CN111825367B - 一种用于超高性能混凝土的降粘剂及其制备方法 - Google Patents
一种用于超高性能混凝土的降粘剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种用于超高性能混凝土的降粘剂,以邻苯二甲酸酐、多元醇聚合物、磷酸化试剂为原料,催化剂反应制成;多元醇聚合物是聚乙二醇或聚丙二醇;磷酸化试剂为磷酸、五氧化二磷、多聚磷酸、磷酸钠中的一种;邻苯二甲酸酐、多元醇聚合物、磷酸化试剂的摩尔比为1:(1.1~1.5):(1.1~1.7)。降粘剂的制备方法是:步骤1,在四口烧瓶中加入多元醇聚合物,控制温度30℃~40℃,搅拌,加入邻苯二甲酸酐,再加入催化剂,搅拌反应1~2小时;步骤2,向步骤1中加入磷酸化试剂水溶液,控制温度50℃~60℃,搅拌反应2~3小时,冷却至室温,得到降粘剂。该降粘剂应用在水胶比为0.12~0.2的超高性能混凝土中,能显著降低混凝土粘度,改善混凝土工作性。
Description
技术领域
本发明涉及混凝土外加剂技术领域,特别是一种用于超高性能混凝土降粘剂及其制备方法。
背景技术
超高性能混凝土具有强度高、负荷能力大,节省资源、耐久性优异等特点。能满足建筑工程轻量化、高层化、大跨度和耐久性需求,是混凝土科技发展的重要方向之一。超高性能混凝土在组成上的特点之一是超低水胶比(0.20以下)。随着水胶比降低,混凝土拌合物粘度增大,引发不易搅拌、泵送困难等施工问题,很大程度上限制了其应用。如何降低混凝土粘度成为超高性能混凝土发展的关键问题。
目前降低混凝土粘度的主要方法有混凝土配合比设计、原料组成优化、降粘型外加剂的开发。其中降粘型外加剂掺量低,使用方法简单,国内外均有大量研究和应用。如日本触媒公司在专利CN100402457C中公开一种多羧酸聚合物作为混凝土降粘剂,该外加剂在降低混凝土粘度的同时还具有坍落度保持性能;D.Hamada等开发研究出的一种多支链结构的新型聚合物(NHBP型),通过引入两个亲阴离子作用单体,提高流变性能,降低粘度;王毅等人用马来酸酐(MAH),乙二醇单丁醚基丙烯酸-聚乙二醇单甲醚酯大单体(MPEGnMA)按照自由基共聚合的方法合成了成低收缩、降粘型聚羧酸系减水剂;仲以林等人在聚羧酸分子主链引入含憎水基团的甲基丙烯酸甲酯、烷基酚聚氧乙烯醚来调节分子结构的亲水亲油性,合成了具有降粘效果的聚羧酸减水剂。
然而他们的研究成果都适用于高中水胶比体系,对于低水胶比体系的研究(水胶比小于 0.28)仅有少量专利报道。专利ZL201810601948提到一种马来酸聚乙二醇酯与不饱和酸聚合得到降粘剂,该降粘剂可应用在0.28水胶比的混凝土中。专利ZL201410770317.3中提到利用金属盐的颗粒特性增强超低水胶比体系分散性能并降低浆体粘度,该专利中报道的应用例采用的混凝土水胶比为0.27。专利ZL201610331188.7中公开了一种以4-羟丁基乙烯基醚、不饱和酰胺以及不饱和磷酸酯为原料聚合而成短侧链降粘剂,该降粘剂与聚羧酸减水剂适应性良好,在较低掺量下即可降低混凝土粘度,且能改善混凝土和易性。该专利在应用例提到此降粘剂可应用在水胶比0.23的混凝土中,在更低的水胶比体系中是否能够应用未见报道。专利ZL201710887711.9中公开了一种以超细颗粒配置的高强混凝土降粘剂,该降粘剂可应用在最低0.21水胶比的混凝土中,降粘效果明显。以上报道的降粘剂的应用范围均是水胶比为 0.2-0.28之间,对于0.2及0.2以下的超低水胶比体系鲜见报道,而超高性能混凝土在配合比设计中,为了提高混凝土强度和耐久性,水胶比大部分均在0.2以下,因此,有必要研发一种适用于超高性能混凝土的降粘剂。
发明内容
本发明的目的是针对现有降粘剂难以适用于水胶比0.2及0.2以下的超高性能混凝土中缺陷,提供一种用于超高性能混凝土的降粘剂及其制备方法。该降粘剂可以超高性能混凝土中硅灰等超细粉料作为吸附载体,在低掺量下提升硅灰等掺合料的颗粒尺寸效应,增强其对水泥颗粒的分散能力,提升浆体中自由水的含量,从而降低粘度。
本发明提供的超高性能混凝土的降粘剂,由邻苯二甲酸酐、多元醇聚合物、磷酸化试剂为原料,在催化剂作用下,通过酯化反应合成。
其中,所述多元醇聚合物是聚乙二醇或聚丙二醇,重均分子量为200-4000g/mol。优选的,重均分子量是200g/mol,400g/mol,600g/mol,800g/mol,1000g/mol,2000g/mol,4000g/mol 中的任意一种。
所述磷酸化试剂为磷酸、五氧化二磷、多聚磷酸、磷酸钠中的一种。使用时,将磷酸化试剂配置成质量百分浓度20%~60%的磷酸化试剂水溶液。
邻苯二甲酸酐、多元醇聚合物、磷酸化试剂物质的量比为1:(1.1~1.5):(1.1~1.7)。所述催化剂为浓硫酸、对甲苯磺酸、柠檬酸、浓盐酸中的一种。催化剂用量占多元醇聚合物质量的0.1%~1%,优选的用量是0.2%~0.8%。
所述超高性能混凝土降粘剂的制备方法,步骤如下:
(1)在四口烧瓶中加入多元醇聚合物,升温至30℃~40℃,搅拌,再加入邻苯二甲酸酐,再加入催化剂,搅拌反应1小时-2小时。
(2)向步骤1中加入磷酸化试剂水溶液,升温至50℃~60℃,搅拌反应1小时-3小时,冷却至室温,得到降粘剂。该降粘剂是聚多元醇双苯甲酸酯和磷酸化聚多元醇单苯甲酸酯的混合物。
上述制备方法中涉及的化学反应过程依次如下(以聚乙二醇、磷酸为例):
式中,n为整数,取自6~40。优选的n取自6~10。制备的降粘剂是分子结构式Ⅰ所示的邻苯二酸酐聚乙二醇磷酸酯和式Ⅱ所示的聚乙二醇双酯的混合物:
如果多元醇聚合物采用聚丙二醇,制得的降粘剂依次类推。
与现有技术相比,本发明的有益之处在于:
(1)本发明利用高活性的具有一定刚性的苯酐与多元醇聚合物在催化剂作用下进行的酯化反应,得到聚多元醇单苯甲酸酯和聚多元醇双苯甲酸酯的混合物;其中的聚多元醇单苯甲酸酯再与具有强吸附作用的磷酸化试剂反应,制得具有一定分子量和结构刚性的聚合物,最终得到降粘剂。该降粘剂是聚多元醇双苯甲酸酯和磷酸化聚多元醇单苯甲酸酯的混合物。降粘剂中的两种聚合物都具有混凝土降粘的效果。该降粘剂具有羧基和磷酸基可吸附在硅灰表面,同时苯酐结构具有一定刚性。聚合物可通过选择多元醇聚合物分子量控制最终产物分子量,且结构中的苯环能增加分子刚性,当吸附在硅灰表面后增强硅灰自身的分散性能,结合颗粒尺寸效应,在超低水胶比体系中打破水泥颗粒的团聚结构,释放自由水,从而降低浆体粘度,适用于水胶比0.2及0.2以下的超高性能混凝土。通过发明人的研究发现,磷酸化的聚多元醇单苯甲酸酯的降粘效果大于聚多元醇双苯甲酸酯,即磷酸化的聚多元醇单苯甲酸酯起到主要降粘作用,聚多元醇双苯甲酸酯为辅。
(2)本发明制备的降粘剂对硅灰有一定的吸附作用,吸附了降粘剂的硅灰能更好的降低低水胶比体系中水泥颗粒间聚集趋势,增强水泥颗粒间的分散。
(3)本发明制备多元醇单酯过程中通过控制反应温度、反应物质的比例和加料顺序有效的控制了多元醇双酯含量,反应过程中无需分离提纯。
(4)本发明制备的降粘剂是基于超低水胶比体系设计,能明显降低超高性能混凝土粘度,改善其工作性能。
(5)本发明所涉及的原料便宜易得,合成过程简便,无需额外添加反应溶剂,无需分离提纯,环境友好,适合推广应用。
本发明的其它优点、目标和特征将部分通过下面的说明体现,部分还将通过对本发明的研究和实践而为本领域的技术人员所理解。
具体实施方式
以下对本发明的优选实施例进行说明,应当理解,此处所描述的优选实施例仅用于说明和解释本发明,并不用于限定本发明。
实施例1
在四口烧瓶中加入聚乙二醇500g(重均分子量200g/mol),升温到30℃,搅拌,再加入邻苯二甲酸酐185g,再加入0.1g浓硫酸,搅拌反应2小时,加入100g磷酸,50g水,升温至60℃,搅拌2小时得到红棕色液体即为降粘剂(固含94.0%)。反应终点以HPLC监测反应液中邻苯二甲酸酐含量小于5%且通过滴定法确定磷酸根含量小于6%,后续实施例同此法。(HPLC检测方法及滴定法测量磷酸根含量均为常规标准方法,在此不做复述)
实施例2
在四口烧瓶中加入聚丙二醇500g(重均分子量800g/mol),升温到40℃,搅拌,再加入邻苯二甲酸酐46g,再加入0.1g浓硫酸,搅拌反应1小时,加入磷酸水溶液(25g磷酸和20g水的混合物),升温至50℃,搅拌3小时得到红棕色液体即为降粘剂(固含96.6%)。
实施例3
在四口烧瓶中加入聚丙二醇500g(重均分子量2000g/mol),升温到40℃,搅拌,再加入邻苯二甲酸酐18.5g,再加入0.1g对甲苯磺酸,搅拌反应2小时,加入磷酸水溶液(10g多聚磷酸和10g水的混合物),升温至60℃,搅拌2小时得到红棕色液体即为降粘剂(固含98%)。
实施例4
在四口烧瓶中加入聚乙二醇500g(重均分子量800g/mol),升温到40℃,搅拌,再加入马来酸酐31g,再加入0.2g浓硫酸,搅拌反应1小时,加入25g五氧化二磷,20g水,升温至50℃,搅拌3小时得到红棕色液体即为降粘剂(固含96.1%)。
应用例
在实际应用中,测试实施例1-4的降粘剂的性能效果。混凝土粘度依据《自密实混凝土应用技术规程》CECS203-2006中规定的V型漏洞通过时间进行测量。其中通过时间越长,粘度越大。混凝土抗压强度按GBT50081-2002《普通混凝土力学性能试验标准》。表1是超高性能混凝土原料组成。减水剂采用西卡高减水型减水剂。表2是超高性能混凝土粘度与强度测试结果。
表1、超高性能混凝土原料组成(kg/m3)
测试样品 | 水泥 | 硅灰 | 粉煤灰 | 钢纤维 | 石英砂 | 水 | 减水剂 | 降粘剂 |
空白对比样 | 648 | 174 | 196 | 12.96 | 1018 | 203.6 | 10.2 | 0 |
实施例1 | 648 | 174 | 196 | 12.96 | 1018 | 203.6 | 10.2 | 0.8 |
实施例2 | 648 | 174 | 196 | 12.96 | 1018 | 203.6 | 10.2 | 0.8 |
实施例3 | 648 | 174 | 196 | 12.96 | 1018 | 203.6 | 10.2 | 0.8 |
实施例4 | 648 | 174 | 196 | 12.96 | 1018 | 203.6 | 10.2 | 0.8 |
表2、超高性能混凝土粘度与强度测试结果
从以上实施例来看,降粘剂对混凝土强度无副作用。多元醇聚合物分子量大小对降粘效果影响显著,分子量过大超细颗粒无法完全进入水泥颗粒空隙,且增加了浆体自身的粘度,因此降粘效果不明显;分子量过小对硅灰的分散效应减弱,当分子量为800时合成的降粘剂效果最佳;而相比马来酸酐,引入苯酐后提升了分子整体的刚性,增强了超细颗粒的分散性能,降粘效果也有一定提升,该降粘剂适用于水胶比0.2及0.2以下的超高性能混凝土。
综上所述,本发明以具有一定刚性的邻苯二甲酸酐与不同分子量二元醇聚合物再加上具有强吸附的磷酸反应制成降粘剂。该降粘剂具有羧基和磷酸基可吸附在硅灰表面,同时苯酐结构具有一定刚性,且可通过选用不同分子量的二元醇聚合物来调节聚合物链长。使用该降粘剂可以超高性能混凝土中硅灰等超细粉料作为吸附载体,在低掺量下提升硅灰等掺合料的颗粒尺寸效应,增强其对水泥颗粒的分散能力,提升浆体中自由水的含量,从而降低粘度。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施例揭露如上,然而并非用以限定本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内,当可利用上述揭示的技术内容作出些许更动或修饰为等同变化的等效实施例,但凡是未脱离本发明技术方案的内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (6)
2.如权利要求1所述的用于超高性能混凝土的降粘剂,其特征在于,使用时,将磷酸配制成质量百分浓度20%~60%的磷酸水溶液。
3.如权利要求1所述的用于超高性能混凝土的降粘剂,其特征在于,n取值6~10。
4.如权利要求1所述的用于超高性能混凝土的降粘剂,其特征在于,所述催化剂为浓硫酸、对甲苯磺酸、柠檬酸、浓盐酸中的一种,催化剂用量占多元醇聚合物质量的0.1%~1%。
5.如权利要求1所述的用于超高性能混凝土的降粘剂,其特征在于,该降粘剂用于水胶比为0.12~0.2的超高性能混凝土中,降粘剂掺量为混凝土胶凝材料质量的0.02%~0.1%。
6.一种如权利要求1-5任意一项所述的用于超高性能混凝土的降粘剂的制备方法,其特征在于,步骤以下:
步骤1:在四口烧瓶中加入聚乙二醇,控制温度30℃~40℃,搅拌,加入邻苯二甲酸酐,再加入催化剂,搅拌反应1~2小时;
步骤2:向步骤1中加入磷酸水溶液,控制温度50℃~60℃,搅拌反应2~3小时,冷却至室温,得到降粘剂。
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