CN111825808A - 一种水性聚氨酯-丙烯酸接枝树脂的制备方法及其应用 - Google Patents
一种水性聚氨酯-丙烯酸接枝树脂的制备方法及其应用 Download PDFInfo
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Abstract
一种水性聚氨酯‑丙烯酸接枝树脂的制备方法及其应用,该方法采用聚醚多元醇,异佛尔酮二异氰酸酯,双羟甲基丙酸,二甲基甲酰胺等聚合成水性聚氨酯预聚体,然后加入接枝剂,作为一个桥连结构接枝丙烯酸单体,接枝完成之后,做氨化反应,水化反应、低温氧化还原反应、pH值和固含量的调整,形成一个稳定的水性PUA分散体结构;本水性聚氨酯‑丙烯酸接枝树脂可用作水性木器漆的底漆修色和基材修色树脂,也可以用于底着色,对酒精具有优异的相容性,同时具有优秀的入孔性、渗透性,制成修色主剂后与水性色精的相容性很好,优秀的再溶性,水性树脂成膜后起颗粒能够再次溶解入新的涂料体系,在塑料基材上具有优秀的附着力和优秀的抗粘连性能。
Description
技术领域
本发明涉及化工涂料技术领域,特别是一种水性聚氨酯-丙烯酸接枝树脂的制备方法及其应用。
背景技术
木器UV地板的着色剂的发展方向都在从油性转向水性,与油性着色剂相比,水性着色剂具有环保无毒,干燥速度快等优点。但以往油性着色剂能很好地与酒精相容,现有的水性着色剂主要以水性丙烯酸为主,水性丙烯酸能通过增加羧基的含量来解决与酒精的相容性,但同时会影响树脂本身的耐水性能和附着力。
木器UV地板的着色剂通过辊涂施工,在间歇性停工会造成胶辊上的着色剂成膜结块成固体物,水性树脂的成膜是不可逆的,重新启动胶辊,这些固体物不能重新溶解进入着色剂,会给后面辊涂带来斑点、缺陷、瑕疵等质量问题,因此,水性木器UV地板的着色剂的再溶性相当重要;同时,水性木器UV地板的着色通常在UV油漆层上面,水性树脂作为木器UV地板的着色剂必须解决在UV层的附着力的问题。
发明内容
为了克服现有技术的上述缺点,本发明的目的是提供一种水性聚氨酯-丙烯酸接枝树脂的制备方法及其应用。
本发明解决其技术问题所采用的技术方案是:一种水性聚氨酯-丙烯酸接枝树脂的制备方法,包括以下接枝步骤:
在水性聚氨酯预聚体中滴入丙烯酸羟乙酯,并加入二甲基甲酰胺进行保温;
加入丙烯酸单体搅拌溶解,保持温度进行反应,得到丙烯酸接枝的水性聚氨酯预聚体。
作为本发明的进一步改进:包括以下制备步骤:
(1)聚合反应:加入聚醚多元醇和二异氰酸酯进行聚合反应,依次加入双羟甲基丙酸和二甲基甲酰胺进行聚合反应,得水性聚氨酯预聚体;
(2)桥接反应:向上述水性聚氨酯预聚体滴入丙烯酸羟乙酯,加入二甲基甲酰胺进行保温;
(3)接枝反应:加入丙烯酸单体搅拌溶解,保持温度进行反应;得到丙烯酸接枝的水性聚氨酯预聚体;
(4)氨化反应和水化反应:加入去离子水降温后加入三乙醇胺进行氨化反应;加入去离子水搅拌进行水化反应;
(5)低温氧化还原反应:降低体系温度,加入叔丁基过氧化氢和VC钠;
(6)pH值调整及防腐处理:降低体系温度,加入氨水、去离子水及杀菌剂。
作为本发明的进一步改进:所述步骤(1)中二异氰酸酯为异佛尔酮二异氰酸酯和氢化苯基甲烷二异氰酸酯。
作为本发明的进一步改进:所述步骤(1)中反应釜温度为90℃,搅拌50转/分钟。
作为本发明的进一步改进:所述步骤(1)加入聚醚多元醇和二异氰酸酯前,将反应釜在100℃下负压加热脱水。
作为本发明的进一步改进:所述步骤(2)中保温温度为82℃,保温30min。
作为本发明的进一步改进:所述步骤(3)中丙烯酸单体包括甲基丙烯酸丁酯、甲基丙烯酸甲酯、丙烯酸丁酯和甲基丙烯酸烯丙酯。
作为本发明的进一步改进:所述步骤(3)中还包括硅烷接枝反应。
作为本发明的进一步改进:所述步骤(4)中水化反应的搅拌速度为80转/min。
作为本发明的进一步改进:所述步骤(4)中去离子水为稀释用去离子水。
作为本发明的进一步改进:所述步骤(5)中低温氧化还原反应温度为60℃,搅拌速度为35转/min,30min内加完叔丁基过氧化氢(70%水溶液),5min后滴加VC钠,滴加时间为15分钟。
为本发明的进一步改进:所述步骤(6)中pH值调整至8.3-8.8,所述氨水为20%氨水,所述杀菌剂为Kathon LX 150。
为本发明的进一步改进:包括以下制备步骤:
(1)聚合反应:加入160重量份聚醚多元醇、15重量份异佛尔酮二异氰酸酯、15重量份氢化苯基甲烷二异氰酸酯和3 0重量份双羟甲基丙酸在90℃下搅拌1h,加入45重量份二甲基甲酰胺,得水性聚氨酯预聚体;
(2)桥接反应:上述水性聚氨酯预聚体降温到82℃,滴入30重量份丙烯酸羟乙酯,加入12重量份二甲基甲酰胺进行保温30min;
(3)接枝反应:在温度在80~81℃下滴加56重量份甲基丙烯酸丁酯、150重量份甲基丙烯酸甲酯、35重量份丙烯酸丁酯和77重量份甲基丙烯酸烯丙酯,在温度80℃保持30min;加入3.6重量份硅烷,得到丙烯酸接枝的水性聚氨酯预聚体;
(4)氨化反应和水化反应:加入12重量份稀释用去离子水降温至75℃,加入41重量份三乙醇胺保温10min进行氨化反应;加入900重量份稀释用去离子水搅拌进行水化反应;
(5)低温氧化还原反应:降低体系温度至60℃,加入1.5重量份叔丁基过氧化氢和0.5重量份VC钠;
(6)pH值调整及防腐处理:降低体系温度至50℃,加入15重量份氨水、12重量份系使用去离子水及1.77重量份杀菌剂。
一种水性聚氨酯-丙烯酸接枝树脂在水性着色剂中的应用。
与现有技术相比,本发明的有益效果是:本发明的水性聚氨酯-丙烯酸接枝树脂可以用作水性木器漆的底漆修色和基材修色树脂,也可以用于底着色,特别是UV地板底着色,适用于滚涂,喷涂,对酒精具有优异的相容性,对水性色精的润色和展色效果非常优异,可以干修,湿修,亦可深修,浅修,静电喷涂,过三辊机均可,同时具有优秀的入孔性,渗透性,制成修色主剂后与水性色精的相容性很好,经修色后漆膜不发花,不起颗粒,不发白,附着力优秀,树脂成膜后起颗粒能够再次溶解入新的涂料体系,在UV基材、PU涂层、PVC、PE、PET、PP等塑料基材,均具有优秀的附着力和优秀的抗粘连性能。
具体实施方式
现结合实施例对本发明进一步说明:
实施案例一:
一种水性聚氨酯-丙烯酸接枝树脂,由以下重量份的原料制成:
包括以下制备步骤:
(1)聚合反应:将反应釜在100℃下负压加热脱水,加入160重量份聚醚多元醇、15重量份异佛尔酮二异氰酸酯、15重量份氢化苯基甲烷二异氰酸酯和3 0重量份双羟甲基丙酸在90℃,50转/min下搅拌1h,加入45重量份二甲基甲酰胺冲洗加料管道,得水性聚氨酯预聚体;
(2)桥接反应:上述水性聚氨酯预聚体降温到82℃,加入30重量份丙烯酸羟乙酯在30min内滴加完,加入12重量份二甲基甲酰胺进行保温30min;
(3)接枝反应:保温完毕无明显升温后,在温度80~81℃下滴加56重量份甲基丙烯酸丁酯、150重量份甲基丙烯酸甲酯、35重量份丙烯酸丁酯和77重量份甲基丙烯酸烯丙酯,120min内滴加完,温度80℃保温30min;加入3.6重量份硅烷,得到丙烯酸接枝的水性聚氨酯预聚体;
(4)氨化反应和水化反应:加入12重量份稀释用去离子水降温至75℃,10min内滴完,加入41重量份三乙醇胺保温10min进行氨化反应;加入900重量份稀释用去离子水,搅拌速度在80转/min进行水化反应;
(5)低温氧化还原反应:降低体系温度至60℃,搅拌速度为35转/min,30min内加入1.5重量份叔丁基过氧化氢,5min后滴加0.5重量份VC钠,15min内滴完;
(6)pH值调整及防腐处理:降低体系温度至50℃,加入15重量份氨水、12重量份系使用去离子水及1.77重量份杀菌剂,得到水性聚氨酯-丙烯酸接枝树脂。
本发明中通过配比丙烯酸羟乙酯的含量调节水性聚氨酯-丙烯酸接枝树脂的再溶性,配比双羟甲基丙酸的含量调节水性聚氨酯-丙烯酸接枝树脂的醇溶性,配比甲基丙烯酸丁酯的的含量调节水性聚氨酯-丙烯酸接枝树脂的显色性,同时接枝硅烷,增加水性聚氨酯-丙烯酸接枝树脂的耐水性,通过本申请中的制备方法获得细粒径的水性聚氨酯-丙烯酸接枝树脂,从而获得良好的附着力。
使用本水性聚氨酯-丙烯酸接枝树脂用于底漆水性修色主剂的配方:10~20%水性聚氨酯-丙烯酸接枝树脂、80~90%医用酒精和0.1~0.2润湿流平剂TEGO 4100。
对本发明水性聚氨酯-丙烯酸接枝树脂进行再溶性、与色精稳定性和附着力进行测试。
表1水性聚氨酯-丙烯酸接枝树脂再溶性测试数据
表2水性聚氨酯-丙烯酸接枝树脂与色精稳定性测试数据
表3水性聚氨酯-丙烯酸接枝树脂附着力性能测试数据
表3中水性聚氨酯-丙烯酸接枝树脂作为修色液基料进行附着力测试,其中修色液配方为:89.4%酒精、0.6%Tego270润湿剂、20%水性聚氨酯-丙烯酸接枝树脂和10%混合水溶性色精,底材为油性UV、PU、PE透明底板,测试结果如表3所示。
根据表1、表2和表3中水性聚氨酯-丙烯酸接枝树脂的性能测试数据可得,本发明水性聚氨酯-丙烯酸接枝树脂具有优异的再溶性和附着力,使用本发明水性聚氨酯-丙烯酸接枝树脂制修色光油可加入小于35%的水溶性色精。
本发明的主要功能:本发明的水性聚氨酯-丙烯酸接枝树脂可以用作水性木器漆的底漆修色和基材修色树脂,也可以用于底着色,特别是UV地板底着色,适用于滚涂,喷涂,对酒精具有优异的相容性,对水性色精的润色和展色效果非常优异,可以干修,湿修,亦可深修,浅修,静电喷涂,过三辊机均可,同时具有优秀的入孔性,渗透性,制成修色主剂后与水性色精的相容性很好,经修色后漆膜不发花,不起颗粒,不发白,附着力优秀,树脂成膜后起颗粒能够再次溶解入新的涂料体系,在UV基材、PU涂层、PVC、PE、PET、PP等塑料基材,均具有优秀的附着力和优秀的抗粘连性能。
综上所述,本领域的普通技术人员阅读本发明文件后,根据本发明的技术方案和技术构思无需创造性脑力劳动而作出其他各种相应的变换方案,均属于本发明所保护的范围。
Claims (10)
1.一种水性聚氨酯-丙烯酸接枝树脂的制备方法,其特征在于,包括以下接枝步骤:
在水性聚氨酯预聚体中滴入丙烯酸羟乙酯,并加入二甲基甲酰胺进行保温;
加入丙烯酸单体搅拌溶解,保持温度进行反应,得到丙烯酸接枝的水性聚氨酯预聚体。
2.一种水性聚氨酯-丙烯酸接枝树脂的制备方法,其特征在于,包括以下制备步骤:
(1)聚合反应:加入聚醚多元醇和二异氰酸酯进行聚合反应,依次加入双羟甲基丙酸和二甲基甲酰胺进行聚合反应,得水性聚氨酯预聚体;
(2)桥接反应:向上述水性聚氨酯预聚体滴入丙烯酸羟乙酯,加入二甲基甲酰胺进行保温;
(3)接枝反应:加入丙烯酸单体搅拌溶解,保持温度进行反应;得到丙烯酸接枝的水性聚氨酯预聚体;
(4)氨化反应和水化反应:加入去离子水降温后加入三乙醇胺进行氨化反应;加入去离子水搅拌进行水化反应;
(5)低温氧化还原反应:降低体系温度,加入叔丁基过氧化氢和VC钠;
(6)pH值调整及防腐处理:降低体系温度,加入氨水、去离子水及杀菌剂。
3.根据权利要求2所述的一种水性聚氨酯-丙烯酸接枝树脂的制备方法,其特征在于,所述步骤(1)中二异氰酸酯为异佛尔酮二异氰酸酯和氢化苯基甲烷二异氰酸酯。
4.根据权利要求3所述的一种水性聚氨酯-丙烯酸接枝树脂的制备方法,其特征在于,所述步骤(1)中反应釜温度为90℃,搅拌50转/分钟。
5.根据权利要求2所述的一种水性聚氨酯-丙烯酸接枝树脂的制备方法,其特征在于,所述步骤(1)加入聚醚多元醇和二异氰酸酯前,将反应釜在100℃下负压加热脱水。
6.根据权利要求2所述的一种水性聚氨酯-丙烯酸接枝树脂的制备方法,其特征在于,所述步骤(2)中保温温度为82℃,保温30min。
7.根据权利要求2所述的一种水性聚氨酯-丙烯酸接枝树脂的制备方法,其特征在于,所述步骤(3)中丙烯酸单体包括甲基丙烯酸丁酯、甲基丙烯酸甲酯、丙烯酸丁酯和甲基丙烯酸烯丙酯。
8.根据权利要求7所述的一种水性聚氨酯-丙烯酸接枝树脂的制备方法,其特征在于,所述步骤(3)中还包括硅烷接枝反应。
9.根据权利要求2所述的一种水性聚氨酯-丙烯酸接枝树脂的制备方法,其特征在于,包括以下制备步骤:
(1)聚合反应:加入160重量份聚醚多元醇、15重量份异佛尔酮二异氰酸酯、15重量份氢化苯基甲烷二异氰酸酯和30重量份双羟甲基丙酸在90℃下搅拌1h,加入45重量份二甲基甲酰胺,得水性聚氨酯预聚体;
(2)桥接反应:上述水性聚氨酯预聚体降温到82℃,滴入30重量份丙烯酸羟乙酯,加入12重量份二甲基甲酰胺进行保温30min;
(3)接枝反应:在温度在80~81℃下滴加56重量份甲基丙烯酸丁酯、150重量份甲基丙烯酸甲酯、35重量份丙烯酸丁酯和77重量份甲基丙烯酸烯丙酯,在温度80℃保持30min;加入3.6重量份硅烷,得到丙烯酸接枝的水性聚氨酯预聚体;
(4)氨化反应和水化反应:加入12重量份稀释用去离子水降温至75℃,加入41重量份三乙醇胺保温10min进行氨化反应;加入900重量份稀释用去离子水搅拌进行水化反应;
(5)低温氧化还原反应:降低体系温度至60℃,加入1.5重量份叔丁基过氧化氢和0.5重量份VC钠;
(6)pH值调整及防腐处理:降低体系温度至50℃,加入15重量份氨水、12重量份系使用去离子水及1.77重量份杀菌剂。
10.根据权利要求1-9中任一项中的制备的一种水性聚氨酯-丙烯酸接枝树脂在水性着色剂中的应用。
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