CN108049160A - 一种高硬度防水碳纤维复合材料及其制备方法 - Google Patents
一种高硬度防水碳纤维复合材料及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种高硬度防水碳纤维复合材料及其制备方法，碳纤维经过防水处理后，用改性锆处理，在提高防水性能和防水性能牢固度基础上，进一步，提高材料硬度。与现有技术相比，本发明提供的高硬度防水碳纤维复合材料，防水效果好，牢固度高；而且，表面形成致密的二氧化锆和氢氧化锆膜层，加强的防水效果，大大提高了碳纤维的硬度。本发明产品制备方法简单，成本低，具有广阔的应用前景。
Description
技术领域
本发明属于复合材料制备领域，具体涉及一种高硬度防水碳纤维复合材料及其制备方法。
背景技术
碳纤维具有许多优良性能，碳纤维的轴向强度和模量高，密度低、比性能高，无蠕变，非氧化环境下耐超高温，耐疲劳性好，比热及导电性介于非金属和金属之间，热膨胀系数小且具有各向异性，耐腐蚀性好，X射线透过性好等特点，具有良好的导电导热性能、电磁屏蔽性好等，现已广泛应用于航天航空、新型纺织机械、石油化工、医药器械、汽车、机械制造、建筑行业、文体用品、电信、电加热等高新技术领域。
碳纤维按原料来源可分为聚丙烯腈基碳纤维、沥青基碳纤维、粘胶基碳纤维、酚醛基碳纤维、气相生长碳纤维。目前应用最广泛的聚丙烯腈基碳纤维，成本低廉，产量约占全球碳纤维总产量的90％以上。
但是，目前很少有高硬度防水碳纤维材料。
发明内容
本发明的目的在于提供一种高硬度防水碳纤维复合材料，碳纤维经过防水处理后，用改性锆处理，在提高防水性能和防水性能牢固度基础上，进一步，提高材料硬度。
本发明还提供了一种高硬度防水碳纤维复合材料的制备方法。
本发明提供的一种高硬度防水碳纤维复合材料的制备方法，包括以下步骤：
1)先将碳纤维进行电晕处理；
2)将处理后的碳纤维置于氨基有机硅防水处理剂中浸-扎处理，烘干；
3)将硅烷偶联剂、锆盐和酸溶液混合，得混合溶液，将步骤2)处理后的碳纤维置于混合溶液中，烘干，即得高硬度防水碳纤维复合材料。
步骤2)所述氨基有机硅防水处理剂的制备方法为：
将辛基三甲氧基硅烷、四乙烯基四甲氧基环四硅氧烷和硅烷偶联剂KH-602混合，加热反应，然后再加入硅酸四甲酯、二氨基二苯甲烷和十二烷基苯磺酸，加热反应，减压蒸馏脱除低沸物，再升温加热反应，即得氨基有机硅防水处理剂。
步骤1)所述电晕处理为在6-10kV条件下处理5-8s。所述碳纤维优选自聚丙烯腈基碳纤维。
进一步的，步骤1)中电晕处理在氧气和氮气混合气体条件下进行，氧气和氮气的体积比为2:8。
步骤2)中第一次加热反应为：90-120℃条件下反应3-4h；
步骤2)中第二次加热反应为：100-120℃反应4-8h；
步骤2)中所述再升温加热反应是指加热升温至145-150℃反应1-2h。
步骤2)中辛基三甲氧基硅烷、四乙烯基四甲氧基环四硅氧烷、硅烷偶联剂KH-602、硅酸四甲酯、二氨基二苯甲烷和十二烷基苯磺酸的摩尔比为：1:2-3:2-4:2-3：0.01-0.2：0.005-0.01。
步骤2)中浸-扎处理中浸渍料液比1:5-8。
步骤2)中所述浸-扎处理具体为,浸渍5-8s，二浸二轧,轧余率55-70％。
步骤2)中所述烘干是指160-165℃烘干2-4min。
步骤3)所述混合溶液的制备方法为：
将硅烷偶联剂、锆盐和酸溶液按照质量比1:5-10:15-20混合，在600-1000r/min条件下搅拌12-18h，即得。
步骤3)所述酸溶液选自冰醋酸溶液或硝酸溶液。所述锆盐为氟锆酸或氟锆酸铵，所述硅烷偶联剂选自γ-缩水甘油醚氧丙基三甲氧基硅烷。
步骤3)中将步骤2)处理后的碳纤维置于混合溶液中1-5min，然后在60-80℃条件下烘干1-8h。
本发明提供的一种高硬度防水碳纤维复合材料，采用上述方法制备得到。
与现有技术相比，本发明先将碳纤维电晕处理，使碳纤维表面的羧基、羟基、羰基等基团增多，更容易与制备的氨基有机硅防水处理剂结合，提高防水效果和防水膜牢固度。在氨基有机硅防水处理剂制备过程中加入二氨基二苯甲烷与硅酸四甲酯配合使用，有利于防水剂在碳纤维表面固化成膜，提高防水层的牢固度；加入的硅酸四甲酯增加疏水性，提高防水效果；十二烷基苯磺酸的加入不仅仅作为乳化剂，使制备的氨基有机硅防水处理剂更稳定，更细化，颗粒更均匀，又容易均匀分散在碳纤维表面；而且，作为催化剂，促进反应进行，提高反应效率。利用改性锆盐的混合溶液改性进一步改性碳纤维，在一定酸度条件下，硅烷偶联剂对锆盐改性，有利于锆盐与氨基有机硅防水处理剂处理后的碳纤维结合。在酸性条件下，锆离子结合在氨基有机硅防水处理剂处理后的碳纤维表面，由于氨基的存在，容易形成较致密的二氧化锆和氢氧化锆膜层，提高碳纤维的硬度。而且，利用偶联剂改性锆盐使锆离子分散均匀，有利于在碳纤维表面均匀结合，使碳纤维性质稳定。
本发明提供的高硬度防水碳纤维复合材料，防水效果好，牢固度高；而且，表面形成致密的二氧化锆和氢氧化锆膜层，加强的防水效果，大大提高了碳纤维的硬度。本发明产品制备方法简单，成本低，具有广阔的应用前景。
具体实施方式
实施例1
一种高硬度防水碳纤维复合材料的制备方法，包括以下步骤：
1)先将聚丙烯腈基碳纤维进行电晕处理：在氧气和氮气混合气体条件下进行，氧气和氮气的体积比为2:8，在7kV条件下处理5s；即可；
2)三口烧瓶中，将1mol辛基三甲氧基硅烷、2mol四乙烯基四甲氧基环四硅氧烷和2.5mol硅烷偶联剂KH-602混合，90℃条件下反应4h，然后再加入2mol硅酸四甲酯、0.01mol二氨基二苯甲烷和0.006mol十二烷基苯磺酸，100℃反应5h，在0.75MPa条件下减压蒸馏脱除低沸物，再升温145℃反应1.5h，即得氨基有机硅防水处理剂。将步骤1)处理后的碳纤维材料置于氨基有机硅防水处理剂中，料液比1:6；进行浸-扎处理，浸渍5s，二浸二轧,轧余率55-70％，然后1605℃烘干2min；
3)将γ-缩水甘油醚氧丙基三甲氧基硅烷、氟锆酸和硝酸溶液按照质量比1:5:15混合，在600r/min条件下搅拌18h得混合溶液，将步骤2)处理后的碳纤维置于混合溶液中浸渍2min，60℃条件下烘干5h，即得高硬度防水碳纤维复合材料。
实施例2
一种高硬度防水碳纤维复合材料的制备方法，包括以下步骤：
1)先将聚丙烯腈基碳纤维进行电晕处理：在氧气和氮气混合气体条件下进行，氧气和氮气的体积比为2:8，在8kV条件下处理6s；即可；
2)三口烧瓶中，将1mol辛基三甲氧基硅烷、3mol四乙烯基四甲氧基环四硅氧烷和2mol硅烷偶联剂KH-602混合，110℃条件下反应3h，然后再加入2.5mol硅酸四甲酯、0.04mol二氨基二苯甲烷和0.008mol十二烷基苯磺酸，120℃反应4h，在0.75MPa条件下减压蒸馏脱除低沸物，再升温150℃反应1h，即得氨基有机硅防水处理剂。将步骤1)处理后的碳纤维材料置于氨基有机硅防水处理剂中，料液比1:6；进行浸-扎处理，浸渍6s，二浸二轧,轧余率55-70％，然后160℃烘干3min；
3)将γ-缩水甘油醚氧丙基三甲氧基硅烷、氟锆酸铵和冰醋酸溶液按照质量比1:6:18混合，在800r/min条件下搅拌15h得混合溶液，将步骤2)处理后的碳纤维置于混合溶液中浸渍3min，70℃条件下烘4h，即得高硬度防水碳纤维复合材料。
对比例1
一种高硬度防水碳纤维复合材料的制备方法，步骤2)利用市售防水剂处理，其他同实施例1。
对比例2
一种高硬度防水碳纤维复合材料的制备方法，不进行步骤3)氟锆酸改性，其他同实施例2。
对实施例1-2、对比例1-2制备的高硬度防水碳纤维复合材料及现有高硬度防水碳纤维复合材料进行防水性、防水层牢固度，测性结果如下表1。
采用AATCC-22进行防水性测试，根据被碳纤维上水滴或水形，可评为0、50、70、80、90、100六个等级。
防水层牢固度的测试方法为：将被测碳纤维洗涤100次后，利用AATCC-22进行防水性测试，根据被测碳纤维上水滴或水形，可评为0、50、70、80、90、100六个等级。
实施例1-2、对比例1-2制备的碳纤维进行防水性及防水层牢固度测试，结果如下表1：
表1
实施例1-2、对比例1-2制备的碳纤维进行硬度测试，实施例1比实施例1硬度提高102.3％；实施例2与对比例2硬度提高152.5％。
本发明提供的高硬度防水碳纤维复合材料，防水效果好，防水层牢固度高，硬度高，制备方法简单，成本低，具有广阔的应用前景。
Claims (10)
1.一种高硬度防水碳纤维复合材料的制备方法，其特征在于，所述制备方法包括以下步骤：
1)先将碳纤维进行电晕处理；
2)将处理后的碳纤维置于氨基有机硅防水处理剂中浸-扎处理，烘干；
3)将硅烷偶联剂、锆盐和酸溶液混合，得混合溶液，将步骤2)处理后的碳纤维置于混合溶液中，烘干，即得高硬度防水碳纤维复合材料。
2.根据权利要求1所述的制备方法，其特征在于，步骤2)所述氨基有机硅防水处理剂的制备方法为：
将辛基三甲氧基硅烷、四乙烯基四甲氧基环四硅氧烷和硅烷偶联剂KH-602混合，加热反应，然后再加入硅酸四甲酯、二氨基二苯甲烷和十二烷基苯磺酸，加热反应，减压蒸馏脱除低沸物，再升温加热反应，即得氨基有机硅防水处理剂。
3.根据权利要求2所述的制备方法，其特征在于，步骤2)中辛基三甲氧基硅烷、四乙烯基四甲氧基环四硅氧烷、硅烷偶联剂KH-602、硅酸四甲酯、二氨基二苯甲烷和十二烷基苯磺酸的摩尔比为：1:2-3:2-4:2-3：0.01-0.2：0.005-0.01。
4.根据权利要求2或3所述的制备方法，其特征在于，步骤2)中第一次加热反应为：90-120℃条件下反应3-4h。
5.根据权利要求2-4任一项所述的制备方法，其特征在于，步骤2)中第二次加热反应为：100-120℃反应4-8h。
6.根据权利要求2-5任一项所述的制备方法，其特征在于，步骤2)中所述再升温加热反应是指加热升温至145-150℃反应1-2h。
7.根据权利要求1-6所述的制备方法，其特征在于，步骤3)所述混合溶液的制备方法为：
将硅烷偶联剂、锆盐和酸溶液按照质量比1:5-10:15-20混合，在600-1000r/min条件下搅拌12-18h，即得。
8.根据权利要求1-7所述的制备方法，其特征在于，所述锆盐为氟锆酸或氟锆酸铵。
9.根据权利要求1-7所述的制备方法，其特征在于，所述硅烷偶联剂选自γ-缩水甘油醚氧丙基三甲氧基硅烷。
10.一种权利要求1-9任一项所制备的高硬度防水碳纤维复合材料。
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