CN111138719A - 一种含纳米纤维素的粉体的制备方法 - Google Patents

一种含纳米纤维素的粉体的制备方法 Download PDF

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CN111138719A
CN111138719A CN201911162928.9A CN201911162928A CN111138719A CN 111138719 A CN111138719 A CN 111138719A CN 201911162928 A CN201911162928 A CN 201911162928A CN 111138719 A CN111138719 A CN 111138719A
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cellulose
powder
nanocellulose
starch
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杜艳芬
刘金刚
陈京环
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China National Pulp and Paper Research Institute
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Abstract

本发明公开了一种制备含纳米纤维素粉体的方法，属于纳米材料制备领域，具体地说是一种将纳米纤维素水分散液干燥以得到高固含量固体的方法。由机械法或化学法处理得到的纳米纤维素分散液，与原淀粉、改性淀粉、碳酸钙、滑石粉、高岭土等的一种或两种及以上粉体或其分散液均匀混合，添加一定量增塑剂。采用室温或者加热在30℃～60℃条件下干燥，经粉碎、过筛后，得到固含量可高达99％的含纳米纤维素的粉体。该粉体可均匀分散于水中。该粉体可添加于塑料、橡胶加工中以提高基体的强度、韧性等性能；也可用于水性体系中。本发明方法操作步骤简单、绿色环保、成本优势明显、易在工业上规模化应用。

Description

一种含纳米纤维素的粉体的制备方法
技术领域
本发明属于纳米材料制备领域，具体地说是一种将纳米纤维素水分散液干燥以得到高固含量固体的方法。
背景技术
纳米纤维素是一种绿色的纤维素基可再生高分子材料，具有高结晶度、高纯度、高杨氏模量、高强度、高亲水性、高透明度等特点，在食品、医药、化妆品、造纸、包装、汽车、塑料、电子产品、新材料等多个领域有巨大的应用前景。
纳米纤维素的制备方法主要分为化学法和机械法两大类。化学法是使用一定浓度的硫酸、盐酸或两者的复合酸，在一定温度和时间条件下处理纤维原料如棉浆、木浆、麻浆、竹浆、蔗渣、麦草、稻草、马铃薯茎秆或玉米芯等，使之发生酸水解反应，纤维素无定形区降解、结晶区保留的方法；该方法得到的纳米纤维素又称为纤维素纳米晶(CNC)，其直径在1～100nm。机械法包括高压均质处理、微射流处理、超细研磨处理、冷冻破碎处理、高强超声处理等。通过高压机械方法处理天然纤维素得到的新型高度润胀的胶体状纳米纤维素，又称为微纤化纤维素(MFC)，其直径为数十纳米至数百纳米。为了降低机械法的能耗，研究人员提出了多种预处理方法，如生物酶预处理、酸-碱抽提预处理、羧甲基化预处理、乙酰化预处理、TEMPO氧化预处理、高碘酸盐氧化等。(董凤霞等，纳米纤维素的制备及应用，2012年第6期；高艳红等，微纤化纤维素及其制备技术的研究进展，化工进展，2017年第1期)
无论是化学还是机械处理制备纳米纤维素均是在液体介质中进行，纳米纤维素的质量分数都比较低，一般为0.3％～3.0％，很少超过6％。低浓度的纳米纤维素分散液不仅会限制其应用范围，如塑料、橡胶、制鞋、汽车等领域需要以固体的形式添加；另一方面也会增加运输、储存成本，还容易滋生细菌，因此有必要对纳米纤维素分散液进行有效浓缩、干燥。而采用常规的方法干燥时，纳米纤维素分散液里的水分快速蒸发、形成紧密结实的膜，纳米纤维素分子间易形成氢键和缠结、发生不可逆的聚集(即角质化)，很难再分散于水中。低温冷冻干燥需要的时间久、效率低、成本高，而且要求分散液初始固含量低，否则会形成气凝胶。喷雾干燥要求分散液固含量低，干燥后纤维易聚集、颗粒尺寸范围大。(高艳红等，微纤化纤维素及其制备技术的研究进展，化工进展，2017年第1期)因此，纳米纤维素如何高效干燥是限制其产业化应用的一个重要问题。
专利CN 102245815 A公开了一种在水中可再分散的干燥形式的纳米晶体纤维素(NCC)，其制备方法是在水悬浮液中用单价阳离子(如Na+，K+，Li+，NH4 +和四烷基铵(R4N+)，质子化的三烷基铵(HR3N+)，质子化的二烷基铵(H2RaN+)，以及质子化的单烷基铵(H3RN+)离子)来交换H-NCC的质子，所得到的M-NCC悬浮液形成膜层，干燥膜层形成固体形式。该方法仅针对酸处理得到的纳米晶体纤维素，而且会在系统中引入新的离子，可能对应用造成不利影响。
专利CN 103304824 A公开了一种高浓度纳米微晶纤维素胶体的制备方法，其将低浓度(0.5％左右)的纳米纤维素胶体通过控制旋转蒸发工艺条件，温度(30℃～50℃)、转速(2～6rpm)来浓缩制备高浓度的纳米纤维素胶体，其质量分数达35％～85％。但此方法必须将溶液中的离子透析掉才能进行浓缩，透析过程耗时长，纳米纤维素的生产成本较高。
专利CN 104072787 B公开了一种制备高浓度纳米纤维素胶体的方法，其将纳米纤维素通过离心或微孔滤布过滤，使其与沉淀物相分离，制得纳米纤维素胶体；将此胶体低温冷冻结冰，然后将冷冻结冰的纳米纤维素胶体放置在0℃以上进行解冻，使纳米纤维素沉淀下来；然后，将沉淀物通过过滤、压滤和洗涤处理，所得产物在机械剪切作用下分散于溶剂中，即制得高浓度纳米纤维素胶体。该方法制备的纳米纤维素胶体的质量分数最高为3.77％。
专利CN 109863199 A公开了一种生产非表面改性的纳米纤维素颗粒(特别是以粉末形式)的方法，其将未曾干燥的非表面改性的纳米纤维素颗粒在水性液体中的悬浮体转移到超临界状态的流体中，使非表面改性的纳米纤维素颗粒的悬浮体与超临界状态的流体接触，除去水性液体和超临界状态的流体，优选通过控制压力和/或温度来进行，以形成非表面改性的纳米纤维素颗粒，收集非表面改性的纳米纤维素颗粒。该方法的水性液体为环状仲胺或其混合物的水溶液，并且优选为吗啉、哌啶或其混合物的水溶液，即需要用到比较特殊的试剂；而且超临界干燥需要复杂的溶剂置换、成本高，无法规模化应用。
发明内容
为克服上述现有技术的不足，本发明提供了一种高效将纳米纤维素分散液干燥为粉体的方法。
具体步骤为：
(1)采用化学法或机械法处理纤维原料制备纳米纤维素分散液，所得纤维素纳米晶分散液的固含量为1％左右，微纤化纤维素分散液固含量可达5％左右。
(2)将步骤(1)制得的纳米纤维素分散液与淀粉、碳酸钙、滑石粉、高岭土等的一种或两种及以上均匀混合，添加一定量的增塑剂。
(3)将步骤(2)均匀混合后的物料放在室温或者加热条件下进行干燥，期间间歇或者连续搅拌以使物料上下部均匀干燥，经过机械粉碎、过筛后，即得到固含量可高达99％的含纳米纤维素的粉体，可用于多种用途。
所述纤维原料为木浆、棉浆、麻浆、竹浆、蔗渣、麦草、稻草、马铃薯茎秆或玉米芯等，可含木素或不含木素。
所述化学法可采用硫酸、盐酸或其混合酸，机械法采用胶体磨、均质机、高压微射流机等。
所述淀粉、碳酸钙、滑石粉、高岭土等可以为粉体或其分散液。
所述淀粉可以为玉米淀粉、木薯淀粉、马铃薯淀粉等；可以为原淀粉，或者经过化学或生物等处理的改性淀粉。
所述碳酸钙、滑石粉、高岭土的粒径为44μm(325目)或更小，甚至为纳米级。
所述碳酸钙可以为研磨碳酸钙或沉淀碳酸钙。
所述纳米纤维素与所添加粉体的绝干质量比为0.1∶100～100∶100。
所述增塑剂为甘油、乙二醇、聚乙二醇等，单独或者两种或两种以上加入，其加入量不超过粉体的50％。
所述混合物加热时的温度为30℃～60℃。
所述干燥后含纳米纤维素的粉体可以用叶片粉碎机、研磨机等进行粉碎，粉碎后的粉末通过24、30、40、60或80等目数的筛网。
所述干燥后含纳米纤维素的粉体的固含量可以控制，最高可达99％。
与现有技术相比，本发明方法操作步骤简单、绿色环保、生产周期短、成本优势明显，所得含纳米纤维素的粉体固含量高、且在水中可均匀分散，既可用于以液体形式添加的流延成膜、施胶、涂布、造纸湿部添加等，也可用于必须添加固体的领域如塑料熔融造粒。
具体实施方式
以下结合实施例和试验数据对本发明上述的和另外的技术特征和优点作更详细的说明，但是不以实施例为限。
实施例1：
将漂白化学针叶木浆打浆后再用研磨机研磨，得到纳米纤维素分散液(MFC)，其固含量为3.0％，纳米纤维素直径为210nm。在该纳米纤维素分散液中加入一定量磷酸酯玉米淀粉，两者绝干质量比为20∶100(纳米纤维素∶淀粉)，用高速搅拌机将其混合均匀，搅拌机转子的速度为60r/min，搅拌时间为5min。将纳米纤维素与淀粉的混合物放入烘箱中进行干燥，烘箱温度为45℃、干燥时间24h，得到固含量为95％的固体。期间每隔一小时左右搅拌一次，将内部的物料翻到表面，以保证物料均匀干燥。用分散机将固体进行粉碎，过40目筛子后即得含纳米纤维素的固体粉末。该粉末加入到水中，高速搅拌后，可以完全分散开，形成均匀半透明的分散液。该含纳米纤维素的粉末可与聚乳酸(PLA)、聚己二酸对苯二甲酸丁二酯(PBAT)、聚乙烯(PE)或聚丙烯(PP)等一起混合、加热、熔融加工，也可分散在水中添加于涂料、胶料、纸浆等体系中。在聚乳酸物料中添加3％该粉末，熔融挤出、制样后，样片的拉伸强度提高10％以上。
实施例2：
采用研磨机研磨含木素的玉米芯，得到含木素的纳米纤维素分散液(LMFC)，其固含量为5.0％，纳米纤维素直径约为350nm。将聚乙二醇(PEG-6000)配制成50％的溶液。用高速混合机将一定量的未经改性玉米淀粉、聚乙二醇混合均匀，然后加入该纳米纤维素分散液，三者的比例为35∶100∶30(纳米纤维素∶淀粉∶聚乙二醇)，混合均匀后，将纳米纤维素与淀粉、聚乙二醇的混合物进行加热干燥，温度为50℃，干燥时间28h，期间机械缓慢搅拌以保证物料均匀干燥，最后得到固含量为97.5％的固体。用高速分散机进行粉碎，过60目筛子后即得含纳米纤维素的固体粉末。将该粉末加入到水中，高速搅拌后，可以完全分散开，形成均匀半透明的分散液。将该粉末与聚己二酸对苯二甲酸丁二酯(PBAT)、淀粉、甘油等一起混合，熔融造粒、吹模成塑料袋，当其加入量为5％时，袋子的拉伸强度提高22％。
实施例3：
将杨木漂白化学机械浆进行打浆后再用高压均质机处理，得到含木素的纳米纤维素分散液(LMFC)，其固含量为1.0％，纳米纤维素直径约为230nm。在该纳米纤维素分散液中加入一定量纳米碳酸钙，两者比例为10∶100(纳米纤维素∶纳米碳酸钙)，用高速搅拌机将其混合均匀，搅拌机转子的速度为100r/min，搅拌时间为7min。将纳米纤维素与纳米碳酸钙的混合物放室温下进行干燥，期间保持缓慢持续搅拌，40h后得到固含量约为70％的固体。用球磨机进行研磨后，过80目筛子后即得含纳米纤维素的固体粉末。经过高速搅拌或超声波处理后，该粉末可在水中完全分散，形成均匀的分散液。
实施例4：
将桉木漂白化学浆进行打浆后再用高压均质机处理，得到纳米纤维素分散液(MFC)，其固含量为1.2％，纳米纤维素直径约为170nm。在该纳米纤维素分散液中加入一定量滑石粉，两者绝干质量比为3∶100(纳米纤维素∶滑石粉)，该滑石粉粒度小于2μm的含量为85％；用高速搅拌机将其混合均匀，搅拌机转子的速度为100r/min，搅拌时间为3min。将混合好的纳米纤维素与滑石粉放入烘箱中进行干燥，温度为35℃，干燥时间为24h，期间每隔一小时取出来搅拌一次，得到固含量为91％的固体。用分散机将此含纳米纤维素、滑石粉的固体进行分散，过80目筛子后即得含纳米纤维素的固体粉末。将该粉末加入到水中，高速搅拌后可以完全分散开，形成均匀的分散液。该含纳米纤维素的粉末可与聚乳酸(PLA)、聚己二酸对苯二甲酸丁二酯(PBAT)、聚乙烯(PE)、聚丙烯(PP)等一起混合、加热、熔融加工，也可分散在水中添加于涂料、胶料、油墨、纸浆等体系中。
实施例5：
用质量浓度为64％的硫酸溶液处理漂白化学竹浆，浆与硫酸的质量体积比为1∶8.75，在45℃条件下保温1.5小时，得到乳白色悬浮液；将此悬浮液进行多次离心后去除酸，收集下层的纳米纤维素悬浮液，其固含量为1％，纳米纤维素直径约为10nm。在该纳米纤维素分散液中加入一定量氧化淀粉和高岭土，高岭土的平均粒径为1.8μm，三者绝干质量比例为5∶100∶50(纳米纤维素∶氧化淀粉∶高岭土)，机械搅拌将其混合均匀，搅拌器转子的速度为80r/min，搅拌时间为5min。此纳米纤维素与氧化淀粉、高岭土的混合物在室温下进行干燥，48h后得到固含量为85％的固体。为使上、下部物料均匀干燥，期间搅拌数次物料。用分散机将此含纳米纤维素、氧化淀粉和高岭土的固体进行分散，过30目筛子后即得含纳米纤维素的固体粉末。将该含纳米纤维素的固体粉末加入到水中，高速搅拌后，可以完全分散开，形成均匀的分散液。
实施例6：
用质量浓度为64％的硫酸溶液处理漂白化学木浆，浆与硫酸的质量体积比为1∶8.75，在45℃条件下保温2小时，得到乳白色悬浮液；将此悬浮液进行多次离心后去除酸，收集下层的纳米纤维素悬浮液(CNC)，其固含量为1％，纳米纤维素直径约为15nm。在该纳米纤维素分散液中加入一定量纳米碳酸钙、甘油，两者比例为1.5∶100∶10(纳米纤维素∶纳米碳酸钙∶甘油)，用高速搅拌机将其混合均匀，搅拌机转子的速度为60r/min，搅拌时间为3min。将纳米纤维素与纳米碳酸钙、甘油的混合物放室温下进行干燥，期间保持缓慢持续搅拌，15h后得到固含量为65％的固体。用球磨机进行研磨后，过100目筛子后即得含纳米纤维素的固体粉末。经过高速搅拌或超声波处理后，该粉末可在水中完全分散，形成均匀的分散液。
实施例7：
采用研磨机研磨含木素的玉米芯，得到含木素的纳米纤维素分散液(LMFC)，其固含量为5.0％，纳米纤维素直径约为350nm。用高速混合机将一定量的纳米纤维素分散液与玉米原淀粉进行混合，两者的比例为50∶50(纳米纤维素∶原淀粉)，混合均匀后，进行加热干燥，温度为45℃，干燥时间17h，期间机械缓慢搅拌以保证物料均匀干燥，最后得到固含量为83％的固体。用高速分散机进行粉碎，过80目筛子后即得含纳米纤维素的固体粉末。将该粉末加入到水中，高速搅拌后，可以完全分散开，形成均匀半透明的分散液。

Claims (10)

1.一种制备含纳米纤维素的粉体的方法，其特征在于具体步骤为：
(1)采用化学法或机械法处理纤维原料制备纳米纤维素分散液；
(2)将步骤(1)制得的纳米纤维素分散液与淀粉、碳酸钙、滑石粉、高岭土等的一种或两种及以上均匀混合，添加一定量的增塑剂；
(3)将步骤(2)均匀混合后的物料放在室温或者加热条件下进行干燥，期间间歇或者连续搅拌以使物料上下部均匀干燥，经过机械粉碎、过筛后，即得到固含量可高达99％的含纳米纤维素的粉体。
2.根据权利要求1所述的一种制备含纳米纤维素的粉体的方法，其特征在于：所述淀粉、碳酸钙、滑石粉、高岭土等可以为粉体或其分散液，淀粉可以为玉米淀粉、木薯淀粉、马铃薯淀粉等，可以为原淀粉或者经过化学或生物等处理的改性淀粉。
3.根据权利要求1所述的一种制备含纳米纤维素的粉体的方法，其特征在于：所述碳酸钙可以为研磨碳酸钙或沉淀碳酸钙，碳酸钙、滑石粉、高岭土的粒径为44μm(325目)或更小，甚至为纳米级。
4.根据权利要求1所述的一种制备含纳米纤维素的粉体的方法，其特征在于：所述纳米纤维素与所添加粉体的绝干质量比为0.1∶100～100∶100。
5.根据权利要求1所述的一种制备含纳米纤维素的粉体的方法，其特征在于：所述增塑剂为甘油、乙二醇、聚乙二醇等，单独或者两种或两种以上加入，其加入量不超过粉体的50％。
6.根据权利要求1所述的一种制备含纳米纤维素的粉体的方法，其特征在于：所述混合物加热时的温度为30℃～60℃。
7.根据权利要求1所述的一种制备含纳米纤维素的粉体的方法，其特征在于：所述干燥后含纳米纤维素的粉体可以用叶片粉碎机、研磨机等进行粉碎，粉碎后的粉末通过24、30、40、60或80等目数的筛网。
8.根据权利要求1所述的一种制备含纳米纤维素的粉体的方法，其特征在于：由该方法得到的含纳米纤维素的粉体的固含量可以控制，最高可达99％。
9.根据权利要求1所述的一种制备含纳米纤维素的粉体的方法，其特征在于：由该方法得到的含纳米纤维素的粉体分散在水中，经过机械搅拌或者超声处理后可形成均匀的分散液，该分散液的用途和用法与纯淀粉、碳酸钙、高岭土、滑石粉等相同。
10.根据权利要求1所述的一种制备含纳米纤维素的粉体的方法，其特征在于：由该方法得到的含纳米纤维素的粉体可添加到PE、PP、PLA、PBAT等树脂或橡胶中进行熔融加工，起到增强、增韧等作用。
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CN103060937A (zh) * 2013-01-29 2013-04-24 武汉大学 纤维素纳米纤维的制备方法
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CN112724512A (zh) * 2020-12-23 2021-04-30 北京理工大学 一种纳米纤维素聚丙烯母料的制备方法
CN115300663A (zh) * 2022-07-28 2022-11-08 贵州民族大学 一种止血复合膜及其制备方法

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