CN112745475A - 建筑工程用纤维改性复合聚氨酯材料及其制备方法 - Google Patents
建筑工程用纤维改性复合聚氨酯材料及其制备方法 Download PDFInfo
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Abstract
本发明属于建筑工程材料技术领域,具体涉及一种建筑工程用纤维改性复合聚氨酯材料及其制备方法,所述的材料由A组分和B组分组成,A组分由玻璃纤维、硅酸盐溶液、稳定剂、催化剂和多羟基化合物组成;B组分由多亚甲基多苯基多异氰酸酯、增塑剂、聚醚多元醇、阻燃剂、防老剂、抗氧剂组成。本发明在硅酸盐溶液中加入玻璃纤维,玻璃纤维的主要成分SiO2通过水合作用与体系中的硅酸盐形成稳定的次级空间结构,同时辅以多羟基化物和稳定剂,通过与多亚甲基多苯基多异氰酸酯进一步反应形成高强度立体骨架结构的复合材料,固化后的材料具有良好的安定性、阻燃性以及抗压和抗折强度,且该材料凝结时间短,可在很短时间内形成具有一定强度的固结体。
Description
技术领域
本发明属于建筑工程用改性复合材料技术领域,具体涉及一种建筑工程用纤维改性复合聚氨酯材料及其制备方法。
背景技术
伴随我国经济社会的快速发展,对建筑工程类材料的需求也随之增加,包括民用建筑、工业建筑、道路桥梁、市政工程、岩土隧道等诸多领域对建筑公衡类材料都提出了不同的要求。一方面传统的砖、钢筋、水泥、混凝土、沥青等材料性能的不断提升、种类不断丰富,给建筑行业提供了更多的选择,另一方面,新型材料的兴起不同程度的添补了传统建筑用材料的不足,包括建筑用石膏、复合金属材料、胶凝材料、塑木复合材料、树脂材料等等。因建筑工程领域在材料消耗量上普遍较大,从成本角度考虑传统的水泥、混凝土更适合广泛的大量使用,但在某些特殊场合,如墙体破损快速修补、城市道路龟裂修补、桥梁隧道地基维护加固等,这些传统材料因凝固时间、力学性能、施工方式等原因无法满足施工要求,这就对材料的技术指标提出了新的要求,也催生了各类新材料的研发。
发明内容
本发明要解决的技术问题是:传统建筑工程用材料的凝固时间长、施工方式复杂、现场操作费时费工的缺点,以及单纯的树脂材料抗老化、易燃等问题。为解决上述问题,提供了一种建筑工程用纤维改性复合聚氨酯材料及其制备方法,通过无机纤维改性水玻璃体系,形成稳定的次级空间结构,辅以聚醚多元醇等有机高分子材料,与多亚甲基多苯基多异氰酸酯反应生成可以快速固化、且具有优良力学性能的材料,解决了传统建筑工程用材料在特殊场合应用的不足,可以有效处理各类突发应急事故。
本发明所述的建筑工程用纤维改性复合聚氨酯材料,其特征在于:由A组分和B组分制成,其中:
A组分为,以重量份数计:
B组分为,以重量份数计:
所述的玻璃纤维直径为2~20μm,长度为5~30mm,优选为直径5~10μm,长度10~15mm。玻璃纤维在高温碱性条件下,会发生水合作用,纤维中的SiO2与水作用生成硅酸,因溶液呈碱性,硅酸分子会进一步反应生成HSiO3(-),与硅酸钠溶液中的硅酸根通过氢键结合,形成空间网状结构,该反应不断进行,最终使溶液中的玻璃纤维与硅酸盐溶液形成稳定均一的溶液,进而提高最终固化物的力学性能。
所述的硅酸盐溶液为硅酸钠溶液或硅酸钾溶液,模数为2.1~2.9,波美度为40°~50°,优选为模数2.5~2.7,波美度44°~46°的硅酸盐溶液。
所述的稳定剂为NP-10、OP-10、十二烷基硫酸钠或不饱和脂肪酸钾中的一种或几种。
所述的催化剂为A-33、PC-5、PC-8、DMAEE或DMDEE中的一种或几种,优选为A-33或DMAEE。
所述的多羟基化合物为五羟基酮、五羟基醛或六羟基醛中的一种或几种,优选为六羟基醛。硅酸盐溶液在与多亚甲基多苯基多异氰酸酯反应过程中会生成二氧化碳,二氧化碳与硅酸盐溶液进一步反应生成硅酸凝胶和碳酸盐,其中硅酸凝胶起到提供力学性能的作用,如果短时间内释放出的二氧化碳过量,会导致碳酸盐与二氧化碳进一步反应生成碳酸氢盐,而碳酸氢盐对加固材料的性能有不利的影响,因此适当的缓释二氧化碳释放量会提高材料的稳定性和使用时间,经长期验证,多羟基化合物对缓释二氧化碳释放量具有一定效果,从而改善材料的使用效果。
所述的增塑剂为邻苯二甲酸二丁酯、邻苯二甲酸二辛酯、乙二醇醋酸酯、乙二醇丁醚醋酸酯或乙酸乙酯中的一种或几种,优选为乙二醇醋酸酯或乙二醇丁醚醋酸酯。乙二醇醋酸酯和乙二醇丁醚醋酸酯在碱性环境下会部分水解生成乙酸,乙酸在一定程度上可以促进硅酸盐水溶液固化,同时,以上两种增塑剂可以有效降低组分的粘度,提高产品的流动性,更利于产品的施工。
所述的聚醚多元醇为以乙二醇作为起始剂,官能度为2,羟值为30~100mgKOH/g的聚醚多元醇,优选为羟值40~55mgKOH/g。经试验验证,官能度为2、羟值在50mgKOH/g左右的聚醚多元醇对产品的韧性有较好的改善作用。
所述的阻燃剂为三(2-氯丙基)磷酸酯、三(2-氯乙基)磷酸酯或三(2-溴丙基)磷酸酯中的一种或几种。
所述的防老剂为亚磷酸三苯酯、亚磷酸三壬基苯酯或亚磷酸三乙酯中的一种或几种。
所述的抗氧剂为四亚甲基(3,5-二-叔丁基-4-羟基苯丙酸)甲酯,3,5-二叔丁基-4-羟基苯丙酸异辛酯中的一种或几种。
本发明所述的建筑工程用纤维改性复合聚氨酯材料的制备方法,包括以下步骤:
(1)将一定重量比的硅酸盐溶液投入至带有加热装置的反应釜中,开启搅拌并升温至50~60℃,依次投入稳定剂、多羟基化合物,搅拌至溶液澄清透明后投入玻璃纤维和催化剂,搅拌30~60min,使玻璃纤维与水玻璃体系充分混合至溶液稳定,按一定重量分装即得到A组分;
(2)多亚甲基多苯基多异氰酸酯、增塑剂、聚醚多元醇、阻燃剂、防老剂、抗氧剂按照一定重量比依次投入到反应釜中,搅拌至混合均匀,按一定重量分装即得到B组分;
(3)产品使用,通过配套的混合装置将A组分和B组分按照体积比1:1混合即可。
本发明在硅酸盐溶液中加入玻璃纤维,玻璃纤维的主要成分SiO2通过水合作用与体系中的硅酸盐形成稳定的次级空间结构,同时辅以多羟基化物和稳定剂,通过与多亚甲基多苯基多异氰酸酯进一步反应形成高强度立体骨架结构的复合材料,固化后的材料具有良好的安定性、阻燃性以及抗压和抗折强度,且该材料凝结时间短,可在很短时间内形成具有一定强度的固结体。
与现有技术相比,本发明的有益效果如下:
1、本发明A组分中玻璃纤维的加入,可与硅酸盐溶液形成了稳固的空间网状结构,较传统的聚氨酯类材料在各项力学性能上均有较大的提升;
2、本发明A、B组分流动性好,可以渗透至细小的裂缝及空洞内部,达到修补的效果;
3、本产品反应速度快,短时间内即可达到一定的力学强度,不影响其他工程的进展;
4、本发明A、B组分为液体,可以随用随取,不需要额外的操作;
5、本发明A组分找那个多羟基化合物的加入,提高了两组分混合后的稳定性,使产品的使用效果得到保障;
6、本发明B组分中聚醚多元醇的加入,进一步提高了产品固结体的韧性;
7、本发明B组分中防老剂和抗氧剂的加入,提高了产品的耐候性,在不同的环境条件下长时间无明显变化,性能稳定。
具体实施方式
下面结合实施例对本发明作进一步的说明。
实施例中用到的所有原料除特殊说明外,均为市购。
实施例1
所述的建筑工程用纤维改性复合聚氨酯材料,由A组分和B组分制成,其中:
A组分为,以重量份数计:
B组分为,以重量份数计:
所述的玻璃纤维直径为直径20μm,长度30mm,硅酸盐溶液为硅酸钠溶液,模数为2.5,波美度为46°,稳定剂为NP-10,催化剂为A-33,多羟基化合物为五羟基酮,多亚甲基多苯基多异氰酸酯为pm200,增塑剂为乙二醇醋酸酯,聚醚多元醇为DL1000,阻燃剂为TCEP,防老剂为亚磷酸三苯酯,抗氧剂为3,5-二叔丁基-4-羟基苯丙酸异辛酯。
制备方法,包括以下步骤:
(1)将一定重量比的硅酸盐溶液投入至带有加热装置的反应釜中,开启搅拌并升温至55℃,依次投入稳定剂、多羟基化合物,搅拌至溶液澄清透明后投入玻璃纤维和催化剂,保持温度55℃搅拌30min后,将釜内液体降温至常温,按一定重量分装即得到A组分;
(2)将pm200、增塑剂、聚醚多元醇、阻燃剂、防老剂、抗氧剂按照一定重量比依次投入到反应釜中,搅拌至混合均匀,按一定重量分装即得到B组分;
(3)产品使用,通过配套的混合装置将A组分和B组分按照体积比1:1混合即可。
实施例2
所述的建筑工程用纤维改性复合聚氨酯材料,由A组分和B组分制成,其中:
A组分为,以重量份数计:
B组分为,以重量份数计:
所述的玻璃纤维直径为直径5μm,长度10mm,硅酸盐溶液为硅酸钠溶液,模数为2.5,波美度为46°,稳定剂为OP-10,催化剂为DMAEE,多羟基化合物为六羟基醛,多亚甲基多苯基多异氰酸酯为pm200,增塑剂为乙二醇丁醚醋酸酯,聚醚多元醇为DL2000,阻燃剂为TCPP,防老剂为亚磷酸三乙酯,抗氧剂为四亚甲基(3,5-二-叔丁基-4-羟基苯丙酸)甲酯。
制备方法,包括以下步骤:
(1)将一定重量比的硅酸盐溶液投入至带有加热装置的反应釜中,开启搅拌并升温至60℃,依次投入稳定剂、多羟基化合物,搅拌至溶液澄清透明后投入玻璃纤维和催化剂,保持温度60℃搅拌30min后,将釜内液体降温至常温,按一定重量分装即得到A组分;
(2)将pm200、增塑剂、聚醚多元醇、阻燃剂、防老剂、抗氧剂按照一定重量比依次投入到反应釜中,搅拌至混合均匀,按一定重量分装即得到B组分;
(3)产品使用,通过配套的混合装置将A组分和B组分按照体积比1:1混合即可。
实施例3
所述的建筑工程用纤维改性复合聚氨酯材料,由A组分和B组分制成,其中:
A组分为,以重量份数计:
B组分为,以重量份数计:
所述的玻璃纤维直径为直径10μm,长度20mm,硅酸盐溶液为硅酸钠溶液,模数为2.6,波美度为45°,稳定剂为NP-10,催化剂为DMAEE,多羟基化合物为六羟基醛,多亚甲基多苯基多异氰酸酯为pm200,增塑剂为邻苯二甲酸二丁酯,聚醚多元醇为DL1000,阻燃剂为TCPP,防老剂为亚磷酸三壬基苯酯,抗氧剂为四亚甲基(3,5-二-叔丁基-4-羟基苯丙酸)甲酯。
制备方法,包括以下步骤:
(1)将一定重量比的硅酸盐溶液投入至带有加热装置的反应釜中,开启搅拌并升温至60℃,依次投入稳定剂、多羟基化合物,搅拌至溶液澄清透明后投入玻璃纤维和催化剂,保持温度60℃搅拌50min后,将釜内液体降温至常温,按一定重量分装即得到A组分;
(2)将pm200、增塑剂、聚醚多元醇、阻燃剂、防老剂、抗氧剂按照一定重量比依次投入到反应釜中,搅拌至混合均匀,按一定重量分装即得到B组分;
(3)产品使用,通过配套的混合装置将A组分和B组分按照体积比1:1混合即可。
性能测试
以市售硅酸盐水泥为对比例,将实施例1-3产品和对比例1-2产品采用现有规定的测试方法进行性能测试,具体测试结果见表1。
表1实施例1-3产品和对比例1-2产品测试结果
当然,上述内容仅为本发明的较佳实施例,不能被认为用于限定对本发明的实施例范围。本发明也并不仅限于上述举例,本技术领域的普通技术人员在本发明的实质范围内所作出的均等变化与改进等,均应归属于本发明的专利涵盖范围内。
Claims (10)
2.根据权利要求1所述的建筑工程用纤维改性复合聚氨酯材料,其特征在于:所述的玻璃纤维直径为2~20μm,长度为5~30mm。
3.根据权利要求1所述的建筑工程用纤维改性复合聚氨酯材料,其特征在于:所述的硅酸盐溶液为硅酸钠溶液或硅酸钾溶液,模数为2.1~2.9,波美度为40°~50°。
4.根据权利要求1所述的建筑工程用纤维改性复合聚氨酯材料,其特征在于:所述的稳定剂为NP-10、OP-10、十二烷基硫酸钠或不饱和脂肪酸钾中的一种或几种。
5.根据权利要求1所述的建筑工程用纤维改性复合聚氨酯材料,其特征在于:所述的催化剂为A-33、PC-5、PC-8、DMAEE或DMDEE中的一种或几种;所述的多羟基化合物为五羟基酮、五羟基醛或六羟基醛中的一种或几种。
6.根据权利要求1所述的建筑工程用纤维改性复合聚氨酯材料,其特征在于:所述的增塑剂为邻苯二甲酸二丁酯、邻苯二甲酸二辛酯、乙二醇醋酸酯、乙二醇丁醚醋酸酯或乙酸乙酯中的一种或几种。
7.根据权利要求1所述的建筑工程用纤维改性复合聚氨酯材料,其特征在于:所述的聚醚多元醇为以乙二醇作为起始剂,官能度为2,羟值为30~100mgKOH/g的聚醚多元醇。
8.根据权利要求1所述的建筑工程用纤维改性复合聚氨酯材料,其特征在于:所述的阻燃剂为三(2-氯丙基)磷酸酯、三(2-氯乙基)磷酸酯或三(2-溴丙基)磷酸酯中的一种或几种。
9.根据权利要求1所述的建筑工程用纤维改性复合聚氨酯材料,其特征在于:所述的防老剂为亚磷酸三苯酯、亚磷酸三壬基苯酯或亚磷酸三乙酯中的一种或几种;所述的抗氧剂为四亚甲基(3,5-二-叔丁基-4-羟基苯丙酸)甲酯,3,5-二叔丁基-4-羟基苯丙酸异辛酯中的一种或几种。
10.一种权利要求1-9任一所述的建筑工程用纤维改性复合聚氨酯材料的制备方法,其特征在于:包括以下步骤:
(1)将硅酸盐溶液搅拌并升温至50~60℃,依次投入稳定剂、多羟基化合物,搅拌至溶液澄清透明后投入玻璃纤维和催化剂,继续搅拌30~60min至体系稳定,即得到A组分;
(2)将多亚甲基多苯基多异氰酸酯、增塑剂、聚醚多元醇、阻燃剂、防老剂和抗氧剂混合后,搅拌至混合均匀,即得到B组分;
(3)使用时,将A组分和B组分按照体积比1:1混合即可。
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