CN114574990B - 一种易染易定型氨纶纤维的制备方法 - Google Patents
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Abstract
本发明提供了一种易染易定型氨纶纤维的制备方法,将氨纶新产品的低温易定型和酸性染料可染特性进行组合,针对组合后氨纶丝表现出来的物性缺点,又通过其它方面配方调整及聚合过程中中间控制参数调整,使得氨纶新产品表现出更加优越的物性特点。
Description
技术领域
本发明属于化学纤维中氨纶产品的开发领域,开发的氨纶产品既具有低温易定型特点,又具备酸性染料可染特点。
背景技术
氨纶同其他聚氨酯材料一样,是由硬软段两部分组成的,虽然软段成分比例大,但其玻璃化转变温度通常在 -20℃左右,室温下分子链段具有良好的运动能力。因此,影响氨纶定形温度的主要是由硬段的成分以及结构相态等因素决定的。硬段所占质量分数一般低于15%,主要包括了由 4,4′-二苯基甲烷二异氰酸酯(MDI)以及小分子扩链剂形成的结构单位。分子结构高度对称且带有刚性苯环的MDI成分易在氢键或其他分子间作用力下紧密堆叠形成结晶。在普通氨纶内部,这些结晶往往是结晶化程度不均一、大小不等的晶相。微晶区的熔融再重结晶过程需要高温提供大量的热量。因此,在较低温度下普通氨纶往往难以有良好的定形效果。
连续聚合干法纺丝氨纶生产技术中的聚合配方包括以下三个方面的配方:1、主原料的PTMG和MDI摩尔配比;2、扩链剂和终止剂配比;3、各种添加剂配比。本发明专利第一个要点是通过在PTMG和MDI摩尔配比中加入一定比例的MDI不对称异构体,用来降低氨纶分子链中硬段的结晶度,从而降低氨纶丝玻璃化温度,进而降低含氨面料的热定型温度;本发明专利第二个要点是在扩链剂和终止剂配比中改变终止剂类型,选择带有不对称二胺作为终止剂,使得氨纶大分子端基为叔氨基,以实现氨纶大分子可以与酸性染料分子形成分子间作用力,进行牢固结合,以达到本发明专利新技术生产的氨纶丝产品与锦纶丝可以进行同步染色的目的,以上是新产品改性的基础技术,因为此技术对整个氨纶生产聚合配方改动比较大,势必影响到氨纶生产是否能够正常进行和产品物性指标是否能够满足用户织造需要,因此通过反复试验,又对扩链剂类型或组合进行重新选择,同时控制纺丝原液粘度、固含量和原液过量胺到一个不同于正常生产的控制范围,以保证生产过程正常和保证产品物性指标正常,充分满足用户使用要求,同时体现更好的质量均匀性。
本发明专利技术生产的新产品主要使用在锦氨面料上,低温易定型特点可以降低锦氨面料热定型温度约10℃左右,这样可以保护高温热定型对锦纶丝的氧化变色及弹力损失,酸性染料可染特性可以达到与锦纶同步染色,一样的上色效果和一样的色牢度,保证了锦氨面料酸性染料染色鲜艳性特点,另外更重要的一点是本发明专利技术生产的新产品会体现更好的条干均匀性,在经编、纬编使用领域极大的提高锦氨面料品质。现有这方面的技术多体现在只对低温易定型或酸性染料可染方面对氨纶丝进行性能改进:有采用物理添加剂方面的,有采用化学改性方面的。现有技术鲜有对生产过程中其它方面改进的描述:如纺丝原液固含量控制范围、纺丝原液粘度控制范围、原液过量胺控制范围、为满足用户正常使用所必须的新产品物性指标控制范围,这些描述是使得新技术能够进行实战,能够进行落地生根的重要保证。本发明专利技术是将氨纶新产品的低温易定型和酸性染料可染特性进行组合,针对组合后氨纶丝表现出来的物性缺点,又通过其它方面配方调整及聚合过程中中间控制参数调整,使得氨纶新产品表现出更加优越的物性特点。
发明内容
对氨纶丝进行低温易定型改性或酸性染料可染改性,现有技术都有各自特点,缺点是没有将这两个改性进行真正意义上的组合,更重要的是没有过多关注改性后的新氨纶产品在物性方面的优化,以及新氨纶产品在条干均匀性方面的优化。本发明的目的就是针对以上问题开展的技术攻关,很好的解决了以上现有技术存在的问题。
为实现上述目的,本发明采用如下技术方案:
聚合配方调整:1、MDI(4,4′-二苯基甲烷二异氰酸酯)分子是4,4体对称结构,在其中加入一定比例的不对称2,4体结构(MDI:2,4′-二苯基甲烷二异氰酸酯),2,4′-二苯基甲烷二异氰酸酯在4,4′-二苯基甲烷二异氰酸酯中含量控制在8%-15%之间;2、在扩链剂和终止剂混合胺调配中,选择不对称二胺(如N,N-二甲基丙二胺、N,N-二乙基丙二胺、N,N-二乙基乙二胺、N,N-二丁基丙二胺、N,N-二丁基乙二胺、N,N-二甲基乙二胺等)作为终止剂,同时在直链型分子扩链剂(如乙二胺等)中加入一定量的带侧甲基二胺(如丙二胺等),两种扩链剂摩尔配比2-10:1。
聚合原液生产过程控制参数:原液固含量控制在40-45%;原液过量胺控制在40-80mmol/ml;纺丝原液粘度控制在6000-9000pa.s。
产品物性指标:断裂强度≧1.4cN/d;氨纶丝条干均匀性CV值≦1.3%。
进一步的,一种易染易定型氨纶纤维的制备方法,该制备方法包括如下步骤:
1)预聚物的制备:将MDI的两种结构体2,4′-二苯基甲烷二异氰酸酯与4,4′-二苯基甲烷二异氰酸酯按照一定比例混合均匀,混合质量比例为8-15:100,然后通过计量泵的计量,与通过计量泵计量的聚醚二元醇(PTMG),按照基团NCO/OH=1.70~1.85的摩尔比例共同进入到预聚合管道连续反应器,管道反应器内置混合单元,使得物料均匀混合、均匀反应生成预聚物,预聚反应温度控制为90~95℃,反应时间为2.5~3.5h,反应后的预聚物NCO含量为2.5%~2.8%。
2)混合胺制备(扩链剂和终止剂混合调配):将选择好的扩链剂(乙二胺、丙二胺或戊二胺)与终止剂(二乙基胺、环己胺、2,2,6,6-四甲基哌啶、N,N-二甲基丙二胺、N,N-二乙基丙二胺、N,N-二乙基乙二胺、N,N-二丁基丙二胺、N,N-二丁基乙二胺、N,N-二甲基乙二胺等) 按照一定摩尔比例(6.5~13:1),在N,N-二甲基乙酰胺中混匀,得到7%质量百分比浓度的混合胺溶液。
3)将上述预聚物经过计量泵计量,与经过计量泵计量的N,N-二甲基乙酰胺在一台溶解机中充分混合,制成预聚物溶液,预聚物溶液和经过计量泵计量的混合胺溶液一起加入到连续聚合反应器中进行扩链反应,反应器夹套通-10℃冷媒冷却,反应器出口温度控制在75~90℃,最终得到固含量为35~45%,粘度为1800~3000pa.s(40℃情况下)的初始透明聚合物原液。
4)添加剂ADD混合溶液的制备:为了提高氨纶丝的抗氧化性、耐热性、耐氯性、防黄变性等,需要在聚合反应后的聚合物溶液中加入一定量的添加剂混合溶液,这个ADD是由二氧化钛、硬脂酸镁、防黄剂NH-150(双(N,N-二甲基酰肼氨基-4-苯基)甲烷)、抗氧剂1790、水滑石(含钙、镁元素)物料等,按照总质量比30~35:100的比例混合在N,N-二甲基乙酰胺中,经过研磨机研磨成符合一定质量要求的添加剂ADD混合溶液。其中,所述添加剂ADD混合溶液中,二氧化钛含量为0.4-0.5wt%,硬脂酸镁含量为0.25-0.45wt%;防黄剂HN-150含量为0.3-0.5wt%,抗氧剂1790含量为0.3-0.5wt%;水滑石含量为2.0-4.0wt%。
5)从反应器出来的初始透明聚合物原液与配制好的添加剂ADD混合溶液(计量泵计量)在一个混合罐中充分混合,然后经过几个串联的原液储罐进一步混合增粘,最终达到粘度6000~9000pa.s(40℃情况下)的纺丝原液,再经过原液过滤器后供纺丝使用。
6)合格的纺丝原液经过纺丝计量泵计量,计量后的原液细流进入到纺丝甬道中,纺丝甬道中的原液细流在250~260℃循环热风的作用下,细流中的溶剂DMAC(N,N-二甲基乙酰胺)蒸发成DMAC气体,被循环热风带到DMAC冷却回收装置,DMAC冷却回收后送到精制系统进行提纯处理,聚合物溶液中的DMAC蒸发后,剩下的聚合物固体丝条在罗拉辊的牵引下进入纺丝卷绕成型装置,在卷绕成型装置作用下形成成型良好的氨纶丝产品。
进一步的,步骤5)中原液储罐里储存的原液是经过前面混合罐混合后的、含有各种添加剂成分的混合原液,此原液含有一定量的过量胺,为后续原液粘度缓慢增加提供条件。这里所描述的原液储罐是带有搅拌装置、且带有夹套水保温装置,从混合罐出来的原液在原液储罐中搅拌器和热水的作用下粘度会进一步增加,这样的原液储罐会设计成几个串联在一起,根据产量和原液存放时间来决定原液在各个原液储罐中的储存量,最终达到原液在纺丝之前的粘度达到6000-9000 pa.s。
本发明的关键点:1、MDI中2,4′-二苯基甲烷二异氰酸酯结构体的含量;2、扩链剂中带支链的二胺所占比例;3、终止剂的选择;4、聚合生产过程中,各个中间控制指标的控制点。
本发明的优点在于:
1、将低温易定型与酸性染料可染两个特性合二为一,在酸性染料可染方面注重染色色牢度,可以与锦纶进行同步染色;2、注重实际生产过程的优化,体现更好的产品质量均匀性。
附图说明
图1为黑色锦氨交织布料的染色牢度检测报告,其中最上面左边的长方形布料为原布料,其右侧的两片中间带有明显圆形痕迹的布料分别是湿态和干态摩擦色牢度检测结果(摩擦检验是一种用其他布料在特定条件下对原布进行摩擦,通过摩擦后检测原布的色素是否褪色到其他布料上,从而判断原布色牢度),通过上述图片可以发现摩擦色牢检验效果较好。其他四组数据为其上方的实验原布和六纤实验布样(六种纤维连接在一起实验用布料)在四种实验条件(分别为皂洗、海水、水渍、汗渍)下对六种纤维的染色程度对比(判断标准为专用灰度比色卡评定),对六种纤维染色越明显评级越低,顶级为5级,最低2级以下不再评级,通过检验评级,原布的色牢度评级在4-5级,效果较好,从而验证了易染氨纶优良的染色牢度效果。
图2为专用灰度比色卡评定标准。
图3展现的是红色料染色情况:根据纯锦纶面料(上部面料)和两种规格氨纶丝(下部丝束,氨纶含量占比为18%,左边为“21D-试验”样品,右边为“20D-2028”样品)绑在一起同时进行同步染色,色泽差异情况如图所示,同样采用灰度比色卡检验的方式进行判断,染色效果较好,达到4级,证明本发明的氨纶丝可以与锦纶进行同步染色,效果理想。
具体实施方式
为让本发明的上述特征和优点能更明显易懂,下文特举实施例,作详细说明。本发明的方法如无特殊说明,均为本领域常规方法。
实施例1
一种易染易定型氨纶纤维的制备方法,该制备方法包括如下步骤:
1)预聚物的制备:将MDI的两种结构体2,4′-二苯基甲烷二异氰酸酯与4,4′-二苯基甲烷二异氰酸酯按照一定比例混合均匀,混合质量比例为13:100,然后通过计量泵的计量,与通过计量泵计量的聚醚二元醇(PTMG),按照基团NCO/OH=1.8的摩尔比例共同进入到预聚合管道连续反应器,管道反应器内置混合单元,使得物料均匀混合、均匀反应生成预聚物,预聚反应温度控制为93℃,反应时间为3h,反应后的预聚物NCO含量为2.6%。
2)混合胺制备(扩链剂和终止剂混合调配):将选择好的扩链剂(乙二胺、丙二胺按摩尔比5:1混合)与终止剂(2,2,6,6-四甲基哌啶、N,N-二丁基丙二胺按摩尔比1:3混合) 按照一定摩尔比例(10.5:1),在N,N-二甲基乙酰胺中混匀,得到7%质量百分比浓度的混合胺溶液。
3)将上述预聚物经过计量泵计量,与经过计量泵计量的N,N-二甲基乙酰胺在一台溶解机中充分混合,制成预聚物溶液,预聚物溶液和经过计量泵计量的混合胺溶液一起加入到连续聚合反应器中进行扩链反应,反应器夹套通-10℃冷媒冷却,反应器出口温度控制在85℃,最终得到固含量为42%,粘度为2500pa.s(40℃情况下)的初始透明聚合物原液。
4)添加剂ADD混合溶液的制备:为了提高氨纶丝的抗氧化性、耐热性、耐氯性、防黄变性等,需要在聚合反应后的聚合物溶液中加入一定量的添加剂混合溶液,这个ADD是由二氧化钛、硬脂酸镁、防黄剂NH-150、抗氧剂1790、钙镁铝水滑石物料等,按照总质量比33:100的比例混合在N,N-二甲基乙酰胺中,经过研磨机研磨成符合一定质量要求的添加剂ADD混合溶液。其中,所述添加剂ADD混合溶液中,二氧化钛含量为0.42wt%,硬脂酸镁含量为0.32wt%;防黄剂HN-150含量为0.33wt%,抗氧剂1790含量为0.41wt%;水滑石含量为3.1wt%。
5)从反应器出来的初始透明聚合物原液与配制好的添加剂ADD混合溶液(计量泵计量)在一个混合罐中充分混合,然后经过4个串联的原液储罐进一步混合增粘,最终达到粘度8000pa.s(40℃情况下)的纺丝原液,再经过原液过滤器后供纺丝使用。
6)合格的纺丝原液经过纺丝计量泵计量,计量后的原液细流进入到纺丝甬道中,纺丝甬道中的原液细流在258℃循环热风的作用下,细流中的溶剂DMAC(N,N-二甲基乙酰胺)蒸发成DMAC气体,被循环热风带到DMAC冷却回收装置,DMAC冷却回收后送到精制系统进行提纯处理,聚合物溶液中的DMAC蒸发后,剩下的聚合物固体丝条在罗拉辊的牵引下进入纺丝卷绕成型装置,在卷绕成型装置作用下形成成型良好的氨纶丝产品。产品物性指标:断裂强度为1.58cN/d;氨纶丝条干均匀性CV值为1.18%。
7)此技术方法生产的易染易定型氨纶丝产品使用要求及注意事项:
a、使用领域:主要与锦纶交织。
b、染选择:酸性染料。
c、染色推荐工艺条件:染缸开始的温度为40℃左右,升温速度1.5℃/min,升温至70或80℃时,保温20分钟后,仍按升温速度1.5℃/min,升温至97℃时,保温30分钟左右。
部分色泽染色推荐配方
d、锦氨织物定型温度:推荐定型温度为185℃-192℃(一般定型温度为198℃),定型时间为45-60秒。
本发明的氨纶丝产品热定型温度约185℃-192℃,对应的热定型效率在80%以上。
e、染色色牢度试验报告及锦氨同步染色图片对比如表2、图1和图3所示:
表1灰度卡检测评级分类
表2为图1中对应的实验原布和六纤实验布样在四种实验条件下对六种纤维的染色程度结果
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (4)
1.一种易染易定型氨纶纤维的制备方法,其特征在于,包括如下步骤:
1)预聚物的制备:将MDI的两种结构体2,4′-二苯基甲烷二异氰酸酯与4,4′-二苯基甲烷二异氰酸酯混合均匀,与聚醚二元醇PTMG,按照NCO/OH=1.70~1.85的摩尔比例共同进入到预聚合管道连续反应器内反应生成预聚物,预聚反应温度控制为90~95℃,反应时间为2.5~3.5h;
2)混合胺制备:将扩链剂与终止剂按照摩尔比6.5~13:1,在N,N 二甲基乙酰胺中混匀,得到混合胺溶液;
3)将上述预聚物和N,N-二甲基乙酰胺充分混合,制成预聚物溶液,预聚物溶液和混合胺溶液一起加入到连续聚合反应器中进行扩链反应,反应器夹套通-10℃冷媒冷却,反应器出口温度控制在75~90℃,最终得到固含量为35~45%,40℃情况下粘度为1800~3000pa.s的初始透明聚合物原液;
4)添加剂ADD混合溶液的制备:由二氧化钛、硬脂酸镁、防黄剂NH-150、抗氧剂1790、水滑石,按照总质量比30~35:100的比例混合在N,N-二甲基乙酰胺中,经过研磨机研磨,得到添加剂ADD混合溶液;
5)从反应器出来的初始透明聚合物原液与配制好的添加剂ADD混合溶液充分混合,然后增粘处理,最终得到40℃情况下粘度为6000~9000pa.s的纺丝原液,过滤后供纺丝使用;
6)将过滤后的纺丝原液细流进入到纺丝甬道中,纺丝甬道中的原液细流在250~260℃循环热风的作用下,细流中的溶剂N,N-二甲基乙酰胺蒸发成气体进行回收,溶剂蒸发后剩下的聚合物固体丝条在罗拉辊的牵引下进入纺丝卷绕成型装置,在卷绕成型装置作用下得到易染易定型氨纶纤维;
所述扩链剂为乙二胺、丙二胺按摩尔比5:1混合;所述终止剂为2,2,6,6-四甲基哌啶、N,N-二丁基-1,3-丙二胺按摩尔比1:3混合;
步骤2)所述混合胺溶液中,扩链剂和终止剂的总质量百分比浓度为7%。
2.根据权利要求1所述的制备方法,其特征在于,步骤1)中2,4′-二苯基甲烷二异氰酸酯与4,4′-二苯基甲烷二异氰酸酯的混合质量比为8-15:100。
3.根据权利要求1所述的制备方法,其特征在于,步骤1)中反应生成的预聚物中NCO含量为2.5%~2.8%。
4.根据权利要求1所述的制备方法,其特征在于,步骤4)所述添加剂ADD混合溶液中,二氧化钛含量为0.4-0.5wt%,硬脂酸镁含量为0.25-0.45wt%;防黄剂HN-150含量为0.3-0.5wt%,抗氧剂1790含量为0.3-0.5wt%;水滑石含量为2.0-4.0wt%。
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