CN114644748A - 一种路基沉降用抬升材料及其制备方法 - Google Patents

一种路基沉降用抬升材料及其制备方法 Download PDF

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CN114644748A
CN114644748A CN202210314946.XA CN202210314946A CN114644748A CN 114644748 A CN114644748 A CN 114644748A CN 202210314946 A CN202210314946 A CN 202210314946A CN 114644748 A CN114644748 A CN 114644748A
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component
parts
agent
lifting material
combination
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裴须强
朱玉雪
尹润平
力乙鹏
吴凯
任硕
隗天骄
王健
宋作宝
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Cnbm Zhongyan Technology Co ltd
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Abstract

本发明涉及一种路基沉降用抬升材料及其制备方法，该抬升材料由A组分和B组分组成，其中A组分为多元醇、交联剂、发泡剂、泡沫稳定剂、抗氧化剂、活性稀释剂、疏水剂、偶联剂、催化剂的混合物，B组分为二苯基甲烷二异氰酸酯、多亚甲基多苯基异氰酸酯和液化MDI中的混合物。本发明利用NCO和OH的高反应活性，通过引入发泡剂、泡沫稳定剂、活性稀释剂、疏水剂等制备出一种疏水性、低粘度、反应速度快、力学性能佳、粘接强度好的路基抬升材料，且材料的发泡倍率可调、闭孔率大、抗疲劳、抗冻融、环境友好。

Description

一种路基沉降用抬升材料及其制备方法
技术领域
本发明涉及材料技术领域，进一步地说，是涉及一种路基沉降用抬升材料及其制备方法。
背景技术
路基作为交通运输的载体，其平顺性往往决定着交通的安全性。但由于长时间在荷载、水、温度等因素综合作用，加之建筑时期压实度不够或地下土质的松动，导致当前公路、机场道面、铁路等路基均出现了不同程度的沉降，尤以高速铁路较为典型。
众所周知，无砟轨道作为高铁运行的载体，以其良好的整体性和稳定性在高速铁路建设中备受青睐，成为高速铁路最为重要的轨道结构形式。然而，相比于有砟轨道，无砟轨道结构仅能在扣件允许的调整范围内对轨道高程进行调整，这就大大限制了无砟轨道结构的平顺性调整、恢复能力。在我国，由于地质条件复杂等多方面原因，部分高速铁路在投入运营后，地基或者路基产生了不可控的沉降，严重影响了线路的平顺性。同时，高铁维修还面临天窗时间短的问题，一般天窗时间是每日零点之后的4h，而其中又包含上线、下线的时间，所以实际施工时间大概只有2～3h左右，这就要求所使用的材料需能快速固化，且早期强度高。
针对以上问题及需求，目前主要采用注浆方法进行治理，浆液在压力下通过管路引导注入到路基病害区域，通过浆液填充和膨胀达到抬升目的。同时，相比传统的水泥基注浆材料，高聚物化学注浆材料具有膨胀压力控制好、路面抬升均匀、长期效果稳定等特点，且能满足天窗时间要求。如专利CN 108359122 A公开了用于高速铁路无砟轨道抬升及同步纠偏用聚氨酯注浆材料，其制备了一种快固化、高粘结、抗压强度高的双组分聚氨酯抬升材料；但材料的力学性能和粘接性能偏低，对于大负荷应用场景易产生二次塌陷，且未对抬升材料的发泡倍率、柔韧性(拉伸强度、断裂伸长率)以及抗冻融性能等进行探究。专利CN104693413 A公开了一种用于高速铁路无砟轨道结构沉降修复用聚氨酯修补材料，其制备了一种反应速度块、高膨胀力的双组分聚氨酯修补材料；但发明中采用的多元醇平均官能度＞4，高官能度使得多元醇体系的粘度偏大，注浆施工时依靠外部加热降低体系粘度，易导致材料发生爆聚，降低其力学性能，且未对材料的抗冻融性能等进行探究。专利CN106893072 A公开了路基加固用聚氨酯注浆液及其制备方法，其适用于机械碾压密实的人工填土加固，与土固结为一体，与本发明的抬升材料性能及应用场景均不一样。专利CN109942779 A公开了一种高铁无砟轨道离缝修补浆液及其制备方法，与本专利所用原材料差别很大，且该专利中A组分和B组分反应后不会产生泡体，不存在膨胀力，主要是用于离缝、裂缝修复，与本专利应用场景不同。
基于此，本发明以多元醇和异氰酸酯为主要原料，通过引入发泡剂、泡沫稳定剂、活性稀释剂、疏水剂等制备出了一种疏水性、低粘度、反应速度快、力学性能佳、粘接强度好的路基抬升材料，且材料的发泡倍率可调、闭孔率大、抗疲劳、抗冻融、环境友好。
发明内容
为解决现有技术中存在的问题，本发明提供了一种路基沉降用抬升材料及其制备方法。通过在异氰酸酯体系中引入高活性二苯基甲烷二异氰酸酯，一方面提升材料整体的反应速率，另一方面也利用该化合物刚性链段堆积结构改善发泡材料的力学性能；此外，在多元醇体系中采用多元醇组合技术，兼顾低官能度多元醇粘度低和高官能度多元醇交联密度大的优势，同时引入发泡剂、泡沫稳定剂、活性稀释剂、疏水剂等功能性助剂，改善体系的粘度、疏水性以及反应活性；最后，两体系按照一定比例混合即可制备出一种疏水性、低粘度、反应速度快、力学性能佳、粘接强度好的路基抬升材料，且材料的发泡倍率可调、闭孔率大、抗疲劳、抗冻融、环境友好。另外，该制备过程原材料易得、制备方法简单、操作简便，对扩大材料的应用具有十分重要的意义。
本发明所述的路基沉降用抬升材料由A组分和B组分组成，其中A组分的具体构成如下：多元醇100份、交联剂5～20份、发泡剂5～15份、泡沫稳定剂1～10份、抗氧化剂0.5～2份、活性稀释剂1～5份、疏水剂0.5～5份、偶联剂1～5份、催化剂0.1～1份；B组分的具体构成如下：二苯基甲烷二异氰酸酯10～30份、多亚甲基多苯基异氰酸酯(PAPI)70～100份、液化MDI 5～10份。
所述的A组分与B组分的质量比为1:1.2～1:2.0。
所述的多元醇，其分子端基或侧基含有两个或两个以上的羟基，也就是平均官能度＞2；分子主链由非极性醚链组成，结构稳定性好，与异氰酸酯反应易造成疏松多孔的发泡特性，且所述多元醇羟值为400～800mgKOH/g。基于此，本发明所用的多元醇优选为聚氧化丙烯二醇、聚氧化丙烯三醇、氧化丙烯-氧化乙烯共聚醚三醇、乙二胺聚醚多元醇、季戊四醇聚醚多元醇、甲苯二胺聚醚多元醇、蔗糖类聚醚多元醇、山梨醇类聚醚多元醇中的一种或组合。考虑到发泡体强度和密实度要求，进一步优选为聚氧化丙烯三醇、氧化丙烯-氧化乙烯共聚醚三醇、乙二胺聚醚多元醇、季戊四醇聚醚多元醇、蔗糖类聚醚多元醇、山梨醇类聚醚多元醇中两种或两种以上组合。
所述的交联剂为低分子量、且官能度≥2的醇或胺，与多元醇共同参与体系反应，其中交联剂的存在可使得体系形成更为完整的聚合物网络，提升材料的力学性能和耐久性能；此外，相比醇类，胺类交联剂在聚氨酯体系中具有自催化特性，具有更高的反应活性，可根据实际情况进行选择。基于此，本发明所用交联剂优选为1，4-丁二醇(BDO)、一缩二乙二醇、二甲基乙醇胺、甘油、三羟甲基丙烷(TMP)、三乙醇胺中的一种或组合。
所述的发泡剂加入到体系中能改善材料的发泡程度，同时可通过控制加入量，产生不同发泡倍率的材料。此外，由于传统的发泡剂CFC是一种破坏大气臭氧层的臭氧消耗物质，已被禁止使用。基于此，本发明所用发泡剂零ODP、环境友好，优选为1,1,1,3,3-五氟丙烷(HFC-245fa)、1,1,1,3,3-五氟丙烷(HFC-365mfc)、正戊烷、环戊烷、去离子水中的一种或组合。
所述的泡沫稳定剂在泡体均匀性方面很重要，能对产生的发泡体起到稳定、均化的作用，避免泡体塌陷，还可提高泡孔的闭孔率和泡体的抗冻融性能。基于此，本发明所用的泡沫稳定剂优选为Si-O-C结构和Si-C结构的聚二甲基硅氧烷-聚氧化烯烃共聚物中的一种或组合。由于含Si-O-C结构的稳定剂与配方中的水长期作用容易水解失效，进一步优选为Si-C结构的聚二甲基硅氧烷-聚氧化烯烃共聚物。
所述的抗氧剂能一定程度上阻止材料发生氧化，提高发泡材料的使用寿命，优选为2，6-二叔丁基对甲酚、四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(抗氧剂1010)、亚磷酸酯中的一种或组合，进一步优选苯酚受阻酚类抗氧剂1010和亚磷酸酯组成复合抗氧剂，二者比例为1:1。
所述的活性稀释剂一方面能降低体系的粘度，另一方面可改善体系的力学性能，提高材料动载荷承受能力(抗疲劳性能)，优选为噁唑烷-酚醛胺、亚丙基碳酸脂、γ-丁内酯中的一种或组合。考虑到与体系的兼容性和材料的力学性能指标，进一步优选为亚丙基碳酸脂。
所述的疏水剂为一种超低粘度且具有憎水效果的物质，加入到体系中一方面能显著降低体系的粘度，另一方面能在体系内形成疏水层，降低副反应的发生，提升抬升材料的湿粘接性能。优选为链烷基硅烷、植物油、溶剂油中的一种或组合，考虑到与多元醇体系的兼容性，进一步优选为溶剂油。
所述的偶联剂具有与无机材料和有机材料结合的反应性基团，能提升抬升材料与混凝土的粘接力，优选为γ-氨丙基三乙氧基硅烷、γ-(2，3-环氧丙氧)丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-氨乙基氨丙基三甲氧基硅烷中的一种。
所述的催化剂能提高A组分和B组分的反应速率，缩短发泡材料的起发时间和表干时间，优选为四亚甲基乙基二胺、三亚乙基二胺(TEDA)、三乙醇胺、三乙胺、羧酸钾类催化剂中的一种或组合。同时，考虑到链增长速率和交联速率间的平衡，进一步优选为三亚乙基二胺(TEDA)、三乙醇胺、三乙胺、羧酸钾类催化剂中的两种或两种以上组合。
所述的二苯基甲烷二异氰酸酯为2，4-MDI和4，4-MDI含量各50％左右的产品的混合物，业内称为MDI-50，可在市面进行直接采购。
所述的液化MDI为二元醇改性MDI和碳化二亚胺改性MDI中的一种。考虑到发泡材料的耐水解性能，进一步优选为碳化二亚胺改性MDI。
本发明的制备方法包括以下步骤：
(1)A组分制备
①按重量份分别称量多元醇、交联剂、发泡剂、泡沫稳定剂、抗氧化剂、活性稀释剂、疏水剂、偶联剂、催化剂；
②首先将称量好的多元醇、交联剂加入带加热装置的搅拌容器内，20～100℃下进行混合搅拌5～60min；然后，冷却到室温加入称量的发泡剂、泡沫稳定剂、抗氧化剂、活性稀释剂、疏水剂、偶联剂、催化剂，继续混合搅拌20～120min，即可得到A组分；
(2)B组分制备
①按重量份分别称量二苯基甲烷二异氰酸酯(MDI)、多苯基甲烷多异氰酸酯(PAPI)和液化MDI；
②将上述物料依次倒入搅拌容器内，在室温下混合搅拌均匀5～40min，即可得到B组分。
本发明的有益结果在于：
(1)低粘疏水：A、B组分粘度均≤100mPa.s；
(2)反应速度快：初始反应时间≤10s，表面干燥时间≤40s；
(3)力学性能佳：发泡倍率4～10倍可调，闭孔率≥92％，自由膨胀抗压强度(15min)≥1.5MPa，自由膨胀抗拉强度(15min)≥1.0MPa，断裂伸长率(15min)≥1.5％，与混凝土的干粘接力≥1.0MPa，与混凝土的湿粘接力≥0.6MPa
(4)抗疲劳：动态荷载200万次(100KPa动荷载、5～10HZ下)发泡材料外观无剥落，残余形变≤0.5％；
(5)抗冻融：冻融循环400次，发泡材料外观无剥落，抗压强度保持率≥80％；
(6)环境友好：挥发性有机物(VOC)含量≤10g/m2，不含可溶性铅、镉、锡等重金属；
(7)易操作：该抬升材料制备所用原材料常见，成本低，方法简便，且施工难度系数较小。
具体实施方式
下面结合实施例，进一步说明本发明。
实施例中所用原料均为市售，实验方法如无特殊说明均为常规试验方法。
实施例1
A组分制备：①按重量份称取多元醇100份(聚氧化丙烯三醇40份和乙二胺聚醚多元醇60份)、交联剂10份(1，4-丁二醇)、发泡剂13份(正戊烷)、泡沫稳定剂3份、抗氧化剂0.8份、活性稀释剂2份、疏水剂2.5份、偶联剂3份(γ-氨丙基三乙氧基硅烷)、催化剂0.6份(三亚乙基二胺(TEDA)0.3份和羧酸钾类催化剂0.3份)；②首先将称量好的多元醇、交联剂加入带加热装置的搅拌容器内，80℃下进行混合搅拌20min；然后，冷却到室温加入称量的发泡剂、泡沫稳定剂、抗氧化剂、活性稀释剂、疏水剂、偶联剂、催化剂，继续混合搅拌30min，即可得到A组分。
B组分制备：按重量份称取二苯基甲烷二异氰酸酯15份、多亚甲基多苯基异氰酸酯(PAPI)80份、液化MDI5份(碳化二亚胺改性MDI)；然后倒入搅拌容器内，在室温下混合搅拌均匀10min，即可得到B组分。
A组分和B组分按照重量比1:1.3称量，然后经过高速混合机混合即可得到一种抬升材料。
实施例2
A组分制备：①按重量份称取多元醇100份(乙二胺聚醚多元醇50份和季戊四醇聚醚多元醇50份)、交联剂15份(三羟甲基丙烷)、发泡剂10份(1,1,1,3,3-五氟丙烷(HFC-365mfc)8份和水2份)、泡沫稳定剂3份、抗氧化剂0.8份、活性稀释剂3份、疏水剂3份、偶联剂3份(γ-氨丙基三乙氧基硅烷)、催化剂0.5份(三亚乙基二胺0.3份和羧酸钾类催化剂0.2份)；②首先将称量好的多元醇、交联剂加入带加热装置的搅拌容器内，60℃下进行混合搅拌25min；然后，冷却到室温加入称量的发泡剂、泡沫稳定剂、抗氧化剂、活性稀释剂、疏水剂、偶联剂、催化剂，继续混合搅拌40min，即可得到A组分。
B组分制备：按重量份称取二苯基甲烷二异氰酸酯16份、多亚甲基多苯基异氰酸酯(PAPI)75份、碳化二亚胺改性MDI9份；然后倒入搅拌容器内，在室温下混合搅拌均匀10min，即可得到B组分。
A组分和B组分按照重量比1:1.5称量，然后经过高速混合机混合即可得到一种抬升材料。
实施例3
A组分制备：①按重量份称取多元醇100份(聚氧化丙烯三醇20份、乙二胺聚醚多元醇40份和蔗糖类聚醚多元醇40份)、交联剂12份(三乙醇胺)、发泡剂12份(环戊烷10份和水2份)、泡沫稳定剂5份、抗氧化剂1份、活性稀释剂4份、疏水剂3份、偶联剂3.5份(γ-(2，3-环氧丙氧)丙基三甲氧基硅烷)、催化剂0.8份(三乙胺0.5份和羧酸钾类催化剂0.3份)；②首先将称量好的多元醇、交联剂加入带加热装置的搅拌容器内，55℃下进行混合搅拌40min；然后，冷却到室温加入称量的发泡剂、泡沫稳定剂、抗氧化剂、活性稀释剂、疏水剂、偶联剂、催化剂，继续混合搅拌40min，即可得到A组分。
B组分制备：按重量份称取二苯基甲烷二异氰酸酯25份、多亚甲基多苯基异氰酸酯(PAPI)68份、液化MDI 7份；然后倒入搅拌容器内，在室温下混合搅拌均匀30min，即可得到B组分。
A组分和B组分按照重量比1:1.7称量，然后经过高速混合机混合即可得到一种抬升材料。
实施例4
A组分制备：①按重量份称取多元醇100份(季戊四醇聚醚多元醇70份和山梨醇类聚醚多元醇30份)、交联剂15份(乙二醇5份和三乙醇胺10份)、发泡剂10份(1,1,1,3,3-五氟丙烷(HFC-245fa)7份和去离子水3份)、泡沫稳定剂8份、抗氧化剂1.5份、活性稀释剂2份、偶联剂4份(γ-氨乙基氨丙基三甲氧基硅烷)、催化剂0.9份(三乙胺0.4份和三亚乙基二胺0.5份)；②首先将称量好的多元醇、交联剂加入带加热装置的搅拌容器内，70℃下进行混合搅拌15min；然后，冷却到室温加入称量的发泡剂、泡沫稳定剂、抗氧化剂、活性稀释剂、偶联剂、催化剂，继续混合搅拌50min，即可得到A组分。
B组分制备：按重量份称取二苯基甲烷二异氰酸酯28份、多亚甲基多苯基异氰酸酯(PAPI)66份、液化MDI 6份；然后倒入搅拌容器内，在室温下混合搅拌均匀10min，即可得到B组分。
A组分和B组分按照重量比1:1.7称量，然后经过高速混合机混合即可得到一种抬升材料。
实施例5
A组分制备：与实施例3中的A组分配方和制备方法一样；
B组分制备：单独采用多亚甲基多苯基多异氰酸酯作为B组分。
A组分和B组分按照重量比1:1.5称量，然后经过高速混合机混合即可得到一种抬升材料。
实施例6
A组分制备：与实施例3中的A组分配方和制备方法一样；
B组分制备：按重量份称取多亚甲基多苯基异氰酸酯(PAPI)92份、液化MDI 8份；然后倒入搅拌容器内，在室温下混合搅拌均匀10min即可。
A组分和B组分按照重量比1:1.5称量，然后经过高速混合机混合即可得到一种抬升材料。
对比例1
专利CN 108359122 A实施例。
对比例2
专利CN 104693413 A实施例。
实施例和对比例具体抬升材料的性能如下：
Figure BDA0003568746380000111
与专利CN 108359122 A和专利CN 104693413 A中的实施例性能对比可以发现，本发明对抬升材料的性能更优异，体系具有更低的粘度，A组分和B组分均≤100mPa.s；力学性能更佳，自由膨胀抗压强度(15min)≥1.5MPa，自由膨胀抗拉强度(15min)≥1.0MPa；材料具有疏水效果，与混凝土的界面结合更为牢固，干粘接力≥1.0MPa，湿粘接力≥0.6MPa。
此外，对比实施例1～3和实施例4可以发现，实施例4多元醇体系中去除了疏水剂，但湿粘接强度测试结果显示为0.51MPa，远低于其它实施例，进一步突出疏水剂在本发明中的特殊性，保证了潮湿环境中发泡材料与界面的粘接力。
对比实施例3和实施例4、5可以发现，实施例4和5中的异氰酸酯体系中均未加入二苯基甲烷二异氰酸酯，但测试出的结果显示发泡材料的力学性能偏低，也进一步突出二苯基甲烷二异氰酸酯的必要性，在提高体系反应活性的同时也提供刚性链段堆积结构，保证发泡材料的力学性能。

Claims (10)

1.一种路基沉降用抬升材料，其特征在于，该抬升材料由A组分和B组分组成，其中A组分为多元醇、交联剂、发泡剂、泡沫稳定剂、抗氧化剂、活性稀释剂、疏水剂、偶联剂、催化剂的混合物，B组分为二苯基甲烷二异氰酸酯、多亚甲基多苯基异氰酸酯和液化MDI中的混合物。
2.如权利要求1所述的一种路基沉降用抬升材料，其特征在于，所述的A组分中各原料的重量份数如下：
Figure FDA0003568746370000011
所述的B组分中各原料的重量份数如下：
二苯基甲烷二异氰酸酯：10～30份，
多亚甲基多苯基异氰酸酯：70～100份，
液化MDI：5～10份；
A组分与B组分的质量比为1:1.2～1:2.0。
3.如权利要求1所述的一种路基沉降用抬升材料，其特征在于，所述的多元醇为聚氧化丙烯二醇、聚氧化丙烯三醇、氧化丙烯-氧化乙烯共聚醚三醇、乙二胺聚醚多元醇、季戊四醇聚醚多元醇、甲苯二胺聚醚多元醇、蔗糖类聚醚多元醇、山梨醇类聚醚多元醇中的一种或组合。
4.如权利要求1所述的一种路基沉降用抬升材料，其特征在于，所述的交联剂为乙二醇、1，4-丁二醇、一缩二乙二醇、二甲基乙醇胺、甘油、三羟甲基丙烷、三乙醇胺中的一种或组合。
5.如权利要求1所述的一种路基沉降用抬升材料，其特征在于，所述的发泡剂为1,1,1,3,3-五氟丙烷、1,1,1,3,3-五氟丙烷、正戊烷、环戊烷、去离子水中的一种或组合，所述的泡沫稳定剂为Si-O-C结构和Si-C结构的聚二甲基硅氧烷-聚氧化烯烃共聚物中的一种或组合。
6.如权利要求1所述的一种路基沉降用抬升材料，其特征在于，所述的抗氧化剂为2，6-二叔丁基对甲酚、四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、亚磷酸酯中的一种或组合。
7.如权利要求1所述的一种路基沉降用抬升材料，其特征在于，所述的活性稀释剂为噁唑烷-酚醛胺、亚丙基碳酸脂、γ-丁内酯中的一种或组合，所述的疏水剂为链烷基硅烷、植物油、溶剂油中的一种或组合，所述的偶联剂为γ-氨丙基三乙氧基硅烷、γ-(2，3-环氧丙氧)丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-氨乙基氨丙基三甲氧基硅烷中的一种。
8.如权利要求1所述的一种路基沉降用抬升材料，其特征在于，所述的催化剂为四亚甲基乙基二胺、三亚乙基二胺、三乙醇胺、三乙胺、羧酸钾类催化剂中的一种或组合。
9.如权利要求1所述的一种路基沉降用抬升材料，其特征在于，所述的液化MDI为多元醇改性MDI和碳化二亚胺改性MDI的一种或组合。
10.如权利要求1-9任一项所述的一种路基沉降用抬升材料的制备方法，其特征在于包括以下步骤：
(1)A组分制备
①按重量份分别称量多元醇、交联剂、发泡剂、泡沫稳定剂、抗氧化剂、活性稀释剂、疏水剂、偶联剂、催化剂；
②首先将称量好的多元醇、交联剂加入带加热装置的搅拌容器内，20～100℃下进行混合搅拌5～60min；然后，冷却到室温加入称量的发泡剂、泡沫稳定剂、抗氧化剂、活性稀释剂、疏水剂、偶联剂、催化剂，继续混合搅拌20～120min，即可得到A组分；
(2)B组分制备
①按重量份分别称量二苯基甲烷二异氰酸酯(MDI)、多苯基甲烷多异氰酸酯(PAPI)和液化MDI；
②将上述物料依次倒入搅拌容器内，在室温下混合搅拌均匀5～40min，即可得到B组分。
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