阅读说明：本技术 改性无溶剂丙烯酸酯分散体、水性涂料及其制备方法和彩砂的制备方法 (Modified solvent-free acrylate dispersoid, water-based paint and preparation method thereof, and preparation method of colored sand ) 是由 姜美佳 秦玉猛 李维亚 孔丁峰 于 2021-08-20 设计创作，主要内容包括：本发明一种改性无溶剂丙烯酸酯分散体、改性无溶剂丙烯酸酯分散体的制备方法、水性涂料、水性涂料的制备方法及彩砂的制备方法。该分散体不含有溶剂,分子量较小,渗透性和润湿性好,提高染色效果,减小色差,并且使染色更牢固和均匀。本发明制备的砂子染色性好、耐候性好,耐水以及耐化性好。(The invention relates to a modified solvent-free acrylate dispersoid, a preparation method of the modified solvent-free acrylate dispersoid, a water-based paint, a preparation method of the water-based paint and a preparation method of colored sand. The dispersion contains no solvent, has small molecular weight and good permeability and wettability, improves the dyeing effect, reduces color difference and ensures that the dyeing is firmer and more uniform. The sand prepared by the invention has good dyeability, good weather resistance, and good water resistance and chemical resistance.)

1. A modified solventless acrylate dispersion characterized by: the composition is prepared from the following components in parts by mass:

the monomer is one or more than two of acrylate monomer, methacrylate monomer and styrene mixed according to any proportion.

2. A modified solventless acrylate dispersion according to claim 1 wherein: the thermal decomposition type initiator is tert-amyl hydroperoxide.

3. A preparation method of a modified solvent-free acrylate dispersion is characterized by comprising the following steps: the method comprises the following steps:

1) synthesis of acrylate resin: adding tertiary carbonic acid glycidyl ester into a container, and then heating to 140-170 ℃; then mixing 30-70% of the total amount of the monomers, half of the total amount of the molecular weight regulator and 43-63% of the total amount of the thermal decomposition type initiator, and dripping into the tertiary carbonic acid glycidyl ester for 3-5 h;

after finishing dropping, mixing the rest monomer, the other half of the molecular weight regulator and 10-20% of the total amount of the thermal decomposition type initiator, and dropping into the tertiary carbonic acid glycidyl ester for 1-2 h; after finishing dripping, adding the rest thermal decomposition type initiator, continuously preserving the heat for 1-2h, and then cooling to 20-40 ℃;

2) preparation of an aqueous acrylate dispersion: heating the acrylate resin obtained in the step 1) to 60-90 ℃, adding a pH regulator to neutralize to be neutral, and finally dripping deionized water at a stirring speed of 2000-3000rpm to obtain the modified solvent-free acrylate dispersion.

4. An aqueous coating characterized by: is formed by mixing a component A and a component B,

the component A is prepared from the following components in parts by mass:

the modified solventless acrylate dispersion of claim 1 or 2

The component B is prepared from the following components in parts by mass:

30.00 to 40.00 portions of organic solvent

60.00-70.00 parts of polyurethane curing agent.

5. The method of claim 4, wherein the aqueous coating composition comprises: the preparation method of the component A comprises the following steps:

(1) adding the anti-settling agent into 4.00-12.00 parts of deionized water with the stirring speed of 200-300rpm, then increasing the rotating speed to 2000-3000rpm, and continuously stirring for 15-25 minutes to prepare anti-settling slurry for later use;

(2) adding the dispersant and the prepared anti-settling slurry into 13.00-21.00 parts of deionized water with the stirring speed of 1000-2000rpm, then adjusting the stirring speed to 300-500rpm, adding the pigment, then increasing the rotating speed to 1000-2000rpm, then adding the defoaming agent which accounts for half of the total amount of the defoaming agent in the component A, and then stirring for 20-30 minutes at 1500-2500 rpm; then transferring the mixture into a dispersion cylinder, dispersing and grinding the mixture at 3000rpm of 2000-;

(3) adding a cosolvent, a wetting agent, the color paste prepared in the step (2), an ultraviolet light absorber, an amine-retardant light stabilizer, a thickening agent, a pH regulator and the defoaming agent of the other half of the total amount of the defoaming agent in the component A into the modified solvent-free acrylate dispersoid, and then stirring at 1000-2000rpm for 20-30 minutes;

the preparation method of the component B comprises the following steps: the organic solvent and the polyurethane curing agent were stirred at 800-.

6. The preparation method of the colored sand is characterized by comprising the following steps: mixing the component A and the component B of the water-based paint in the mass ratio of 4.5-5:1 according to the claim 5, stirring for 3-8 minutes at 800-1200rpm, adding deionized water with the mass being 10-20% of the total mass of the component A and the component B, and stirring for 3-8 minutes at 800-1200rpm to prepare a water-based two-component paint mixed solution;

then mixing quartz sand and the obtained water-based two-component coating mixed solution according to the mass ratio of 960-980: 20-50 and stirring at 800-; then the mixture is baked for 25 to 35 minutes at the temperature of 110 ℃ and 130 ℃ and cooled.

Technical Field

The invention relates to a modified solvent-free acrylate dispersoid, a water-based paint, a preparation method of the water-based paint and a preparation method of colored sand.

Background

The sand with rich colors is used as an important 'decorative seasoning element' and is widely used in the fields of building materials such as real stone paint, epoxy terrace, relief, glass fiber asphalt tile and the like, and the demand is increased year by year. However, the disordered mining of natural color stone resources causes the destruction of ecological environment, and the supply of natural color sand is increasingly limited along with the strict requirements of environmental protection policies on ore sources. Meanwhile, most of natural colored sand is chaotic in color and luster, poor in strength and easy to pulverize due to direct crushing from nature, and the large batch color difference brings difficulty to production and use. Some natural colored sands with bright colors are few in quantity, expensive in price and large in limitation. The color sand manufactured by a certain process has the advantages of various and rich colors, bright colors, consistent colors, uniform granularity, high hardness, good durability and the like, and is gradually the preferred material for producing modern real stone paint. Therefore, the preparation process of the color sand, which can achieve the use effect of the natural color sand, has reasonable price and simple preparation process and meets the resource-saving production requirement, is urgently needed to be developed.

The method adopted at present for producing the non-natural colored sand comprises the following steps: normal temperature dyeing method, resin curing method, high temperature sintering method. With the improvement of the process in recent years, a ceramic color glaze method appears. However, the above methods all have some disadvantages, the normal temperature dyeing method is to directly stir and mix quartz sand and organic dye, and the color sand prepared by the method is easy to fade and has poor weather resistance. The high-temperature sintering method and the ceramic color glaze method both require higher temperature, have higher requirements on equipment and have higher energy consumption. Most of the currently used resin curing methods adopt solvent-type acrylic resin, use a large amount of solvents, are not environment-friendly and have great influence on the environment. CN 104261711B adopts a waterborne epoxy resin curing method to prepare the color sand, and has the problems of poor color fastness, acid and alkali resistance and weather resistance. CN 106478861B adopts a water-based hydroxy acrylic emulsion curing method to prepare the colored sand, the resin has poor wettability to the sand, color difference is easy to occur, and meanwhile, the emulsion has poor compatibility with a curing agent, and certain problems exist in crosslinking.

In conclusion, the normal-temperature dyeing method is to directly stir and mix quartz sand and organic dye, and the color sand prepared by the method is easy to fade and has poor weather resistance.

The high-temperature sintering method and the ceramic color glaze method both require higher temperature, have higher requirements on equipment and have higher energy consumption.

Most of the common resin curing methods adopt solvent type acrylic resin, use a large amount of solvents, are not environment-friendly and have great influence on the environment.

The common aqueous resin curing method has the problems of color fastness, color difference, acid and alkali resistance, weather resistance and the like.

Disclosure of Invention

The modified solvent-free acrylate dispersoid does not contain a solvent, has small molecular weight and good permeability and wettability, improves the dyeing effect, reduces color difference and ensures that the dyeing is firmer and more uniform. The sand prepared by the invention has good dyeability, good weather resistance, and good water resistance and chemical resistance.

The invention is realized by the following technical scheme:

the modified solvent-free acrylate dispersion is prepared from the following components in parts by mass:

the monomer is one or more of acrylate monomer, methacrylate monomer and styrene.

The molecular weight regulator is 2, 4-diphenyl-4-methyl-1-pentene.

The thermal decomposition type initiator is tert-amyl hydroperoxide.

A preparation method of a modified solvent-free acrylate dispersion comprises the following steps:

1) synthesis of acrylate resin: adding tertiary carbonic acid glycidyl ester into a container, and then heating to 140-170 ℃; then, beginning to dropwise add a mixture of 30-70% of the total amount of the monomers, half of the total amount of the molecular weight regulator and 43-63% of the total amount of the thermal decomposition type initiator for 3-5 h; after finishing dropping, beginning to drop the mixture of the rest monomers, the other half of the molecular weight regulator and 10-20% of the total amount of the thermal decomposition type initiator for 1-2 h; after finishing dripping, adding the rest thermal decomposition type initiator, continuously preserving the heat for 1-2h, and cooling to 20-40 ℃;

2) preparation of an aqueous acrylate dispersion: heating the acrylate resin obtained in the step 1) to 60-90 ℃, adding a pH regulator to neutralize to be neutral, and finally dripping deionized water at a stirring speed of 2000-3000rmp to obtain the modified solvent-free acrylate dispersion.

A water paint is prepared by mixing component A and component B.

The component A is prepared from the following components in parts by mass:

the component B is prepared from the following components in parts by mass:

30.00 to 40.00 portions of organic solvent

60.00-70.00 parts of polyurethane curing agent.

The preparation method of the component A comprises the following steps:

(1) adding the anti-settling agent into 4.00-12.00 parts of deionized water with the stirring speed of 200-300rpm, then increasing the rotating speed to 2000-3000rpm, and continuously stirring for 20 minutes to prepare anti-settling slurry for later use;

(2) adding the dispersant and the prepared anti-settling slurry into 13.00-21.00 parts of deionized water with the stirring speed of 1000-2000rpm, then adding the pigment at the stirring speed of 300-500rpm, then increasing the rotating speed to 1000-2000rpm, then adding half of the defoaming agent, and then stirring at 1500-2500rpm for 20-30 minutes; then adding the mixture into a dispersion cylinder, dispersing and grinding the mixture at 3000rpm of 2000-;

(3) adding a cosolvent, a wetting agent, the color paste prepared in the step (2), an ultraviolet light absorber, an amine-blocking light stabilizer, a thickening agent, a pH regulator and the other half of a defoaming agent into the modified solvent-free acrylate dispersion, and stirring at 1000-2000rpm for 20-30 minutes;

the preparation method of the component B comprises the following steps: the organic solvent and the polyurethane curing agent were stirred at 800-.

The preparation method of the colored sand is characterized by comprising the following steps: mixing the component A and the component B of the water-based paint in the mass ratio of 4.5-5:1 according to the claim 5, stirring for 3-8 minutes at 800-1200rpm, adding deionized water with the mass being 10-20% of the total mass of the component A and the component B, and stirring for 3-8 minutes at 800-1200rpm to prepare a water-based two-component paint mixed solution;

then mixing quartz sand and the obtained water-based two-component coating mixed solution according to the mass ratio of 960-980: 20-50 and stirring at 800-; then the mixture is baked for 25 to 35 minutes at the temperature of 110 ℃ and 130 ℃ and cooled.

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

the modified solvent-free acrylate dispersoid is green and environment-friendly, and has good wettability, permeability, coating rate and dyeing effect, and bright color without color difference.

The paint of the present invention can dye white sand into sand of various colors, and the dyed sand has good weather resistance, water resistance and chemical resistance.

Detailed Description

The invention will be further elucidated with reference to the embodiments described hereinafter

Example 1

The modified solvent-free acrylate dispersion is prepared from the following components in parts by mass:

the monomer is one or more of acrylate monomer, methacrylate monomer and styrene.

The molecular weight regulator is 2, 4-diphenyl-4-methyl-1-pentene.

The thermal decomposition type initiator is tert-amyl hydroperoxide.

The pH regulator is dimethylethanolamine

A preparation method of a modified solvent-free acrylate dispersion comprises the following steps:

1) synthesis of acrylate resin: adding tertiary carbonic acid glycidyl ester into a container, and then heating to 140 ℃; then, a mixture of 30% of the total amount of the monomers, half of the total amount of the molecular weight regulator and 43% of the total amount of the thermal decomposition type initiator is added dropwise for 3 hours; after the dropping, starting to drop the mixture of the rest monomer, the other half of the molecular weight regulator and 10 of the total amount of the thermal decomposition type initiator for 1 h; after finishing dripping, adding the rest thermal decomposition type initiator, continuously preserving the heat for 1h, and cooling to 20 ℃;

2) preparation of an aqueous acrylate dispersion: heating the acrylate resin obtained in the step 1) to 60 ℃, adding a pH regulator to neutralize to be neutral, and finally dripping deionized water at a stirring speed of 2000rmp to obtain the modified solvent-free acrylate dispersion.

The first portion of the monomers of example 1 was 9g of acrylic acid + 20g of styrene + 8g of butyl acrylate + 8g of methyl methacrylate and the second portion of the monomers was 4g of acrylic acid + 8g of butyl acrylate + 8g of methyl methacrylate + 4g of hydroxyethyl methacrylate.

A water paint is prepared by mixing component A and component B.

The component A is prepared from the following components in parts by mass:

the component B is prepared from the following components in parts by mass:

30.00 parts of organic solvent

60.00 parts of polyurethane curing agent.

The preparation method of the component A comprises the following steps:

(1) adding the anti-settling agent into 4.00 parts of deionized water with the stirring speed of 200rpm, then increasing the rotating speed to 2000rpm, and continuously stirring for 20 minutes to prepare anti-settling slurry for later use;

(2) adding a dispersing agent and the prepared anti-settling slurry into 21.00 parts of deionized water with the stirring speed of 1000rpm, then adding a pigment at the stirring speed of 300rpm, then increasing the rotating speed to 1000rpm, then adding half of a defoaming agent, and then stirring at 1500rpm for 20 minutes; then adding the mixture into a dispersion cylinder, dispersing and grinding the mixture at 2000rpm until the fineness of the mixture is less than 10 mu m, and filtering color paste for later use;

(3) adding a cosolvent, a wetting agent, the color paste prepared in the step (2), an ultraviolet light absorber, an amine-blocking light stabilizer, a thickening agent, a pH regulator and the other half of a defoaming agent into the modified solvent-free acrylate dispersion, and then stirring at 1000rpm for 20 minutes;

the preparation method of the component B comprises the following steps: the organic solvent and polyurethane curing agent were stirred at 800rpm for 5 minutes.

A sand dyeing method comprises the following steps of mixing a component A and a component B of an aqueous coating according to a mass ratio of 5:1, stirring at 800rpm for 3 minutes, adding deionized water accounting for 10 percent of the total mass of the component A and the component B, and stirring at 800rpm for 8 minutes to prepare a water-based two-component coating mixed solution;

then mixing quartz sand and the obtained water-based two-component coating mixed solution according to the mass ratio of 960: 40 and stirred at 800rpm for 10 minutes; then baking the mixture at 120 ℃ for 25 minutes, and cooling the mixture.

Example 2

The modified solvent-free acrylate dispersion is prepared from the following components in parts by mass:

the monomer is one or more of acrylate monomer, methacrylate monomer and styrene.

The molecular weight regulator is 2, 4-diphenyl-4-methyl-1-pentene.

The thermal decomposition type initiator is tert-amyl hydroperoxide.

A preparation method of a modified solvent-free acrylate dispersion comprises the following steps:

1) synthesis of acrylate resin: adding tertiary carbonic acid glycidyl ester into a container, and then heating to 140-170 ℃; then, a mixture of 70% of the total amount of the monomers, half of the total amount of the molecular weight regulator and 63% of the total amount of the thermal decomposition type initiator is dripped for 5 hours; after finishing dropping, beginning to drop the mixture of the rest monomers, the other half of the molecular weight regulator and 20 percent of the total amount of the thermal decomposition type initiator for 2 hours; after finishing dripping, adding the rest thermal decomposition type initiator, continuously preserving the heat for 2 hours, and cooling to 40 ℃;

2) preparation of an aqueous acrylate dispersion: heating the acrylate resin obtained in the step 1) to 90 ℃, adding a pH regulator to neutralize to be neutral, and finally dripping deionized water at a stirring speed of 3000rmp to obtain the modified solvent-free acrylate dispersion.

The first portion of the monomers added dropwise in example 2 was 9g of acrylic acid + 20g of styrene + 8g of butyl acrylate + 8g of methyl methacrylate, and the second portion was 2g of acrylic acid + SipomPAM 2002g + 8g of butyl acrylate + 8g of methyl methacrylate + 4g of hydroxyethyl methacrylate.

A water paint is prepared by mixing component A and component B.

The component A is prepared from the following components in parts by mass:

the component B is prepared from the following components in parts by mass:

30.00 parts of organic solvent

60.00 parts of polyurethane curing agent.

The preparation method of the component A comprises the following steps:

(1) adding the anti-settling agent into 12.00 parts of deionized water with the stirring speed of 300rpm, then increasing the rotating speed to 3000rpm, and continuously stirring for 20 minutes to prepare anti-settling slurry for later use;

(2) adding a dispersing agent and the prepared anti-settling slurry into 21.00 parts of deionized water with the stirring speed of 2000rpm, then adding a pigment at the stirring speed of 500rpm, then increasing the rotating speed to 2000rpm, then adding half of a defoaming agent, and then stirring for 30 minutes at 2500 rpm; then adding the mixture into a dispersion cylinder, dispersing and grinding the mixture at 3000rpm until the fineness of the mixture is less than 10 mu m, and then filtering color paste for later use;

(3) adding a cosolvent, a wetting agent, the color paste prepared in the step (2), an ultraviolet light absorber, an amine-blocking light stabilizer, a thickening agent, a pH regulator and the other half of a defoaming agent into the modified solvent-free acrylate dispersion, and then stirring at 2000rpm for 30 minutes;

the preparation method of the component B comprises the following steps: the organic solvent and polyurethane curing agent were stirred at 1200rpm for 15 minutes.

A sand dyeing method comprises the following steps of mixing a component A and a component B of an aqueous coating according to a mass ratio of 4.5: 1, stirring at 1200rpm for 8 minutes, adding deionized water accounting for 20 percent of the total mass of the component A and the component B, and stirring at 1200rpm for 8 minutes to prepare a water-based two-component coating mixed solution;

then mixing quartz sand and the obtained water-based two-component coating mixed solution according to the mass ratio of 980: 20 and stirred at 800rpm for 20 minutes; then baking at 110 deg.C for 25-35 min, and cooling.

Example 3

The modified solvent-free acrylate dispersion is prepared from the following components in parts by mass:

the monomer is one or more of acrylate monomer, methacrylate monomer and styrene.

The molecular weight regulator is 2, 4-diphenyl-4-methyl-1-pentene.

The thermal decomposition type initiator is tert-amyl hydroperoxide.

A preparation method of a modified solvent-free acrylate dispersion comprises the following steps:

1) synthesis of acrylate resin: adding tertiary carbonic acid glycidyl ester into a container, and then heating to 140-170 ℃; then, a mixture of 50% of the total amount of the monomers, half of the total amount of the molecular weight regulator and 50% of the total amount of the thermal decomposition type initiator is dripped for 4 hours; after the dripping is finished, the mixture of the rest monomer, the other half of the molecular weight regulator and 15 percent of the total amount of the thermal decomposition type initiator is dripped for 1.5 h; after finishing dripping, adding the rest thermal decomposition type initiator, continuously preserving the heat for 1.5h, and cooling to 30 ℃;

2) preparation of an aqueous acrylate dispersion: heating the acrylate resin obtained in the step 1) to 70 ℃, adding a pH regulator to neutralize to be neutral, and finally dripping deionized water at a stirring speed of 2500rmp to obtain the modified solvent-free acrylate dispersion.

The first part of monomers are acrylic acid 9g, methyl methacrylate 20g, butyl acrylate 8g and methyl methacrylate 8 g; the second monomer fraction was 2g of acrylic acid + SipomEPM 2002g + butyl acrylate 8g + methyl methacrylate 8g + hydroxyethyl methacrylate 4 g.

The component B is prepared from the following components in parts by mass:

35.00 parts of organic solvent

65.00 parts of polyurethane curing agent.

The preparation method of the component A comprises the following steps:

(1) adding the anti-settling agent into 4.00 parts of deionized water with the stirring speed of 250rpm, then increasing the rotating speed to 2500rpm, and continuously stirring for 20 minutes to prepare anti-settling slurry for later use;

(2) adding a dispersing agent and the prepared anti-settling slurry into 13.00 parts of deionized water with the stirring speed of 1500rpm, then adding a pigment at the stirring speed of 400rpm, then increasing the rotating speed to 1500rpm, then adding half of a defoaming agent, and then stirring at 2000rpm for 25 minutes; then adding the mixture into a dispersion cylinder, dispersing and grinding the mixture at 2500rpm until the fineness of the mixture is less than 10 mu m, and filtering color paste for later use;

(3) adding a cosolvent, a wetting agent, the color paste prepared in the step (2), an ultraviolet light absorber, an amine-blocking light stabilizer, a thickening agent, a pH regulator and the other half of a defoaming agent into the modified solvent-free acrylate dispersion, and then stirring at 1500rpm for 25 minutes;

the preparation method of the component B comprises the following steps: the organic solvent and polyurethane curing agent were stirred at 1000rpm for 10 minutes.

A sand dyeing method comprises the following steps of mixing a component A and a component B of an aqueous coating according to a mass ratio of 4.6: 1, stirring at 1000rpm for 5 minutes, adding deionized water accounting for 15 percent of the total mass of the component A and the component B, and stirring at 1000rpm for 5 minutes to prepare a water-based two-component coating mixed solution;

then mixing quartz sand and the obtained water-based two-component coating mixed solution according to the mass ratio of 960: 40 and stirred at 1000rpm for 15 minutes; then baking at 130 deg.C for 30 min, and cooling.

The particle size of the quartz sand is 40-120 meshes.

The dispersant was BYK-2015 (Picker chemical Co., Ltd.)

The pigment is titanium dioxide (DuPont pigment chemical Co., Ltd.) or CINELEXDPPREDSR 1C (Nicek pigment Co., Ltd.);

the antifoaming agent is Tego810 (winning Chuang Delousai chemical Co., Ltd.)

The cosolvent is dipropylene glycol butyl ether

The humectant is Twin-4100 (Wingchuang Texaco chemical Co., Ltd.)

The ultraviolet light absorber is Tinuvin400DW (N) (Bassfu chemical Co., Ltd.)

The hindered amine light stabilizer is Tinuvin123DW (N) (Bassfu chemical Co., Ltd.)

The thickener is SN-660T (san Nuo Puke chemical Co., Ltd.)

The pH regulator is DMEA

The organic solvent is diethylene glycol ethyl ether acetate

The polyurethane curing agent is N3900 (Corsai Chuang chemical Co., Ltd.)

The anti-settling agent adopts LT of Haimines.

Comparative example 1:

the main resin for sand dyeing is prepared from the following conventional hydroxy acrylic emulsion and curing agent:

the preparation method comprises the following steps of mixing a hydroxyl acrylic emulsion commonly used in the market and a curing agent according to a mass ratio of 5:1, then adding quartz sand, wherein the mass ratio of the quartz sand to the mixture of the hydroxyl acrylic emulsion and the curing agent is 960: 40, and stirring at 800rpm for 10 minutes; then baking the mixture at 120 ℃ for 25 minutes, and cooling the mixture.

Comparative example 2: the main resin of sand dyeing is water-based epoxy resin and curing agent commonly used in the market:

the method comprises the following steps of mixing commercially common water-based epoxy resin and a curing agent according to a mass ratio of 5:1, then adding quartz sand, wherein the mass ratio of the quartz sand to the mixture of the waterborne epoxy resin and the curing agent is 960: 40, and stirring at 800rpm for 10 minutes; then baking the mixture at 120 ℃ for 25 minutes, and cooling the mixture.

The results of the comparative tests on the color sands prepared in the examples and the comparative examples are as follows:

as can be seen from the above table, the coating rate of the examples 1 to 3 is high, the dyeing effect is good, the sand has good weather resistance, and the water resistance, the alkali resistance, the solvent resistance, the ultraviolet irradiation resistance, the mechanical stability and the corrosion resistance are good. Comparative example 1 has poor dyeing effect mainly because the wetting and dispersing ability to sand is poor, and the wrapping effect is influenced; the dyeing effect of comparative example 2 is better, but the epoxy resin is not resistant to acid and ultraviolet light mainly because the epoxy resin is not resistant to acid and ultraviolet light due to the structure of the epoxy resin.