CN111992156A - Continuous synthesis method and application of sulfonated ketone-aldehyde condensation compound - Google Patents

Continuous synthesis method and application of sulfonated ketone-aldehyde condensation compound Download PDF

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CN111992156A
CN111992156A CN202010878756.1A CN202010878756A CN111992156A CN 111992156 A CN111992156 A CN 111992156A CN 202010878756 A CN202010878756 A CN 202010878756A CN 111992156 A CN111992156 A CN 111992156A
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姚型军
姜松
舒东博
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Abstract

本发明提供一种磺化酮醛缩合物的连续合成方法及其应用,属于高分子化合物制备技术领域。本发明通过将微结构反应器用于SAF的制备,有效克服了合成SAF过程中存在的反应过程强放热造成的控温不准确,反应时间长,反应混合物容易生成副产物,不能连续生产的问题,真正实现了对SAF的连续合成,因此具有良好的实际推广应用之价值。

Figure 202010878756

The invention provides a continuous synthesis method and application of a sulfonated ketone-aldehyde condensate, and belongs to the technical field of polymer compound preparation. By using the microstructure reactor for the preparation of SAF, the invention effectively overcomes the problems of inaccurate temperature control, long reaction time, easy generation of by-products in the reaction mixture, and inability to continuous production caused by strong exotherm in the reaction process in the process of synthesizing SAF. , truly realize the continuous synthesis of SAF, so it has a good value for practical promotion and application.

Figure 202010878756

Description

一种磺化酮醛缩合物的连续合成方法及其应用A kind of continuous synthesis method of sulfonated ketone aldehyde condensate and its application

技术领域technical field

本发明属于高分子化合物制备技术领域,涉及一种磺化酮醛缩合物的连续合成方法及其应用。The invention belongs to the technical field of polymer compound preparation, and relates to a continuous synthesis method and application of a sulfonated ketone-aldehyde condensate.

背景技术Background technique

公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解,而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。The information disclosed in this Background section is only for enhancement of understanding of the general background of the invention and should not necessarily be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.

脂肪族减水剂是以醛、酮羰基化合物为主要原料,在碱性条件下缩合,得到脂肪族高分子链,并通过亚硫酸盐的加成作用,在其分子链上引入亲水性的磺酸基团,形成具有表面活性的一种高分子减水剂。最具代表性的是以甲醛、丙酮为原料,以亚硫酸钠和亚硫酸氢钠为磺化剂制备的磺化丙酮-甲醛缩合物(SAF),它是一种脂肪族磺酸盐高效减水剂,分子量在4000~10000范围内。起初它被用作深井固井作业水泥高温分散减阻剂,具有较高的减水率,能明显地改善水泥的流变性,降低新拌水泥浆的经时损失,使水泥浆具有良好的和易性的同时,增强效果明显,并且具有良好的耐高温和抗盐能力,适用于深井、超深井和盐水井的固井作业,在钻井行业迅速取代了萘系磺酸盐减水剂(张鑫,SAF的合成与改性研究[D].济南:济南大学,2012)。SAF减水剂能降低水的表面张力,是一种有引气作用的新型减水剂。作为混凝土高效减水剂,不引气、不缓凝、坍落度损失小,尤其适宜在温度较高的条件下使用,是一类很有发展前途的高效减水剂(EP0163459,DE3429068,CN1066448A)。由于其原料易得,生产工艺简单,减水效果优良等特点,广泛应用于各种工程中。脂肪族磺酸盐减水剂的生产过程中无“三废”排放,生产和使用过程对环境无污染,因此,生产脂肪族磺酸盐减水剂与萘系高效减水剂相比,具有较好的性价比,因此引起外加剂生产商和使用单位的广泛关注,加快了对其生产工艺和应用性能方面的研究。目前合成磺化丙酮甲醛缩聚物的方法有两种,一种是向45℃亚硫酸钠水溶液中滴加丙酮,机械搅拌20min至溶液变澄清,接着继续滴加37%的甲醛水溶液,控制反应温度在65℃以下。滴加完后,反应体系升温至80~85℃。反应3h,结束反应,将反应液冷却至室温,最终的pH高于11,得到产物固含量为35%。通过控制反应过程滴加甲醛的量,控制SAF分子量的大小,控制亚硫酸钠的用料量来控制磺酸基团的含量,产物分子量大小在2.08~3.18万,PDI=1.16~1.59。(R.Li et al.EnergyConversion and Management,64(2012)139~144;Hongming Lou et.al,Cement andConcrete Research 42(2012)1043~1048);周明松等,精细化工,2005,22(3):18-188)。Aliphatic superplasticizers use aldehyde and ketone carbonyl compounds as the main raw materials, condense under alkaline conditions to obtain aliphatic polymer chains, and introduce hydrophilic molecules into their molecular chains through the addition of sulfites. The sulfonic acid group forms a polymer water reducing agent with surface activity. The most representative is the sulfonated acetone-formaldehyde condensate (SAF) prepared with formaldehyde and acetone as raw materials and sodium sulfite and sodium bisulfite as sulfonating agents. It is an aliphatic sulfonate superplasticizer. , the molecular weight is in the range of 4000 to 10000. At first, it was used as a high-temperature dispersion drag-reducing agent for cement in deep well cementing operations. It has a high water-reducing rate, can significantly improve the rheological properties of cement, reduce the loss of freshly mixed cement over time, and make the cement slurry have good performance and stability. At the same time of workability, the enhancement effect is obvious, and it has good high temperature resistance and salt resistance. It is suitable for cementing operations in deep wells, ultra-deep wells and brine wells. It has quickly replaced naphthalene sulfonate water reducers in the drilling industry. Xin, Synthesis and modification of SAF [D]. Jinan: Jinan University, 2012). SAF water reducing agent can reduce the surface tension of water and is a new type of water reducing agent with air-entraining effect. As a high-efficiency water-reducing agent for concrete, it has no air-entraining, no retardation, and small slump loss, and is especially suitable for use under high temperature conditions. ). Due to its easy availability of raw materials, simple production process and excellent water-reducing effect, it is widely used in various projects. There is no "three wastes" discharge in the production process of aliphatic sulfonate water-reducing agent, and the production and use process has no pollution to the environment. Therefore, the production of aliphatic sulfonate water-reducing agent is more efficient than naphthalene-based high-efficiency water-reducing agent. The good cost performance has attracted extensive attention from admixture manufacturers and user units, and accelerated the research on its production process and application performance. At present, there are two methods for synthesizing sulfonated acetone-formaldehyde polycondensate. One is to add acetone dropwise to an aqueous solution of sodium sulfite at 45°C, mechanically stir for 20 minutes until the solution becomes clear, and then continue to add 37% aqueous formaldehyde solution dropwise, and control the reaction temperature at 65 °C. ℃ or lower. After the dropwise addition, the temperature of the reaction system was raised to 80-85°C. The reaction was completed for 3 hours, the reaction solution was cooled to room temperature, the final pH was higher than 11, and the solid content of the product was 35%. By controlling the amount of formaldehyde added dropwise in the reaction process, the molecular weight of SAF and the amount of sodium sulfite are controlled to control the content of sulfonic acid groups. (R.Li et al.EnergyConversion and Management, 64(2012)139~144; Hongming Lou et.al, Cement and Concrete Research 42(2012)1043~1048); Zhou Mingsong et al, Fine Chemicals, 2005, 22(3) : 18-188).

制备SAF的另外一种方法是将丙酮、甲醛和亚硫酸钠按照如下配比:丙酮:甲醛亚硫酸钠=6:3:1加入反应瓶中,在强碱的作用下,发生缩聚反应,通过控制碱液的加入速度来控制反应的进行。开始反应混合物中碱的浓度低,反应速度慢,当碱的浓度超过一定值时,反应速度明显加快,反应热难以及时散发,反应物体内温度急剧上升,使原料挥发严重,很容易出现冲料现象,难以控制产品的质量。Another method for preparing SAF is to add acetone, formaldehyde and sodium sulfite according to the following proportions: acetone: sodium formaldehyde sulfite=6:3:1 is added to the reaction flask, under the effect of strong alkali, a polycondensation reaction occurs, and by controlling the lye The rate of addition controls the progress of the reaction. At the beginning, the concentration of alkali in the reaction mixture is low, and the reaction speed is slow. When the concentration of alkali exceeds a certain value, the reaction speed is obviously accelerated, the heat of reaction is difficult to dissipate in time, and the temperature in the reactant rises sharply, which makes the raw materials volatilize seriously, and it is easy to appear flushing phenomenon, it is difficult to control the quality of the product.

在对合成方法进行的实验研究中,发现不同的加料顺序对合成反应及磺化缩聚物的分散性能均有很大的影响,说明加料方法不同,反应机理也不相同。如果先将亚硫酸盐配成适当浓度的溶液,常温下加入丙酮,并在低温下反应一段时间后,再滴加甲醛溶液,反应温度易于控制,所得磺化缩聚物的分散性能良好。可能的反应机理是磺化剂与丙酮的亲核加成反应,再次是丙酮与甲醛的交叉羟醛缩合反应,最后是磺化产物和缩合产物的缩聚反应:In the experimental research on the synthesis method, it is found that different feeding sequences have a great influence on the synthesis reaction and the dispersion properties of the sulfonated polycondensate, indicating that different feeding methods have different reaction mechanisms. If sulfite is prepared into a solution of appropriate concentration, acetone is added at room temperature, and after a period of reaction at low temperature, formaldehyde solution is added dropwise, the reaction temperature is easy to control, and the obtained sulfonated polycondensate has good dispersibility. The possible reaction mechanism is the nucleophilic addition reaction of the sulfonating agent and acetone, again the cross-aldol condensation reaction of acetone and formaldehyde, and finally the polycondensation reaction of the sulfonated product and the condensation product:

a)在亚硫酸盐溶液中加入丙酮,生成α-羟基磺酸盐,反应可逆:a) Add acetone to the sulfite solution to generate α-hydroxysulfonate, and the reaction is reversible:

Figure BDA0002653450950000021
Figure BDA0002653450950000021

Figure BDA0002653450950000022
Figure BDA0002653450950000022

Figure BDA0002653450950000023
Figure BDA0002653450950000023

反应一段时间后滴加甲醛,由于此时反应体系中丙酮过量,在碱性介质中丙酮与醛发生交叉的羟醛缩合反应,生成二羟甲基丙酮。Formaldehyde is added dropwise after the reaction for a period of time, since the acetone in the reaction system is excessive at this time, the aldol condensation reaction in which the acetone and the aldehyde are crossed in an alkaline medium generates dimethylol acetone.

Figure BDA0002653450950000024
Figure BDA0002653450950000024

随着反应时间延长,溶液中二羟甲基丙酮浓度增大;;由于反应放热,温度升高,二羟甲基丙酮之间发生脱水反应生成缩聚物。With the prolongation of the reaction time, the concentration of dimethylolacetone in the solution increases; due to the exothermic reaction, the temperature rises, and the dehydration reaction occurs between the dimethylolacetones to form a polycondensate.

Figure BDA0002653450950000025
Figure BDA0002653450950000025

Figure BDA0002653450950000031
Figure BDA0002653450950000031

二羟甲基丙酮缩聚物的聚合度大小是影响SAF性能的关键因素;聚合度太小,分散性能不好,聚合度太大,水溶性不好,可通过控制聚合工艺来获得具有良好水溶性和分散性能的SAF。采用先加入丙酮与亚硫酸盐反应的方法,保证溶液有足够的羟基磺酸盐存在,由于羟基磺酸盐对缩聚而言是单官能团的,一旦与二羟甲基丙酮作用,即可中止链增长反应;采用滴加甲醛的方式,既可有效地控制二羟甲基丙酮的平均聚合度,又可有效防止因生成多羟甲基丙酮而发生交联反应,避免凝胶沉淀的生成。如果将丙酮和甲醛一起加入到亚硫酸盐溶液中,由于α-羟基磺酸盐的生成是可逆的(反应(1)-(3)),大量的丙酮和甲醛发生交叉的羟醛缩合反应(反应(4)),由于缩聚反应速率较快,反应热难以及时排除,反应温度急剧升高,容易发生冲料事故;同时,生成的二羟甲基丙酮快速发生脱水反应生成缩聚物(反应(5)),导致缩聚物平均聚合度过大,水溶性和分散性能降低。此外,由于大量甲醛的存在,容易生成多羟甲基丙酮,脂肪链之间的交联导致凝胶沉淀生成(庞金兴等,武汉理工大学学报,2002,24(6):15-17)。The degree of polymerization of dimethylol acetone polycondensate is a key factor affecting the performance of SAF; too small degree of polymerization, poor dispersion performance, too large degree of polymerization, poor water solubility, good water solubility can be obtained by controlling the polymerization process and dispersion properties of SAF. The method of first adding acetone and reacting with sulfite is used to ensure that there is enough hydroxysulfonate in the solution. Since hydroxysulfonate is a monofunctional group for polycondensation, once it reacts with dimethylol acetone, the chain can be terminated. Growth reaction; by adding formaldehyde dropwise, the average degree of polymerization of dimethylol acetone can be effectively controlled, and the cross-linking reaction caused by the formation of polymethylol acetone can be effectively prevented, and the formation of gel precipitation can be avoided. If acetone and formaldehyde are added together to the sulfite solution, since the formation of α-hydroxysulfonate is reversible (reactions (1)-(3)), a large amount of acetone and formaldehyde undergo cross aldol condensation ( Reaction (4)), because the polycondensation reaction rate is faster, the heat of reaction is difficult to remove in time, the temperature of reaction rises sharply, and is prone to material punching accident; Simultaneously, the dimethylol acetone that generates quickly takes place dehydration reaction to generate polycondensate (reaction ( 5)), resulting in excessive average polymerization of the polycondensate, and reduced water solubility and dispersibility. In addition, due to the presence of a large amount of formaldehyde, polymethylol acetone is easily generated, and the cross-linking between aliphatic chains leads to the formation of gel precipitation (Pang Jinxing et al., Wuhan University of Technology, 2002, 24(6): 15-17).

发明人发现,以上合成SAF的方法都是间歇操作,加料过程中都是采取滴加进料的方式防止反应局部过热。控温不准确,反应时间长,原料利用率低,操作工艺繁琐。连续合成SAF的方法至今没有报道。The inventors found that the above methods for synthesizing SAF are all intermittent operations, and during the feeding process, the method of dropping feed is adopted to prevent local overheating of the reaction. The temperature control is inaccurate, the reaction time is long, the utilization rate of raw materials is low, and the operation process is cumbersome. The method of continuous synthesis of SAF has not been reported so far.

发明内容SUMMARY OF THE INVENTION

针对现有技术合成磺化丙酮甲醛缩聚物过程中存在的反应过程强放热造成的控温不准确,反应时间长,反应混合物容易生成副产物,不能连续生产等问题,本发明提供一种磺化酮醛缩合物(如磺化丙酮甲醛缩聚物)的连续合成方法及其应用,本发明通过将微结构反应器用于磺化丙酮甲醛缩合物的制备,有效克服了合成磺化醛酮缩聚物过程中存在的反应过程强放热造成的控温不准确,反应时间长,反应混合物容易生成副产物,不能连续生产的问题,真正实现了对磺化醛酮缩聚物的连续合成,因此具有良好的实际推广应用之价值。Aiming at the problems of inaccurate temperature control caused by strong exotherm in the reaction process, long reaction time, easy generation of by-products in the reaction mixture, and inability to continuously produce in the prior art synthesis of sulfonated acetone-formaldehyde polycondensate, the present invention provides a sulfonic acid The continuous synthesis method of sulfonated acetone-formaldehyde condensate (such as sulfonated acetone-formaldehyde polycondensate) and its application, the invention effectively overcomes the synthetic method of sulfonated acetone-formaldehyde condensate by using a microstructure reactor for the preparation of the sulfonated acetone-formaldehyde condensate In the process, the temperature control caused by the strong exotherm of the reaction process is inaccurate, the reaction time is long, the reaction mixture is easy to generate by-products, and the problems cannot be continuously produced. The continuous synthesis of the sulfonated aldehyde and ketone polycondensate is truly realized, so it has good performance. The value of practical promotion and application.

为了实现所述目的,本发明涉及以下技术方案:In order to achieve the purpose, the present invention relates to the following technical solutions:

本发明的第一个方面,提供连续反应器在连续合成磺化酮醛缩合物中的应用。The first aspect of the present invention provides the application of a continuous reactor in the continuous synthesis of sulfonated ketone-aldehyde condensate.

其中,所述连续反应器为微结构反应器;本发明通过研究发现,通过在微结构反应器中合成磺化酮醛缩聚物(如SAF),可以对温度精确控制,有效降低后续缩聚反应中放出的热量的积累,避免了反应体系过热引起的原料挥发严重、聚合过快形成胶化物的问题,反应固含量可达52%以上。同时,由于微结构反应器中磺化聚合可在毫秒内完成,反应动力学的差异对反应物的选择性的提升作用显著增强,仅通过反应物比例和温度的调控即可以方便地控制SAF的分子量的大小、分布及固含量。Wherein, the continuous reactor is a microstructure reactor; through research, the present invention finds that by synthesizing a sulfonated ketone aldehyde polycondensate (such as SAF) in a microstructure reactor, the temperature can be precisely controlled, and the subsequent polycondensation reaction can be effectively reduced. The accumulation of the released heat avoids the problems of serious volatilization of raw materials caused by overheating of the reaction system, and the formation of gelatinous products caused by excessive polymerization, and the solid content of the reaction can reach more than 52%. At the same time, since the sulfonation polymerization in the microstructured reactor can be completed in milliseconds, the difference in reaction kinetics significantly enhances the selectivity of the reactants, and the SAF can be easily controlled only by adjusting the ratio and temperature of the reactants. The size, distribution and solids content of molecular weight.

需要说明的是,与微结构反应器类似,全混流反应器、管式反应器也属于连续反应器,都可以控制反应时间,提高反应效率,不同程度提高反应物的选择性,因此上述连续反应器在连续合成磺化酮醛缩聚物(如SAF)中的应用同样属于本申请的保护范围。It should be noted that, similar to the microstructure reactor, the fully mixed flow reactor and the tubular reactor are also continuous reactors, which can control the reaction time, improve the reaction efficiency, and improve the selectivity of reactants to varying degrees. Therefore, the above continuous reaction The application of the device in the continuous synthesis of sulfonated ketone-aldehyde polycondensates (such as SAF) also falls within the protection scope of this application.

本发明的第二个方面,提供一种连续合成磺化酮醛缩合物的方法,所述方法包括:在连续反应器中基于酮磺化法连续合成磺化酮醛缩合物。A second aspect of the present invention provides a method for continuously synthesizing a sulfonated ketone-aldehyde condensate, the method comprising: continuously synthesizing a sulfonated ketone-aldehyde condensate based on a ketone sulfonation method in a continuous reactor.

如在合成SAF中,由于磺化丙酮来不及形成大颗粒沉淀就直接与二羟基丙酮进行缩合,连续反应器中以微结构反应器的效果最好。需要说明的是,在研究中,本发明还对其他的脂肪醛制备方法进行了实验,但由于其他工艺流程较长,操作过程环节较多,产品收率并不稳定。For example, in the synthesis of SAF, the sulfonated acetone is directly condensed with dihydroxyacetone before it can form a large particle precipitate, and the microstructure reactor is the best in the continuous reactor. It should be noted that, in the research, the present invention has also carried out experiments on other preparation methods of fatty aldehydes, but because other technological processes are long and there are many operation process links, the product yield is not stable.

具体的,所述方法包括:Specifically, the method includes:

磺化剂与酮类化合物在连续反应器中反应,得到磺化酮类化合物溶液;The sulfonating agent reacts with the ketone compound in a continuous reactor to obtain a solution of the sulfonated ketone compound;

将上述磺化酮类化合物溶液与醛类化合物溶液在碱性条件的连续反应器中反应,反应产物经纯化后得到磺化酮醛缩合物产品。The sulfonated ketone compound solution and the aldehyde compound solution are reacted in a continuous reactor under alkaline conditions, and the reaction product is purified to obtain a sulfonated ketone aldehyde condensate product.

所述纯化步骤包括中和、(旋蒸)干燥、(乙醇)析出结晶、二次干燥和研磨。The purification steps include neutralization, (rotary evaporation) drying, (ethanol) crystallization, secondary drying and grinding.

其中,所述连续反应器为微结构反应器、全混流反应器或管式反应器;优选为微结构反应器。Wherein, the continuous reactor is a microstructure reactor, a total mixed flow reactor or a tubular reactor; preferably a microstructure reactor.

优选的,所述磺化剂与酮类化合物的摩尔比为1:0.1~5;进一步优选为1:0.5~5;Preferably, the molar ratio of the sulfonating agent to the ketone compound is 1:0.1-5; more preferably, it is 1:0.5-5;

优选的,所述磺化剂与酮类化合物在连续反应器中反应的条件具体为:温度为10~60℃,停留时间为0.1~600s;进一步优选为:温度为10~50℃,停留时间为0.5~600s。Preferably, the conditions for the reaction of the sulfonating agent and the ketone compound in the continuous reactor are as follows: the temperature is 10-60°C, and the residence time is 0.1-600s; more preferably, the temperature is 10-50°C, and the residence time is 10-50°C. For 0.5 ~ 600s.

其中,所述磺化剂包括但不限于木质素磺酸钠、亚硫酸钠、焦亚硫酸钠、含咪唑基磺酸钠、噻唑基磺酸钠、吡啶基磺酸钠、芳香基磺酸钠、取代萘磺酸钠、脂肪基磺酸钠溶液;Wherein, the sulfonating agent includes but is not limited to sodium lignosulfonate, sodium sulfite, sodium metabisulfite, sodium imidazole sulfonate, sodium thiazolyl sulfonate, sodium pyridyl sulfonate, sodium aryl sulfonate, substituted naphthalene sulfonate Sodium, aliphatic sodium sulfonate solution;

所述酮类化合物包括但不限于芳香酮、芳香多酮、脂肪酮或脂肪多酮,如丙酮、丁酮、甲乙酮、苯乙酮等。The ketone compounds include, but are not limited to, aromatic ketones, aromatic polyketones, aliphatic ketones or aliphatic polyketones, such as acetone, butanone, methyl ethyl ketone, acetophenone, and the like.

所述磺化酮与醛类的摩尔比为(0.8~4):1。The molar ratio of the sulfonated ketone to the aldehyde is (0.8-4):1.

所述醛类化合物包括但不限于脂肪醛、脂肪多醛、芳香醛或芳香多醛;如甲醛、乙醛等。The aldehyde compounds include, but are not limited to, aliphatic aldehydes, aliphatic polyaldehydes, aromatic aldehydes or aromatic polyaldehydes; such as formaldehyde, acetaldehyde, and the like.

优选的,所述微结构反应器包括依次连接的微混合器和微通道反应器,进一步优选的,所述微结构反应器均置于恒温水浴中。Preferably, the microstructure reactor includes a micromixer and a microchannel reactor connected in sequence, and further preferably, the microstructure reactors are placed in a constant temperature water bath.

加入碱液形成碱性环境,所述碱性环境pH为7~12;Add lye to form an alkaline environment, and the pH of the alkaline environment is 7-12;

优选的,溶解磺化剂与固体碱所用的溶剂为水;水与氢氧化钠质量比为1~8:1;特别地,当质量比为6:1时,反应物的固含量提升了5.3%左右。Preferably, the solvent used for dissolving the sulfonating agent and the solid base is water; the mass ratio of water to sodium hydroxide is 1-8:1; in particular, when the mass ratio is 6:1, the solid content of the reactant is increased by 5.3 %about.

优选的,所述微结构反应器材质可以是不锈钢、玻璃、石英、陶瓷、聚四氟乙烯、无机硅或Peek材料;Preferably, the material of the microstructure reactor can be stainless steel, glass, quartz, ceramics, polytetrafluoroethylene, inorganic silicon or Peek material;

优选的,所述的微结构反应器通道尺寸为0.1μm~10mm;Preferably, the channel size of the microstructure reactor is 0.1 μm~10 mm;

优选的,所述的微结构反应器为管式结构。Preferably, the microstructure reactor is a tubular structure.

本发明的第三个方面,提供一种较优的连续反应制备磺化丙酮甲醛缩合物的方法,包括:A third aspect of the present invention provides a method for preparing a sulfonated acetone formaldehyde condensate by a preferred continuous reaction, comprising:

S1、将液体原料亚硫酸钠与丙酮按亚硫酸钠与丙酮的摩尔比1:(2~5)分别用泵同时注入串联的全混流反应器、管式反应器或微结构反应器中,在反应温度20~50℃,停留时间为0.1~600s的条件下进行反应,得到磺化丙酮溶液;S1, the liquid raw material sodium sulfite and acetone are respectively injected into the series-connected fully mixed flow reactor, tubular reactor or microstructure reactor by the mol ratio of sodium sulfite and acetone 1: (2~5) respectively with a pump, at a reaction temperature of 20~ The reaction is carried out at 50°C with a residence time of 0.1 to 600s to obtain a sulfonated acetone solution;

S2、将步骤S1中的反应产物磺化丙酮溶液与甲醛水溶液按照磺化丙酮与甲醛的摩尔比为(0.8~4):1注入另外一个全混流反应器、管式反应器或微结构反应器中,pH=7~12,控制反应温度为20~50℃,停留时间为0.5~600s的条件下进行反应;反应物经旋蒸干燥,乙醇析出结晶,干燥,研磨后得到SAF产品。S2, inject the reaction product sulfonated acetone solution and formaldehyde solution in step S1 into another fully mixed flow reactor, tubular reactor or microstructure reactor according to the molar ratio of sulfonated acetone and formaldehyde as (0.8~4): 1 , pH=7~12, control the reaction temperature to be 20~50℃, and carry out the reaction under the condition that the residence time is 0.5~600s; the reactant is dried by rotary evaporation, and ethanol is precipitated to crystallize, dried, and ground to obtain the SAF product.

加入碱液形成碱性条件,所述的碱可以为氢氧化钠、磷酸钠、乙酸钠、碳酸钠或碱性离子液体;优选为氢氧化钠水溶液;水与氢氧化钠质量比为1~8:1;优选为5~6:1。Add lye to form alkaline conditions, and the alkali can be sodium hydroxide, sodium phosphate, sodium acetate, sodium carbonate or alkaline ionic liquid; preferably an aqueous sodium hydroxide solution; the mass ratio of water to sodium hydroxide is 1 to 8 : 1; preferably 5 to 6: 1.

优选的,所述的微结构反应器为微混合器或者是由微混合器与微通道反应器连接组成。Preferably, the microstructured reactor is a micromixer or is formed by connecting a micromixer and a microchannel reactor.

所述的管式反应器直径为10~100mm,长度为5~15m。The tubular reactor has a diameter of 10-100 mm and a length of 5-15 m.

微混合器和微通道反应器的通道尺寸为0.2m~8mm,微通道反应器的长度为0.5m~20m。The channel size of the micro-mixer and the micro-channel reactor is 0.2m-8mm, and the length of the micro-channel reactor is 0.5m-20m.

本发明的第三个方面,提供采用上述任一方法制备的磺化酮醛缩合物;优选的,所述磺化酮醛缩合物为磺化丙酮甲醛缩合物。The third aspect of the present invention provides a sulfonated ketone-aldehyde condensate prepared by any of the above methods; preferably, the sulfonated ketone-aldehyde condensate is a sulfonated acetone-formaldehyde condensate.

本发明的第四个方面,提供上述磺化酮醛缩合物在如下任意一种或多种中的应用:The fourth aspect of the present invention provides the application of the above-mentioned sulfonated ketone aldehyde condensate in any one or more of the following:

1)分散剂;1) dispersant;

2)减水剂。2) Water reducing agent.

所述一个或多个技术方案的有益技术效果:Beneficial technical effects of the one or more technical solutions:

(1)上述技术方案提供一种利用连续反应器制备磺化酮醛缩合物特别是SAF的工艺方法,该方法解决了在常规釜式反应器中因为反应时间过长,温度控制不准确,磺化丙酮不稳定易发生沉淀反应,丙酮易挥发、产品固含量低的问题;(1) above-mentioned technical scheme provides a kind of process method utilizing continuous reactor to prepare sulfonated ketone aldehyde condensate especially SAF, this method solves in conventional tank reactor because the reaction time is too long, temperature control is inaccurate, sulfonated ketone is The acetone is unstable and prone to precipitation reaction, acetone is volatile and the product solid content is low;

(2)上述技术方案解决了因为反应过程存在局部热点,造成生产过程不安全的问题,实现了SAF的连续安全生产,操作方便。反应混合物经过旋蒸干燥、乙醇析出、研磨,得到SAF。(2) The above technical solution solves the problem of unsafe production process due to the existence of local hot spots in the reaction process, realizes continuous safe production of SAF, and is easy to operate. The reaction mixture was dried by rotary evaporation, precipitated with ethanol, and ground to obtain SAF.

(3)上述技术方案中制备方法简单、高效、实用性强,易于推广。(3) The preparation method in the above technical scheme is simple, efficient, practical, and easy to popularize.

附图说明Description of drawings

构成本发明的一部分的说明书附图用来提供对本发明的进一步理解,本发明的示意性实施例及其说明用于解释本发明,并不构成对本发明的不当限定。The accompanying drawings forming a part of the present invention are used to provide further understanding of the present invention, and the exemplary embodiments of the present invention and their descriptions are used to explain the present invention, and do not constitute an improper limitation of the present invention.

图1是本发明实施例中微结构反应器制备SAF的装置流程示意图;Fig. 1 is the schematic flow diagram of the device for preparing SAF in the microstructure reactor in the embodiment of the present invention;

其中,A1,A2,A3为液相色谱泵,B1,B2为微混合器,C1,C2为微通道反应器,D1,D2微结构反应器,E1,E2为恒温箱,F1,F2,F3分别为磺化剂,酮类化合物,醛类化合物溶液试剂瓶。Among them, A1, A2, A3 are liquid chromatography pumps, B1, B2 are micromixers, C1, C2 are microchannel reactors, D1, D2 microstructure reactors, E1, E2 are incubators, F1, F2, F3 Respectively, reagent bottles for sulfonating agent, ketone compound and aldehyde compound solution.

图2是本发明实施例3中SAF的FTIR图,其中图例B即为SAF。FIG. 2 is an FTIR diagram of SAF in Example 3 of the present invention, wherein legend B is SAF.

具体实施方式Detailed ways

应该指出,以下详细说明都是例示性的,旨在对本发明提供进一步的说明。除非另有指明,本文使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。It should be noted that the following detailed description is exemplary and intended to provide further explanation of the invention. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

需要注意的是,这里所使用的术语仅是为了描述具体实施方式,而非意图限制根据本发明的示例性实施方式。如在这里所使用的,除非上下文另外明确指出,否则单数形式也意图包括复数形式,此外,还应当理解的是,当在本说明书中使用术语“包含”和/或“包括”时,其指明存在特征、步骤、操作、器件、组件和/或它们的组合。应理解,本发明的保护范围不局限于下述特定的具体实施方案;还应当理解,本发明实施例中使用的术语是为了描述特定的具体实施方案,而不是为了限制本发明的保护范围。It should be noted that the terminology used herein is for the purpose of describing specific embodiments only, and is not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly dictates otherwise, the singular is intended to include the plural as well, furthermore, it is to be understood that when the terms "comprising" and/or "including" are used in this specification, it indicates that There are features, steps, operations, devices, components and/or combinations thereof. It should be understood that the protection scope of the present invention is not limited to the following specific specific embodiments; it should also be understood that the terms used in the examples of the present invention are for describing specific specific embodiments, rather than for limiting the protection scope of the present invention.

如前所述,现有的SAF合成工艺主要有以下6种:As mentioned above, the existing SAF synthesis processes mainly include the following six types:

(1)把NaOH溶于一定量的水中成溶液,将其加入带有回流冷凝器的反应器中,而后加入丙酮,控制温度在52℃以下,加完后滴加甲醛(37%)、焦亚硫酸钠及水组成的混合物;滴加结束后,升温至80℃恒温反应2h,再加水稀释,冷却到50℃以下即得成品。该工艺的主要特点是:反应周期较长(约为22h),反应产物的分子量分布不均匀,产品颜色深,而且产品的分散性和稳定性均较差,加入混凝土中,具有一定的引气性。(1) Dissolve NaOH in a certain amount of water to form a solution, add it to a reactor with a reflux condenser, then add acetone, control the temperature below 52 ° C, add dropwise formaldehyde (37%), coke The mixture composed of sodium sulfite and water; after the dropwise addition, the temperature was raised to 80°C for constant temperature reaction for 2h, then diluted with water, and cooled to below 50°C to obtain the finished product. The main features of this process are: the reaction period is long (about 22h), the molecular weight distribution of the reaction product is uneven, the color of the product is dark, and the dispersibility and stability of the product are poor. sex.

(2)在带有回流冷凝器的反应瓶内,先配制一定浓度的亚硫酸钠溶液,低温下(40℃)加入丙酮,回流一定时间后,由滴液漏斗缓慢加入甲醛,搅拌,防止溢锅:加完后加热升温至80℃~120℃,恒温反应3~6h,可得到浓度为30%~4 0%的棕红色液态成品。该工艺的主要特点是:工艺过程操作简单,设备投入少,合成过程中碱量和温度控制是关键,反应过程中可以通过调节甲醛滴加速度来控制体系升温速度,所得到的产品色泽较深,减水率即分散性较好。(2) In a reaction flask with a reflux condenser, first prepare a sodium sulfite solution with a certain concentration, add acetone at a low temperature (40°C), and after refluxing for a certain period of time, slowly add formaldehyde from a dropping funnel, and stir to prevent the pot from overflowing: After the addition, the temperature is heated to 80°C to 120°C, and the constant temperature reaction is performed for 3 to 6 hours to obtain a brown-red liquid product with a concentration of 30% to 40%. The main features of this process are: the process is simple to operate, the equipment investment is small, the control of the amount of alkali and temperature in the synthesis process is the key, and the rate of temperature rise of the system can be controlled by adjusting the drop rate of formaldehyde during the reaction process, and the obtained product has a darker color. The water reduction rate means better dispersibility.

(3)将要求量的亚硫酸钠及适量的水加入到带有回流冷凝器的反应瓶中,控制体系温度(70℃以下),在规定的时间内,逐步加入丙酮、甲醛和焦亚硫酸钠的混合液;加完后,在50~70℃下反应0.5~3h,然后升温到60~70C恒温反应1~3h,即得深棕红色液体产品。该工艺是通过分步添加甲醛、丙酮和焦亚硫酸钠的混合液来控制反应温度。工艺过程中加料温度低、原材料挥发少;所得产品色泽深,减水率即分散性适中;但缺点是设备复杂,生产步骤多,受环境和气候影响较大。(3) Add the required amount of sodium sulfite and an appropriate amount of water into the reaction flask with the reflux condenser, control the temperature of the system (below 70 ° C), and gradually add the mixed solution of acetone, formaldehyde and sodium metabisulfite within the specified time. ; After adding, react at 50~70℃ for 0.5~3h, then heat up to 60~70℃ for constant temperature reaction for 1~3h to obtain dark brown-red liquid product. The process is to control the reaction temperature by adding a mixed solution of formaldehyde, acetone and sodium metabisulfite step by step. During the process, the feeding temperature is low and the volatilization of raw materials is low; the color of the obtained product is dark, and the water reduction rate, that is, the dispersibility is moderate; but the disadvantage is that the equipment is complicated, the production steps are many, and it is greatly affected by the environment and climate.

(4)取一定量的焦亚硫酸钠溶于一定量的水中,分别加入浓度为30%的NaOH溶液和37%的甲醛,加完后加热至50~70℃,再滴入丙酮与甲醛的混合溶液,反应lh后,加热至95℃,再回流反应1h,即得成品。该工艺过程操作简单,但温度控制是关键。所得产品色泽浅,水溶性好,对减水剂来说,减水率和保坍效果都比较好;缺点是生产过程中易胶化,反应时间长,过程复杂,需外加催化剂。(4) Dissolve a certain amount of sodium metabisulfite in a certain amount of water, add 30% NaOH solution and 37% formaldehyde respectively, heat to 50-70°C after adding, and then dropwise add the mixed solution of acetone and formaldehyde , after the reaction for 1h, heated to 95 ℃, and then refluxed for 1h to obtain the finished product. The process is simple to operate, but temperature control is the key. The obtained product is light in color and good in water solubility, and has good water reducing rate and slump retention effect for the water reducing agent; the disadvantage is that it is easy to gel during the production process, the reaction time is long, the process is complicated, and an external catalyst is required.

(5)在带有回流冷凝器的反应器中,搅拌下将磺化剂和催化剂溶于水中,加入37%的甲醛,于60~65℃下滴加由丙酮和甲醛组成的混合液;加完后再迅速滴加甲醛,于95℃下反应2h,而后降温到50℃以下即得成品。该工艺对反应温度的控制要求不高,反应周期短(约为7h)。所得产品颜色浅,减水率高,高温保坍效果好,且对不同水泥具有较好的适应性;缺点是甲醛需分三次来加,每次的添加量很难准确确定。(5) in a reactor with a reflux condenser, dissolve the sulfonating agent and the catalyst in water under stirring, add 37% formaldehyde, and dropwise add a mixed solution consisting of acetone and formaldehyde at 60 to 65 ° C; add After finishing, add formaldehyde dropwise rapidly, react at 95°C for 2h, and then cool down to below 50°C to obtain the finished product. The process does not have high requirements on the control of the reaction temperature, and the reaction period is short (about 7h). The obtained product has light color, high water reduction rate, good slump protection effect at high temperature, and good adaptability to different cements; the disadvantage is that formaldehyde needs to be added in three times, and the amount added each time is difficult to accurately determine.

(6)在带有回流冷凝器的反应瓶中依次加入水、亚硫酸钠和丙酮,搅拌均匀后,加热至50~60℃保温一段时间后;滴加定量的甲醛和丁烯醛混合物,要求加料过程中,保持温度为70℃;待醛加完后,在90℃下恒温反应4h;冷却至室温,用浓度为50%的硫酸溶液调节产品的pH值为2左右;再将反应溶液加热到60℃,连续将氮气通入反应器中排出空气;称取定量的亚硫酸铁、水和衣糠醛分别加入到反应器中;然后加入一定量30%浓度的过氧化氢溶液,在60℃下搅拌反应2h;冷却至室温后,用浓度为35%的氢氧化钠调节至中性,得到固含量为27%的接枝聚合物溶液。该工艺的特点是工艺过程比较复杂,精密度要求较高;合成产品颜色较浅,粘度较小,减水率即分散性也较好;缺点是设备复杂,不易操作。以上六种工艺各自存在不同的问题,本发明采用连续工艺,将(2)中原料丙酮、甲醛和亚硫酸钠按如下配比:丙酮:甲醛:亚硫酸钠=6:3:1,通过控制工艺条件来进行分子设计,制备磺化丙酮.甲醛缩聚物SAF水煤浆分散剂。(6) Add water, sodium sulfite and acetone in turn in the reaction flask with reflux condenser, after stirring evenly, heat to 50~60 ℃ and keep for a period of time; add a quantitative mixture of formaldehyde and crotonaldehyde dropwise, and require the feeding process After adding the aldehyde, keep the temperature at 90°C for 4h; cool to room temperature, adjust the pH of the product to about 2 with sulfuric acid solution with a concentration of 50%; then heat the reaction solution to 60 ℃, continuously feed nitrogen into the reactor to discharge air; weigh quantitative iron sulfite, water and furfural and add them to the reactor; then add a certain amount of 30% hydrogen peroxide solution, stir at 60 ℃ The reaction was carried out for 2 hours; after cooling to room temperature, the solution was adjusted to neutrality with sodium hydroxide with a concentration of 35% to obtain a graft polymer solution with a solid content of 27%. The characteristics of this process are that the process is more complicated and the precision is high; the color of the synthetic product is lighter, the viscosity is small, and the water reduction rate, that is, the dispersibility, is also good; the disadvantage is that the equipment is complex and difficult to operate. There are different problems in each of the above six processes, the present invention adopts a continuous process, and the raw materials acetone, formaldehyde and sodium sulfite in (2) are proportioned as follows: acetone: formaldehyde: sodium sulfite=6:3:1, and carry out by controlling the process conditions Molecular design, preparation of sulfonated acetone. Formaldehyde polycondensate SAF coal-water slurry dispersant.

根据以上合成SAF的方法,SAF的合成反应机理分3步,即交叉羟醛缩合反应、酮的亲核加成反应以及随后的缩合反应。其中交叉羟醛缩合反应在碱性介质中,有α-氢的丙酮产生烯醇负离子与无α-氢的甲醛中羰基提供的碳正离子反应生成羟甲基丙酮,这样,羟甲基丙酮与烯酮在第一阶段达到化学平衡,并与亚硫酸盐磺化亲核反应组分进行加成反应,最后溶液中的羟基化合物在加热条件下脱水反应生成缩聚物羟基磺酸盐。常温下先滴加丙酮,并在低温反应一段时间后,再滴加甲醛溶液,反应温度容易控制且所得SAF为水溶性良好的缩合物。但该工艺当丙酮和甲醛一起滴加到亚硫酸钠溶液中时,反应温度难以控制,所得SAF为凝胶。在缩合反应阶段随着黏度增大,减水剂的减水性能先升高,达到最大之后逐渐下降,反应产物黏度也同步增大,若不及时终止反应,体系产物将转变为体型聚合物而失去减水性能和水溶性能。由于体系是在常压水溶液中持续反应,缩合过程仍有甲醛参与,而不仅仅是线性聚合物之间的脱水缩合过程。According to the above method for synthesizing SAF, the synthesis reaction mechanism of SAF is divided into three steps, namely cross aldol condensation reaction, nucleophilic addition reaction of ketone and subsequent condensation reaction. Wherein the cross-aldol condensation reaction is in an alkaline medium, acetone with α-hydrogen generates enolate anion and the carbocation provided by carbonyl in formaldehyde without α-hydrogen reacts to generate methylolacetone, in this way, methylolacetone reacts with The ketene reaches a chemical equilibrium in the first stage, and undergoes an addition reaction with the sulfonated nucleophilic reaction component of sulfite. Finally, the hydroxyl compound in the solution is dehydrated under heating conditions to form a polycondensate hydroxysulfonate. Acetone is added dropwise at room temperature first, and after a period of reaction at low temperature, formaldehyde solution is added dropwise, the reaction temperature is easy to control and the obtained SAF is a condensate with good water solubility. However, in this process, when acetone and formaldehyde are added dropwise to the sodium sulfite solution, the reaction temperature is difficult to control, and the obtained SAF is a gel. In the condensation reaction stage, as the viscosity increases, the water-reducing performance of the water-reducing agent first increases, reaches the maximum and then gradually decreases, and the viscosity of the reaction product also increases simultaneously. If the reaction is not terminated in time, the system product will turn into a bulk polymer instead of Loss of water-reducing properties and water-solubility. Since the system is continuously reacting in an aqueous solution at atmospheric pressure, formaldehyde still participates in the condensation process, not just the dehydration condensation process between linear polymers.

有鉴于此,本发明创新性地提出在微结构反应器中合成SAF,从可以对温度精确控制,有效降低后续缩聚反应中放出的热量的积累,避免了反应体系过热引起的原料挥发严重、聚合过快形成胶化物的问题,反应固含量可达55%以上。同时,由于微结构反应器中磺化聚合可在毫秒内完成,反应动力学的差异对反应物的选择性的提升作用显著增强,仅通过反应物比例和温度的调控既可以方便地控制SAF的分子量的大小、分布及固含量。In view of this, the present invention innovatively proposes to synthesize SAF in a microstructure reactor, which can precisely control the temperature, effectively reduce the accumulation of heat released in the subsequent polycondensation reaction, and avoid serious volatilization and polymerization of raw materials caused by overheating of the reaction system. The problem of forming a gel too quickly, the solid content of the reaction can reach more than 55%. At the same time, since the sulfonation polymerization in the microstructured reactor can be completed in milliseconds, the difference in reaction kinetics significantly enhances the selectivity of the reactants, and the SAF can be easily controlled only by adjusting the ratio and temperature of the reactants. The size, distribution and solids content of molecular weight.

如图1,以连续合成SAF为例,亚硫酸钠溶液与有机酮分别由液相色谱泵A1,A2泵入微混合器B1发生反应,然后进入微通道反应器C1继续反应,在反应器的出口得到磺化酮中间产品溶液,继续与液相色谱泵A3打入的醛溶液在微混合器B2和微通道反应器C2中反应一定时间得到SAF溶液,经旋蒸,乙醇析出,干燥研磨,得到SAF产品。D1,D2分别置于不同温度的恒温水浴中,采用的原料为分析纯。实施例的磺化及缩合反应为液液反应。As shown in Figure 1, taking the continuous synthesis of SAF as an example, the sodium sulfite solution and the organic ketone are respectively pumped into the micro-mixer B1 by the liquid chromatography pumps A1 and A2 to react, and then enter the micro-channel reactor C1 to continue the reaction, and the sulfonic acid is obtained at the outlet of the reactor. The ketone intermediate product solution is continuously reacted with the aldehyde solution injected by the liquid chromatography pump A3 in the micro-mixer B2 and the micro-channel reactor C2 for a certain period of time to obtain the SAF solution, which is subjected to rotary evaporation, ethanol precipitation, and dry grinding to obtain the SAF product . D1 and D2 were placed in constant temperature water baths at different temperatures, and the raw materials used were analytically pure. The sulfonation and condensation reactions of the embodiments are liquid-liquid reactions.

实施例1,2,3,4,5中的磺化反应分别以对甲基苯磺酸钠、氨基取代萘磺酸钠、焦亚硫酸钠溶液、亚硫酸钠和木质素磺酸钠为磺化剂,以第一步反应中生成的磺化丙酮为原料进行缩合反应;实施例1,2是在连续釜式反应器中以丙酮,苯乙酮为原料进行磺化反应;实施例3,4是在管式反应器中分别以甲醛和乙醛为原料进行缩合反应。实施例5是在微结构反应器中以氢氧化钠的水溶液(水与氢氧化钠质量比为5:1)为催化剂进行磺化丙酮的缩合反应。The sulfonation reactions in Examples 1, 2, 3, 4, and 5 used sodium p-toluenesulfonate, sodium amino-substituted naphthalenesulfonate, sodium metabisulfite solution, sodium sulfite and sodium lignosulfonate as sulfonating agents, respectively, with The sulfonated acetone generated in the first step reaction is a raw material to carry out the condensation reaction; Embodiments 1 and 2 are to carry out the sulfonation reaction with acetone and acetophenone as raw materials in a continuous tank reactor; Formaldehyde and acetaldehyde were used as raw materials for the condensation reaction in the reactor. Example 5 is to carry out the condensation reaction of sulfonated acetone in a microstructure reactor using an aqueous solution of sodium hydroxide (the mass ratio of water to sodium hydroxide is 5:1) as a catalyst.

以下通过实施例对本发明做进一步解释说明,但不构成对本发明的限制。应理解这些实施例仅用于说明本发明而不用于限制本发明的范围。The present invention is further explained and illustrated by the following examples, but it does not constitute a limitation of the present invention. It should be understood that these examples are only intended to illustrate the present invention and not to limit the scope of the present invention.

本发明实施例中测定产物固含量的方法:先称量干燥过的称量瓶及盖的质量m1,再把充分搅拌过的分散剂加入称量瓶中,立即加盖,称取质量m2,最后称取经干燥冷却后的总质量m3,固含量一般用百分数来表示。The method for determining the solid content of the product in the embodiment of the present invention: firstly weigh the mass m 1 of the dried weighing bottle and the cap, then add the fully stirred dispersant into the weighing bottle, immediately add the cap, and weigh the mass m 2. Finally, weigh the total mass m 3 after drying and cooling, and the solid content is generally expressed as a percentage.

计算式如下:分散剂固含量(%)=((m3-m1)/(m2-m1))×100。The calculation formula is as follows: dispersant solid content (%)=((m 3 -m 1 )/(m 2 -m 1 ))×100.

本发明实施例中测定产物分子量大小及分子量分布的设备条件:凝胶渗透色谱Waters1515,Waters 2487Dual Absorbance Detector,USA,Ultrahydrogel 120and250columns,流动相0.10mol/L NaNO3,以聚苯乙烯磺酸钠标样为基准相对分子质量,流动相流速为0.50ml/min。水煤浆的表观黏度和浆体流变性由ARES-G2,Anton Paar MCR302测定。Equipment conditions for determining the molecular weight and molecular weight distribution of the product in the examples of the present invention: Gel Permeation Chromatography Waters1515, Waters 2487Dual Absorbance Detector, USA, Ultrahydrogel 120and250columns, mobile phase 0.10mol/L NaNO 3 , with sodium polystyrene sulfonate standard sample As the reference relative molecular mass, the flow rate of the mobile phase was 0.50ml/min. The apparent viscosity and slurry rheology of CWS were determined by ARES-G2, Anton Paar MCR302.

实施例1Example 1

将对甲基苯磺酸钠与丙酮溶液通入体积为10m3的连续搅拌釜式反应器中,对甲基苯磺酸钠与丙酮的当量比为2.0:1,生成的磺化丙酮溶液与甲醛溶液分别通入另外一个连续搅拌釜式反应器中,温度控制在-10℃,搅拌速度为218r/min,平均停留时间为160min,出口收集反应产物,产物溶液经过中和、旋蒸干燥,乙醇析出、干燥研磨,得到磺化丙酮甲醛缩聚物,其固含量为18%。The sodium p-toluenesulfonate and the acetone solution are passed into the continuous stirred tank reactor with a volume of 10m , the equivalent ratio of the sodium p-toluenesulfonate and the acetone is 2.0:1, and the generated sulfonated acetone solution and The formaldehyde solution was respectively passed into another continuous stirred tank reactor, the temperature was controlled at -10°C, the stirring speed was 218r/min, the average residence time was 160min, the reaction product was collected at the outlet, and the product solution was neutralized and rotary evaporated to dry. Ethanol was precipitated, dried and ground to obtain a sulfonated acetone-formaldehyde polycondensate with a solid content of 18%.

实施例2Example 2

将苯乙酮溶液与氨基取代萘磺酸钠溶液通入体积为10m3的连续搅拌釜式反应器中,苯乙酮溶液与氨基取代萘磺酸钠为1:1.5,生成的磺化苯乙酮溶液与甲醛分别通入另外一个连续搅拌釜式反应器中,温度控制在0℃,搅拌速度为120r/min,平均停留时间为160min,出口收集反应产物,产物溶液经过中和、旋蒸干燥,乙醇析出、干燥研磨,得到取代萘磺化苯乙酮甲醛缩聚物,其固含量为28%。The acetophenone solution and the amino-substituted sodium naphthalene sulfonate solution are passed into the continuous stirred tank reactor with a volume of 10 m , the acetophenone solution and the amino-substituted sodium naphthalene sulfonate are 1: 1.5, and the sulfonated styrene generated The ketone solution and formaldehyde were respectively passed into another continuous stirred tank reactor, the temperature was controlled at 0°C, the stirring speed was 120r/min, the average residence time was 160min, the reaction product was collected at the outlet, and the product solution was neutralized and rotary evaporated to dry. , ethanol was precipitated, dried and ground to obtain a substituted naphthalenesulfonated acetophenone-formaldehyde polycondensate with a solid content of 28%.

实施例3Example 3

将亚硫酸钠溶液与丙酮按照1:3的当量比,同时由液相色谱泵泵入温度控制在20℃、直径为100mm、长度为5m的管式反应器中,物料的停留时间为10min,生成的磺化丙酮溶液与甲醛溶液分别通入另外一个管式反应器中,温度控制在90℃,平均停留时间为20min,产物溶液经过中和、旋蒸干燥,乙醇析出、干燥研磨,得到SAF,其固含量为35%。The sodium sulfite solution and acetone were pumped into a tubular reactor whose temperature was controlled at 20 ° C, the diameter was 100 mm, and the length was 5 m according to the equivalent ratio of 1:3 by a liquid chromatography pump, and the residence time of the material was 10 min. The sulfonated acetone solution and the formaldehyde solution were respectively passed into another tubular reactor, the temperature was controlled at 90 ° C, the average residence time was 20 min, the product solution was neutralized, rotary evaporated and dried, ethanol was precipitated, and dried and ground to obtain SAF, which was The solids content is 35%.

从图2谱图看出,3425.5cm为羟基的伸缩振动吸收峰;2923.2cm为脂肪族分子链上C-H键的伸缩振动峰,2852.5cm处为CH3的伸缩振动峰,1619.6cm为羰基的伸缩振动吸收峰;1449.4cm为甲基的不对称变形振动吸收峰;1180、l045cm处为-SO3烷基磺酸盐的伸缩振动峰;说明SAF为含有羰基、羟基和磺酸基等亲水基团的高分子化合物,这些基团不仅提供了SAF缩聚物的水溶性,而且还作为生色或助色基团使缩聚物产生颜色。It can be seen from the spectrum in Figure 2 that 3425.5cm is the stretching vibration absorption peak of the hydroxyl group; 2923.2cm is the stretching vibration peak of the CH bond on the aliphatic molecular chain, 2852.5cm is the stretching vibration peak of CH 3 , and 1619.6cm is the stretching vibration peak of the carbonyl group. Vibrational absorption peak; 1449.4cm is the asymmetric deformation vibrational absorption peak of methyl; 1180, 1045cm is the stretching vibration peak of -SO 3 alkyl sulfonate; indicating that SAF is a hydrophilic group containing carbonyl, hydroxyl and sulfonic acid groups These groups not only provide the water solubility of the SAF polycondensate, but also act as chromogenic or auxochromic groups to make the polycondensate produce color.

实施例4Example 4

将亚硫酸钠溶液与丙酮按照1:5的当量比,同时由液相色谱泵泵入温度控制在20℃、直径为10mm、长度为15m的管式反应器中,物料的停留时间为15min,生成的磺化丙酮溶液与乙醛溶液分别通入另外一个管式反应器中,温度控制在65℃,平均停留时间为25min,产物溶液经过中和、旋蒸干燥,乙醇析出、干燥研磨,得到磺化丙酮乙醛缩聚物,其固含量为40%。The sodium sulfite solution and acetone were pumped into a tubular reactor with a temperature of 20°C, a diameter of 10mm, and a length of 15m according to the equivalent ratio of 1:5 by a liquid chromatography pump, and the residence time of the material was 15min. The sulfonated acetone solution and the acetaldehyde solution were respectively passed into another tubular reactor, the temperature was controlled at 65°C, and the average residence time was 25min. Acetone acetaldehyde polycondensate with a solid content of 40%.

实施例5Example 5

将木质素磺酸钠与丙酮按照1:3的当量比,同时由液相色谱泵泵入温度控制在0℃的交叉趾形微混合反应器中(V2,IMM,Germany),其通道尺寸(μm)为25×21×37,后面接内径为0.6mm,长度为10m的聚四氟乙烯毛细管,其出反应产物与甲醛溶液分别注入另外一个玻璃T型微混合器:T-mixer(width×height=50×50μm,Microglas,Germany),反应温度控制在10℃,收集的反应产物溶液经过中和、旋蒸干燥,乙醇析出、干燥研磨,得到木质素磺化丙酮甲醛缩聚物,其固含量为52%。Sodium lignosulfonate and acetone in an equivalent ratio of 1:3 were simultaneously pumped by a liquid chromatography pump into a cross-toed micro-mixing reactor (V2, IMM, Germany) whose temperature was controlled at 0 °C. The channel size ( μm) is 25×21×37, followed by a polytetrafluoroethylene capillary with an inner diameter of 0.6mm and a length of 10m. The reaction product and formaldehyde solution are injected into another glass T-type micro-mixer: T-mixer (width× height=50×50μm, Microglas, Germany), the reaction temperature was controlled at 10°C, the collected reaction product solution was neutralized, rotary evaporated and dried, ethanol was precipitated, and dried and ground to obtain a lignosulfonated acetone formaldehyde polycondensate with a solid content of was 52%.

实施例6~11Examples 6 to 11

实施例6~8是于连续管式反应器中,采用同实施例4相同的反应条件,以亚硫酸钠溶液与丙酮为原料于B1,C1中进行磺化反应,中间产物磺化丙酮与二羟基丙酮溶液于B2,C2中进行缩合反应,产品固含量见表一。In Examples 6-8, the same reaction conditions as in Example 4 were used in a continuous tubular reactor, and sodium sulfite solution and acetone were used as raw materials to carry out sulfonation reaction in B 1 and C 1 , and the intermediate products were sulfonated acetone and disulfide. The hydroxyacetone solution is subjected to condensation reaction in B 2 and C 2 , and the solid content of the product is shown in Table 1.

实施例9~11是于微结构反应器中,采用同实施例5相同的反应条件(不同的反应条件见下表一),以木质素磺酸钠溶液及丙酮为原料B1,C1进行磺化反应,以甲醛溶液于B2,C2进行缩聚反应,产品固含量见表一。Examples 9 to 11 are in the microstructure reactor, using the same reaction conditions as in Example 5 (see Table 1 for different reaction conditions), using sodium lignosulfonate solution and acetone as raw materials B 1 , C 1 is carried out. Sulfonation reaction is carried out polycondensation reaction with formaldehyde solution in B 2 , C 2 , and the solid content of the product is shown in Table 1.

表一 实施例6~8,实施例9~11Table 1 Examples 6-8, Examples 9-11

Figure BDA0002653450950000111
Figure BDA0002653450950000111

最后应该说明的是,以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述实施例所记载的技术方案进行修改,或者对其中部分进行等同替换。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。上述虽然结合附图对本发明的具体实施方式进行了描述,但并非对本发明保护范围的限制,所属领域技术人员应该明白,在本发明的技术方案的基础上,本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围以内。Finally, it should be noted that the above are only preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will still Modifications may be made to the technical solutions described in the foregoing embodiments, or equivalent replacements may be made to some of them. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention. Although the specific embodiments of the present invention have been described above in conjunction with the accompanying drawings, they do not limit the scope of protection of the present invention. Those skilled in the art should understand that on the basis of the technical solutions of the present invention, those skilled in the art do not need to pay creative efforts. Various modifications or deformations that can be made are still within the protection scope of the present invention.

Claims (10)

1. The application of a continuous reactor in the continuous synthesis of sulfonated ketone-aldehyde condensates;
wherein the continuous reactor is a micro-structure reactor, a full mixed flow reactor or a tubular reactor; preferably a microstructured reactor.
2. A method for continuously synthesizing a sulfonated ketone aldehyde condensate, comprising: the sulfonated ketone-aldehyde condensate is continuously synthesized in a continuous reactor based on the ketone sulfonation method.
3. The method of claim 2, wherein the method comprises:
the sulfonating agent and the ketone compound react in a continuous reactor to obtain sulfonated ketone compound solution;
and (3) reacting the sulfonated ketone compound solution with the aldehyde compound solution in a continuous reactor under an alkaline environment, and purifying a reaction product to obtain a sulfonated ketone-aldehyde condensation product.
4. The method of claim 3, wherein the purifying step comprises neutralization, drying, crystallization, secondary drying, and grinding.
5. The method of claim 2, wherein the continuous reactor is a micro-structured reactor, a fully mixed flow reactor, or a tubular reactor; preferably a micro-structured reactor;
preferably, the molar ratio of the sulfonating agent to the ketone compound is 1: 0.1 to 5; more preferably 1: 0.5 to 5;
preferably, the reaction conditions of the sulfonating agent and the ketone compound in the continuous reactor are as follows: the temperature is 10-60 ℃, and the retention time is 0.1-600 s; more preferably: the temperature is 10-50 ℃, and the retention time is 0.5-600 s.
Wherein the sulfonating agent comprises sodium lignosulfonate, sodium sulfite, sodium pyrosulfite, sodium imidazolyl-containing sulfonate, thiazolyl sodium sulfonate, pyridyl sodium sulfonate, aryl sodium sulfonate, substituted naphthalene sodium sulfonate and aliphatic sodium sulfonate solution;
the ketone compound comprises aromatic ketone, aromatic polyketone, aliphatic ketone or aliphatic polyketone, and further comprises acetone, butanone, methyl ethyl ketone and acetophenone;
the molar ratio of the sulfonated acetone to the aldehydes is (0.8-4): 1.
the aldehyde compound comprises aliphatic aldehyde, aliphatic polyaldehyde, aromatic aldehyde or aromatic polyaldehyde; further comprising formaldehyde, acetaldehyde;
preferably, the microstructure reactor comprises a micro mixer and a micro channel reactor which are connected in sequence, and further preferably, the microstructure reactor is placed in a constant temperature water bath;
adding alkali liquor to form an alkaline environment, wherein the pH value of the alkaline environment is 7-12;
preferably, the solvent used for dissolving the sulfonating agent and the solid base is water; the mass ratio of water to sodium hydroxide is 1-8: 1.
6. The method of claim 5, wherein the micro-structured reactor is made of stainless steel, glass, quartz, ceramic, teflon, inorganic silicon or Peek material;
preferably, the size of the channel of the micro-structure reactor is 0.1 mu m-10 mm;
preferably, the microstructure reactor is of a tubular structure.
7. A method for preparing a sulfonated ketone aldehyde condensate by a continuous reaction, wherein the sulfonated ketone aldehyde condensate is SAF, the method comprising:
s1, mixing liquid raw materials of sodium sulfite and acetone according to the molar ratio of the sodium sulfite to the acetone of 1: (2-5) respectively injecting the mixture into a full mixed flow reactor, a tubular reactor or a micro-structure reactor which are connected in series by a pump at the same time, and reacting at the reaction temperature of 20-50 ℃ for 0.1-600 s to obtain a sulfonated acetone solution;
s2, mixing the reaction product sulfonated acetone solution in the step S1 with a formaldehyde water solution according to the molar ratio of sulfonated acetone to formaldehyde being (0.8-4): 1, injecting the mixture into another full mixed flow reactor, a tubular reactor or a micro-structure reactor, and reacting under the alkaline condition, wherein the reaction temperature is controlled to be 20-50 ℃ and the retention time is 0.5-600 s; and drying the reactant by rotary evaporation, precipitating crystals by ethanol, drying and grinding to obtain the SAF product.
8. The method of claim 7,
adding alkali liquor to form an alkaline condition, wherein the alkali is sodium hydroxide, sodium phosphate, sodium acetate, sodium carbonate or alkaline ionic liquid; preferably, the water is sodium hydroxide aqueous solution, and the mass ratio of water to sodium hydroxide is 1-8: 1;
preferably, the micro-structure reactor is a micro mixer or is formed by connecting a micro mixer and a micro-channel reactor;
the diameter of the tubular reactor is 10-100 mm, and the length of the tubular reactor is 5-15 m.
The channel size of the micro mixer and the micro channel reactor is 0.2-8 mm, and the length of the micro channel reactor is 0.5-20 m.
9. The sulfonated ketone-aldehyde condensate produced by any one of claims 2 to 8.
10. Use of the sulfonated acetone formaldehyde condensate of claim 9 in any one or more of the following:
1) a dispersant;
2) a water reducing agent.
CN202010878756.1A 2020-08-27 2020-08-27 Continuous synthesis method and application of sulfonated ketone-aldehyde condensation compound Pending CN111992156A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112608059A (en) * 2020-11-30 2021-04-06 科之杰新材料集团河南有限公司 Water reducing agent and improvement method and application thereof
CN115678625A (en) * 2021-07-23 2023-02-03 中国科学院宁波材料技术与工程研究所 A modified narrow distribution coal water slurry dispersant and its preparation method and application

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101066850A (en) * 2007-06-05 2007-11-07 江苏海润化工有限公司 Continuous production process of efficient aliphatic concrete water reducing agent
CN106117027A (en) * 2016-06-20 2016-11-16 聊城大学 Utilize the method that micro-structured reactor prepares cyclocitral
CN108715639A (en) * 2018-04-26 2018-10-30 南京工业大学 Method for preparing lignosulfonate by using microchannel reaction device
US20200079714A1 (en) * 2018-09-06 2020-03-12 Changzhou University PROCESS FOR ACID-CATALYZED DECOMPOSITION OF ARYL a- HYDROPEROXIDE WITH CONTINUOUS FLOW TUBULAR REACTOR

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101066850A (en) * 2007-06-05 2007-11-07 江苏海润化工有限公司 Continuous production process of efficient aliphatic concrete water reducing agent
CN106117027A (en) * 2016-06-20 2016-11-16 聊城大学 Utilize the method that micro-structured reactor prepares cyclocitral
CN108715639A (en) * 2018-04-26 2018-10-30 南京工业大学 Method for preparing lignosulfonate by using microchannel reaction device
US20200079714A1 (en) * 2018-09-06 2020-03-12 Changzhou University PROCESS FOR ACID-CATALYZED DECOMPOSITION OF ARYL a- HYDROPEROXIDE WITH CONTINUOUS FLOW TUBULAR REACTOR

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
赵晖等: "SAF高效减水剂的合成与分散性研究", 《低温建筑技术》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112608059A (en) * 2020-11-30 2021-04-06 科之杰新材料集团河南有限公司 Water reducing agent and improvement method and application thereof
CN112608059B (en) * 2020-11-30 2022-04-01 科之杰新材料集团河南有限公司 Water reducing agent and improvement method and application thereof
CN115678625A (en) * 2021-07-23 2023-02-03 中国科学院宁波材料技术与工程研究所 A modified narrow distribution coal water slurry dispersant and its preparation method and application
CN115678625B (en) * 2021-07-23 2023-07-18 中国科学院宁波材料技术与工程研究所 A modified narrow distribution coal water slurry dispersant and its preparation method and application

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