CN109440466A - 一种液晶纤维及其制备方法 - Google Patents

一种液晶纤维及其制备方法 Download PDF

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CN109440466A
CN109440466A CN201811153848.2A CN201811153848A CN109440466A CN 109440466 A CN109440466 A CN 109440466A CN 201811153848 A CN201811153848 A CN 201811153848A CN 109440466 A CN109440466 A CN 109440466A
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fiber
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付少海
张丽平
关玉
李敏
田安丽
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Jiangnan University
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Abstract

本发明公开了一种液晶纤维的制备方法,属于精细化工和材料科学技术领域。本发明搭建了适用于纤维的“浸轧”方法,使得单根纤维经过浸轧含有液晶的整理液,从而均匀的固着在纤维上。本发明方法制备工艺简单,所制备的液晶纤维皮层厚度为10~100μm,克服了静电纺丝的弊端;本发明方法制备的液晶纤维可以通过改变中心纤维的颜色、尺寸、形状来调节性能,并且同时可以具有中心纤维的优势与液晶特性,具有明显的颜色,变色效果佳。

Description

一种液晶纤维及其制备方法
技术领域
本发明属于精细化工和材料科学技术领域,具体涉及一种液晶纤维的制备方法。
背景技术
胆甾型液晶具有有序的螺旋结构,能对可见光发生Bragg反射(λ=nPcosθ),从而显示出亮丽的色彩,并且,随着温度的变化可以显示不同的颜色,变色过程可逆可重复、响应速度快。目前,液晶的应用多集中在显示领域,在纺织品上的应用还较少。1974年,日本最早申请液晶类变色织物的专利,几年后,法国人将温致变色液晶涂覆在皮革上制成变色皮革。国内对于这方面的研究也主要集中在将液晶涂覆在纺织品上和制备成液晶墨水应用在纺织品上。液晶主要存在于织物表层,这种液晶变色织物存在耐洗牢度低,手感不佳,光稳定性差等问题。为了克服这些问题,可以将液晶直接装载到纤维中,这样获得的液晶纤维具有手感好、耐洗涤性好和变色效果较持久等特点。
将液晶装载到纤维中这项技术在近几十年才开始发展起来,仍旧处于起步阶段。国外在制备这种液晶纤维的研究主要采用静电纺丝的方法。Jan P.F.Lagerwall课题组利用同轴静电纺的方法,以向列相液晶为芯层,PVP/TiO2为皮层制备了具有皮芯结构的液晶纤维。Buyuktanir和West采用溶液静电纺的方法制备了一种光响应向列相液晶核-壳纤维,研究了液晶核的大小和在纤维中的分布对纤维热学和力学性能的影响。这些研究主要集中在研究液晶在纤维中对电场或者化学气体的响应,即使在纳米级别的纤维中,液晶分子也能根据外界刺激发生偏转从而做出响应,因此可以采用静电纺丝的方法制备。
然而,静电纺丝得到的是纳米级的纤维束或纤维膜,难以得到单根纳米纤维,且即使能够抽离出单根纤维,其纤维直径也较小,远不到10μm。胆甾相液晶Bragg反射是基于螺距P的变化,P的特征值为300nm左右,一般需要达到8个螺距以上才能显示出较为明亮的颜色,向列型液晶与手性添加剂组合的液晶也是螺旋结构,考虑到其颜色性能,当把这类结构的液晶装载到纤维中时,纤维直径需要足够大(10μm以上)才能够有较佳的颜色性能。所以,现有的静电纺丝方法并不能满足该类螺旋结构的液晶在纤维中有效负载,运用静电纺丝方法负载该类结构的液晶所得到的液晶纤维,由于纤维直径不到10μm,导致液晶显色效果差,从而制约了胆甾相液晶类螺旋结构的液晶在制备相应液晶纤维中的应用。
发明内容
为了解决上述问题,本发明对制备具有较大螺距的的液晶纤维的纺丝方法做了探索。“浸轧”法常用于织物的染色和整理,其方法是将织物在染液/整理液中浸渍后,用轧辊轧压,使染液/整理液均匀地分布在织物上。受此方法启发,本发明搭建了适用于纤维的“浸轧”方法,使得单根纤维经过浸轧含有液晶的整理液,从而均匀的固着在纤维上。这种方法制备的液晶纤维可以通过改变中心纤维的颜色、尺寸、形状来调节性能,并且同时可以具有中心纤维的优势与液晶特性。基于此,本发明采用“浸轧”法制备一种液晶纤维,将提前准备好的芯层纤维单根浸轧含有液晶的整理液,液晶在纤维外层均匀的固着形成变色纤维的皮层。该方法制备工艺简单,所制备的液晶纤维具有明显的颜色。
本发明第一个目的在于提供一种液晶纤维的制备方法,所述方法是将单根芯层纤维浸轧含有液晶的整理液,烘干固着后液晶固着在纤维皮层形成具有皮芯层结构的液晶纤维。
在本发明的一种实施方式中,所述的芯层纤维截面有圆形,直径为0.1-2mm;有长方形,长为0.1-2mm。
在本发明的一种实施方式中,所述芯层纤维颜色包括黑、红、蓝或黄。
在本发明的一种实施方式中,所述芯层纤维选用涤纶或锦纶。
在本发明的一种实施方式中,所述整理液包括:重量分数20~30%液晶,重量分数5~25%成膜物质,重量分数0~8%助剂,重量分数70~100%溶剂。
在本发明的一种实施方式中,所述成膜物质包括聚乙烯醇,聚乙烯吡咯烷酮,聚(甲基)丙烯酸甲酯,聚(甲基)丙烯酸丁酯,聚丙烯酰胺,聚丙烯腈,聚苯乙烯,脲醛树脂,三聚氰胺甲醛树脂,聚酰胺多胺环氧氯丙烷,聚氨酯。
在本发明的一种实施方式中,所述助剂包括重量分数0~5%分散剂、重量分数0~2%消泡剂。
在本发明的一种实施方式中,所述分散剂包括十二烷基硫酸钠、十二烷基磺酸钠、十二烷基苯磺酸钠、油酸钾、烷基萘磺酸钠、松香酸钠,OP-7、OP-10或OP-15、平平加O-10、平平加O-20、平平加O-25或平平加A-20、Tween40、Tween60、Tween65、Tween80、SG-10、SE-10、OE-15。
在本发明的一种实施方式中,所述消泡剂包括有乳化硅油、高碳醇脂肪酸酯复合物、聚氧乙烯聚氧丙烯季戊四醇醚、聚氧乙烯聚氧丙醇胺醚、聚氧丙烯甘油醚和聚氧丙烯聚氧乙烯甘油醚、聚二甲基硅氧烷等。
在本发明的一种实施方式中,所述液晶是胆甾型液晶中的两种或多种组合或者是向列型液晶与手性添加剂组合。
在本发明的一种实施方式中,所述胆甾型液晶包括胆固醇乙酸酯、胆固醇丙酸酯、胆甾醇正丁酸酯、胆固醇壬酸酯、胆甾醇油酸酯、胆甾烯基亚油酸酯、胆甾醇苯甲酸酯、胆甾醇肉桂酸酯、胆甾醇乙基碳酸酯,胆固醇油醇碳酸酯、胆甾烯基异硬脂酰基碳酸酯、胆甾烯基丁烯酸酯、胆甾烯基碳酸酯、氯化胆固醇。
在本发明的一种实施方式中,所述向列型液晶包括乙基联苯腈、4'-正丁基-4-氰基联苯、4-丙基-4'-氰基联苯、4-氰基-4'-戊基联苯、4-庚基-4'-氰基联苯、反式-4'-(4-戊基环己基)-[1,1'-联苯]-4-腈、E7。
在本发明的一种实施方式中,所述手性添加剂包括S811、S1011、R811、R6N、R5011、R1011、CB15。
在本发明的一种实施方式中,所述皮芯层结构的皮层厚度为10~100μm。
本发明的第二个目的是得到上述方法制备的液晶纤维。
本发明的第三个目的是提供一种液晶变色织物,所述织物是利用上述液晶纤维制备得到。
本发明的第四个目的是将上述液晶纤维应用于纺织领域中。
本发明有益效果:
向列型液晶和手性添加剂组合的液晶与胆甾型液晶结构类似,都具有较大螺距的螺旋结构,在纤维应用中受到较大限制,本发明首先提出了利用“浸轧”结合纺丝实现该类液晶的纤维负载的方法,制备工艺简单,所制备的液晶纤维皮层厚度为10~100μm,克服了静电纺丝的弊端,所得的液晶纤维可以通过改变中心纤维的颜色、尺寸、形状来调节性能,并且同时可以具有中心纤维的优势与液晶特性,具有明显的颜色,变色效果佳。
具体实施方式
下面通过实施例子,进一步阐述本发明的突出优点和显著特点,但本发明决不局限于实施例子。
实施例1
整理液的制备:将3g胆固醇壬酸酯和7g胆固醇油醇碳酸酯混合后加热到刚好全部溶解并成透明状,在此温度下搅拌2h后,降温到混合液晶出现颜色或浑浊后,再升温至恰好透明,恒温搅拌4h,制备得到液晶;将制备得到的10g液晶与10g聚乙烯醇分散于60mL水中,混合均与后得到整理液;
纤维浸轧:选用直径为2mm圆形截面的黑色锦纶纤维作为芯层纤维,芯层纤维浸入整理液后,放入100℃烘箱焙烘10min,得到液晶纤维。
所得到的液晶纤维的皮层厚度为10μm,液晶纤维的变色规律如、表1所示:
表1所得液晶纤维的变色规律
实施例2
整理液的制备:将1g胆固醇丙酸酯、1.5g胆甾醇油酸酯、2g胆甾醇苯甲酸酯、0.5g胆甾醇乙基碳酸酯混合后加热到刚好全部溶解,在此温度下搅拌2h后,降温到混合液晶出现颜色或浑浊后,再升温至恰好透明,恒温搅拌4h,制备得到液晶;将所得到的5g液晶与4.2g聚乙烯吡咯烷酮、0.83g助剂分散于7mL乙醇中,混合均与后得到整理液;
纤维浸轧:选用直径为0.1mm圆形截面的红色锦纶纤维作为芯层纤维,芯层纤维浸轧整理液后,放入60℃烘箱焙烘10min,得到液晶纤维。
所得到的液晶纤维的皮层厚度50μm,液晶纤维的变色规律如表2所示:
表2所得液晶纤维的变色规律
实施例3
整理液的制备:将3.8g CB15和6.2g E7混合后加热到刚好全部溶解,在此温度下搅拌2h后,降温到混合液晶出现颜色或浑浊后,再升温至恰好透明,恒温搅拌4h,制备得到液晶;将10g液晶、10g聚甲基丙烯酸甲酯、3.2g助剂分散于17mL二氯甲烷中,混合均与后得到整理液;
纤维浸轧:选用直径0.1mm方形截面的黄色涤纶纤维作为芯层纤维,芯层纤维浸轧整理液后,放入80℃烘箱焙烘15min,得到液晶纤维;
所得到的液晶纤维的皮层厚度100μm,液晶纤维的变色规律如表3所示:
表3所得液晶纤维的变色规律
实施例4
整理液的制备:将4.1g S1011和5.9g E7混合后加热到刚好全部溶解,在此温度下搅拌2h后,降温到混合液晶出现颜色或浑浊后,再升温至恰好透明,恒温搅拌4h,制备得到液晶;将2.5g液晶、2.5g聚氨酯、1g助剂分散于5mL水中,混合均与后得到整理液;
纤维浸轧:选用直径2mm方形截面的蓝色涤纶纤维作为芯层纤维,芯层纤维浸轧整理液后,放入120℃烘箱焙烘5min,得到液晶纤维;
所得到的液晶纤维的皮层厚度10μm,液晶纤维的变色规律如表4所示,25℃下显示蓝色,颜色随温度变化规律为深蓝→浅蓝。
表4所得液晶纤维的变色规律
实施例5
整理液的制备:将1g胆固醇丙酸酯、1.5g胆甾醇油酸酯、2g胆甾醇苯甲酸酯、0.5g胆甾醇乙基碳酸酯混合后加热到刚好全部溶解,在此温度下搅拌2h后,降温到混合液晶出现颜色或浑浊后,再升温至恰好透明,恒温搅拌4h,制备得到液晶;将所得到的5g液晶与4.2g聚乙烯吡咯烷酮、0.83g助剂分散于7mL乙醇中,混合均与后得到整理液;
纤维浸轧:选用直径为0.1mm圆形截面的红色锦纶纤维作为芯层纤维,芯层纤维浸入整理液后,通过孔径为1mm圆孔,去除多余整理液,然后放入60℃烘箱焙烘10min,得到液晶纤维;
所得到的液晶纤维的皮层厚度20μm,液晶纤维的变色规律如下表5所示:
表5所得液晶纤维的变色规律
整理液中液晶含量对液晶纤维性能影响的考察:
对比例1
整理液的制备:将3g胆固醇壬酸酯和7g胆固醇油醇碳酸酯混合后加热到刚好全部溶解并成透明状,在此温度下搅拌2h后,降温到混合液晶出现颜色或浑浊后,再升温至恰好透明,恒温搅拌4h,制备得到液晶;将制备得到的1g液晶与10g聚乙烯醇分散于60mL水中,混合均与后得到整理液;
纤维浸轧:选用直径为2mm圆形截面的黑色锦纶纤维作为芯层纤维,芯层纤维浸入整理液后,放入100℃烘箱焙烘10min,得到液晶纤维;
所得到的液晶纤维的皮层厚度10μm,纤维呈现黑色,显色效果不明显。
对比例2
整理液的制备:将3.8g CB15和6.2g E7混合后加热到刚好全部溶解,在此温度下搅拌2h后,降温到混合液晶出现颜色或浑浊后,再升温至恰好透明,恒温搅拌4h,制备得到液晶;将10g液晶、2g聚甲基丙烯酸甲酯、3.2g助剂分散于17mL二氯甲烷中,混合均与后得到整理液;
纤维浸轧:选用直径0.1mm方形截面的黄色涤纶纤维作为芯层纤维,芯层纤维浸轧整理液后,放入80℃烘箱焙烘15min,得到液晶纤维;
所得到的液晶纤维液晶裸露在纤维外,无法良好的固着在纤维上。
虽然本发明已以较佳实施例公开如上,但其并非用以限定本发明,任何熟悉此技术的人,在不脱离本发明的精神和范围内,都可做各种的改动与修饰,因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (10)

1.一种液晶纤维的制备方法,其特征在于,所述方法是利用单根芯层纤维浸轧含有液晶的整理液,烘干固着后,将液晶固着在纤维皮层形成具有皮芯层结构的液晶纤维。
2.根据权利要求1所述方法,其特征在于,所述整理液包括:重量分数20~30%液晶,重量分数5~25%成膜物质,重量分数0~8%助剂,重量分数70~100%溶剂。
3.根据权利要求1所述方法,其特征在于,所述液晶是胆甾型液晶中的两种或多种组合,或者是向列型液晶与手性添加剂组合。
4.根据权利要求1所述方法,其特征在于,所述手性添加剂包括S811、S1011、R811、R6N、R5011、R1011、CB15中的一种或两种以上。
5.根据权利要求2所述方法,其特征在于,所述助剂包括重量分数0~5%分散剂、重量分数0~2%消泡剂。
6.根据权利要求1-5所述方法,其特征在于,所述芯层纤维的截面包括直径为0.1-2mm的圆形截面,或者长为0.1-2mm的长方形截面。
7.根据权利要求1-5任一所述方法,其特征在于,所述芯层纤维颜色包括黑、红、蓝、黄中的一种。
8.一种根据权利要求1-5所述方法制备的液晶纤维。
9.一种液晶变色织物,其特征在于,所述液晶变色织物是利用权利要求8所述液晶纤维制备得到。
10.权利要求8所述液晶纤维在纺织领域中的应用。
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