CN111471385B - 一种除甲醛的水性环保涂料及其制备方法 - Google Patents
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Abstract
本发明属于涂料领域,具体涉及一种除甲醛的水性环保涂料,按照重量份数计算,每100份包含,除醛水性聚氨酯乳液10‑50份、水性丙烯酸树脂10‑30份、钛白粉5‑8份、滑石粉3‑5份、分散剂0.1‑0.5份、成膜助剂2‑5份、流变助剂0.1‑1份、消泡剂0.1‑0.3份、增稠剂0.1‑1份、防腐剂0.1‑0.5份、硅烷偶联剂0.5‑2份和去离子水余量。本发明的有益效果是:本发明中除甲醛的水性涂料的主要成分是除醛水性聚氨酯乳液,是通过化学反应在水性聚氨酯树脂中引入可以与甲醛反应的活性基团。同时,由于中和剂的加入,是聚合物乳液呈弱碱性,使咪唑衍生物的活性基团可与甲醛进行高效反应,同时在整个反应过程中可以抑制甲醛的产生。
Description
技术领域
本发明属于涂料领域,具体涉及一种除甲醛的水性环保涂料及其制备方法。
背景技术
目前,随着经济的迅速发展,人们对生活品质的追求也越来越高,家庭装修也越来越被重视。但在家庭装修中,各种装修材料带来的挥发性有机化学物质造成家装污染和室内有害物质超标,对人体造成一定干扰。甲醛是这些挥发性有机化学物质中毒性较大,难以去除的一种。人体长期处于这种含有甲醛的空气中,会引起各种疾病,严重的还会危及到人体的生命安全。甲醛已被列为我国建筑装饰工程强制执行的检测项目,不同国家对甲醛的达标浓度的规定不同。国标GB/T18883-2002《室内空气质量标准》规定室内甲醛达标浓度为0.1mg/m3,GB50325-2001《民用建筑工程室内环境污染控制规范》规定一类民用建筑的甲醛达标浓度为0.08mg/m3,二类民用建筑的甲醛的达标浓度为0.12mg/m3。因此,很多化工人员都在研究如何从源头上消除甲醛的引入,同时在研究如何长期持续的消除缓慢释放的游离甲醛。
为了降低有机物的挥发,大部分室内油漆被水性涂料代替,但是普通水性涂料干燥后仍会有甲醛的释放。
发明内容
为了解决上述问题,本发明的目的是提供一种除甲醛的水性环保涂料及其制备方法,来解决除醛效率低,时效短等问题。
本发明提供了如下的技术方案:
一种除甲醛的水性环保涂料,按照重量份数计算,每100份包含,
优选的,所述除醛水性聚氨酯乳液制备方法如下:以水性聚氨酯中非水性和非溶剂性组分的质量为基准,将按该基准质量30%-60%的大分子二元醇、环氧树脂在100-120℃脱水0.5-1h、再按该基准质量加入15%-40%的二异氰酸酯和0.01-0.08%的催化剂,在60-100℃反应2-4h后再按该基准质量加入3-10%小分子二元醇、4-8%的亲水扩链剂、10-30%的咪唑衍生物、0.5-3%交联剂和10-50%丙酮或丁酮,在65-80℃反应1-4h后降温至0-40℃,加入3-7%中和剂搅拌至pH为7-9,在1200rpm剪切搅拌下再加入该基准质量200-400%的水,搅拌反应5-30min后在40-50℃、0.01-0.03MPa真空条件下除去溶剂,得到主链中含有大量咪唑衍生物的除醛水性聚氨酯乳液。
优选的,所述大分子二元醇选自苯酐聚酯二元醇(APP)、聚丙二醇(PPG)、聚己二酸-1,4-丁二醇酯二醇(PBA)、聚己内酯二元醇(PCL)、聚碳酸酯二元醇(PCDL)或聚四氢呋喃醚二元醇(PTMG)中的任意一种或多种;
所述环氧树脂为E44、E20或E51的任意一种或多种。
优选的,所述二异氰酸酯选自异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)中的任意一种或多种;
所述催化剂选自二月桂酸二丁基锡(DBTDL)、异辛酸铋、有机铋(DY-20)中的一种或多种。
优选的,所述小分子二元醇扩链剂选自乙二醇(EG)、1,4-丁二醇(BDO)、新戊二醇(NPG)、1,6-己二醇(HDO)或一缩二乙二醇(DEG)中的一种或多种;
所述亲水扩链剂选自二羟甲基丙酸(DMPA)或酒石酸(TA)中的任意一种或多种。
优选的,所述交联剂选自三羟甲基丙烷(TMP)、季戊四醇(PER)、蓖麻油、甘油中的任意一种或多种;
所述中和剂选用氢氧化钠、氢氧化钾、三乙胺中的任意一种或几种。
优选的,所述咪唑结构式如下:
其中R1为:任选被O、S、H取代的C1-C4烷基或任选被O、S、H取代的C1-C4链烯基不包括C1的链烯基或任选被O、S、H取代的C1-C4的链炔基不包括C1的链炔基;
R2为:任选被O、S、H取代的C1-C4烷基或任选被O、S、H取代的C1-C4链烯基不包括C1的链烯基或任选被O、S、H取代的C1-C4的链炔基不包括C1的链炔基。
优选的,所述分散剂选自帝司巴隆的AQ320、AQ340、AQ360、AQ380或者德国毕克的BYK-180、BYK-110、BYK-111或迪高的740W、760W的中的任意一种或多种;
所述成膜助剂选自选自陶氏的二丙二醇丁醚(DPnB)、二丙二醇甲醚(DPM)中任意一种或两种;
所述流变助剂选自德国毕克的BYK-333、BYK-349或者赢创迪高TEGO GLIDE 450、TEGO GLIDE 425、TEGO GLIDE 100中一种或两种。
优选的,所述消泡剂选自深竹化工的SN5710、SN5702、SN6725或迪高的TEGO902W、TEGO800W、TEGO805W中的任意一种或多种;
所述增稠剂选自德国明凌公司的TAFIGEL PUR 64、TAFIGEL AP20或罗门哈斯公司的ACRYSOL RM 8W、ACRYSOL 12W、ACRYSOL 5000与ACRYSOL RM2020NPR中的任意一种或多种;
所述防腐剂选自蓝盾生物科技的BAC-106D、BAC-86D、陶氏LXE中任意一种或两种;
所述硅烷偶联剂选自KH-550、KH-560、KH-570和KH-792中的任意一种或多种。
本发明还提供一种除甲醛的水性环保涂料的制备方法,将除醛水性聚氨酯乳液、水性丙烯酸树脂、钛白粉、滑石粉、分散剂和水按照配比均匀混合后,在2000-3000转/min高速搅拌分散20-40min,预分散至细度达到20微米以内后,按照配比加入成膜助剂、流变助剂、消泡剂、防腐剂、增稠剂、硅烷偶联剂及余量的水,1000-2000转/min的转速分散20-40min,搅拌均匀后即可
本发明的有益效果是:
1、本发明中除甲醛的水性涂料的主要成分是除醛水性聚氨酯乳液,是通过化学反应在水性聚氨酯树脂中引入可以与甲醛反应的活性基团。同时,由于中和剂的加入,是聚合物乳液呈弱碱性,使咪唑衍生物的活性基团可与甲醛进行高效反应,同时在整个反应过程中可以抑制甲醛的产生。
2、本发明中除醛水性聚氨酯是一种用环氧树脂改性的水性聚氨酯使水性涂料具有环氧树脂的高耐性、高黏结性及高强度。
3、本发明制备的除醛水性聚氨酯是植物油改性的水性聚氨酯,植物油具有度羟基结构,易与异氰酸酯反应形成互穿网状结构,使其具有极佳的耐热性能和机械性能。同时长链烷烃结构引入水性聚氨酯结构可以提高其疏水性,从而提高其耐水性。
4、本发明的除醛水性聚氨酯可以与水性丙烯酸乳液搭配使用来提高涂料的保色性、光稳定性、硬度。但是水性丙烯酸乳液与水性聚氨酯乳液物理掺混时相容性较差,为了改善两者的相容性,我们添加少量硅烷偶联剂来实现两者的化学交联,从而提高其稳定性。
5、本发明制备的除醛水性涂料制备工艺简单、成本低、性能极佳、除醛效果极佳。
具体实施方式
下面结合具体实施例对本发明做具体说明。
实施例1
将数均分子量Mn为2000的PCDL 40g,Mn为2000的PPG 10g,6g环氧树脂E44在110℃下脱水30min后冷却至50℃,取42g IPDI加入到500毫升的三口烧瓶中,再加入22g TDI,搅拌并升温至75℃反应2h后,加入10g DMPA、0.02g DBTDL、8.0g NPG、3.0g TMP、7.5g咪唑衍生物及20g丙酮,恒温在70℃搅拌反应4h后降温至40℃,加入三乙胺搅拌调节pH至8.0左右,在高速剪切搅拌下再加入基准质量260g的水,搅拌20min后在40–50℃、0.01MPa真空条件下除去溶剂,得到除醛水性聚氨酯乳液1#。
实施例2
将数均分子量Mn为2000的PCDL 40g,Mn为2000的PPG 10g,6g环氧树脂E44在110℃下脱水30min后冷却至50℃,取42g IPDI加入到500毫升的三口烧瓶中,再加入22g TDI,搅拌并升温至75℃反应2h后,加入10g DMPA、0.02g DBTDL、5.5gNPG、3.0gTMP、15g咪唑衍生物及20g丙酮,恒温在70℃搅拌反应4h后降温至40℃,加入三乙胺搅拌调节pH至8.0左右,在高速剪切搅拌下再加入基准质量260g的水,搅拌20min后在40–50℃、0.01MPa真空条件下除去溶剂,得到除醛水性聚氨酯乳液2#。
实施例3
将数均分子量Mn为2000的PCDL 40g,Mn为2000的PPG 10g,6g环氧树脂E44在110℃下脱水30min后冷却至50℃,取42g IPDI加入到500毫升的三口烧瓶中,再加入22g TDI,搅拌并升温至75℃反应2h后,加入10g DMPA、0.02g DBTDL、3.0g NPG、3.0g TMP、22.5g咪唑衍生物及20g丙酮,恒温在70℃搅拌反应4h后降温至40℃,加入三乙胺搅拌调节pH至8.0左右,在高速剪切搅拌下再加入基准质量260g的水,搅拌20min后在40–50℃、0.01MPa真空条件下除去溶剂,得到除醛水性聚氨酯乳液3#。
实施例4
将数均分子量Mn为2000的PCDL 40g,Mn为2000的PPG 10g,6g环氧树脂E44在110℃下脱水30min后冷却至50℃,取42g IPDI加入到500毫升的三口烧瓶中,再加入22g TDI,搅拌并升温至75℃反应2h后,加入10g DMPA、0.02g DBTDL、1.0g NPG、2.0g TMP、30g咪唑衍生物及20g丙酮,恒温在70℃搅拌反应4h后降温至40℃,加入三乙胺搅拌调节pH至8.0左右,在高速剪切搅拌下再加入基准质量260g的水,搅拌20min后在40–50℃、0.01MPa真空条件下除去溶剂,得到除醛水性聚氨酯乳液4#。
实施例5
将数均分子量Mn为2000的PCDL 40g,Mn为2000的PPG 10g,6g环氧树脂E44在110℃下脱水30min后冷却至50℃,取42g IPDI加入到500毫升的三口烧瓶中,再加入22g TDI,搅拌并升温至75℃反应2h后,加入10g DMPA、0.02g DBTDL、4.0g NPG、2.0g TMP、5.0g蓖麻油、20g咪唑衍生物及20g丙酮,恒温在70℃搅拌反应4h后降温至40℃,加入三乙胺搅拌调节pH至8.0左右,在高速剪切搅拌下再加入基准质量260g的水,搅拌20min后在40–50℃、0.01MPa真空条件下除去溶剂,得到除醛水性聚氨酯乳液5#。
实施例6
将数均分子量Mn为2000的PCDL 40g,Mn为2000的PPG 10g,6g环氧树脂E44在110℃下脱水30min后冷却至50℃,取42g IPDI加入到500毫升的三口烧瓶中,再加入22g TDI,搅拌并升温至75℃反应2h后,加入10g DMPA、0.02g DBTDL、8.0g NPG、2.0g TMP、10g蓖麻油及20g丙酮,恒温在70℃搅拌反应4h后降温至40℃,加入三乙胺搅拌调节pH至8.0左右,在高速剪切搅拌下再加入基准质量260g的水,搅拌20min后在40–50℃、0.01MPa真空条件下除去溶剂,得到除醛水性聚氨酯乳液6#。
除甲醛的水性环保涂料的制备
在分散桶中依次加入100g除醛水性聚氨酯乳液1#、100g水性丙烯酸树脂,80g钛白粉、40g滑石粉、2g分散剂迪高740W,50g水2000转/min高速搅拌分散30min,进行预分散。刮板当细度达到20微米以内后,再加入250g除醛水性聚氨酯1#,250g水性丙烯酸树脂,20g流变助剂BYK-333、20g消泡剂迪高902W、10g防腐剂陶氏LXE、20g增稠剂PUR 64、50g硅烷偶联剂KH-560及余量的水,1000转/min的转速分散30min,搅拌均匀后,制备得到除醛水性涂料1#。
按照上述同样的方法,将除醛水性聚氨酯乳液1#换成水性聚氨酯乳液2#,制备得到除甲醛的水性环保涂料2#。
按照上述同样的方法,将除醛水性聚氨酯乳液1#换成水性聚氨酯乳液3#,制备得到除甲醛的水性环保涂料3#。
按照上述同样的方法,将除醛水性聚氨酯乳液1#换成水性聚氨酯乳液4#,制备得到除甲醛的水性环保涂料4#。
按照上述同样的方法,将除醛水性聚氨酯乳液1#换成水性聚氨酯乳液5#,制备得到除甲醛的水性环保涂料5#。
按照上述同样的方法,将市售普通水性聚氨酯乳液换成水性聚氨酯乳液6#,制备得到除甲醛的水性环保涂料6#。
结果与检测
准备6个相同的密封容器,容器内加入甲醛源使甲醛浓度达到120mg/m2,在6个容器内分别放入相应地的除甲醛的水性环保涂料,其清除效果如表1,表1中的序号分别对应6个容器,清除试剂对应于所放置的除甲醛涂料的种类,每个容器放置水性涂料的重量一样,按有效量10g/m2,其中实施例1-6均对应于本发明中的实施例1-6。
表1不同的除甲醛水性涂料的除甲醛情况
编号 | 3h(mg/m<sup>2</sup>) | 12h(mg/m<sup>2</sup>) | 24h(mg/m<sup>2</sup>) |
1# | 90.8 | 60.5 | 48.9 |
2# | 82.4 | 53.6 | 38.1 |
3# | 68.7 | 29.7 | 10.8 |
4# | 64.2 | 24.6 | 8.2 |
5# | 70.2 | 30.4 | 11.2 |
6# | 102.5 | 82.7 | 52.8 |
从表1可知,1#-6#均能达到去除甲醛的效果,其中效果比较好的是3#-5#,效果最佳的3#在24小时内甲醛浓度仅为8.2mg/m2。
根据GB/T1723-93、GB/T 1724-89、GB/T 1731-93、GB/T 1732-93、GB/T1733-93、GB/T 1734-93标准来评定1-6#水性涂料的性能,结果列于表2。
表2不同的除甲醛水性涂料的性能结果
从表2中可知,1#-6#的储存状态、耐盐水性、耐湿热性均具有优良的效果,除甲醛效果最好的3#在耐弯曲性上效果一般。
结合表1、2可知:本发明制备的除甲醛的水性环保涂料5#具有最佳的综合性能,随着咪唑衍生物比例的升高,除醛效率增加,但增加到30%时会影响涂料的部分性能。
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种除甲醛的水性环保涂料,其特征在于,按照重量份数计算,每100份包含,
除醛水性聚氨酯乳液 10-50份
水性丙烯酸树脂 10-30份
钛白粉 5-8份
滑石粉 3-5份
分散剂 0.1-0.5份
成膜助剂 2-5份
流变助剂 0.1-1份
消泡剂 0.1-0.3份
增稠剂 0.1-1份
防腐剂 0.1-0.5份
硅烷偶联剂 0.5-2份
去离子水 余量;
所述除醛水性聚氨酯乳液制备方法如下:以水性聚氨酯中非水性和非溶剂性组分的质量为基准,将按该基准质量30%−60%的大分子二元醇、环氧树脂在100-120℃脱水0.5-1h、再按该基准质量加入15%−40%的二异氰酸酯和0.01−0.08%的催化剂,在60−100℃反应2−4h后再按该基准质量加入3-10%小分子二元醇、4−8%的亲水扩链剂、10−30%的咪唑衍生物、0.5-3%交联剂和10−50%丙酮或丁酮,在65−80℃反应1−4h后降温至0−40℃,加入3-7%中和剂搅拌至pH为7-9,在1000-1500rpm剪切搅拌下再加入该基准质量200-400%的水,搅拌反应5-30min后在40-50℃、0.01-0.03MPa真空条件下除去溶剂,得到主链中含有大量咪唑衍生物的除醛水性聚氨酯乳液;
所述咪唑衍生物的结构式如下:
其中R1为:任选被O、S、H取代的C1-C4烷基或任选被O、S、H取代的C1-C4链烯基不包括C1的链烯基或任选被O、S、H取代的C1-C4的链炔基不包括C1的链炔基;
R2为:任选被O、S、H取代的C1-C4烷基或任选被O、S、H取代的C1-C4链烯基不包括C1的链烯基或任选被O、S、H取代的C1-C4的链炔基不包括C1的链炔基。
2.根据权利要求1所述的一种除甲醛的水性环保涂料,其特征在于,所述大分子二元醇选自苯酐聚酯二元醇(APP)、聚丙二醇(PPG)、聚己二酸-1,4-丁二醇酯二醇(PBA)、聚己内酯二元醇(PCL)、聚碳酸酯二元醇(PCDL)或聚四氢呋喃醚二元醇(PTMG)中的任意一种或多种;
所述环氧树脂为E44、E20或E51的任意一种或多种。
3.根据权利要求1所述的一种除甲醛的水性环保涂料,其特征在于,所述二异氰酸酯选自异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)中的任意一种或多种;
所述催化剂选自二月桂酸二丁基锡(DBTDL)、异辛酸铋、有机铋中的一种或多种。
4.根据权利要求1所述的一种除甲醛的水性环保涂料,其特征在于,所述小分子二元醇扩链剂选自乙二醇(EG)、1,4-丁二醇(BDO)、新戊二醇(NPG)、1,6-己二醇(HDO) 或一缩二乙二醇(DEG)中的一种或多种;
所述亲水扩链剂选自二羟甲基丙酸(DMPA)或酒石酸(TA)中的任意一种或多种。
5.根据权利要求1所述的一种除甲醛的水性环保涂料,其特征在于,所述交联剂选自三羟甲基丙烷(TMP)、季戊四醇(PER)、蓖麻油、甘油中的任意一种或多种;
所述中和剂选用氢氧化钠、氢氧化钾、三乙胺中的任意一种或几种。
6.根据权利要求1所述的一种除甲醛的水性环保涂料,其特征在于,所述分散剂选自帝司巴隆的AQ320、AQ340、AQ360、AQ380或者德国毕克的BYK-180、BYK-110、BYK-111或迪高的740W、760W的中的任意一种或多种;
所述成膜助剂选自陶氏的二丙二醇丁醚(DPnB)、二丙二醇甲醚(DPM)中任意一种或两种;
所述流变助剂选自德国毕克的BYK-333、BYK-349或者赢创迪高TEGO GLIDE 450、TEGOGLIDE 425、TEGO GLIDE 100中一种或两种。
7.根据权利要求1所述的一种除甲醛的水性环保涂料,其特征在于,所述消泡剂选自深竹化工的SN5710、SN5702、SN6725或迪高的TEGO902W、TEGO800W、TEGO805W中的任意一种或多种;
所述增稠剂选自德国明凌公司的TAFIGEL PUR 64、TAFIGEL AP20或罗门哈斯公司的ACRYSOL RM 8W、ACRYSOL 12W、ACRYSOL 5000与ACRYSOL RM2020NPR中的任意一种或多种;
所述防腐剂选自蓝盾生物科技的BAC-106D、BAC-86D、陶氏LXE中任意一种或两种;
所述硅烷偶联剂选自KH-550、KH-560、KH-570和KH-792中的任意一种或多种。
8.根据权利要求1-7任一项所述除甲醛的水性环保涂料的制备方法,其特征在于,将除醛水性聚氨酯乳液、水性丙烯酸树脂、钛白粉、滑石粉、分散剂和水按照配比均匀混合后,在2000-3000 转/min高速搅拌分散20-40 min,预分散至细度达到20微米以内后,按照配比加入成膜助剂、流变助剂、消泡剂、防腐剂、增稠剂、硅烷偶联剂及余量的水,1000-2000转/min的转速分散20-40min,搅拌均匀后即可。
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