CN117507511B - 一种阻燃耐腐蚀环氧树脂基覆铜板及其制备方法 - Google Patents

一种阻燃耐腐蚀环氧树脂基覆铜板及其制备方法 Download PDF

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CN117507511B
CN117507511B CN202311467029.6A CN202311467029A CN117507511B CN 117507511 B CN117507511 B CN 117507511B CN 202311467029 A CN202311467029 A CN 202311467029A CN 117507511 B CN117507511 B CN 117507511B
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朱利明
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Jiangsu Yaohong Electronics Co ltd
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Abstract

本发明涉及覆铜板技术领域，具体为一种阻燃耐腐蚀环氧树脂基覆铜板及其制备方法。具体包括以下步骤：S1：对氧化石墨烯进行氨化、分散预处理，后与DOPO反应接枝，得到改性石墨烯；S2：用端氨基超支化聚酰胺对环氧树脂进行改性处理，得到改性环氧树脂；S3：对玻璃纤维、丙纶纤维进行改性处理，制成纤维布；S4：将树脂胶液涂覆到纤维布上，制成半固化片，将铜箔覆于半固化片两面，经热压制成阻燃耐腐蚀环氧树脂基覆铜板。所述树脂胶液包括以下组分，按质量份数计：改性环氧树脂40～60份、改性石墨烯15～30份、溶剂60～90份、阻燃剂5～10份、抗氧剂2～4份、固化剂5～10份、固化促进剂0.05～0.2份。

Description

一种阻燃耐腐蚀环氧树脂基覆铜板及其制备方法
技术领域
本发明涉及覆铜板技术领域，具体为一种阻燃耐腐蚀环氧树脂基覆铜板及其制备方法。
背景技术
覆铜板是将补强材料浸以树脂，一面或两面覆以铜箔，再经热压处理形成的一种板状材料，称为覆铜箔层压板。覆铜板是电子工业领域的基础材料，主要用于加工制造印制电路板，目前已广泛应用到电视机、收音机、计算机、移动终端、手机等通讯设备和其他电子设备的领域。覆铜板为电子信息工业的基础材料，常常会因为阻燃性不高，导致覆铜板引起失火，损害物件，所以其阻燃性显得尤为重要。此外，随着电子技术的高速发展，部分产品对覆铜板耐腐蚀要求也相应提高，所以需要开发研究出一种具有良好耐腐蚀性、阻燃性能的覆铜板，以适应市场需求。
综上所述，为了适应生产需要，本发明将制备一种阻燃耐腐蚀环氧树脂基覆铜板，其具有重要意义。
发明内容
本发明的目的在于提供一种阻燃耐腐蚀环氧树脂基覆铜板及其制备方法，以解决上述背景技术中提出的问题。
为了解决上述技术问题，本发明提供如下技术方案：
一种阻燃耐腐蚀环氧树脂基覆铜板的制备方法，包括以下步骤：
步骤一：对氧化石墨烯进行预处理，后与DOPO反应接枝，得到改性石墨烯；
步骤二：用端氨基超支化聚酰胺对环氧树脂进行改性处理，得到改性环氧树脂；
步骤三：对玻璃纤维、丙纶纤维进行改性处理，制成纤维布；
步骤四：将改性环氧树脂、改性石墨烯、溶剂、阻燃剂、抗氧剂、固化剂、固化促进剂混合均匀，配制得到树脂胶液；将树脂胶液涂覆到若干张纤维布上，经干燥制成若干张半固化片，将铜箔覆于半固化片两面，经热压制成阻燃耐腐蚀环氧树脂基覆铜板。
进一步的，所述氧化石墨烯预处理过程为：（1）先对氧化石墨烯进行微波处理，再将其置于20~28wt%的氨水溶液中，在80~90℃下，超声分散处理4~8h后，待其反应液自然冷却至室温，经过滤、洗涤、干燥，得到氨化石墨烯；（2）再将无水乙醇、分散剂和氨化石墨烯混合，超声分散处理2~4h后，经旋蒸处理，除去无水乙醇，得到预处理石墨烯。
进一步的，所述微波处理为低火加热，微波功率为100~120W，加热时间10~30s。
进一步的，所述无水乙醇、分散剂、氨化石墨烯三者质量比为10:(0.01~0.5):1。
进一步的，所述改性石墨烯的制备方法为：（1）将DOPO、溶剂、三乙胺混合，得到混合液；（2）调节混合液的温度至-5~10℃，搅拌下，在0.5~1h内，向混合液中滴加四氯化碳，滴加完毕后，继续搅拌反应2~5h，得到反应液A；（3）调节温度至30~60℃，向反应液A中加入预处理石墨烯，回流反应24~48h后，经减压蒸馏、过滤、洗涤、干燥，得到改性石墨烯。
进一步的，所述DOPO、溶剂、三乙胺、四氯化碳、预处理石墨烯五者质量比为(0.5~1):10:5:2:1。
进一步的，所述溶剂包括但不限于无水乙醇、乙二醇、异丙醇、正丁醇、环己醇、乙醚、氯仿、二氯甲烷中的一种或多种的组合。
进一步的，所述改性环氧树脂的制备方法为：氮气保护下，将环氧树脂加热熔融，然后加入端氨基超支化聚酰胺、2,5-二吡啶羧酸，以300~400r/min的转速搅拌3~6h，得到改性环氧树脂，备用。
进一步的，所述环氧树脂、端氨基超支化聚酰胺、2,5-二吡啶羧酸三者的质量为(0.5~1.5):1:(0.05~0.15)。
进一步的，所述环氧树脂包括双酚A型环氧树脂、双酚F型环氧树脂中的任一种。
进一步的，所述纤维布的制备方法为：（1）将玻璃纤维和丙纶纤维超声分散在去离子水中，在45~60℃下，边搅拌边滴加钛酸四丁酯的乙醇溶液，滴加完毕后继续反应6~18h，再加入γ-氨丙基三乙氧基硅烷，调节温度至70~80℃，机械搅拌20~30min，最后经过滤、洗涤、干燥，得到改性纤维；（2）将改性纤维单丝平织，密度为20~60目/cm，得到基础纤维布；（3）再将基础纤维布置于改性环氧树脂中浸渍1~3h，后挤出基础纤维布上多余浆料，排除气泡，得到预成型纤维布；（4）再将改性纤维短切成10~12mm长度，将其均匀铺设在预成型纤维布上，再涂覆上一层改性环氧树脂，涂覆密度1.5~2.3g/cm2，送入烘箱中以100~140℃烘烤10~30min，最后在365nm紫外光下紫外固化1~3h，得到纤维布。
进一步的，所述丙纶纤维加入量为玻璃纤维质量的10~30%。
进一步的，所述钛酸四丁酯加入量为纤维总质量的10~15%。
进一步的，所述γ-氨丙基三乙氧基硅烷加入量为纤维总质量的3~8%。
进一步的，所述步骤四的具体过程为：（1）向步骤二得到的改性环氧树脂中加入改性石墨烯、溶剂、阻燃剂、抗氧剂、固化剂、固化促进剂混合均匀，配制得到树脂胶液；（2）用浸渍胶液法将纤维布浸入树脂胶液中5~10min后，在烘箱中以110~140℃烘烤30~60min，得到半固化片；（3）将若干张半固化片叠加到一起，铜箔覆于半固化片两面，以12~20MPa的压力，在200~220℃下热压2~5h，得到阻燃耐腐蚀环氧树脂基覆铜板。
进一步的，所述树脂胶液包括以下组分，按质量份数计：改性环氧树脂40~60份、改性石墨烯15~30份、溶剂60~90份、阻燃剂5~10份、抗氧剂2~4份、固化剂5~10份、固化促进剂0.05~0.2份。
与现有技术相比，本发明所达到的有益效果是：本发明通过对氧化石墨烯微波处理后，再进行氨化、分散预处理，后与DOPO反应，解决了氧化石墨烯在树脂中分散性不好的问题，使其具有良好的分散性，同时赋予氧化石墨烯更高的阻燃性能；再对环氧树脂进行改性，接枝引入超支化聚酰胺，使环氧树脂的耐热性能进一步加强；通过对氧化石墨烯和环氧树脂改性，两者与阻燃剂协同赋予树脂良好的阻燃性能；另外石墨烯能够赋予树脂耐腐蚀性能，通过对其改性后，由于其分散性差的问题得到了解决，其促进树脂耐腐蚀性能也得到了加强。为了进一步对覆铜板的阻燃和耐腐蚀性能进行加强，本发明对纤维布也进行了处理，使纤维布的耐腐蚀性能得到了改善，与树脂胶液结合也更牢固，进而促进覆铜板的阻燃、耐腐蚀性能。综上所述，本发明最终制备得到了一种具有高阻燃性能和高耐腐蚀性能的环氧树脂基覆铜板。
（1）石墨烯具有良好的耐腐蚀性能，本发明先对氧化石墨烯进行微波处理，微波处理后可以增大氧化石墨烯的层间距，使其更易分散，再通过与氨水反应，在氧化石墨烯表面引入氨基，再通过分散剂处理，使氧化石墨烯在树脂中分散性较差的问题的得到了解决；
（2）DOPO是一种优异的阻燃剂，将预处理后的氧化石墨烯和DOPO进行反应接枝，氮磷协同增强氧化石墨烯的阻燃性能，使氧化石墨烯可作为一种阻燃耐腐蚀填料；
（3）本发明中对环氧树脂进行了接枝改善，使改性石墨烯能够更好的分散在其中，进而使树脂具有更好的阻燃性能和耐腐蚀性能；方案中将其与端氨基超支化聚酰胺、2,5-二吡啶羧酸进行了接枝，引入了酰胺基、吡啶基，进一步增强环氧树脂的阻燃性能；
（4）本发明中通过将玻璃纤维、丙纶纤维两者按一定比例混合，并在其表面沉积一层二氧化钛，再通过γ-氨丙基三乙氧基硅烷改性处理和紫外光辐照处理，使其与树脂结合性更好，促进相容，最终使得覆铜板具有优异的阻燃性能、耐腐蚀性能。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
以下实施例中，氧化石墨烯纯度为99%，单层，片径：0.5~5μm，厚度：0.8~1.2nm，（昀冠（上海）生物科技有限公司）、25wt%、20wt%、28%wt氨水（济南源飞伟业化工有限公司）、十二烷基苯磺酸钠的纯度为99%，货号：R180（盼得（上海）国际贸易有限公司）、DOPO的纯度为97%，货号：S46419（上海源叶生物科技有限公司）、三乙胺纯度为99.5%（昆山惠尔众化工有限公司）、四氯化碳纯度为99%（茂名市雄大化工有限公司深圳分公司）、双酚A型环氧树脂纯度为99%，型号：E-12（604），货号：0002（武汉普洛夫生物科技有限公司）、端氨基超支化聚酰胺纯度为99%，货号：094032（上海科拉曼试剂有限公司）、2,5-二吡啶羧酸纯度为98%（上海源叶生物科技有限公司）、玻璃纤维纯度为99%，货号：S30527（上海源叶生物科技有限公司）、钛酸四正丁酯纯度为99%（天门恒昌化工有限公司）、无水乙醇纯度为99%（河南天孚化工有限公司）、丙纶纤维纯度为99%，型号：PE6269，（苏州闪塑新材料有限公司）、γ-氨丙基三乙氧基硅烷纯度为98%（上海源叶生物科技有限公司）、丁酮的纯度为99%（南京试剂股份有限公司）、四苯基卟啉纯度为98%，货号：杰克斯JACS（门捷列夫-郑州研德生物科技有限公司）、抗氧剂264纯度为99%（山东瑞琪化工有限公司）、三乙醇胺的纯度为99%（河北陌槿生物科技有限公司）、2-甲基咪唑的纯度为97%，CAS号：693-98-1，货号：S25048（上海源叶生物科技有限公司）。
实施例1：一种阻燃耐腐蚀环氧树脂基覆铜板的制备方法：
步骤一：氧化石墨烯预处理：（1）在120W的微波功率下，对35份氧化石墨烯加热20s，完成微波处理，再将其置于25wt%的氨水溶液中，在85℃下，超声分散处理6h后，待其反应液自然冷却至室温，经过滤、洗涤、干燥，得到氨化石墨烯；（2）再将350份无水乙醇、8.75份十二烷基苯磺酸钠和35份氨化石墨烯混合，超声分散处理2h后，经旋蒸处理，除去无水乙醇，得到预处理石墨烯；
改性石墨烯的制备方法为：（1）将20份DOPO、350份无水乙醇、175份三乙胺混合，得到混合液；（2）调节混合液的温度至0℃，搅拌下，在0.5h内，向混合液中滴加70份四氯化碳，滴加完毕后，继续搅拌反应4h，得到反应液A；（3）调节温度至45℃，向反应液A中加入35份预处理石墨烯，回流反应48h后，经减压蒸馏、过滤、洗涤、干燥，得到改性石墨烯；
步骤二：改性环氧树脂的制备方法为：氮气保护下，将60份双酚A型环氧树脂加热熔融，然后加入45份端氨基超支化聚酰胺、3.6份2,5-二吡啶羧酸，以300r/min的转速搅拌3h，得到改性环氧树脂，备用；
步骤三：纤维布的制备方法为：（1）将300份玻璃纤维和丙纶纤维以5:1的比例混合的混合纤维加入到去离子水中超声分散，在50℃下，边搅拌边滴加100份10wt%钛酸四丁酯的乙醇溶液，滴加完毕后继续反应12h，再加入15份γ-氨丙基三乙氧基硅烷，调节温度至70℃，机械搅拌30min，最后经过滤、洗涤、干燥，得到改性纤维；（2）将改性纤维单丝平织，密度为30目/cm，得到基础纤维布；（3）再将基础纤维布置于改性环氧树脂中浸渍2h，后挤出基础纤维布上多余浆料，排除气泡，得到预成型纤维布；（4）再将改性纤维短切成10~12mm长度，将其均匀铺设在预成型纤维布上，再涂覆上一层改性环氧树脂，涂覆密度2.1g/cm2，送入烘箱中以120℃烘烤20min，最后在365nm紫外光下紫外固化2h，得到纤维布；
步骤四：（1）将改性环氧树脂、改性石墨烯、丁酮、四苯基卟啉、抗氧剂264、三乙醇胺、2-甲基咪唑混合均匀，配制得到树脂胶液；（2）用浸渍胶液法将5张纤维布浸入树脂胶液中10min后，在烘箱中以120℃烘烤60min，得到5张半固化片；（3）将3张半固化片叠加到一起，铜箔覆于半固化片两面，以18MPa的压力，在200℃下热压3h，得到阻燃耐腐蚀环氧树脂基覆铜板；
所述树脂胶液包括以下组分，按质量份数计：改性环氧树脂55份、改性石墨烯23份、丁酮75份、四苯基卟啉8份、抗氧剂264 3份、三乙醇胺7份、2-甲基咪唑0.15份。
实施例2：一种阻燃耐腐蚀环氧树脂基覆铜板的制备方法：
步骤一：氧化石墨烯预处理：（1）在100W的微波功率下，对35份氧化石墨烯加热10s，完成微波处理，再将其置于20wt%的氨水溶液中，在80℃下，超声分散处理4h后，待其反应液自然冷却至室温，经过滤、洗涤、干燥，得到氨化石墨烯；（2）再将350份无水乙醇、3.5份十二烷基苯磺酸钠和35份氨化石墨烯混合，超声分散处理2h后，经旋蒸处理，除去无水乙醇，得到预处理石墨烯；
改性石墨烯的制备方法为：（1）将17.5份DOPO、350份无水乙醇、175份三乙胺混合，得到混合液；（2）调节混合液的温度至-5℃，搅拌下，在1h内，向混合液中滴加70份四氯化碳，滴加完毕后，继续搅拌反应2h，得到反应液A；（3）调节温度至30℃，向反应液A中加入35份预处理石墨烯，回流反应24h后，经减压蒸馏、过滤、洗涤、干燥，得到改性石墨烯；
步骤二：改性环氧树脂的制备方法为：氮气保护下，将60份双酚A型环氧树脂加热熔融，然后加入60份端氨基超支化聚酰胺、3份2,5-二吡啶羧酸，以300r/min的转速搅拌3h，得到改性环氧树脂，备用；
步骤三：纤维布的制备方法为：（1）将300份玻璃纤维和丙纶纤维以10:1的比例混合的混合纤维加入到去离子水中超声分散，在45℃下，边搅拌边滴加100份10wt%钛酸四丁酯的乙醇溶液，滴加完毕后继续反应6h，再加入9份γ-氨丙基三乙氧基硅烷，调节温度至70℃，机械搅拌20min，最后经过滤、洗涤、干燥，得到改性纤维；（2）将改性纤维单丝平织，密度为20目/cm，得到基础纤维布；（3）再将基础纤维布置于改性环氧树脂中浸渍1h，后挤出基础纤维布上多余浆料，排除气泡，得到预成型纤维布；（4）再将改性纤维短切成10~12mm长度，将其均匀铺设在预成型纤维布上，再涂覆上一层改性环氧树脂，涂覆密度1.5g/cm2，送入烘箱中以100℃烘烤10min，最后在365nm紫外光下紫外固化1h，得到纤维布；
步骤四：（1）将改性环氧树脂、改性石墨烯、丁酮、四苯基卟啉、抗氧剂264、三乙醇胺、2-甲基咪唑混合均匀，配制得到树脂胶液；（2）用浸渍胶液法将5张纤维布浸入树脂胶液中5min后，在烘箱中以110℃烘烤30min，得到5张半固化片；（3）将3张半固化片叠加到一起，铜箔覆于半固化片两面，以12MPa的压力，在200℃下热压2h，得到阻燃耐腐蚀环氧树脂基覆铜板；
所述树脂胶液包括以下组分，按质量份数计：改性环氧树脂55份、改性石墨烯23份、丁酮75份、四苯基卟啉8份、抗氧剂264 3份、三乙醇胺7份、2-甲基咪唑0.15份。
实施例3：一种阻燃耐腐蚀环氧树脂基覆铜板的制备方法：
步骤一：氧化石墨烯预处理：（1）在120W的微波功率下，对35份氧化石墨烯加热30s，完成微波处理，再将其置于28wt%的氨水溶液中，在90℃下，超声分散处理8h后，待其反应液自然冷却至室温，经过滤、洗涤、干燥，得到氨化石墨烯；（2）再将350份无水乙醇、17.5份十二烷基苯磺酸钠和35份氨化石墨烯混合，超声分散处理4h后，经旋蒸处理，除去无水乙醇，得到预处理石墨烯；
改性石墨烯的制备方法为：（1）将35份DOPO、350份无水乙醇、175份三乙胺混合，得到混合液；（2）调节混合液的温度至10℃，搅拌下，在1h内，向混合液中滴加70份四氯化碳，滴加完毕后，继续搅拌反应5h，得到反应液A；（3）调节温度至60℃，向反应液A中加入35份预处理石墨烯，回流反应48h后，经减压蒸馏、过滤、洗涤、干燥，得到改性石墨烯；
步骤二：改性环氧树脂的制备方法为：氮气保护下，将60份双酚A型环氧树脂加热熔融，然后加入40份端氨基超支化聚酰胺、6份2,5-二吡啶羧酸，以400r/min的转速搅拌6h，得到改性环氧树脂，备用；
步骤三：纤维布的制备方法为：（1）将300份玻璃纤维和丙纶纤维以10:3的比例混合的混合纤维加入到去离子水中超声分散，在60℃下，边搅拌边滴加150份10wt%钛酸四丁酯的乙醇溶液，滴加完毕后继续反应18h，再加入24份γ-氨丙基三乙氧基硅烷，调节温度至80℃，机械搅拌30min，最后经过滤、洗涤、干燥，得到改性纤维；（2）将改性纤维单丝平织，密度为60目/cm，得到基础纤维布；（3）再将基础纤维布置于改性环氧树脂中浸渍3h，后挤出基础纤维布上多余浆料，排除气泡，得到预成型纤维布；（4）再将改性纤维短切成10~12mm长度，将其均匀铺设在预成型纤维布上，再涂覆上一层改性环氧树脂，涂覆密度2.3g/cm2，送入烘箱中以140℃烘烤30min，最后在365nm紫外光下紫外固化3h，得到纤维布；
步骤四：（1）将改性环氧树脂、改性石墨烯、丁酮、四苯基卟啉、抗氧剂264、三乙醇胺、2-甲基咪唑混合均匀，配制得到树脂胶液；（2）用浸渍胶液法将5张纤维布浸入树脂胶液中10min后，在烘箱中以120℃烘烤60min，得到5张半固化片；（3）将3张半固化片叠加到一起，铜箔覆于半固化片两面，以20MPa的压力，在220℃下热压5h，得到阻燃耐腐蚀环氧树脂基覆铜板；
所述树脂胶液包括以下组分，按质量份数计：改性环氧树脂55份、改性石墨烯23份、丁酮75份、四苯基卟啉8份、抗氧剂264 3份、三乙醇胺7份、2-甲基咪唑0.15份。
对比例1：所述树脂胶液包括以下组分，按质量份数计：改性环氧树脂40份、改性石墨烯15份、丁酮75份、四苯基卟啉8份、抗氧剂264 3份、三乙醇胺7份、2-甲基咪唑0.15份；其它同实施例1；
对比例2：所述树脂胶液包括以下组分，按质量份数计：改性环氧树脂60份、改性石墨烯30份、丁酮75份、四苯基卟啉8份、抗氧剂264 3份、三乙醇胺7份、2-甲基咪唑0.15份；其它同实施例1；
对比例3：不对氧化石墨烯进行改性；所述树脂胶液包括以下组分，按质量份数计：改性环氧树脂55份、氧化石墨烯23份、丁酮75份、四苯基卟啉8份、抗氧剂264 3份、三乙醇胺7份、2-甲基咪唑0.15份；其它同实施例1；
对比例4：不对双酚A型环氧树脂进行改性；所述树脂胶液包括以下组分，按质量份数计：双酚A型环氧树脂55份、改性石墨烯23份、丁酮75份、四苯基卟啉8份、抗氧剂264 3份、三乙醇胺7份、2-甲基咪唑0.15份；其它同实施例1；
对比例5：不制备纤维布；使用常规玻璃纤维布；其它同实施例1；
步骤四：（1）将改性环氧树脂、改性石墨烯、丁酮、四苯基卟啉、抗氧剂264、三乙醇胺、2-甲基咪唑混合均匀，配制得到树脂胶液；（2）用浸渍胶液法将5张玻璃纤维布浸入树脂胶液中10min后，在烘箱中以120℃烘烤60min，得到5张半固化片；（3）将3张半固化片叠加到一起，铜箔覆于半固化片两面，以18MPa的压力，在200℃下热压3h，得到阻燃耐腐蚀环氧树脂基覆铜板。
性能测试：对实施例1~3和对比例1~5制备得到的阻燃耐腐蚀环氧树脂基覆铜板进行阻燃性能和耐腐蚀性能测试；根据GB/T 2406-80的标准对制备得到的阻燃耐腐蚀环氧树脂基覆铜板的阻燃性能进行测试；在40℃下，用10%的硝酸均匀喷洒半固化片在上，测试其24h后的耐硝酸劣化率、侧蚀现象，对其耐腐蚀性能进行评定，具体如下表所示：
结果分析：从上表中，可以看出本发明中对氧化石墨烯进行改性处理，极大的改善了氧化石墨烯的分散性，明显提高了覆铜板的阻燃性能和耐腐蚀性能；此外，对双酚A型环氧树脂的改性，引入了端氨基超支化聚酰胺，也极大的改善了树脂的阻燃性能，且其也影响到石墨烯在树脂中的分散性，对于本发明覆铜板的性能影响较大。对比实施例和对比例，可以得知，本发明制备得到了一种具有高阻燃性能、高耐腐蚀性能的环氧树脂基覆铜板。
最后应说明的是：以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (3)

1.一种阻燃耐腐蚀环氧树脂基覆铜板的制备方法，其特征在于：包括以下步骤：
步骤一：对氧化石墨烯进行预处理，后与DOPO反应接枝，得到改性石墨烯；
步骤二：用端氨基超支化聚酰胺对环氧树脂进行改性处理，得到改性环氧树脂；
步骤三：对玻璃纤维、丙纶纤维进行改性处理，制成纤维布；
步骤四：将树脂胶液涂覆到若干张纤维布上，经干燥制成若干张半固化片，将铜箔覆于半固化片两面，经热压制成阻燃耐腐蚀环氧树脂基覆铜板；
所述氧化石墨烯预处理过程为：（1）在100~120W的微波功率下，对氧化石墨烯低火加热10~30s，完成微波处理，再将其置于20~28wt%的氨水溶液中，在80~90℃下，超声分散处理4~8h后，待其反应液自然冷却至室温，经过滤、洗涤、干燥，得到氨化石墨烯；（2）再将无水乙醇、分散剂和氨化石墨烯混合，超声分散处理2~4h后，经旋蒸处理，除去无水乙醇，得到预处理石墨烯；
所述改性石墨烯的制备方法为：（1）将DOPO、溶剂、三乙胺混合，得到混合液；（2）调节混合液的温度至-5~10℃，搅拌下，在0.5~1h内，向混合液中滴加四氯化碳，滴加完毕后，继续搅拌反应2~5h，得到反应液A；（3）调节温度至30~60℃，向反应液A中加入预处理石墨烯，回流反应24~48h后，经减压蒸馏、过滤、洗涤、干燥，得到改性石墨烯；其中DOPO、溶剂、三乙胺、四氯化碳、预处理石墨烯五者质量比为(0.5~1):10:5:2:1，溶剂包括无水乙醇、乙二醇、异丙醇、正丁醇、环己醇、乙醚、氯仿、二氯甲烷中的一种或多种的组合；
所述改性环氧树脂的制备方法为：氮气保护下，将环氧树脂加热熔融，然后加入端氨基超支化聚酰胺、2,5-二吡啶羧酸，以300~400r/min的转速搅拌3~6h，得到改性环氧树脂；其中环氧树脂、端氨基超支化聚酰胺、2,5-二吡啶羧酸三者的质量为(0.5~1.5):1:(0.05~0.15)，环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂中的任一种；
所述纤维布的制备方法为：（1）将玻璃纤维和丙纶纤维超声分散在去离子水中，在45~60℃下，边搅拌边滴加钛酸四丁酯的乙醇溶液，滴加完毕后继续反应6~18h，再加入γ-氨丙基三乙氧基硅烷，调节温度至70~80℃，机械搅拌20~30min，最后经过滤、洗涤、干燥，得到改性纤维；（2）将改性纤维单丝平织，密度为20~60目/cm，得到基础纤维布；（3）再将基础纤维布置于改性环氧树脂中浸渍1~3h，后挤出基础纤维布上多余浆料，排除气泡，得到预成型纤维布；（4）再将改性纤维短切成10~12mm长度，将其均匀铺设在预成型纤维布上，再涂覆上一层改性环氧树脂，涂覆密度1.5~2.3g/cm2，送入烘箱中以100~140℃烘烤10~30min，最后在365nm紫外光下紫外固化1~3h，得到纤维布，其中丙纶纤维加入量为玻璃纤维质量的10~30%；所述钛酸四丁酯加入量为纤维总质量的10~15%；所述γ-氨丙基三乙氧基硅烷加入量为纤维总质量的3~8%；
所述树脂胶液由以下组分组成，按质量份数计：改性环氧树脂40~60份、改性石墨烯15~30份、溶剂60~90份、阻燃剂5~10份、抗氧剂2~4份、固化剂5~10份、固化促进剂0.05~0.2份。
2.根据权利要求1所述的一种阻燃耐腐蚀环氧树脂基覆铜板的制备方法，其特征在于：所述步骤四的具体过程为：
（1）向改性环氧树脂中加入改性石墨烯、溶剂、阻燃剂、抗氧剂、固化剂、固化促进剂混合均匀，配制得到树脂胶液；
（2）用浸渍胶液法将纤维布浸入树脂胶液中5~10min后，在烘箱中以110~140℃烘烤30~60min，得到半固化片；
（3）将若干张半固化片叠加到一起，用铜箔覆于半固化片两面，以12~20MPa的压力，在200~220℃下热压2~5h，得到阻燃耐腐蚀环氧树脂基覆铜板。
3.根据权利要求1~2中任一项所述的一种阻燃耐腐蚀环氧树脂基覆铜板的制备方法制备得到的阻燃耐腐蚀环氧树脂基覆铜板。
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