CN110527371B - 具有火灾预警和超疏水功能的三明治结构高效阻燃涂层及其制备方法与应用 - Google Patents
具有火灾预警和超疏水功能的三明治结构高效阻燃涂层及其制备方法与应用 Download PDFInfo
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- CN110527371B CN110527371B CN201910706515.6A CN201910706515A CN110527371B CN 110527371 B CN110527371 B CN 110527371B CN 201910706515 A CN201910706515 A CN 201910706515A CN 110527371 B CN110527371 B CN 110527371B
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Abstract
本发明公开了具有火灾预警和超疏水功能的三明治结构高效阻燃涂层及其制备方法与应用。该制备方法通过在易燃基材上依次制备底部导电层、中部温敏传感层和顶部超疏水导电层,其中底部导电层制备是将金属纳米材料和油溶性长链高分子一起均匀分散于有机溶剂中形成涂料A,然后将涂料A喷涂于基材上,第一次干燥;喷涂并干燥的过程重复1~10次。与现有技术相比,本发明制备的阻燃涂层即便是应用在大面积基材上,也能表现出超灵敏的火灾预警功能和优异的阻燃性能;涂层表面还具有超疏水性,使其表现出出色的自清洁和耐水性能。本发明所制备的阻燃涂层可赋予易燃材料可靠的火灾安全性,可广泛应用于交通运输、家具电器、建筑装饰和电线电缆等领域。
Description
技术领域
本发明涉及阻燃涂料,具体是涉及一种具有火灾预警和超疏水功能的三明治结构高效阻燃涂层及其制备方法与应用。
背景技术
近年来,世界范围内火灾频发,如2019年4月15日,法国巴黎圣母院因电线短路发生火灾,木质塔顶在火灾中被焚毁,给人类文明造成不可挽回的损失;2017年6月14日凌晨,伦敦一栋24层公寓“格兰菲尔塔”发生重大火灾事故,造成79人死亡。这主要是由于:一方面,易燃轻质材料(如塑料、橡胶和木材等)的广泛应用存在巨大的火灾隐患;另一方面,当前的火灾预警防御***灵敏性差,预警时间迟滞(一般>100s,ACS Nano 2017,12(1),416-424),往往导致错过火灾初期最佳的灭火和逃生时间。因此,若想要有效减少火灾的发生,不仅要提高轻质材料的阻燃性能,还要缩短当前火灾预警***的预警时间。而在轻质材料表面制备温度响应火灾预警阻燃涂层是同时解决上述两个问题的最有效方法之一。
由于二维纳米材料氧化石墨烯具有片层阻隔效益和快速热还原特性,是制备温度响应火灾预警阻燃涂层的优选材料。然而,对于现有的氧化石墨烯基火灾预警电路(CN108109317A,CN109593343A),当只有电极间的石墨烯涂层被快速并充分地加热还原,才能使电路的电阻显著下降并表现出灵敏的火灾预警响应。因此,这些预警涂层只能局限于小尺寸材料上应用(电极距离一般≤5cm)。此外,石墨烯基水性涂层耐水性差的缺陷同样限制会严重限制其实际应用(Cellulose,2018,25,3135-3149)。
发明内容
本发明的目的是针对轻质材料易燃、水性涂层耐水性差,当前火灾预警***灵敏度低,无法适用于大尺寸材料等问题,提供一种具有灵敏火灾预警和超疏水功能的高效阻燃涂层及其制备方法。
本发明的另一目的是提供具有火灾预警和超疏水功能的三明治结构高效阻燃涂层在塑料和木材等易燃基材上的应用。
本发明通过配制三种不同的涂料先后在易燃基材上制备了底部导电层、中部温敏传感层和顶部疏水导电层,制备了一种具有火灾预警和超疏水功能的三明治结构高效阻燃涂层。将底部导电层和顶部疏水导电层作为电极,与电源和报警器连接可形成预警电路。当涂层遇到高温时,中部的氧化碳纳米材料基温敏传感层会发生快速热还原,电阻急剧下降并连通底部导电层和顶部疏水导电层,从而触发报警器。由于中部温敏传感层厚度仅为微米级,因此其受到高温时,热还原速度极快,可发挥出超灵敏的火灾预警响应。本发明底部导电层和顶部疏水导电层发挥了电极的作用,使得涂层的温敏传感通路保持为垂直方向的微米级,不会随着涂层面积的变化而变化,因此该涂层即便是在大面积应用时,也能保持高灵敏火灾预警响应。同时,由于涂层中的金属纳米材料和氧化碳纳米材料具有优异的热稳定性,而油溶性长链高分子和水溶性长链高分子具有突出的成炭性能,因此涂层在遭遇火焰时可形成具有优异热稳定性和阻隔性能的多孔炭层,发挥高效阻燃作用。而且,顶部疏水导电层赋予了涂层优异的耐水性能和自清洁性能,极大地拓宽了其应用领域并保证了其应用的便捷性。因此,本发明提供的具有火灾预警和超疏水功能的三明治结构高效阻燃涂层可有效提高各种易燃材料的火灾安全性,可广泛应用于对阻燃性能要求较高的交通运输、家具电器、建筑装饰和电线电缆等领域。
本发明的目的可以通过以下技术方案实现:
通过三种涂料的先后涂覆制备三明治结构高效阻燃涂层:
1)底部导电层的制备:将金属纳米材料和油溶性长链高分子一起均匀分散于有机溶剂中形成涂料A,然后将涂料A喷涂于基材上,涂覆量为0.05~0.20mL/cm2,然后放入烘箱中在40~100℃下干燥5~120min,该过程重复1~10次,制得底部导电层;
2)中部温敏传感层的制备:将氧化碳纳米材料和水溶性长链高分子一起均匀分散于去离子水中形成涂料B,然后将涂料B喷涂于步骤1)制备的底部导电层上,涂覆量为0.05~0.20mL/cm2,然后放入烘箱中在40~100℃下干燥5~120min,该过程重复5~20次,制得中部温敏传感层;
3)顶部超疏水导电层的制备:在50~150℃条件下,将油溶性长链高分子溶解于有机溶剂中,然后加入氟硅烷和催化剂,回流反应2~12h。反应结束后将混合溶液冷却至室温,通过6000~10000r/min离心将产物分离,使用有机溶剂洗涤2~5遍,然后放入烘箱中在40~100℃下干燥2~12h,得到氟化长链高分子。将金属纳米材料和制备的氟化长链高分子一起均匀分散于有机溶剂中形成涂料C,然后将涂料C喷涂于步骤2)制备的中部温敏传感层上,涂覆量为0.05~0.20mL/cm2,然后放入烘箱中在40~100℃下干燥5~120min,该过程重复1~10次,制得顶部超疏水导电层。
优选地,步骤1)和步骤3)所述的金属纳米材料是银纳米线、银纳米粒子、铜纳米线和铜纳米粒子中的一种或多种。
优选地,步骤1)和步骤3)所述的油溶性长链高分子为聚氨酯、聚乙烯醇缩丁醛、酚醛树脂、聚己内酯和乙基纤维素中的一种或多种。
优选地,步骤1)和步骤3)所述的有机溶剂为丙酮、甲醇、己烷、乙醇、异丙醇、正丁醇、乙二醇二甲醚、二甲苯和N,N-二甲基甲酰胺中的一种或多种。
所述的氧化碳纳米材料是羧基化单壁碳纳米管、羟基化单壁碳纳米管、羧基化多壁碳纳米管、羟基化多壁碳纳米管、氧化石墨烯纳米带和氧化石墨烯纳米片中的一种或多种。
优选地,所述的水溶性长链高分子为聚乙烯醇,羧甲基壳聚糖、羟乙基壳聚糖、羟丙基壳聚糖、羟乙基纤维素、羟丙基纤维素和羟丙基甲基纤维素中的一种或多种。
优选地,所述的氟硅烷是全氟癸基三氯硅烷、全氟癸基三甲氧基硅烷、全氟癸基三乙氧基硅烷、全氟辛基三氯硅烷、全氟辛基三甲氧基硅烷、全氟辛基三乙氧基硅烷和3,3,3-三氟丙基甲基二甲氧基硅烷中的一种或多种。
优选地,所述的催化剂为氨水、氢氧化钠水溶液、稀盐酸、乙酸、二月桂酸二丁基锡和二醋酸二丁基锡中的一种或多种。
优选地,步骤1)所述的金属纳米材料和油溶性长链高分子的质量比为0.1:1~6:1,所述的涂料A浓度为0.2wt%~10wt%;步骤2)所述的碳纳米材料和水溶性长链高分子的质量比为0.2:1~5:1,所述的涂料B浓度为0.2wt%~5wt%;步骤3)所述的金属纳米材料和氟化长链高分子的质量比为0.1:1~6:1,所述的涂料C浓度为0.2wt%~10wt%。
优选地,步骤3)所述的氟硅烷和油溶性长链高分子的质量比为0.01:1~5:1,所述的催化剂与氟硅烷的质量比为1:100~1:10。
优选地,步骤1)、步骤2)和步骤3)所述的均匀分散是通过10~480min的强力机械搅拌、超声处理或两者共同作用实现的。
优选地,所述的基材为聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯、聚酯、聚酰胺、环氧树脂、榆木、樟子松木、榉木、红橡木和黑胡桃木中的一种或多种。
相对于现有技术,本发明具有以下优点:
1、由于本发明提供的三明治结构涂层中温敏传感层的微米级纵向导电通路及其中氧化碳纳米材料快速热还原的特性,三明治结构涂层即便是应用在大面积基材上,也能表现出超灵敏的火灾预警响应。
2、本发明提供的阻燃涂层在遭遇火焰时,其中的油溶性长链高分子和水溶性长链高分子可快速发生炭化反应,并将有机金属纳米材料和氧化碳纳米材料粘接在一起,形成具有优异热稳定性能和阻隔性能的多孔炭层,对易燃基体发挥高效阻燃作用。
3、由于低表面能的氟化长链高分子在涂层表面聚集并形成粗糙结构,本发明提供的阻燃涂层表面可达到超疏水状态,从而赋予涂层优异的耐水和自清洁性能。
4、本发明提供的涂料适用性广,所制备的阻燃涂层在多种易燃材料上表现出良好的粘附性和稳定性。并且其制备工艺简单,容易控制,对生产设备要求低,因此可广泛应用于汽车外饰、家具电器、建筑材料和电线电缆等领域。
附图说明
图1为实施例1聚乙烯醇缩丁醛、全氟癸基三甲氧基硅烷和氟化聚乙烯醇缩丁醛的FT-IR谱图。
图2为实施例1制备的阻燃涂层的截面SEM照片(放大倍数:500X)。
图3为实施例1制备的阻燃涂层在遭遇火焰后的表面SEM照片(放大倍数:2000X)。
图4为实施例1制备的阻燃涂层在遭遇火焰后的截面SEM照片(放大倍数:500X)。
图5为实施例5中三明治结构预警阻燃涂层在(A)泡水前和(B)泡水后在火灾预警测试中的电阻变化曲线。
具体实施方式
为更好地理解本发明,下面结合附图和实施例对本发明作进一步说明,但是本发明的实施方式不限于此。
实施例1
1)底部导电层的制备:将0.8g银纳米线和1.2g聚乙烯醇缩丁醛一起加入98g乙醇中,超声搅拌40min使它们充分分散,配制成涂料A,然后将涂料A分别喷涂于聚丙烯和樟子松基材上,涂覆量为0.1mL/cm2,然后放入烘箱中在50℃下干燥10min;喷涂并干燥的过程重复4次,制得底部导电层,厚度约为5μm;
2)中部温敏传感层的制备:将1g氧化石墨烯和1g羧甲基壳聚糖一起加入98g去离子水中,超声搅拌60min使它们充分分散,配制成涂料B,然后将涂料B喷涂于步骤1)制备的底部导电层上,涂覆量为0.1mL/cm2,然后放入烘箱中在70℃下干燥30min,喷涂并干燥的过程重复10次,制得中部温敏传感层,厚度约为40μm;
3)顶部超疏水导电层的制备:在80℃条件下,将10g聚乙烯醇缩丁醛溶解于250mL乙醇中,然后加入5g全氟癸基三甲氧基硅烷加入和20g浓度为25wt%的氨水,回流反应6h。反应结束后将混合溶液冷却至室温,通过8000r/min的离心速度将产物分离,使用乙醇洗涤3遍,然后放入烘箱中在80℃下干燥5h,得到氟化聚乙烯醇缩丁醛。
对氟化聚乙烯醇缩丁醛进行傅里叶红外光谱(FT-IR,图1)分析。从图1氟化聚乙烯醇缩丁醛的FT-IR曲线可观察到-CH2-(3100~2750cm-1)、COOC(1750cm-1)、Si-O-C(1138cm-1)、C-O-C(1053cm-1)、Si-C(811cm-1)和C-F(700cm-1)的特征吸收峰,而-OH(3460cm-1)的特征吸收峰削弱,表明已经成功合成了氟化聚乙烯醇缩丁醛。
将0.8g银纳米线和1.2g氟化聚乙烯醇缩丁醛一起加入98g乙醇中,超声搅拌40min使它们充分分散,配制成涂料C,然后将涂料C喷涂于步骤2)制备的中部温敏传感层上,涂覆量为0.1mL/cm2,然后放入烘箱中在50℃下干燥10min,喷涂并干燥的过程重复4次,制得顶部超疏水导电层,厚度约为5μm。
对涂覆后的聚丙烯进行垂直燃烧、火灾预警和耐水性测试,结果如表1和表2所示。
实施例2
本实施例与实施例1的不同之处在于:步骤1)和步骤3)中0.8g银纳米线替换为1.2g铜纳米线,聚乙烯醇缩丁醛用量提高到2.8g,乙醇用量减少到96g,超声搅拌时间延长至60min,涂覆量减少到0.05mL/cm2,干燥温度提高到60℃,重复过程减少至2次。垂直燃烧、火灾预警和耐水性测试结果如表1和表2所示,有关测试方法同实施例1。
实施例3
本实施例与实施例1的不同之处在于:步骤1)和步骤3)中0.8g银纳米线替换为0.6g银纳米颗粒,聚乙烯醇缩丁醛用量减少到0.4g,乙醇用量提高到99g,超声搅拌时间缩短为20min,重复过程增加至6次。垂直燃烧、火灾预警和耐水性测试结果如表1和表2所示,有关测试方法同实施例1。
实施例4
本实施例与实施例1的不同之处在于:步骤1)和步骤3)中的聚乙烯醇缩丁醛替换为酚醛树脂,步骤3)中的乙醇替换为异丙醇,反应温度提高到90℃,回流反应时间提高到8h,离心速度降低到6000r/min,氟化聚乙烯醇缩丁醛替换为氟化酚醛树脂。垂直燃烧、火灾预警和耐水性测试结果如表1和表2所示,有关测试方法同实施例1。
实施例5
本实施例与实施例1的不同之处在于:步骤1)和步骤3)中的聚乙烯醇缩丁醛替换为乙基纤维素,步骤3)中的乙醇替换为二甲苯,反应温度提高到140℃,回流反应时间缩短到4h,离心速度提高到9000r/min,氟化聚乙烯醇缩丁醛替换为氟化乙基纤维素。垂直燃烧、火灾预警和耐水性测试结果如表1和表2所示,有关测试方法同实施例1。
实施例6
本实施例与实施例1的不同之处在于:步骤2)中1g氧化石墨烯替换为0.4g羟基化单壁碳纳米管,羧甲基壳聚糖的用量减少到0.6g,去离子水用量增加到99g,超声搅拌时间减少到40min,涂覆量减少到0.08mL/cm2,干燥温度降低到50℃,干燥时间缩短到20min,重复过程增加至14次。垂直燃烧、火灾预警和耐水性测试结果如表1和表2所示,有关测试方法同实施例1。
实施例7
本实施例与实施例1的不同之处在于:步骤2)中1g氧化石墨烯替换为1.8g氧化石墨烯纳米带,羧甲基壳聚糖的用量增加到1.2g,去离子水用量减少到97g,超声搅拌时间增加到120min,涂覆量增加到0.16mL/cm2,干燥温度提高到100℃,重复过程减少至6次。垂直燃烧、火灾预警和耐水性测试结果如表1和表2所示,有关测试方法同实施例1。
实施例8
本实施例与实施例1的不同之处在于:步骤2)中1g羧甲基壳聚糖替换为0.8g羟乙基壳聚糖,氧化石墨烯用量增加到1.2g,超声搅拌时间增加到90min,干燥温度降低到50℃。垂直燃烧、火灾预警和耐水性测试结果如表1和表2所示,有关测试方法同实施例1。
实施例9
本实施例与实施例1的不同之处在于:步骤2)中1g羧甲基壳聚糖替换为1.2g羟丙基甲基纤维素,氧化石墨烯用量减少到0.8g,超声搅拌时间缩短到30min,涂覆量提高到0.15mL/cm2,干燥温度升高到80℃,干燥时间提高到100min,重复次数减少到6次。垂直燃烧、火灾预警和耐水性测试结果如表1和表2所示,有关测试方法同实施例1。
实施例10
本实施例与实施例1的不同之处在于:步骤3)中的5g全氟癸基三甲氧基硅烷替换为3g全氟辛基三氯硅烷,20g浓度为25%的氨水替换为2g二月桂酸二丁基锡,乙醇替换为己烷,反应温度降低到70℃,反应时间缩短到5h,洗涤次数提高到5次。垂直燃烧、火灾预警和耐水性测试结果如表1和表2所示,有关测试方法同实施例1。
实施例11
本实施例与实施例1的不同之处在于:步骤3)中的5g全氟癸基三甲氧基硅烷替换为8g全氟癸基三乙氧基硅烷,20g浓度为25%的氨水替换为10g浓度为10%的稀盐酸,乙醇替换为正丁醇,反应温度提高到120℃,反应时间提高到8h,离心速度提高到10000r/min,洗涤次数提高到4次,干燥温度提高到100℃,干燥时间提高到12h。垂直燃烧、火灾预警和耐水性测试结果如表1和表2所示,有关测试方法同实施例1。
比较例1
为了验证本发明所制备的具有火灾预警和超疏水功能的三明治结构高效阻燃涂层可以通过简单的喷涂在易燃基材上制备阻燃涂层并发挥高效阻燃和高灵敏火灾预警作用,以未涂覆阻燃涂料的聚丙烯样条和樟子松木条作为对比。垂直燃烧测试结果如表1所示,有关测试方法同实施例1。比较例1中的样品都是纯的木条和塑料条,并没有作特殊处理。
比较例2
为了验证本发明所制备的具有火灾预警和超疏水功能的三明治结构高效阻燃涂层具有更为灵敏的预警响应速度和更大的预警面积,以单纯的氧化石墨烯基预警阻燃涂层作为对比。
将1g氧化石墨烯和1g羧甲基壳聚糖一起加入98g去离子水中,超声搅拌60min使它们充分分散,配制成涂料B,然后将涂料B喷涂于步骤1)制备的底部导电层上,涂覆量为0.1mL/cm2,然后放入烘箱中在70℃下干燥30min,该过程重复10次。垂直燃烧、火灾预警和耐水性测试结果如表1和表2所示,有关测试方法同实施例1。
测试方法
1、傅里叶红外光谱(FT-IR)分析:在傅里叶红外光谱分析仪(德国布鲁克公司,型号:TENSOR27)上进行。将功能化层状纳米材料粉末与溴化钾粉末混合并压制成片,检测其400~4000cm-1波数范围内的红外光谱信息。
2、扫描电镜(SEM):在热场发射扫描电镜(德国卡尔蔡司公司,型号:Merlin)上进行。通过导电胶将样品粘附在样品台上,并进行表面喷金处理。以加速电压为5kV的电子束扫描成像,观察样品表面形貌。
3、垂直燃烧测试:将125mm×13mm×3.2mm的样品垂直放置于本生灯上方19mm处,使其暴露于高度为40mm的本生灯火焰,20s后移走火焰,记录燃烧现象和数据。
4、火灾预警测试:通过导线将300mm×50mm×3.2mm的样品与预警灯和直流电源(36V)连接,然后将样品放置于酒精灯上方20mm处,使其暴露于高度为40mm的酒精灯火焰,20s后移走火焰,记录样品触发预警灯的时间。
5、耐水性测试:将样品完全泡入去离子水中,2h后取出放入烘箱中在80℃条件下干燥12h,然后进行垂直燃烧和火灾预警测试。
通过表1和表2中实施例1~11的数据可以看出,使用不同的金属纳米材料、氧化碳纳米材料、油溶性长链高分子、水溶性长链高分子和氟硅烷在不同工艺条件下制备的具有火灾预警和超疏水功能的三明治结构高效阻燃涂层,均可以赋予塑料和木材等易燃基材高效的阻燃性能,同时所制备的阻燃涂层具有超灵敏的火灾预警功能和耐水性能。
表1
表2
从表1和表2可以看出,本发明所提供的具有火灾预警和超疏水功能的三明治结构高效阻燃涂层可以对塑料和木材等易燃基材发挥高效的阻燃作用。如实施例1,喷涂了三明治结构预警阻燃涂层的聚丙烯样条和樟子松木条在垂直燃烧测试过程中均能达到UL-94V-0级。相比之下,未涂覆阻燃涂料的聚丙烯样条和樟子松木条(见比较例1)在垂直燃烧测试过程中均剧烈燃烧,直至完全烧尽。
为了观察阻燃涂层在燃烧前后其微观形貌的变化,本发明采用扫描电镜对其燃烧前后的截面和表面进行了分析。图2为实施例1所制备的三明治结构预警阻燃涂层的截面扫描电镜照片(放大倍数:500X),从图中可见本发明阻燃涂料在干燥过程中可以在易燃基材表面自行共组装形成层层紧密堆叠的结构。图3为实施例1所制备的三明治结构预警阻燃涂层在遭遇火焰后的表面扫描电镜照片(放大倍数:2000X),从图中可见在遭遇火焰时,顶部超疏水导电层中的长链高分子会快速发生炭化反应,其炭化产物将具有骨架增强作用的银纳米线粘接在一起,形成致密而稳定的表面。图4为实施例1所制备的三明治结构预警阻燃涂层在遭遇火焰后的截面扫描电镜照片(放大倍数:500X),从图中可见在遭遇火焰时,中部温敏传感层中的长链高分子的炭化产物将具有片层阻隔作用的氧化石墨烯粘合在一起,在热降解气体的作用下膨胀形成了具有优异阻隔性能层状多孔炭层,由此对易燃基材发挥超高效保护作用。
同时,从表1和表2可以看出,本发明所提供的具有火灾预警和超疏水功能的三明治结构高效阻燃涂层可以赋予塑料和木材等易燃基材超灵敏的火灾预警功能。如实施例5,喷涂了三明治结构预警阻燃涂层的聚丙烯样条和樟子松木条在遭遇火焰后均能快速触发预警装置,它们的火灾预警时间分别为0.88s和0.80s。在火灾预警测试过程中,通过万用表对实施例5所制备的三明治结构预警阻燃涂层的电阻变化进行了记录,得到的电阻曲线如图5所示,从图中可以看到涂层在遭遇火焰后其电阻急剧下降,这是因为中部温敏传感层中的氧化石墨烯上的含氧基团在高温环境中会快速降解,使其还原为导电性良好的石墨烯,并连通底部导电层和顶部疏水导电层从而形成导电通路,从而触发与涂层连接的预警装置,实现超灵敏火灾预警。相比之下,当单纯的氧化石墨烯基预警阻燃涂层应用于较大面积(125mm×13mm)的基材时,在遭遇火焰后并不能触发预警装置(见比较例2)。
此外,从表1和表2可以看出,本发明所提供的三明治结构预警阻燃涂层具有优异的耐水性能。如实施例5,喷涂了三明治结构预警阻燃涂层的聚丙烯样条和樟子松木条在泡水2h之后,它们在垂直燃烧测试中依然能达到UL-94V-0级,在火灾预警测试中依然能在0.81s和0.71s内触发预警装置。这是因为在本发明所提供的三明治结构预警阻燃涂层中,低表面能的氟化长链高分子可在涂层表面聚集并形成粗糙结构(见图4),从而使涂层表面达到超疏水状态并赋予涂层优异的耐水性能。相比之下,单纯的氧化石墨烯基预警阻燃涂层耐水性差,其在泡水2h后丧失了原有的阻燃性能,所涂覆的聚丙烯样条和樟子松木条在垂直燃烧测试中直接烧尽(见比较例2)。
综上所述,本发明所提供的三明治结构预警阻燃涂层具有超灵敏的火灾预警功能、优异的阻燃性能和耐水性能,可有效提高各种易燃材料(如塑料和木材等)的火灾安全性,可广泛应用于对阻燃性能要求较高的交通运输、家具电器、建筑装饰和电线电缆等领域。
本发明不受上述实施例约束,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的替代方式,都包含在本发明的保护范围之内。
Claims (9)
1.具有火灾预警和超疏水功能的三明治结构高效阻燃涂层的制备方法,其特征在于包括如下步骤:
1)底部导电层的制备:将金属纳米材料和油溶性长链高分子一起均匀分散于有机溶剂中形成涂料A,然后将涂料A喷涂于基材上,第一次干燥;喷涂并干燥的过程重复1~10次,制得底部导电层;
2)中部温敏传感层的制备:将氧化碳纳米材料和水溶性长链高分子一起均匀分散于去离子水中形成涂料B,然后将涂料B喷涂于步骤1)制备的底部导电层上,第二次干燥;喷涂并干燥的过程重复5~20次,制得中部温敏传感层;
3)顶部超疏水导电层的制备:在50~150℃条件下,将油溶性长链高分子溶解于有机溶剂中,然后加入氟硅烷和催化剂,回流反应2~12h;反应结束后将混合溶液冷却至室温,离心分离,使用有机溶剂洗涤,第三次干燥,得到氟化长链高分子;将金属纳米材料和氟化长链高分子一起均匀分散于有机溶剂中形成涂料C,然后将涂料C喷涂于步骤2)制备的中部温敏传感层上,第四次干燥;喷涂并干燥的过程重复1~10次,制得顶部超疏水导电层;
步骤1)和步骤3)所述的金属纳米材料为银纳米线、银纳米粒子、铜纳米线和铜纳米粒子中的一种或多种;
步骤1)和步骤3)所述的油溶性长链高分子为聚氨酯、聚乙烯醇缩丁醛、酚醛树脂、聚己内酯和乙基纤维素中的一种或多种;
所述的水溶性长链高分子为聚乙烯醇,羧甲基壳聚糖、羟乙基壳聚糖、羟丙基壳聚糖、羟乙基纤维素、羟丙基纤维素和羟丙基甲基纤维素中的一种或多种;
所述的催化剂为氨水、氢氧化钠水溶液、稀盐酸、乙酸、二月桂酸二丁基锡和二醋酸二丁基锡中的一种或多种;
所述的氟硅烷是全氟癸基三氯硅烷、全氟癸基三甲氧基硅烷、全氟癸基三乙氧基硅烷、全氟辛基三氯硅烷、全氟辛基三甲氧基硅烷、全氟辛基三乙氧基硅烷和3,3,3-三氟丙基甲基二甲氧基硅烷中的一种或多种。
2.根据权利要求1所述的具有火灾预警和超疏水功能的三明治结构高效阻燃涂层的制备方法,其特征在于,步骤1)和步骤3)所述的有机溶剂为丙酮、甲醇、己烷、乙醇、异丙醇、正丁醇、乙二醇二甲醚、二甲苯和N,N-二甲基甲酰胺中的一种或多种。
3.根据权利要求1所述的具有火灾预警和超疏水功能的三明治结构高效阻燃涂层的制备方法,其特征在于,所述的氧化碳纳米材料为羧基化单壁碳纳米管、羟基化单壁碳纳米管、羧基化多壁碳纳米管、羟基化多壁碳纳米管、氧化石墨烯纳米带和氧化石墨烯纳米片中的一种或多种。
4.根据权利要求1所述的具有火灾预警和超疏水功能的三明治结构高效阻燃涂层的制备方法,其特征在于,步骤1)中,所述的金属纳米材料和油溶性长链高分子的质量比为0.1:1~6:1,所述的涂料A的浓度为0.2wt%~10wt%;所述的涂料A喷涂于基材上的涂覆量为0.05~0.20mL/cm2;所述的干燥为放入烘箱中在40~100℃下干燥5~120min;所述的基材为聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯、聚酯、聚酰胺、环氧树脂、榆木、樟子松木、榉木、红橡木和黑胡桃木中的一种或多种。
5.根据权利要求1所述的具有火灾预警和超疏水功能的三明治结构高效阻燃涂层的制备方法,其特征在于,步骤2)中,所述的碳纳米材料和水溶性长链高分子的质量比为0.2:1~5:1,所述的涂料B的浓度为0.2wt%~5wt%;所述的涂料B的涂覆量为0.05~0.20mL/cm2;所述的干燥为放入烘箱中在40~100℃下干燥5~120min。
6.根据权利要求1所述的具有火灾预警和超疏水功能的三明治结构高效阻燃涂层的制备方法,其特征在于,步骤3)中,所述的金属纳米材料和氟化长链高分子的质量比为0.1:1~6:1,所述的氟硅烷和油溶性长链高分子的质量比为0.01:1~5:1,所述的催化剂与氟硅烷的质量比为1:100~1:10;所述的涂料C浓度为0.2wt%~10wt%;所述的涂料C的涂覆量为0.05~0.20mL/cm2;所述的离心分离的转速为6000~10000r/min;所述的有机溶剂洗涤的次数为2~5次;所述的第三次干燥为放入烘箱中在40~100℃下干燥2~12h;所述的第四次干燥为放入烘箱中在40~100℃下干燥5~120min。
7.根据权利要求1所述的具有火灾预警和超疏水功能的三明治结构高效阻燃涂层的制备方法,其特征在于,步骤1)、步骤2)和步骤3)所述的均匀分散是通过10~480min的强力机械搅拌、超声处理或两者共同作用实现的。
8.一种具有火灾预警和超疏水功能的三明治结构高效阻燃涂层,其特征在于其由权利要求1-7任一项所述的制备方法制得;三明治结构高效阻燃涂层所述的底部导电层、中部温敏传感层和顶部超疏水导电层的厚度分别为2~100μm,10~500μm和2~100μm。
9.权利要求8所述的具有火灾预警和超疏水功能的三明治结构高效阻燃涂层在塑料和木材上的应用。
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