CN114891471A - 一种葡萄糖基非异氰酸酯聚氨酯胶黏剂及其制备方法 - Google Patents
一种葡萄糖基非异氰酸酯聚氨酯胶黏剂及其制备方法 Download PDFInfo
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Abstract
本发明属于胶黏剂制备技术领域，具体涉及一种葡萄糖基非异氰酸酯聚氨酯胶黏剂及其制备方法；以葡萄糖为原料，通过与碳酸二甲酯、二胺反应成功制备得葡萄糖基非异氰酸酯聚氨酯胶黏剂，可适用于人造板中胶合板、刨花板、纤维板等的生产。所制得的胶黏剂具有良好的胶接强度和耐水性能，性能指标满足国家标准GB/T9846.3‑2004中规定的I类胶合板要求。
Description
技术领域
本发明属于胶黏剂制备技术领域，具体涉及一种葡萄糖基非异氰酸酯聚氨酯胶黏剂及其制备方法。
背景技术
聚氨酯(PU)是木材工业中的一种重要胶黏剂，因其优异的粘接强度，较短的热压时间，优良的耐水性、耐候性，并消除了胶合制品的甲醛释放问题等优点而备受行业关注。传统的聚氨酯合成工艺多由异氰酸酯单体，如二苯甲烷二异氰酸酯(MDI)、甲苯二异氰酸酯(TDI)，与多羟基化合物聚合而成的主链含氨基甲酸酯(-NHCOO-)结构单元的一类聚合物。然而异氰酸酯价格昂贵且是一种高毒性物质，对自然环境和人体健康有很大危害，而且在其生产过程需要使用毒性更大的光气作为制备原料。而随着人们环保理念、健康安全意识的增强，尤其是发展建设绿色文明的当下，异氰酸酯的危害问题被社会极度重视。此外，异氰酸酯对使用环境中的湿汽敏感，在存储和使用过程中易与空气中水汽反应生成二氧化碳而降低产品性能。因此，有研究者研制合成了具有环境友好、性能优越的非异氰酸酯聚氨酯物质以替代传统聚氨酯，并在化工领域尤其是涂料、泡沫材料制备方面取得良好的应用效果。然而在木材胶黏剂领域，非异氰酸酯聚氨酯并不为众所周知，是一个完完全全的“新生儿”。
非异氰酸酯聚氨酯，顾名思义，即不采用异氰酸酯而合成的具有氨基甲酸酯结构的聚氨酯化合物。目前NIPU最主要的合成方法是通过环碳酸酯与脂肪族伯胺反应，其合成原理为：
目前，环碳酸脂的合成主要有两种方法，第一种是在高温高压的条件下通环氧基于CO2催化合成五元环碳酸酯，工艺比较复杂，设备要求高且存在一定的安全隐患；第二种是通过碳酸二甲酯邻羟基物质反应得到，操作流程简单，反应条件相对温和。
申请号为CN201810659091.8的专利文件公开了一种低表面张力水性聚氨酯胶粘剂及其制备方法，所述胶黏剂按重量份计包括以下原料：葡萄糖苷200-1000份、2，2-二羟甲基丙酸10-30份、多羟基化合物500-1500份、异氰酸酯500-1000份、扩链剂5-50份、消泡剂1-5份、增稠剂2-10份、杀菌剂1-5份、水1000-3000份。
申请号为CN201810389579.3的专利文件公开了一种耐热性聚氨酯胶黏剂，其原料按重量份包括：聚己内酯二元醇50-88份、甲苯二异氰酸酯22-40份、腐殖酸7-12份、葡萄糖2-9份、亲水扩链剂3-15份、椰油酸二乙醇酰胺2-5份、纳米二氧化硅1.5-3份、氧化石墨烯1-3份、空心微珠2-5份、环氧树脂3-9份、固化剂1.3-2.1份、二月桂酸二丁基锡0.5-2份、三乙胺2-3.2份、1,4-丁二醇2-3份、内交联剂2-5份、1,2-二羟甲基碳硼烷0.9-1.7份。
以上两个专利技术所涉及的原材料较多，制备方法相对较为繁琐。
文献《微波法合成葡萄糖三聚氰胺树脂胶黏剂》(陈栓虎，吴伟佳，张蕾，化学与黏合，2007.)以葡萄糖代替甲醛，在酸性条件下用微波法合成了类似于脲醛树脂的绿色环保型葡萄糖三聚氰胺树脂，得到一种不含甲醛、无毒的绿色环保型胶黏剂。其采用葡萄糖代替甲醛合成胶黏剂，但三聚氰胺树树脂胶黏剂与非异氰酸酯聚氨酯所制备的胶黏剂并不相同。
发明内容
本发明为解决上述问题，提供了一种葡萄糖基非异氰酸酯聚氨酯胶黏剂及其制备方法。
具体是通过以下技术方案来实现的：
1、一种葡萄糖基非异氰酸酯聚氨酯胶黏剂，由以下原料制成：蒸馏水20-40g、碳酸二甲酯20-40g、葡萄糖30-50g、胺20-50g、催化剂0.3-1.0g。
进一步，所述的胺为乙二胺、己二胺、二乙烯三胺、三亚乙基四胺中的任意一种。
进一步，所述的催化剂为碳酸钠、碳酸钾、碳酸氢铵中的任意一种。
2、上述葡萄糖基非异氰酸酯聚氨酯胶黏剂的制备方法，具体包括以下步骤：
在70℃水浴环境下，向配有搅拌棒、温度计和冷凝管的三口圆底烧瓶中加入碳酸二甲酯和蒸馏水，开启搅拌器，加入葡萄糖和催化剂，升温至70-90℃，保温并搅拌反应2-2.5h，向烧瓶中添加胺，继续保温反应1-1.5h，冷却出料即得到葡萄糖基非异氰酸酯聚氨酯胶黏剂。
3、上述葡萄糖基非异氰酸酯聚氨酯胶黏剂可应用于胶合板、刨花板、纤维板的制作，性能指标为：干状剪切强度大于2.3MPa，24小时冷水浸泡后湿强度大于2.5MPa，63±3℃水浸泡3小时后的湿强度在2.5MPa以上，参照国标进行“沸水4h--烘干--沸水4h--冷水1h”处理后测试胶合强度大于0.80MPa，满足国标中I类胶合板标准，且试样均无开胶现象。
综上所述，本发明的有益效果在于：本发明以葡萄糖为原料，通过与碳酸二甲酯、二胺反应成功制备得葡萄糖基非异氰酸酯聚氨酯胶黏剂，可适用于人造板中胶合板、刨花板、纤维板等的生产。所制得的胶黏剂具有良好的胶接强度和耐水性能，性能指标满足国家标准GB/T9846.3-2004中规定的I类胶合板要求。
传统聚氨酯相比，NIPU具有一些不同的结构与性能,即其结构单元氨基甲酸酯的β位碳原子上含有羟基,能与氨基甲酸酯键中的羰基形成分子内氢键六元环状的稳定结构。这弥补了传统聚氨酯中的弱键结构特点,使得NIPU具有较为优异耐化学性、耐水解性以及抗渗透性等。加之其反应过程中不使用高毒害物质原料，因而备受人们青睐，并一直是研究的热点。
本发明具体的优势在于：
1.材料来源广。葡萄糖是一种几乎普遍存在于所有动植物体内、细胞内的生物质原料，并可通过水解、酶解淀粉及纤维素得到。而纤维素在自然界中储备量极大，由此可见葡萄糖来源广、储备丰。
2.制备简单。该反应只在常压、水浴加热条件下进行，相较于现有常见的有关非异氰酸酯聚氨酯制备中需高温加压催化而言，本发明合成反应条件更温和，设备要求更低，能耗较少。
3.绿色环保。该胶黏剂主要原料来源可再生型生物质材料，符合可持续发展大局。合成中不使用甲醛、异氰酸酯等有害物质，产品绿色环保，符合当前绿色技术知识产权保护的理念倡导与政策发展。
4.作为一种生物质胶粘剂，符合绿色生态文明建设要求和人们日益增长的环保意识和消费观，并有利于降低木材工业对以石化资源为基础的合成树脂的依赖程度，为胶合板生产提供一种绿色环保型胶黏剂，对于木材工业的发展和应对石化危机问题都具有重要意义。
具体实施方式
下面对本发明的具体实施方式作进一步详细的说明，但本发明并不局限于这些实施方式，任何在本实施例基本精神上的改进或代替，仍属于本发明权利要求所要求保护的范围。
实施例1
1、一种葡萄糖基非异氰酸酯聚氨酯胶黏剂，由以下原料制成：蒸馏水30g、碳酸二甲酯30g、葡萄糖40g、己二胺35g、碳酸钠0.4g。
2、上述葡萄糖基非异氰酸酯聚氨酯胶黏剂的制备方法，具体包括以下步骤：
在70℃水浴环境下，向配有搅拌棒、温度计和冷凝管的三口圆底烧瓶中加入碳酸二甲酯和蒸馏水，开启搅拌器，加入葡萄糖和碳酸钠，升温至80℃，保温并搅拌反应2h，向烧瓶中添加己二胺，继续保温反应1h，冷却出料即得到葡萄糖基非异氰酸酯聚氨酯胶黏剂。
实施例2
1、一种葡萄糖基非异氰酸酯聚氨酯胶黏剂，由以下原料制成：蒸馏水20g、碳酸二甲酯20g、葡萄糖30g、乙二胺20g、碳酸钾0.3g。
2、上述葡萄糖基非异氰酸酯聚氨酯胶黏剂的制备方法，具体包括以下步骤：
在70℃水浴环境下，向配有搅拌棒、温度计和冷凝管的三口圆底烧瓶中加入碳酸二甲酯和蒸馏水，开启搅拌器，加入葡萄糖和碳酸钾，升温至90℃，保温并搅拌反应2h，向烧瓶中添加乙二胺，继续保温反应1.5h，冷却出料即得到葡萄糖基非异氰酸酯聚氨酯胶黏剂。
实施例3
1、一种葡萄糖基非异氰酸酯聚氨酯胶黏剂，由以下原料制成：蒸馏水40g、碳酸二甲酯40g、葡萄糖50g、二乙烯三胺50g、碳酸氢铵0.5g。
2、上述葡萄糖基非异氰酸酯聚氨酯胶黏剂的制备方法，具体包括以下步骤：
在70℃水浴环境下，向配有搅拌棒、温度计和冷凝管的三口圆底烧瓶中加入碳酸二甲酯和蒸馏水，开启搅拌器，加入葡萄糖和碳酸氢铵，升温至70℃，保温并搅拌反应2.5h，向烧瓶中添加二乙烯三胺，继续保温反应1.5h，冷却出料即得到葡萄糖基非异氰酸酯聚氨酯胶黏剂。
实验例
在不同葡萄糖、碳酸二甲酯、己二胺三种原料配比条件下合成了6组葡萄糖基非异氰酸酯聚氨酯(GNIPU)树脂胶黏剂，并用以制备三层胶合板，测试其干状剪切强度、24h冷水浸泡湿强度及3h热水(63℃)浸泡湿强度如表1所示，所制板材胶合性能高于国标GB/T9846-2015中II类板材要求(≥0.7MPa)。其中第1组物料配比条件下所制备GNIPU1胶黏剂的干状剪切强度、24h冷水浸泡湿强度、3h热水(63℃)浸泡湿强分别高达2.37MPa、2.94MPa、2.87MPa，远高于相关标准要求。
表1 GNIPU原料配比及所制备胶合板性能
Claims (7)
1.一种葡萄糖基非异氰酸酯聚氨酯胶黏剂，其特征在于，由以下原料组成：蒸馏水20-40g、碳酸二甲酯20-40g、葡萄糖30-50g、胺20-50g、催化剂0.3-1.0g。
2.如权利要求1所述的一种葡萄糖基非异氰酸酯聚氨酯胶黏剂，其特征在于，所述的胺为乙二胺、己二胺、二乙烯三胺、三亚乙基四胺中的任意一种。
3.如权利要求1所述的一种葡萄糖基非异氰酸酯聚氨酯胶黏剂，其特征在于，所述的催化剂为碳酸钠、碳酸钾、碳酸氢铵中的任意一种。
4.如权利要求1所述的葡萄糖基非异氰酸酯聚氨酯胶黏剂的制备方法，其特征在于，包括以下步骤：
在水浴环境下，将碳酸二甲酯和蒸馏水加入烧瓶中，边搅拌边加入葡萄糖和催化剂，升温反应，再加入胺继续保温反应，冷却后即得到葡萄糖基非异氰酸酯聚氨酯胶黏剂。
5.如权利要求4所述的葡萄糖基非异氰酸酯聚氨酯胶黏剂的制备方法，其特征在于，所述的升温反应，是指将温度升至70-90℃后恒温反应，反应时间2-2.5h。
6.如权利要求4所述的葡萄糖基非异氰酸酯聚氨酯胶黏剂的制备方法，其特征在于，所述的保温反应，温度为70-90℃，反应时间为1-1.5h。
7.如权利要求4所述的葡萄糖基非异氰酸酯聚氨酯胶黏剂的制备方法，其特征在于，制备方法具体为：
在70℃水浴环境下，向配有搅拌棒、温度计和冷凝管的三口圆底烧瓶中加入碳酸二甲酯和蒸馏水，开启搅拌器，加入葡萄糖和催化剂，升温至70-90℃，保温并搅拌反应2-2.5h，向烧瓶中添加胺，继续保温反应1-1.5h，冷却出料即得到葡萄糖基非异氰酸酯聚氨酯胶黏剂。
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