CN106146857B - 端羧基液体氟橡胶增韧改性环氧树脂体系的制备方法 - Google Patents
端羧基液体氟橡胶增韧改性环氧树脂体系的制备方法 Download PDFInfo
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Abstract
本发明公开了端羧基液体氟橡胶增韧改性环氧树脂体系的制备方法。本发明以端羧基液体氟橡胶和环氧树脂为原料，加热到150℃，氮气保护下反应2‑5h，通过一步法制备出改性环氧树脂预聚物。该合成方法操作简单、安全、产率高。本发明还公开了端羧基液体氟橡胶增韧改性环氧预聚物的固化方法，选择合适的固化剂六氢化邻苯二甲酸酐、聚醚胺等，在60℃‑80℃/2h+125℃/1.5h+160℃/2h固化，固化产物的韧性有了很大提高，拉伸强度最高达到31.6MP，断裂伸长率最高达到45.5％。
Description
技术领域
本发明涉及端羧基液体氟橡胶增韧改性环氧树脂体系的制备方法。
背景技术
环氧树脂是一种重要的热固性树脂，具有良好的力学性能、粘接性能、电绝缘性能、化学稳定性和尺寸稳定性，在涂料、胶粘剂、电子及航空航天等领域发挥着重要的作用。但是环氧树脂在固化过程中易产生裂纹，使其固化物质脆、抗冲击性能和耐热性较差等。从而在一定程度上限制了其在高科技领域内的应用。因此，必须对环氧树脂进行增韧改性，在不显著影响环氧树脂的力学性能的同时，使韧性得到提高。
环氧树脂的增韧方法主要分为三类:(1)添加橡胶弹性体、热塑性树脂、粒子、有机硅、液晶高分子和超支化聚合物等来增韧环氧树脂；(2)引入互穿网络提高环氧树脂的韧性；(3)研究含有柔性链段的新型固化剂，从而使环氧树的韧性提高。
液体橡胶很久以来便被用于韧性改性，本发明采用的端羧基液体氟橡胶可以从CN200910236784.7中获得。端羧基的液体氟橡胶既可以作为橡胶的增韧剂，也可作为原料来制备密封剂、胶黏剂和涂料等。另外，由于在端羧基液体氟橡胶增韧改性的环氧树脂预聚物的结构中嵌入偏氟乙烯-四氟乙烯等链段起到增韧作用，可以明显改善环氧树脂的质脆、耐冲击性差、耐介质性、耐热性不好等缺点。因此，制备端羧基液体氟橡胶改性环氧树脂预聚物在提高拉伸强度和韧性方面具有重要意义。
发明内容
本发明的目的是提供一种端羧基液体氟橡胶增韧改性环氧树脂的制备方法。
本发明通过端羧基液体氟橡胶与环氧树脂反应，制备出端羧基液体氟橡胶增韧改性的环氧树脂预聚物。包括以下步骤：
(a)以环氧树脂的质量份数(100份)与端羧基液体氟橡胶质量份数(5-25份)为原料，在150℃氮气保护下反应2-5h，通过一步反应法制备环氧树脂预聚物。
(b)在环氧树脂预聚物中加入固化剂，通过改变固化工艺，所得固化物的韧性得到改善。
本发明中所用的端羧基液体氟橡胶是偏氟乙烯-四氟乙烯共聚物、偏氟乙烯-一氯三氟乙烯共聚物、偏氟乙烯-全氟甲基乙烯基醚共聚物、偏氟乙烯-六氟丙烯共聚物、偏氟乙烯-全氟乙基乙烯基醚共聚物、偏氟乙烯-四氟乙烯-六氟丙烯三元共聚物、偏氟乙烯-丙烯-四氟乙烯三元共聚物或偏氟乙烯-四氟乙烯-全氟乙基乙烯基醚三元共聚物。
本发明中所用的环氧树脂是环氧树脂E51。
本发明中所用的固化剂可以是聚醚胺D400、二氨基二苯基砜、2-乙基-4甲基-咪唑、三乙烯四胺、酸酐类、DMP-30、三乙醇胺。固化剂的添加量以环氧树脂质量份数为100份计算为22份-39份。
所得的端羧基液体氟橡胶增韧改性的环氧树脂预聚物其结构式如下所示。
将环氧树脂预聚物和环氧树脂放到均质搅拌机中搅拌均匀后，加入固化剂，再次搅拌均匀后真空脱泡，最后将混合好的树脂注入到预热60℃的模具中，放入烘箱中程序升温固化成型，固化温度为60℃-80℃/2h+125℃/1.5h+160℃/2h。
本发明中所涉及的预聚物制备方法为一步法，过程简单易行，且羧基的转化率较高，反应过程中无需添加溶剂，安全无污染。
端羧基液体氟橡胶可以作为橡胶的增韧剂，同时也可作为原料来制备密封剂、胶黏剂和涂料等。经端羧基液体氟橡胶改性过后的环氧树脂预聚物可以与固化剂反应，固化交联后的环氧树脂的断裂伸长率有较大提高的同时，也保持了树脂的力学性能，增韧效果明显。
具体实施方式
下面结合具体实施案例对本发明作进一步的阐述。应理解，本发明不限于以下实施案例，所述方法如无特别说明均为常规方法。所述材料如无特别说明均能从公开商业途径获得。
实施例1-13为端羧基液体氟橡胶增韧改性环氧树脂的制备。
实施例1
将100g的环氧树脂E51与5g的端羧基液体氟橡胶(偏氟乙烯-六氟丙烯共聚物)加入到带有温度计、搅拌器和通氮气装置的500ml三口烧瓶中，油浴加热，打开氮气 阀，边搅拌边升温到150℃，氮气保护下反应3h，产物经红外分析测定在1763cm-1的羧基的特征峰消失，说明羧基基本全部参加反应，环氧基团也没有其他损失，最终得到端羧基液体氟橡胶改性的环氧树脂预聚物。
实施例2
将100g的环氧树脂E51与15g的端羧基液体氟橡胶(偏氟乙烯-六氟丙烯共聚物)加入到带有温度计、搅拌器和通氮气装置的500ml三口烧瓶中，油浴加热，打开氮气阀，边搅拌边升温到150℃，氮气保护下反应3h，产物经红外分析测定在1763cm-1的羧基的特征峰消失，说明羧基已全部参加反应，环氧基团也没有其他损失，最终得到端羧基液体氟橡胶改性的环氧树脂预聚物。
实施例3
将100g的环氧树脂E51与20g的端羧基液体氟橡胶(偏氟乙烯-六氟丙烯共聚物)加入到带有温度计、搅拌器和通氮气装置的500ml三口烧瓶中，油浴加热，边搅拌边升温到150℃，氮气保护中反应3h，其他与实施案例1相同，得到环氧树脂预聚物。
实施例4
将100g的环氧树脂E51与25g的端羧基液体氟橡胶(偏氟乙烯-六氟丙烯共聚物)加入到带有温度计、搅拌器和通氮气装置的500ml三口烧瓶中，油浴加热，边搅拌边升温到150℃，氮气保护中反应3h，其他与实施案例1相同，得到环氧树脂预聚物。
实施例5
将100g的环氧树脂E51与15g的端羧基液体氟橡胶(偏氟乙烯-四氟乙烯-六氟丙烯三元共聚物)加入到带有温度计、搅拌器和通氮气装置的500ml三口烧瓶中，油浴加热，边搅拌边升温到150℃，氮气保护中反应3h，其他与实施案例1相同，得到环氧树脂预聚物。
实施例6-13
具体实施方法列于下表中：
注：实施例8和10的端羧基液体氟橡胶为偏氟乙烯-六氟丙烯共聚物；实施例6、12和13的端羧基液体氟橡胶为氟乙烯-四氟乙烯-六氟丙烯三元共聚物；实施例7、9和11的端羧基液体氟橡胶为为偏氟乙烯-一氯三氟乙烯共聚物。
实施例14-20为环氧树脂预聚物的固化。
实施例14
取100g实施例1的环氧树脂预聚物和10g的环氧树脂E51在室温下混合均匀后加入32g二氨基二苯基砜固化剂和1.5g的DMP-30，再次搅拌均匀后于25℃真空脱泡，最后将混合好的树脂注入到预热至60℃的模具中，放入烘箱中程序升温固化成型，固化温度为60℃/2h+125℃/1.5h+150℃/2h。固化完全后，脱模，室温放置三天后，测试性能。拉伸强度为18.7MP，断裂伸长率为45.5％(拉伸测试按照GB/T 2567-2008)。
实施例15
取100g实施例3的环氧树脂预聚物和10g的环氧树脂E51在室温下混合均匀后加入32g二氨基二苯基砜固化剂和1.5g的DMP-30，再次搅拌均匀后于25℃真空脱泡，最后将混合好的树脂注入到预热至60℃的模具中，放入烘箱中程序升温固化成型，固化温度为60℃/2h+125℃/1.5h+150℃/2h。固化完全后，脱模，室温放置三天后，测试性能。拉伸强度为28.8MP，断裂伸长率为30.3％(拉伸测试按照GB/T 2567-2008)。
实施例16
取100g实施例3的环氧树脂预聚物和10g的环氧树脂E51在室温下混合均匀后加入22g六氢化邻苯二甲酸酐和1.1g的三乙烯四胺，再次搅拌均匀后于25℃真空脱泡，最后将混合好的树脂注入到预热至60℃的模具中，放入烘箱中程序升温固化成型，固化温度为60℃/2h+125℃/1.5h+150℃/2h。固化完全后，脱模，室温放置三天后，测试性能。拉伸强度为26.2MP，断裂伸长率为29％(拉伸测试按照GB/T 2567-2008)。
实施例17
取100g实施例3的环氧树脂预聚物和10g的环氧树脂E51在室温下混合均匀后加入36g的聚醚胺D400和2g的三乙醇胺，再次搅拌均匀后于25℃真空脱泡，最后将混合好的树脂注入到预热至60℃的模具中，放入烘箱中程序升温固化成型，固化温度为80℃/2h+125℃/1.5h。固化完全后，脱模，室温放置三天后，测试性能。拉伸强度为18.9MP，断裂伸长率为39％(拉伸测试按照GB/T 2567-2008)。
实施例18
取100g实施例3的环氧树脂预聚物和20g的环氧树脂E51在室温下混合均匀后加入25g六氢化邻苯二甲酸酐和1.3g的三乙醇胺，再次搅拌均匀后于25℃真空脱泡，最后将混合好的树脂注入到预热至60℃的模具中，放入烘箱中程序升温固化成型，固化温度为60℃/2h+125℃/1.5h+150℃/2h。固化完全后，脱模，室温放置三天后，测试性能。拉伸强度为31MP，断裂伸长率为21％(拉伸测试按照GB/T 2567-2008)。
实施例19
取100g实施例4的环氧树脂预聚物和20g的环氧树脂E51在室温下混合均匀后加入25g六氢化邻苯二甲酸酐和1.3g的三乙醇胺，再次搅拌均匀后于25℃真空脱泡，最后将混合好的树脂注入到预热至60℃的模具中，放入烘箱中程序升温固化成型，固化温度为60℃/2h+125℃/1.5h+150℃/2h。固化完全后，脱模，室温放置三天后，测试性能。拉伸强度为31.6MP，断裂伸长率为19.9％(拉伸测试按照GB/T 2567-2008)。
实施例20
取100g实施例4的环氧树脂预聚物和20g的环氧树脂E51在室温下混合均匀后加入39g的聚醚胺D400和2.2g的三乙烯四胺，固化工艺与测性方法实施例16相同，拉伸强度为21.2MP，断裂伸长率为28％。
实施例21
取100g实施例10的环氧树脂预聚物和10g的环氧树脂E51在室温下混合均匀后 加入22g六氢化邻苯二甲酸酐和1.1g的三乙醇胺，固化工艺与测性方法实施例15相同。拉伸强度为25.2MP，断裂伸长率为26％。
实施例22
取100g实施例10的环氧树脂预聚物和20g的环氧树脂在室温下混合均匀后加入25g六氢化邻苯二甲酸酐和1.3g的三乙醇胺，固化工艺与测性方法实施例15相同。拉伸强度为28.8MP，断裂伸长率为23％。
实施例23
取100g实施例12的环氧树脂预聚物和10g的环氧树脂E51在室温下混合均匀后加入22g六氢化邻苯二甲酸酐和1.1g的三乙醇胺，固化工艺与测性方法实施例15相同。拉伸强度为23.8MP，断裂伸长率为27％。
实施例24
取100g实施例12的环氧树脂预聚物和20g的环氧树脂E51在室温下混合均匀后加入25g六氢化邻苯二甲酸酐和1.3g的三乙醇胺，固化工艺与测性方法实施例15相同。拉伸强度为26.6MP，断裂伸长率为24.5％。
Claims (5)
1.一种端羧基液体氟橡胶增韧改性环氧树脂体系的制备方法，其特征在于，包括以下步骤：
(a)以环氧树脂质量份数100份与端羧基液体氟橡胶质量份数5份～25份为原料，在150℃氮气保护下反应2～5h，得到环氧树脂预聚物；
(b)在环氧树脂预聚物中加入固化剂和环氧树脂，放入烘箱中升温固化成型；
所述的固化剂是二氨基二苯基砜、2-乙基-4甲基-咪唑、三乙烯四胺、六氢化邻苯二甲酸酐、DMP-30、三乙醇胺；
固化温度为60℃-80℃/2h+125℃/1.5h+160℃/2h。
2.按照权利要求1所述的制备方法，其特征在于，所述的端羧基液体氟橡胶是偏氟乙烯-四氟乙烯共聚物、偏氟乙烯-一氯三氟乙烯共聚物、偏氟乙烯-全氟甲基乙烯基醚共聚物、偏氟乙烯-六氟丙烯共聚物、偏氟乙烯-全氟乙基乙烯基醚共聚物、偏氟乙烯-四氟乙烯-六氟丙烯三元共聚物、偏氟乙烯-丙烯-四氟乙烯三元共聚物或偏氟乙烯-四氟乙烯-全氟乙基乙烯基醚三元共聚物。
3.按照权利要求1所述的制备方法，其特征在于，所述的环氧树脂是环氧树脂E51。
4.按照权利要求1所述的制备方法，其特征在于，固化剂的添加量以环氧树脂质量份数为100份计算为22份-39份。
5.按照权利要求1所述的制备方法，其特征在于，将环氧树脂预聚物和环氧树脂放到均质搅拌机中搅拌均匀后，加入固化剂，再次搅拌均匀后真空脱泡，最后将混合好的树脂注入到预热至60℃的模具中，放入烘箱中程序升温固化成型。
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