CN108252111A - 一种温变纺织品及其制造方法 - Google Patents

一种温变纺织品及其制造方法 Download PDF

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CN108252111A
CN108252111A CN201810081053.9A CN201810081053A CN108252111A CN 108252111 A CN108252111 A CN 108252111A CN 201810081053 A CN201810081053 A CN 201810081053A CN 108252111 A CN108252111 A CN 108252111A
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于美花
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Abstract

本发明涉及一种温变纺织品,其中形成的纳米胶具有核壳结构,具有优良的胶体稳定性,是一种对温度响应的智能型材料。织物表面涂覆有温变材料,制造方法步骤包括:(1)制备链转移剂;(2)制备温变材料;(3)制造织物;(4)将步骤(2)的温变材料30‑60%(重量)、粘合剂5‑20%(重量)以及乙二醇制成整理液,将温变整理液涂覆在织物表面,厚度为0.4‑0.6mm。

Description

一种温变纺织品及其制造方法
技术领域
本发明属于一种功能性纺织品领域。
背景技术
随着社会科学和经济水平的提高、审美观念的改变,人们对服装已经突破了传统的舒适耐用的需求,这就要求服装材料有时代感、科学性、创造性。因此,在新的时代开发出新型的智能响应性服用新材料具有重要的战略地位和行业推动作用。虽然美国太空棉,日本的阳光蓄热纤维,以及天津纺织工学院发明的发射和吸收远红外的纤维等已经极大的改善了纺织品的性能,但是这些纤维纺织品仅具有单向温度调节功能,不能根据环境温度变化自动调节内部温度。上世纪70年代相变材料研究成为热点,一些专家将其应用于纺织领域,即出现了智能纤维。智能调温纺织品中的相变材料能根据外界环境温度的变化,利用相变材料在相变过程中吸收和释放大量热量,通过自动蓄热/放热形成热缓冲作用,在一定的温度范围内自由调节纺织品内部温度。但是这些相变材料多是单一相变材料,单一相变材料存在各种各样的缺点,如相变温度过高或过低,导热性差等,本发明将两种相变材料混合,克服单一相变材料的缺点。
中国专利CN2760092Y公开了一种名称为《可感温变色的布/塑料体》的实用新型专利。该专利给出的技术方案是:感温变色布的表面铺设有由印料形成的具有图案及色系的变化图区,该变化图区含有感温剂及变色剂成份,变化图区的上表面设有透明保护膜。从上述方案中可以看出,该专利从结构上限定了感温变色布由基布、变化图区和保护膜三层叠置形成,其中保护膜的作用是保护变化图区的印花图案不易脱落。这种设计不仅结构复杂,而且三层结构制造工艺难度大,成本高,不利于推广应用。另外,该专利并未公开感温剂和变色剂成份以及配比,使得本领域技术人员无法根据说明书记载来实施。
CN107142728 A公开了一种表面疏水的感温变色面料的制备方法,可以形成一种功能面料,该面料由普通聚酯面料后整理而得到。预先制备得到由疏水热塑性聚合物与感温变色纳米粉体复合的超细微粒,将超微粒子负载在面料表面后,在面料表面形成类似于荷叶结构的微观结构,具备优异的疏水性。同时超微粒子内含有感温变色纳米粉体,可以根据人体表温度的变化实现颜色的改变。但是对于感温变色纳米粉体的制造方法却没有公开。
发明内容
本发明的目的在于提供一种温变纺织品的制备方法,其中形成的纳米胶具有核壳结构,具有优良的胶体稳定性,是一种对温度响应的智能型材料,可以包裹温变成分,提高成分的发挥相变作用的耐久性, 并能达到随温度变化而智能化释放所载带分子的效果。
一种温变纺织品,其特征在于:织物表面涂覆有温变材料,制造方法步骤包括:
(1)制备链转移剂:将0.5-0.7 g的羧甲基纤维素钠,交联剂 1-4g 和偶氮类化合物1-3g 溶于40-80 mL的除水提纯后的二氯甲烷, 加到200mL的烧瓶中搅拌,通入氮气保持无氧环境,搅拌均匀后,将其置于冰水浴中,保持0℃ ,然后加入1-5g亚甲基双丙烯酰胺或双甲基丙烯酰氧苯基丙烷中的任意一种,在0℃反应4-6个小时后,逐渐恢复到室温,室温下总共反应20小时。抽滤除去白色沉淀,再将滤液滴入过量的乙醚中,抽滤收集固体;又进一步将固体溶于二氯甲烷,过层析柱;
(2)制备温变材料:将步骤(1)得到的链转移剂9-10mg、过氧化异辛酸叔丁酯(TBPO)40-50 mg,交联剂3-4 mg,水4-10mg加入到密封的钳口瓶,在冰水浴中,用氮气鼓泡除氧10-30分钟, 加入引发剂同时在同样的条件下除氧10-20 分钟。再将反应容器放入预先预热好的70℃的油浴中搅拌反应,待温度稳定后,加入50 -60μL已除氧的2,2'-偶氮(2-甲基丙基脒)二盐酸盐储备液,恒温反应1-3小时后,将反应容器浸没在冰水中猝灭反应,得到温变材料
(3)制造织物,织物为机织物、针织物或非织造布;采用粘胶纤维、超细旦丙纶纤维、毛纤维、 棉纤维、腈纶、锦纶、涤纶、维纶或氨纶制造;
(4)将步骤(2)的温变材料30-60%(重量)、粘合剂5-20%(重量)以及乙二醇制成整理液,将温变整理液涂覆在织物表面,厚度为0.4-0.6mm。
其中交联剂为聚乙二醇(1000)二丙烯酸酯、聚乙二醇(400)二甲基丙烯酸酯、聚乙二醇(600)二甲基丙烯酸酯、聚乙二醇(1000)二甲基丙烯酸酯、乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、甲基丙烯酸烯丙酯、三羟甲基丙烷三甲基丙烯酸酯、丙二醇二丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、1,9-壬二醇二甲基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯或双季戊四醇六甲基丙烯酸酯。
引发剂为偶氮二异丁腈(AIBN)、偶氮二异庚腈、过氧化二苯甲酰(BPO)
偶氮类化合物包括偶氮二甲酰胺、偶氮二异丁腈、偶氮二二甲基戊腈、偶氮二环己烷甲腈、偶氮二异戊腈、偶氮二异庚腈、偶氮二异丁酸二甲酯、1-((氰基-1-甲基乙基)偶氮)甲酰胺、1,1'-偶氮(环己基-1-氰基)、2,2'-偶氮(2-甲基丙基脒)·二盐酸盐、4,4'-偶氮(4-氰基戊酸)或2,2'-偶氮[2-(2-咪唑啉-2-基)丙烷]二盐酸盐
所述温变材料为纳米胶其粒径为50-80 nm,分散度为0.04-0.08,体积相转变温度(VPTT)位于30~34℃。
本发明先形成高分子链转移剂,然后通过单体交联的方式形成核壳结构纳米胶,这种温变材料具有尺寸稳定,优良的生物兼容性和相变性能,以及耐久的织物附着性能。
附图
图1 温变材料中纳米粒子的分布
图2 温变材料中纳米粒的粒度表征
图1、图2显示温变材料中纳米粒子粒度均匀,分散性好。
具体实施方式
实施例1
(1)制备链转移剂:将0.5 g的羧甲基纤维素钠,交联剂聚乙二醇(1000)二丙烯酸酯4g和偶氮二甲酰胺3g 溶于80 mL的除水提纯后的二氯甲烷, 加到200mL的烧瓶中搅拌,通入氮气保持无氧环境,搅拌均匀后,将其置于冰水浴中,保持0℃ ,然后加入5g亚甲基双丙烯酰胺中,在0℃反应6个小时后,逐渐恢复到室温,室温下总共反应20小时。抽滤除去白色沉淀,再将滤液滴入过量的乙醚中,抽滤收集固体;又进一步将固体溶于二氯甲烷,过层析柱;
(2)制备温变材料:将步骤(1)得到的链转移剂10mg、过氧化异辛酸叔丁酯(TBPO) 50mg,交联剂4 mg,水10mg加入到密封的钳口瓶,在冰水浴中,用氮气鼓泡除氧30 分钟, 加入引发剂偶氮二异丁腈(AIBN)同时在同样的条件下除氧20 分钟。再将反应容器放入预先预热好的70℃的油浴中搅拌反应,待温度稳定后,加入60μL已除氧的2,2'-偶氮(2-甲基丙基脒)二盐酸盐储备液(含0.192 mg, 0.7 μmol),恒温反应3小时后,将反应容器浸没在冰水中猝灭反应,得到温变材料
(3)制造织物,织物为粘胶机织物;
(4)将步骤(2)的温变材料60%(重量)、粘合剂20%(重量)以及乙二醇制成整理液,将温变整理液涂覆在织物表面,厚度为0.6mm。
实施例2
(1)制备链转移剂:将0.5g的羧甲基纤维素钠,交联剂乙二醇二丙烯酸酯1g 和4,4'-偶氮(4-氰基戊酸)1g 溶于40 mL的除水提纯后的二氯甲烷, 加到200mL的烧瓶中搅拌,通入氮气保持无氧环境,搅拌均匀后,将其置于冰水浴中,保持0℃ ,然后加入1g双甲基丙烯酰氧苯基丙烷,在0℃反应6个小时后,逐渐恢复到室温,室温下总共反应20小时。抽滤除去白色沉淀,再将滤液滴入过量的乙醚中,抽滤收集固体;又进一步将固体溶于二氯甲烷,过层析柱;
(2)制备温变材料:将步骤(1)得到的链转移剂9mg、过氧化异辛酸叔丁酯(TBPO)40 mg,交联剂三羟甲基丙烷三甲基丙烯酸酯3 mg,水4mg加入到密封的钳口瓶,在冰水浴中,用氮气鼓泡除氧10分钟, 加入引发剂过氧化二苯甲酰(BPO)同时在同样的条件下除氧10 分钟。再将反应容器放入预先预热好的70℃的油浴中搅拌反应,待温度稳定后,加入50μL已除氧的2,2'-偶氮(2-甲基丙基脒)二盐酸盐储备液,恒温反应1小时后,将反应容器浸没在冰水中猝灭反应,得到温变材料
(3)制造织物,织物为腈纶针织物;
(4)将步骤(2)的温变材料30%(重量)、粘合剂5%(重量)以及乙二醇制成整理液,将温变整理液涂覆在织物表面,厚度为0.4mm。
比较例1
(1)制备高分子链转移剂:将0.6148 g的乙基氰基戊酸三硫碳酸酯5.6909 g,聚乙二醇5000(PEG5000)0.142 g 和 4-二甲氨基吡啶 0.2 g 溶于60 mL的二氯甲烷(已除水提纯),加到150 mL的烧瓶中搅拌,通入氮气保持无氧环境,搅拌均匀后,将其置于冰水浴中,保持0℃。分三次加入0.467 g N,N’-二环己基碳化二亚胺。在0℃反应5个小时后,逐渐恢复到室温,室温下总共反应35小时。抽滤除去白色沉淀,再将滤液滴入过量的乙醚中,抽滤收集固体。又进一步将固体溶于二氯甲烷,过层析柱。最终得到3.0 g黄色固体,即为直链高分子链转移剂I。
(2)制备纳米胶:将步骤1所得直链高分子链转移剂(9.8 mg)、单体2-甲基-2-丙烯酸-2-(2-甲氧基乙氧基)乙酯(MEO2MA) (52.5 mg),交连剂聚乙二醇二酯(M n ~ 750) (4mg),水(5.0 g)加入到密封的钳口瓶,在冰水浴中,用氮气鼓泡除氧40 分钟, 引发剂2,2'-偶氮(2-甲基丙基脒)二盐酸盐同时在同样的条件下除氧20 分钟。再将反应容器放入预先预热好的70℃的油浴中搅拌反应,待温度稳定后,加入50 μL已除氧的2,2'-偶氮(2-甲基丙基脒)二盐酸盐储备液(含0.192 mg, 0.7 μmol),恒温反应2.5小时后,将反应容器浸没在冰水中猝灭反应,得到呈现蓝色的纳米凝胶;其粒径为56.3 nm分散度为0.06。得到温变材料。
步骤(3)(4)同实施例1.
比较例2
采用市售掺杂BaTiO3的相变粉体,其余同实施例2。
采用NETZSCH DSC 200 F3差示扫描量热仪(DSC),在氮气保护下,测试10℃/min升温过程和-10℃/min降温过程的DSC扫描曲线得到熔融热焓、Tm-吸热温度;Tc-放热温度。
表1
温变材料稳定性(天)
本发明温变材料 6
市售掺杂BaTiO3相变粉体 1
将待测材料稀释到100%的牛血清中,测试血清中蛋白的峰和纳米球的峰是否存在。测试显示,本申请温变纳米胶在放入测试血清6天后,血清中蛋白的峰和纳米球的峰依然存在,且大小未变,未检测出大的的颗粒,说明纳米胶与血清之间没有发生吸附,因此证明表面带有刷子状高分子的纳米胶具有极强的抗吸附性和稳定性。而市售相变粉体只能维持1天。
表2
ΔHm(J/g) Tm(℃) Tc(℃) 洗涤50次后ΔHm(J/g)
实施例1 100 34 30 91
实施例2 130 33.5 30 100
比较例1 50 47.9 37.5 无相变现象
比较例2 67 49.2 38.9 无相变现象
表2中:ΔHm-熔融热焓;Tm-吸热温度;Tc-放热温度。

Claims (6)

1.一种温变纺织品,其特征在于:织物表面涂覆有温变材料。
2.一种制备权利要求1所述温变纺织品的方法,步骤包括:
(1)制备链转移剂:将0.5-0.7 g的羧甲基纤维素钠,交联剂 1-4g 和偶氮类化合物1-3g 溶于40-80 mL的除水提纯后的二氯甲烷, 加到200mL的烧瓶中搅拌,通入氮气保持无氧环境,搅拌均匀后,将其置于冰水浴中,保持0℃ ,然后加入1-5g亚甲基双丙烯酰胺或双甲基丙烯酰氧苯基丙烷中的任意一种,在0℃反应4-6个小时后,逐渐恢复到室温,室温下总共反应20小时,抽滤除去白色沉淀,再将滤液滴入过量的乙醚中,抽滤收集固体;又进一步将固体溶于二氯甲烷,过层析柱;
(2)制备温变材料:将步骤(1)得到的链转移剂9-10mg、过氧化异辛酸叔丁酯(TBPO)40-50 mg,交联剂3-4 mg,水4-10mg加入到密封的钳口瓶,在冰水浴中,用氮气鼓泡除氧10-30分钟, 加入引发剂同时在同样的条件下除氧10-20 分钟,再将反应容器放入预先预热好的70℃的油浴中搅拌反应,待温度稳定后,加入50-60μL已除氧的2,2'-偶氮(2-甲基丙基脒)二盐酸盐储备液,恒温反应1-3小时后,将反应容器浸没在冰水中猝灭反应,得到温变材料;
(3)制造基底织物,织物为机织物、针织物或非织造布;采用粘胶纤维、超细旦丙纶纤维、毛纤维、 棉纤维、腈纶、锦纶、涤纶、维纶或氨纶制造;
(4)将步骤(2)的温变材料30-60%(重量)、粘合剂5-20%(重量)以及乙二醇制成整理液,将温变整理液涂覆在织物表面,厚度为0.4-0.6mm。
3.根据权利要求2所述的方法,其特征在于:其中交联剂为聚乙二醇(1000)二丙烯酸酯、聚乙二醇(400)二甲基丙烯酸酯、聚乙二醇(600)二甲基丙烯酸酯、聚乙二醇(1000)二甲基丙烯酸酯、乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、甲基丙烯酸烯丙酯、三羟甲基丙烷三甲基丙烯酸酯、丙二醇二丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、1,9-壬二醇二甲基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯或双季戊四醇六甲基丙烯酸酯。
4.根据权利要求2所述的方法,其特征在于所述引发剂为偶氮二异丁腈(AIBN)、偶氮二异庚腈、过氧化二苯甲酰(BPO)。
5.根据权利要求2所述的方法,其特征在于所述偶氮类化合物包括偶氮二甲酰胺、偶氮二异丁腈、偶氮二二甲基戊腈、偶氮二环己烷甲腈、偶氮二异戊腈、偶氮二异庚腈、偶氮二异丁酸二甲酯、1-((氰基-1-甲基乙基)偶氮)甲酰胺、1,1'-偶氮(环己基-1-氰基)、2,2'-偶氮(2-甲基丙基脒)·二盐酸盐、4,4'-偶氮(4-氰基戊酸)或2,2'-偶氮[2-(2-咪唑啉-2-基)丙烷]二盐酸盐。
6.根据权利要求2所述的方法,其特征在于:所述温变材料为纳米胶,其粒径为50-80nm,分散度为0.04-0.08,体积相转变温度 (VPTT)位于30~34℃。
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