CN111253538B - 一种环胺基脂肪醇醚结构的早强型聚羧酸减水剂的制备方法 - Google Patents

一种环胺基脂肪醇醚结构的早强型聚羧酸减水剂的制备方法 Download PDF

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CN111253538B
CN111253538B CN202010118535.4A CN202010118535A CN111253538B CN 111253538 B CN111253538 B CN 111253538B CN 202010118535 A CN202010118535 A CN 202010118535A CN 111253538 B CN111253538 B CN 111253538B
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徐仕睿
刘勇
李鹏
刘威
左小青
李小梅
李天书
柳新江
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Fushun Dongke Fine Chemical Co ltd
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Abstract

本发明的公开了一种环胺基脂肪醇醚结构的早强型聚羧酸减水剂的制备方法，包括如下步骤：①功能性环胺基聚合物单体的制备；②环胺基脂肪醇醚结构的早强型聚羧酸减水剂的制备。本方法制备的聚羧酸高性能减水剂在保持减水和保坍功能的同时兼具早强功能，由于脂肪醇侧链的存在，更提高了产品4％‑5％的减水率，使聚羧酸减水剂在混凝土领域的应用得到了更进一步的扩展。本发明方法控制简单、产品结构稳定、产品性能优异。

Description

一种环胺基脂肪醇醚结构的早强型聚羧酸减水剂的制备方法
一、技术领域
本发明属于混凝土助剂技术领域，具体涉及一种环胺基脂肪醇醚结构的早强型聚羧酸减水剂的制备方法。
二、背景技术
聚羧酸减水剂是一种高性能减水剂，具有掺量低、减水率高、功能可调、绿色环保等优点，作为混凝土助剂广泛的应用于公路、桥梁、大坝、隧道、高层建筑等工程。近年来，随着我国城市化进程快速推进，拉动了混凝土的广泛需求，在传统的混凝土设计中，通常采用降低单方用水量、提高水泥的强度等级、增加单方混凝土中胶凝材料的使用量以及改善砂石料的质量等手段提高混凝土强度。但随着资源的日益枯竭以及环境要求的不断提高，国内建筑用砂石资源逐渐出现劣化,砂石含泥量也大大增加。与此同时，随着大量重大、重点项目的推进与建设周期的要求，对于大方量混凝土浇筑工程，尤其以模板工程做成型支护，考虑到模板周转效率提高，需要将混凝土的脱模时间大大缩短；对于类似于水泥混凝土地面、道路或者堆场，要求混凝土在最短的时间内达到一定强度，方便车辆的行驶；对于分层浇筑的混凝土，要求第一次浇筑的混凝土迅速达到一定强度后，才允许在混凝土上部进行第二次的施工浇筑活动。针对上述种种情况，混凝土早期强度的提高有着十分重要的意义。
随着混凝土早强问题的不断凸显，需要不断地发展新技术来解决混凝土的早强问题。国内对早强型聚羧酸减水剂的研究起步比较晚，起初只是靠复配无机盐(如NaCl、CaCl2、Na2SO4、Na2S2O3、NaNO2以及NaNO3等其中的一种或者几种)提高混凝土的早期强度，如今又有以含胺类化合物为起始剂合成单体或是合成聚羧酸单体后再进行胺醚封端，以提高聚羧酸减水剂的早强性能。但上述这类单体对合成聚羧酸减水剂后，在早强功能的基础上对于提高减水性能没有发生明显的变化。
三、发明内容
本发明的目的是提供一种环胺基脂肪醇醚结构的早强型聚羧酸减水剂的制备方法，采用该方法所制备的早强型聚羧酸减水剂的减水率得到有效提高。
本发明采用的技术方案包括如下步骤：
①功能性环胺基聚合物单体的制备：将脂肪醇聚氧乙烯醚加到入容器中，加热到50-60℃使其全部熔化，向容器中加入定量催化剂，搅拌均匀，升温T＝75-85℃，向容器中缓慢滴加环胺化合物，2-3h滴加完毕，滴加后升温T＝90-95℃，继续保温1h，保温结束后升温T＝110-130℃进行减压蒸馏0.5-1.0h，降温至T＝75-85℃，向瓶中加入少量浓硫酸和不饱和羧酸类小单体，同时减压蒸馏并保温0.5h，得到功能性环胺基聚合物单体；
②环胺基脂肪醇醚结构的早强型聚羧酸减水剂的制备：将步骤①所得功能性环胺基聚合物单体与不饱和大单体加到入容器中，加入一定量的蒸馏水，加热到50-60℃使其全部熔化，同时向容器中加入引发剂、还原剂及链转移剂进行自由基聚合反应，继续保温2h-3h，即得环胺基脂肪醇醚功能性聚羧酸减水剂。
所述步骤①中脂肪醇聚氧乙烯醚的平均分子量为1400-1600。
所述步骤①中环胺化合物与脂肪醇聚氧乙烯醚的摩尔比为1:1.02-1.15。
所述步骤①中环胺化合物为环己胺或环戊胺。
所述步骤①中催化剂为尿素，其用量为脂肪醇聚氧乙烯醚和环胺化合物总量的3.0‰-4.5‰。
所述步骤①中不饱和羧酸类小单体与环胺化合物的摩尔比为1:1.00-2.00。
所述步骤①中不饱和羧酸类小单体为丙烯酸、亚甲基丁二酸、甲基丙烯酸、甲基烯丙基磺酸钠的一种或两种以上组合。
所述步骤①中浓硫酸用量为脂肪醇聚氧乙烯醚和环胺化合物总量的7.0‰-9.0‰。
所述步骤②中不饱和大单体为烯丙基聚氧乙烯醚、甲基烯丙基聚氧乙烯醚、异戊烯基聚氧乙烯醚的一种，其分子量为1800g/mol-4000g/mol。
所述步骤②中蒸馏水用量为步骤①中功能性环胺基聚合物单体和不饱和大单体总质量的1.5-1.7倍。
所述步骤②中引发剂为双氧水、过硫酸铵、过硫酸钠、过硫酸钾的一种或两种以上组合；还原剂为抗坏血酸；链转移剂为巯基乙酸、2-巯基丙酸、3-巯基丙酸、巯基乙醇的一种或两种以上组合；功能性环胺基聚合物单体、不饱和大单体、引发剂、还原剂和链转移剂的摩尔比为1：1.00-2.00：0.05-0.20：0.01-0.05：0.10-0.50。
本发明方法采用有别于以往有机胺类化合物为起始剂来合成单体或合成封端胺醚的方式获得减水剂早强性能，而采取了将脂肪醇与环胺化合物制备得到功能性聚合物，再利用氨基与羧基缩合脱水得到功能性环胺基聚合物单体，这样在不破坏聚羧酸单体本身结构的前提下合成出了早强型聚羧酸减水剂。本方法制备的聚羧酸高性能减水剂在保持减水和保坍功能的同时兼具早强功能，由于脂肪醇侧链的存在，更提高了产品4％-5％的减水率，使聚羧酸减水剂在混凝土领域的应用得到了更进一步的扩展。本发明方法控制简单、产品结构稳定、产品性能优异。
四、具体实施方式
实施例1：
将1400分子量脂肪醇聚氧乙烯醚600g加到入四口烧瓶中，加热到50℃使其全部熔化。向烧瓶中加入2g尿素，搅拌均匀。升温T＝80℃，向瓶中缓慢滴加环己胺40.4g，环己胺与所述脂肪醇聚氧乙烯醚的摩尔比为1:1.05，2h滴加完毕。滴加后升温T＝92℃，继续保温1h。保温结束后升温T＝125℃进行减压蒸馏1h，降温至T＝80℃，向瓶中加入浓硫酸4.5g和丙烯酸21g，丙烯酸与环己胺的摩尔比为1:1.4，同时减压蒸馏并保温0.5h，得到分子量为1535的功能性环胺基聚合物单体667.9g。
将功能性环胺基聚合物单体200g与分子量2400的甲基烯丙基聚氧乙烯醚375g加到入四口烧瓶中，加入920g蒸馏水，加热到55℃使其全部熔化，同时向烧瓶中加入过硫酸钠2.48g、抗坏血酸0.69g和巯基乙酸2.4g进行自由基聚合反应，继续保温2h即可得到环胺基脂肪醇醚功能性聚羧酸减水剂880.57g。功能性环胺基聚合物单体、分子量2400的甲基烯丙基聚氧乙烯醚、过硫酸钠、抗坏血酸和巯基乙酸的摩尔比为1：1.2：0.08：0.03：0.2。
实施例2：
将1500分子量脂肪醇聚氧乙烯醚500g加到入四口烧瓶中，加热到55℃使其全部熔化。向烧瓶中加入2.2g尿素，搅拌均匀。升温T＝80℃，向瓶中缓慢滴加环戊胺26.2g，环戊胺与所述脂肪醇聚氧乙烯醚的摩尔比为1:1.08，2.5h滴加完毕。滴加后升温T＝92℃，继续保温1h。保温结束后升温T＝125℃进行减压蒸馏1h，降温至T＝80℃，向瓶中加入浓硫酸3.9g和甲基烯丙基磺酸钠32.5g，甲基烯丙基磺酸钠与环戊胺的摩尔比为1:1.5，同时减压蒸馏并保温0.5h，得到分子量为1723的功能性环胺基聚合物单体564.8g。
将功能性环胺基聚合物单体150g与分子量3000的异戊烯基聚氧乙烯醚522.3g加到入四口烧瓶中，加入1042g蒸馏水，加热到55℃使其全部熔化，同时向烧瓶中加入过硫酸铵1.99g、抗坏血酸0.77g和3-巯基丙酸2.77g进行自由基聚合反应，继续保温2h即可得到环胺基脂肪醇醚功能性聚羧酸减水剂977.83g。功能性环胺基聚合物单体、分子量3000的异戊烯基聚氧乙烯醚、过硫酸铵、抗坏血酸和3-巯基丙酸的摩尔比为1：2：0.1：0.05：0.3。
实施例3：
将1600分子量脂肪醇聚氧乙烯醚600g加到入四口烧瓶中，加热到55℃使其全部熔化。向烧瓶中加入2.5g尿素，搅拌均匀。升温T＝85℃，向瓶中缓慢滴加环戊胺36.7g，环戊胺与所述脂肪醇聚氧乙烯醚的摩尔比为1:1.15，3h滴加完毕。滴加后升温T＝90℃，继续保温1h。保温结束后升温T＝125℃进行减压蒸馏0.5h，降温至T＝80℃，向瓶中加入浓硫酸5.7g和甲基丙烯酸18.5g，甲基丙烯酸与环戊胺的摩尔比为1:2.0，同时减压蒸馏并保温0.5h，得到分子量为1735的功能性环胺基聚合物单体663.4g。
将功能性环胺基聚合物单体160g与分子量4000的烯丙基聚氧乙烯醚405.8g加到入四口烧瓶中，加入850g蒸馏水，加热到55℃使其全部熔化，同时向烧瓶中加入过硫酸钾4.49、抗坏血酸0.32g和巯基乙醇3.60g进行自由基聚合反应，继续保温2h即可得到环胺基脂肪醇醚功能性聚羧酸减水剂874.21g。功能性环胺基聚合物单体、分子量4000的烯丙基聚氧乙烯醚、过硫酸钾、抗坏血酸和巯基乙醇的摩尔比为1：1.1：0.18：0.02：0.5。
实施例4：
将1450分子量脂肪醇聚氧乙烯醚600g加到入四口烧瓶中，加热到55℃使其全部熔化。向烧瓶中加入2.3g尿素，搅拌均匀。升温T＝85℃，向瓶中缓慢滴加环己胺40.2g，环己胺与所述脂肪醇聚氧乙烯醚的摩尔比为1:1.02，2h滴加完毕。滴加后升温T＝90℃，继续保温1h。保温结束后升温T＝130℃进行减压蒸馏1h，降温至T＝85℃，向瓶中加入浓硫酸5.4g和丙烯酸29.2g，丙烯酸与环己胺的摩尔比为1:1.0，同时减压蒸馏并保温0.5h，得到分子量为1585的功能性环胺基聚合物单体677.1g。
将功能性环胺基聚合物单体200g与分子量1800的甲基烯丙基聚氧乙烯醚340.7g加到入四口烧瓶中，加入910g蒸馏水，加热到55℃使其全部熔化，同时向烧瓶中加入过硫酸铵5.76、抗坏血酸0.22g和巯基乙酸1.16g进行自由基聚合反应，继续保温2h即可得到环胺基脂肪醇醚功能性聚羧酸减水剂847.84g。功能性环胺基聚合物单体、分子量1800的甲基烯丙基聚氧乙烯醚、过硫酸铵、抗坏血酸和巯基乙酸的摩尔比为1：1.5：0.20：0.01：0.1。
实施例5：
将1550分子量脂肪醇聚氧乙烯醚580g加到入四口烧瓶中，加热到55℃使其全部熔化。向烧瓶中加入2.2g尿素，搅拌均匀。升温T＝85℃，向瓶中缓慢滴加环戊胺36.7g，环戊胺与所述脂肪醇聚氧乙烯醚的摩尔比为1:1.15，3h滴加完毕。滴加后升温T＝90℃，继续保温1h。保温结束后升温T＝125℃进行减压蒸馏0.5h，降温至T＝80℃，向瓶中加入浓硫酸5.4g和甲基丙烯酸37g，甲基丙烯酸与环戊胺的摩尔比为1:1.0，保温0.5h得到功能性环胺基聚合物单体分子量1685单体661.3g。
将功能性环胺基聚合物单体155g与分子量2000的异戊烯基聚氧乙烯醚276.7g加到入四口烧瓶中，加入648g蒸馏水，加热到55℃使其全部熔化，同时向烧瓶中加入过硫酸钾1.50g、抗坏血酸0.64g和巯基乙醇3.60g进行自由基聚合反应，继续保温2h即可得到环胺基脂肪醇醚功能性聚羧酸减水剂737.44g。功能性环胺基聚合物单体、分子量2000的异戊烯基聚氧乙烯醚、过硫酸钾、抗坏血酸和巯基乙醇的摩尔比为1：1.5：0.06：0.04：0.5。
实施例6：
将1600分子量脂肪醇聚氧乙烯醚637g加到入四口烧瓶中，加热到55℃使其全部熔化。向烧瓶中加入2.4g尿素，搅拌均匀。升温T＝85℃，向瓶中缓慢滴加环己胺40.2g，环己胺与所述脂肪醇聚氧乙烯醚的摩尔比为1:1.06，2h滴加完毕。滴加后升温T＝90℃，继续保温1h。保温结束后升温T＝130℃进行减压蒸馏1h，降温至T＝85℃，向瓶中加入浓硫酸4.8和丙烯酸19.5g，丙烯酸与环己胺的摩尔比为1:1.5，保温0.5h得到功能性环胺基聚合物单体分子量1735单体703.9g。
将功能性环胺基聚合物单体200g与分子量2000的烯丙基聚氧乙烯醚415g加到入四口烧瓶中，加入978g蒸馏水，加热到55℃使其全部熔化，同时向烧瓶中加入过硫酸铵3.42、抗坏血酸0.41g和巯基乙醇2.70g进行自由基聚合反应，继续保温2h即可得到环胺基脂肪醇醚功能性聚羧酸减水剂921.53g。功能性环胺基聚合物单体、分子量2000的烯丙基聚氧乙烯醚、过硫酸铵、抗坏血酸和巯基乙酸的摩尔比为1：1.8：0.13：0.02：0.3。

Claims (8)

1.一种环胺基脂肪醇醚结构的早强型聚羧酸减水剂的制备方法，该方法包括下步骤：
①功能性环胺基聚合物单体的制备：将脂肪醇聚氧乙烯醚加到入容器中，加热到50-60℃使其全部熔化，向容器中加入定量催化剂，搅拌均匀，升温T＝75-85℃，向容器中缓慢滴加环胺化合物，2-3h滴加完毕，滴加后升温T＝90-95℃，继续保温1h，保温结束后升温T＝110-130℃进行减压蒸馏0.5-1.0h，降温至T＝75-85℃，向瓶中加入少量浓硫酸和不饱和羧酸类小单体，同时减压蒸馏并保温0.5h，得到功能性环胺基聚合物单体；
②环胺基脂肪醇醚结构的早强型聚羧酸减水剂的制备：将步骤①所得功能性环胺基聚合物单体与不饱和大单体加到入容器中，加入一定量的蒸馏水，加热到50-60℃使其全部熔化，同时向容器中加入引发剂、还原剂及链转移剂进行自由基聚合反应，继续保温2h-3h，即得环胺基脂肪醇醚功能性聚羧酸减水剂；
所述步骤①中环胺化合物为环己胺或环戊胺；
所述步骤①中脂肪醇聚氧乙烯醚的平均分子量为1400-1600；
所述步骤②中不饱和大单体为烯丙基聚氧乙烯醚、甲基烯丙基聚氧乙烯醚、异戊烯基聚氧乙烯醚的一种，其分子量为1800g/mol-4000g/mol。
2.根据权利要求1所述的一种环胺基脂肪醇醚结构的早强型聚羧酸减水剂的制备方法，其特征是：所述步骤①中环胺化合物与脂肪醇聚氧乙烯醚的摩尔比为1:1.02-1.15。
3.根据权利要求1所述的一种环胺基脂肪醇醚结构的早强型聚羧酸减水剂的制备方法，其特征是：所述步骤①中催化剂为尿素，其用量为脂肪醇聚氧乙烯醚和环胺化合物总量的3.0‰-4.5‰。
4.根据权利要求1所述的一种环胺基脂肪醇醚结构的早强型聚羧酸减水剂的制备方法，其特征是：所述步骤①中不饱和羧酸类小单体与环胺化合物的摩尔比为1:1.00-2.00。
5.根据权利要求1所述的一种环胺基脂肪醇醚结构的早强型聚羧酸减水剂的制备方法，其特征是：所述步骤①中不饱和羧酸类小单体为丙烯酸、亚甲基丁二酸、甲基丙烯酸、甲基烯丙基磺酸钠的一种或两种以上组合。
6.根据权利要求1所述的一种环胺基脂肪醇醚结构的早强型聚羧酸减水剂的制备方法，其特征是：所述步骤①中浓硫酸用量为脂肪醇聚氧乙烯醚和环胺化合物总量的7.0‰-9.0‰。
7.根据权利要求1所述的一种环胺基脂肪醇醚结构的早强型聚羧酸减水剂的制备方法，其特征是：所述步骤②中蒸馏水用量为步骤①中功能性环胺基聚合物单体和不饱和大单体总质量的1.5-1.7倍。
8.根据权利要求1所述的一种环胺基脂肪醇醚结构的早强型聚羧酸减水剂的制备方法，其特征是：所述步骤②中引发剂为双氧水、过硫酸铵、过硫酸钠、过硫酸钾的一种或两种以上组合；还原剂为抗坏血酸；链转移剂为巯基乙酸、2-巯基丙酸、3-巯基丙酸、巯基乙醇的一种或两种以上组合；功能性环胺基聚合物单体、不饱和大单体、引发剂、还原剂和链转移剂的摩尔比为1：1.00-2.00：0.05-0.20：0.01-0.05：0.10-0.50。
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