CN105778014B - 一种高固含聚羧酸减水剂的制备方法 - Google Patents
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Abstract
本发明公开了一种高固含聚羧酸减水剂的制备方法,步骤包括a)、将不饱和聚氧乙烯醚单体加入底水中配制成60—75%浓度在20—40℃下提前搅拌预溶解,待溶解后将底料泵送至反应釜中;b)、在反应釜搅拌状态下一次性加入浓度为25—30%的双氧水溶液;c)、将链转移剂与还原剂配制成4—10%的混合溶液,缓慢滴加于上述反应釜中,15min后开始滴加单体A、单体B配制成的混合溶液,其中单体A、单体B混合溶液浓度为60—75%;d)、滴加结束,保温老化1h,加入浓度为30—40%的碱溶液调整产物为中性,即可泵送至母液储罐。本发明采用无热源的常温反应生产得到的高固含聚羧酸减水剂,固含量可达50—63.4%,相对于传统40%固含聚羧酸减水剂,生产效率明显提高,可提高储存效率。
Description
技术领域
本发明属于混凝土外加剂领域,具体涉及一种高固含聚羧酸减水剂的常温合成方法。
背景技术
在混凝土行业,聚羧酸醚类减水剂由于其减水率高、保坍性好、掺量低、对环境友好等优点,已成为制备高性能混凝土的关键材料之一。目前聚羧酸减水剂的合成技术已经较为成熟稳定,但仍存在合成温度较高(60—80℃),能耗大,反应时间长,生产成本高等。因而无热源常温制备聚羧酸减水剂成为一种新型的合成工艺,很多研究者也对其进行了深入研究探讨,但合成的聚羧酸减水剂相对固含量较低(20—40%),合成与运输成本高,生产效率低,发展受限。
然而,目前高固含(60%以上)聚羧酸制备方法尚处于研究探索阶段,相关研究报导较少。
CN102627743A提供了一种先酯化后聚合两步法合成高固含聚羧酸减水剂的制备方法,合成所需时间长,工艺繁琐。
CN102875746A则提供了一种高固含醚类聚羧酸减水剂的直接制备方法,该发明采用提高反应物浓度在高温下(50—70℃)采用过硫酸铵经自由基共聚合成减水剂,工艺反应温度较高,能耗大,且过硫酸铵作为引发体系需较高反应温度才能引发自由基形成。
发明内容
为解决上述问题,本发明目的在于提供一种高固含聚羧酸减水剂的常温合成方法。
本发明解决其技术问题所采用的技术方案是:一种高固含聚羧酸减水剂的制备方法,包括以下步骤:a)、将不饱和聚氧乙烯醚单体加入底水中20—40℃下提前搅拌预溶解,控制不饱和聚氧乙烯醚在底水中的浓度为60—75%,待溶解后将底料泵送至反应釜中;b)、在反应釜搅拌状态下加入浓度为25—30%的双氧水溶液;c)、将链转移剂与还原剂配制成4—10%的混合溶液,缓慢滴加于上述反应釜中,滴加时间3—3.5h;将单体A、单体B配制成60—75%混合溶液,待链转移剂和还原剂的混合溶液滴加15min后开始滴加,滴加时间2.5—3h;所述的单体A为丙烯酸、甲基丙烯酸或丙烯酰胺中的一种或多种;所述的单体B为丙烯酸—α—羟乙酯、丙烯酸—β—羟丙酯或2—丙烯酰胺—2—甲基丙磺酸中的一种或多种;d)、滴加结束,保温老化1h,加入浓度为30—40%的碱溶液调整产物为中性,即可泵送至母液储罐。
所述的一种高固含聚羧酸减水剂的制备方法,其不饱和聚氧乙烯醚为甲基烯丙醇聚氧乙烯醚或异戊烯醇聚氧乙烯醚或异丁烯醇聚氧乙烯醚。
所述的一种高固含聚羧酸减水剂的制备方法,三种单体各组份的重量百分比为:不饱和聚氧乙烯醚为80—90%、单体A为10—20%、单体B为0—10%。
所述的一种高固含聚羧酸减水剂的制备方法,其碱溶液为氢氧化钠溶液。
所述的一种高固含聚羧酸减水剂的制备方法,其双氧水溶液的加入量为三种单体总质量的0.16—0.51%。
所述的一种高固含聚羧酸减水剂的制备方法,其链转移剂为巯基丙酸或巯基乙酸或两者的混合,其加入量为三种单体总质量的0.49—0.8%。
所述的一种高固含聚羧酸减水剂的制备方法,其还原剂为酒石酸、维生素C、次硫酸氢钠甲醛或过氧苯甲酰中的一种或多种,其加入量为三种单体总质量的0.17—0.64%。
本发明的有益效果是:
1、本发明产品通过活化能较低的氧化还原体系实现常温下聚合,再以链转移剂、引发剂等合理浓度逐步滴加降低高浓反应的粘度,使链段更易重排,自由基聚合更易控制,合成产品稳定性更好;
2、依照本发明方法制备的产品固含量可达50—63.4%,相对于传统40%固含聚羧酸减水剂,生产效率明显提高,可提高储存效率;
3、本发明合成工艺采用无热源常温合成,副产物少,有效降低了生产能效,生产周期短,能够有效节约运输成本、人力成本以及生产成本。
具体实施方式
本发明公开了一种高固含聚羧酸减水剂的常温制备方法,由80—90%的不饱和聚氧乙烯醚、10—20%的单体A、0—10%的单体B三种单体,在活化能较低的“双氧水—还原剂”体系下,提高反应浓度;其中不饱和聚氧乙烯醚反应浓度为60—75%,单体A与单体B混合水溶液浓度为60—75%,再在常温下合理滴加单体A、单体B、引发剂、链转移剂等合成原料溶液,加碱中和后得到固含量达50—63.4%的聚羧酸减水剂。
本合成工艺选用活化能较低的“双氧水—还原剂”氧化还原体系可有效实现常温合成,进而降低生产能效,缩短生产周期,节约运输成本、人力成本以及生产成本。
实施例1
1)将180g异戊烯醇聚氧乙烯醚于20℃下溶解在95g水中,待完成溶解后泵送至反应釜,加入25%双氧水溶液1.30g。
2)依次称取1.20g巯基丙酸,0.33g维生素C加入28.5g水,混合均匀后匀速滴加于反应釜中,控制滴加时间为3.5h。
4)称取20.00g丙烯酸溶于8.55g水中,该溶液待巯基丙酸与维生素C混合溶液滴加15min后开始滴加,滴加时间为3h。
5)滴加结束后,30℃下保温老化1h,加入30%的氢氧化钠溶液24.69g中和溶液pH为6—7,补充59g水即得固含为50.0%的本发明产品PC-1。
实施例2
1)将180g甲基烯丙醇聚氧乙烯醚35℃下溶于77g底水中,待完全溶解后泵送至反应釜,一次性加入30%双氧水溶液1.50g。
2)将1.50g巯基乙酸与0.60g酒石酸混合于19.00g水中,摇匀后均匀滴加于反应釜中,设置滴加时间为3h。
3)称取26.00g丙烯酸与8.60g丙烯酸-α-羟乙酯,加入11.53g水,混合均匀,待2)中混合液滴加15min后开始滴加,设置滴加时间为2.5h。
4)滴加结束后,30℃下保温老化1h,加入30%的氢氧化钠溶液30.09g至溶液pH为6—7,补充22.00g水即得固含为60.0%的本发明产品PC-2。
实施例3
1)将180g异戊烯醇聚氧乙烯醚加入120g水,40℃下溶解完全后一次性加入2g 30%双氧水溶液。
2)称取1.17g巯基丙酸与0.60g维生素C,加入15.90g水摇匀,设置滴加时间为3.5h。
3)称取25.00g丙烯酸与15.00g丙烯酰胺,溶解于21.50g水中,充分摇匀待溶解完后,滴加2)中混合溶液15min后开始滴加此混合溶液,设置滴加时间为3h。
4)滴加结束后,30℃下保温老化1h,加入40%的氢氧化钠溶液23.15g中和溶液pH为6—7,补充16.50g水即得固含为55.0%的本发明产品PC-3。
实施例4
1)将180g异戊烯醇聚氧乙烯醚加入60g水,40℃下溶解完全后一次性加入4g 27%双氧水溶液。
2)依次称取1.05g巯基丙酸与1.30g次硫酸氢钠甲醛配制成7.9%混合溶液,该混合溶液均匀滴加于反应釜中,设置滴加时间为3.5h。
3)依次称取22.00g丙烯酸、10.70g2-丙烯酰胺-2-甲基丙磺酸配制成60%溶液,该2)中混合溶液滴加15min后开始滴加,设置滴加时间为2.5h。
5)滴加结束后,30℃下保温老化1h,加入32%的氢氧化钠溶液25.46g中和至溶液pH为6—7,即得固含为63.4%的本发明产品PC-4。
比较例1
在四口烧瓶中加入异戊烯基聚氧乙烯醚,其占单体总重90%,加入去离子水,控制单体浓度为65%,升温至60℃。配制过硫酸钾水溶液(引发剂),过硫酸钾的用量占单体总重量的2.5%,搅拌充分溶解,滴加时间为3.5h。配制浓度为60%的丙烯酸和巯基丙酸混合溶液,其中巯基丙酸用量为三种单体总质量的1.2%,滴加时间为3h。滴加完在60℃下保温1.5h,降温至40℃,加入30%浓度的液碱中和至pH为6—7,即得固含为60%的减水剂PC。
实验效果
参照GB 8077—2012《混凝土外加剂匀质性试验方法》测定水泥净浆流动度,W/C=0.29,减水剂折固掺量为0.10%。参照GB 8076—2008《混凝土外加剂》标准检测,依据混凝土拌合物性能实验方法,用水量应使混凝土坍落度控制在210±10mm,减水剂折固掺量0.125%,测试新拌混凝土初始坍落度(TL0h)及1 h坍落度(TL1h)。试验结果如下表1所示。
表1结果表明,本发明方法常温制备的高固含聚羧酸减水剂具有良好的减水性与保坍性,其中实施例2及实施例3与对比例1及国内产品对比,其减水率高、保坍性好,适宜用作偏减水型产品。而实施例1与实施例4因配方中酸醚略低,减水效果略低于实施2与3,但保坍效果较佳,适宜用作保坍型产品。因此可认为实施例2为本发明偏减水型聚羧酸减水剂的最佳配方,实施例1为减水偏保坍型聚羧酸减水剂的最佳配方。
表1 水泥净浆及混凝土试验结果
上述实施例仅例示性说明本发明的原理及其功效,以及部分运用的实施例,对于本领域的普通技术人员来说,在不脱离本发明创造构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。
Claims (4)
1.一种高固含聚羧酸减水剂的制备方法,其特征在于:包括以下步骤
a)、将不饱和聚氧乙烯醚单体加入底水中20—40℃下提前搅拌预溶解,控制不饱和聚氧乙烯醚在底水中的浓度为60—75%,待溶解后将底料泵送至反应釜中;所述的不饱和聚氧乙烯醚为甲基烯丙醇聚氧乙烯醚或异戊烯醇聚氧乙烯醚;
b)、在反应釜搅拌状态下加入浓度为25—30%的双氧水溶液;
c)、将链转移剂与还原剂配制成4—10%的混合溶液,缓慢滴加于上述反应釜中,滴加时间3—3.5h;将单体A、单体B配制成60—75%混合溶液,待链转移剂和还原剂的混合溶液滴加15min后开始滴加,滴加时间2.5—3h;
所述的单体A为甲基丙烯酸或丙烯酰胺中的一种或多种;
所述的单体B为丙烯酸—α—羟乙酯、丙烯酸—β—羟丙酯中的一种或多种;
所述链转移剂为巯基丙酸,其加入量为三种单体总质量的0.49—0.8%;
所述还原剂为酒石酸、维生素C或次硫酸氢钠甲醛中的一种或多种,其加入量为三种单体总质量的0.17—0.64%;
d)、滴加结束,保温老化1h,加入浓度为30—40%的碱溶液调整产物为中性,即可泵送至母液储罐。
2.根据权利要求1所述的一种高固含聚羧酸减水剂的制备方法,其特征在于,所述三种单体各组份的重量百分比为:不饱和聚氧乙烯醚为80—90%、单体A为10—20%、单体B为0—10%。
3.根据权利要求1所述的一种高固含聚羧酸减水剂的制备方法,其特征在于,所述的碱溶液为氢氧化钠溶液。
4.根据权利要求1所述的一种高固含聚羧酸减水剂的制备方法,其特征在于,所述双氧水溶液的加入量为三种单体总质量的0.16—0.51%。
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