CN107201076A - Hyper-dispersant for water-based paint and preparation method thereof - Google Patents

Abstract

The invention provides a hyperdispersant for a water-based paint and a preparation method thereof, wherein the hyperdispersant for the water-based paint comprises the following raw materials: epoxy resin, amino acid compound and long carbon chain tertiary amine, and the like. The hyperdispersant prepared by the invention can be used for high-solid-content water-based paint, and has good fluidity, high stability and bright color; the hyper-dispersant of the invention has cheap and easily obtained raw materials, simple preparation process, reaction which can be carried out at lower temperature and no waste water and gas emission.

Description

A kind of hyperdispersant for water-based paint and preparation method thereof

technical field

The invention belongs to the field of paint chemical industry, and relates to a hyperdispersant for water-based paint and a preparation method thereof.

technical background

Coating refers to a fine chemical product that is coated on the surface of an object by a specific construction method, and then cured to form a continuous protective film with a certain strength on the surface of the object, or a coating film with a special function.

Coatings are generally composed of film-forming substances, solvents, pigments and additives. Film-forming substances, also known as base materials, are the main substances that make the paint firmly adhere to the surface of the coated object to form a continuous film; solvents are volatile components, mainly organic solvents and water; pigments are insoluble fine particles dispersed in the paint , can be divided into coloring pigments and extender pigments, which are mainly used for coloring, protection, decoration and cost reduction; additives account for a small share in paint formulations, but they play a key role. The storage, application, film formation and resistance properties of additives play the most important role in coatings. Common additives in coatings are: leveling agent, thickener, surfactant, pigment dispersant, plasticizer, drier, curing agent, fungicide, anti-fungal agent, etc.

Pigment dispersants are also known as wetting and dispersing agents. The commonly used pigment dispersants mainly include inorganic, surfactant and polymer. agent. Polymers include natural polymers, which are mainly used for solvent-based coatings; synthetic polymers include polycarboxylates, polyacrylates, polymethacrylates, maleic acid-isobutylene (or styrene) copolymer salts, polyethylene Pyrrolidone, polyether derivatives, etc.

In the patent CN2008102009611, a dispersant for pigment based on salicylic acid derivatives and its preparation method and application are introduced; in the patent CN201110235613X, a dispersant and its preparation method are introduced. The method is to use cardanol and oxidation Styrene is ring-opened and polymerized under the action of sodium alkoxide, and then polymerized with ethylene oxide after obtaining an intermediate product to prepare a hyperdispersant for pigments; patent CN2012105602412 discloses a water-based pigment dispersant, which uses malic acid Based on the product of reaction with polyethylene oxide, it can be further polycondensed. Patent CN2007100241525 introduces a kind of methyl n-butyl ketone as solvent, using various diisocyanate, branched polyester and polyether as raw material hyperbranched nonionic water-based dispersant; patent CN2005800303658 introduces a kind of itaconic acid, lemon Polyoxyethylene ester of acid and (meth)acrylic acid are raw materials, dispersant prepared by free radical copolymerization, but this dispersant is mainly used in the field of cement dispersion and concrete water reducer; patent CN2007100241525 introduces a kind of hyperbranched non- The preparation method of ionic dispersant, its used raw material is hyperbranched polyester, diisocyanate compound and polyether etc.;

CN201080054508 has introduced a kind of preparation method of cationic water-based paint dispersant. The specific method is prepared by reacting polyacrylic acid-maleic acid copolymer with hydrophilic primary amine; CN201110119702.8 reports a method using acrylic acid, methacrylic acid and sodium methacrylsulfonate, 2-acrylamide-2 -The preparation method of water-based paint dispersion obtained by copolymerization of monomers such as methyl propane sulfonic acid; CN2007800190165 reported a method of utilizing various unsaturated monomers, such as: maleic acid polyether monoester, acrylic acid, maleic anhydride, etc. A non-ionic water-based paint dispersant obtained by free radical copolymerization.

Patent 201511016207.9 introduces a hyperdispersant for water-based pigment paste prepared by using epoxy resin, alkanolamine and phosphorus oxychloride.

The present invention provides a hyperdispersant for water-based coatings and a preparation method thereof. Compared with the prior art, the present invention has the following advantages:

The present invention is at first with the tertiary amine (such as: trihexylamine, trioctylamine, didodecylmethylamine, N, N-dimethyldecylamine, N, N) of long carbon chain (carbon number greater than 6) -Dimethyldodecylamine, N,N-dimethyltetradecylamine, etc.) phase transfer catalyst and extractant, epoxy resin (bisphenol A epoxy resin or bisphenol F epoxy resin) and sulfamic acid Compounds (4-aminobenzenesulfonic acid or taurine) are reacted to prepare hyperdispersants. The hyperdispersant has simple preparation method, safe operation, low cost and excellent performance.

The epoxy resin is used as the hydrophobic part, and the polyphenyl ring structure in the resin can provide enough "anchor points" to combine with the pigment particles, and further react the epoxy resin with the sodium sulfamate compound to increase the macromolecular strength. Hydrophilicity and hydration ability, as a water-soluble group. The water-based paint prepared by using this dispersant can obtain high solid content, good fluidity, high stability, and bright colors; the raw materials of this product are cheap and easy to obtain, the preparation process is simple, the reaction can be carried out at a relatively low temperature, and there is basically no waste water Exhaust emissions.

Contents of the invention

The invention provides a hyperdispersant for water-based paint and a preparation method thereof.

The main raw materials used in the hyperdispersant provided by the invention are epoxy resin and sodium sulfamate compound as the main raw materials, and the phase transfer catalyst and extractant are tertiary amines with long carbon chains.

Preferably, the epoxy resin may be bisphenol A epoxy resin or bisphenol F epoxy resin. in,

Described bisphenol A epoxy resin structural formula is:

Described bisphenol F epoxy resin structural formula is:

Preferably, the sulfamic acid compound is p-aminobenzenesulfonic acid and taurine, wherein,

Described p-sulfanilic acid structural formula is:

Described taurine structural formula is:

Preferably, the tertiary amines used as phase transfer catalysts and extractants are: trihexylamine, trioctylamine, didodecylmethylamine, N,N-dimethyldecylamine, N,N-dimethyl Dodecylamine, N,N-Dimethyltetradecylamine, wherein,

The structural formula of described trihexylamine is:

The structural formula of described trioctylamine is:

The structural formula of described didodecylmethylamine is:

Described N, the structural formula of N-dimethyldecylamine is:

Described N, the structural formula of N-dimethyl dodecylamine is:

Described N, the structural formula of N-dimethyl tetradecylamine is:

The preparation method of hyperdispersant provided by the present invention is:

(1) Extraction. Dissolving the sulfamic acid compound in water, adding 1.2-2 times the amount of long-chain tertiary amine compound for extraction, and separating the organic phase and the aqueous phase with a separatory funnel;

(2) Reaction. Add epoxy resin with the amount of sulfamic acid compound and other substances to the organic phase, heat up to 130-140°C, and react for 3-4 hours;

(3) Separation. Add sodium hydroxide solution to the reaction system to make the pH of the system 7.5-8, after fully stirring, separate the layers at rest, and separate the aqueous phase and the organic phase with a separatory funnel;

(4) Recycling. The tertiary amine in the organic phase is recovered. After the aqueous phase was adjusted to pH 7 with hydrochloric acid, it was spun dry to collect the hyperdispersant.

Wherein, in step (1), the sulfamic acid compound is p-aminobenzenesulfonic acid or taurine, and the long carbon chain tertiary amine is trihexylamine, trioctylamine, didodecylmethyl Amine, N,N-dimethyldecylamine, N,N-dimethyldodecylamine or N,N-dimethyltetradecylamine;

In step (2), described epoxy resin is bisphenol A epoxy resin or bisphenol F epoxy resin;

Wherein, in the preparation raw material of water-based paint hyperdispersant, described tertiary amine is trioctylamine, and sulfamic acid compound is taurine, and when epoxy resin is bisphenol A epoxy resin, utilize above-mentioned raw material to prepare hyperdispersant The reaction equation is as follows:

(1) Extraction and separation

(2) Catalysis and reaction

(3) Separation and recovery

The beneficial effect of above-mentioned technical scheme is as follows:

The epoxy resin is used as the hydrophobic part, and the polyphenyl ring structure in the resin can provide enough "anchor points" to combine with the pigment particles, and further react the epoxy resin with the sodium sulfamate compound to increase the macromolecular strength. Hydrophilicity and hydration ability, as a water-soluble group. The water-based paint prepared by using this dispersant can obtain high solid content, good fluidity, high stability, and bright colors; the raw materials of this product are cheap and easy to obtain, the preparation process is simple, the reaction can be carried out at a relatively low temperature, and there is basically no waste water Exhaust emissions.

detailed description

The following examples are further illustrations of the present invention, but the present invention is not limited thereto.

Example 1

Dissolve 17.3 g (0.1 mol) of p-aminobenzenesulfonic acid in 100 ml of water, add 50 g of trioctylamine, stir well for 1 hour, let it stand, and separate the organic phase. Add 100g of bisphenol A epoxy resin CYD-011 (about 0.1mol, produced by Baling Petrochemical Company, epoxy equivalent 450-500) into a 500ml four-neck flask, heat up to 90°C, after the epoxy resin is melted, add The organic phase separated in the first operation. Continue to heat up to 140°C, keep warm for 4 hours and then cool to 90°C, add a certain amount of 10% sodium hydroxide solution at 80°C to adjust the pH of the system to 7.5-8. After continuing to stir at 90°C for 2 hours, cool and stand still, and the reaction system was separated into layers, and the organic phase was separated with a separatory funnel and washed with water. Collect the organic phase, which is a trioctylamine solution, adjust the pH of the water phase to 7 with hydrochloric acid, and then rotatively evaporate at 80°C. The collected solid matter is the hyperdispersant prepared in the present invention.

Example 2

Dissolve 34.6g (0.2mol) of p-aminobenzenesulfonic acid in 200ml of water, add 70g (0.26mol) of trihexylamine, stir thoroughly for 1 hour, let it stand, and separate the organic phase. Add 74g of bisphenol A epoxy resin CYD-0128 (about 0.2mol, produced by Baling Petrochemical Company, epoxy equivalent 184-194) into a 500ml four-necked flask, raise the temperature to 90°C, and add the out the organic phase. Continue to heat up to 140°C, keep warm for 4 hours and then cool to 90°C, add a certain amount of 15% sodium hydroxide solution at 80°C to adjust the pH of the system to 7.5-8. After continuing to stir at 90°C for 2 hours, cool and stand still, and the reaction system was separated into layers, and the organic phase was separated with a separatory funnel and washed with water. Collect the organic phase, which is a trihexylamine solution, adjust the pH of the water phase to 7 with hydrochloric acid, and then evaporate at 80° C. The collected solid matter is the hyperdispersant prepared in the present invention.

Example 3

Dissolve 35.55g (0.3mol) of taurine in 100ml of water, add 147g (0.4mol) of didodecylmethylamine, stir well for 1 hour, let stand, and separate the organic phase. Add 100g of bisphenol A epoxy resin CYD-011 (about 0.1mol) and 74g of bisphenol A epoxy resin CYD-0128 (about 0.2mol) into a 1000ml four-neck flask, raise the temperature to 90°C, and wait until the epoxy resin is melted , add the organic phase separated in the first step operation. Continue to heat up to 140°C, keep warm for 4 hours and cool to 90°C, add a certain amount of 20% sodium hydroxide solution at 80°C to adjust the pH of the system to 7.5-8. After continuing to stir at 90°C for 2 hours, cool and stand still, and the reaction system was separated into layers, and the organic phase was separated with a separatory funnel and washed with water. The organic phase was collected, which was didodecylmethylamine. After adjusting the pH of the aqueous phase to 7 with hydrochloric acid, it was rotatively evaporated at 80° C., and the collected solid matter was the hyperdispersant prepared in the present invention.

Example 4

Dissolve 17.3g of p-aminobenzenesulfonic acid and 12.5g of taurine in 200ml of water, add 100g of dimethyltetradecylamine, stir well for 1 hour, let it stand, and separate the organic phase. Add 100g of bisphenol A epoxy resin CYD-011 and 35g of bisphenol F epoxy resin REF-170 (produced by Huitefa Chemical Co., Ltd., epoxy equivalent 160-180) into a 500ml four-necked flask, heat up to 90°C, and add The organic phase separated in a one-step operation. Continue to heat up to 140°C, keep warm for 4 hours and cool to 90°C, add a certain amount of 20% sodium hydroxide solution at 80°C to adjust the pH of the system to 7.5-8. After continuing to stir at 90°C for 2 hours, cool and let stand until the reaction system is layered, separate the organic phase with a separatory funnel and wash it with water to collect the organic phase, which is a solution of dimethyltetradecamine, adjust the pH of the aqueous phase with hydrochloric acid After 7, 80 ° C rotary evaporation, the collected solid matter is the hyperdispersant prepared in the present invention.

Example 5

Dissolve 125.15g of taurine in 1000ml of warm water, add 350g of N,N-dimethyldodecylamine, stir well for 2 hours, let stand, and separate the organic phase. Add 430g of bisphenol A epoxy resin CYD-546 (about 1mol, produced by Baling Petrochemical Company, epoxy equivalent 210-230) into a 5000ml four-necked flask, raise the temperature to 90°C, and add the the organic phase. Continue to heat up to 130°C, keep warm for 5 hours and then cool to 90°C, add a certain amount of 30% sodium hydroxide solution at 80°C to adjust the pH of the system to 7.5-8. After continuing to stir at 90°C for 2 hours, cool and stand still, and the reaction system was separated into layers, and the organic phase was separated with a separatory funnel and washed with water. Collect the organic phase, which is N,N-dimethyldodecylamine solution, adjust the pH of the water phase to 7 with hydrochloric acid, and then evaporate at 80°C, and collect the solid matter, which is the hyperdispersant prepared in the present invention.

Example 6

Dissolve 173g of p-aminobenzenesulfonic acid in 2000ml of water, add 530g of trioctylamine, stir well for 2 hours, let stand, and separate the organic phase. In a 5000ml four-necked flask, add 230 bisphenol A epoxy resin CYD-134 (about 0.5mol, produced by Baling Petrochemical Company, epoxy equivalent is 230-270) and 85g bisphenol F epoxy resin Epikote 862 (0.5mol, Produced by Hansen Company in the Netherlands, the epoxy equivalent is 165-170), the temperature is raised to 90°C, and after the epoxy resin is melted, the organic phase separated in the first step operation is added. Continue to heat up to 140°C, keep warm for 4 hours and then cool to 90°C, add a certain amount of 30% sodium hydroxide solution at 80°C to adjust the pH of the system to 7.5-8. After continuing to stir at 90°C for 2 hours, cool and stand still, and the reaction system was separated into layers, and the organic phase was separated with a separatory funnel and washed with water. Collect the organic phase, which is a trioctylamine solution, adjust the pH of the water phase to 7 with hydrochloric acid, and then rotatively evaporate at 80°C. The collected solid matter is the hyperdispersant prepared in the present invention.

Claims (7)

1. a water-based coating hyperdispersant, it is characterized in that the raw material of its preparation comprises: epoxy resin, sodium sulfamate compound and tertiary amine, the amount of substances such as described epoxy resin and sodium sulfamate compound, described The tertiary amine is a tertiary amine containing at least one long carbon chain (carbon number greater than 6). 2. water-based coating superdispersant according to claim 1, is characterized in that epoxy resin is bisphenol A epoxy resin or bisphenol F epoxy resin, wherein, Described bisphenol A epoxy resin structural formula is: Described bisphenol F epoxy resin structural formula is: 3. water-based paint superdispersant according to claim 1, is characterized in that, described amino compound is p-aminobenzenesulfonic acid, taurine, wherein, The structural formula of described sulfanilic acid is: The structural formula of described taurine is: 4. water-based coating hyperdispersant according to claim 1, is characterized in that, described tertiary amine that contains at least one long carbon chain (carbon number is greater than 6) is trihexylamine, trioctylamine, double dodecylamine Alkylmethylamine, N,N-dimethyldecylamine, N,N-dimethyldodecylamine, N,N-dimethyltetradecylamine, among them, The structural formula of described trihexylamine is: The structural formula of described trioctylamine is: The structural formula of described didodecylmethylamine is: Described N, the structural formula of N-dimethyldecylamine is: Described N, the structural formula of N-dimethyl dodecylamine is: Described N, the structural formula of N-dimethyl tetradecylamine is: 5. a kind of preparation method of water-based coating hyperdispersant as claimed in claim 1～4, is characterized in that, comprises the steps: 1) Extraction. Dissolving the sulfamic acid compound in water, adding 1.2-2 times the amount of long-chain tertiary amine compound for extraction, and separating the organic phase and the aqueous phase with a separatory funnel; (2) Reaction. Add epoxy resin with the amount of sulfamic acid compound and other substances to the organic phase, heat up to 130-140°C, and react for 3-4 hours; (3) Separation. Add a certain amount of sodium hydroxide solution to the reaction system to make the pH of the system 7.5-8, after stirring for a long time, keep the layers static, and separate the aqueous phase and the organic phase with a separatory funnel; (4) Recycling. The tertiary amine in the organic phase is recovered. After the aqueous phase was adjusted to pH 7 with hydrochloric acid, it was spin-dried to collect the hyperdispersant. 6. the preparation method of superdispersant for water-based paint according to claim 5, is characterized in that, the aminosulfonic acid compound described in step (1) is p-aminobenzenesulfonic acid or taurine, and described long carbon The chain tertiary amine is trihexylamine, trioctylamine, didodecylmethylamine, N,N-dimethyldecylamine, N,N-dimethyldodecylamine or N,N-dimethyldeca tetramine; The epoxy resin described in step (2) is bisphenol A epoxy resin or bisphenol F epoxy resin. 7. the preparation method of water-based paint superdispersant according to claim 5, is characterized in that, described epoxy resin is bisphenol A epoxy resin or bisphenol F epoxy resin, and sodium sulfamate compound is P-aminobenzenesulfonic acid or taurine, tertiary amines are trihexylamine, trioctylamine, didodecylmethylamine, N,N-dimethyldecylamine, N,N-dimethyldodecylamine Or N, N-dimethyltetradecamine, utilize above-mentioned raw material to prepare the reaction formula of water-based paint hyperdispersant as follows: (1) Extraction and separation (2) Catalysis and reaction (3) Separation and recovery