CN101348604A - Aqueous alkide resin emulsion and preparation thereof - Google Patents
Aqueous alkide resin emulsion and preparation thereof Download PDFInfo
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- CN101348604A CN101348604A CNA2008101958559A CN200810195855A CN101348604A CN 101348604 A CN101348604 A CN 101348604A CN A2008101958559 A CNA2008101958559 A CN A2008101958559A CN 200810195855 A CN200810195855 A CN 200810195855A CN 101348604 A CN101348604 A CN 101348604A
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Abstract
The invention relates to a water alkyd resin emulsion and a preparation method thereof. The emulsion contains emulsifier resin and host alkyd resin, and the weight ratio of the two is between 3 to 1 and 1 to 3; emulsion particles are the host alkyd resin of which the exterior surface is surrounded by the emulsifier resin; the theoretical acid value of the emulsifier resin is between 10 and 20 milligram KOH/g; the emulsifier resin is formed by neutralizing alkyd resin via volatile amine, wherein the alkyd resin is obtained by jointly modifying an addition product and polyurethane; the dosage of the volatile amine is 1.0 to 2.5 percent of the gross weight of the emulsifier resin; the addition product is the polymer containing nonionic hydrophilic ether linkage; a molecule of the emulsifier resin contains anionic hydrophilic carboxyl and nonionic hydrophilic ether linkage; and the acid value of the host alkyd resin is less than or equal to 5 milligram KOH/g, and the host alkyd resin is hydrophobic resin. The coating-4 cup viscosity change of the emulsion is less than 5 percent after six-month storage, and is more than a half lower than the prior water alkyd resin emulsion sold on market, thereby the storage stability of the emulsion is obviously improved. A preparation method for the emulsion is simple and easy to operate.
Description
Technical field
The present invention relates to a kind of aqueous alkide resin emulsion and preparation method thereof.Aqueous alkide resin emulsion of improving of package stability and preparation method thereof particularly.
Background technology
Synolac is a kind of crucial Chemicals, in fields such as coating, printing ink purposes is widely arranged.Synolac after Synolac or the process modification owing to contain more unsaturated link(age) and hydroxyl, can realize that atmospheric oxidation is dry or it is crosslinked to toast, because its synthesis material is easy to get, therefore application is very extensive in the coating of various uses again.Present Synolac is still based on solvent-borne type, still, along with expanding economy and environmental protection requirement, the Synolac Water-borne modification has been become development trend.The Synolac Water-borne modification mainly contains three kinds of methods: first kind is salt forming method.Modal be on the side chain of Synolac molecule, introduce a large amount of hydrophilic radicals (carboxyl) and with organic amine with it in and salify to obtain water soluble alkyd resin or aqueous-dispersing alkyd resin.For example adopting trimellitic anhydride or pyromellitic acid acid anhydride is aqueous monomers, prepare water soluble alkyd resin by single stage method and two-step approach, the Water-borne modification of free-radical polymerized incompatible realization Synolac and for example takes place by the unsaturated dibasic acid (MALEIC ANHYDRIDE) in acrylic monomer and the alkyd prepolymer, the conjugated double bond on the grease etc.But, owing to utilize the aqueous alkide resin that salt forming method makes all will be by in the organic amine and obtain the Synolac of Water-borne modification, and therefore, the Synolac system after the neutralization, its pH value is generally more than 8.5.In such weakly alkaline environment, the ester bond adjacent with hydroxy-acid group is easy to degraded on the Synolac main chain, and the result shows as aqueous alkide resin after storing 6 months, and viscosity significantly reduces over half approximately; CN1554689A also discloses a kind of method that improves the aqueous alkide resin performance, but still with trimellitic anhydride as the carboxyl that keeps and neutralized and realize the Water-borne modification of Synolac, so still there is the danger of ester bond degraded under the weak base condition in it, fail to solve the problem of package stability; Second kind is the non-ionic group method, promptly introduces the polymkeric substance of non-ionic group hydroxyl and ether in Synolac.For example, by introduce the Water-borne modification that polyoxyethylene glycol is realized Synolac in Synolac, the polyoxyethylene glycol of and for example introducing monoalkoxy in Synolac is realized the Water-borne modification of Synolac.But owing to utilize in the aqueous alkide resin molecule of this method formation, the ester bond that plays ligation is in connection with hydrophilic radical, and they directly are faced with " attack " of water, equally also can cause package stability poor, and the cured coating water tolerance are also bad; The third is to adopt to add the Water-borne modification that small-molecular emulsifier is realized Synolac.For example, realize the Water-borne modification of Synolac as the emulsifying agent of Synolac with alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether etc., but, because these emulsifying agents are the surfactant of lower molecular weight normally, it can not participate in film forming, thereby has all brought negative impact for dryness, hardness, gloss and the water tolerance etc. of last film forming matter.The above-mentioned existing drawback of universal method that makes the Synolac Water-borne modification has had a strong impact on the application of aqueous alkide resin.
Summary of the invention
First purpose of the present invention is: the aqueous alkide resin emulsion that provides a kind of package stability to improve.
The technical scheme that realizes first purpose of the present invention is: a kind of aqueous alkide resin emulsion, be characterized in: contain emulsifier resin and main body Synolac, the weight ratio of the two is 3: 1～1: 3, and emulsion particle is the main body Synolac, and emulsified dose of resin of its appearance surrounds;
The theoretical acid number of described emulsifier resin is 10～20mgKOH/g, it is the Synolac by affixture and the common modification of urethane, form through the volatile amine neutralization again, the consumption of volatile amine is 1.0%～2.5% of an emulsifier resin gross weight, and affixture is the polymkeric substance that contains nonionic wetting ability ehter bond; Contain anionic hydrophilic carboxyl and nonionic wetting ability ehter bond in the emulsifier resin molecule;
Acid number≤the 5mgKOH/g of described main body Synolac is hydrophobic resin.
Above-mentioned aqueous alkide resin emulsion, in the emulsifier resin gross weight, affixture accounts for 15%～30%, and the urethane segment accounts for 5%～20%.
The affixture of above-mentioned aqueous alkide resin emulsion is to be raw material with poly glycol monomethyl ether and tetrahydrophthalic anhydride, and the mol ratio of the two is 0.95: 1.05～1.05: 0.95, in the presence of catalyzer, carries out the product of ring-opening polymerization.
The main body Synolac of above-mentioned aqueous alkide resin emulsion is dryness or semi-drying oil and alcoholysis polyvalent alcohol, after alcoholysis under high temperature and the alcoholysis catalysts effect, carry out the product of esterification again with polyprotonic acid, or carry out the product of esterification by dryness oleic acid or semi-drying oleic acid and polyprotonic acid and polyvalent alcohol, or with commercially available solvent-borne type Synolac through removing solvent and modification product to acid number≤5mgKOH/g.
Above-mentioned aqueous alkide resin emulsion, its emulsion appearance are little Huang, blue slightly phase emulsion liquid; Solids content 40～60%; The pH value is in 7～8 scopes; Stored 6 months ,-4 glasss of viscosity that are coated with of emulsion change less than 5%.
Second purpose of the present invention is: the method for the above-mentioned aqueous alkide resin emulsion of preparation is provided, and the aqueous alkide resin emulsion that makes stability improves, and method is simple, easy to operate.
The technical scheme that realizes second purpose of the present invention is: a kind of method for preparing above-mentioned aqueous alkide resin emulsion comprises the following steps:
1. prepare affixture: as raw material, the mol ratio of the two is 0.95: 1.05～1.05: 0.95 with poly glycol monomethyl ether and tetrahydrophthalic anhydride, in the presence of catalyzer, be warming up to 190 ℃ after and isothermal reaction can be standby to reaching theoretical acid number;
2. prepare the emulsifier resin that acid number is 10～20mgKOH/g: earlier by dryness or semi-drying oil and alcoholysis polyvalent alcohol after alcoholysis under high temperature and the alcoholysis catalysts effect, 1. affixture and the polyprotonic acid that makes with step carries out esterification again, or the affixture that directly 1. makes by dryness oleic acid or semi-drying oleic acid and step, polyprotonic acid and polyvalent alcohol carry out esterification and obtain the Synolac prepolymer of affixture modification, then carry out modification with aliphatic polyisocyante and carboxylic polyvalent alcohol through the urethane that the ammonia esterification forms again, obtain the Synolac of affixture and the common modification of urethane, after the volatile amine neutralization makes emulsifier resin;
3. the main body Synolac for preparing theoretical acid number≤5mgKOH/g: by dryness or semi-drying oil and alcoholysis polyvalent alcohol, after alcoholysis under high temperature and the alcoholysis catalysts effect, carry out the main body Synolac that esterification makes theoretical acid number≤5mgKOH/g with polyprotonic acid again, or carry out the main body Synolac that esterification makes theoretical acid number≤5mgKOH/g by dryness oleic acid or semi-drying oleic acid and polyprotonic acid and polyvalent alcohol, or with commercially available solvent-borne type Synolac through removing solvent and modification main body Synolac to theoretical acid number≤5mgKOH/g.
4. prepare aqueous alkide resin emulsion: the main body Synolac that 3. emulsifier resin that 2. step is made and step make, be mixing in 3: 1～1: 3 by weight, after stirring, the limit slowly adds the waterside high-speed stirring, makes aqueous alkide resin emulsion after being uniformly dispersed.
The preparation method of above-mentioned aqueous alkide resin emulsion, its step is used for preparing the oil of Synolac prepolymer of affixture modification or lipid acid, polyvalent alcohol and polyprotonic acid and step in 2., and 3. to be used to prepare oil or lipid acid, polyvalent alcohol and the polyprotonic acid of main body Synolac of theoretical acid number≤5mgKOH/g identical, perhaps different.
The preparation method of above-mentioned aqueous alkide resin emulsion, when 2. its step prepared emulsifier resin, the consumption of affixture calculated by making it account for 15%～30% in the emulsifier resin gross weight; The raw material consumption that forms the urethane segment calculates by making it account for 5%～20% in the emulsifier resin gross weight; The volatile amine consumption calculates by making it account for 1.0%～2.5% in the emulsifier resin gross weight.
The preparation method of above-mentioned aqueous alkide resin emulsion, its emulsion appearance that makes is little Huang, blue slightly phase emulsion liquid; Solids content 40～60%; The pH value is in 7～8 scopes; Stored 6 months ,-4 glasss of viscosity that are coated with of emulsion change less than 5%.
Technique effect of the present invention: emulsion of the present invention is both to have contained the anionic hydrophilic carboxyl in the molecule, the Synolac that contains the urethane of nonionic wetting ability ehter bond and the common modification of affixture again is as emulsifier resin, the aqueous alkide resin emulsion that comes the main body Synolac of emulsification acid number≤5mgKOH/g to form.Because easily acid number≤the 5mgKOH/g of the main body Synolac of degraded has hydrophobicity, hydrophilic radical such as carboxyl and ehter bond then is distributed in the urethane segment of emulsifier resin, thereby after the formation emulsion, at the aqueous phase emulsifier resin emulsion particle (main body Synolac) is enclosed in inside, can avoid the ester bond of main body Synolac Yin Qiyi degraded to contact preferably, and cause emulsion viscosity significantly to reduce, store unsettled phenomenon with the direct of water.Evidence, emulsion of the present invention was stored 6 months, and viscosity changes less than 5%, and package stability significantly improves, and general commercially available aqueous alkide resin emulsion is after storing 6 months, but significantly reduction is over half approximately for viscosity; In addition, owing to both contained the anionic hydrophilic carboxyl in the emulsifier resin molecule of the present invention, contain nonionic wetting ability ehter bond again, therefore, emulsifier resin of the present invention has the character of anionic emulsifier and nonionic emulsifier simultaneously, thereby emulsifying effectiveness obviously is better than having surpassed the general emulsion of only using nonionic emulsifier especially with the mechanical stability of single nonionic emulsifier or single anionic emulsifier, especially emulsion;
In addition, because the emulsifier resin that institute of the present invention synthetic plays emulsifying effect is the Synolac through urethane and the common modification of affixture, after volatile amine neutralization is made, in the Synolac segment of its molecule, contain two keys and hydroxyl, therefore, the effect that not only has emulsifying agent, can also participate in the dry solidification of main body Synolac, thereby the drying property of filming is improved, carry out the emulsive emulsion but also overcome the use small-molecular emulsifier, because of small-molecular emulsifier wherein can not participate in the coating film forming, and the shortcoming of infringement film performance (as water tolerance etc.).
When the synthetic emulsifier resin, the volatile amine consumption that the present invention adopts is 1.0%～2.5% of an emulsifier resin gross weight, the pH value that has guaranteed aqueous alkide resin emulsion of the present invention is in 7～8 scopes, be bordering on neutrality, thereby, can also avoid existing aqueous alkide resin emulsion to accelerate the disadvantageous effect of ester bond degraded because of the pH value is too high.
Embodiment
Below in conjunction with embodiment the present invention is further described, but is not limited thereto.The raw materials used coating commercially available product that is among the embodiment, the raw material consumption is the weight part in gram.Resinous acid value is measured by the method for stipulating among the GB/T6743-86 among the embodiment.
Embodiment 1 preparation affixture (being called for short J)
(1) prescription sees Table 1;
(2) concrete operations
In the four-hole boiling flask that agitator, thermometer, condenser device are housed, the poly glycol monomethyl ether-1000 or the poly glycol monomethyl ether-2000 that add formula ratio in the table 1) and the tetrahydrophthalic anhydride component, and the triethylamine catalyzer that adds total amount 0.1% (weight part), after slowly being warming up to 190 ℃, it is qualified that isothermal reaction to theoretical acid number is, make affixture J1 and J2, store standby;
Table 1
| Affixture | J1 | J2 |
| Poly glycol monomethyl ether-1000 | 92.9(0.046mol) | - |
| Poly glycol monomethyl ether-2000 | - | 86.8(0.087mol) |
| Tetrahydrophthalic anhydride | 7.1(0.047mol) | 13.2(0.087mol) |
| The acid number of affixture (mgKOH/g) | 26.5 | 49.0 |
Annotate 1: the poly glycol monomethyl ether of affixture J1-1000 with the mol ratio of tetrahydrophthalic anhydride is: 0.98; The poly glycol monomethyl ether of affixture J2-2000 with the mol ratio of tetrahydrophthalic anhydride is: 1.00;
Annotate 2: poly glycol monomethyl ether-the 1000th, molecular weight are 1000 poly glycol monomethyl ether; Poly glycol monomethyl ether-the 2000th, molecular weight are 2000 poly glycol monomethyl ether;
Embodiment 2 preparation emulsifier resins (being called for short A)
(1) prescription sees Table 2-1,2-2 and 2-3;
Raw material consumption when table 2-1 uses the affixture modification
| Material name | A1 | A2 | A3 | A4 |
| Dehydrated castor oleic acid | 35.9 | 42.9 | 42.9 | 46.5 |
| Affixture J1 | 56.1 | 28.1 | - | - |
| Affixture J2 | - | - | 56.1 | 28.1 |
| Tetra hydro Phthalic anhydride | 46.2 | 13.3 | 46.2 | 13.3 |
| TriMethylolPropane(TMP) | 53.9 | - | 53.9 | - |
| Tetramethylolmethane | - | 19.3 | - | 19.3 |
| Reflux solvent (dimethylbenzene) | 20 | 20 | 20 | 20 |
| The acid number (mgKOH/g) of affixture modified alkyd resin prepolymer | 3.5 | 2.1 | 4.3 | 3.3 |
The raw material consumption of table 2-2 when polyurethane-modified
| Material name | A1 | A2 | A3 | A4 |
| Isophorone diisocyanate | 19.8 | 13.6 | 19.8 | 13.6 |
| Dimethylol propionic acid | 6.0 | 4.1 | 6.0 | 4.1 |
| Dibutyl tin laurate | 0.01 | 0.01 | 0.01 | 0.01 |
| N-Methyl pyrrolidone | 60 | 30 | 60 | 30 |
| Theoretical acid number (mgKOH/g) | 12.0 | 14.7 | 11.6 | 13.7 |
Table 2-3 with in the volatile amine and the time the raw material consumption
| Material name | A1 | A2 | A3 | A4 |
| Triethylamine | 3.6 | 2.5 | 3.6 | 2.5 |
(2) concrete operations
In the four-hole boiling flask that agitator, thermometer, condenser, water trap and logical nitrogen device are housed, add all raw materials among the table 2-1, open nitrogen, slowly be warming up to 180 ℃ of reflux dewaterings after two hours, be warming up to 235 ℃ of reactions and kept sampling 8～9 hours, after the survey acid number is qualified, extract solvent xylene, be cooled to then and make affixture modified alkyd resin prepolymer below 80 ℃, standby.
On above-mentioned reaction unit basis, remove water trap, connect behind the condenser N-Methyl pyrrolidone and the dimethylol propionic acid of formula ratio among the adding table 2-2, be warming up to 80 ℃, keep half an hour, after treating that dimethylol propionic acid all dissolves, the isophorone diisocyanate and the dibutyl tin laurate that add formula ratio, 80 ℃ of insulation reaction 3～5 hours, reaction finishes when being about zero by dibutylamine method detection-NCO content, makes the alkyd resin of affixture and the common modification of urethane, be cooled to below 40 ℃, with the triethylamine neutralization among the table 2-3, stir discharging after 15 minutes, make emulsifier resin A1, A2, A3 and A4 preserve standby.
In gained emulsifier resin A1, A2, A3 and A4 gross weight, affixture, urethane segment and volatile amine consumption proportion see Table 2-4.
Table 2-4
| A1 | A2 | A3 | A4 | |
| The shared per-cent of affixture, % | 19.93 | 18.27 | 19.44 | 17.85 |
| The shared per-cent of urethane segment, % | 9.16 | 11.51 | 8.94 | 11.24 |
| The shared per-cent of volatile amine consumption, % | 1.28 | 1.63 | 1.25 | 1.59 |
Embodiment 3 preparation main body Synolac (being called for short B)
(1) prescription sees Table 3;
Table 3
| Material name | B1 | B2 |
| Dehydrated castor oleic acid | 40.5 | 64.0 |
| Tetra hydro Phthalic anhydride | 33.9 | 21.5 |
| TriMethylolPropane(TMP) | 32.3 | - |
| Tetramethylolmethane | - | 21.2 |
| Reflux solvent (dimethylbenzene) | 20 | 20 |
| Final control acid number (mgKOH/g) | ≤5 | ≤5 |
| Hydroxyl value (mgKOH/g) | 67.6 | 58.3 |
(2) concrete operations
In the four-hole boiling flask that agitator, thermometer, condenser, water trap and logical nitrogen device are housed, add all feed composition in the table 3, open nitrogen, slowly be warming up to 180 ℃ of reflux dewaterings after two hours, be warming up to 235 ℃ of reactions and kept sampling 8～9 hours, after the survey acid number is qualified, extract solvent xylene, cooling discharge makes main body Synolac B1 and B2 and preserves standby then.
The commercially available solvent borne alkyd resin production of embodiment 4 usefulness main body Synolac B3
In the four-hole boiling flask that agitator, thermometer, condenser and logical nitrogen device are housed, add 200 parts of commercially available Synolac (trade mark 389-9), removed solvent in 1 hour at 180 ℃ of reduced-pressure backflows, again with 4.9 parts of tertiary carbonic acid glycidyl esters, reacted 2 hours at 190 ℃～200 ℃, sampling detecting acid number＜5mgKOH/g, cooling discharge make main body Synolac B3 and preserve standby.
Embodiment 5 preparations aqueous alkide resin emulsion R1 of the present invention
Get the emulsifier resin A1 of 100 parts of embodiment, 1 preparation and the main body Synolac B1 of 100 parts of embodiment 3 preparations, after stirring, under high-speed stirring, slowly add 186 parts in water, the back discharging is uniformly dispersed, promptly make aqueous alkide resin emulsion R1 of the present invention, it is blue phase emulsion liquid, and solids content is about 45%, and the pH value is 7.5, viscosity changes (stored 6 months, and be coated with-4 glasss) less than 5%.
Embodiment 6 preparations aqueous alkide resin emulsion R2 of the present invention
Get the emulsifier resin A1 of 100 parts of embodiment, 2 preparations and the main body Synolac B2 of 200 parts of embodiment 3 preparations, after stirring, under high-speed stirring, slowly add 237 parts in water, the back discharging is uniformly dispersed, promptly make aqueous alkide resin emulsion R2 of the present invention, it is little yellow emulsion liquid, and solids content is about 50%, and the pH value is 7.6, viscosity changes (stored 6 months, and be coated with-4 glasss) less than 5%.
Embodiment 7 preparations aqueous alkide resin emulsion R3 of the present invention
Get the emulsifier resin A4 of 200 parts of embodiment, 2 preparations and the main body Synolac B1 of 100 parts of embodiment 3 preparations, after stirring, under high-speed stirring, slowly add 158 parts in water, the back discharging is uniformly dispersed, promptly make aqueous alkide resin emulsion R3 of the present invention, it is blue phase emulsion liquid, and solids content is about 55%, and the pH value is 7.6, viscosity changes (stored 6 months, and be coated with-4 glasss) less than 5%.
Embodiment 8 preparations aqueous alkide resin emulsion R4 of the present invention
Get the emulsifier resin A4 of 150 parts of embodiment, 2 preparations and the main body Synolac B2 of 100 parts of embodiment 3 preparations, after stirring, under high-speed stirring, slowly add 176 parts in water, the back discharging is uniformly dispersed, promptly make aqueous alkide resin emulsion R4 of the present invention, it is blue phase emulsion liquid, and solids content is about 50%, and the pH value is 7.5, viscosity changes (stored 6 months, and be coated with-4 glasss) less than 5%.
Embodiment 9 preparations aqueous alkide resin emulsion R5 of the present invention
Get the emulsifier resin A4 of 100 parts of embodiment, 2 preparations and the main body Synolac B3 of 150 parts of embodiment 4 preparations, after stirring, under high-speed stirring, slowly add 210 parts in water, the back discharging is uniformly dispersed, promptly make aqueous alkide resin emulsion R5 of the present invention, it is the mutually little yellow emulsion liquid of indigo plant, and solids content is about 50%, and the pH value is 7.5, viscosity changes (stored 6 months, and be coated with-4 glasss) less than 5%.
Commercially available aqueous alkide resin emulsion (trade mark HD-DS006) is measured the viscosity variation (to be stored 6 months, be coated with-4 glasss), the result is than more than the original viscosity drop by half, and the aqueous alkide resin emulsion viscosity variation of the present invention of embodiment 5～9 (was stored 6 months, be coated with-4 glasss) less than 5%, show that aqueous alkide resin emulsion of the present invention and preparation method thereof can make the package stability (representing with the viscosity variation) of emulsion obviously improve.
Aqueous alkide resin emulsion of the present invention can be according to the height of the hydroxyl value of emulsified main body Synolac, be mixed with air drying type (atmospheric oxidation drying) coating or drying-type coating, be applicable to general industry protective coating or civilian paint field, both can be used as finish paint and used, also can be used as priming paint and use.When adopting the present invention to prepare colored paint, both can use non-ionic dispersing agent, also can use the negatively charged ion non-ionic dispersing agent.
Claims (9)
1, a kind of aqueous alkide resin emulsion is characterized in that, contains emulsifier resin and main body Synolac, and the weight ratio of the two is 3: 1～1: 3, and emulsion particle is the main body Synolac, and emulsified dose of resin of its appearance surrounds;
The theoretical acid number of described emulsifier resin is 10～20mgKOH/g, it is the Synolac by affixture and the common modification of urethane, form through the volatile amine neutralization again, the consumption of volatile amine is 1.0%～2.5% of an emulsifier resin gross weight, and affixture is the polymkeric substance that contains nonionic wetting ability ehter bond; Contain anionic hydrophilic carboxyl and nonionic wetting ability ehter bond in the emulsifier resin molecule;
Acid number≤the 5mgKOH/g of described main body Synolac is hydrophobic resin.
2, aqueous alkide resin emulsion according to claim 1 is characterized in that, in the emulsifier resin gross weight, affixture accounts for 15%～30%, and the urethane segment accounts for 5%～20%.
3, aqueous alkide resin emulsion according to claim 1, it is characterized in that, described affixture be with poly glycol monomethyl ether and tetrahydrophthalic anhydride as raw material, the mol ratio of the two is 0.95: 1.05～1.05: 0.95, in the presence of catalyzer, carry out the product of ring-opening polymerization.
4, aqueous alkide resin emulsion according to claim 1, it is characterized in that, the main body Synolac is dryness or semi-drying oil and alcoholysis polyvalent alcohol, after alcoholysis under high temperature and the alcoholysis catalysts effect, carry out the product of esterification again with polyprotonic acid, or carry out the product of esterification by dryness oleic acid or semi-drying oleic acid and polyprotonic acid and polyvalent alcohol, or with commercially available solvent-borne type Synolac through removing solvent and modification product to acid number≤5mgKOH/g.
5, aqueous alkide resin emulsion according to claim 1 is characterized in that, emulsion appearance is little Huang, blue slightly phase emulsion liquid; Solids content 40～60%; The pH value is in 7～8 scopes; Stored 6 months ,-4 glasss of viscosity that are coated with of emulsion change less than 5%.
6, the preparation method of the described aqueous alkide resin emulsion of a kind of claim 1 is characterized in that, comprises the following steps:
1. prepare affixture: as raw material, the mol ratio of the two is 0.95: 1.05～1.05: 0.95 with poly glycol monomethyl ether and tetrahydrophthalic anhydride, in the presence of catalyzer, be warming up to 190 ℃ after and isothermal reaction can be standby to reaching theoretical acid number;
2. prepare the emulsifier resin that acid number is 10～20mgKOH/g: earlier by dryness or semi-drying oil and alcoholysis polyvalent alcohol after alcoholysis under high temperature and the alcoholysis catalysts effect, 1. affixture and the polyprotonic acid that makes with step carries out esterification again, or the affixture that directly 1. makes by dryness oleic acid or semi-drying oleic acid and step, polyprotonic acid and polyvalent alcohol carry out esterification and obtain the Synolac prepolymer of affixture modification, then carry out modification with aliphatic polyisocyante and carboxylic polyvalent alcohol through the urethane that the ammonia esterification forms again, obtain the Synolac of affixture and the common modification of urethane, after the volatile amine neutralization makes emulsifier resin;
3. the main body Synolac for preparing theoretical acid number≤5mgKOH/g: by dryness or semi-drying oil and alcoholysis polyvalent alcohol, after alcoholysis under high temperature and the alcoholysis catalysts effect, carry out the main body Synolac that esterification makes theoretical acid number≤5mgKOH/g with polyprotonic acid again, or carry out the main body Synolac that esterification makes theoretical acid number≤5mgKOH/g by dryness oleic acid or semi-drying oleic acid and polyprotonic acid and polyvalent alcohol, or with commercially available solvent-borne type Synolac through removing solvent and modification main body Synolac to theoretical acid number≤5mgKOH/g.
4. prepare aqueous alkide resin emulsion: the main body Synolac that 3. emulsifier resin that 2. step is made and step make, be mixing in 3: 1～1: 3 by weight, after stirring, the limit slowly adds the waterside high-speed stirring, makes aqueous alkide resin emulsion after being uniformly dispersed.
7, the preparation method of aqueous alkide resin emulsion according to claim 6, it is characterized in that, step is used for preparing the oil of Synolac prepolymer of affixture modification or lipid acid, polyvalent alcohol and polyprotonic acid and step in 2., and 3. to be used to prepare oil or lipid acid, polyvalent alcohol and the polyprotonic acid of main body Synolac of theoretical acid number≤5mgKOH/g identical, perhaps different.
8, the preparation method of aqueous alkide resin emulsion according to claim 6 is characterized in that, when 2. step prepared emulsifier resin, the consumption of affixture calculated by making it account for 15%～30% in the emulsifier resin gross weight; The raw material consumption that forms the urethane segment calculates by making it account for 5%～20% in the emulsifier resin gross weight; The volatile amine consumption calculates by making it account for 1.0%～2.5% in the emulsifier resin gross weight.
9, the preparation method of aqueous alkide resin emulsion according to claim 6 is characterized in that, the emulsion appearance that makes is little Huang, blue slightly phase emulsion liquid; Solids content 40～60%; The pH value is in 7～8 scopes; Stored 6 months ,-4 glasss of viscosity that are coated with of emulsion change less than 5%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626956A (en) * | 2013-11-22 | 2014-03-12 | 深圳市新纶科技股份有限公司 | Modified polyisocyanate, water dispersible crosslinking agent and preparation method thereof |
| 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 |
| CN107200852A (en) * | 2017-05-22 | 2017-09-26 | 成都杰晟蜀邦新材料科技有限公司 | A kind of emulsifying agent of alkide resin emulsion and preparation method thereof |
| CN113874422A (en) * | 2019-04-08 | 2021-12-31 | 帕思嘉公司 | Novel nanoemulsions, methods for their production and related uses and products |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100494274C (en) * | 2006-06-05 | 2009-06-03 | 中国化工建设总公司常州涂料化工研究院 | A kind of aqueous alkyd resin emulsion and preparation method thereof |
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2008
- 2008-09-05 CN CN2008101958559A patent/CN101348604B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103626956A (en) * | 2013-11-22 | 2014-03-12 | 深圳市新纶科技股份有限公司 | Modified polyisocyanate, water dispersible crosslinking agent and preparation method thereof |
| CN103626956B (en) * | 2013-11-22 | 2016-03-30 | 深圳市新纶科技股份有限公司 | A kind of modified polyisocyanate, water dispersible crosslinker and preparation method thereof |
| 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 |
| CN106866950B (en) * | 2017-01-10 | 2018-10-30 | 河北晨阳工贸集团有限公司 | Interior wall sealing wax aqueous alkide resin emulsion and preparation method thereof |
| CN107200852A (en) * | 2017-05-22 | 2017-09-26 | 成都杰晟蜀邦新材料科技有限公司 | A kind of emulsifying agent of alkide resin emulsion and preparation method thereof |
| CN113874422A (en) * | 2019-04-08 | 2021-12-31 | 帕思嘉公司 | Novel nanoemulsions, methods for their production and related uses and products |
| CN113874422B (en) * | 2019-04-08 | 2025-03-25 | 帕思嘉公司 | Nanoemulsion, its production method and related uses and products |
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| CN101348604B (en) | 2012-04-04 |
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