CN106496518A - 石墨烯改性聚氨酯保温板及其生产方法 - Google Patents

石墨烯改性聚氨酯保温板及其生产方法 Download PDF

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CN106496518A
CN106496518A CN201610891811.4A CN201610891811A CN106496518A CN 106496518 A CN106496518 A CN 106496518A CN 201610891811 A CN201610891811 A CN 201610891811A CN 106496518 A CN106496518 A CN 106496518A
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modified polyurethane
graphene
warming plate
graphene modified
cement
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CN106496518B (zh
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王永信
王永胜
孔祥荣
张责宇
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Beijing Shengxin Xinyuan New Building Materials Co Ltd
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Abstract

本发明公开了一种石墨烯改性聚氨酯保温板，包括由上至下排布的：第一水泥防火布、石墨烯改性聚氨酯保温层和第二水泥防火布，石墨烯改性聚氨酯保温层包括下述以重量份表示的组分：本发明提供一种石墨烯改性聚氨酯保温板及其生产方法，其目的在于解决目前制备的聚氨酯保温板无法很好的兼具保温性能和阻燃性能的问题。

Description

石墨烯改性聚氨酯保温板及其生产方法
技术领域
本发明涉及外墙保温阻燃节能材料技术领域，更具体地说，它涉及一种石墨烯改性聚氨酯保温板及其生产方法。
背景技术
聚氨酯保温板是一种闭孔率高达93％的轻质保温材料，抗压强度大、隔热效果好，经常用于建筑墙体、冷藏室以及化工罐体等领域。由于聚氨酯保温板的应用场合多为人口密集区域、货物集放地以及化工产品聚集地，而且我国对建筑保温材料的防火等级也有明确要求，因此，聚氨酯保温板不仅需要具备保温的性能还需要具有突出的防火性能。为改善聚氨酯保温板的阻燃性能，通常需要在聚氨酯保温板中添加反应型阻燃剂或者非反应型阻燃剂达到阻燃效果。
授权公告号为CN102911341B的发明专利改进了阻燃材料，使用偏钨酸铵为主的钨系无机阻燃剂和纳米气凝胶二氧化硅无机复合阻燃剂提高聚氨酯保温板的阻燃性能。燃烧时间减至4s，导热系数<0.024W/mK。改进了阻燃材料之后，聚氨酯保温板的阻燃性能大大提升，保温效果没有明显提升。
发明内容
针对现有技术存在的不足，本发明提供一种石墨烯改性聚氨酯保温板，包括由上至下排布的：第一水泥防火布、石墨烯改性聚氨酯保温层和第二水泥防火布，石墨烯改性聚氨酯保温层包括下述以重量份表示的组分：
其中，黑料和白料是生产聚氨酯保温板使用的常规材料。白料为聚醚多元醇，官能度为4-5、分子量为500-700。聚醚多元醇是端羟基的低聚物，主链上的羟基由醚键连接，作为发泡剂同时也可以作为分散剂。黑料为多次甲基多苯基异氰酸酯，作为粘结剂，使成型的聚氨酯保温板具有一定的强度。在黑料和白料中添加阻燃剂，使聚合物具有阻燃性能。为进一步增加材料的阻燃性能，在混合物中加入石墨粉，石墨粉通过延缓或中断固态物质产生可燃性物质而实现阻燃效果，受热到一定程度，石墨粉形成一个较厚的多孔碳化层，该多孔碳化层把阻燃主体和热源隔开，从而延缓和终止聚合物的分解。石墨烯改性聚氨酯保温板由第一水泥防火布、石墨烯改性聚氨酯保温层和第二水泥防火布构成，石墨烯改性聚氨酯保温层本身具有一定的强度，而且还具有保温阻燃的特点，并且在低温下不收缩，可用于冷库。
在混合物中加入的石墨烯一方面可以辅助阻燃剂和石墨粉阻燃，另一方面，石墨烯可以稳定石墨烯改性聚氨酯保温板中的闭孔泡沫，增强隔热性能。由于石墨烯为纳米材料，而且在使用改性的Hummers法制备过程中，在石墨烯表面增加羟基、羧基、环氧基或者醌基等一些含氧官能团，石墨烯微观上体现出双亲性。在黑料和白料混合发泡过程中，产生的泡沫多为闭孔结构，而聚醚多元醇和石墨烯表面的含氧官能团之间发生静电排斥力，使闭孔结构的孔壁液体层膜增厚，从而稳定气泡。石墨烯受热到一定程度，其表面的含氧官能团发生分解，官能团分解产生H2O或者CO2不可燃气体，与石墨膨胀形成多孔碳化层协同，增强阻燃性能。
石墨烯作为添加剂加入混合物中，其本身含有含氧官能团，而且石墨烯纳米粉末之间不能互相搭接，无法实现热量的传递。此外，制备的石墨烯具有双亲性，可以稳定形成的闭孔泡沫。因此，在宏观上，石墨烯改性聚氨酯保温板表现出隔热的性能。
进一步地，所述的阻燃剂为磷酸三氯乙酯或者甲基膦酸二甲酯中的一种。
磷酸三氯乙酯和甲基膦酸二甲酯为有机磷阻燃剂，在受热时产生结构较稳定的碳化层，碳化层的形成一方面阻止聚合物进一步热解，另一方面阻止其内部的热分解产生物进入气相参与燃烧过程。此外，磷酸三氯乙酯中的氯元素分解产生HCl不燃气体，可稀释燃烧区内的氧含量，并且生成的HCl可以捕获氢自由基或者羟基自由基，延缓或者终止反应。
进一步地，所述石墨粉为膨胀石墨、200目石墨、500目石墨和800目石墨中的一种；所述石墨烯为由石墨粉作为原料，通过改进的Hummers法制备所得。
由于石墨粉为多层结构，层与层之间通过范德华力结合。选用的石墨粒径均大于0.015mm，使石墨在200-300℃之间可膨胀形成蜂窝状多孔复合结构，该结构为较厚的多孔碳化层，碳化层热稳定性好可以把阻燃主体和热源隔开，阻止热量由热源传到内层，从而延缓和终止聚合物的分解。本发明中所用的石墨烯，使用石墨作为原料，通过改进的Hummers法得到的氧化石墨烯再经过还原得到石墨烯。使用该方法制备石墨烯，得到的石墨烯可以保留一部分的含氧官能团，利于稳定生产过程中产生的泡沫。
作为优选，所述的石墨烯改性聚氨酯保温板包括下述以重量份表示的组分：聚醚多元醇1000份，多次甲基多苯基异氰酸酯1500份，石墨粉250份，石墨烯5份，阻燃剂5份。
使用以上配比得到的石墨烯改性聚氨酯保温板隔热性能和阻燃性能较佳。
进一步地，上述石墨烯改性聚氨酯保温板的生产方法如下：
步骤1：所述白料与石墨粉、石墨烯和阻燃剂常温常压下在高速分散机中预混成为白料预混物；
步骤2：白料预混物和黑料在高压发泡机中经过加聚反应发泡形成发泡混合料；
步骤3：步骤2中的发泡混合料在层压机中定型的同时在混合物上下表面铺布水泥防火布形成石墨烯改性聚氨酯保温板。
生产石墨烯改性聚氨酯保温板的方法主要为：预混、发泡、成型。由于白料发泡过程比较缓慢，首先将白料与石墨粉、石墨烯以及阻燃剂在高速分散机的作用下分散均匀并且混合完全；之后将混合均匀的白料预混物和黑料混合，多次甲基多苯基异氰酸酯中的异氰酸根与聚醚多元醇中的羟基发生加聚链增长反应。由于是在高压发泡机中进行，在此过程中，高压发泡机在高速搅拌过程中会混入一部分空气，这部分空气可以作为造孔剂。黑料和白料在高压发泡机中混合，白料作为具有发泡作用也会产生很多细小均匀的泡沫。层压机包括上下两个链板，在发泡混合料放入层压机之前，在层压机的下链板上预先铺设第二水泥防火布，在层压机的上链板通过转轴传送第一水泥防火布。之后，将发泡混合料转移至层压机中，调节层压机内部的温度，使聚氨酯发泡达到最佳条件，发泡混合料可以继续发泡。层压机的厚度可通过调整层压机上下两个链板之间的间距实现，经过层压、定型，石墨烯改性聚氨酯保温板的上下两个表面已经与水泥防火布紧密贴合成一体。
优选地，所述步骤1中高速分散机的转速为：1500-3000r/s，分散时间为10-15min。
混合物在高速分散机内互相撞击，分子间互相反应、渗透和分散。此外，由于石墨烯纳米颗粒本身比表面积大，容易发生团聚，在1500-3000r/s的转速下可以使石墨烯粉末均匀分散于混合物中。经过10-15min的分散后，混合物可以混合均匀。若分散时间太长，混合物中的高分子链在高速剪切情况下，分子间作用力减弱，粘度下降，影响成型。
优选地，所述步骤2中高压发泡机的压力为：0.17-0.24MPa。
高压发泡机中的压力选择0.17-0.24MPa之间，若压力太低，发泡效果不好。若压力较高，泡沫可能互相融合或者破裂，影响保温板的性能，压力在0.17-0.24MPa之间，发泡大小适中，而且泡沫之间不容易融并。
进一步地，第一水泥防火布和第二水泥防火布由聚丙烯纤维、混凝土和砂浆浸渍延压制得。
紧贴石墨烯改性聚氨酯保温层的第一水泥防火布和第二水泥防火布主要由聚丙烯纤维、混凝土和砂浆浸渍延压制得。其中，聚丙烯纤维强度高、耐磨性好并且抗微生物，可以作为水泥砂浆布的“骨架”，混凝土将聚丙烯纤维包裹起来，并且还可以起到粘结作用，砂浆和混凝土中含有SiO2，成分稳定，不易燃。
综上所述，本发明的有益效果如下：
在常规的聚氨酯保温板中加入石墨粉和石墨烯，石墨粉受热到一定程度，层状结构膨胀形成一个较厚的多孔碳化层，该碳化层把阻燃主体和热源隔开，从而延缓和终止聚合物的分解，起到阻燃作用。使用改性的Hummers法制备的石墨烯比表面积大，并且具有双亲性，石墨烯表面的含氧官能团与聚醚多元醇中的亲水基团发生静电排斥力，使形成的液体层膜增厚，稳定气泡，增强材料的保温性能。
使用本发明中的工艺过程，经过预混处理，石墨粉和石墨烯可以均匀与白料混合。白料预混物和黑料混合，在高压发泡机中发泡形成的泡沫最终为成型保温板中闭孔结构，调整高压发泡机的压力为0.17-0.24MPa，使发泡细小均匀。在层压机中石墨烯改性聚氨酯保温板上下两个表面与水泥防火布紧密贴合，一体成型。
制备得到的石墨烯改性聚氨酯保温板，本身具有一定的强度，兼具保温阻燃的性能，并且在低温下不收缩。在石墨烯改性聚氨酯保温板的上下两个表面贴合的水泥防火布具有阻燃、耐磨和抗微生物的特点。石墨烯改性聚氨酯保温复合板在使用过程中，具有保温、阻燃、不收缩、耐磨以及抗微生物的特点，方便实用。
附图说明
图1为制备石墨烯改性聚氨酯保温板工艺流程图；
图2为石墨烯改性聚氨酯保温复合板的结构图。
附图标记说明：1、第一水泥防火布；2、石墨烯改性聚氨酯保温层；3、第二水泥防火布。
具体实施方式
本发明实施例中所涉及的所有物质均为市售。
实施例中涉及的具体原材料如表1。
表1各原材料的规格以及生产厂家
本实施例中的石墨烯(NIHY)按照公告号为CN102020270A发明专利中的方法制备。
实施例一：结合图1和图2对石墨烯改性聚氨酯保温板的制备过程做如下描述：
(1)将聚醚多元醇1000g，200目石墨250g，石墨烯5g，甲基膦酸二甲酯5g放于反应釜中预混15min，使用高速分散机分散，转速设为3000r/s，得到白料预混物。
(2)将白料预混物和1500g多次甲基多苯基异氰酸酯混合并置于高压发泡机中，设置压力为0.22MPa，得到混合物。
(3)层压机包括上下两个链板，混合物放入层压机之前，在层压机的下链板上预先铺设第二水泥防火布3，在层压机的上链板通过转轴传送第一水泥防火布1。在下链板上的第二水泥防火布3上均匀涂敷混合物。混合物随链板的传送方向移动，进入层压机后，设置层压机内的温度为28℃，混合物在层压机内部发泡，发泡高度达到位于上链板的第一水泥防火布1，发泡后的混合物在层压机上下两个链板的限制下成型构筑为石墨烯改性聚氨酯保温层2，在层压机的出料端，通过在石墨烯改性聚氨酯保温层2的上下两面贴合水泥防火布，得到一体成型的石墨烯改性聚氨酯保温板。
(4)切割石墨烯改性聚氨酯保温复合板，得到符合实际需求的不同尺寸。
使用以上配比以及工艺得到的石墨烯改性聚氨酯保温复合板的芯密度为37kg/m3；在10％的压缩应力下，相应的压缩强度为200kPa；导热系数为0.016W/mK；氧指数为31％；燃烧增长速率指数237W/s；600s的总放热量5.3MJ；火焰横向蔓延未到达试样长翼边缘；60s内焰尖高度<150mm；60s内燃烧滴落物无引燃滤纸现象。
实施例：
以下各实施例中的工艺流程与实施例一中相似，区别仅在于组分的配比以及工艺参数。实施例一和以下各实施例中各组分的质量如表2所示。实施例一和以下各实施例中涉及的工艺参数如表3所示。
表2实施例1至实施例6中各组分的质量
表3实施例1至实施例6中涉及的工艺参数
按照《建筑绝热用硬质聚氨酯泡沫塑料》(GB/T21558-2008)和《建筑材料及制品燃烧性能分级》(GB8624-2012)，对制备得到的石墨烯改性聚氨酯保温复合板进行强度、热导率以及燃烧性能的测试，燃烧试样安装依照GB/T20284-2006。实施例1-6的性能测试结果如表4所示。
表4实施例1-6制备得到的石墨烯改性聚氨酯保温复合板的性能测试结果比较
综合上述测试结果，实施例1具有较佳的性能，因此实施例1为较为优选的方案。
实施例1中石墨烯改性聚氨酯保温复合板包括下述以重量份表示的组分：聚醚多元醇1000份，多次甲基多苯基异氰酸酯1500份，甲基膦酸二甲酯5份，200目石墨粉250份，石墨烯5份。
对比例：
各对比例中的组分质量如表5所示。
表5对比例1-6中各组分的质量对比
各对比例中的工艺参数对比如表6所示。
表6对比例1-6中工艺参数比较
按照《建筑绝热用硬质聚氨酯泡沫塑料》(GB/T21558-2008)和《建筑材料及制品燃烧性能分级》(GB8624-2012)，对制备得到的石墨烯改性聚氨酯保温复合板进行强度、热导率以及燃烧性能的测试，燃烧试样安装依照GB/T20284-2006。各对比例中的性能测试结果比较如表7所示。
表7对比例1-6中性能测试结果比较
与实施例1相比，对比例1没有添加石墨粉和石墨烯，对比例2仅添加石墨粉，对比例3仅添加石墨烯。对比例4和对比例5与对比例1的区别在于石墨的添加量不同。对比例6是授权公告号为CN102936328B的发明专利中的参数。经对比发现，加入石墨粉有助于阻燃性能的提升，加入石墨烯有助于保温性能的提升。若石墨粉加入量太多，容易发生消泡现象，石墨粉加入量太少，石墨烯改性聚氨酯保温复合板的强度变差。
以上所述仅是本发明的优选实施方式，本发明的保护范围并不仅局限于上述实施例，凡属于本发明思路下的技术方案均属于本发明的保护范围。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理前提下的若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (10)

1.一种石墨烯改性聚氨酯保温板，包括由上至下排布的：第一水泥防火布、石墨烯改性聚氨酯保温层和第二水泥防火布，其特征在于，石墨烯改性聚氨酯保温层包括下述以重量份表示的组分：
2.根据权利要求1所述的石墨烯改性聚氨酯保温板，其特征在于：所述的白料为聚醚多元醇，所述聚醚多元醇的官能度为4-5、分子量为500-700。
3.根据权利要求1所述的石墨烯改性聚氨酯保温板，其特征在于：所述的黑料为多次甲基多苯基异氰酸酯。
4.根据权利要求1所述的石墨烯改性聚氨酯保温板，其特征在于：所述的阻燃剂为磷酸三氯乙酯或者甲基膦酸二甲酯中的一种。
5.根据权利要求1所述的石墨烯改性聚氨酯保温板，其特征在于：所述石墨粉为膨胀石墨、200目石墨、500目石墨和800目石墨中的一种；所述石墨烯以石墨粉作为原料，通过改进的Hummers法制备所得。
6.根据权利要求1所述的石墨烯改性聚氨酯保温板，其特征在于：所述的石墨烯改性聚氨酯保温板包括下述以重量份表示的组分：聚醚多元醇1000份，多次甲基多苯基异氰酸酯1500份，石墨粉250份，石墨烯5份，阻燃剂5份。
7.根据权利要求1所述的石墨烯改性聚氨酯保温板，其特征在于：第一水泥防火布和第二水泥防火布由聚丙烯纤维、混凝土和砂浆浸渍延压制得。
8.一种制备权利要求1-6任意一项所述的石墨烯改性聚氨酯保温板的生产方法，其特征在于：
步骤1：所述白料与石墨粉、石墨烯和阻燃剂常温常压下在高速分散机中预混成为白料预混物；
步骤2：白料预混物和黑料在高压发泡机中经过加聚反应发泡形成发泡混合料；
步骤3：步骤2中的发泡混合料在层压机中定型的同时在混合物上下表面铺布水泥防火布形成石墨烯改性聚氨酯保温板。
9.根据权利要求8所述的石墨烯改性聚氨酯保温板的生产方法，其特征在于：所述步骤1中高速分散机的转速为：1500-3000r/s，分散时间为10-15min。
10.根据权利要求8所述的石墨烯改性聚氨酯保温板的生产方法，其特征在于：所述步骤2中高压发泡机的压力为：0.17-0.24MPa。
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CN107759243A (zh) * 2017-10-31 2018-03-06 广西旭腾实业集团有限公司 一种基于石墨烯与石材发泡轻质墙板及其制备方法
CN107761990A (zh) * 2017-10-31 2018-03-06 广西旭腾实业集团有限公司 新型装配式建筑体系及其装配方法
CN107816127A (zh) * 2017-10-31 2018-03-20 广西旭腾实业集团有限公司 铝合金结构新型装配式建筑体系及其装配方法
CN107816130A (zh) * 2017-10-31 2018-03-20 广西旭腾实业集团有限公司 钢结构新型装配式建筑体系及其装配方法
CN107761963A (zh) * 2017-10-31 2018-03-06 广西旭腾实业集团有限公司 混凝土结构新型装配式建筑体系及其装配方法
CN107816127B (zh) * 2017-10-31 2018-12-11 广西旭腾实业集团有限公司 铝合金结构装配式建筑体系及其装配方法
CN108047410A (zh) * 2017-12-29 2018-05-18 广西通祥投资有限公司 一种聚氨酯保温板材及其生产工艺
CN109130377A (zh) * 2018-08-22 2019-01-04 北京建筑材料科学研究总院有限公司 一种缝制玻璃棉板和硬泡聚氨酯的复合外墙外保温板及其制备方法
CN109627740A (zh) * 2018-11-06 2019-04-16 梦百合家居科技股份有限公司 一种石墨烯记忆绵的制备方法
CN110229304A (zh) * 2019-07-09 2019-09-13 兰州大学 一种阻燃石墨烯聚氨酯复合泡沫材料及其制备方法
CN112160435A (zh) * 2020-09-24 2021-01-01 冯学阳 一种房建施工用聚氨酯保温板及其制备方法
CN112277418A (zh) * 2020-10-29 2021-01-29 陕西保利新科技有限公司 一种石墨改性硬泡聚胺酯复合板

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