CN102127213B - Waterborne acrylic alkyd resin and preparation method and application thereof - Google Patents
Waterborne acrylic alkyd resin and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides waterborne acrylic alkyd resin and emulsion thereof. The waterborne acrylic alkyd resin is prepared by the following steps of: performing free radical polymerization on four acrylic monomers, namely acrylic acid, methyl methacrylate, methyl acrylate and butyl methacrylate, an initiating agent and a chain transfer agent in an organic solvent to obtain an acrylic prepolymer, then performing ester exchange reaction on vegetable oil and trimethylolpropane to obtain an alcoholysis product, and performing polycondensation reaction on the acrylic prepolymer and the alcoholysis product to obtain the product; and the emulsion is prepared by adding a neutralizer, a cosolvent and distilled water to the waterborne acrylic alkyd resin. In the waterborne acrylic alkyd resin provided by the invention, long alkane structures are connected with carbon atoms on the alpha and beta positions on two sides of an ester bond in the resin molecule, thus improving the hydrolytic stability of the ester bond. Therefore, the waterborne acrylic alkyd resin has good hydrolytic resistance and storage stability and can be used as a main component of waterborne paints and adhesives, and varnish prepared from the resin provided by the invention has good dryness, adhesive force and hardness.
Description
Technical field
The invention belongs to chemical field, be specifically related to aqueous alkide resin and preparation method thereof.
Background technology
Synolac is a kind of common coating resin, and its raw material sources are abundant and price is low, and synthetic technology is ripe, the resin coating film good combination property, so Synolac becomes one of kind that in synthetic resins, consumption is maximum, purposes is the widest.Present Synolac is still take solvent-borne type as main, still, and along with the requirement of expanding economy and environmental protection has become Water-borne Modification of Alkyd Resin the development trend of industry.With water to replace organic solvent, can effectively reduce the environmental pollution that VOCs (volatile organic compounds) brings, again can Cost reduction.But, in the safety and Health benefit that Water-borne Modification of Alkyd Resin brings, the film performance of its hydrolytic resistance, package stability and coating will reach or surpass the standard of performance of solvent-borne type Synolac, is but the problem of fine solution of failing in most of Water-borne Modification of Alkyd Resin research.
The Water-borne modification research purpose of Synolac is oil-soluble resin is converted into water-base resin.According to Synolac degree of scatter in water, can be divided into water-soluble and water-dispersion Synolac two classes; According to the Water-borne Modification of Alkyd Resin thinking, can be divided into internal emulsification method and outer emulsion process; According to the preparation technology of Synolac, can be divided into solvent method and scorification; According to hydrophilic monomer, can be divided into trimellitic acid anhydride modification, acrylic monomer modification, DMPA modification, organic-silicon-modified, poly ethyldiol modified, polyurethane-modified, organic acid salt modification etc.
The Water-borne modification thinking has determined synthetic method.Outer emulsification refers to make the Synolac molecular dispersion in water by the tensio-active agent that adds, and therefore finding suitable tensio-active agent is the research emphasis of outer emulsification.But these emulsifying agents can not participate in film forming usually, thereby have affected dryness, hardness, gloss and the water tolerance etc. of filming.Internal emulsification is that molecular resin is carried out direct modifying and decorating, usually introduces various hydrophilic functional groups or oligopolymer, in and salify after molecular resin can be scattered in water.Its pH value of Synolac system after neutralization is generally in 8 left and right, and under this weakly alkaline environment, the ester bond on the Synolac molecular backbone chain very solution is hydrolyzed, and along with the growth of period of storage, the molecular resin amount reduces gradually like this, and viscosity and decentralized obviously descend.
If be connected with long alkane structure on the carbon atom of the α of ester bond both sides, β position in the Synolac molecule, can well improve the stability to hydrolysis of this ester bond, if use like this acrylic polymer to replace traditional multi-carboxy compound (as phthalic anhydride, m-phthalic acid etc.) directly and monoglyceride polycondensation resin molecular chain, pass through in the amine alkaline matter and the acrylic acid modified alkyd resin emulsion that obtains after salify, have good hydrolytic resistance and package stability.
Summary of the invention
Task of the present invention is to provide a kind of waterborne acrylic alkyd resin and emulsion thereof, makes it have the advantages that hydrolytic resistance is good, package stability is high.The preparation method of the present invention also provides this simultaneously kind waterborne acrylic alkyd resin and emulsion thereof.
In addition, the present invention also provides the clear coat composition with this waterborne acrylic alkyd resin emulsion preparation provided by the invention.
Realize that concrete scheme of the present invention is:
This waterborne acrylic alkyd resin provided by the invention, to carry out with vinylformic acid, methyl methacrylate, methyl acrylate, four kinds of Acrylic Acid Monomers of butyl methacrylate and initiator and chain-transfer agent the acrylic acid or the like prepolymer that Raolical polymerizable obtains in organic solvent, separately carry out transesterification reaction with vegetables oil and TriMethylolPropane(TMP) again and obtain alcoholysis product, then carry out with acrylic acid or the like prepolymer and alcoholysis product the product that polycondensation obtains.
This waterborne acrylic alkyd resin emulsion provided by the invention is the emulsion that adds neutralizing agent, solubility promoter and distilled water to obtain in above-mentioned waterborne acrylic alkyd resin.
The preparation method of this waterborne acrylic alkyd resin provided by the invention comprises the following steps:
Step a: with vinylformic acid, methyl methacrylate, methyl acrylate, four kinds of Acrylic Acid Monomers of butyl methacrylate and initiator and chain-transfer agent synthetic acrylic acid or the like prepolymer that obtains in organic solvent;
Step b: obtain alcoholysis product with oleum lini and TriMethylolPropane(TMP) reaction;
Step c: carry out polycondensation with acrylic acid or the like prepolymer and alcoholysis product and namely obtain waterborne acrylic alkyd resin.
the described vinylformic acid of using of above-mentioned steps a, methyl methacrylate, methyl acrylate, the concrete grammar of these four kinds of Acrylic Acid Monomer synthesizing propylene acids prepolymers of butyl methacrylate is: mechanical stirring is being housed, reflux condensing tube, add organic solvent in the reactor of 2 constant pressure funnels, keep magnetic agitation, logical shielding gas nitrogen 30min-60min also is heated to 100-105 ℃, then respectively the acrylic monomer mixture and the chain-transfer agent that are dissolved with initiator, be placed in 2 constant pressure funnels, under constant temperature, 3-3.5h at the uniform velocity drips off rear insulation reaction 1-1.5h, be cooled to room temperature, obtain acrylic polymer, described organic solvent is N-BUTYL ACETATE or dimethylbenzene, described initiator is dibenzoyl peroxide BPO or Diisopropyl azodicarboxylate AIBN, described chain-transfer agent is dodecyl mercaptans, the gross weight of four kinds of Acrylic Acid Monomers used equals the weight of organic solvent used, and the weight ratio of four kinds of Acrylic Acid Monomers used is vinylformic acid: methyl methacrylate: methyl acrylate: butyl methacrylate=1: 1: 3.5: 4.5, the consumption of chain-transfer agent is the 2%-7% of four kinds of Acrylic Acid Monomer gross weights used, and the consumption of initiator is the 0.2%-0.5% of four kinds of Acrylic Acid Monomer gross weights used.
Above-mentioned steps b is described to carry out with vegetables oil and TriMethylolPropane(TMP) the concrete grammar that transesterification reaction obtains alcoholysis product and is: add vegetables oil, polyvalent alcohol and catalyzer in the reaction vessel that agitator, thermometer, reflux exchanger are housed, logical shielding gas nitrogen 30min-60min, and be heated to 230-240 ℃, insulation alcoholysis 0.5-1h, be cooled to room temperature, obtain alcoholysis product, described vegetables oil is oleum lini or tung oil; Described polyvalent alcohol is TriMethylolPropane(TMP) or tetramethylolmethane; Described catalyzer is lithium hydroxide; Vegetables oil is 3.5 with the weight consumption ratio of polyvalent alcohol: 1-4: 1, and the consumption of catalyzer is the 0.3%-0.5% of four kinds of Acrylic Acid Monomer gross weights used;
above-mentioned steps c is described to carry out with acrylic acid or the like prepolymer and alcoholysis product the concrete grammar that polycondensation obtains waterborne acrylic alkyd resin and is: agitator is being housed, thermometer, add the acrylic polymer that makes by preparation method claimed in claim 4 and alcoholysis product and the reflux condensation mode agent that makes by preparation method claimed in claim 6 in the reactor of reflux exchanger, acrylic polymer is 1 with the weight consumption ratio of alcoholysis product: 0.8-1: 1.1, the consumption of reflux condensation mode agent is the 8%-10% of acrylic polymer and alcoholysis product total mass, be warming up to 210-215 ℃, insulation reaction 70-90min namely gets acrylic acid resin, described reflux condensation mode agent can be toluene or dimethylbenzene.
The preparation method of waterborne acrylic alkyd resin emulsion provided by the invention comprises the following steps:
Step 1: carry out Raolical polymerizable with vinylformic acid, methyl methacrylate, methyl acrylate, four kinds of Acrylic Acid Monomers of butyl methacrylate and initiator and chain-transfer agent in organic solvent and prepare the acrylic acid or the like prepolymer;
Step 2: carry out transesterification reaction with vegetables oil and TriMethylolPropane(TMP) and obtain alcoholysis product;
Step 3: acrylic acid or the like prepolymer and alcoholysis product are carried out polycondensation obtain waterborne acrylic alkyd resin;
Step 4: add neutralizing agent, solubility promoter and distilled water namely to obtain the waterborne acrylic alkyd resin emulsion in waterborne acrylic alkyd resin.
the described vinylformic acid of using of above-mentioned steps one, methyl methacrylate, methyl acrylate, the concrete grammar of these four kinds of Acrylic Acid Monomer synthesizing propylene acids prepolymers of butyl methacrylate is: mechanical stirring is being housed, reflux condensing tube, add organic solvent in the reactor of 2 constant pressure funnels, keep magnetic agitation, logical shielding gas nitrogen 30min-60min also is heated to 100-105 ℃, then respectively the acrylic monomer mixture and the chain-transfer agent that are dissolved with initiator, be placed in 2 constant pressure funnels, under constant temperature, 3-3.5h at the uniform velocity drips off rear insulation reaction 1-1.5h, be cooled to room temperature, obtain acrylic polymer.Wherein said organic solvent is N-BUTYL ACETATE or dimethylbenzene; Described initiator is dibenzoyl peroxide BPO or Diisopropyl azodicarboxylate AIBN; Described chain-transfer agent is dodecyl mercaptans; The gross weight of four kinds of Acrylic Acid Monomers used equals the weight of organic solvent used, and the weight ratio of four kinds of Acrylic Acid Monomers used is vinylformic acid: methyl methacrylate: methyl acrylate: butyl methacrylate=1: 1: 3.5: 4.5, the consumption of chain-transfer agent is the 2%-7% of four kinds of Acrylic Acid Monomer gross weights used, and the consumption of initiator is the 0.2%-0.5% of four kinds of Acrylic Acid Monomer gross weights used.
Above-mentioned steps two is described carries out with vegetables oil and TriMethylolPropane(TMP) the concrete grammar that transesterification reaction obtains alcoholysis product and is: add vegetables oil, polyvalent alcohol and catalyzer in the reaction vessel that agitator, thermometer, reflux exchanger are housed, logical shielding gas nitrogen 30min-60min, and be heated to 230-240 ℃, insulation alcoholysis 0.5-1h, be cooled to room temperature, obtain alcoholysis product, described vegetables oil is oleum lini or tung oil; Described polyvalent alcohol is TriMethylolPropane(TMP) or tetramethylolmethane; Described catalyzer is lithium hydroxide; Vegetables oil is 3.5 with the weight consumption ratio of polyvalent alcohol: 1-4: 1, and the consumption of catalyzer is the 0.3%-0.5% of four kinds of Acrylic Acid Monomer gross weights used.
above-mentioned steps three is described carries out with acrylic acid or the like prepolymer and alcoholysis product the concrete grammar that polycondensation obtains waterborne acrylic alkyd resin and is: agitator is being housed, thermometer, add the acrylic polymer that makes by preparation method claimed in claim 4 and alcoholysis product and the reflux condensation mode agent that makes by preparation method claimed in claim 6 in the reactor of reflux exchanger, acrylic polymer is 1 with the weight consumption ratio of alcoholysis product: 0.8-1: 1.1, the consumption of reflux condensation mode agent is the 8%-10% of acrylic polymer and alcoholysis product total mass, be warming up to 210-215 ℃, insulation reaction 70-90min namely gets acrylic acid resin, described reflux condensation mode agent can be toluene or dimethylbenzene.
the described neutralizing agent that adds in waterborne acrylic alkyd resin of above-mentioned steps four, the concrete grammar that solubility promoter and distilled water namely obtain the waterborne acrylic alkyd resin emulsion is: add after the acrylic acid resin that claim 7 is prepared is cooled to 125 ℃ neutralizing agent to system pH between 7 to 8, add again solubility promoter, the solubility promoter consumption is the 10%-15% of acrylic polymer and alcoholysis product total mass, be cooled to and add distilled water to solid content 45%-55% after 75 ℃ under the stirring velocity of 800rpm, insulation disperses 30min, discharging namely gets the acrylic acid resin emulsion, described neutralizing agent is sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution, sodium hydrogen carbonate solution, ammoniacal liquor, triethylamine, trolamine, N, the mixture of one or more in the N-dimethylethanolamine, described solubility promoter is butyl glycol ether or propandiol butyl ether.
Waterborne acrylic alkyd resin provided by the invention can be used as the main component of environment-friendly type self-drying paint for the preparation of the environment-friendly type self-drying paint.
Clear coat composition provided by the invention, obtained by waterborne acrylic alkyd resin emulsion provided by the invention and siccative mixing, the amount ratio of acrylic acid resin emulsion and siccative (w/w) is 1: 0.008-1: 0.01, described siccative is the metallic soap of naphthenic acid or the metallic soap of isocaprylic acid, metal contained in the metallic soap of described naphthenic acid or the metallic soap of isocaprylic acid is cobalt, manganese, cerium, vanadium, iron, lithium, potassium, calcium, strontium, barium, aluminium, tin, lead, bismuth, titanium, chromium, nickel, copper, zinc, zirconium, molybdenum or neodymium, is preferably cobalt, manganese or cerium.
Preparation method of the present invention can explain with following reaction equation:
waterborne acrylic alkyd resin of the present invention is different from traditional Synolac or Water-borne modification Synolac, waterborne acrylic alkyd resin of the present invention uses acrylic polymer to replace phthalic anhydride to participate in polycondensation, contain the low molecule segment of acrylic polymer inside making resin backbone, the α of ester bond both sides in acrylic acid resin molecule of the present invention, be connected with long alkane structure on the carbon atom of β position, can well improve the stability to hydrolysis of this ester bond, hang down simultaneously the introducing of molecule segment due to vinylformic acid, can make the Synolac side chain that a lot of carboxyls are arranged, in neutralizing agent and after, just can obtain hydrolytic resistance good, the waterborne acrylic alkyd resin emulsion that package stability is high.
The outward appearance of waterborne acrylic alkyd resin emulsion provided by the invention is little yellow liquid emulsion, and solid content is at 40-60%, and the pH value is in the 7-8 scope, can stablize and store more than 6 months,-4 glasss of viscosity that are coated with of emulsion change less than 5%, illustrate that its hydrolytic resistance is good, and package stability is high.
Waterborne acrylic alkyd resin emulsion of the present invention can be used as the main ingredient of the water-borne coatings with good characteristic, and the embodiment of the present invention should be used as in more detail it and describe.
Description of drawings
The infared spectrum of the waterborne acrylic alkyd resin emulsion of the present invention of Fig. 1 embodiment 1 preparation;
The infared spectrum of the waterborne acrylic alkyd resin emulsion of the present invention of Fig. 2 embodiment 2 preparations.
Embodiment
The invention will be further described below in conjunction with embodiment, but be not limited to this.In embodiment, resinous acid value is pressed prescriptive procedure mensuration in GB/T6743-2008.
The preparation of embodiment 1 waterborne acrylic alkyd resin emulsion
Add 100ml organic solvent N-BUTYL ACETATE in the four-hole boiling flask that mechanical stirring, reflux condensing tube, 2 constant pressure funnels are housed, logical nitrogen 30min also is heated to 105 ℃, then separately acrylic monomer and initiator and chain-transfer agent are placed in 2 constant pressure funnels, at the uniform velocity drip off in 3.5h under constant temperature.Insulation reaction 1.5h is cooled to and preserves that to obtain acrylic polymer standby after room temperature.The consumption of four kinds of Acrylic Acid Monomers is: methyl methacrylate 35.0g, butyl methacrylate 45.0g, methacrylic acid 10g, vinylformic acid 12.5g; Initiator is Diisopropyl azodicarboxylate (AIBN), and its consumption is the 0.4wt% of four kinds of total consumptions of Acrylic Acid Monomer, and chain-transfer agent is lauryl mercaptan, and its consumption is the 8wt% of four kinds of total consumptions of Acrylic Acid Monomer.
Add oleum lini 21.5g, TriMethylolPropane(TMP) 7.5g, lithium hydroxide 0.11g in the four-hole boiling flask that agitator, thermometer, reflux exchanger are housed, logical nitrogen 40min also is heated to 230 ℃, and insulation alcoholysis 1.5h is cooled to 130 ℃ and obtains alcoholysis product; Add aforesaid propylene acid prepolymer 22.5g and dimethylbenzene 5ml, be warming up to 215 ℃, insulation reaction 1.5h, be cooled to 130 ℃ and add triethylamine neutralization and butyl glycol ether 8.5ml to pH=7-8, be cooled to 75 ℃, add distilled water to solid content approximately 55% under the stirring velocity of 800rpm, insulation disperses 30min, discharging namely gets the waterborne acrylic alkyd resin emulsion, and its infared spectrum is seen Fig. 1, at 838cm
-1The characteristic peak of polyacrylic ester appears in the place, and at 1450cm
-1～1650cm
-1Phenyl ring feature skeleton absorption peak does not appear.Illustrated that acrylic polymer has replaced containing the phthalic anhydride of phenyl ring, product is really the waterborne acrylic alkyd resin emulsion.
The preparation of embodiment 2 waterborne acrylic alkyd resin emulsions
Add 105ml dimethylbenzene in the four-hole boiling flask that mechanical stirring, reflux condensing tube, 2 constant pressure funnels are housed, logical nitrogen is 30min and be heated to 100 ℃ approximately, then separately four kinds of Acrylic Acid Monomer mixture (methyl methacrylate 35.0g, β-dimethyl-aminoethylmethacrylate 40.0g, methacrylic acid 12g, vinylformic acid 10g, Diisopropyl azodicarboxylate (AIBN): 0.2wt%) and chain-transfer agent (lauryl mercaptan: 10wt%) be placed in 2 constant pressure funnels, under constant temperature, 3h at the uniform velocity drips off.Insulation reaction 1.5h is cooled to and preserves that to obtain acrylic polymer standby after room temperature.
Add tung oil 20.8g, tetramethylolmethane 8.6g, lithium hydroxide 0.12g in the four-hole boiling flask that agitator, thermometer, reflux exchanger are housed, logical nitrogen 30min also is heated to 230 ℃, and insulation alcoholysis 1.5h is cooled to 130 ℃ and obtains alcoholysis product; Add above-mentioned product acrylic polymer 22.5g, phenylformic acid 1.5g and phthalic anhydride 5.6g, be warming up to 210 ℃, about insulation esterification 2h, be cooled to 125 ℃, add triethylamine to be neutralized to pH=7-8, butyl glycol ether 9.6ml is cooled to 80 ℃, adds distilled water to solid content approximately 50% under the stirring velocity of 1000rpm, insulation disperses 30min, discharging namely gets the waterborne acrylic alkyd resin emulsion, and its infared spectrum is seen Fig. 2, at 838cm
-1The characteristic peak of polyacrylic ester appears in the place, and at 1450cm
-1～1650cm
-1Phenyl ring feature skeleton absorption peak does not appear.Illustrated that acrylic polymer has replaced containing the phthalic anhydride of phenyl ring, product is really the waterborne acrylic alkyd resin emulsion.
Embodiment 3
Waterborne acrylic alkyd resin emulsion package stability of the present invention and hydrolytic resistance
The waterborne acrylic alkyd resin emulsion of utilizing embodiment 1 to prepare is placed in 25 ℃ of thermostat containers, and storing and testing its pH value after 6 months is 7.5, and viscosity changes (being coated with-4 glasss) less than 5%.Test result shows that this waterborne acrylic alkyd resin emulsion has good storage stability and hydrolytic resistance.
Embodiment 4
The test of filming with the varnish of waterborne acrylic alkyd resin emulsion of the present invention preparation
Utilize waterborne acrylic alkyd resin emulsion and the siccative cobalt iso-octoate that embodiment 1 prepares to be mixed with varnish, the consumption of siccative is 0.8% of varnish gross weight, surplus is the waterborne acrylic alkyd resin emulsion, and film with the spread coating preparation on the tinplate sheet by GB1727-1992 " the general preparation method of paint film ", room temperature (approximately 25 ℃) is tested its paint film property after dry 7 days, and get the unmodified solvent-borne type Synolac that business uses and test its paint film property according to same steps as, the results list is as follows:
| Project | Waterborne acrylic alkyd resin | Synolac | Testing method |
| Surface drying time | 2 hours | 5 hours | GB1728-79 |
| Do solid work the time | 12 hours | 12 hours | GB1728-79 |
| Hardness (pencil) | HB | H | GB/T67-1996 |
| Resistance to impact shock | 50cm | 50cm | GB/T 1732-93 |
| Sticking power (drawing a circle) | 1 |
1 grade | GB/T9286-98 |
| Sticking power (frame) | 1 |
1 grade | GB/T 1720-89 |
Contrast as can be known from table, use with the varnish of synthetic waterborne acrylic alkyd resin emulsion as main component, paint film property reaches or approaches solvent-borne type Synolac paint film property index on the market, so this product will have the wide market requirement and commercial value.
Claims (18)
1. waterborne acrylic alkyd resin, it is characterized in that, it is to carry out with vinylformic acid, methyl methacrylate, methyl acrylate, four kinds of acrylic monomers of butyl methacrylate and initiator and chain-transfer agent the acrylic acid or the like prepolymer that Raolical polymerizable obtains in organic solvent, separately carry out transesterification reaction with vegetables oil and TriMethylolPropane(TMP) again and obtain alcoholysis product, then carry out with acrylic acid or the like prepolymer and alcoholysis product the product that polycondensation obtains.
2. a waterborne acrylic alkyd resin emulsion, is characterized in that, it is in adding in waterborne acrylic alkyd resin claimed in claim 1 and the emulsion that obtains of agent ﹑ solubility promoter and distilled water.
3. the preparation method of waterborne acrylic alkyd resin emulsion claimed in claim 2, is characterized in that, comprises the following steps:
Step 1: carry out Raolical polymerizable with Bing Xi Suan ﹑ Jia base Bing olefin(e) acid Jia Zhi ﹑ Bing olefin(e) acid Jia Zhi four kinds of acrylic monomers of ﹑ butyl methacrylate and initiator and chain-transfer agent in organic solvent and prepare the acrylic acid or the like prepolymer;
Step 2: carry out transesterification reaction with vegetables oil and TriMethylolPropane(TMP) and obtain alcoholysis product;
Step 3: acrylic acid or the like prepolymer and alcoholysis product are carried out polycondensation obtain waterborne acrylic alkyd resin;
Step 4: add Zhong with Ji ﹑ solubility promoter and distilled water namely obtain the waterborne acrylic alkyd resin emulsion in waterborne acrylic alkyd resin.
4. preparation method according to claim 3, it is characterized in that, the concrete grammar of described use third alkene acid ﹑ first base third olefin(e) acid first ester ﹑ third these the four kinds of acrylic monomer synthesizing propylene acids prepolymers of olefin(e) acid first ester ﹑ butyl methacrylate of step 1 is: mechanical stirring is being housed, reflux condensing tube, add organic solvent in the reactor of 2 constant pressure funnels, keep magnetic agitation, logical shielding gas nitrogen 30min-60min also is heated to 100-105 ℃, then respectively the acrylic monomer mixture and the chain-transfer agent that are dissolved with initiator, be placed in 2 constant pressure funnels, under constant temperature, 3-3.5h at the uniform velocity drips off rear insulation reaction 1-1.5h, be cooled to room temperature, obtain the acrylic acid or the like prepolymer.
5. preparation method according to claim 4, is characterized in that, described organic solvent is N-BUTYL ACETATE or dimethylbenzene; Described initiator is dibenzoyl peroxide BPO or Diisopropyl azodicarboxylate AIBN; Described chain-transfer agent is dodecyl mercaptans; The gross weight of four kinds of acrylic monomers used equals the weight of organic solvent used, and the weight ratio of four kinds of acrylic monomers used is vinylformic acid: methyl methacrylate: methyl acrylate: butyl methacrylate=1: 1: 3.5: 4.5, the consumption of chain-transfer agent is the 2%-7% of four kinds of acrylic monomer gross weights used, and the consumption of initiator is the 0.2%-0.5% of four kinds of acrylic monomer gross weights used.
6. preparation method according to claim 3, it is characterized in that, step 2 is described carries out with vegetables oil and TriMethylolPropane(TMP) the concrete grammar that transesterification reaction obtains alcoholysis product and is: add vegetables oil, TriMethylolPropane(TMP) and catalyzer in the reaction vessel that agitator, thermometer, reflux exchanger are housed, logical shielding gas nitrogen 30min-60min, and be heated to 230-240 ℃, insulation alcoholysis 0.5-1h, be cooled to room temperature, obtain alcoholysis product, described vegetables oil is oleum lini or tung oil; Described catalyzer is lithium hydroxide; Vegetables oil is 3.5 with the weight consumption ratio of TriMethylolPropane(TMP): 1-4: 1, and the consumption of catalyzer is the 0.3%-0.5% of four kinds of acrylic monomer gross weights used.
7. preparation method according to claim 3, it is characterized in that, step 3 is described carries out with acrylic acid or the like prepolymer and alcoholysis product the concrete grammar that polycondensation obtains waterborne acrylic alkyd resin and is: agitator is being housed, thermometer, add the acrylic acid or the like prepolymer that makes in claim 4 in the reactor of reflux exchanger and by the alcoholysis product that makes in claim 6 and reflux condensation mode agent, the acrylic acid or the like prepolymer is 1 with the weight consumption ratio of alcoholysis product: 0.8-1: 1.1, the consumption of reflux condensation mode agent is the 8%-10% of acrylic acid or the like prepolymer and alcoholysis product total mass, be warming up to 210-215 ℃, insulation reaction 70-90min namely gets acrylic acid resin.
8. preparation method according to claim 7, is characterized in that, described reflux condensation mode agent can be toluene or dimethylbenzene.
9. preparation method according to claim 3, it is characterized in that, step 4 is described adds Zhong with Ji ﹑ solubility promoter and distilled water namely obtain the concrete grammar of waterborne acrylic alkyd resin emulsion is in waterborne acrylic alkyd resin: add after the acrylic acid resin for preparing in claim 7 is cooled to 125 ℃ neutralizing agent to system pH between 7 to 8, add again solubility promoter, the solubility promoter consumption is the 10%-15% of acrylic acid or the like prepolymer and alcoholysis product total mass, be cooled to and add distilled water to solid content 45%-55% after 75 ℃ under the stirring velocity of 800rpm, insulation disperses 30min, discharging namely gets the acrylic acid resin emulsion.
10. preparation method according to claim 9, it is characterized in that, described neutralizing agent is sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution, sodium hydrogen carbonate solution, ammoniacal liquor, triethylamine, trolamine, N, the mixture of one or more in the N-dimethylethanolamine; Described solubility promoter is butyl glycol ether or propandiol butyl ether.
11. clear coat composition, obtained by waterborne acrylic alkyd resin emulsion claimed in claim 2 and siccative mixing, the weight ratio of acrylic acid resin emulsion and siccative is 1: 0.008-1: 0.01, described siccative is the metallic soap of naphthenic acid or the metallic soap of isocaprylic acid, and in the metallic soap of described naphthenic acid or the metallic soap of isocaprylic acid, contained metal is cobalt, manganese, cerium, vanadium, iron, lithium, potassium, calcium, strontium, barium, aluminium, tin, lead, bismuth, titanium, chromium, nickel, copper, zinc, zirconium, molybdenum or neodymium.
12. clear coat composition according to claim 11 is characterized in that metal is preferably cobalt, manganese or cerium.
13. waterborne acrylic alkyd resin claimed in claim 1 is as the application of the main component of environment-friendly type self-drying paint.
14. the preparation method of waterborne acrylic alkyd resin claimed in claim 1 comprises the following steps:
Step a: with Bing Xi Suan ﹑ Jia base Bing olefin(e) acid Jia Zhi ﹑ Bing olefin(e) acid Jia Zhi four kinds of acrylic monomers of ﹑ butyl methacrylate and initiator and chain-transfer agent synthetic acrylic acid or the like prepolymer that obtains in organic solvent;
Step b: obtain alcoholysis product with oleum lini and TriMethylolPropane(TMP) reaction;
Step c: carry out polycondensation with acrylic acid or the like prepolymer and alcoholysis product and namely obtain waterborne acrylic alkyd resin.
15. the preparation method of waterborne acrylic alkyd resin according to claim 14, it is characterized in that, the concrete grammar of described use third alkene acid ﹑ first base third olefin(e) acid first ester ﹑ third these the four kinds of acrylic monomer synthesizing propylene acids prepolymers of olefin(e) acid first ester ﹑ butyl methacrylate of step a is: mechanical stirring is being housed, reflux condensing tube, add organic solvent in the reactor of 2 constant pressure funnels, keep magnetic agitation, logical shielding gas nitrogen 30min-60min also is heated to 100-105 ℃, then respectively the acrylic monomer mixture and the chain-transfer agent that are dissolved with initiator, be placed in 2 constant pressure funnels, under constant temperature, 3-3.5h at the uniform velocity drips off rear insulation reaction 1-1.5h, be cooled to room temperature, obtain the acrylic acid or the like prepolymer, described organic solvent is N-BUTYL ACETATE or dimethylbenzene, described initiator is dibenzoyl peroxide BPO or Diisopropyl azodicarboxylate AIBN, described chain-transfer agent is dodecyl mercaptans, the gross weight of four kinds of acrylic monomers used equals the weight of organic solvent used, and the weight ratio of four kinds of acrylic monomers used is vinylformic acid: methyl methacrylate: methyl acrylate: butyl methacrylate=1: 1: 3.5: 4.5, the consumption of chain-transfer agent is the 2%-7% of four kinds of acrylic monomer gross weights used, and the consumption of initiator is the 0.2%-0.5% of four kinds of acrylic monomer gross weights used.
16. the preparation method of waterborne acrylic alkyd resin according to claim 14, it is characterized in that, step b is described to carry out with oleum lini and TriMethylolPropane(TMP) the concrete grammar that transesterification reaction obtains alcoholysis product and is: add vegetables oil, polyvalent alcohol and catalyzer in the reaction vessel that agitator, thermometer, reflux exchanger are housed, logical shielding gas nitrogen 30min-60min, and be heated to 230-240 ℃, insulation alcoholysis 0.5-1h, be cooled to room temperature, obtain alcoholysis product, described catalyzer is lithium hydroxide; Oleum lini is 3.5 with the weight consumption ratio of TriMethylolPropane(TMP): 1-4: 1, and the consumption of catalyzer is the 0.3%-0.5% of four kinds of acrylic monomer gross weights used;
17. the preparation method of waterborne acrylic alkyd resin according to claim 14, it is characterized in that, step c is described to carry out with acrylic acid or the like prepolymer and alcoholysis product the concrete grammar that polycondensation obtains waterborne acrylic alkyd resin and is: agitator is being housed, thermometer, add in the reactor of reflux exchanger by the acrylic acid or the like prepolymer that makes in claim 15 with by the alcoholysis product that makes in claim 16 and reflux condensation mode agent, the acrylic acid or the like prepolymer is 1 with the weight consumption ratio of alcoholysis product: 0.8-1: 1.1, the consumption of reflux condensation mode agent is the 8%-10% of acrylic acid or the like prepolymer and alcoholysis product total mass, be warming up to 210-215 ℃, insulation reaction 70-90min namely gets acrylic acid resin.
18. the preparation method of waterborne acrylic alkyd resin according to claim 17 is characterized in that, described reflux condensation mode agent can be toluene or dimethylbenzene.
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| CN103173110A (en) * | 2011-12-26 | 2013-06-26 | 西安长庆图博可特石油管道涂层有限公司 | Oil pipe external anticorrosive coating and preparation method thereof |
| CN102876463A (en) * | 2012-10-18 | 2013-01-16 | 河南省科学院高新技术研究中心 | Hydroxylated linseed oil |
| CN102993424B (en) * | 2012-11-27 | 2015-02-04 | 上海振华重工（集团）常州油漆有限公司 | Novel acrylic acid modified alkyd resin and method for preparing same |
| KR20160041956A (en) * | 2013-08-03 | 2016-04-18 | 아리스테크 서페이시스 엘엘씨 | Composition and method for producing a textured acrylic surface |
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| CN104945605A (en) * | 2015-05-20 | 2015-09-30 | 安徽省金盾涂料有限责任公司 | Acrylic-acid-modified water-based alkyd resin and preparation method thereof |
| CN105778069B (en) * | 2016-03-10 | 2017-12-12 | 湖北大学 | A kind of composite water soluble alkyd resin with high storage stability |
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| CN110225932B (en) * | 2017-01-25 | 2021-11-19 | Dic株式会社 | Active energy ray-curable aqueous resin composition and primer for inorganic material film |
| CN107814945B (en) * | 2017-10-30 | 2021-04-06 | 擎天材料科技有限公司 | Saturated polyester-acrylic resin graft copolymer containing carboxyl functional group and preparation method and application thereof |
| CN110835859A (en) * | 2019-12-05 | 2020-02-25 | 广东海纳新材料科技有限公司 | Preparation method of damp-proof, waterproof and environment-friendly artificial leather and artificial leather |
| CN111500195A (en) * | 2020-05-25 | 2020-08-07 | 郑州中岳高新材料有限公司 | Preparation method of drier for preventing surface skinning |
| CN112250850B (en) * | 2020-11-05 | 2021-04-13 | 韶关德瑞化学工业有限公司 | Environment-friendly alkyd resin and preparation method and application thereof |
| CN114773970A (en) * | 2022-04-26 | 2022-07-22 | 山东奔腾漆业股份有限公司 | Water-based high-volume solid-content steel structure normal-temperature anticorrosive paint and preparation method thereof |
| CN115850567A (en) * | 2023-03-03 | 2023-03-28 | 雅涂科技(张家港)有限公司 | Preparation method and application of high-molecular acrylic acid modified defoaming agent |
| CN116478413A (en) * | 2023-05-10 | 2023-07-25 | 扬州市祥华新材料科技有限公司 | Method for modifying alkyd resin by acrylic acid prepolymer block type and application thereof |
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| EP1185567B1 (en) * | 1999-05-28 | 2005-01-12 | Eastman Chemical Company | Acrylic modified waterborne alkyd or uralkyd dispersions |
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