CN114481624B - 一种抗黄变添加剂及其制备方法与应用 - Google Patents
一种抗黄变添加剂及其制备方法与应用 Download PDFInfo
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- CN114481624B CN114481624B CN202210118125.9A CN202210118125A CN114481624B CN 114481624 B CN114481624 B CN 114481624B CN 202210118125 A CN202210118125 A CN 202210118125A CN 114481624 B CN114481624 B CN 114481624B
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
本发明公开了一种抗黄变添加剂及其制备方法与应用。以质量百分含量计,由下述组分制成:10‑35%小分子芳基磺酸化合物、0‑10%酚类化合物、0‑4%催化剂、0‑8%甲醛水溶液、0‑3%甲醛捕捉剂、10‑30%有机胺类化合物、2‑10%酰肼化合物、0.1‑6%亚磷酸酯抗氧剂、0‑9%乳化剂、1‑6%分散剂、0‑15%助溶剂和余量的水。本发明的抗黄变添加剂具有优异的抗黄变性能及耐候性能,能有效改善含氮高分子材料在高温热处理及储存运输过程的泛黄问题。
Description
技术领域
本发明涉及一种抗黄变添加剂及其制备方法与应用,属于纺织品染整技术领域。
背景技术
聚酰胺(又称“尼龙”、“锦纶”)、聚氨酯(又称“氨纶”)等高聚物分子结构中带有—NH—基团,具有独特的服用性能,已成为纺织纤维材料的重要成员,在高端泳衣、内衣、文胸、运动服、丝袜、花边等纺织服装领域发挥了难以替代的作用。但是,由于—NH—基团中与氮原子直接相连的氢原子较为活泼,易于受高温、光照、烟熏等外界环境影响而发生复杂的化学反应造成纤维材料泛黄,而且泛黄程度会随接触时间的延长而加重,聚酰胺、聚氨酯的黄变问题已成为制约该类纤维材料进一步发展的行业难题,亟待解决。
涉及到这类纺织品的常见黄变有高温黄变、储存(酚)黄变、光照黄变和烟熏黄变等。高温黄变主要与高温热定型、压模成型等加工过程相关,而储存(酚)黄变、光照黄变和烟熏黄变几乎贯穿于储存运输、商场展示及服用等全过程,在任一个环节发生黄变都会直接影响到纺织品的品质。这几种黄变的诱发机理各不一样,抑制黄变原理也不尽相同,而且有的还会相互负面影响,例如,有的抗酚黄变剂对高温黄变、光照黄变、烟熏黄变有负面影响,有的抗高温黄变剂对酚黄变有负面影响。因此,协同解决好这四方面的黄变,对于提升含锦纶、氨纶成分的纺织品品质具有重要意义。
发明内容
本发明的目的是提供一种抗黄变添加剂及其制备方法与应用,改善聚酰胺、聚氨酯等高分子纺织材料在高温、日照、烟熏、储存等过程的易泛黄问题,进而提升含锦纶、氨纶成分纺织服装的品质。
本发明所提供的抗黄变添加剂,是由特选的芳香族磺酸化合物与有机胺类化合物反应生成相应的铵盐后,与具有还原性的酰肼化合物、亚磷酸酯类抗氧剂复配增效而成。
上述抗黄变添加剂中,所述芳香族磺酸化合物,可为小分子芳基磺酸化合物,和/或高分子芳基磺酸聚合物按一定比例组合而成;
所述的高分子芳基磺酸聚合物,可为由小分子芳基磺酸化合物,和/或酚类化合物,在催化剂和水存在条件下与甲醛水溶液进行缩聚反应而成的芳基磺酸甲醛缩聚物。
具体地,本发明提供的抗黄变添加剂,以质量百分含量计,由下述组分制成:10-35%小分子芳基磺酸化合物、0-10%酚类化合物、0-4%催化剂、0-8%甲醛水溶液、0-3%甲醛捕捉剂、10-30%有机胺类化合物、2-10%酰肼化合物、0.1-6%亚磷酸酯抗氧剂、0-9%乳化剂、1-6%分散剂、0-15%助溶剂和余量的水。
上述的抗黄变添加剂中,所述的小分子芳基磺酸化合物,可为对甲苯磺酸、二甲苯磺酸、二壬基萘磺酸、二壬基萘二磺酸、苯酚磺酸、β-萘磺酸中的一种或多种;
上述的抗黄变添加剂中,所述的酚类化合物可为萘酚或双酚S中的一种或多种;
上述的抗黄变添加剂中,所述的催化剂可为质量分数大于等于98%的浓硫酸、对甲苯磺酸、二甲苯磺酸中的一种或多种;
上述的抗黄变添加剂中,所述的甲醛水溶液为36-42%的工业甲醛;
上述的抗黄变添加剂中,所述的甲醛捕捉剂可为尿素、2-咪唑烷酮中的一种或两种;
上述的抗黄变添加剂中,所述的有机胺类化合物可为二乙醇胺、三乙醇胺、二甲基乙醇胺、二乙基乙醇胺、甲基肼和偏二甲肼中的一种或多种;
上述的抗黄变添加剂中,所述的酰肼化合物可为碳酰肼、乙氧基甲酰肼、4-羟基丁酸肼中的一种或多种;
上述的抗黄变添加剂中,所述的亚磷酸酯抗氧剂可为一缩二丙二醇双亚磷酸酯、二亚磷酸季戊四醇二异癸酯、聚二丙二醇苯基亚磷酸酯中的一种或多种。
上述的抗黄变添加剂中,所述的乳化剂可为丙二醇嵌段聚醚,具体可为L61、L62、L64中的一种或多种;
上述的抗黄变添加剂中,所述的分散剂可为木质素磺酸盐,具体可为木质素磺酸铵;
上述的抗黄变添加剂中,所述的助溶剂可为一缩二乙二醇、乙二醇苯醚、二甲基亚砜中的一种或多种。
所述抗黄变添加剂不含酚类化合物、催化剂、甲醛水溶液及甲醛捕捉剂时,所述抗黄变添加剂通过包括如下步骤的方法制备得到:
1)将去离子水、助溶剂、芳基磺酸加入反应装置中,搅拌30-60min直至溶解均匀;
2)将有机胺类化合物分批滴加入步骤1)所得反应液中,持续搅拌30-120min,并控制反应液温度不超过70℃;
3)调节反应液pH值至4.0-7.0;
4)加入酰肼化合物,控制反应温度在50-70℃,持续搅拌30-120min,直至全部溶解均匀;
5)加入乳化剂、分散剂搅拌10-30min,加入亚磷酸酯抗氧剂继续搅拌60-180min,直至全部溶解分散均匀;
其中,步骤4)、5)的顺序可以互换;
6)调节反应液的pH值至4.0-7.0,过滤,出料,即制得所述的抗黄变添加剂。
所述抗黄变添加剂含酚类化合物、催化剂、甲醛水溶液及甲醛捕捉剂,所述抗黄变添加剂通过包括如下步骤的方法制备得到:
1)将去离子水、芳基磺酸、酚类化合物及催化剂依次加入到反应装置中,开启搅拌,控制转速在40-80转/分钟,加热;
2)待物料温度升至80-98℃后,将转速调至150-250转/分钟;
3)向反应物料中滴加甲醛水溶液,滴加时间控制在1-2小时;
4)甲醛滴加完成后,再恒温反应1-3小时;
5)升温至98-120℃,恒温反应4-8小时;
6)将物料温度快速降温至70-90℃;
7)加入甲醛捕捉剂,恒温反应1-3小时;
8)将物料温度快速降温至30-60℃;
9)将有机胺类化合物分批滴加入步骤8)所得反应液中,持续搅拌30-60min,控制反应液温度不超过70℃;
10)调节反应液pH值至4.0-7.0;
11)加入乳化剂、分散剂、亚磷酸酯抗氧剂,控制反应温度在40-70℃,继续搅拌60-180min,直至全部溶解分散均匀;
12)加入酰肼化合物,控制反应温度在50-70℃,持续搅拌30-120min,直至全部溶解均匀;
其中,步骤11)12)的顺序可以互换;
13)调节反应液pH值至4.0-7.0,过滤,出料,即得所述的抗黄变添加剂。
上述抗黄变添加剂应用于含氮高分子材料的抗黄变处理中。
所述应用中,所述高分子材料的分子结构中带有—NH2、—NH—、—CONH2、—CONH—、—NHCOO—等基团,包括但不限于聚氨酯助剂、聚氨酯纤维、聚氨酯海绵、聚氨酯薄膜、聚酰胺纤维、聚酰胺树脂、锦纶织物、锦氨纶织物等。
所述应用中,所述聚氨酯助剂可为粘合剂、交联剂、胶水、防水剂、柔软剂、固色剂、湿摩擦牢度提升剂、吸湿排汗整理剂等。
所述抗黄变添加剂可在聚合阶段、后处理阶段添加到所述的高分子材料中。
所述的聚合反应阶段添加,可为在合成高分子材料的聚合反应阶段与单体同时添加到反应体系中。
所述的聚合反应阶段添加,可为聚氨酯海绵在发泡阶段与发泡单体同时添加到发泡体系中。
所述的后处理阶段添加,可为在聚氨酯聚合物合成结束后加入到聚氨酯助剂中。
所述的后处理阶段添加,可为通过浸渍、浸轧或涂覆的方式施加到纤维、织物或薄膜上。
本发明的抗黄变添加剂具有如下有益效果:
1)本发明的抗黄变添加剂具有优异的抗黄变性能及耐候性能,能有效改善含氮高分子材料在高温热处理及储存运输过程的泛黄问题。
2)本发明的抗黄变添加剂,可在聚合、后处理等不同阶段施加到高分子材料上,处理方式灵活,应用领域广泛。
3)本发明的抗黄变添加剂,不含甲醛、己二酸二酰肼(简称“ADH”)、重金属离子及双酚A等禁限用物质,符合国内外纺织标准及品牌商对纺织材料的各项环保要求
具体实施方式
下面结合具体实施方式对本发明进行进一步的详细描述,给出的实施例仅为了阐明本发明,而不是为了限制本发明的范围。以下提供的实施例可作为本技术领域普通技术人员进行进一步改进的指南,并不以任何方式构成对本发明的限制。
下述实施例中的实验方法,如无特殊说明,均为常规方法,按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。下述实施例中所用的材料、试剂等,如无特殊说明,均可从商业途径得到。
实施例1
将8.5份乙二醇苯醚、6.5份二甲基亚砜、25.6份二壬基萘磺酸、6.7份二甲苯磺酸及1.3份β-萘磺酸加入到带有搅拌器的反应装置中,持续搅拌30分钟;再依次加入6.9份二乙醇胺、1.2份二甲基乙醇胺和21.2份二乙基乙醇胺,继续搅拌30分钟,并控制反应液温度不超过70℃,调节反应液的pH值至6.0;再加入3.8份嵌段聚醚L61、5.1份嵌段聚醚L62和1.2份木质素磺酸铵,搅拌10分钟;再滴加5.5份聚二丙二醇苯基亚磷酸酯,搅拌60分钟;再加入6.5份4-羟基丁酸肼,继续搅拌90分钟,调节反应液的pH值至6.0,过滤,出料,即制得抗黄变添加剂。
实施例1的各组分百分含量为:芳族磺酸33.6%,有机胺化合物29.3%,酰肼化合物6.5%,亚磷酸酯抗氧剂5.5%,乳化剂8.9%,分散剂1.2%和助溶剂15%。
实施例2
将6.5份一缩二乙二醇、3.5份二甲基亚砜、3.5份对甲苯磺酸、3.5份萘磺酸、22.9份二壬基萘二磺酸和17.9份去离子水加入到带有搅拌器的反应装置中,持续搅拌20分钟;再依次加入2.1份偏二甲肼、8.5份二甲基乙醇胺和17.1份三乙醇胺,继续搅拌60分钟后,调节反应液的pH值至5.0;再加入3.2份嵌段聚醚L61、3.2份嵌段聚醚L64和4.2份木质素磺酸铵,继续搅拌20分钟;再加入0.3份二亚磷酸季戊四醇二异癸酯和3.6份乙氧基甲酰肼,继续搅拌120分钟,调节反应液的pH值至5.0,过滤,出料,即制得抗黄变添加剂。
实施例2的各组分百分含量为:芳族磺酸29.9%,有机胺化合物27.7%,酰肼化合物3.6%,亚磷酸酯抗氧剂0.3%,乳化剂6.4%,分散剂4.2%,助溶剂10%,和去离子水17.9%。
实施例3
将2.9份一缩二乙二醇、7.5份对甲苯磺酸、7.5份二甲苯磺酸、7.5份二壬基萘二磺酸和41.3份去离子水加入到带有搅拌器的反应装置中,持续搅拌30分钟;再依次加入1.3份甲基肼、5.5份二甲基乙醇胺和10.8份二乙醇胺,继续搅拌60分钟,调节反应液的pH值至6.5;再加入2.2份嵌段聚醚L62和5.5份木质素磺酸铵,继续搅拌10分钟;再加入0.2份一缩二丙二醇双亚磷酸酯和7.8份碳酰肼,继续搅拌60分钟,调节反应液的pH值至5.0,过滤,出料,即制得抗黄变添加剂。
实施例3的各组分百分含量为:芳族磺酸22.5%,有机胺化合物17.6%,酰肼化合物7.8%,亚磷酸酯抗氧剂0.2%,乳化剂2.2%,分散剂5.5%,助溶剂2.9%,和去离子水41.3%。
实施例4
将16.6份β-萘磺酸、7份双酚S、1.3份硫酸(98%浓硫酸)和15.2份去离子水加入带有搅拌器、温度计、平衡加料器和冷凝器的反应装置中,开启搅拌,控制转速在40转/分钟,加热升温至90℃;调节搅拌转速至150转/分钟,滴加6.2份甲醛水溶液,1.5小时内滴加完成后,保温反应2小时;升温至120℃,保温回流反应4小时;开启冷却水,降温至70℃后,加入1.3份尿素和1.3份2-咪唑烷酮,继续保温反应2小时;加入15.7份去离子水,并再次通入冷却水将反应物料降温至40℃以下;向上述反应液中再加入22.8份三乙醇胺,持续搅拌40分钟,调节反应液pH值至7.0;再加入2.5份嵌段聚醚L62和3.1份木质素磺酸铵,继续搅拌20分钟;再加入0.2份一缩二丙二醇双亚磷酸酯和6.8份碳酰肼,继续搅拌50分钟,调节反应液pH值至7.0,过滤,出料,即制得抗黄变添加剂。
实施例4中各组分百分含量为:芳族磺酸16.6%,酚类化合物7%,甲醛水溶液6.2%,催化剂1.3%,甲醛捕捉剂2.6%,有机胺化合物22.8%,酰肼化合物6.8%,亚磷酸酯抗氧剂0.2%,乳化剂2.5%,分散剂3.1%和去离子水30.9%。
实施例5
将13份苯酚磺酸、5.1份双酚S、0.9份硫酸(98%浓硫酸)、2.6份对甲苯磺酸和13.3份去离子水加入带有搅拌器、温度计、平衡加料器和冷凝器的反应装置中,开启搅拌,控制转速在60转/分钟,加热升温至80℃;调节搅拌转速至200转/分钟,滴加7.3份甲醛水溶液,2小时内滴加完成后,保温反应2.5小时;升温至98℃,保温回流反应8小时;开启冷却水,降温至90℃后,加入1.5份2-咪唑烷酮,继续保温反应1.5小时;加入21.6份去离子水,并再次通入冷却水将反应物料降温至40℃以下;向上述反应液中再加入5.5份二乙醇胺和12.5份二甲基乙醇胺,持续搅拌30分钟,调节反应液pH值至6.8;再加入3.5份嵌段聚醚L62和5.0份木质素磺酸铵,继续搅拌30分钟;再加入0.2份聚二丙二醇苯基亚磷酸酯、5.5份碳酰肼和2.5份乙氧基甲酰肼,继续搅拌60分钟,即制得抗黄变添加剂。
实施例5中各组分百分含量为:芳族磺酸13%,酚类化合物5.1%,甲醛水溶液7.3%,甲醛捕捉剂1.5%,催化剂3.5%,有机胺化合物18%,酰肼化合物8%,亚磷酸酯抗氧剂0.2%,乳化剂3.5%,分散剂5%,和去离子水34.9%。
实施例6
将8.8份苯酚磺酸、4.8份二壬基萘二磺酸、8.8份萘酚、0.6份硫酸(98%浓硫酸)、2.4份二甲苯磺酸和10.8份去离子水加入带有搅拌器、温度计、平衡加料器和冷凝器的反应装置中,开启搅拌,控制转速在60转/分钟,加热升温至92℃;调节搅拌转速至180转/分钟,滴加5.1份甲醛水溶液,1小时内滴加完成后,保温反应2小时;升温至105℃,保温回流反应6小时;开启冷却水,降温至75℃后,加入1.8份尿素,继续保温反应2小时;加入22.8份去离子水,并再次通入冷却水将反应物料降温至50℃以下;再加入14.6份二乙基乙醇胺,持续搅拌30分钟,调节反应液pH值至5.5;再加入4.5份嵌段聚醚L62和6.0份木质素磺酸铵,继续搅拌30分钟;再加入0.2份一缩二丙二醇双亚磷酸酯、6.0份碳酰肼和2.8份4-羟基丁酸肼,继续搅拌60分钟,调节反应液pH值至5.8,过滤,出料,即制得抗黄变添加剂。
实施例6中各组分百分含量为:芳族磺酸13.6%,酚类化合物8.8%,甲醛水溶液5.1%,催化剂3%,甲醛捕捉剂1.8%,有机胺化合物14.6%,酰肼化合物8.8%,亚磷酸酯抗氧剂0.2%,乳化剂4.5%,分散剂6%,和去离子水33.6%。
为了验证本发明实施例在锦纶、氨纶纺织品上的抗黄变应用效果,分别将本发明实施例应用于聚氨酯海绵发泡及锦氨纶泳衣织物,以未处理样品作为空白参照样,对比测试纺织品的抗高温黄变性能、抗酚黄变性能、耐日光黄变性能及耐烟熏黄变性能,具体测试方法如下:
(1)高温黄变采用如下方法进行测试:将待测海绵或织物在压模机上进行压模处理(压模工艺:200℃×200sec),然后采用GB/T 250-2008《纺织品色牢度试验评定变色用灰色样卡》进行色变评级。
(2)酚黄变参照国际标准ISO 105-X18:2007《纺织品酚黄变色牢度测试试验》进行测试。
(3)日光黄变参照HG/T 3689-2014《鞋类耐黄变试验方法》B法紫外线灯管法进行测试,光照时间6小时。
(4)烟熏黄变参照GB/T11039.2《纺织品烟熏色牢度试验耐大气污染物色牢度第2部分:燃气烟熏》进行测试。
一、抗黄变添加剂在聚氨酯海绵发泡上的应用
将实施例1的抗黄变添加剂在聚氨酯海绵发泡时按2%用量加入到发泡液中,以未加抗黄变添加剂的发泡海绵作为空白参照样,按照上述测试方法测试处理海绵的高温黄变、酚黄变、日光黄变及烟熏黄变性能,结果如表1所示:
表1抗黄变添加剂在海绵发泡上的应用结果
项目 | 高温黄变/级 | 酚黄变/级 | 日光黄变/级 | 烟熏黄变/级 |
实施例1 | 4 | 4 | 4 | 3-4 |
空白样 | 3-4 | 2-3 | 3-4 | 3 |
二、抗黄变添加剂在锦氨纶织物后整理上的应用
将实施例2-6的抗黄变添加剂应用于浅肤色锦氨纶弹性针织物(锦纶82%氨纶18%,克重150g/m2)的染整后处理,试验工艺如下:
试验工艺:浸轧抗黄变添加剂(用量30g/L,二浸二轧,带液率70%)→热定型(160℃×60sec)
然后按上述测试方法对比测试处理织物的高温黄变、酚黄变、日光黄变及烟熏黄变,试验结果见表2。
表2抗黄变添加剂在锦氨纶织物上的应用结果
项目 | 高温黄变/级 | 酚黄变/级 | 日光黄变/级 | 烟熏黄变/级 |
实施例2 | 3-4 | 4-5 | 4 | 3-4 |
实施例3 | 4 | 4 | 4 | 3-4 |
实施例4 | 4 | 4-5 | 4 | 3-4 |
实施例5 | 4 | 4 | 4 | 3-4 |
实施例6 | 4 | 3-4 | 4 | 3-4 |
空白样 | 2-3 | 2 | 4 | 3 |
综上可知,不管是聚氨酯发泡海绵,还是锦氨纶织物,经本发明抗黄变添加剂处理后,在抗高温黄变、抗酚黄变及抗烟熏黄变性能方面均得到了显著提升,说明本发明的抗黄变添加剂能有效改善聚氨酯、聚酰胺纤维材料的泛黄问题,有助于提升锦氨纶纺织品的服用品质。
以上对本发明进行了详述。对于本领域技术人员来说,在不脱离本发明的宗旨和范围,以及无需进行不必要的实验情况下,可在等同参数、浓度和条件下,在较宽范围内实施本发明。虽然本发明给出了特殊的实施例,应该理解为,可以对本发明作进一步的改进。总之,按本发明的原理,本申请欲包括任何变更、用途或对本发明的改进,包括脱离了本申请中已公开范围,而用本领域已知的常规技术进行的改变。
Claims (9)
1.一种抗黄变添加剂,由芳香族磺酸化合物与有机胺类化合物反应生成相应的铵盐后,与具有还原性的酰肼化合物、亚磷酸酯类抗氧剂复配增效而成;
所述抗黄变添加剂,以质量百分含量计,由下述组分制成:10-35%小分子芳基磺酸化合物、0-10%酚类化合物、0-4%催化剂、0-8%甲醛水溶液、0-3%甲醛捕捉剂、10-30%有机胺类化合物、2-10%酰肼化合物、0.1-6%亚磷酸酯抗氧剂、0-9%乳化剂、1-6%分散剂、0-15%助溶剂和余量的水;
所述小分子芳基磺酸化合物为二壬基萘磺酸、二壬基萘二磺酸、苯酚磺酸、β-萘磺酸、对甲苯磺酸、二甲苯磺酸中的一种或多种;
所述酚类化合物为萘酚和双酚S中的一种或两种;
所述有机胺类化合物为二乙醇胺、三乙醇胺、二甲基乙醇胺、二乙基乙醇胺、甲基肼和偏二甲肼中的一种或多种;
所述酰肼化合物为碳酰肼、乙氧基甲酰肼、4-羟基丁酸肼中的一种或多种;
所述亚磷酸酯抗氧剂为一缩二丙二醇双亚磷酸酯、二亚磷酸季戊四醇二异癸酯、聚二丙二醇苯基亚磷酸酯中的一种或多种;
所述抗黄变添加剂的制备方法,为下述方法(一)或方法(二);
所述方法(一)包括如下步骤:
1)将水、助溶剂、小分子芳基磺酸化合物加入反应装置中,搅拌30-60min直至溶解均匀;
2)将有机胺类化合物分批滴加入步骤1)所得反应液中,持续搅拌30-120min,并控制反应液温度不超过70℃;
3)调节反应液pH值至4.0-7.0;
4)加入酰肼化合物,控制反应温度在50-70℃,持续搅拌30-120min,直至全部溶解均匀;
5)加入乳化剂、分散剂、亚磷酸酯抗氧剂,继续搅拌60-180min,直至全部溶解分散均匀;
其中,步骤4)5)的顺序可以互换;
6)调节反应液的pH值至4.0-7.0,过滤,出料,即制得不含酚类化合物、催化剂、甲醛水溶液及甲醛捕捉剂的抗黄变添加剂;
所述方法(二)包括如下步骤:
1)将水、小分子芳基磺酸化合物、酚类化合物及催化剂依次加入到反应装置中,开启搅拌,控制转速在40-80转/分钟,加热;
2)待物料温度升至80-98℃后,将转速调至150-250转/分钟;
3)向反应物料中滴加甲醛水溶液,滴加时间控制在1-2小时;
4)甲醛滴加完成后,再恒温反应1-3小时;
5)升温至98-120℃,恒温反应4-8小时;
6)将物料温度快速降温至70-90℃;
7)加入甲醛捕捉剂,恒温反应1-3小时;
8)将物料温度快速降温至30-60℃;
9)将有机胺类化合物分批滴加入步骤8)所得反应液中,持续搅拌30-60min,控制反应液温度不超过70℃;
10)调节反应液pH值至4.0-7.0;
11)加入乳化剂、分散剂、亚磷酸酯抗氧剂,控制反应温度在40-70℃,继续搅拌60-180min,直至全部溶解分散均匀;
12)加入酰肼化合物,控制反应温度在50-70℃,持续搅拌30-120min,直至全部溶解均匀;
其中,步骤11)12)的顺序可以互换;
13)调节反应液pH值至4.0-7.0,过滤,出料,即得含酚类化合物、催化剂、甲醛水溶液及甲醛捕捉剂的抗黄变添加剂。
2.根据权利要求1所述的抗黄变添加剂,其特征在于:所述的催化剂为质量分数大于等于98%的浓硫酸、对甲苯磺酸、二甲苯磺酸中的一种或多种;
所述的甲醛水溶液为36-42%的工业甲醛;
所述的甲醛捕捉剂为尿素、2-咪唑烷酮中的一种或两种。
3.根据权利要求1或2所述的抗黄变添加剂,其特征在于:所述的乳化剂为丙二醇嵌段聚醚;
所述的分散剂为木质素磺酸盐;
所述的助溶剂为一缩二乙二醇、乙二醇苯醚、二甲基亚砜中的一种或多种。
4.根据权利要求3所述的抗黄变添加剂,其特征在于:所述的乳化剂为L61、L62、L64中的一种或多种;
所述的分散剂为木质素磺酸铵。
5.制备权利要求1-4中任一项所述的不含酚类化合物、催化剂、甲醛水溶液及甲醛捕捉剂的抗黄变添加剂的方法,包括如下步骤:
1)将水、助溶剂、小分子芳基磺酸化合物加入反应装置中,搅拌30-60min直至溶解均匀;
2)将有机胺类化合物分批滴加入步骤1)所得反应液中,持续搅拌30-120min,并控制反应液温度不超过70℃;
3)调节反应液pH值至4.0-7.0;
4)加入酰肼化合物,控制反应温度在50-70℃,持续搅拌30-120min,直至全部溶解均匀;
5)加入乳化剂、分散剂、亚磷酸酯抗氧剂,继续搅拌60-180min,直至全部溶解分散均匀;
其中,步骤4)5)的顺序可以互换;
6)调节反应液的pH值至4.0-7.0,过滤,出料,即制得不含酚类化合物、催化剂、甲醛水溶液及甲醛捕捉剂的抗黄变添加剂。
6.制备权利要求1-4中任一项所述的含酚类化合物、催化剂、甲醛水溶液及甲醛捕捉剂的抗黄变添加剂的方法,包括如下步骤:
1)将水、小分子芳基磺酸化合物、酚类化合物及催化剂依次加入到反应装置中,开启搅拌,控制转速在40-80转/分钟,加热;
2)待物料温度升至80-98℃后,将转速调至150-250转/分钟;
3)向反应物料中滴加甲醛水溶液,滴加时间控制在1-2小时;
4)甲醛滴加完成后,再恒温反应1-3小时;
5)升温至98-120℃,恒温反应4-8小时;
6)将物料温度快速降温至70-90℃;
7)加入甲醛捕捉剂,恒温反应1-3小时;
8)将物料温度快速降温至30-60℃;
9)将有机胺类化合物分批滴加入步骤8)所得反应液中,持续搅拌30-60min,控制反应液温度不超过70℃;
10)调节反应液pH值至4.0-7.0;
11)加入乳化剂、分散剂、亚磷酸酯抗氧剂,控制反应温度在40-70℃,继续搅拌60-180min,直至全部溶解分散均匀;
12)加入酰肼化合物,控制反应温度在50-70℃,持续搅拌30-120min,直至全部溶解均匀;
其中,步骤11)12)的顺序可以互换;
13)调节反应液pH值至4.0-7.0,过滤,出料,即得含酚类化合物、催化剂、甲醛水溶液及甲醛捕捉剂的抗黄变添加剂。
7.权利要求1-4中任一项所述的抗黄变添加剂应用于含氮高分子材料的抗黄变处理中。
8.根据权利要求7所述的应用,其特征在于:所述高分子材料为聚氨酯纤维、聚氨酯海绵、聚氨酯薄膜、聚酰胺纤维、聚酰胺树脂、锦纶织物、锦氨纶织物中任一种。
9.根据权利要求7或8所述的应用,其特征在于:所述抗黄变添加剂在聚合阶段、后处理阶段添加到所述的高分子材料中。
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