CN113004578B - 一种防水保温幕墙及其制备方法 - Google Patents
一种防水保温幕墙及其制备方法 Download PDFInfo
- Publication number
- CN113004578B CN113004578B CN202110361598.7A CN202110361598A CN113004578B CN 113004578 B CN113004578 B CN 113004578B CN 202110361598 A CN202110361598 A CN 202110361598A CN 113004578 B CN113004578 B CN 113004578B
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- China
- Prior art keywords
- curtain wall
- polyvinyl alcohol
- gel
- halloysite nanotube
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 17
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 33
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- 229960001763 zinc sulfate Drugs 0.000 claims description 9
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- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 235000015165 citric acid Nutrition 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 8
- JWWJAGDZCDDNHU-UHFFFAOYSA-N n-(2,2-dihydroxyethyl)formamide Chemical compound OC(O)CNC=O JWWJAGDZCDDNHU-UHFFFAOYSA-N 0.000 claims description 8
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 7
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
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- ZEKREUNQYGIUTB-UHFFFAOYSA-N n,n-dihydroxypropanamide Chemical compound CCC(=O)N(O)O ZEKREUNQYGIUTB-UHFFFAOYSA-N 0.000 description 6
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Abstract
本发明涉及建筑材料领域,具体为一种防水保温幕墙及其制备方法,由幕墙本体、粘结层和表面膜层组成;其中,幕墙本体为淀粉基保温材料;表面膜层为改性聚乙烯醇‑纳米SiO2凝胶‑埃洛石纳米管胶膜。所述粘结层为氰基丙烯酸酯粘结剂、氰基丙烯酸酯‑乙酰化羟丙基纤维素粘结剂、氰基丙烯酸酯‑聚乙二醇粘结剂中的任意一种,具有良好防水性能的表面膜层将幕墙本体紧密包覆,这就避免了幕墙本体吸水导致力学性能降低,而且所制备的幕墙本体密度小,力学强度高,保温性能优越,耐火阻燃,本申请克服了上述缺陷,具有广泛的应用前景。
Description
技术领域
本发明涉及建筑材料领域,具体涉及一种防水保温幕墙及其制备方法。
背景技术
幕墙是建筑的外墙围护,不承重,是现代大型和高层建筑常用的带有装饰效果的轻质墙体,由面板和支承结构体系组成的,可相对主体结构有一定位移能力或自身有一定变形能力、不承担主体结构所作用的建筑外围护结构或装饰性结构(外墙框架式支撑体系也是幕墙体系的一种),为了响应节能的号召,目前建筑幕墙材料大多选择保温性能良好的聚苯乙烯或聚氨酯发泡材料,但是聚苯乙烯或聚氨酯发泡材料作为塑料,大规模使用必然带来环保方面的风险,目前也有使用淀粉基发泡材料作为保温建筑材料的相关研究,如苏琼;王彦斌;王济乾等.多元发泡剂制备复合改性淀粉发泡材料及性能研究[J].化工新型材料,2016,44(2):247-249,杨莹,黄丽婕.改性淀粉的制备方法及应用的研究进展[J].食品工业科技,2013,34(20):381-385,但是淀粉基发泡材料普遍存在力学强度和阻燃性能较差的问题,更重要的是,淀粉基发泡材料受潮后易吸水,这进一步阻碍了其作为室外建筑材料的使用。
发明内容
发明目的:针对上述技术问题,本发明提供了一种防水保温幕墙及其制备方法。
为了达到上述发明目的,本发明所采用的技术方案如下:
本发明提供了一种防水保温幕墙,由幕墙本体、粘结层和表面膜层组成;
其中,幕墙本体为淀粉基保温材料;
表面膜层为改性聚乙烯醇-纳米SiO2凝胶-埃洛石纳米管胶膜。
所述粘结层为氰基丙烯酸酯粘结剂、氰基丙烯酸酯-乙酰化羟丙基纤维素粘结剂、氰基丙烯酸酯-聚乙二醇粘结剂中的任意一种。
进一步地,本发明还公开了改性聚乙烯醇-纳米SiO2凝胶-埃洛石纳米管胶膜的制备方法:
S1:将聚乙烯醇用水溶解后,升温至60-80℃,加入戊二醛,搅拌5-10min后加入乙酸,继续搅拌20-40min后用碱液调节体系pH至中性,接着搅拌反应50-80min冷却至室温,得到改性聚乙烯醇溶液;
S2:将正硅酸乙酯、无水乙醇加入到水中,混合均匀后滴加稀盐酸,滴毕后反应2-3h,用氨水调节体系pH至6-7,再将埃洛石纳米管加入,搅拌5-10min后静置10-20h得到凝胶,40-50℃下用无水乙醇浸泡凝胶20-25h后,再用正己烷浸泡凝胶10-15h,最后将凝胶取出粉碎后干燥;
S3:将干燥后的凝胶加入到改性聚乙烯醇溶液中,搅拌均匀后得到溶胶,将溶胶制膜后干燥即可。
进一步地,干燥后的凝胶与改性聚乙烯醇溶液的质量比为1:3-5。
进一步地,所述淀粉基保温材料由以下重量份数的原料制备而成:
所述埃洛石纳米管复合阻燃剂为埃洛石纳米管经过POSS改性且在其表面沉积纳米硼酸锌粒子所得到的。
进一步地,所述埃洛石纳米管复合阻燃剂的制备方法如下:
S1:将乙烯基三甲氧基硅烷、甲醇、盐酸混合均匀后密封,室温反应20-25d后过滤,固体用甲醇洗涤后,用四氢呋喃溶解,再将埃洛石纳米管加入,缓慢滴加甲醇,使POSS在埃洛石纳米管上生长,过滤后固体干燥,得到中间体;
S2:将上述中间体、硼砂水溶液、甲醇、油酸加热至60-70℃,在逐滴滴加硫酸锌水溶液,滴毕后反应5-8h后,过滤,水洗后乙醇洗涤,再干燥即可。
进一步地,所述塑化剂为质量比为3-5:1的N,N-二羟乙基甲酰胺和山梨醇。
进一步地,所述发泡组分由柠檬酸、碳酸氢钠、滑石粉、微晶石蜡组成,所述柠檬酸、碳酸氢钠、滑石粉、微晶石蜡的质量比为1-2:1-2:1-1.5:1-1.5。
上述淀粉基保温材料的制备方法如下:
将聚乙烯醇、羟丙基淀粉、塑化剂加入到高速混合机中100-120℃混合均匀后加入到挤出机中挤出,再加入到水中、再将膨胀珍珠岩、埃洛石纳米管复合阻燃剂、聚磷酸铵、发泡组分加入,升温至70-75℃搅拌1-3h后,将混合料注入模具中,干燥固化,固化后的材料经过400-800W、20-30s的微波辐照发泡后切割养护,即可获得所述淀粉基保温材料。
上述防水保温幕墙的制备方法如下:
先在幕墙本体的表面均匀涂抹粘结剂形成粘结层,再将表面膜层粘附于粘结层之上,0.01-0.02MPa的压力下压制1-10min后,30-35℃下固化5-10h即可。
本发明的有益效果:
目前淀粉基发泡材料作为建筑材料普遍存在力学强度、阻燃性能较差和受潮后易吸水,导致力学性能降低的问题,本申请中的防水保温幕墙由幕墙本体、粘结层和表面膜层组成,具有良好防水性能的表面膜层将幕墙本体紧密包覆,这就避免了幕墙本体吸水导致力学性能降低,而且所制备的幕墙本体密度小,力学强度高,保温性能优越,耐火阻燃,本申请克服了上述缺陷,具有广泛的应用前景。
幕墙本体组份中,羟丙基淀粉中的羟丙基一方面会产生空间位阻效应,阻止淀粉链的聚集和结晶;另一方面,羟丙基能减弱淀粉颗粒结构的内部氢键强度,具有更好的膨胀和发泡性能,聚乙烯醇具有高度的结晶性,致密度高,加入后可以改善淀粉基材料的耐冲击性、压缩强度,但由于分子结构中大量羟基的存在,聚乙烯醇分子内和分子间均存在很强的氢键,分子间作用力极大,加工性差,本发明加入复合的塑化剂,可与聚乙烯醇形成氢键,破坏聚乙烯醇自身分子内和分子间的氢键,破坏结晶区,提高了加工性和羟丙基淀粉的相容性,埃洛石纳米管是一种广泛存在的天然粘土矿物中空纳米管,具有价格低廉、绿色环保和协同阻燃等优势,利用POSS对埃洛石纳米管进行改性,可以改善埃洛石纳米管的韧性和分散性,降低热释放速率及CO生成量,纳米硼酸锌作为最早使用的无机阻燃剂之一,具有阻燃技术成熟,成本低的优势,利用热沉淀法将其沉积到埃洛石纳米管的管壁上,可以与埃洛石纳米管协同阻燃,进一步提升幕墙本体的耐火性能,聚磷酸铵安全环保,分解温度高,价格低廉,加入后可以进一步改善阻燃耐火性能,降低成本,本申请幕墙本体利用微波辐照发泡,具有操作简单,易于控制,发泡均匀的优势;
表面膜层组份中,聚乙烯醇成本低廉,是成膜的基础成分,且幕墙本体中也含有聚乙烯醇两者有很好的粘结性,添加戊二醛改性,可以将聚乙烯醇分子链上的羟基基团,通过交联反应,转化为耐水性基团,既提高其力学性能,也改善了耐水抗水能力,纳米SiO2凝胶加入后,可以提高膜层接触角,进一步改善防水性能,埃洛石纳米管的加入可以防止纳米SiO2凝胶团聚,而且能提升膜层的力学性能。
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。
实施例1:
一种防水保温幕墙,由幕墙本体、粘结层和表面膜层组成;
制备时,先在幕墙本体的表面均匀涂抹氰基丙烯酸酯-聚乙二醇粘结剂形成粘结层,再将表面膜层粘附于粘结层之上,0.01MPa的压力下压制5min后,30℃下固化10h即可。
其中,幕墙本体为淀粉基保温材料,其制备方法如下:
取羟丙基淀粉55g、膨胀珍珠岩20g、埃洛石纳米管复合阻燃剂10g、聚磷酸铵1g、聚乙烯醇6g、N,N-二羟乙基甲酰胺0.75g、山梨醇0.25g、柠檬酸0.25g、碳酸氢钠0.25g、滑石粉0.25g、微晶石蜡0.25g、水140g。
将聚乙烯醇、羟丙基淀粉、N,N-二羟乙基甲酰胺、山梨醇加入到高速混合机中100℃混合均匀后加入到挤出机中挤出,再加入到水中、再将膨胀珍珠岩、埃洛石纳米管复合阻燃剂、聚磷酸铵、柠檬酸、碳酸氢钠、滑石粉、微晶石蜡加入,升温至70℃搅拌2h后,将混合料注入模具中,50℃干燥固化至含水率为15%,固化后的材料经过400W、25s的微波辐照发泡后切割养护,即可获得幕墙本体。
其中,埃洛石纳米管复合阻燃剂的制备方法如下:
将9mL乙烯基三甲氧基硅烷、200mL甲醇、12mL盐酸混合均匀后密封,室温搅拌反应20d后过滤,固体用甲醇洗涤后,用50mL四氢呋喃溶解,再将20g埃洛石纳米管加入,缓慢滴加甲醇,使POSS在埃洛石纳米管上生长,滴毕后静置1h,过滤后固体干燥,得到中间体,取中间体20g、100mL 0.1mol/L的硼砂水溶液、20mL甲醇、1mL油酸加热至65℃,在逐滴滴加10mL2mol/L的硫酸锌水溶液,滴毕后反应5h后,过滤,水洗后乙醇洗涤,再80℃干燥即可。
表面膜层为改性聚乙烯醇-纳米SiO2凝胶-埃洛石纳米管胶膜,制备方法如下:
将聚乙烯醇40g用1.6L水溶解后,升温至80℃,加入2g戊二醛,搅拌5min后加入1g乙酸,继续搅拌30min后用氨水调节体系pH至中性,接着搅拌反应60min冷却至室温,得到改性聚乙烯醇溶液,将正硅酸乙酯20.8g、无水乙醇23g加入到水7.2g中,混合均匀后滴加稀盐酸0.1mL,滴毕后反应3h,用氨水调节体系pH至6,再将埃洛石纳米管15g加入,搅拌10min后静置20h得到凝胶,50℃下用50mL无水乙醇浸泡凝胶25h后,再用50mL正己烷浸泡凝胶12h,最后将凝胶取出粉碎后50℃干燥,取干燥后的凝胶10g加入到4倍于其质量的改性聚乙烯醇溶液中,搅拌均匀后得到溶胶,将溶胶制膜后35℃干燥即可。
实施例2:
一种防水保温幕墙,由幕墙本体、粘结层和表面膜层组成;
制备时,先在幕墙本体的表面均匀涂抹氰基丙烯酸酯-聚乙二醇粘结剂形成粘结层,再将表面膜层粘附于粘结层之上,0.015MPa的压力下压制4min后,30℃下固化10h即可。
其中,幕墙本体为淀粉基保温材料,其制备方法如下:
取羟丙基淀粉60g、膨胀珍珠岩20g、埃洛石纳米管复合阻燃剂12g、聚磷酸铵1g、聚乙烯醇5g、N,N-二羟乙基甲酰胺0.75g、山梨醇0.25g、柠檬酸0.25g、碳酸氢钠0.25g、滑石粉0.25g、微晶石蜡0.25g、水120g。
将聚乙烯醇、羟丙基淀粉、N,N-二羟乙基甲酰胺、山梨醇加入到高速混合机中110℃混合均匀后加入到挤出机中挤出,再加入到水中、再将膨胀珍珠岩、埃洛石纳米管复合阻燃剂、聚磷酸铵、柠檬酸、碳酸氢钠、滑石粉、微晶石蜡加入,升温至70℃搅拌1.5h后,将混合料注入模具中,50℃干燥固化至含水率为13%,固化后的材料经过800W、20s的微波辐照发泡后切割养护,即可获得幕墙本体。
其中,埃洛石纳米管复合阻燃剂的制备方法如下:
将9mL乙烯基三甲氧基硅烷、200mL甲醇、12mL盐酸混合均匀后密封,室温搅拌反应25d后过滤,固体用甲醇洗涤后,用50mL四氢呋喃溶解,再将20g埃洛石纳米管加入,缓慢滴加甲醇,使POSS在埃洛石纳米管上生长,滴毕后静置1h,得到中间体,取中间体20g、100mL0.1mol/L的硼砂水溶液、20mL甲醇、1mL油酸加热至60℃,在逐滴滴加10mL 2mol/L的硫酸锌水溶液,滴毕后反应8h后,过滤,水洗后乙醇洗涤,再60℃干燥即可。
表面膜层为改性聚乙烯醇-纳米SiO2凝胶-埃洛石纳米管胶膜,制备方法如下:
将聚乙烯醇40g用1.6L水溶解后,升温至70℃,加入2g戊二醛,搅拌5min后加入1g乙酸,继续搅拌40min后用氨水调节体系pH至中性,接着搅拌反应60min冷却至室温,得到改性聚乙烯醇溶液,将正硅酸乙酯20.8g、无水乙醇23g加入到水7.2g中,混合均匀后滴加稀盐酸0.1mL,滴毕后反应3h,用氨水调节体系pH至7,再将埃洛石纳米管15g加入,搅拌10min后静置20h得到凝胶,45℃下用50mL无水乙醇浸泡凝胶25h后,再用50mL正己烷浸泡凝胶12h,最后将凝胶取出粉碎后60℃干燥,取干燥后的凝胶10g加入到5倍于其质量的改性聚乙烯醇溶液中,搅拌均匀后得到溶胶,将溶胶制膜后35℃干燥即可。
实施例3:
一种防水保温幕墙,由幕墙本体、粘结层和表面膜层组成;
制备时,先在幕墙本体的表面均匀涂抹氰基丙烯酸酯-聚乙二醇粘结剂形成粘结层,再将表面膜层粘附于粘结层之上,0.01MPa的压力下压制1min后,30℃下固化5h即可。
其中,幕墙本体为淀粉基保温材料,其制备方法如下:
取羟丙基淀粉50g、膨胀珍珠岩30g、埃洛石纳米管复合阻燃剂10g、聚磷酸铵2g、聚乙烯醇5g、N,N-二羟乙基甲酰胺0.75g、山梨醇0.25g、柠檬酸0.25g、碳酸氢钠0.25g、滑石粉0.25g、微晶石蜡0.25g、水120g。
将聚乙烯醇、羟丙基淀粉、N,N-二羟乙基甲酰胺、山梨醇加入到高速混合机中100℃混合均匀后加入到挤出机中挤出,再加入到水中、再将膨胀珍珠岩、埃洛石纳米管复合阻燃剂、聚磷酸铵、柠檬酸、碳酸氢钠、滑石粉、微晶石蜡加入,升温至70℃搅拌1h后,将混合料注入模具中,55℃干燥固化至含水率为16%,固化后的材料经过600W、30s的微波辐照发泡后切割养护,即可获得幕墙本体。
其中,埃洛石纳米管复合阻燃剂的制备方法如下:
将9mL乙烯基三甲氧基硅烷、200mL甲醇、12mL盐酸混合均匀后密封,室温搅拌反应25d后过滤,固体用甲醇洗涤后,用50mL四氢呋喃溶解,再将20g埃洛石纳米管加入,缓慢滴加甲醇析晶,使POSS在埃洛石纳米管上生长,滴毕后静置1h,得到中间体,取中间体20g、100mL 0.1mol/L的硼砂水溶液、20mL甲醇、1mL油酸加热至60℃,在逐滴滴加10mL 2mol/L的硫酸锌水溶液,滴毕后反应5h后,过滤,水洗后乙醇洗涤,再80℃干燥即可。
表面膜层为改性聚乙烯醇-纳米SiO2凝胶-埃洛石纳米管胶膜,制备方法如下:
将聚乙烯醇40g用1.6L水溶解后,升温至60℃,加入2g戊二醛,搅拌5min后加入1g乙酸,继续搅拌20min后用氨水调节体系pH至中性,接着搅拌反应50min冷却至室温,得到改性聚乙烯醇溶液,将正硅酸乙酯20.8g、无水乙醇23g加入到水7.2g中,混合均匀后滴加稀盐酸0.1mL,滴毕后反应2h,用氨水调节体系pH至6,再将埃洛石纳米管15g加入,搅拌5min后静置10h得到凝胶,40℃下用50mL无水乙醇浸泡凝胶20h后,再用50mL正己烷浸泡凝胶10h,最后将凝胶取出粉碎后50℃干燥,取干燥后的凝胶10g加入到3倍于其质量的改性聚乙烯醇溶液中,搅拌均匀后得到溶胶,将溶胶制膜后30℃干燥即可。
实施例4:
一种防水保温幕墙,由幕墙本体、粘结层和表面膜层组成;
制备时,先在幕墙本体的表面均匀涂抹氰基丙烯酸酯-聚乙二醇粘结剂形成粘结层,再将表面膜层粘附于粘结层之上,0.02MPa的压力下压制10min后,35℃下固化10h即可。
其中,幕墙本体为淀粉基保温材料,其制备方法如下:
取羟丙基淀粉50g、膨胀珍珠岩25g、埃洛石纳米管复合阻燃剂15g、聚磷酸铵1g、聚乙烯醇5g、N,N-二羟乙基甲酰胺0.75g、山梨醇0.25g、柠檬酸0.25g、碳酸氢钠0.25g、滑石粉0.25g、微晶石蜡0.25g、水150g。
将聚乙烯醇、羟丙基淀粉、N,N-二羟乙基甲酰胺、山梨醇加入到高速混合机中120℃混合均匀后加入到挤出机中挤出,再加入到水中、再将膨胀珍珠岩、埃洛石纳米管复合阻燃剂、聚磷酸铵、柠檬酸、碳酸氢钠、滑石粉、微晶石蜡加入,升温至70℃搅拌1h后,将混合料注入模具中,55℃干燥固化至含水率为13%,固化后的材料经过800W、30s的微波辐照发泡后切割养护,即可获得幕墙本体。
其中,埃洛石纳米管复合阻燃剂的制备方法如下:
将9mL乙烯基三甲氧基硅烷、200mL甲醇、12mL盐酸混合均匀后密封,室温搅拌反应25d后过滤,固体用甲醇洗涤后,用50mL四氢呋喃溶解,再将20g埃洛石纳米管加入,缓慢滴加甲醇,使POSS在埃洛石纳米管上生长,滴毕后静置1h,得到中间体,取中间体20g、100mL0.1mol/L的硼砂水溶液、20mL甲醇、1mL油酸加热至70℃,在逐滴滴加10mL 2mol/L的硫酸锌水溶液,滴毕后反应5h后,过滤,水洗后乙醇洗涤,再65℃干燥即可。
表面膜层为改性聚乙烯醇-纳米SiO2凝胶-埃洛石纳米管胶膜,制备方法如下:
将聚乙烯醇40g用1.6L水溶解后,升温至80℃,加入2g戊二醛,搅拌10min后加入1g乙酸,继续搅拌40min后用氨水调节体系pH至中性,接着搅拌反应80min冷却至室温,得到改性聚乙烯醇溶液,将正硅酸乙酯20.8g、无水乙醇23g加入到水7.2g中,混合均匀后滴加稀盐酸0.1mL,滴毕后反应3h,用氨水调节体系pH至7,再将埃洛石纳米管15g加入,搅拌10min后静置20h得到凝胶,50℃下用50mL无水乙醇浸泡凝胶25h后,再用50mL正己烷浸泡凝胶15h,最后将凝胶取出粉碎后60℃干燥,取干燥后的凝胶10g加入到5倍于其质量的改性聚乙烯醇溶液中,搅拌均匀后得到溶胶,将溶胶制膜后35℃干燥即可。
实施例5:
一种防水保温幕墙,由幕墙本体、粘结层和表面膜层组成;
制备时,先在幕墙本体的表面均匀涂抹氰基丙烯酸酯-聚乙二醇粘结剂形成粘结层,再将表面膜层粘附于粘结层之上,0.01MPa的压力下压制10min后,30℃下固化10h即可。
其中,幕墙本体为淀粉基保温材料,其制备方法如下:
羟丙基淀粉60g、膨胀珍珠岩20g、埃洛石纳米管复合阻燃剂15g、聚磷酸铵1g、聚乙烯醇8g、N,N-二羟乙基甲酰胺0.75g、山梨醇0.25g、柠檬酸0.25g、碳酸氢钠0.25g、滑石粉0.25g、微晶石蜡0.25g、水130g。
将聚乙烯醇、羟丙基淀粉、N,N-二羟乙基甲酰胺、山梨醇加入到高速混合机中120℃混合均匀后加入到挤出机中挤出,再加入到水中、再将膨胀珍珠岩、埃洛石纳米管复合阻燃剂、聚磷酸铵、柠檬酸、碳酸氢钠、滑石粉、微晶石蜡加入,升温至70℃搅拌3h后,将混合料注入模具中,50℃干燥固化至含水率为18%,固化后的材料经过400W、30s的微波辐照发泡后切割养护,即可获得幕墙本体。
其中,埃洛石纳米管复合阻燃剂的制备方法如下:
将9mL乙烯基三甲氧基硅烷、200mL甲醇、12mL盐酸混合均匀后密封,室温搅拌反应25d后过滤,固体用甲醇洗涤后,用50mL四氢呋喃溶解,再将20g埃洛石纳米管加入,缓慢滴加甲醇,使POSS在埃洛石纳米管上生长,滴毕后静置1h,过滤后固体干燥,得到中间体,取中间体20g、100mL 0.1mol/L的硼砂水溶液、20mL甲醇、1mL油酸加热至60℃,在逐滴滴加10mL2mol/L的硫酸锌水溶液,滴毕后反应8h后,过滤,水洗后乙醇洗涤,再60℃干燥即可。
表面膜层为改性聚乙烯醇-纳米SiO2凝胶-埃洛石纳米管胶膜,制备方法如下:
将聚乙烯醇40g用1.6L水溶解后,升温至60℃,加入2g戊二醛,搅拌10min后加入1g乙酸,继续搅拌20min后用氨水调节体系pH至中性,接着搅拌反应80min冷却至室温,得到改性聚乙烯醇溶液,将正硅酸乙酯20.8g、无水乙醇23g加入到水7.2g中,混合均匀后滴加稀盐酸0.1mL,滴毕后反应3h,用氨水调节体系pH至6,再将埃洛石纳米管15g加入,搅拌5min后静置20h得到凝胶,40℃下用50mL无水乙醇浸泡凝胶25h后,再用50mL正己烷浸泡凝胶10h,最后将凝胶取出粉碎后60℃干燥,取干燥后的凝胶10g加入到5倍于其质量的改性聚乙烯醇溶液中,搅拌均匀后得到溶胶,将溶胶制膜后30℃干燥即可。
实施例6:
一种防水保温幕墙,由幕墙本体、粘结层和表面膜层组成;
制备时,先在幕墙本体的表面均匀涂抹氰基丙烯酸酯-聚乙二醇粘结剂形成粘结层,再将表面膜层粘附于粘结层之上,0.01MPa的压力下压制10min后,35℃下固化10h即可。
其中,幕墙本体为淀粉基保温材料,其制备方法如下:
取羟丙基淀粉60g、膨胀珍珠岩30g、埃洛石纳米管复合阻燃剂15g、聚磷酸铵2g、聚乙烯醇8g、N,N-二羟乙基甲酰胺0.75g、山梨醇0.25g、柠檬酸0.25g、碳酸氢钠0.25g、滑石粉0.25g、微晶石蜡0.25g、水150g。
将聚乙烯醇、羟丙基淀粉、N,N-二羟乙基甲酰胺、山梨醇加入到高速混合机中120℃混合均匀后加入到挤出机中挤出,再加入到水中、再将膨胀珍珠岩、埃洛石纳米管复合阻燃剂、聚磷酸铵、柠檬酸、碳酸氢钠、滑石粉、微晶石蜡加入,升温至75℃搅拌3h后,将混合料注入模具中,55℃干燥固化至含水率为18%,固化后的材料经过800W、30s的微波辐照发泡后切割养护,即可获得幕墙本体。
其中,埃洛石纳米管复合阻燃剂的制备方法如下:
将9mL乙烯基三甲氧基硅烷、200mL甲醇、12mL盐酸混合均匀后密封,室温搅拌反应25d后过滤,固体用甲醇洗涤后,用50mL四氢呋喃溶解,再将20g埃洛石纳米管加入,缓慢滴加甲醇,使POSS在埃洛石纳米管上生长,滴毕后静置1h,过滤后固体干燥,得到中间体,取中间体20g、100mL 0.1mol/L的硼砂水溶液、20mL甲醇、1mL油酸加热至70℃,在逐滴滴加10mL2mol/L的硫酸锌水溶液,滴毕后反应8h后,过滤,水洗后乙醇洗涤,再80℃干燥即可。
表面膜层为改性聚乙烯醇-纳米SiO2凝胶-埃洛石纳米管胶膜,制备方法如下:
将聚乙烯醇40g用1.6L水溶解后,升温至70℃,加入2g戊二醛,搅拌5min后加入1g乙酸,继续搅拌25min后用氨水调节体系pH至中性,接着搅拌反应80min冷却至室温,得到改性聚乙烯醇溶液,将正硅酸乙酯20.8g、无水乙醇23g加入到水7.2g中,混合均匀后滴加稀盐酸0.1mL,滴毕后反应2h,用氨水调节体系pH至7,再将埃洛石纳米管15g加入,搅拌10min后静置20h得到凝胶,45℃下用50mL无水乙醇浸泡凝胶25h后,再用50mL正己烷浸泡凝胶15h,最后将凝胶取出粉碎后50℃干燥,取干燥后的凝胶10g加入到5倍于其质量的改性聚乙烯醇溶液中,搅拌均匀后得到溶胶,将溶胶制膜后35℃干燥即可。
对比例1:
与实施例1基本相同,区别在于,幕墙本体制备时,将原料中的埃洛石纳米管复合阻燃剂用埃洛石纳米管替换。
对比例2:
与实施例1基本相同,区别在于,幕墙本体制备时,将埃洛石纳米管复合阻燃剂用埃洛石纳米管、POSS、硼酸锌替换。
对比例3:
与实施例1基本相同,区别在于,幕墙本体制备时,埃洛石纳米管不沉积硼酸锌。
其中,埃洛石纳米管复合阻燃剂的制备方法如下:
将9mL乙烯基三甲氧基硅烷、200mL甲醇、12mL盐酸混合均匀后密封,室温搅拌反应20d后过滤,固体用甲醇洗涤后,用50mL四氢呋喃溶解,再将20g埃洛石纳米管加入,缓慢滴加甲醇,使POSS在埃洛石纳米管上生长,滴毕后静置1h,过滤后固体干燥即可。
对比例4:
与实施例1基本相同,区别在于,幕墙本体制备时,埃洛石纳米管不引入POSS。
其中,埃洛石纳米管复合阻燃剂的制备方法如下:
取埃洛石纳米管20g、100mL 0.1mol/L的硼砂水溶液、20mL甲醇、1mL油酸加热至65℃,在逐滴滴加10mL 2mol/L的硫酸锌水溶液,滴毕后反应5h后,过滤,水洗后乙醇洗涤,再80℃干燥即可。
对比例5:
与实施例1基本相同,区别在于,改性聚乙烯醇-纳米SiO2凝胶-埃洛石纳米管胶膜制备时,聚乙烯醇不经过改性处理。
对比例6:
与实施例1基本相同,区别在于,改性聚乙烯醇-纳米SiO2凝胶-埃洛石纳米管胶膜制备时,不加入埃洛石纳米管。
对比例7:
与实施例1基本相同,区别在于,改性聚乙烯醇-纳米SiO2凝胶-埃洛石纳米管胶膜制备时,将同等质量的纳米SiO2凝胶和埃洛石纳米管分开加入;
制备方法如下:
将聚乙烯醇40g用1.6L水溶解后,升温至80℃,加入2g戊二醛,搅拌5min后加入1g乙酸,继续搅拌30min后用氨水调节体系pH至中性,接着搅拌反应60min冷却至室温,得到改性聚乙烯醇溶液,取干燥后的埃洛石纳米管5g和纳米SiO2凝胶5g加入到4倍于其质量的改性聚乙烯醇溶液中,搅拌均匀后得到溶胶,将溶胶制膜后35℃干燥即可。
性能测试
①对本发明实施例1-6及对比例1-4所制备的幕墙本体进行性能测试,其中,密度按照GB/T6343-2009标准测试:压缩强度按照GB/T8813-2008标准测试;导热系数按照GB10294-2008标准测试:氧指数按照GB/T2406-2008标准测试,结果如表1所示:
表1:
由上表1可以看出,本申请所制备的幕墙本体由环保材料制成,密度小,力学强度高,保温性能优越,耐火阻燃,应用前景广泛。
②
Ⅰ:采用Instron公司5900型电子拉力机测试本发明实施例1-6及对比例1-4所制备表面膜层的力学性能,测试在25℃进行,拉伸速率100mm/min。
Ⅱ:将本发明实施例1-6及对比例1-4所制备表面膜层制成20mm×20mm的样品后,测其质量为m0,室温下将胶膜浸泡于水中静置24h后取出,以定性滤纸擦干其表面水渍后再快速测得其质量m1,按以下公式计算吸水率η:
η=[(m1-m0)/m0]×100%
Ⅲ:采用DSA30型接触角测试仪在25℃下测试接触角。
以上测试结果如表2所示:
表2:
由上表2可以看出,本申请所制备的表面膜层具有良好的力学性能,且接触角均在117°左右,具有良好的抗水防水性能。
对于本领域技术人员而言,显然本发明不限于上述示范性实施例的细节,而且在不背离本发明的精神或基本特征的情况下,能够以其他的具体形式实现本发明。因此,无论从哪一点来看,均应将实施例看作是示范性的,而且是非限制性的,本发明的范围由所附权利要求而不是上述说明限定,因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。
Claims (9)
1.一种防水保温幕墙,其特征在于,由幕墙本体、粘结层和表面膜层组成;
所述幕墙本体为淀粉基保温材料;
所述表面膜层为改性聚乙烯醇-纳米SiO2凝胶-埃洛石纳米管胶膜;
所述改性聚乙烯醇-纳米SiO2凝胶-埃洛石纳米管胶膜的制备方法如下:
S1:将聚乙烯醇用水溶解后,升温至60-80℃,加入戊二醛,搅拌5-10min后加入乙酸,继续搅拌20-40min后用碱液调节体系pH至中性,接着搅拌反应50-80min冷却至室温,得到改性聚乙烯醇溶液;S2:将正硅酸乙酯、无水乙醇加入到水中,混合均匀后滴加稀盐酸,滴毕后反应2-3h,用氨水调节体系pH至6-7,再将埃洛石纳米管加入,搅拌5-10min后静置10-20h得到凝胶,40-50℃下用无水乙醇浸泡凝胶20-25h后,再用正己烷浸泡凝胶10-15h,最后将凝胶取出粉碎后干燥;
S3:将干燥后的凝胶加入到改性聚乙烯醇溶液中,搅拌均匀后得到溶胶,将溶胶制膜后干燥即可。
2.如权利要求1所述的防水保温幕墙,其特征在于,所述粘结层为氰基丙烯酸酯粘结剂、氰基丙烯酸酯-乙酰化羟丙基纤维素粘结剂、氰基丙烯酸酯-聚乙二醇粘结剂中的任意一种。
3.如权利要求1所述的防水保温幕墙,其特征在于,干燥后的凝胶与改性聚乙烯醇溶液的质量比为1:3-5。
4.如权利要求1所述的防水保温幕墙,其特征在于,所述淀粉基保温材料由以下重量份数的原料制备而成:
羟丙基淀粉 50-60份
膨胀珍珠岩 20-30份
埃洛石纳米管复合阻燃剂 10-15份
聚磷酸铵 1-2份
聚乙烯醇 5-8份
塑化剂 1-2份
发泡组分 0.5-1份
水 120-150份
所述埃洛石纳米管复合阻燃剂为埃洛石纳米管经过POSS改性且在其表面沉积纳米硼酸锌粒子所得到的。
5.如权利要求4所述的防水保温幕墙,其特征在于,所述埃洛石纳米管复合阻燃剂的制备方法如下:
S1:将乙烯基三甲氧基硅烷、甲醇、盐酸混合均匀后密封,室温反应20-25d后过滤,固体用甲醇洗涤后,用四氢呋喃溶解,再将埃洛石纳米管加入,缓慢滴加甲醇,使POSS在埃洛石纳米管上生长,过滤后固体干燥,得到中间体;
S2:将上述中间体、硼砂水溶液、甲醇、油酸加热至60-70℃,在逐滴滴加硫酸锌水溶液,滴毕后反应5-8h后,过滤,水洗后乙醇洗涤,再干燥即可。
6.如权利要求4所述的防水保温幕墙,其特征在于,所述塑化剂为质量比为3-5:1的N,N-二羟乙基甲酰胺和山梨醇。
7.如权利要求4所述的防水保温幕墙,其特征在于,所述发泡组分由柠檬酸、碳酸氢钠、滑石粉、微晶石蜡组成,所述柠檬酸、碳酸氢钠、滑石粉、微晶石蜡的质量比为1-2:1-2:1-1.5:1-1.5。
8.如权利要求4所述的防水保温幕墙,其特征在于,所述淀粉基保温材料的制备方法如下:
将聚乙烯醇、羟丙基淀粉、塑化剂加入到高速混合机中100-120℃混合均匀后加入到挤出机中挤出,再加入到水中、再将膨胀珍珠岩、埃洛石纳米管复合阻燃剂、聚磷酸铵、发泡组分加入,升温至70-75℃搅拌1-3h后,将混合料注入模具中,干燥固化,固化后的材料经过400-800W、20-30s的微波辐照发泡后切割养护,即可获得所述淀粉基保温材料。
9.一种如权利要求1-8中任一项所述的防水保温幕墙的制备方法,其特征在于,具体如下:
先在幕墙本体的表面均匀涂抹粘结剂形成粘结层,再将表面膜层粘附于粘结层之上,0.01-0.02MPa的压力下压制1-10min后,30-35℃下固化5-10h即可。
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