CN112898625B - 一种水下弹性纤维素气凝胶及其制备方法与应用 - Google Patents

一种水下弹性纤维素气凝胶及其制备方法与应用 Download PDF

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CN112898625B
CN112898625B CN202110212618.4A CN202110212618A CN112898625B CN 112898625 B CN112898625 B CN 112898625B CN 202110212618 A CN202110212618 A CN 202110212618A CN 112898625 B CN112898625 B CN 112898625B
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cellulose
aerogel
underwater
dispersion liquid
nano
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CN112898625A (zh
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王猛
孙佩佩
庞怀鹏
刘国然
李勇
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New Material Institute of Shandong Academy of Sciences
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Abstract

本公开属于纤维素气凝胶的制备领域，具体提供一种水下弹性纤维素气凝胶及其制备方法与应用。所述水下弹性纤维素气凝胶由纳米纤维素和长链高分子聚合物交联而成。其制备方法包括如下步骤：1)将纳米纤维素原料分散于水中，通过化学氧化及机械均质进行处理，得到纳米纤维素分散液；2)在步骤1)中的纳米纤维素分散液中加入长链高分子聚合物、交联剂及催化剂，将混合液加热搅拌一段时间形成均一分散液，将均一分散液冷却后放置于模具中冷冻干燥，得到中间物；3)将中间物放置于烘箱中反应一段时间，既得。解决现有技术中纤维素气凝胶在水中极易分散，限制了纤维素气凝胶的应用问题。

Description

一种水下弹性纤维素气凝胶及其制备方法与应用
技术领域
本公开属于纤维素气凝胶的制备领域，具体提供一种水下弹性纤维素气凝胶及其制备方法与应用。
背景技术
这里的陈述仅提供与本公开有关的背景信息，而不必然构成现有技术。
气凝胶是一种具备连续多孔网络结构的新材料，其具有孔隙率高、导热系数低、比表面积大和密度低等优点，在吸附、隔热、催化和储能领域均有非常高的潜在应用价值。气凝胶按照组成可以分为有机气凝胶、无机气凝胶、碳气凝胶和杂化气凝胶等。有机气凝胶一般是以间苯二酚/甲醛等为前驱体，通过溶胶-凝胶法和超临界干燥法处理，从而形成具有纳米多孔网络结构的气凝胶。无机气凝胶以二氧化硅气凝胶为主，碳气凝胶是以有机气凝胶为前驱体，在惰性气体氛围下热解得到，既具有有机气凝胶的多孔性以并赋予其高的导电性。
纤维素是自然界最丰富的可再生高分子之一，其具有来源广、成本低、可降解等优点，受到国内外广泛关注。以纤维素为前驱体制备纤维素气凝胶是纤维素领域重要的一个分支，纤维素气凝胶通常是将纤维素溶解或分散获得纤维素的均一溶液或分散液，再通过冷冻干燥或超临界干燥得到柔性多孔气凝胶材料。现有技术中，提供了一种将纤维素溶液经过数次冷冻解融循环后，加入到酸性溶液中进行纤维素溶液置换，通过干燥得到轻质高强度纤维素气凝胶。现有技术中还提供了一种将纤维素加入改性剂进行化学修饰得到改性纤维素悬浮液，然后将改性纤维素悬浮液分散在有机溶剂中，通过成型，烘干，形成改性纤维素凝胶，最后将改性纤维素凝胶通过热处理制得多功能纤维素弹性气凝胶。
但发明人发现，纤维素气凝胶弹性和强度主要来源于纤维素链条之间的氢键，当纤维素气凝胶浸入水中后，水分子易与纤维素形成氢键，破坏原有纤维之间的氢键作用，导致纤维素气凝胶在水中极易分散，极大的限制了其应用领域。
发明内容
针对现有技术中纤维素气凝胶在水中极易分散，限制了纤维素气凝胶的应用问题，本公开旨在提供一种能够在水下正常回弹的纤维素气凝胶及其制备方法。
本公开一个或一些实施方式中，提供一种水下弹性纤维素气凝胶，所述水下弹性纤维素气凝胶由纳米纤维素和长链高分子聚合物交联而成。
本公开一个或一些实施方式中，提供一种水下弹性纤维素气凝胶的制备方法，包括如下步骤：
1)将纳米纤维素原料分散于水中，通过化学氧化及机械均质进行处理，得到纳米纤维素分散液；
2)在步骤1)中的纳米纤维素分散液中加入长链高分子聚合物、交联剂及催化剂，将混合液加热搅拌一段时间形成均一分散液，将均一分散液冷却后放置于模具中冷冻干燥，得到中间物；
3)将中间物放置于烘箱中反应一段时间，既得。
本公开一个或一些实施方式中，提供上述水下弹性纤维素气凝胶或上述水下弹性纤维素气凝胶的制备方法在水下受力回弹中的应用。
本公开一个或一些实施方式中，提供上述水下弹性纤维素气凝胶或上述水下弹性纤维素气凝胶的制备方法在水下吸附中的应用。
本公开一个或一些实施方式中，提供上述水下弹性纤维素气凝胶或上述水下弹性纤维素气凝胶的制备方法在伤口止血中的应用。
上述技术方案中的一个或一些技术方案具有如下优点或有益效果：
1)本公开将纤维素和高分子聚合物复合，通过添加交联剂及催化剂促进酯化交联反应，成功制备出水下超弹纤维素气凝胶，有效解决了现有技术中纤维素气凝胶水下易分散、弹性差的问题，拓宽了纤维素气凝胶的应用领域，尤其是在水下吸附、止血伤口敷料等领域。
2)本公开涉及的气凝胶制备过程不需要复杂的溶胶-凝胶化过程，制备工艺相对简单，易于实施，可操作性强，且气凝胶的尺寸及形状不受原料限制，可以按需要制备、加工或切割。
附图说明
构成本公开一部分的说明书附图用来提供对本公开的进一步理解，本公开的示意性实施例及其说明用于解释本公开，并不构成对本公开的不当限定。
图1为对比实施例2与实施例3纤维素气凝胶的扫描电镜图，其中，a为实施例2，b为实施例3。
图2为实施例3制备的纤维素气凝胶在空气中和水下的压缩回弹照片。
图3为实施例3制备的气凝胶在水下的应力应变曲线。
图4为实施例3制备的气凝胶的在50％应变下100次循环的应力应变曲线。
具体实施方式
下面将对本公开实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本公开的一部分实施例，而不是全部实施例。基于本公开的实施例，本领域技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本公开保护的范围。
针对现有技术中纤维素气凝胶在水中极易分散，限制了纤维素气凝胶的应用问题，本公开旨在提供一种能够在水下正常回弹的纤维素气凝胶及其制备方法。
本公开一个或一些实施方式中，提供一种水下弹性纤维素气凝胶，所述水下弹性纤维素气凝胶由纳米纤维素和长链高分子聚合物交联而成。
优选的，所述纳米纤维素为针叶木浆板、阔叶木浆板、棉花中的一种或几种混合物；优选为针叶木浆板；
或，所述长链高分子聚合物为聚乙二醇(PEG)、聚乙烯醇(PVA)、淀粉、聚乳酸(PLA)、羧甲基纤维素(CMC)中的一种或几种混合物，优选为聚乙二醇或聚乙烯醇或二者混合物。
本公开一个或一些实施方式中，提供一种水下弹性纤维素气凝胶的制备方法，包括如下步骤：
1)将纳米纤维素原料分散于水中，通过化学氧化及机械均质进行处理，得到纳米纤维素分散液；
2)在步骤1)中的纳米纤维素分散液中加入长链高分子聚合物、交联剂及催化剂，将混合液加热搅拌一段时间形成均一分散液，将均一分散液冷却后放置于模具中冷冻干燥，得到中间物；
3)将中间物放置于烘箱中反应一段时间，既得。
优选的，步骤1)中，纤维素分散液质量分数为0.1～1wt％；
或，步骤1)中，纤维素和长链高分子聚合物的比例是1-5:1-2；
优选的，纤维素和长链高分子聚合物的比例是1-1:1-2。
优选的，步骤2)中，将混合液在50～100℃加热搅拌；
或，步骤2)中，搅拌时间为1-3h；
或，步骤3)中，烘箱温度为40-80℃，优选为50℃；
或，步骤3)中，反应时间为1-3h，优选为2h。
优选的，化学氧化及机械均质为TEMPO氧化法及高压均质处理，
优选的，包括如下步骤：通过TEMPO氧化体系对其进行氧化，在碱性条件下升温反应一段时间后，再通过高压均质方法制备出纳米纤维素悬浮液；
进一步优选的，反应温度为20-30℃；
进一步优选的，反应时间为3-8h；
进一步优选的，反应pH为9-11；
进一步优选的，所述TEMPO氧化体系为NaBr、TEMPO、NaClO。
优选的，纳米纤维素原料为针叶木浆板、阔叶木浆板、棉花中的一种或几种混合物；优选为针叶木浆板；
或，所述长链高分子聚合物为聚乙二醇(PEG)、聚乙烯醇(PVA)、淀粉、聚乳酸(PLA)、羧甲基纤维素(CMC)中的一种或几种混合物，优选为聚乙二醇或聚乙烯醇或二者混合物；
或，交联剂是单宁酸、柠檬酸、硼酸的一种或几种混合物，优选为柠檬酸；
或，催化剂是磷酸、硝酸、盐酸中的一种或几种混合物；优选为磷酸。
本公开一个或一些实施方式中，提供上述水下弹性纤维素气凝胶或上述水下弹性纤维素气凝胶的制备方法在水下受力回弹中的应用。
本公开一个或一些实施方式中，提供上述水下弹性纤维素气凝胶或上述水下弹性纤维素气凝胶的制备方法在水下吸附中的应用。
本公开一个或一些实施方式中，提供上述水下弹性纤维素气凝胶或上述水下弹性纤维素气凝胶的制备方法在伤口止血中的应用。
实施例1
本实施例提供一种水下弹性纤维素气凝胶的制备方法，包括如下步骤：
称取1g棉花放置于搅拌机中并加50mL去离子水，分散均匀后倒入250mL烧杯中，加入40mL去离子水、0.016g TEMPO氧化剂以及0.1g NaBr搅拌均匀，随后缓慢加入10mmolNaClO溶液，25℃下搅拌反应5h，反应过程中用0.5mol/L NaOH溶液调节反应体系pH值维持在10左右。反应结束后用砂芯漏斗过滤，并用大量去离子水洗至中性，得到TEMPO氧化纤维素。配置1wt％浓度的氧化纤维素悬浮液，在高压均质机100MPa压力下循环均质10次，随后调节氧化纤维素悬浮液浓度为0.5wt％。
在100mL纳米纤维素悬浮液(0.5wt％)中加入1.2g柠檬酸和1.2mL磷酸搅拌均匀后倒入模具，将样品放置液氮中冻结后冷冻干燥48h得到白色纤维素气凝胶，随后在50℃烘箱中交联2h得到气凝胶。
经测试，本实施例制得的气凝胶，由于缺少高分子聚合物，在气凝胶中无法形成足量酯键，导致所得纤维素气凝胶在水下以50％应力压缩，10次后即压溃，无法回弹。
实施例2
本实施例提供一种水下弹性纤维素气凝胶的制备方法，包括如下步骤：
称取1g针叶木浆板(银鹰纸业，α纤维素>90％)放置于搅拌机中并加50mL去离子水，分散均匀后倒入250mL烧杯中，加入40mL去离子水、0.016g TEMPO氧化剂以及0.1g NaBr搅拌均匀，随后缓慢加入10mmol NaClO溶液，25℃下搅拌反应5h，反应过程中用0.5mol/LNaOH溶液调节反应体系pH值维持在10左右。反应结束后用砂芯漏斗过滤，并用大量去离子水洗至中性，得到TEMPO氧化纤维素。配置1wt％浓度的氧化纤维素悬浮液，在高压均质机100MPa压力下循环均质10次，随后调节氧化纤维素悬浮液浓度为0.5wt％。
取一定质量PEG加入到100mL纳米纤维素悬浮液中，使PEG和纤维素质量比在1:1，在95℃下加热搅拌2h至溶解，再加入1.2g柠檬酸和1.2mL磷酸搅拌均匀后倒入模具，将样品放置液氮中冻结后冷冻干燥48h得到白色纤维素气凝胶，随后在50℃烘箱中交联2h得到气凝胶。
经测试，本实施例制得的气凝胶，纤维素与PEG和柠檬酸之间形成氢键，所得纤维素气凝胶在水下以50％应力压缩，10次后仍可回复至初始形态，恢复时间大于5s。
从图1来看，本实施例制得的气凝胶多孔，具有丰富的表面积，形貌良好。
实施例3
本实施例提供一种水下弹性纤维素气凝胶的制备方法，包括如下步骤：
称取1g针叶木浆板(银鹰纸业，α纤维素>90％)放置于搅拌机中并加50mL去离子水，分散均匀后倒入250mL烧杯中，加入40mL去离子水、0.016g TEMPO氧化剂以及0.1g溴化钠搅拌均匀，随后缓慢加入10mmol NaClO溶液，25℃下搅拌反应5h，反应过程中用0.5mol/LNaOH溶液调节反应体系pH值维持在10左右。反应结束后用砂芯漏斗过滤，并用大量去离子水洗至中性，得到TEMPO氧化纤维素。配置1wt％浓度的氧化纤维素悬浮液，在高压均质机100MPa压力下循环均质10次，随后调节氧化纤维素悬浮液浓度为0.5wt％。
取一定质量PVA(1788型)加入到100mL纳米纤维素悬浮液中，使PVA和纤维素质量比为1:1，在95℃下加热搅拌2h至溶解，再加入1.2g C6H8O7和1.2mL H3PO4搅拌均匀后倒入模具，将样品放置液氮中冻结后冷冻干燥48h得到白色纤维素气凝胶，随后在50℃烘箱中交联2h得到气凝胶。
加热后促进纤维素与PVA和柠檬酸之间形成酯键，经测试，本实施例制得的气凝胶，所得纤维素气凝胶在水下以80％应力压缩可以恢复至初始形态，恢复时间小于3s，在50％应变下100次后仍可回复至初始形态，且磁滞环面积较小。
从图1来看，本实施例制得的气凝胶多孔，具有丰富的表面积，形貌良好。
从图2来看，本实施例制得的气凝胶在空气中和水下的压缩回弹效果较好，适合水下吸附、止血伤口敷料等。
图3为本实施例制备的气凝胶在水下的应力应变曲线，从曲线上来看，本实施例制得的气凝胶水下应力良好。
图4为本实施例制备的气凝胶的在50％应变下100次循环的应力应变曲线，从曲线上来看，本实施例制得的气凝胶循环性能良好，耐久性好。
实施例4
本实施例提供一种水下弹性纤维素气凝胶的制备方法，包括如下步骤：
称取1g针叶木浆板(银鹰纸业，α纤维素>90％)放置于搅拌机中并加50mL去离子水，分散均匀后倒入250mL烧杯中，加入40mL去离子水、0.016gTEMPO氧化剂以及0.1g溴化钠搅拌均匀，随后缓慢加入10mmol NaClO溶液，25℃下搅拌反应5h，反应过程中用0.5mol/LNaOH溶液调节反应体系pH值维持在10左右。反应结束后用砂芯漏斗过滤，并用大量去离子水洗至中性，得到TEMPO氧化纤维素。配置1wt％浓度的氧化纤维素悬浮液，在高压均质机100MPa压力下循环均质10次，随后调节氧化纤维素悬浮液浓度为0.5wt％。
取一定质量PVA(1788型)加入到100mL纳米纤维素悬浮液中，使PVA和纤维素质量比为2:1，在95℃下加热搅拌2h至溶解，再加入1.2g柠檬酸和1.2mL磷酸搅拌均匀后倒入模具，将样品放置液氮中冻结后冷冻干燥48h得到白色纤维素气凝胶，随后在50℃烘箱中交联2h得到气凝胶。
经测试，本实施例制得的气凝胶，随着PVA含量增加，所得纤维素气凝胶逐渐变硬，在水下压缩后无法回弹至初始形态。
实施例5
本实施例提供一种水下弹性纤维素气凝胶的制备方法，包括如下步骤：
称取1g针叶木浆板(银鹰纸业，α纤维素>90％)，分散均匀后倒入250mL烧杯中，加入40mL去离子水、0.016g TEMPO氧化剂以及0.1g溴化钠搅拌均匀，随后缓慢加入10mmolNaClO溶液，25℃下搅拌反应5h，反应过程中用0.5mol/L NaOH溶液调节反应体系pH值维持在10左右。反应结束后用砂芯漏斗过滤，并用大量去离子水洗至中性，得到TEMPO氧化纤维素。配置1wt％浓度的氧化纤维素悬浮液，在高压均质机100MPa压力下循环均质10次，随后调节氧化纤维素悬浮液浓度为0.5wt％。
取一定质量PVA(1788型)加入到100mL纳米纤维素悬浮液中，使PVA和纤维素质量比为1:1，在95℃下搅拌溶解2h，再加入1.2g C6H8O7和1.2mL H3PO4搅拌均匀后冷冻干燥48h后得到纳米纤维素气凝胶，后续不加热。
经测试，本实施例制得的气凝胶，未加热导致纤维素与PVA和柠檬酸分子间无法形成酯键，所得纤维素气凝胶在水下以50％应力压缩，恢复时间大于10s，水下弹性较差。
从实施例1-5来看，仅实施例2,3制得的水下弹性纤维素气凝胶压缩恢复时间短，水下弹性较好，显然，本公开各步骤间相互配合才能实现满足水下弹性的效果。
以上所揭露的仅为本公开的优选实施例而已，当然不能以此来限定本公开之权利范围，因此依本公开申请专利范围所作的等同变化，仍属本公开所涵盖的范围。

Claims (9)

1.一种水下弹性纤维素气凝胶的制备方法，其特征在于，包括如下步骤：
1）将纳米纤维素原料分散于水中，通过化学氧化及机械均质进行处理，得到纳米纤维素分散液；步骤1）中，纤维素分散液质量分数为0.1~1wt%；化学氧化及机械均质为TEMPO氧化法及高压均质处理；
所述TEMPO氧化法及高压均质处理包括如下步骤：通过TEMPO氧化体系对其进行氧化，在碱性条件下升温反应一段时间后，再通过高压均质方法制备出纳米纤维素悬浮液；步骤1）中，反应pH为9-11；
2）在步骤1）中的纳米纤维素分散液中加入长链高分子聚合物、交联剂及催化剂，将混合液加热搅拌一段时间形成均一分散液，将均一分散液冷却后放置于模具中冷冻干燥，得到中间物；步骤2）中，将混合液在50~100℃加热搅拌；步骤2）中，搅拌时间为1-3h；步骤2）中，纳米纤维素和长链高分子聚合物的比例是1:1；
3）将中间物放置于烘箱中反应一段时间，即得；
所述纳米纤维素原料为针叶木浆板；
所述长链高分子聚合物为聚乙烯醇；
所述交联剂是柠檬酸。
2.如权利要求1所述的水下弹性纤维素气凝胶的制备方法，其特征在于，步骤3）中，烘箱温度为40-80℃，反应时间为1-3h。
3.如权利要求2所述的水下弹性纤维素气凝胶的制备方法，其特征在于，步骤3）中，烘箱温度为50℃，反应时间为2h。
4.如权利要求1所述的水下弹性纤维素气凝胶的制备方法，其特征在于，所述TEMPO氧化法及高压均质处理的反应温度为20-30℃，反应时间为3-8h；
所述TEMPO氧化体系为NaBr、TEMPO、NaClO。
5.如权利要求1所述的水下弹性纤维素气凝胶的制备方法，其特征在于，催化剂是磷酸、硝酸、盐酸中的一种或几种混合物。
6. 如权利要求5所述的水下弹性纤维素气凝胶的制备方法，其特征在于， 所述催化剂为磷酸。
7.权利要求1-6任一项所述的方法制备的水下弹性纤维素气凝胶在水下受力回弹中的应用。
8.权利要求1-6任一项所述的方法制备的水下弹性纤维素气凝胶在水下吸附中的应用。
9.权利要求1-6任一项所述的方法制备的水下弹性纤维素气凝胶在伤口止血中的应用。
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