能提高环氧丙烯酸酯在水中的分散性和稳定性,本发明的水性UV固化环氧丙烯酸酯树脂不含挥发性有机化合物,绿色环保,其固含量可达60%以上,干燥速度快,且乳液稳定性好,还具有优良的耐候性、耐高温性、耐磨性、耐腐蚀性和力学性能。
Description
技术领域
本发明属于环氧丙烯酸酯技术领域,具体涉及一种水性UV固化环氧丙烯酸酯树脂及其制备方法和应用。
背景技术
UV固化树脂-环氧丙烯酸酯具有耐化学腐蚀、硬度高等特性,广泛应用于涂料、油墨和胶黏剂等领域,适用于木材、塑料、金属、无机非金属等多种材质。传统的环氧丙烯酸酯的耐候性与耐黄变性能差、粘度高,常温下为半固态胶状,通常需要添加大量的活性稀释剂以降低涂料的施工粘度,部分未固化稀释剂残留漆膜中,不但会降低涂料的性能,也会造成成本的增加,同时对环境还会造成污染。随着环保要求日益提高,开发不含挥发性有机化合物的水稀释性UV树脂以替代现有溶剂型环氧树脂体系成为热点。
现有的水性环氧丙烯酸酯通常都会含有一定量的有机溶剂,同时固含量一般在30-50%,其干燥速度一般,限制了涂料的应用。为了提高固含量,通常需要提高乳化剂用量,易导致乳化剂残留,还降低了漆膜的耐水性能。此外,现有的水性环氧丙烯酸酯含有大量苯环,耐候性较差。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此,本发明提出一种水性UV固化环氧丙烯酸酯树脂及其制备方法和应用。
根据本发明的一个方面,提出了一种水性UV固化环氧丙烯酸酯树脂,由包含以下重量份的原料制成:环氧树脂29-36份、乳化剂2.8-5份、丙烯酸20-26份、催化剂、阻聚剂、水,其中所述乳化剂由聚乙二醇与脂肪族酸酐反应得到,所述环氧树脂为异氰脲酸三缩水甘油酯或二缩水甘油基异氰尿酸酯中的至少一种。
在本发明的一些实施方式中,所述环氧树脂为32-36份。
在本发明的一些实施方式中,所述丙烯酸为23-26份。
在本发明的一些实施方式中,所述阻聚剂为0.01-0.1份,进一步为0.03-0.09份。
在本发明的一些实施方式中,催化剂为0.01-0.1份,进一步为0.03-0.09份。
在本发明的一些实施方式中,所述水为35-43份,进一步为35-40份。
在本发明的一些实施方式中,所述原料按以下重量份计:环氧树脂32-36份、乳化剂2.8-5份、丙烯酸23-26份、催化剂0.03-0.09份、阻聚剂0.03-0.09份、水35-40份。
在本发明的一些实施方式中,所述脂肪族酸酐中酸酐与所述聚乙二醇中羟基的摩尔比为1.0-1.1。
在本发明的一些优选的实施方式中,所述丙烯酸与所述环氧树脂中环氧基的摩尔比不低于1:1。
在本发明的一些实施方式中,所述脂肪族酸酐为六氢苯酐或琥珀酸酐中的至少一种。其中六氢苯酐是个圆环结构,稳定性好、抗水解,另外无苯环结构,对紫外线不敏感,耐候性、耐高温性良好。
在本发明的一些实施方式中,所述聚乙二醇的数均分子量为800-3000。作为示例,所述聚乙二醇的分子量为1000-2000,或1500-2500,例如可以为PEG1000、PEG1500、PEG2000等。
在本发明的一些优选的实施方式中,所述水性UV固化环氧丙烯酸酯树脂的固含量≥60%。
在本发明的一些实施方式中,所述阻聚剂为对羟基苯甲醚、叔丁基邻苯二酚或甲基对苯二酚中的至少一种。
在本发明的一些实施方式中,所述催化剂为三苯基膦、苄基三乙基氯化铵或三乙胺中的至少一种。
本领域技术人员可以理解,催化剂和阻聚剂的用量可以根据经验进行调整,因而本发明中,催化剂和阻聚剂含量并不限于上述范围。水含量可以根据对固含量的要求进行调整,由于本发明的环氧丙烯酸酯树脂在水中具有良好分散稳定性,可以实现固含在60%以上。
本发明还提供所述的水性UV固化环氧丙烯酸酯树脂的制备方法,包括以下步骤:
S1:将所述聚乙二醇加热,再加入所述脂肪族酸酐进行反应,得到所述乳化剂;
S2:将部分配方量的水与环氧树脂混合,加热一段时间,再加入所述乳化剂进行反应;
S3:步骤S2反应结束后,降温,加入所述阻聚剂、催化剂和丙烯酸,再加热反应一段时间,然后降温,在搅拌下加入余下配方量的水,即得所述水性UV固化环氧丙烯酸酯树脂。
所述制备方法具有以下优点:(1)用脂肪族酸酐与聚乙二醇反应,引入的羧基相当于架桥剂,反应平稳容易控制,反应无副产物生产,无可逆反应(如不使用酸酐,直接将聚乙二醇与环氧树脂反应,其反应为可逆反应,且反应中有低分子副产物如水等产生,合成过程中需要加入大量的脱水剂把水分子脱出才有利于正反应进行);(2)乳化剂的合成过程中无需添加催化剂,设备简单;(3)工艺简单,操作容易,无副产物产生,无需脱水溶剂,产品气味低;(4)合成周期短,节约能源。
在本发明的一些实施方式中,步骤S1的过程为:将所述聚乙二醇加热至90-100℃抽真空0.5-1.5h,再降温至70-90℃,加入所述脂肪族酸酐在80-100℃下进行反应,得到所述乳化剂。
在本发明的一些实施方式中,步骤S2中,所述加热的温度为90-100℃;所述反应的温度为90-105℃。
在本发明的一些实施方式中,步骤S3中,所述加热反应的过程为:先加热至80-85℃反应1-2h,再升温至100-110℃继续反应。
本发明还提供一种涂料,所述涂料包括所述的水性UV固化环氧丙烯酸酯树脂。
本发明还提供一种涂层,所述涂层采用所述的涂料制得。
本发明还提供所述的涂料在制备木制品、石器、金属制品或塑料制品中的应用。
根据本发明的一种优选的实施方式,至少具有以下有益效果:
1、本发明的乳化剂中含有亲水性非离子型聚乙二醇链段,一定长度的聚乙二醇亲水链段能包裹环氧丙烯酸酯,具有良好的乳化能力,能提高环氧丙烯酸酯在水中的分散性和稳定性,提高固含量。进一步通过控制聚乙二醇与脂肪族酸酐的摩尔比,可以得到羧基封端的乳化剂,羧基起架桥作用,能与环氧基团反应,从而在乳化剂中引入活性基团,便于树脂固化成膜。
2、环氧树脂含氮量高,例如异氰脲酸三缩水甘油酯含氮量高达14%,具有优良的耐电弧性和自熄性,同时无苯环结构,对紫外线不敏感,耐候性、耐高温性能良好,还具有优良的耐磨性、耐腐蚀性和力学性能。
3、本发明的水性UV固化环氧丙烯酸酯树脂不含挥发性有机化合物,绿色环保,其固含量可达60%以上,干燥速度快,且乳液稳定性好。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述,以充分地理解本发明的目的、特征和效果。显然,所描述的实施例只是本发明的一部分实施例,而不是全部实施例,基于本发明的实施例,本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例,均属于本发明保护的范围。
设计水性UV固化环氧丙烯酸酯树脂的实施例与对比例配方,具体如表1所示。
表1实施例与对比例配方设计
制备方法:
(1)乳化剂合成:将聚乙二醇投入反应釜内,升温至100℃抽真空1h,再降温至80℃,加入六氢苯酐,在90℃反应1h,测得酸值为48±2mgKOH/g,合格后备用;
(2)将TGIC和配方量20%的水混合,加热至90℃保温2h,清澈透明后加入合成好的乳化剂在95℃下反应至酸值<1mgKOH/g;
(3)步骤(2)反应结束后,降温至80℃以下,加入对羟基苯甲醚、三苯基膦和丙烯酸,再缓慢加热至80-85℃反应1h,反应结束后约13℃/h升至110℃保温反应,反应至酸值<1mgKOH/g,后降温至60-65℃,高速搅拌下缓慢滴加剩下80%的水,即得水性UV固化环氧丙烯酸酯树脂。
部分反应式如下:
试验例
将实施例与对比例的水性UV固化环氧丙烯酸酯树脂加入2%的光引发剂2959,制备成涂料试样,将试样喷涂在马口铁基材上,经60℃流平3min,然后在2KW紫外灯下固化,测试漆膜性能。
1、稳定性:用离心机检测,转速3000r/min,每隔0.5h取出观察,根据乳液的分层进行评定,结果如表2所示。
表2离心稳定性
常温常压下密封静置,记录乳液出现分层的时间,结果如表3所示。
表3静置稳定性
从表2和表3可以看出,其他条件基本相同的条件下,在一定范围内随着聚乙二醇分子量增加,树脂的粒径越细,储存稳定性越好。由于乳化剂的分子量越大,亲水的链段越长,能更好地包裹环氧丙烯酸酯微粒,提高乳化效果,制得的水性环氧丙烯酸酯分散粒径更细、储存稳定。
但随着乳化剂用量进一步增加,乳液储存稳定性反而更差。对这一现象,可用相反转机理进行解释。当乳化剂浓度适当时,随着加水量的增加,有足够的乳化剂即时地扩散到新形成的水滴表面,将细小的水滴包裹,形成具有一定张力的界面膜,此时水滴间的排斥力大于水滴间的吸引力,保证水滴具有恒定的尺寸。进一步加入蒸馏水将使水滴的间距变小,吸引力急剧增加,当水含量达到某临界值时,水滴间的吸引力稍大于水滴间的排斥力,这时体系的表面张力很低,水滴在剪切作用下融合为连续相,发生相反转,形成O/W型乳液,这样得到的乳液稳定性很好,分散相微粒的尺寸较小。反之,当乳化剂浓度过高时,随着乳化剂用量的增加,所得乳胶粒的粒径变小,相界面面积增大,能量升高,根据胶体稳定性DLVO理论,乳胶粒总势能增加,乳液的化学稳定性下降。
2、硬度测定:采用铅笔硬度法,按照GB6739,选用中华铅笔,硬度范围2B-6H测定,结果如表4所示。
表4硬度测试
从表4可知,随着乳化剂分子量的增加,硬度逐渐下降,因聚乙二醇是线性结构的软链段,分子量越大,软性链段越长,硬度越低。同理,随着乳化剂用量的增加,硬度逐渐降低,因乳化剂是长链亲水基团软链段,用量越多硬度越低,反之越高。
3、耐水性测定:采用浸水试验法:(1)试样的浸泡:在玻璃容器中加入纯水,将样品放入其中,并使每件样品长度的2/3浸泡于水中,在室温下静置,直到产品标准规定的浸泡时间(48h)结束;(2)试样的检查:将试样从水中取出,用滤纸吸干,立即进行目视检查,并记录是否有失光、变色、起泡、脱落、生锈等现象。结果如表5所示。
表5耐水性测定
从表5可知,在一定范围内,随着乳化剂分子量的增加,漆膜的耐水性变差,因聚乙二醇是亲水性原料,分子量越大,亲水链段越长,耐水性下降。同理,随着乳化剂用量的增加,漆膜耐水性逐渐降低。
4、耐黄变测定:采用紫外线灯管法(灯管式耐黄变试验机),根据浅色或白色制品在紫外线长时间照射下易发生颜色黄变现象,以紫外线照射式样,在规定的时间内,观察样品表面颜色发生变化,确定样品的变色程度,从而判定材料在紫外线辐射下耐黄变的能力。使用仪器JZ-300进行检测,用△E表示总色差大小,△E越大耐黄变越差,反之越好。结果如表6所示。
表6耐黄变测定
从表6可知,随着乳化剂分子量及用量的增加,漆膜耐黄变相对稳定,说明乳化剂对漆膜耐黄变影响不大。另外说明该树脂耐候性比较好,应用领域更广泛,特别对耐候性要求较高场所。
上面对本发明实施例作了详细说明,但是本发明不限于上述实施例,在所属技术领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。此外,在不冲突的情况下,本发明的实施例及实施例中的特征可以相互组合。
Claims (10)
1.一种水性UV固化环氧丙烯酸酯树脂,其特征在于,由包含以下重量份的原料制成:环氧树脂29-36份、乳化剂2.8-5份、丙烯酸20-26份、催化剂、阻聚剂、水,其中所述乳化剂由聚乙二醇与脂肪族酸酐反应得到,所述环氧树脂为异氰脲酸三缩水甘油酯或二缩水甘油基异氰尿酸酯中的至少一种。
2.根据权利要求1所述的水性UV固化环氧丙烯酸酯树脂,其特征在于,所述脂肪族酸酐中酸酐与所述聚乙二醇中羟基的摩尔比为1.0-1.1。
3.根据权利要求1所述的水性UV固化环氧丙烯酸酯树脂,其特征在于,所述脂肪族酸酐为六氢苯酐或琥珀酸酐中的至少一种。
4.根据权利要求1所述的水性UV固化环氧丙烯酸酯树脂,其特征在于,所述聚乙二醇的数均分子量为800-3000。
5.根据权利要求1所述的水性UV固化环氧丙烯酸酯树脂,其特征在于,所述水性UV固化环氧丙烯酸酯树脂的固含量≥60%。
6.权利要求1-5任一项所述的水性UV固化环氧丙烯酸酯树脂的制备方法,其特征在于,包括以下步骤:
S1:将所述聚乙二醇加热,再加入所述脂肪族酸酐进行反应,得到所述乳化剂;
S2:将部分配方量的水与环氧树脂混合,加热一段时间,再加入所述乳化剂进行反应;
S3:步骤S2反应结束后,降温,加入所述阻聚剂、催化剂和丙烯酸,再加热反应一段时间,然后降温,在搅拌下加入余下配方量的水,即得所述水性UV固化环氧丙烯酸酯树脂。
7.根据权利要求6所述的制备方法,其特征在于,步骤S1的过程为:将所述聚乙二醇加热至90-100℃抽真空0.5-1.5h,再降温至70-90℃,加入所述脂肪族酸酐在80-100℃下进行反应,得到所述乳化剂。
8.一种涂料,其特征在于,所述涂料包括如权利要求1-5任一项所述的水性UV固化环氧丙烯酸酯树脂。
9.一种涂层,其特征在于,所述涂层采用如权利要求8所述的涂料制得。
10.如权利要求8所述的涂料在制备木制品、石器、金属制品或塑料制品中的应用。
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101397363A (zh) * | 2008-08-19 | 2009-04-01 | 东莞市佳景印刷材料有限公司 | 一种水性紫外光固化环氧丙烯酸酯接枝聚氨酯及其制备方法 |
CN101831053A (zh) * | 2010-04-26 | 2010-09-15 | 浙江顺虎德邦涂料有限公司 | 一种水性紫外光固化环氧丙烯酸酯树脂及其制备方法 |
CN102587201A (zh) * | 2012-02-01 | 2012-07-18 | 苏州大学 | Uv固化纳米杂化环氧丙烯酸酯乳液纸张上光涂料及制法 |
CN102675528A (zh) * | 2012-05-24 | 2012-09-19 | 上海中新裕祥化工有限公司 | Uv固化水性脂环族环氧丙烯酸酯乳液 |
CN104356359A (zh) * | 2014-10-27 | 2015-02-18 | 上海应用技术学院 | 一种可uv固化水性环氧丙烯酸酯树脂及制备方法 |
CN105693999A (zh) * | 2016-04-19 | 2016-06-22 | 深圳职业技术学院 | 一种紫外光固化水性阳离子树脂及其制备方法 |
WO2017020513A1 (zh) * | 2015-07-31 | 2017-02-09 | 华南理工大学 | 一种羟基聚丙烯酸酯乳液及其制备方法与应用 |
CN111690151A (zh) * | 2020-06-10 | 2020-09-22 | 华南理工大学 | 一种水性uv固化环氧丙烯酸酯乳液的制备方法 |
-
2022
- 2022-04-29 CN CN202210464445.XA patent/CN114853982B/zh active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101397363A (zh) * | 2008-08-19 | 2009-04-01 | 东莞市佳景印刷材料有限公司 | 一种水性紫外光固化环氧丙烯酸酯接枝聚氨酯及其制备方法 |
CN101831053A (zh) * | 2010-04-26 | 2010-09-15 | 浙江顺虎德邦涂料有限公司 | 一种水性紫外光固化环氧丙烯酸酯树脂及其制备方法 |
CN102587201A (zh) * | 2012-02-01 | 2012-07-18 | 苏州大学 | Uv固化纳米杂化环氧丙烯酸酯乳液纸张上光涂料及制法 |
CN102675528A (zh) * | 2012-05-24 | 2012-09-19 | 上海中新裕祥化工有限公司 | Uv固化水性脂环族环氧丙烯酸酯乳液 |
CN104356359A (zh) * | 2014-10-27 | 2015-02-18 | 上海应用技术学院 | 一种可uv固化水性环氧丙烯酸酯树脂及制备方法 |
WO2017020513A1 (zh) * | 2015-07-31 | 2017-02-09 | 华南理工大学 | 一种羟基聚丙烯酸酯乳液及其制备方法与应用 |
CN105693999A (zh) * | 2016-04-19 | 2016-06-22 | 深圳职业技术学院 | 一种紫外光固化水性阳离子树脂及其制备方法 |
CN111690151A (zh) * | 2020-06-10 | 2020-09-22 | 华南理工大学 | 一种水性uv固化环氧丙烯酸酯乳液的制备方法 |
Non-Patent Citations (1)
Title |
---|
王渴望;曲文娟;王杰;李少香;: "环氧丙烯酸酯无皂核-壳乳液的合成及其性能", 电镀与涂饰, no. 14 * |
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