CN106478712B - 一种环氧端基对苯撑苯并二噁唑前驱体的制备方法 - Google Patents
一种环氧端基对苯撑苯并二噁唑前驱体的制备方法 Download PDFInfo
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Abstract
本发明提供了一种环氧端基对苯撑苯并二噁唑前驱体的制备方法，基于TBS‑DAR合成PBO的方案，通过中间体TPC‑prePBO的酰氯基团与羟基反应，将含有环氧基团的缩水甘油引入到PBO分子结构中，制备出Epoxy‑prePBO。本发明采用与PBO纤维具有较好相容性的环氧端基对苯撑苯并二噁唑前驱体Epoxy‑prePBO对BADCy树脂进行共聚改性，使Epoxy‑prePBO/BADCy改性树脂和PBO纤维的界面粘接强度得到改善，PBO纤维/BADCy微复合材料的单丝拔出强度由现有技术的2.93MPa增加到3.02～3.10。
Description
技术领域
本发明属于化学技术领域，涉及一种新型环氧端基对苯撑苯并二噁唑前驱体的制备方法。
背景技术
目前我国雷达天线罩用树脂基体如环氧树脂(EP)、聚酰亚胺(PI)和双马来酰亚胺(BMI)等不同程度的存在或耐湿热性差、或介电性能不佳、或尺寸稳定性差等缺陷。随着信息通讯技术的发展，雷达的使用功率越来越高，迫切需要新一代宽频、低损耗，耐高温、耐湿热性和力学性能优异的树脂基透波复合材料。氰酸酯(CE)树脂被公认为是树脂基透波复合材料最佳基体候选材料，具有极优的介电性能，可在宽广的温度和频率范围内保持稳定的低介电常数(2.6～3.0)和介质损耗角正切值(0.005～0.01)，优异的机械强度、良好的耐湿热性和较高的尺寸稳定性等，已广泛应用于雷达天线罩和卫星天线系统。
聚对苯撑苯并二噁唑(PBO)纤维具有较低的密度(1.56g/cm3)，优异的介电性能(介电常数为3.0，介电损耗因子为0.001)，卓越的力学性能(强度达5.8GPa，模量达270GPa)，且最高分解温度为650℃，被誉为21世纪的超级纤维，正被广泛应用于国防、航空/航天和星球探测等重要领域。然而，PBO纤维表面光滑，活性基团少，表现出很强的化学惰性，与CE树脂基体的界面相容性(界面粘接强度)差，导致PBO纤维/CE树脂基复合材料的层间剪切强度(ILSS)差。因此，如何提高PBO纤维与CE树脂基体间的界面相容性(界面粘接强度)已成为该领域的研究热点和难点。
目前，国内外大多采用化学改性(包括表面化学刻蚀、偶联剂改性和酶改性)、等离子体改性和辐射改性等方法对PBO表面进行处理来改善PBO纤维的表面性能，改进PBO纤维与聚合物树脂基体界面相容性，提高界面粘接强度。但现有PBO纤维表面改性方法易对PBO纤维本身造成损伤，影响PBO纤维的本体性能；同时采用表面改性方法处理的PBO纤维量太少，无法满足大批量低成本复合材料的制备要求。
发明内容
为了克服现有技术的不足，本发明提供一种与PBO纤维具有较好相容性的新型环氧端基对苯撑苯并二噁唑前驱体(Epoxy-prePBO)，利用酰氯基团与羟基的反应，将含环氧端基的缩水甘油键接到PBO分子结构中，再经共聚方式引入到双酚A氰 酸酯(BADCy)三嗪环结构中，制备Epoxy-prePBO/BADCy改性树脂，有效提高PBO纤维和BADCy树脂基体的界面粘接强度(层间剪切强度)。
本发明解决以上技术问题的方案包括以下步骤：
(a)氩气环境下，将2.13g的4,6-二氨基间苯二酚二盐酸盐溶于100ml的N,N-二甲基甲酰胺中；随后加入15g的叔丁基二甲基氯硅烷及20ml的缚酸剂三乙胺，室温下磁力搅拌24h；用500ml去离子水沉降，经抽滤、水洗后在80℃真空中干燥24h得黄色固体TBS-DAR；
(b)氩气冰浴环境下，将2.98g TBS-DAR、2.13g的对苯二甲酰氯及250ml的二氯甲烷依次混合，磁力搅拌24h，得到反应液；
(c)向反应液中逐滴加入1.06g的TEA，磁力搅拌1h，然后加入1.56g的缩水甘油，继续磁力搅拌12h；抽滤后于35℃旋蒸，将旋蒸后固体倒入500ml去离子水中充分搅拌，再经抽滤、水洗后在60℃烘箱中真空干燥12h，得黄色粉末即环氧端基对苯撑苯并二噁唑前驱体。
所述的步骤(b)中，吸取不少于25ml的反应液于35℃旋蒸，得黄绿色粉末TPC-prePBO，作为对反应液的表征。
所述的步骤(c)之后，将环氧端基对苯撑苯并二噁唑前驱体中加入N,N-二甲基甲酰胺中，搅拌、超声至酒红色澄清溶液；然后按一定质量比加入双酚A环氧树脂和双酚A型氰酸酯树脂，于150℃油浴锅中预聚3.5h，得Epoxy-prePBO/BADCy改性树脂，测量PBO纤维/Epoxy-prePBO/BADCy微复合材料的单丝拔出强度，作为对界面性能的表征。
本发明的有益结果是：采用自行合成的与PBO纤维具有较好相容性的新型环氧端基对苯撑苯并二噁唑前驱体Epoxy-prePBO对BADCy树脂进行共聚改性，使Epoxy-prePBO/BADCy改性树脂和PBO纤维的界面粘接强度得到改善，PBO纤维/BADCy微复合材料的单丝拔出强度由现有技术的2.93MPa增加到3.02～3.10。
附图说明
图1为本发明实施例1、2中TBS-DAR、TPC-prePBO、Epoxy-prePBO及Epoxy-prePBO/BADCy改性树脂的合成示意图。
图2为本发明实施例1、2中TBS-DAR的1H NMR图。
图3为本发明实施例1、2中TPC-prePBO的1H NMR图。
图4为本发明实施例1、2中Epoxy-prePBO的1H NMR图。
图5为本发明实施例1、2中Epoxy-prePBO/BADCy改性树脂与PBO纤维的单丝拔出强度分析图。
具体实施方式
下面结合附图和具体实施例子对本发明的技术方案做进一步详细的说明。
本发明的思路是：基于TBS-DAR合成PBO的方案，通过中间体TPC-prePBO的酰氯基团与羟基反应，将含有环氧基团的缩水甘油引入到PBO分子结构中，制备出Epoxy-prePBO。利用Epoxy-prePBO的可溶性，将Epoxy-prePBO溶于DMF中，与BADCy充分共聚制备Epoxy-prePBO/BADCy改性树脂，研究Epoxy-prePBO用量对Epoxy-prePBO/BADCy改性树脂与PBO纤维界面性能的影响。
本发明包括以下步骤：
(a)氩气环境下，将2.13g的4,6-二氨基间苯二酚二盐酸盐(DAR)溶于100ml的N,N-二甲基甲酰胺(DMF)中，倒入到无水Schelenk瓶中；随后加入15.00g的叔丁基二甲基氯硅烷(TBS)及20ml的缚酸剂三乙胺(TEA)，室温下磁力搅拌24h。用500ml去离子水沉降，经抽滤、水洗后在80℃烘箱中真空干燥24h得黄色固体TBS-DAR；
(b)氩气冰浴环境下，将2.98g步骤(a)的TBS-DAR、2.13g的对苯二甲酰氯(TPC)及250ml的二氯甲烷依次加入到无水Schelenk瓶中，磁力搅拌24h。若要对产物进行表征，可吸取不少于25ml的反应液于35℃旋蒸，得黄绿色粉末TPC-prePBO；
(c)向步骤(b)的反应体系中逐滴加入1.06g的TEA，磁力搅拌1h，然后加入1.56g的缩水甘油，继续磁力搅拌12h。抽滤后于35℃旋蒸，将旋蒸后固体倒入500ml去离子水中充分搅拌，再经抽滤、水洗后在60℃烘箱中真空干燥12h，得黄色粉末即环氧端基对苯撑苯并二噁唑前驱体Epoxy-prePBO。
将步骤(c)Epoxy-prePBO加入盛有DMF的烧杯中，搅拌、超声至酒红色澄清溶液然后按一定质量比加入双酚A环氧树脂(E-51)和双酚A型氰酸酯树脂(BADCy)，于150℃油浴锅中预聚3.5h，得Epoxy-prePBO/BADCy改性树脂，测量PBO纤维/Epoxy-prePBO/BADCy微复合材料的单丝拔出强度，对界面性能进行表征。
实施例1：
(a)氩气环境下，将2.13g的4,6-二氨基间苯二酚二盐酸盐(DAR)溶于100ml的N,N-二甲基甲酰胺(DMF)中，倒入到无水Schelenk瓶中；随后加入15.00g的叔丁基二甲基氯硅烷(TBS)及20ml的缚酸剂三乙胺(TEA)，室温下磁力搅拌24h。用500ml去离子水沉降，经抽滤、水洗后在80℃烘箱中真空干燥24h得黄色固体TBS-DAR；
(b)氩气冰浴环境下，将2.98g步骤(a)的TBS-DAR、2.13g的对苯二甲酰氯(TPC)及250ml的二氯甲烷依次加入到无水Schelenk瓶中，磁力搅拌24h。若要对产物进行表征，可吸取不少于25ml反应液于35℃旋蒸，得黄绿色粉末TPC-prePBO；
(c)向步骤(b)的反应体系中逐滴加入1.06g的TEA，磁力搅拌1h，然后加入1.56g的缩水甘油，继续磁力搅拌12h。抽滤后于35℃旋蒸，将旋蒸后固体倒入500ml去离子水中充分搅拌，再经抽滤、水洗后在60℃烘箱中真空干燥12h，得黄色粉末即环氧端基对苯撑苯并二噁唑前驱体Epoxy-prePBO；
(d)将0.12g步骤(c)的Epoxy-prePBO粉末加入盛有DMF的25ml小烧杯中，搅拌、超声至酒红色澄清溶液。然后加入0.19g的E-51和3.69g的BADCy，于150℃油浴锅中预聚3.5h，得3wt％Epoxy-prePBO用量的Epoxy-prePBO/BADCy改性树脂，测量PBO纤维/Epoxy-prePBO/BADCy微复合材料的单丝拔出强度。
经测试，PBO纤维/Epoxy-prePBO/BADCy微复合材料的单丝拔出强度为3.02MPa。
实施例2：
注：在本发明中TBS-DAR、TPC-prePBO、Epoxy-prePBO及单丝拔出试样的制备及与实施例1的描述均一致，在以下的实施案例中只介绍7wt％Epoxy-prePBO用量的Epoxy-prePBO/BADCy改性树脂的制备及单丝拔出强度测试。
将0.28g步骤(c)的Epoxy-prePBO粉末加入盛有DMF的25ml小烧杯中，搅拌、超声至酒红色澄清溶液。然后加入0.19g的E-51和3.53g的BADCy，于150℃油浴锅中预聚3.5h，得7wt％Epoxy-prePBO用量的Epoxy-prePBO/BADCy改性树脂，测量PBO纤维/Epoxy-prePBO/BADCy微复合材料的单丝拔出强度。
经测试，PBO纤维/Epoxy-prePBO/BADCy微复合材料的单丝拔出强度为3.10MPa。
以上所述，仅为本发明较佳的具体实施方案，本发明的保护范围不限于此，任何熟悉本技术领域的技术人员在本发明披露的技术范围内，可显而易见的得到的技术方案的简单变化或等效替换均落入本发明的保护范围内。
Claims (3)
1.一种环氧端基对苯撑苯并二噁唑前驱体的制备方法，其特征在于包括下述步骤：
(a)氩气环境下，将2.13g的4,6-二氨基间苯二酚二盐酸盐溶于100ml的N,N-二甲基甲酰胺中；随后加入15g的叔丁基二甲基氯硅烷及20ml的缚酸剂三乙胺，室温下磁力搅拌24h；用500ml去离子水沉降，经抽滤、水洗后在80℃真空中干燥24h得黄色固体TBS-DAR；
(b)氩气冰浴环境下，将2.98g TBS-DAR、2.13g的对苯二甲酰氯及250ml的二氯甲烷依次混合，磁力搅拌24h，得到反应液；
(c)向反应液中逐滴加入1.06g的TEA，磁力搅拌1h，然后加入1.56g的缩水甘油，继续磁力搅拌12h；抽滤后于35℃旋蒸，将旋蒸后固体倒入500ml去离子水中充分搅拌，再经抽滤、水洗后在60℃烘箱中真空干燥12h，得黄色粉末即环氧端基对苯撑苯并二噁唑前驱体。
2.根据权利要求1所述的环氧端基对苯撑苯并二噁唑前驱体的制备方法，其特征在于：所述的步骤(b)中，吸取不少于25ml的反应液于35℃旋蒸，得黄绿色粉末TPC-prePBO，作为对反应液的表征。
3.根据权利要求1所述的环氧端基对苯撑苯并二噁唑前驱体的制备方法，其特征在于：所述的步骤(c)之后，将环氧端基对苯撑苯并二噁唑前驱体加入N,N-二甲基甲酰胺中，搅拌、超声至酒红色澄清溶液；然后按一定质量比加入双酚A环氧树脂和双酚A型氰酸酯树脂，于150℃油浴锅中预聚3.5h，得Epoxy-prePBO/BADCy改性树脂，测量PBO纤维/Epoxy-prePBO/BADCy微复合材料的单丝拔出强度，作为对界面性能的表征。
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