WO2019144567A1 - 一种抗菌防紫外多功能化学纤维 - Google Patents

一种抗菌防紫外多功能化学纤维 Download PDF

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WO2019144567A1
WO2019144567A1 PCT/CN2018/093197 CN2018093197W WO2019144567A1 WO 2019144567 A1 WO2019144567 A1 WO 2019144567A1 CN 2018093197 W CN2018093197 W CN 2018093197W WO 2019144567 A1 WO2019144567 A1 WO 2019144567A1
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polymer
chemical fiber
antibacterial
monomer
antibacterial anti
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PCT/CN2018/093197
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English (en)
French (fr)
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郑敏
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南通纺织丝绸产业技术研究院
苏州大学
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Priority claimed from CN201810084187.6A external-priority patent/CN108193308A/zh
Priority claimed from CN201810344876.6A external-priority patent/CN110387598B/zh
Application filed by 南通纺织丝绸产业技术研究院, 苏州大学 filed Critical 南通纺织丝绸产业技术研究院
Priority to EP18902844.2A priority Critical patent/EP3748048A4/en
Priority to US16/647,398 priority patent/US11319647B2/en
Priority to JP2020562805A priority patent/JP7197607B2/ja
Publication of WO2019144567A1 publication Critical patent/WO2019144567A1/zh

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  • aqueous solution having a gold soluble salt concentration of 5 to 10% Preparing an aqueous solution having a gold soluble salt concentration of 5 to 10% ; adding the aqueous solution to the polymer monomer under vigorous stirring, the molar concentration of the soluble metal salt in the polymer monomer is 0.01 to 0.5 M , The temperature is 130 ⁇ 180 ° ( : microwave or hydrothermal reaction 30 ⁇ 5 01 ⁇ 11 , evaporation under vacuum to remove water, control the water content below 2% , to obtain polymer monomers containing nano-oxide;
  • the soluble metal salt includes two or more of zinc, magnesium, calcium, titanium, copper, zinc, zirconium, lanthanum, cerium, silicon;
  • the polymer complexing dispersing agent comprises polyacrylamide, polyacrylic acid , polyvinylpyrrolidone, polyvinyl alcohol, polymaleic anhydride, polyquaternary ammonium salt, polyethylene glycol, polyurethane, polyamide, amino acid;
  • the copper acetate, zinc acetate, titanium sulfate, polyvinylpyrrolidone is dissolved in water at a mass ratio of 0.4:0.3:0.3:0.2 to prepare a 7% aqueous solution; the aqueous solution is gradually added to 5 000 ml 1 with vigorous stirring.
  • the titanium sulfate, zinc nitrate, zirconium oxychloride, polyethylene glycol is dissolved in water at a mass ratio of 0.3 :0.4:0.3: 0.5 to prepare a 6% aqueous solution; the aqueous solution is gradually added to 5000 ml under vigorous stirring.

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Abstract

本发明公开了一种抗菌防紫外多功能化学纤维。将可溶性金属盐及高分子络合分散剂溶解在水中配制成水溶液，加入到聚合物单体中，在微波或水热作用下反应得到含多功能纳米氧化物的聚合物单体，与聚合物、催化剂、引发剂、稳定剂等加入到聚合反应釜中,经过酯化、缩聚或共聚反应，得到聚合物熔体，经纺丝或铸带切粒，得到抗菌防紫外多功能化学纤维丝或母粒切片。本发明通过在聚合反应前单体中原位生成纳米金属氧化物，保证了纳米金属氧化物的小粒径及分散性，不影响后续纺丝及织造；提供的抗菌防紫外多功能化学纤维，具有高效持久的抗菌防紫外多功能，无金属离子析出，有效地克服了现有技术使用银离子导致的析出变色及功能单一等问题，使用安全环保。

Description

\¥0 2019/144567 卩（：17€\2018/093197
一种抗菌防紫外多功能化学纤维 技术领域
[0001] 本发明涉及一种原位聚合得到抗菌防紫外多功能化学纤维， 属于特种纺织材料 技术领域。
背景技术
[0002] 化学纤维以其优良的物理性能和化学性能得到了广泛的应用。 但是随着科学技 术的发展和人们生活水平的进一步提高， 功能性化纤纺织品的开发与应用成为 我国目前功能纺织品研究和发展的一大方向。 由于化学纤维的特性， 要想获得 较持久的功能效果， 功能化学纤维的生产方法主要以共混纺丝法为主。 例如：
Figure imgf000003_0001
和预处理纳米银抗菌剂、抗氧化剂、润滑剂及分散剂， 经熔融共混挤出制成， 预处理纳米银抗菌剂是采用聚乙烯蜡包覆处理得到的纳米银抗菌剂。 解决了纳
Figure imgf000003_0002
效的抗菌涤纶纤维。 中国发明专利 0X103184575八提供了一种抗菌锦纶的生产方 法， 包括以下步骤： （1） 制备抗菌锦纶母粒： 将锦纶 6切片与纳米银磷酸盐共 混造粒， 得到抗菌锦纶母粒； （2） 纺丝： 将步骤 （1） 中制成的抗菌锦纶与锦 纶 6切片共混纺丝， 经过上油卷绕、平衡和拉伸， 得到抗菌锦纶。 该技术方案由 于将纳米银磷酸盐直接添加于锦纶中， 导致锦纶的物理性能下降， 影响产品使 用寿命。 也有文献报道了将事先制备的纳米材料直接分散到聚合物单体中， 再 与其他聚合物单体混合进行聚合， 如中国发明专利CN102345179A公开了一种纳 米氧化锌改性涤纶纤维的制备方法， 直接把氧化锌等金属氧化物分散到聚合物 单体中混合， 中国发明专利 0X105962510八采用将纳米矿物能改质剂从高分子单 体的聚合端添加的方法， 得到一种纳米矿物能纤维。 上述方法纳米材料不容易 均匀分散到聚合物单体中， 所用氧化物的粒子尺寸大于 2011111， 因而影响性能的 发挥和造成喷丝堵塞。 美国专利1¾952791862公开了一种先把一些含锌的盐类溶 \¥0 2019/144567 卩（：17€\2018/093197 解到聚合物单体中， 然后与其他单体聚合纺丝， 其不足之处在于产品的抗菌性 仍然依赖锌离子的析出， 因此只是尽可能控制锌离子析出在一个较低的浓度， 没有从根本上解决问题， 而且功能单一。
发明概述
技术问题
问题的解决方案
技术解决方案
[0003] 本发明针对现有多功能化学纤维技术存在的不足， 提供一种原位聚合得到抗菌 防紫外多功能化学纤维， 具有高效持久的抗菌防紫外多功能， 无金属离子析出 ， 使用安全环保。
[0004] 实现本发明目的的技术方案是提供一种抗菌防紫外多功能化学纤维， 它按如下 步骤制备得到：
[0005] (1) 将可溶性金属盐与高分子络合分散剂按质量比为 1: 0.02〜 0.5溶解于水中
， 制备得到金可溶性属盐质量浓度为 5〜 10%的水溶液； 在剧烈搅拌下将水溶液 加入到聚合物单体中， 可溶性金属盐在聚合物单体中的摩尔浓度为 0.01〜 0.5M， 在温度为 130〜 180° (:的微波或水热条件下反应 30〜 501^11， 真空状态下蒸发除去 水分， 控制含水率在 2%以下， 得到含有纳米氧化物的聚合物单体； 所述可溶性 金属盐包括锌、镁、钙、 钛、铜、招、锆、钡、锶、硅的化合物中的两种或多 种； 所述的高分子络合分散剂包括聚丙烯酰胺、 聚丙烯酸、 聚乙烯吡咯烷酮、 聚乙烯醇、 聚马来酸酐、 聚季胺盐、 聚乙二醇、 聚氨酯、 聚酰胺、氨基酸； 所 述聚合物单体包括乙醇、 丙酮、 乙二醇、 丙二醇、 丁二醇、 丙三醇、 丙烯醇、 乙二胺、 己内酰胺、氨基酸；
[0006] (2) 在聚合反应开始或中间阶段， 将步骤 (1) 得到的含有纳米氧化物的聚合 物单体加入到常规聚合物单体及聚合所需的其他单体中， 充分混合， 按常规聚 合物单体的聚合工艺条件进行聚合反应， 制备得到抗菌防紫外多功能聚合物熔 融体；
[0007] (3) 步骤 (2) 制备的聚合物熔融体经纺丝， 得到抗菌防紫外多功能化学纤维 或聚合物熔融体经铸带切粒， 得到抗菌防紫外多功能母粒切片。 \¥0 2019/144567 卩（：17€\2018/093197
Figure imgf000005_0001
[0009] 本发明以化学纤维聚合所用的单体之一为介质， 直接在介质中原位合成小于5 的纳米氧化物， 是一种含多功能纳米氧化物的单体， 再将其与其他常规聚合物 单体进行聚合反应， 从而得到高效多功能的化学纤维或母粒。
0010] 本发明所得抗菌防紫外多功能化学纤维不仅工艺简单、 效率高、 节能环保， 而 且产品具有高效持久的抗菌防紫外多功能， 无金属离子析出， 使用安全环保， 有效地克服了目前普遍使用的银离子导致的析出变色问题以及功能单一等问题 。 通过在聚合反应前单体中原位生成纳米金属氧化物， 保证了纳米金属氧化物 的小粒径及分散性， 不影响后续纺丝及织造， 同时纳米金属氧化物的半导体催 化作用加速了单体的聚合速度， 比常规的节省了三分之一时间， 节约了能量。
[0011] 与传统功能化学纤维相比， 由于纳米氧化物事先在单体中原位合成， 粒径小、 分散性好， 不影响后续纺丝及织造， 同时功能优异， 且没有金属离子析出， 非 常安全环保。 与传统化学纤维合成相比， 利用纳米金属氧化物的催化效应， 极 大缩短了聚合时间， 提高了效率， 节约了能量。
[0012] 由于纳米氧化物在聚合物单体中原位合成， 粒径小、 分散性好， 不影响后续纺 丝及织造， 同时功能优异， 且没有金属离子析出， 非常安全环保。 与传统化学 纤维合成相比， 利用纳米金属氧化物的催化效应， 极大缩短了聚合时间， 提高 了效率， 节约了能量。
发明的有益效果
有益效果
[0013] 与现有技术相比， 本发明的突出优点是：
Figure imgf000005_0002
氧化物， 无需再次分散， 与其他聚合单体相容性好；
[0015] 2.利用纳米金属氧化物的催化效应， 极大缩短了聚合时间， 提高了效率， 节约 了能量；
[0016] 3.本发明提供的抗菌防紫外多功能纤维具有极强持久的抗菌防紫外功能， 且无 金属离子析出， 使用安全环保。 \¥0 2019/144567 卩（：17€\2018/093197 对附图的简要说明
附图说明
[0017] 图 1是本发明实施例 1提供的纳米抗菌防紫外多功能涤纶的紫外防护效果图。
[0018] 图 2是本发明实施例 1提供的纳米抗菌防紫外多功能涤纶纤维的抗菌效果图。
发明实施例
本发明的实施方式
[0019] 下面结合实施例和附图， 对本发明的技术方案作进一步的阐述。
[0020] 实施例 1:
[0021] 将硫酸钛、醋酸锌、 聚乙二醇按 0.5: 0.5: 0.1质量比溶解在水中配制成 6%的水 溶液； 将水溶液在剧烈搅拌下逐渐加到 5000毫升乙二醇中， 再放入微波炉， 在 温度为 150° (:的条件下反应 4011^， 冷却， 得到粒子尺寸在 5 以下的含有纳米金 属氧化物的乙二醇单体； 再在真空状态下蒸发其中的水分直到含量在 2%以下； 将上述含有纳米金属氧化物的乙二醇单体、对苯二甲酸按摩尔比为 1.2:1加入到 酯化聚合反应釜中， 再按质量百分比加入催化剂三氧化锑 0.05%、稳定剂三乙基 磷酸酯 0.02%,在釜压为 2.0MPa、温度为 200 ° (:的条件下酯化反应 111; 开启真空 ***， 升温到 270° (:， 缩聚反应 2.511; 反应结束后， 产物经喷丝、 冷却、成形， 得到一种具有抗菌防紫外功能的涤纶纤维。
[0022] 参见附图 1， 它为本实施例提供的功能涤纶织物与普通涤纶产品的紫外防护效 果对比图， 由图中曲线可以看出， 本实施例提供的纳米抗菌防紫外多功能涤纶 的紫外防护指数明显高于普通涤纶。
[0023] 参见附图 2, 它为本发明实施例提供的纳米抗菌防紫外多功能涤纶纤维与普通 涤纶的抗菌效果对比图； 其中， 图为普通涤纶， ：8图为本实施例提供的抗菌防 紫外多功能涤纶， :图为抗菌防紫外多功能涤纶水洗 50次后。
[0024] 实施例 2:
[0025] 将醋酸铜、醋酸锌、硫酸钛、 聚乙烯吡咯烷酮按 0.4: 0.3: 0.3: 0.2质量比溶解 在水中配制成 7%的水溶液； 将水溶液在剧烈搅拌下逐渐加到 5000毫升 1， 3丙二 醇中； 放入微波炉中， 在 170° (:下反应 301^11， 冷却， 得到粒子尺寸在 5 以下的 含纳米金属氧化物的 1， 3丙二醇单体； 在真空状态下蒸发其中的水分直到含量 \¥02019/144567 卩（：17€\2018/093197 在 2%以下， 将含纳米金属氧化物的 1， 3丙二醇单体和对苯二甲酸二甲酯按摩尔 比 1.5:1、 催化剂钛酸四丁酯 0.05%、稳定剂三乙基磷酸酯 0.03%加入到反应釜中， 在氮气保护下， 在釜压 0.1MPa和 210 ° (:下酯化 111;然后发送到缩聚反应釜中， 在 高真空下， 升温到 250 °(：开始缩聚，反应时间 4.511;反应结束后产物通过喷丝、
Figure imgf000007_0001
[0026] 实施例 3:
[0027] 将硫酸钛、硝酸锌、氧氯化锆、 聚乙二醇按 0.3: 0.4: 0.3: 0.5质量比溶解在水 中配制成 6%的水溶液； 将水溶液在剧烈搅拌下逐渐加到 5000毫升己二酸中； 放 入水热反应釜中， 在 160° (:下反应 401^11， 冷却得到粒子尺寸在 511111以下的含纳米 金属氧化物的己二酸单体； 将己内酰胺单体和少量的水、醋酸钴、耐纶单体盐 等物质加入到反应釜中，在氮气的氛围下， 在釜压 2.0MPa和 235 °(：下反应 411;然 后加入含纳米金属氧化物的己二酸单体， 继续反应 211， 加入聚乙二醇软段、 钛 酸四丁酯催化剂， 升温至 247 ° (:， 继续反应 211， 得到抗菌防紫外? 6熔融体， 反 应结束后产物通过喷丝、 冷却、切片， 即得抗菌防紫外远红外? 6尼龙母粒。

Claims

\¥0 2019/144567 卩（：17€\2018/093197 权利要求书
[权利要求 1] 一种抗菌防紫外多功能化学纤维的制备方法， 其特征在于包括如下步 骤：
(!)将可溶性金属盐与高分子络合分散剂按质量比为1: 0.02〜0.5溶解 于水中， 制备得到可溶性金属盐质量浓度为5〜10%的水溶液； 在剧 烈搅拌下将水溶液加入到聚合物单体中， 可溶性金属盐在聚合物单体 中的摩尔浓度为0.01〜0.5M， 在温度为130〜180°(:的微波或水热条件 下反应30〜5〇^， 真空状态下蒸发除去水分， 控制含水率在2%以下 ， 得到含有纳米氧化物的聚合物单体； 所述可溶性金属盐选自锌、 镁 、 钙、 钛、 铜、 招、 锆、 钡、 锶、 硅的化合物中的两种或多种； 所述 的高分子络合分散剂选自聚丙烯酰胺、 聚丙烯酸、 聚乙烯吡咯烷酮、 聚乙烯醇、 聚马来酸酐、 聚季胺盐、 聚乙二醇、 聚氨酯、 聚酰胺、 氨 基酸； 所述聚合物单体选自乙醇、 丙酮、 乙二醇、 丙二醇、 丁二醇、 丙三醇、 丙烯醇、 乙二胺、 己内酰胺、 氨基酸；
(2)在聚合反应开始或中间阶段， 将步骤(1)得到的含有纳米氧化物的 聚合物单体加入到常规聚合物的单体及聚合所需的其它单体中， 充分 混合， 按常规聚合物单体的聚合工艺条件进行聚合反应， 制备得到抗 菌防紫外多功能聚合物熔融体；
(3)步骤(2)制备的聚合物熔融体经纺丝， 得到抗菌防紫外多功能化学 纤维； 或聚合物熔融体经铸带切粒， 得到抗菌防紫外多功能母粒切片
[权利要求 2] 根据权利要求1所述的一种抗菌防紫外多功能化学纤维的制备方法，
Figure imgf000008_0001
、 八6 、 、 £、 (:、 11。
[权利要求 3] 采用权利要求1或2所述制备方法获得的抗菌防紫外多功能化学纤维。
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