CN106496503B - 水不敏感型聚氨酯注浆材料及其制备方法 - Google Patents

水不敏感型聚氨酯注浆材料及其制备方法 Download PDF

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CN106496503B
CN106496503B CN201610908495.7A CN201610908495A CN106496503B CN 106496503 B CN106496503 B CN 106496503B CN 201610908495 A CN201610908495 A CN 201610908495A CN 106496503 B CN106496503 B CN 106496503B
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张天水
朱彦
王朝阳
潘利军
崔燕军
唐劲松
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Shanghai Huafon New Material Research & Development Technology Co Ltd
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Abstract

本发明公开了一种水不敏感型聚氨酯注浆材料及其制备方法,所述水不敏感型聚氨酯注浆材料,包括A和B两个组分,A组分与B组分的体积比为1∶1~1∶1.2;所述A组分为多元醇改性二苯基甲烷二异氰酸酯和多亚甲基多苯基异氰酸酯的混合物;所述B组分为多元醇、增塑剂、扩链剂、催化剂、表面活性剂和发泡剂的混合物。本发明的选用优选结构的原料,并将各原料以确定配方进行混合,通过原料间的物理化学协同作用使本注浆材料具有优异的水不敏感性,大大提高了其在富水环境下的承载能力和耐久性。

Description

水不敏感型聚氨酯注浆材料及其制备方法
技术领域
本发明涉及聚氨酯半硬泡塑料,具体涉及一种聚氨酯注浆材料及其制备方法。
背景技术
对于一些具有软弱地基地区,其建筑或道路若在设计或施工阶段未考虑或未采取有效的地基处理措施,则在建成后或使用过程中容易出现大面积的地面沉降。具有混凝土板层结构的建筑、道路或铁路在沉降过程中,往往还伴随着大面积的脱空,形成非常大的安全隐患,严重的可能导致坍塌事故。
目前地基加固处理的方法有多种,传统的开挖重建造成资源极大的浪费,而且往往耐久性较差,重建之后仍然会发生沉降;注浆加固是一项针对软弱地基,地基穴洞缺陷,地基沉降,建筑物偏斜的地基加固技术。为了防止地基发生持续的不均匀沉降,可通过专业机械设备注浆到发生沉降的地基中进行加固。注浆加固地基的实质是通过一定的压力将可固化的化学浆液或水泥浆液注入地基土的裂缝或孔隙,以改善地基的物理力学性能。
传统的注浆材料,如水泥等,由于其水化反应耗时长,会导致封闭交通时间过长,严重影响交通(特别是高速公路)运输效率。而对于高速铁路地基的修复,由于可用于修复施工的天窗期只有几小时,故传统的注浆材料不能用于高速铁路的地基修复。
而高聚物注浆技术完美地解决了这些问题。与传统的水泥注浆养护修复技术相比,以双组份发泡聚氨酯为代表的聚合物注浆材料具有反应速度快,并可随意调节、浆液粘度较小流动性好、膨胀率高、抬升力大、耐久性好、环保安全等特点,从根本上解决了接缝透水、板底脱空带来的问题,能有效地防止翻浆冒泥、断板等病害的发生,施工快捷,养生时间短、甚至无需养生,对交通扰动小,已成为一种综合性能优良的新型堵漏补强材料。高聚物注浆材料技术改变了以往路面开挖,长时间交通封闭的修补方式,大大节约了成本,是维护既有建筑、高速公路、高速铁路经济且有效的方法。
但在一些潮湿多雨的地区,地基内部或下方脱空处常常会有积水情况发生,一般的聚氨酯注浆材料在进行注浆施工时,由于其对水较敏感,注入到地基里的浆液遇到积水或潮湿的岩土会发生化学反应,使其性能(如密度、压缩强度等)大幅劣化,降低其承载能力和耐久性。
发明内容
本发明的目的在于提供一种水不敏感型聚氨酯注浆材料及其制备方法,以克服现有技术存在的缺陷,满足相关领域应用的需要。
所述的水不敏感型聚氨酯注浆材料,包括A和B两个组分,A组分与B组分的体积比为1∶1~1∶1.2;
其中:
所述A组分为多元醇改性二苯基甲烷二异氰酸酯(简称多元醇改性MDI)和多亚甲基多苯基异氰酸酯(简称PAPI)的混合物;
所述的A组分为有刺激性气味浅黄色至褐色粘稠液体,官能度为2.2-2.9,其中,多元醇改性二苯基甲烷二异氰酸酯中,多元醇为2官能度聚醚多元醇,如PPG或PTMEG,分子量为200~800;
所述多亚甲基多苯基多异氰酸酯(聚合MDI)是由亚甲基架桥的多苯环芳香族异氰酸酯组成的混合物,选自烟台万华的PM200、科思创公司44v20或巴斯夫公司M20S;
多元醇改性二苯基甲烷二异氰酸酯和多亚甲基多苯基异氰酸酯的重量配比为1:4~1:11,A组分中-NCO含量为20%~35%,25℃粘度为50mPa.s~300mPa.s;
所述B组分为多元醇、增塑剂、扩链剂、催化剂、表面活性剂和发泡剂的混合物;
优选的,所述的B组分包括如下重量份数的组分:
所述B组分在25℃下粘度为150mPa.s~500mPa.s;
所述B组分中,所述的多元醇为聚醚多元醇、聚酯多元醇、聚脲多元醇、聚烯烃多元醇、接枝多元醇、生物基多元醇中的两种或两种以上的混合物;多元醇平均官能度为3~8,分子量为200~800;
本发明并不限制所述聚醚多元醇中醇羟基的个数,可以是聚醚三元醇、聚醚四元醇等中的一种和/或一种以上的混合物,优选的是结构简单、性能稳定的小分子多元醇,包括聚醚三元醇、聚醚四元醇或二者的混合物。
所述的增塑剂为酯类物质,为邻苯二甲酸二辛酯(DOP)、邻苯二甲酸二丁酯(DBP)、己二酸二辛脂(DOA)、柠檬酸三丁酯(TBC)、2,2,4-三甲基-1,3-戊二醇双异丁酸酯(TXIB)、2,2,4-三甲基-1,3-戊二醇单异丁酸酯、蓖麻油等中的一种或多种的混合物,上述所用的增塑剂与聚氨酯相容性好,基本不迁移或很少迁移,稳定性和协同性显著。
所述扩链剂为一缩二乙二醇(DEG)、一缩二丙二醇(DPG)、1,4-丁二醇(BDO)、新戊二醇(NPG)、甘油或三羟甲基丙烷(TMP)中的一种或多种的混合物。
所述的催化剂选自脂肪胺类、脂环胺类、芳香胺类和醇胺类及其铵盐类化合物等叔胺类催化剂以及二月桂酸二丁基锡(T12)、辛酸亚锡(T9)、异辛酸铅等有机金属催化剂一种或多种的混合物。
所述的表面活性剂有机硅表面活性剂,主要为聚硅氧烷-氧化烯烃嵌段共聚物。
所述B组分中的发泡剂为一氟二氯乙烷(HCFC-141b)和水的混合物,水为主发泡剂,141b为辅助发泡剂。
本发明的制备方法是:
先将上述B组分中的各原料以确定配比投入到容器内搅拌均匀,再将A组分与B组分按设定质量比充分混合反应,即可获得所述的的水不敏感型聚氨酯注浆材料;
本发明对环境的水不敏感、反应速度快、流动性好、高膨胀力、高粘结性能、具有优良的体积稳定性、低残余变形和抗水解性能优异的双组份聚氨酯注浆修补材料,以克服现有普通材料存在的缺陷,提高注浆材料在有水及潮湿环境下的承载能力和耐久性。该材料可用于道路路面抬升以及解决工厂厂房地坪的沉降修复等问题,也可用于高速铁路无砟轨道路基的沉降修复。
采用本发明方法生产的水不敏感型聚氨酯注浆材料,其水不敏感性相比普通聚氨酯注浆材料有大幅提高,在全水环境中的密度保持率由50%左右提高到85%左右,压缩强度保持率由30%左右提高到70%左右;并且材料收缩率也有明显降低,由5%左右降至0.5%左右。本发明的另一意义是,大幅提高了聚氨酯注浆材料的环境适应性,使其在潮湿、积水的地基岩土环境中仍能保持较高的承载强度和耐久性,可广泛地应用于高速公路、高速铁路、隧道、房屋建筑等的地基加固、堵漏、抬升工程。
本发明的优点在于:
选用优选结构的原料,并将各原料以确定配方进行混合,通过原料间的物理化学协同作用使本注浆材料具有优异的水不敏感性,大大提高了其在富水环境下的承载能力和耐久性。
具体实施方式
以下结合本发明提供实施例,但本发明并不仅仅局限于此。
实施例均按以下方法制备:
先将B组分中各原料按设定配比投入到容器内搅拌均匀,再将A组分与B组分按设定的质量比充分混合反应,得到水不敏感型聚氨酯注浆材料。
水不敏感性的判断方法为:将A、B混合后的浆料迅速倒入水中(水需完全没过浆液),发泡得到的即为全水环境下的注浆材料泡沫。测泡沫芯部的密度及10%压缩强度,与空气中发泡得来的自由泡的芯部密度及压缩强度进行对比,即可得出密度保持率及压缩强度保持率。密度保持率和压缩强度保持率越高,则水不敏感性越好。
实施例1-10
各个实施例中,所述多苯环芳香族异氰酸酯中:
实施例1:多亚甲基多苯基多异氰酸酯(PAPI)由万华公司提供,产品牌号为PM200;多元醇改性二苯基甲烷二异氰酸酯中,多元醇为2官能度聚醚多元醇,PPG分子量为200;
实施例2:多亚甲基多苯基多异氰酸酯(PAPI)由科思创公司提供,产品牌号为44V20;多元醇改性二苯基甲烷二异氰酸酯中,多元醇为2官能度聚醚多元醇,PPG分子量为800;
实施例3:多亚甲基多苯基多异氰酸酯(PAPI)由巴斯夫公司提供,产品牌号为M20S;多元醇改性二苯基甲烷二异氰酸酯中,多元醇为2官能度聚醚多元醇,PPG分子量为300;
实施例4:多亚甲基多苯基多异氰酸酯(PAPI)由万华公司提供,产品牌号为PM200;多元醇改性二苯基甲烷二异氰酸酯中,多元醇为2官能度聚醚多元醇,PPG分子量为400;
实施例5:多亚甲基多苯基多异氰酸酯(PAPI)由万华公司提供,产品牌号为PM200;多元醇改性二苯基甲烷二异氰酸酯中,多元醇为2官能度聚醚多元醇,PPG分子量为500;
实施例6:多亚甲基多苯基多异氰酸酯(PAPI)由科思创公司提供,产品牌号为44V20;多元醇改性二苯基甲烷二异氰酸酯中,多元醇为2官能度聚醚多元醇,PTMEG分子量为800;
实施例7:多亚甲基多苯基多异氰酸酯(PAPI)由科思创公司提供,产品牌号为44V20;多元醇改性二苯基甲烷二异氰酸酯中,多元醇为2官能度聚醚多元醇,PPG分子量为300;
实施例8:多亚甲基多苯基多异氰酸酯(PAPI)由巴斯夫公司提供,产品牌号为M20S;多元醇改性二苯基甲烷二异氰酸酯中,多元醇为2官能度聚醚多元醇,PPG分子量为200;
实施例9:多亚甲基多苯基多异氰酸酯(PAPI)由巴斯夫公司提供,产品牌号为M20S;多元醇改性二苯基甲烷二异氰酸酯中,多元醇为2官能度聚醚多元醇,PTMEG分子量为600;
实施例10:多亚甲基多苯基多异氰酸酯(PAPI)由巴斯夫公司提供,产品牌号为M20S;多元醇改性二苯基甲烷二异氰酸酯中,多元醇为2官能度聚醚多元醇,PPG分子量为700;
对照例1:多亚甲基多苯基多异氰酸酯(PAPI)由科思创公司提供,产品牌号为44V20;多元醇改性二苯基甲烷二异氰酸酯中,多元醇为2官能度聚醚多元醇,PPG分子量为200;
对照例2:多亚甲基多苯基多异氰酸酯(PAPI)由巴斯夫公司提供,产品牌号为M20S;多元醇改性二苯基甲烷二异氰酸酯中,多元醇为2官能度聚醚多元醇,PPG分子量为800;
表1具体实施例及对比例配方及性能对照表
下面表2是续接的表1。
表2接表1
注:1.原料皆以重量份数计算。
2.泡沫密度、压缩强度、尺寸变化率皆按国家标准进行测定。
由表可见,本发明中以实施例制备的水不敏感型聚氨酯注浆材料,其密度保持率、压缩强度保持率、尺寸稳定性都明显好于对照例中的普通配方材料,显示出本材料优异的水不敏感性,作为注浆材料能大幅提高在恶劣富水地基环境下的承载能力和耐久性。

Claims (2)

1.水不敏感型聚氨酯注浆材料,其特征在于,由A和B两个组分组成,所述的B组分由如下重量份数的组分组成:
所述的A组分由如下重量份数的组分组成:
PAPI 90份
多元醇改性MDI 20份;
或者,所述的B组分由如下重量份数的组分组成:
所述的A组分由如下重量份数的组分组成:
PAPI 90份
多元醇改性MDI 20份;
或者,所述的B组分由如下重量份数的组分组成:
所述的A组分由如下重量份数的组分组成:
PAPI 90份
多元醇改性MDI 30份;
或者,所述的B组分由如下重量份数的组分组成:
所述的A组分由如下重量份数的组分组成:
PAPI 90份
多元醇改性MDI 30份;
或者,所述的B组分由如下重量份数的组分组成:
所述的A组分由如下重量份数的组分组成:
PAPI 100份
多元醇改性MDI 20份;
或者,所述的B组分由如下重量份数的组分组成:
所述的A组分由如下重量份数的组分组成:
PAPI 100份
多元醇改性MDI 20份;
或者,所述的B组分由如下重量份数的组分组成:
所述的A组分由如下重量份数的组分组成:
PAPI 110份
多元醇改性MDI 10份;
或者,所述的B组分由如下重量份数的组分组成:
所述的A组分由如下重量份数的组分组成:
PAPI 110份
多元醇改性MDI 10份。
2.根据权利要求1所述的水不敏感型聚氨酯注浆材料的制备方法,其特征在于,包括如下步骤:
先将上述B组分中的各原料投入到容器内搅拌均匀,再将A组分与B组分充分混合反应,即可获得所述的的水不敏感型聚氨酯注浆材料。
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