CN119217841A - 一种防火双金属复合板及其制备方法 - Google Patents
一种防火双金属复合板及其制备方法 Download PDFInfo
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- CN119217841A CN119217841A CN202411738794.1A CN202411738794A CN119217841A CN 119217841 A CN119217841 A CN 119217841A CN 202411738794 A CN202411738794 A CN 202411738794A CN 119217841 A CN119217841 A CN 119217841A
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Classifications
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- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
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- Architecture (AREA)
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- Civil Engineering (AREA)
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Abstract
本发明涉及双金属复合板领域,公开了一种防火双金属复合板及其制备方法,该制备方法包括以下步骤:选取铝板作为基层,在铝板上表面覆上高分子膜,形成粘接层,在粘接层上表面覆上铜板,在150~200℃温度条件下复合制成防火双金属复合板;高分子膜包括:乙烯‑醋酸乙烯共聚物、环氧树脂、聚甲基丙烯酸甲酯、改性聚甲基丙烯酸缩水甘油酯、复合填料、聚酰胺,本发明制备的双金属复合板是在铝板上通过高分子膜覆以铜板制成,高分子膜添加有复合填料和改性聚甲基丙烯酸缩水甘油酯,提升了高分子膜的剥离强度和力学性能,抗氧化、耐腐蚀性能佳,阻燃性能和防火等级高。
Description
技术领域
本发明属于双金属复合板技术领域,具体涉及一种防火双金属复合板及其制备方法。
背景技术
随着工业化进程的加快,城市中的大型建筑逐渐增多,大型建筑所面临的消防难度较普通建筑增大,国家对于高层建筑所使用材料的防火性能提出了越来越高的要求,传统铝塑板的聚乙烯夹层本身存在诸多缺陷,例如:易燃材料,在高压、放热、放电等条件下极易引起火灾。
防火铝复合板是一种新型不燃产品,表面为铝合金,中间芯材为天然无机材料,板结构采用特殊高分子膜粘结,加热固化,通过先进的工艺使其达到完美结合,提高板材的力学性能,从而形成一种外观时尚、性能优越、施工方便的新一代室内外装饰材料。但是铝复合板往往是依靠表面涂饰油漆来搏取色彩,防火性能差,且芯材与铝合金的剥离强度不高,造成了使用寿命短,抗氧化、耐腐蚀的能力不佳。
现有单一组元金属材料的性能已无法满足现代工业飞速发展的需求,而双金属复合板作为替代产品不仅兼具双金属各自的优点,而且大幅度减少了稀贵金属的使用量,降低了生产成本,具有极高的性价比。金属复合板在实际应用中的防火性能备受重视,其中用于粘接的高分子膜也是判定防火性能的重要指标。当用于建筑幕墙以及内外墙装饰时,长时间受到自然环境下老化后性能出现明显下降,导致金属面板容易与高分子膜分离,使金属复合板的使用寿命降低。
发明内容
为解决上述背景技术中提到的不足,本发明的目的在于提供一种防火双金属复合板及其制备方法,双金属复合板是在铝板上通过高分子膜覆以铜板制备,高分子膜添加有复合填料和改性聚甲基丙烯酸缩水甘油酯,提升了高分子膜的剥离强度和力学性能,抗氧化、耐腐蚀性能佳,阻燃性能和防火等级高。
本发明的目的可以通过以下技术方案实现:
一种防火双金属复合板的制备方法,包括以下步骤:选取铝板作为基层,在铝板上表面覆上高分子膜,形成粘接层,在粘接层上表面覆上铜板,在150~200℃温度条件下复合制成防火双金属复合板;
所述高分子膜包括以下重量份原料:乙烯-醋酸乙烯共聚物50~70份、环氧树脂10~20份、聚甲基丙烯酸甲酯10~15份、改性聚甲基丙烯酸缩水甘油酯5~10份、复合填料2~5份、聚酰胺1~3份;
所述复合填料为利用化学反应将合成的阻燃剂共同接枝二氧化硅和碳纳米管制成;所述改性聚甲基丙烯酸缩水甘油酯为利用化学反应将氧化石墨烯包覆在聚甲基丙烯酸缩水甘油酯表面制成。
优选地,所述高分子膜的制备方法包括以下步骤:按重量份称取各原料,取乙烯-醋酸乙烯共聚物、环氧树脂、聚甲基丙烯酸甲酯、复合填料、改性聚甲基丙烯酸缩水甘油酯和聚酰胺混合后经螺杆造粒机造粒,然后经螺杆挤出机挤出后利用压延机压延成型,制备得到高分子膜。
优选地,所述复合填料的制备方法包括以下步骤:
A、取1,5-萘二胺和N-(2-氨乙基)-3-氨丙基三甲氧基硅烷于反应器中,加入乙醇溶剂,超声分散均匀,取对苯二甲醛溶于乙醇后加入至反应器中搅拌混合,置于55~70℃下回流反应4~6h,然后取DOPO溶于乙醇后加入至反应器中,置于75~90℃下继续反应5~6h,反应完成后冷却至室温,经过滤、洗涤、干燥,制备得到DOPO衍生物;
B、取碳纳米管于浓硫酸和浓硝酸的混合液中,置于70~85℃下反应4~6h,产物经抽滤洗涤至中性并进行干燥,将得到的氧化碳纳米管置于反应器中,加入二氯亚砜和N,N-二甲基甲酰胺,超声分散1~2h,然后置于70~85℃下回流反应20~24h,反应完成后经旋转蒸发、干燥,制备得到酰氯化碳纳米管;
C、取纳米二氧化硅和酰氯化碳纳米管超声分散于N,N-二甲基甲酰胺中,加入DOPO衍生物和吡啶混合均匀,置于70~80℃下回流反应18~24h,制备得到复合填料。
优选地,所述步骤A中1,5-萘二胺、N-(2-氨乙基)-3-氨丙基三甲氧基硅烷、对苯二甲醛和DOPO的摩尔比为0.33~0.4:0.65~0.72:1:1.4~2。
优选地,所述改性聚甲基丙烯酸缩水甘油酯的制备方法包括以下步骤:
(1)取聚乙烯吡咯烷酮于无水乙醇中搅拌溶解,通氮气搅拌25~40min,然后加入甲基丙烯酸缩水甘油酯,升温至65~75℃,加入偶氮二异丁腈反应7~9h,反应完成后经洗涤、干燥,得到聚甲基丙烯酸缩水甘油酯;
(2)取氧化石墨烯超声分散于去离子水中得到分散液,取对苯二胺溶于去离子水后加入至分散液中,超声混合并置于30~50℃下反应18~24h,反应完成后经过滤、洗涤、干燥,制备得到氨基化氧化石墨烯;
(3)取聚甲基丙烯酸缩水甘油酯和氨基化氧化石墨烯于反应器中,加入去离子水超声分散,置于40~50℃下反应18~24h,反应完成后经洗涤、干燥,制备得到改性聚甲基丙烯酸缩水甘油酯。
优选地,所述步骤(1)中聚乙烯吡咯烷酮和甲基丙烯酸缩水甘油酯的质量比为1:3.2~3.5。
优选地,所述步骤(3)中聚甲基丙烯酸缩水甘油酯和氨基化氧化石墨的质量比为1:1.8~2.1。
一种防火双金属复合板,由如上所述的制备方法制成。
本发明的有益效果:
本发明利用1,5-萘二胺、N-(2-氨乙基)-3-氨丙基三甲氧基硅烷和对苯二甲醛为原料制备阻燃剂DOPO衍生物,然后将DOPO衍生物一端的硅羟基与纳米二氧化硅表面的羟基发生缩合反应,DOPO衍生物另一端的氨基和酰氯化碳纳米管表面的酰氯基团发生反应,从而以DOPO衍生物为连接物共同接枝二氧化硅和碳纳米管。其中碳纳米管具有极高的比表面积、优良的弹性模量、优异的热性能和极低的热膨胀系数,由于DOPO衍生物的连接与限制,使得碳纳米管与纳米二氧化硅结合紧密,同时进一步促进了纳米二氧化硅和碳纳米管的分散,避免因纳米二氧化硅和碳纳米管发生团聚现象导致高分子膜粘结强度下降,且碳纳米管配合纳米二氧化硅提高了高分子膜的耐热性和力学性能。
本发明通过自由基聚合反应制备聚甲基丙烯酸缩水甘油酯,同时本发明利用防老剂对苯二胺一端的氨基与氧化石墨烯结构中的环氧基发生接枝反应,制备得到氨基化氧化石墨烯,然后利用化学反应将氨基化氧化石墨烯结构中的氨基基团与聚甲基丙烯酸缩水甘油酯表面的环氧基团发生开环反应,制备得到氧化石墨烯包覆的改性聚甲基丙烯酸缩水甘油酯,其中氧化石墨烯力学性能优异,且具有对氧气和水的不渗透性和高比表面积的优点,将氧化石墨烯包覆在聚甲基丙烯酸缩水甘油酯表面,增大了氧化石墨烯的层间距,有利于氧化石墨烯的分散,同时增加了氧化石墨烯与基体的接触面积,提高材料与基体的相容性,且环氧树脂和改性聚甲基丙烯酸缩水甘油酯可以与固化剂聚酰胺共固化,形成两种交联网络,增强高分子膜的致密性,强化与金属板材的粘结能力,增大剥离强度,同时提高了高分子膜的防腐效果和力学性能。
本发明制备的高分子膜具有优异的阻燃性,更加安全可靠,铜板与铝板通过高分子膜粘结固定,粘结的面积更大,粘合效果更好,且高分子粘接膜具有剥离强度高、耐热氧老化、抗压能力强的优点。另外本发明制备的双金属复合板是在铝板上通过高分子膜覆以铜板的复合板,以达到在不改变外观效果的前提下节约资源、降低成本的效果。
具体实施方式
下面将结合本发明实施例,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作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1 一种复合填料的制备方法包括以下步骤:
A、取5.28g1,5-萘二胺和14.46gN-(2-氨乙基)-3-氨丙基三甲氧基硅烷于反应器中,加入50mL乙醇溶剂,超声分散均匀,取13.41g对苯二甲醛溶于50mL乙醇后加入至反应器中搅拌混合,置于65℃下回流反应6h,然后取34.59gDOPO溶于100mL乙醇后加入至反应器中,置于85℃下继续反应6h,反应完成后冷却至室温,经过滤、洗涤、干燥,制备得到DOPO衍生物;
B、取2g碳纳米管于87mL浓硫酸和29mL浓硝酸的混合液中,置于80℃下反应5h,产物经抽滤洗涤至中性并进行干燥,取0.4g得到的氧化碳纳米管置于反应器中,加入100mL二氯亚砜和2mLN,N-二甲基甲酰胺,超声分散1h,然后置于80℃下回流反应24h,反应完成后经旋转蒸发、干燥,制备得到酰氯化碳纳米管;
C、取0.1g纳米二氧化硅和0.4g酰氯化碳纳米管超声分散于100mLN,N-二甲基甲酰胺中,加入0.8gDOPO衍生物和0.15mL吡啶混合均匀,置于80℃下回流反应24h,制备得到复合填料。
实施例2 一种改性聚甲基丙烯酸缩水甘油酯的制备方法包括以下步骤:
(1)取3.2g聚乙烯吡咯烷酮于200mL无水乙醇中搅拌溶解,通氮气搅拌30min,然后加入10.3g甲基丙烯酸缩水甘油酯,升温至70℃,加入0.15g偶氮二异丁腈反应8h,反应完成后经洗涤、干燥,得到聚甲基丙烯酸缩水甘油酯;
(2)取1g氧化石墨烯超声分散于100mL去离子水中得到分散液,取1.7g对苯二胺溶于100mL去离子水后加入至分散液中,超声混合并置于50℃下反应20h,反应完成后经过滤、洗涤、干燥,制备得到氨基化氧化石墨烯;
(3)取1g聚甲基丙烯酸缩水甘油酯和2g氨基化氧化石墨烯于反应器中,加入200mL去离子水超声分散,置于45℃下反应24h,反应完成后经洗涤、干燥,制备得到改性聚甲基丙烯酸缩水甘油酯。
实施例3 一种高分子膜包括以下重量份原料:乙烯-醋酸乙烯共聚物52份、环氧树脂10份、聚甲基丙烯酸甲酯10份、实施例2制备的改性聚甲基丙烯酸缩水甘油酯5份、实施例1制备的复合填料2份、聚酰胺1份。
上述高分子膜的制备方法包括以下步骤:按重量份称取各原料,取乙烯-醋酸乙烯共聚物、环氧树脂、聚甲基丙烯酸甲酯、复合填料、改性聚甲基丙烯酸缩水甘油酯和聚酰胺混合后经螺杆造粒机造粒,然后经螺杆挤出机挤出后利用压延机压延成型,制备得到高分子膜。
一种防火双金属复合板的制备方法,包括以下步骤:选取铝板作为基层,在铝板上表面覆上高分子膜,形成粘接层,在粘接层上表面覆上铜板,在150℃的温度条件下,用压力机施加0.5MPa的压力制成。
实施例4 一种高分子膜包括以下重量份原料:乙烯-醋酸乙烯共聚物63份、环氧树脂15份、聚甲基丙烯酸甲酯12份、实施例2制备的改性聚甲基丙烯酸缩水甘油酯7份、实施例1制备的复合填料4份、聚酰胺2份。
上述高分子膜的制备方法同实施例3。
一种防火双金属复合板的制备方法,包括以下步骤:选取铝板作为基层,在铝板上表面覆上高分子膜,形成粘接层,在粘接层上表面覆上铜板,在180℃的温度条件下,用压力机施加0.6MPa的压力制成。
实施例5 一种高分子膜包括以下重量份原料:乙烯-醋酸乙烯共聚物70份、环氧树脂18份、聚甲基丙烯酸甲酯15份、实施例2制备的改性聚甲基丙烯酸缩水甘油酯10份、实施例1制备的复合填料5份、聚酰胺3份。
上述高分子膜的制备方法同实施例3。
一种防火双金属复合板的制备方法,包括以下步骤:选取铝板作为基层,在铝板上表面覆上高分子膜,形成粘接层,在粘接层上表面覆上铜板,在200℃的温度条件下,用压力机施加0.8MPa的压力制成。
对比例1 一种高分子膜包括以下重量份原料:乙烯-醋酸乙烯共聚物70份、环氧树脂18份、聚甲基丙烯酸甲酯15份、实施例2制备的改性聚甲基丙烯酸缩水甘油酯10份、纳米二氧化硅1份、碳纳米管4份、聚酰胺3份。
上述高分子膜的制备方法同实施例3。
一种防火双金属复合板的制备方法同实施例5。
对比例2 一种高分子膜包括以下重量份原料:乙烯-醋酸乙烯共聚物70份、环氧树脂18份、聚甲基丙烯酸甲酯15份、实施例2制备的聚甲基丙烯酸缩水甘油酯10份、实施例1制备的复合填料5份、聚酰胺3份。
上述高分子膜的制备方法同实施例3。
一种防火双金属复合板的制备方法同实施例5。
性能检测
将实施例3-5以及对比例1-2制备的高分子膜和防火双金属复合板进行性能检测:按照GB/T 7124-2008测定拉伸剪切强度,加载速度为5mm/min;按照GB/T 7122-1996测定剥离强度,并测定90℃/504h热老化后的剥离强度,加载速度为30mm/min;盐雾老化按照GJB150.11A测试,试验前调节试验箱温度为35℃,并在喷雾前将试件保持在该条件下至少2h,喷盐雾48h,在此期间,盐雾沉降率和沉降溶液的pH值至少每隔24h测量一次,保证盐溶液的沉降率为1~3mL/(80cm2·h),干燥48h,于盐雾试验时间480h后取出试验件,在标准条件下放置24h后进行性能测试;按照GB/T 2406.2-2009测定高分子膜的极限氧指数;双金属复合板的弯曲强度根据JCT 2561-2020进行测定;双金属复合板的燃烧性能等级根据GB8624-2012进行测定,得到数据结果如表1所示。
表1 试样性能检测结果
从表1中数据结果可以看出,本发明实施例3-5制备的材料具有较高的剪切强度和剥离强度,且经热老化和盐雾老化后剥离强度未见明显降低,同时具备优异的抗拉强度和弯曲强度,阻燃性能和防火等级较高。其中对比例1中将纳米二氧化硅和碳纳米管简单共混,其测得的剪切强度、剥离强度、力学性能、阻燃性和防火等级较实施例3-5降低,对比例2中未对聚甲基丙烯酸缩水甘油酯进行改性处理,其经热老化和盐雾老化后测得的剥离强度明显降低,同时抗拉强度和弯曲强度较实施例3-5略差。
在本说明书的描述中,参考术语“一个实施例”、“示例”、“具体示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不一定指的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。
Claims (8)
1.一种防火双金属复合板的制备方法,其特征在于,包括以下步骤:选取铝板作为基层,在铝板上表面覆上高分子膜,形成粘接层,在粘接层上表面覆上铜板,在150~200℃温度条件下复合制成防火双金属复合板;
所述高分子膜包括以下重量份原料:乙烯-醋酸乙烯共聚物50~70份、环氧树脂10~20份、聚甲基丙烯酸甲酯10~15份、改性聚甲基丙烯酸缩水甘油酯5~10份、复合填料2~5份、聚酰胺1~3份;
所述复合填料为利用化学反应将合成的阻燃剂共同接枝二氧化硅和碳纳米管制成;所述改性聚甲基丙烯酸缩水甘油酯为利用化学反应将氧化石墨烯包覆在聚甲基丙烯酸缩水甘油酯表面制成。
2.根据权利要求1所述的防火双金属复合板的制备方法,其特征在于,所述高分子膜的制备方法包括以下步骤:按重量份称取各原料,取乙烯-醋酸乙烯共聚物、环氧树脂、聚甲基丙烯酸甲酯、复合填料、改性聚甲基丙烯酸缩水甘油酯和聚酰胺混合后经螺杆造粒机造粒,然后经螺杆挤出机挤出后利用压延机压延成型,制备得到高分子膜。
3.根据权利要求1所述的防火双金属复合板的制备方法,其特征在于,所述复合填料的制备方法包括以下步骤:
A、取1,5-萘二胺和N-(2-氨乙基)-3-氨丙基三甲氧基硅烷于反应器中,加入乙醇溶剂,超声分散均匀,取对苯二甲醛溶于乙醇后加入至反应器中搅拌混合,置于55~70℃下回流反应4~6h,然后取DOPO溶于乙醇后加入至反应器中,置于75~90℃下继续反应5~6h,反应完成后冷却至室温,经过滤、洗涤、干燥,制备得到DOPO衍生物;
B、取碳纳米管于浓硫酸和浓硝酸的混合液中,置于70~85℃下反应4~6h,产物经抽滤洗涤至中性并进行干燥,将得到的氧化碳纳米管置于反应器中,加入二氯亚砜和N,N-二甲基甲酰胺,超声分散1~2h,然后置于70~85℃下回流反应20~24h,反应完成后经旋转蒸发、干燥,制备得到酰氯化碳纳米管;
C、取纳米二氧化硅和酰氯化碳纳米管超声分散于N,N-二甲基甲酰胺中,加入DOPO衍生物和吡啶混合均匀,置于70~80℃下回流反应18~24h,制备得到复合填料。
4.根据权利要求3所述的防火双金属复合板的制备方法,其特征在于,所述步骤A中1,5-萘二胺、N-(2-氨乙基)-3-氨丙基三甲氧基硅烷、对苯二甲醛和DOPO的摩尔比为0.33~0.4:0.65~0.72:1:1.4~2。
5.根据权利要求1所述的防火双金属复合板的制备方法,其特征在于,所述改性聚甲基丙烯酸缩水甘油酯的制备方法包括以下步骤:
(1)取聚乙烯吡咯烷酮于无水乙醇中搅拌溶解,通氮气搅拌25~40min,然后加入甲基丙烯酸缩水甘油酯,升温至65~75℃,加入偶氮二异丁腈反应7~9h,反应完成后经洗涤、干燥,得到聚甲基丙烯酸缩水甘油酯;
(2)取氧化石墨烯超声分散于去离子水中得到分散液,取对苯二胺溶于去离子水后加入至分散液中,超声混合并置于30~50℃下反应18~24h,反应完成后经过滤、洗涤、干燥,制备得到氨基化氧化石墨烯;
(3)取聚甲基丙烯酸缩水甘油酯和氨基化氧化石墨烯于反应器中,加入去离子水超声分散,置于40~50℃下反应18~24h,反应完成后经洗涤、干燥,制备得到改性聚甲基丙烯酸缩水甘油酯。
6.根据权利要求5所述的防火双金属复合板的制备方法,其特征在于,所述步骤(1)中聚乙烯吡咯烷酮和甲基丙烯酸缩水甘油酯的质量比为1:3.2~3.5。
7.根据权利要求5所述的防火双金属复合板的制备方法,其特征在于,所述步骤(3)中聚甲基丙烯酸缩水甘油酯和氨基化氧化石墨的质量比为1:1.8~2.1。
8.一种防火双金属复合板,其特征在于,由权利要求1~7中任意一项所述的制备方法制成。
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