CN116926711A - 一种阳离子染料可染锦纶纤维的制造方法 - Google Patents
一种阳离子染料可染锦纶纤维的制造方法 Download PDFInfo
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- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
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Abstract
本发明涉及一种阳离子染料可染锦纶纤维的制造方法。旨在通过将常规锦纶切片、阳离子染料可染改性剂、分散剂混合均匀，经熔融纺丝制造一种阳离子染料可染锦纶纤维。所述阳离子染料可染锦纶改性剂主要成分为(甲基)丙烯酸甲酯、不饱和羧酸盐、不饱和磺酸盐的无规共聚高分子化合物，其中不饱和羧酸盐和磺酸盐的用量不低于80％。改性后的锦纶纤维含有大量带负电荷的‑COONa和‑SO3Na，可以与阳离子染料以盐式键结合，这样就赋予了锦纶纤维阳离子染料可染性。这种方法简单易实施、易推广；也可以解决目前锦纶用弱酸性染料、中性染料染色牢度不理想、有重金属离子等困扰，充分发挥阳离子染料色谱全、颜色鲜艳、牢度好等优点。
Description
技术领域
本发明涉及纺织纤维技术领域，特别涉及在常规锦纶切片中加入阳离子染料可染锦纶改性剂，经共混熔融纺丝制造一种阳离子染料可染锦纶纤维。
背景技术
锦纶又称为尼龙、聚酰胺，大分子链有很多酰胺键、分子链末端含有氨基和羧基，可以用活性染料、弱酸性染料、中性染料等进行染色，实际生产中最常用的是弱酸性染料和中性染料染色。弱酸性染料主要靠氢键和范德华力与锦纶纤维结合，色牢度不理想；中性染料色牢度高，但颜色不够鲜艳、含有重金属离子；活性染料主要是与锦纶大分子链末端的氨基反应形成共价键，色牢度虽好，但端氨基的数量有限，很难染得深色。阳离子染料颜色鲜艳、耐光耐洗牢度好，因此一种阳离子染料可染锦纶纤维的研究近年来成为研究热点。
通过改性在锦纶纤维中引入能与阳离子染料形成盐式键的阴离子染座，赋予锦纶阳离子染料可染性。常用的改性的方法主要有共聚改性(含接枝共聚)和共混改性两种。
CN113005795A公开了一种制备阳离子染料可染的锦纶纤维的方法，通过醋酸对锦纶纤维制品预处理，结合接枝硫辛酸、二硫键还原和氧化聚合反应，在锦纶纤维上引入羧基，提升锦纶纤维染色性能。CN112458567A公开了阳离子染料可染聚酰胺纤维及有色聚酰胺织物，纤维中含有聚酰胺纤维总量0.01-15.0％wt的耐光助剂，这种纤维或织物具有阳离子染料可染性。CN 108774908A公开了一种阳离子染料可染尼龙6纤维，采用氧化-还原引发体系、丙烯酸为单体，在常规尼龙6纤维的表面通过接枝聚合引入羧基，赋予其阳离子染料可染性；CN108976408A公开了一种阳离子易染尼龙66树脂及其制备方法，先将间苯二甲酸-5-磺酸盐与己二胺溶液反应成盐，然后该盐溶液再与66盐共聚，通过共聚改性实现阳离子染料可染；CN103232596B公开了一种脂肪族聚酰胺改性共聚酯、脂肪族聚酰胺改性共聚酯纤维及它们的制备方法，通过在常规聚酯大分子链中同时引入磺酸盐基团和柔性的脂肪族聚酰胺，改性后的聚酯纤维可以用阳离子染料进行染色；CN111364117A公开了一种阳离子易染聚酯酰胺纤维，将己内酰胺、间苯二甲酸二元醇酯-5-磺酸碱金属盐、间苯二甲酸-5-磺酸碱金属盐进行聚合得到阳离子易染聚酯酰胺树脂，切片、纺丝制得阳离子易染聚酯酰胺纤维。
发明内容
本发明提供了一种阳离子染料可染锦纶纤维的制造方法。该方法是采用含有磺酸钠基团和羧酸钠基团的高分子改性剂、分散剂与常规锦纶切片混合进行熔融纺丝制造阳离子染料可染锦纶(一步法)；也可以用改性剂、分散剂与常规锦纶切片先制成改性切片，再用改性切片与常规锦纶切片共混熔融纺丝(两步法)；还可以将常规锦纶切片、改性剂、分散剂混合均匀，经熔融铸带、切片、干燥，得到改性切片，用阳离子染料对改性切片染色，得到有色切片，再将有色切片与常规锦纶切片计量混合，进行熔融纺丝，制得有色锦纶纤维(三步法)。该方法既适合切片生产企业又适合锦纶纺丝企业，既可以先用改性切片染色，然后再与常规切片共混纺有色丝，又可以纺丝、织造后再染色，成本低，方法灵活，适合工业化大规模生产。
本发明的具体技术方法为：
一种阳离子染料可染锦纶纤维的制备方法，其特征在于，可以选择一步法、两步法或者三步法之一，将常规锦纶切片、阳离子染料可染改性剂、分散剂共混，经熔融纺丝制造阳离子染料可染锦纶纤维。
阳离子染料可染锦纶改性剂主要成分为(甲基)丙烯酸甲酯、不饱和羧酸盐、不饱和磺酸盐的无规共聚物，其中不饱和羧酸盐和磺酸盐的用量不低于80％。其基本结构为：
其中：
X＝H或者CH3
M3可以是苯乙烯-3-磺酸钠、或者苯乙烯-4-磺酸钠或者它们的混合物。
M4中：Y＝Z＝H时，M4代表丙烯酸钠；
Y＝COONa、Z＝H，M4代表马来酸二钠盐；
Y＝H、Z＝CH2COONa，M4代表衣康酸二钠盐。
M4也可以是上述三种钠盐一定比例的混合物。
一步法时阳离子染料可染锦纶改性剂的用量为纺丝切片总质量的1-10％，优选2-5％。两步法和三步法制备改性切片时阳离子染料可染锦纶改性剂的用量为改性切片总质量的20-50％，优先30-40％。
分散剂为阴离子分散剂，如所酸盐类(R-COONa)、磺酸盐类(R-SO3Na)、硫酸酯盐类(R-OSO3Na)、低分子量聚丙烯酸钠、低分子量马丙共聚的钠盐等。其用量为改性切片总质量的1-8％，优先2-5％。
制备改性切片和纺丝时熔融温度为240-300℃，优先260-280℃。针对不同的锦纶熔融温度应该适当调整。
两步法和三步法纺丝时改性切片或者有色切片与常规锦纶切片的计量比例可根据颜色深浅调整，建议质量比为1:5-40，优选1:6-30。
具体实施方式
下面列举一部分具体实施例对本发明进行说明，有必要在此指出的是以下具体实施例只用于对本发明作进一步说明，不代表对本发明保护范围的限制。其他人根据本发明做出的一些非本质的修改和调整仍属于本发明的保护范围。以下所有份数均为质量份数。
实施例1:
将4份阳离子染料可染锦纶改性剂、3份分散剂、93份常规锦纶66切片混合均匀，275℃进行熔融纺丝制造阳离子染料可染锦纶66。该锦纶66纤维可以用阳离子染料染需要的任何颜色。
实施例2:
A、将40份阳离子染料可染锦纶改性剂、4份分散剂、56份常规锦纶6切片混合均匀，265℃熔融铸带、切片、130℃干燥1小时，得到改性切片；
B、将8份改性切片与92份常规锦纶6切片混合均匀，265-270℃进行熔融纺丝，制得阳离子染料可染锦纶6纤维，该锦纶6纤维或织物可以用阳离子染料染需要的任何颜色。
实施例3：
A、将66.5份常规锦纶6切片、30份阳离子染料可染锦纶改性剂、3.5分散剂混合均匀，265℃熔融铸带、切片、135℃干燥1小时，得到改性切片；
B、用1-5％阳离子染料对改性切片染色，得到有色切片；
C、将10份有色切片与90份常规锦纶6切片混合均匀，进行265-270℃熔融纺丝，制得有色锦纶6纤维。
实施例4：
A、将40份阳离子染料可染锦纶改性剂、4份分散剂、56份常规锦纶66切片混合均匀，275℃熔融铸带、切片、130℃干燥1小时，得到改性切片；
B、将8份改性切片与92份常规锦纶66切片混合均匀，275-280℃进行熔融纺丝，制得阳离子染料可染锦纶66纤维，该锦纶66纤维或织物可以用阳离子染料染需要的任何颜色。
实施例5：
A、将61.5份常规锦纶66切片、35份阳离子染料可染锦纶改性剂、3.5分散剂混合均匀，275℃熔融铸带、切片、135℃干燥1小时，得到改性切片；
B、用1-5％阳离子染料对改性切片染色，得到有色切片；
C、将10份有色切片与90份常规锦纶66切片混合均匀，275-280℃进行熔融纺丝，制得有色锦纶66纤维。
实施例6：
A、将40份阳离子染料可染锦纶改性剂、4.5份分散剂、20份常规锦纶66切片、35.5份常规锦纶6切片混合均匀，275℃熔融铸带、切片、130℃干燥1小时，得到改性切片；
B、将8份改性切片与92份常规锦纶66切片混合均匀，275-280℃进行熔融纺丝，制得阳离子染料可染锦纶混纺纤维，该锦纶混纺纤维可以用阳离子染料染需要的任何颜色。
实施例7：
A、将60份常规锦纶6切片、35份阳离子染料可染锦纶改性剂、5分散剂混合均匀，275℃熔融铸带、切片、135℃干燥1小时，得到改性切片；
B、用1-5％阳离子染料对改性切片染色，得到有色切片；
C、将10份有色切片与60份常规锦纶6切片、30份常规锦纶66切片混合均匀，270-280℃进行熔融纺丝，制得有色的锦纶66与锦纶6混纺纤维。
实施例8：
将5份阳离子染料可染锦纶改性剂、2.5份分散剂、92.5份常规锦纶6切片混合均匀，265℃进行熔融纺丝制造阳离子染料可染锦纶6。该锦纶6纤维可以用阳离子染料染需要的任何颜色。
Claims (8)
1.一种阳离子染料可染锦纶纤维的制造方法，其特征在于，将常规锦纶切片、阳离子染料可染锦纶改性剂、分散剂共混，经熔融纺丝制造阳离子染料可染锦纶纤维，包括三种具体方法：
一步法：常规锦纶切片、阳离子染料可染锦纶改性剂、分散剂混合均匀，→熔融纺丝→阳离子染料可染锦纶纤维；
两步法：(1)改性切片的制备：常规纤维级锦纶切片、阳离子染料可染锦纶改性剂、分散剂混合均匀→熔融铸带、切片、干燥→改性切片；(2)改性锦纶纤维的制备：改性切片、常规锦纶切片计量混合→熔融纺丝→阳离子染料可染锦纶纤维；
三步法：(1)改性切片的制备：常规纤维级锦纶切片、阳离子染料可染锦纶改性剂、分散剂混合均匀→熔融铸带、切片、干燥→改性切片，(2)有色切片的制备：阳离子染料、改性切片、水→有色切片；(3)有色锦纶纤维的制备：有色切片、常规锦纶切片计量混合→熔融纺丝→有色锦纶纤维。
2.如权利要求1所述的一种阳离子染料可染锦纶纤维的制造方法，其特征在于，所述的阳离子染料可染锦纶改性剂主要成分为(甲基)丙烯酸甲酯、不饱和羧酸盐、不饱和磺酸盐的无规共聚高分子化合物，其中不饱和羧酸盐和磺酸盐的用量不低于80％。
3.如权利要求1所述的一种阳离子染料可染锦纶纤维的制造方法，其特征在于，所述的一步法时改性剂的用量为纺丝切片总质量的1-10％，优选2-5％。
4.如权利要求1所述的一种阳离子染料可染锦纶纤维的制造方法，其特征在于，所述的两步法和三步法时阳离子染料可染锦纶改性剂的用量为改性切片总质量的20-50％，优先30-40％。
5.如权利要求1所述的一种阳离子染料可染锦纶纤维的制造方法，其特征在于，所述的分散剂为阴离子分散剂，如所酸盐类(R-COONa)、磺酸盐类(R-SO3Na)、硫酸酯盐类(R-OSO3Na)、低分子量聚丙烯酸钠、低分子量马丙共聚的钠盐等，其用量为改性单体总质量的1-8％，优先2-5％。
6.如权利要求1所述的一种阳离子染料可染锦纶纤维的制造方法，其特征在于，所述的制备改性切片和纺丝时熔融温度为240-300℃，优先260-280℃，可针对不同的锦纶熔融温度应该适当调整。
7.如权利要求1所述的一种阳离子染料可染锦纶纤维的制造方法，其特征在于，所述的纺丝时改性切片或者有色切片与常规锦纶切片的计量比例可根据颜色深浅调整，建议质量比为1:5-40，优选1:6-30。
8.如权利要求1所述的一种阳离子染料可染锦纶纤维的制造方法，适用于常见的锦纶6和锦纶66，也适用但不限于其它锦纶产品，如锦纶11、锦纶610等。
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