CN114574143B - 一种合成革用高性能水性聚氨酯胶粘剂的制备方法 - Google Patents
一种合成革用高性能水性聚氨酯胶粘剂的制备方法 Download PDFInfo
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Abstract
本发明属于聚氨酯技术领域，具体涉及一种合成革用高性能水性聚氨酯胶粘剂的制备方法，利用环氧树脂和聚丙烯酸酯的协同作用对水性聚氨酯胶粘剂进行改性，制备成膜自交联型高固含量水性聚氨酯胶粘剂乳液。本发明解决了现有聚氨酯胶粘剂的缺陷，采用高强度性能特征的环氧树脂和耐水性优异的聚丙烯酸酯对水性聚氨酯胶粘剂进行协同改性，达到改善聚氨酯的粘结强度和耐水性的双重目的。
Description
技术领域
本发明属于聚氨酯技术领域，具体涉及一种合成革用高性能水性聚氨酯胶粘剂的制备方法。
背景技术
合成革模拟天然皮革组织结构和使用性能，作为天然皮革代用品的复合材料，广泛应用于制作鞋、靴、箱包和球类等。经过几十年的发展，我国已成为世界合成革最主要的生产国。据初步统计，我国合成革产业规模以上企业主要集中在浙江、福建、江苏等省，已经形成了丽水、福鼎、临海等合成革特色产业基地，其产能占全球的80％左右。
水性聚氨酯是以水代替有机溶剂作为分散介质的新型聚氨酯体系。与溶剂型聚氨酯相比，水性聚氨酯虽具有绿色环保的优点，但存在固含量低、粘结强度不高和耐水性较差等主要缺点，严重制约着水性聚氨酯胶粘剂在合成革行业中的产业化应用。为了改善水性聚氨酯的粘结强度、耐水性这两项性能，研究采用具有高强度性能特征的环氧树脂和高耐水性特征的聚丙烯酸酯对聚氨酯进行交联改性或制成核壳结构的复合乳液，但因环氧树脂和丙烯酸酯均在聚合或乳化过程中与聚氨酯发生交联反应，增大了聚合物的分子量，导致乳液粒径增大，甚至乳化困难，最终影响乳液的存贮稳定性。
发明内容
针对现有技术中的问题，本发明提供一种合成革用水性聚氨酯胶粘剂的制备方法，解决了现有聚氨酯胶粘剂的缺陷，采用高强度性能特征的环氧树脂和耐水性优异的聚丙烯酸酯对水性聚氨酯胶粘剂进行协同改性，达到改善聚氨酯的粘结强度和耐水性的双重目的。
为实现以上技术目的，本发明的技术方案是：
一种合成革用水性聚氨酯胶粘剂的制备方法，利用环氧树脂和聚丙烯酸酯的协同作用对水性聚氨酯胶粘剂进行改性，制备成膜自交联型高固含量水性聚氨酯胶粘剂乳液。
所述方法具体包括如下步骤：
步骤1：肼基封端环氧树脂改性水性聚氨酯乳液的制备：以TDI、HMDI、IPDI为异氰酸酯，以聚己内酯多元醇PLG、聚醚二元醇PPG和聚醚二元醇PTMG为聚合物二元醇，以环氧树脂和己二酸二酰肼为改性剂，得到改性聚氨酯乳液；
所述步骤1的具体步骤包括：a1，将10-20％聚合物二元醇加入反应设备中，于真空条件下进行脱水2-3h，再加入8-12％异氰酸酯和3-5滴二月桂酸二丁基锡，升温至60-80℃，反应时间2-3h；a2，将1-2％扩链剂和5-10％环氧树脂加入，并继续反应2-4h，然后加入0.2-0.5％三乙胺中和掉扩链剂中的酸根离子；a3，采用0.5-1％乙二酸二酰肼对中和处理后的聚氨酯预聚体端基进行封闭处理，制得肼基封端环氧树脂改性聚氨酯乳液；所述扩链剂采用1,4-丁二醇、丙二醇、二乙烯三安、丙二胺、丁二胺中的一种。
步骤2，含酮羰基丙烯酸酯共聚乳液的制备：以丙烯酸丁酯、丙烯酸异辛酯和苯乙烯为单体材料、以双丙酮丙烯酰胺为改性剂，得到含酮羰基丙烯酸酯共聚乳液；
所述步骤2的具体步骤包括：b1，将引发剂溶于去离子水，得到引发剂溶液，所述引发剂的质量浓度为10-15％，b2，质量浓度为5-10％的分散剂和0.05％的消泡剂加入去离子水中，在100r/min的搅拌速度搅拌至完全溶解；该步骤采用低速搅拌，能够有效的控制泡沫的产生；b3，将质量浓度为10-20％单体加入b2得到的溶液中，在冰水浴中以200-300r/min的速度搅拌30-60min，直至单体分散均匀；b4，将反应液移至油浴锅中，边搅拌边加热，以1-2℃/min的速度升至70℃，在5-10min中加完引发剂溶液，引发剂加完后，在搅拌的条件下反应3-5h，加入1-2％的双丙酮丙烯酰胺，继续反应1-2h，冷却至室温进行乳化，制得含酮羰基的聚丙烯酸酯乳液；
其中，所述分散剂为十二烷基苯磺酸钠和OP-10以质量比为1:2-3组成的混合物；
所述单体为丙烯酸丁酯、丙烯酸异辛酯和苯乙烯以质量比为1:1:0.3-0.5组成的混合物，作为优选，丙烯酸丁酯、丙烯酸异辛酯和苯乙烯的质量比为1:1:0.4。所述丙烯酸丁酯和丙烯酸异辛酯提供柔软性和粘性，苯乙烯用于改善胶粘剂膜的坚韧性。
所述引发剂采用过硫酸钾；
步骤3，成膜自交联水性聚氨酯胶粘剂乳液的制备：以含酮羰基丙烯酸酯共聚乳液为分散液，采用倒相分散法将改性聚氨酯预聚体进行乳化，在真空条件下，于20-30℃烘燥10-20min，得到膜自交联型高固含量水性聚氨酯胶粘剂乳液；其中，所述乳化反应的pH为9-10，pH值会影响胶粘剂乳液的稳定性，pH值在9.0-10.0范围内时，存储过程中羰肼不会发生交联反应，达到提高乳液稳定性的作用；所述含酮羰基丙烯酸酯共聚乳液与改性聚氨酯预聚体的质量比为1:1-2，优选为1:1.6。
从以上描述可以看出，本发明具备以下优点：
1.本发明解决了现有聚氨酯胶粘剂的缺陷，采用高强度性能特征的环氧树脂和耐水性优异的聚丙烯酸酯对水性聚氨酯胶粘剂进行协同改性，达到改善聚氨酯的粘结强度和耐水性的双重目的。
2.本发明采用倒相分散法将肼基封端环氧树脂改性聚氨酯预聚体分散于含酮羰基的聚丙烯酸酯乳液中形成复合乳液，以提高乳液固含量。这是因为肼基封端环氧树脂改性聚氨酯与含酮羰基的聚丙烯酸酯在乳液中并不发生反应，只有在烘干过程中随着水分的减少而反应生成更大分子量的物质。
3.本发明于亲水扩链阶段，用环氧树脂对水性聚氨酯预聚体进行交联改性，通过聚合速率控制制备聚合度适中的PU预聚体；其次，用己二酸二酰肼对中和处理后的聚氨酯预聚体端基进行封闭处理；最后，利用羰肼交联的水抑制性，以含酮羰基的聚丙烯酸酯乳液为分散液，采用倒相分散法对改性聚氨酯预聚体进行乳化，制得固含量高、耐水性和胶粘强度好的水性聚氨酯胶粘剂乳液。
4.本发明于羰肼自交联反应的水抑制性，含酮羰基聚丙烯酸酯与肼基封端环氧树脂改性聚氨酯预聚体在水介质中可稳定共存，成膜干燥过程中随着水分的挥发而发生交联反应。该技术可有效提高乳液的固含量，但不会影响聚氨酯预聚体的乳化性能。
5.本发明显著改善聚氨酯胶粘剂的粘结强度和耐水性，同时有效提高乳液的固含量，同时，制得的高性能的水性聚氨酯胶粘剂，可助推合成革加工企业的绿色转型。
具体实施方式
结合实施例详细说明本发明，但不对本发明的权利要求做任何限定。
实施例1
一种合成革用水性聚氨酯胶粘剂的制备方法，利用环氧树脂和聚丙烯酸酯的协同作用对水性聚氨酯胶粘剂进行改性，制备成膜自交联型高固含量水性聚氨酯胶粘剂乳液，具体包括如下步骤：
步骤1：肼基封端环氧树脂改性水性聚氨酯乳液的制备：以TDI为异氰酸酯，以聚己内酯多元醇PLG为聚合物二元醇，以环氧树脂和己二酸二酰肼为改性剂，得到改性聚氨酯乳液；
所述步骤1的具体步骤包括：a1，将12％聚合物二元醇加入反应设备中，于真空条件下进行脱水2h，再加10％入异氰酸酯和3-5滴二月桂酸二丁基锡，升温至60℃，反应时间2h；a2，将1.2％1,4-丁二醇和6％环氧树脂加入，并继续反应2h，然后加入0.3％三乙胺中和；a3，采用0.6％乙二酸二酰肼对中和处理后的聚氨酯预聚体端基进行封闭处理，制得肼基封端环氧树脂改性聚氨酯乳液；
步骤2，含酮羰基丙烯酸酯共聚乳液的制备：以丙烯酸丁酯、丙烯酸异辛酯和苯乙烯为单体材料、以双丙酮丙烯酰胺为改性剂，得到含酮羰基丙烯酸酯共聚乳液；
所述步骤2的具体步骤包括：b1，将引发剂溶于去离子水，得到引发剂溶液，所述引发剂的质量浓度为12％，b2，质量浓度为5％的分散剂和0.05％的消泡剂加入去离子水中，在100r/min的搅拌速度搅拌至完全溶解；b3，将质量浓度为10％单体加入b2得到的溶液中，在冰水浴中以200r/min的速度搅拌30min，直至单体分散均匀；b4，将反应液移至油浴锅中，边搅拌边加热，以1℃/min的速度升至70℃，在5min中加完引发剂溶液，引发剂加完后，在搅拌的条件下反应3h，加入1％的双丙酮丙烯酰胺，继续反应1h，冷却至室温进行乳化，制得含酮羰基的聚丙烯酸酯乳液；所述分散剂为十二烷基苯磺酸钠和OP-10以质量比为1:2组成的混合物；所述单体为丙烯酸丁酯、丙烯酸异辛酯和苯乙烯以质量比为1:1:0.3组成的混合物；
步骤3，成膜自交联水性聚氨酯胶粘剂乳液的制备：以含酮羰基丙烯酸酯共聚乳液为分散液，采用倒相分散法将改性聚氨酯预聚体进行乳化，在真空条件下，于25℃烘燥20min，得到膜自交联型高固含量水性聚氨酯胶粘剂乳液；其中，所述乳化反应的pH为9；所述含酮羰基丙烯酸酯共聚乳液与改性聚氨酯预聚体的质量比为1:1。
实施例2
一种合成革用水性聚氨酯胶粘剂的制备方法，利用环氧树脂和聚丙烯酸酯的协同作用对水性聚氨酯胶粘剂进行改性，制备成膜自交联型高固含量水性聚氨酯胶粘剂乳液，具体包括如下步骤：
步骤1：肼基封端环氧树脂改性水性聚氨酯乳液的制备：以HMDI为异氰酸酯，以聚醚二元醇PPG为聚合物二元醇，以环氧树脂和己二酸二酰肼为改性剂，得到改性聚氨酯乳液；
所述步骤1的具体步骤包括：a1，将15％聚合物二元醇加入反应设备中，于真空条件下进行脱水2-3h，再加入10％异氰酸酯和3-5滴二月桂酸二丁基锡，升温至60-80℃，反应时间2-3h；a2，将1.5％丙二醇和8％环氧树脂加入，并继续反应2-4h，然后加入0.4％三乙胺中和；a3，采用1.2％乙二酸二酰肼对中和处理后的聚氨酯预聚体端基进行封闭处理，制得肼基封端环氧树脂改性聚氨酯乳液；
步骤2，含酮羰基丙烯酸酯共聚乳液的制备：以丙烯酸丁酯、丙烯酸异辛酯和苯乙烯为单体材料、以双丙酮丙烯酰胺为改性剂，得到含酮羰基丙烯酸酯共聚乳液；
所述步骤2的具体步骤包括：b1，将引发剂溶于去离子水，得到引发剂溶液，所述引发剂的质量浓度为15％，b2，质量浓度为10％的分散剂和0.05％的消泡剂加入去离子水中，在100r/min的搅拌速度搅拌至完全溶解；b3，将质量浓度为20％单体加入b2得到的溶液中，在冰水浴中以300r/min的速度搅拌60min，直至单体分散均匀；b4，将反应液移至油浴锅中，边搅拌边加热，以2℃/min的速度升至70℃，在10min中加完引发剂溶液，引发剂加完后，在搅拌的条件下反应5h，加入2％的双丙酮丙烯酰胺，继续反应2h，冷却至室温进行乳化，制得含酮羰基的聚丙烯酸酯乳液；所述分散剂为十二烷基苯磺酸钠和OP-10以质量比为1:3组成的混合物；所述单体为丙烯酸丁酯、丙烯酸异辛酯和苯乙烯以质量比为1:1:0.5组成的混合物；
步骤3，成膜自交联水性聚氨酯胶粘剂乳液的制备：以含酮羰基丙烯酸酯共聚乳液为分散液，采用倒相分散法将改性聚氨酯预聚体进行乳化，在真空条件下，于25℃烘燥15min，得到膜自交联型高固含量水性聚氨酯胶粘剂乳液；其中，所述乳化反应的pH为10；所述含酮羰基丙烯酸酯共聚乳液与改性聚氨酯预聚体的质量比为1:2，优选为1:1.6。
实施例3
一种合成革用水性聚氨酯胶粘剂的制备方法，利用环氧树脂和聚丙烯酸酯的协同作用对水性聚氨酯胶粘剂进行改性，制备成膜自交联型高固含量水性聚氨酯胶粘剂乳液，具体包括如下步骤：
步骤1：肼基封端环氧树脂改性水性聚氨酯乳液的制备：以IPDI为异氰酸酯，以聚醚二元醇PTMG为聚合物二元醇，以环氧树脂和己二酸二酰肼为改性剂，得到改性聚氨酯乳液；
所述步骤1的具体步骤包括：a1，将18％聚合物二元醇加入反应设备中，于真空条件下进行脱水2-3h，再加入12％异氰酸酯和3-5滴二月桂酸二丁基锡，升温至60-80℃，反应时间2-3h；a2，将2％丁二胺和10％环氧树脂加入，并继续反应2-4h，然后加入0.5％三乙胺中和；a3，采用1.2％乙二酸二酰肼对中和处理后的聚氨酯预聚体端基进行封闭处理，制得肼基封端环氧树脂改性聚氨酯乳液；步骤2，含酮羰基丙烯酸酯共聚乳液的制备：以丙烯酸丁酯、丙烯酸异辛酯和苯乙烯为单体材料、以双丙酮丙烯酰胺为改性剂，得到含酮羰基丙烯酸酯共聚乳液；
所述步骤2的具体步骤包括：b1，将引发剂溶于去离子水，得到引发剂溶液，所述引发剂的质量浓度为15％，b2，质量浓度为8％的分散剂和0.05％的消泡剂加入去离子水中，在100r/min的搅拌速度搅拌至完全溶解；b3，将质量浓度为15％单体加入b2得到的溶液中，在冰水浴中以300r/min的速度搅拌50min，直至单体分散均匀；b4，将反应液移至油浴锅中，边搅拌边加热，以1-2℃/min的速度升至70℃，在8min中加完引发剂溶液，引发剂加完后，在搅拌的条件下反应4h，加入2％的双丙酮丙烯酰胺，继续反应1h，冷却至室温进行乳化，制得含酮羰基的聚丙烯酸酯乳液；所述分散剂为十二烷基苯磺酸钠和OP-10以质量比为1:3组成的混合物；所述单体为丙烯酸丁酯、丙烯酸异辛酯和苯乙烯以质量比为1:1:0.4；
步骤3，成膜自交联水性聚氨酯胶粘剂乳液的制备：以含酮羰基丙烯酸酯共聚乳液为分散液，采用倒相分散法将改性聚氨酯预聚体进行乳化，在真空条件下，于25℃烘燥15min，得到膜自交联型高固含量水性聚氨酯胶粘剂乳液；其中，所述乳化反应的pH为10；所述含酮羰基丙烯酸酯共聚乳液与改性聚氨酯预聚体的质量比为1:1.6。
性能检测：
1.乳液固含量的测试
具体步骤包括：乳液固含量采用恒重法进行测定，具体操作：将烘制恒重的称量皿的质量记为m0，移取一定量的乳液加入称量皿中，其重量记为m1，在105℃烘箱中烘制恒重，其重量记为m2，通过下式计算乳液固含量：
固含量％＝(m2-m0)/(m1-m0)×100％；
2.耐水性能的测试：
取一定质量的乳液倒入模具内，将模具置于60℃烘箱中烘至质量不再发生变化，裁取4cm2大小的胶膜(质量记为m0)，在25℃条件下，将胶膜放在去离子水中浸泡24h，取出，用滤纸将胶膜表面的水擦干，其质量记为m1，通过下式计算乳液胶膜吸水率：
乳液胶膜吸水率％＝(m1-m0)/m0×100％
3.粘结强度的测试
样品制备方法：将胶粘剂乳液涂在尺寸为100mm×25mm的铝片上，涂抹尺寸约为20mm×25mm，在空气中自然干燥2h后，将两铝片在涂抹乳液位置相交叠粘在一起，用夹子固定，再将其放入80℃的烘箱中干燥48h，然后在万能材料试验机中测试拉伸强力，以最大拉伸强力评价粘结强度。
以实施例1-3为例，采用上述的方法进行检测，其结果如下表：
| 乳液固含量 | 耐水性能 | 粘结强度 | |
| 实施例1 | 40±5％ | 0.80±0.05％ | 1500±50N |
| 实施例2 | 42±5％ | 0.56±0.05％ | 1630±50N |
| 实施例3 | 45±5％ | 0.71±0.05％ | 1750±50N |
| 对比例 | 45±1％ | 12.3±0.5％ | 1390±50N |
所述对比例采用安徽某新材料有限公司的水性聚氨酯胶黏剂AH-0201C
可以理解的是，以上关于本发明的具体描述，仅用于说明本发明而并非受限于本发明实施例所描述的技术方案。本领域的普通技术人员应当理解，仍然可以对本发明进行修改或等同替换，以达到相同的技术效果；只要满足使用需要，都在本发明的保护范围之内。
Claims (1)
1.一种合成革用水性聚氨酯胶粘剂的制备方法，其特征在于:利用环氧树脂和聚丙烯酸酯的协同作用对水性聚氨酯胶粘剂进行改性，制备成膜自交联型高固含量水性聚氨酯胶粘剂乳液；
所述方法具体包括如下步骤：
步骤1：肼基封端环氧树脂改性水性聚氨酯乳液的制备：以TDI、HMDI、IPDI为异氰酸酯，以聚己内酯多元醇PLG、聚醚二元醇PPG和聚醚二元醇PTMG为聚合物二元醇，以环氧树脂和己二酸二酰肼为改性剂，得到改性聚氨酯乳液；
步骤2，含酮羰基丙烯酸酯共聚乳液的制备：以丙烯酸丁酯、丙烯酸异辛酯和苯乙烯为单体材料、以双丙酮丙烯酰胺为改性剂，得到含酮羰基丙烯酸酯共聚乳液；
步骤3，成膜自交联水性聚氨酯胶粘剂乳液的制备：以含酮羰基丙烯酸酯共聚乳液为分散液，采用倒相分散法将改性聚氨酯预聚体进行乳化，在真空条件下，于20-30℃烘燥10-20min，得到膜自交联型高固含量水性聚氨酯胶粘剂乳液；
所述步骤1的具体步骤包括：a1，将10-20％聚合物二元醇加入反应设备中，于真空条件下进行脱水2-3h，再加入8-12％异氰酸酯和3-5滴二月桂酸二丁基锡，升温至60-80℃，反应时间2-3h；a2，将1-2％扩链剂和5-10％环氧树脂加入，并继续反应2-4h，然后加入0.2-0.5％三乙胺中和掉扩链剂中的酸根离子；a3，采用0.5-1％己二酸二酰肼对中和处理后的聚氨酯预聚体端基进行封闭处理，制得肼基封端环氧树脂改性聚氨酯乳液；所述扩链剂采用1,4-丁二醇、丙二醇、二乙烯三胺、丙二胺、丁二胺中的一种；
所述步骤2的具体步骤包括：b1，将引发剂溶于去离子水，得到引发剂溶液，所述引发剂的质量浓度为10-15％，b2，质量浓度为5-10％的分散剂和0.05％的消泡剂加入去离子水中，在100r/min的搅拌速度搅拌至完全溶解；b3，将质量浓度为10-20％单体加入b2得到的溶液中，在冰水浴中以200-300r/min的速度搅拌30-60min，直至单体分散均匀；b4，将反应液移至油浴锅中，边搅拌边加热，以1-2℃/min的速度升至70℃，在5-10min中加完引发剂溶液，引发剂加完后，在搅拌的条件下反应3-5h，加入1-2％的双丙酮丙烯酰胺，继续反应1-2h，冷却至室温进行乳化，制得含酮羰基的聚丙烯酸酯乳液；
所述分散剂为十二烷基苯磺酸钠和OP-10以质量比为1:2-3组成的混合物；
所述单体为丙烯酸丁酯、丙烯酸异辛酯和苯乙烯以质量比为1:1:0.3-0.5组成的混合物；
所述丙烯酸丁酯、丙烯酸异辛酯和苯乙烯的质量比为1:1:0.4；所述引发剂采用过硫酸钾；所述乳化反应的pH为9-10；所述含酮羰基丙烯酸酯共聚乳液与改性聚氨酯预聚体的质量比为1:1-2。
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