CN109593335A - One kind modified water-based alkyd resin of polystyrene microsphere containing carboxyl and preparation method thereof - Google Patents
One kind modified water-based alkyd resin of polystyrene microsphere containing carboxyl and preparation method thereof Download PDFInfo
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- CN109593335A CN109593335A CN201811521757.XA CN201811521757A CN109593335A CN 109593335 A CN109593335 A CN 109593335A CN 201811521757 A CN201811521757 A CN 201811521757A CN 109593335 A CN109593335 A CN 109593335A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/08—Polyesters modified with higher fatty oils or their acids, or with resins or resin acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
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- Wood Science & Technology (AREA)
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Abstract
The present invention relates to a kind of modified water-based alkyd resins of polystyrene microsphere containing carboxyl, neutralize and are made after being reacted under the effect of the catalyst by refined plant oil, polystyrene microsphere containing carboxyl, polyalcohol, organic acid, benzoic acid；Originally it returns and a kind of preparation method of modified water-based alkyd resin of polystyrene microsphere containing carboxyl is provided；The modified water-based alkyd resin of polystyrene microsphere containing carboxyl produced by the present invention, with high rigidity and storage stability, manufactured film has excellent adhesive force, wearability, hot water resistance, heat-resisting quantity, resistance to ag(e)ing, crack resistance, corrosion resistance and high photosensitiveness, can be used for aqueous wooden ware and applies production, water-based anticorrosive paint, aqueous engineering coating, aqueous concrete paint and aqueous fire-proof coating.
Description
Technical field
The present invention relates to a kind of modified water-based alkyd resins, more particularly to a kind of modified water of polystyrene microsphere containing carboxyl
Property alkyd resin and preparation method thereof, belongs to aqueous functional resin technology field.
Technical background
Alkyd resin is a kind of highly important chemical products, has extensive purposes in fields such as coating, ink.Alkyd
Resin passes through modified alkyd resin, and due to containing more unsaturated bond and hydroxyl, it is dry that air oxidation may be implemented
Or baking crosslinking, and since its synthesis material is easy to get, it is very widely used in coating for various purposes.Current alkyd
Resin is still still, with the development of economy with the requirement of environmental protection, Water-borne Modification of Alkyd Resin to be had become hair based on solvent type
Exhibition trend.
Phthalic resin coating has good brushability and wetability, but its dried coating film is slow, hardness is low, water resistance,
It is corrosion-resistant it is poor, weatherability is bad.Since water is nontoxic, tasteless, non-ignitable and cheap, solvent is made by water not only reduces cost, together
When, VOC is reduced, so aqueous alkide resin has obtained development faster.Nineteen fifty, people have studied on strand containing parent
The internal emulsification type aqueous alkide resin of water base group；Nineteen ninety, research introduce ionic carboxylic with trimellitic anhydride on strand
The aqueous alkide resin of base；Jiang Hongmin et al., which has studied, is modified it by introducing trimellitic anhydride in polyacid, makes
It is distributed hydrophilic carboxyl on macromolecular chain, obtains water dispersible by neutralizing, so that aqueous alkide resin be made.
The modification of aqueous alkide resin has acid anhydrides, styrene, acrylic acid, isocyanates, organosilicon, epoxy resin, organic
The methods of fluorine, nano material: anhydride modified alkyd resin, which can improve resin, hydrophily, rate of drying and storage stability；
Phenylethene modified alkyd resin can improve the performances such as the solvent resistance of resin, storage stability, and not influence transparency, together
When reduce the cost of resin；Acrylic acid modified alkyd resin have excellent colour retention, gloss retention, weatherability, durability,
Corrosion resistance and quick-drying, high rigidity also have the characteristics that solvent-borne alkyd resins are possessed；Isocyanate-modified alkyd tree
Hardness, weatherability, corrosion resistance, water resistance and the yellowing resistance of coating can be improved in rouge；Organic-silicon-modified alkyd resin has
Excellent heat resistance and electrical insulating property, coating have wearability, high temperature resistant, humidity, water resistance, atmospheric corrosion resistance and resistance to
Hou Xing；The alkyd resin of epoxy resin modification can improve hardness, water resistance, oil resistivity, corrosion resistance and the adhesive force of coating；Have
The alkyd resin of machine fluorine richness has excellent weatherability, water resistance, oil resistivity, corrosion resistance and self-cleaning；Nano-oxide
Modified alkyd resin improves crack resistance, hardness, antibiotic property and the anti-uv-ray of coating.
Polystyrene functional microballoon can prepare ion exchange resin, chelating resin and absorption resin；It can synthetic catalyst load
Body is for organic synthesis and combinatorial chemistry system；The function high score for large biological molecule immobilization, separation, purifying can also be prepared
Sub- microballoon and chromatographic stationary phases.But polystyrene functional microballoon is for the modification of aqueous alkide resin that there is not yet reported.
Summary of the invention
The purpose of the present invention is intended to provide a kind of containing more carboxyl polystyrene microsphere modified water-based alkyd resins and its preparation
Method.
The polystyrene microsphere containing carboxyl is polystyrene-maleic anhydride microballoon (PS-MA), polystyrene-phthalic anhydride is micro-
Ball (PS-PA), polystyrene-itaconic acid microballoon (PS-IA) contain more than two carboxyls in microballoon molecular structure, pass through
Microballoon is grafted in alkyd resin strand by esterification, can effectively improve the hardness after aqueous alkide resin solidifies, cracking resistance
Property, gloss, temperature tolerance, water resistance, wearability and corrosion resistance.
In order to overcome the shortcomings of the prior art and insufficient, the present invention takes following technical scheme, and described one kind is poly- containing carboxyl
Phenylethylene micro ball modified water-based alkyd resin, according to parts by weight, main component are as follows: 12.0~25.0 parts of refined plant oil,
5.0~10.0 parts of polystyrene microspheres containing carboxyl, 8.0~12.0 parts of polyalcohols, 8.0~15.0 parts of organic acids, 2~5.0 parts of benzene
Formic acid, 0.05~0.5 part of catalyst, 2.0~5.0 parts of neutralizers, 45.0~60.0 parts of deionized waters.
But in preparation process, it is sufficiently molten in methylene chloride and xylene mixture solvent will first to contain carboxyl polystyrene microsphere
It is swollen, be conducive to esterification progress；In addition alkyd resin preparation process is flowed back and is adjusted using dimethylbenzene and is viscous, finally in vacuum
Under be distilled off.
The polystyrene-maleic anhydride microballoon passes through (patent " the dispersion copolymerization method preparation applied of dispersion copolymerization method
Polystyrene-maleic anhydride microballoon " in description) or self-stabilization precipitation polymerization method be made；The polystyrene-phthalic anhydride microballoon
It is made by acylating agent suspension copolymerization method；The polystyrene-itaconic acid microballoon passes through dispersion copolymerization method or radiation copolymerization method
It is made.
The refined plant oil be one of linseed oil, soybean oil, castor oil, tall oil, coconut oil, rapeseed oil or
Several combinations.
The organic acid is one of phthalic anhydride, cis-butenedioic anhydride, tetrahydrophthalic anhydride, M-phthalic acid, hexanedioic acid, decanedioic acid or several
The combination of kind.
The polyalcohol is ethylene glycol, propylene glycol, butanediol, hexylene glycol, neopentyl glycol, Diethylene Glycol, a contracting
The combination of one or more of dipropylene glycol, trimethylolpropane, glycerol, trimethylolethane, pentaerythrite.
The catalyst is Dibutyltin oxide, Dibutyltin oxide chloride, dibutyl tin dilaurate, dibutyl
At least one of oxalic acid tin, monobutyl-tin-trichloride, lithium hydroxide.
The neutralizer is triethylamine, N, the group of one or more of N- dimethylethanolamine, 2- amino -1- propyl alcohol
It closes.
The present invention provides a kind of preparation method of modified water-based alkyd resin of polystyrene microsphere containing carboxyl, preparation step
It is as follows:
A), polystyrene microsphere containing carboxyl is first added to the in the mixed solvent of methylene chloride and dimethylbenzene, stirring is to filling
Divide swelling, goes after supernatant liquor for use；
B), in the reactor that thermometer, condenser, water segregator, blender are housed, by formulation weight ratio, sequentially add
Refined plant oil, organic acid, polyalcohol, catalyst and dimethylbenzene, stir at low speed down and are passed through N2, to remove the O in reaction kettle2；
C), 105 DEG C are heated to flowing back, and are kept the temperature 0.5h, are removed part water, be continuously heating to 140~160 DEG C, to
After material dissolution, the polystyrene microsphere containing carboxyl and benzoic acid being swollen is added, insulation reaction 1h then heats to 180 DEG C,
1~2h of insulation reaction is warming up to 210~220 DEG C, 2~3h of insulation reaction with 20 DEG C/h speed, reacts the water that generates with dividing water
Device separates；
D), hereafter primary every 0.5h measurement acid value, stop reaction when the acid value of detection reaches Theoretical Design value, and drop
Solvent is evaporated off to 120 DEG C in temperature under vacuum, then is cooled to 50 DEG C, and neutralizer is added, is dispersed with stirring 20~30min, addition go from
Sub- water continues to stir 0.5h, and filtering obtains the modified water-based alkyd resin of polystyrene microsphere containing carboxyl.
One kind modified water-based alkyd resin of polystyrene microsphere containing carboxyl produced by the present invention, has high rigidity and storage steady
Qualitative, manufactured film has excellent adhesive force, wearability, hot water resistance, heat-resisting quantity, resistance to ag(e)ing, crack resistance, corrosion resistant
Corrosion and high photosensitiveness can be used for aqueous wooden ware and apply production, water-based anticorrosive paint, aqueous engineering coating, aqueous concrete paint and water
Property fireproof coating.
Specific embodiment
One kind modified water-based alkyd resin of polystyrene microsphere containing carboxyl of the invention is done into one below with reference to embodiment
The description of step.It is understood that specific embodiment described herein is used only for explaining related invention, rather than to the invention
Restriction.
Embodiment 1
A kind of microsphere modified aqueous alkide resin of PS-MA, preparation step are as follows:
A), first 6.0 parts of PS-MA microballoon are added to the in the mixed solvent of 20.0 parts of methylene chloride and 10.0 parts of dimethylbenzene,
Stirring is gone after supernatant liquor for use to abundant swelling；
B), in the reactor that thermometer, condenser, water segregator, blender are housed, by formulation weight ratio, sequentially add
Refine 16.0 parts of linseed oil, 7.6 parts of phthalic anhydride, M-phthalic acid 4.5,2.6 parts of neopentyl glycol, 6.8 parts of trimethylolethane, two fourths
0.3 part of base tin dilaurate tin, 4.5 parts of dimethylbenzene, stir at low speed down and are passed through N2, to remove the O in reaction kettle2；
C), 105 DEG C are heated to flowing back, and are kept the temperature 0.5h, are removed part water, be continuously heating to 140~160 DEG C, to
After material dissolution, 6.0 parts and 2.8 parts of benzoic acid of PS-MA microballoon be swollen are added, insulation reaction 1h then heats to 180
DEG C, insulation reaction 1.5h is warming up to 210~220 DEG C, insulation reaction 3h with 20 DEG C/h speed, reacts the water that generates with dividing water
Device separates；
D), hereafter primary every 0.5h measurement acid value, stop reaction when the acid value of detection reaches Theoretical Design value, and drop
Solvent is evaporated off to 120 DEG C in temperature under vacuum, then is cooled to 50 DEG C, is added 3.2 parts of triethylamine, is dispersed with stirring 20~30min, adds
Enter 50.0 parts of deionized water, continues to stir 0.5h, the solid microsphere modified water alcohol acid tree of PS-MA containing for 50.6% is made in filtering
Rouge.
Embodiment 2
A kind of microsphere modified aqueous alkide resin of PS-PA, preparation step are as follows:
A), first 8.0 parts of PS-PA microballoon are added to the in the mixed solvent of 25.0 parts of methylene chloride and 12.0 parts of dimethylbenzene,
Stirring is gone after supernatant liquor for use to abundant swelling；
B), in the reactor that thermometer, condenser, water segregator, blender are housed, by formulation weight ratio, sequentially add
Refine 15.0 parts of soya-bean oil, 5.6 parts of cis-butenedioic anhydride, M-phthalic acid 6.0,2.4 parts of adipic acid, 3.0 parts of butanediol, trimethylolethane
6.0 parts, 0.3 part of dibutyl tin dilaurate, 5.0 parts of dimethylbenzene, stir at low speed down and are passed through N2, to remove the O in reaction kettle2；
C), 105 DEG C are heated to flowing back, and are kept the temperature 0.5h, are removed part water, be continuously heating to 140~160 DEG C, to
After material dissolution, 8.0 parts and 2.2 parts of benzoic acid of PS-PA microballoon be swollen are added, insulation reaction 1h then heats to 180
DEG C, insulation reaction 2h is warming up to 210~220 DEG C, insulation reaction 2.5h with 20 DEG C/h speed, reacts the water that generates with dividing water
Device separates；
D), hereafter primary every 0.5h measurement acid value, stop reaction when the acid value of detection reaches Theoretical Design value, and drop
Solvent is evaporated off to 120 DEG C in temperature under vacuum, then is cooled to 50 DEG C, is added 2.5 parts of triethylamine, is dispersed with stirring 20~30min, adds
Enter 49.0 parts of deionized water, continues to stir 0.5h, the solid microsphere modified water alcohol acid tree of PS-PA containing for 51.2% is made in filtering
Rouge.
Embodiment 3
A kind of microsphere modified aqueous alkide resin of PS-IA, preparation step are as follows:
A), first 5.0 parts of PS-IA microballoon are added to the in the mixed solvent of 18.0 parts of methylene chloride and 10.0 parts of dimethylbenzene,
Stirring is gone after supernatant liquor for use to abundant swelling；
B), in the reactor that thermometer, condenser, water segregator, blender are housed, by formulation weight ratio, sequentially add
20.0 parts of refined caster oil, 8.5 parts of phthalic anhydride, M-phthalic acid 5.0,2.5 parts of neopentyl glycol, 6.0 parts of glycerol, lithium hydroxide 0.3
Part, 6.0 parts of dimethylbenzene, stir at low speed down and are passed through N2, to remove the O in reaction kettle2；
C), 105 DEG C are heated to flowing back, and are kept the temperature 0.5h, are removed part water, be continuously heating to 140~160 DEG C, to
After material dissolution, 5.0 parts and 2.2 parts of benzoic acid of PS-IA microballoon be swollen are added, insulation reaction 1h then heats to 180
DEG C, 1~2h of insulation reaction is warming up to 210~220 DEG C, 2~3h of insulation reaction with 20 DEG C/h speed, and the water that reaction generates is used
Water segregator separates；
D), hereafter primary every 0.5h measurement acid value, stop reaction when the acid value of detection reaches Theoretical Design value, and drop
Solvent is evaporated off to 120 DEG C in temperature under vacuum, then is cooled to 50 DEG C, and N is added, 2.0 parts of N- dimethylethanolamine, is dispersed with stirring 20
~30min is added 48.5 parts of deionized water, continues stirring 0.5h, and filtering is made solid microsphere modified containing the PS-IA for being 51.6%
Aqueous alkide resin.
By in the embodiment of the present invention the modified water-based alkyd resin of polystyrene microsphere containing carboxyl with it is phenylethene modified aqueous
Alkyd resin (comparative example) is configured to water paint and carries out performance contrast test under the same conditions, is examined according to relevant criterion
It surveys, test data is as shown in table 1:
1 modified alkyd resin water paint performance technologies index of table
Although the present invention has been explained in detail and has referred to embodiment, for those of ordinary skill in the art, show
Various schemes, modification and the change that can so make as specified above, should be construed as being included within the scope of the claims.
Claims (6)
1. a kind of preparation method of the modified water-based alkyd resin of polystyrene microsphere containing carboxyl as described in claim 1, feature
Be: the preparation method, its step are as follows:
A), polystyrene microsphere containing carboxyl is first added to the in the mixed solvent of methylene chloride and dimethylbenzene, is stirred to sufficiently molten
It is swollen, it goes after supernatant liquor for use；
B), in the reactor that thermometer, condenser, water segregator, blender are housed, by formulation weight ratio, purification is sequentially added
Vegetable oil, organic acid, polyalcohol, catalyst and dimethylbenzene, stir at low speed down and are passed through N2, to remove the O in reaction kettle2；
C), 105 DEG C are heated to flowing back, and are kept the temperature 0.5h, are removed part water, 140~160 DEG C are continuously heating to, to material
After dissolution, the polystyrene microsphere containing carboxyl and benzoic acid being swollen is added, insulation reaction 1h then heats to 180 DEG C, heat preservation
1~2h is reacted, is warming up to 210~220 DEG C, 2~3h of insulation reaction with 20 DEG C/h speed, reacts the water water segregator point generated
Out；
D), hereafter primary every 0.5h measurement acid value, stop reaction when the acid value of detection reaches Theoretical Design value, and cool to
120 DEG C, solvent is evaporated off under vacuum, then is cooled to 50 DEG C, neutralizer is added, is dispersed with stirring 20~30min, deionization is added
Water continues to stir 0.5h, and filtering obtains the modified water-based alkyd resin of polystyrene microsphere containing carboxyl；
According to parts by weight, primary raw material ingredient are as follows:
Wherein, the polystyrene microsphere containing carboxyl is polystyrene-maleic anhydride microballoon, polystyrene-phthalic anhydride microballoon or poly-
Styrene-itaconic acid microballoon；
The polystyrene-maleic anhydride microballoon is made by dispersion copolymerization method or self-stabilization precipitation polymerization method；Described is poly-
Styrene-phthalic anhydride microballoon is made by acylating agent suspension copolymerization method；The polystyrene-itaconic acid microballoon passes through dispersion copolymerization
Method or radiation copolymerization method are made.
2. the modified water-based alkyd resin of polystyrene microsphere containing carboxyl according to claim 1, it is characterised in that: described
Refined plant oil is the combination of one or more of linseed oil, soybean oil, castor oil, tall oil, coconut oil, rapeseed oil.
3. the modified water-based alkyd resin of polystyrene microsphere containing carboxyl according to claim 1, it is characterised in that: described
Organic acid is the combination of one or more of phthalic anhydride, cis-butenedioic anhydride, tetrahydrophthalic anhydride, M-phthalic acid, hexanedioic acid, decanedioic acid.
4. the modified water-based alkyd resin of polystyrene microsphere containing carboxyl according to claim 1, it is characterised in that: described
Polyalcohol is ethylene glycol, propylene glycol, butanediol, hexylene glycol, neopentyl glycol, Diethylene Glycol, dipropylene glycol, three hydroxyl first
The combination of one or more of base propane, glycerol, trimethylolethane, pentaerythrite.
5. the modified water-based alkyd resin of polystyrene microsphere containing carboxyl according to claim 1, it is characterised in that: described
Catalyst is Dibutyltin oxide, Dibutyltin oxide chloride, dibutyl tin dilaurate, dibutyl tin acetate, only son
At least one of base tin trichloride, lithium hydroxide.
6. the modified water-based alkyd resin of polystyrene microsphere containing carboxyl according to claim 1, it is characterised in that: described
Neutralizer is triethylamine, N, the combination of one or more of N- dimethylethanolamine, 2- amino -1- propyl alcohol.
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| CN112708334A (en) * | 2020-12-27 | 2021-04-27 | 山东齐鲁漆业有限公司 | High-tension water-based paint suitable for steel structure surface and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110862525A (en) * | 2019-11-19 | 2020-03-06 | 合众（佛山）化工有限公司 | APAO modified waterborne alkyd resin and preparation method thereof |
| CN111701544A (en) * | 2020-05-22 | 2020-09-25 | 湖北新纵科病毒疾病工程技术有限公司 | Preparation method of magnetic polystyrene microspheres |
| CN112708334A (en) * | 2020-12-27 | 2021-04-27 | 山东齐鲁漆业有限公司 | High-tension water-based paint suitable for steel structure surface and preparation method thereof |
| CN114835883A (en) * | 2022-04-01 | 2022-08-02 | 佛山市国化新材料科技有限公司 | Carboxylic acid micro-nano cellulose-based alkyd resin and preparation method thereof |
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