CN103788304A - Amino resin-grafted modified water-based acrylic resin and preparation method thereof - Google Patents
Amino resin-grafted modified water-based acrylic resin and preparation method thereof Download PDFInfo
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- CN103788304A CN103788304A CN201410008498.6A CN201410008498A CN103788304A CN 103788304 A CN103788304 A CN 103788304A CN 201410008498 A CN201410008498 A CN 201410008498A CN 103788304 A CN103788304 A CN 103788304A
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Abstract
The invention discloses amino resin-grafted modified water-based acrylic resin and a preparation method thereof. The amino resin-grafted modified water-based acrylic resin is prepared from the following raw materials in parts by weight: 20-30 parts of water-based special mixed organic solvent, 20-30 parts of isobutanol etherified melamine resin, 2-5 parts of methacrylic acid, 5-10 parts of methyl methacrylate, 1-3 parts of propyl acrylate, 2-8 parts of hydroxyethyl acrylate, 8-20 parts of butyl acrylate, 2-8 parts of styrene and 1-2 parts of compound initiator. The amino resin-grafted modified water-based acrylic resin has the advantages of excellent comprehensive performance, low odor, high hardness, high strength, high adhesion, quick curing, excellent solvent resistance, weather resistance, corrosion resistance and heat stability, no discoloring or yellowing during high-temperature baking, safety, environmental friendliness and wide application prospect.
Description
Technical field
The present invention relates to a kind of aminoresin graft modification water soluble acrylic resin and preparation method thereof, belong to acrylic resin synthesis technical field.
Background technology
Acrylic resin is the resin of being made up of esters of acrylic acid and methyl acrylic ester and other olefinic type monomers copolymerization, by selecting different resin structures, different formula, production technique and solvent composition, can synthesize the acrylic resin of dissimilar, different performance and different application occasion.Water soluble acrylic resin is to be a certain amount of hydrophilic radical of grafting on water-insoluble resin originally, add in part hydrophilic organic solvent or water and after make water soluble resin.With organic solvent type resin-phase ratio, water soluble acrylic resin have price low, use safety, save the energy, reduce the features such as environmental pollution and public hazards.Water-borne acrylic resin due to acid and alkali-resistance, high rigidity, the feature such as fire-retardant, glossiness is high, sticking power is good, do not fade, good weatherability, chemicals-resistant are good, be commonly used for the base-material of water-borne coatings and water color ink.At present, the acrylic resin of China is take solvent-borne type product as main, and its VOC value is high, and along with new environmental regulation is put into effect, solvent type acrylic resin is subject to increasing challenge, and water soluble acrylic resin's practical value and development prospect more and more come into one's own.
Summary of the invention
The object of the present invention is to provide a kind of excellent combination property, aminoresin graft modification water soluble acrylic resin that the feature of environmental protection is good and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of aminoresin graft modification water soluble acrylic resin, is made up of the raw material of following weight part:
Water-soluble special mixed organic solvents 20-30
Isopropylcarbinol etherify melamine resin 20-30
Methacrylic acid 2-5
Methyl methacrylate 5-10
Propylene glycol monoacrylate 1-3
Hydroxyethyl acrylate 2-8
Butyl acrylate 8-20
Vinylbenzene 2-8
Composite initiator 1-2.
Aminoresin graft modification water soluble acrylic resin's a preparation method, comprises the following steps:
(1) isopropylcarbinol etherify melamine resin and water-soluble special mixed organic solvents are mixed, at logical N
2under the condition of protection, be warming up to 100-150 ℃, stir isopropylcarbinol etherify melamine resin is dissolved completely, stand-by;
(2) take the 60-80% of methacrylic acid, methyl methacrylate, Propylene glycol monoacrylate, Hydroxyethyl acrylate, butyl acrylate and composite initiator amount by formulation ratio, mix, be transferred in constant pressure funnel stand-by;
(3) mixing solutions step (1) being made adds in the reactor that agitator, prolong, thermometer, dropping funnel are housed, at logical N
2under the condition of protection, be warming up to 120-130 ℃, start slowly to drip the mixture that step (2) makes, in 2-3h, dropwise, insulation reaction 1-2h at 115-125 ℃, then add remaining composite initiator, in 15-20min, drip, continue to protect reaction temperature 2-3 h at 115-125 ℃, when transformation efficiency reaches 95% when above, be cooled to 50-60 ℃, adding triethylamine regulates pH value to 8-8.5, add appropriate deionized water dilution, ultrasonic dispersion 20-30min, ultrasonic power is 600-800W, be cooled to room temperature, discharging, obtain uniform and stable aminoresin graft modification water soluble acrylic resin.
Described water-soluble special mixed organic solvents by vinyl acetic monomer, dimethylbenzene, Virahol, ethylene glycol ether acetate, propandiol butyl ether by volume the ratio of 4:3:3:2:1 mix.
Described composite initiator is mixed according to the ratio of weight ratio 7:5:4:2:1 by peroxidized t-butyl perbenzoate, dibenzoyl peroxide, ditertiary butyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, azo-bis-isobutyl cyanide.
Beneficial effect of the present invention:
Product of the present invention had both had the features such as the high rigidity of aminoresin, good wear resistance, water tolerance, thermostability, solidified nature, the features such as the high gloss, the fullness ratio that have again acrylic resin concurrently are good, good weatherability, the aminoresin graft modification water soluble acrylic resin who makes has excellent over-all properties, low smell, high rigidity, high strength, high adhesive force, quick solidifying, there is the performances such as good solvent resistance, weathering resistance, erosion resistance, thermostability, nondiscoloration when high bake, brightness reversion not, safety and environmental protection, has broad application prospects.
Embodiment
Embodiment 1:
A kind of aminoresin graft modification water soluble acrylic resin, is made up of the raw material of following weight (kg):
Water-soluble special mixed organic solvents 30
Isopropylcarbinol etherify melamine resin 30
Methacrylic acid 2
Methyl methacrylate 8
Propylene glycol monoacrylate 2
Hydroxyethyl acrylate 6
Butyl acrylate 12
Vinylbenzene 2
Composite initiator 1.5.
Aminoresin graft modification water soluble acrylic resin's a preparation method, comprises the following steps:
(1) isopropylcarbinol etherify melamine resin and water-soluble special mixed organic solvents are mixed, at logical N
2under the condition of protection, be warming up to 100 ℃, stir isopropylcarbinol etherify melamine resin is dissolved completely, stand-by;
(2) take 80% of methacrylic acid, methyl methacrylate, Propylene glycol monoacrylate, Hydroxyethyl acrylate, butyl acrylate and composite initiator amount by formulation ratio, mix, be transferred in constant pressure funnel stand-by;
(3) mixing solutions step (1) being made adds in the reactor that agitator, prolong, thermometer, dropping funnel are housed, at logical N
2under the condition of protection; be warming up to 125 ℃; start slowly to drip the mixture that step (2) makes; in 3h, dropwise; insulation reaction 2h at 120 ℃, then adds remaining composite initiator, in 20min, drips; continue to protect reaction temperature 3 h at 120 ℃; when transformation efficiency reaches 95% when above, be cooled to 50 ℃, add triethylamine and regulate pH value to 8.2; add appropriate deionized water dilution; ultrasonic dispersion 30min, ultrasonic power is 600W, is cooled to room temperature; discharging, obtains uniform and stable aminoresin graft modification water soluble acrylic resin.
Described water-soluble special mixed organic solvents by vinyl acetic monomer, dimethylbenzene, Virahol, ethylene glycol ether acetate, propandiol butyl ether by volume the ratio of 4:3:3:2:1 mix.
Described composite initiator is mixed according to the ratio of weight ratio 7:5:4:2:1 by peroxidized t-butyl perbenzoate, dibenzoyl peroxide, ditertiary butyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, azo-bis-isobutyl cyanide.
Embodiment 2:
A kind of aminoresin graft modification water soluble acrylic resin, is made up of the raw material of following weight (kg):
Water-soluble special mixed organic solvents 25
Isopropylcarbinol etherify melamine resin 22
Methacrylic acid 3
Methyl methacrylate 5
Propylene glycol monoacrylate 1
Hydroxyethyl acrylate 2
Butyl acrylate 8
Vinylbenzene 6
Composite initiator 1.
Aminoresin graft modification water soluble acrylic resin's a preparation method, comprises the following steps:
(1) isopropylcarbinol etherify melamine resin and water-soluble special mixed organic solvents are mixed, at logical N
2under the condition of protection, be warming up to 125 ℃, stir isopropylcarbinol etherify melamine resin is dissolved completely, stand-by;
(2) take 70% of methacrylic acid, methyl methacrylate, Propylene glycol monoacrylate, Hydroxyethyl acrylate, butyl acrylate and composite initiator amount by formulation ratio, mix, be transferred in constant pressure funnel stand-by;
(3) mixing solutions step (1) being made adds in the reactor that agitator, prolong, thermometer, dropping funnel are housed, at logical N
2under the condition of protection; be warming up to 120 ℃; start slowly to drip the mixture that step (2) makes; in 2.5h, dropwise; insulation reaction 1h at 115 ℃, then adds remaining composite initiator, in 20min, drips; continue to protect reaction temperature 2 h at 115 ℃; when transformation efficiency reaches 95% when above, be cooled to 55 ℃, add triethylamine and regulate pH value to 8.0; add appropriate deionized water dilution; ultrasonic dispersion 20min, ultrasonic power is 800W, is cooled to room temperature; discharging, obtains uniform and stable aminoresin graft modification water soluble acrylic resin.
Described water-soluble special mixed organic solvents by vinyl acetic monomer, dimethylbenzene, Virahol, ethylene glycol ether acetate, propandiol butyl ether by volume the ratio of 4:3:3:2:1 mix.
Described composite initiator is mixed according to the ratio of weight ratio 7:5:4:2:1 by peroxidized t-butyl perbenzoate, dibenzoyl peroxide, ditertiary butyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, azo-bis-isobutyl cyanide.
Embodiment 3
A kind of aminoresin graft modification water soluble acrylic resin, is made up of the raw material of following weight (kg):
Water-soluble special mixed organic solvents 20
Isopropylcarbinol etherify melamine resin 20
Methacrylic acid 5
Methyl methacrylate 10
Propylene glycol monoacrylate 3
Hydroxyethyl acrylate 8
Butyl acrylate 20
Vinylbenzene 8
Composite initiator 2.
Aminoresin graft modification water soluble acrylic resin's a preparation method, comprises the following steps:
(1) isopropylcarbinol etherify melamine resin and water-soluble special mixed organic solvents are mixed, at logical N
2under the condition of protection, be warming up to 150 ℃, stir isopropylcarbinol etherify melamine resin is dissolved completely, stand-by;
(2) take 60% of methacrylic acid, methyl methacrylate, Propylene glycol monoacrylate, Hydroxyethyl acrylate, butyl acrylate and composite initiator amount by formulation ratio, mix, be transferred in constant pressure funnel stand-by;
(3) mixing solutions step (1) being made adds in the reactor that agitator, prolong, thermometer, dropping funnel are housed, at logical N
2under the condition of protection; be warming up to 130 ℃; start slowly to drip the mixture that step (2) makes; in 2h, dropwise; insulation reaction 1.5h at 120 ℃, then adds remaining composite initiator, in 15min, drips; continue to protect reaction temperature 2h at 125 ℃; when transformation efficiency reaches 95% when above, be cooled to 60 ℃, add triethylamine and regulate pH value to 8.5; add appropriate deionized water dilution; ultrasonic dispersion 25min, ultrasonic power is 700W, is cooled to room temperature; discharging, obtains uniform and stable aminoresin graft modification water soluble acrylic resin.
Described water-soluble special mixed organic solvents by vinyl acetic monomer, dimethylbenzene, Virahol, ethylene glycol ether acetate, propandiol butyl ether by volume the ratio of 4:3:3:2:1 mix.
Described composite initiator is mixed according to the ratio of weight ratio 7:5:4:2:1 by peroxidized t-butyl perbenzoate, dibenzoyl peroxide, ditertiary butyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, azo-bis-isobutyl cyanide.
The water soluble acrylic resin that above-described embodiment 1-3 is made is modulated into aluminium powder dip-coating paint, by the tank liquor being blown into after rare gas element, and dip-coating after standing 0.5h, film is in 140 ℃ of baking 30min, and film performance is as shown in table 1 following table:
Table 1 embodiment 1-3 water soluble acrylic resin and ortho-water soluble acrylic resin Performance Ratio are
| Project | Embodiment 1 | Embodiment 2 | Embodiment 2 | Ortho-water soluble acrylic resin |
| Paint film appearance | Smooth, smooth | Smooth, smooth | Smooth, smooth | Smooth, smooth |
| Paint film adhesion | 3 grades | 3 grades | 3 grades | 2 grades |
| Gloss of film degree (%) | 122 | 118 | 124 | 106 |
| Viscosity (is coated with 4 glasss, s) | 102 | 106 | 109 | 98 |
| Hardness | 0.714 | 0.735 | 0.728 | 0.672 |
| Snappiness (mandrel rod 7.35mm × 10mm × 1 ± 0.1mm) | Paint film is without reticulate pattern, crackle and the breakoff phenomenon such as peel off | Paint film is without reticulate pattern, crackle and the breakoff phenomenon such as peel off | Paint film is without reticulate pattern, crackle and the breakoff phenomenon such as peel off | Paint film has reticulate pattern, crackle and the breakoff phenomenon such as peels off |
| Shock strength (5.0J) | Paint film flawless, wrinkle and the phenomenon such as peel off | Paint film is without reticulate pattern, crackle and the breakoff phenomenon such as peel off | Paint film is without reticulate pattern, crackle and the breakoff phenomenon such as peel off | Paint film has reticulate pattern, crackle and the breakoff phenomenon such as peels off |
| Water tolerance (50h) (water-fast rear surface quality) | Paint film without bubbling, wrinkling, the phenomenon such as come off, get rusty | Paint film without bubbling, wrinkling, the phenomenon such as come off, get rusty | Paint film without bubbling, wrinkling, the phenomenon such as come off, get rusty | Paint film has foaming, wrinkling, the phenomenon such as come off, get rusty |
| Petrol-resistance (72h) (resistance to gasoline rear surface quality) | Paint film without elephant skin, bubble, peel off, the phenomenon such as deliquescing | Paint film without elephant skin, bubble, peel off, the phenomenon such as deliquescing | Paint film without elephant skin, bubble, peel off, the phenomenon such as deliquescing | The phenomenons such as paint film has elephant skin, bubbles, peels off, deliquescing |
Show from above to show and can find out, products obtained therefrom of the present invention, compared with prior art, has obvious advantage.
Claims (4)
1. an aminoresin graft modification water soluble acrylic resin, is characterized in that, is made up of the raw material of following weight part:
Water-soluble special mixed organic solvents 20-30
Isopropylcarbinol etherify melamine resin 20-30
Methacrylic acid 2-5
Methyl methacrylate 5-10
Propylene glycol monoacrylate 1-3
Hydroxyethyl acrylate 2-8
Butyl acrylate 8-20
Vinylbenzene 2-8
Composite initiator 1-2.
2. aminoresin graft modification water soluble acrylic resin's as claimed in claim 1 preparation method, is characterized in that comprising the following steps:
(1) isopropylcarbinol etherify melamine resin and water-soluble special mixed organic solvents are mixed, at logical N
2under the condition of protection, be warming up to 100-150 ℃, stir isopropylcarbinol etherify melamine resin is dissolved completely, stand-by;
(2) take the 60-80% of methacrylic acid, methyl methacrylate, Propylene glycol monoacrylate, Hydroxyethyl acrylate, butyl acrylate and composite initiator amount by formulation ratio, mix, be transferred in constant pressure funnel stand-by;
(3) mixing solutions step (1) being made adds in the reactor that agitator, prolong, thermometer, dropping funnel are housed, at logical N
2under the condition of protection, be warming up to 120-130 ℃, start slowly to drip the mixture that step (2) makes, in 2-3h, dropwise, insulation reaction 1-2h at 115-125 ℃, then add remaining composite initiator, in 15-20min, drip, continue to protect reaction temperature 2-3 h at 115-125 ℃, when transformation efficiency reaches 95% when above, be cooled to 50-60 ℃, adding triethylamine regulates pH value to 8-8.5, add appropriate deionized water dilution, ultrasonic dispersion 20-30min, ultrasonic power is 600-800W, be cooled to room temperature, discharging, obtain uniform and stable aminoresin graft modification water soluble acrylic resin.
3. aminoresin graft modification water soluble acrylic resin according to claim 1 and 2, it is characterized in that, described water-soluble special mixed organic solvents by vinyl acetic monomer, dimethylbenzene, Virahol, ethylene glycol ether acetate, propandiol butyl ether by volume the ratio of 4:3:3:2:1 mix.
4. aminoresin graft modification water soluble acrylic resin according to claim 1 and 2, it is characterized in that, described composite initiator is mixed according to the ratio of weight ratio 7:5:4:2:1 by peroxidized t-butyl perbenzoate, dibenzoyl peroxide, ditertiary butyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, azo-bis-isobutyl cyanide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410008498.6A CN103788304A (en) | 2014-01-09 | 2014-01-09 | Amino resin-grafted modified water-based acrylic resin and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410008498.6A CN103788304A (en) | 2014-01-09 | 2014-01-09 | Amino resin-grafted modified water-based acrylic resin and preparation method thereof |
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| CN103788304A true CN103788304A (en) | 2014-05-14 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106590475A (en) * | 2016-10-20 | 2017-04-26 | 太仓驰太电子新材料有限公司 | Novel acrylic ester glue and preparation method thereof |
| CN108504233A (en) * | 2018-03-26 | 2018-09-07 | 江阴恒兴涂料有限公司 | A kind of preparation method of low gloss extinction electrophoresis coating |
| CN109554056A (en) * | 2018-10-16 | 2019-04-02 | 韶关市合众化工有限公司 | It is a kind of functional from anti-flaming dope |
| CN111484577A (en) * | 2020-04-27 | 2020-08-04 | 广东工业大学 | β -dicarbonyl compound modified acrylic resin composition, preparation method and application thereof, and modified acrylic resin paint film |
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2014
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106590475A (en) * | 2016-10-20 | 2017-04-26 | 太仓驰太电子新材料有限公司 | Novel acrylic ester glue and preparation method thereof |
| CN108504233A (en) * | 2018-03-26 | 2018-09-07 | 江阴恒兴涂料有限公司 | A kind of preparation method of low gloss extinction electrophoresis coating |
| CN108504233B (en) * | 2018-03-26 | 2020-06-30 | 江阴恒兴涂料有限公司 | Preparation method of low-gloss extinction electrophoretic coating |
| CN109554056A (en) * | 2018-10-16 | 2019-04-02 | 韶关市合众化工有限公司 | It is a kind of functional from anti-flaming dope |
| CN109554056B (en) * | 2018-10-16 | 2021-06-08 | 韶关市合众化工有限公司 | Functional self-flame-retardant coating |
| CN111484577A (en) * | 2020-04-27 | 2020-08-04 | 广东工业大学 | β -dicarbonyl compound modified acrylic resin composition, preparation method and application thereof, and modified acrylic resin paint film |
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Application publication date: 20140514 |
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