CN112126077A - 一种单组分水性环氧树脂 - Google Patents
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Abstract
一种单组分水性环氧树脂，包含100%固含量的自乳化水性环氧树脂100份，水0~1000份，有机硼胺化合物潜伏性固化剂1~10份，促进剂0~3份。本发明的一种单组分水性环氧树脂由于水性环氧树脂不含乳化剂、溶剂，无乳化剂和溶剂毒性残存和排放，既环保、又能在较长时间稳定保存，方便运输和储存，且具有制备工艺简单易行、粘结性能强、稳定性高、固化温度和时间可调等特性。
Description
技术领域
本发明涉及环氧树脂领域，具体涉及一种单组分水性环氧树脂。
背景技术
环氧树脂因其优良的机械物理性能、粘结性能和工艺性能等，已被广泛应用于各个领域。但目前使用的环氧树脂多为溶剂型，在生产施工过程中挥发大量溶剂，对人类健康造成严重威胁。近年来，随着人们环保意识的增强以及我国对环境保护要求的日益严格，环境友好型水性环氧树脂体越来越受到重视。然而，目前水性环氧树脂体系一般是外交联型的双组份体系，在施工前往往需要加入固化剂，从而导致体系存在固化温度、固化时间和储存稳定性之间的矛盾。双组份体系，两种组分必须分装贮存、现配现用，两个组分混合后的使用时间一般很短，必须一次性用完；而单组分自交联体系可以避免双组分体系施工操作繁琐等缺陷。因此，单组分水性环氧树脂的制备具有广阔的市场前景和应用价值。
发明内容
解决的技术问题：本发明提供一种单组分水性环氧树脂，解决目前双组份体系中存在着的环氧树脂与固化剂之间相容性差、储存稳定性差以及难以分散均匀等问题。
技术方案：一种单组分水性环氧树脂，按质量份的组成为：100％固含量自乳化水性环氧树脂：100份；水：不超过1000份；有机硼胺化合物潜伏性固化剂：1～10份；促进剂：不超过3份。
优选的，上述100％固含量自乳化水性环氧树脂为接枝法自乳化水性环氧树脂、羧基反应法自乳化水性环氧树脂、胺基反应法自乳化水性环氧树脂中至少一种。
优选的，上述有机硼胺化合物潜伏性固化剂为594、595硼胺潜伏性固化剂中的至少一种，其结构分别为：
或者
优选的，上述促进剂为三甲胺、三乙胺、三乙醇胺、吡啶、DMP-30、2,4,6-三(二甲氨基甲基)苯酚盐、DBU、DBU盐、咪唑、2-甲基咪唑、2-乙基-4-甲基咪唑中的至少一种。
有益效果：①本发明制备的单组分水性环氧树脂室温下可稳定保存，不存在双组份水性环氧树脂存在着的环氧树脂与固化剂之间相容性差、储存稳定性差以及难以分散均匀等问题。②本发明制备的单组分水性环氧树脂固化温度范围比较广：80-180℃。③本发明制备过程无三废排放，工艺简单，适合于大规模工业生产。
附图说明
图1为实施例4的单组分水性环氧树脂乳液数码照片图：(a)放置1月的竖直图、(b)放置1月的斜躺图、(c)放置1年的竖直图、(d)放置1年的斜躺图。
图2为实施例4的单组分水性环氧树脂应力应变曲线。
具体实施方式
下面通过实例对本发明进行具体描述，实施例给出详细的实施方式和具体的操作步骤，只用于对本发明的进一步说明，不能理解为对本发明保护范围的限制。
实施例1
100g酚A型环氧树脂(E-51)升温至70℃，加入丙酮溶解的过氧化苯甲酰(5g)和75mL N,N’-二甲基甲酰胺溶解的2-丙烯酰胺基-2-甲基丙磺酸(40g)，70℃反应2h，减压蒸馏除去溶剂得到2-丙烯酰胺基-2-甲基丙磺酸接枝的自乳化水性环氧树脂AMPS-EP。100％固含量AMPS-EP 100g，水100g，潜伏性固化剂594 10g，促进剂DMP-30 1g，均质机10000rpm混合乳化成水性乳液，其稳定性情况见表1，起始固化温度见表2。
实施例2
100g酚A型环氧树脂(E-44)、马来酸酐8.6g和100g醋酸丁酯，搅拌形成均相溶液之后，再加入二月桂酸二丁基锡0.1g，升温至130℃反应4h除去溶剂得到自乳化水性环氧树脂MA-EP。100％固含量MA-EP 100g，水100g，潜伏性固化剂595 10g，促进剂DMP-30 3g，均质机10000rpm混合乳化成水性乳液，其稳定性情况见表1，起始固化温度见表2。
实施例3
60g环氧树脂E-44并将其加入三口烧瓶中；用量筒量取20mL乙二醇丁醚然后加入三口烧瓶中。然后量取12.5mL二乙醇胺加入分液漏斗中，待用。加热水浴锅，控制温度在65℃，并开启机械搅拌30min，使树脂完全溶解。开始将二乙醇胺缓慢地滴加至三口烧瓶中。待二乙醇胺滴加完毕后，升温至80℃，持续反应3h，除去溶剂即得自乳化水性环氧树脂EGA-EP。100％固含量EGA-EP500 g，水200g，潜伏性固化剂595 2g，均质机10000rpm混合乳化成水性乳液，其稳定性情况见表1，起始固化温度见表2。
实施例4
购置南京赛润得新材料科技有限公司固含量为50％的自乳化水性环氧乳液200g，潜伏性固化剂594 8g，均质机10000rpm混合乳化成水性乳液，其放置1年未发生固化沉淀，稳定性极好，如表1所示。其初始固化温度为120℃，如表2所示。固化后的拉伸强度可达61.6MPa,断裂伸长率可达16.3％。
实施例5
购置南京赛润得新材料科技有限公司固含量为50％的自乳化水性环氧乳液200g，潜伏性固化剂594 8g，促进剂DMP-30 1g，均质机10000rpm混合乳化成水性乳液，其稳定性情况见表1，起始固化温度见表2。
实施例6
购置南京赛润得新材料科技有限公司固含量为50％的自乳化水性环氧乳液200g，潜伏性固化剂594 8g，促进剂DMP-30 3g，均质机10000rpm混合乳化成水性乳液，其稳定性情况见表1，起始固化温度见表2。
实施例7
购置南京赛润得新材料科技有限公司固含量为50％的自乳化水性环氧乳液200g，潜伏性固化剂594 8g，促进剂DBU 1g，均质机10000rpm混合乳化成水性乳液，其稳定性情况见表1，起始固化温度见表2。
实施例8
购置南京赛润得新材料科技有限公司固含量为50％的自乳化水性环氧乳液200g，潜伏性固化剂594 8g，促进剂三甲胺1g，均质机10000rpm混合乳化成水性乳液，其稳定性情况见表1，起始固化温度见表2。
实施例9
购置南京赛润得新材料科技有限公司固含量为50％的自乳化水性环氧乳液200g，潜伏性固化剂594 8g，促进剂三乙胺1g，均质机10000rpm混合乳化成水性乳液，其稳定性情况见表1，起始固化温度见表2。
实施例10
购置南京赛润得新材料科技有限公司固含量为50％的自乳化水性环氧乳液200g，潜伏性固化剂594 8g，促进剂三乙醇胺1g，均质机10000rpm混合乳化成水性乳液，其稳定性情况见表1，起始固化温度见表2。
实施例11
购置南京赛润得新材料科技有限公司固含量为50％的自乳化水性环氧乳液200g，潜伏性固化剂594 8g，促进剂吡啶1g，均质机10000rpm混合乳化成水性乳液，其稳定性情况见表1，起始固化温度见表2。
实施例12
购置南京赛润得新材料科技有限公司固含量为50％的自乳化水性环氧乳液200g，潜伏性固化剂594 8g，促进剂DMP-30苯酚盐1g，均质机10000rpm混合乳化成水性乳液，其稳定性情况见表1，起始固化温度见表2。
实施例13
购置南京赛润得新材料科技有限公司固含量为50％的自乳化水性环氧乳液200g，潜伏性固化剂594 8g，促进剂DBU甲酸盐1g，均质机10000rpm混合乳化成水性乳液，其稳定性情况见表1，起始固化温度见表2。
实施例14
购置南京赛润得新材料科技有限公司固含量为50％的自乳化水性环氧乳液200g，潜伏性固化剂594 8g，促进剂咪唑1g，均质机10000rpm混合乳化成水性乳液，其稳定性情况见表1，起始固化温度见表2。
实施例15
购置南京赛润得新材料科技有限公司固含量为50％的自乳化水性环氧乳液200g，潜伏性固化剂594 8g，促进剂2-甲基咪唑1g，均质机10000rpm混合乳化成水性乳液，其稳定性情况见表1，起始固化温度见表2。
实施例16
购置南京赛润得新材料科技有限公司固含量为50％的自乳化水性环氧乳液200g，潜伏性固化剂594 8g，促进剂2-乙基-4-甲基咪唑1g，均质机10000rpm混合乳化成水性乳液，其稳定性情况见表1，起始固化温度见表2。
表1单组分水性环氧稳定性表
表2单组分水性环氧初始固化温度
Claims (4)
1.一种单组分水性环氧树脂，其特征在于按质量份的组成为：100％固含量自乳化水性环氧树脂：100份；水：不超过1000份；有机硼胺化合物潜伏性固化剂：1～10份；促进剂：不超过3份。
2.根据权利要求1所述一种单组分水性环氧树脂，其特征在于所述100％固含量自乳化水性环氧树脂为接枝法自乳化水性环氧树脂、羧基反应法自乳化水性环氧树脂、胺基反应法自乳化水性环氧树脂中至少一种。
3.根据权利要求1所述一种单组分水性环氧树脂，其特征在于所述有机硼胺化合物潜伏性固化剂为594、595硼胺潜伏性固化剂中的至少一种，其结构分别为：
或者
4.根据权利要求1所述一种单组分水性环氧树脂，其特征在于所述促进剂为三甲胺、三乙胺、三乙醇胺、吡啶、DMP-30、2,4,6-三(二甲氨基甲基)苯酚盐、DBU、DBU盐、咪唑、2-甲基咪唑、2-乙基-4-甲基咪唑中的至少一种。
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