CN114434930B - 一种综丝基膜及其制备方法 - Google Patents
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Abstract
本发明公开了一种综丝基膜,所述综丝基膜包括支撑层及设置在所述支撑层两外侧的功能层;所述支撑层的材料为聚酯切片,所述功能层由以下重量份数的原料组成:100份聚酯切片、5~12份增塑剂、0.2~0.7份改性纳米填料、15~18份添加剂、1~5份颜料和10~15份助剂。本发明的综丝基膜,综合机械性能和尺寸稳定性好,其不仅具有优异的抗粘连和抗静电效果,而且具有优异的自清洁和耐热性,可满足纺丝与聚酯薄膜综丝的工作要求,提高工作质量和工作效率。
Description
技术领域
本发明涉及膜材料的技术领域,尤其涉及一种综丝基膜及其制备方法。
背景技术
综丝是织造机织物用的易耗配件。一般综丝呈横截面不变的带状,两端部分别开有综耳,中央开有用于穿过并携带织物的经纱,综丝通过综耳安装在综框上,并随综框上下运动,每根综丝控制一根经纱。综丝上下运动时将经纱分开,形成梭口,以便引入纬纱。早期综丝一般采用不锈钢材料制成,其存在材料价格贵、自重大、容易生锈、对机器的损耗大等缺点。随着塑料技术的不断发展,后期采用聚甲醛塑料综丝和聚酯塑料综丝。聚甲醛材料分子存在不易加工、综合机械性能差等问题;聚酯切片材料制作的塑料综丝得以发展,比如专利文献CN101942727A,公开了一种聚酯薄膜综丝及其制备方法,其由三层薄膜共挤而成,并通过在表层聚酯切片中简单添加抗静电剂和抗粘连母料,即可一定程度上提高塑料综丝的综合机械强度和耐磨性能,但其仍无法很好地满足严苛条件下的长期连续运行要求。
发明内容
鉴于以上现有技术的不足之处,本发明提供了一种综丝基膜,以解决现有综丝基膜无法兼顾抗粘连、抗静电及自清洁和耐热性等性能,难以满足纺丝与聚酯薄膜综丝在严苛条件下的长期连续稳定工作要求的问题。
为达到以上目的,本发明采用的技术方案为:
一种综丝基膜,其包括支撑层及设置在所述支撑层两外侧的功能层;所述支撑层的材料为聚酯切片,所述功能层由以下重量份数的原料组成:100份聚酯切片、5~12份
增塑剂、0.2~0.7份改性纳米填料、15~18份添加剂、1~5份颜料和10~15份助剂。
优选地,所述聚酯切片选用聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚萘二甲酸乙二醇酯(PEN)或其共聚改性聚酯中的至少一种。
优选地,所述增塑剂为环形对苯二甲酸丁二醇酯、甘油三苯甲酸酯、环氧脂肪酸辛酯中的至少一种。所述增塑剂利于提高综丝基膜的加工性能。
优选地,所述改性纳米填料为通过接枝有三氟甲基和丙烯酸酯官能团的吡啶衍生物与烯丙基三甲基氯化铵和异戊二烯共聚形成的高聚物包覆纳米填料后得到。
优选地,所述添加剂由六氟双酚A二丙烯酸酯、丙烯酰氧乙基三甲基氯化铵和1-甲基-2-(三甲氧基硅烷基)乙基甲基丙烯酸酯共聚得到。本发明的添加剂,通过各组分的丙烯酸酯官能团进行共聚反应,丙烯酸酯官能团有利于提高与聚酯切片的相溶性,引入的氟硅官能团,不仅有助于提高综丝基膜的抗粘连性,而且有助于提高综丝基膜的自清洁和热稳定性,进一步有助于棉纺过程中塑料综丝飞棉吸附的问题;而三甲基氯化铵基团的引入,则有助于提高综丝基膜的抗静电性能,有效解决棉纺织过程中塑料综丝会吸附大量飞棉的问题。
优选地,所述六氟双酚A二丙烯酸酯、丙烯酰氧乙基三甲基氯化铵和1-甲基-2-(三甲氧基硅烷基)乙基甲基丙烯酸酯的摩尔比为2:1:1。
优选地,所述颜料为酞菁红、酞菁蓝、酞菁绿、玫瑰红、中铬黄、偶氮红中的至少一种。
优选地,所述助剂由吡啶盐离子液体与高沸点溶剂组成。通过吡啶盐离子液体与高沸点溶剂复配的助剂,有助于提高原料各组分在超临界状态下的相容性,从而提高染色效果,并使综丝基膜具有较高的耐热性,长期稳定性好。
优选地,所述吡啶盐离子液体为1-乙基吡啶六氟磷酸盐、1-乙基吡啶四氟硼酸盐、1-乙基吡啶三氟甲磺酸盐中的至少一种。
优选地,所述高沸点助剂为碳酸丙烯酯、丁内酯或γ-戊内酯中的至少一种。
本发明的另外一方面是提供一种如上述的综丝基膜的制备方法,其包括以下步骤:
步骤S1:将0.2mol的三氟甲基吡啶化合物和0.2mol的卤代丙烯酸酯溶于1L四氢呋喃溶液中,在搅拌下加热回流溴代反应24~48小时后过滤,得到吡啶衍生物;取0.1mol的吡啶衍生物,加入5.5g的纳米填料和100g的甘油,超声搅拌混合均匀;再加入0.05mol的烯丙基三甲基氯化铵作为功能助剂,加入0.3mol的异戊二烯作为扩链剂,加入0.25g偶氮二异丁腈作为自由基引发剂在纳米填料表面进行共聚反应,得到吡啶盐衍生物包覆的改性纳米填料;本发明的改性纳米填料,先通过三氟甲基吡啶化合物和卤代丙烯酸酯进行亲核取代反应,使丙烯酸酯官能团接枝在三氟甲基吡啶化合物的N原子上,然后在纳米填料的表面与烯丙基三甲基氯化铵和异戊二烯进行共聚形成高聚物,得到吡啶盐衍生物包覆的改性纳米填料。通过改性处理后的纳米填料易于均匀分散在功能层的原料中,进而提升功能层的整体性能,防止局部缺陷的出现。高聚物接枝的三氟甲基官能团,提高了综丝基膜的自清洁性能,并防止综丝基膜在加工过程中粘结到压延辊上,造成膜层性能的下降;通过三甲基氯化铵功能基团的引入,有助于进一步提高综丝基膜的抗静电效果。
步骤S2:将50份聚酯切片和1~5份颜料置于高压釜中,并加入5~6份添加剂和3~5份助剂,自高压釜底部通入超临界二氧化碳进行染色和改性处理;所述高压釜内的操作温度50~90℃,操作压力为80~100bar,处理时间10~30min;
步骤S3:取0.2~0.7份步骤S1得到的改性纳米填料、50份聚酯切片、5~12份增塑剂、10~12份添加剂和7~10份助剂,搅拌混合均匀,再加入步骤S2处理后的聚酯切片,得到功能熔体;
步骤S4:将作为支撑层的聚酯切片熔体从三层模头的中间层挤出厚片,同时将步骤S3得到的功能熔体从三层模头的上下层同时挤出厚片,经铸片,双向拉伸,热定型处理,冷却,收卷,得到厚度为0.30~0.35mm的所述综丝基膜。
优选地,所述综丝基膜表面功能层的厚度为0.01~0.05mm。
优选地,所述三氟甲基吡啶化合物为3-氟-4-(三氟甲基)吡啶、2-氟-4-三氟甲基吡啶、4-(三氟甲基)-2-吡啶羧酸乙酯、4-(三氟甲基)-3-吡啶羧酸乙酯、4-三氟甲基吡啶-2-羧酸甲酯中的至少一种。本申请三氟甲基吡啶化合物进一步优选4-(三氟甲基)-2-吡啶羧酸乙酯、4-(三氟甲基)-3-吡啶羧酸乙酯或4-三氟甲基吡啶-2-羧酸甲酯,通过羧酸乙酯或羧酸甲酯官能团的引入,进一步提高了改性纳米填料与功能层原料的相容性。
优选地,所述卤代丙烯酸酯为2-溴乙基丙烯酸酯、2-溴乙基甲基丙烯酸酯、2-氯乙基甲基丙烯酸酯中的至少一种。
优选地,所述纳米填料为二氧化钛和/或二氧化硅。填料的二氧化钛使聚酯切片具有消光或半消光的效果,少量二氧化硅的填料有助于与添加剂发挥协同效应,提高综丝基膜的抗粘连性能。
本发明的有益效果:
本发明的综丝基膜,综合机械性能和尺寸稳定性好,其不仅具有优异的抗粘连和抗静电效果,而且具有优异的自清洁和耐热性,满足纺丝与聚酯薄膜综丝在严苛条件下的长期连续稳定工作要求,提高工作质量、工作效率和工作寿命。
具体实施方式
以下描述用于揭露本发明以使本领域技术人员能够实现本发明。以下描述中的优选实施例只作为举例,本领域技术人员可以想到其他显而易见的变型。
实施例1
本实施例的综丝基膜,其包括支撑层及设置在所述支撑层两外侧的功能层;所述支撑层的材料为聚酯切片,所述功能层由以下重量份数的原料组成:100份聚酯切片、5份增塑剂、0.2份改性纳米填料、15份添加剂、1份颜料和10份助剂。所述聚酯切片选用聚对苯二甲酸乙二醇酯(PET)。所述增塑剂为环氧脂肪酸辛酯。所述颜料为酞菁红。所述助剂由质量比为3:2的吡啶盐离子液体与高沸点溶剂组成。所述吡啶盐离子液体为1-乙基吡啶六氟磷酸盐。所述高沸点助剂为碳酸丙烯酯。
所述改性纳米填料为通过接枝有三氟甲基和丙烯酸酯官能团的吡啶衍生物与烯丙基三甲基氯化铵和异戊二烯共聚形成的高聚物包覆纳米填料后得到。所述三氟甲基吡啶化合物为4-(三氟甲基)-2-吡啶羧酸乙酯。所述卤代丙烯酸酯为2-溴乙基丙烯酸酯。所述纳米填料由质量比为1:1的二氧化钛和二氧化硅组成。
所述添加剂由六氟双酚A二丙烯酸酯、丙烯酰氧乙基三甲基氯化铵和1-甲基-2-(三甲氧基硅烷基)乙基甲基丙烯酸酯在自由基引发剂(过硫酸铵)的作用下通过烯烃双键的加成反应进行共聚反应得到。所述六氟双酚A二丙烯酸酯、丙烯酰氧乙基三甲基氯化铵和1-甲基-2-(三甲氧基硅烷基)乙基甲基丙烯酸酯的摩尔比为2:1:1。
本实施例综丝基膜的制备方法,其包括以下步骤:
步骤S1:将0.2mol的三氟甲基吡啶化合物和0.2mol的卤代丙烯酸酯溶于1L四氢呋喃溶液中,在搅拌下加热回流溴代反应24小时后过滤,得到吡啶衍生物;取0.1mol的吡啶衍生物,加入5.5g的纳米填料和100g的甘油,超声搅拌混合均匀;再加入0.05mol的烯丙基三甲基氯化铵作为功能助剂,加入0.3mol的异戊二烯作为扩链剂,加入0.25g偶氮二异丁腈作为自由基引发剂在纳米填料表面进行共聚反应,得到吡啶盐衍生物包覆的改性纳米填料;
步骤S2:将50份聚酯切片和1份颜料置于高压釜中,并加入5份添加剂和3份助剂,自高压釜底部通入超临界二氧化碳进行染色和改性处理;所述高压釜内的操作温度50℃,操作压力为80bar,处理时间10min;
步骤S3:取0.2份步骤S1得到的改性纳米填料、50份聚酯切片、5份增塑剂、10份添加剂和7份助剂,搅拌混合均匀,再加入步骤S2处理后的聚酯切片,得到功能熔体;
步骤S4:将作为支撑层的聚酯切片熔体从三层模头的中间层挤出厚片,同时将步骤S3得到的功能熔体从三层模头的上下层同时挤出厚片,经铸片,双向拉伸,热定型处理,冷却,收卷,得到厚度为0.30mm的所述综丝基膜。所述综丝基膜表面功能层的厚度为0.01mm。
实施例2
本实施例的综丝基膜,其包括支撑层及设置在所述支撑层两外侧的功能层;所述支撑层的材料为聚酯切片,所述功能层由以下重量份数的原料组成:100份聚酯切片、7份增塑剂、0.5份改性纳米填料、16份添加剂、3份颜料和12份助剂。所述聚酯切片选用聚对苯二甲酸乙二醇酯(PET)。所述增塑剂为甘油三苯甲酸酯。所述颜料为偶氮红。所述助剂由质量比3:2的吡啶盐离子液体与高沸点溶剂组成。所述吡啶盐离子液体为1-乙基吡啶四氟硼酸盐。所述高沸点助剂为丁内酯。
所述改性纳米填料和添加剂同实施例1。
本实施例综丝基膜的制备方法基本同实施例1,不同之处在于,步骤S2中,颜料为3份,添加剂为5.5份和助剂4份,高压釜内的操作温度为70℃,操作压力为90bar,处理时间20min;得到的所述综丝基膜厚度为0.33mm,所述综丝基膜表面功能层的厚度为0.03mm。
实施例3
本实施例的综丝基膜,其包括支撑层及设置在所述支撑层两外侧的功能层;所述支撑层的材料为聚酯切片,所述功能层由以下重量份数的原料组成:100份聚酯切片、12份增塑剂、0.7份改性纳米填料、18份添加剂、5份颜料和15份助剂。所述聚酯切片选用聚对苯二甲酸乙二醇酯(PET)。所述增塑剂为环形对苯二甲酸丁二醇酯。所述颜料为酞菁绿。所述助剂、改性纳米填料和添加剂同实施例1。
本实施例综丝基膜的制备方法基本同实施例1,不同之处在于,步骤S2中,颜料为5份,添加剂为6份和助剂5份,高压釜内的操作温度为70℃,操作压力为90bar,处理时间30min;得到的所述综丝基膜厚度为0.35mm,所述综丝基膜表面功能层的厚度为0.05mm。
对比例1
本对比例的综丝基膜,其原料组成与制备步骤基本与实施例1相同,不同之处在于,本对比例的综丝基膜,功能层原料中纳米填料未经改性处理。
对比例2
本对比例的综丝基膜,其原料组成与制备步骤基本与实施例1相同,不同之处在于,本对比例的综丝基膜,功能层原料中未包括添加剂。
对比例3
本对比例的综丝基膜,其原料组成与制备步骤基本与实施例1相同,不同之处在于,本对比例综丝基膜的制备方法中,步骤S2中原料未经超临界二氧化碳处理,而是直接作为步骤3的原料进行混合。
将实施例1~3和对比例1~3制备得到的综丝基膜进行性能测试,其性能结果如表1所示:
其中,拉伸强度、热收缩率、吸湿性和击穿电压按标准GB/T 13542.2-2009进行测试,动摩擦系数按标准GB/T 10006-1988进行测试。
耐高温高湿性测试:将样品放置于预先设置温度为85℃、相对湿度为85%的试验箱中144h,取出进行动摩擦系数测试。
耐老化性测试:将样品置于高压蒸汽加速试验老化箱中,温度设置为121±2℃,压力范围为14psi至18psi,测试72h,取出进行动摩擦系数测试。
表1
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是本发明的原理,在不脱离本发明精神和范围的前提下本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明的范围内。
Claims (6)
1.一种综丝基膜,其特征在于,所述综丝基膜包括支撑层及设置在所述支撑层两外侧的功能层;所述支撑层的材料为聚酯切片,所述功能层由以下重量份数的原料组成:100份聚酯切片、5~12份增塑剂、0.2~0.7份改性纳米填料、15~18份添加剂、1~5份颜料和10~15份助剂;
所述改性纳米填料为通过接枝有三氟甲基和丙烯酸酯官能团的吡啶衍生物与烯丙基三甲基氯化铵和异戊二烯共聚形成的高聚物包覆纳米填料后得到;
所述添加剂由六氟双酚A二丙烯酸酯、丙烯酰氧乙基三甲基氯化铵和1-甲基-2-(三甲氧基硅烷基)乙基甲基丙烯酸酯共聚得到;
所述助剂由吡啶盐离子液体与高沸点溶剂组成;
所述综丝基膜的制备方法包括以下步骤:
步骤S1:将0.2mol的三氟甲基吡啶化合物和0.2mol的卤代丙烯酸酯溶于1L四氢呋喃溶液中,在搅拌下加热回流溴代反应24~48小时后过滤,得到吡啶衍生物;取0.1mol的吡啶衍生物,加入5.5g的纳米填料和100g的甘油,超声搅拌混合均匀;再加入0.05mol的烯丙基三甲基氯化铵作为功能助剂,加入0.3mol的异戊二烯作为扩链剂,加入0.25g偶氮二异丁腈作为自由基引发剂在纳米填料表面进行共聚反应,得到吡啶盐衍生物包覆的改性纳米填料;
步骤S2:将50份聚酯切片和1~5份颜料置于高压釜中,并加入5~6份添加剂和3~5份助剂,自高压釜底部通入超临界二氧化碳进行染色和改性处理;
步骤S3:取0.2~0.7份步骤S1得到的改性纳米填料、50份聚酯切片、5~12份增塑剂、10~12份添加剂和7~10份助剂,搅拌混合均匀,再加入步骤S2处理后的聚酯切片,得到功能熔体;
步骤S4:将作为支撑层的聚酯切片熔体从三层模头的中间层挤出厚片,同时将步骤S3得到的功能熔体从三层模头的上下层同时挤出厚片,经铸片,双向拉伸,热定型处理,冷却,收卷,得到厚度为0.30~0.35mm的所述综丝基膜。
2.如权利要求1所述的综丝基膜,其特征在于,所述聚酯切片选用聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚萘二甲酸乙二醇酯(PEN)或其共聚改性聚酯中的至少一种。
3.如权利要求1所述的综丝基膜,其特征在于,所述增塑剂为环形对苯二甲酸丁二醇酯、甘油三苯甲酸酯、环氧脂肪酸辛酯中的至少一种,所述纳米填料为二氧化钛和/或二氧化硅。
4.如权利要求1所述的综丝基膜,其特征在于,所述六氟双酚A二丙烯酸酯、丙烯酰氧乙基三甲基氯化铵和1-甲基-2-(三甲氧基硅烷基)乙基甲基丙烯酸酯的摩尔比为2:1:1。
5.如权利要求1所述的综丝基膜,其特征在于,所述颜料为酞菁红、酞菁蓝、酞菁绿、玫瑰红、中铬黄、偶氮红中的至少一种。
6.如权利要求1所述的综丝基膜,其特征在于,步骤S2中,所述高压釜内的操作温度50~90℃,操作压力为80~100bar,处理时间10~30min。
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