CN106243887A - 一种耐寒水性聚丙烯酸酯可剥涂料及其制备方法 - Google Patents
一种耐寒水性聚丙烯酸酯可剥涂料及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种耐寒水性聚丙烯酸酯可剥涂料及其制备方法,所述涂料的原料按重量份包括:聚合单体35‑55份,引发剂0.003‑0.005份,乳化剂2~5份,无机填料5~10份,增稠剂0.5~1份;总量为100份,余量为水。制备方法包括:将丙烯酸丁酯,丙烯酸或甲基丙烯酸和乳化剂加到水中搅拌混匀,预乳化,加入引发剂搅拌,得混合乳液;将引发剂,乳化剂,甲基丙烯酸甲酯和水混合,搅拌加热至80℃,至发出蓝光滴加混合乳液,保温,调节pH,加无机填料,搅拌溶解,降温,过滤出料并加入增稠剂。本发明的产品成膜后在较低的温度下仍具有优良的可剥性能,可在聚氨酯漆面上大面积剥落;产品涂膜耐酸耐碱,透气性良好。
Description
技术领域
本发明属于涂料及制备领域,特别涉及一种耐寒水性聚丙烯酸酯可剥涂料及其制备方法。
背景技术
可剥离涂料是一种新型优质的表面保护膜,具有制备工艺简单、防护性能好、后处理方便等优点,广泛用于对精密零件、仪表、电子设备等器件的表面保护。水性可剥离涂料的出现顺应了消费者对环保的要求,避免使用大量挥发性有机物。因而水性可剥离涂料的研究对国家科技发展、社会的进步都有十分重要的意义,是近年被广泛关注的领域之一。
聚丙烯酸酯乳液是水性涂料中的一种。聚丙烯酸酯乳液以水为分散介质,不仅具有环保无污染、原料来源广泛、反应条件温和等优点,而且其乳胶膜柔韧性好、透明性高等,广泛应用于建筑、汽车、电子电器、皮革、书籍、织物及医用高分子等众多领域。但是聚丙烯酸酯乳液也存在一些缺点,如其乳胶膜耐水耐油性差、耐候性差、力学性能差,难以满足高性能领域的要求,成为限制其进一步应用的主要因素。
可剥涂料实际应用中会出现比较寒冷的情况,比如2015-2016年冬春的这场大寒潮。这就要求涂料要具有较强的耐寒性能,在寒冷的情况下不开裂且仍然可剥。目前关于涂料耐寒的性能研究及产品报道比较少。
发明内容
本发明所要解决的技术问题是提供一种耐寒水性聚丙烯酸酯可剥涂料及其制备方法,该方法得到的涂料为无毒无污染,耐寒性极好,可大面积剥落的水性可剥涂料;产品耐酸耐碱,且透气性良好。
本发明的一种耐寒水性聚丙烯酸酯可剥涂料,所述涂料的原料按重量份包括:聚合单体35-55份,引发剂0.003-0.005份,乳化剂2~5份,无机填料5~10份,增稠剂0.5~1份;总量为100份,余量为水;其中,聚合单体为甲基丙烯酸甲酯、丙烯酸丁酯和甲基丙烯酸或丙烯酸。
所述涂料是以甲基丙烯酸甲酯为核,其余单体为壳的硬核软壳结构。
所述丙烯酸丁酯、甲基丙烯酸甲酯和丙烯酸或甲基丙烯酸的质量比为50-70:40-60:10。
所述乳化剂为十二烷基硫酸钠、十二烷基磺酸钠和OP-10中的至少一种。
所述无机填料为硬脂酸锌、二氧化钛或硫酸钡。
所述增稠剂为聚氨酯、聚丙烯酸分散体或羟基纤维素。
本发明的一种耐寒水性聚丙烯酸酯可剥涂料的制备方法,包括:
(1)将丙烯酸丁酯、丙烯酸或甲基丙烯酸和部分乳化剂加入到水中搅拌混匀;然后进行预乳化,然后加入部分引发剂继续搅拌,得到混合乳液;
(2)将剩余引发剂、剩余乳化剂、甲基丙烯酸甲酯和水加入到反应容器中混合,搅拌加热至80℃,至反应溶液发出蓝光滴加(1)中的混合乳液,保温2-3小时,调节乳液pH为7~9,加入无机填料,继续搅拌至溶解,然后将乳液降温到常温,用200目的筛子后过滤出料并加入增稠剂(聚氨酯或聚丙烯酸分散体或羟基纤维素);
上述各原料的加入量按重量份为:聚合单体35-55份,引发剂0.003-0.005份,乳化剂2~5份,无机填料5~10份,增稠剂0.5~1份;总量为100份,余量为水;其中,聚合单体为甲基丙烯酸甲酯,丙烯酸丁酯和甲基丙烯酸或丙烯酸;
步骤(1)中乳化剂的加入量为乳化剂总量的2/3;步骤(2)中乳化剂的用量为乳化剂总用量的1/3;步骤(1)中引发剂过硫酸钾用量为引发剂总用量2/3;步骤(2)中引发剂过硫酸钾用量为引发剂总用量1/3。
所述预乳化的条件为:先超声10-20min,然后用高速分散均质机在1000r/min搅拌0.5-1min。
本发明中水性聚丙烯酸酯乳液由丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸甲酯和丙烯酸,通过核壳半连续反应聚合而成;以硬单体甲基丙烯酸甲酯为核,其余软单体为壳,形成硬核软壳的结构,产品成膜后能在较低的温度下保持涂膜的性能不变化,仍具有优良的可剥性能,可在聚氨酯漆面上大面积剥落。本发明产品涂膜耐酸耐碱,透气性良好。
有益效果
(1)本发明所制备的涂料成膜后耐寒性极佳,在-20℃下放置72h以上,涂膜依旧完整无损,没有起泡泛白或开裂,并且还能被完整剥落。
(2)产品施工方便,与基材结合力适中,实际应用在聚氨酯漆面上,经过寒冷天气后,可以被大面积剥落,基材表面没有残胶,且对基材表面没有破坏作用;
(3)所制备的涂料成膜后耐酸耐碱,透气性良好。长时间浸泡在酸液和碱液中,涂膜没有出现起泡,发皱,脱落的现象。
(4)本发明采用预乳化半连续工艺制备了聚丙烯酸酯乳液,形成以硬单体(甲基丙烯酸甲酯)为核,软单体为壳的核壳结构;具有操作简单、环境友好,可大量生产以及成本低的特点。
附图说明
图1是实施例1产品在聚氨酯漆面涂膜后经过寒冷天气(-5℃—-15℃)后被大面积剥落的实际应用情况图片;
图2是实施例1产品常温静置储存稳定性图片(乳液静置储存3个月);
图3是实施例2产品的分别涂在惰性基材表面(A)和聚氨酯漆面(B)的涂膜红外谱图;
图4是实施例3产品涂膜耐酸性试验的图片;
图5是实施例3产品涂膜耐低温试验(-20℃放置72h)的图片。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围
实施例中丙烯酸丁酯密度为0.8975g/ml,丙烯酸密度为1.0495g/ml,苯乙烯密度为0.9g/ml,甲基丙烯酸甲酯密度为0.9395g/ml。
实施例1
取15.59ml丙烯酸丁酯、2.40ml丙烯酸、1.00g十二烷基硫酸钠和25ml去离子水加入烧杯中混合均匀,然后通过超声20min、高速分散均质机搅拌1min(1000r/min)进行预乳化;然后加入0.24g过硫酸钾继续搅拌,得到混合乳液。
在三角烧瓶中加入10ml水、9.65ml甲基丙烯酸甲酯0.5g十二烷基硫酸钠和0.12g过硫酸钾,搅拌加热至80℃,反应溶液出现蓝光时开始滴加上述混合乳液,控制在2-3h内滴加完成。
滴加完毕后保温2h,用氨水调节pH至7.5,加入3.50g硬脂酸锌,搅拌至溶解,然后降温至室温后用200目的筛子后过滤,出料并加入0.45g聚氨酯,得到耐寒水性聚丙烯酸酯可剥涂料。
将涂料喷涂到样板上,在室温中静置2h干燥。
图1是本实施例产品在聚氨酯漆面涂膜后经过寒冷天气(-5℃—-15℃)后被大面积剥落的实际应用情况图片;图2是本实施例中产品常温静置储存稳定性图片(乳液静置储存3个月)。
实施例2
取15.59ml丙烯酸丁酯、2.40ml丙烯酸、0.60g十二烷基硫酸钠和0.40g OP-10和25ml去离子水加入烧杯中混合均匀,然后通过超声20min、高速分散均质机搅拌(1000r/min)1min进行预乳化;然后加入0.24g过硫酸钾继续搅拌,得到混合乳液。
在三角烧瓶中加入10ml水、9.65ml甲基丙烯酸甲酯、0.30g十二烷基硫酸钠和0.20gOP-10和0.12g过硫酸钾,搅拌加热至80℃,反应溶液出现蓝光时开始滴加上述混合乳液,控制在2-3h内滴加完成。
滴加完毕后保温2h,用氨水调节pH至7.5,加入3.50g硬脂酸锌,搅拌至溶解,然后降温至室温后用200目的筛子后过滤,出料并加入0.45g聚丙烯酸分散体,得到耐寒水性聚丙烯酸酯可剥涂料。
将涂料喷涂到样板上,在室温中静置2h干燥。
图3是本实施例产品分别涂在惰性基材表面(A)和聚氨酯漆面(B)的涂膜的红外谱图。根据谱图所示,在1640cm-1—1680cm-1没有C=C键典型的伸缩振动吸收峰;在1727cm-1是聚丙烯酸酯中C=O典型的伸缩振动吸收峰;在1453cm-1、1494cm-1、1581cm-1、1602cm-1是苯环四个强度不等的特征峰;所以根据红外谱图分析合成了聚丙烯酸酯乳液。根据两个谱图的比较,涂膜在惰性基材表面和聚氨酯漆表面的红外谱图基本一致,说明本产品对聚氨酯漆面没有破坏影响作用。
实施例3
取15.59ml丙烯酸丁酯、2.40ml丙烯酸、1.00g十二烷基硫酸钠和25ml去离子水加入烧杯中混合均匀,然后通过超声20min、高速分散均质机搅拌(1000r/min)1min进行预乳化;然后加入0.24g过硫酸钾继续搅拌,得到混合乳液。
在三角烧瓶中加入10ml水、9.65ml甲基丙烯酸甲酯、0.5g十二烷基硫酸钠和0.12g过硫酸钾,搅拌加热至80℃,反应溶液出现蓝光时开始滴加上述混合乳液,控制在2-3h内滴加完成。
滴加完毕后保温2h,用氨水调节pH至7.5,加入3.50g二氧化钛,搅拌至溶解,然后降温至室温后用200目的筛子后过滤,出料并加入0.45g羟基纤维素,得到耐寒水性聚丙烯酸酯可剥涂料。
将涂料喷涂到样板上,在室温中静置2h干燥。
图4是本实施例产品涂膜耐酸性试验的图片;图5是本实施例产品涂膜耐低温试验(-20℃放置72h)的图片。
实施例4
取15.59ml丙烯酸丁酯、2.40ml甲基丙烯酸、1.00g十二烷基硫酸钠和25ml去离子水加入烧杯中混合均匀,然后通过超声20min、高速分散均质机搅拌(1000r/min)1min进行预乳化;然后加入0.24g过硫酸钾继续搅拌,得到混合乳液。
在三角烧瓶中加入10ml水、9.65ml甲基丙烯酸甲酯、0.5g十二烷基硫酸钠和0.12g过硫酸钾,搅拌加热至80℃,反应溶液出现蓝光时开始滴加上述混合液,控制在2-3h内滴加完成。
滴加完毕后保温2h,用氨水调节pH至7.5,加入3.50g二氧化钛,搅拌至溶解,然后降温至室温后用200目的筛子后过滤,出料并加入0.50g羟基纤维素,得到耐寒水性聚丙烯酸酯可剥涂料。
将涂料喷涂到样板上,在室温中静置2h干燥。
对上述实施例1~实施例4中得到的产品进行性能测试,如下。
表1为实施例1-4的涂膜的断裂强度和断裂伸长率:
表1
实施例 | 1 | 2 | 3 | 4 |
断裂强度/MPa | 9.83 | 11.04 | 9.37 | 12.61 |
断裂伸长率/% | 1012 | 998 | 1005 | 986 |
表2为实施例1-4的乳液粒径:
表2
实施例 | 1 | 2 | 3 | 4 |
粒径/nm | 89 | 88 | 87 | 84 |
PDI | 0.066 | 0.037 | 0.065 | 0.04 |
对上述实施例制备的涂膜进行以下性能测试:
A.剥离性实验:考察涂膜是否容易剥离。
◎易于剥离;○剥离性良好;Δ剥离较难;×不能剥离
B.耐酸实验:将40%的硫酸滴在涂膜上保持12小时后,观察有无腐蚀痕迹。
◎有腐蚀痕迹;×无腐蚀痕迹
C.耐碱性实验:将0.1标准浓度的氢氧化钠滴在涂膜上保持12小时,然后观察有无腐蚀痕迹。
◎有腐蚀痕迹;×无腐蚀痕迹
D.耐水实验:将涂膜浸泡在去离子水中24h,观察涂膜有没有起泡开裂,是否易于剥离。
◎无起泡开裂,易于剥离;○无起泡开裂,剥离性良好;
×起泡、开裂或者不能剥离
E.耐低温实验,将涂膜放置-20℃72h试验,观察涂膜是否开裂及易于剥离。
◎不开裂,易于剥离;×开裂或者不能剥离
实施例1-4的试验结果如下面表3所示:
表3
试验 | A | B | C | D | E |
实施例1 | ◎ | ○ | ○ | ◎ | ○ |
实施例2 | ◎ | ○ | ○ | ○ | ◎ |
实施例3 | ○ | ◎ | ○ | ○ | ◎ |
实施例4 | ○ | ○ | ◎ | ◎ | ○ |
Claims (9)
1.一种耐寒水性聚丙烯酸酯可剥涂料,其特征在于,所述涂料的原料按重量份包括:聚合单体35-55份,引发剂0.003-0.005份,乳化剂2~5份,无机填料5~10份,增稠剂0.5~1份;总量为100份,余量为水;其中,聚合单体为甲基丙烯酸甲酯、丙烯酸丁酯和甲基丙烯酸或丙烯酸。
2.根据权利要求1所述的一种耐寒水性聚丙烯酸酯可剥涂料,其特征在于,所述涂料是以甲基丙烯酸甲酯为核,其余单体为壳的硬核软壳结构。
3.根据权利要求1所述的一种耐寒水性聚丙烯酸酯可剥涂料,其特征在于,所述丙烯酸丁酯、甲基丙烯酸甲酯和丙烯酸或甲基丙烯酸的质量比为50-70:40-60:10。
4.根据权利要求1所述的一种耐寒水性聚丙烯酸酯可剥涂料,其特征在于,所述引发剂为过硫酸钾。
5.根据权利要求1所述的一种耐寒水性聚丙烯酸酯可剥涂料,其特征在于,所述乳化剂为十二烷基硫酸钠、十二烷基磺酸钠和OP-10中的至少一种。
6.根据权利要求1所述的一种耐寒水性聚丙烯酸酯可剥涂料,其特征在于,所述无机填料为硬脂酸锌、二氧化钛或硫酸钡。
7.根据权利要求1所述的一种耐寒水性聚丙烯酸酯可剥涂料,其特征在于,所述增稠剂为聚氨酯、聚丙烯酸分散体或羟基纤维素。
8.一种耐寒水性聚丙烯酸酯可剥涂料的制备方法,包括:
(1)将丙烯酸丁酯、丙烯酸或甲基丙烯酸和部分乳化剂加入到水中搅拌混匀;然后进行预乳化,然后加入部分引发剂继续搅拌,得到混合乳液;
(2)将剩余引发剂、剩余乳化剂、甲基丙烯酸甲酯和水混合,搅拌加热至80℃,至反应溶液发出蓝光滴加(1)中的混合乳液,保温2-3小时,调节乳液pH为7~9,加入无机填料,继续搅拌至溶解,然后将乳液降温到常温,过滤出料并加入增稠剂;
上述各原料的加入量按重量份为:聚合单体35-55份,乳化剂2~5份,无机填料5~10份,增稠剂0.5~1份;总量为100份,余量为水;其中,聚合单体为甲基丙烯酸甲酯,丙烯酸丁酯和甲基丙烯酸或丙烯酸。
9.根据权利要求8所述的一种耐寒水性聚丙烯酸酯可剥涂料的制备方法,其特征在于,所述预乳化的条件为:先超声10-20min,然后1000r/min搅拌0.5-1min。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030094592A1 (en) * | 2001-11-12 | 2003-05-22 | Rolf Gertzmann | Emulsion polymers and their use as peelable coatings |
CN101768403A (zh) * | 2009-12-22 | 2010-07-07 | 北京航材百慕新材料技术工程股份有限公司 | 水性透明可剥离防护涂料 |
CN102199239A (zh) * | 2010-03-24 | 2011-09-28 | 东莞大宝化工制品有限公司 | 一种自交联核壳结构丙烯酸微乳液的制备方法 |
CN104962161A (zh) * | 2015-07-15 | 2015-10-07 | 张子健 | 一种水性可剥离涂料 |
-
2016
- 2016-08-04 CN CN201610632547.2A patent/CN106243887B/zh not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030094592A1 (en) * | 2001-11-12 | 2003-05-22 | Rolf Gertzmann | Emulsion polymers and their use as peelable coatings |
CN101768403A (zh) * | 2009-12-22 | 2010-07-07 | 北京航材百慕新材料技术工程股份有限公司 | 水性透明可剥离防护涂料 |
CN102199239A (zh) * | 2010-03-24 | 2011-09-28 | 东莞大宝化工制品有限公司 | 一种自交联核壳结构丙烯酸微乳液的制备方法 |
CN104962161A (zh) * | 2015-07-15 | 2015-10-07 | 张子健 | 一种水性可剥离涂料 |
Non-Patent Citations (1)
Title |
---|
甘孟瑜等: "核壳结构丙烯酸酯乳液的合成及性能研究", 《涂料工业》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113004758A (zh) * | 2020-12-29 | 2021-06-22 | 东华大学 | 一种核-壳型丙烯酸酯可剥涂料及其制备方法 |
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