CN115478439B - 具有仿羊毛卷曲结构的多孔纤维及其制备方法 - Google Patents

具有仿羊毛卷曲结构的多孔纤维及其制备方法 Download PDF

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CN115478439B
CN115478439B CN202211031995.9A CN202211031995A CN115478439B CN 115478439 B CN115478439 B CN 115478439B CN 202211031995 A CN202211031995 A CN 202211031995A CN 115478439 B CN115478439 B CN 115478439B
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filaments
solvent
polymer
solution
fiber
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CN115478439A (zh
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王斐
田昱城
丁彬
张世超
张欣欣
吴凡
俞建勇
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Donghua University
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Abstract

本发明涉及一种具有仿羊毛卷曲结构的多孔纤维及其制备方法,制备时先热塑性发泡溶液与热塑性聚合物溶液,随后将长丝进行发泡处理,得到表面具有初级孔结构的长丝,接着将上述长丝进行聚合物溶液相分离处理,得到表面具有多级孔的长丝,再将得到的多孔长丝放入热定型机中,经过定向热风使长丝发生定向卷曲,进行连续化卷曲定型,最后将得到的卷曲多孔长丝进行切断处理,最终获得长度和卷曲度可控多孔纤维。与现有技术相比,本发明纤维的卷曲率在10~60%内可控,由该卷曲多孔短纤经过纺纱加工、织造工艺得到的织物或通过层叠铺网得到的蓬松纤维絮片均具有优异的保暖性能,由该纤维纺纱织造获得的织物热阻为0.15~0.4m2K/W。

Description

具有仿羊毛卷曲结构的多孔纤维及其制备方法
技术领域
本发明涉及保暖材料技术领域,尤其是涉及一种具有仿羊毛卷曲结构的多孔纤维及其制备方法。
背景技术
高寒天气不仅易导致人体冻伤,并易引发呼吸系统及心脑血管系统疾病。因此,需要穿着高效保暖服装来抵御严寒天气。现有高效保暖材料以羽绒为主,羽绒因其分形结构具有质轻和保暖两大特性,在保暖市场上具有统治地位。但目前该材料保暖性能的提升主要通过增加厚度和重量的方式,从而带来厚重、穿着者行动不便等问题。羊毛卷曲纤维具有良好的蓬松性和垫弹性,天然纤维中,羊毛的自然形态就是沿长度方向呈现周期性的卷曲,这种天然卷曲是由于纤维截面的不对称性。通常,羊毛同一截面内存在着正皮质细胞和副皮质细胞,两种皮质细胞的结构、所占比例不同,并呈双边排列,使得纤维围绕轴心呈扭曲或螺旋形弯曲状,表现出卷曲形态。卷曲纤维有较好的柔软性、高度蓬松和良好的回弹性,纤维的卷曲还可提高纤维加工时的抱合力以及织物的尺寸稳定性。类羊毛卷曲材料可在一定程度上解决羽绒材料厚度大带来穿着不便的问题,但由于其直径较大、无孔腔结构导致其能保留的静止空气含量较低,保暖性能远不如羽绒。
目前,已有相关技术人员在本领域做了一些研究。专利CN202010221964.4介绍了一种针织用复合卷曲纤维的制备方法,该方法通过改变全拉伸丝工艺中的喷丝孔形状和排布,并对出丝后的纤维进行松弛热处理的纺丝改变材料卷曲形态,该方法可以获得截面形状为三叶形的卷曲纤维,但该技术存在工艺复杂、生产效率较低、使用原料单一等缺陷。专利CN202011469274.7介绍了一种自卷曲纤维的制备方法,该方法利用双组份熔体纺丝技术经过复合纺丝、牵伸、热定型实现卷曲纤维的制备,该技术可制备得到卷曲度可控的纤维材料,但该材料湿度敏感性大,应用场景有限,且该纤维保暖性能与力学性质较差,限制了其实际应用。专利CN200610117221.2介绍了一种PA6/PU复合三维卷曲纤维及其制备方法,该方法利用装配有偏心皮芯组件的螺杆熔融挤出装置制备出了偏心皮芯结构卷曲纤维,该方法利用了不同聚合物受热变化量不同与偏心结构的方式获得了卷曲结构,但该技术存在流程繁琐、成本较高、纤维力学强度较差与偏心结构带来的织造稳定性差等缺陷。专利CN201711386867.5介绍了一种柔软吸湿易染卷曲纤维及其制备方法,该方法先将聚酰胺熔体与聚酯熔体在纺丝箱体中的复合纺丝组件汇合后,经皮芯复合喷丝板喷出,冷却处理,生成初生丝,再对所述初生丝进行后处理,得到所述的柔软吸湿易染卷曲纤维,该技术得到纤维的卷曲程度可控,但存在使用原料单一、生产效率较低和结构不稳定等缺陷。
因此,制备既具有优异的力学强度,卷曲程度又可控且表面多孔的纤维材料至关重要。
发明内容
本发明的目的就是为了解决上述问题而提供一种具有仿羊毛卷曲结构的多孔纤维及其制备方法,解决现有技术中存在的保暖材料难以同时兼具轻薄、高强度与高保暖性能的缺陷。
本发明的目的通过以下技术方案实现:
本发明的目的是提供一种具有仿羊毛卷曲结构的多孔纤维的制备方法,包括以下步骤:
S1:将长丝放入聚合物发泡溶液中进行超声浸渍,使溶液完全均匀包覆在长丝表面;
S2:将S1中表面包覆聚合物发泡溶液的长丝取出,放入模具中进行发泡处理,使长丝表面的发泡溶液产生气泡,干燥,使溶剂挥发,溶质多孔的形状固化,在长丝表面形成初级孔结构;
S3:将S2中得到的具有初级孔结构的长丝放入聚合物溶液中,进行旋转浸渍处理,使溶液充分浸透在初级孔结构中,随后将其放入溶剂蒸汽梯度控制装置中,并在装置中加入溶液中聚合物对应的非溶剂,对溶液进行非溶剂诱导相分离,使得长丝表面初级孔内聚合物溶液相分离成均匀的次级孔,经干燥处理后获得表面具有多级孔的皮芯结构长丝;
S4:将得到的多孔长丝放入热定型机中,经过定向热风使长丝发生定向卷曲,完成对长丝的连续化卷曲定型;
S5:将卷曲多孔长丝进行切断处理,获得具有仿羊毛卷曲结构的多孔纤维。
进一步地,S1中,所述长丝选自聚乳酸-己内酯、聚氧化乙烯、聚四氟乙烯、聚乙烯醇、聚乙烯醇缩丁醛、酚醛树脂、聚丙烯酸、聚甲基丙烯酸甲酯、聚醚醚酮、聚偏氟乙酸、聚环氧乙烷、聚乙烯咔唑、聚偏氟乙烯、聚酰胺、聚苯胺、聚三羟基丁酸酯、聚羟基丁酸酯、聚碳酸酯、聚酰亚胺、聚醚酰亚胺、聚苯并咪唑、聚苯并恶嗪、聚对苯二甲酰间苯二胺、聚对苯二甲酰对苯二胺、聚对苯二甲酸乙二酯、聚对苯二甲酸丙二酯、聚芳酰胺、聚偏氟乙烯酸、聚吡咯烷酮、聚乳酸、聚乳酸乙醇酸、聚砜、聚乙二炔、聚苯乙烯共聚马来酸酐、聚甲基三乙氧基硅烷、聚谷氨酸、聚己内酯、聚对苯乙炔、聚乙丙交酯、聚氨酯、聚苯乙烯、聚丙烯腈、聚醋酸乙烯酯、聚丙烯、聚乙二醇、聚丙烯酰胺、聚乙烯、聚氯乙烯、聚二氧环己酮、聚丁二酸丁二醇酯和聚对苯二甲酸-共-丁二酸丁二醇酯长丝中的一种或几种组合。
进一步地,S1中,所述的聚合物发泡溶液由聚合物、发泡剂和溶剂均匀搅拌制成,发泡溶液中聚合物的含量为15~60wt%,发泡溶液中发泡剂的含量为1~25wt%,其余为溶剂。
进一步地,S1中,所述聚合物选自聚偏二氟乙烯、聚乙烯、聚丙烯、聚丙烯腈、聚苯乙烯、丙烯腈-丁二烯-苯乙烯共聚物、聚丁二酸丁二醇酯、聚碳酸酯、聚氨酯、聚乳酸、苯乙烯-丙烯腈共聚物、聚醚酰亚胺、聚乙烯亚胺、聚酰亚胺、聚己内酯、芳纶1313、聚砜、聚酰胺、聚乙烯醇、聚甲基丙烯酸甲酯、聚对苯二甲酸丙二醇酯或聚对苯二甲酸丁二醇酯的一种或几种;
所述发泡剂为偶氮二甲酰胺、偶氮二异丁腈、二亚硝基五亚甲基四胺、对甲苯磺酰肼、戊烷或氢化氟烷烃的一种或几种;
所述溶剂选自乙酸乙酯、丙酮、四氢呋喃、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、水、甲醇、乙醇、六氟异丙醇、异丁醇、正丙醇、四氯化碳、苯、甲苯、二氯乙烷、二氯甲烷、乙醚、二苯醚、甲酚、二甲基亚砜、甲苯、环己酮、乙酸丁酯、乙酸乙酯或氯仿中的一种或几种;
所述超声频率为20~50kHz,超声浸渍时间为10~60min。
进一步地,S2中,所述发泡的时间为20~100min,干燥温度为40~120℃,干燥时间为1~4h。
进一步地,S3中,所述的聚合物溶液由聚合物和溶剂均匀搅拌制成,且S3中采用的到溶剂为S1中聚合物的难容溶剂;
S3中,所述聚合物溶液中聚合物的含量为6~40wt%,其余为溶剂。
进一步地,S3中,所述聚合物选用聚砜、聚丁二酸丁二醇酯、聚甲基丙烯酸甲酯、聚碳酸酯、聚氨酯、聚乳酸、聚酰胺、聚乙烯醇、聚偏二氟乙烯、聚乙烯、聚丙烯、聚丙烯腈、聚苯乙烯、丙烯腈-丁二烯-苯乙烯共聚物、苯乙烯-丙烯腈共聚物、聚醚酰亚胺、聚乙烯亚胺、聚酰亚胺、聚己内酯、芳纶1313、聚对苯二甲酸丙二醇酯或聚对苯二甲酸丁二醇酯中的一种或几种;
所述溶剂选自水、甲醇、乙醇、六氟异丙醇、异丁醇、正丙醇、四氯化碳、苯、甲苯、二氯乙烷、二氯甲烷、乙醚、二苯醚、乙酸乙酯、丙酮、四氢呋喃、N-甲基吡咯烷酮、N,N-二甲基甲酰胺中、N,N-二甲基乙酰胺、甲酚、二甲基亚砜、甲苯、环己酮、乙酸丁酯、乙酸乙酯和氯仿中的一种或几种;
所述旋转浸渍的旋转速度50~400rpm,旋转浸渍时间为15~50min。
进一步地,S3中,所述溶剂蒸汽梯度控制装置由4组溶剂蒸汽控制组件和6组长丝传送组件共同组成,纱线传送组件位于纱线溶剂蒸汽控制装置的入口和出口处,可分四级梯度控制长丝表面聚合物溶液所处环境的非溶剂蒸汽浓度,从而调节长丝表面聚合物溶液的相分离速度,最终实现相分离膜孔结构的精确调控。
溶剂蒸汽控制组件主要由溶剂环境仓、温度控制台和通风系统组成,通过多个蒸汽控制组件的组合实现对环境溶剂蒸汽环境的梯度控制,能够通过独立控制单个传送组件,使每个传送组件之间形成一定的速度差,确保纱线在行进过程中具有合适的张力,防止纱线在蒸汽罩内的热作用以及气流的冲击下产生变形,对进气、排气通量和加热温度精确调控,在保证溶剂蒸汽浓度保持稳定可控的同时,确保加工环境安全,有效避免有机溶剂泄露造成的人员健康损害、环境污染等问题。
溶剂环境仓主要由蒸汽罩、溶剂蒸汽浓度检测仪、孔眼板、金属网眼和溶剂储存槽组成,蒸汽罩由耐溶剂腐蚀的透明材料制成,孔眼板为纱线与溶剂环境连接的出入口,分布在蒸汽罩前后两侧,孔眼板中孔眼的大小根据纱线的直径调整,且方便拆卸更换;金属网眼位于溶剂储存槽的上方,形状大小与蒸汽罩底面相同;溶剂储存槽位于金属网眼的下方,为耐溶剂腐蚀的材料制成,外部配有开合式仓门与抽屉式滑轮,方便溶剂的放置与取出。
表面包覆聚合物溶液的纱线在纱线传送组件的控制下,以一定速度边旋转边从蒸汽罩上的孔眼板进入蒸汽罩内,角速度和传送速度根据溶液中聚合物的浊点、占比及所需相分离速度的快慢调整;在加热台的作用下,溶剂储存仓内的非溶剂转化为非溶剂蒸汽,布满蒸汽罩,罩内蒸汽含量由加热温度和新风量共同控制,根据溶剂和非溶剂的相容性、非溶剂的沸点以及所需孔径大小等因素共同决定;在进风组件的作用下,外界空气经过气体干燥组件的干燥处理后,从进风管流入蒸汽罩内,干燥空气携带蒸汽罩内的溶剂蒸汽形成混合蒸汽,在抽风组件的负压作用下,以一定的流速在蒸汽罩内流动并与纱线接触,诱导纱线表面的聚合物溶液产生相分离,形成相分离膜孔结构,通过控制加热温度、通风速度以及纱线传输速度控制与纱线表面接触蒸汽的浓度梯度、温度和作用时间,实现可控相分离,精确调控多孔膜孔径大小和孔隙率,作用后的混合蒸汽经活性炭吸附箱吸附回收,以干燥空气的形式排入大气,在精确控制的同时减少环境污染。
进一步地,S3中,所述聚合物对应的非溶剂选自水、醇类溶剂、酸类溶剂、醚类溶剂、脂类溶剂、脂肪类溶剂、芳香类溶剂或杂环类溶剂中的一种或几种;
非溶剂蒸汽梯度处理时间为10~50min;
干燥处理的干燥温度为40~180℃,干燥时间为1~4h。
本发明的第二个目的是提供由上述方法制备的具有仿羊毛卷曲结构的多孔纤维,该纤维的卷曲率在10~60%内可控,由该纤维纺纱织造获得的织物热阻为0.15~0.4m2K/W,由该纤维铺网得到的蓬松絮片热阻为0.5~1m2K/W。
本技术方案具有以下技术优势:
(1)本发明的一种具有仿羊毛卷曲结构的多孔纤维,皮层的多层次孔结构可有效储存静止空气,起到提高保暖性能的效果;芯层致密排列的取向纤维提供力学强度。经过表面多孔化处理的纤维制备的织物与未处理的相比热阻可提升至0.15~0.4m2K/W,与同样材料制备得到的蓬松絮片相比热阻可提升至0.5~1m2K/W,且其它性能可完好保留。
(2)本发明的一种具有仿羊毛卷曲结构的多孔纤维的制备方法,可在应用于不同种类和不同功能的纤维,方法通用性强,适用范围广。
具体实施方式
下面结合具体实施例对本发明进行详细说明,但绝不是对本发明的限制。本技术方案中如未明确说明的制备手段、材料、结构或组成配比等特征,均视为现有技术中公开的常见技术特征。
本发明中的具有仿羊毛卷曲结构的多孔纤维的制备方法,包括以下步骤:
S1:将长丝放入聚合物发泡溶液中进行超声浸渍,使溶液完全均匀包覆在长丝表面;
S2:将S1中表面包覆聚合物发泡溶液的长丝取出,放入模具中进行发泡处理,使长丝表面的发泡溶液产生气泡,干燥,使溶剂挥发,溶质多孔的形状固化,在长丝表面形成初级孔结构;
S3:将S2中得到的具有初级孔结构的长丝放入聚合物溶液中,进行旋转浸渍处理,使溶液充分浸透在初级孔结构中,随后将其放入溶剂蒸汽梯度控制装置中,并在装置中加入溶液中聚合物对应的非溶剂,对溶液进行非溶剂诱导相分离,使得长丝表面初级孔内聚合物溶液相分离成均匀的次级孔,经干燥处理后获得表面具有多级孔的皮芯结构长丝;
S4:将得到的多孔长丝放入热定型机中,经过定向热风使长丝发生定向卷曲,完成对长丝的连续化卷曲定型;
S5:将卷曲多孔长丝进行切断处理,获得具有仿羊毛卷曲结构的多孔纤维。
具体实施时可根据需要选择/替换地,S1中,所述长丝选自聚乳酸-己内酯、聚氧化乙烯、聚四氟乙烯、聚乙烯醇、聚乙烯醇缩丁醛、酚醛树脂、聚丙烯酸、聚甲基丙烯酸甲酯、聚醚醚酮、聚偏氟乙酸、聚环氧乙烷、聚乙烯咔唑、聚偏氟乙烯、聚酰胺、聚苯胺、聚三羟基丁酸酯、聚羟基丁酸酯、聚碳酸酯、聚酰亚胺、聚醚酰亚胺、聚苯并咪唑、聚苯并恶嗪、聚对苯二甲酰间苯二胺、聚对苯二甲酰对苯二胺、聚对苯二甲酸乙二酯、聚对苯二甲酸丙二酯、聚芳酰胺、聚偏氟乙烯酸、聚吡咯烷酮、聚乳酸、聚乳酸乙醇酸、聚砜、聚乙二炔、聚苯乙烯共聚马来酸酐、聚甲基三乙氧基硅烷、聚谷氨酸、聚己内酯、聚对苯乙炔、聚乙丙交酯、聚氨酯、聚苯乙烯、聚丙烯腈、聚醋酸乙烯酯、聚丙烯、聚乙二醇、聚丙烯酰胺、聚乙烯、聚氯乙烯、聚二氧环己酮、聚丁二酸丁二醇酯和聚对苯二甲酸-共-丁二酸丁二醇酯长丝中的一种或几种组合。
具体实施时可根据需要选择/替换地,S1中,所述的聚合物发泡溶液由聚合物、发泡剂和溶剂均匀搅拌制成,发泡溶液中聚合物的含量为15~60wt%,发泡溶液中发泡剂的含量为1~25wt%,其余为溶剂。
具体实施时可根据需要选择/替换地,S1中,所述聚合物选自聚偏二氟乙烯、聚乙烯、聚丙烯、聚丙烯腈、聚苯乙烯、丙烯腈-丁二烯-苯乙烯共聚物、聚丁二酸丁二醇酯、聚碳酸酯、聚氨酯、聚乳酸、苯乙烯-丙烯腈共聚物、聚醚酰亚胺、聚乙烯亚胺、聚酰亚胺、聚己内酯、芳纶1313、聚砜、聚酰胺、聚乙烯醇、聚甲基丙烯酸甲酯、聚对苯二甲酸丙二醇酯或聚对苯二甲酸丁二醇酯的一种或几种;
所述发泡剂为偶氮二甲酰胺、偶氮二异丁腈、二亚硝基五亚甲基四胺、对甲苯磺酰肼、戊烷或氢化氟烷烃的一种或几种;
所述溶剂选自乙酸乙酯、丙酮、四氢呋喃、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、水、甲醇、乙醇、六氟异丙醇、异丁醇、正丙醇、四氯化碳、苯、甲苯、二氯乙烷、二氯甲烷、乙醚、二苯醚、甲酚、二甲基亚砜、甲苯、环己酮、乙酸丁酯、乙酸乙酯或氯仿中的一种或几种;
所述超声频率为20~50kHz,超声浸渍时间为10~60min。
具体实施时可根据需要选择/替换地,S2中,所述发泡的时间为20~100min,干燥温度为40~120℃,干燥时间为1~4h。
具体实施时可根据需要选择/替换地,S3中,所述的聚合物溶液由聚合物和溶剂均匀搅拌制成,且S3中采用的到溶剂为S1中聚合物的难容溶剂;
S3中,所述聚合物溶液中聚合物的含量为6~40wt%,其余为溶剂。
具体实施时可根据需要选择/替换地,S3中,所述聚合物选用聚砜、聚丁二酸丁二醇酯、聚甲基丙烯酸甲酯、聚碳酸酯、聚氨酯、聚乳酸、聚酰胺、聚乙烯醇、聚偏二氟乙烯、聚乙烯、聚丙烯、聚丙烯腈、聚苯乙烯、丙烯腈-丁二烯-苯乙烯共聚物、苯乙烯-丙烯腈共聚物、聚醚酰亚胺、聚乙烯亚胺、聚酰亚胺、聚己内酯、芳纶1313、聚对苯二甲酸丙二醇酯或聚对苯二甲酸丁二醇酯中的一种或几种;
所述溶剂选自水、甲醇、乙醇、六氟异丙醇、异丁醇、正丙醇、四氯化碳、苯、甲苯、二氯乙烷、二氯甲烷、乙醚、二苯醚、乙酸乙酯、丙酮、四氢呋喃、N-甲基吡咯烷酮、N,N-二甲基甲酰胺中、N,N-二甲基乙酰胺、甲酚、二甲基亚砜、甲苯、环己酮、乙酸丁酯、乙酸乙酯和氯仿中的一种或几种;
所述旋转浸渍的旋转速度50~400rpm,旋转浸渍时间为15~50min。
具体实施时可根据需要选择/替换地,S3中,所述聚合物对应的非溶剂选自水、醇类溶剂、酸类溶剂、醚类溶剂、脂类溶剂、脂肪类溶剂、芳香类溶剂或杂环类溶剂中的一种或几种;非溶剂蒸汽梯度处理时间为10~50min;干燥处理的干燥温度为40~180℃,干燥时间为1~4h。
本发明制得的具有仿羊毛卷曲结构的多孔纤维不同于普通的卷曲纤维,具体体现在:
(1)本发明的具有仿羊毛卷曲结构的多孔纤维的保暖性能得到了有效提升;这是因为与普通卷曲纤维相比,本发明的卷曲纤维表面具有丰富且大量的孔结构,有利于阻止空气流动,防止因空气流动引起的热量散失,经过精细调节的相分离小孔结构的存在可有效阻碍空气分子的运动并有效减少气体分子间的热量传递,在增加静止空气保有量的同时降低了长丝周围空气本体的导热系数,极大提升了保暖性能。
(2)本发明的具有仿羊毛卷曲结构的多孔纤维制备得到的织物或絮片具有较好的力学性能;这是因为表面的粗糙多孔结构可大大加强纤维之间的滑移阻力,从而有效提高了织物的抗顶破、剪切、拉伸断裂等力学强度,同时卷曲纤维兼具较好的柔软性、高度蓬松和良好的回弹性等优点,穿着舒适性和实用性大大提高。
实施例1
本实施例中具有仿羊毛卷曲结构的多孔纤维的制备方法,具体步骤如下:
将聚氨酯溶解在N,N-二甲基甲酰胺中,随后加入偶氮二甲酰胺作为发泡剂,均匀搅拌后获得聚合物发泡溶液,发泡溶液中聚氨酯的含量为29wt%,偶氮二甲酰胺的含量为8wt%;第二步:将聚乳酸溶解在六氟异丙醇中,均匀搅拌后获得聚合物溶液,聚合物溶液中聚乳酸的含量为18wt%;
第一步:将聚乙烯长丝放入聚合物发泡溶液中进行超声浸渍,超声频率为40kHz,超声浸渍时间为20min,使溶液完全均匀包覆在长丝表面;
第二步:将表面包覆聚合物发泡溶液的长丝取出,放入模具中进行发泡处理,使长丝表面的发泡溶液产生气泡,发泡时间为40min,随后进行干燥处理,干燥温度为80℃,干燥时间为2h,使溶剂挥发,溶质多孔的形状固化,在长丝表面形成初级孔结构;
第三步:将上述具有初级孔结构的长丝放入聚合物溶液中,进行旋转浸渍处理,旋转速度279rpm,旋转浸渍时间为20min,使溶液充分浸透在初级孔结构中,随后将表面包覆聚合物溶液的长丝放入溶剂蒸汽梯度控制系统中,并在装置中加入溶水作为聚乳酸的非溶剂,对其进行非溶剂诱导相分离,使得长丝表面初级孔内聚合物溶液相分离成均匀的次级孔,随后将表面完成相分离成孔的长丝放入鼓风烘箱中干燥,干燥温度为40℃,干燥时间为4h,去除剩余溶剂,最终获得表面具有多级孔的皮芯结构长丝;
第四步:将得到的多孔长丝放入热定型机中,经过定向热风使长丝发生定向卷曲,完成对长丝的连续化卷曲定型,得到卷曲长丝;
第五步:将卷曲多孔长丝放入切断装置中进行切断处理,获得卷曲多孔短纤;
最终获得多孔短纤的卷曲率为45%,且由所述纤维纺纱织造获得的织物热阻为0.25m2K/W,由所述纤维铺网得到的蓬松絮片热阻为0.7m2K/W,由所述纤维铺网得到的蓬松絮片的拉伸强力为45N/g。
需要说明的是,本实施例中涉及的组分选择和配比、工艺参数均可基于上方指出的可选择/替换内容进行按需调整,对应的性能均与本实施例相似,即调整后的方案均可实现本技术方案中声称的技术效果。
实施例2
本实施例中具有仿羊毛卷曲结构的多孔纤维的制备方法,具体步骤如下:
将聚碳酸酯溶解在氯仿中,随后加入偶氮二异丁腈作为发泡剂,均匀搅拌后获得聚合物发泡溶液,所述发泡溶液中聚碳酸酯的含量为35wt%,偶氮二异丁腈的含量为16wt%;将聚苯乙烯溶解在N,N-二甲基乙酰胺中,均匀搅拌后获得聚合物溶液,所述聚合物溶液中聚苯乙烯的含量为22wt%;
第一步:将聚四氟乙烯长丝放入聚合物发泡溶液中进行超声浸渍,超声频率为37kHz,超声浸渍时间为25min,使溶液完全均匀包覆在长丝表面;
第二步:将表面包覆聚合物发泡溶液的长丝取出,放入模具中进行发泡处理,使长丝表面的发泡溶液产生气泡,发泡时间为24min,随后进行干燥处理,干燥温度为120℃,干燥时间为2h,使溶剂挥发,溶质多孔的形状固化,在长丝表面形成初级孔结构;
第三步:将上述具有初级孔结构的长丝放入聚合物溶液中,进行旋转浸渍处理,旋转速度256rpm,旋转浸渍时间为20min,使溶液充分浸透在初级孔结构中,随后将表面包覆聚合物溶液的长丝放入溶剂蒸汽梯度控制系统中,并在装置中加入溶水作为聚苯乙烯的非溶剂,对其进行非溶剂诱导相分离,使得长丝表面初级孔内聚合物溶液相分离成均匀的次级孔,随后将表面完成相分离成孔的长丝放入鼓风烘箱中干燥,干燥温度为60℃,干燥时间为3h,去除剩余溶剂,最终获得表面具有多级孔的皮芯结构长丝;
第四步:将得到的多孔长丝放入热定型机中,经过定向热风使长丝发生定向卷曲,完成对长丝的连续化卷曲定型,得到卷曲长丝;
第五步:将卷曲多孔长丝放入切断装置中进行切断处理,获得卷曲多孔短纤;
最终获得多孔短纤的卷曲率为55%,且由所述纤维纺纱织造获得的织物热阻为0.31m2K/W,由所述纤维铺网得到的蓬松絮片热阻为0.8m2K/W,由所述纤维铺网得到的蓬松絮片的拉伸强力为43N/g。
实施例3
本实施例中具有仿羊毛卷曲结构的多孔纤维的制备方法,具体步骤如下:
将聚酰胺溶解在甲酸中,随后加入二亚硝基五亚甲基四胺作为发泡剂,均匀搅拌后获得聚合物发泡溶液,所述发泡溶液中聚酰胺的含量为32wt%,二亚硝基五亚甲基四胺的含量为12wt%;将聚丙烯腈溶解在N,N-二甲基甲酰胺中,均匀搅拌后获得聚合物溶液,所述聚合物溶液中聚丙烯腈的含量为12wt%;
第一步:将聚对苯二甲酸乙二酯长丝放入聚合物发泡溶液中进行超声浸渍,超声频率为42kHz,超声浸渍时间为15min,使溶液完全均匀包覆在长丝表面;
第二步:将表面包覆聚合物发泡溶液的长丝取出,放入模具中进行发泡处理,使长丝表面的发泡溶液产生气泡,发泡时间为35min,随后进行干燥处理,干燥温度为110℃,干燥时间为2h,使溶剂挥发,溶质多孔的形状固化,在长丝表面形成初级孔结构;
第三步:将上述具有初级孔结构的长丝放入聚合物溶液中,进行旋转浸渍处理,旋转速度180rpm,旋转浸渍时间为15min,使溶液充分浸透在初级孔结构中,随后将表面包覆聚合物溶液的长丝放入溶剂蒸汽梯度控制系统中,并在装置中加入溶水作为聚丙烯腈的非溶剂,对其进行非溶剂诱导相分离,使得长丝表面初级孔内聚合物溶液相分离成均匀的次级孔,随后将表面完成相分离成孔的长丝放入鼓风烘箱中干燥,干燥温度为130℃,干燥时间为2h,去除剩余溶剂,最终获得表面具有多级孔的皮芯结构长丝。
第四步:将得到的多孔长丝放入热定型机中,经过定向热风使长丝发生定向卷曲,完成对长丝的连续化卷曲定型,得到卷曲长丝;
第五步:将卷曲多孔长丝放入切断装置中进行切断处理,获得卷曲多孔短纤;
最终获得多孔短纤的卷曲率为10%,且由所述纤维纺纱织造获得的织物热阻为0.29m2K/W,由所述纤维铺网得到的蓬松絮片热阻为0.6m2K/W,由所述纤维铺网得到的蓬松絮片的拉伸强力为46N/g。
实施例4
本实施例中具有仿羊毛卷曲结构的多孔纤维的制备方法,具体步骤如下:
将聚丙烯溶解在环己酮中,随后加入偶氮二甲酰胺作为发泡剂,均匀搅拌后获得聚合物发泡溶液,所述发泡溶液中聚丙烯的含量为40wt%,偶氮二甲酰胺的含量为9wt%;将聚砜溶解在N,N-二甲基乙酰胺中,均匀搅拌后获得聚合物溶液,所述聚合物溶液中聚砜的含量为25wt%;
第一步:将聚碳酸酯长丝放入聚合物发泡溶液中进行超声浸渍,超声频率为50kHz,超声浸渍时间为22min,使溶液完全均匀包覆在长丝表面;
第二步:将表面包覆聚合物发泡溶液的长丝取出,放入模具中进行发泡处理,使长丝表面的发泡溶液产生气泡,发泡时间为16min,随后进行干燥处理,干燥温度为80℃,干燥时间为3h,使溶剂挥发,溶质多孔的形状固化,在长丝表面形成初级孔结构;
第三步:将上述具有初级孔结构的长丝放入聚合物溶液中,进行旋转浸渍处理,旋转速度310rpm,旋转浸渍时间为20min,使溶液充分浸透在初级孔结构中,随后将表面包覆聚合物溶液的长丝放入溶剂蒸汽梯度控制系统中,并在装置中加入溶水作为聚砜的非溶剂,对其进行非溶剂诱导相分离,使得长丝表面初级孔内聚合物溶液相分离成均匀的次级孔,随后将表面完成相分离成孔的长丝放入鼓风烘箱中干燥,干燥温度为160℃,干燥时间为2h,去除剩余溶剂,最终获得表面具有多级孔的皮芯结构长丝。
第四步:将得到的多孔长丝放入热定型机中,经过定向热风使长丝发生定向卷曲,完成对长丝的连续化卷曲定型,得到卷曲长丝;
第五步:将卷曲多孔长丝放入切断装置中进行切断处理,获得卷曲多孔短纤;
最终获得多孔短纤的卷曲率为60%,且由所述纤维纺纱织造获得的织物热阻为0.4m2K/W,由所述纤维铺网得到的蓬松絮片热阻为0.1m2K/W,由所述纤维铺网得到的蓬松絮片的拉伸强力为42N/g。
实施例5
本实施例中具有仿羊毛卷曲结构的多孔纤维的制备方法,具体步骤如下:
将聚乙烯溶解在甲苯中,随后加入偶氮二异丁腈作为发泡剂,均匀搅拌后获得聚合物发泡溶液,所述发泡溶液中聚乙烯的含量为38wt%,偶氮二异丁腈的含量为17wt%;将聚甲基丙烯酸甲酯溶解在N,N-二甲基甲酰胺中,均匀搅拌后获得聚合物溶液,所述聚合物溶液中聚甲基丙烯酸甲酯的含量为20wt%;
第一步:将聚四氟乙烯长丝放入聚合物发泡溶液中进行超声浸渍,超声频率为48kHz,超声浸渍时间为28min,使溶液完全均匀包覆在长丝表面;
第二步:将表面包覆聚合物发泡溶液的长丝取出,放入模具中进行发泡处理,使长丝表面的发泡溶液产生气泡,发泡时间为27min,随后进行干燥处理,干燥温度为70℃,干燥时间为3h,使溶剂挥发,溶质多孔的形状固化,在长丝表面形成初级孔结构;
第三步:将上述具有初级孔结构的长丝放入聚合物溶液中,进行旋转浸渍处理,旋转速度290rpm,旋转浸渍时间为15min,使溶液充分浸透在初级孔结构中,随后将表面包覆聚合物溶液的长丝放入溶剂蒸汽梯度控制系统中,并在装置中加入溶乙醇作为聚砜的非溶剂,对其进行非溶剂诱导相分离,使得长丝表面初级孔内聚合物溶液相分离成均匀的次级孔,随后将表面完成相分离成孔的长丝放入鼓风烘箱中干燥,干燥温度为100℃,干燥时间为3h,去除剩余溶剂,最终获得表面具有多级孔的皮芯结构长丝。
第四步:将得到的多孔长丝放入热定型机中,经过定向热风使长丝发生定向卷曲,完成对长丝的连续化卷曲定型,得到卷曲长丝;
第五步:将卷曲多孔长丝放入切断装置中进行切断处理,获得卷曲多孔短纤;
最终获得多孔短纤的卷曲率为30%,且由所述纤维纺纱织造获得的织物热阻为0.15m2K/W,由所述纤维铺网得到的蓬松絮片热阻为0.5m2K/W,由所述纤维铺网得到的蓬松絮片的拉伸强力为44N/g。
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 (9)

1.一种具有仿羊毛卷曲结构的多孔纤维的制备方法,其特征在于,包括以下步骤:
S1:将长丝放入聚合物发泡溶液中进行超声浸渍,使溶液完全均匀包覆在长丝表面;
S2:将S1中表面包覆聚合物发泡溶液的长丝取出,放入模具中进行发泡处理,使长丝表面的发泡溶液产生气泡,干燥,使溶剂挥发,溶质多孔的形状固化,在长丝表面形成初级孔结构;
S3:将S2中得到的具有初级孔结构的长丝放入聚合物溶液中,进行旋转浸渍处理,使溶液充分浸透在初级孔结构中,随后将其放入溶剂蒸汽梯度控制装置中,并在装置中加入溶液中聚合物对应的非溶剂,对溶液进行非溶剂诱导相分离,使得长丝表面初级孔内聚合物溶液相分离成均匀的次级孔,经干燥处理后获得表面具有多级孔的皮芯结构长丝;
S4:将得到的多孔长丝放入热定型机中,经过定向热风使长丝发生定向卷曲,完成对长丝的连续化卷曲定型;
S5:将卷曲多孔长丝进行切断处理,获得具有仿羊毛卷曲结构的多孔纤维;
S1中,所述的聚合物发泡溶液由聚合物、发泡剂和溶剂均匀搅拌制成,发泡溶液中聚合物的含量为15~60wt%,发泡溶液中发泡剂的含量为1~25wt%,其余为溶剂。
2.根据权利要求1所述的一种具有仿羊毛卷曲结构的多孔纤维的制备方法,其特征在于,S1中,所述长丝选自聚乳酸-己内酯、聚氧化乙烯、聚四氟乙烯、聚乙烯醇、聚乙烯醇缩丁醛、酚醛树脂、聚丙烯酸、聚甲基丙烯酸甲酯、聚醚醚酮、聚偏氟乙酸、聚环氧乙烷、聚乙烯咔唑、聚偏氟乙烯、聚酰胺、聚苯胺、聚三羟基丁酸酯、聚羟基丁酸酯、聚碳酸酯、聚酰亚胺、聚醚酰亚胺、聚苯并咪唑、聚苯并恶嗪、聚对苯二甲酰间苯二胺、聚对苯二甲酰对苯二胺、聚对苯二甲酸乙二酯、聚对苯二甲酸丙二酯、聚芳酰胺、聚偏氟乙烯酸、聚吡咯烷酮、聚乳酸、聚乳酸乙醇酸、聚砜、聚乙二炔、聚苯乙烯共聚马来酸酐、聚甲基三乙氧基硅烷、聚谷氨酸、聚己内酯、聚对苯乙炔、聚乙丙交酯、聚氨酯、聚苯乙烯、聚丙烯腈、聚醋酸乙烯酯、聚丙烯、聚乙二醇、聚丙烯酰胺、聚乙烯、聚氯乙烯、聚二氧环己酮、聚丁二酸丁二醇酯和聚对苯二甲酸-共-丁二酸丁二醇酯长丝中的一种或几种组合。
3.根据权利要求1所述的一种具有仿羊毛卷曲结构的多孔纤维的制备方法,其特征在于,S1中,所述聚合物选自聚偏二氟乙烯、聚乙烯、聚丙烯、聚丙烯腈、聚苯乙烯、丙烯腈-丁二烯-苯乙烯共聚物、聚丁二酸丁二醇酯、聚碳酸酯、聚氨酯、聚乳酸、苯乙烯-丙烯腈共聚物、聚醚酰亚胺、聚乙烯亚胺、聚酰亚胺、聚己内酯、芳纶1313、聚砜、聚酰胺、聚乙烯醇、聚甲基丙烯酸甲酯、聚对苯二甲酸丙二醇酯或聚对苯二甲酸丁二醇酯的一种或几种;
所述发泡剂为偶氮二甲酰胺、偶氮二异丁腈、二亚硝基五亚甲基四胺、对甲苯磺酰肼、戊烷或氢化氟烷烃的一种或几种;
所述溶剂选自乙酸乙酯、丙酮、四氢呋喃、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、水、甲醇、乙醇、六氟异丙醇、异丁醇、正丙醇、四氯化碳、苯、二氯乙烷、二氯甲烷、乙醚、二苯醚、甲酚、二甲基亚砜、甲苯、环己酮、乙酸丁酯或氯仿中的一种或几种;
所述超声频率为20~50kHz,超声浸渍时间为10~60min。
4.根据权利要求1所述的一种具有仿羊毛卷曲结构的多孔纤维的制备方法,其特征在于,S2中,所述发泡的时间为20~100min,干燥温度为40~120℃,干燥时间为1~4h。
5.根据权利要求1所述的一种具有仿羊毛卷曲结构的多孔纤维的制备方法,其特征在于,S3中,所述的聚合物溶液由聚合物和溶剂均匀搅拌制成,且S3中采用的到溶剂为S1中聚合物的难容溶剂;
S3中,所述聚合物溶液中聚合物的含量为6~40wt%,其余为溶剂。
6.根据权利要求5所述的一种具有仿羊毛卷曲结构的多孔纤维的制备方法,其特征在于,S3中,所述聚合物选用聚砜、聚丁二酸丁二醇酯、聚甲基丙烯酸甲酯、聚碳酸酯、聚氨酯、聚乳酸、聚酰胺、聚乙烯醇、聚偏二氟乙烯、聚乙烯、聚丙烯、聚丙烯腈、聚苯乙烯、丙烯腈-丁二烯-苯乙烯共聚物、苯乙烯-丙烯腈共聚物、聚醚酰亚胺、聚乙烯亚胺、聚酰亚胺、聚己内酯、芳纶1313、聚对苯二甲酸丙二醇酯或聚对苯二甲酸丁二醇酯中的一种或几种;
所述溶剂选自水、甲醇、乙醇、六氟异丙醇、异丁醇、正丙醇、四氯化碳、苯、二氯乙烷、二氯甲烷、乙醚、二苯醚、乙酸乙酯、丙酮、四氢呋喃、N-甲基吡咯烷酮、N,N-二甲基甲酰胺中、N,N-二甲基乙酰胺、甲酚、二甲基亚砜、甲苯、环己酮、乙酸丁酯和氯仿中的一种或几种;
所述旋转浸渍的旋转速度50~400rpm,旋转浸渍时间为15~50min。
7.根据权利要求1所述的一种具有仿羊毛卷曲结构的多孔纤维的制备方法,其特征在于,S3中,所述溶剂蒸汽梯度控制装置由4组溶剂蒸汽控制组件和6组长丝传送装置共同组成,可分四级梯度控制长丝表面聚合物溶液所处环境的非溶剂蒸汽浓度,从而调节长丝表面聚合物溶液的相分离速度,最终实现相分离膜孔结构的精确调控。
8.根据权利要求1所述的一种具有仿羊毛卷曲结构的多孔纤维的制备方法,其特征在于,S3中,所述聚合物对应的非溶剂选自水、醇类溶剂、酸类溶剂、醚类溶剂、脂类溶剂、脂肪类溶剂、芳香类溶剂或杂环类溶剂中的一种或几种;
非溶剂蒸汽梯度处理时间为10~50min;
干燥处理的干燥温度为40~180℃,干燥时间为1~4h。
9.一种如权利要求1至8中任意一项所述方法制备的具有仿羊毛卷曲结构的多孔纤维,其特征在于,该纤维的卷曲率在10~60%内可控,由该纤维纺纱织造获得的织物热阻为0.15~ 0.4m2K/W,由该纤维铺网得到的蓬松絮片热阻为0.5~1m2K/W。
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