CN115449265B - 一种去甲醛涂料及其制备方法 - Google Patents
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- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 6
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- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 3
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
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- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
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- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/10—Homopolymers or copolymers of propene
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Abstract
本发明提出了一种去甲醛涂料及其制备方法,属于涂料技术领域,由以下原料按重量份制备而成:聚丙烯树脂15‑30份、分散剂1‑3份、消泡剂2‑3份、流平剂2‑4份、甲醛捕获剂5‑7份、水30‑50份;所述甲醛捕获剂为金属氧化物掺杂的CoCuSO。本发明氧化锌和氧化钛的掺杂CoCuSO,具有极好的捕获、降解甲醛的效果,还大大降低了涂料的成本,同时具有更好的耐高温耐火性能,具有广阔的应用前景。
Description
技术领域
本发明涉及涂料技术领域,具体涉及一种去甲醛涂料及其制备方法。
背景技术
涂料工业已经成为一个国家国民经济的重要组成部分,涂料产量及人均产量已成为当代世界各国衡量经济水平的重要标志之一。但是,涂料工业自身具有污染环境的特性。这已引起了全社会的极大关注。因此,大力发展环境友好型涂料,是世界涂料发展的总的趋势。
甲醛的主要危害表现为对皮肤粘膜的刺激作用,甲醛在室内达到一定浓度时,人就有不适感。大于0.08m3的甲醛浓度可引起眼红、眼痒、咽喉不适或疼痛、声音嘶哑、喷嚏、胸闷、气喘、皮炎等。新装修的房间甲醛含量较高,是众多疾病的主要诱因。甲醛主要来源于室内家具的人造板材、以甲醛为主要原料的黏合剂,以及含有甲醛成分并会向外界散发的其他各类装饰材料。甲醛为毒性较高的物质,在我国有毒化学品优先控制名单上高居第二位。
针对这种情况,各种治理甲醛的技术应运而生。目前使用的治理方法可以粗略地分为臭氧氧化法、吸附法、光催化氧化法和金属氧化物法,其中吸附法具有原料广泛,操作简单、能耗低等优点。
现有技术中,用于吸附法去除甲醛的材料多是在活性炭,但是有效裸露面积不够,成本较高。中国发明专利ZL2017112704875采用载银方式对活性炭进行改性活化,原料中含阴离子,原材料成本比较高,此外还存在去甲醛不长效的缺点。
现有装饰涂料游离单体、游离甲醛含量高,时常有装修后引起咳嗽、咽喉疼痛、气味令人难以忍受的状况出现,对人体呼吸道造成严重伤害。
发明内容
本发明的目的在于提出一种去甲醛涂料及其制备方法,通过氧化锌和氧化钛的掺杂CoCuSO,具有极好的捕获、降解甲醛的效果,还大大降低了涂料的成本,同时具有更好的耐高温耐火性能,具有广阔的应用前景。
本发明的技术方案是这样实现的:
本发明提供一种去甲醛涂料,由以下原料按重量份制备而成:聚丙烯树脂15-30份、分散剂1-3份、消泡剂2-3份、流平剂2-4份、甲醛捕获剂5-7份、水30-50份;所述甲醛捕获剂为金属氧化物掺杂的CoCuSO。
作为本发明的进一步改进,所述甲醛捕获剂的制备方法如下:将钴盐溶于水中,加热后,加入铜盐,搅拌混合均匀后,加入碱液调节溶液pH值,搅拌反应1-2h后,加入硫脲和阳离子表面活性剂,继续搅拌0.5-1h后,加入有机金属化合物,遮光搅拌1-2h,过滤,洗涤,干燥,煅烧,研细,得到金属氧化物掺杂的CoCuSO,即为甲醛捕获剂。
作为本发明的进一步改进,所述钴盐选自氯化钴、硝酸钴、硫酸钴中的至少一种;所述铜盐选自氯化铜、硝酸铜、硫酸铜中的至少一种;所述碱液为2-4mol/L NaOH或KOH溶液;所述阳离子表面活性剂选自十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、十二烷基三甲基溴化铵、十二烷基三甲基氯化铵、十八烷基三甲基溴化铵、十八烷基三甲基氯化铵中的至少一种。
作为本发明的进一步改进,所述加热至温度为40-50℃,所述溶液pH值调节至8-9;所述煅烧温度为500-700℃,时间为2-4h。
作为本发明的进一步改进,所述钴盐、铜盐、硫脲、阳离子表面活性剂、有机金属化合物的质量比为1:1.2-1.4:0.5-1:0.01-0.1:1.2-2.2。
作为本发明的进一步改进,所述有机金属化合物选自钛酸四丁酯、二水合醋酸锌、锆酸四丁酯中的至少一种。
作为本发明的进一步改进,所述有机金属化合物为钛酸四丁酯、二水合醋酸锌的复合物,质量比为3-5:2。
作为本发明的进一步改进,所述分散剂选自己烯基双硬脂酰胺、三硬脂酸甘油酯、硬脂酸单甘油酯、硬脂酸钡、硬脂酸镁、硬脂酸锌、硬脂酸铜中的至少一种;所述消泡剂选自乳化硅油、高碳醇脂肪酸酯复合物、聚氧乙烯聚氧丙烯季戊四醇醚、聚氧乙烯聚氧丙醇胺醚、聚氧丙烯甘油醚和聚氧丙烯聚氧乙烯甘油醚、聚二甲基硅氧烷中的至少一种;所述流平剂选自聚二甲基硅氧烷、聚甲基苯基硅氧烷、异佛尔酮、二丙酮醇中的至少一种。
本发明进一步保护一种上述的去甲醛涂料的制备方法,包括以下步骤:
S1.将聚丙烯树脂和甲醛捕获剂混合加入水中,搅拌混合均匀,得到浆料;
S2.将分散剂、消泡剂和流平剂混合均匀,得到助剂;
S3.将步骤S2中助剂加入步骤S1中浆料中,加热至50-70℃,搅拌混合15-30min,然后乳化,冷却至室温,出料,得到去甲醛涂料。
作为本发明的进一步改进,所述乳化条件为12000-15000r/min转速下乳化3-5min。
本发明具有如下有益效果:本发明制备了一种光催化剂CoCuSO,钴元素轨道的孤对变形可能导致价带中氧元素和钴元素轨道的明显重叠,有利于光生电荷载流子的迁移,从而提高光催化活性,因此,本发明制备的CoCuSO具有极好的光催化活性,同时,氧硫属元素化合物可能是提高捕获效率和降解污染物的良好选择,进一步,在制得的CoCuSO中通过溶胶凝胶法负载氧化锌和氧化钛,进一步提高了材料的光催化活性,使得制得的涂料能大大提高对甲醛的催化能力,从而制得的涂料不仅不会散发甲醛,还可以净化空气中无色无味的甲醛残留,相比重金属掺杂,本发明氧化锌和氧化钛的掺杂大大降低了涂料的成本,是一种极好的环保涂料,另外,本发明掺杂的氧化锌和氧化钛复配后制得的涂料,还意外的发现,具有更好的耐高温耐火性能,具有广阔的应用前景。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
本实施例提供一种去甲醛涂料。
原料组成(重量份):聚丙烯树脂15份、硬脂酸钡1份、聚氧乙烯聚氧丙烯季戊四醇醚2份、聚二甲基硅氧烷2份、甲醛捕获剂5份、水30份。
甲醛捕获剂的制备方法如下:将1重量份氯化钴溶于水中,加热至40℃后,加入1.2重量份氯化铜,搅拌混合均匀后,加入2mol/L NaOH溶液调节溶液pH值8,搅拌反应1h后,加入0.5重量份硫脲和0.01重量份十二烷基三甲基氯化铵,继续搅拌0.5h后,加入1.2重量份有机金属化合物,遮光搅拌1h,过滤,洗涤,干燥,500℃煅烧2h,研细,得到金属氧化物掺杂的CoCuSO,即为甲醛捕获剂;
所述有机金属化合物为钛酸四丁酯、二水合醋酸锌的复合物,质量比为3:2。
去甲醛涂料的制备方法包括以下步骤:
S1.将聚丙烯树脂和甲醛捕获剂混合加入水中,搅拌混合均匀,得到浆料;
S2.将硬脂酸钡、聚氧乙烯聚氧丙烯季戊四醇醚和聚二甲基硅氧烷混合均匀,得到助剂;
S3.将步骤S2中助剂加入步骤S1中浆料中,加热至50℃,搅拌混合15min,12000r/min转速下乳化3min,冷却至室温,出料,得到去甲醛涂料。
实施例2
本实施例提供一种去甲醛涂料。
原料组成(重量份):聚丙烯树脂30份、三硬脂酸甘油酯3份、聚二甲基硅氧烷3份、二丙酮醇4份、甲醛捕获剂7份、水50份。
甲醛捕获剂的制备方法如下:将1重量份硫酸钴溶于水中,加热至50℃后,加入1.4重量份硫酸铜,搅拌混合均匀后,加入4mol/L KOH溶液调节溶液pH值9,搅拌反应2h后,加入1重量份硫脲和0.1重量份十六烷基三甲基氯化铵,继续搅拌1h后,加入2.2重量份有机金属化合物,遮光搅拌2h,过滤,洗涤,干燥,700℃煅烧4h,研细,得到金属氧化物掺杂的CoCuSO,即为甲醛捕获剂;
所述有机金属化合物为钛酸四丁酯、二水合醋酸锌的复合物,质量比为5:2。
去甲醛涂料的制备方法包括以下步骤:
S1.将聚丙烯树脂和甲醛捕获剂混合加入水中,搅拌混合均匀,得到浆料;
S2.将三硬脂酸甘油酯、聚二甲基硅氧烷和二丙酮醇混合均匀,得到助剂;
S3.将步骤S2中助剂加入步骤S1中浆料中,加热至70℃,搅拌混合30min,15000r/min转速下乳化5min,冷却至室温,出料,得到去甲醛涂料。
实施例3
本实施例提供一种去甲醛涂料。
原料组成(重量份):聚丙烯树脂22份、硬脂酸单甘油酯2份、聚氧丙烯聚氧乙烯甘油醚2.5份、异佛尔酮3份、甲醛捕获剂6份、水40份。
甲醛捕获剂的制备方法如下:将1重量份硝酸钴溶于水中,加热至45℃后,加入1.3重量份硝酸铜,搅拌混合均匀后,加入3mol/L NaOH溶液调节溶液pH值8.5,搅拌反应1.5h后,加入0.7重量份硫脲和0.05重量份十八烷基三甲基氯化铵,继续搅拌1h后,加入1.7重量份有机金属化合物,遮光搅拌1.5h,过滤,洗涤,干燥,600℃煅烧3h,研细,得到金属氧化物掺杂的CoCuSO,即为甲醛捕获剂;
所述有机金属化合物为钛酸四丁酯、二水合醋酸锌的复合物,质量比为4:2。
去甲醛涂料的制备方法包括以下步骤:
S1.将聚丙烯树脂和甲醛捕获剂混合加入水中,搅拌混合均匀,得到浆料;
S2.将硬脂酸单甘油酯、聚氧丙烯聚氧乙烯甘油醚和异佛尔酮混合均匀,得到助剂;
S3.将步骤S2中助剂加入步骤S1中浆料中,加热60℃,搅拌混合22min,13500r/min转速下乳化4min,冷却至室温,出料,得到去甲醛涂料。
实施例4
与实施例3相比,有机金属化合物为单一的钛酸四丁酯,其他条件均不改变。
实施例5
与实施例3相比,有机金属化合物为单一的二水合醋酸锌,其他条件均不改变。
对比例1
与实施例3相比,未添加有机金属化合物,其他条件均不改变。
对比例2
与实施例3相比,甲醛捕获剂由氧化钛替代,其他条件均不改变。
测试例1
称取实施例1-5和对比例1-2制得的去甲醛涂料10g,置入初始浓度为50mg/m3甲醛的5L干燥器中,然后测定12h、24h时干燥器内气体中甲醛浓度经时变化,结果见表1。
表1
组别 | 12h时甲醛浓度(mg/m3) | 24h时甲醛浓度(mg/m3) |
实施例1 | 5.5 | 1.2 |
实施例2 | 5.2 | 1.0 |
实施例3 | 4.9 | 0.8 |
实施例4 | 12.4 | 6.5 |
实施例5 | 11.5 | 5.7 |
对比例1 | 20.2 | 9.6 |
对比例2 | 25.7 | 14.2 |
由上表可知,本发明实施例1-3制得的去甲醛涂料具有极好的去除甲醛的效果,24h后甲醛去除率达到98.4%。
测试例2
将实施例1-5和对比例1-2制得的去甲醛涂料进行性能测试。
防火测试方法如下:根据GB/T15442.2-95《防火涂料防火性能试验方法-大板燃烧法》进行防火测试。
耐高温测试方法如下:烘箱烘烤210℃/3h后,烘箱烘烤145℃/15天;铅笔硬度测试按照《GB/T6739-2006》的标准测定(三菱铅笔45°角,五次瑕疵判断)。
结果见表2。
表2
组别 | 耐燃时间(min) | 耐高温性能 |
国标要求 | 一级≧20、二级≧10 | |
实施例1 | 29 | 无异状 |
实施例2 | 28 | 无异状 |
实施例3 | 30 | 无异状 |
实施例4 | 25 | 有少量裂纹 |
实施例5 | 24 | 有少量裂纹 |
对比例1 | 17 | 有裂纹 |
对比例2 | 14 | 有裂纹 |
由表2可知,实施例1-3制备的去甲醛涂料的具有很好的防火功能、耐高温性能。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,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 (7)
1.一种去甲醛涂料,其特征在于,由以下原料按重量份制备而成:聚丙烯树脂15-30份、分散剂1-3份、消泡剂2-3份、流平剂2-4份、甲醛捕获剂5-7份、水30-50份;所述甲醛捕获剂为金属氧化物掺杂的CoCuSO;
所述甲醛捕获剂的制备方法如下:将钴盐溶于水中,加热后,加入铜盐,搅拌混合均匀后,加入碱液调节溶液pH值,搅拌反应1-2h后,加入硫脲和阳离子表面活性剂,继续搅拌0.5-1h后,加入有机金属化合物,遮光搅拌1-2h,过滤,洗涤,干燥,煅烧,研细,得到金属氧化物掺杂的CoCuSO,即为甲醛捕获剂;
所述有机金属化合物为钛酸四丁酯、二水合醋酸锌的复合物,质量比为3-5:2。
2.根据权利要求1所述去甲醛涂料,其特征在于,所述钴盐选自氯化钴、硝酸钴、硫酸钴中的至少一种;所述铜盐选自氯化铜、硝酸铜、硫酸铜中的至少一种;所述碱液为2-4mol/LNaOH或KOH溶液;所述阳离子表面活性剂选自十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、十二烷基三甲基溴化铵、十二烷基三甲基氯化铵、十八烷基三甲基溴化铵、十八烷基三甲基氯化铵中的至少一种。
3.根据权利要求1所述去甲醛涂料,其特征在于,所述加热至温度为40-50℃,所述溶液pH值调节至8-9;所述煅烧温度为500-700℃,时间为2-4h。
4.根据权利要求1所述去甲醛涂料,其特征在于,所述钴盐、铜盐、硫脲、阳离子表面活性剂、有机金属化合物的质量比为1:1.2-1.4:0.5-1:0.01-0.1:1.2-2.2。
5.根据权利要求1所述去甲醛涂料,其特征在于,所述分散剂选自己烯基双硬脂酰胺、三硬脂酸甘油酯、硬脂酸单甘油酯、硬脂酸钡、硬脂酸镁、硬脂酸锌、硬脂酸铜中的至少一种;所述消泡剂选自乳化硅油、高碳醇脂肪酸酯复合物、聚氧乙烯聚氧丙烯季戊四醇醚、聚氧乙烯聚氧丙醇胺醚、聚氧丙烯甘油醚和聚氧丙烯聚氧乙烯甘油醚、聚二甲基硅氧烷中的至少一种;所述流平剂选自聚二甲基硅氧烷、聚甲基苯基硅氧烷、异佛尔酮、二丙酮醇中的至少一种。
6.一种如权利要求1-5任一项所述的去甲醛涂料的制备方法,其特征在于,包括以下步骤:
S1.将聚丙烯树脂和甲醛捕获剂混合加入水中,搅拌混合均匀,得到浆料;
S2.将分散剂、消泡剂和流平剂混合均匀,得到助剂;
S3.将步骤S2中助剂加入步骤S1中浆料中,加热至50-70℃,搅拌混合15-30min,然后乳化,冷却至室温,出料,得到去甲醛涂料。
7.根据权利要求6所述的制备方法,其特征在于,所述乳化条件为12000-15000r/min转速下乳化3-5min。
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