CN104530322A - Waterborne acrylic modified alkyd resin and aqueous dispersion thereof - Google Patents
Waterborne acrylic modified alkyd resin and aqueous dispersion thereof Download PDFInfo
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- CN104530322A CN104530322A CN201410736521.3A CN201410736521A CN104530322A CN 104530322 A CN104530322 A CN 104530322A CN 201410736521 A CN201410736521 A CN 201410736521A CN 104530322 A CN104530322 A CN 104530322A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
Belonging to the field of waterborne paint, the invention relates to a waterborne acrylic modified alkyd resin and an aqueous dispersion thereof. The formula involves 11-30 parts of fatty acid, 11-40 parts of polyol, 0.5-2 parts of maleic anhydride, 12-30 parts of diacid, 0-0.033 part of a catalyst, 17-30 parts of a solvent, 2-6 parts of a (methyl) acrylic acid monomer, 5-30 parts of a (methyl) acrylic acid ester or styrene monomer, and 0.3-3 parts of an initiator. The waterborne acrylic modified alkyd resin obtained by reaction has an acid value of 18-25mgKOH/g and a solid content of 75-85%, and has strong stability in water. 4-6 parts of a neutralizing agent and 80-150 parts of water are added into 100 parts of the obtained resin, the materials are stirred and dispersed into the water to form an aqueous dispersion, then methylated amino resin, a substrate wetting agent and the like are added into the aqueous dispersion to prepare waterborne alkyd amino bake type varnish, or various fillers and pigments and additives are added to be blended into colored paint of various colors by an appropriate technology. The paint film has good hardness, adhesion and water resistance, and emission of VOC is greatly reduced in the construction process.
Description
Technical field
The present invention belongs to water-borne coatings field, and it is a kind of waterborne acrylic modified alkyd resins and water dispersion thereof.
Background technology
Water-borne coatings replaces solvent with water, can reduce the discharge of VOC to a great extent, be reduced to less than 15% from about 70% of solvent-thinned paint, its environmental acceptability is much higher than solvent type coating, and save petroleum resources, reduce disaster hidden-trouble, improve operating environment.
Alkyd baking vanish occupies very large share at Coating Market, alkyd baking vanish application is originally with dimethylbenzene always, vinyl acetic monomer, N-BUTYL ACETATE equal solvent is diluent solvent type coating, has very large smell, the health of serious harm people, and be easy to initiation fire, and these risks evaded by water-borne coatings, greatly reduced the discharge of VOC, replacing solvent also greatly to save petroleum resources with water, is the novel product of environmental protection always.
As the main film forming matter of alkyd baking vanish, resin plays conclusive effect.Even if the present invention is so always for the waterborne acrylic modified alkyd resins of water alcohol acid baking vanish, can well replace solvent based coating Synolac, its performance can meet the demands.
Summary of the invention
The invention provides a kind of water-based amino-stoving varnish, the formula of colored paint use acrylic acid modified alkyd resin and water dispersion.
The present invention belongs to water-borne coatings field, is a kind of waterborne acrylic modified alkyd resins and water dispersion thereof.Wherein lipid acid 11-30 part in formula, polyvalent alcohol 11-40 part, MALEIC ANHYDRIDE 0.5-2 part, diprotic acid 12-30 part, catalyzer 0-0.033 part, solvent 17-30 part, (methyl) Acrylic Acid Monomer 2-6 part, (methyl) esters of acrylic acid or styrene monomer 5-30 part, initiator 0.3-3 part.
Preferred proportion is lipid acid 13-25 part, polyvalent alcohol 13-32 part, MALEIC ANHYDRIDE 0.7-1.5 part, diprotic acid 14-24 part, catalyzer 0-0.03 part, solvent 17-30 part, (methyl) Acrylic Acid Monomer 2-4 part, (methyl) esters of acrylic acid or styrene monomer 7-17 part, initiator 0.5-2 part.
A preparation method for waterborne acrylic modified alkyd resins and water dispersion thereof, concrete steps are:
(1) by the lipid acid in formula, polyvalent alcohol, MALEIC ANHYDRIDE, polyprotonic acid, catalyzer adds in reaction vessel according to proportioning, is under agitation progressively warming up to 180-240 DEG C, deviate from micromolecular water in reaction process, control column temperature 98-105 DEG C, react to acid number and be less than 10mgKOH/g;
(2) be cooled to below solvent boiling point, add solvent 7-10 part and stir, and temperature is remained on 110-150 DEG C;
(3) mixture of (methyl) vinylformic acid 2-6 part and (methyl) acrylic ester monomer, styrene monomer 5-30 part and initiator 0.3-1 part is at the uniform velocity dripped with 2.5-3hr, after dripping, residue initiator 0-2 part is become 3 parts, per hourly add portion, finally continue at 110-150 DEG C of reaction 3hr;
(4) be cooled to below added solvent boiling point, add remaining 10-20 part solvent, stir, obtain waterborne acrylic modified alkyd resins.Wherein the acid number of resin is at 18-25mgKOH/g, admittedly containing 75-85%.
The preparation method of waterborne acrylic modified alkyd resins water dispersion, the resin obtained 100 parts, adds neutralizing agent 4-6 part, water 80-150 part, and dispersed with stirring forms waterborne acrylic modified alkyd resins water dispersion.
Add methyl-etherified aminoresin, substrate wetting agents etc. by waterborne acrylic modified alkyd resins water dispersion, the amino baking-type varnish of water alcohol acid can be obtained, or add various color stuffing and the auxiliary agent colored paint through suitable technique furnishing shades of colour.The hardness that various paint class paint film has had, sticking power, water tolerance, greatly reduces VOC discharge in construction process.
The molecular formula of resin or skeleton symbol
Lipid acid described in formula is behenic acid, cocinic acid, linolenic acid, one or more in tall oil acid.
Polyvalent alcohol described in formula is TriMethylolPropane(TMP), tetramethylolmethane, glycerine, neopentyl glycol, one or more in propylene glycol.
Diprotic acid described in formula is phthalic anhydride, hexanodioic acid, m-phthalic acid, one or more in terephthalic acid.
Described catalyzer is titanium tetraethoxide, four n-propyl alcohol titaniums, four n-butyl titaniums, four (20 ethylhexanol) titanium, butyl titanium isopropylate, Mono-n-butyltin, one or more of Dibutyltin oxide.
Described solvent is butyl glycol ether, butanols, butyl, propandiol butyl ether, dipropylene, propylene glycol monomethyl ether, Virahol, sec-butyl alcohol, one or more in the water-soluble alcohol ether solvents such as ethanol.
Described Acrylic Acid Monomer is one or both of acrylic or methacrylic acid, provides resin water-soluble.
Described (methyl) acrylic ester monomer is (methyl) butyl acrylate, vinylbenzene, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, isobornyl methacrylate, several in methyl methacrylate.
Described initiator is perbenzoic acid, the benzoyl peroxide tert-butyl ester, ditertiary butyl peroxide, two t-amyl peroxy compounds, hydrogen phosphide cumene, one or both in peroxidation (2 ethyl hexanoic acid) tert-butyl ester.
Described neutralizing agent is N, N-dimethylethanolamine, triethylamine, N-ethylmorpholine, ammoniacal liquor, one or several in AMP95 (2-amino-2-methyl-1-propanol).
Advantage of the present invention
The present invention with a kind of Synolac for core, shell is become with (methyl) acrylic acid and propynoic acid ester class monomer copolymerization of band acidic group, carboxyl on vinylformic acid provides water soluble group, in and salify after be distributed in water, Synolac is caused to be core, ester bond is well protected, be conducive to the raising of the stability to hydrolysis of ester bond, make resin in water, have good stability, hydroxyl in the remaining hydroxyl of Synolac and acrylics monomer provides a large amount of oh groups, can be cross-linked with the carrying out of the linking agents such as aminoresin, after making the temperature baking of prepared paint more than 120 DEG C, form film, there is certain protectiveness and decorative effect.
Resin is made water soluble resin by the present invention, is thinner, greatly reduces the discharge of VOC, be reduced to less than 15%, improve environment from about 70% of solvent-thinned paint, reduce the injury to human body, also reduce the hidden danger of fire simultaneously with water.
So product of the present invention can be applied to aminoresin, urea-formaldehyde resin etc. are crosslinked makes baking-type coating, the hardness had, sticking power, water tolerance, and construction process gather greatly reduce VOC discharge, have very large benefit to environment protection.
Embodiment
Embodiment 1
By soy(a)-bean oil fatty acid 23 parts, TriMethylolPropane(TMP) 20 parts, MALEIC ANHYDRIDE 0.93 part, phthalic anhydride 10 parts, hexanodioic acid 5.5 parts, add in reaction vessel, stir and be progressively warming up to 220 DEG C, control column temperature less than 105 DEG C, reaction to acid number is less than 10mgKOH/g, be cooled to 160 DEG C, add butyl glycol ether 7 parts to stir, and temperature is remained on 115 DEG C, then 2 parts, vinylformic acid and methyl methacrylate 11 parts is at the uniform velocity dripped with 2.5-3hr, butyl acrylate 1.8 parts, Hydroxyethyl acrylate 1.6 parts, the mixture that initiator perbenzoic acid is 0.5 part, at 130 DEG C, initiator peroxidized t-butyl perbenzoate 0.99 part is divided into 3 parts after dripping, per hourly add portion, finally continue at reaction 3hr at 130 DEG C, be cooled to 80 DEG C, add remaining 11 parts of butanols, stir, obtain aqueous acrylic acid modified alkyd resin, wherein the acid number of resin is at about 18mgKOH/g, admittedly containing 80%.Get the above waterborne acrylic modified alkyd resins obtained, dilute according to the ratio propylene glycol monomethyl ether of 1:1, viscosity 50-200cp after dilution.The resin obtained 100 parts, adds neutralizing agent N, N-dimethylethanolamine 5 parts, then dispersed with stirring is in 120 parts of water, then adds 15 parts, part methyl-etherified aminoresin, substrate wetting agents 0.4 part, alcohol acid amido baking varnish can be obtained, be sprayed on the tinplate after polishing, 140 DEG C of baking 30min, gained hardness of paint film H, impacts 50cm, snappiness 1mm, adhesion 1 grade, water-fast, salt spray resistance 120hr is non-foaming, non-corrosive, VOC can be controlled in less than 15%, and stability in storage can reach half a year more than.
Embodiment 2
By cocinic acid 17 parts, TriMethylolPropane(TMP) 21 parts, MALEIC ANHYDRIDE 1 part, phthalic anhydride 10.5 parts, hexanodioic acid 6.5 parts, add in reaction vessel, stir and be progressively warming up to 220 DEG C, control column temperature less than 105 DEG C, reaction to acid number is less than 10mgKOH/g, be cooled to 160 DEG C, add butyl glycol ether 8 parts to stir, and temperature is remained on 115 DEG C, then 2.2 parts, vinylformic acid and methyl methacrylate 12 parts is at the uniform velocity dripped with 2.5-3hr, butyl acrylate 1.9 parts, Hydroxyethyl acrylate 1.7 parts, the mixture that initiator perbenzoic acid is 0.6 part, at 130 DEG C, initiator peroxidized t-butyl perbenzoate 1 part is divided into 3 parts after dripping, per hourly add portion, finally continue at reaction 3hr at 130 DEG C, be cooled to 80 DEG C, add remaining 12 parts of butanols, stir, obtain aqueous acrylic acid modified alkyd resin, wherein the acid number of resin is at about 19mgKOH/g, solid content 79%.Get the above waterborne acrylic modified alkyd resins obtained, dilute according to the ratio propylene glycol monomethyl ether of 1:1, viscosity 50-200cp after dilution.The resin obtained 100 parts, add neutralizing agent N, N-dimethylethanolamine 5 parts, then dispersed with stirring is in 100-part water, then adds 20 parts, part methyl-etherified aminoresin, substrate wetting agents 0.4 part, alcohol acid amido baking varnish can be obtained, be sprayed on the tinplate after polishing, 140 DEG C of bakings 30min, gained hardness of paint film H, impact 50cm, snappiness 1mm, adhesion 1 grade, water-fast, salt spray resistance 120hr is non-foaming, non-corrosive, VOC can be controlled in less than 15%, and resin stability in storage can reach half a year more than.
Embodiment 3
By soy(a)-bean oil fatty acid 14.2 parts, TriMethylolPropane(TMP) 13.4 parts, neopentyl glycol 10.4 parts, MALEIC ANHYDRIDE 1 part, phthalic anhydride 16.2 parts, hexanodioic acid 5.8 parts, organotin catalysts 0.03 part, add in reaction vessel, stir and be progressively warming up to 220 DEG C, control column temperature less than 105 DEG C, reaction to acid number is less than 10mgKOH/g, be cooled to 160 DEG C, add butyl glycol ether 9 parts to stir, and temperature is remained on 145 DEG C, then 2.5 parts, vinylformic acid and methyl methacrylate 5.6 parts is at the uniform velocity dripped with 2.5-3hr, vinylbenzene 5.6 parts, Hydroxyethyl acrylate 1.6 parts, the mixture that initiator ditertiary butyl peroxide is 0.6 part, at 145 DEG C of reaction 3hr after dripping, be cooled to 80 DEG C, add 11 parts of propylene glycol monomethyl ethers, stir. obtain aqueous acrylic acid modified alkyd resin, wherein the acid number of resin is at about 22mgKOH/g, admittedly containing 79%.Get the above waterborne acrylic modified alkyd resins obtained, dilute according to the ratio propylene glycol monomethyl ether of 1:1, viscosity 50-200cp after dilution.The resin obtained 100 parts, adds neutralizing agent N, N-dimethylethanolamine 5 parts, then dispersed with stirring is in 100 parts of water, then adds 20 parts, part methyl-etherified aminoresin, substrate wetting agents 0.4 part, alcohol acid amido baking varnish can be obtained, be sprayed on the tinplate after polishing, 140 DEG C of baking 30min, gained hardness of paint film H, impacts 50cm, snappiness 1mm, adhesion 1 grade, water-fast, salt spray resistance 120hr is non-foaming, non-corrosive.VOC can be controlled in less than 15%.The resin stability in storage that this formula obtains can reach half a year more than.
Embodiment 4
By soy(a)-bean oil fatty acid 24 parts, glycerine 14 parts, MALEIC ANHYDRIDE 0.9 part, phthalic anhydride 16.7 parts, add in reaction vessel, stir and be progressively warming up to 220 DEG C, control column temperature 105 DEG C, reaction to acid number is less than 10mgKOH/g, be cooled to 115 DEG C, then 4 parts, vinylformic acid and methyl methacrylate 7.7 parts is at the uniform velocity dripped with 2.5-3hr, the mixture that initiator perbenzoic acid is 0.6 part, after dripping, peroxidized t-butyl perbenzoate 0.2 part is added in 130 DEG C of reaction 3hr, be cooled to 80 DEG C, add 10 parts of butanols, 5 parts of butyl glycol ethers, stir, obtain aqueous acrylic acid modified alkyd resin, wherein the acid number of resin is at about 18mgKOH/g, admittedly containing 80%.Get the above waterborne acrylic modified alkyd resins obtained, dilute according to the ratio propylene glycol monomethyl ether of 1:1, viscosity 50-200cp after dilution.The resin obtained 100 parts, adds neutralizing agent N, N-dimethylethanolamine 5 parts, then dispersed with stirring is in 100 parts of water, then adds 15 parts, part methyl-etherified aminoresin, substrate wetting agents 0.4 part, alcohol acid amido baking varnish can be obtained, be sprayed on the tinplate after polishing, 140 DEG C of baking 30min, gained hardness of paint film H, impacts 50cm, snappiness 1mm, adhesion 1 grade, water-fast, salt spray resistance 120hr is non-foaming, non-corrosive.The resin VOC that this formula obtains controls below 15%, and stability in storage can reach half a year more than.
Claims (10)
1. a waterborne acrylic modified alkyd resins, it is characterized in that: each component of synthesizing formula is lipid acid 11-30 part, polyvalent alcohol 11-40 part, MALEIC ANHYDRIDE 0.5-2 part, diprotic acid 12-30 part, catalyzer 0-0.033 part, solvent 17-30 part, (methyl) Acrylic Acid Monomer 2-6 part, (methyl) esters of acrylic acid or styrene monomer 5-30 part, initiator 0.3-3 part.
2. waterborne acrylic modified alkyd resins as claimed in claim 1, it is characterized in that: each component of synthesizing formula is lipid acid 13-25 part, polyvalent alcohol 13-32 part, MALEIC ANHYDRIDE 0.7-1.5 part, diprotic acid 14-24 part, catalyzer 0-0.03 part, solvent 17-30 part, (methyl) Acrylic Acid Monomer 2-4 part, (methyl) esters of acrylic acid or styrene monomer 7-17 part, initiator 0.5-2 part.
3. waterborne acrylic modified alkyd resins as claimed in claim 1, is characterized in that: lipid acid described in formula is behenic acid, cocinic acid, linolenic acid, one or more in tall oil acid.
4. waterborne acrylic modified alkyd resins as claimed in claim 1, is characterized in that: polyvalent alcohol described in formula is TriMethylolPropane(TMP), tetramethylolmethane, glycerine, neopentyl glycol, one or more in propylene glycol.
5. waterborne acrylic modified alkyd resins as claimed in claim 1, is characterized in that: diprotic acid described in formula is phthalic anhydride, hexanodioic acid, m-phthalic acid, one or more in terephthalic acid.
6. waterborne acrylic modified alkyd resins as claimed in claim 1, is characterized in that: described catalyzer is titanium tetraethoxide, four n-propyl alcohol titaniums, four n-butyl titaniums, four (20 ethylhexanol) titanium, butyl titanium isopropylate, Mono-n-butyltin, one or more of Dibutyltin oxide.
7. waterborne acrylic modified alkyd resins as claimed in claim 1, it is characterized in that: described solvent is butyl glycol ether, butanols, butyl, propandiol butyl ether, dipropylene, propylene glycol monomethyl ether, Virahol, sec-butyl alcohol, one or more in the water-soluble alcohol ether solvents such as ethanol.
8. waterborne acrylic modified alkyd resins as claimed in claim 1, is characterized in that: described Acrylic Acid Monomer is one or both of acrylic or methacrylic acid; Described (methyl) acrylic ester monomer is (methyl) butyl acrylate, vinylbenzene, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, isobornyl methacrylate, several in methyl methacrylate.
9. waterborne acrylic modified alkyd resins as claimed in claim 1, it is characterized in that: described initiator is perbenzoic acid, the benzoyl peroxide tert-butyl ester, ditertiary butyl peroxide, two t-amyl peroxy compounds, hydrogen phosphide cumene, one or both in peroxidation (2 ethyl hexanoic acid) tert-butyl ester.
10. a waterborne acrylic modified alkyd resins dispersion, it adopts arbitrary formula range in claim 1-9 to obtain waterborne acrylic modified alkyd resins, get 100 parts and add neutralizing agent 4-6 part, water 80-150 part, dispersed with stirring forms waterborne acrylic modified alkyd resins water dispersion, wherein neutralizing agent is N, N-dimethylethanolamine, triethylamine, N-ethylmorpholine, ammoniacal liquor, one or several in AMP95 (2-amino-2-methyl-1-propanol).
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410736521.3A CN104530322A (en) | 2014-12-04 | 2014-12-04 | Waterborne acrylic modified alkyd resin and aqueous dispersion thereof |
| CN201510249716.XA CN104877514A (en) | 2014-12-04 | 2015-05-15 | Amino resin stoving varnish containing water-borne acrylic modified alkyd resin and preparation method thereof |
| CN201510313955.7A CN104877084A (en) | 2014-12-04 | 2015-06-09 | Aqueous acrylic acid modified alkyd resin and water dispersion thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410736521.3A CN104530322A (en) | 2014-12-04 | 2014-12-04 | Waterborne acrylic modified alkyd resin and aqueous dispersion thereof |
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| CN104530322A true CN104530322A (en) | 2015-04-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201410736521.3A Pending CN104530322A (en) | 2014-12-04 | 2014-12-04 | Waterborne acrylic modified alkyd resin and aqueous dispersion thereof |
| CN201510249716.XA Pending CN104877514A (en) | 2014-12-04 | 2015-05-15 | Amino resin stoving varnish containing water-borne acrylic modified alkyd resin and preparation method thereof |
| CN201510313955.7A Pending CN104877084A (en) | 2014-12-04 | 2015-06-09 | Aqueous acrylic acid modified alkyd resin and water dispersion thereof |
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| CN201510249716.XA Pending CN104877514A (en) | 2014-12-04 | 2015-05-15 | Amino resin stoving varnish containing water-borne acrylic modified alkyd resin and preparation method thereof |
| CN201510313955.7A Pending CN104877084A (en) | 2014-12-04 | 2015-06-09 | Aqueous acrylic acid modified alkyd resin and water dispersion thereof |
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| CN104877514A (en) | 2015-09-02 |
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