CN109988537B - 一种淀粉改性聚氨酯胶黏剂及其制备方法 - Google Patents
一种淀粉改性聚氨酯胶黏剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种淀粉改性聚氨酯胶黏剂及其制备方法，涉及胶粘剂产品制备技术领域，由如下重量份数的原料制成：二异氰酸酯30‑60份、聚醚多元醇100‑400份、淀粉100‑600份、小分子扩链剂2‑10份、消泡剂1‑5份、催化剂2‑10份、填充剂100‑500份、环保增塑剂100‑300份、有机溶剂10‑40份；本发明使用组合型的聚醚多元醇与填充剂、氧化玉米淀粉混合均匀，再缓慢滴加异氰酸酯，控制反应温度不超过90℃，再加入小分子扩链剂，反应合成带有填充物的淀粉改性聚氨酯的预聚体大分子，最后加入催化剂、消泡剂和有机溶剂。
Description
技术领域：
本发明涉及胶粘剂产品制备技术领域，具体涉及一种淀粉改性聚氨酯胶黏剂及其制备方法。
背景技术：
根据有关资料显示，2006-2015年，我国人造板工业用胶黏剂消耗量年平均增长率为10.1％。2015年我国木材胶黏剂87.8％用于人造板工业，主要品种为脲醛树脂胶(含改性)和酚醛树脂胶。脲醛树脂胶(含改性)消耗量约为1392万t，占人造板工业胶黏剂用量近91％。酚醛树脂胶消耗量约为138万t，约占人造板工业胶黏剂用量的9％。
聚氨酯胶粘剂是指在分子链中含有氨基甲酸酯基团(－NHCOO－)的高分子材料，具有优异的性能。聚氨酯胶黏剂已经成为继脲醛树脂(UF)、酚醛树脂(PF)、三聚氰胺-甲醛树脂(MF)和聚醋酸乙烯乳液(PVAc)之后的又一重要木材工业用胶黏剂。
聚氨酯胶黏剂与木材的水分和羟基反应，固化交联而形成稳定的化学结构。该类型胶黏剂具有力学强度高、绝缘、耐热、耐水、耐腐蚀性高、用于木材工业中使得产品具有尺寸稳定性好、不含甲醛等优点。目前由于价格昂贵，主要用于高端板材加工领域。目前行业开发者正通过引入价格较低的改性材料来降低材料成本，使聚氨酯胶黏剂成本降低而获得更快的推广使用。
淀粉胶粘剂是近年来采用较多的一种瓦楞纸箱生产用胶粘剂，主要原料是玉米淀粉或木薯淀粉。由于生产淀粉胶粘剂原料来源广、价格低、粘接性能较好，因此推广使用较快。
由于原淀粉中含有羟基，通过在聚氨酯预聚阶段引入原淀粉，淀粉中的羟基与异氰酸根进行接枝共聚反应，淀粉易于获得且成本较低，可制备得到一种聚氨酯-淀粉胶黏剂。该胶黏剂成本较低，且同时具备了聚氨酯高强度、高粘结性能的特点，可以应用于木材胶黏剂领域，以替代传统的“三醛”胶黏剂。
发明内容：
本发明所要解决的技术问题在于提供一种淀粉改性聚氨酯胶黏剂，利用淀粉所含羟基与-NCO发生接枝反应来对聚氨酯进行改性，显著改善所制胶黏剂的使用性能。
本发明所要解决的技术问题采用以下的技术方案来实现：
一种淀粉改性聚氨酯胶黏剂，由如下重量份数的原料制成：
二异氰酸酯30-60份、聚醚多元醇100-400份、淀粉100-600份、小分子扩链剂2-10份、消泡剂1-5份、催化剂2-10份、填充剂100-500份、环保增塑剂100-300份、有机溶剂10-40份。
所述二异氰酸酯选自异佛尔酮二异氰酸酯IPDI、二苯基甲烷二异氰酸酯MDI、1,6-己二异氰酸酯HDI、苯二亚甲基二异氰酸酯XDI、萘-1,5-二异氰酸酯NDI中的一种或两种。
所述聚醚多元醇选自官能度为2～4、数均分子量为1000～5000的聚醚多元醇中的两种。
所述淀粉为氧化玉米淀粉。
所述小分子扩链剂选自新戊二醇、三羟甲基丙烷、二羟甲基丙酸中的一种。
所述消泡剂为聚醚改性硅氧烷共聚合物。
所述催化剂选自有机金属化合物类催化剂，优选辛酸亚锡或二月桂酸二丁基锡。
所述填充剂选自滑石粉、高岭土、碳酸钙、白炭黑中的一种或几种。
所述环保增塑剂选自长链氯化石蜡、氯代棕榈油甲酯、环氧大豆油中的一种或两种。
所述有机溶剂选自碳酸二甲酯、丙酮中的一种。
上述淀粉改性聚氨酯胶黏剂的制备方法，包括以下步骤：
向反应釜中依次加入聚醚多元醇、淀粉、填充剂和环保增塑剂，边搅拌边升温至100-110℃真空脱水，真空度控制在0.07-0.09MPa；脱水结束后降温至70-80℃，并缓慢加入二异氰酸酯，控制温度不超过90℃，滴加完毕后保温反应；再加入小分子扩链剂保温反应；然后加入催化剂和消泡剂，最后加入有机溶剂，搅拌均匀，继续降温至50-60℃，出料，密封保存。
本发明的有益效果是：
(1)本发明使用组合型的聚醚多元醇与填充剂、氧化玉米淀粉混合均匀，再缓慢滴加异氰酸酯，控制反应温度不超过90℃，再加入小分子扩链剂，反应合成带有填充物的淀粉改性聚氨酯的预聚体大分子，最后加入催化剂、消泡剂和有机溶剂，催化剂可以加快胶黏剂在使用时的固化速度，消泡剂可以消除固化成膜时的气泡，有机溶剂适当降低体系粘度，同时设计使体系的-NCO/-OH摩尔比为1.3-2.5。
(2)氧化玉米淀粉的结构中含有羟基、羰基和羧基，羟基可与-NCO接枝反应，羧基可提升与基材的附着力，同时氧化玉米淀粉的加入极大降低了聚氨酯胶黏剂的制备成本。
具体实施方式：
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合具体实施例，进一步阐述本发明。
实施例1
配料表如下：
向反应釜中依次加入聚醚二元醇2000、聚醚三元醇3000、氧化玉米淀粉、滑石粉和长链氯化石蜡，边搅拌边升温至110℃真空脱水，真空脱水2h，真空度控制在0.08MPa；脱水结束后降温至80℃，并缓慢加入二异氰酸酯MDI，时间控制在2h，控制温度不超过90℃，滴加完毕后保温反应3h；再加入新戊二醇保温反应3h；然后加入二月桂酸二丁基锡和聚醚改性硅氧烷共聚合物，最后加入丙酮，搅拌均匀，继续降温至50℃，出料，密封保存。
实施例2
配料表如下：
| 原料 | 用量/g |
| 聚醚三元醇3000 | 120 |
| 聚醚二元醇4000 | 80 |
| 氯代棕榈油甲酯 | 140 |
| 重质碳酸钙 | 200 |
| 氧化玉米淀粉 | 300 |
| 二异氰酸酯MDI | 48 |
| 二羟甲基丙酸 | 2 |
| 二月桂酸二丁基锡 | 1 |
| 聚醚改性硅氧烷共聚合物 | 1 |
| 碳酸二甲酯 | 15 |
向反应釜中依次加入聚醚三元醇3000、聚醚二元醇4000、氧化玉米淀粉、重质碳酸钙和氯代棕榈油甲酯，边搅拌边升温至110℃真空脱水，真空脱水2h，真空度控制在0.08MPa；脱水结束后降温至80℃，并缓慢加入二异氰酸酯MDI，时间控制在2h，控制温度不超过90℃，滴加完毕后保温反应3h；再加入二羟甲基丙酸保温反应3h；然后加入二月桂酸二丁基锡和聚醚改性硅氧烷共聚合物，最后加入碳酸二甲酯，搅拌均匀，继续降温至50℃，出料，密封保存。
实施例3
配料表如下：
| 原料 | 用量/g |
| 聚醚三元醇5000 | 100 |
| 聚醚二元醇4000 | 120 |
| 环氧大豆油 | 180 |
| 高岭土 | 150 |
| 氧化玉米淀粉 | 350 |
| 二异氰酸酯IPDI | 42 |
| 二羟甲基丙酸 | 4 |
| 二月桂酸二丁基锡 | 3 |
| 聚醚改性硅氧烷共聚合物 | 2 |
| 碳酸二甲酯 | 20 |
向反应釜中依次加入聚醚三元醇5000、聚醚二元醇4000、氧化玉米淀粉、高岭土和环氧大豆油，边搅拌边升温至110℃真空脱水，真空脱水2h，真空度控制在0.08MPa；脱水结束后降温至80℃，并缓慢加入二异氰酸酯IPDI，时间控制在2h，控制温度不超过90℃，滴加完毕后保温反应3h；再加入二羟甲基丙酸保温反应3h；然后加入二月桂酸二丁基锡和聚醚改性硅氧烷共聚合物，最后加入碳酸二甲酯，搅拌均匀，继续降温至50℃，出料，密封保存。
实施例4
配料表如下：
向反应釜中依次加入聚醚三元醇5000、聚醚三元醇3000、氧化玉米淀粉、重质碳酸钙和长链氯化石蜡，边搅拌边升温至110℃真空脱水，真空脱水2h，真空度控制在0.08MPa；脱水结束后降温至80℃，并缓慢加入二异氰酸酯IPDI，时间控制在2h，控制温度不超过90℃，滴加完毕后保温反应3h；再加入三羟基丙烷保温反应3h；然后加入二月桂酸二丁基锡和聚醚改性硅氧烷共聚合物，最后加入碳酸二甲酯，搅拌均匀，继续降温至50℃，出料，密封保存。
对照例1
以实施例4为对照，设置以等量玉米淀粉替代氧化玉米淀粉的对照例1，其余操作完全相同。
对照例2
以实施例4为对照，设置不添加氧化玉米淀粉的对照例2，其余操作完全相同。
对照例3
以实施例4为对照，设置不添加催化剂的对照例3，其余操作完全相同。
分别利用实施例1-4、对照例1-3制备胶黏剂，对照例3因不加催化剂，所制胶黏剂在室温下固化十分缓慢，24h后仍未固化，因此不评价其使用性能。
依照国标GB/T 17657-2013制作胶合板试件并测定胶合强度，测定结果如表1所示。
表1所制胶黏剂的胶合性能
由表1可知，通过氧化玉米淀粉的添加能够显著增强所制胶黏剂的胶合性能，并且常规玉米淀粉的增强效果远不如氧化玉米淀粉，同时实施例1-4所制胶黏剂对木材的胶合性能明显优于目前现有胶黏剂。
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (8)
1.一种淀粉改性聚氨酯胶黏剂，其特征在于：由如下重量份数的原料制成：
二异氰酸酯 30-60份、聚醚多元醇 100-400份、淀粉 100-600份、小分子扩链剂 2-10份、消泡剂 1-5份、催化剂 2-10份、填充剂 100-500份、环保增塑剂 100-300份、有机溶剂10-40份；
所述淀粉为氧化玉米淀粉；
其制备方法包括以下步骤：
向反应釜中依次加入聚醚多元醇、淀粉、填充剂和环保增塑剂，边搅拌边升温至100-110℃真空脱水，真空度控制在0.07-0.09 MPa；脱水结束后降温至70-80℃，并缓慢加入二异氰酸酯，控制温度不超过90℃，滴加完毕后保温反应；再加入小分子扩链剂保温反应；然后加入催化剂和消泡剂，最后加入有机溶剂，搅拌均匀，继续降温至50-60℃，出料，密封保存。
2.根据权利要求1所述的淀粉改性聚氨酯胶黏剂，其特征在于：所述二异氰酸酯选自异佛尔酮二异氰酸酯IPDI、二苯基甲烷二异氰酸酯MDI、1,6-己二异氰酸酯HDI、苯二亚甲基二异氰酸酯XDI、萘-1,5-二异氰酸酯NDI中的一种或两种；所述聚醚多元醇选自官能度为2~4、数均分子量为1000~5000的聚醚多元醇中的两种。
3.根据权利要求1所述的淀粉改性聚氨酯胶黏剂，其特征在于：所述小分子扩链剂选自新戊二醇、三羟甲基丙烷、二羟甲基丙酸中的一种。
4.根据权利要求1所述的淀粉改性聚氨酯胶黏剂，其特征在于：所述消泡剂为聚醚改性硅氧烷共聚合物。
5.根据权利要求1所述的淀粉改性聚氨酯胶黏剂，其特征在于：所述催化剂选自有机金属化合物类催化剂。
6.根据权利要求5所述的淀粉改性聚氨酯胶黏剂，其特征在于：所述催化剂为辛酸亚锡或二月桂酸二丁基锡。
7.根据权利要求1所述的淀粉改性聚氨酯胶黏剂，其特征在于：所述填充剂选自滑石粉、高岭土、碳酸钙、白炭黑中的一种或几种；所述环保增塑剂选自长链氯化石蜡、氯代棕榈油甲酯、环氧大豆油中的一种或两种。
8.根据权利要求1所述的淀粉改性聚氨酯胶黏剂，其特征在于：所述有机溶剂选自碳酸二甲酯、丙酮中的一种。
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