CN110041505A - 一种发泡型杂化高分子堵漏材料及其制备方法 - Google Patents
一种发泡型杂化高分子堵漏材料及其制备方法 Download PDFInfo
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- C08G18/3895—Inorganic compounds, e.g. aqueous alkalimetalsilicate solutions; Organic derivatives thereof containing no direct silicon-carbon bonds
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Abstract
本发明属于建筑材料领域,具体涉及一种发泡型杂化高分子堵漏材料及其制备方法。该堵漏材料A组分按照重量份计包括:多异氰酸酯75~90份、无机材料10~25份;B组分按照重量份计包括:硅酸钠40~65份、水30~55份、催化剂0.1~2.5份、泡沫稳定剂1.5~2.5份;C组分包括固化剂;D组分包括增韧剂;A组分、B组份、C组分和D组分重量份配比为150~250份:100份:0.5~5份:5~10份。该堵漏材料克服了无机材料膨胀性能不佳、渗透性能差的缺点和有机材料反应速度快、易燃烧、反应过程产热量大等缺点,可广泛的应用于坝基防渗堵漏,煤矿抽采瓦斯钻孔封堵等地下空间工程中的充填施工。
Description
技术领域
本发明属于建筑材料领域,具体涉及一种发泡型杂化高分子堵漏材料及其制备方法。
背景技术
随着经济的发展和社会的进步,人们的很多行为如矿业生产、水利生产、国防建设和交通运输等与地下空间的关系日益密切,地下工程在水利水电、道路交通、矿山开采工程中发挥了举足轻重的作用。大量岩土体开挖引起的大型地下工程的稳定性问题逐渐成为人类工程活动中所面临的一个重要难题。地下工程施工过程中的扰动会使岩体内部产生裂缝,进一步使岩体失稳,轻则引起小面积破碎岩石的脱落,重则会造成大面积的塌方。除此之外出现在煤岩中的裂隙不仅会引起岩体失稳,更严重的是煤岩裂隙漏风导致的煤自燃。煤炭自燃所引发的火灾事故占矿井火灾总数的90%以上,每年由此所导致的矿山直接和间接经济损失达百亿元。充填施工作为地下空间施工过程中的一个重要环节,充填材料能够进入岩体内部裂隙,将裂隙周围的岩体紧密地粘结在一起,从而防止碎岩掉落、煤体漏风的发生。目前常见的堵漏材料主要有聚氨酯材料、脲醛树脂等有机材料,其具有自身成本高、阻燃效果差、反应过程易产生高温,容易引起热量积聚,在煤岩中使用时会加速煤的自燃氧化进程,而且在高湿环境下发泡倍数增长过快,毒性较大等缺点,而水玻璃系化学浆、水泥基浆材料等无机材料具有反应速度过慢,无法及时封堵裂隙,膨胀效果较差,渗透距离较短等缺点。
发明内容
针对现有技术缺陷,本发明提供一种发泡型杂化高分子堵漏材料及其制备方法。以有机组分多异氰酸酯和无机组分水玻璃为主要合成原料,具有反应时间可控,阻燃性能优异,发泡效果明显,成本较低等优点的杂化高分子聚合物堵漏材料。
本发明的技术方案是:该发泡型杂化高分子堵漏材料包括多异氰酸酯为主的A组分、以硅酸钠为主的B组分、C组分和D组分,其中A组分按照重量份计包括:多异氰酸酯75~90份、无机材料10~25份;B组分按照重量份计包括:硅酸钠40~65份、水30~55份、催化剂0.1~2.5份、泡沫稳定剂1.5~2.5份;C组分包括固化剂;D组分包括增韧剂;A组分、B组份、C组分和D组分重量份配比为150~250份:100份:0.5~5份:5~10份。
所述的多异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯中的一种或几种的混合物。
所述的硅酸钠模数为1.6~1.9。
所述的无机材料为短切玻璃纤维、空心玻璃微珠、轻质沉淀碳酸钙、水泥单体中的一种或几种的混合物。
优选的短切玻璃纤维的长度为4~6mm,直径为10~125μm;空心玻璃微珠的粒径为50~70μm;轻质沉淀碳酸钙的粒径为1~5μm;水泥单体的粒为10~20μm。
所述的固化剂为乙二醇乙醚乙酸酯、聚丙烯酸、丁四醇中的一种或几种的混合物。
所述增韧剂为聚二乙醇-200,聚二乙醇-600,聚二乙醇-1000,聚二乙醇-1500中的一种或几种的混合物,多异氰酸酯与聚乙二醇反应,能够引入较长的柔性链,最终得到的化合物明显增韧,减少合成材料的脆性。
所述的催化剂为N,N-二甲基乙醇胺、氧化二辛基锡、辛酸亚锡、二醋酸二丁基锡中的一种或几种的混合物,能够有效的催化异氰酸酯根基团和羟基的反应。
所述的泡沫稳定剂为磺化的蓖麻醇钠盐和水溶性的聚醚硅氧烷中的一种或两种的混合物,使原料混合物的表面张力降低,在泡沫上升至熟化期间,通过表面张力阻止泡沫由于热力学不稳定状态出现泡沫破裂。
本发明提供的一种发泡型杂化高分子堵漏材料的制备方法包括下述步骤:
1)按照配比称取无机材料、多异氰酸酯剂加入搅拌容器中,在常温下利用震荡或搅拌5~10分钟至混合均匀后得到A组分;
2)在室温下,按照配比将硅酸钠置于水中,在搅拌罐中搅拌至全部溶解,然后把催化剂、泡沫稳定剂等加入搅拌罐中,加入完毕后搅拌4~8分钟至物料混合均匀得到B组分;
3)按照A组分和B组分的配比进行混合搅拌45~70秒后得到混合物E;
4)按照配比称取C组分和D组分加入到混合物E中进行混合发泡。
本发明中的主要原料为A组分中的多异氰酸酯和B组分中的水玻璃。主要反应为:
其中增韧剂材料起到辅助作用,针对添加大量的水玻璃,专门添加了固化剂,以增加其强度效果。如果缺少固化剂,产品的性能参数下降很大,本发明所采用的催化剂主要为有机锡类催化剂。根据本发明提供的技术方案,所获得的材料阻燃性能优异(LOI达到33%以上),并且此参数是在未添加阻燃剂的前提下测试得出。在一些特殊情况下,也可以在本技术方案的技术中添加阻燃剂,满足实际的需求,可添加的常见的阻燃剂为三(1,3-二氯异丙基)磷酸酯、四(2-氯乙基)二亚乙基醚二磷酸酯、氢氧化镁和氢氧化铝的一种或几种的混合物。
本发明的优点和有益效果:本发明以无机物水玻璃和有机物多异氰酸酯为主剂,通过调节固化剂和催化剂添加量,控制材料的反应时间,保证了材料的安全性能,提高了材料的控制范围。解决了有机材料堵漏材料阻燃性能差,反应发热量大,成本高,容易受到环境中水分含量的影响,毒性较大等缺点,也解决了无机堵漏材料反应速度过慢,膨胀效果较差,渗透距离较短等缺点。
本发明提供的技术方案按照堵漏工艺进行施工,经检测:本发明技术方案可以控制反应时间,阻燃性能优异(氧指数≥33%)不受周围环境含水量影响,反应温度低(≤100摄氏度),力学性能好(压缩强度≥4MPa,剪切强度≥2MPa)等优异性能。本发明提供的一种发泡型杂化高分子堵漏材料可广泛的应用于坝基防渗堵漏,煤矿抽采瓦斯钻孔封堵等地下空间工程中的充填施工,具有很好的应用前景。
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
在200L不锈钢干燥的搅拌容器内,分别称取多异氰酸酯(甲苯二异氰酸酯)83份、无机材料(空心玻璃微珠)17份。将其依次加入搅拌容器内,在常温下搅拌5~10分钟即可得到A组分。在200L不锈钢干燥的搅拌容器内,先加入硅酸钠51份、水47.2份,搅拌至全部溶解,再加入催化剂(氧化二辛基锡)0.12份、泡沫稳定剂(磺化的蓖麻醇钠盐)1.68份,在常温下搅拌4~8分钟至物料混合均匀即可得到B组分。称取乙二醇乙醚乙酸酯100份作为C组分。称取100份聚二乙醇-600作为D组分。将A组分、B组分、C组分、D组分按照200:100:2.5:7的质量比,按照A组分和B组分的配比进行混合搅拌45~70秒后得到混合物E,按照配比称取C组分和D组分加入到混合物E中进行混合发泡。采用手动注浆泵混合发泡成型得到样品1。
实施例2
在200L不锈钢干燥的搅拌容器内,分别称取多异氰酸酯(甲苯二异氰酸酯52份、二苯基甲烷二异氰酸酯24份)76份、无机材料(空心玻璃微珠15份、轻质沉淀碳酸钙9份)24份。将其依次加入搅拌容器内,在常温下搅拌5~10分钟即可得到A组分。在200L不锈钢干燥的搅拌容器内,先加入硅酸钠53份、水43.5份,搅拌至全部溶解,再加入催化剂(氧化二辛基锡1份、二醋酸二丁基锡0.5份)1.5份、泡沫稳定剂(水溶性的聚醚硅氧烷)2份,在常温下搅拌4~8分钟只物料混合均匀即可得到B组分。称取聚丙烯酸60份、丁四醇40份作为C组分。称取40份聚二乙醇-600、60份聚二乙醇-1000作为D组分。将A组分、B组分、C组分、D组分分别按照150:100:1.5:6的质量比,按照A组分和B组分的配比进行混合搅拌45~70秒后得到混合物E,按照配比称取C组分和D组分加入到混合物E中进行混合发泡。采用手动注浆泵混合发泡成型得到样品2。
实施例3
在200L不锈钢干燥的搅拌容器内,分别称取多异氰酸酯(二苯基甲烷二异氰酸酯50份、六亚甲基二异氰酸酯35份)85份、无机材料(短切玻璃纤维10份、空心玻璃微珠5份)15份。将其依次加入搅拌容器内,在常温下搅拌5~10分钟即可得到A组分。在200L不锈钢干燥的搅拌容器内,先加入硅酸钠62份、水35.5份,搅拌至全部溶解,再加入催化剂(二醋酸二丁基锡)1份、泡沫稳定剂(水溶性的聚醚硅氧烷)1.5份,在常温下搅拌4~8分钟至物料混合均匀即可得到B组分。称取乙二醇乙醚乙酸酯50份、聚丙烯酸50份作为C组分。称取25份聚二乙醇-200、37.5份聚二乙醇-1000、37.5份聚二乙醇-1500作为D组分。将A组分、B组分、C组分、D组分分别按照250:100:3.5:9的质量比,按照A组分和B组分的配比进行混合搅拌45~70秒后得到混合物E,按照配比称取C组分和D组分加入到混合物E中进行混合发泡。采用手动注浆泵混合发泡成型得到样品3。
本实施例制备的堵漏材料与市场上常见的三种堵漏材料进行对比
根据上述检测结果可知,相比于有机堵漏材料,按照实施例制备的膨胀堵漏材料反应时间长,阻燃性能优异(氧指数≥33%)不受周围环境含水量影响,反应温度低(≤100摄氏度),力学性能好(压缩强度≥4MPa,剪切强度≥2MPa)等优异性能;相比于无机堵漏材料,按照实施例制备的膨胀堵漏材料反应时间比无机堵漏材料反应时间短,本发明的技术方案克服了无机材料反应过慢的缺点。本发明以无机物水玻璃和有机物多异氰酸酯为主剂,通过调节固化剂和催化剂添加量,控制材料的反应时间,保证了材料的安全性能,提高了材料的控制范围,解决了有机材料堵漏材料阻燃性能差,反应发热量大,成本高,容易受到环境中水分含量的影响,毒性较大等缺点,也解决了无机堵漏材料反应速度过慢,膨胀效果较差,渗透距离较短等缺点。该发明可广泛的应用于坝基防渗堵漏,煤矿抽采瓦斯钻孔封堵等地下空间工程中的充填施工,具有很好的应用前景。
Claims (10)
1.一种发泡型杂化高分子堵漏材料,其特征在于:该发泡型杂化高分子堵漏材料包括多异氰酸酯为主的A组分、以硅酸钠为主的B组分、固化剂为C组分和增韧剂为D组分;其中A组分按照重量份计包括:多异氰酸酯75~90份、无机材料10~25份;B组分按照重量份计包括:硅酸钠40~65份、水30~55份、催化剂0.1~2.5份、泡沫稳定剂1.5~2.5份;C组分包括固化剂;D组分包括增韧剂;A组分、B组份、C组分和D组分重量份配比为150~250份:100份:0.5~5份:5~10份。
2.根据权利要求1所述的一种发泡型杂化高分子堵漏材料,其特征在于:多异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯中的一种或几种的混合物。
3.根据权利要求1所述的一种发泡型杂化高分子堵漏材料,其特征在于:硅酸钠的模数为1.6~1.9。
4.根据权利要求1所述的一种发泡型杂化高分子堵漏材料,其特征在于:无机材料为短切玻璃纤维、空心玻璃微珠、轻质沉淀碳酸钙、水泥单体中的一种或几种的混合物。
5.根据权利要求4所述的一种发泡型杂化高分子堵漏材料,其特征在于:所述的短切玻璃纤维的长度为4~6mm,直径为10~125μm;空心玻璃微珠的粒径为50~70μm;轻质沉淀碳酸钙的粒径为1~5μm;水泥单体的粒为10~20μm。
6.根据权利要求1所述的一种发泡型杂化高分子堵漏材料,其特征在于:固化剂为乙二醇乙醚乙酸酯、聚丙烯酸、丁四醇中的一种或几种的混合物。
7.根据权利要求1所述的一种发泡型杂化高分子堵漏材料,其特征在于:增韧剂为聚二乙醇-200、聚二乙醇-600、聚二乙醇-1000、聚二乙醇-1500中的一种或几种的混合物。
8.根据权利要求1所述的一种发泡型杂化高分子堵漏材料,其特征在于:催化剂为N,N-二甲基乙醇胺、氧化二辛基锡、辛酸亚锡、二醋酸二丁基锡中的一种或几种的混合物。
9.根据权利要求1所述的一种发泡型杂化高分子堵漏材料,其特征在于:泡沫稳定剂为磺化的蓖麻醇钠盐、水溶性的聚醚硅氧烷中的一种或两种的混合物。
10.权利要求1所述的一种发泡型杂化高分子堵漏材料的制备方法,其特征在于:包括下述步骤:
1)按照配比称取无机材料、多异氰酸酯剂加入搅拌容器中,在常温下震荡或搅拌5~10分钟至混合均匀后得到A组分;
2)在室温下,按照配比将硅酸钠置于水中,在搅拌罐中搅拌至全部溶解,然后把催化剂、泡沫稳定剂加入搅拌罐中,加入完毕后搅拌4~8分钟至物料混合均匀得到B组分;
3)按照A组分和B组分的配比进行混合搅拌45~70秒后得到混合物E;
4)按照配比称取C组分和D组分加入到混合物E中进行混合发泡。
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