CN111763416B - 抗水分散型聚氨酯硬质泡沫注浆止水加固材料及制备方法 - Google Patents
抗水分散型聚氨酯硬质泡沫注浆止水加固材料及制备方法 Download PDFInfo
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- CN111763416B CN111763416B CN202010581668.5A CN202010581668A CN111763416B CN 111763416 B CN111763416 B CN 111763416B CN 202010581668 A CN202010581668 A CN 202010581668A CN 111763416 B CN111763416 B CN 111763416B
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Abstract
本申请公开了抗水分散型聚氨酯硬质泡沫注浆止水加固材料及制备方法,该材料包括A组分和B组分,所述A组分包括:异氰酸酯:210~230重量份数,聚醋酸乙烯酯7~14重量份数,溶剂:4~10重量份数,发泡剂:0~10重量份数,所述B组分包括:聚合物多元醇:100重量份数,增塑剂:20~25重量份数,扩链剂:10~27重量份数,发泡剂:0~10重量份数,泡沫稳定剂:1~2重量份数,催化剂:1~1.5重量份数。该制备方法包括:将所述组分A和组分B按比例混合后搅拌均匀,即可获得。本申请具有良好的抗水分散性,在流动的水体中不易被水冲散,且强度高,纯泡沫抗压强度不小于2MPa,耐久性好,固化时间可调,价格低廉,适用于封堵涌水和射流,具有良好的经济性、安全性和环保性。
Description
技术领域
本申请属于复合材料技术领域,具体涉及抗水分散型聚氨酯硬质泡沫注浆止水加固材料及制备方法。
背景技术
隧道和矿山工程中时常遇到突涌水现象,易造成围岩失稳、边坡塌滑等灾害,不仅造成人员伤亡、财产损失、工期延误,还会影响工程结构的长期稳定性、恶化施工条件和破坏周边生态环境。注浆止水加固技术是改善松散或含水地层力学性能与稳定性,以及预防和治理塌方、渗漏、涌水、突泥和流沙等最常用、最有效的手段之一。
目前,常用的注浆材料主要有水泥基无机注浆材料以及脲醛树脂注浆材料、丙烯酰胺注浆材料、环氧树脂注浆材料和聚氨酯注浆材料等高分子有机注浆材料。水泥基注浆原料易得、价格低廉、结石体强度高、抗渗性能好,适用于较大裂隙的破碎岩体的大批量注浆;但是凝胶时间长、易流失浪费、可注性较差、强度增长慢、结石率低、抗水分散性差,难以用于治理突涌水;脲醛树脂注浆材料强度低,耐久性差;丙烯酰胺类注浆材料毒性较大;环氧树脂注浆材料成本高,粘度大,可注性较差。相比之下,聚氨酯注浆材料强度较高、固化时间短且可调、施工方便快捷、粘度低、流动性好、渗透性高、膨胀率高、抬升力大、抗渗堵漏加固等能力强,是一种综合性能优良的新型止水加固注浆材料,正逐渐获得广泛应用。
聚氨酯注浆材料可分为水反应性和非水反应性,水反应性聚氨酯浆液遇水膨胀并凝固,适用于常规堵漏处理,但是易被水冲散,难以封堵涌水或射流,且固化过程需有水参与反应以及固结体易水解的特点导致其强度和耐久性较差,对工程的长期稳定性造成潜在威胁;非水反应性聚氨酯浆液疏水性和耐水解稳定性好,性能稳定,不受注浆环境水含量的影响,适用于封堵涌水或射流,但仍存在抗水分散性较差的问题,易造成对水源和周边生态环境的污染。
发明内容
针对上述现有技术的缺点或不足,本申请要解决的技术问题是提供抗水分散型聚氨酯硬质泡沫注浆止水加固材料。
为解决上述技术问题,本申请通过以下技术方案来实现:
本申请提出了抗水分散型聚氨酯硬质泡沫注浆止水加固材料,包括A组分和B组分,其中,所述A组分的组成及其重量份数如下:
异氰酸酯:210~230重量份数,
聚醋酸乙烯酯7~14重量份数,
溶剂:4~10重量份数,
发泡剂:0~10重量份数,
所述B组分的组成及其重量份数如下:
聚合物多元醇:100重量份数,
增塑剂:20~25重量份数,
扩链剂:10~27重量份数,
发泡剂:0~10重量份数,
泡沫稳定剂:1~2重量份数,
催化剂:1~1.5重量份数。
进一步地,上述的抗水分散型聚氨酯硬质泡沫注浆止水加固材料,其中,所述异氰酸酯为甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、二苯基甲烷二异氰酸酯(MDI)、碳化二亚胺改性MDI(液化MDI)、多亚甲基多苯基异氰酸酯(PAPI)、二环己基甲烷二异氰酸酯(HMDI)或六亚甲基二异氰酸酯(HDI)中的一种或多种的任意比例混合物,其中,NCO含量为25%-50%,平均官能度为2.4~3.0,25℃下的粘度<500mpa·s,熔点<20℃。
进一步地,上述的抗水分散型聚氨酯硬质泡沫注浆止水加固材料,其中,所述溶剂为环状酯类化合物,为γ-丁内酯(GBL)、γ-戊内酯(GVL)、ε-己内酯(ECL)、碳酸乙烯酯(EC)、碳酸丙烯酯(PC)等中的一种或多种的任意比例混合物,熔点<20℃。
进一步地,上述的抗水分散型聚氨酯硬质泡沫注浆止水加固材料,其中,所述发泡剂为臭氧消耗潜值(ODP)与全球变暖潜能值(GWP)均较小的含氢氯氟烃类化合物和戊烷类化合物,为1-氯-1,1-二氟乙烷(HCFC-142b)、1-氟-1,1-二氯乙烷(HCFC-141b)、1-氯-3,3,3-三氟丙烯(HCFO-1233zd)、正戊烷、异戊烷和环戊烷等中的一种或多种的任意比例混合物。
进一步地,上述的抗水分散型聚氨酯硬质泡沫注浆止水加固材料,其中,所述聚合物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、超支化多元醇、生物基多元醇等中的一种或多种的任意比例混合物;多元醇的平均官能度为3~8,平均分子量为400-4000,羟值为400~850mg KOH/g。
进一步地,上述的抗水分散型聚氨酯硬质泡沫注浆止水加固材料,其中,所述增塑剂为酯类化合物,为己二酸二辛酯(DOA)、癸二酸二辛酯(DOS)、邻苯二甲酸二辛酯(DOP)、对苯二甲酸二辛酯(DOTP)、邻苯二甲酸二癸酯(DIDP)、偏苯三酸三辛酯(TOTM)、十三烷醇偏苯三酸酯(TDTM)、乙酰基柠檬酸三丁酯(ATBC)和2,2,4-三甲基-1-3-戊二醇二异丁酸酯(TXIB)等中的一种或多种的任意比例混合物。
进一步地,上述的抗水分散型聚氨酯硬质泡沫注浆止水加固材料,其中,所述扩链剂为小分子多元醇类化合物,为乙二醇(EG)、一缩二乙二醇(DEG)、1,2-丙二醇(PG)、一缩二丙二醇(DPG)、1,4-丁二醇(BDO)、新戊二醇(NPG)、1,6-己二醇(HDO)、丙三醇(GLY)和三羟甲基丙烷(TMP)等中的一种或多种的任意比例混合物。
进一步地,上述的抗水分散型聚氨酯硬质泡沫注浆止水加固材料,其中,所述泡沫稳定剂为有机硅类表面活性剂。
进一步地,上述的抗水分散型聚氨酯硬质泡沫注浆止水加固材料,其中,所述催化剂为叔胺类化合物,为:N,N-二甲基环己胺(DMCHA)、三乙烯二胺(TEDA)、六亚甲基四胺(HMTA)、五甲基二乙烯三胺(PMDETA)、四甲基乙二胺(TMEDA)、N,N-二甲基苄胺(BDMA)等中的一种或多种的任意比例混合物。
进一步地,上述的抗水分散型聚氨酯硬质泡沫注浆止水加固材料,其中,所述A组分与所述B组分的质量比为1:1~2.5:1。
本申请还提出了抗水分散型聚氨酯硬质泡沫注浆止水加固材料的制备方法,所述制备方法包括如下步骤:
制备所述A组分时,先将7~14重量份数的聚醋酸乙烯酯溶解于4~10重量份数的溶剂,再与210~230重量份数的异氰酸酯混合搅拌均匀,最后加入0~10重量份的发泡剂,混合后搅拌至混合物成为均匀透明液体,得到A组分;
制备所述B组分时,向混合器中加入100重量份的聚合物多元醇、20~25重量份数的增塑剂、10~27重量份数的扩链剂、1~2重量份数的泡沫稳定剂和1~1.5重量份数的催化剂并混合搅拌均匀,再加入0~10重量份的发泡剂,混合后搅拌至混合物成为均匀透明液体,得到B组分;
使用时,将所述组分A和组分B按比例混合后搅拌均匀,即可获得所述的抗水分散型聚氨酯硬质泡沫注浆止水加固材料。
需要说明地是,用溶剂溶解聚醋酸乙烯酯(PVAC)时,可将溶剂先加热到50℃~90℃并保持温度不低于50℃,再向其中边搅拌边加入聚醋酸乙烯酯,搅拌至混合物变为均质的、无颗粒的半透明高黏度液体,或将聚醋酸乙烯酯加入常温的溶剂中并在不低于20℃的环境中密封静置24~120h,得到半透明高黏度液体;将聚醋酸乙烯酯溶液加入异氰酸酯时,需预先将聚醋酸乙烯酯溶液和异氰酸酯都加热到40℃以上,优选地,将聚醋酸乙烯酯溶液加热到60℃以上,向预先加热好的异氰酸酯中边搅拌边加入预先加热好的聚醋酸乙烯酯溶液,加入聚醋酸乙烯酯溶液后继续搅拌至混合物转变为透明的深色液体;发泡剂加在A组分和B组分其中的一个中,或分别加在A组分和B组分中,优选地,若所用的发泡剂与异氰酸酯难以互溶,或加入A组分后会造成A组分黏度上升或聚醋酸乙烯酯析出,则该发泡剂应加在B组分中,若所用的发泡剂与异氰酸酯可互溶且加入A组分后不会造成A组分黏度上升和聚醋酸乙烯酯析出,则将发泡剂加入(或相对较多地加入)未加发泡剂时黏度相对较高的组分中,使加入发泡剂后A组分和B组分黏度尽可能相近。
与现有技术相比,本申请具有如下技术效果:
(1)本申请通过A组分和B组分混合后聚醋酸乙烯酯析出的物理变化使浆液黏度上升从而提高浆液的抗水分散性能,与传统的直接在A组分或B组分中加入增黏剂、填料、树脂使A组分或B组分黏度增大的抗水分散型聚氨酯注浆止水加固材料相比,本申请抗水分散型聚氨酯硬质泡沫注浆止水加固材料的A组分和B组分黏度更小,仅在A组分和B组分接触后混合物黏度才开始增大,因此使用注浆泵进行注浆的过程中,能耗更小,且A组分和B组分更易混匀;与传统的增大催化剂用量,加速凝胶反应,使浆液黏度迅速增大的抗水分散型聚氨酯注浆止水加固材料相比,本申请抗水分散型聚氨酯硬质泡沫注浆止水加固材料的聚醋酸乙烯酯析出的物理变化更温和可控,无明显放热,不会造成浆液固化过快和浆液过热,保证充足的注浆操作时间以及施工安全性。
(2)本申请抗水分散型聚氨酯硬质泡沫注浆止水加固材料具有良好的抗水分散性,在流动的水体中不易被水冲散,且强度高,纯泡沫抗压强度不小于2MPa,耐久性好,固化时间可调,价格低廉,适用于封堵涌水和射流,具有良好的经济性、安全性和环保性。
(3)本申请通过各原料的物理与化学协同作用,保证浆液在水中注浆过程中的抗水分散性和水不敏感性,进而起到止水与加固的作用,可应用于隧道突涌水的封堵工程。
具体实施方式
以下将对本申请的构思、具体结构及产生的技术效果作进一步说明,以充分地了解本申请的目的、特征和效果。
以下实施例中所用的原料如无特别说明均为市售工业级的化工原料。
以下实施例中的数据采用如下情况获得:参照国家标准GB/T 1041-2008《塑料压缩性能的测定》测试聚氨酯泡沫的泡沫体抗压强度;聚氨酯浆液的抗水分散性按如下方法评价:在200mL透明塑料杯中注入100mL水,将约20g搅拌均匀的聚氨酯浆液缓慢连续地倒入杯中,观察浆液的分散和水体浑浊情况,若浆液倒入水中时水清澈,且浆液在水中发泡后水较清澈,泡沫体与无水环境中制得的泡沫体无异,泡沫结构均匀,泡沫体完整且表面光滑饱满,则可视为该浆液具有良好的抗水分散性。
实施例1
本实施例抗水分散型聚氨酯硬质泡沫注浆止水加固材料,按如下方法进行制备:
称取7g碳酸丙烯酯,在其中加入7g聚醋酸乙烯酯并静置48h,得到聚醋酸乙烯酯溶液,将配置好的聚醋酸乙烯酯溶液加热到60℃,边搅拌边倒入到230g预热到40℃的多亚甲基多苯基多异氰酸酯PM200中,以1800r/min的转速搅拌120s,得到A组分;
称取46g聚醚多元醇4110P,在其中加入9g聚醚多元醇HKOL-403A、45g聚酯多元醇P455N、20g癸二酸二辛酯、27g二丙二醇、2g泡沫稳定剂BL-8468、1.5g催化剂A33;以1200r/min的转速搅拌60s,再向其中加入10g一氟二氯乙烷,继续以1200r/min的转速搅拌60s,得到B组分;
将配好的A组分倒入B组分中,以1800r/min的转速搅拌20s,得到抗水分散型聚氨酯硬质泡沫注浆止水加固材料。
对本实施例抗水分散型聚氨酯硬质泡沫注浆止水加固材料的抗压强度和抗水分散性进行了测试,具体测试数据见下文表1所示。
实施例2
本实施例抗水分散型聚氨酯硬质泡沫注浆止水加固材料,按如下方法进行制备:
称取4g碳酸丙烯酯,在其中加入4g碳酸乙烯酯、8g聚醋酸乙烯酯,加热到90℃并用玻璃棒搅拌至半透明均质粘稠液体,边搅拌边倒入到230g预热到40℃的多亚甲基多苯基多异氰酸酯PM200中,以1800r/min的转速搅拌120s,得到A组分;
称取80g聚醚多元醇HK-1302,在其中加入20g聚醚多元醇4110G、25g癸二酸二辛酯、10g丙三醇、2g泡沫稳定剂BL-8468、1g催化剂A33;以1200r/min的转速搅拌60s,再向其中加入10g一氟二氯乙烷,继续以1200r/min的转速搅拌60s,得到B组分;
将配好的A组分倒入B组分中,以1800r/min的转速搅拌20s,得到抗水分散型聚氨酯硬质泡沫注浆止水加固材料。
对本实施例抗水分散型聚氨酯硬质泡沫注浆止水加固材料的抗压强度和抗水分散性进行了测试,具体测试数据见下文表1所示。
实施例3
本实施例抗水分散型聚氨酯硬质泡沫注浆止水加固材料,按如下方法进行制备:
称取5g碳酸丙烯酯,在其中加入7g聚醋酸乙烯酯,加热到70℃并用玻璃棒搅拌至半透明均质粘稠液体,边搅拌边倒入到220g预热到40℃的多亚甲基多苯基多异氰酸酯PM200中,以1800r/min的转速搅拌120s,得到A组分;
称取60g聚酯多元醇P455N,在其中加入40g聚醚多元醇4110G、20g对苯二甲酸二辛酯、21.5g新戊二醇、2g泡沫稳定剂BL-8468、1g催化剂A33;以1200r/min的转速搅拌60s,再向其中加入10g一氟二氯乙烷,继续以1200r/min的转速搅拌60s,得到B组分;
将配好的A组分倒入B组分中,以1800r/min的转速搅拌20s,得到抗水分散型聚氨酯硬质泡沫注浆止水加固材料。
对本实施例抗水分散型聚氨酯硬质泡沫注浆止水加固材料的抗压强度和抗水分散性进行了测试,具体测试数据见下文表1所示。
实施例4
本实施例抗水分散型聚氨酯硬质泡沫注浆止水加固材料,按如下方法进行制备:
称取10g碳酸丙烯酯,在其中加入14g聚醋酸乙烯酯,加热到70℃并用玻璃棒搅拌至半透明均质粘稠液体,边搅拌边倒入到210g预热到40℃的多亚甲基多苯基多异氰酸酯PM200中,以1800r/min的转速搅拌120s,再向其中加入10g一氟二氯乙烷,继续以1200r/min的转速搅拌60s,得到A组分;
称取46g聚醚多元醇4110P,在其中加入9g聚醚多元醇HKOL-403A、45g聚酯多元醇P455N、25g对苯二甲酸二辛酯、11g丙二醇、2g泡沫稳定剂BL-8468、1.5g催化剂A33;以1200r/min的转速搅拌120s,得到B组分;
将配好的A组分倒入B组分中,以1800r/min的转速搅拌20s,得到抗水分散型聚氨酯硬质泡沫注浆止水加固材料。
对本实施例抗水分散型聚氨酯硬质泡沫注浆止水加固材料的抗压强度和抗水分散性进行了测试,具体测试数据见下文表1所示。
表1:不同实施例抗水分散型聚氨酯硬质泡沫注浆止水加固材料的抗压强度和抗水分散性测试结果
由上述表1可见,本申请抗水分散型聚氨酯硬质泡沫注浆止水加固材料具有抗水分散性好、抗压强度高的特点,纯泡沫抗压强度不小于2MPa,因此能发挥较好的止水加固效果,适用于封堵涌水和射流,具有良好的经济性、安全性和环保性。
本申请中的A组分中含有聚醋酸乙烯酯,B组分中含有酯类增塑剂,当A组分和B组分混合时,酯类增塑剂使聚醋酸乙烯酯部分析出,使混合物的黏度迅速增大,进而提高浆液的抗水分散性能。
本申请通过A组分和B组分混合后聚醋酸乙烯酯析出的物理变化使浆液黏度上升从而提高浆液的抗水分散性能,与传统的直接在A组分或B组分中加入增黏剂、填料、树脂使A组分或B组分黏度增大的抗水分散型聚氨酯注浆止水加固材料相比,本申请抗水分散型聚氨酯硬质泡沫注浆止水加固材料的A组分和B组分黏度更小,仅在A组分和B组分接触后混合物黏度才开始增大,因此使用注浆泵进行注浆的过程中,能耗更小,且A组分和B组分更易混匀;与传统的增大催化剂用量,加速凝胶反应,使浆液黏度迅速增大的抗水分散型聚氨酯注浆止水加固材料相比,本申请抗水分散型聚氨酯硬质泡沫注浆止水加固材料的聚醋酸乙烯酯析出的物理变化更温和可控,无明显放热,不会造成浆液固化过快和浆液过热,保证充足的注浆操作时间以及施工安全性。本申请抗水分散型聚氨酯硬质泡沫注浆止水加固材料具有良好的抗水分散性,在流动的水体中不易被水冲散,且强度高,纯泡沫抗压强度不小于2MPa,耐久性好,固化时间可调,价格低廉,适用于封堵涌水和射流,具有良好的经济性、安全性和环保性。本申请通过各原料的物理与化学协同作用,保证浆液在水中注浆过程中的抗水分散性和水不敏感性,进而起到止水与加固的作用,可应用于隧道突涌水的封堵工程。
以上实施例仅用以说明本申请的技术方案而非限定,参照较佳实施例对本申请进行了详细说明。本领域的普通技术人员应当理解,可以对本申请的技术方案进行修改或等同替换,而不脱离本申请技术方案的精神和范围,均应涵盖在本申请的权利要求范围内。
Claims (6)
1.抗水分散型聚氨酯硬质泡沫注浆止水加固材料,其特征在于,包括A组分和B组分,其中,所述A组分的组成及其重量份数如下:异氰酸酯:210~230重量份数,
聚醋酸乙烯酯7~14重量份数,
溶剂:4~10重量份数,
发泡剂:0~10重量份数,
所述B组分的组成及其重量份数如下:
聚合物多元醇:100重量份数,
增塑剂:20~25重量份数,
扩链剂:10~27重量份数,
发泡剂:0~10重量份数,
泡沫稳定剂:1~2重量份数,
催化剂:1~1.5重量份数;
所述A组分与所述B组分的质量比为1:1~2.5:1;
所述异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、碳化二亚胺改性MDI、多亚甲基多苯基异氰酸酯、二环己基甲烷二异氰酸酯或六亚甲基二异氰酸酯中的一种或多种的任意比例混合物,其中,NCO含量为25%-50%,平均官能度为2.4~3.0,25℃下的粘度<500mpa·s,熔点<20℃;
所述聚合物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、超支化多元醇、生物基多元醇等中的一种或多种的任意比例混合物;多元醇的平均官能度为3~8,平均分子量为400-4000,羟值为400~850mg KOH/g;
所述扩链剂为小分子多元醇类化合物,为乙二醇、一缩二乙二醇、1,2-丙二醇、一缩二丙二醇、1,4-丁二醇、新戊二醇、1,6-己二醇、丙三醇和三羟甲基丙烷中的一种或多种的任意比例混合物;
制备所述A组分时,先将7~14重量份数的聚醋酸乙烯酯溶解于4~10重量份数的溶剂,再与210~230重量份数的异氰酸酯混合搅拌均匀,最后加入0~10重量份的发泡剂,混合后搅拌至混合物成为均匀透明液体,得到A组分;
制备所述B组分时,向混合器中加入100重量份的聚合物多元醇、20~25重量份数的增塑剂、10~27重量份数的扩链剂、1~2重量份数的泡沫稳定剂和1~1.5重量份数的催化剂并混合搅拌均匀,再加入0~10重量份的发泡剂,混合后搅拌至混合物成为均匀透明液体,得到B组分;
使用时,将所述组分A和组分B按比例混合后搅拌均匀,即可获得所述的抗水分散型聚氨酯硬质泡沫注浆止水加固材料。
2.根据权利要求1所述的抗水分散型聚氨酯硬质泡沫注浆止水加固材料,其特征在于,所述溶剂为环状酯类化合物,为γ-丁内酯、γ-戊内酯、ε-己内酯、碳酸乙烯酯、碳酸丙烯酯中的一种或多种的任意比例混合物,熔点<20℃。
3.根据权利要求1或2所述的抗水分散型聚氨酯硬质泡沫注浆止水加固材料,其特征在于,所述发泡剂为臭氧消耗潜值与全球变暖潜能值均较小的含氢氯氟烃类化合物和戊烷类化合物,为1-氯-1,1-二氟乙烷、1-氟-1,1-二氯乙烷、1-氯-3,3,3-三氟丙烯、正戊烷、异戊烷和环戊烷等中的一种或多种的任意比例混合物。
4.根据权利要求1所述的抗水分散型聚氨酯硬质泡沫注浆止水加固材料,其特征在于,所述增塑剂为酯类化合物,为己二酸二辛酯、癸二酸二辛酯、邻苯二甲酸二辛酯、对苯二甲酸二辛酯、邻苯二甲酸二癸酯、偏苯三酸三辛酯、十三烷醇偏苯三酸酯、乙酰基柠檬酸三丁酯和2,2,4-三甲基-1-3-戊二醇二异丁酸酯中的一种或多种的任意比例混合物。
5.根据权利要求1或2或4所述的抗水分散型聚氨酯硬质泡沫注浆止水加固材料,其特征在于,所述泡沫稳定剂为有机硅类表面活性剂。
6.根据权利要求1或2或4所述的抗水分散型聚氨酯硬质泡沫注浆止水加固材料,其特征在于,所述催化剂为叔胺类化合物,为:N,N-二甲基环己胺、三乙烯二胺、六亚甲基四胺、五甲基二乙烯三胺、四甲基乙二胺、N,N-二甲基苄胺中的一种或多种的任意比例混合物。
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