阅读说明：本技术 一种蓖麻油基季铵盐抗泥剂及其制备方法 (Castor oil-based quaternary ammonium salt anti-mud agent and preparation method thereof ) 是由 颜秀花 许伟 石文艳 唐兰勤 邵荣 于 2019-09-27 设计创作，主要内容包括：本发明公开了一种蓖麻油基季铵盐抗泥剂及其制备方法,该抗泥剂由蓖麻油酸、N,N-二甲基-1,3-丙二胺、环氧氯丙烷制成,具体制备方法为：将蓖麻油和催化剂置于反应容器中,通入氮气,室温下边搅拌边滴加N,N-二甲基-1,3-丙二胺,滴加完毕后加热进行反应,处理后得到蓖麻油酸酰胺；再将蓖麻油酸酰胺置于反应容器中,通入氮气,边搅拌边缓慢滴加环氧氯丙烷,控制温度在48℃,滴加完毕后升温至50℃,保温反应1h,再用正己烷除去过量的环氧氯丙烷,真空干燥,即得。该抗泥剂能够快速吸附泥土,降低聚羧酸减水剂掺量且保证混凝土性能,该制备方法合成原料易得,反应条件温和,产物可生物降解,对环境无影响,合成成本及后处理费用低。(The invention discloses a castor oil based quaternary ammonium salt anti-mud agent and a preparation method thereof, the anti-mud agent is prepared from ricinoleic acid, N-dimethyl-1, 3-propane diamine and epichlorohydrin, and the preparation method comprises the following steps: placing castor oil and a catalyst in a reaction container, introducing nitrogen, dropwise adding N, N-dimethyl-1, 3-propane diamine at room temperature while stirring, heating for reaction after dropwise adding is finished, and treating to obtain ricinoleic acid amide; and then placing ricinoleic acid amide in a reaction container, introducing nitrogen, slowly dropwise adding epoxy chloropropane while stirring, controlling the temperature at 48 ℃, heating to 50 ℃ after dropwise adding, preserving heat for reaction for 1h, removing excessive epoxy chloropropane by using n-hexane, and drying in vacuum to obtain the ricinoleic acid amide. The anti-mud agent can quickly adsorb mud, reduce the mixing amount of the polycarboxylate superplasticizer and ensure the performance of concrete, and the preparation method has the advantages of easily obtained synthetic raw materials, mild reaction conditions, biodegradable products, no influence on the environment, low synthesis cost and low post-treatment cost.)

1. The castor oil based quaternary ammonium salt anti-mud agent is characterized by being prepared from ricinoleic acid, N-dimethyl-1, 3-propane diamine and epichlorohydrin, and the molecular structural formula of the castor oil based quaternary ammonium salt anti-mud agent is shown as a formula I:

in formula I: r is

2. The preparation method of the castor oil based quaternary ammonium salt anti-mud agent as claimed in claim 1, characterized by comprising the following steps:

step 1) adding castor oil and a catalyst NaOH into a reaction container, introducing nitrogen, dropwise adding N, N-dimethyl-1, 3-propane diamine at room temperature while stirring, heating to 65-90 ℃ after dropwise adding, and reacting for 5-10 hours;

step 2) washing the reaction product obtained in the step 1) with distilled water, standing, removing the turbid liquid at the lower layer, washing repeatedly until the lower layer liquid is clear, removing the lower layer liquid, and keeping the ricinoleic acid amide crude product at the upper layer;

step 3) drying the ricinoleic acid amide crude product obtained in the step 2) in vacuum to remove redundant moisture, so as to obtain ricinoleic acid amide;

and 4) weighing the ricinoleic acid amide obtained in the step 3) into a reaction container, introducing nitrogen, slowly dropwise adding epoxy chloropropane while stirring within 30min, controlling the temperature to be 48 ℃, heating to 50 ℃ after dropwise adding, preserving heat for reaction for 1h, removing excessive epoxy chloropropane by using n-hexane, and performing vacuum drying to obtain the castor oil based quaternary ammonium salt anti-mud agent.

3. The preparation method of the castor oil based quaternary ammonium salt anti-mud agent according to claim 2, wherein the time for introducing the nitrogen in the step 1) and the step 4) is 5 min.

4. The preparation method of the castor oil-based quaternary ammonium salt anti-mud agent according to claim 2, wherein the molar ratio of the N, N-dimethyl-1, 3-propanediamine to the castor oil in the step 1) is 3: 1-8: 1.

5. The preparation method of the castor oil-based quaternary ammonium salt anti-mud agent according to claim 2, wherein the amount of NaOH used as the catalyst in the step 1) is 2-10% by mass of the castor oil.

6. The preparation method of the castor oil-based quaternary ammonium salt anti-mud agent according to claim 2, wherein the molar ratio of the epichlorohydrin to the ricinoleic acid amide in the step 4) is 1: 3.

Technical Field

The invention belongs to the field of building materials, relates to the field of concrete admixtures, and particularly relates to a castor oil based quaternary ammonium salt mud-resisting agent and a preparation method thereof.

Background

The concrete admixture is used as an important component of concrete and plays an important role in the process of mixing the concrete. Particularly, the concrete water reducing agent brings great leap to the workability, mechanical property and durability of concrete. The polycarboxylate superplasticizer has the advantages of environmental protection, low mixing amount, high water reducing rate, good slump retaining property, easy adjustment of molecular structure, high performance, great potential and the like, and is widely applied to engineering. However, polycarboxylic acid water reducing agents also face a number of technical difficulties in practical use, of which the high sensitivity to soil is most prominent. However, the amount of sand stock used in modern concrete is becoming less and less due to the extensive development of sand raw materials. The sand generally has a high content of mud and a poor particle size distribution, so that the properties of the concrete are seriously affected. Particularly, the water reducing performance of the water reducing agent in concrete is reduced and even loses efficacy due to the over-high mud content. Resulting in poor concrete rheology, greatly reduced initial slump loss and slump loss with time, and reduced durability and strength.

In order to solve the influence of the mud content on the concrete water reducing agent, the measures adopted in the current engineering are 3: washing sandstone, doping an excessive water reducing agent and adding an anti-mud agent. However, the water reducing agent is too high in mixing amount, so that the concrete is often caused to bleed and separate, the slump and the strength of the concrete are negatively affected, and the cost of the concrete is increased. The washing of the sand and stone needs to increase construction links, has high cost and pollutes the environment, leads to easy washing away of fine particles of the sand, seriously influences the particle composition of the sand and is difficult to realize in actual construction. The anti-mud agent is added and compounded with the water reducing agent to be used as a sacrificial agent, so that the excellent anti-mud effect can be generated, the operation is easy in actual construction, and the method is a solution with a very good application prospect. Therefore, the search for new anti-mud type and anti-mud type water reducing system is urgent.

At present, related researches on the anti-mud agent and the anti-mud type water reducing agent exist in China, and the problem that the performance of concrete is deteriorated due to overhigh mud content is solved to a certain extent. The existing process for preparing the quaternary ammonium salt type anti-mud agent involves toxic and harmful chemical reagents or high-temperature reaction, and has poor environmental protection property, serious pollution and higher operation risk. For example, patents CN109734612A, CN109535016A, CN108997146A and CN108821627A use highly toxic raw materials in the preparation process or toxic and harmful tetrahydrofuran, acetonitrile, toluene, ethanol, acetone and biphenyl dibenzyl chloride as reaction solvents.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides the castor oil based quaternary ammonium salt anti-mud agent and the preparation method thereof, which can quickly adsorb mud, reduce the mixing amount of the polycarboxylic acid water reducing agent and ensure the performance of concrete.

The invention is realized by the following technical scheme:

the castor oil based quaternary ammonium salt anti-mud agent is prepared from ricinoleic acid, N-dimethyl-1, 3-propane diamine and epichlorohydrin, and the molecular structural formula of the castor oil based quaternary ammonium salt anti-mud agent is shown as the formula I:

in formula I: r is

A preparation method of a castor oil based quaternary ammonium salt anti-mud agent comprises the following steps:

step 1) adding castor oil and a catalyst NaOH into a reaction container, introducing nitrogen, dropwise adding N, N-dimethyl-1, 3-propane diamine at room temperature while stirring, heating to 65-90 ℃ after dropwise adding, and reacting for 5-10 hours;

step 2) washing the reaction product obtained in the step 1) with distilled water, standing, removing the turbid liquid at the lower layer, washing repeatedly until the lower layer liquid is clear, removing the lower layer liquid, and keeping the ricinoleic acid amide crude product at the upper layer;

step 3) drying the ricinoleic acid amide crude product obtained in the step 2) in vacuum to remove redundant moisture, so as to obtain ricinoleic acid amide;

and 4) weighing the ricinoleic acid amide obtained in the step 3) into a reaction container, introducing nitrogen, slowly dropwise adding epoxy chloropropane while stirring within 30min, controlling the temperature to be 48 ℃, heating to 50 ℃ after dropwise adding, preserving heat for reaction for 1h, removing excessive epoxy chloropropane by using n-hexane, and performing vacuum drying to obtain the castor oil based quaternary ammonium salt anti-mud agent.

Preferably, the nitrogen is introduced in the steps 1) and 4) for 5 min.

Preferably, the molar ratio of the N, N-dimethyl-1, 3-propanediamine to the castor oil in the step 1) is 3: 1-8: 1.

Preferably, the amount of the catalyst NaOH in the step 1) is 2-10% of the mass of the castor oil.

Preferably, the molar ratio of epichlorohydrin to ricinoleic acid amide in step 4) is 1: 3.

Compared with the prior art, the invention has the following remarkable advantages:

1. the invention takes a large amount of castor oil resources with strong regeneration capability in China and castor oil which is a renewable resource as a raw material, the synthetic raw material is easy to obtain, the reaction condition is mild, the product can be biodegraded, the environment is not influenced, and the synthesis cost and the post-treatment cost are low.

2. The molecular structure of the anti-mud agent prepared by the invention contains various functional groups such as quaternary ammonium salt, amide, hydroxyl and the like. The quaternary ammonium salt group can preferentially adsorb the surface of negatively charged soil, and reduce the adsorption of the soil on the polycarboxylate superplasticizer, thereby reducing the mixing amount of the polycarboxylate superplasticizer, reducing the cost, simultaneously ensuring the good working performance of concrete, and having a certain inhibiting effect on the water absorption expansion of cement. The hydroxyl groups can adsorb water molecules through the action of hydrogen bonds and Van der Waals force, a hydration film is formed on the surface of the cement, and the linking structure among cement particles is damaged, so that the dispersing performance is improved. Meanwhile, compared with small molecules, the castor oil-based quaternary ammonium salt molecules prepared by the method have larger steric hindrance, and the dispersibility of concrete is improved due to the steric hindrance when cement particles are close to each other, so that a good anti-mud effect is achieved.

Drawings

FIG. 1 is a castor oil based amide FTIR spectrum;

FIG. 2 is an FTIR spectrum of a castor oil based quaternary ammonium salt anti-mud agent;

FIG. 3 is a surface tension diagram of a castor oil based quaternary ammonium salt anti-mud agent;

FIG. 4 shows the influence of the castor oil based quaternary ammonium salt anti-mud agent on the dispersion performance of the cement containing 3% of montmorillonite.

Detailed Description

The technical solution of the present invention is further described in detail with reference to the accompanying drawings and specific embodiments.

A castor oil based quaternary ammonium salt anti-mud agent is prepared from ricinoleic acid, N-dimethyl-1, 3-propane diamine and epichlorohydrin, and the molecular structural formula of the castor oil based quaternary ammonium salt anti-mud agent is shown as the following formula I:

in the formula I, R is

The preparation reaction of the castor oil based quaternary ammonium salt anti-mud agent is shown as a reaction formula II:

the preparation method of the castor oil based quaternary ammonium salt anti-mud agent comprises the following specific steps:

(1) adding castor oil and a catalyst NaOH into a reaction container, introducing nitrogen for 5min, dropwise adding N, N-dimethyl-1, 3-propane diamine at room temperature while stirring, heating to 65-90 ℃ after dropwise adding, and reacting for 5-10 h.

(2) Washing the reaction product obtained in the step (1) with distilled water, standing, removing the lower turbid liquid, washing repeatedly until the lower liquid is clear, removing the lower liquid, and keeping the upper ricinoleic acid amide crude product.

(3) And (3) drying the ricinoleic acid amide crude product in vacuum to remove redundant moisture to obtain the ricinoleic acid amide.

(4) Weighing the ricinoleic acid amide, putting the ricinoleic acid amide into a reaction container, introducing 5min of nitrogen, slowly dropwise adding epoxy chloropropane while stirring within 30min, controlling the temperature to be 48 ℃, heating to 50 ℃ after dropwise adding, keeping the temperature for reaction for 1h, removing excessive epoxy chloropropane by using n-hexane, and drying in vacuum to obtain the castor oil based quaternary ammonium salt anti-mud agent.

The experimental procedures in the following examples are conventional unless otherwise specified. The reagent materials and the like used in the following examples are commercially available products unless otherwise specified.