CN109455971B - 一种粉状羧酸减水剂的制备方法 - Google Patents

一种粉状羧酸减水剂的制备方法 Download PDF

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CN109455971B
CN109455971B CN201811084996.3A CN201811084996A CN109455971B CN 109455971 B CN109455971 B CN 109455971B CN 201811084996 A CN201811084996 A CN 201811084996A CN 109455971 B CN109455971 B CN 109455971B
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reducing agent
polycarboxylate superplasticizer
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CN109455971A (zh
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陈艳丹
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李玉博
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JIAHUA CHEMICAL (FUSHUN) NEW MATERIALS Co.,Ltd.
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Abstract

本发明提供了一种粉状聚羧酸减水剂的制备方法，包括如下步骤：(1)将减水剂单体与水混合，并加热熔融；(2)向所述步骤(1)熔融的体系中加入引发剂、链转移剂和不饱和羧酸，发生本体聚合反应，生成聚羧酸减水剂前体；(3)所述聚羧酸减水剂前体经中和、粉碎处理，制得粉状聚羧酸减水剂。上述的制备方法在本体聚合中加入水，水作为反应物与减水剂单体、不饱和羧酸共同反应，在保证本体聚合反应的高效发生、生成固体聚羧酸减水剂时，降低本体聚合反应的体系粘度，合成具有高性能的粉状聚羧酸减水剂；有利于减水剂的远距离运输，降低运输成本；并且扩大了聚羧酸减水剂的应用范围，使减水剂适用于干混砂浆、高效混凝土等产品。

Description

一种粉状羧酸减水剂的制备方法
技术领域
本发明属于混凝土外加剂技术领域，具体涉及一种粉状聚羧酸减水剂的制备方法。
背景技术
混凝土已经成为人类生活的基础，是目前用量最大的建筑材料。混凝土外加剂是混凝土中除了水泥、砂、石、水之外的第五组分，在高性能混凝土的应用中扮演着非常重要的角色。作为混凝土外加剂的一种，减水剂(又称超塑化剂，Superplasticizer)在混凝土和易性、水泥用量不变的条件下，能够减少拌合用水量、提高混凝土强度，成为混凝土外加剂领域研究的热点和开发的重点。减水剂通过表面活性作用、络合作用、静电排斥力或立体排斥力等来阻碍或破坏水泥颗粒的絮凝结构，从而在节约水泥用量的同时，保证混凝土和易性及强度。聚羧酸减水剂具有掺量低、减水率高、分子结构设计自由度大，以及环境友好等优点，被誉为第三代混凝土超塑化剂，广泛应用于高铁、公路、桥梁、隧道和高层建筑等工程中。
目前，关于聚羧酸减水剂的合成研究大多数是通过水溶液聚合而得到的，市场上出售的聚羧酸产品也大多都是水溶型，其质量分数在20％～50％。液体聚羧酸减水剂不便于包装和运输，在施工地点较远时会致使运输成本大幅度增加，并且不能用于如干混砂浆等需要固体高效减水剂的情况，因此，开发高浓度或固体聚羧酸减水剂显得十分必要。
本体聚合是在无溶剂条件下，反应单体受引发剂作用发生的聚合反应过程。本体聚合法合成聚羧酸减水剂具有高的引发速度和引发强度，适于合成具有高固含量的固体聚羧酸减水剂。但是，本体聚合的反应过程中放热速率快，容易造成由于反应速率快，反应过程中放热较多，反应体系粘度增大，使得对流导热系数降低，造成局部反应过热甚至发生爆聚，出现凝胶效应，影响产品性能。
发明内容
因此，本发明要解决的技术问题在于克服现有技术中通过本体聚合合成聚羧酸减水剂时容易发生反应体系粘度过大，易发生局部过热甚至爆聚，造成聚羧酸减水剂性能降低的缺陷。
为此，本发明提供了如下技术方案：
本发明提供了一种粉状聚羧酸减水剂的制备方法，包括如下步骤：
(1)将减水剂单体与水混合，并加热熔融；
(2)向所述步骤(1)熔融的体系中加入引发剂、链转移剂和不饱和羧酸，发生本体聚合反应，生成聚羧酸减水剂前体；
(3)所述聚羧酸减水剂前体经中和、粉碎处理，制得粉状聚羧酸减水剂。
可选地，上述的制备方法，
所述步骤(1)中，所述水的加入量是所述减水剂单体的0.8-1.2wt％。
可选地，上述的制备方法，所述步骤(2)中还包括，将所述链转移剂和所述不饱和羧酸混合的步骤。
可选地，上述的制备方法，所述步骤(3)中，所述聚羧酸减水剂前体与碱溶液在捏合机中混合，进行所述中和、粉碎处理，制得pH为5-8的粉状聚羧酸减水剂。
可选地，上述的制备方法，所述步骤(2)中：
所述引发剂为异丙苯过氧化氢和过氧化二异丙苯中的至少一种，所述本体聚合反应的反应温度为80-120℃；或者，
所述引发剂为过氧化十二酰，所述本体聚合反应的反应温度为70-100℃；或者，
所述引发剂为过氧化苯甲酸叔丁酯和氧化二碳酸二环己酯中的至少一种，所述本体聚合反应的反应温度为50-70℃。
可选地，上述的制备方法，所述步骤(2)中，所述本体聚合反应的反应时间为2-2.5小时；反应完成后，继续在60-75℃下熟化2-2.5小时，生成所述聚羧酸减水剂前体。
可选地，上述的制备方法，所述步骤(1)中，在45-55℃的温度下熔融所述减水剂单体。
可选地，上述的制备方法，所述减水剂单体：所述不饱和羧酸：所述链转移剂：所述引发剂的质量比为1：(0.05-0.15)：(0.1-0.15)：(0.45-0.65)。
可选地，上述的制备方法，所述减水剂单体选自下述化合物中的至少一种：
丙烯醇、甲基丙烯醇、异戊烯醇、丁烯醇、庚烯醇、丙烯醇乙二醇醚、甲基丙烯醇乙二醇醚、四羟丁基乙烯基醚、四羟丁基甲基丙烯醇、甲基烯丙基聚氧乙烯醚、异丁烯醇聚氧乙烯醚、烯丙醇聚氧乙烯醚、烯丙基胺、二烯丙基胺、甲基烯丙基胺、乙基烯丙基胺，和上述任一种化合物的同系物。
可选地，上述的制备方法，所述不饱和羧酸选自下述化合物中的至少一种：
丙烯酸、马来酸酐、甲基丙烯酸、肉桂酸和巴豆酸。
可选地，上述的制备方法，所述链转移剂选自下述化合物中的至少一种：
巯基乙酸、巯基丙酸、甲基丙烯磺酸钠和巯基乙醇。
本发明相对现有技术具有如下优点：
1、本发明提供的粉状聚羧酸减水剂的制备方法，包括(1)将减水剂单体与水混合，并加热熔融；(2)向所述步骤(1)熔融的体系中加入引发剂、链转移剂和不饱和羧酸，发生本体聚合反应，生成聚羧酸减水剂前体；(3)所述聚羧酸减水剂前体经中和、粉碎处理，制得粉状聚羧酸减水剂。
目前聚羧酸减水剂的合成主要通过水溶液聚合或者本体聚合得到。水溶液聚合反应中是利用水作为溶剂为合成减水剂创造良好的反应环境，反应条件易于控制，但是合成的聚羧酸生产浓度仅为20％-40％，不适于储存和运输。本体聚合反应在无溶剂的环境下发生，能够合成高固含量的固体聚羧酸减水剂，但本体聚合反应剧烈，热量不易散失，容易发生局部爆聚，导致合成的聚羧酸减水剂性能降低。
本发明通过研究发现，在本体聚合反应中加入水，与水溶液聚合时以水作为溶剂提供反应环境的性能不同，水在本体聚合反应过程中能够作为反应物与减水剂单体、不饱和羧酸共同反应，与减水剂单体等相互作用，使合成的聚羧酸减水剂对水泥分散性能提升；并且，在反应过程中，掺入的水能够增加本体聚合反应体系中减水剂单体和不饱和羧酸的自由度，增大了反应体系的流动性，降低体系粘度，提高了反应体系的热传导性能，避免局部反应过热过高或爆聚，使生成的固体聚羧酸减水剂前体中起分散作用的有效成分增加，对水泥的分散性能好，提高水泥净浆流动度。
上述合成的聚羧酸减水剂前体在经中和、粉碎处理后，最终生成粉状聚羧酸减水剂，不仅有利于减水剂的远距离运输，降低运输成本；还扩大了聚羧酸减水剂的应用范围，使减水剂适用于干混砂浆、压浆料等产品。同时，粉状聚羧酸减水剂产品在室内施工时，还可以降低甲醛等易挥发组分的含量。
2、本发明提供的制备方法，所述步骤(1)中，所述水的加入量是所述减水剂单体的0.8-1.2wt％。本发明通过大量实验证实，当水的加入量在减水剂单体加入量的0.8-1.2wt％范围内时，既能够保证本体聚合反应的高效率发生，得到固体的高固含量减水剂，降低减水剂的运输和储存成本；还能够使水参与本体聚合反应，降低体系粘度，增加热传导，合成高性能的聚羧酸减水剂，减水剂对水泥的净浆流动度高。
3、本发明提供的粉状聚羧酸减水剂的制备方法，步骤(3)中将聚羧酸减水剂前体与碱溶液在捏合机中混合，进行中和、粉碎处理，制得pH为5-8的粉状聚羧酸减水剂。
在捏合机中完成减水剂的中和、粉碎处理，聚羧酸减水剂前体与碱溶液在捏合机中搅拌混合，利用碱溶液中和聚羧酸减水剂，使减水剂的pH值分布于5-8，有利于提高减水剂的熔点，促进减水剂相态的改变，得到固体的聚羧酸减水剂；聚羧酸减水剂在被中和的同时还可以在捏合机中可以被压碎，在一步操作过程中生成了粉状的聚羧酸减水剂。与传统喷雾干燥生成粉体聚羧酸减水剂的工艺相比，能够避免高温处理工艺导致的减水剂丧失减水性能或结块，并且解决了由于高温产生的能耗问题，一步法完成了聚羧酸减水剂的粉体化处理过程。
4、本发明提供的粉状聚羧酸减水剂的制备方法，设置反应温度以及减水剂单体、不饱和羧酸、链转移剂和引发剂的使用比例，以避免局部反应温度过高和爆聚，避免出现凝胶效应，提高聚羧酸减水剂的有效减水成分，增加对水泥的分散性和净浆流动度。
具体实施方式
提供下述实施例是为了更好地进一步理解本发明，并不局限于所述最佳实施方式，不对本发明的内容和保护范围构成限制，任何人在本发明的启示下或是将本发明与其他现有技术的特征进行组合而得出的任何与本发明相同或相近似的产品，均落在本发明的保护范围之内。
实施例中未注明具体实验步骤或条件者，按照本领域内的文献所描述的常规实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规试剂产品。下述实施例中的1质量份代表500g的物质质量。
实施例1
本实施例提供一种粉状聚羧酸减水剂的制备方法，具体包括以下步骤：
(1)向反应釜中投入1质量份的异丁烯醇聚氧乙烯醚(SPEG，分子量：2400)，0.01质量份的去离子水，用氮气置换反应釜内空气；升高反应釜内温度，使釜温上升至55℃，熔融异丁烯醇聚氧乙烯醚；
(2)向熔融的异丁烯醇聚氧乙烯醚中加入0.5质量份的异丙苯过氧化氢，然后升高反应釜内温度至115℃后，开始滴加0.05质量份的丙烯酸和0.1质量份的巯基丙酸的混合液；
(3)控制反应釜内温度为115-120℃，反应釜内压力＜0.1MPa，在2h内滴加完成丙烯酸和巯基丙酸的混合液；滴加完毕(本体聚合反应完成)后，继续在75℃的温度下熟化2h，得到聚羧酸减水剂前体；
将聚羧酸减水剂前体出料至捏合机中，向捏合机中加入NaOH溶液，聚羧酸减水剂前体与NaOH溶液在捏合机中搅拌混合，中和聚羧酸减水剂前体，调节其pH值为6；同时，聚羧酸减水剂前体在捏合机中被搅拌压碎，得到粉状聚羧酸减水剂成品。产品外观：微黄色粉末。
实施例2
本实施例提供一种粉状聚羧酸减水剂的制备方法，具体包括以下步骤：
(1)向反应釜中投入0.3质量份的甲基烯丙基聚氧乙烯醚(TPEG，分子量：2400)，0.7质量份的异丁烯醇聚氧乙烯醚(SPEG，分子量：2400)，0.008质量份的去离子水，用氮气置换反应釜内空气；升高反应釜内温度，使釜温上升至45℃，熔融甲基烯丙基聚氧乙烯醚和异丁烯醇聚氧乙烯醚；
(2)向熔融的甲基烯丙基聚氧乙烯醚和异丁烯醇聚氧乙烯醚中加入0.65质量份的过氧化二异丙苯，然后升高反应釜内温度至80℃后，开始滴加0.1质量份的甲基丙烯酸和0.15质量份的巯基乙酸的混合液；
(3)控制反应釜内温度为80-85℃，反应釜内压力＜0.1MPa，在2.5h内滴加完成甲基丙烯酸和巯基乙酸的混合液；滴加完毕后，继续在65℃的温度下保温2h，得到聚羧酸减水剂前体；
将聚羧酸减水剂前体出料至捏合机中，向捏合机中加入三羟丙基羟乙基乙二胺溶液，聚羧酸减水剂前体与三羟丙基羟乙基乙二胺溶液在捏合机中搅拌混合，中和聚羧酸减水剂前体，调节其pH值为5；同时，聚羧酸减水剂前体在捏合机中被搅拌压碎，得到粉状聚羧酸减水剂成品。产品外观：微黄色粉末。
实施例3
本实施例提供一种粉状聚羧酸减水剂的制备方法，具体包括以下步骤：
(1)向反应釜中投入1质量份的烯丙醇聚氧乙烯醚(APEG，分子量：3000)，0.012质量份的去离子水，用氮气置换反应釜内空气；升高反应釜内温度，使釜温上升至55℃，熔融烯丙醇聚氧乙烯醚；
(2)向熔融的烯丙醇聚氧乙烯醚中加入0.45质量份的过氧化十二酰，然后升高反应釜内温度至70℃后，开始滴加0.15质量份的马来酸酐和0.11质量份的巯基丙酸的混合液；
(3)控制反应釜内温度为70-75℃，反应釜内压力＜0.1MPa，在2h内滴加完成马来酸酐和巯基丙酸的混合液；滴加完毕后，继续在70℃的温度下保温2.5h，得到聚羧酸减水剂前体；
将聚羧酸减水剂前体出料至捏合机中，向捏合机中加入四羟丙基乙二胺溶液，聚羧酸减水剂前体与四羟丙基乙二胺溶液在捏合机中搅拌混合，中和聚羧酸减水剂前体，调节其pH值为7；同时，聚羧酸减水剂前体在捏合机中被搅拌压碎，得到粉状聚羧酸减水剂成品。产品外观：微黄色粉末。
实施例4
本实施例提供一种粉状聚羧酸减水剂的制备方法，具体包括以下步骤：
(1)向反应釜中投入1质量份的异丁烯醇聚氧乙烯醚(SPEG，分子量：3000)，0.011质量份的去离子水，用氮气置换反应釜内空气；升高反应釜内温度，使釜温上升至48℃，熔融异丁烯醇聚氧乙烯醚；
(2)向熔融的异丁烯醇聚氧乙烯醚中加入0.55质量份的过氧化十二酰，然后升高反应釜内温度至100℃后，开始滴加0.08质量份的肉桂酸和0.13质量份的巯基乙醇的混合液；
(3)控制反应釜内温度为95-100℃，反应釜内压力＜0.1MPa，在2.5h内滴加完成肉桂酸和巯基乙醇的混合液；滴加完毕后，继续在75℃的温度下保温2h，得到聚羧酸减水剂前体；
将聚羧酸减水剂前体出料至捏合机中，向捏合机中加入三羟丙基羟乙基乙二胺溶液，聚羧酸减水剂前体与三羟丙基羟乙基乙二胺溶液在捏合机中搅拌混合，中和聚羧酸减水剂前体，调节其pH值为8；同时，聚羧酸减水剂前体在捏合机中被搅拌压碎，得到粉状聚羧酸减水剂成品。产品外观：微黄色粉末。
实施例5
本实施例提供一种粉状聚羧酸减水剂的制备方法，具体包括以下步骤：
(1)向反应釜中投入0.2质量份的甲基丙烯醇乙二醇醚(分子量：2400)，0.8质量份的异丁烯醇聚氧乙烯醚(SPEG，分子量：2400)，0.009质量份的去离子水，用氮气置换反应釜内空气；升高反应釜内温度，使釜温上升至52℃，熔融甲基丙烯醇乙二醇醚和异丁烯醇聚氧乙烯醚；
(2)向熔融的甲基丙烯醇乙二醇醚和异丁烯醇聚氧乙烯醚中加入0.6质量份的过氧化苯甲酸叔丁酯，然后控制反应釜内温度在50℃，开始滴加0.05质量份的巴豆酸和0.12质量份的甲基丙烯磺酸钠的混合液；
(3)控制反应釜内温度为50-55℃，反应釜内压力＜0.1MPa，在2h内滴加完成丙烯酸和巯基丙酸的混合液；滴加完毕后，继续在60℃的温度下保温2.5h，得到聚羧酸减水剂前体；
将聚羧酸减水剂前体出料至捏合机中，向捏合机中加入NaOH溶液，聚羧酸减水剂前体与NaOH溶液在捏合机中搅拌混合，中和聚羧酸减水剂前体，调节其pH值为8；同时，聚羧酸减水剂前体在捏合机中被搅拌压碎，得到粉状聚羧酸减水剂成品。产品外观：微黄色粉末。
实施例6
本实施例提供一种粉状聚羧酸减水剂的制备方法，具体包括以下步骤：
(1)向反应釜中投入1质量份的甲基烯丙基胺，0.01质量份的去离子水，用氮气置换反应釜内空气；升高反应釜内温度，使釜温上升至45℃，熔融甲基烯丙基胺；
(2)向熔融的甲基烯丙基胺中加入0.45质量份的氧化二碳酸二环己酯，然后升高反应釜内温度至70℃后，开始滴加0.12质量份的丙烯酸和0.14质量份的巯基丙酸的混合液；
(3)控制反应釜内温度为65-70℃，反应釜内压力＜0.1MPa，在2.5h内滴加完成丙烯酸和巯基丙酸的混合液；滴加完毕后，继续在73℃的温度下保温2h，得到聚羧酸减水剂前体；
将聚羧酸减水剂前体出料至捏合机中，向捏合机中加入三羟丙基羟乙基乙二胺溶液，聚羧酸减水剂前体与三羟丙基羟乙基乙二胺溶液在捏合机中搅拌混合，中和聚羧酸减水剂前体，调节其pH值为6；同时，聚羧酸减水剂前体在捏合机中被搅拌压碎，得到粉状聚羧酸减水剂成品。产品外观：微黄色粉末。
对比例1
本实施例提供一种粉状聚羧酸减水剂的制备方法，与实施例1中提供的粉状聚羧酸减水剂的制备方法的区别仅在于：去离子水的加入量为0.5％质量份。产品外观：微黄色粉末。
对比例2
本实施例提供一种粉状聚羧酸减水剂的制备方法，与实施例1中提供的粉状聚羧酸减水剂的制备方法的区别仅在于：去离子水的加入量为1.8％质量份。产品外观：微黄色粉末。
检测例1
检测实施例1-实施例6中制得的聚羧酸减水剂成品与对比例1-对比例2中制得的聚羧酸减水剂成品对基准水泥的水泥流动性的作用效果。试验参照国标GB/T8077-2000《混凝土外加剂匀质性试验方法》进行，W/C＝0.29，聚羧酸减水剂成品的掺量(折固掺量)为0.08％，检测结果如表1所示。
表1聚羧酸减水剂的对水泥的分散性能检测
Figure BDA0001802666310000101
Figure BDA0001802666310000111
由表1可知，与对比例1-对比例2中制备的聚羧酸减水剂相比，以本发明实施例1-6制备的粉状聚羧酸减水剂，当水的加入量在0.8-1.2wt％范围内时，水泥的净浆流动度提高，减水剂对水泥的分散性能提升。因此，利用本发明的制备方法制得的粉状聚羧酸减水剂，通过加入水，能够合成高性能的聚羧酸减水剂，并在当水的加入量在0.8-1.2wt％范围内时，能够得到对水泥的分散性能最优的聚羧酸减水剂。同时，本发明提供的制备方法通过一步法完成了对固体聚羧酸减水剂的粉碎处理过程，得到粉状的聚羧酸减水剂，简化了传统粉体聚羧酸减水剂的生产和加工工艺，降低了粉体聚羧酸减水剂的加工能耗，制得的减水剂成品适于远距离运输，降低了运输成本。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (8)

1.一种粉状聚羧酸减水剂的制备方法，其特征在于，包括如下步骤：
（1）将减水剂单体与水混合，并加热熔融；
（2）向所述步骤（1）熔融的体系中加入引发剂、链转移剂和不饱和羧酸，发生本体聚合反应，生成聚羧酸减水剂前体；
（3）所述聚羧酸减水剂前体经中和、粉碎处理，制得粉状聚羧酸减水剂；
所述步骤（1）中，所述水的加入量是所述减水剂单体的0.8-1.2 wt%；所述减水剂单体：所述不饱和羧酸：所述链转移剂：所述引发剂的质量比为1：（0.05-0.15）：（0.1-0.15）：（0.45-0.65）；所述减水剂单体选自下述化合物中的至少一种：丙烯醇、甲基丙烯醇、异戊烯醇、丁烯醇、庚烯醇、丙烯醇乙二醇醚、甲基丙烯醇乙二醇醚、四羟丁基乙烯基醚、四羟丁基甲基丙烯醇、甲基烯丙基聚氧乙烯醚、异丁烯醇聚氧乙烯醚、烯丙醇聚氧乙烯醚、烯丙基胺、二烯丙基胺、甲基烯丙基胺、乙基烯丙基胺，和上述任一种化合物的同系物。
2.根据权利要求1所述的制备方法，其特征在于，所述步骤（2）中还包括，将所述链转移剂和所述不饱和羧酸混合的步骤。
3.根据权利要求1或2所述的制备方法，其特征在于，所述步骤（3）中，所述聚羧酸减水剂前体与碱溶液在捏合机中混合，进行所述中和、粉碎处理，制得pH为5-8的粉状聚羧酸减水剂。
4.根据权利要求1或2所述的制备方法，其特征在于，所述步骤（2）中：
所述引发剂为异丙苯过氧化氢和过氧化二异丙苯中的至少一种，所述本体聚合反应的反应温度为80-120℃；或者，
所述引发剂为过氧化十二酰，所述本体聚合反应的反应温度为70-100℃；或者，
所述引发剂为过氧化苯甲酸叔丁酯和氧化二碳酸二环己酯中的至少一种，所述本体聚合反应的反应温度为50-70℃。
5.根据权利要求1或2所述的制备方法，其特征在于，所述步骤（2）中，所述本体聚合反应的反应时间为2-2.5小时；反应完成后，继续在60-75℃下熟化2-2.5小时，生成所述聚羧酸减水剂前体。
6.根据权利要求1或2所述的制备方法，其特征在于，所述步骤（1）中，在45-55℃的温度下熔融所述减水剂单体。
7.根据权利要求1或2所述的制备方法，其特征在于，所述不饱和羧酸选自下述化合物中的至少一种：
丙烯酸、马来酸酐、甲基丙烯酸、肉桂酸和巴豆酸。
8.根据权利要求1或2所述的制备方法，其特征在于，所述链转移剂选自下述化合物中的至少一种：
巯基乙酸、巯基丙酸、甲基丙烯磺酸钠和巯基乙醇。
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