CN107022297B - 一种耐水水性双组分聚氨酯涂料及其制备方法 - Google Patents
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Abstract
本发明提供一种耐水水性双组分聚氨酯涂料的制备方法,包括以下步骤:以二异氰酸酯、低聚物二元醇、亲水扩链剂、不饱和脂肪酸单甘油酯及少量溶剂发生聚合反应,加中和剂中和,加水分散,即得水性聚氨酯羟基组分A。向其加入水可分散异氰酸酯固化剂,得到水性双组分聚氨酯涂料。本发明具有以下优点:得到高固含量低粘度的耐水水性聚氨酯羟基组分,能与水可分散异氰酸酯固化剂混合均匀,通过不饱和脂肪酸单甘油酯对水性聚氨酯进行改性,提高了其耐水性和机械性能,具有常温自干,硬度高、耐水性、耐冲击好等优点。
Description
技术领域
本发明涉及一种具有疏水性聚氨酯羟基组分的制备方法,并涉及用这种方法得到的高耐水性聚氨酯羟基组分和水性聚氨酯固化剂组成的双组分水性聚氨酯涂料。
背景技术
随着社会的发展和环境的逐渐恶化,含有VOC的涂料正在逐渐被市场淘汰,转而被水性涂料所代替。水性聚氨酯具有韧性好、耐高温、耐低温、抗紫外线性能优异的特点,并且不具有易挥发、易燃、易爆、有毒等缺点,目前已成为涂料应用较多的成膜物质。但是目前的水性聚氨酯涂料的耐水性、固化时间和耐老化性能还无法满足工业设备防腐的要求,需要进行改性。
聚氨酯具有较好的耐磨、耐水、耐溶剂和优异的机械性能,目前在弹性体、泡沫塑料、涂料、黏合剂及生物医用材料等方面获得了广泛应用。聚氨酯涂料因其涂膜具有良好的耐磨性、耐腐蚀性、耐化学品性、硬度大、高弹性等优点,且组分调节灵活,已广泛用作木器漆、建筑涂料、汽车漆及防水涂料等,虽然聚氨酯具有优异的性能,但是其也存在某些局限,例如,其分子链上的亲水性基团易吸水,导致聚氨酯耐水性能下降,在水环境下严重影响聚氨酯涂层的耐腐蚀性和使用寿命,从而限制其应用范围。
文献《双组分水性聚氨酯涂料的合成与工业应用》(白昀,陈新等人发表的复旦大学硕士学位论文,2011)将丙烯酸多元醇接枝到端-NCO的聚氨酯预聚体上制备了双组分聚氨酯涂料,但其聚氨酯预聚体上没有引入疏水基团,所得到的产品耐水性很差,且在制备过程中有CO2逸出,不能满足环保要求,其硬度、耐化学性等性能也达不到双组分漆的要求。
中国专利CN 103773210A双组分水性聚氨酯涂料组合物,由A和B组成,A组分是一种或多种多元醇水性分散体或水性乳液;B组分是一种或多种亲水改性的异佛尔酮二异氰酸酯多聚体或预聚体。该专利所述双组分水性聚氨酯涂料组合物具有耐高温黄变性,由其制备的涂膜在150℃下烘烤1天后的色差值小于3.0。所得的产品没有疏水基团,耐水性很差,且不能常温固化。
为了满足环保要求,中国专利CN 106398503A制备了水性双组份聚氨酯面漆涂料,由A和B组成,A组分是由水性羟基聚丙烯酸酯分散体、水性阴离子聚丙烯酸酯分散体、消泡剂、流平剂、润湿分散剂、防流挂助剂、附着力促进剂、防老化剂和水共混,搅拌5-10分钟;再加入耐紫外填料、体积填料高速搅拌30-40分钟;B组分是将溶剂加入亲水改性脂肪族聚异氰酸酯固化剂搅拌所得。所得的产品VOC过高,不能满足环保要求,其耐水性也达不到双组分面漆的要求。
发明内容
本发明所要解决的技术问题是针对现有技术所存在的问题,提供一种具有羟基、烷基、不饱和脂肪酸结构的耐水水性聚氨酯羟基组分的制备方法以及由其和水可分散异氰氨酯固化剂组成的双组分水性聚氨酯涂料。
本发明提供的技术方案是:一种耐水水性双组分聚氨酯涂料,由水性聚氨酯羟基组分A和水可分散异氰酸酯固化剂组分B组成;所述水性聚氨酯羟基组分A由下法制得:以二异氰酸酯、低聚物二元醇、亲水扩链剂、不饱和脂肪酸单甘油酯发生反应,反应温度为70~80℃,反应时间为2~4h,所用的二异氰酸酯、低聚物二元醇、亲水扩链剂、不饱和脂肪酸单甘油酯的加料摩尔比为2~5:1~3:1~2:1~3,加中和剂中和,加水分散,即得水性聚氨酯羟基组分A。所述低聚物二元醇为聚醚多元醇或聚酯多元醇。
所述水性聚氨酯羟基组分A与水可分散异氰酸酯固化剂组分B的用量比为,n(OH):n(NCO)=1:0.5~2。
所述的水可分散多异氰酸酯固化剂选自广东天银化工生产的TX-1350水可分散多异氰酸酯固化剂和拜耳DesmodurDN水可分散多异氰酸酯。
所述亲水扩链剂为含有一个羧基的二元醇。
本发明还提供了一种耐水水性双组分聚氨酯涂料的制备方法,包括以下步骤:
1)以二异氰酸酯、低聚物二元醇、亲水扩链剂、不饱和脂肪酸单甘油酯发生反应,反应温度为70~80℃,反应时间为2~4h,所用的二异氰酸酯、低聚物二元醇、亲水扩链剂、不饱和脂肪酸单甘油酯的加料摩尔比为2~5/1~3/1~2/1~3,加中和剂中和,加水分散,即得水性聚氨酯羟基组分A。
2)使用前,按n(OH):n(NCO)=1/0.5~2向水性聚氨酯羟基组分A中加入水可分散异氰酸酯固化剂,得到水性双组分聚氨酯涂料。
按上述方案,步骤1)中所用的二异氰酸酯为甲苯二异氰酸酯、二苯甲烷二异氰酸酯、己二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基二亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、三甲基己二异氰酸酯、六氢甲苯二异氰酸酯中的任意一种或者他们的混合。
按上述方案,步骤1)中所用的低聚物二元醇包括分子量为400~2000的聚醚多元醇和聚酯多元醇。
按上述方案,步骤1)中所述的聚醚多元醇又包括聚环氧乙烷二醇、聚环氧丙烷二醇、聚四氢呋喃二醇以及他们的共聚二醇。
按上述方案,步骤1)中所述的聚酯二元醇又包括聚酯型多元醇比较常用的有聚己内酯二醇、聚己二酸乙二醇酯二醇、聚己二酸- 1,4 -丁二醇酯二醇、聚己二酸己二醇酯二醇等。
按上述方案,步骤1)中所用的不饱和脂肪酸单甘油酯中的不饱和脂肪酸包括十八碳烯(9)酸,十八碳二(9,12)烯酸、十八碳三(9,12,15)烯酸、十八碳三(9,12,13)烯酸、2,4-葵二烯酸。
按上述方案,步骤1)中所用的亲水扩链剂包括二羟甲基丙酸、二羟甲基丁酸、二羟甲基戊酸、二羟甲基己酸、二羟甲基庚酸、二羟甲基辛酸、二羟甲基壬酸、二羟甲基葵酸。
按上述方案,步骤1)中所用中和剂包括二乙醇胺、三乙醇胺、三乙胺。
按上述方案,步骤2)中所用的水性固化剂为水可分散多异氰酸酯固化剂,型号包括广东天银化工生产的TX-1350和拜耳DesmodurDN等水性固化剂。
其中,步骤1)所涉及的反应方程式如下:
其中R1表示碳原子数为2~18的脂肪族碳链或者是碳原子数为6的脂环族或芳香族基团;
其中 R2表示碳原子数为10~20的不饱和脂肪酸;
R3表示含有1~8个碳原子数的烷基;
n的范围为6≤n≤34;的范围为;的范围为;的范围为。
由所述的耐水水性聚氨酯羟基组分和水性固化剂组成一种双组分水性聚氨酯涂料,耐水水性聚氨酯羟基组分和水性固化剂用量比(n(OH):n(NCO))为1/0.5~2,所述的水性固化剂为水可分散多异氰酸酯固化剂,包括广东天银化工生产的TX-1350和拜耳DesmodurDN等水性固化剂。
两种固化剂的性能指标如下:
型号 | 厂家 | NCO/% | 粘度(25℃)/cp | 有效成分/% |
TX-1350 | 广东天银化工 | 9±1 | 1000-3000 | 50±1 |
DesmodurDN | 拜耳 | 21.8±0.5 | 1250-300 | 98 |
本发明所得的双组分水性聚氨酯涂料具有以下优点:由于不饱和脂肪酸单甘油酯改性的水性聚氨酯具有疏水基团的烷基、不饱和脂肪酸结构和亲水基团的羟基结构,能与水可分散异氰酸酯固化剂混合均匀,常温自干,且涂膜的硬度、耐水性、耐冲击性明显提高。
具体实施方式
为了更好地理解本发明,下面结合实施例对本发明进一步详细说明。本发明要求保护的范围并不局限与实施例表示的范围。
实施例1:
称1.33g二羟甲基丙酸(DMPA),4g聚环氧丙烷二醇400(PPG400),3.54g二羟基丙基十八碳烯(9)酸酯,5gN-甲基吡咯烷酮(NMP),5g丙酮于四口烧瓶中,升温至75℃左右回流至形成均相溶液之后(1h左右),一次加入3.48g甲苯二异氰酸酯(TDI),在75℃下反应3h ,降温至50℃加入1.05g二乙醇胺中和,继续搅拌30min,降温至20℃以下,再滴加去离子水乳化,减压脱除丙酮,制得固含量为65%的耐水水性聚氨酯羟基组分A。
按照耐水水性聚氨酯羟基组分与固化剂的用量比(n(OH):n(NCO),下同)为1/0.5,向上述极耐水水性聚氨酯羟基组分中加入水可分散异氰酸酯固化剂DesmodurDN,搅拌均匀,加水稀释至所需粘度,搅拌,即得耐水双组分水性聚氨酯涂料。
实施例2:
称1.76g二羟甲基丁酸(DMBA),11.2g聚环氧乙烷二醇800(PPG800),4.696g二羟基丙基十八碳二(9,12)烯酸酯,5gN-甲基吡咯烷酮(NMP),5g丙酮四口烧瓶中,升温至75℃左右回流至形成均相溶液之后(1h左右),一次加入6.256g二苯甲烷二异氰酸酯,在75℃下反应3h ,降温至50℃加入1.26g二乙醇胺中和,继续搅拌30min,降温至20℃以下,再滴加去离子水乳化,减压脱除丙酮,制得固含量为65%的耐水水性聚氨酯羟基组分A。
按照耐水水性聚氨酯羟基组分与固化剂的用量比为1/0.8,向上述耐水水性聚氨酯羟基组分中加入水可分散异氰酸酯固化剂DesmodurDN,搅拌均匀,加水稀释至所需粘度,搅拌,即得耐水双组分水性聚氨酯涂料。
实施例3:
称2.26g二羟甲基戊酸,18g聚四氢呋喃二醇1000(PPG1500),3.53g二羟基丙基十八碳三(9,12,15)烯酸酯,5gN-甲基吡咯烷酮(NMP),5g丙酮于四口烧瓶中,升温至75℃左右回流至形成均相溶液之后(1h左右),一次加入5.22g苯二亚甲基二异氰酸酯,在75℃下反应3h ,降温至50℃加入2.09g三乙醇胺中和,继续搅拌30min,降温至20℃以下,再滴加去离子水乳化,减压脱除丙酮,制得固含量为65%的耐水水性聚氨酯羟基组分A。
按照耐水水性聚氨酯羟基组分与固化剂的用量比为1/1,向上述耐水水性聚氨酯羟基组分中加入水可分散异氰酸酯固化剂DesmodurDN,搅拌均匀,加水稀释至所需粘度,搅拌,即得耐水双组分水性聚氨酯涂料。
实施例4:
称2.63g二羟甲基己酸,24g聚己内酯二醇1200(PPG1000),3.92g二羟基丙基十八碳三(9,12,13)烯酸酯,5gN-甲基吡咯烷酮(NMP),5g丙酮于四口烧瓶中,升温至75℃左右回流至形成均相溶液之后(1h左右),一次加入5.88g四甲基二亚甲基二异氰酸酯,在75℃下反应3h ,降温至50℃加入2.24g三乙醇胺中和,继续搅拌30min,降温至20℃以下,再滴加去离子水乳化,减压脱除丙酮,制得固含量为65%的耐水水性聚氨酯羟基组分A。
按照耐水水性聚氨酯羟基组分与固化剂的用量比为1./1.2,向上述耐水水性聚氨酯羟基组分中加入水可分散异氰酸酯固化剂DesmodurDN,搅拌均匀,加水稀释至所需粘度,搅拌,即得耐水双组分水性聚氨酯涂料。
实施例5:
称4.54g二羟甲基庚酸,36g聚己二酸乙二醇酯二醇1500(PPG1500), 6.29g二羟基丙基2,4-葵二烯酸单甘酯,5gN-甲基吡咯烷酮(NMP),5g丙酮于四口烧瓶中,升温至75℃左右回流至形成均相溶液之后(1h左右),一次加入10.49g二环己基甲烷二异氰酸酯,75℃下反应3h,降温至50℃加入2.54g三乙醇胺中和,继续搅拌30min,降温至20℃以下,再滴加去离子水乳化,减压脱除丙酮,制得固含量为65%的耐水水性聚氨酯羟基组分A。
按照耐水水性聚氨酯羟基组分与固化剂的用量比为1.5/1,向上述耐水水性聚氨酯羟基组分中加入水可分散异氰酸酯固化剂DesmodurDN,搅拌均匀,加水稀释至所需粘度,搅拌,即得耐水双组分水性聚氨酯涂料。
实施例6:
称3.96g二羟甲基辛酸,50.4g聚己二酸- 1,4 -丁二醇酯二醇1800(PPG1800),8.75g二羟基丙基十八碳烯(9)酸酯和二羟基丙基十八碳二(9,12)烯酸酯的混合物,5gN-甲基吡咯烷酮(NMP),5g丙酮于四口烧瓶中,升温至75℃左右回流至形成均相溶液之后(1h),一次加入10g异佛尔酮二异氰酸酯,在75℃下反应3h ,降温至50℃加入1.92g三乙胺中和,继续搅拌30min,降温至20℃以下,再滴加去离子水乳化,减压脱除丙酮,制得固含量为65%的耐水水性聚氨酯羟基组分A。
按照耐水水性聚氨酯羟基组分与固化剂的质量比为1/1.8,向上述耐水水性聚氨酯羟基组分中加入水可分散异氰酸酯固化剂DesmodurDN,搅拌均匀,加水稀释至所需粘度,搅拌,即得耐水双组分水性聚氨酯涂料。
实施例7:
称4.34g二羟甲基壬酸,60g聚己二酸己二醇酯二醇2000(PPG2000),5.88g二羟基丙基十八碳三(9,12,15)烯酸酯和二羟基丙基十八碳三(9,12,13)烯酸酯的混合物,5gN-甲基吡咯烷酮(NMP),5g丙酮于四口烧瓶中,升温至75℃左右回流至形成均相溶液之后(1h左右),一次加入8.7g六氢甲苯二异氰酸酯,75℃下反应3h ,降温至50℃加入2.02g三乙胺中和,继续搅拌30min,降温至20℃以下,再滴加去离子水乳化,减压脱除丙酮,制得固含量为65%的耐水水性聚氨酯羟基组分A。
按照耐水水性聚氨酯羟基组分与固化剂的用量比为1/2,向上述耐水水性聚氨酯羟基组分中加入水可分散异氰酸酯固化剂DesmodurDN,搅拌均匀,加水稀释至所需粘度,搅拌,即得耐水双组分水性聚氨酯涂料。
按照中国国家标准检测性能,漆膜性能结果检测如下表:
常温固化
实施例编号 | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
表干时间/h | 2 | 2 | 2 | 3 | 2 | 2 | 2 |
外观 | 光滑 | 光滑 | 光滑 | 光滑 | 光滑 | 光滑 | 光滑 |
耐冲击/cm | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
柔韧性/mm | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
硬度 | HB | H | H | HB | 2H | H | H |
耐水性 | 24h通过 | 32h通过 | 48h通过 | 72h通过 | 96h通过 | 120h通过 | 168h通过 |
Claims (10)
1.一种耐水水性双组分聚氨酯涂料,由水性聚氨酯羟基组分A和水可分散异氰酸酯固化剂组分B组成;所述水性聚氨酯羟基组分A由下法制得:以二异氰酸酯、低聚物二元醇、亲水扩链剂、不饱和脂肪酸单甘油酯发生反应,反应温度为70~80℃,反应时间为2~4h,所用的二异氰酸酯、低聚物二元醇、亲水扩链剂、不饱和脂肪酸单甘油酯的加料摩尔比为2~5:1~3:1~2:1~3,加中和剂中和,加水分散,即得水性聚氨酯羟基组分A;所述低聚物二元醇为聚醚多元醇或聚酯多元醇;所用的不饱和脂肪酸单甘油酯选自二羟基丙基十八碳烯(9)酸酯、二羟基丙基十八碳二(9,12)烯酸酯、二羟基丙基十八碳三(9,12,15)烯酸酯、二羟基丙基十八碳三(9,12,13)烯酸酯、羟基丙基2,4-葵二烯酸单甘酯中一种或几种。
2.根据权利要求1所述的耐水水性双组分聚氨酯涂料,其特征在于:所述水性聚氨酯羟基组分A与水可分散异氰酸酯固化剂组分B的用量比为,n(OH):n(NCO)=1:0.5~2。
3.根据权利要求1或2所述的耐水水性双组分聚氨酯涂料,其特征在于:所述亲水扩链剂为含有一个羧基的二元醇。
4.根据权利要求1或2所述的耐水水性双组分聚氨酯涂料,其特征在于:所述的水可分散多异氰酸酯固化剂选自广东天银化工生产的TX-1350水可分散多异氰酸酯固化剂和拜耳DesmodurDN水可分散多异氰酸酯。
5.一种耐水水性双组分聚氨酯涂料的制备方法,包括以下步骤:
1)以二异氰酸酯、低聚物二元醇、亲水扩链剂、不饱和脂肪酸单甘油酯发生反应,反应温度为70~80℃,反应时间为2~4h,所用的二异氰酸酯、低聚物二元醇、亲水扩链剂、不饱和脂肪酸单甘油酯的加料摩尔比为2~5/1~3/1~2/1~3,加中和剂中和,加水分散,即得水性聚氨酯羟基组分A;所述低聚物二元醇为聚醚多元醇或聚酯多元醇;
2)在使用前,按n(OH):n(NCO)=1/0.5~2,向水性聚氨酯羟基组分A中加入水可分散异氰酸酯固化剂,得到水性双组分聚氨酯涂料。
6.如权利要求5所述的制备方法,其特征在于步骤1)中所用的二异氰酸酯为甲苯二异氰酸酯、二苯甲烷二异氰酸酯、己二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基二亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、三甲基己二异氰酸酯、六氢甲苯二异氰酸酯中的任意一种或者他们的混合;步骤1)中所用的不饱和脂肪酸单甘油酯选自二羟基丙基十八碳烯(9)酸酯、二羟基丙基十八碳二(9,12)烯酸酯、二羟基丙基十八碳三(9,12,15)烯酸酯、二羟基丙基十八碳三(9,12,13)烯酸酯、羟基丙基2,4-葵二烯酸单甘酯中一种或几种;所述亲水扩链剂为含有一个羧基的二元醇。
7.如权利要求5所述的制备方法,其特征在于:步骤1)中所用的低聚物二元醇分子量为400~2000。
8.如权利要求5所述的制备方法,其特征在于步骤1)中所述的聚醚多元醇包括聚环氧乙烷二醇、聚环氧丙烷二醇、聚四氢呋喃二醇以及它们的共聚二醇;所述的聚酯多元醇选自聚己内酯二醇、聚己二酸乙二醇酯二醇、聚己二酸- 1,4 -丁二醇酯二醇、聚己二酸己二醇酯二醇。
9.如权利要求5所述的制备方法,其特征在于步骤1)中所用的亲水扩链剂包括二羟甲基丙酸、二羟甲基丁酸、二羟甲基戊酸、二羟甲基己酸、二羟甲基庚酸、二羟甲基辛酸、二羟甲基壬酸、二羟甲基葵酸;步骤1)中所用中和剂包括二乙醇胺、三乙醇胺、三乙胺、N,N-二甲基异丙醇胺。
10.如权利要求5所述的制备方法,其特征在于:步骤2)中所述的水可分散多异氰酸酯固化剂选自广东天银化工生产的TX-1350水可分散多异氰酸酯固化剂和拜耳DesmodurDN水可分散多异氰酸酯。
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