CN114085517A - 一种木质素改性的水性聚氨酯薄膜及其制备方法 - Google Patents
一种木质素改性的水性聚氨酯薄膜及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种木质素改性的水性聚氨酯薄膜及其制备方法，属于水性聚氨酯材料的制备技术领域。所述水性聚氨酯薄膜包括低聚物多元醇、多元异氰酸酯、亲水性扩链剂、肟基化合物、多元胺化合物、酸类化合物、有机溶剂和木质素。本发明将木质素以水相原位填加的方式引入到合成的聚氨酯乳液中，实现了木质素在水性聚氨酯体系中的原位纳米分散效果，加热固化得到水性聚氨酯薄膜，极大地提高了力学性能，并有效保留了自修复功能，提高了材料的循环使用性能。
Description
技术领域
本发明涉及一种木质素改性的水性聚氨酯薄膜及其制备方法，属于水性聚氨酯材料的制备技术领域。
背景技术
近年来，随着人们环保意识的提高，材料的安全问题越来越受到人们的广泛关注。水性聚氨酯材料是以水作为分散介质，具有环保、安全可靠，易储存等优点目前广泛应用于涂料、胶粘剂、织物涂层与整理剂、皮革涂饰剂、纸张和纤维表面处理剂等领域。普通的水性聚氨酯材料在使用的过程中，其表面和内部会不可避免地出现损伤，导致材料的性能变差，使用寿命减少，而且强度不是很高，耐水解性能也较差。现在大多数具有自修复功能的水性聚氨酯多采用石油化工产品为原料，价格昂贵且不可再生。因此，寻找合适的方法实现水性聚氨酯自修复和提高耐水解性及力学性能是现实而重要的问题。
国内外研究人员主要通过在聚氨酯中接枝硅、环氧树脂、聚丙烯酸树脂、有机氟等方法来提高其性能。CN102093530A通过引入有机硅来改性水性聚氨酯，采用物理共混的方法，提高耐水解性，耐高温性，但是有机硅和聚氨酯链段的相容性不好，常规分散效果不好，需要大量的有机溶剂，而且，这些改性实验材料大多来自石油化工资源，价格昂贵且不可再生。CN109337043A公开了一种无溶剂性自修复水性聚氨酯的制备方法，通过硫辛酸和碳碳双键封端制备聚氨酯预聚体，该方法虽然无溶剂，绿色环保，但是也同样存在原价贵且强度低的特点。
与石化资源相比，生物质资源丰富，具有无毒、可再生、价格低廉、生物相容性好等优点。利用天然可再生生物质对高分子材料进行改性已成为研究热点，木质素作为一种来源于植物的天然高分子聚合物，从植物中提取，来源广泛，价格便宜。目前献有对于水性聚氨酯/木质素复合材料的研究报道，Yuanbin Lai等人报道了一种木质素基水性聚氨酯乳液的制备方法(Industrial Crops&Products，2021，170，113739)，然而上述制备方法虽然应用了生物基材料木质素，但是其并没有自修复功能，并且力学强度也没有有效地提高。
发明内容
本发明针对上述问题，提供了一种木质素改性的水性聚氨酯乳液及其制备方法，本发明将木质素以水相原位填加的方式引入到本发明所合成的聚氨酯乳液中，实现了木质素在水性聚氨酯体系中的原位纳米分散效果，加热固化得到水性聚氨酯薄膜，极大地提高了力学性能，并有效保留了自修复功能，提高了材料的循环使用性能。本发明的技术方案如下：
一种木质素改性的水性聚氨酯薄膜，包括以下质量份的原料：
低聚物多元醇100份；
多元异氰酸酯50-100份；
亲水性扩链剂5-15份；
肟基化合物20-30份；
多元胺化合物5-15份；
酸类化合物5-15份；
有机溶剂30-100份；
木质素10-20份。
优选的，所述低聚物多元醇包括但不限于聚醚二元醇、聚酯二元醇、聚己内脂二元醇、聚碳酸酯二元醇、聚己二酸乙二醇或聚四氢呋喃醚中的至少一种；优选的，所述低聚物多元醇的羟值为40-80mgKOH/g，更优选羟值范围为50-60mgKOH/g。
优选的，本发明中所述的多元异氰酸酯可广泛取自市面上各种可以满足水性聚氨酯生产的多异氰酸酯产品；所述多异氰酸酯包括但不限于甲苯二异氰酸酯、异佛尔酮二异氰酸酯、甲烷二异氰酸酯、1,6-六亚甲基二异氰酸酯或二环己基甲烷二异氰酸酯中的至少一种。
优选的，所述亲水性扩链剂选自2,2-二羟甲基丁酸、2,2-二羟甲基丙酸，2,2-二羟甲基丙酸铵，N甲基二乙醇胺，N乙基二乙醇胺，油酸二乙醇酰胺中的至少一种。
优选的，所述肟基化合物选自丁二酮肟、丁醛肟或环己酮肟、对苯醌二肟中的至少一种。
优选的，所述多元胺选自三乙胺、乙二胺、1,4-丁二胺、1,6-己二胺或1,3-丙二胺中的至少一种；更优选的，所述多元胺为三乙胺或乙二胺。
优选的，所述酸类化合物选自硫酸、盐酸、磷酸、硝酸、甲酸、乙酸、乙二酸、苯甲酸中的至少一种。
优选的，所述有机溶剂为丙酮或丁酮。
优选的，所述木质素选自碱木质素、脱碱木质素、木质素磺酸钠或木质素磺酸钙中的至少一种。
进一步的，上述木质素改性的水性聚氨酯薄膜的制备方法，步骤如下：
将多元异氰酸酯和低聚物多元醇加入到反应容器中进行搅拌，并逐渐升温到80-90℃，反应1-3小时后加入亲水性扩链剂，1-2小时后加入肟基化合物，反应一个小时后每隔半小时加入10-15份有机溶剂，保持反应温度在80-90℃，反应3-5小时后降温至50-60℃，加入多元胺或酸类化合物，反应0.5-1小时，倒出前加入丙酮降低粘度，后将反应物从反应容器中倒出，加入去离子水在高速分散机下进行乳化，减压蒸馏除去丙酮，最后加入木质素再进行高速机械混合，即得到稳定的高强度自修复特性的改性水性聚氨酯乳液；在玻璃板上涂抹自修复水性聚氨酯乳液并固化，得到自修复水性聚氨酯薄膜。本发明与现有技术相比具有以下优点：
实现了所合成的水性聚氨酯与木质素的原位纳米复合，整个过程不需外加高污染有机溶剂，不需高能耗剪切混合设备，即可以实现极佳的水相纳米分散，绿色环保；本发明所制备的木质素/水性聚氨酯体系，即可实质性提高水性聚氨酯薄膜的机械强度和耐水解性能，又同时有效保留了水性聚氨酯薄膜的自修复效果，提高了循环利用能力；此外，木质素的引入显著提升了材料抗紫外线吸收能力，延长了使用稳定性。
附图说明
图1为未加木质素的水性聚氨酯薄膜与添加质量分数3％木质素的水性聚氨酯薄膜强度对比。添加木质素后可有效提高薄膜的最高强度；
图2为未加木质素的水性聚氨酯薄膜与添加质量分数3％木质素的聚氨酯薄膜在65℃下浸泡20小时后的强度对比，结果表明，添加木质素后强度几乎不变，说明可有效提高其耐水解性；
图3为完全切断的聚氨酯薄膜在140℃下修复1小时后与完好的聚氨酯薄膜强度对比，其强度达到初始样品的80％以上，说明其具有良好的修复能力；
图4为聚氨酯薄膜被切成毫米尺寸碎片，在145℃下使用10MPa的压力加热10min实现材料重塑后的相片，证明材料具有良好的循环使用特性。
具体实施方式
下面结合具体实施例来进一步描述本发明，本发明的优点和特点将会随着描述而更为清楚。但实施例仅是范例性的，并不对本发明的范围构成任何限制。本领域技术人员应该理解的是，在不偏离本发明的精神和范围下可以对本发明技术方案的细节和形式进行修改或替换，但这些修改和替换均落入本发明的保护范围内。
实施例1：一种木质素改性的水性聚氨酯薄膜及其制备方法
将19.78g1,6-六亚甲基二异氰酸酯，2.62g异佛尔酮二异氰酸酯和30g分子量为2000的聚己内酯多元醇加入到三口瓶中，开动机械搅拌，并逐渐升温到85℃，反应1小时后加入2.15g油酸二乙醇酰胺，1小时后加入7.67g对苯醌二肟，一小时后每隔半小时加入5mL丙酮，保持反应温度在85℃，反应3小时后降温至60℃，待温度降至60℃加入1.75g盐酸，反应0.5小时后，倒出加入150mL去离子水在高速分散机下进行乳化，减压蒸馏除去有机溶剂，最后保留一半未改性乳液，一半乳液加入0.88g碱木质素再进行高速机械混合，即得到稳定的高强度自修复特性的改性水性聚氨酯乳液。在玻璃板上涂抹自修复水性聚氨酯乳液并在烘箱中105℃固化2小时，得到自修复水性聚氨酯薄膜。
实施例2：一种木质素改性的水性聚氨酯薄膜及其制备方法
将15.32g 1,6-六亚甲基二异氰酸酯和3.75g甲苯二异氰酸酯，24g分子量为2000的聚四氢呋喃醚多元醇加入到三口瓶中，开动机械搅拌，并逐渐升温到85℃，反应1小时后加入2.65g油酸二乙醇酰胺，1小时后加入7.67g对苯醌二肟，一小时后每隔半小时加入5mL丙酮，保持反应温度在85℃，反应3小时后降温至60℃，待温度降至60℃加入1.50g盐酸，反应0.5小时后，倒出加入150mL去离子水在高速分散机下进行乳化，减压蒸馏除去有机溶剂，最后保留一半未改性乳液，一半乳液加入0.88g碱木质素再进行高速机械混合，即得到稳定的高强度自修复特性的改性水性聚氨酯乳液。在玻璃板上涂抹自修复水性聚氨酯乳液并在烘箱中105℃固化2小时，得到自修复水性聚氨酯薄膜。
实施例3：一种木质素改性的水性聚氨酯薄膜及其制备方法
将19.78g异佛尔酮二异氰酸酯，3.21g甲苯二异氰酸酯和26g分子量为2000的聚碳酸酯多元醇加入到三口瓶中，开动机械搅拌，并逐渐升温到85℃，反应1小时后加入2.20g油酸二乙醇酰胺，1小时后加入5.77g对苯醌二肟，一小时后每隔半小时加入5mL丙酮，保持反应温度在85℃，反应3小时后降温至60℃，待温度降至60℃加入1.85g盐酸，反应0.5小时后，倒出加入150mL去离子水在高速分散机下进行乳化，减压蒸馏除去有机溶剂，最后保留一半未改性乳液，一半乳液加入0.88g碱木质素再进行高速机械混合，即得到稳定的高强度自修复特性的改性水性聚氨酯乳液。在玻璃板上涂抹自修复水性聚氨酯乳液并在烘箱中105℃固化2小时，得到自修复水性聚氨酯薄膜。
实施例4：一种木质素改性的水性聚氨酯薄膜及其制备方法
将14.78g异佛尔酮二异氰酸酯和4.34g甲苯二异氰酸酯和26g分子量为2000的聚四氢呋喃醚多元醇加入到三口瓶中，开动机械搅拌，并逐渐升温到85℃，反应1小时后加入2.8g油酸二乙醇酰胺，1小时后加入6.67g对苯醌二肟，一小时后每隔半小时加入5mL丙酮，保持反应温度在85℃，反应3小时后降温至60℃，待温度降至60℃加入3.55g盐酸，反应0.5小时后，倒出加入150mL去离子水在高速分散机下进行乳化，减压蒸馏除去有机溶剂，最后保留一半未改性乳液，一半乳液加入0.88g碱木质素再进行高速机械混合，即得到稳定的高强度自修复特性的改性水性聚氨酯乳液。在玻璃板上涂抹自修复水性聚氨酯乳液并在烘箱中105℃固化2小时，得到自修复水性聚氨酯薄膜。
试验例：对实施例1中所制备的自修复水性聚氨酯薄膜进行了强度性能测试，用裁刀将薄膜裁成哑铃型，在质构仪上进行拉伸测试，测试结果如图1所示。对实施例2中所制备的自修复水性聚氨酯薄膜进行了耐水解性能测试，未加木质素的水性聚氨酯薄膜与添加质量分数3％木质素的聚氨酯薄膜在65℃下浸泡20小时后，在质构仪上进行强度测试，测试结果如图2所示。对实施例3所制备的自修复水性聚氨酯薄膜进行了自修复实验，实验步骤为：用干净刀片用刀片将未改性水性聚氨酯薄膜切断，将被切断的水性聚氨酯薄膜切口对齐，放入150℃烘箱中，于20min后取出。质构仪测修复前后强度，结果如图3所示。对实施例4所制备的自修复水性聚氨酯薄膜进行了再循环性能测试，实验步骤为：将未改性薄膜剪成碎片，在10MPa，145℃下10分钟后查看重塑效果，结果如图4所示。
Claims (10)
1.一种木质素改性的水性聚氨酯薄膜，其特征在于，所述水性聚氨酯薄膜包括以下质量份的原料：
低聚物多元醇100份；
多元异氰酸酯50-100份；
亲水性扩链剂5-15份；
肟基化合物20-30份；
多元胺化合物5-15份；
酸类化合物5-15份；
有机溶剂30-100份；
木质素10-20份。
2.根据权利要求1所述的水性聚氨酯薄膜，其特征在于，所述低聚物多元醇包括但不限于聚醚二元醇、聚酯二元醇、聚己内脂二元醇、聚碳酸酯二元醇、聚己二酸乙二醇或聚四氢呋喃醚中的至少一种。
3.根据权利要求1所述的水性聚氨酯薄膜，其特征在于，所述低聚物多元醇的羟值为40-80mgKOH/g；优选的，所述低聚物多元醇的羟值为50-60mgKOH/g。
4.根据权利要求1所述的水性聚氨酯薄膜，其特征在于，所述多异氰酸酯包括但不限于甲苯二异氰酸酯、异佛尔酮二异氰酸酯、甲烷二异氰酸酯、1,6-六亚甲基二异氰酸酯或二环己基甲烷二异氰酸酯中的至少一种。
5.根据权利要求1所述的水性聚氨酯薄膜，其特征在于，所述亲水性扩链剂选自2,2-二羟甲基丁酸、2,2-二羟甲基丙酸，2,2-二羟甲基丙酸铵，N甲基二乙醇胺，N乙基二乙醇胺，油酸二乙醇酰胺中的至少一种。
6.根据权利要求1所述的水性聚氨酯薄膜，其特征在于，所述肟基化合物选自丁二酮肟、丁醛肟或环己酮肟、对苯醌二肟中的至少一种。
7.根据权利要求1所述的水性聚氨酯薄膜，其特征在于，所述多元胺选自三乙胺、乙二胺、1,4-丁二胺、1,6-己二胺或1,3-丙二胺中的至少一种；更优选的，所述多元胺为三乙胺或乙二胺。
8.根据权利要求1所述的水性聚氨酯薄膜，其特征在于，所述酸类化合物选自硫酸、盐酸、磷酸、硝酸、甲酸、乙酸、乙二酸、苯甲酸中的至少一种；所述有机溶剂为丙酮或丁酮。
9.根据权利要求1所述的水性聚氨酯薄膜，其特征在于，所述木质素选自碱木质素、脱碱木质素、木质素磺酸钠或木质素磺酸钙中的至少一种。
10.如上述1-9任一项所述木质素改性的水性聚氨酯薄膜的制备方法，步骤如下：
将多元异氰酸酯和低聚物多元醇加入到反应容器中进行搅拌，并逐渐升温到80-90℃，反应1-3小时后加入亲水性扩链剂，1-2小时后加入肟基化合物，反应一个小时后每隔半小时加入10-15份有机溶剂，保持反应温度在80-90℃，反应3-5小时后降温至50-60℃，加入多元胺或酸类化合物，反应0.5-1小时，倒出前加入丙酮降低粘度，后将反应物从反应容器中倒出，加入去离子水在高速分散机下进行乳化，减压蒸馏除去丙酮，最后加入木质素再进行高速机械混合，即得到稳定的高强度自修复特性的改性水性聚氨酯乳液；在玻璃板上涂抹自修复水性聚氨酯乳液并固化，得到自修复水性聚氨酯薄膜。
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| CN115386063B (zh) * | 2022-09-19 | 2024-02-27 | 广东拓普合成科技股份有限公司 | 一种木质素基水性聚氨酯及其制备方法 |
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