CN101348604B - Aqueous alkide resin emulsion and preparation thereof - Google Patents
Aqueous alkide resin emulsion and preparation thereof Download PDFInfo
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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.It is main that present Synolac is still with 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 will be wherein with salify to obtain water soluble alkyd resin or aqueous-dispersing alkyd resin.For example adopting trimellitic anhydride or PMA acid anhydride is aqueous monomers; Prepare water soluble alkyd resin through single stage method and two-step approach, the Water-borne modification of free-radical polymerized incompatible realization Synolac and for example takes place through the unsaturated dibasic acid (MALEIC ANHYDRIDE) in acrylic monomer and the alkyd prepolymer, the conjugated double bond on the grease etc.But, since utilize aqueous alkide resin that salt forming method makes all will through in the organic amine with the Synolac that obtains Water-borne modification, 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 neutralize 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 in Synolac, introduces the polymkeric substance of non-ionic group hydroxyl and ether.For example, through in Synolac, introducing the Water-borne modification that polyoxyethylene glycol is realized Synolac, the polyoxyethylene glycol of and for example in Synolac, introducing monoalkoxy 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 TX10, AEO 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 its outer indumentum emulsifier resin surrounds;
The theoretical acid number of said 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 property carboxyl and nonionic wetting ability ehter bond in the emulsifier resin molecule;
Acid number≤the 5mgKOH/g of said 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 THPA, 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 THPA, in the presence of catalyzer, be warming up to 190 ℃ after and isothermal reaction can be subsequent use 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. the affixture and the polyprotonic acid that make with step carry out esterification again; Or the affixture, polyprotonic acid and the polyvalent alcohol that are directly 1. made by dryness oleic acid or semi-drying oleic acid and step 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; By weight being 3:1～1:3 mixing; 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; Oil or lipid acid, polyvalent alcohol and the polyprotonic acid of main body Synolac that 3. oil or lipid acid, polyvalent alcohol and polyprotonic acid and the step that its step is used for preparing the Synolac prepolymer of affixture modification in 2. be used to prepare theoretical acid number≤5mgKOH/g is 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 in the emulsifier resin gross weight, account for 15%～30%; The raw material consumption that forms the urethane segment calculates by making it in the emulsifier resin gross weight, account for 5%～20%; The volatile amine consumption calculates by making it in the emulsifier resin gross weight, account for 1.0%～2.5%.
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 anionic hydrophilic property carboxyl in the molecule; The Synolac of urethane and the common modification of affixture that contains nonionic wetting ability ehter bond again is as emulsifier resin, the aqueous alkide resin emulsion that comes the main body Synolac of emulsification acid number≤5mgKOH/g to form.Has hydrophobicity owing to be prone to the acid number≤5mgKOH/g of the main body Synolac of degraded; 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 avoids 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 anionic hydrophilic property 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 superior to 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 neutralizes and processes; In the Synolac segment of its molecule, contain two keys and hydroxyl; Therefore, not only have the effect of 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 be participated in the coating film forming, and the shortcoming of infringement film performance (like 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 be not limited thereto.The raw materials used coating that is is used commercially available article among the embodiment, and 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 is seen table 1;
(2) concrete operations
In the four-hole boiling flask that whisking appliance, TM, 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 THPA component; And the triethylamine catalyzer that adds total amount 0.1% (weight part), slowly be warming up to 190 ℃ after, it is qualified that isothermal reaction to theoretical acid number is; Make affixture J1 and J2, store subsequent use;
Table 1
| Affixture | J1 | J2 |
| Poly glycol monomethyl ether-1000 | 92.9(0.046mol) | - |
| Poly glycol monomethyl ether-2000 | - | 86.8(0.087mol) |
| THPA | 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 THPA is: 0.98;
The poly glycol monomethyl ether of affixture J2-2000 with the mol ratio of THPA 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 is seen table 2-1,2-2 and 2-3;
Raw material consumption when showing 2-1 with 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 (YLENE) | 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 |
The 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 whisking appliance, TM, condensing surface, 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 ℃, subsequent use.
On above-mentioned reaction unit basis, remove water trap, connect behind the condensing surface N-Methyl pyrrolidone and the dimethylol propionic acid of formula ratio among the adding table 2-2; Be warming up to 80 ℃, keep half a hour, treat that dimethylol propionic acid is all after the dissolving; The isophorone diisocyanate and the dibutyl tin laurate that add formula ratio, 80 ℃ of insulation reaction 3～5 hours, reaction end when being about zero by dibutylamine method detections-NCO content; Make 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 and preserve subsequent use.
In gained emulsifier resin A1, A2, A3 and A4 gross weight, affixture, urethane segment and volatile amine consumption proportion are seen 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 is seen 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 (YLENE) | 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 whisking appliance, TM, condensing surface, 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 subsequent use then.
The commercially available solvent borne alkyd resin production of embodiment 4 usefulness main body Synolac B3
In the four-hole boiling flask that whisking appliance, TM, condensing surface 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, with 4.9 parts of tertiary carbonic acid glycidyl esters, reacted 2 hours again at 190 ℃～200 ℃; < 5mgKOH/>g, cooling discharge make main body Synolac B3 and preserve subsequent use sampling detecting acid number.
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 that is uniformly dispersed promptly makes 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 that is uniformly dispersed promptly makes 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 that is uniformly dispersed promptly makes 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 that is uniformly dispersed promptly makes 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 that is uniformly dispersed promptly makes 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 of the present invention of embodiment 5～9 changes (stored 6 months, and be coated with-4 glasss) less than 5%, shows 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 by the height of the hydroxyl value of emulsive main body Synolac; Be mixed with air drying type (atmospheric oxidation is dry) 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 (8)
1. an 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 its outer indumentum emulsifier resin surrounds;
The theoretical acid number of said emulsifier resin is 10～20mgKOH/g, and it is the Synolac by affixture and the common modification of urethane, forms through the volatile amine neutralization again; The consumption of volatile amine is 1.0%～2.5% of an emulsifier resin gross weight; Affixture is the polymkeric substance that contains nonionic wetting ability ehter bond, be with poly glycol monomethyl ether and THPA 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; Contain anionic hydrophilic property carboxyl and nonionic wetting ability ehter bond in the emulsifier resin molecule;
Acid number≤the 5mgKOH/g of said 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; 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.
4. 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%.
5. the preparation method of the described aqueous alkide resin emulsion 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 THPA, in the presence of catalyzer, be warming up to 190 ℃ after and isothermal reaction can be subsequent use 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. the affixture and the polyprotonic acid that make with step carry out esterification again; Or the affixture, polyprotonic acid and the polyvalent alcohol that are directly 1. made by dryness oleic acid or semi-drying oleic acid and step 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.
4. prepare aqueous alkide resin emulsion: the main body Synolac that 3. emulsifier resin that 2. step is made and step make; By weight being mixing in 3: 1～1: 3; After stirring, the limit slowly adds the waterside high-speed stirring, makes aqueous alkide resin emulsion after being uniformly dispersed.
6. the preparation method of aqueous alkide resin emulsion according to claim 5; It is characterized in that; Oil or lipid acid, polyvalent alcohol and the polyprotonic acid of main body Synolac that 3. oil or lipid acid, polyvalent alcohol and polyprotonic acid and the step that step is used for preparing the Synolac prepolymer of affixture modification in 2. be used to prepare theoretical acid number≤5mgKOH/g is identical, perhaps different.
7. the preparation method of aqueous alkide resin emulsion according to claim 5 is characterized in that, when 2. step prepared emulsifier resin, the consumption of affixture calculated by making it in the emulsifier resin gross weight, account for 15%～30%; The raw material consumption that forms the urethane segment calculates by making it in the emulsifier resin gross weight, account for 5%～20%; The volatile amine consumption calculates by making it in the emulsifier resin gross weight, account for 1.0%～2.5%.
8. the preparation method of aqueous alkide resin emulsion according to claim 5 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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| 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 |
| 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 |
| EP3953414B1 (en) * | 2019-04-08 | 2023-06-07 | Palsgaard A/S | Novel nanoemulsions, methods of their production and related uses and products |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085858A (en) * | 2006-06-05 | 2007-12-12 | 中国化工建设总公司常州涂料化工研究院 | Water alkyd resin emulsion and preparing method thereof |
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2008
- 2008-09-05 CN CN2008101958559A patent/CN101348604B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085858A (en) * | 2006-06-05 | 2007-12-12 | 中国化工建设总公司常州涂料化工研究院 | Water alkyd resin emulsion and preparing method thereof |
Non-Patent Citations (2)
| Title |
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| JP昭56-88425A 1981.07.17 |
| 胡涛等.《水性醇酸树脂涂料的研究及应用》.《国内外涂料工业》.2004,(第5期),全文. * |
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| CN101348604A (en) | 2009-01-21 |
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