CN116333231A - 一种超高分散型减水剂及其制备方法 - Google Patents
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Abstract
本发明涉及建筑材料外加剂技术领域,尤其是涉及一种超高分散型减水剂及其制备方法,通过采用具有长度相同或近似、侧链整齐的超支化大单体,配合常规聚醚大单体、不饱和酸和功能单体调整聚羧酸减水剂分子结构,平衡位阻效应和电荷分布,实现减水剂超高分散性的效果,并具有降低混凝土粘度的功效。
Description
技术领域
本发明涉及建筑材料外加剂技术领域,尤其是涉及一种超高分散型减水剂及其制备方法。
背景技术
近年来,随着混凝土市场对超高性能混凝土(UHPC)需求量的快速增长,其强度等级也逐渐提升,相应的水胶比越来越低。对于用量最多的C30~C50中等标号混凝土而言,亟需大幅度降低混凝土中的水泥用量,以达到降低碳排放的目的,与此同时需要大幅降低水胶比,从而提高混凝土的密实性以保证混凝土强度和耐久性不受影响。上述两种应用场景,都要求减水剂在低水胶比下能够快速分散浆体,且随着掺量的提高,可以达到更高的极限减水率。
聚羧酸减水剂作为新一代减水剂,可通过不饱和单体的调整实现聚羧酸减水剂聚合物的分子结构设计,近年来,超支化型聚羧酸减水剂由于可以发挥更大空间位阻效应备受关注,其中,现有技术CN112011050A公开一种超高性能减水剂的其制备方法,先以环氧丙烷/环氧丁烷、环氧乙烷、L-天门冬氨酸作为原料进行聚合反应合成侧链Ⅰ;再以二乙醇氨基羧酸、环氧乙烷、L-天门冬氨酸作为原料进行聚合反应合成侧链Ⅱ;最后将侧链Ⅰ、侧链Ⅱ、L-天门冬氨酸作为原料进行接枝聚合反应得到超高性能减水剂,然而,上述式Ⅱ左支两个O原子是等位的,由于二乙醇胺基羧酸间的自聚,可知其侧链结构可无限聚合,导致该减水剂生产条件严格,制备出的聚羧酸减水剂各支链之间的长度不易控制,阻碍空间位阻效应的发挥,并且,该现有技术超支化单体侧链含有大量醚键,混凝土粘度大,且支链电荷容易导致易于混凝土中粘土等发生吸附,对原材料较为敏感,适应性较差。
发明内容
为解决现有技术中存在的问题,本发明提供一种超高分散型减水剂及其制备方法,通过采用具有长度相同或近似、侧链整齐的超支化大单体,配合常规聚醚大单体、不饱和酸和功能单体调整聚羧酸减水剂分子结构,平衡位阻效应和电荷分布,实现减水剂超高分散性的效果,并具有降低混凝土粘度的功效。
具体的,本发明超高分散型减水剂,由底料、A溶液、B溶液、稀释剂组成,其中,
底料由如下重量份原料组成:超支化聚醚30-100份,常规聚醚大单体40-70份,不饱和酸0.8-1份,链转移剂1.4-1.8份,引发剂0.6-1份,水70-90份;
A溶液由如下重量份原料组成:不饱和酸4-8份,功能单体4-6份,水10-15份;
B溶液由如下重量份原料组成:还原剂0.2-0.5份,水10-15份;
稀释剂由如下重量份原料组成:水50-60份;
底料中超支化聚醚结构通式为:
其中R1、R2、R3代表为氢或有1-6碳原子数的烷基基团,m为1-2的整数,P1、P2、P3、P4为5-100的整数,更优选的,P1-P4为相同的整数。
本发明通过利用减水剂分子主链快速吸附和侧链高空间位阻来提高其分散性,使其在低水胶比下与混凝土材料具有更高的适应性和分散性。
优选的,所述常规聚醚大单体为烯丙基聚乙二醇醚、异丁烯基聚乙二醇醚、异戊烯基聚乙二醇醚、乙二醇单乙烯基聚乙二醇醚、4-羟丁基乙烯基聚乙二醇醚中的至少一种。
优选的,所述不饱和酸为丙烯酸、甲基丙烯酸、顺丁烯二酸、顺丁烯二酸酐的至少一种。
优选的,所述功能单体为带有磺酸基团、磷酸基团、酰胺基团至少一种的不饱和单体。更优选的,所述功能单体为甲基烯丙基磺酸钠。
优选的,所述链转移剂为巯基乙酸、巯基丙酸、巯基乙醇的至少一种。
优选的,所述引发剂为双氧水、过硫酸铵、过硫酸钾和过硫酸钠的至少一种。
优选的,所述还原剂为次亚磷酸钠、维生素C、抗坏血酸、硫酸亚铁、草酸和硫代硫酸钠中的至少一种。
优选的,所述水为去离子水。
本发明还涉及上述超高分散型减水剂的制备方法,具体的,包括如下步骤:
1)将超支化聚醚30-100份,常规聚醚大单体40-70份,不饱和酸0.8-1份,链转移剂1.4-1.8份,引发剂0.6-1份,水70-90份混合成为底料,并控制温度为20-30℃;
2)向底料中同时滴加A溶液和B溶液,滴加完毕后保温老化;
3)加入稀释剂调节固含量,即得。
优选的,步骤2)滴加时间为2-3h。
优选的,步骤2)保温老化时间为1-2h。
一般聚羧酸系减水剂的高分散性能和降粘性能与其主链长度、官能团种类,侧链结构、长度和接枝密度等相关。本发明超高分散型减水剂以超支化聚醚为核心大单体,刚性亲水基团为小单体,调整氧化-还原体系,进行共聚形成主链刚硬、侧链具有超支化结构的聚羧酸减水剂,通过引入含氨基的超支化侧链结构来提高减水剂分子的亲水性、调整侧链分子疏密度和长度,大幅度提高其空间位阻,以此达到减水剂超高分散性的目的。
本发明超高分散型聚羧酸减水剂的大单体为新型超支化聚醚和市售常规聚醚混合而成的大单体,缩减新型超支化聚醚的使用量,降低了成本。
本发明超支化聚醚与常规聚醚和不饱和酸进行自由基共聚,制备超高分散型聚羧酸减水剂,合成机理示意如下:
其中R1、R2、R3代表为氢或有1-6碳原子数的烷基基团,m为1-2的整数,n、P1、P2、P3、P4为5-100的整数,n2、n5为1-10的整数,n3、n4为1-60的整数。
具体实施方式
为对本发明超高分散型减水剂的效果进行描述,对合成的减水剂进行试验,试验按照GB/T50080 2016《普通混凝土拌合物性能试验方法标准》对混凝土的流动性能进行测试,混凝土的配合比为(kg/m3):基准水泥:330,高岭土:30,粗砂:870,大石:600,小石:400,拌合水:170,减水剂折固掺量为胶凝材料的0.15%,试验过程中添加部分高岭土对减水剂进行干扰吸附,从而表征减水剂减水效果和降粘效果,具体检测项目为坍落度、扩展度和倒坍时间。
实施例1
超高分散型减水剂,底料由如下重量份原料组成:超支化聚醚50份,异丁烯基聚乙二醇醚50份,丙烯酸1份,巯基乙酸1.6份,双氧水0.8份,去离子水80份;A溶液由如下重量份原料组成:丙烯酸5份,甲基烯丙基磺酸钠4份,去离子水12份;B溶液由如下重量份原料组成:维生素C 0.4份,去离子水13份;稀释剂由如下重量份原料组成:去离子水60份。
经检测,混凝土1h坍落度225mm,1h扩展度565mm,倒坍时间7s。
实施例2
超高分散型减水剂,底料由如下重量份原料组成:超支化聚醚60份,异丁烯基聚乙二醇醚40份,丙烯酸1份,巯基乙酸1.7份,双氧水0.8份,去离子水80份;A溶液由如下重量份原料组成:丙烯酸6份,甲基烯丙基磺酸钠5份,去离子水12份;B溶液由如下重量份原料组成:维生素C 0.5份,去离子水13份;稀释剂由如下重量份原料组成:去离子水60份。
经检测,混凝土1h坍落度235mm,1h扩展度575mm,倒坍时间5s。
对比例1
减水剂,底料由如下重量份原料组成:异丁烯基聚乙二醇醚100份,丙烯酸1份,巯基乙酸1.7份,双氧水0.8份,去离子水80份;A溶液由如下重量份原料组成:丙烯酸6份,甲基烯丙基磺酸钠5份,去离子水12份;B溶液由如下重量份原料组成:维生素C 0.5份,去离子水13份;稀释剂由如下重量份原料组成:去离子水60份。
经检测,混凝土1h坍落度200mm,1h扩展度490mm,倒坍时间14s。
对比例2
依照CN112011050A实施例1合成具有式Ⅱ结构的侧链Ⅱ作为聚醚单体合成减水剂。
减水剂,底料由如下重量份原料组成:侧链Ⅱ聚醚单体60份,异丁烯基聚乙二醇醚40份,丙烯酸1份,巯基乙酸1.7份,双氧水0.8份,去离子水80份;A溶液由如下重量份原料组成:丙烯酸6份,甲基烯丙基磺酸钠5份,去离子水12份;B溶液由如下重量份原料组成:维生素C 0.5份,去离子水13份;稀释剂由如下重量份原料组成:去离子水60份。
经检测,混凝土1h坍落度190mm,1h扩展度500mm,倒坍时间13s。
由上述结果可知,与对比例相比,实施例中的减水剂不仅提升了新拌混凝土的流动性能,还降低了混凝土的粘度,大幅度提高了其分散性,满足了混凝土超高分散的目的。
最后应说明的是:以上各实施方式仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施方式对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施方式所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施方式技术方案的范围。
Claims (10)
2.根据权利要求1所述的超高分散型减水剂,其特征在于,所述常规聚醚大单体为烯丙基聚乙二醇醚、异丁烯基聚乙二醇醚、异戊烯基聚乙二醇醚、乙二醇单乙烯基聚乙二醇醚、4-羟丁基乙烯基聚乙二醇醚中的至少一种。
3.根据权利要求1所述的超高分散型减水剂,其特征在于,所述不饱和酸为丙烯酸、甲基丙烯酸、顺丁烯二酸、顺丁烯二酸酐的至少一种。
4.根据权利要求1所述的超高分散型减水剂,其特征在于,所述功能单体为带有磺酸基团、磷酸基团、酰胺基团至少一种的不饱和单体。
5.根据权利要求4所述的超高分散型减水剂,其特征在于,所述功能单体为甲基烯丙基磺酸钠。
6.根据权利要求1所述的超高分散型减水剂,其特征在于,所述链转移剂为巯基乙酸、巯基丙酸、巯基乙醇的至少一种。
7.根据权利要求1所述的超高分散型减水剂,其特征在于,所述引发剂为双氧水、过硫酸铵、过硫酸钾和过硫酸钠的至少一种。
8.根据权利要求1所述的超高分散型减水剂,其特征在于,所述还原剂为次亚磷酸钠、维生素C、抗坏血酸、硫酸亚铁、草酸和硫代硫酸钠中的至少一种。
9.根据权利要求1所述的超高分散型减水剂,其特征在于,所述水为去离子水。
10.根据权利要求1-9任一项所述超高分散型减水剂的制备方法,其特征在于,包括如下步骤:
1)将超支化聚醚30-100份,常规聚醚大单体40-70份,不饱和酸0.8-1份,链转移剂1.4-1.8份,引发剂0.6-1份,水70-90份混合成为底料,并控制温度为20-30℃;
2)向底料中同时滴加A溶液和B溶液,滴加完毕后保温老化;
3)加入稀释剂调节固含量,即得。
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