CN114644746A - 一种聚氨酯改性环氧树脂及其制备方法与应用 - Google Patents
一种聚氨酯改性环氧树脂及其制备方法与应用 Download PDFInfo
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Abstract
本发明属于高分子材料技术领域，具体公开了一种聚氨酯改性环氧树脂及其制备方法与应用。聚氨酯改性环氧树脂的制备原料包括：异氰酸酯单体、多元醇和缩水甘油。本发明通过缩水甘油引入环氧基团，采用缩水甘油为单体合成聚氨酯改性环氧树脂，在制备时，先采用异氰酸酯单体，经过和多元醇反应后，制备成含—NCO的异氰酸酯预聚体；然后再用缩水甘油和剩余的—NCO反应，相对于传统的制备方法，环氧树脂环氧当量高，固化后赋予了漆膜优异的柔韧性、断裂伸长率和耐冲击性能，且耐腐蚀性能与环氧树脂相当，柔韧性低至1mm，附着力级别为1级；断裂伸长率达76‑120％，耐冲击性>50cm。
Description
技术领域
本发明属于高分子材料技术领域，具体涉及一种聚氨酯改性环氧树脂及其制备方法与应用。
背景技术
环氧树脂由于具有优异的耐化学品性能、对多种基材附着力强和成本低廉等优点，广泛应用于胶粘剂、涂料、等领域。但环氧树脂也存在交联固化后因交联密度高导致内应力大，涂层脆、耐冲击性差、易开裂和耐湿热性较差等不足，限制了它在应用领域和应用场景。
聚氨酯拥有良好的理化性能，优异的柔韧性赋予涂层较好的耐寒性、拉伸强度、高光高丰满度以及耐有机溶剂等优点。因此，可采用聚氨酯对环氧树脂进行改性以提高环氧树脂的韧性。
传统的聚氨酯改性环氧树脂一般是利用含—OH基团的环氧树脂和含—NCO基团的异氰酸酯进行反应，但是环氧树脂的羟基含量往往较低，可提供的交联点较少，改性程度受到极大的制约，导致由其配制成的漆膜的柔韧性、断裂伸长率和耐冲击性能均不佳。
因此，希望提供一种聚氨酯改性环氧树脂，当这种聚氨酯改性环氧树脂配制成漆膜后，具有优异的柔韧性、断裂伸长率和耐冲击性能。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种聚氨酯改性环氧树脂，所述聚氨酯改性环氧树脂具有良好的柔韧性能，将所述聚酯树脂配制成漆膜(即将本发明的聚氨酯改性环氧树脂与环氧固化剂混合制成的涂膜)，具有良好的柔韧性、断裂伸长率和耐冲击性能，且耐化学腐蚀性能与环氧树脂相当。
本发明的第一方面提供了一种聚氨酯改性环氧树脂。
具体的，一种聚氨酯改性环氧树脂，制备原料包括：异氰酸酯单体、多元醇和缩水甘油。
优选的，所述多元醇包括小分子多元醇和聚醚/酯多元醇。
优选的，所述多元醇包括所述小分子多元醇包括二元醇和/或三元醇。
进一步优选的，所述小分子多元醇选自乙二醇、1,2-丙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、3,5-庚二醇、1,8-辛二醇、三羟甲基丙烷(TMP)、三羟甲基乙烷、甘油、季戊四醇中的至少一种。上述各小分子多元醇可以单独使用，亦可以将两种或两种以上混合使用。
优选的，所述聚醚多元醇为所述小分子多元醇作为起始剂开环的环氧乙烷、环氧丙烷、环氧乙烷\环氧丙烷的加成物，分子量为1000-2000，官能度为2或3。
优选的，所述聚酯多元醇为所述小分子多元醇与多元羧酸或其酯、酸酐、卤化物等酯通过酯化反应得到的含有羟基的化合物，分子量为2000，官能度为2。
优选的，所述小分子多元醇与的聚醚/酯多元醇的质量比为(5-15)：(5-20)。
优选的，所述异氰酸酯单体选自甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、二苯基甲烷二异氰酸酯(MDI)、二环己基甲烷二异氰酸酯(HMDI)、六亚甲基二异氰酸酯(HDI)、赖氨酸二异氰酸酯(LDI)中至的的至少一种。
优选的，所述制备原料还包括酯类溶剂、三聚催化剂、阻聚剂中的至少一种。
优选的，所述酯类溶剂选自醋酸丁酯、醋酸乙酯、醋酸仲丁酯、丙二醇甲醚醋酸酯中的至少一种。
优选的，所述三聚催化剂选自2,4,6—三(二甲胺基甲基)苯酚(DMP-30)、三(二甲氨基丙基)六氢三嗪(PC-41)、基于双酚A/二甲胺的曼尼希碱、三正丁基磷中的至少一种。
优选的，所述阻聚剂选自磷酸、苯甲酰氯、对甲苯磺酸甲酯中的至少一种。
优选的，所述制备原料，按重量份计包括：
本发明的第二方面提供了一种聚氨酯改性环氧树脂的的制备方法。
具体的，一种聚氨酯改性环氧树脂的的制备方法，包括以下步骤：
(1)将异氰酸酯单体，第一次升温，搅拌，然后分批次加入多元醇，第二次升温，进行反应，得异氰酸酯预聚体，降温；
(2)在步骤(1)制得的异氰酸酯预聚体中加入缩水甘油，第三次升温进行反应后，得所述聚氨酯改性环氧树脂。
优选的，步骤(1)中，所述第一次升温至55-65℃，第二次升温至75-85℃，所述加成反应的时间为1-2小时，所述降温至65-75℃。
优选的，步骤(2)中，所述第三次升温至75-85℃，保温时间为1-3小时。
优选的，在步骤(2)之前，还包括在步骤(1)所制得的异氰酸酯预聚体中先加入三聚催化剂，到达指定NCO后加入阻聚剂进行反应的步骤。
本发明的第三方面提供了一种聚氨酯改性环氧树脂的应用。
具体的，一种漆，所述漆包括本发明所述的聚氨酯改性环氧树脂。
优选的，所述漆包括甲组份和乙组份，所述甲组份包括本发明所述的聚氨酯改性环氧树脂、颜料、填料、流平剂、消泡剂和分散剂；所述乙组份为环氧固化剂聚酰胺和环氧促进剂DMP-30。
本发明的第四方面提供了一种本发明所述的漆的应用。
具体的，一种涂层，所述涂层由本发明所述的漆制成。
本发明的上述技术方案相对于现有技术，至少具有如下技术效果或优点：
本发明通过缩水甘油引入环氧基团，采用缩水甘油为单体合成聚氨酯改性环氧树脂，相对于传统采用环氧树脂合成的聚氨酯环氧树脂，所制备的环氧树脂环氧当量高，固化后可赋予漆膜优异的柔韧性、断裂伸长率和耐冲击性能，且耐化学腐蚀性能与环氧树脂相当。
本发明的聚氨酯改性环氧树脂，在制备时，先采用异氰酸酯单体，经过和多元醇反应后，制备成含—NCO的异氰酸酯预聚体；然后再用缩水甘油和剩余的—NCO反应；制得的聚氨酯改性环氧树脂，环氧当量可调、交联度可控。
本发明的聚氨酯改性环氧树脂，制成漆膜后，其柔韧性低至1mm，附着力级别为1级；断裂伸长率达76-120％，耐冲击性>50cm。
具体实施方式
以下通过实施例对本发明进行具体描述，以便于所属技术领域的人员对本发明的理解，有必要在此特别指出的是，实施例只是用于对本发明做进一步说明，不能理解为对本发明保护范围的限制，所属领域技术人员，根据上述发明内容对本发明作出的非本质性的改进和调整，应仍属于本发明的保护范围，同时，下述所提及的原料未详细说明的，均为市售产品，未详细提及的工艺步骤或制备方法均为本领域技术人员所知晓的工艺步骤或制备方法。
实施例1
一种聚氨酯改性环氧树脂，由以下原料反应制得：
一种聚氨酯改性环氧树脂的制备方法，包括以下步骤：
(1)将异氰酸酯单体TDI加入醋酸丁酯中，第一次升温至55℃，搅拌，然后分三次加入(每次加入的量相同)多元醇TMP，第二次升温至75℃，保温2小时，进行反应，得异氰酸酯预聚体后降温至65℃；
(2)在步骤(1)制得的异氰酸酯预聚体中加入缩水甘油，第三次升温至75℃，保温2小时，进行反应后，制得本实施例的聚氨酯改性环氧树脂。
实施例2
一种聚氨酯改性环氧树脂，由以下原料反应制得：
一种聚氨酯改性环氧树脂的制备方法，包括以下步骤：
(1)将异氰酸酯单体TDI加入醋酸丁酯中，第一次升温至65℃，搅拌，然后分三次加入(每次加入的量相同)多元醇(TMP和聚醚多元醇)，第二次升温至85℃，保温1小时，进行反应，得异氰酸酯预聚体后降温至75℃；
(2)在步骤(1)制得的异氰酸酯预聚体中加入三聚催化剂DMP-30进行三聚反应，到达指定NCO后加入阻聚剂苯甲酰氯，得中间产物；
(3)在步骤(2)制得的中间产物中加入缩水甘油，第三次升温至85℃，保温2小时，进行反应后，制得本实施例的聚氨酯改性环氧树脂。
实施例3
一种聚氨酯改性环氧树脂，由以下原料反应制得：
一种聚氨酯改性环氧树脂的制备方法，包括以下步骤：
(1)先投HDI单体，第一次升温至60℃，搅拌，然后分三次加入(每次加入的量相同)多元醇(TMP和聚酯多元醇)，第二次升温至80℃，保温1.5小时，进行反应，得异氰酸酯预聚体后降温至70℃；
(2)在步骤(1)制得的异氰酸酯预聚体中加入三聚催化剂PC-41进行三聚反应，到达指定NCO后加入阻聚剂苯甲酰氯，得中间产物；
(3)在步骤(2)制得的中间产物中加入缩水甘油，第三次升温至80℃，保温2小时，进行反应后，制得本实施例的聚氨酯改性环氧树脂。
对比例1
市售的聚氨酯改性环氧树脂。
对比例2
市售的环氧树脂NPEL-128，南亚。
产品性能测试
取实施例1-3及对比例1-2的树脂，按表1的重量份配成甲组份，经搅拌，研磨至细度为＜30μm，备用；采用市售的环氧固化剂聚酰胺650和环氧促进剂DMP-30，作为乙组份，其中：聚酰胺650和环氧促进剂DMP-30的质量比为1:1；甲组份和乙组份按环氧酯严格计算加溶剂至施工粘度；将漆乳液制板后养护7天，测试其漆膜的性能，具体如表2所示。
表1：甲组份的原料组成
| 原料 | 聚氨酯改性环氧树脂 | 颜料 | 填料 | 流平剂 | 消泡剂 | 分散剂 |
| 质量(份) | 55 | 5 | 38 | 0.5 | 0.5 | 1 |
表2：各实施例和对比例的性能对比表
由表2可知，本发明实施例1-3制备的聚氨酯改性环氧树脂，其具有优异的柔韧性、断裂伸长率和耐冲击性，且本发明通过接枝改性的聚氨酯环氧树脂有着类似对比例2的环氧树脂优异的耐化学腐蚀性能。对比例1为市售的聚氨酯改性环氧树脂，环氧当量较低，耐化学腐蚀性能较差。对比例2为纯的环氧树脂。柔韧性、断裂伸长率和耐冲击性较差。
显然，上述实施例仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明的保护范围之中。
Claims (10)
1.一种聚氨酯改性环氧树脂，其特征在于，制备原料包括：异氰酸酯单体、多元醇和缩水甘油。
2.根据权利要求1所述的聚氨酯改性环氧树脂，其特征在于，所述多元醇包括小分子多元醇和聚醚/酯多元醇。
3.根据权利要求2所述的聚氨酯改性环氧树脂，其特征在于，所述小分子多元醇包括二元醇和/或三元醇；所述小分子多元醇与的聚醚/酯多元醇的质量比为(5-15)：(5-20)。
4.根据权利要求1所述的聚氨酯改性环氧树脂，其特征在于，所述制备原料还包括酯类溶剂、三聚催化剂、阻聚剂中的至少一种；所述酯类溶剂选自醋酸乙酯、醋酸仲丁酯、丙二醇甲醚醋酸酯中的至少一种。
5.根据权利要求4所述的聚氨酯改性环氧树脂，所述制备原料，按重量份计包括：
6.权利要求1至5任意一项所述的聚氨酯改性环氧树脂的制备方法，其特征在于，包括以下步骤：
(1)将异氰酸酯单体，第一次升温，搅拌，然后分批次加入多元醇，第二次升温，进行反应，得异氰酸酯预聚体，降温；
(2)在步骤(1)制得的异氰酸酯预聚体中加入缩水甘油，第三次升温进行反应后，得所述聚氨酯改性环氧树脂。
7.根据权利要求6所述的聚氨酯改性环氧树脂的制备方法，其特征在于，步骤(1)中，所述第一次升温至55-65℃，第二次升温至75-85℃，所述加成反应的时间为1-2小时，所述降温至65-75℃；步骤(2)中，所述第三次升温至75-85℃，保温时间为1-3小时。
8.根据权利要求6所述的聚氨酯改性环氧树脂的制备方法，其特征在于，在步骤(2)之前，还包括在步骤(1)所制得的异氰酸酯预聚体中先加入三聚催化剂，到达指定NCO后加入阻聚剂进行反应的步骤。
9.一种漆，其特征在于，所述漆包括权利要求1至6任意一项所述的聚氨酯改性环氧树脂。
10.一种涂层，其特征在于，所述涂层由权利要求9所述的漆制得。
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