CN107501511B - 一种阴离子型复配水性聚氨酯基黑色染料及其制备方法 - Google Patents
一种阴离子型复配水性聚氨酯基黑色染料及其制备方法 Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/30—Low-molecular-weight compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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Abstract
本发明公开了一种阴离子型复配水性聚氨酯基黑色染料及其制备方法,将聚合物多元醇加热至100~140℃,真空度≤0.1MPa条件下,脱水处理1~2h,通入氮气保护;降温至60~90℃,加入多异氰酸酯、催化剂,反应1~3h;将小分子红、蓝、紫、黄色染料溶于溶剂中,依次加入50~90℃下反应,50~100℃下反应,制得带复配黑色聚氨酯预聚体;加入亲水性单体,50~90℃下反应;降温至30~50℃,加入成盐剂反应;加入去离子水高速分散,真空度脱溶剂制得阴离子型复配水性聚氨酯基高分子黑色染料乳液。本发明制备的聚氨酯基黑色高分子染料,将红、蓝、紫、黄染料接入聚氨酯链中制得,不但提高染料乌黑度和利用率,也提高染料的染色性能和色牢度性能。
Description
技术领域
本发明涉及一种高分子染料,尤其涉及的是一种阴离子型复配水性聚氨酯基黑色染料及其制备方法。
背景技术
小分子染料结合力不强、染料利用率低,以及耐迁移、耐热和耐溶剂等性能方面的欠缺,并且在使用过程中对环境造成的污染严重。将传统小分子染料高分子化即可有效解决上述问题。高分子染料是通过一定的化学反应将发色基团引入高分子的主链或侧链上而形成的一类新的有色高分子聚合物,即有高分子的高强度、易成膜性、耐溶剂性、耐迁移性、耐热性和可加工性,又有机染料对光的强吸收性和多彩性,表现出颜色鲜艳、色牢度好、染料利用率高、无毒和使用方便等特点
市场上,黑色染料用量约占染料总量的65%,黑色染料在纺织、印染、皮革、涂装、油墨等领域有着举足轻重的地位。早期黑色染料主要是由联苯胺衍生的偶氮染料,具有乌黑度好、上染率和固色率高的优点。但在生产与使用中会释放出致癌中间体联苯胺,严重污染环境,如果这些染料被人体吸收,又会危害人体健康造成严重后果。为此,上世纪70年代由联苯胺衍生的所有品种的黑色染料相继被禁用。
目前,黑色染料大多数是单一组分的小分子的分散黑染料存在的乌黑度低、提升力不足、牢度较差以及环境污染严重等主要问题。
复配技术是当前染料研究的热点,取得一定进展。通过复配技术获得黑色染料。不但可以提高染料乌黑度和利用率,也可以提高染料的染色性能和牢度性能。
《染料与染色》(2015年52卷第4期10-14页)报道了环保型黑色分散染料的复配技术。以C.I.分散紫93、C.I.分散蓝291∶1、C.I.分散橙73以及C.I.分散橙44为原料进行复配,获得染色性能更为优越的复配型分散黑染料。
《天津纺织科技》(2015年第204期22-25页)报道了复配技术对分散黑染料进行配方设计。经过复配配方设计所得的分散黑ECTT染料具有良好的染色性能,较市场上应用较多的分散黑EX-SF300%在染深性以及染色牢度上均有所提高。
阴离子型水性聚氨酯是在聚氨酯链上引入阴离子基团,使其具有足够的亲水性而分散在水中形成稳定的乳液。具有无毒、不易燃烧、不污染环境等优点,已被广泛应用于皮革涂饰、汽车涂装、纤维处理、造纸工业助剂、涂料和胶粘剂等领域。
发明内容
本发明的目的在于克服现有技术的不足,提供了一种阴离子型复配水性聚氨酯基黑色染料及其制备方法,通过复配技术实现将红、蓝、紫、黄染料接入聚氨酯链中。
本发明是通过以下技术方案实现的:本发明的一种阴离子型复配水性聚氨酯基黑色染料的制备方法,包括以下步骤:
(1)按重量计,将12~25%聚合物多元醇加热至100~140℃,真空度≤0.1MPa条件下,脱水处理1~2h,通入氮气保护;
(2)降温至60~90℃,加入6~15%多异氰酸酯、0.01~0.03%催化剂,反应1~3h;
(3)将10~20%的小分子红、蓝、紫、黄色染料溶于溶剂中,依次加入50~90℃下反应6~12h,50~100℃下反应6~12h,加入10~20%的有机溶剂调节黏度,制得带复配黑色聚氨酯预聚体;
(4)加入2~6%亲水性单体,50~90℃下反应1~3h;
(5)降温至30~50℃,加入2~6%成盐剂反应30~60min;
(6)加入50~75%的去离子水高速分散10~30min;
(7)真空度脱溶剂制得阴离子型复配水性聚氨酯基高分子黑色染料乳液。
作为本发明的优选方式之一,所述聚合物多元醇选自聚醚多元醇、聚酯多元醇中的至少一种。
作为本发明的优选方式之一,所述多异氰酸酯单体选自芳香族多异氰酸酯、脂肪族多异氰酸酯、脂环族多异氰酸酯中的任一种。
作为本发明的优选方式之一,所述小分子红色染料选自分散红17、分散红11(C.I.62015)中的至少一种。
作为本发明的优选方式之一,所述小分子蓝色染料选自分散蓝60(C.I.61104)、分散蓝14(C.I.61500)、分散蓝1(C.I.64500)中的至少一种。
作为本发明的优选方式之一,所述小分子紫色染料选自分散紫4BN(C.I.62030)、溶剂紫59(C.I.62025)中的至少一种。
作为本发明的优选方式之一,所述小分子黄色染料为分散荧光黄(CAS-RN:58232-21-6)。
作为本发明的优选方式之一,所述亲水扩链剂选自酒石酸、二羟甲基丙酸、二氨基苯甲酸、顺丁烯二酸酐、苯酐、丁二酸酐、戊二酸酐中的至少一种。
作为本发明的优选方式之一,所述有机溶剂选自丙酮、丁酮、甲乙酮、二氧六环、N,N-二甲基酰胺、N-甲基吡咯烷酮、乙酸乙酯中的至少一种。
作为本发明的优选方式之一,所述催化剂为有机锡类、叔胺类中的至少一种。
作为本发明的优选方式之一,所述成盐剂选自三乙胺,氨水、氢氧化钠中的至少一种。
一种使用所述的阴离子型复配水性聚氨酯基黑色染料的制备方法制得的染料。
本发明相比现有技术具有以下优点:本发明制备的聚氨酯基黑色高分子染料,具有优异的耐摩擦、耐迁移、耐候、耐迁移和安全性高特点。本发明制备的聚氨酯基黑色高分子染料,利用三基色原理,通过复配技术,将红、蓝、紫、黄染料接入聚氨酯链中制得,不但提高染料乌黑度和利用率,也提高染料的染色性能和色牢度性能。使用时可以直接染色,省去复杂的分散过程。
具体实施方式
下面对本发明的实施例作详细说明,本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
实施例1
在N2保护下,将装有搅拌器、冷凝管、温度计的四口瓶中加入100g,0.1mol聚四氢呋喃二醇,110℃,0.1MPa条件下,脱水处理2h。
降温至80℃,滴加44.5g,0.2mol异佛尔酮二异氰酸酯、40ml N-甲基吡咯烷酮和0.02g二月桂酸二丁基锡,90℃下反应3h。
将0.023mol7.9g C.I.分散红17、0.023mol 8.7g分散蓝60、0.023mol 6.5g分散紫4BN、0.023mol6.7g荧光黄分别溶于20ml丙酮,依次间隔2h加入反应器80℃下反应10h。
降温至70℃,加入0.05mol7g二羟甲基丙酸反应3h。
降温至30℃,加入0.06mol6g三乙胺反应30min。转移至乳化桶,加入300ml去离子水高速分散30min。
最后真空度脱溶剂制得阴离子型复配水性聚氨酯基高分子黑色染料乳液。
所得乳液平均粒径40nm,pH=8.0,固含量为38%,粘度52mPa·s。
所得染料,第一个阶段热分解温度270~350℃,第二个阶段热分解温度350~550℃,玻璃化转变温度60℃。
实施例2
在N2保护下,将装有搅拌器、冷凝管、温度计的四口瓶中加入100g,0.1mol聚己内酯二醇,110℃,0.1MPa条件下,脱水处理2h。
降温至70℃,50g,0.2mol4,4-二苯基甲烷二异氰酸酯(MDI)、20ml二氧六环和0.02g辛酸亚锡,80℃下反应3h。
将0.023mol7.9g C.I.分散红17、0.023mol6.1g分散蓝14、0.023mol9.7g溶剂紫59、0.023mol6.7g荧光黄分别溶于20ml丙酮,依次间隔2h加入反应器80℃下反应10h。
降温至70℃,加入0.05mol7g二羟甲基丙酸反应3h。
降温至30℃,加入0.06mol6g三乙胺反应30min。转移至乳化桶,加入300ml去离子水高速分散30min。
最后真空度脱溶剂制得阴离子型复配水性聚氨酯基高分子黑色染料乳液。
所得乳液平均粒径80nm,pH=9.0,固含量为38%,粘度70mPa·s。
所得染料,第一个阶段热分解温度275~370℃,第二个阶段热分解温度370~550℃,玻璃化转变温度64℃。
实施例3
向装备有温度计、搅拌器、回流冷凝器和滴液漏斗烧瓶内,加入100g,0.1mol聚氧化丙烯二醇,110℃,0.1MPa条件下,脱水处理1.5h。
降温至80℃,滴加34.8g,0.2mol甲苯二异氰酸酯、20ml丁酮和0.02g辛酸亚锡,90℃下反应3h。
将0.023mol 7.9g C.I.分散红17、0.023mol6.2g分散蓝1、0.023mol9.7g溶剂紫59、0.023mol6.7g荧光黄分别溶于20ml丙酮,依次间隔2h加入反应器80℃下反应10h。
降温至70℃,加入0.05mol7g二羟甲基丙酸反应3h。
降温至30℃,加入0.06mol6g三乙胺反应30min。转移至乳化桶,加入300ml去离子水高速分散30min。
最后真空度脱溶剂制得阴离子型复配水性聚氨酯基高分子黑色染料乳液。
所得乳液平均粒径85nm,pH=9.0,固含量为38%,粘度80mPa·s。
所得染料,第一个阶段热分解温度222~345℃,第二个阶段热分解温度345~550℃,玻璃化转变温度56℃。
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、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (6)
1.一种阴离子型复配水性聚氨酯基黑色染料的制备方法,其特征在于,包括以下步骤:
(1)按重量计,将12~25%聚合物多元醇加热至100~140℃,真空度≤0.1MPa条件下,脱水处理1~2h,通入氮气保护;
(2)降温至60~90℃,加入6~15%多异氰酸酯、0.01~0.03%催化剂,反应1~3h;
(3)将10~20%的小分子红、蓝、紫、黄色染料溶于溶剂中,依次加入50~90℃下反应6~12h,50~100℃下反应6~12h,加入10~20%的有机溶剂调节黏度,制得带复配黑色聚氨酯预聚体;
(4)加入2~6%亲水性单体,50~90℃下反应1~3h;
(5)降温至30~50℃,加入2~6%成盐剂反应30~60min;
(6)加入50~75%的去离子水高速分散10~30min;
(7)真空度脱溶剂制得阴离子型复配水性聚氨酯基高分子黑色染料乳液;
所述小分子红色染料选自分散红17、分散红11中的至少一种;
所述小分子蓝色染料选自分散蓝60、分散蓝14、分散蓝1中的至少一种;
所述小分子紫色染料选自分散紫4BN、溶剂紫59中的至少一种;
所述小分子黄色染料为分散荧光黄。
2.根据权利要求1所述的一种阴离子型复配水性聚氨酯基黑色染料的制备方法,其特征在于,所述聚合物多元醇选自聚醚多元醇、聚酯多元醇中的至少一种。
3.根据权利要求1所述的一种阴离子型复配水性聚氨酯基黑色染料的制备方法,其特征在于,所述多异氰酸酯单体选自芳香族多异氰酸酯、脂肪族多异氰酸酯、脂环族多异氰酸酯中的任一种。
4.根据权利要求1所述的一种阴离子型复配水性聚氨酯基黑色染料的制备方法,其特征在于,所述亲水扩链剂选自酒石酸、二羟甲基丙酸、二氨基苯甲酸、顺丁烯二酸酐、苯酐、丁二酸酐、戊二酸酐中的至少一种。
5.根据权利要求1所述的一种阴离子型复配水性聚氨酯基黑色染料的制备方法,其特征在于,所述有机溶剂选自丙酮、丁酮、甲乙酮、二氧六环、N,N-二甲基酰胺、N-甲基吡咯烷酮、乙酸乙酯中的至少一种。
6.一种使用如权利要求1~5任一项所述的阴离子型复配水性聚氨酯基黑色染料的制备方法制得的染料。
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