CN115124690A - 一种超支化阳离子水性聚氨酯固色剂及其制备方法 - Google Patents
一种超支化阳离子水性聚氨酯固色剂及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种超支化阳离子水性聚氨酯固色剂及其制备方法,固色剂由包括以下质量百分含量的原料制备得到:多官能度小分子多元醇5%~10%,二异氰酸酯40%~50%,低聚物多元醇35%~45%,亲水扩链剂3%~6%,封端剂2%~5%,中和剂1%~3%,催化剂0.1~0.3%。与现有技术相比,本发明超支化阳离子水性聚氨酯具有分子量高、粘度低、活性位点多的特点,将其应用于活性染料染色织物固色后处理过程,具有较好的固色效果,同时由于其不含甲醛,符合环保要求。
Description
技术领域
本发明涉及染色助剂制备技术领域,具体涉及一种超支化阳离子水性聚氨酯固色剂及其制备方法。
背景技术
织物在制造过程中,为获得多彩的颜色,一般都需要染料对其染色。目前用染色的主要染料有活性染料、直接染料、硫化染料及还原染料等。其中活性染料因其色泽鲜艳、色谱齐全、工艺经济、匀染性好、价格较低等优点,而备受印染行业的喜爱且已成为当今的主流。但是,因为活性染料分子结构中含有水溶性基团(磺酸基、羧酸基等)导致织物染色的耐湿牢度较低,并且活性染料也会因水解或皂洗不充分使湿处理牢度下降。为了改进织物色牢度,需要使用固色剂进行固色处理。
因相继出台的限制纺织品上游离甲醛含量的有关规定,使得含有甲醛的固色剂纷纷被淘汰,因此印染厂家对无甲醛固色剂的需求与日俱增。目前使用的无醛固色剂有多阳离子型聚合物、多胺缩合物、胺与环氧氯丙烷缩合物的反应型固色剂、季铵盐型固色剂等,这些种类的固色剂虽然解决了环保问题,但其固色性能和效果不佳,且生产工艺较为复杂。所以,还没有一种性能优良,制造方便的无甲醛固色剂。
超支化聚合物具有高度支化的结构,有大量可改性的活性端基,以及分子链较少缠结,不结晶、溶解性良好、低粘度,高反应活性的特质。其合成过程相对简单,效率高、成本低,有利于工业化的生产。聚氨酯在固色剂领域有着重要应用,如中国专利CN105175672A提到的阴离子聚氨酯固色剂,中国专利CN101736619A提到的阳离子型反应性聚氨酯固色剂等具有较好的固色效果,但都是直链型结构,超支化型结构未见报道。
发明内容
本发明的目的是提供一种超支化阳离子水性聚氨酯固色剂及其制备方法,方法简单,不含甲醛。
本发明的目的可以通过以下技术方案来实现:一种超支化阳离子水性聚氨酯固色剂,其特征在于,由包括以下质量百分含量的原料制备得到:多官能度小分子多元醇5%~10%,二异氰酸酯40%~50%,低聚物多元醇35%~45%,亲水扩链剂3%~6%,封端剂2%~5%,中和剂1%~3%,催化剂0.1~0.3%。
优选地,所述的多官能度小分子多元醇的核分子选自丙三醇、三羟甲基丙烷、季戊四醇中的一种。
进一步优选地,所述的多官能度小分子多元醇的核分子为丙三醇、季戊四醇。
优选地,所述的二异氰酸酯选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、1,6-己基二异氰酸酯、六亚甲基二异氰酸酯、二环己基二异氰酸酯、四甲基环己基甲烷二异氰酸酯、二苯基甲烷二异氰酸酯中的一种或一种以上的混合。
进一步优选地,所述的二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯。
优选地,所述的低聚物多元醇选自聚乙二醇、聚丙二醇、聚四氢呋喃醚二醇、聚碳酸酯多元醇、聚己内酯多元醇的一种或一种以上的混合。
进一步优选地,所述的低聚物多元醇为聚乙二醇、聚丙二醇。
优选地,所述的亲水扩链剂为N-甲基二乙醇胺。
优选地,所述的封端剂为甲乙酮肟、亚硫酸氢钠、苯酚、咪唑、ε-己内酰胺中的一种。
进一步优选地,所述的封端剂为甲乙酮肟。
优选地,所述的中和剂为冰醋酸。
优选地,所述的催化剂为二月桂酸二丁基锡(DBTDL)。
一种上述超支化阳离子水性聚氨酯固色剂的制备方法,包括以下步骤:
(1)将已除水的多官能度小分子多元醇、二异氰酸酯和催化剂,在惰性气体保护的条件下催化反应;
(2)加入低聚物多元醇和亲水扩链剂反应,期间加入溶剂;
(3)加入封端剂进行封端;
(4)加入中和剂进行中和;
(5)加入去离子水乳化,之后除去溶剂得到所述的超支化阳离子水性聚氨酯固色剂。
进一步优选地,所述的制备方法具体包括以下步骤:
(1)将已除水的多官能度小分子多元醇、二异氰酸酯和催化剂,在温度为70~90℃、搅拌转速为70~110r/min、惰性气体保护的条件下催化反应至产物的NCO含量接近理论值时,停止反应;
(2)缓慢降温至60~80℃,调整搅拌转速为50~70r/min,加入低聚物多元醇和亲水扩链剂反应,当反应至产物的NCO含量接近理论值时,停止反应,期间根据粘度变化情况加入溶剂;
(3)降温至50~60℃,加入封端剂进行封端;
(4)降温至40℃,加入中和剂进行中和;
(5)降温至30℃,在1500~2000r/min的转速下,加入计量好的去离子水,乳化0.5h,之后旋蒸除去溶剂得到超支化阳离子水性聚氨酯固色剂。
优选地,步骤(1)所述的保护气体为干燥氮气。
优选地,步骤(1)中的反应温度为70℃,反应时间为3h。
优选地,步骤(2)所述的溶剂为丙酮、丁酮、甲苯中的一种或一种以上的混合物。
进一步优选地,步骤(2)所述的溶剂为丙酮。
优选地,步骤(2)中的反应温度为65℃,反应时间为2h。
优选地,步骤(3)中的封端温度为55℃,封端时间为2h。
优选地,步骤(4)中的中和时间为30min。
本发明以多官能度的小分子多元醇为核分子,在催化剂的作用下依次与二异氰酸酯、低聚物多元醇、亲水扩链剂反应,合成一种端异氰酸酯基的超支化聚合物,再使用封端剂将异氰酸酯基团封闭,最后经中和、乳化分散得热反应型的超支化阳离子水性聚氨酯。
与现有技术相比,本发明具有以下优点:
1.本发明方法简单,不含甲醛,制得固色剂的分子结构中含有待解封的异氰酸酯基团,解封后能与染料分子中的活泼氢反应,增进染料与织物的结合力,季铵盐基团与纤维表面的染料阴离子基团(羧基、磺酸基)形成静电结合,将水溶性基团封闭,使染料在纤维上沉着;
2.本发明得益于超支化结构,有着分子量大、粘度低的特点,并且相比相同分子量的固色剂,有着多触点、活性位点多的优势,可使固色剂能与活性染料进行高效的结合,大大增强固色效果;
3.本发明合成工艺简单,反应过程稳定,易于控制,合成的超支化聚合物粘度较低,大大减少了有机溶剂的使用,对环境友好,并且本发明方法中的高分子链段的刚柔可按需设计,适用范围广,实用性强。
具体实施方式
下面对本发明的实施例作详细说明,以下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
(1)称取2.6g丙三醇于四口烧瓶中,加入17.8g异佛尔酮二异氰酸酯及0.04g二月桂酸二丁基锡,在76r/min的搅拌转速下,在氮气保护下,80℃反应,期间视粘度增大情况加入2g丙酮降低粘度,反应3h,测得-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值13.4%~14.7%时降温。
(2)缓慢降温至65℃,称取11.7g聚丙二醇-1000、1.3g聚乙二醇-1000、1.2gN-甲基二乙醇胺加入其中,调整搅拌转速为56r/min,期间视粘度增大情况加入8g丙酮降低粘度,反应2h,测得-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值2.35%~3%时降温。
(3)降温至55℃,加入1.09g甲乙酮肟封端,反应2h,至剩余-NCO完全被封闭。
(4)降温至40℃,称取0.6g冰醋酸加入体系,调整转速至100r/min,中和30min。
(5)继续降温至30℃,在2000r/min的转速下,向上述预聚体中加入84.7g去离子水,乳化30min,降温出料,旋蒸除去溶剂,得到超支化阳离子水性聚氨酯乳液。
实施例2
(1)称取2.88g季戊四醇于四口烧瓶中,加入17.8g异佛尔酮二异氰酸酯及0.04g二月桂酸二丁基锡,在76r/min的搅拌转速下,在氮气保护下,80℃反应,期间视粘度增大情况加入2g丙酮降低粘度,反应3h,测得-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值13.2%~14.5%时降温。
(2)缓慢降温至65℃,称取11.7g聚丙二醇-1000、1.3g聚乙二醇-1000、1.2gN-甲基二乙醇胺加入其中,调整搅拌转速为56r/min,期间视粘度增大情况加入8g丙酮降低粘度,反应2h,测得-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值2.35%~3%时降温。
(3)降温至55℃,加入1.09g甲乙酮肟封端,反应2h,至剩余-NCO完全被封闭。
(4)降温至40℃,称取0.6g冰醋酸加入体系,调整转速至100r/min,中和30min。
(5)继续降温至30℃,在2000r/min的转速下,向上述预聚体中加入85.3g去离子水,乳化30min,降温出料,旋蒸除去溶剂,得到超支化阳离子水性聚氨酯乳液。
实施例3
(1)称取2.6g丙三醇于四口烧瓶中,加入13.1g甲苯二异氰酸酯及0.04g二月桂酸二丁基锡,在76r/min的搅拌转速下,在氮气保护下,70℃反应,期间视粘度增大情况加入2g丙酮降低粘度,反应3h,测得-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值15.7%~17.7%时降温。
(2)缓慢降温至65℃,称取11.7g聚丙二醇-1000、1.3g聚乙二醇-1000、1.2gN-甲基二乙醇胺加入其中,调整搅拌转速为56r/min,期间视粘度增大情况加入8g丙酮降低粘度,反应2h,测得-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值2.12%~2.83%时降温。
(3)降温至55℃,加入0.88g甲乙酮肟封端,反应2h,至剩余-NCO完全被封闭。
(4)降温至40℃,称取0.6g冰醋酸加入体系,调整转速至100r/min,中和30min。
(5)继续降温至30℃,在2000r/min的转速下,向上述预聚体中加入73.2g去离子水,乳化30min,降温出料,旋蒸除去溶剂,得到超支化阳离子水性聚氨酯乳液。
实施例4
(1)称取2.88g季戊四醇于四口烧瓶中,加入13.1g甲苯二异氰酸酯及0.04g二月桂酸二丁基锡,在76r/min的搅拌转速下,在氮气保护下,70℃反应,期间视粘度增大情况加入2g丙酮降低粘度,反应3h,测得-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值15.4%~17.3%时降温。
(2)缓慢降温至65℃,称取11.7g聚丙二醇-1000、1.3g聚乙二醇-1000、1.2gN-甲基二乙醇胺加入其中,调整搅拌转速为56r/min,期间视粘度增大情况加入8g丙酮降低粘度,反应2h,测得-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值2.07~2.76%时降温。
(3)降温至55℃,加入0.86g甲乙酮肟封端,反应2h,至剩余-NCO完全被封闭。
(4)降温至40℃,称取0.6g冰醋酸加入体系,调整转速至100r/min,中和30min。
(5)继续降温至30℃,在2000r/min的转速下,向上述预聚体中加入73.8g去离子水,乳化30min,降温出料,旋蒸除去溶剂,得到超支化阳离子水性聚氨酯乳液。
对实施例1-4制备的超支化阳离子水性聚氨酯进行13C-NMR谱图分析,由聚合物的谱图中对应峰面积计算出的支化度如表1所示:
表1超支化阳离子聚氨酯支化度
实例 | 支化度(DB) |
实例1 | 0.65 |
实例2 | 0.76 |
实例3 | 0.65 |
实例4 | 0.76 |
对于完全支化具有规整结构的树枝状大分子,只存在末端单元和支化单元,因此树枝状大分子的支化度为1,超支化聚合物的支化度都小于1。实例1-4制备的聚合物的支化度都小于1,说明已经合成超支化结构的聚合物。
下面对本发明制备的固色剂进行性能测试。
将上述实施例所得产品和两种市售固色剂对纺织品进行固色处理,按照如下实验方法评价其应用效果:
固色工艺:染色-水洗-二浸二轧(固色剂,浴比1:10,轧余率75%)-预烘(80℃,4min)-焙烘(130℃,3min)-测试。摩擦牢度测试方法按GB/T3920-2008《纺织品色牢度试验耐摩擦色牢度》方法测定,皂洗牢度测试方法按GB/T3921-2008《纺织品色牢度试验耐洗色牢度》方法测定。测试结果如表2所示:
表2超支化阳离子水性聚氨酯固色剂性能测试
由上表可以看出,本发明合成的超支化阳离子水性聚氨酯固色剂与市售固色剂相比,皂洗色牢度提高1~1.5级,干摩擦牢度提高0.5~1.5级,湿摩擦牢度提高0.5~1级,固色性能优异。
本发明的超支化阳离子水性聚氨酯具有分子量高、粘度低、活性位点多的特点,将其应用于活性染料染色织物固色后处理过程,具有较好的固色效果,同时由于其不含甲醛,符合环保要求。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (10)
1.一种超支化阳离子水性聚氨酯固色剂,其特征在于,由包括以下质量百分含量的原料制备得到:多官能度小分子多元醇5%~10%,二异氰酸酯40%~50%,低聚物多元醇35%~45%,亲水扩链剂3%~6%,封端剂2%~5%,中和剂1%~3%,催化剂0.1~0.3%。
2.根据权利要求1所述的超支化阳离子水性聚氨酯固色剂,其特征在于,所述的多官能度小分子多元醇的核分子选自丙三醇、三羟甲基丙烷、季戊四醇中的一种。
3.根据权利要求1所述的超支化阳离子水性聚氨酯固色剂,其特征在于,所述的二异氰酸酯选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、1,6-己基二异氰酸酯、六亚甲基二异氰酸酯、二环己基二异氰酸酯、四甲基环己基甲烷二异氰酸酯、二苯基甲烷二异氰酸酯中的一种或一种以上的混合。
4.根据权利要求1所述的超支化阳离子水性聚氨酯固色剂,其特征在于,所述的低聚物多元醇选自聚乙二醇、聚丙二醇、聚四氢呋喃醚二醇、聚碳酸酯多元醇、聚己内酯多元醇的一种或一种以上的混合。
5.根据权利要求1所述的超支化阳离子水性聚氨酯固色剂,其特征在于,所述的亲水扩链剂为N-甲基二乙醇胺。
6.根据权利要求1所述的超支化阳离子水性聚氨酯固色剂,其特征在于,所述的封端剂为甲乙酮肟、亚硫酸氢钠、苯酚、咪唑、ε-己内酰胺中的一种。
7.根据权利要求1所述的超支化阳离子水性聚氨酯固色剂,其特征在于,所述的中和剂为冰醋酸。
8.根据权利要求1所述的超支化阳离子水性聚氨酯固色剂,其特征在于,所述的催化剂为二月桂酸二丁基锡。
9.一种如权利要求1~8任一项所述的超支化阳离子水性聚氨酯固色剂的制备方法,其特征在于,包括以下步骤:
(1)将已除水的多官能度小分子多元醇、二异氰酸酯和催化剂,在惰性气体保护的条件下催化反应;
(2)加入低聚物多元醇和亲水扩链剂反应,期间加入溶剂;
(3)加入封端剂进行封端;
(4)加入中和剂进行中和;
(5)加入去离子水乳化,之后除去溶剂得到所述的超支化阳离子水性聚氨酯固色剂。
10.根据权利要求9所述的超支化阳离子水性聚氨酯固色剂的制备方法,其特征在于,所述的惰性气体为干燥氮气;溶剂为丙酮、丁酮、甲苯中的一种或一种以上的混合物。
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