CN106675303A - Water-based polyurethane polyaniline anticorrosive paint and preparation method thereof - Google Patents

Abstract

The invention discloses a waterborne polyurethane polyaniline anticorrosion coating and a preparation method thereof. The invention adopts a microemulsion polymerization method, uses aniline and p-phenylenediamine as monomers, hydrochloric acid as a dopant, ammonium persulfate as an oxidant, and dedoping with ammonia water to obtain an aniline-p-phenylenediamine copolymer. Using in-situ emulsion polymerization method, using vinyl monomer as continuous phase, polyester polyol, diisocyanate, hydrophilic chain extender and internal crosslinking agent as raw materials to prepare polyurethane prepolymer and vinyl monomer mixture, through ethylene Neutralize the end-capping of the group, add deionized water containing polymerizable surface-active monomers to disperse at high speed to obtain a polyurethane dispersion, and then add an initiator to polymerize vinyl monomers with polyurethane and surface-active monomers containing double bonds, and at the same time introduce diplomatic Linking agent obtains water-based polyurethane acrylate composite emulsion. Using the emulsion as a base, adding aniline-p-phenylenediamine copolymer, a thickener, a defoamer, and a film-forming aid can obtain an anti-corrosion coating, which is economical and environment-friendly.

Description

A kind of waterborne polyurethane polyaniline anticorrosion coating and preparation method thereof

【Technical field】

The invention relates to the technical field of preparation of water-based anti-corrosion coatings, in particular to an aniline-p-phenylenediamine copolymer/water-based polyurethane-acrylate anti-corrosion coating and a preparation method thereof.

【Background technique】

The economic loss and environmental pollution caused by metal corrosion to the society are becoming more and more serious every year. It has become a development trend to develop pollution-free, high-performance and economical anti-corrosion coatings. Polyaniline is a non-toxic, easy-to-obtain raw material, good stability conductive polymer, and has excellent anti-corrosion properties. However, due to the rigid structure of polyaniline molecular chains and the strong interaction between molecular chains, it will be insoluble and insoluble. Processing limits its application, so people try to modify its structure to improve its application, and polyaniline derivative aniline-p-phenylenediamine copolymer is one of them. At present, there are few research reports on the application of aniline-p-phenylenediamine copolymers in anticorrosion. Due to the poor adhesion of polyaniline and its derivative aniline-p-phenylenediamine copolymer to the substrate, a large number of pure polyaniline or aniline-p-phenylenediamine copolymer is used as an anti-corrosion coating in terms of comprehensive performance and economical performance of the coating film. Neither is ideal. Therefore, people try to blend polyaniline or aniline-p-phenylenediamine copolymer with other resins with strong adhesion to form composite anti-corrosion coatings, and use the interaction or chemical bonds between them and other blending components to improve the corrosion resistance of the coating. Anti-corrosion properties. At present, blended resins include epoxy resin, alkyd resin, polyurethane, acrylate, etc., most of which are oily systems, and there are few reports on water-based systems. Water-based systems reduce the content of organic volatiles, save a lot of resources, and are economical. Environmental friendly. At present, the most widely used water-based coatings are polyacrylate emulsion (PA) and polyurethane emulsion (PU). Among them, PU emulsion has the advantages of safety, non-toxicity, environmental protection, and excellent film-forming performance, but its stability, adhesion, hardness, etc. There are deficiencies in aspects such as PA emulsion film forming and chemical resistance, but the coating film has excellent weather resistance, yellowing resistance, water resistance and mechanical properties. PU and PA have good complementarity, and can prepare PUA composite emulsion with good wear resistance, good weather resistance, high hardness, good water resistance and mechanical properties.

【Content of invention】

In order to solve the problems in the prior art, the invention provides a waterborne polyurethane polyaniline anticorrosion coating and a preparation method thereof. The method of the invention effectively increases the solid content of the water-based polyurethane emulsion, improves the strength, water resistance, hardness, etc. of the coating film, and the preparation process is economical and environment-friendly.

To achieve the above object, the key technical solution of the present invention is:

A waterborne polyurethane polyaniline anticorrosion coating,

Described waterborne polyurethane polyaniline anticorrosion coating is aniline-p-phenylenediamine copolymer/waterborne polyurethane-acrylic ester anticorrosion coating, comprises the raw material of following weight portion:

100 parts of water-based polyurethane-acrylate composite emulsion, 0.4-2 parts of aniline-p-phenylenediamine copolymer, 0.05-0.2 parts of thickener, 0.1-0.5 parts of defoamer, 3-10 parts of film-forming aid;

The preparation method of aniline-p-phenylenediamine copolymer is:

First, add 10-30 parts of aniline and 10-35 parts of p-phenylenediamine into the reactor after secondary distillation, adjust the pH value of the system to 1-4 with an acid solution, and stir evenly in an ice-water bath to obtain aniline and p-phenylenediamine. Mixed solution of phenylenediamine; dissolve 49-98 parts of oxidizing agent in aqueous acid solution, add dropwise to the above mixed solution while stirring, the molar ratio of oxidizing agent to mixed monomer of aniline and p-phenylenediamine is between 1:1 and Between 1:2; and add 0.3-0.9 parts of non-ionic surfactant as an emulsifier, fully react to the end after the dropwise addition, pour out the reactant, filter with suction, wash with distilled water until neutral, and then use ammonia water After dedoping, washing with distilled water until neutral, washing with absolute ethanol again, and drying, the aniline-p-phenylenediamine copolymer in intrinsic state is obtained.

Described acid is hydrochloric acid, acetic acid, phosphoric acid or dodecylbenzenesulfonic acid;

The oxidizing agent is ammonium persulfate or potassium persulfate;

The nonionic surfactant is octylphenol polyoxyethylene ether.

A kind of preparation method of waterborne polyurethane polyaniline anticorrosion paint, comprises the following steps:

Step 1) prepare aniline-p-phenylenediamine copolymer:

a. In parts by weight, first add 10-30 parts of aniline and 10-35 parts of p-phenylenediamine through secondary distillation to the reactor equipped with an acidic aqueous solution with a pH value of 1-4, Stir evenly, and add 0.3-0.9 parts of nonionic surfactant;

b. Dissolve 49-98 parts of oxidizing agent in an acidic aqueous solution, and add it dropwise to the reaction system in step a under stirring. Neutral, then dedoped with ammonia water, washed with distilled water until neutral, washed with absolute ethanol again, and dried to obtain the intrinsic aniline-p-phenylenediamine copolymer;

Step 2) prepare aqueous polyurethane-acrylate composite emulsion:

c. In parts by weight, add 10 to 28 parts of inert vinyl monomers, 5 to 15 parts of polyester polyols, 5 to 12 parts of diisocyanates, 1 to 2.8 parts of anionic hydrophilic chain extenders and 0.3-2 parts of internal crosslinking agent, the reaction temperature is constant at 70-80°C, and the reaction time is 3-4 hours;

d. Add 3 to 5 parts of hydroxyl-containing hydrophilic vinyl monomers for capping, react for 0.5 to 1 hour, and keep the system temperature at 70 to 80°C, then add 1 to 4 parts of alkali salt-forming agents to neutralize After the reaction, add a mixed solution containing 0.02-0.04 parts of polymerizable surface-active monomer and 75-85 parts of water, stir and disperse evenly;

e. At a constant temperature of 70-80°C, add 0.02-0.08 parts of initiator in 0.2-0.8 parts of water to the reactor dropwise. After the addition, add 1.5-4 parts of external linking agent Add it dropwise to the reactor simultaneously within 0.5 hours, after the dropwise addition is completed, continue to keep warm for 1 hour and then drop to room temperature to obtain the water-based polyurethane-acrylate composite emulsion;

Step 3) prepare anticorrosion coating:

Take 100 parts of water-based polyurethane-acrylate composite emulsion as the matrix resin, add 0.4-2 parts of aniline-p-phenylenediamine copolymer, 0.05-0.2 parts of thickener, 0.1-0.5 parts of defoamer, and 3-3 parts of film-forming aid 10 parts, mixed uniformly by physical blending method to obtain aniline-p-phenylenediamine copolymer/waterborne polyurethane-acrylate anticorrosion coating.

As a further improvement of the present invention, the acid is hydrochloric acid, acetic acid, phosphoric acid or dodecylbenzenesulfonic acid;

The oxidizing agent is ammonium persulfate or potassium persulfate;

The nonionic surfactant is octylphenol polyoxyethylene ether.

As a further improvement of the present invention, the inert vinyl monomer is methyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, styrene, n-octyl acrylate, hexyl acrylate, methacrylic acid One of n-octyl and hexyl methacrylate or a mixture of two or more in any proportion.

As a further improvement of the present invention, the polyester polyol is polycaprolactone diol, polycarbonate diol or polyhexamethylene adipate diol.

As a further improvement of the present invention, the diisocyanate is isophorone diisocyanate, diphenylmethane diisocyanate or hexamethylene diisocyanate;

The anionic hydrophilic chain extender is dimethylol propionic acid or dimethylol butyric acid;

The internal crosslinking agent is trimethylolpropane.

As a further improvement of the present invention, the vinyl monomer end-capping agent is hydroxyethyl methacrylate or hydroxyethyl acrylate;

The polymerizable surface-active monomer is sodium α-alkenyl sulfonate or sodium 1-propenyloxy-2-hydroxypropane sulfonate;

The alkali salt-forming agent is ammonia water or triethylamine.

As a further improvement of the present invention, the initiator is ammonium persulfate or potassium persulfate;

The external linking agent is γ-methacryloxypropyl trimethoxysilane and/or glycidyl methacrylate.

As a further improvement of the present invention, the thickener is LS-112 or DL-80;

The defoamer is BYK-034, BYK-035 or BYK-037 produced by BYK Company in Germany;

The film-forming aid is lauryl alcohol ester or ethylene glycol butyl ether.

Compared with the prior art, the present invention has the following beneficial technical effects:

In the preparation process of the water-based polyurethane-acrylate composite emulsion, the invention effectively increases the solid content of the emulsion by introducing a polymerizable surface active monomer, adopts internal and external links to form a network structure, and improves the strength, water resistance and hardness of the coating film Wait. Specifically, the present invention adopts a microemulsion polymerization method, using aniline and p-phenylenediamine as monomers, nonionic surfactants as emulsifiers, acids as dopants, adding oxidants, and dedoping with alkali salt-forming agents to obtain aniline - p-phenylenediamine copolymers. Using in-situ emulsion polymerization method, using vinyl monomer as continuous phase, polyester polyol, diisocyanate, hydrophilic chain extender and internal crosslinking agent as raw materials to prepare polyurethane prepolymer and vinyl monomer mixture, through ethylene neutralization by end capping, high-speed dispersion with deionized water containing polymerizable surface-active monomers to obtain a polyurethane dispersion, and then adding an initiator to polymerize vinyl monomers with polyurethane and surface-active monomers containing double bonds, and at the same time introduce diplomatic Joint agent obtains water-based polyurethane-acrylic ester composite emulsion. Using the emulsion as a matrix, add a certain proportion of aniline-p-phenylenediamine copolymer, thickener, defoamer, and film-forming aid to obtain aniline-p-phenylenediamine copolymer/waterborne polyurethane-acrylate anti-corrosion coating . Due to the excellent anti-corrosion performance of polyaniline and its derivatives and copolymers, water-based polyurethane-acrylate is selected as the base material, and aniline-p-phenylenediamine copolymer/water-based polyurethane-acrylate anti-corrosion coatings are prepared according to the physical blending method. Compared with pure polyaniline coating or solvent-based coating, it is economical and environmentally friendly.

The waterborne polyurethane polyaniline anticorrosion coating prepared by the invention has high solid content, excellent properties such as strength, water resistance and hardness of the coating film, and is economical and environment-friendly.

【detailed description】

The present invention is described in further detail below in conjunction with specific embodiment: (by weight part)

Example 1:

Take 100 parts of water-based polyurethane-acrylate composite emulsion, 0.4 parts of aniline-p-phenylenediamine copolymer, 0.1 part of thickener, 0.3 parts of defoamer, 5 parts of film-forming aid, and stir at high speed for 5 hours to obtain aniline-p-phenylenediamine Phenylenediamine copolymer/waterborne polyurethane-acrylate anti-corrosion coating.

Wherein, the synthetic technique of aniline-p-phenylenediamine copolymer is as follows:

Add 28 parts of aniline and 32 parts of p-phenylenediamine that have been distilled twice into a three-necked flask with a certain concentration of acid, stir evenly under ice-water bath conditions, and add 0.3 parts of nonionic surfactant; take 68 parts The oxidizing agent is dissolved in a certain concentration of acidic aqueous solution, and is added dropwise to the reaction system under stirring. After the dropwise addition is completed within 1.5 hours, the reaction is completed after 4 hours. Dedoping with a certain concentration of ammonia water, washing with distilled water until neutral, and then washing with a small amount of absolute ethanol, and drying at 40°C for 48 hours, the intrinsic aniline-p-phenylenediamine copolymer is obtained.

The acid is acetic acid. The oxidizing agent is potassium persulfate.

Wherein, the preparation process of water-based polyurethane-acrylate emulsion is as follows:

a. First, add 20 parts of inert vinyl monomer, 10 parts of polyester polyol, 8 parts of diisocyanate, 1.5 parts of anionic hydrophilic chain extender and 1 part of internal crosslinking agent into the drying reactor, and the reaction temperature is constant at 80°C, the reaction time is 3 hours.

b. Then, add 3.5 parts of hydroxyl-containing hydrophilic vinyl monomers for capping, react for 0.5 hours, and keep the system temperature at 80°C, then add 1.5 parts of alkali salt-forming agents, and after 20 minutes of neutralization, add The mixed solution containing 0.02 parts of surface active monomer and 75 parts of water is stirred and dispersed at high speed for 5-7 minutes, and the constant temperature is 80°C.

c. Finally, at a constant temperature of 80°C, add the aqueous initiator solution (0.03 parts of the initiator) dropwise into the reactor. After 1.5 hours of dropping, add 2 parts of the external linking agent dropwise into the reactor within 0.5 hours at the same time After the dropwise addition, continue to keep warm for 1 hour and then drop to room temperature to obtain the prepared water-based polyurethane-acrylate composite emulsion.

The inert vinyl monomer is a mixture of methacrylic acid monomer (MMA) and butyl acrylate (BA), wherein the mass ratio of MMA to BA is 4:1; the polyester polyol is polycaprolactone Dibasic alcohol; the diisocyanate is isophorone diisocyanate; the anionic hydrophilic chain extender is dimethylol propionic acid; the internal crosslinking agent is trimethylol propane; the vinyl mono The body-blocking agent is hydroxyethyl methacrylate; the polymerizable surface-active monomer is sodium α-alkenyl sulfonate; the alkali salt-forming agent is ammonia; the initiator is ammonium persulfate; The external linking agent is γ-methacryloxypropyl trimethoxysilane (KH570) and glycidyl methacrylate (GMA); the thickener is LS-112; the defoamer is BYK- 034; The coalescent is lauryl alcohol ester.

Example 2:

Take 100 parts of water-based polyurethane-acrylate composite emulsion, 1.2 parts of aniline-p-phenylenediamine copolymer, 0.05 parts of thickener, 0.1 part of defoamer, 3 parts of film-forming aid, and stir at high speed for 5 hours to obtain aniline-p-phenylenediamine Phenylenediamine copolymer/waterborne polyurethane-acrylate anti-corrosion coating.

Wherein, the synthetic technique of aniline-p-phenylenediamine copolymer is as follows:

Add 20 parts of aniline and 25 parts of p-phenylenediamine that have been distilled twice into a three-necked flask with a certain concentration of acid, stir evenly under ice-water bath conditions, and add 0.9 parts of nonionic surfactant; take 50 parts of oxidizing agent Soluble in a certain concentration of acidic aqueous solution, add dropwise to the reaction system under stirring, finish the reaction within 1.5h after 4h, pour out the reactant, filter with suction, wash with distilled water until neutral, and then use a certain Dedoping with concentrated ammonia water, washing with distilled water to neutrality, washing with a small amount of absolute ethanol, and drying at 40°C for 48 hours to obtain aniline-p-phenylenediamine copolymer in intrinsic state.

The acid is hydrochloric acid. The oxidizing agent is ammonium persulfate.

Wherein, the preparation process of water-based polyurethane-acrylate emulsion is as follows:

a. First, add 15 parts of inert vinyl monomers, 12 parts of polyester polyols, 10 parts of diisocyanates, 2 parts of anionic hydrophilic chain extenders and 1.5 parts of internal crosslinking agents into the drying reactor, and the reaction temperature is constant at 80°C, the reaction time is 3.5 hours.

b. Then, add 4 parts of hydroxyl-containing hydrophilic vinyl monomers for capping, react for 0.7 hours, and keep the system temperature at 80°C, then add 2 parts of alkali salt-forming agents, and after 25 minutes of neutralization, add A mixed liquid containing 0.03 parts of surface active monomer and 80 parts of water is stirred and dispersed at high speed for 5-7 minutes, and the constant temperature is 80°C.

c. Finally, at a constant temperature of 80°C, add the aqueous solution of the initiator (0.06 parts of the initiator) dropwise to the reactor. After 1.5 hours of dropping, add 3 parts of the external linking agent to the reactor simultaneously within 0.5 hours After the dropwise addition, continue to keep warm for 1 hour and then drop to room temperature to obtain a water-based polyurethane-acrylate composite emulsion.

The vinyl monomer is a mixture of methacrylic acid monomer (MMA) and butyl acrylate (BA), wherein the mass ratio of MMA to BA is 3:1; the polyester polyol is polyadipic acid and Dibasic alcohol; The diisocyanate is diphenylmethane diisocyanate; The anionic hydrophilic chain extender is dimethylol butyric acid; The internal crosslinking agent is trimethylol propane; The vinyl mono The body-blocking agent is hydroxyethyl acrylate; the polymerizable surface-active monomer is sodium 1-propyleneoxy-2-hydroxypropanesulfonate; the alkali salt-forming agent is triethylamine; the initiator is Potassium persulfate; The external linking agent is γ-methacryloxypropyl trimethoxysilane (KH570) and glycidyl methacrylate (GMA); The thickener is DL-80; The The defoaming agent is BYK-035; the film-forming aid is ethylene glycol butyl ether.

Example 3:

Take 100 parts of water-based polyurethane-acrylate composite emulsion, 2 parts of aniline-p-phenylenediamine copolymer, 0.2 part of thickener, 0.5 part of defoamer, 10 parts of film-forming aid, and stir at high speed for 5 hours to obtain aniline-p-phenylenediamine Phenylenediamine copolymer/waterborne polyurethane-acrylate anti-corrosion coating.

Wherein, the synthetic technique of aniline-p-phenylenediamine copolymer is as follows:

Add 25 parts of aniline and 35 parts of p-phenylenediamine after secondary distillation to a three-necked flask with a certain concentration of acid, stir evenly under ice-water bath conditions, and add 0.6 parts of nonionic surfactant; take 98 parts of oxidizing agent Soluble in a certain concentration of acid aqueous solution, add dropwise to the reaction system under stirring, finish the reaction within 1.5h after 4h, pour out the reactant, filter with suction, wash with distilled water until neutral, and then use a certain Dedoping with concentrated ammonia water, washing with distilled water to neutrality, washing with a small amount of absolute ethanol, and drying at 40°C for 48 hours to obtain aniline-p-phenylenediamine copolymer in intrinsic state.

The acid is dodecylbenzenesulfonic acid. The oxidizing agent is ammonium persulfate.

Wherein, the preparation process of water-based polyurethane-acrylate emulsion is as follows:

a. First, add 28 parts of inert vinyl monomer, 15 parts of polyester polyol, 12 parts of diisocyanate, 2.8 parts of anionic hydrophilic chain extender and 2 parts of internal crosslinking agent into the dry reactor, and the reaction temperature is constant at 80°C, and the reaction time was 3.5 hours.

b. Then, add 5 parts of hydroxyl-containing hydrophilic vinyl monomers for capping, react for 1 hour, and keep the system temperature at 80°C, then add 2.8 parts of alkali salt-forming agents, and after neutralization for 30 minutes, add The mixed solution containing 0.04 parts of surface active monomer and 85 parts of water is stirred and dispersed at high speed for 5-7 minutes, and the constant temperature is 80°C.

c. Finally, at a constant temperature of 80°C, add the aqueous solution of the initiator (0.08 parts of the initiator) dropwise to the reactor. After 1.5 hours of dropping, 3.5 parts of the external linking agent are simultaneously added dropwise to the reactor within 0.5 hours After the dropwise addition, continue to keep warm for 1 hour and then drop to room temperature to obtain a water-based polyurethane-acrylate composite emulsion.

The vinyl monomer is a mixture of methacrylic acid monomer (MMA) and butyl acrylate (BA), wherein the mass ratio of MMA to BA is 3.5:1; the polyester polyol is polycarbonate binary alcohol; the diisocyanate is hexamethylene diisocyanate; the anionic hydrophilic chain extender is dimethylol propionic acid; the internal crosslinking agent is trimethylol propane; the vinyl monomer seal The terminal agent is hydroxyethyl methacrylate; the polymerizable surface-active monomer is sodium α-alkenyl sulfonate; the alkali salt-forming agent is triethylamine; the initiator is ammonium persulfate; The external linking agent is γ-methacryloxypropyltrimethoxysilane (KH570) and glycidyl methacrylate (GMA); the thickener is DL-80; the defoamer is BYK- 038; The coalescent is lauryl alcohol ester.

The aniline-p-phenylenediamine copolymer/waterborne polyurethane-acrylic ester anticorrosion coating that example 1-3 obtains adopts the method for scraping to be coated on the polished tinplate respectively, and the performance of paint film is detected, and the results are shown in Table 1 .

Table 1

Example 4:

Take 100 parts of water-based polyurethane-acrylate composite emulsion, 2 parts of aniline-p-phenylenediamine copolymer, 0.2 part of thickener, 0.5 part of defoamer, 10 parts of film-forming aid, and stir at high speed for 5 hours to obtain aniline-p-phenylenediamine Phenylenediamine copolymer/waterborne polyurethane-acrylate anti-corrosion coating.

Wherein, the synthetic technique of aniline-p-phenylenediamine copolymer is as follows:

Add 10 parts of aniline and 10 parts of p-phenylenediamine that have been distilled twice into a three-necked flask with a certain concentration of acid, stir evenly under ice-water bath conditions, and add 0.5 parts of nonionic surfactant; take 19 parts The oxidizing agent is dissolved in a certain concentration of acidic aqueous solution, and is added dropwise to the reaction system under stirring. After the dropwise addition is completed within 1.5 hours, the reaction is completed after 4 hours. Dedoping with a certain concentration of ammonia water, washing with distilled water until neutral, and then washing with a small amount of absolute ethanol, and drying at 40°C for 48 hours, the intrinsic aniline-p-phenylenediamine copolymer is obtained.

The acid is dodecylbenzenesulfonic acid. The oxidizing agent is ammonium persulfate.

Wherein, the preparation process of water-based polyurethane-acrylate emulsion is as follows:

a. First, add 10 parts of inert vinyl monomer, 5 parts of polyester polyol, 5 parts of diisocyanate, 1 part of anionic hydrophilic chain extender and 0.3 part of internal crosslinking agent into the drying reactor, and the reaction temperature is constant at 80°C, the reaction time is 4 hours.

b. Then, add 3 parts of hydroxyl-containing hydrophilic vinyl monomers for capping, react for 0.8 hours, and keep the system temperature at 80°C, then add 1 part of alkali salt-forming agent, and after 30 minutes of neutralization reaction, add The mixed solution containing 0.04 parts of surface active monomer and 75 parts of water is stirred and dispersed at high speed for 5-7 minutes, and the constant temperature is 80°C.

c. Finally, at a constant temperature of 80°C, add the aqueous solution of the initiator (0.02 parts of the initiator) dropwise into the reactor, and after 1.5 hours of dropping, add 1.5 parts of the external linking agent dropwise into the reactor within 0.5 hours at the same time , after the dropwise addition, continue to keep warm for 1 hour and then drop to room temperature to obtain a water-based polyurethane-acrylate composite emulsion.

The vinyl monomer is a mixture of methyl acrylate, butyl acrylate and methyl methacrylate; the polyester polyol is polycarbonate diol; the diisocyanate is hexamethylene diisocyanate; the The anionic hydrophilic chain extender is dimethylol propionic acid; the internal crosslinking agent is trimethylolpropane; the vinyl monomer end-capping agent is hydroxyethyl methacrylate; the polymerizable surface The active monomer is sodium α-alkenyl sulfonate; the alkali salt forming agent is triethylamine; the initiator is ammonium persulfate; the external linking agent is γ-methacryloxypropyl trimethyl Oxygen silane (KH570) and glycidyl methacrylate (GMA); the thickener is DL-80; the defoamer is BYK-038; the film-forming aid is lauryl alcohol ester.

Example 5:

Take 100 parts of water-based polyurethane-acrylate composite emulsion, 0.4 parts of aniline-p-phenylenediamine copolymer, 0.1 part of thickener, 0.3 parts of defoamer, 5 parts of film-forming aid, and stir at high speed for 5 hours to obtain aniline-p-phenylenediamine Phenylenediamine copolymer/waterborne polyurethane-acrylate anti-corrosion coating.

Wherein, the synthetic technique of aniline-p-phenylenediamine copolymer is as follows:

Add 28 parts of aniline and 32 parts of p-phenylenediamine after double distillation to a three-necked flask with a certain concentration of acid, stir evenly under ice-water bath conditions, and add 0.8 parts of nonionic surfactant; take 68 parts of oxidant Soluble in a certain concentration of acidic aqueous solution, add dropwise to the reaction system under stirring, finish the reaction within 1.5h after 4h, pour out the reactant, filter with suction, wash with distilled water until neutral, and then use a certain Dedoping with concentrated ammonia water, washing with distilled water to neutrality, washing with a small amount of absolute ethanol, and drying at 40°C for 48 hours to obtain aniline-p-phenylenediamine copolymer in intrinsic state.

The acid is hydrochloric acid. The oxidizing agent is ammonium persulfate.

Wherein, the preparation process of water-based polyurethane-acrylate emulsion is as follows:

a. First, add 10 parts of inert vinyl monomer, 5 parts of polyester polyol, 5 parts of diisocyanate, 1 part of anionic hydrophilic chain extender and 0.3 part of internal crosslinking agent into the drying reactor, and the reaction temperature is constant at 80°C, the reaction time is 4 hours.

b. Then, add 3 parts of hydroxyl-containing hydrophilic vinyl monomers for capping, react for 0.8 hours, and keep the system temperature at 80°C, then add 4 parts of alkali salt-forming agents, and after 30 minutes of neutralization reaction, add The mixed solution containing 0.04 parts of surface active monomer and 75 parts of water is stirred and dispersed at high speed for 5-7 minutes, and the constant temperature is 80°C.

c. Finally, at a constant temperature of 80°C, add the aqueous solution of the initiator (0.02 parts of the initiator) dropwise into the reactor. After 1.5 hours of dropping, add 4 parts of the external linking agent dropwise into the reactor within 0.5 hours at the same time , after the dropwise addition, continue to keep warm for 1 hour and then drop to room temperature to obtain a water-based polyurethane-acrylate composite emulsion.

The vinyl monomer is butyl acrylate; the polyester polyol is polyadipic acid and glycol; the diisocyanate is diphenylmethane diisocyanate; the anionic hydrophilic chain extender is dihydroxy Methylbutyric acid; the internal crosslinking agent is trimethylolpropane; the vinyl monomer end-capping agent is hydroxyethyl acrylate; the polymerizable surface-active monomer is 1-propyleneoxy-2- Sodium hydroxypropane sulfonate; the alkali salt forming agent is triethylamine; the initiator is potassium persulfate; the external linking agent is γ-methacryloxypropyltrimethoxysilane (KH570) and glycidyl methacrylate (GMA); the thickener is DL-80; the defoamer is BYK-035; the film-forming aid is butyl glycol ether.

Butyl acrylate in embodiment 5 can also be methyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, styrene, n-octyl acrylate, hexyl acrylate, n-octyl methacrylate, A mixture of one or more than two kinds of hexyl methacrylate in any proportion.

The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments. It cannot be determined that the specific embodiments of the present invention are limited thereto. Under the circumstances, some simple deduction or replacement can also be made, which should be regarded as belonging to the scope of patent protection determined by the submitted claims of the present invention.

Claims (10)

1. a kind of aqueous polyurethane polyaniline anti-corrosive paint, it is characterised in that：

Described aqueous polyurethane polyaniline anti-corrosive paint is anti-for aniline-p-phenylenediamine copolymer/aqueous polyurethane-acrylate Rotten coating, including the raw material of following weight portion：

100 parts of aqueous polyurethane-acrylate composite emulsion, aniline -0.4~2 part of p-phenylenediamine copolymer, thickening agent 0.05~ 0.2 part, 0.1~0.5 part of defoamer, 3~10 parts of coalescents；

The preparation method of described aniline-p-phenylenediamine copolymer is：

First 10-30 parts aniline of Jing second distillations and 10-35 parts p-phenylenediamine are added in reactor, is adjusted using acidic aqueous solution Section system pH is to 1-4, the mixed liquor of stir under conditions of ice-water bath prepared aniline and p-phenylenediamine；Take 49-98 parts Oxidant is dissolved in acidic aqueous solution, and during above-mentioned mixed liquor is added drop-wise to while stirring, oxidant mixes with aniline and p-phenylenediamine The mol ratio of monomer is between 1:1 to 1:Between 2；And add 0.3-0.9 part nonionic surfactants as emulsifying agent, drip Fully react to terminating afterwards, reactant is poured out, sucking filtration；Neutrality is first washed with distilled water to, ammonia dedoping is then used, then is used Distilled water wash, again with absolute ethanol washing, after being dried, that is, obtains eigenstate aniline-p-phenylenediamine copolymer to neutrality.

2. a kind of aqueous polyurethane polyaniline anti-corrosive paint according to claim 1, it is characterised in that：

The acid is hydrochloric acid, acetic acid, phosphoric acid or DBSA；

The oxidant is Ammonium persulfate. or potassium peroxydisulfate；

The nonionic surfactant is OPEO.

3. a kind of preparation method of aqueous polyurethane polyaniline anti-corrosive paint, it is characterised in that：Comprise the following steps：

Step 1) prepare aniline-p-phenylenediamine copolymer：

A. by weight, first 10-30 parts aniline of Jing second distillations and 10-35 part p-phenylenediamine are added to and are equipped with pH value In the reactor of the acidic aqueous solution of 1-4, stir under the conditions of ice-water bath, and add 0.3-0.9 parts non-ionic surface to live Property agent；

B. 49-98 part oxidants are taken to be dissolved in acidic aqueous solution, is added drop-wise under stirring in the reaction system in step a, dripped After react to terminating, reactant is poured out, sucking filtration, be first washed with distilled water to neutrality, then use ammonia dedoping, then with distillation Water washing, again with absolute ethanol washing, after dried, that is, obtains eigenstate aniline-p-phenylenediamine copolymer to neutrality；

Step 2) prepare aqueous polyurethane-acrylate composite emulsion：

C. by weight, 10~28 parts of inertia vinyl monomers, 5~15 parts of polyester polyols are added in dry reactor Alcohol, 5~12 parts of diisocyanate, 1~2.8 part of anionic hydrophilic chain extender and 0.3~2 part of internal crosslinker, reaction temperature is constant For 70~80 DEG C, the response time is 3~4 hours；

D. add the hydrophilic vinylic monomer of 3~5 parts of hydroxyls to be blocked, react 0.5~1 hour, system temperature keeps At 70~80 DEG C, 1~4 part of bases salt forming agent is added, after neutralization reaction, add and contain 0.02~0.04 part of polymerizable surface activity The mixed liquor of monomer and 75~85 parts of water, dispersed with stirring is uniform；

E. at 70~80 DEG C of constant temperature, 0.02~0.08 part of initiator is dissolved in into initiator solution made by 0.2~0.8 part of water In being added drop-wise to reactor, after dripping, by 1.5~4 especially cross-linking agent be added drop-wise in reactor simultaneously in 0.5 hour, Deca After finishing, continue to be incubated 1 hour and then be down to room temperature, that is, aqueous polyurethane-acrylate composite emulsion is obtained；

Step 3) prepare anticorrosive paint：

100 parts of aqueous polyurethane-acrylate composite emulsion adds aniline-p-phenylenediamine copolymer 0.4 as matrix resin ~2 parts, 0.05~0.2 part of thickening agent, 0.1~0.5 part of defoamer, 3~10 parts of coalescents are equal using physical blending process mixing It is even, that is, obtain aniline-p-phenylenediamine copolymer/aqueous polyurethane-acrylate anticorrosive paint.

4. the preparation method of a kind of aqueous polyurethane polyaniline anti-corrosive paint according to claim 3, it is characterised in that：

The acid is hydrochloric acid, acetic acid, phosphoric acid or DBSA；

The oxidant is Ammonium persulfate. or potassium peroxydisulfate；

The nonionic surfactant is OPEO.

5. the preparation method of a kind of aqueous polyurethane polyaniline anti-corrosive paint according to claim 3, it is characterised in that：

The inertia vinyl monomer be acrylic acid methyl ester., butyl acrylate, methyl methacrylate, butyl methacrylate, One or two in styrene, n-octyl, Hexyl 2-propenoate, n octyl methacrylate, N-Hexyl methacrylate The mixture of any of the above proportioning.

6. the preparation method of a kind of aqueous polyurethane polyaniline anti-corrosive paint according to claim 3, it is characterised in that：Institute PEPA is stated for the own dihydroxylic alcohols of polycaprolactone diols, PCDL or polyadipate.

7. the preparation method of a kind of aqueous polyurethane polyaniline anti-corrosive paint according to claim 3, it is characterised in that：

The diisocyanate is isophorone diisocyanate, methyl diphenylene diisocyanate or the Carbimide. of hexa-methylene two Ester；

The anionic hydrophilic chain extender is dihydromethyl propionic acid or dimethylolpropionic acid；

The internal crosslinker is trimethylolpropane.

8. the preparation method of a kind of aqueous polyurethane polyaniline anti-corrosive paint according to claim 3, it is characterised in that：

The vinyl monomer end-capping reagent is hydroxyethyl methylacrylate or 2-(Acryloyloxy)ethanol；

The polymerizable surface active monomer is α-sodium olefin sulfonate or 1- propenyloxy group -2- hydroxypropanesulfonic acid sodium；

The bases salt forming agent is ammonia or triethylamine.

9. the preparation method of a kind of aqueous polyurethane polyaniline anti-corrosive paint according to claim 3, it is characterised in that：

The initiator is Ammonium persulfate. or potassium peroxydisulfate；

The outside cross-linking agent is γ-methacryloxypropyl trimethoxy silane and/or glycidyl methacrylate.

10. the preparation method of a kind of aqueous polyurethane polyaniline anti-corrosive paint according to claim 3, it is characterised in that：

The thickening agent is LS-112 or DL-80；

The defoamer is BYK-034, BYK-035 or BYK-037 of German BYK companies production；

The coalescents are lauryl alcohol ester or butyl glycol ether.