CN100392017C - Acrylate polyurethane water-dispersed resin and its making method - Google Patents
Acrylate polyurethane water-dispersed resin and its making method Download PDFInfo
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Abstract
The present invention relates to an acrylic acid polyurethane water dispersible resin with high solid content, and a preparation method of the resin. The solid content of the resin reaches 41 to 45%, and the resin does not contain free emulsifying agents and organic solvents. The preparation method of the resin is characterized in that firstly, under the condition that partial vinyl monomers which can be freely polymerized are used as mediums, NCO group terminated polyurethane prepolymer is prepared, and then, the prepolymer is neutralized and dispersed by water to obtain water dispersible polyurethane dispersoid which is coated with the vinyl monomers; residual vinyl monomers and initiating agents are added into the dispersoid to carry out free radical polymerization, and then, the acrylic acid polyurethane water dispersible resin in a structure with a nucleus and a shell is formed. The resin of the present invention has the advantages of high solid content, high drying speed, stable storage, good adhesive force, good flexibility, good hardness, good water resistance, low VOC content, proper price performance, etc., and a film can be formed at normal temperature. The resin of the present invention can be used for preparing high-grade woodenware paint and aqueous leather lacquer, and can also be used for coating the surfaces of plastics, metals, textiles, automobiles, etc.
Description
Technical field
The present invention relates to a kind of acrylate polyurethane water-dispersed resin and preparation method thereof, particularly a kind of high solid acrylate polyurethane water-dispersed resin and preparation method thereof.
Background technology
Because the special segmented structure of urethane makes it have more excellent physical and mechanical properties, as performances such as hardness, snappiness, shock resistance, sticking power; Water tolerance, solvent resistance and cost are lower preferably and acrylic ester emulsion has.Therefore a lot of researchists combine the two to obtain more excellent performance being devoted to.Through the development of recent years, acrylate polyurethane water-dispersed resin has obtained development faster.The acrylate polyurethane water-dispersed resin that adopts chemical process to prepare has not only had both the characteristic of acrylate and urethane, and film formation at low temp is good, excellent storage stability.But at present a large amount of acrylate polyurethane water-dispersed resins has used certain amount of organic solvent and emulsifying agent in preparation process, and this has not only reduced the patience of filming, and also can bring certain influence to environment and people are healthy simultaneously.Acrylate polyurethane water-dispersed resin amount of solid content a large amount of before the more important thing is is not high, usually below 35%.Because solid part is low, the water-content height has prolonged the time of drying of filming, and has influenced the construction application performance with its coatings formulated, has limited the use range of acrylate polyurethane water-dispersed resin.
Summary of the invention
The object of the present invention is to provide acrylate polyurethane water-dispersed resin of a kind of amount of solid content height and compliance with environmental protection requirements and preparation method thereof, this resin is a shell with urethane, is nuclear with the acrylate, and amount of solid content reaches 41～45%.Owing to have higher solid part, not only rate of drying is fast, and the film performance excellence with the aqueous woodware paint of resins of the present invention, and for example hardness, snappiness, water tolerance, alcohol resistance etc. are better, also do not contain organic solvent simultaneously, compliance with environmental protection requirements.
The technical scheme that realizes the object of the invention is: a kind of acrylate polyurethane water-dispersed resin, its resin particle comprises a kind of shell of urethane and a kind of nuclear of acrylate, amount of solid content does not contain free emulsifying agent and organic solvent up to 41～45%, and the composition of forming shell comprises:
1. polyisocyanates,
2. polymer polyatomic alcohol,
3. low molecular weight polyols,
4. the polyvalent alcohol that contains hydrophilic and ionic groups,
5. neutralizing agent,
6. chainextender,
Wherein the NCO/OH mol ratio is 1.1～2.0; The mass percent that the polyvalent alcohol content that contains hydrophilic and ionic groups accounts for whole resin solid is 1～15%; The neutralizing agent consumption is to need neutral ionic group normal 90%～120% in the system; The consumption of chainextender is at least system residue NCO group normal 80～110%; The composition of forming nuclear comprises the vinyl monomer and the initiator of at least a free redical polymerization; The mass ratio of its mesochite and nuclear is 4: 1～1: 2.
In above-mentioned water-dispersed resin, polyisocyanates is an aliphatics, alicyclic, aromatic diisocyanate, or its miscellany, for example, 1, hexamethylene-diisocyanate (HDI), 2,4-tolylene diisocyanate (2,4-TDI), 2,6 tolylene diisocyanates (2,6-TDI), ditan-4,4 '-vulcabond (MDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), 1,4-cyclohexyl diisocyanate (CHDI), 4,4 '-dicyclohexyl methane diisocyanate (HMDI), tetramethylxylylene diisocyanate (TMXDI), 2,2,4-trimethylammonium hexamethylene diisocyanate (TMDI), naphthalene-1,5-vulcabond (NDI), Methylcyclohexyl diisocyanate (HTDI) wherein is preferably HDI, MDI, TDI, HMDI, IPDI, TMXDI; Also can use a spot of triisocyanate, for example the biuret of hexamethylene diisocyanate or tripolymer and isophorone tripolymer.
In above-mentioned water-dispersed resin, can and the polymer polyatomic alcohol of NCO radical reaction be polyether Glycols, polyester diol, polycaprolactone dibasic alcohol, poly-carbonic acid dibasic alcohol or its mixture of molecular weight between 800～2000.Polyether Glycols is the polymer diatomic alcohol of oxyethane, propylene oxide, butylene oxide ring or tetrahydrofuran (THF), or its grafting or segmented copolymer dibasic alcohol, for example, polyoxyethylene enediol, polyoxypropyleneglycol, polytetrahydrofuran diol, polyoxyethylene-propylene oxide copolymerization glycol, alkene under high pressure with the graft copolymer glycol of epoxy alkane; Polyester diol is a dibasic alcohol (ethylene glycol for example, 1, the 2-propylene glycol, 1, the 4-butyleneglycol, 1, the 6-hexylene glycol, neopentyl glycol, glycol ether, dipropylene glycol, TriMethylolPropane(TMP), glycerine, dihydroxyphenyl propane, tetramethylolmethane) and di-carboxylic acid or acid anhydrides (hexanodioic acid for example, nonane diacid, sebacic anhydride, Succinic Acid, terephthalic acid, m-phthalic acid, maleic acid, behenic acid, cocinic acid) obtains by polycondensation, for example, the polyethylene glycol adipate glycol, poly-adipate glycol-propylene glycol ester glycol, poly-hexanodioic acid glycol ether esterdiol, poly-adipate glycol-glycol ether esterdiol, poly-hexanodioic acid-1,4-butanediol ester glycol, poly-adipate glycol-1,4-butanediol ester glycol, poly-hexanodioic acid neopentyl glycol-1,6-hexylene glycol esterdiol, poly-hexanodioic acid Viscotrol C esterdiol; Polycaprolactone polyol, for example polycaprolactone dibasic alcohol and poly-trimethylammonium penta lactones glycol; PCDL, for example, poly-carbonic acid-1,6-hexylene glycol esterdiol, poly-carbonic acid-1,5-pentadiol ester glycol, poly-carbonic acid-1,4-butanediol ester glycol, poly-carbonic acid-1,4-butyleneglycol-1,6-hexylene glycol esterdiol; Wherein better polymerization thing polyvalent alcohol is polyoxygenated glycol, polytetrahydrofuran diol, poly-adipate glycol-1,4-butanediol ester glycol, poly-hexanodioic acid neopentyl glycol-1,6-hexylene glycol esterdiol, polycaprolactone glycol, poly-carbonic acid-1,6-hexylene glycol esterdiol.Best polymer polyatomic alcohol is polyoxygenated glycol, polytetrahydrofuran diol.Can also use polyether triol, acrylate polyvalent alcohol, polybutadiene diol etc. in addition.
In above-mentioned water-dispersed resin, can and the low molecular weight polyols of NCO radical reaction be carbonatoms between 2～15, molecular weight is at the dibasic alcohol below 400, trivalent alcohol, tetravalent alcohol, or its mixture.For example ethylene glycol, propylene glycol, 1,4-butyleneglycol, glycol ether, 1,6-hexylene glycol, neopentyl glycol, Diethylene Glycol, TriMethylolPropane(TMP), glycerine, tetramethylolmethane etc., or its mixture.Wherein low molecular weight polyols is 1 preferably, 4-butyleneglycol, glycol ether, Diethylene Glycol and neopentyl glycol.
An amount of low molecular weight polyols can telomerized polymer segmented structure, change the polymericular weight size, make polymkeric substance obtain some property.
In above-mentioned water-dispersed resin, in order to guarantee that prepolymer can disperse well in water, will in prepolymer, introduce hydrophilic and ionic groups, these hydrophilic and ionic groups can be carboxylic acid group, sulfonic group, sulfate or phosphate, for example, have the mercaptan of dibasic alcohol, diamine and two functional groups of a hydroxy-acid group, wherein best is the hydroxy-acid group that contains activity hydroxy; The hydrophilic and ionic groups such as hydroxy-acid group of certain content will be arranged in the polyurethane prepolymer, and hydrophilic and ionic groups such as hydroxy-acid group are neutralized salify, thereby make polyurethane prepolymer have water dispersible.The best polyvalent alcohol that contains hydrophilic and ionic groups is dimethylol propionic acid, dimethylolpropionic acid.Usually, the mass percent that the polyvalent alcohol content that contains hydrophilic and ionic groups accounts for whole resin solid is 1～15%, preferably 2～10%.
In above-mentioned water-dispersed resin, can Trimethylamine 99, triethylamine, tri-isopropyl amine, Tributylamine, triethylene diamine, N be arranged with salifiable neutralizing agents of hydrophilic and ionic groups reaction shape such as carboxylic acid, sulfonic acid, N-dimethylcyclohexylam,ne, N, accelerine, N-methylmorpholine, N-ethylmorpholine, N-crassitude, N, N-dimethylethanolamine, N, N-diethylethanolamine, N methyl piperazine.Also can use the neutralizing agent of some other type, be best with tertiary amines neutralizing agent (for example triethylamine) still, because the tertiary amines neutralizing agent can not react with the isocyanate groups of surplus in the prepolymer.For the stability of guarantee system, the amount that adds neutralizing agent is at least needs the neutralize ions group normal 90% in the system, be preferably 100%, higher again, also can as height to 120%.Need the neutral ionic group normal 90% in the system if the neutralizing agent consumption is less than, system can be unstable, the gel of easily flocculating.
In above-mentioned water-dispersed resin, the functional compound that can carry out chain extension to the polyurethane prepolymer water dispersion is polyamine and polyalcohols: aliphatics, alicyclic, aromatic primary amine or secondary amine, or heterocyclic amine or diamines, aminosilane or aminosiloxane, water-dispersion or emulsifying water polyisocyanates, for example, quadrol, propylene diamine, butanediamine, the methylpent diamines, isophorone diamine, piperazine, the 2-methylpiperazine, phenylenediamine, tolylene diamine, diphenyl diamine, hydrazine, dimethylhydrazine, hexanediamide, diethylenetriamine, polynary amine such as triethylene tetramine; Ethylene glycol, glycerol, tetramethylolmethane, 1,2-propylene glycol, 1, ammediol, neopentyl glycol, 1, polyalcohols such as 4-butyleneglycol; Or its mixture.Wherein be preferably quadrol, methylpent diamines, isophorone diamine, hydrazine, ethylene glycol, 1,4-butyleneglycol etc.It is normal 80% that the consumption of chainextender is at least system residue NCO group, is preferably between 100～110%.For ternary or the chainextender more than the ternary, control their consumption in order to avoid cause over-drastic crosslinked.
In above-mentioned water-dispersed resin, the vinyl monomer of free redical polymerization can contain specific groups such as organic siloxane group, hydroxyl, diene ester, amide group, carbonyl or its mixture for containing the vinyl monomer of 1 unsaturated double-bond at least in the monomer.
Typical unsaturated vinyl monomer has vinyl ester monomer, acrylic ester monomer.
The vinyl ester monomer can be vinyl-acetic ester, propionate, vinyl butyrate, vinyl acetate-isopropyl esters, and similar vinyl ester monomer;
Acrylic ester monomer can be a lower alkyl acrylate, the methacrylic acid lower alkyl esters, the alkyl carbon atoms number is between 1～12, for example, (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) propyl acrylate, (methyl) ethyl acrylate, (methyl) cyclohexyl acrylate, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) benzyl acrylate;
The vinyl monomer that can also use some to contain specific groups, for example, the vinyl-based unsaturated monomer of hydroxyl has (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid hydroxy butyl ester, or its mixture; The vinyl-based unsaturated monomer that contains siloxanes group has vinyltriethoxysilane, vinyltrimethoxy silane, allyltrimethoxysilanis, acryloxy Trimethoxy silane, γ-methacryloxypropyl trimethoxy silane, acryloxy propyl trimethoxy silicane, γ-methacryloxypropyl three isopropoxy silane etc.; The vinyl-based unsaturated monomer that contains the diene ester has glycol diacrylate, three polypropyleneglycol diacrylates etc.
Can be according to the require performance of filming, this monomer that contains specific groups is comprised that the dienes monomer selects, the consumption of these particular monomers generally accounts for 0～40% of the whole vinyl-based unsaturated monomer total amount that participates in reaction, is preferably 5～20%.
These monomers can be singly with or be used in combination more than 2 kinds.
On this basis, can also add part and can react the vinyl monomer that forms acrylic ester polymer with above-mentioned vinyl-based unsaturated monomer, as allyl glycidyl, vinyl cyanide, acrylamide, diacetone-acryloamide(DAA), vinylchlorid, vinyl fluoride, 1,1-vinylidene chloride, vinylbenzene, alpha-methyl styrene and similar low alkyl group vinylbenzene.
In above-mentioned water-dispersed resin, being used for causing the initiator that vinyl-based unsaturated monomer carries out radical polymerization can be water-soluble or oil-soluble initiator, for example, Potassium Persulphate, ammonium persulphate, hydrogen peroxide, dibenzoyl peroxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), tert-butyl peroxide and formaldehyde or sodium sulfoxylate formaldehyde, or its mixture.Initiator amount is 0.1～1.0% of a vinyl monomer total amount, is preferably 0.3～0.7%.
A kind of method for preparing the described acrylate polyurethane water-dispersed resin of claim 1 provided by the invention, it is characterized in that: at first in that vinyl-based unsaturated monomer is the polyurethane prepolymer that synthesizes the NCO group end capping under the condition of medium with part, after neutralization and water-dispersion, obtain being wrapped in the polyurethane aqueous dispersion body of vinyl-based unsaturated monomer, last refabrication acrylate polyurethane water-dispersed resin, concrete preparation process in turn includes the following steps:
1.. with the vinyl-based unsaturated monomer of part is medium, add polyisocyanates, polymer polyatomic alcohol, the low molecular weight polyols of formula ratio and contain the polyvalent alcohol of hydrophilic and ionic groups, in the presence of the ammonia esterifying catalyst, in 65～90 ℃ of reactions 4～6 hours, is terminal point with remaining NCO content near theoretical value, obtains the polyurethane prepolymer of above-mentioned NCO group end capping;
2.. resultant 1. is cooled to below 60 ℃, adds the neutralization of tertiary amines neutralizing agent, obtain water dispersible polyurethane prepolymer;
3.. resultant 2. is dispersed in the water of formula ratio, adds chainextender, stir 10～30min, obtain being wrapped in the polyurethane aqueous dispersion body of vinyl-based unsaturated monomer;
4.. resultant 3. is warming up to 70～90 ℃, short run added remaining vinyl monomer and initiator in the prescription in 1～2 hour several times, carry out Raolical polymerizable, be incubated 2～3 hours, obtaining with urethane is that shell, acrylate are the polyurethane water-dispersed resin of nuclear.
In the preparation process of polyurethane prepolymer, need to use the ammonia esterifying catalyst, common catalyzer mainly contains organic tin and tertiary amines, the organic tin catalyzer is effective especially to catalyzing N CO/OH reaction, and tertiary amine catalyst is effective especially to the reaction of isocyanic ester and water, and therefore, the present invention selects the organic tin catalyzer for use, for example, dibutyl tin laurate, stannous octoate etc., its consumption are 0.01～0.2% of polyurethane prepolymer, preferably 0.05～0.10%.
The high solid acrylate polyurethane water-dispersed resin that the present invention is prepared, outward appearance is the sub-translucent liquid of oyster white, resin viscosity is low, amount of solid content is up to 41～45%, and median size is at 50～200nm, and VOC content is less than 1.5%, the physical and mechanical properties excellence, water-tolerant, excellent storage stability, film formation at low temp is good.
The prepared high solid acrylate polyurethane water-dispersed resin of the present invention can prepare various coating, be particularly useful for making high-performance environment protection type woodwork coating and water-based leather dope, also can be used for the application of substrate surface such as paper, scrim, plastics, metal and concrete.
Technique effect of the present invention: because the present invention adopts the soap-free core-shell emulsion technology of preparing, and in preparation process with vinyl-based unsaturated monomer replace organic solvent, and with polyurethane aqueous dispersion body as emulsifying agent, so, the acrylate polyurethane water-dispersed resin with nucleocapsid structure of preparation is the amount of solid content height not only, and do not contain organic solvent and emulsifying agent, compliance with environmental protection requirements.The present invention has mainly comprehensively taked following measure to improve solid part of acrylate polyurethane water-dispersed resin:
1) the ionic charge quantity in the regulation system.
By the consumption of control hydrophilic and ionic groups, the ionic charge quantity that makes system is guaranteeing that prepolymer has suff water and looses low as much as possible under the property condition.
2) structure of regulating the nucleocapsid component is formed and mass ratio.
Main by the relatively low NCO of control: the composition shell that the ratio of OH and selection are suitable and the composition of nuclear, regulating the structure of nucleocapsid component forms and mass ratio, make the polyurethane molecular amount of the composition shell that is synthesized want big, molecule segment will be grown, and in the composition of forming shell, do not use polyfunctional compound or polymkeric substance as far as possible, help shell nuclear is coated; In the composition of forming nuclear, then to add a certain amount of polyfunctional monomer, make its compact construction, so that nuclear is coated by shell;
3) size of adjusting latex particle.
By controlling lower NCO: the ratio of OH, the size that can also regulate latex particle.Make the particle diameter of final resin become big, help reducing the viscosity of resin system, thereby also help improving solid part of resin.”
In addition, in order to guarantee that unsaturated vinyl monomer can be emulsified well, successfully carry out Raolical polymerizable, adopting repeatedly to remaining unsaturated vinyl monomer and initiator, the short run addition method carries out polymerization, help improving the transformation efficiency of unsaturated vinyl monomer, thereby further help improving the amount of solid content of acrylate polyurethane water-dispersed resin.And this technological reaction process is steady, simple to operate, good stability between product batches.
For further improving the performance of filming, in unsaturated vinyl monomer, introduce special function monomer, as specific groups such as hydroxyl, organic siloxane group, diene ester, amide group, carbonyls, synthetic self-crosslinking resin.Film in film process, forming between particle inside, the particle and between particle and the base material suitable crosslinkedly, this self-crosslinking can further promote the performance of filming effectively.
Specific implementation method
Below in conjunction with embodiment the preparation method of water-dispersed resin of the present invention is further described, while also is described the several typical prescription of water-dispersed resin of the present invention, can go out water-dispersed resin of the present invention by these several typical formulation, but the present invention is not limited thereto.
Embodiment 1
At first adopt standard polymerization techniques to synthesize the end capped polyurethane prepolymer of NCO.In the reaction flask of the dried and clean that thermometer, whipping appts, condenser are housed, add 368.6g polyoxypropyleneglycol (molecular-weight average is 1167.0); 56.4g dimethylol propionic acid; 23.0g1; the 4-butyleneglycol, 337.0g isophorone diisocyanate, 300.0g methyl methacrylate; 60.0g butyl acrylate and 1.0g dibutyl tin laurate; 80 ℃ are stirred and be warming up to logical nitrogen protection, insulation reaction 4 hours.Measure nco value near theoretical value, be cooled to below 56 ℃, add the neutralization of 38.0g triethylamine, be scattered in the 2284.5g deionized water after 10～30 minutes in 50 ℃ of insulations, the aqueous solution (40%) that adds the 52.5g quadrol simultaneously carries out chain extension, keeps reaction standby after 15～30 minutes.
Secondly, again according to the synthetic water-dispersed resin of the present invention of soap-free core-shell emulsion synthetic technology.The above-mentioned polyurethane aqueous dispersion body that obtains is warming up to 80 ℃, mixture with 476.0g methyl methacrylate, 134.0g butyl acrylate and 4.2g Potassium Persulphate in 1 hour divides four addings, in 80～85 ℃ of insulations cooling after 2～3 hours, filter discharging, obtain solids content and be 42.0% acrylate polyurethane water-dispersed resin.
Embodiment 2
At first adopt standard polymerization techniques to synthesize the end capped polyurethane prepolymer of NCO.In the reaction flask of the dried and clean that thermometer, whipping appts, condenser are housed, add 322.0g polytetrahydrofuran diol (molecular-weight average is 1000.0); 41.5g dimethylol propionic acid; 29.4g glycol ether; 316.0g isophorone diisocyanate; 280.0g methyl methacrylate, 50.0g butyl acrylate and 1.0g dibutyl tin laurate, logical nitrogen protection; stirring also is warming up to 80 ℃, insulation reaction 4 hours.Measure nco value near theoretical value, be cooled to below 56 ℃, add the neutralization of 38.0g triethylamine, be scattered in the 2083.4g deionized water after 10～30 minutes in 50 ℃ of insulations, the aqueous solution (40%) that adds the 72.5g quadrol simultaneously carries out chain extension, keeps standby after 15～30 minutes.
Secondly, synthesizing water-dispersed resin of the present invention according to the soap-free core-shell emulsion synthetic technology.The above-mentioned polyurethane aqueous dispersion body that obtains is warming up to 80 ℃, mixture with 418.4g methyl methacrylate, 124.6g butyl acrylate, 97g vinyltriethoxysilane and 4.8g Diisopropyl azodicarboxylate in 1 hour divides four addings, in 80～85 ℃ of insulations cooling after 2～3 hours, filter discharging, obtain solids content and be 43.7% acrylate polyurethane water-dispersed resin.
Embodiment 3
At first adopt standard polymerization techniques to synthesize the end capped polyurethane prepolymer of NCO.In the reaction flask of the dried and clean that thermometer, whipping appts, condenser are housed, add 381.4g polyoxypropyleneglycol (molecular-weight average is 1167.0); 44.8g dimethylol propionic acid; 24.0g Diethylene Glycol; 334.0g isophorone diisocyanate; 302.0g methyl methacrylate, 58.0g butyl acrylate and 1.0g dibutyl tin laurate, logical nitrogen protection; stirring also is warming up to 80 ℃, insulation reaction 4 hours.Measure nco value near theoretical value, be cooled to below 56 ℃, add the neutralization of 37.0g triethylamine, be scattered in the 2225.0g deionized water after 10～30 minutes in 50 ℃ of insulations, the aqueous solution (40%) that adds the 67.5g quadrol simultaneously carries out chain extension, keeps standby after 15～30 minutes.
Secondly, synthesizing water-dispersed resin of the present invention according to the soap-free core-shell emulsion synthetic technology.The above-mentioned polyurethane aqueous dispersion body that obtains is warming up to 80 ℃, mixture with 413.0g methyl methacrylate, 120.0g butyl acrylate, 47.0 tripropylene glycol diacrylates and 4.7g ammonium persulphate in 1 hour divides four addings, in 80～85 ℃ of insulations cooling after 2～3 hours, filter discharging, obtain solids content and be 44.2% acrylate polyurethane water-dispersed resin.
Embodiment 4
At first adopt standard polymerization techniques to synthesize the end capped polyurethane prepolymer of NCO.In the reaction flask of the dried and clean that thermometer, whipping appts, condenser are housed, add 325.7g polyoxypropyleneglycol (molecular-weight average is 1167.0); 61.2g dimethylol propionic acid; 20.4g neopentyl glycol; 286.6g isophorone diisocyanate; 256.7g methyl methacrylate, 49.3g butyl acrylate and 1.0g dibutyl tin laurate, logical nitrogen protection; stirring also is warming up to 80 ℃, insulation reaction 4 hours.Measure nco value near theoretical value, be cooled to below 56 ℃, add the neutralization of 31.4g triethylamine, be scattered in the 1827.0g deionized water after 10～30 minutes in 50 ℃ of insulations, the aqueous solution (40%) that adds the 63.1g quadrol simultaneously carries out chain extension, keeps standby after 15～30 minutes.
Secondly, synthesizing water-dispersed resin of the present invention according to the soap-free core-shell emulsion synthetic technology.The above-mentioned polyurethane aqueous dispersion body that obtains is warming up to 80 ℃, mixture with 331.5.0g methyl methacrylate, 97.7.0g butyl acrylate, 63.8 Rocryl 410s and 4.8g Diisopropyl azodicarboxylate in 1 hour divides four addings, in 80～85 ℃ of insulations cooling after 2～3 hours, filter discharging, obtain solids content and be 44.6% acrylate polyurethane water-dispersed resin.
Performance measurement
Pencil hardness: acrylate polyurethane water-dispersed resin is brushed on the standard tinplate dry 1 week under the standard conditions, build 20 ± 2 μ m.Testing method is referring to GB/T6739-1996.
Resistance to impact shock: acrylate polyurethane water-dispersed sanction resin is brushed on the standard tinplate dry 1 week under the standard conditions, build 20 ± 2 μ m.Testing method is referring to GB/T1732-93.
Water drop test: acrylate polyurethane water-dispersed resin is brushed on the standard plank, the brushing twice, every square decimeter of brushing of brushing amount 1.0 gram resins, drying is 10 days under the standard conditions.With water droplet drop in film on, observe the situation of filming after 24 hours.
Hot storage stability: acrylate polyurethane water-dispersed resin is placed in the 100ml Plastic Bottle, is placed in 50 ℃ of baking ovens after airtight, place and observe the resin situation after 1 month.
Table 1
From the result of table 1 as can be seen, contain organic siloxane group (embodiment 2), diene ester (embodiment 3), the prepared resin property of hydroxyl (embodiment 4) in the vinyl monomer and obviously be better than the prepared resin of embodiment 1.
Claims (8)
1. acrylate polyurethane water-dispersed resin, its resin particle comprises a kind of shell of urethane and a kind of nuclear of acrylate, does not contain free emulsifying agent and organic solvent, the composition of forming shell comprises:
1. polyisocyanates,
2. polymer polyatomic alcohol,
3. low molecular weight polyols,
4. the polyvalent alcohol that contains hydrophilic and ionic groups,
5. neutralizing agent,
6. chainextender,
Wherein the NCO/OH mol ratio is 1.1～2.0; The neutralizing agent consumption is to need neutral ionic group normal 90%～120% in the system; The consumption of chainextender is a system residue NCO group normal 80～110%; The composition of forming nuclear comprises the vinyl monomer and the initiator of at least a free redical polymerization; The mass ratio of its mesochite and nuclear is 4: 1～1: 2, it is characterized in that: solid part of resin is 41～45%; The mass percent that the polyvalent alcohol content that contains hydrophilic and ionic groups accounts for whole resin solid is 1～2%;
Described low molecular weight polyols be carbonatoms between 2～15, molecular weight is at the dibasic alcohol below 400, trivalent alcohol, tetravalent alcohol, or its mixture.
2. water-dispersed resin according to claim 1 is characterized in that: polyisocyanates is aliphatics, alicyclic, aromatic vulcabond, or its mixture.
3. water-dispersed resin according to claim 1, it is characterized in that: can be molecular weight with the polymer polyatomic alcohol of NCO radical reaction in 800～2000 polyether Glycols, polyester diol, polycaprolactone dibasic alcohol, PCDL, or its mixture.
4. water-dispersed resin according to claim 1 is characterized in that: the polyvalent alcohol that contains hydrophilic and ionic groups is dimethylol propionic acid, dimethylolpropionic acid.
5. water-dispersed resin according to claim 1 is characterized in that: neutralizing agent is a tertiary amine compounds.
6. water-dispersed resin according to claim 1 is characterized in that: chainextender is polyalcohols, polynary amine, hydrazine, or its mixture.
7. water-dispersed resin according to claim 1, it is characterized in that: the vinyl monomer of free redical polymerization is for containing the vinyl monomer of 1 unsaturated double-bond at least, contain organic siloxane group, hydroxyl, diene ester, amide group, carbonyl in the monomer, or its mixture.
8. method for preparing the described acrylate polyurethane water-dispersed resin of claim 1 in turn includes the following steps:
1.. with the vinyl-based unsaturated monomer of part is medium, add polyisocyanates, polymer polyatomic alcohol, the low molecular weight polyols of formula ratio and contain the polyvalent alcohol of hydrophilic and ionic groups, in the presence of the ammonia esterifying catalyst, in 65～90 ℃ of reactions 4～6 hours, is terminal point with remaining NCO content near theoretical value, obtains the polyurethane prepolymer of above-mentioned NCO group end capping;
2.. resultant 1. is cooled to below 60 ℃, adds the neutralization of tertiary amines neutralizing agent, obtain water dispersible polyurethane prepolymer;
3.. resultant 2. is dispersed in the water of formula ratio, adds chainextender, stir 10～30min, obtain wrapping the polyurethane aqueous dispersion body of assisting vinyl-based unsaturated monomer, it is characterized in that:
4.. resultant 3. is warming up to 70～90 ℃, short run added remaining vinyl monomer and initiator in the prescription in 1～2 hour several times, carry out Raolical polymerizable, be incubated 2～3 hours, obtaining with urethane is that shell, acrylate are the acrylate polyurethane water-dispersed resin of nuclear.
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| KR101363238B1 (en) * | 2008-05-26 | 2014-02-12 | 디아이씨 가부시끼가이샤 | Coating agent and method for production thereof |
| CN101481451B (en) * | 2009-01-23 | 2011-06-08 | 华南理工大学 | High solid content latent curing polyurethane acroleic acid hybrid emulsion |
| KR101751767B1 (en) * | 2009-09-18 | 2017-06-28 | 디아이씨 가부시끼가이샤 | Acrylic modified urethane urea resin composition and molded article obtained using same |
| CN101792570B (en) * | 2010-02-10 | 2011-10-12 | 汤汉良 | Hydroxyl-containing crylic acid polyurethane aqueous dispersion body and application |
| CN102516465B (en) * | 2011-11-19 | 2014-10-29 | 万华化学（广东）有限公司 | High-elasticity waterborne polyurethane-acrylate composite resin, and preparation method and application thereof |
| AU2011384367B2 (en) | 2011-12-22 | 2016-09-22 | Dow Global Technologies Llc | A new process for making crosslinkable polyurethane/acrylic hybrid dispersions |
| JP6377640B2 (en) * | 2013-12-27 | 2018-08-22 | 関西ペイント株式会社 | Acrylic urethane composite resin particles |
| CN105669938B (en) * | 2016-03-24 | 2018-07-10 | 万华化学集团股份有限公司 | Aqueous radiation curable urethane acrylate composition and preparation method and coating |
| CN114341217A (en) * | 2019-10-07 | 2022-04-12 | Dic株式会社 | Aqueous resin composition, aqueous coating material, and plastic molded article coated with the aqueous coating material |
| CN112194804B (en) * | 2020-09-04 | 2022-05-03 | 安徽志诚机电零部件有限公司 | Preparation method of multi-crosslinking polyurethane damping material |
| CN114516937B (en) * | 2020-11-18 | 2024-02-27 | 万华化学(四川)有限公司 | Process for preparing aqueous acrylic modified polyurethane resin by solvent-free method |
| CN112876932B (en) * | 2021-01-18 | 2022-09-20 | 万华化学集团股份有限公司 | Coating with lasting color fixing effect and preparation method thereof |
| CN114195948B (en) * | 2021-11-25 | 2024-04-05 | 上海展辰涂料有限公司 | Acrylic acid aqueous dispersion for collapse-preventing wood device and preparation method thereof |
| CN113980256A (en) * | 2021-11-30 | 2022-01-28 | 珠海展辰新材料股份有限公司 | Water-based alkyd resin and preparation method thereof |
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| CN1556145A (en) * | 2003-12-31 | 2004-12-22 | 中国化工建设总公司常州涂料化工研究 | Polyurethane-acrylate water dispersion resin and its preparation |
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