CN114989770B - 一种可降解的生物基聚氨酯胶粘剂组合物及其制备方法 - Google Patents
一种可降解的生物基聚氨酯胶粘剂组合物及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种聚氨酯胶粘剂组合物，其特征在于，所述的聚氨酯胶粘剂组合物包括如下质量份的组分：鞣质改性多元醇10‑20份、聚酯二醇30‑50份、异氰酸酯15‑35份和催化剂0.1‑1份，所述鞣质改性多元醇由鞣质与丙内酯通过分子间酯交换反应得到，所述聚酯二醇由聚乳酸与2,5‑呋喃二甲醇通过酯化反应制备得到。本发明的组合物经反应固化后得到的聚氨酯具有适宜的粘接强度，鞣质、聚乳酸和2,5‑呋喃二甲醇均可源自可再生的生物质，可以减轻对化石原料的依赖；崩解后的产物可在自然界中进一步降解为水、二氧化碳等物质，对环境污染少。
Description
【技术领域】
本发明属于聚氨酯胶粘剂制备技术领域，具体涉及一种可降解的生物基聚氨酯胶粘剂组合物及其制备方法。
【背景技术】
聚氨酯胶粘剂是指在分子链中含有氨基甲酸酯基团(－NHCOO－)或异氰酸酯基(－NCO)的胶粘剂。聚氨酯胶粘剂分为多异氰酸酯和聚氨酯两大类。多异氰酸酯分子链中含有异氰基(-NCO)和氨基甲酸酯基(-NH-COO-)，故聚氨酯胶粘剂表现出高度的活性与极性。与含有活泼氢的基材，如泡沫、塑料、木材、皮革、织物、纸张、陶瓷等多孔材料，以及金属、玻璃、橡胶、塑料等表面光洁的材料都有优良的化学粘接力。
聚氨酯胶粘剂作为聚氨酯大家族中的一种，其产品废弃物对环境的污染不可小觑，聚氨酯胶粘剂废料资源化回收再利用率较低，而热解法、氨解法、醇解法、碱解法等化学回收法工艺成本较高；掩埋处理则自然降解缓慢，从而导致大量固体废物的产生；焚烧处理产生HCN、CO2、CO易造成二次污染。随着聚氨酯胶粘剂产量的递增和在不同领域的大规模使用，以可再生的生物基原料为前驱物制备绿色、均质、高性能的新型聚氨酯胶粘剂产品受到了人们的广泛关注。
【发明内容】
本发明的目的在于针对现有技术中的聚氨酯胶粘剂降解难度较大的技术问题，提供了一种可在自然环境中破碎、降解且具有良好粘接强度的生物基聚氨酯胶粘剂组合物，为解决上述技术问题，本申请采用如下技术方案：
一种聚氨酯胶粘剂组合物，包括如下质量份的组分：鞣质改性多元醇10-20份、聚酯二醇30-50份、异氰酸酯15-35份和催化剂0.1-1份，所述鞣质改性多元醇由鞣质与丙内酯通过分子间酯交换反应得到，所述聚酯二醇由聚乳酸与2,5-呋喃二甲醇通过酯化反应制备得到。优选的，本发明所述聚乳酸的平均分子量为3000-5000g/mol。
进一步，本发明所述异氰酸酯选自4，4’-二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯、六亚甲基二异氰酸酯三聚体、1,4-环己烷二异氰酸酯、异佛尔酮二异氰酸酯、三甲基-1,6-六亚甲基二异氰酸酯以及甲基环己基二异氰酸酯中的一种或多种，优选为4，4`-二苯基甲烷二异氰酸酯。
进一步，本发明所述催化剂选自胺类催化剂或有机金属。优选的，所述胺类催化剂选自N,N-二甲基环己胺、双(2-二甲氨基乙基)醚、N,N,N',N'-四甲基亚烷基二胺、三乙胺、N,N-二甲基苄胺、N-乙基吗啉、N-甲基吗啉、N,N'-二乙基哌嗪、吡啶，N,N’-二甲基吡啶、双吗啉基二乙基醚中的一种或多种。优选的，所述有机金属催化剂选自二丁基锡二月桂酸酯、辛酸亚锡以及钛酸四丁酯中的一种或多种。
进一步的，本发明的鞣质是一种多酚类化合物，结构复杂，示例性结构可表示为R1(OH)n，所述R1为鞣质中除酚羟基外的基团，n表示酚羟基的平均数目，示例性结构也可表示为：
以上仅为本申请的示例性化合物，本发明的鞣质可来源于天然产物，市售鞣质(混合物)或植物提取的鞣质也在本申请的保护范围之内。
进一步的，本发明所述鞣质与丙内酯在碱性催化剂的作用下在惰性有机溶剂中进行反应制备得到。优选的，所述碱性催化剂选自三乙胺、二异丙基乙基胺、吡啶、DBU、DMAP中的一种或多种。优选的，所述有机溶剂包括甲苯、二甲苯、二氯甲烷、氯仿、四氢呋喃、乙醚、DMF、DMSO、丙酮中的一种或几种。优选的，反应温度为10-40℃，进一步优选为20-30℃，最优选为室温。所述的反应可表示为：
其中，n为酚羟基的平均数目，所述m≤n，且m大于2。所述鞣质、碱性催化剂、丙内酯的质量比为1：(0.4-0.6)：(0.8-1.2)，反应结束后通过减压蒸馏出去过量的溶剂、碱性催化剂和过量的丙内酯以及其他杂质；≤表示小于或者等于。
进一步的，本发明所述的聚酯二醇的制备反应方程式可表示为：
本发明还提供了一种生物基聚氨酯胶粘剂的制备方法，该方法包括以下步骤：将所述鞣质改性多元醇、聚酯二醇和异氰酸酯加入反应容器，加入干燥的惰性有机溶剂，通干燥的惰性气体排除体系内的空气，加入催化剂在100-140℃的温度下搅拌反应；反应结束后减压蒸馏除去溶剂、过量的反应物和其他可蒸除的杂质。
本发明具有以下有益效果：
(1)本发明的鞣质改性多元醇还有多个醇结构，在一定的条件下可形成“枝化”的聚氨酯胶粘剂，客观上起到了一定的交联作用，固化后得到的产物具有适宜的粘接强度。
(2)本发明制备得到的鞣质改性多元醇中的酚酯基易于水解，随着酚酯基的水解，暴露的酚羟基在土壤中可提供弱酸性的局部微环境，有利于土壤微生物的生长，土壤微生物的生长可进一步提供可供酯基、酰胺基水解的酶；固化后得到的产物可以在有机质存在的土壤中更易于崩解、降解为粉末状结构，增加了其与外部环境接触的比表面积；崩解后的粉末状结构可在自然界中进一步降解，对环境污染少。
(3)本发明的鞣质、聚乳酸和2,5-呋喃二甲醇均可源自可再生的生物质，可以减轻对化石原料的依赖。
【具体实施方式】
为便于更好地理解本发明，通过以下实例加以说明，这些实例属于本发明的保护范围，但不限制本发明的保护范围。下面通过更具体实施例对本发明进行说明。
实施例1：鞣质改性多元醇的制备
将市售食品级鞣质100g加入圆底烧瓶，然后加入200ml干燥的二氯甲烷、50g三乙胺和100g丙内酯，加毕在25-35℃的温度下搅拌反应12小时，使用旋转蒸发仪蒸除溶剂和三乙胺，然后减压蒸馏除去过量的丙内酯，获得157克产物。干燥，粉碎备用。
实施例2：聚酯二醇的制备
将100g平均分子量为4000g/mol的聚乳酸和200ml干燥的DMSO加入圆底烧瓶，加入2个当量的2,5-呋喃二甲醇和1g钛酸四丁酯，加毕在180-190℃的温度下搅拌反应6小时；将所述混合物转入分液漏斗，加入1000ml乙醚，混合均匀，使用250ml水洗涤3次，用100ml饱和食盐水洗涤1次，无水硫酸钠干燥，使用旋转蒸发仪蒸除溶剂，减压蒸馏除去过量的2,5-呋喃二甲醇和其他杂质。干燥，粉碎备用。
实施例3：聚氨酯胶粘剂的制备
称取10质量份的实施例1制备得到的鞣质改性多元醇，30质量份实施例2制备得到的聚酯二醇，40质量份4，4’-二苯基甲烷二异氰酸酯，置入反应容器，加入100ml干燥的甲苯和0.8质量份的双吗啉基二乙基醚，通干燥的氮气排除体系内的空气，搅拌下加热回流反应2.5小时；反应结束后减压蒸馏除去溶剂和其他杂质。
实施例4：聚氨酯胶粘剂的制备
称取15质量份的实施例1制备得到的鞣质改性多元醇，40质量份实施例2制备得到的聚酯二醇，50质量份4，4’-二苯基甲烷二异氰酸酯，置入反应容器，加入100ml干燥的甲苯和1质量份的二丁基锡二月桂酸酯，通干燥的氮气排除体系内的空气，搅拌下加热回流反应3小时；反应结束后减压蒸馏除去溶剂和其他杂质。
实施例5：聚氨酯胶粘剂的制备
称取20质量份的实施例1制备得到的鞣质改性多元醇，50质量份实施例2制备得到的聚酯二醇，60质量份4，4’-二苯基甲烷二异氰酸酯，置入反应容器，加入100ml干燥的二甲苯和1.2质量份的双吗啉基二乙基醚，通干燥的氮气排除体系内的空气，搅拌下加热回流反应3小时；反应结束后减压蒸馏除去溶剂和其他杂质。
对比例1：物料比和制备方法参照实施例3，不同之处在于，使用淀粉作为多元醇替换鞣质改性多元醇。
对比例2：物料比和制备方法参照实施例3，不同之处在于，使用由聚乳酸与乙二醇通过酯化反应制备得到产物替换替换本发明的聚酯二醇。
测试例1：聚氨酯胶粘剂的粘接性能测试
对实施例3-5和对比例1-2制得样品的拉伸剪切强度进行测试，固化后的拉伸剪切强度按照标准GB/T7124-2008在25℃进行测试，拉伸速度为10mm/min，测试使用铝合金作为测试样件。
测试例2：聚氨酯胶粘剂的降解性能测试
将实施例3-5制备得到的聚氨酯胶粘剂埋在江苏省中部环境的30厘米深的田园土中，检测其剩余质量随时间的变化：
以上内容不能认定本发明具体实施只局限于这些说明，对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思前提下，还可以做出若干简单推演或替换，都应当视为属于本发明由所提交的权利要求书确定的专利保护范围。
Claims (9)
1.一种聚氨酯胶粘剂组合物，其特征在于,所述聚氨酯胶粘剂组合物包括如下质量份的组分：鞣质改性多元醇10-20份、聚酯二醇30-50份、异氰酸酯15-35份和催化剂0.1-1份，所述鞣质改性多元醇由鞣质与丙内酯通过分子间酯交换反应得到，所述聚酯二醇由聚乳酸与2,5-呋喃二甲醇通过酯化反应制备得到；所述异氰酸酯选自4，4’-二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯、六亚甲基二异氰酸酯三聚体、1,4-环己烷二异氰酸酯、异佛尔酮二异氰酸酯、三甲基-1,6-六亚甲基二异氰酸酯以及甲基环己基二异氰酸酯中的一种或多种。
2.根据权利要求1所述的聚氨酯胶粘剂组合物，其特征在于，所述聚乳酸的平均分子量为3000-5000g/mol。
3.根据权利要求1所述的聚氨酯胶粘剂组合物，其特征在于，所述催化剂选自胺类催化剂或有机金属催化剂。
4.根据权利要求3所述的聚氨酯胶粘剂组合物，其特征在于，所述胺类催化剂选自N,N-二甲基环己胺、双(2-二甲氨基乙基)醚、N,N,N',N'-四甲基亚烷基二胺、三乙胺、N,N-二甲基苄胺、N-乙基吗啉、N-甲基吗啉、N,N'-二乙基哌嗪、吡啶，N,N’-二甲基吡啶、双吗啉基二乙基醚中的一种或多种；所述有机金属催化剂选自二丁基锡二月桂酸酯、辛酸亚锡以及钛酸四丁酯中的一种或多种。
5.根据权利要求1所述的聚氨酯胶粘剂组合物，其特征在于，所述鞣质的结构为R1(OH)n，所述鞣质改性多元醇结构为：
6.根据权利要求1所述的聚氨酯胶粘剂组合物，其特征在于，所述鞣质改性多元醇的制备方法包括以下步骤：鞣质与丙内酯在碱性催化剂的作用下在惰性有机溶剂中通过分子间酯交换反应得到。
7.根据权利要求6所述的聚氨酯胶粘剂组合物，其特征在于，所述碱性催化剂选自三乙胺、二异丙基乙基胺、吡啶、DBU、DMAP中的一种或多种；所述惰性有机溶剂包括甲苯、二甲苯、二氯甲烷、氯仿、四氢呋喃、乙醚、DMF、DMSO、丙酮中的一种或几种；反应温度为10-40℃。
8.根据权利要求1所述的聚氨酯胶粘剂组合物，其特征在于，所述聚酯二醇的制备方法的反应方程式如下：
9.一种权利要求1-8任一项所述聚氨酯胶粘剂组合物的制备方法，该方法包括以下步骤：将所述鞣质改性多元醇、聚酯二醇和异氰酸酯加入反应容器，加入干燥的惰性有机溶剂，通干燥的惰性气体排除体系内的空气，加入催化剂在100-140℃的温度下搅拌反应；反应结束后减压蒸馏除去溶剂、过量的反应物和其他可蒸除的杂质。
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