CN108587029B - 一种相变材料液及其所形成的固相支撑剂 - Google Patents
一种相变材料液及其所形成的固相支撑剂 Download PDFInfo
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Abstract
本发明提供了一种相变材料液及其所形成的固相支撑剂。其中,以质量百分比计,制备该相变材料液的组分包括:超分子构筑单元10‑60wt%、超分子功能单元20‑50wt%、分散剂0.1‑2wt%、无机助构剂0.1‑1wt%、引发剂0.1‑1wt%,其余为溶剂;超分子构筑单元包括三聚氰胺类物质和/或三嗪类物质;超分子功能单元包括双环戊二烯树脂;分散剂包括带羟基的多糖类物质和表面活性剂。该相变材料液进入储层后在超分子化学、物理的作用下,可以形成固相物质支撑裂缝。由于无固相的注入,因此,可有效地降低管柱摩阻,对施工设备、地面管线及井口和施工管柱要求降低,有效降低施工成本,同时降低施工风险及安全隐患。
Description
技术领域
本发明属于油藏开发技术领域,具体涉及一种相变材料液及其所形成的固相支撑剂。
背景技术
水力压裂技术作为油气井增产、水井增注的主要措施已广泛应用在油气田的开发中,为油气田的稳产、稳注做出了重要贡献。水力压裂是通过对目的储层泵注高粘度的前置液,以高压形成裂缝并延展,而后泵注混有支撑剂的携砂液,携砂液可继续延展裂缝,同时携带支撑剂深入裂缝,最好使压裂液破胶降解为低粘度流体流向井底返排而出,在地层中留下一条由支撑剂支撑裂缝壁面所形成的高导流能力的流动通道,以利于油气从远井地层流向井底。
然而从水力压裂技术及其发展上看,目前所有压裂技术都是基于液体压裂液压开裂缝后注入固体支撑剂至水力裂缝后,支撑裂缝保持裂缝张开,从而获得高导流能力的流体通道。2010年斯伦贝谢提出的HIWAY高速通道流动的裂缝导流能力不受支撑剂渗透性的影响,该技术与常规压裂技术相比,同样需要向地层注入固相支撑剂,且工艺实施复杂。
水力压裂的目的在于将汇集于井筒的径向流变成与井筒相连通的导流裂缝中的线性流,裂缝中的导流能力必须远远大于地层中的导流能力,要获得高渗透率的裂缝,必须加入支撑剂,支撑剂的作用在于支撑裂缝的两壁,以使停止泵注后,井底压力下降到小于闭合压力,而通向油气井眼的导流裂缝依然保持张开。水力压裂20世纪40年代末开始以来,其支撑剂经历了半个多世纪的发展,所用支撑剂大致可分为天然的和人造的两大类,前者以石英砂为代表,后者主要为电解、烧结陶粒。石英砂的相对密度较低(2.65左右),便于施工泵送,石英强度低、易破碎。陶粒强度高、相对密度高(2.7-3.6),对压裂液的性能及泵送条件都提出更高要求。且在施工过程中,固相支撑剂的注入很容易造成脱砂、砂堵、注不进等,使得施工不能达到预期效果,甚至造成井筒砂堵。石油工作者为此一直致力于低密度高强度支撑剂的研究,目的都是为了使支撑剂容易注入。不管是低密度还是高密度支撑剂,都需要从井口向地层注入固相支撑剂,而常规加砂压裂施工过程中的固相支撑剂会出现注入难、难注入等问题。
常规的水力压裂施工容易造成固相支撑剂的注入脱砂、砂堵、注不进等,使得施工不能达到预期效果,甚至造成井筒砂堵。对于该问题,CN105971579公开了一种相变水力压裂工艺,该工艺是向压裂后的裂缝中注入可发生相变的材料液,材料液在地层温度下发生相变(超分子自组装)后形成固相支撑剂,实现对裂缝壁面的支撑,从而在地层形成高导流能力的通道。该工艺虽然解决了常规水力压裂中固相支撑剂注入方面的一些主要问题,但是,自身也存在一些缺陷:一方面,相变得到的固相支撑剂(固相颗粒)韧性不足,容易发生破碎,堵塞固相颗粒间的间隙,影响支撑裂缝的导流能力。另一方面,相变材料液成型为固相支撑剂的反应速度较慢,需要较长的施工作业时间,而在此期间,一旦在裂缝闭合以前相变材料还没有相变成具有一定承压能力的支撑剂,那相变压裂工艺就会失败。
发明内容
为解决上述问题,本发明的目的在于提供一种相变材料液。
本发明的另一目的在于提供一种由上述相变材料液相变形成的固相支撑剂。
为达到上述目的,本发明提供了一种相变材料液,其中,以质量百分比计,制备该相变材料液的组分包括:超分子构筑单元10-60wt%、超分子功能单元20-50wt%、分散剂0.1-2wt%、无机助构剂0.1-1wt%、引发剂0.1-1wt%,其余为溶剂;
所述超分子构筑单元包括三聚氰胺类物质和/或三嗪类物质;
所述超分子功能单元包括双环戊二烯树脂;
所述分散剂包括带羟基的多糖类物质和表面活性剂。
本发明提供的相变材料液可以在地面上配制,其粘度低流动性好,容易注入地层。当该相变材料液进入储层后,在地层温度下(一般为60-120℃)反应一段时间后,流体中的各组分可以自组装(超分子材料的熵驱动有序理论)成具有一定强度和韧性的固相支撑剂,实现对裂缝的支撑。相比于现有的相变支撑剂,本发明提供的方案在超分子自组装的空间中引入高分子聚合反应,使物理、化学交联协同作用,从而可提高产品的韧性,并缩短材料液成型为固相支撑剂的时间。
对于该相变材料液的制备,其并无特殊要求,将各组分加入溶剂后搅拌均匀即可。另外,在制备上述相变材料液时,本领域技术人员可以根据需要添加一些超分子自组装反应中的常规助剂。
在进行压裂施工时,常规方式是使该相变材料液在压裂液压开裂缝后注入,但本发明中相变材料液的使用不限于这种具体方式。另外,注入该相变材料液时,既可以单独注入,也可以通过常规流体(非相变流体即可)携带注入。一般情况下,大多数不与相变材料液发生反应的流体都可以作为携带流体,可选自常规的压裂液、海水、地层水或地面水。
在上述相变材料液中,优选地,以质量百分比计,制备该相变材料液的组分包括:超分子构筑单元30-40wt%、超分子功能单元20-30wt%、分散剂0.5-1wt%、无机助构剂0.5-1wt%、引发剂0.5-1wt%,其余为溶剂。
在上述相变材料液中,超分子构筑单元是超分子自组装的基础材料,本领域技术人员可以在三聚氰胺类物质和三嗪类物质这两类常用基础组装材料中选择合适的化合物。
在本发明提供的优选实施方式中,三聚氰胺类物质可以选自三聚氰胺、烯基取代的三聚氰胺或三聚氰胺的酯化物;三嗪类物质可以选自三嗪或烯基取代的三嗪。相较于三聚氰胺或三嗪,取代或酯化后的物质不仅溶解度可调;而且,取代或酯化后增加了物理、化学的交联点,可以使体系更稳定,自组装速度更快,生成的固相材料不仅具有高强度、同时具有更好的韧性。上述烯基取代的三聚氰胺、烯基取代的三嗪指的都是对胺基上的氢元素进行取代后的物质。
在本发明提供的优选实施方式中,烯基取代的三聚氰胺可以为丙烯基取代三聚氰胺;三聚氰胺的酯化物可以为1,3,5-三聚氰酸三烯丙基酯。进一步地,优选为使用取代度为2-3丙烯基取代三聚氰胺。
在本发明提供的优选实施方式中,烯基取代的三嗪可以为丙烯基取代三嗪;例如,2,4-二氨基-6-二烯丙氨基-1,3,5-三嗪。进一步地,优选为使用取代度为2-3的丙烯基取代三嗪。
另外,对于烯基取代的三嗪和烯基取代的三聚氰胺,可以按照本领域的常规方法制备。在本发明提供的一具体实施方式中,制备烯基取代的三嗪的方法为:(1)将三聚氯氰溶解于溶剂(如,甲苯)中,然后在低温条件下向其中滴加烯醇,滴加完毕后升温反应一段时间;反应结束后经冷却、过滤,收集沉淀物。(2)将沉淀物加入含有无机强碱(如,NaOH)的有机溶剂(如,二氯甲烷)中,加热反应一段时间,反应结束后过滤,收集滤液。(3)蒸除滤液中的溶剂,然后对固体进行洗涤精制(如,使用二氯甲烷和甲苯的混合溶液),得到烯基取代的三嗪产品。在本发明提供的一具体实施方式中,制备烯基取代的三聚氰胺的方法为:(1)将三聚氰胺溶解于溶剂(如,N-甲基吡咯烷酮)中,加入弱碱(如,碳酸钾)以形成弱碱环境,然后在加热条件下向其中卤代烯烃,滴加完毕后继续反应一段时间;反应结束后经冷却、过滤,收集滤液。(2)将滤液浓缩后获得粗产物,粗产物进行洗涤精制后,获得烯基取代的三聚氰胺产品。
在上述相变材料液中,超分子功能单元使用了高分子材料双环戊二烯树脂,相比于现有技术中使用的小分子化合物,本方案在超分子自组装的空间中引入高分子聚合反应,使物理、化学交联协同作用可提高产品的韧性以及缩短形成材料的时间。
在上述相变材料液中,超分子构筑单元中还可以包括构筑助剂;优选地,构筑助剂包括1,4-丁二醇二丙烯酸酯、N,N-亚甲基双丙烯酰胺和三烯丙基异氰脲酸酯中的一种或几种的组合。
在上述相变材料液中,所使用的分散剂为带羟基的多糖类物质和表面活性剂的混合分散体系。在体系中使用带羟基的多糖类物质,不仅可通过这些高分子材料本身的高粘性实现分散,而且分子中的羟基可协助超分子自组装,加速分子的自组装从而缩短成型时间。另外,对于两种分散剂的使用比例,本领域技术人员可根据需要进行确定;在本发明的具体实施方式中,带羟基的多糖类物质和表面活性剂的重量比例为(0.1-10):1。在本发明提供的优选实施方式中,带羟基的多糖类物质包括羟丙基甲基纤维素、聚乙烯醇、羟甲基纤维素、乙基纤维素和蔗糖脂肪酸酯中的一种或几种的组合。
在上述相变材料液中,表面活性剂的作用是协助体系中无机与有机物的稳定与分散。本领域技术人员可以根据所使用的具体无机物和有机物进行合适的选取。在本发明提供的优选实施方式中,选用阴离子表面活性剂或非离子表面活性剂。进一步地,阴离子表面活性剂可以选自烷基硫酸类表面活性剂、烷基磺酸类表面活剂或烷基苯磺酸类表面活性剂;更进一步优选地,烷基硫酸类表面活性剂具体可以为十二烷基硫酸钠,烷基磺酸类表面活剂具体可以为十二烷基磺酸钠,烷基苯磺酸类表面活性剂具体可以为十二烷基苯磺酸钠。进一步地,非离子表面活性剂可以选自聚醚类表面活性剂;更进一步地,聚醚类表面活性剂可以选自聚氧乙烯醚型表面活性剂;具体可以为辛基酚聚氧乙烯醚或壬基酚聚氧乙烯醚。
在上述相变材料液中,无机助构剂用于形成无机凝胶,在超分子构筑中起着中间作用,可以选用本领域中常用的无机助构剂。在本发明提供的优选实施方式中,无机助构剂可以为碳酸氢钠,或可以为磷酸和氯化钙的组合物。
在上述相变材料液中,引发剂的作用是引发聚合反应,可以根据反应物选择合适的引发剂。在本发明提供的优选实施方式中,选用过氧化物引发剂;具体地,可以为过氧化二苯甲酰、过氧化十二酰、异丙苯过氧化氢、叔丁基过氧化氢、过氧化二异丙苯、过氧化二叔丁基、过氧化苯甲酸叔丁酯、过氧化叔戊酸叔丁酯、过氧化二碳酸二异丙酯、过氧化二碳酸二环己酯和过氧化二碳酸二乙基己酯中的一种或几种的组合。
在上述相变材料液中,溶剂的作用是协助溶解有机物,可以根据所确定的组分选用合适的溶剂。在本发明提供的优选实施方式中,选用苯类溶剂;具体地,可以为苯乙烯、二乙烯基苯、二甲苯和甲苯中的一种或几种的组合。
在上述相变材料液中,制备组分还包括造孔剂。造孔剂的使用是本申请的另一重要改进。CN105971579公开的方案中,材料液相变后形成的是一种不带孔固相支撑材料,在施工过程中,相变后形成的固相支撑材料本身不具备导流能力,要使压裂裂缝闭合后具有导流能力必须是支撑剂相互之间有间隔,也就是必须形成渠道式支撑。在相变压裂施工过程中,是将相变流体与非相变流体同时注入储层,使非相变流体走过后空出流体通道,形成裂缝导流能力。但在施工过程中可能会出现相变流体在某些局部位置聚集然后发生变相,比如一些天然分支裂缝通道或者天然溶洞压开通道,如果这种情况发生,相变后的固相支撑剂就很有可能造成局部堵塞。为了克服上述缺陷,更有效的提高压后渗透率、裂缝导流能力,避免相变压裂液聚集引起的相变后局部不流通。本方案中,包含造孔剂的相变材料液在地层发生相态变化后,可形成自身带孔的固体支撑材料,即使发生相变压裂液局部聚集,储层流体也能通过自生孔使流体流动通过,能有效的实现压裂裂缝的高导流能力,更进一步提高相变压裂的作业效果。
在上述相变材料液中,造孔剂的用量一般为0.2-5wt%。对于造孔剂的类型,既可以使用加热生气造孔型试剂,也可以使用热熔排出造孔型试剂,或者二者组合使用。在本发明提供的优选实施方式中,加热生气造孔型试剂为偶氮二异丁腈和/或碳酸氢铵;热熔排出造孔型试剂为固体石蜡、十二醇和庚烷中的一种或两种。
本发明还提供了一种固相支撑剂,该固相支撑剂是上述相变材料液相变后形成的固相产物。
本发明提供的方案具有以下有益效果:
(1)与常规水力压裂相比,本发明方案不用向地层中注入固相支撑剂,而是向压出裂缝的地层注入相变材料液,该相变材料液在地面以及注入过程中是可流动的液相,进入储层后在超分子化学、物理的作用下,相变材料液形成固相物质支撑裂缝。由于无固相的注入,因此可有效地降低管柱摩阻,对施工设备、地面管线及井口和施工管柱要求降低,有效降低施工成本,同时降低施工风险及安全隐患。
(2)与现有技术中的相变支撑剂相比,本发明提供的方案不仅缩短了固相支撑剂的反应成型时间,而且所制得的固相支撑剂具有更好的韧性。
(3)与现有技术中的相变支撑剂相比,本发明提供的自生孔方案可以生成自带孔固相支撑剂,该支撑剂本身具有流体导流能力,即使相变流体在某些局部位置聚集变相也能通过自生孔使流体流动通过,可有效的提高压后裂缝的导流能力。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解,现对本发明的技术方案进行以下详细说明,但不能理解为对本发明的可实施范围的限定。
实施例1
本实施例提供了一类以三聚氰胺类物质作为超分子构筑单元的相变材料液以及固相支撑剂。
两种相变材料液HPP1和HPP2的制备过程分别如下:
HPP1:先取二甲苯50g,然后加入三聚氰胺40g,双环戊二烯树脂30g,羟丙基甲基纤维素0.5g,十二烷基硫酸钠0.5g,磷酸0.5g,氯化钙0.5g,过氧化二苯甲酰1g。全部置于烧瓶中,在室温下搅拌均匀即完成相变材料液HPP1的制备。
HPP2:先取二甲苯50g,然后加入2,4-二氨基-6-二烯丙氨基-1,3,5-三嗪40g,双环戊二烯树脂30g,羟丙基甲基纤维素0.5g,十二烷基硫酸钠0.5g,磷酸0.5g,氯化钙0.5g,过氧化二苯甲酰1g。全部置于烧瓶中,在室温下搅拌均匀即完成相变材料液HPP2的制备。
固相支撑剂的制备过程如下:
将制得的相变材料液放置于恒温油浴锅中,HPP1升温至90℃反应1小时,出现了珠状、块状固相物,即固相支撑剂,记为H1。HPP2升温至90℃反应0.7小时,出现了珠状、块状固相物,即固相支撑剂,记为H2。可见,上述两种相变材料液都可以实现了从液相到固相的转变,因此,可用于转相压裂。
对上述固相支撑剂H1和H2进行性能测试,测试数据见表1。
表1固相支撑剂的性能测试数据
对比HPP1、HPP2,使用烯丙基取代后的三聚氰胺比三聚氰胺缩短了材料液成型为固相支撑剂的时间。在相同承压下H2的破碎率低于H1,说明H2比H1具有更好的韧性。
实施例2
本实施例提供了一类包含造孔剂的相变材料液以及固相支撑剂。
三种相变材料液HPP3、HPP4、HPP5的制备过程分别如下:
HPP3:先取二甲苯50g,然后依次加入丙烯基取代三嗪40g,双环戊二烯树脂30g,聚乙烯醇0.7g,十二烷基磺酸钠0.3g,磷酸0.5g,氯化钙0.5g,过氧化二苯甲酰1g,碳酸氢铵5g。全部置于烧瓶中,在室温下搅拌均匀即完成地下相变材料液HPP3的制备。
HPP4:先取二甲苯50g,然后依次加入丙烯基取代三聚氰胺40g,双环戊二烯树脂30g,羟丙基甲基纤维素0.5g,十二烷基磺酸钠0.5g,碳酸氢钠1g,过氧化二叔丁基1g,固体石蜡5g。全部置于烧瓶中,在室温下搅拌均匀即完成地下相变材料液HPP4的制备。
HPP5:先取二甲苯50g,然后依次加入三聚氰胺40g,双环戊二烯树脂30g,聚乙烯醇0.5g,壬基酚聚氧乙烯醚0.5g,碳酸氢钠1g,过氧化二苯甲酰1g,十二醇5g。全部置于烧瓶中,在室温下搅拌均匀即完成地下相变材料液HPP5的制备。
固相支撑剂的制备过程如下:
将制得的相变材料液放置于恒温油浴锅中,HPP3升温至100℃反应0.5小时,出现了珠状、块状固相物,即固相支撑剂,记为H3。HPP4升温至100℃反应0.5小时,出现了珠状、块状固相物,即固相支撑剂,记为H4。HPP5升温至100℃反应0.7小时,出现了珠状、块状固相物,即固相支撑剂,记为H5。可见,上述三种相变材料液都可以实现了从液相到固相的转变,因此,可用于转相压裂。
其中,本实施例中所使用的丙烯基取代三嗪具体是通过以下步骤制备的:
在一个250mL的三口烧瓶内,加入4.6g(25mmol)三聚氯氰,用15mL甲苯溶解;冷却到0℃,然后在1-3h内滴加2.9-5.1g(50mmol-87.5mmol)丙烯醇。然后逐渐加热到80℃继续反应2h。冷却到室温,过滤,收集沉淀。加入3.0g NaOH和150mL二氯甲烷,加热至NaOH完全溶解,再回流30min。过滤,收集滤液。蒸干溶剂,将粗产物用二氯甲烷/甲苯(1:5,V/V)混合溶液洗涤,得到取代度为2-3的丙烯基取代三嗪。
本实施例中所使用的丙烯基取代三聚氰胺具体是通过以下步骤制备的:
在一个250mL的三口烧瓶内,加入3.2g(25mmol)三聚氰胺,用30mL N-甲基吡咯烷酮溶解;然后加入6.9-12.1g(50mmol-87.5mmol)碳酸钾,加热到60℃;在1-3h内滴加6.0-10.6g(50mmol-87.5mmol)溴丙烯。然后逐渐加热到70℃继续反应2h。冷却到室温,过滤,收集滤液。浓缩溶剂,将粗产物用乙醚/甲醇(3:1,V/V)混合溶液洗涤,得到取代度为2-3的丙烯基取代三聚氰胺。
对上述固相支撑剂H3、H4、H5进行性能测试,测试数据见表2。
表2固相支撑剂的性能测试数据
对比HPP3、HPP4、HPP5,使用烯丙基取代后的三聚氰胺比三聚氰胺缩短了材料液成型为固相支撑剂的时间。由于固相支撑剂H3、H4、H5为带孔结构,因此,其体密度明显小于H1和H2。在相同承压下H2的破碎率低于H1,说明H2比H1具有更好的韧性。
将实施例1制得的固相支撑剂H1、H2以及本实施例制得的H3、H4、H5进行渗透率测试。具体过程为:
将固相支撑剂H1、H2、H3、H4、H5筛选出40-60目的固相颗粒,将筛选出的固相颗粒用岩心机在10MPa下压制成长8cm、直径2.54cm的小岩心。将小岩心置于岩心流动实验装置测其气测渗透率。测试结果为:KH1=483mD、KH2=426mD、KH3=617mD、KH4=633mD、KH5=675mD。通过五个样品的测试数据可知,气孔的产生可大大提高固相支撑剂的渗透率。
实施例3
本实施例提供了一类以三聚氰胺类物质作为超分子构筑单元的相变材料液以及固相支撑剂。
两种相变材料液HPP1和HPP2的制备过程分别如下:
HPP6:先取二甲苯45g,然后加入三聚氰胺12g,双环戊二烯树脂60g,羟丙基甲基纤维素0.5g,十二烷基硫酸钠0.5g,磷酸0.5g,氯化钙0.5g,过氧化二苯甲酰1g。全部置于烧瓶中,在室温下搅拌均匀即完成相变材料液HPP6的制备。
HPP7:先取二甲苯20g,然后加入三聚氰胺60g,双环戊二烯树脂20g,羟丙基甲基纤维素0.5g,十二烷基硫酸钠0.5g,磷酸0.5g,氯化钙0.5g,过氧化二苯甲酰1g。全部置于烧瓶中,在室温下搅拌均匀即完成相变材料液HPP7的制备。
固相支撑剂的制备过程如下:
将制得的相变材料液放置于恒温油浴锅中,HPP6升温至90℃反应1.5小时,出现了珠状、块状固相物,即固相支撑剂,记为H6。HPP7升温至90℃反应0.6小时,出现了珠状、块状固相物,即固相支撑剂,记为H7。可见,上述两种相变材料液都可以实现了从液相到固相的转变,因此,可用于转相压裂。
对上述固相支撑剂H6和H7进行性能测试,测试数据见表3。
表3固相支撑剂的性能测试数据
对比HPP6、HPP7,由于主要组成含量不同,成型时间有一定的差异,同时成型的固相支撑剂形状有差异。同时由于含量的不同,材料承压破碎有一些差异。
Claims (19)
1.一种相变材料液,其中,以质量百分比计,制备该相变材料液的组分包括:超分子构筑单元10-60wt%、超分子功能单元20-50wt%、分散剂0.1-2wt%、无机助构剂0.1-1wt%、引发剂0.1-1wt%、造孔剂0.2-5wt%,其余为溶剂;
所述超分子构筑单元包括三聚氰胺类物质和/或三嗪类物质;
所述超分子功能单元包括双环戊二烯树脂;
所述分散剂为羟丙基甲基纤维素、聚乙烯醇、羟甲基纤维素和蔗糖脂肪酸酯中的一种或几种的组合与表面活性剂以(0.1~10):1的质量比复配而得;
所述造孔剂包括加热生气造孔型试剂和/或热熔排出造孔型试剂;
所述加热生气造孔型试剂包括偶氮二异丁腈或碳酸氢铵;所述热熔排出造孔型试剂包括固体石蜡、十二醇和庚烷中的一种或几种的组合。
2.根据权利要求1所述的相变材料液,其中,以质量百分比计,制备该相变材料液的组分包括:超分子构筑单元30-40wt%、超分子功能单元20-30wt%、分散剂0.5-1wt%、无机助构剂0.5-1wt%、引发剂0.5-1wt%、造孔剂0.2-5wt%,其余为溶剂。
3.根据权利要求1所述的相变材料液,其中,所述三聚氰胺类物质包括三聚氰胺、烯丙基取代的三聚氰胺或三聚氰胺的酯化物。
4.根据权利要求3所述的相变材料液,其中,所述三聚氰胺的酯化物包括1,3,5-三聚氰酸三烯丙基酯。
5.根据权利要求3所述的相变材料液,其中,所述烯丙基取代的三聚氰胺的取代度为2-3。
6.根据权利要求1所述的相变材料液,其中,所述三嗪类物质包括三嗪或烯丙基取代的三嗪。
7.根据权利要求6所述的相变材料液,其中,所述烯丙基取代的三嗪的取代度为2-3。
8.根据权利要求1所述的相变材料液,其中,所述超分子构筑单元还包括构筑助剂;所述构筑助剂包括1,4-丁二醇二丙烯酸酯、N,N-亚甲基双丙烯酰胺和三烯丙基异氰脲酸酯中的一种或几种的组合。
9.根据权利要求1所述的相变材料液,其中,所述表面活性剂包括阴离子表面活性剂或非离子表面活性剂。
10.根据权利要求9所述的相变材料液,其中,所述阴离子表面活性剂包括烷基硫酸类表面活性剂、烷基磺酸类表面活剂或烷基苯磺酸类表面活性剂;
所述非离子表面活性剂包括聚醚类表面活性剂。
11.根据权利要求10所述的相变材料液,其中,所述烷基硫酸类表面活性剂包括十二烷基硫酸钠,所述烷基磺酸类表面活剂包括十二烷基磺酸钠,所述烷基苯磺酸类表面活性剂包括十二烷基苯磺酸钠。
12.根据权利要求10所述的相变材料液,其中,所述聚醚类表面活性剂包括聚氧乙烯醚型表面活性剂。
13.根据权利要求12所述的相变材料液,其中,所述聚氧乙烯醚型表面活性剂为辛基酚聚氧乙烯醚或壬基酚聚氧乙烯醚。
14.根据权利要求1所述的相变材料液,其中,所述无机助构剂包括碳酸氢钠,或磷酸和氯化钙的组合物。
15.根据权利要求1所述的相变材料液,其中,所述引发剂包括过氧化物引发剂。
16.根据权利要求15所述的相变材料液,其中,所述过氧化物引发剂为过氧化二苯甲酰、过氧化十二酰、异丙苯过氧化氢、叔丁基过氧化氢、过氧化二异丙苯、过氧化二叔丁基、过氧化苯甲酸叔丁酯、过氧化叔戊酸叔丁酯、过氧化二碳酸二异丙酯、过氧化二碳酸二环己酯和过氧化二碳酸二乙基己酯中的一种或几种的组合。
17.根据权利要求1所述的相变材料液,其中,所述溶剂包括苯类溶剂。
18.根据权利要求17所述的相变材料液,其中,所述苯类溶剂为苯乙烯、二乙烯基苯、二甲苯和甲苯中的一种或几种的组合。
19.一种固相支撑剂,该固相支撑剂是权利要求1-18任一项所述的相变材料液相变后形成的固相产物。
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