CN110437764A - 一种树脂改性淀粉粘合剂及其制备方法 - Google Patents
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Abstract
本发明涉及一种树脂改性淀粉粘合剂，其特征在于，按重量计算包括如下组成：干淀粉100份、去离子水300‑500份、环氧树脂20‑40份、叠氮聚醚5‑10份、3,5‑二氨基‑1,2,4‑三唑1‑2份、氰基丙烯酸酯1‑3份、次氯酸钠溶液5‑10份、三聚磷酸钠3‑8份、水滑石2‑5份、高岭土3‑8份、硫酸钠1‑4份。该淀粉粘合剂采用叠氮聚醚改性的环氧树脂改性氧化淀粉乳液，引入反应性官能团和耐水性五元环结构，大幅提升了粘合剂的剪切强度和耐水性能。
Description
技术领域
本发明属于胶粘剂技术领域，具体涉及一种瓦楞纸板用的树脂改性玉米淀粉粘合剂及其制备方法。
背景技术
早期的瓦楞纸用粘合剂为泡花碱，由于泡花碱结膜快、价格低，长期为纸箱厂使用，但用泡花碱粘合的纸箱易吸潮泛碱，破坏了箱面的抗压延力，脱胶现象时有发生，甚至腐蚀被包装的商品，还会对环境造成污染。1935年美国的Stein Hall研制出玉米淀粉粘合剂，与泡花碱相比，它具有粘接强度高，重量轻，无腐蚀性，防潮性好，挺力大，韧性好，制造简便，成本低等优点，更适合作瓦楞纸粘合。国外在50年代初期就将玉米淀粉粘合剂广泛应用于瓦楞纸箱的生产，我国在1984年将淀粉粘合剂的使用作为纸箱生产厂的重点推广项目，外贸部也已明文规定出口纸箱必须使用玉米淀粉粘合剂。
淀粉是由D-葡萄糖单体脱水缩合形成的均聚物，分子量为106-107数量级，在每个葡萄糖单位的C2、C3和C6上各有一个羟基，因而每个淀粉分子链上几十万到上百万个羟基，形成大量的分子内、分子间氢键。淀粉分子中大量氢键的存在，使其具备成为胶粘剂的条件。但是，氢键作用力与化学键力相比要弱的多，其粘合强度达不到应用要求。所以，需要通过向淀粉分子链中引入大量均匀分布的化学键，使其与周围的氢键的弱化学作用力有效配合，才能达到粘合强度要求。而且，淀粉分子链上大量的羟基，极易与水形成氢键，耐水性很差。因此，提高淀粉粘合剂的粘接强度和耐水性能是淀粉粘结剂研究的重要方向。如中国专利CN201210241327.9公开了一种改性淀粉胶粘剂，该胶粘剂加入了与氧化淀粉乳相容性好的高内聚能组分醋酸乙烯酯，增强淀粉胶粘剂的粘接强度，采用环氧树脂做交联剂，环氧树脂与氧化淀粉的羧基发生交联反应，明显提高其耐水性能。然而，为了扩大淀粉胶粘剂的应用范围，仍需开发更高粘接强度，更好耐水性的淀粉粘合剂材料。
发明内容
为解决现有技术的不足，本发明提供一种树脂改性淀粉粘合剂及其制备方法，具体方案如下：
一种树脂改性淀粉粘合剂，按重量计算包括如下组成：干淀粉100份、去离子水300-500份、环氧树脂20-40份、叠氮聚醚5-10份、3,5-二氨基-1,2,4-三唑1-2份、氰基丙烯酸酯1-3份、次氯酸钠溶液5-10份、三聚磷酸钠3-8份、水滑石2-5份、高岭土3-8份、硫酸钠1-4份；
所述淀粉为玉米干淀粉，蛋白质含量小于0.3％，控制淀粉含量是为了减少蛋白质变性造成的胶粘剂发霉和异味，提高粘合剂的储存期和环境友好性。
所述环氧树脂为E44牌号环氧树脂，环氧值在0.41-0.47之间；
所述叠氮聚醚为端羟基缩水甘油叠氮聚醚，结构通式如下，
叠氮聚醚分子中含有大量的羟基，能够与淀粉中的羟基、羧基和醛基形成氢键，实现较好的缔合。同时，分子中的叠氮基还能与氰基丙烯酸酯中的氰基反应生产四唑五元环结构，具有较好的耐吸水性能。
所述氰基丙烯酸酯为α-氰基丙烯酸酯，结构式为CH2＝C(CN)-COOCH3。该结构中含有氰基，能够与叠氮基反应生成四唑五元环，五元环结构不仅提高了耐水性，还提高了粘接强度；该结构中还含有活泼氢，能够与环氧基、羟基反应进与氧化淀粉、叠氮聚醚、环氧树脂形成交叉网络，提高粘接强度；另外，该分子结构中还含有酯基，具有一定的增韧效果，不至于使形成的交叉网络结构过硬。
所述3,5-二氨基-1,2,4-三唑能够与环氧树脂固化，起到固化剂作用。同时，三唑结构可进一步与淀粉中的羟基和羧基等吸水基团作用，避免其直接与水作用，从而提高了其耐水性；同时唑类基团也是较好的增强基团，对胶体的强度有利。因此，3,5-二氨基-1,2,4-三唑可同时提高粘合剂的粘接强度和耐水性。
所述次氯酸钠为自制的次氯酸钠水溶液，有效氯含量为5％-10％，是将氯气通入30％的氢氧化钠溶液制备而成。所述次氯酸钠溶液显碱性，在氧化淀粉时还起到催化剂的作用，不需另外加碱。
所述高岭土、水滑石、硫酸钠为固体填料，主要起到增强和催干作用，同时水滑石还具有一定的杀灭细菌和微生物的作用，可以有效防止淀粉粘合剂变质，有效延长了淀粉粘合剂的储存时间；
所述三聚磷酸钠具有较强的络合作用，能够吸附在水滑石、高岭土、硫酸钠的表面，提高固体颗粒的溶解性。
所述改性淀粉粘合剂的制备方法，具体包括如下步骤：
1.将各组分按配方组成称量后备用；
2.将环氧树脂与叠氮聚醚按质量比混合后依次加入搅拌釜中，然后加入无水乙醇，升高温度至50-60℃，保温反应30-40min后，蒸发掉无水乙醇得叠氮聚醚改性环氧树脂；
3.向反应釜中加入去离子水，然后加入玉米淀粉配成20-30％的淀粉乳液，逐滴加入次氯酸钠溶液，加完后升高温度至40-50℃，保温反应2-4h，反应完毕后加入0.1mol/L的盐酸溶液，调节pH值到9-10之间，降温出料得氧化淀粉乳液；
4.向步骤(3)制得的氧化淀粉乳液中按质量比依次加入步骤(2)改性的环氧树脂、3,5-二氨基-1,2,4-三唑、氰基丙烯酸酯、三聚磷酸钠、水滑石、高岭土、硫酸钠，加完料后室温下搅拌并超声反应30-50min，确保填料和改性树脂均匀分散到体系中，
然后升高温度至60-70℃，保温反应1-2h，降温出料得树脂改性淀粉粘合剂。
本发明的有益效果在于：(1)采用叠氮聚醚改性的环氧树脂制备的改性玉米淀粉粘合剂，具有较高的粘接强度；(2)改性粘合剂中含有唑类五元环结构，具有较好的耐水性能；(3)本发明所述粘合剂还具有优良的抗菌和快干的效果，具有较高的储存性能和使用性能。
具体实施方式
下面结合实施例对本发明作进一步的描述，所描述的实施例仅仅是本发明一部分实施例。基于本发明实施例，本领域的普通技术人员在没有做出创造性劳动所做的等同替换或改进，都在本发明的保护范围之内。
以下实施例所用氧化剂次氯酸钠的制备方法为：30℃下，将氯气通入30％的强氧化钠溶液中，通20mi n后，得次氯酸钠水溶液，测定有效氯含量为6.4％。
以下实施例所有叠氮聚醚为端羟基缩水甘油叠氮聚醚；所述环氧树脂为E44环氧树脂，环氧值0.45；所述干淀粉为玉米干淀粉，蛋白质含量为0.23％。
实施例1.
一种树脂改性淀粉粘合剂，按重量计算包括如下组成：玉米干淀粉100份、去离子水400份、环氧树脂35份、端羟基缩水甘油叠氮聚醚6份、3,5-二氨基-1,2,4-三唑1份、氰基丙烯酸酯2份、次氯酸钠溶液6份、三聚磷酸钠4份、水滑石4份、高岭土5份、硫酸钠3份；
1.将各组分按配方组成称量后备用；
2.将环氧树脂35g与端羟基缩水甘油叠氮聚醚6g按质量比混合后依次加入搅拌釜中，然后加入无水乙醇，升高温度至50-60℃，保温反应30-40min后，蒸发掉无水乙醇得叠氮聚醚改性环氧树脂41g；
3.向反应釜中加入去离子水400g，然后加入玉米干淀粉100g配成淀粉乳液，逐滴加入次氯酸钠溶液6g，加完后升高温度至40-50℃，保温反应2-4h，反应完毕后加入0.1mol/L的盐酸溶液，调节pH值到9-10之间，降温出料得氧化淀粉乳液；
4.向步骤(3)制得的氧化淀粉乳液中按质量比依次加入步骤(2)改性的环氧树脂41g、3,5-二氨基-1,2,4-三唑1g、氰基丙烯酸酯2g、三聚磷酸钠4g、水滑石4g、高岭土5g、硫酸钠3g，加完料后室温下搅拌并超声反应30-50min，确保填料和改性树脂均匀分散到体系中，然后升高温度至60-70℃，保温反应1-2h，降温出料得树脂改性淀粉粘合剂。
实施例2.
一种树脂改性淀粉粘合剂，按重量计算包括如下组成：玉米干淀粉100份、去离子水380份、环氧树脂28份、端羟基缩水甘油叠氮聚醚5份、3,5-二氨基-1,2,4-三唑1份、氰基丙烯酸酯1份、次氯酸钠溶液10份、三聚磷酸钠7份、水滑石3份、高岭土7份、硫酸钠4份；
制备方法同实施例1，各组分质量按本实施例称量。
实施例3.
一种树脂改性淀粉粘合剂，按重量计算包括如下组成：玉米干淀粉100份、去离子水450份、环氧树脂36份、端羟基缩水甘油叠氮聚醚8份、3,5-二氨基-1,2,4-三唑2份、氰基丙烯酸酯1.5份、次氯酸钠溶液6份、三聚磷酸钠4份、水滑石5份、高岭土5份、硫酸钠2份；
制备方法同实施例1，各组分质量按本实施例称量。
为进一步验证本发明的技术效果，参照现有专利技术CN2012102413279制备同样的胶粘剂，具体配方为：玉米淀粉60份，去离子水100份，次氯酸钠水溶液30份，环氧氯丙烷2.5份，聚醋酸乙烯酯乳液60份，环氧树脂25份，叔胺催化剂4份，高岭土5份，硫酸钠3份，滑石粉4份，钛白粉3份。
对上述实施例和对比例制备的粘合剂分别按照GB/T9846-2004标准测试剪切强度，按照GB/T17657-1999标准测试耐水剪切强度，具体结果如表1所示：
由表中数据可见，本发明所制备的粘合剂在剪切强度和耐水剪切强度方面明显优于现有技术。以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (7)
1.一种树脂改性淀粉粘合剂，其特征在于，按重量计算包括如下组成：干淀粉100份、去离子水300-500份、环氧树脂20-40份、叠氮聚醚5-10份、3,5-二氨基-1,2,4-三唑1-2份、氰基丙烯酸酯1-3份、次氯酸钠溶液5-10份、三聚磷酸钠3-8份、水滑石2-5份、高岭土3-8份、硫酸钠1-4份。
2.根据权利要求1所述一种树脂改性淀粉粘合剂，其特征在于，所述淀粉为玉米干淀粉，蛋白质含量小于0.3％。
3.根据权利要求1所述一种树脂改性淀粉粘合剂，其特征在于，所述环氧树脂为E44牌号环氧树脂，环氧值在0.41-0.47之间。
4.根据权利要求1所述一种树脂改性淀粉粘合剂，其特征在于，所述叠氮聚醚为端羟基缩水甘油叠氮聚醚。
5.根据权利要求1所述一种树脂改性淀粉粘合剂，其特征在于，述氰基丙烯酸酯为α-氰基丙烯酸酯，结构式为CH2＝C(CN)-COOCH3。
6.根据权利要求1所述一种树脂改性淀粉粘合剂，其特征在于，所述次氯酸钠为自制的次氯酸钠水溶液，有效氯含量为5％-10％。
7.权利要求1-6任一项所述改性淀粉粘合剂的制备方法，具体包括如下步骤：
(1)将各组分按配方组成称量后备用；
(2)将环氧树脂与叠氮聚醚按质量比混合后依次加入搅拌釜中，然后加入无水乙醇，升高温度至50-60℃，保温反应30-40min后，蒸发掉无水乙醇得叠氮聚醚改性环氧树脂；
(3)向反应釜中加入去离子水，然后加入玉米淀粉配成20-30％的淀粉乳液，逐滴加入次氯酸钠溶液，加完后升高温度至40-50℃，保温反应2-4h，反应完毕后加入0.1mol/L的盐酸溶液，调节pH值到9-10之间，降温出料得氧化淀粉乳液；
(4)向步骤(3)制得的氧化淀粉乳液中按质量比依次加入步骤(2)改性的环氧树脂、3,5-二氨基-1,2,4-三唑、氰基丙烯酸酯、三聚磷酸钠、水滑石、高岭土、硫酸钠，加完料后室温下搅拌并超声反应30-50min，确保填料和改性树脂均匀分散到体系中，然后升高温度至60-70℃，保温反应1-2h，降温出料得树脂改性淀粉粘合剂。
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