CN110387202B - 一种改性环保玉米淀粉粘合剂的制备方法 - Google Patents
一种改性环保玉米淀粉粘合剂的制备方法 Download PDFInfo
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Abstract
本发明涉及一种改性环保玉米淀粉粘合剂，所述玉米淀粉粘合剂的组成，按重量份数包括如下组分：玉米淀粉30份、水300‑400份、氧化剂0.2‑3份、聚乙烯醇80‑120份、交联剂1‑5份、氯化钙3‑5份、尿素0.1‑3份、消泡剂0.2‑0.5份、氢氧化钠适量(调节pH值)；其特征在于，所述交联剂为改性硼酸交联剂，由硼酸、环氧氯丙烷、水和柠檬酸在80‑100℃下反应制得。改性后的硼酸交联剂的表面键合有大量环氧基、羧基基团，可与氧化后淀粉中的羧基、醛基反应，这些反应与硼酸形成协同效应，共同提高了键合效率，提高了胶体的粘接强度；由于多基团的共同作用，大幅提高了胶膜的耐湿性能。本发明所制备的粘合剂的粘合强度达到了瓦楞纸板粘合剂出口标准。
Description
技术领域
本发明属于胶粘剂技术领域，具体涉及一种纸箱用玉米淀粉粘合剂。
背景技术
我国每年生产的瓦楞纸数量巨大，年产量已达到近千亿立方米。如果按每生产1M3耗用90-120g粘合剂计算，每年耗用粘合剂近千万吨。我国已严格限制泡花碱用于瓦楞纸的生产，目前大部分纸箱厂都使用以玉米淀粉为原料制成的粘合剂。玉米淀粉粘合剂是一种性能好、无毒害、价格低廉的粘合剂，自1935年在美国问世以来，特别是在环境危机日趋严重的当代，越来越受到人们的重视。然而，大部分纸箱厂属单机生产，缺乏干燥设备，完全依靠自然干燥，干燥时间长，胶液易渗透，使用传统的玉米淀粉粘合剂不太适应生产的需要。因此，对玉米淀粉粘合剂的加工是提高其粘结性能的重要渠道。淀粉粘合剂的加工工艺包括预糊化、氧化、加碱糊化、加入稳定剂等工序，其中氧化是最为关键的工序。
玉米淀粉是由α-D-六环葡萄糖组成的天热高分子化合物，从分子结构上看又可分为直链淀粉和支链淀粉，其中直链淀粉在玉米淀粉中约占23％，可溶于热水。它是通过α-1,4-糖甙键将α-D-六环葡萄糖连在一起的，平均聚合度约为70-350。支链淀粉在玉米淀粉中约占77％，不溶于水，大分子主链以α-1,4-糖甙链方式连接而成，支叉由一些短直链淀粉组成，平均聚合度约为280-5700。在氧化剂的作用下，淀粉分子中第六个碳原子上的伯醇基(-CH2OH)先被氧化成醛基(-CHO)，有的还被进一步氧化成羧基(-COOH)，这些基团可与改性剂反应生成高分子薄膜，阻止粘合剂向瓦楞纸内部渗透，提高初粘性能。然而，现有工艺制备的胶粘剂还存在粘接性弱，耐水性差等问题。
发明内容
为解决现有技术的不足，本发明提供一种改性环保玉米淀粉粘合剂，所述玉米淀粉粘合剂的组成，按重量份数包括如下组分，包括如下组分：玉米淀粉30份、水300-400份、氧化剂0.2-3份、聚乙烯醇80-120份、交联剂1-5份、氯化钙3-5份、尿素0.1-3份、消泡剂0.2-0.5份、氢氧化钠适量(调节pH值)；
所述玉米淀粉蛋白质含量小于0.6％，水含量为12％-14％，二氧化硫小于0.4％；控制淀粉蛋白质含量的目的在于避免过多蛋白质与氧化剂反应造成的粘结剂长期放置产生异味的问题。同时，二氧化硫的含量过多容易使淀粉聚集，发生凝沉现象；
所述氧化剂为高锰酸钾氧化剂，是使大分子分解断链的氧化剂，通过氧化反应可改变粘结剂的粘性和流动性。
所述交联剂为改性硼酸交联剂，该交联剂由硼酸、环氧氯丙烷、水和柠檬酸在80-100℃下反应制得。所述水、硼酸、环氧氯丙烷和柠檬酸的质量比为100:20-30:2-5:0.2-3；
改性后的硼酸交联剂的表面键合有大量环氧基、羧基基团，可与氧化后淀粉中的羧基、醛基反应，这些反应与硼酸形成协同效应，共同提高了键合效率，提高了胶体的粘接强度；由于多基团的共同作用，大幅提高了胶膜的耐湿性能。
所述消泡剂为水溶性有机硅类Q-119，Y-610中的至少一种，水溶性消泡剂可更好的溶解在反应体系中，提高消泡效率。
所述氯化钙主要起到分散剂的作用，少量氯化钙的加入可使体系分散更均匀，同时与消泡剂协同进一步降低气泡量。
所述尿素起到交联助剂的作用，其结构中的酰胺基团可与淀粉中的羟基和羧基键合，从而阻止淀粉间的快速络合，起到抗凝沉效果。
本发明还提供所述淀粉粘合剂的制备方法，具体包括如下步骤：
(1)硼酸交联剂改性：将水、硼酸、环氧氯丙烷和柠檬酸按质量比混合后，加入氢氧化钠调节pH值至8-10，升温到80-100℃下反应1-2h，反应完毕后加入一定量的无水乙醇后继续搅拌10-20min，过滤干燥得改性硼酸交联剂。
所述无水乙醇的作用在于实现固液相的快速分离。
(2)向三口瓶中加入一定量的水，升温至50℃，搅拌条件下依次加入玉米淀粉、固体高锰酸钾，并用盐酸调节pH值至2-3，保温反应2-3h，然后升温至75℃，加入改性硼酸交联剂，保温反应1h；然后加入聚乙烯醇和氯化钙，并用超声分散；继续升温至90℃并保温反应1h；加入一定量的氢氧化钠调节pH值至中性，加入尿素、氯化钙和消泡剂，并继续保温反应1h，降温出料得环保玉米淀粉粘合剂。
由于聚乙烯醇的团聚效应，传统的搅拌分散很难实现聚乙烯醇的均匀扩散，本发明采用氯化钙作为分散剂，利用氯离子和钙离子的渗透效应并结合超声物理作用使其快速扩散。
本发明的有益效果是，通过使用改性的硼酸交联剂，可大幅提升交联剂与淀粉氧化物的交联效果，粘接性能更强，固化时间短，耐水性更好。本发明的制备方法简洁，可操作性强。
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。为确保本发明制备的淀粉粘合剂的透明度和使用寿命，本发明使用的玉米淀粉蛋白质含量小于0.6％，水12％-14％，二氧化硫小于0.4％。
实施例1.
一种改性环保玉米淀粉粘合剂，包括如下重量份数的组成：玉米淀粉30份、水360份、高锰酸钾0.4份、聚乙烯醇100份、改性硼酸交联剂3份、氯化钙4份、尿素0.8份、Q-119型有机硅消泡剂0.3份，氢氧化钠适量(调节pH值)；
所述改性环保玉米淀粉粘合剂的制备方法，包括如下步骤：
(1)硼酸交联剂改性：将水100g、硼酸25g、环氧氯丙烷3g和柠檬酸1g按质量比混合后，加入氢氧化钠调节pH值至8-10，升温到90℃下反应60min，反应完毕后加入乙醇20mL后继续搅拌15min，过滤干燥得改性硼酸交联剂。
(2)向三口瓶中加入350g的水，升温至50℃，搅拌条件下加入玉米淀粉30g，待玉米淀粉充分分散后加入固体高锰酸钾0.4g，并用盐酸调节pH值至2-3，保温反应2.5h，然后升温至75℃，加入改性硼酸交联剂3g继续搅拌20min确保改性硼酸交联剂完全分散到体系中，然后加入100g的聚乙烯醇，4g的氯化钙，保温反应并超声分散30min，待分散完毕后继续升温至90℃并保温反应1h；加入一定量的氢氧化钠调节pH值至中性，加入尿素0.8g、和消泡剂0.3g，并继续保温反应1h，降温出料得环保玉米淀粉粘合剂。
实施例2.
一种改性环保玉米淀粉粘合剂，包括如下重量份数的组成：玉米淀粉30份、水360份、高锰酸钾1份、聚乙烯醇100份、改性硼酸交联剂3份、氯化钙4份、尿素0.8份、Y-610型有机硅消泡剂0.3份，氢氧化钠适量(调节pH值)；
所述改性环保玉米淀粉粘合剂的制备方法，包括如下步骤：
(1)硼酸交联剂改性：将水100g、硼酸21g、环氧氯丙烷3g和柠檬酸0.8g按质量比混合后，加入氢氧化钠调节pH值至8-10，升温到90℃下反应60min，反应完毕后加入乙醇15mL后继续搅拌25min，过滤干燥得改性硼酸交联剂。
(2)向三口瓶中加入350g的水，升温至50℃，搅拌条件下加入玉米淀粉30g，待玉米淀粉充分分散后加入固体高锰酸钾1g，并用盐酸调节pH值至2-3，保温反应2.5h，然后升温至75℃，加入改性硼酸交联剂3g继续搅拌20min确保改性硼酸交联剂完全分散到体系中，然后加入100g的聚乙烯醇，4g的氯化钙，保温反应并超声分散30min，待分散完毕后继续升温至90℃并保温反应1h；加入一定量的氢氧化钠调节pH值至中性，加入尿素0.8g、和Y-610消泡剂0.3g，并继续保温反应1h，降温出料得环保玉米淀粉粘合剂。
实施例3.
一种改性环保玉米淀粉粘合剂，包括如下重量份数的组成：玉米淀粉30份、水380份、高锰酸钾0.6份、聚乙烯醇110份、改性硼酸交联剂4份、氯化钙4份、尿素2份、Y-610型有机硅消泡剂0.3份，氢氧化钠适量(调节pH值)；
所述改性环保玉米淀粉粘合剂的制备方法，包括如下步骤：
(1)硼酸交联剂改性：将水100g、硼酸28g、环氧氯丙烷3g和柠檬酸1g按质量比混合后，加入氢氧化钠调节pH值至8-10，升温到90℃下反应60min，反应完毕后加入乙醇15mL后继续搅拌25min，过滤干燥得改性硼酸交联剂。
(2)向三口瓶中加入380g的水，升温至50℃，搅拌条件下加入玉米淀粉30g，待玉米淀粉充分分散后加入固体高锰酸钾0.6g，并用盐酸调节pH值至2-3，保温反应2.5h，然后升温至75℃，加入改性硼酸交联剂4g继续搅拌20min确保改性硼酸交联剂完全分散到体系中，然后加入110g的聚乙烯醇，4g的氯化钙，保温反应并超声分散30min，待分散完毕后继续升温至90℃并保温反应1h；加入一定量的氢氧化钠调节pH值至中性，加入尿素2g、和Y-610消泡剂0.3g，并继续保温反应1h，降温出料得环保玉米淀粉粘合剂。
对上述实施例制备的胶粘剂进行粘合强度测试，测试方法为GB/T6548-1998瓦楞纸板粘合强度的测定方法，测试结果分别为：
实施例1:71,2N/10cm；
实施例2:69.4N/10cm；
实施例3：70.1N/10cm。
上述实施例结果表明所制备的胶粘剂的粘合强度均大于58.8N/10cm，达到了GB5034-85出库产品包装用瓦楞纸板的标准要求。
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 (5)
1.一种改性环保玉米淀粉粘合剂，所述玉米淀粉粘合剂的组成，按重量份数包括如下组分：玉米淀粉30份、水300-400份、氧化剂0.2-3份、聚乙烯醇80-120份、交联剂1-5份、氯化钙3-5份、尿素0.1-3份、消泡剂0.2-0.5份、氢氧化钠调节pH值；其特征在于，所述交联剂为改性硼酸交联剂，由硼酸、环氧氯丙烷、水和柠檬酸在80-100℃下反应制得，硼酸交联剂改性所用水、硼酸、环氧氯丙烷和柠檬酸的质量比为 100:20-30:2-5:0.2-3。
2.根据权利要求1所述一种改性环保玉米淀粉粘合剂，其特征在于，所述玉米淀粉蛋白质含量小于0.6%，水12%-14%，二氧化硫小于0.4%。
3.根据权利要求1所述一种改性环保玉米淀粉粘合剂，其特征在于，所述氧化剂为高锰酸钾氧化剂。
4.根据权利要求1所述一种改性环保玉米淀粉粘合剂，其特征在于，所述消泡剂为水溶性有机硅类Q-119，Y-610中的至少一种。
5.权利要求1-4中任一项所述的改性环保玉米淀粉粘合剂的制备方法，包括如下步骤：
(1)硼酸交联剂改性：将水、硼酸、环氧氯丙烷和柠檬酸按质量比混合后，加入氢氧化钠调节pH值至8-10，升温到80-100℃下反应1-2h，反应完毕后加入一定量的无水乙醇后继续搅拌10-20min，过滤干燥得改性硼酸交联剂，
(2)向三口瓶中加入一定量的水，升温至50℃，搅拌条件下依次加入玉米淀粉、固体高锰酸钾，并用盐酸调节pH值至2-3，保温反应2-3h，然后升温至75℃，加入改性硼酸交联剂，保温反应1h；然后加入聚乙烯醇和氯化钙，并用超声分散；继续升温至90℃并保温反应1h；加入一定量的氢氧化钠调节pH值至中性，加入尿素、氯化钙和消泡剂，并继续保温反应1h，降温出料得环保玉米淀粉粘合剂。
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