CN102127213A - 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, the synthetic technology maturation, and the resin coating film good combination property, so Synolac becomes one of consumption maximum in the synthetic resins, kind that purposes is the widest.Present Synolac is still based on solvent-borne type, still, the Synolac Water-borne modification has been become the development trend of industry along with expanding economy and environmental protection requirement.With water to replace organic solvent, can effectively reduce the environmental pollution that VOCs (volatile organic compounds) brings, can reduce cost again.But, in safety and health benefit that the Synolac Water-borne modification is brought, the film performance of its hydrolytic resistance, package stability and coating will reach or surpass the standard of performance of solvent-borne type Synolac, but is the problem of fine solution of failing in the research of most of Synolac Water-borne modification.
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 Synolac Water-borne modification 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 is meant by the tensio-active agent that adds and makes the Synolac molecular dispersion in water that therefore finding suitable tensio-active agent is outer emulsive research emphasis.But these emulsifying agents can not participate in film forming usually, thereby have influenced dryness, hardness, gloss and the water tolerance etc. of filming.Internal emulsification is that molecular resin is carried out direct modifying and decorating, introduces various hydrophilic functional groups or oligopolymer usually, in and salify after molecular resin can be scattered in the water.Its pH value of Synolac system after the neutralization generally about 8, under this weakly alkaline environment, very solution hydrolysis of the ester bond on the Synolac molecular backbone chain, along with the growth of period of storage, the molecular resin amount reduces gradually like this, viscosity and decentralized obviously descend.
If in the Synolac molecule, be connected with long alkane structure on the α of ester bond both sides, the β position carbon atom, can well improve the stability to hydrolysis of this ester bond, if use acrylic polymer to replace the direct and monoglyceride polycondensation resin molecular chain of traditional multi-carboxy compound (as phthalic anhydride, m-phthalic acid etc.) like this, pass through in the amine alkaline matter and the acrylic acid modified alkyd resin emulsion that obtains behind the salify, have good hydrolytic resistance and package stability.
Summary of the invention
Task of the present invention provides a kind of water soluble acrylic acid Synolac 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 water soluble acrylic acid Synolac and emulsion thereof.
In addition, the present invention also provides the clear coat composition with this water soluble acrylic acid alkide resin emulsion preparation provided by the invention.
Realize that concrete scheme of the present invention is:
This water soluble acrylic acid Synolac provided by the invention, be in organic solvent, to carry out the acrylic acid or the like prepolymer that Raolical polymerizable obtains with vinylformic acid, methyl methacrylate, methyl acrylate, four kinds of Acrylic Acid Monomers of butyl methacrylate and initiator and chain-transfer agent, carrying out transesterification reaction with vegetables oil and TriMethylolPropane(TMP) obtains alcoholysis product in addition again, carries out the product that polycondensation obtains with acrylic acid or the like prepolymer and alcoholysis product then.
This water soluble acrylic acid alkide resin emulsion provided by the invention is to add the emulsion that neutralizing agent, solubility promoter and distilled water obtain in above-mentioned water soluble acrylic acid Synolac.
The preparation method of this water soluble acrylic acid Synolac provided by the invention may further comprise the 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 promptly obtain the water soluble acrylic acid Synolac.
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, place 2 constant pressure funnels, 3-3.5h at the uniform velocity drips off back insulation reaction 1-1.5h under the constant temperature, 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 a dodecyl mercaptans; The gross weight of four kinds of used Acrylic Acid Monomers equals the weight of used organic solvent, and the weight ratio of four kinds of used Acrylic Acid Monomers is a 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 used four kinds of Acrylic Acid Monomer gross weights, and the consumption of initiator is the 0.2%-0.5% of used four kinds of Acrylic Acid Monomer gross weights.
Above-mentioned steps b is described to carry out the concrete grammar that transesterification reaction obtains alcoholysis product with vegetables oil and TriMethylolPropane(TMP) 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 a lithium hydroxide; Vegetables oil is 3.5 with the weight consumption ratio of polyvalent alcohol: 1-4: 1, and catalyst consumption is the 0.3%-0.5% of used four kinds of Acrylic Acid Monomer gross weights;
Above-mentioned steps c is described to carry out the concrete grammar that polycondensation obtains the water soluble acrylic acid Synolac with acrylic acid or the like prepolymer and alcoholysis product and is: agitator is being housed, thermometer, add acrylic polymer that makes by the described preparation method of claim 4 and alcoholysis product and the reflux condensation mode agent that makes by the described preparation method of 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 promptly gets the vinylformic acid Synolac, and described reflux condensation mode agent can be toluene or dimethylbenzene.
The preparation method of water soluble acrylic acid alkide resin emulsion provided by the invention may further comprise the steps:
Step 1: in organic solvent, 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 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 the water soluble acrylic acid Synolac;
Step 4: in the water soluble acrylic acid Synolac, add neutralizing agent, solubility promoter and distilled water and promptly obtain the water soluble acrylic acid alkide resin emulsion.
The above-mentioned steps one described vinylformic acid of using; 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; place 2 constant pressure funnels; 3-3.5h at the uniform velocity drips off back insulation reaction 1-1.5h under the constant temperature; 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 a dodecyl mercaptans; The gross weight of four kinds of used Acrylic Acid Monomers equals the weight of used organic solvent, and the weight ratio of four kinds of used Acrylic Acid Monomers is a 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 used four kinds of Acrylic Acid Monomer gross weights, and the consumption of initiator is the 0.2%-0.5% of used four kinds of Acrylic Acid Monomer gross weights.
Above-mentioned steps two is described carries out the concrete grammar that transesterification reaction obtains alcoholysis product with vegetables oil and TriMethylolPropane(TMP) 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 a lithium hydroxide; Vegetables oil is 3.5 with the weight consumption ratio of polyvalent alcohol: 1-4: 1, and catalyst consumption is the 0.3%-0.5% of used four kinds of Acrylic Acid Monomer gross weights.
Above-mentioned steps three is described carries out the concrete grammar that polycondensation obtains the water soluble acrylic acid Synolac with acrylic acid or the like prepolymer and alcoholysis product and is: agitator is being housed, thermometer, add acrylic polymer that makes by the described preparation method of claim 4 and alcoholysis product and the reflux condensation mode agent that makes by the described preparation method of 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 promptly gets the vinylformic acid Synolac, and described reflux condensation mode agent can be toluene or dimethylbenzene.
Above-mentioned steps four is described to add neutralizing agent in the water soluble acrylic acid Synolac, the concrete grammar that solubility promoter and distilled water promptly obtain the water soluble acrylic acid alkide resin emulsion is: add after the vinylformic acid Synolac that claim 7 is prepared is cooled to 125 ℃ neutralizing agent to system pH between 7 to 8, add solubility promoter again, the solubility promoter consumption is the 10%-15% of acrylic polymer and alcoholysis product total mass, be cooled to and under the stirring velocity of 800rpm, add distilled water after 75 ℃ to solid content 45%-55%, insulation disperses 30min, discharging promptly gets the vinylformic acid alkide resin emulsion, described neutralizing agent is a 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 propylene glycol butyl ether.
The main component that water soluble acrylic acid Synolac provided by the invention can be used as the environment-friendly type self-drying paint is used to prepare the environment-friendly type self-drying paint.
Clear coat composition provided by the invention, obtain by water soluble acrylic acid alkide resin emulsion provided by the invention and siccative mixing, the amount ratio of vinylformic acid alkide 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:
Water soluble acrylic acid Synolac of the present invention is different from traditional Synolac or Water-borne modification Synolac, water soluble acrylic acid Synolac of the present invention uses acrylic polymer to replace phthalic anhydride to participate in polycondensation, make the resin backbone the inside contain the low molecule segment of acrylic polymer, the α of ester bond both sides in the vinylformic acid Synolac 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, simultaneously because the introducing of the low molecule segment of vinylformic acid, can make the Synolac side chain that a lot of carboxyls are arranged, in neutralizing agent and after, it is good just to obtain hydrolytic resistance, the water soluble acrylic acid alkide resin emulsion that package stability is high.
The outward appearance of water soluble acrylic acid alkide 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, the package stability height.
Water soluble acrylic acid alkide 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 invention should be used as in more detail it and describe.
Description of drawings
The infared spectrum of the water soluble acrylic acid alkide resin emulsion of the present invention of Fig. 1 embodiment 1 preparation;
The infared spectrum of the water soluble acrylic acid alkide resin emulsion of the present invention of Fig. 2 embodiment 2 preparations.
Embodiment
Below in conjunction with embodiment the present invention is further described, but is not limited thereto.Resinous acid value is pressed prescriptive procedure mensuration among the GB/T6743-2008 among the embodiment.
The preparation of embodiment 1 water soluble acrylic acid alkide resin emulsion
In the four-hole boiling flask that mechanical stirring, reflux condensing tube, 2 constant pressure funnels are housed, add 100ml organic solvent N-BUTYL ACETATE, logical nitrogen 30min also is heated to 105 ℃, separately acrylic monomer and initiator and chain-transfer agent are placed 2 constant pressure funnels then, at the uniform velocity drip off in the 3.5h under the constant temperature.Insulation reaction 1.5h is cooled to and preserves that to obtain acrylic polymer standby after the 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 a 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 under the stirring velocity of 800rpm to solid content about 55%, insulation disperses 30min, discharging promptly gets the water soluble acrylic acid alkide 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 really is the water soluble acrylic acid alkide resin emulsion.
The preparation of embodiment 2 water soluble acrylic acid alkide resin emulsions
In the four-hole boiling flask that mechanical stirring, reflux condensing tube, 2 constant pressure funnels are housed, add 105ml dimethylbenzene, the logical about 30min of nitrogen also is heated to 100 ℃, then separately four kinds of Acrylic Acid Monomer mixture (methyl methacrylate 35.0g, Jia Jibingxisuanyizhi 40.0g, methacrylic acid 12g, vinylformic acid 10g, Diisopropyl azodicarboxylate (AIBN): 0.2wt%) and chain-transfer agent (lauryl mercaptan: 10wt%) place 2 constant pressure funnels, 3h at the uniform velocity drips off under the constant temperature.Insulation reaction 1.5h is cooled to and preserves that to obtain acrylic polymer standby after the 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 and be neutralized to pH=7-8, butyl glycol ether 9.6ml is cooled to 80 ℃, adds distilled water under the stirring velocity of 1000rpm to solid content about 50%, insulation disperses 30min, discharging promptly gets the water soluble acrylic acid alkide 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 really is the water soluble acrylic acid alkide resin emulsion.
Embodiment 3
Water soluble acrylic acid alkide resin emulsion package stability of the present invention and hydrolytic resistance
The water soluble acrylic acid alkide resin emulsion that utilizes embodiment 1 to prepare places 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 water soluble acrylic acid alkide resin emulsion has good storage stability and hydrolytic resistance.
Embodiment 4
The test of filming with the varnish of water soluble acrylic acid alkide resin emulsion of the present invention preparation
The water soluble acrylic acid alkide resin emulsion and the siccative cobalt iso-octoate that utilize embodiment 1 to prepare are mixed with varnish, the consumption of siccative is 0.8% of a varnish gross weight, surplus is the water soluble acrylic acid alkide resin emulsion, and on the tinplate sheet, film with spread coating preparation by GB1727-1992 " the general preparation method of paint film ", room temperature (about 25 ℃) is its paint film property of test after dry 7 days, and the unmodified solvent-borne type Synolac of getting commercial usefulness tests its paint film property according to same steps as, and the results list is as follows:
| Project | The water soluble acrylic acid Synolac | 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 water soluble acrylic acid alkide resin emulsion as main component, paint film property reaches or approaching solvent-borne type Synolac paint film property index on the market, so this product will have vast market demand and commercial value.
Claims (15)
1. water soluble acrylic acid Synolac, it is characterized in that, it is to carry out the acrylic acid or the like prepolymer that Raolical polymerizable obtains 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, carrying out transesterification reaction with vegetables oil and TriMethylolPropane(TMP) obtains alcoholysis product in addition again, carries out the product that polycondensation obtains with acrylic acid or the like prepolymer and alcoholysis product then.
2. a water soluble acrylic acid alkide resin emulsion is characterized in that, it is to add the emulsion that neutralizing agent, solubility promoter and distilled water obtain in the described water soluble acrylic acid Synolac of claim 1.
3. the preparation method of the described water soluble acrylic acid alkide resin emulsion of claim 2 is characterized in that, may further comprise the steps:
Step 1: in organic solvent, 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 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 the water soluble acrylic acid Synolac;
Step 4: in the water soluble acrylic acid Synolac, add neutralizing agent, solubility promoter and distilled water and promptly obtain the water soluble acrylic acid alkide resin emulsion.
4. preparation method according to claim 3; it is characterized in that; the described vinylformic acid of using of step 1; 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; place 2 constant pressure funnels; 3-3.5h at the uniform velocity drips off back insulation reaction 1-1.5h under the constant temperature; be cooled to room temperature, obtain acrylic polymer.
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 a dodecyl mercaptans; The gross weight of four kinds of used Acrylic Acid Monomers equals the weight of used organic solvent, and the weight ratio of four kinds of used Acrylic Acid Monomers is a 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 used four kinds of Acrylic Acid Monomer gross weights, and the consumption of initiator is the 0.2%-0.5% of used four kinds of Acrylic Acid Monomer gross weights.
6. preparation method according to claim 3, it is characterized in that, step 2 is described carries out the concrete grammar that transesterification reaction obtains alcoholysis product with vegetables oil and TriMethylolPropane(TMP) 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 a lithium hydroxide; Vegetables oil is 3.5 with the weight consumption ratio of polyvalent alcohol: 1-4: 1, and catalyst consumption is the 0.3%-0.5% of used four kinds of Acrylic Acid Monomer gross weights.
7. preparation method according to claim 3, it is characterized in that, step 3 is described carries out the concrete grammar that polycondensation obtains the water soluble acrylic acid Synolac with acrylic acid or the like prepolymer and alcoholysis product and is: agitator is being housed, thermometer, add acrylic polymer that makes by the described preparation method of claim 4 and alcoholysis product and the reflux condensation mode agent that makes by the described preparation method of 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 promptly gets the vinylformic acid Synolac, and described reflux condensation mode agent can be toluene or dimethylbenzene.
8. preparation method according to claim 3, it is characterized in that, step 4 is described to add neutralizing agent in the water soluble acrylic acid Synolac, the concrete grammar that solubility promoter and distilled water promptly obtain the water soluble acrylic acid alkide resin emulsion is: add after the vinylformic acid Synolac that claim 7 is prepared is cooled to 125 ℃ neutralizing agent to system pH between 7 to 8, add solubility promoter again, the solubility promoter consumption is the 10%-15% of acrylic polymer and alcoholysis product total mass, be cooled to and under the stirring velocity of 800rpm, add distilled water after 75 ℃ to solid content 45%-55%, insulation disperses 30min, and discharging promptly gets the vinylformic acid alkide resin emulsion.
9. preparation method according to claim 8, 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 propylene glycol butyl ether.
10. clear coat composition, obtain by described water soluble acrylic acid alkide resin emulsion of claim 2 and siccative mixing, the amount ratio of vinylformic acid alkide 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.
11. the described water soluble acrylic acid Synolac of claim 1 is as the application of the main component of environment-friendly type self-drying paint.
12. the preparation method of the described water soluble acrylic acid Synolac of claim 1 may further comprise the 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 promptly obtain the water soluble acrylic acid Synolac.
13. the preparation method of water soluble acrylic acid Synolac according to claim 12, it is characterized in that, the described vinylformic acid of using of step 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, place 2 constant pressure funnels, 3-3.5h at the uniform velocity drips off back insulation reaction 1-1.5h under the constant temperature, 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 a dodecyl mercaptans; The gross weight of four kinds of used Acrylic Acid Monomers equals the weight of used organic solvent, and the weight ratio of four kinds of used Acrylic Acid Monomers is a 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 used four kinds of Acrylic Acid Monomer gross weights, and the consumption of initiator is the 0.2%-0.5% of used four kinds of Acrylic Acid Monomer gross weights.
14. the preparation method of water soluble acrylic acid Synolac according to claim 12, it is characterized in that, step b is described to carry out the concrete grammar that transesterification reaction obtains alcoholysis product with vegetables oil and TriMethylolPropane(TMP) 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 a lithium hydroxide; Vegetables oil is 3.5 with the weight consumption ratio of polyvalent alcohol: 1-4: 1, and catalyst consumption is the 0.3%-0.5% of used four kinds of Acrylic Acid Monomer gross weights.
15. the preparation method of water soluble acrylic acid Synolac according to claim 12, it is characterized in that, step c is described to carry out the concrete grammar that polycondensation obtains the water soluble acrylic acid Synolac with acrylic acid or the like prepolymer and alcoholysis product and is: agitator is being housed, thermometer, add acrylic polymer that makes by the described preparation method of claim 4 and alcoholysis product and the reflux condensation mode agent that makes by the described preparation method of 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 promptly gets the vinylformic acid Synolac, and described reflux condensation mode agent can be toluene or dimethylbenzene.
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| 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 |
| CN102993424A (en) * | 2012-11-27 | 2013-03-27 | 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 |
| 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 |
| CN104945567A (en) * | 2015-05-20 | 2015-09-30 | 安徽省金盾涂料有限责任公司 | Modified waterborne alkyd resin and preparation method thereof |
| 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 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1185567B1 (en) * | 1999-05-28 | 2005-01-12 | Eastman Chemical Company | Acrylic modified waterborne alkyd or uralkyd dispersions |
| CN101831234A (en) * | 2010-05-25 | 2010-09-15 | 北京化工大学 | Method for preparing aqueous acrylic acid modified alkyd resin coating |
-
2011
- 2011-01-17 CN CN 201110009508 patent/CN102127213B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1185567B1 (en) * | 1999-05-28 | 2005-01-12 | Eastman Chemical Company | Acrylic modified waterborne alkyd or uralkyd dispersions |
| CN101831234A (en) * | 2010-05-25 | 2010-09-15 | 北京化工大学 | Method for preparing aqueous acrylic acid modified alkyd resin coating |
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| 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 |
| CN102993424A (en) * | 2012-11-27 | 2013-03-27 | 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 |
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| CN104945567B (en) * | 2015-05-20 | 2019-02-15 | 安徽省金盾涂料有限责任公司 | A kind of modified water-based alkyd resin and preparation method thereof |
| CN105778069A (en) * | 2016-03-10 | 2016-07-20 | 湖北大学 | Composite waterborne alkyd resin with high storage stability |
| CN106866950A (en) * | 2017-01-10 | 2017-06-20 | 河北晨阳工贸集团有限公司 | Interior wall sealing wax aqueous alkide resin emulsion and preparation method thereof |
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