CN111088602B - 高柔韧性可生物降解无纺布 - Google Patents
高柔韧性可生物降解无纺布 Download PDFInfo
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- CN111088602B CN111088602B CN201911350956.3A CN201911350956A CN111088602B CN 111088602 B CN111088602 B CN 111088602B CN 201911350956 A CN201911350956 A CN 201911350956A CN 111088602 B CN111088602 B CN 111088602B
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Abstract
本发明高柔韧性可生物降解无纺布，所述的无纺布包括：上层纤维网层和下层纤网层；其中，上层纤维网层由增韧聚乳酸纤维、纯棉纤维；所述的下层纤网层由增韧聚乳酸纤维和粗旦ES纤维制备。本发明在的无纺布中采用在聚乳酸母料中增加5‑30％重量份的改性麻纳米纤维制备的增韧聚乳酸纤维；表面改性作为增韧剂，提高了聚乳酸的韧性；同时破坏了纳米纤维素表面致密的氢键，提高了纳米纤维素的再分散性，有利于纳米纤维填料在聚乳酸体系中的分散；同时表面光滑及凉感处理可消除麻纤维与人体接触时的刺痛感。
Description
技术领域
本发明涉及一种高柔韧性可生物降解无纺布。
背景技术
非织造无纺布是不需经纬纺织和交织编结、只需将人造或天然的长丝或短纤维经过较为随机撑列、分丝铺网、加固形成的纤网状织物。由于其产品特点，非织造布的制备具有流程简单、生产效率较高、成本低廉、用途广泛、来源多样等优点，以致其被广泛地应用于服装里料、医疗敷料、工业滤衬、保温包装等诸多领域。
出于环境的要求，现有无纺布大量采用可生物降解的天然高分子材料-聚乳酸(PLA)来制作无纺布，聚乳酸(PLA)是一种较易由天然植物转化制备的无毒可完全生物降解的新型高分子材料，其推广应用有望使得传统塑料导致的环境污染得到更多更大的缓解。但其具有脆性，且柔韧性差，降解时间久等问题。
发明内容
为克服上述缺陷，本发明的目的在于提供一种高柔韧性可生物降解无纺布。
为达到上述目的，本发明高柔韧性可生物降解无纺布，所述的无纺布包括：上层纤维网层和下层纤网层；其中，上层纤维网层由增韧聚乳酸纤维、纯棉纤维；所述的下层纤网层由增韧聚乳酸纤维和粗旦ES纤维制备。
进一步的，还包括喷涂负载微胶囊的ZnO纳米线的中间层。
进一步的，中间层的制备方法为：
31)制备ZnO纳米线分散液
在含有甘油1-2份、羧甲基纤维素0.2-1份、聚丙烯酸钠1-2份、聚乙烯吡咯烷酮3-5份的水溶液分散体系中加入单烷氧基型钛酸酯偶联亲水改性剂1-2份，搅拌均匀后，缓慢加入10-30份的表面处理后的ZnO纳米线，制备成亲水型ZnO纳米线分散液；
32)制备香精自包裹微胶囊
将10-20份香精添加至含有C12-15链烷醇聚醚-12 1-5份、聚乙烯醇1-3份、羟甲基纤维素1-3份、羧甲基纤维素钠0.1-0.5份、果胶0.5-2份、聚乙烯吡咯烷酮1-2份、聚丙烯酸钠体系1-2份中形成香精自包裹微胶囊；
33)将制备香精自包裹微胶囊投入到制备ZnO纳米线分散液中充分混合。
进一步的，所述的增韧聚乳酸纤维的制备方法为：在聚乳酸母料中增加5-30％重量份的改性麻纳米纤维。
进一步的，所述的改性麻纳米纤维的改性处理步骤为：
51)麻纳米纤维预处理，溶胀12-24，5000rpm离心，过滤，再溶于DMF中，制得麻纳米纤维预混液；
52)加入催化剂，硅烷偶联剂，增韧剂，植物油、珍珠粉、玉石粉，分散剂后进行真空干燥，时间为5h～10h，真空度为0～5000Pa，最后制得改性麻纤维粉末。
进一步的，ZnO纳米线表面处理方法为：
61)将ZnO纳米线分散至浓度为0.5％氨基酸水溶液中浸泡1-5分钟，氨基酸为pI大于7的组氨酸(pI＝7.59)或赖氨酸(pI＝9.74)或二者的组合物；由于ZnO在水溶液中由于羟基作用而带负电荷，在pH小于等电点pI时氨基酸带正电荷，氨基酸吸附于ZnO纳米线部分表面。
62)将浸泡后ZnO纳米线取出干燥；
63)利用浓度0.1-1％的HF对干燥后ZnO纳米线进行刻蚀，以形成多个缺陷点；
64)将刻蚀后的后ZnO纳米线再次分散于pH大于pI的氢氧化钠解吸。
本发明在的无纺布中采用在聚乳酸母料中增加5-30％重量份的改性麻纳米纤维制备的增韧聚乳酸纤维；表面改性作为增韧剂，提高了聚乳酸的韧性；同时破坏了纳米纤维素表面致密的氢键，提高了纳米纤维素的再分散性，有利于纳米纤维填料在聚乳酸体系中的分散；同时表面光滑及凉感处理可消除麻纤维与人体接触时的刺痛感。
具体实施方式
实施例1
本实施例中的高柔韧性可生物降解无纺布，包括：上层纤维网层和下层纤网层；其中，上层纤维网层由增韧聚乳酸纤维、纯棉纤维；所述的下层纤网层由增韧聚乳酸纤维和粗旦ES纤维制备。
其中，增韧聚乳酸纤维的制备方法为：在聚乳酸母料中增加15％重量份的麻纳米纤维。麻纳米纤维包括麻纤维素纳米晶须、麻纤维素纳米纤丝、麻微纤纤维素中的至少一种。
实施例2
本实施例中的高柔韧性可生物降解无纺布，包括：上层纤维网层和下层纤网层；其中，上层纤维网层由增韧聚乳酸纤维、纯棉纤维；所述的下层纤网层由增韧聚乳酸纤维和粗旦ES纤维制备。
其中，增韧聚乳酸纤维的制备方法为：在聚乳酸母料中增加10％重量份的改性麻纳米纤维。麻纳米纤维包括麻纤维素纳米晶须、麻纤维素纳米纤丝、麻微纤纤维素中的至少一种。
改性麻纳米纤维的改性处理步骤为：
1)预处理，溶胀12-24，5000rpm离心，过滤，再溶于DMF中，制得麻纳米纤维预混液，
2)加入(三乙胺作为催化剂，硅烷偶联剂(如γ-氨丙基三乙氧基硅烷(KH-550)，增韧剂(己内酰胺，甲基丙烯酸叔丁基氨基乙酯、甲基丙烯酸二甲氨基乙酯、甲基丙烯酸二乙氨基乙酯)，环氧大豆油等植物油、珍珠粉、玉石粉等凉感物质，分散剂(羧甲基纤维素、羧乙基纤维素等)。真空干燥，时间为5h～10h，真空度为0～5000Pa，最后制得改性麻纤维粉末。
3)与聚乳酸熔融，与相容剂、抗氧化剂、热稳定剂等助剂共混，双螺杆熔融纺丝，制得增韧性PLA纤维。
实施例3
本实施例中的高柔韧性可生物降解无纺布，包括：上层纤维网层、中层纳米线层、下层纤网层；其中，上层纤维网层由增韧聚乳酸纤维、纯棉纤维；所述的下层纤网层由增韧聚乳酸纤维和粗旦ES纤维制备。
所述的中间层的制备方法为：
1)制备ZnO纳米线分散液
在含有甘油1-2份、羧甲基纤维素0.2-1份、聚丙烯酸钠1-2份、聚乙烯吡咯烷酮3-5份的水溶液分散体系中加入单烷氧基型钛酸酯偶联亲水改性剂1-2份，搅拌均匀后，缓慢加入10-30份的表面处理后的ZnO纳米线，制备成亲水型ZnO纳米线分散液；
2)制备香精自包裹微胶囊
将10-20份香精添加至含有C12-15链烷醇聚醚-12 1-5份数、聚乙烯醇1-3份数、羟甲基纤维素1-3份、羧甲基纤维素钠0.1-0.5份、果胶0.5-2份、聚乙烯吡咯烷酮1-2份、聚丙烯酸钠体系1-2份中形成香精自包裹微胶囊；
3)将制备香精自包裹微胶囊投入到制备ZnO纳米线分散液中充分混合。
4)通过喷涂的形式将纳米线溶液喷涂在上层纤维网层的下表面或下层纤网层的上表面。
上述的ZnO纳米线的处理方法为：
11)制备ZnO纳米线，采用直接物理蒸发法制备ZnO纳米线，直径控制为10-50nm，长度为5-100um，同时利用利用等离子刻蚀的方法在ZnO纳米线制造缺陷点以促进纳米线与偶联剂的互相作用。上述利用等离子刻蚀制造缺陷点方法为：
12)将ZnO纳米线分散至浓度为1％氨基酸水溶液中浸泡，氨基酸的pI大于7；
13)将浸泡后ZnO纳米线取出干燥；
14)利用等离子对干燥后的ZnO纳米线进行表面处理1-10秒；
15)表面处理后ZnO纳米线再次分散于pH大于pI的溶液中解吸。
上述的香精可以为普通香精，也可以其它功能香精，如：香茅油、茶树油、柠檬桉叶油、艾叶油、薰衣草油、薄荷油中的一种或几种的组合。
实施例4
本实施例中的高柔韧性可生物降解无纺布，包括：上层纤维网层、中层纳米线层、下层纤网层；其中，上层纤维网层由增韧聚乳酸纤维、纯棉纤维；所述的下层纤网层由增韧聚乳酸纤维和粗旦ES纤维制备。
所述的中间层的制备方法为：
1)制备ZnO纳米线分散液
在含有甘油1-2份、羧甲基纤维素0.2-1份、聚丙烯酸钠1-2份、聚乙烯吡咯烷酮3-5份的水溶液分散体系中加入单烷氧基型钛酸酯偶联亲水改性剂1-2份，搅拌均匀后，缓慢加入10-30份的表面处理后的ZnO纳米线，制备成亲水型ZnO纳米线分散液；
2)制备香精自包裹微胶囊
将10-20份香精添加至含有C12-15链烷醇聚醚-12 1-5份、聚乙烯醇1-3份、羟甲基纤维素1-3份、羧甲基纤维素钠0.1-0.5份、果胶0.5-2份、聚乙烯吡咯烷酮1-2份、聚丙烯酸钠体系1-2份中形成香精自包裹微胶囊；
3)将制备香精自包裹微胶囊投入到制备ZnO纳米线分散液中充分混合。
4)通过喷涂的形式将纳米线溶液喷涂在上层纤维网层的下表面或下层纤网层的上表面。
所述的ZnO纳米线的处理方法为：
11)将ZnO纳米线分散至浓度为0.5％氨基酸水溶液中浸泡1-5分钟，氨基酸为pI大于7的组氨酸(pI＝7.59)或赖氨酸(pI＝9.74)或二者的组合物；由于ZnO在水溶液中由于羟基作用而带负电荷，在pH小于等电点pI时氨基酸带正电荷，氨基酸吸附于ZnO纳米线部分表面。
12)将浸泡后ZnO纳米线取出干燥；
13)利用浓度0.1-1％的HF对干燥后ZnO纳米线进行刻蚀，以形成多个缺陷点；
14)将刻蚀后的后ZnO纳米线再次分散于pH大于pI的氢氧化钠解吸。
上述的香精可以为普通香精，也可以其它功能香精，如：香茅油、茶树油、柠檬桉叶油、艾叶油、薰衣草油、薄荷油中的一种或几种的组合。
增韧聚乳酸纤维的制备方法为：在聚乳酸母料中增加25％重量份的改性麻纳米纤维。麻纳米纤维包括麻纤维素纳米晶须、麻纤维素纳米纤丝、麻微纤纤维素中的至少一种。
改性麻纳米纤维的改性处理步骤为：
1)预处理，溶胀12-24，5000rpm离心，过滤，再溶于DMF中，制得麻纳米纤维预混液，
2)加入(三乙胺作为催化剂，硅烷偶联剂(如γ-氨丙基三乙氧基硅烷(KH-550)，增韧剂(己内酰胺，甲基丙烯酸叔丁基氨基乙酯、甲基丙烯酸二甲氨基乙酯、甲基丙烯酸二乙氨基乙酯)，环氧大豆油等植物油、珍珠粉、玉石粉等凉感物质，分散剂(羧甲基纤维素、羧乙基纤维素等)。真空干燥，时间为5h～10h，真空度为0～5000Pa，最后制得改性麻纤维粉末。
3)与聚乳酸熔融，与相容剂、抗氧化剂、热稳定剂等助剂共混，双螺杆熔融纺丝，制得增韧性PLA纤维。
Claims (1)
1.一种高柔韧性可生物降解无纺布，其特征在于，所述的无纺布包括：上层纤维网层和下层纤网层；其中，上层纤维网层由增韧聚乳酸纤维、纯棉纤维制备；所述的下层纤网层由增韧聚乳酸纤维和粗旦ES纤维制备；还包括喷涂负载微胶囊的ZnO纳米线的中间层；
所述的中间层的制备方法为：
1）制备ZnO纳米线分散液
在含有甘油1-2份、羧甲基纤维素0.2-1份、聚丙烯酸钠1-2份、聚乙烯吡咯烷酮3-5份的水溶液分散体系中加入单烷氧基型钛酸酯偶联亲水改性剂1-2份，搅拌均匀后，缓慢加入10-30份的表面处理后的ZnO纳米线，制备成亲水型ZnO纳米线分散液；
2）制备香精自包裹微胶囊
将10-20份香精添加至含有C12-15链烷醇聚醚-12 1-5份、聚乙烯醇1-3份、羟甲基纤维素1-3份、羧甲基纤维素钠0.1-0.5份、果胶0.5-2份、聚乙烯吡咯烷酮1-2份、聚丙烯酸钠1-2份体系 中形成香精自包裹微胶囊；
3）将制备的香精自包裹微胶囊投入到制备好的ZnO纳米线分散液中充分混合；
4）通过喷涂的形式将纳米线溶液喷涂在上层纤维网层的下表面或下层纤网层的上表面；
所述的增韧聚乳酸纤维的制备方法为：在聚乳酸母料中增加5-30%重量份的改性麻纳米纤维；
ZnO纳米线表面处理方法为：
1）将ZnO纳米线分散至浓度为0.5%氨基酸水溶液中浸泡1-5分钟，氨基酸为pI大于7的组氨酸（pI=7.59)或赖氨酸（pI=9.74）或二者的组合物；由于ZnO在水溶液中由于羟基作用而带负电荷，在pH小于等电点pI时氨基酸带正电荷，氨基酸吸附于ZnO纳米线部分表面；
2）将浸泡后ZnO纳米线取出干燥；
3）利用浓度0.1-1%的HF对干燥后ZnO纳米线进行刻蚀，以形成多个缺陷点；
4）将刻蚀后的后ZnO纳米线再次分散于pH大于pI的氢氧化钠解吸。
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| CN105088793A (zh) * | 2015-08-25 | 2015-11-25 | 无锡市长安曙光手套厂 | 一种无纺布、其制备方法及其应用 |
| CN106350941A (zh) * | 2016-09-22 | 2017-01-25 | 黄沁 | 一种抗菌反渗透多功能无纺布及其生产工艺 |
| CN109486139A (zh) * | 2018-11-14 | 2019-03-19 | 江苏省农业科学院 | 环保增韧纳米纤维素-聚乳酸生物降解材料及其制备方法 |
| CN110965202A (zh) * | 2019-09-30 | 2020-04-07 | 福建恒安集团有限公司 | 一种改性牛奶蛋白抑菌纤维无纺布及其制备方法 |
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