CN110229282A - A kind of GMA graft type waterborne acrylic modified alkyd resins and preparation method thereof - Google Patents
A kind of GMA graft type waterborne acrylic modified alkyd resins and preparation method thereof Download PDFInfo
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- CN110229282A CN110229282A CN201910375137.8A CN201910375137A CN110229282A CN 110229282 A CN110229282 A CN 110229282A CN 201910375137 A CN201910375137 A CN 201910375137A CN 110229282 A CN110229282 A CN 110229282A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
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Abstract
The present invention relates to high-molecular coating fields more particularly to a kind of GMA graft type waterborne acrylic modified alkyd resins and preparation method thereof.GMA graft type waterborne acrylic modified alkyd resins designed by the present invention, by weight percentage, it is prepared from the following components: vegetable oil acid 32~38%, polyalcohol 5~10%, 2,2- dihydromethyl propionic acid 2~9%, polyacid 10~20%, catalyst 0.1~1%, glycidyl methacrylate 5~10%, water entrainer 2~8%, acrylic monomers 10~20%, initiator 0.1~10, cosolvent 10~15%, polymerization inhibitor 0.1~0.5%.By introducing double bond on alkyd resin side chain, reacts with acrylic monomers, avoid the reduction of unsaturated carbon carbon double bond quantity, improve surface drying speed.
Description
Technical field
The present invention relates to high-molecular coating field more particularly to a kind of GMA graft type waterborne acrylic modified alkyd resins
And preparation method thereof.
Background technique
Alkyd resin is important coating resin, passes through esterification by polyalcohol, polyacid and fatty acid or vegetable oil
The resin of polycondensation reaction synthesis, a kind of linear macromolecule that alkyd resin is modified using vegetable oil acid as side chain, from molecule knot
It is analyzed on structure, polyalcohol reacts the linear resin that the ester bond generated is main chain with polyacid, by the type for controlling vegetable oil acid
The alkyd resin with different oil content can be synthesized with content, is applied to different field of coating.
Traditional solvent-borne alkyd resins coating contains a large amount of VOC (volatile organic compounds), to human health and
Environment causes serious harm, while also resulting in a large amount of wasting of resources.With the development of society, the environmental consciousness of people mentions
Height, various countries successively promulgate the laws and regulations of stringent limitation VOC emission amount.Become as the Research Emphasis of coatings industry and development
Gesture, Environmentally friendly coatings by be coatings industry inexorable trend, traditional solvent-borne alkyd resins hydrotropism's alkyd resin
Transformation is also exactly the developing direction of alkyd resin.
Water alcohol acid is using water as solvent, only with a small amount of hypotoxicity alcohol ethers organic solvent as cosolvent.It is aqueous
The main composition of alkyd resin and common solvent type alkyd resin are essentially identical, by polyacid, polyalcohol and fatty acid or plant
Object oil is formed by esterifying polycondensation.But there is also deficiencies for water alcohol acid: (1) evaporation latent heat of water is high, and relative evaporation rate is low, special
Not under low temperature and high humidity, the drying time of paint film extends；(2) there is a large amount of ester bond in alkyd, water resistance is poor,
Chemical-resistant is poor；(3) for water paint generally in alkalinity, ester bond is degradable to cause storage stability poor, is easy to happen layering
Or precipitating.
To solve the above problems, generalling use acrylic acid modified alkyd resin, it is good, easy alkyd resin richness has both been retained
The advantages that construction, and the characteristics of inherit acrylic resin quick-drying, enhance weather resistance.Patent 201510569593.8 is reported
Waterborne acrylic modified alkyd resins, then first acrylic acid synthesizing prepolymer prepares aqueous acrylamide using this prepolymer as raw material
Sour modified alkyd resin, since acroleic acid polymerization is free radical random copolymerization, reaction temperature, reaction time and initiator amount shadow
Molecular weight and its distribution of prepolymer are rung, and then influences the performance of prepolymer, finally influences this water-based acrylic acid modified alcoholic acid tree
The batch production stability of rouge.Patent CN201510259667.8 reports first synthetic alkyd resin, carries out Water-borne modification, then with third
Acrylic monomer is modified, this technique is easy to happen oil due to no additional emulsifier, acrylic monomers in being added drop-wise to water phase
Water is incompatible, and compatibility is poor, and it is higher to will lead to gel fraction during the reaction, yield decline.Patent
CN201510475955.7, which is reported, is first prepared for alkyd resin using vegetable seed oleic acid and cocinic acid as fatty acid, then with oleic acid
On conjugated double bond reacted with acrylic monomers, waterborne acrylic modified alkyd resins are prepared, due to aqueous acrylic modified alcohol
The drying of acid resin is to be occurred by unsaturated carbon-carbon double bond on oleic acid oxidation cross-linked, and it is double that this technique consumes part oleic acid
Key causes drying time to extend.
Summary of the invention
In order to solve the above problem, the object of the present invention is to provide a kind of GMA graft type waterborne acrylic modified alkyd resins
And preparation method thereof, by introducing double bond on alkyd resin side chain, reacts with acrylic monomers, avoid unsaturated carbon carbon
The reduction of double bond quantity improves surface drying speed.
To achieve the above object, the GMA graft type waterborne acrylic modified alkyd resins designed by the present invention, by weight hundred
Divide than meter, is prepared from the following components: vegetable oil acid 32~38%, polyalcohol 5~10%, 2,2- dihydromethyl propionic acid 2~
9%, polyacid 10~20%, catalyst 0.1~1%, glycidyl methacrylate 5~10%, water entrainer 2~8%, third
Acrylic monomer 10~20%, initiator 0.1~10, cosolvent 10~15%, polymerization inhibitor 0.1~0.5%.
The acrylic monomers is acrylic acid hard monomer and/or acrylic acid soft monomer, and the acrylic acid hard monomer is propylene
Acid, styrene, methyl methacrylate, acrylonitrile it is one or more；The acrylic acid soft monomer is butyl acrylate, propylene
Acetoacetic ester, Isooctyl acrylate monomer it is one or more.
Preferably, the vegetable oil acid is castor-oil plant Chinese catalpa oleic acid, linoleic acid, Perillaseed oleic acid, behenic acid, corn
Oleic acid, cocinic acid, walnut oil, oleic acid it is one or more.
Preferably, the polyalcohol is pentaerythrite, ethylene glycol, 1,3-BDO, neopentyl glycol, diethyl two
Alcohol, glycerine, 2,2,4- trimethyl -1,3- pentanediol, glycerine, dipentaerythritol, trimethylolpropane it is one or more.
Preferably, the polyacid be benzoic acid, adipic acid, fumaric acid, maleic anhydride, phthalic anhydride,
M-phthalic acid, decanedioic acid, trimellitic anhydride, pyromellitic dianhydride it is one or more.
Preferably, the water entrainer is petroleum ether, benzene,toluene,xylene, hexamethylene, chloroform and carbon tetrachloride
It is one or more.
Preferably, the initiator is peroxidized t-butyl perbenzoate, benzoyl peroxide, peroxidating 2- ethyl
Hexyl acid tert-pentyl ester, peroxidating 2- ethylhexyl tert-butyl acrylate, peroxidating acetic acid tert-pentyl ester, peroxide acid tert-amyl acetate, mistake
Aoxidize the one or more of diisopropylbenzene (DIPB), di t-amyl peroxide, di-t-butyl peroxide.
Preferably, the cosolvent be butyl glycol ether, it is propylene glycol monobutyl ether, propylene glycol methyl ether acetate, different
Propyl alcohol, isobutanol and sec-butyl alcohol it is one or more.
Preferably, the neutralizer is triethylamine, N, N- dimethylethanolamine, ammonium hydroxide, -2- amino-2-methyl -
1- propyl alcohol it is one or more.
Preferably, the polymerization inhibitor is hydroquinone or p-hydroxyanisole.
Preferably, the catalyst is the one or more of triphenylphosphine, tetrabutylammonium bromide and stannous chloride.
A kind of preparation method of GMA graft type waterborne acrylic modified alkyd resins, it is characterised in that: comprising steps of
(1) alkyd resin is prepared: by vegetable oil acid, polyalcohol, 2,2- dihydromethyl propionic acid, polyacid, water entrainer, catalysis
Agent is added in reactor, and esterification is carried out under the atmosphere of nitrogen and obtains the first reaction solution；
(2) double bond is introduced on alkyd resin side chain: polymerization inhibitor, catalyst and methyl-prop being added dropwise into the first reaction solution
Olefin(e) acid glycidyl ester monomer obtains the second reaction solution；
(3) acrylic monomers copolyreaction: the dropwise addition cosolvent, initiator, acrylic monomers into the second reaction solution, third
Acrylic monomer occurs free radicals copolymerization reaction and obtains GMA graft type waterborne acrylic modified alkyd resins.
Preferably, the preparation method of the GMA graft type waterborne acrylic modified alkyd resins, specifically:
(1) it prepares alkyd resin: vegetable oil acid, polyalcohol, 2,2- dihydromethyl propionic acid, polyacid, water entrainer is added
Into reactor, 1~5h is kept the temperature in the condition that nitrogen protection and temperature are 150~190 DEG C, then heats to 210~240 DEG C directly
Reach 10~50mgKOH/g to acid value, be cooled to 120~150 DEG C, obtains the first reaction solution；
(2) double bond is introduced on alkyd resin side chain: polymerization inhibitor, catalyst and methyl-prop being added dropwise into the first reaction solution
Olefin(e) acid glycidyl ester monomer is added dropwise in 2 hours, obtains the second reaction solution；
(3) under conditions of 110~130 DEG C, hydrotropy acrylic monomers copolyreaction: is added dropwise into the second reaction solution
Agent, initiator, acrylic monomers are added dropwise in 3 hours, and initiator is added in heat preservation after 1~3 hour, after heat preservation 1~3 hour
Cooling discharge obtains GMA graft type waterborne acrylic modified alkyd resins.
Realizing the preferable technical solution of the present invention is:
A kind of preparation method of GMA graft type waterborne acrylic modified alkyd resins, comprising steps of
(1) alkyd resin is prepared: by vegetable oil acid, polyalcohol, 2,2- dihydromethyl propionic acid, polyacid, water entrainer, catalysis
Agent is added in reactor, and esterification is carried out under the atmosphere of nitrogen and obtains the first reaction solution；
(2) double bond is introduced on alkyd resin side chain: polymerization inhibitor, catalyst and methyl-prop being added dropwise into the first reaction solution
Olefin(e) acid glycidyl ester monomer obtains the second reaction solution；
(3) acrylic monomers copolyreaction: the dropwise addition cosolvent, initiator, acrylic monomers into the second reaction solution, third
Acrylic monomer occurs free radicals copolymerization reaction and obtains GMA graft type waterborne acrylic modified alkyd resins；
The acrylic monomers is the mixture of acrylic acid, styrene, butyl acrylate, ethyl acrylate；The initiation
Agent is the mixture of peroxidized t-butyl perbenzoate and benzoyl peroxide；The catalyst is tetrabutylammonium bromide and protochloride
The mixture of tin.The surface drying time for the product for using preferable technical solution of the invention to obtain is 19~20 minute.
Detailed description of the invention
Fig. 1 is the infrared spectrogram for the GMA graft type waterborne acrylic modified alkyd resins that embodiment 1 obtains.
Specific embodiment
For a better understanding of the invention, invention is described in detail below with reference to drawings and concrete examples.
Existing waterborne acrylic modified alkyd resins are by the unsaturated carbon-carbon double bond and acrylic acid generation oxygen on oleic acid
Change the preparation process of crosslinking, existing waterborne acrylic modified alkyd resins preparation process consumes part oleic acid double bond, causes
The problem of drying time extends, to solve the problems, such as that existing waterborne acrylic modified alkyd resins drying time is long, the present invention
A kind of GMA graft type waterborne acrylic modified alkyd resins and preparation method thereof are provided, are prepared first containing dihydroxymethyl third
The alkyd resin of acid, then with the carboxyl of GMA epoxy group and dihydromethyl propionic acid generation epoxy ring opening reaction introducing double bond, then with
Free radicals copolymerization reaction occurs for acrylic monomers, GMA graft type waterborne acrylic modified alkyd resins is obtained, using of the invention
GMA graft type waterborne acrylic modified alkyd resins preparation process can be avoided the reduction of oleic acid unsaturated carbon carbon double bond quantity,
Improve surface drying speed.
Embodiment 1
A kind of preparation method of GMA graft type waterborne acrylic modified alkyd resins, comprising steps of
(1) alkyd resin is prepared: by behenic acid 270g, trimethylolpropane 30g, neopentyl glycol 12.5g, pentaerythrite
17.5g, benzoic acid 7.5g, phthalic anhydride 87.5g, 2,2- dihydromethyl propionic acid 65g, dimethylbenzene 39.2g, stannous chloride 0.5g are added to
In reactor, 1 hour is kept the temperature under conditions of nitrogen protection and temperature are 180 DEG C, starts the dimethylbenzene that flows back in reactor, is continued
It is warming up to 210 DEG C, keeps the temperature 4 hours, acid value reaches 10mgKOH/g, is cooled to 150 DEG C, and vacuum distillation obtains the except removal xylene
One reaction solution；
(2) double bond being introduced on alkyd resin side chain: being cooled to 120 DEG C, hydroquinone is added dropwise into the first reaction solution
0.34g, stannous chloride 0.34g and GMA monomer 68.91g, are added dropwise for 30 minutes, and 120 DEG C of stirring 30min obtain the second reaction
Solution；
(3) under conditions of 120 DEG C, butyl glycol ether acrylic monomers copolyreaction: is added dropwise into the second reaction solution
60g, peroxidized t-butyl perbenzoate 3g, acrylic acid 2.8g, styrene 61.3g, methyl methacrylate 31g, are added dropwise in 3 hours
It finishes, heat preservation added peroxidized t-butyl perbenzoate 0.8g and butyl glycol ether 12g after 1 hour, was added dropwise in half an hour, protected
Cooling discharge obtains GMA graft type waterborne acrylic modified alkyd resins after temperature 1 hour.
The product that embodiment 1 is obtained carries out infrared spectrometry, as a result as shown in Figure 1,3463cm-1There are hydrogen bonds to form at place
The hydroxyl peak of conjunction is the typical characteristic peak of alkyd resin.In 3058~2930cm-1There is the unsaturated peak C=C, wherein
3058cm-1Place is unsaturated C-H characteristic peak, 2930cm-1Bands of a spectrum be as caused by unsaturated=C-H stretching vibration,
3005cm-1Caused by being the C=C stretching vibration of cis-structure.Alkyl characteristic peak is in 2929~2863cm-1Place.In 1736cm-1
Place is strong carbonyl absorption peak.In 990cm-1There is double bond absorption peak in place, shows that alkyd resin introduces the unsaturation of vegetable oil
Fatty acid, double bond form a film for alkyd resin oxidation drying.In 842cm-1And 650cm-1There is apparent acrylate feature in place
Peak shows to be successfully prepared aqueous GMA graft type quick-drying acrylic acid modified alkyd resin.The product table that embodiment 1 obtains
The dry time is 25 minutes.
Embodiment 2
A kind of preparation method of GMA graft type waterborne acrylic modified alkyd resins, comprising steps of
(1) alkyd resin is prepared: by castor-oil plant Chinese catalpa oleic acid 200g, linoleic acid 56g, ethylene glycol 10g, 1,3 butylene glycol
10g, neopentyl glycol 10g, diethylene glycol 10g, 2,2- dihydromethyl propionic acid 16g, benzoic acid 20g, adipic acid 20g, anti-butylene two
Sour 20g, maleic anhydride 20g, petroleum ether 64g, tetrabutylammonium bromide 0.1g and stannous chloride 0.4g are added in reactor,
Keep the temperature 5 hours in the condition that nitrogen protection and temperature are 150 DEG C, in reactor in start the dimethylbenzene that flows back, be continuously heating to 220
DEG C, 2 hours are kept the temperature, acid value reaches 25mgKOH/g, is cooled to 120 DEG C, it is molten that vacuum distillation removing petroleum ether obtains the first reaction
Liquid；
(2) being introduced into double bond on alkyd resin side chain: 120 DEG C at a temperature of be added dropwise to hydroxyl into the first reaction solution
Methyl phenyl ethers anisole 2.4g, tetrabutylammonium bromide 0.2g and stannous chloride 0.9g and GMA monomer 80g, are added dropwise, 120 DEG C are stirred for 30 minutes
It mixes 30min and obtains the second reaction solution；
(3) under conditions of 120 DEG C, propyleneglycol monobutyl acrylic monomers copolyreaction: is added dropwise into the second reaction solution
Ether 80g, peroxidized t-butyl perbenzoate 2g, benzoyl peroxide 1g, acrylic acid 15g, styrene 30g, butyl acrylate 65, third
Olefin(e) acid ethyl ester 50g, is added dropwise in 3 hours, and heat preservation added peroxidized t-butyl perbenzoate 1g and propylene glycol monobutyl ether after 3 hours
16g is added dropwise in half an hour, and cooling discharge obtains GMA graft type waterborne acrylic modified alkyd resins after heat preservation 3 hours.
The product surface drying time that embodiment 2 obtains is 20 minutes.
Embodiment 3
A kind of preparation method of GMA graft type waterborne acrylic modified alkyd resins, comprising steps of
(1) alkyd resin is prepared: by Perillaseed oleic acid 150g, behenic acid 65g, corn oleic acid 89g, glycerine 20g, 2,2,4-
Trimethyl -1,3- pentanediol 20g, dipentaerythritol 40g, decanedioic acid 12, trimellitic anhydride 18, trimellitic anhydride 25,
Benzene tetracarboxylic acid acid anhydride 33g, toluene 16g, 2,2- dihydromethyl propionic acid 24g, tetrabutylammonium bromide 0.1g and stannous chloride 0.4g, it is added
Into reactor, keep the temperature 2 hours in the condition that nitrogen protection and temperature are 190 DEG C, in reactor in start the dimethylbenzene that flows back, after
It is continuous to be warming up to 240 DEG C, 3 hours are kept the temperature, acid value reaches 50mgKOH/g, is cooled to 120 DEG C, and vacuum distillation removes toluene and obtains the
One reaction solution；
(2) being introduced into double bond on alkyd resin side chain: 120 DEG C at a temperature of be added dropwise to hydroxyl into the first reaction solution
Methyl phenyl ethers anisole 1.6g, tetrabutylammonium bromide 0.1g and stannous chloride 0.2g and GMA monomer 40g, are added dropwise, 120 DEG C are stirred for 60 minutes
It mixes 30min and obtains the second reaction solution；
(3) under conditions of 120 DEG C, propyleneglycol monobutyl acrylic monomers copolyreaction: is added dropwise into the second reaction solution
Ether 100g, peroxidized t-butyl perbenzoate 2g, benzoyl peroxide 1g, acrylic acid 15g, styrene 30g, butyl acrylate 65,
Ethyl acrylate 10g, is added dropwise in 3 hours, and heat preservation added benzoyl peroxide 2.6g and propylene glycol monobutyl ether after 3 hours
20g is added dropwise in half an hour, and cooling discharge obtains GMA graft type waterborne acrylic modified alkyd resins after heat preservation 3 hours.
The product surface drying time that embodiment 3 obtains is 19 minutes.
Embodiment 4
A kind of preparation method of GMA graft type waterborne acrylic modified alkyd resins, comprising steps of
(1) alkyd resin is prepared: walnut oil 110g, corn oleic acid 80g, oleic acid 90g, glycerine 12g, two Ji Wusi
Alcohol 20g, trimethylolpropane 16g, decanedioic acid 35g, trimellitic anhydride 26g, trimellitic anhydride 24g, pyromellitic dianhydride
75g, it 2,2- dihydromethyl propionic acid 72g, hexamethylene 32g, triphenylphosphine 2g, is added in reactor, in nitrogen protection and temperature
2 hours are kept the temperature for 190 DEG C of conditions, middle beginning reflux of cyclohexane in reactor is continuously heating to 230 DEG C, keeps the temperature 2 hours, acid
Value reaches 30mgKOH/g, is cooled to 130 DEG C, vacuum distillation removes hexamethylene and obtains the first reaction solution；
(2) being introduced into double bond on alkyd resin side chain: 120 DEG C at a temperature of be added dropwise to hydroxyl into the first reaction solution
Methyl phenyl ethers anisole 3.2g, triphenylphosphine 2g and GMA monomer 40g, are added dropwise for 60 minutes, and it is molten that 120 DEG C of stirring 30min obtain the second reaction
Liquid；
(3) under conditions of 120 DEG C, propyleneglycol monobutyl acrylic monomers copolyreaction: is added dropwise into the second reaction solution
Ether 60g, cumyl peroxide 0.5g, acrylic acid 15g, acrylonitrile 10g, butyl acrylate 23g, ethyl acrylate 14g, propylene
The different monooctyl ester 18g of acid, is added dropwise in 3 hours, and heat preservation added cumyl peroxide 0.3g and propylene glycol monobutyl ether after 3 hours
20g, 1 when is interior to be added dropwise, and cooling discharge obtains GMA graft type waterborne acrylic modified alkyd resins after heat preservation 3 hours.Implement
The product surface drying time that example 4 obtains is 26 minutes.
Embodiment 5
A kind of preparation method of GMA graft type waterborne acrylic modified alkyd resins, comprising steps of
(1) alkyd resin is prepared: corn oleic acid 144, cocinic acid 25, walnut oil 36, corn oleic acid 83g, glycerine
10g, dipentaerythritol 6g, trimethylolpropane 48g, decanedioic acid 60g, trimellitic anhydride 21g, trimellitic anhydride 15g, 2,
2- dihydromethyl propionic acid 48g, it chloroform 36, triphenylphosphine 4g, is added in reactor, is 190 DEG C in nitrogen protection and temperature
Condition keeps the temperature 2 hours, middle beginning refluxing chloroform in reactor, is continuously heating to 230 DEG C, keeps the temperature 2 hours, acid value reaches
40mgKOH/g is cooled to 130 DEG C, and vacuum distillation removes chloroform and obtains the first reaction solution；
(2) being introduced into double bond on alkyd resin side chain: 120 DEG C at a temperature of be added dropwise to hydroxyl into the first reaction solution
Methyl phenyl ethers anisole 4g, triphenylphosphine 4g and GMA monomer 64g, are added dropwise for 60 minutes, and it is molten that 120 DEG C of stirring 30min obtain the second reaction
Liquid；
(3) under conditions of 120 DEG C, propyleneglycol monobutyl acrylic monomers copolyreaction: is added dropwise into the second reaction solution
Ether 66g, cumyl peroxide 5g, acrylic acid 23g, acrylonitrile 10g, butyl acrylate 23g, ethyl acrylate 14g, acrylic acid
Different monooctyl ester 18g, is added dropwise in 3 hours, and cumyl peroxide 3g and propylene glycol monobutyl ether 30g is added in heat preservation after 3 hours, and 1
When it is interior be added dropwise, heat preservation 3 hours after cooling discharge obtain GMA graft type waterborne acrylic modified alkyd resins.Embodiment 5
The product surface drying time arrived is 29 minutes.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (9)
1. a kind of GMA graft type waterborne acrylic modified alkyd resins are prepared from the following components by weight percentage:
Vegetable oil acid 32~38%, polyalcohol 5~10%, 2,2- dihydromethyl propionic acid 2~9%, polyacid 10~20%, catalyst
0.1~1%, glycidyl methacrylate 5~10%, water entrainer 2~8%, acrylic monomers 10~20%, initiator
0.1~10, cosolvent 10~15%, polymerization inhibitor 0.1~0.5%.
2. GMA graft type waterborne acrylic modified alkyd resins according to claim 1, which is characterized in that the propylene
Acid monomers are acrylic acid hard monomer and/or acrylic acid soft monomer, and the acrylic acid hard monomer is acrylic acid, styrene, methyl-prop
E pioic acid methyl ester, acrylonitrile it is one or more；The acrylic acid soft monomer is that butyl acrylate, ethyl acrylate, acrylic acid are different
Monooctyl ester it is one or more.
3. GMA graft type waterborne acrylic modified alkyd resins according to claim 1, which is characterized in that the plant
Oleic acid is castor-oil plant Chinese catalpa oleic acid, linoleic acid, Perillaseed oleic acid, behenic acid, corn oleic acid, cocinic acid, walnut oil, oleic acid
It is one or more.
4. GMA graft type waterborne acrylic modified alkyd resins according to claim 1, which is characterized in that described polynary
Alcohol is pentaerythrite, ethylene glycol, 1,3 butylene glycol, neopentyl glycol, diethylene glycol, glycerine, 2,2,4- trimethyl -1,3- penta 2
Alcohol, glycerine, dipentaerythritol, trimethylolpropane it is one or more.
5. GMA graft type waterborne acrylic modified alkyd resins according to claim 1, which is characterized in that described polynary
Acid is benzoic acid, adipic acid, fumaric acid, maleic anhydride, phthalic anhydride, M-phthalic acid, decanedioic acid, trimellitic acid
Acid anhydride, pyromellitic dianhydride it is one or more.
6. GMA graft type waterborne acrylic modified alkyd resins according to claim 1, which is characterized in that the initiation
Agent is peroxidized t-butyl perbenzoate, benzoyl peroxide, peroxidating 2- ethylhexyl acid tert-pentyl ester, peroxidating 2- ethylhexyl
Tert-butyl acrylate, peroxidating acetic acid tert-pentyl ester, peroxide acid tert-amyl acetate, cumyl peroxide, di t-amyl peroxide, mistake
Aoxidize the one or more of di-t-butyl.
7. GMA graft type waterborne acrylic modified alkyd resins according to claim 1, which is characterized in that the catalysis
Agent is the one or more of triphenylphosphine, tetrabutylammonium bromide and stannous chloride.
8. a kind of preparation method of GMA graft type waterborne acrylic modified alkyd resins, it is characterised in that: comprising steps of
(1) it prepares alkyd resin: vegetable oil acid, polyalcohol, 2,2- dihydromethyl propionic acid, polyacid, water entrainer, catalyst is added
Enter into reactor, esterification is carried out under the atmosphere of nitrogen and obtains the first reaction solution；
(2) double bond is introduced on alkyd resin side chain: polymerization inhibitor, catalyst and methacrylic acid being added dropwise into the first reaction solution
Glycidyl ester monomer obtains the second reaction solution；
(3) cosolvent, initiator, acrylic monomers, acrylic acid acrylic monomers copolyreaction: are added dropwise into the second reaction solution
Monomer occurs free radicals copolymerization reaction and obtains GMA graft type waterborne acrylic modified alkyd resins.
9. the preparation method of GMA graft type waterborne acrylic modified alkyd resins according to claim 8, it is characterised in that:
Comprising steps of
(1) it prepares alkyd resin: vegetable oil acid, polyalcohol, 2,2- dihydromethyl propionic acid, polyacid, water entrainer is added to instead
It answers in device, keeps the temperature 1~5h in the condition that nitrogen protection and temperature are 150~190 DEG C, then heat to 210~240 DEG C until acid
Value reaches 10~50mgKOH/g, is cooled to 120~150 DEG C, obtains the first reaction solution；
(2) double bond is introduced on alkyd resin side chain: polymerization inhibitor, catalyst and methacrylic acid being added dropwise into the first reaction solution
Glycidyl ester monomer is added dropwise in 2 hours, obtains the second reaction solution；
(3) acrylic monomers copolyreaction: under conditions of 110~130 DEG C, cosolvent is added dropwise into the second reaction solution, draws
Agent, acrylic monomers are sent out, is added dropwise in 3 hours, initiator is added in heat preservation after 1~3 hour, heat preservation cools down out after 1~3 hour
Material obtains GMA graft type waterborne acrylic modified alkyd resins.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110790869A (en) * | 2019-10-30 | 2020-02-14 | 广州擎天材料科技有限公司 | Modified water-based polyester copolymer and preparation method thereof |
| CN111072882A (en) * | 2019-12-31 | 2020-04-28 | 深圳市安品有机硅材料有限公司 | Modified waterborne polyurethane resin, coating and preparation method thereof |
| CN111234126A (en) * | 2020-03-31 | 2020-06-05 | 南京长江涂料有限公司 | High-solid-content high-performance glycidyl versatate modified alkyd resin and preparation method thereof |
| CN113024821A (en) * | 2021-03-03 | 2021-06-25 | 江苏富琪森新材料有限公司 | Water-based alkyd acrylic hybrid resin and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790869A (en) * | 2019-10-30 | 2020-02-14 | 广州擎天材料科技有限公司 | Modified water-based polyester copolymer and preparation method thereof |
| CN110790869B (en) * | 2019-10-30 | 2022-08-16 | 擎天材料科技有限公司 | Modified water-based polyester copolymer and preparation method thereof |
| CN111072882A (en) * | 2019-12-31 | 2020-04-28 | 深圳市安品有机硅材料有限公司 | Modified waterborne polyurethane resin, coating and preparation method thereof |
| CN111234126A (en) * | 2020-03-31 | 2020-06-05 | 南京长江涂料有限公司 | High-solid-content high-performance glycidyl versatate modified alkyd resin and preparation method thereof |
| CN111234126B (en) * | 2020-03-31 | 2022-12-06 | 南京长江涂料有限公司 | High-solid-content high-performance glycidyl versatate modified alkyd resin and preparation method thereof |
| CN113024821A (en) * | 2021-03-03 | 2021-06-25 | 江苏富琪森新材料有限公司 | Water-based alkyd acrylic hybrid resin and preparation method thereof |
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