CN115403541A - 一种含有羧基的自固化环氧树脂及其制备方法 - Google Patents
一种含有羧基的自固化环氧树脂及其制备方法 Download PDFInfo
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Abstract
Description
技术领域
本发明涉及一种环氧树脂技术领域,进一步地说,是涉及一种含有羧基的自固化环氧树脂及其制备方法。
背景技术
一般的环氧树脂需要与固化剂等混合后,在光或热等条件下才能形成三维交联网络。但这样配置的环氧树脂固化体系存在一定的局限性:(1)称量时的误差会导致固化剂与树脂的比例偏离理论的比例,进而影响固化后材料的性能;(2)固化过程中固化剂的挥发,会导致固化过程中形成孔洞,造成材料内部的缺陷,影响材料的性能;(3)固化剂与环氧树脂的相容性差,导致混合不均匀,甚至发生相分离,影响固化后材料的性能。自固化环氧树脂因其分子上存在活性反应基团,在加热条件下可与环氧基发生开环反应,形成三维网络结构,解决了多组分体系中的多相不相容,固化剂高温会挥发以及需现配现用等问题。目前在自固化树脂方面,虽然已经有多种带有活性基团的环氧树脂被合成出来,但因其调控环氧基团与活性基团的比例的工艺过于复杂,限制了单组分的自固化树脂的推广。
鉴于此,目前急需合成一种快速、精准调节固化基团含量的自固化环氧树脂。
发明内容
为解决现有技术中出现的问题,本发明提供了一种含有羧基的自固化环氧树脂及其制备方法。本发明的含有羧基的自固化环氧树脂的结构式为:
本发明利用巯基羧酸、有机溶剂、含有双键的环氧树脂单体与光引发剂混合搅拌溶解,紫外光照射反应,结束后除去多余有机溶剂,制备得到含有羧基的自固化环氧树脂。该制备方法具有反应速度快,转换率高,制备周期短,羧基含量可调控,产率高以及所得到的环氧树脂可自固化等特点。
本发明的目的之一是提供一种含有羧基的自固化环氧树脂。
所述含有羧基的自固化环氧树脂的结构式为:
X为-H、C1-C4烷烃基或-CH2COOH;优选为-H、-CH3、-CH2CH3或-CH2COOH;
n=1~17;优选为n=1~7;
其中:-*表示为R1-O的部分,-**表示为S-R1的部分;
其中:-*表示为R2-O的部分,-**表示为S-R2的部分。
本发明的目的之二是提供一种本发明的目的之一的自固化环氧树脂的制备方法。
包括:
将巯基羧酸、有机溶剂、含有双键的环氧树脂单体与光引发剂混合搅拌溶解,紫外光照射反应,旋蒸脱除溶剂,制得所述含有羧基的自固化环氧树脂。
所述巯基羧酸具有如下的结构:
其中,X为-H、C1-C4烷烃基或-CH2COOH;
n=1~17;
本发明的一种优选的实施方式中,
所述巯基羧酸为巯基乙酸、3-巯基丙酸、4-巯基丁酸、巯基丁二酸、2-巯基丙酸、2-巯基丁酸、5-巯基戊酸、6-巯基己酸、7-巯基庚酸、8-巯基辛酸中的至少一种。
本发明的一种优选的实施方式中,
所述含有双键的环氧树脂单体具有如下的结构:
具有单官能度的环氧基团的单体结构为:
其中:-*表示为R3-O的部分;
具有双官能度的环氧基团的单体结构为:
R4为
其中:-*表示为R4-O的部分。
本发明的一种优选的实施方式中,
所述含有双键的环氧树脂单体为烯丙醇缩水甘油醚、4,4'-二烯丙基双酚A环氧树脂或丁香酚环氧树脂的中的一种。
本发明的一种优选的实施方式中,
所述有机溶剂为丙酮、四氢呋喃中的至少一种;和/或,
所述光引发剂为2-羟基-2-甲基-1-苯基-1-丙酮、2-甲基-1-[4-(甲基硫代)苯基]-2-(4-吗啉基)-1-丙酮、1-羟基环己基苯基甲酮或安息香双甲醚中的至少一种。
本发明的一种优选的实施方式中,
所述环氧树脂单体中的双键与巯基羧酸中的巯基的摩尔比为1:(0.1~2);优选为1:(0.5~1.5);
所述有机溶剂与巯基羧酸的质量比为1:1~4:1;
所述光引发剂的用量为反应物总量的0.1wt%~1.5wt%。
本发明的一种优选的实施方式中,
紫外光光源为面光源,其紫外光波长范围为360~370nm;紫外光照射时间为30~60分钟;旋蒸压力为-0.05~-0.1MPa;旋蒸温度为30~50℃;旋蒸时间为10~20min。
本发明的具体技术方案如下:
将巯基羧酸、有机溶剂、含有双键的环氧树脂单体与光引发剂投入到单口瓶中,充分搅拌后溶解。在紫外光的照射下进行反应。反应结束后,除去体系内多余的有机溶剂,得到产物羧基自固化环氧树脂。
紫外光波长范围为360~370nm,优选为365nm;控制紫外光照射时间为30~60分钟;脱除溶剂时,控制旋蒸过程中压力为-0.05MPa~-0.1MPa之间,优选为-0.1MPa;控制旋蒸过程中的温度为30~50℃之间,优选为40℃;控制旋蒸过程的时间为10~20min,优选为15min。
本发明的原理如下:
本发明主要是基于巯基-烯点击化学反应,该反应遵循自由基加成机理:光引发剂在紫外光的引发下首先产生自由基,随后引发剂上的自由基夺取巯基上的氢原子生成巯基自由基,巯基自由基随后与双键进行加成反应且自由基转移在双键上生成一个新的自由基,该自由基再夺取未反应的巯基上的氢原子得到最终的加成产物并且生成新的巯基自由基,从而使得反应可以不断进行下去。
本发明的有益效果如下:
该制备方法具有反应速度快,转换率高,制备周期短,羧基含量可调控,产率高以及所得到的环氧树脂可自固化等特点。由于得到的树脂上接枝有羧酸基团,该树脂还可应用于水下粘接领域。
附图说明
图1为实施例1反应产物的红外光谱图,横坐标表示波数,纵坐标表示吸光度;
图2为实施例1反应产物的核磁氢谱图,横坐标表示化学位移;
图3为实施例5反应产物的红外光谱图,横坐标表示波数,纵坐标表示吸光度;
图4为实施例5反应产物的核磁氢谱图,横坐标表示化学位移;
图5为实施例7反应产物的红外光谱图,横坐标表示波数,纵坐标表示吸光度。
具体实施方式
下面结合具体附图及实施例对本发明进行具体的描述,有必要在此指出的是以下实施例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,本领域技术人员根据本发明内容对本发明做出的一些非本质的改进和调整仍属本发明的保护范围。
本发明所用的含有双键的环氧树脂单体可以由相应的化合物与环氧氯丙烷反应制得或者直接购买得到,所用的巯基羧酸可以直接购得。自制的4,4'-二烯丙基双酚A环氧树脂的制备方法参考CN1618830A,丁香酚环氧树脂的制备方法参考CN105924623A。
本发明中应用到的检测设备及型号:
1.美国NICIOL公司ALPHA型傅里叶红外光谱仪;
2.瑞士Bruker公司A-400型核磁共振波谱仪;
3.美斯特工业系统有限公司CMT4204型电子万能材料试验机。
实施例1:
本实施例制备的含有羧基的自固化环氧树脂的结构如下所示:
在50ml的单口瓶中,加入8.192g的巯基丁二酸,20g四氢呋喃,10g的4,4'-二烯丙基双酚A环氧树脂和0.18g的光引发剂1173,搅拌10分钟后溶解,在365nm紫外光面光源的照射下,室温反应40min。然后在40℃/-0.1MPa下旋蒸15min除去多余的四氢呋喃,得到产物。反应产物的红外谱图见图1,核磁氢谱见图2。图1和图2均说明成功合成了如实施例1结构图所示的产物。红外光谱中位于1638cm-1处的烯丙基双键峰的消失,同时位于1726cm-1处的羰基峰的出现,说明成功合成了该产物;核磁氢谱中位于5.0-6.0ppm的烯丙基双键峰的消失以及位于12ppm左右有明显的-OH峰生成,这也表明产物的成功合成。
实施例2:
本实施例制备的含有羧基的自固化环氧树脂的结构如下所示:
在50ml的单口瓶中,加入9.729g的巯基乙酸,20g丙酮,12g的烯丙醇缩水甘油醚和0.21g的光引发剂1173,搅拌10分钟后溶解,在365nm紫外光面光源的照射下,室温反应30min。然后在40℃/-0.1MPa下旋蒸15min除去多余的丙酮,得到产物。
实施例3:
本实施例制备的含有羧基的自固化环氧树脂的结构如下所示:
在100ml的单口瓶中,加入15.45g的8-巯基辛酸,20g丙酮,10g的烯丙醇缩水甘油醚和0.40g的光引发剂184,搅拌10分钟后溶解,在365nm紫外光面光源的照射下,室温反应30min。然后在40℃/-0.1MPa下旋蒸15min除去多余的丙酮,得到产物。
实施例4:
本实施例制备的含有羧基的自固化环氧树脂的结构如下所示:
在100ml的单口瓶中,加入20.619g的2-巯基丁酸,40g四氢呋喃,19.5g的烯丙醇缩水甘油醚和0.80g的光引发剂184,搅拌10分钟后溶解,在365nm紫外光面光源的照射下,室温反应50min。然后在40℃/-0.1MPa下旋蒸15min除去多余的四氢呋喃,得到产物。
实施例5:
本实施例制备的含有羧基的自固化环氧树脂的结构如下所示:
在100ml的单口瓶中,加入8.601g的3-巯基丙酸,30g四氢呋喃,21g的4,4'-二烯丙基双酚A环氧树脂和0.63g的光引发剂184,搅拌10分钟后溶解,在365nm紫外光面光源的照射下,室温反应30min。然后在40℃/-0.1MPa下旋蒸15min除去多余的四氢呋喃,得到产物。反应产物的红外谱图见图3,核磁谱图见图4。图3和图4均说明成功合成了如实施例5结构图所示的产物。红外光谱中位于1638cm-1处的烯丙基双键峰的消失,同时位于1729cm-1处的羰基峰的出现,说明成功合成了该产物;核磁氢谱中位于5.0-6.0ppm的烯丙基双键峰的消失以及位于12ppm左右有明显的-OH峰生成,这也表明产物的成功合成。
实施例6:
本实施例制备的含有羧基的自固化环氧树脂的结构如下所示:
在100ml的单口瓶中,加入4.916g的巯基丁二酸,3.476g的3-巯基丙酸,25g丙酮,12g的4,4'-二烯丙基双酚A环氧树脂和0.50g的光引发剂184,搅拌10分钟后溶解,在365nm紫外光面光源的照射下,室温反应30min。然后在40℃/-0.1MPa下旋蒸15min除去多余的丙酮,得到产物。
实施例7:
本实施例制备的含有羧基的自固化环氧树脂的结构如下所示:
在50ml的单口瓶中,加入6.601g的巯基丁二酸,15g四氢呋喃,10g的烯丙醇缩水甘油醚和0.24g的光引发剂184,搅拌10分钟后溶解,在365nm紫外光面光源的照射下,室温反应40min。然后在40℃/-0.1MPa下旋蒸15min除去多余的四氢呋喃,得到产物。反应产物的红外谱图见图5。图5说明成功合成了如实施例7结构图所示的产物。红外光谱中位于1638cm-1处的烯丙基双键峰的消失,同时位于1726cm-1处的羰基峰的出现,说明成功合成了该产物。
实施例8:
本实施例将实施例1至实施例7制备的含有羧基的自固化环氧树脂用于水下粘接领域:
加入3g制备的环氧树脂,然后加入0.03g的1-甲基咪唑,混合均匀后在水中涂膜在打磨好的铝合金板和碳钢板上。在水中放置4天后对铝合金板之间的粘接强度和碳钢板之间的粘接强度进行测试。得到结果如表6所示。结果表明,这种含有羧基的自固化环氧树脂可以应用在水下粘接的领域。
表1为实施例1至实施例7制备的环氧树脂的水下粘接性能。测试标准参考GB/T7124-2008。
表1实施例1至实施例7制备的环氧树脂的水下粘接性能
样品 | 水下铝合金样件 | 水下碳钢板样件 |
实施例1制备的环氧树脂 | 1.93MPa | 3.77MPa |
实施例2制备的环氧树脂 | 3.13MPa | 4.88MPa |
实施例3制备的环氧树脂 | 3.05MPa | 4.76MPa |
实施例4制备的环氧树脂 | 3.22MPa | 5.04MPa |
实施例5制备的环氧树脂 | 4.32MPa | 5.35MPa |
实施例6制备的环氧树脂 | 3.02MPa | 4.56MPa |
实施例7制备的环氧树脂 | 1.56MPa | 2.89MPa |
Claims (10)
3.一种根据权利要求1~2任一所述的自固化环氧树脂的制备方法,其特征在于所述方法包括:
将巯基羧酸、有机溶剂、含有双键的环氧树脂单体与光引发剂混合搅拌溶解,紫外光照射反应,旋蒸脱除溶剂,制得所述含有羧基的自固化环氧树脂。
5.根据权利要求4所述的自固化环氧树脂的制备方法,其特征在于:
所述巯基羧酸为巯基乙酸、3-巯基丙酸、4-巯基丁酸、巯基丁二酸、2-巯基丙酸、2-巯基丁酸、5-巯基戊酸、6-巯基己酸、7-巯基庚酸、8-巯基辛酸中的至少一种。
7.根据权利要求6所述的自固化环氧树脂的制备方法,其特征在于:
所述含有双键的环氧树脂单体为烯丙醇缩水甘油醚、4,4'-二烯丙基双酚A环氧树脂或丁香酚环氧树脂的中的一种。
8.根据权利要求3所述的自固化环氧树脂的制备方法,其特征在于:
所述有机溶剂为丙酮、四氢呋喃中的至少一种;和/或,
所述光引发剂为2-羟基-2-甲基-1-苯基-1-丙酮、2-甲基-1-[4-(甲基硫代)苯基]-2-(4-吗啉基)-1-丙酮、1-羟基环己基苯基甲酮或安息香双甲醚中的至少一种。
9.根据权利要求3所述的自固化环氧树脂的制备方法,其特征在于:
所述环氧树脂单体中的双键与巯基羧酸中的巯基的摩尔比为1:(0.1~2);
所述有机溶剂与巯基羧酸的质量比为1:1~4:1;
所述光引发剂的用量为反应物总量的0.1wt%~1.5wt%。
10.根据权利要求3所述的自固化环氧树脂的制备方法,其特征在于:
紫外光光源为面光源,其紫外光波长范围为360~370nm;紫外光照射时间为30~60分钟;旋蒸压力为-0.05~-0.1MPa;旋蒸温度为30~50℃;旋蒸时间为10~20min。
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