CN106978129A - 一种具有低温活化性的高固含量双组份水性聚氨酯胶粘剂及其制备方法 - Google Patents

一种具有低温活化性的高固含量双组份水性聚氨酯胶粘剂及其制备方法 Download PDF

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CN106978129A
CN106978129A CN201710156954.5A CN201710156954A CN106978129A CN 106978129 A CN106978129 A CN 106978129A CN 201710156954 A CN201710156954 A CN 201710156954A CN 106978129 A CN106978129 A CN 106978129A
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chain extender
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曹高华
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Huizhou Hengdi Resin Products Co Ltd
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Abstract

本发明提供一种具有低温活化性的高固含量双组份水性聚氨酯胶粘剂及其制备方法，由质量百分比为90～97％的A组分和质量百分比为3～10％的B组分组成，其特征在于，所述的A组分的组成成份及质量百分比为：0～50％的混合多元醇、0～2％的催化剂、0～9％的多异氰酸酯、0～5％的多羟基小分子扩链剂、0～5％的氨基磺酸盐亲水扩链剂、0～50％的去离子水、0～4％的胺类后扩链剂、0～3％的消泡剂、0～3％的润湿分散剂、0～3％的流平增稠剂，所述B组分为脂肪族聚异氰酸酯固化剂，所制备的水性胶粘剂固含量超过50％，可在低于室温条件下干燥和活化，剥离强度高、耐热性好，可应用于鞋材、汽车内饰材料等的粘合，具有较大的经济价值。

Description

一种具有低温活化性的高固含量双组份水性聚氨酯胶粘剂及 其制备方法
技术领域
本发明涉及一种水性聚氨酯胶粘剂制备技术领域，具体为具有低温活化性的高固含量双组份水性聚氨酯胶粘剂的制备方法。
背景技术
溶剂型胶粘剂生产过程中需要大量有机溶剂，使用时对环境和人体造成很大的危害，水性胶粘剂不仅能大幅减轻有机溶剂对大气环境的破坏，而且节约了资源。
目前在鞋用胶粘剂中，氯丁橡胶和聚氨酯胶用量最大。鞋用氯丁橡胶活化温度较低，待溶剂或水分挥发后，可于室温下粘接，但氯丁橡胶内聚强度较聚氨酯差、耐热不佳、不耐黄变，因此多用于鞋面内里或鞋垫的复合等；鞋用聚氨酯胶粘剂一般采用分子链段高度对称的聚酯型多元醇为软段原料，其分子结构规整、结晶快，胶膜强度高，耐黄变、耐热佳，常用于鞋底与鞋面的贴合。聚氨酯胶粘剂一般需要50℃以上进行活化，如GB/T 30779-2014《鞋用水性聚氨酯聚氨酯胶粘剂》附录A中，建议鞋用水性聚氨酯胶粘剂施胶后在70±5℃下进行干燥和活化。德国拜耳公司的Dispercoll U54/U53系列水性聚氨酯胶粘剂的建议最低活化温度为55℃。事实上，目前鞋企的生产流水线均配备了烘道(多采用红外线或电阻丝为热源)，每双鞋上的胶粘剂需要3～5min的烘烤时间以保证胶膜充分干燥和活化，这需要耗费大量的电能。
专利申请号为201610236087.1的专利公开了一种双组份水性聚氨酯汽车内饰胶粘剂的制备方法，加入适量固化剂后，该胶黏剂的剥离强度、耐高低温冲击和湿热耐候性俱佳，但其干燥和活化过程需要在烘箱中烘烤30～50s，如此快的干燥速率需要更高的瞬时热量。
专利申请号为20151077443.5的专利申请报道了一种单组份水性聚氨酯胶粘剂的制备方法，该胶粘剂含有被封闭剂封端的潜在可固化交联剂，解决了双组份聚氨酯胶粘剂存在的开放时间短的问题，但其使用时分子中潜在的活化基团仍然需要高温解封或活化，施胶过程仍需消耗大量热能。
发明内容
本发明针对上述现有技术的不足而提供一种具有低温活化性的高固含量双组份水性聚氨酯胶粘剂及其制备方法。
本发明为解决上述问题所采用的技术方案为：
本发明提供一种具有低温活化性的高固含量双组份水性聚氨酯胶粘剂，由质量百分比为90～97％的A组分和质量百分比为3～10％的B组分组成，其特征在于，所述的A组分的组成成份及质量百分比为：0～50％的混合多元醇、0～2％的催化剂、0～9％的多异氰酸酯、0～5％的多羟基小分子扩链剂、0～5％的氨基磺酸盐亲水扩链剂、0～50％的去离子水、0～4％的胺类后扩链剂、0～3％的消泡剂、0～3％的润湿分散剂、0～3％的流平增稠剂，所述B组分为脂肪族聚异氰酸酯固化剂。
进一步地，所述混合多元醇为分子量2000或3000的聚己二酸1，4-丁二醇酯二醇、分子量2000的聚乙二醇己二酸1，4-丁二醇酯二醇、分子量为1000或2000的聚四氢呋喃二醇、分子量为2000的聚丙二醇中的一种或几种的组合；
所述催化剂为有机铋催化剂，型号为BICAT8118、BICAT81082或BICAT8124；
所述多异氰酸酯为二环己基甲烷－4、4－二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的一种或几种的组合；
所述多羟基小分子扩链剂为乙二醇、1，4-丁二醇和1，6-己二醇中的一种或几种的组合；
所述氨基类磺酸型亲水扩链剂为乙二胺基乙磺酸钠、3，5-二氨基苯磺酸钠或2，4-二氨基苯磺酸钠中的一种或几种的组合；
所述胺类后扩链剂为乙二胺或己二胺中的一种或几种的组合。
一种具有低温活化性的高固含量双组份水性聚氨酯胶粘剂的制备方法，包括如下步骤：
(1)将混合多元醇于110℃真空脱水120min，降温至70～80℃，开启搅拌，加入定量催化剂，然后在氮气保护下加入多异氰酸酯，控制70～95℃，初步聚合反应60～120min，制得聚氨酯初聚物，异氰酸酯的用量需满足初步聚合反应的起始R1值为1.41～1.69，R1＝(异氰酸酯中-NCO的摩尔总数)/(混合多元醇中-OH的摩尔总数)；
(2)将步骤(1)中所得的聚氨酯初聚物加入丙酮进行稀释，加入多羟基小分子扩链剂，保持60～80℃下扩链反应60～180min，得到聚氨酯预聚物；
(3)将步骤(1)中所得聚氨酯预聚物再次加入丙酮稀释，滴加氨基磺酸盐亲水扩链剂，控制在10～30min内滴完，然后控制50～60℃继续反应30～60min，制得聚氨酯离聚物；
(4)在高速剪切下，向步骤(3)中所制得聚氨酯离聚物中迅速加入定量的去离子水，5～10min后加入胺类后扩链剂，控制30℃以下继续反应30～60min，得到含有丙酮的乳液；
(5)真空脱除步骤(4)中所得乳液中的丙酮，制得白色泛蓝光的水性聚氨酯原液；
(6)在步骤(5)中所得的水性聚氨酯原液中加入定量消泡剂、润湿分散剂、流平增稠剂，得到水性聚氨酯胶粘剂，即A组分，施胶前在A组分中添加B组分，在1000r/min下搅拌10min即可使用。
进一步地，步骤(1)中所述混合多元醇中至少包含一种分子结构不完全对称的聚酯多元醇或一种聚醚多元醇。
进一步地，步骤(2)中所述丙酮用量为聚氨酯初聚物的13.5％～17.3％；多羟基小分子扩链剂用量为聚氨酯初聚物的0.29％～0.97％。
进一步地，所述步骤(3)中，所述丙酮用量为聚氨酯预聚物的107％～115％，氨基磺酸盐亲水扩链剂的用量为聚氨酯预聚物的1.68％～2.07％。
进一步地，步骤(4)中所述去离子水的温度为6℃左右，其用量需保证聚氨酯离聚物的固含量在51％～53％之间；胺类后扩链剂用量需保证后扩链完成后体系的R2为1.06～1.09，R2＝(异氰酸酯中-NCO的摩尔数)/(混合多元醇种-OH的摩尔数+多羟基小分子扩链剂总-OH的摩尔总数+氨基磺酸盐亲水扩链剂的摩尔数*2+胺类后扩链剂中-NH2的摩尔总数)。
进一步地，所述步骤(5)中，减压脱除丙酮的温度为50℃、真空度为0.085MPa。
进一步地，所述步骤(6)中消泡剂为BYK-019、BYK-023和BYK-028中的任意一种或几种的组合，其用量为水性聚氨酯原液总量的0.73‰～0.75‰；
所述润湿分散剂为Dynol-604或Dynol-607中的一种或几种的组合，其用量为水性聚氨酯原液总量的6.2‰～8.8‰；
所述流平增稠剂为Acrysol RM-2020、Acrysol RM-8W中的一种或两种的组合，其用量为水性聚氨酯原液总量的1.7‰～2.3‰。
进一步地，所述B组分为Desmodur DN、Desmodur N3600脂肪族聚异氰酸酯固化剂中的一种，添加量为A组分的3％～10％。
本发明的有益效果在于：
本发明通过在水性聚氨酯胶粘剂的制备过程中引入分子结构不完全规整的混合多元醇作为软段原料、一定硬度和长度的混合多异氰酸酯，配合结构规整的的小分子扩链剂作为硬段来调控水性聚氨酯胶粘剂的分子结构和结晶速率，以实现其低温活化性，另外，采用亲水性强的二氨磺酸盐为亲水扩链剂，在保证产品的高固含量的同时，形成的强极性脲键可提高产品的粘接性能，所制备的水性胶粘剂固含量超过50％，可在低于室温条件下干燥和活化，剥离强度高、耐热性好，可应用于鞋材、汽车内饰材料等的粘合，具有较大的经济使用价值。
与现有技术相比，本发明的优点在于：
(1)本发明制备的水性聚氨酯胶粘剂具有高固含量和低温活化特性，可在自然条件下干燥和活化，无需额外的烘干设备；
(2)本发明制备的水性聚氨酯胶粘剂不含有高沸点溶剂(如NMP、DMF等)，不使用毒性强的有机锡、有机汞为催化剂，更环保；
(3)本发明制备的水性聚氨酯胶粘剂采用的多元醇和异氰酸酯原料均为脂肪族或脂环族类，产品耐黄变性佳，可用于浅色物料的粘接。
具体实施方式
下面结合实施例具体阐明本发明的实施方式，仅供参考和说明使用，不构成对本发明专利保护范围的限制。
实施例1
将400g PTMEG2000、200g PEBA2000混合后于110℃真空脱水120min，降温至70℃，加入0.35g有机铋催化剂(BICAT8118，下同)，在氮气保护下再加入30g IPDI和76g H12MDI，升温至85℃反应75min；降温至60℃，加入100g丙酮，再加入2.1g 1，4-丁二醇，保温70℃反应120min；再次加入780g丙酮，降温至50℃，匀速滴加30g乙二胺基乙磺酸钠去离子水(质量分数为50％，下同)，30min内滴完，然后控温50～55℃反应50min，得到聚氨酯离聚体，该离聚体在6000r/min高速分散下加入650g去离子水，再加入2.5g乙二胺进行后扩链反应30min，得到含有溶剂的乳液；减压蒸馏脱除溶剂丙酮，然后加入消泡剂、润湿分散剂和流平增稠剂各1.0g、10.0g和2.8g，得到水性聚氨酯胶粘剂A组分，固含量为52.7％(按照GB/T14518所述方法测定)，在A组分中加入45g Desmodur DN搅拌均匀。所得产品的最低活化温度为17℃，剥离强度为8.9N/mm(按照GB/T 30779-2014所述方法测定，下同)，耐热老化性为8.7N/mm(按照GB/T 30779-2014所述方法测定，下同)。
实施例2
将真空脱水后的300g PBA3000和300g PEBA2000降温至75℃，在氮气氛围下加入0.43g有机铋催化剂，然后加入61g HDI、13.5g IPDI，控温80～85℃反应60min；降温至70℃以下，加入120g丙酮、1.95g乙二醇，4.6g 1，6-己二醇，控温70～80℃反应180min；加入800g丙酮并使体系降温至50℃，15min内匀速滴加23.4g 2，4-二氨基苯磺酸钠的去离子水(50％)，再保温55～60℃反应30min后在高速分散下加入660g去离子水，5min后加入2.38g乙二胺反应60min，然后真空脱除丙酮，加入1.0g消泡剂、12.0g润湿分散剂、2.3g流平增稠剂，即得水性聚氨酯胶粘剂A组分，其固含量为51.2％，在A组分中加入43g Desmodur DN搅拌均匀，所得产品的最低活化温度为21℃，剥离强度为9.7N/mm，耐热老化性为7.9N/mm。
实施例3
本实施例与实施例1的不同之处在于，该配方中混合多元醇为PBA3000、PTMEG2000、和PPG2000，其用量分别为300g、220g和80g，有机铋催化剂的用量为0.38g；混合多异氰酸酯为HDI、IPDI和H12MDI，其用量分别为28g、7.5g和44g；1，4-丁二醇、乙二胺基乙酸钠和去离子水的用量分别为3.6g、24.4g和620g，所用胺类后扩链剂为己二胺，用量为4.8g；消泡剂、润湿分散剂和流平增稠剂各1.0g、9.0g和3.1g，所得水性聚氨酯胶粘剂A组分的固含量为52.9％，在A组分中加入50g Desmodur N3600搅拌均匀，所得产品的最低活化温度为15℃，剥离强度为9.5N/mm，耐热老化性为8.2N/mm。
实施例4
本实施例与实施例2的不同之处在于，该配方中混合多元醇为PTMEG 2000、PBA2000和PEBA2000，其用量分别为360g、160g和80g，有机铋催化剂的用量为0.52g；HDI和IPDI其用量分别为50g和47.3g；所用醇类小分子扩链剂为1，4-丁二醇和1，6-己二醇，其用量分别为2g和5g；乙二胺基乙酸钠、去离子水和乙二胺的用量分别为26.2g、650g和2.22g；消泡剂、润湿分散剂和流平增稠剂各1.0g、8.5g和3.2g，所得水性聚氨酯胶粘剂A组分的固含量为52.5％，在A组分中加入48g Desmodur N3600搅拌均匀。所得产品的最低活化温度为12℃，剥离强度为8.7N/mm，耐热老化性为7.3N/mm。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

1.一种具有低温活化性的高固含量双组份水性聚氨酯胶粘剂，由质量百分比为90～97％的A组分和质量百分比为3～10％的B组分组成，其特征在于，所述的A组分的组成成份及质量百分比为：0～50％的混合多元醇、0～2％的催化剂、0～9％的多异氰酸酯、0～5％的多羟基小分子扩链剂、0～5％的氨基磺酸盐亲水扩链剂、0～50％的去离子水、0～4％的胺类后扩链剂、0～3％的消泡剂、0～3％的润湿分散剂、0～3％的流平增稠剂，所述B组分为脂肪族聚异氰酸酯固化剂。
2.根据权利要求1所述的一种具有低温活化性的高固含量双组份水性聚氨酯胶粘剂，其特征在于：所述混合多元醇为分子量2000或3000的聚己二酸1，4-丁二醇酯二醇、分子量2000的聚乙二醇己二酸1，4-丁二醇酯二醇、分子量为1000或2000的聚四氢呋喃二醇、分子量为2000的聚丙二醇中的一种或几种的组合；
所述催化剂为有机铋催化剂，型号为BICAT8118、BICAT81082或BICAT8124；
所述多异氰酸酯为二环己基甲烷－4、4－二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的一种或几种的组合；
所述多羟基小分子扩链剂为乙二醇、1，4-丁二醇和1，6-己二醇中的一种或几种的组合；
所述氨基类磺酸型亲水扩链剂为乙二胺基乙磺酸钠、3，5-二氨基苯磺酸钠或2，4-二氨基苯磺酸钠中的一种或几种的组合；
所述胺类后扩链剂为乙二胺或己二胺中的一种或几种的组合。
3.一种具有低温活化性的高固含量双组份水性聚氨酯胶粘剂的制备方法，其特征在于，包括如下步骤：
(1)将混合多元醇于110℃真空脱水120min，降温至70～80℃，开启搅拌，加入定量催化剂，然后在氮气保护下加入多异氰酸酯，控制70～95℃，初步聚合反应60～120min，制得聚氨酯初聚物，异氰酸酯的用量需满足初步聚合反应的起始R1值为1.41～1.69，R1＝(异氰酸酯中-NCO的摩尔总数)/(混合多元醇中-OH的摩尔总数)；
(2)将步骤(1)中所得的聚氨酯初聚物加入丙酮进行稀释，加入多羟基小分子扩链剂，保持60～80℃下扩链反应60～180min，得到聚氨酯预聚物；
(3)将步骤(2)中所得聚氨酯预聚物再次加入丙酮稀释，滴加氨基磺酸盐亲水扩链剂，控制在10～30min内滴完，然后控制50～60℃继续反应30～60min，制得聚氨酯离聚物；
(4)在高速剪切下，向步骤(3)中所制得聚氨酯离聚物中迅速加入定量的去离子水，5～10min后加入胺类后扩链剂，控制30℃以下继续反应30～60min，得到含有丙酮的乳液；
(5)真空脱除步骤(4)中所得乳液中的丙酮，制得白色泛蓝光的水性聚氨酯原液；
(6)在步骤(5)中所得的水性聚氨酯原液中加入定量消泡剂、润湿分散剂、流平增稠剂，得到水性聚氨酯胶粘剂，即A组分，施胶前在A组分中添加B组分，在1000r/min下搅拌10min即可使用。
4.根据权利要求3所述的一种具有低温活化性的高固含量双组份水性聚氨酯胶粘剂的制备方法，其特征在于：步骤(1)中所述混合多元醇中至少包含一种分子结构不完全对称的聚酯多元醇或一种聚醚多元醇。
5.根据权利要求3所述的一种具有低温活化性的高固含量双组份水性聚氨酯胶粘剂的制备方法，其特征在于：步骤(2)中所述丙酮用量为聚氨酯初聚物的13.5％～17.3％；多羟基小分子扩链剂用量为聚氨酯初聚物的0.29％～0.97％。
6.根据权利要求3所述的一种具有低温活化性的高固含量双组份水性聚氨酯胶粘剂的制备方法，其特征在于：所述步骤(3)中，所述丙酮用量为聚氨酯预聚物的107％～115％，氨基磺酸盐亲水扩链剂的用量为聚氨酯预聚物的1.68％～2.07％。
7.根据权利要求3所述的一种具有低温活化性的高固含量双组份水性聚氨酯胶粘剂的制备方法，其特征在于：步骤(4)中所述去离子水的温度为6℃左右，其用量需保证聚氨酯离聚物的固含量在51％～53％之间；胺类后扩链剂用量需保证后扩链完成后体系的R2为1.06～1.09，R2＝(异氰酸酯中-NCO的摩尔数)/(混合多元醇种-OH的摩尔数+多羟基小分子扩链剂总-OH的摩尔总数+氨基磺酸盐亲水扩链剂的摩尔数*2+胺类后扩链剂中-NH2的摩尔总数)。
8.根据权利要求3所述的一种具有低温活化性的高固含量双组份水性聚氨酯胶粘剂的制备方法，其特征在于：所述步骤(5)中，减压脱除丙酮的温度为50℃、真空度为0.085MPa。
9.根据权利要求3所述的一种具有低温活化性的高固含量双组份水性聚氨酯胶粘剂的制备方法，其特征在于：所述步骤(6)中消泡剂为BYK-019、BYK-023和BYK-028中的任意一种或几种的组合，其用量为水性聚氨酯原液总量的0.73‰～0.75‰；
所述润湿分散剂为Dynol-604或Dynol-607中的一种或几种的组合，其用量为水性聚氨酯原液总量的6.2‰～8.8‰；
所述流平增稠剂为Acrysol RM-2020、Acrysol RM-8W中的一种或两种的组合，其用量为水性聚氨酯原液总量的1.7‰～2.3‰。
10.根据权利要求3所述的一种具有低温活化性的高固含量双组份水性聚氨酯胶粘剂的制备方法，其特征在于:所述B组分为Desmodur DN、Desmodur N3600脂肪族聚异氰酸酯固化剂中的一种。
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