CN104722241A - Carboxylate-sulfonate terpolymer dispersant and preparation process thereof - Google Patents

Abstract

The invention relates to a copolymer dispersant, a carboxylate sulfonate terpolymer dispersant and a preparation process thereof. The invention consists of the following substances in mass ratio: 10-20 parts of styrene, 30-50 parts of homologues of acrylic acid, and 20-30 parts of sodium vinyl sulfonate. The invention has the advantages that: the carboxylate sulfonate terpolymer dispersant containing acrylic acid homologue units and sulfonate groups has good water solubility and good adaptability to the pH value of the dispersion system; the dispersant It has an ideal degree of polymerization, carboxyl group and sulfonate group, and the dispersed substance is dispersed and stable through steric hindrance effect and electrostatic repulsion, and the system viscosity is low; the preparation process is simple, easy to operate, short production cycle, low cost, no environmental pollution, suitable for Industrial scale production.

Description

Carboxylate sulfonate terpolymer dispersant and its preparation process

technical field

The invention belongs to the synthesis technology of a novel copolymer dispersant, in particular to a carboxylate sulfonate terpolymer dispersant and a preparation process thereof.

Background technique

Dispersants play a role in dispersing and stabilizing the dispersed substances, and have important applications in industries such as pigments, dyes, aqueous coal slurry, and pesticides. The disadvantages of traditional small molecule dispersants are: the adsorption on the surface of solid particles is not firm, and it is easy to dissociate from the surface to cause re-aggregation or precipitation. Carboxylate sulfonate copolymer dispersants can stabilize the system through steric hindrance and electrostatic repulsion, and have better dispersion effects than small molecule dispersants; compared with traditional lignin sulfonate and naphthalene sulfonate Compared with formaldehyde condensate dispersants, carboxylate sulfonate copolymer dispersants are not sensitive to ions, pH and temperature of the dispersion system, and can significantly reduce the viscosity of the system. When this type of copolymer is used as a dispersant, the molecular weight is low, generally between several thousand to tens of thousands, and the molecular weight is crucial to the dispersion ability of the dispersant. Due to the relatively high polymerization activity of the monomers used in the preparation of such copolymers, the control of polymer molecular weight has become a key technology for the preparation of such dispersants.

The inventor's research group has done a lot of work on polymer molecular weight control before, such as Chinese patent ZL200810201806.1 (styrene-sodium styrene sulfonate-hydroxypropyl acrylate terpolymer dispersant), CN201110055926. 7 (methacrylic acid-styrene-hydroxypropyl acrylate terpolymer dispersant), CN201110440872.6 (methacrylic acid-styrene binary copolymer dispersant), CN201110440854.8 (methacrylic acid-styrene- Maleic anhydride terpolymer dispersant), "Synthesis and Dispersion Properties of Acrylic Copolymer Dispersant" published in Process Engineering Journal. In addition, methods for controlling the molecular weight of polymers in this technical field include: using mercapto compounds as chain transfer agents to control polymer molecular weights, patent literature: EP1304314; using metal salts as molecular weight regulators, patent literature: CN1085570; Polymerization in water-isopropanol mixed solvent to achieve the purpose of controlling the molecular weight of the polymer, patent literature US4301226 and so on. The disadvantages of these methods are: substances with pungent smell are introduced into the product, pollute the environment, increase the difficulty of post-processing, and the production cost is expensive.

Existing technology has drawbacks:

Carboxylate sulfonate copolymer dispersants are more and more widely used, but the synthesis process of this kind of dispersants still has difficult technical problems such as difficult control of molecular weight, high viscosity of the system, and unsatisfactory dispersion effect. Therefore, it is very important to invent a carboxylate sulfonate terpolymer dispersant with excellent dispersibility, low preparation cost and environmental friendliness and its preparation process.

Contents of the invention

The object of the present invention is to invent a carboxylate sulfonate terpolymer dispersant with easy controllable molecular weight, low system viscosity, excellent dispersion performance, low preparation cost and environment-friendly and its preparation process.

The ratio of the monomers used is as follows:

Styrene 10-20 parts

Acrylic acid homologue 30-50 parts

Sodium vinyl sulfonate 20-30 parts

Taking the acrylic acid homologue as methacrylic acid as an example, the synthetic route of the carboxylate sulfonate terpolymer dispersant is as follows:

The purpose of the present invention is achieved in that the steps are as follows:

a) Add a certain amount of double-distilled water and an aqueous solution of chain transfer agent into the reaction flask, stir and heat to 60-90°C;

b) Add styrene, acrylic acid homologues, sodium vinylsulfonate and initiator solution dropwise to the above solution, complete the dropwise addition within 1 to 5 hours, and keep the reaction for 2 to 10 hours;

c) Stir the solution obtained in step b, cool to room temperature, neutralize the carboxylic acid in the system with an alkali, and the neutralization amount is 50% to 100% of the molar number of carboxyl groups;

The chain transfer agent is sodium bisulfite and isopropanol, and the dosage is 0.5-10% of the total mass of monomers.

The initiator is one of ammonium persulfate, potassium persulfate and hydrogen peroxide, and the dosage is 2-16% of the total mass of monomers.

The alkali is one or two of sodium hydroxide, potassium hydroxide, ammonia solution, triethylamine, and triethanolamine, and the neutralization amount is 50-100% of the molar number of carboxyl groups.

The gist of the present invention is: use styrene, acrylic acid homologues and sodium vinyl sulfonate as main raw materials, chain transfer agent, initiator and alkali as auxiliary raw materials, react at 60-90°C, then cool and use alkali Neutralize to obtain the target dispersant solution; the solid content of the dispersant solution is 20-50%.

The technical effect of the application of the present invention: the carboxylate sulfonate terpolymer dispersant of the present invention has a good dispersion effect on inorganic powders such as calcium carbonate and zinc oxide; at the same time, it is effective against 43% tebuconazole in terms of pesticide formulations. SC, 50% atrazine SC, 5% fipronil SC, 480g/L imidacloprid SC have good dispersion properties; in addition, they can also be used in disperse pigments, dyes, coal water slurry, etc., also have good dispersion Effect.

Compared with prior art, beneficial effect and innovation of the present invention are as follows:

1. The carboxylate sulfonate terpolymer dispersant of the present invention has a new structure and belongs to a new type of dispersant.

2. Acrylic acid homologues contain functionalized carboxylic acid groups, and sodium vinyl sulfonate provides sulfonate groups simultaneously. Therefore, the carboxylate sulfonate terpolymer dispersant of the present invention has good water solubility and is suitable for dispersing The pH value of the system has good adaptability.

3. The carboxylate sulfonate terpolymer dispersant of the present invention has an ideal degree of polymerization and functional groups of carboxyl and sulfonate groups, and can stabilize the dispersed material through steric hindrance effect and electrostatic repulsion. the

The present invention has prominent substantive technical features and significant technological progress; therefore, the present invention is inventive.

After extensively consulting public publications and patent documents at home and abroad, there is no technical data completely identical to the technical solution of the present invention, and the present invention has novelty. The invention has wide application in the field of pesticide dosage form, and the invention has practicability. 

The invention has the advantages of simple preparation process, easy operation, short production period, low cost, no environmental pollution and suitable for industrial scale production.

Detailed ways

Below in conjunction with embodiment, the present invention is described in further detail and completely:

Example 1:

1) Preparation of dispersant:

Add 1000 parts of double distilled water, 10 parts of chain transfer agent, and the composition of the chain transfer agent is 1:1 sodium bisulfite and isopropanol aqueous solution into a four-necked reaction flask, and heat while stirring; when the solution in the reaction flask When the temperature rises to 60°C, add 200 parts of styrene, 500 parts of acrylic acid homologues, 250 parts of sodium vinyl sulfonate and 30 parts of initiator solution within 3 hours, and then keep the reaction at 60°C for 2 hours; the heat preservation reaction ends Down to room temperature while stirring behind, neutralize the carboxylic acid in the system with sodium hydroxide solution, the neutralization amount is 50% of the carboxyl mole number, makes the target dispersant solution.

2) Determination of the dispersibility of the prepared dispersant to inorganic minerals:

Add 0.4 g of the dispersant prepared in step (1) and 50 ml of distilled aqueous solution to a 100 ml stoppered measuring cylinder, add 1.00 g of solid particles to be dispersed after the dispersant is dissolved, then add the aqueous solution to 100 ml, within 1 min Upside down 30 times, first upside down 180 °, and then return to the original position for 1 time. Place the graduated cylinder vertically in a constant temperature water bath at 25°C, keep it still without vibration, and avoid direct sunlight. At 30 minutes, use a straw to draw out 90 ml of the upper suspension, and complete within 15 seconds. Transfer the remaining 10 ml suspension to a weighed dry Petri dish with a mass of _m1 , and rinse the graduated cylinder with distilled water to ensure that all the sediment in the graduated cylinder is transferred to the Petri dish, and put the Petri dish into the oven Dry at 80°C, weigh m ₂ , and calculate the mass M of insoluble matter,

M = m ₂ - m ₁ , calculate the suspension rate according to the following formula:

Among them: M is the mass (g) of dispersant and solid particles contained in 10 ml suspension at the bottom of 100 ml stoppered measuring cylinder, and 1.400 is the total mass (g) of dispersant and solid particles contained in 100 ml stoppered measuring cylinder.

According to the above operation steps, the suspension rate of the prepared dispersant to the calcium carbonate suspension was measured to be 98.50%, and the suspension rate of the prepared dispersant to the aluminum oxide suspension was 98.08%.

3) Determination of the dispersibility of the dispersant to pesticides:

Use the above dispersant to prepare pesticide water suspension (SC), weigh 1.0 g of this pesticide SC into a beaker, add 50 ml of distilled aqueous solution, leave it for 30 s, stir with a glass rod for 30 s to disperse it evenly, and then use distilled aqueous solution to dissolve Transfer this suspension to a 100 ml stoppered measuring cylinder, add distilled aqueous solution to 100 ml. Cover the stopper, turn the stoppered measuring cylinder upside down 30 times within 1 min, and turn the measuring cylinder upside down 180° and then return to the original position once. Place the graduated cylinder vertically in a super constant temperature aqueous solution bath at 30°C, keep it still without vibration, and avoid direct sunlight. After standing still for 30 minutes, remove the upper 90 ml suspension with a straw. This process makes the tip of the tube a few millimeters below the liquid surface. Make sure not to shake or stir up the sediment at the bottom of the graduated cylinder. Transfer the remaining 10 ml suspension to a weighed Petri dish with a mass of _m1 , and rinse the graduated cylinder with distilled water to ensure that all the sediment at the bottom of the graduated cylinder is transferred to the Petri dish, and put the Petri dish in an oven for 80 Dry at ℃, weigh m ₂ , calculate the mass of insoluble matter M = (m ₂ -m ₁ ), and then calculate the suspension rate according to the following formula:

Among them, 1.0 is the mass of the added water suspension concentrate (SC); the effective content is the percentage of pesticide in SC; M is the mass of the sediment at the bottom of the stoppered measuring cylinder.

According to the above operation steps, the suspension ratio of the above-mentioned dispersant to the 43% tebuconazole aqueous suspension concentrate is 96.04%.

Example 2:

Add 1000 parts of double distilled water and 80 parts of chain transfer agent, the composition of chain transfer agent is sodium bisulfite and isopropanol aqueous solution of 1:1.2 into a four-necked reaction flask, and heat while stirring; when the solution in the reaction flask When the temperature rises to 70°C, add 200 parts of styrene, 300 parts of sodium vinyl sulfonate, 400 parts of acrylic acid homologues and 60 parts of initiator solution within 5 hours, and then keep the reaction for 3 hours; stir after the heat preservation reaction is completed While cooling down to room temperature, neutralize the carboxylic acid in the system with sodium hydroxide solution, the neutralization amount is 75% of the carboxyl moles, and obtain the target dispersant solution. the

According to the operation steps described in Example 1, the suspension rate of the above-mentioned dispersant to the calcium carbonate suspension is 96.24%, the suspension rate to the aluminum oxide suspension is 96.49%, and the suspension rate to the 43% tebuconazole suspension. The suspension rate was 97.12%.

Example 3:

Add 1000 parts of double distilled water and 20 parts of chain transfer agent, the composition of chain transfer agent is sodium bisulfite and isopropanol aqueous solution of 1:0.8 into a four-necked reaction flask, and heat while stirring; when the solution in the reaction flask When the temperature rises to 80°C, add 200 parts of styrene, 250 parts of sodium vinyl sulfonate, 450 parts of acrylic acid homologues and 60 parts of initiator solution within 2 hours, and then keep the reaction for 5 hours; stir after the heat preservation reaction is completed While cooling down to room temperature, neutralize the carboxylic acid in the system with sodium hydroxide solution, the neutralization amount is 85% of the carboxyl moles, and obtain the target dispersant solution.

According to the operation steps described in Example 1, the suspension rate of the above-mentioned dispersant to the calcium carbonate suspension is 97.37%, the suspension rate to the aluminum oxide suspension is 97.22%, and the suspension rate to the 43% tebuconazole suspension. The suspension rate was 96.04%.

Example 4:

Add 1000 parts of double distilled water and 40 parts of chain transfer agent, the composition of chain transfer agent is sodium bisulfite and isopropanol aqueous solution of 1:1, into a four-necked reaction flask, and heat while stirring; when the reaction flask When the temperature of the solution rises to 70°C, add 100 parts of styrene, 400 parts of acrylic acid homologues, 300 parts of sodium vinyl sulfonate and 30 parts of initiator solution within 2 hours, and then keep warm for 3 hours; While stirring, be down to room temperature, neutralize the carboxylic acid in the system with sodium hydroxide solution, and the neutralization amount is 80% of the carboxyl mole number, and obtain the target dispersant solution.

According to the operation steps described in Example 1, the suspension rate of the above-mentioned dispersant to the calcium carbonate suspension is 96.89%, the suspension rate to the aluminum oxide suspension is 97.64%, and the suspension rate to the 43% tebuconazole suspension. The suspension rate is 96.81%.

Example 5:

Add 1000 parts of double-distilled water and 40 parts of chain transfer agent, the composition of which is 1:1 sodium bisulfite and isopropanol aqueous solution, into a four-necked reaction flask, and heat while stirring; when the reaction flask When the temperature of the solution rises to 90°C, add 300 parts of styrene, 350 parts of acrylic acid homologues, 300 parts of sodium vinyl sulfonate and 40 parts of initiator solution within 3 hours, and then keep the reaction for 4 hours; While stirring, it is down to room temperature, and the carboxylic acid in the system is neutralized with sodium hydroxide solution, and the neutralization amount is 70% of the carboxyl moles to obtain the target dispersant solution.

According to the operation steps described in Example 1, the suspension rate of the above-mentioned dispersant to the calcium carbonate suspension is 98.65%, the suspension rate to the aluminum oxide suspension is 97.61%, and the suspension rate to the 43% tebuconazole suspension. The suspension rate was 97.14%.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have modifications and variations. All modifications, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims (7)

1. A carboxylate sulfonate terpolymer dispersant, consisting of the following mass ratio materials: Styrene 10-20 parts Acrylic acid homologue 30-50 parts Sodium vinyl sulfonate 20-30 parts. 2. According to claim 1, the acrylic acid homologue comprises: acrylic acid, methacrylic acid. 3. a preparation process of carboxylate sulfonate terpolymer dispersant, the steps are as follows: Add a certain amount of double distilled water and chain transfer agent aqueous solution into the reaction flask, heat to 60-90°C, then add styrene, acrylic acid homologue, sodium vinyl sulfonate and initiator solution dropwise, within 1-5 hours After the dropwise addition, keep the reaction for 2-10 hours; cool to room temperature, neutralize the carboxylic acid in the system with alkali, and the neutralization amount is 50-100% of the carboxyl moles. 4. the preparation technology of carboxylate sulfonate terpolymer dispersant according to claim 3 is characterized in that: described chain transfer agent is sodium bisulfite and Virahol, and consumption is monomer total 0.5-10% of the mass. 5. the preparation technology of carboxylate sulfonate terpolymer dispersant according to claim 3, is characterized in that: described initiator is the one in ammonium persulfate, potassium persulfate, hydrogen peroxide , the dosage is 2-16% of the total mass of the monomer. 6. the preparation technology of carboxylate sulfonate terpolymer dispersant according to claim 3 is characterized in that: described alkali is sodium hydroxide, potassium hydroxide, ammoniacal solution, triethylamine, three One or two kinds of ethanolamines, the neutralization amount is 50-100% of the moles of carboxyl groups. 7. an application of the described terpolymer dispersant of claim 1, is characterized in that: described dispersant has good dispersion effect to inorganic powders such as calcium carbonate, aluminum oxide; % Tebuconazole SC, 50% Atrazine SC, 5% Fipronil SC, 480g/L Imidacloprid SC have good dispersion properties; in addition, they can also be used in disperse pigments, dyes, coal water slurry, etc. Has a good dispersion effect.