WO2020238158A1

WO2020238158A1 - Wet mixing mortar stabilizer and preparation method therefor

Info

Publication number: WO2020238158A1
Application number: PCT/CN2019/125175
Authority: WO
Inventors: 柯余良; 方云辉; 张小芳; 钟丽娜; 朱少宏; 郭元强; 林添兴
Original assignee: 科之杰新材料集团有限公司
Priority date: 2019-05-29
Filing date: 2019-12-13
Publication date: 2020-12-03
Also published as: CN110255958B; CN110255958A

Abstract

The present invention relates to the technical field of external building additives, and specifically relates to a wet mixing mortar stabilizer and a preparation method therefor. The preparation method comprises the following steps: mixing a 4-hydroxybutyl vinyl polyoxyethylene ether monomer, acrylic acid, methacryloyloxyethyl succinate monoester and water, and adding hydrogen peroxide; after the reaction, successively adding an aqueous solution of a reducing agent, an aqueous solution of a cocatalyst and an aqueous solution composed of acrylic acid, 2-amino-3-p-hydroxyphenyl propionate, 3-hydroxyphenylphosphoryl propionate dihydromyrcenol ester and a chain transfer agent, and after the reaction is finished, adding polyvinyl alcohol, and then adjusting the pH to 7-8, so as to prepare the wet mixing mortar stabilizer. Compared with the prior art, the mortar synthesized by the prepared wet mixing mortar stabilizer has the advantages of low consistency loss, better water retention rate, and high compressive strength and long-term stability of the mortar, having notable progress.

Description

Plastic stabilizer for wet-mixed mortar and preparation method thereof

Technical field

The invention relates to the technical field of building admixtures, in particular to a wet-mixed mortar plastic stabilizer and a preparation method thereof.

Background technique

With the acceleration of China's new urbanization, the number of municipal infrastructure and residential buildings in cities will inevitably increase significantly, and building energy consumption has already accounted for a considerable part of the overall energy consumption. As a bulk building material second only to wall materials and concrete, building mortar is used annually in hundreds of millions of tons. Wet-mixed mortar will gradually replace traditional on-site preparation mortar with its advantages of stable quality, energy saving, environmental protection, and centralized clean production; wet-mixed mortar is an inevitable result of industry development due to its energy-saving, environmentally friendly, and sustainable characteristics.

Judging from the current domestic situation, the promotion of wet-mixed mortar, a green building material, is imperative. Compared with developed countries, the research on wet-mixed mortar in my country started late, and its popularization and popularization is slower. Therefore, it is very important to study how to formulate and maintain wet-mixed mortar with strong performance and durability. Necessary. Wet-mixed mortar supporting admixtures play an indispensable role in wet-mixed mortar production, which can give wet-mixed mortar excellent water retention and workability. Therefore, under the premise of vigorously promoting the use of wet-mixed mortar, wet-mixed mortar The development of mixed mortar additives is of great significance.

Among the existing wet-mixed mortar additives, the plastic stabilizer is undoubtedly very critical. As a supporting additive for masonry, plastering, bottom, and anti-cracking waterproof mortar produced specifically for concrete mixing plants, it can realize wet-mixed mortar The effect of maintaining plasticity for a long time is particularly important. However, the existing plastic stabilizers have the problem of insufficient plasticity retention.

Summary of the invention

In order to solve the above-mentioned problems in the background art, the present invention provides a method for preparing a wet-mix mortar plastic stabilizer, which includes the following steps:

Add 4-hydroxybutyl vinyl polyoxyethylene ether monomer, acrylic acid, methacryloxyethyl succinic acid monoester and water into the reaction kettle and mix and stir evenly, add hydrogen peroxide, the above-mentioned hydrogen peroxide is preferably added It is a one-time addition; after the reaction, the aqueous solution of the reducing agent, the aqueous solution of the co-catalyst and the aqueous solution of the mixed reagent A are sequentially added. The above-mentioned aqueous solution is preferably added dropwise, and the dropping time is preferably 2 to 3 hours; after the reaction, add Polyvinyl alcohol is then preferably incubated for 30 minutes. The temperature of the holding is preferably 0-15°C, and then the pH is adjusted to 7-8. The pH adjusting agent is preferably a sodium hydroxide solution with a mass fraction of 30%. Prepared the wet-mixed mortar stabilizer;

Wherein, the mixed reagent A is composed of acrylic acid, 2-amino-3-p-hydroxyphenyl propionate, 3-hydroxyphenyl phosphoryl propionate dihydromyrcenol ester and a chain transfer agent.

On the basis of the above scheme, preferably, the preparation method of the 2-amino-3-p-hydroxyphenyl propionate is:

Mix 2-amino-3-p-hydroxyphenylpropionic acid and unsaturated alcohol in a weight ratio of 1:1 to 3, add a catalyst, and carry out the esterification reaction at 80-120°C. The esterification reaction time is preferably For 2 to 5 hours, remove excess unsaturated alcohol to prepare the 2-amino-3-p-hydroxyphenyl propionate.

On the basis of the above solution, preferably, the unsaturated alcohol is at least one of allyl alcohol, butenol, and isopentenol.

On the basis of the above solution, preferably, the catalyst is at least one of ferric ammonium sulfate dodecahydrate, sodium hydrogen sulfate monohydrate, and aluminum sulfate octahydrate.

On the basis of the above scheme, preferably, the preparation method of the 3-hydroxyphenylphosphoryl propionate dihydromyrcenol ester is:

After mixing 3-hydroxyphenylphosphoryl propionic acid and cyclohexane, add dihydromyrcenol, add 732 cation exchange resin and hydroquinone at the same time and stir evenly, then raise the temperature to 30-60℃, The reaction time is preferably 2 to 4 hours. After filtration and atmospheric distillation, 3-hydroxyphenylphosphoryl propionate dihydromyrcenol ester is obtained.

On the basis of the above scheme, preferably, the mass ratio of 3-hydroxyphenylphosphoryl propionic acid to dihydromyrcenol is 1:1 to 3, and the amount of 732 cation exchange resin is 3-hydroxyphenylphosphoryl The mass of propionic acid is 0.5%-2%, the amount of hydroquinone is 0.5%-1% of the mass of 3-hydroxyphenylphosphorylpropionic acid, and the atmospheric distillation temperature is 70-75°C.

On the basis of the above solution, preferably, the 4-hydroxybutyl vinyl polyoxyethylene ether monomer, acrylic acid, methacryloxyethyl succinic acid monoester, water, hydrogen peroxide, an aqueous solution of a reducing agent, The weight ratio of the aqueous solution of the promoter to the aqueous solution of the mixed reagent A is 100:5:10:100:1 to 3:20 to 30:5 to 10:40 to 50.

On the basis of the above solution, preferably, the molecular weight of the 4-hydroxybutyl vinyl polyoxyethylene ether monomer is 4000.

On the basis of the above scheme, preferably, the reducing agent is azobisisobutylamidine hydrochloride (AIBA, V-50 initiator), azobisisobuimidazoline hydrochloride (abbreviated as AIBI, VA -044 initiator), at least one of azobiscyanovaleric acid (ACVA, V-501 for short), and azodiisopropylimidazoline (AIP for short, VA-061 initiator).

On the basis of the above solution, preferably, the co-catalyst is at least one of N,N-dimethylaniline, N,N-diethylaniline, and tetraethyleneimine.

Based on the above solution, preferably, the chain transfer agent is at least one of thioglycolic acid, 3-mercaptopropionic acid, 2-mercaptopropanol, and mercaptoethanol.

On the basis of the above scheme, preferably, the reaction temperature is 0-15°C; the mass percentage concentration of the reducing agent is 5%; the mass percentage concentration of the promoter is 5%, and the mixed reagent A The mass percentage concentration is 50%.

The present invention also provides a wet-mixed mortar plastic stabilizer prepared by any of the above-mentioned wet-mixed mortar plastic stabilizer preparation methods.

On the basis of the above solution, preferably, the molecular weight of the wet-mixed mortar plastic stabilizer is 60,000 to 120,000.

The preparation method of the present invention and the wet-mix mortar plastic stabilizer prepared by the preparation method of the present invention have the following technical principles and beneficial effects:

1. In the preparation method of the present invention, the ultra-long PEO long side chain forms a thicker polymer molecule adsorption layer in the liquid phase, the adsorption capacity increases, and the surface tension decreases, thereby forming a huge three-dimensional adsorption structure to produce steric hindrance. , Increase the dispersion of plastic stabilizer.

2. In the present invention, the esterification product of 2-amino-3-p-hydroxyphenylpropionic acid monomer and unsaturated alcohol is used in the synthesis of plastic stabilizer for wet-mixed mortar. The steric hindrance effect of the chain is enhanced, and the esterification product will gradually hydrolyze in the alkaline environment of the concrete to release some carboxylic acid groups with a dispersing effect, so that the prepared wet-mixed mortar plastic stabilizer has better performance The plastic preservation effect.

3. A phosphoryl structure is introduced at the end of the molecular branch of the plastic stabilizer of the wet mixed mortar. The phosphoryl structure makes the molecular branch of the plastic stabilizer of the wet mixed mortar not only have a steric hindrance effect, but also have an electrostatic repulsion effect, which makes the prepared wet Mixing mortar stabilizer has higher dispersibility.

Detailed ways

In order to make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the following will clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not All examples. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.

The present invention also provides the following embodiments:

Example one

(1) The first esterification reaction:

Add 50g of 2-amino-3-p-hydroxyphenylpropionic acid and 50g of allyl alcohol into the reaction vessel, raise the temperature to 80°C, then add 2g of ferric ammonium sulfate dodecahydrate, react for 3 hours, reflux the excess propylene The alcohol is removed to obtain propenyl 2-amino-3-p-hydroxyphenylpropionate.

(2) The second esterification reaction:

Add 100g of 3-hydroxyphenylphosphorylpropionic acid and cyclohexane into the reaction kettle, then add 100g of dihydromyrcenol, and add p-732 cation exchange resin and hydroquinone at the same time, stir well, and then increase the temperature React for 2 hours at 30°C, filter and distill under atmospheric pressure to obtain 3-hydroxyphenylphosphoryl propionate dihydromyrcenol ester;

Among them, the amount of 732 cation exchange resin is 0.5% of the mass of 3-hydroxyphenylphosphorylpropionic acid, the amount of hydroquinone is 0.5% of the mass of 3-hydroxyphenylphosphorylpropionic acid, and the atmospheric distillation temperature is 70°C.

(3) Copolymerization reaction:

At 10°C, 100g of 4-hydroxybutyl vinyl polyoxyethylene ether monomer with a molecular weight of 4000, 5g of acrylic acid, 10g of methacryloxyethyl succinic acid monoester and 100g of water were added to the reactor After stirring and dispersing uniformly; then add 3g hydrogen peroxide at one time, 10min later, add 30g 5% azobisisobutylamidine hydrochloride solution and 5g 5% N,N-dimethyl Aniline solution, after 10 minutes, add 40g of 50% concentration of mixed reagent A (wherein the mixed reagent A includes 5g of acrylic acid, 5g of 2-amino-3-p-hydroxyphenylpropionate, 10g of 3-hydroxybenzene (Aqueous solution of dihydromyrcenol phosphonopropionate and 1 g of thioglycolic acid); the dropping time is 2.5h.

2) After the dripping is finished, add 2g of polyvinyl alcohol, then keep the temperature for 30min, add 23g of sodium hydroxide solution (30%) to neutralize to pH=7-8, and then obtain the wet-mixed mortar plastic stabilizer.

Example two

(1) The first esterification reaction:

Add 50g of 2-amino-3-p-hydroxyphenylpropionic acid and 100g of butenol into the reaction vessel, raise the temperature to 90°C, then add 1g of sodium hydrogen sulfate monohydrate, react for 4 hours, reflux the excess butenol The enol is removed to obtain butenyl 2-amino-3-p-hydroxyphenylpropionate.

(2) The second esterification reaction:

Add 100g of 3-hydroxyphenylphosphorylpropionic acid and cyclohexane to the reactor, then add 200g of dihydromyrcenol, and add 732 cation exchange resin and hydroquinone at the same time, stir well, and then raise the temperature to After reacting at 50°C for 3 hours, filtered and distilled at atmospheric pressure, 3-hydroxyphenylphosphoryl propionate dihydromyrcenol ester is obtained;

Among them, the amount of 732 cation exchange resin is 1% of the mass of 3-hydroxyphenylphosphorylpropionic acid, the amount of hydroquinone is 0.5% of the mass of 3-hydroxyphenylphosphorylpropionic acid, and the atmospheric distillation temperature is 75°C.

(3) Copolymerization reaction:

At 15°C, 100g of 4-hydroxybutyl vinyl polyoxyethylene ether monomer with a molecular weight of 4000, 5g of acrylic acid, 10g of methacryloxyethyl succinic acid monoester and 100g of water were added to the reactor After stirring and dispersing uniformly; then add 2g of hydrogen peroxide at one time. After 10 minutes, add 20g of azobisisobuimidazoline hydrochloride solution with a concentration of 5% and 5g of N,N-diethyl with a concentration of 5%. Aniline solution, after 10 minutes, add 45g of mixed reagent A (wherein the mixed reagent A includes 10g of acrylic acid, 5g of 2-amino-3-p-hydroxyphenylpropionate: 20g of 3-hydroxyphenylphosphoryl Dihydromyrcenol propionate, and 2g of thioglycolic acid in water); the dripping time is 3h.

After the dripping is finished, 2g of polyvinyl alcohol is added, and the temperature is kept for 30 minutes, and 30g of sodium hydroxide solution (30%) is added to neutralize to pH=7-8 to obtain the wet-mixed mortar plastic stabilizer.

Example three

(1) The first esterification reaction:

Add 50g of 2-amino-3-p-hydroxyphenylpropionic acid and 150g of unsaturated alcohol into the reaction vessel, raise the temperature to 70-90°C, then add 1-3 parts by weight of catalyst, react for 2 to 5 hours, and reflux The excess isopentenol is removed to obtain 2-amino-3-p-hydroxyphenyl propionate.

(2) The second esterification reaction:

Add 100g of 3-hydroxyphenylphosphorylpropionic acid and cyclohexane to the reactor, then add 250g of dihydromyrcenol, and add 732 cation exchange resin and hydroquinone at the same time, stir well, and then raise the temperature to After reacting at 60°C for 3 hours, filtered and distilled under atmospheric pressure, 3-hydroxyphenylphosphoryl propionate dihydromyrcenol ester is obtained;

Among them, the amount of 732 cation exchange resin is 1.5% of the mass of 3-hydroxyphenylphosphorylpropionic acid, the amount of hydroquinone is 1% of the mass of 3-hydroxyphenylphosphorylpropionic acid, and the atmospheric distillation temperature is 72°C.

(3) Copolymerization reaction:

At 5°C, 100 g of 4-hydroxybutyl vinyl polyoxyethylene ether monomer with a molecular weight of 4000, 5 g of acrylic acid, 10 g of methacryloxyethyl succinate and 100 g of water were added to the reaction In the kettle, wait to stir and disperse evenly; then add 1.5g of hydrogen peroxide at one time, and after 10 minutes, first add 25g of 5% azodicyanovaleric acid solution and 7g of 5% tetraethyleneimine solution. After 10 minutes, add 45g of 50% mixed reagent A (mixed reagent A includes 7g of acrylic acid, 8g of 2-amino-3-p-hydroxyphenylpropionate: 15g of 3-hydroxyphenylphosphoryl Dihydromyrcenol propionate, and 3g of thioglycolic acid in water); the dripping time is 2h.

Example four

(1) The first esterification reaction:

Add 50g of 2-amino-3-p-hydroxyphenylpropionic acid and 150g of allyl alcohol into the reaction vessel, raise the temperature to 90°C, then add 1g of ferric ammonium sulfate dodecahydrate, react for 4 hours, reflux the excess propylene The alcohol is removed to obtain 2-amino-3-p-hydroxyphenyl propionate.

(2) The second esterification reaction:

Add 100g of 3-hydroxyphenylphosphorylpropionic acid and cyclohexane to the reaction kettle, then add 300g of dihydromyrcenol, and add 732 cation exchange resin and hydroquinone at the same time, stir well, and then raise the temperature to After reacting at 40°C for 4 hours, filtered and distilled at atmospheric pressure, 3-hydroxyphenylphosphoryl propionate dihydromyrcenol ester is obtained;

Among them, the amount of 732 cation exchange resin is 2% of the mass of 3-hydroxyphenylphosphorylpropionic acid, the amount of hydroquinone is 1% of the mass of 3-hydroxyphenylphosphorylpropionic acid, and the atmospheric distillation temperature is 70°C.

(3) Copolymerization reaction:

At 15°C, 100g of 4-hydroxybutyl vinyl polyoxyethylene ether monomer with a molecular weight of 4000 (molecular weight of 4000), 5g of acrylic acid, 10g of methacryloxyethyl succinate and Add 100g of water to the reaction kettle, and wait to stir and disperse evenly; then add 1g of hydrogen peroxide at one time, and after 10 minutes, add 30g of 5% diisopropylimidazoline solution and 8g of 5% tetraethylene dropwise The imine solution, after 10 minutes, add 40g of 50% mixed reagent A (wherein the mixed reagent A includes 5g of acrylic acid, 10g of 2-amino-3-p-hydroxyphenylpropionate: 20g of 3-hydroxyl Dihydromyrcenol phenylphosphorylpropionate, and 2g of thioglycolic acid in water); the dripping time is 2.5h.

After the dripping is completed, 2g of polyvinyl alcohol is added, and the temperature is kept for 30 minutes, and 20g of sodium hydroxide solution (30%) is added to neutralize to pH=7-8 to obtain the wet-mixed mortar plastic stabilizer.

It should be noted that the specific parameters or some commonly used reagents in the above-mentioned embodiments are specific or preferred embodiments under the concept of the present invention, rather than limiting them; those skilled in the art are within the concept and protection scope of the present invention, Can be adjusted adaptively.

The wet-mixed mortar plastic stabilizer prepared in the foregoing embodiment of the present invention has a molecular weight of 60,000 to 100,000. The wet-mixed mortar plastic stabilizer prepared in the above-mentioned examples was carried out in accordance with GB8076-2008 "Concrete admixtures" and JGJ70-2009 "Test method standards for basic properties of building mortars". Standard cement is used, and the initial consistency of the mortar is controlled within (90±10)mm, the mortar mix ratio is shown in Table 2. The consistency, 2h consistency, water retention rate and compressive strength of the mortar are measured, and the results are shown in Table 2.

Table 1 Mixing ratio of wet mixed mortar

Among them, C means: cement; FA means: fly ash; S means: sand; W means: water; A means: plastic stabilizer.

Table 2 Mortar properties of samples synthesized in the examples

Among them, the plastic stabilizer used in the comparative example is a commercially available common mortar plastic stabilizer; in the sample mortar synthesized in each embodiment, except for the different plastic stabilizer, the other conditions remain the same, and the test conditions and environment are also consistent.

It can be seen from Table 1 that the sample synthesized by the wet-mixed mortar plastic stabilizer prepared by the present invention has low consistency loss, better water retention rate and higher The compressive strength of the mortar and the long-term stability of the mortar's plastic retention performance have also been greatly improved, which has made significant progress.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand: It is still possible to modify the technical solutions described in the foregoing embodiments, or equivalently replace some or all of the technical features; these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the embodiments of the present invention range.

Claims

A method for preparing a plastic stabilizer for wet-mixed mortar, which is characterized in that it comprises the following steps:

After mixing 4-hydroxybutyl vinyl polyoxyethylene ether monomer, acrylic acid, methacryloxyethyl succinate and water, add hydrogen peroxide; after the reaction, add the aqueous solution of reducing agent and the aqueous solution of co-catalyst in sequence And mixed with an aqueous solution of reagent A; after the reaction, polyvinyl alcohol is added, and the pH is adjusted to 7-8 to prepare the wet-mixed mortar plastic stabilizer;

The mixed reagent A is composed of acrylic acid, 2-amino-3-p-hydroxyphenylpropionate, 3-hydroxyphenylphosphoryl propionate dihydromyrcenol ester and a chain transfer agent.
The method for preparing a plastic stabilizer for wet-mixed mortar according to claim 1, wherein the method for preparing 2-amino-3-p-hydroxyphenyl propionate is:

Mix 2-amino-3-p-hydroxyphenylpropionic acid and unsaturated alcohol in a weight ratio of 1:1 to 3, add a catalyst, and perform an esterification reaction at 80 to 120°C to remove excess unsaturated alcohol. The 2-amino-3-p-hydroxyphenyl propionate is obtained.
The method for preparing a plastic stabilizer for wet-mixed mortar according to claim 2, wherein the unsaturated alcohol is at least one of allyl alcohol, butenol, and isopentenol.
The method for preparing wet-mixed mortar plastic stabilizer according to claim 2, wherein the catalyst is at least one of ferric ammonium sulfate dodecahydrate, sodium hydrogen sulfate monohydrate, and aluminum sulfate octahydrate.
The preparation method of wet-mixed mortar plastic stabilizer according to claim 1, wherein the preparation method of 3-hydroxyphenylphosphoryl propionate dihydromyrcenol ester is:

After mixing 3-hydroxyphenylphosphoryl propionic acid and cyclohexane, add dihydromyrcenol, add 732 cation exchange resin and hydroquinone and stir at the same time, then raise the temperature to 30～60℃ and react After filtration and atmospheric distillation, 3-hydroxyphenylphosphoryl propionate dihydromyrcenol ester is obtained.
The method for preparing wet-mixed mortar plastic stabilizer according to claim 5, characterized in that: the mass ratio of 3-hydroxyphenylphosphoryl propionic acid to dihydromyrcenol is 1:1 to 3,732 cations The amount of exchange resin is 0.5% to 2% of the mass of 3-hydroxyphenylphosphorylpropionic acid, the amount of hydroquinone is 0.5% to 1% of the mass of 3-hydroxyphenylphosphorylpropionic acid, and the atmospheric distillation temperature is 70 ～75℃.
The method for preparing a plastic stabilizer for wet-mixed mortar according to claim 1, wherein the 4-hydroxybutyl vinyl polyoxyethylene ether monomer, acrylic acid, methacryloxyethyl succinic acid monomer The weight ratio of ester, water, hydrogen peroxide, aqueous solution of reducing agent, aqueous solution of co-catalyst, and aqueous solution of mixed reagent A is 100:5:10:100:1 to 3:20 to 30:5 to 10:40 to 50.
The method for preparing wet-mixed mortar plastic stabilizer according to claim 1, wherein the molecular weight of the 4-hydroxybutyl vinyl polyoxyethylene ether monomer is 4000.
The method for preparing wet-mixed mortar plastic stabilizer according to claim 1, wherein the reducing agent is azobisisobutylamidine hydrochloride, azobisisobuimidazoline hydrochloride, azo At least one of dicyanovaleric acid and azodiisopropyl imidazoline.
The method for preparing a plastic stabilizer for wet-mixed mortar according to claim 1, wherein the co-catalyst is N,N-dimethylaniline, N,N-diethylaniline, and tetraethyleneimine. At least one.
The method for preparing a plastic stabilizer for wet-mixed mortar according to claim 1, wherein the chain transfer agent is at least one of thioglycolic acid, 3-mercaptopropionic acid, 2-mercaptopropanol, and mercaptoethanol.
The method for preparing a plastic stabilizer for wet-mixed mortar according to claim 1, wherein the reaction temperature is 0-15°C; the mass percentage concentration of the reducing agent is 5%; the mass percentage of the promoter The concentration is 5%, and the mass percentage concentration of the mixed reagent A is 50%.
A wet-mix mortar plastic stabilizer prepared according to the method for preparing a wet-mix mortar plastic stabilizer according to any one of claims 1-12.
The wet-mixed mortar plastic stabilizer according to claim 13, wherein the molecular weight of the wet-mixed mortar plastic stabilizer is 60,000 to 120,000.