WO2019233085A1 - Phosphorus-containing polycarboxylate superplasticizer and preparation method therefor - Google Patents

Abstract

Disclosed by the present invention are a phosphorus-containing polycarboxylate superplasticizer and a preparation method therefor, the molecular weight thereof being 10,000-150,000, and the structural formula thereof being as shown in (I). The present invention introduces a benzene ring and a phosphate group structure at branch ends of polycarboxylate superplasticizer molecules by means of using an unsaturated polyether monomer and an esterified product of a first compound in the synthesis of the polycarboxylate superplasticizer; the benzene ring structure enhances the steric effect of the branches of the polycarboxylate superplasticizer molecules, and the phosphate group structure causes the branches of the polycarboxylate superplasticizer molecules to not only have a steric effect, but also have an electrostatic repulsion effect so that the prepared polycarboxylate superplasticizer has a higher water reduction rate.

Description

Phosphorus-containing polycarboxylic acid water reducing agent and preparation method thereof Technical field

The invention belongs to the technical field of building admixtures, and particularly relates to a phosphorus-containing polycarboxylic acid water reducing agent and a preparation method thereof.

Background technique

Polycarboxylic acid water reducing agent, as a new type of high performance water reducing agent, has low dosage, high water reduction rate, good slump retention, small shrinkage rate, relatively good adaptability to cement and admixtures, and enhanced effects. Obviously waiting for a series of outstanding performance. At the same time, the production process is environmentally friendly and has been widely used in various engineering fields. However, due to the rapid development of China's real estate market and infrastructure construction, a large number of engineering constructions have consumed huge amounts of cement and sand and stone, which has increased the tight supply of sand and stone resources. Natural sand and stone resources in many regions of the country are increasingly scarce. The supply of sandstone materials is in short supply, resulting in extremely unstable sandstone materials and high and unstable mud content of sandstone. Polycarboxylic acid water reducing agents are applied to concrete, which results in insufficient water reduction rate, poor slump retention, and increasing sensitivity issues. Therefore, it is of great significance to develop a water-reducing agent with high water reduction, high collapse resistance, and insensitivity to the mud content of the material.

Summary of the Invention

The purpose of the present invention is to overcome the defects of the prior art and provide a phosphorus-containing polycarboxylic acid water reducing agent.

Another object of the present invention is to provide a method for preparing the phosphorus-containing polycarboxylic acid water reducing agent.

The technical scheme of the present invention is as follows:

A phosphorus-containing polycarboxylic acid water reducing agent, the molecular weight of which is 10,000 to 150,000, and its structural formula is as follows:

Wherein R ₁ is H or CH ₃ , R ₂ is an alkyl group of 1 to 4 carbons, R ₃ is an alkyl group of 1 to 4 carbons, R ₄ is an alkyl group of 1 to 4 carbons, R ₅ is H or COOM, R ₆ is H or CH ₃ , R ₇ is H or COOM, R ₈ is H or CH ₃ , R ₉ is an empty or 1 to 4 carbon alkyl group, and R ₁₀ is an alkyl group having one alkane In the naphthalene ring of the phosphate substituent, M is H, Na, K or NH ₄ ; the relationship between R ₃ and R ₄ relative to the benzene ring is ortho, meta or para.

The preparation method of the above-mentioned phosphorus-containing polycarboxylic acid water reducing agent includes the following steps:

(1) The first esterification reaction: the unsaturated polyether and the first compound are mixed, and the temperature is increased to 70-90 ° C under the protection of nitrogen, and then a catalyst is added, and the reaction is maintained for 0.5-3.0h, during which a vacuum or nitrogen is passed. The method with water is used to remove water, and after the reaction is completed, the temperature is lowered to room temperature to obtain a first mixture containing an esterified product and an unreacted unsaturated polyether. The unsaturated polyether is an allyl polyethylene with a molecular weight of 600 to 5000. At least one of alcohol, 3-methyl-3-butene-1-polyethylene glycol, and 2-methylallyl polyethylene glycol; the structural formula of the first compound is as follows:

(2) The second esterification reaction: mixed unsaturated carboxylic acid or unsaturated carboxylic anhydride, hydroxynaphthalene phosphoric acid and polymerization inhibitor, heated under nitrogen protection to 90-120 ° C, and then added a catalyst, and kept the reaction at 0.5-3.0 h, during the period of time, the water is removed by vacuum or nitrogen gas, and the temperature is reduced to room temperature after the reaction, to obtain a second mixture containing the esterified product and unreacted unsaturated carboxylic acid or unsaturated carboxylic anhydride; The acid or unsaturated carboxylic anhydride is at least one of acrylic acid, methacrylic acid, maleic acid, and maleic anhydride; the hydroxynaphthalene phosphate is 1-hydroxynaphthalene-4 phosphate, 1-hydroxynaphthalene-5 phosphate, and 1-hydroxyl Naphthalene-6 phosphate, 1-hydroxynaphthalene-7 phosphate, 2-hydroxynaphthalene-4 phosphate, 2-hydroxynaphthalene-5 phosphate, 2-hydroxynaphthalene-6 phosphate, 2-hydroxynaphthalene-7 phosphate, 1-hydroxymethyl Naphthalene-4 phosphate, 1-hydroxymethylnaphthalene-5 phosphate, 1-hydroxymethylnaphthalene-6 phosphate, 1-hydroxymethylnaphthalene-7 phosphate, 2-hydroxymethylnaphthalene-4 phosphate, 2-hydroxymethyl Naphthalene-5 phosphate, 2-hydroxymethylnaphthalene-6 phosphate, 2-hydroxymethylnaphthalene-7 phosphate, 1-hydroxynaphthalene-4 methylphosphate, 1-hydroxynaphthalene-5methylphosphate, 1-hydroxynaphthalene- 6 methyl phosphate, 1-hydroxynaphthalene-7 methyl Acid, 2-hydroxynaphthalene-4 methyl phosphate, 2-hydroxynaphthalene-5 methyl phosphate, 2-hydroxynaphthalene-6 methyl phosphate, 2-hydroxynaphthalene-7 methyl phosphate, 1-hydroxymethylnaphthalene-4 Methyl phosphate, 1-hydroxymethylnaphthalene-5 methyl phosphate, 1-hydroxymethylnaphthalene-6 methyl phosphate, 1-hydroxymethylnaphthalene-7 methyl phosphate, 2-hydroxymethylnaphthalene-4 methyl At least one of phosphoric acid, 2-hydroxymethylnaphthalene-5methylphosphoric acid, 2-hydroxymethylnaphthalene-6methylphosphoric acid, 2-hydroxymethylnaphthalene-7methylphosphoric acid:

(3) monomer blending: mixing the first mixture obtained in step (1) and the second mixture obtained in step (2) at a mass ratio of 100: 6 to 18, and adding water to dissolve them to obtain copolymerization Monomer mixture solution;

(4) Copolymerization reaction: The above comonomer mixture solution, initiator aqueous solution and molecular weight regulator aqueous solution are dropped into water for reaction. The reaction temperature is 10-60 ° C, and the dropping time is 0.2-6.0h. After the dropwise addition, the temperature is maintained. 0 ～ 3.0h, copolymerization product is obtained;

(5) Neutralization reaction: The copolymerized product obtained in step (3) is adjusted to a pH of 5 to 7 with an alkali to obtain the phosphorus-containing polycarboxylic acid water reducing agent.

In a preferred embodiment of the present invention, in the step (1), the molar ratio of the unsaturated polyether and the first compound is 1 to 1.5: 1, and the amount of the catalyst is the unsaturated polyether and the first compound. 0.05 to 0.3% of the total mass.

In a preferred embodiment of the present invention, in the step (2), the molar ratio of the unsaturated carboxylic acid or unsaturated carboxylic anhydride to hydroxynaphthalene phosphate is 2 to 7: 1, and the amount of the catalyst used is The total mass of the saturated carboxylic acid or unsaturated carboxylic anhydride and hydroxynaphthalene phosphoric acid is 0.03 to 0.3%; the amount of the polymerization inhibitor is 0.2 to 3.0% of the total mass of the unsaturated carboxylic acid or unsaturated carboxylic anhydride and hydroxynaphthalene phosphoric acid.

In a preferred embodiment of the present invention, the total amount of water used in step (3) and step (4) is such that the mass concentration of the copolymerization product is 20 to 70%, and the amount of the initiator is the copolymerization. 0.5 to 3.0% of the total mass of the solute in the monomer mixture solution, and the amount of the molecular weight modifier is 0.2 to 2.0% of the total mass of the solute in the comonomer mixture solution.

Further preferably, the catalyst is at least one of pyromellitic acid, nitrogen sulfur acid, and trinitrobenzenesulfonic acid.

Further preferably, the polymerization inhibitor is at least one of hydroquinone, phenothiazine, and diphenylamine.

Further preferably, the initiator is a water-soluble redox initiator system or a water-soluble azo initiator.

Further preferably, the molecular weight modifier is at least one of mercaptoacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium hypophosphite, trisodium phosphate, sodium formate, sodium acetate, and dodecanethiol.

The beneficial effects of the present invention are:

1. The present invention uses an esterified product of an unsaturated polyether monomer and a first compound for the synthesis of a polycarboxylic acid water reducing agent. A benzene ring and a phosphate group structure are introduced at the branched end of the polycarboxylic acid water reducing agent molecule. The benzene ring structure makes the steric hindrance effect of the molecular branches of the polycarboxylic acid superplasticizer enhanced, and the phosphate group structure makes the molecular branches of the polycarboxylic acid superplasticizer not only have a steric hindrance effect, but also have an electrostatic repulsive effect, making The water reduction rate of the prepared polycarboxylic acid water reducing agent is higher.

2. In the present invention, a naphthalene phosphate side is introduced into the main chain of a polycarboxylic acid water reducing agent molecule by using an esterified product of an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride and a hydroxynaphthalene phosphate for the synthesis of a polycarboxylic acid water reducing agent. It changes the adsorption effect of polycarboxylic acid water reducing agent on cement, mud, and stone powder, so that the prepared polycarboxylic acid water reducing agent has the effect of low sensitivity to mud and powder content in concrete aggregate.

3. The ester structure in the polycarboxylic acid water reducing agent of the present invention will gradually hydrolyze and release part of the carboxylic acid group with water reducing effect under the alkaline environment of concrete, so that the prepared polycarboxylic acid water reducing agent also has Has a certain slump effect.

Detailed ways

The technical solutions of the present invention are further illustrated and described below through specific embodiments.

The molecular weight of the phosphorus-containing polycarboxylic acid water reducing agent obtained in the following examples is 10,000 to 150,000, and its structural formula is as follows:

Wherein R ₁ is H or CH ₃ , R ₂ is an alkyl group of 1 to 4 carbons, R ₃ is an alkyl group of 1 to 4 carbons, R ₄ is an alkyl group of 1 to 4 carbons, R ₅ is H or COOM, R ₆ is H or CH ₃ , R ₇ is H or COOM, R ₈ is H or CH ₃ , R ₉ is an empty or 1 to 4 carbon alkyl group, and R ₁₀ is an alkyl group having one alkane In the naphthalene ring of the phosphate substituent, M is H, Na, K or NH ₄ ; the relationship between R ₃ and R ₄ relative to the benzene ring is ortho, meta or para.

Example 1

(1) The first esterification reaction: 600.00 g of allyl polyethylene glycol with a molecular weight of 1000 and 100.00 g of ortho-carboxybenzene phosphoric acid are mixed, and the temperature is increased to 75 ° C. under nitrogen protection, and then 0.38 g of pyromellitic acid is added, and the temperature is maintained. The reaction was carried out for 2.0 hours. During the reaction, water was removed by vacuuming or passing nitrogen through water. After the reaction, the temperature was reduced to room temperature to obtain a first mixture containing an esterified product and unreacted allyl polyethylene glycol.

(2) The second esterification reaction: 75.00 g of acrylic acid, 100.00 g of 1-hydroxynaphthalene-4 phosphoric acid, and 1.80 g of hydroquinone are mixed, and the temperature is increased to 105 ° C. under the protection of nitrogen, and 0.15 g of pyrohexacarboxylic acid is added, and the temperature is maintained The reaction was carried out for 2.0 hours. During the reaction, water was removed by vacuum or nitrogen gas. After the reaction, the temperature was reduced to room temperature to obtain a second mixture containing the esterified product and unreacted acrylic acid.

(3) monomer blending: 100.00 g of the first mixture obtained in step (1) and 11.00 g of the second mixture obtained in step (2) are mixed, and 40.00 g of water is added to dissolve it to obtain a comonomer mixture Solution

(4) Copolymerization reaction: the above comonomer mixture solution, hydrogen peroxide aqueous solution (wherein 0.90 g of hydrogen peroxide and 10.00 g of water), aqueous ascorbic acid solution (of which 0.20 g, water 10.00 g) and aqueous thioglycolic acid solution (wherein 0.70 g of thioglycolic acid, water 10.00g) dropwise into 40.00g of water to carry out the reaction, the reaction temperature is 40 ° C, the dropping time is 3.0h, and the temperature is maintained for 1.5h after the dropwise addition, to obtain a copolymer product;

(5) Neutralization reaction: Adjust the pH of the copolymerized product obtained in step (4) to 5 to 7 with alkali to obtain the phosphorus-containing polycarboxylic acid water reducing agent PCE-1.

Example 2

(1) The first esterification reaction: 1050.00 g of 3-methyl-3-butene-1-polyethylene glycol with a molecular weight of 2000 and 100.00 g of m-carboxymethylbenzenephosphoric acid are mixed, and the temperature is increased to 75 under the protection of nitrogen. ℃, then add 1.50g of nitrogen sulfur sulfuric acid, keep the reaction for 1.5h, remove the water by vacuum or nitrogen water during the reaction, after the reaction is completed, reduce to room temperature to obtain the esterified product and unreacted 3-methyl A first mixture of 3-butene-1-polyethylene glycol.

(2) The second esterification reaction: 88.00 g of methacrylic acid, 100.00 g of 1-hydroxynaphthalene-5 phosphoric acid, and 1.60 g of phenothiazine are mixed, and the temperature is increased to 100 ° C. under the protection of nitrogen, and then 0.30 g of nitrosulfuric acid is added. , Holding the reaction for 2.0h, during which the water was removed by vacuuming or passing nitrogen through water, and after the reaction was completed, the temperature was lowered to obtain a second mixture containing the esterified product and unreacted methacrylic acid;

(3) monomer blending: 100.00 g of the first mixture prepared in step (1) and 13.00 g of the second mixture prepared in step (2) are mixed, and 40.00 g of water is added to dissolve them to obtain a comonomer mixture Solution

(4) Copolymerization reaction: the above comonomer mixture solution, azobisisobutylphosphonium hydrochloride aqueous solution (among which azobisisobutylphosphonium hydrochloride 1.20g, water 10.00g) and aqueous sodium hypophosphite ( Among them, sodium hypophosphite (0.90 g, water 10.00 g) was dropped into 40.00 g of water to carry out the reaction, the reaction temperature was 45 ° C, the dropping time was 2.0 h, and the temperature was maintained for 1.0 h after the dropping was completed to obtain a copolymer product;

(5) Neutralization reaction: Adjust the pH of the copolymerized product obtained in step (4) to 5 to 7 with alkali to obtain the phosphorus-containing polycarboxylic acid water reducing agent PCE-2.

Example 3

(1) The first esterification reaction: 1140.00 g of 2-methylallyl polyethylene glycol having a molecular weight of 2400 and 100.00 g of p-carboxyethyl phenylphosphoric acid are mixed, and the temperature is increased to 85 ° C. under the protection of nitrogen, and then 2.80 is added. g Trinitrobenzenesulfonic acid, holding the reaction for 1.5h, during which the water is removed by evacuation or nitrogen flow with water. After the reaction, the temperature is reduced to room temperature to obtain an esterified product and unreacted 2-methylallyl group. A first mixture of polyethylene glycol.

(2) The second esterification reaction: 165.00g of maleic acid, 100.00g of 1-hydroxynaphthalene-6 phosphate and 1.80g of diphenylamine are mixed, and the temperature is increased to 110 ° C under the protection of nitrogen, and then 0.60g of trinitrobenzenesulfonate is added. Acid, keep the reaction for 2.5h, remove the water by vacuuming or passing nitrogen gas into the water during the reaction. After the reaction, the temperature is reduced to room temperature to obtain a second mixture containing the esterified product and unreacted maleic acid;

(3) monomer blending: 100.00 g of the first mixture obtained in step (1) and 15.00 g of the second mixture obtained in step (2) are mixed, and 40.00 g of water is added to dissolve them to obtain a comonomer mixture Solution

(4) Copolymerization reaction: the above comonomer mixture solution, an azobiscyanovaleric acid aqueous solution (wherein 2.20 g of azodicyanovaleric acid and 10.00 g of water) and an aqueous solution of trisodium phosphate (wherein 1.60 g of trisodium phosphate) , Water 10.00g) dropwise into 40.00g water to carry out the reaction, the reaction temperature is 50 ° C., the dropping time is 2.0h, and the temperature is maintained for 0.5h after the dropwise addition, to obtain a copolymer product;

(5) Neutralization reaction: Adjust the pH of the copolymerized product obtained in step (4) to 5 to 7 with alkali to obtain the phosphorus-containing polycarboxylic acid water reducing agent PCE-3.

Example 4

(1) First esterification reaction: 1450.00g of allyl polyethylene glycol having a molecular weight of 3000 and 100.00g of o-carboxybenzyl phosphoric acid are mixed, and the temperature is increased to 90 ° C under the protection of nitrogen, and then 4.40g of pyromellitic acid is added. The reaction was kept at a temperature of 3.0 h, during which the water was removed by vacuum or nitrogen gas, and the temperature was reduced to room temperature after the reaction was completed to obtain a first mixture containing an esterified product and unreacted allyl polyethylene glycol.

(2) The second esterification reaction: 170.00 g of maleic anhydride, 100.00 g of 1-hydroxynaphthalene-7 phosphoric acid, and 2.00 g of hydroquinone are mixed, and the temperature is increased to 100 ° C under the protection of nitrogen, and then 0.70 g of trinitro group is added. Benzene sulfonic acid, which was incubated for 1.5 h. During the reaction, water was removed by evacuation or nitrogen with water. After the reaction, the temperature was reduced to room temperature to obtain a second mixture containing the esterified product and unreacted maleic anhydride.

(3) monomer blending: 100.00 g of the first mixture prepared in step (1) and 16.00 g of the second mixture prepared in step (2) are mixed, and 40.00 g of water is added to dissolve it to obtain a comonomer mixture Solution

(4) Copolymerization reaction: the above comonomer mixture solution, hydrogen peroxide aqueous solution (including hydrogen peroxide 1.20 g, water 10.00 g), trisodium phosphate aqueous solution (including trisodium phosphate 1.00 g, water 10.00 g), and ascorbic acid aqueous solution (where , Ascorbic acid 0.20, water 10.00g) dropwise into 40.00g water for reaction, the reaction temperature is 35 ° C, the drop time is 2.5h, and the temperature is maintained for 1.0h after the dropwise addition, to obtain a copolymer product;

(5) Neutralization reaction: Adjust the pH of the copolymerized product obtained in step (4) to 5 to 7 with alkali to obtain the phosphorus-containing polycarboxylic acid water reducing agent PCE-4.

Example 5

(1) First esterification reaction: 1990.00g of 3-methyl-3-butene-1-polyethylene glycol having a molecular weight of 4000 and 100.00g of p-carboxymethylphenethylphosphoric acid are mixed, and the temperature is increased under the protection of nitrogen. To 80 ° C, add 6.00g of trinitrobenzenesulfonic acid, and keep the reaction for 3.0h. During the period, remove the water by vacuuming or passing nitrogen into the water. After the reaction, the temperature is reduced to room temperature to obtain the esterified product and unreacted A first mixture of 3-methyl-3-butene-1-polyethylene glycol.

(2) The second esterification reaction: 99.00 g of acrylic acid, 100.00 g of 2-hydroxynaphthalene-4 phosphoric acid and 3.60 g of phenothiazine are mixed, and the temperature is increased to 115 ° C. under the protection of nitrogen, and 0.40 g of nitrogen sulfur sulfuric acid is added, and the temperature is maintained The reaction was carried out for 1.5 hours. During the reaction, water was removed by evacuation or nitrogen gas. After the reaction, the temperature was reduced to room temperature to obtain a second mixture containing the esterified product and unreacted acrylic acid.

(3) monomer blending: 100.00 g of the first mixture prepared in step (1) and 13.00 g of the second mixture prepared in step (2) are mixed, and 40.00 g of water is added to dissolve them to obtain a comonomer mixture Solution

(4) Copolymerization reaction: the comonomer mixture solution, an azodicyanovaleric acid aqueous solution (wherein, azodicyanovaleric acid 1.80g, water 10.00g), an aqueous sodium hypophosphite solution (wherein sodium hypophosphite 1.40g, water 20.00g) dropwise into 40.00g water to carry out the reaction, the reaction temperature is 40 ° C, the dropping time is 2.0h, and the temperature is maintained for 2.0h after the dropwise addition, to obtain a copolymer product;

(5) Neutralization reaction: The copolymerized product obtained in step (4) is adjusted to a pH of 5 to 7 with an alkali to obtain the phosphorus-containing polycarboxylic acid water reducing agent PCE-5.

According to GB / T8076-2008, the phosphorus-containing polycarboxylic acid water-reducing agents prepared in Examples 1 to 5 were tested. When the solid content was 0.2% (relative to the amount of cement), the water reduction rates were higher than The compressive strength ratios at 45% and 28d were all greater than 140%, and the shrinkage ratios at 28d were less than 110%.

Minfu PO 42.5 ordinary Portland cement is used. The concrete mix ratio is: cement 300kg / m ³ , fly ash 100kg / m ³ , mineral powder 100kg / m ³ , sand 690kg / m ³ , stone 1050kg / m ³ , water 160kg / m ³ , and adding 3.5% of bentonite (relative to the amount of cement), the phosphorus-containing polycarboxylic acid water reducing agent and commercially available polycarboxylic acid water reducing agent (PCE) prepared in Examples 1 to 5 were added in accordance with Folding solid content of 0.15% for performance testing. Test the initial slump and spread of the concrete, 2h slump and spread.

Table 1 Test results of different admixtures

It can be seen from Table 1 that, for the materials doped with bentonite, the examples synthesized in this patent compare with commercially available polycarboxylic acid water reducing agent (PCE), which has a larger water reduction rate and better slump retention performance. The patented polycarboxylic acid water reducing agent has low sensitivity to materials with high mud content and has anti-mud effect.

Those of ordinary skill in the art may know that when the technical solution of the present invention is changed within the following range, the same or similar technical effects as those of the above embodiments can still be obtained, and still belong to the protection scope of the present invention:

A phosphorus-containing polycarboxylic acid water reducing agent, the molecular weight of which is 10,000 to 150,000, and its structural formula is as follows:

Wherein R ₁ is H or CH ₃ , R ₂ is an alkyl group of 1 to 4 carbons, R ₃ is an alkyl group of 1 to 4 carbons, R ₄ is an alkyl group of 1 to 4 carbons, R ₅ is H or COOM, R ₆ is H or CH ₃ , R ₇ is H or COOM, R ₈ is H or CH ₃ , R ₉ is an empty or 1 to 4 carbon alkyl group, and R ₁₀ is an alkyl group having one alkane In the naphthalene ring of the phosphate substituent, M is H, Na, K or NH ₄ ; the relationship between R ₃ and R ₄ relative to the benzene ring is ortho, meta or para.

The preparation method of the above-mentioned phosphorus-containing polycarboxylic acid water reducing agent includes the following steps:

(1) The first esterification reaction: the unsaturated polyether and the first compound are mixed, and the temperature is increased to 70-90 ° C under the protection of nitrogen, and then a catalyst is added, and the reaction is maintained for 0.5-3.0h, during which a vacuum or nitrogen is passed. The method with water is used to remove water, and after the reaction is completed, the temperature is lowered to room temperature to obtain a first mixture containing an esterified product and an unreacted unsaturated polyether. The unsaturated polyether is an allyl polyethylene with a molecular weight of 600 to 5000. At least one of alcohol, 3-methyl-3-butene-1-polyethylene glycol, and 2-methylallyl polyethylene glycol; the structural formula of the first compound is as follows:

(2) The second esterification reaction: mixed unsaturated carboxylic acid or unsaturated carboxylic anhydride, hydroxynaphthalene phosphoric acid and polymerization inhibitor, heated under nitrogen protection to 90-120 ° C, and then added a catalyst, and kept the reaction at 0.5-3.0 h, during the period of time, the water is removed by vacuum or nitrogen gas, and the temperature is reduced to room temperature after the reaction, to obtain a second mixture containing the esterified product and unreacted unsaturated carboxylic acid or unsaturated carboxylic anhydride; The acid or unsaturated carboxylic anhydride is at least one of acrylic acid, methacrylic acid, maleic acid, and maleic anhydride; the hydroxynaphthalene phosphate is 1-hydroxynaphthalene-4 phosphate, 1-hydroxynaphthalene-5 phosphate, and 1-hydroxyl Naphthalene-6 phosphate, 1-hydroxynaphthalene-7 phosphate, 2-hydroxynaphthalene-4 phosphate, 2-hydroxynaphthalene-5 phosphate, 2-hydroxynaphthalene-6 phosphate, 2-hydroxynaphthalene-7 phosphate, 1-hydroxymethyl Naphthalene-4 phosphate, 1-hydroxymethylnaphthalene-5 phosphate, 1-hydroxymethylnaphthalene-6 phosphate, 1-hydroxymethylnaphthalene-7 phosphate, 2-hydroxymethylnaphthalene-4 phosphate, 2-hydroxymethyl Naphthalene-5 phosphate, 2-hydroxymethylnaphthalene-6 phosphate, 2-hydroxymethylnaphthalene-7 phosphate, 1-hydroxynaphthalene-4 methylphosphate, 1-hydroxynaphthalene-5methylphosphate, 1-hydroxynaphthalene- 6 methyl phosphate, 1-hydroxynaphthalene-7 methyl Acid, 2-hydroxynaphthalene-4 methyl phosphate, 2-hydroxynaphthalene-5 methyl phosphate, 2-hydroxynaphthalene-6 methyl phosphate, 2-hydroxynaphthalene-7 methyl phosphate, 1-hydroxymethylnaphthalene-4 Methyl phosphate, 1-hydroxymethylnaphthalene-5 methyl phosphate, 1-hydroxymethylnaphthalene-6 methyl phosphate, 1-hydroxymethylnaphthalene-7 methyl phosphate, 2-hydroxymethylnaphthalene-4 methyl At least one of phosphoric acid, 2-hydroxymethylnaphthalene-5 methylphosphate, 2-hydroxymethylnaphthalene-6methylphosphate, 2-hydroxymethylnaphthalene-7methylphosphoric acid;

(3) monomer blending: mixing the first mixture obtained in step (1) and the second mixture obtained in step (2) at a mass ratio of 100: 6 to 18, and adding water to dissolve them to obtain copolymerization Monomer mixture solution;

(4) Copolymerization reaction: The above comonomer mixture solution, initiator aqueous solution and molecular weight regulator aqueous solution are dropped into water for reaction. The reaction temperature is 10-60 ° C, and the dropping time is 0.2-6.0h. 0 ～ 3.0h, copolymerization product is obtained;

(5) Neutralization reaction: The copolymerized product obtained in step (3) is adjusted to a pH of 5 to 7 with an alkali to obtain the phosphorus-containing polycarboxylic acid water reducing agent.

In the step (1), the molar ratio of the unsaturated polyether to the first compound is 1 to 1.5: 1, and the amount of the catalyst used is 0.05 to 0.3% of the total mass of the unsaturated polyether and the first compound. In the step (2), the molar ratio of the unsaturated carboxylic acid or unsaturated carboxylic anhydride to hydroxynaphthalene phosphoric acid is 2 to 7: 1, and the amount of the catalyst used is unsaturated carboxylic acid or unsaturated carboxylic anhydride and hydroxy 0.03 to 0.3% of the total mass of naphthalene phosphate; the amount of the polymerization inhibitor is 0.2 to 3.0% of the total mass of unsaturated carboxylic acid or unsaturated carboxylic anhydride and hydroxynaphthalene phosphate. The total amount of water used in step (3) and step (4) is such that the mass concentration of the copolymerization product is 20 to 70%, and the amount of the initiator is equal to the total mass of the solute in the comonomer mixture solution. 0.5 to 3.0%, and the amount of the molecular weight modifier is 0.2 to 2.0% of the total mass of the solute in the comonomer mixture solution.

The catalyst is at least one of pyromellitic acid, nitrogen sulfur acid, and trinitrobenzenesulfonic acid. The polymerization inhibitor is at least one of hydroquinone, phenothiazine, and diphenylamine. The initiator is a water-soluble redox initiator system or a water-soluble azo initiator. The molecular weight modifier is at least one of mercaptoacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium hypophosphite, trisodium phosphate, sodium formate, sodium acetate, and dodecyl mercaptan.

The above are only the preferred embodiments of the present invention, so the scope of implementation of the present invention cannot be limited accordingly, that is, equivalent changes and modifications made according to the patent scope of the present invention and the contents of the description should still be covered by the present invention. In the range.

Claims (9)

A phosphorus-containing polycarboxylic acid water reducing agent, which is characterized in that its molecular weight is 10,000 to 150,000 and its structural formula is as follows:

Wherein R ₁ is H or CH ₃ , R ₂ is an alkyl group of 1 to 4 carbons, R ₃ is an alkyl group of 1 to 4 carbons, R ₄ is an alkyl group of 1 to 4 carbons, R ₅ is H or COOM, R ₆ is H or CH ₃ , R ₇ is H or COOM, R ₈ is H or CH ₃ , R ₉ is an empty or 1 to 4 carbon alkyl group, and R ₁₀ is an alkyl group having one alkane In the naphthalene ring of the phosphate substituent, M is H, Na, K or NH ₄ ; the relationship between R ₃ and R ₄ relative to the benzene ring is ortho, meta or para. The method for preparing a phosphorus-containing polycarboxylic acid water reducing agent according to claim 1, comprising the following steps: (1) The first esterification reaction: the unsaturated polyether and the first compound are mixed, and the temperature is increased to 70-90 ° C under the protection of nitrogen, and then a catalyst is added, and the reaction is maintained for 0.5-3.0h, during which a vacuum or nitrogen is passed. The method with water is used to remove water, and after the reaction is completed, the temperature is lowered to room temperature to obtain a first mixture containing an esterified product and an unreacted unsaturated polyether. The unsaturated polyether is an allyl polyethylene with a molecular weight of 600 to 5000. At least one of alcohol, 3-methyl-3-butene-1-polyethylene glycol, and 2-methylallyl polyethylene glycol; the structural formula of the first compound is as follows:

(2) The second esterification reaction: mixed unsaturated carboxylic acid or unsaturated carboxylic anhydride, hydroxynaphthalene phosphoric acid and polymerization inhibitor, heated under nitrogen protection to 90-120 ° C, and then added a catalyst, and kept the reaction at 0.5-3.0 h, during the period of time, the water is removed by vacuum or nitrogen gas, and the temperature is reduced to room temperature after the reaction, to obtain a second mixture containing the esterified product and unreacted unsaturated carboxylic acid or unsaturated carboxylic anhydride; The acid or unsaturated carboxylic anhydride is at least one of acrylic acid, methacrylic acid, maleic acid, and maleic anhydride; the hydroxynaphthalene phosphate is 1-hydroxynaphthalene-4 phosphate, 1-hydroxynaphthalene-5 phosphate, and 1-hydroxyl Naphthalene-6 phosphate, 1-hydroxynaphthalene-7 phosphate, 2-hydroxynaphthalene-4 phosphate, 2-hydroxynaphthalene-5 phosphate, 2-hydroxynaphthalene-6 phosphate, 2-hydroxynaphthalene-7 phosphate, 1-hydroxymethyl Naphthalene-4 phosphate, 1-hydroxymethylnaphthalene-5 phosphate, 1-hydroxymethylnaphthalene-6 phosphate, 1-hydroxymethylnaphthalene-7 phosphate, 2-hydroxymethylnaphthalene-4 phosphate, 2-hydroxymethyl Naphthalene-5 phosphate, 2-hydroxymethylnaphthalene-6 phosphate, 2-hydroxymethylnaphthalene-7 phosphate, 1-hydroxynaphthalene-4 methylphosphate, 1-hydroxynaphthalene-5methylphosphate, 1-hydroxynaphthalene- 6 methyl phosphate, 1-hydroxynaphthalene-7 methyl Acid, 2-hydroxynaphthalene-4 methyl phosphate, 2-hydroxynaphthalene-5 methyl phosphate, 2-hydroxynaphthalene-6 methyl phosphate, 2-hydroxynaphthalene-7 methyl phosphate, 1-hydroxymethylnaphthalene-4 Methyl phosphate, 1-hydroxymethylnaphthalene-5 methyl phosphate, 1-hydroxymethylnaphthalene-6 methyl phosphate, 1-hydroxymethylnaphthalene-7 methyl phosphate, 2-hydroxymethylnaphthalene-4 methyl At least one of phosphoric acid, 2-hydroxymethylnaphthalene-5 methylphosphate, 2-hydroxymethylnaphthalene-6methylphosphate, 2-hydroxymethylnaphthalene-7methylphosphoric acid; (3) monomer blending: mixing the first mixture obtained in step (1) and the second mixture obtained in step (2) at a mass ratio of 100: 6 to 18, and adding water to dissolve them to obtain copolymerization Monomer mixture solution; (4) Copolymerization reaction: The above comonomer mixture solution, initiator aqueous solution and molecular weight regulator aqueous solution are dropped into water for reaction. The reaction temperature is 10-60 ° C, and the dropping time is 0.2-6.0h. After the dropwise addition, the temperature is maintained. 0 ～ 3.0h, copolymerization product is obtained; (5) Neutralization reaction: The copolymerized product obtained in step (3) is adjusted to a pH of 5 to 7 with an alkali to obtain the phosphorus-containing polycarboxylic acid water reducing agent. The method according to claim 2, wherein in the step (1), the molar ratio of the unsaturated polyether to the first compound is 1 to 1.5: 1, and the amount of the catalyst is unsaturated polyether. And 0.05 to 0.3% of the total mass of the first compound. The preparation method according to claim 2, characterized in that in the step (2), the molar ratio of the unsaturated carboxylic acid or unsaturated carboxylic anhydride and hydroxynaphthalene phosphoric acid is 2 to 7: 1, and the catalyst The amount used is 0.03 to 0.3% of the total mass of the unsaturated carboxylic acid or unsaturated carboxylic anhydride and hydroxynaphthalene phosphate; the amount of the polymerization inhibitor is 0.2 to 3.0 of the total mass of the unsaturated carboxylic acid or unsaturated carboxylic anhydride and hydroxynaphthalene phosphoric acid. %%. The preparation method according to claim 2, characterized in that the total amount of water used in the steps (3) and (4) is such that the mass concentration of the copolymerization product is 20 to 70%, and the amount of the initiator is used. It is 0.5 to 3.0% of the total mass of the solute in the comonomer mixture solution, and the amount of the molecular weight regulator is 0.2 to 2.0% of the total mass of the solute in the comonomer mixture solution. The preparation method according to any one of claims 2 to 5, characterized in that the catalyst is at least one of pyromellitic acid, nitrogen sulfur acid, and trinitrobenzenesulfonic acid. The preparation method according to any one of claims 2 to 5, wherein the polymerization inhibitor is at least one of hydroquinone, phenothiazine, and diphenylamine. The preparation method according to any one of claims 2 to 5, wherein the initiator is a water-soluble redox initiator system or a water-soluble azo initiator. The preparation method according to any one of claims 2 to 5, wherein the molecular weight modifier is mercaptoacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium hypophosphite, trisodium phosphate, and sodium formate At least one of sodium acetate, sodium acetate, and dodecanethiol.