CN101709108B - Method for preparing room-temperature self-crosslinking water-based polyurethane emulsion - Google Patents
Method for preparing room-temperature self-crosslinking water-based polyurethane emulsion Download PDFInfo
- Publication number
- CN101709108B CN101709108B CN 200910242639 CN200910242639A CN101709108B CN 101709108 B CN101709108 B CN 101709108B CN 200910242639 CN200910242639 CN 200910242639 CN 200910242639 A CN200910242639 A CN 200910242639A CN 101709108 B CN101709108 B CN 101709108B
- Authority
- CN
- China
- Prior art keywords
- ester
- compound
- acetoacetyl
- add
- emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a method for preparing water-based polyurethane emulsion with a room-temperature self-crosslinking characteristic. The emulsion is prepared from the following raw materials by weight part: 1) 100 parts of low-polymer diol, 2) 50 to 150 parts of polyisocyanate, 3) 8 to 28 parts of hydrophilic compound or potential hydrophilic compound, 4) 5 to 50 parts of acetoacetyl compound, 5) 1 to 20 parts of micro-molecule dolichol compound, 6) 0.5 to 10 parts of polyamine compound, 7) 1 to 21 parts of ammonia or organic amine, selectively, 8) 0.01 to 0.1 parts of polyurethane reaction catalyst, and selectively, 9) 20 to 310 parts of organic solvent. The film formed by the emulsion prepared by the method has excellent water resistance, acid and alkali resistance and chemical resistance, and also has the excellent physical and mechanical properties of high hardness, high elasticity, scratch resistance and the like.
Description
Technical field
The present invention relates to a kind of preparation method of aqueous polyurethane emulsion, be specifically related to a kind of preparation method with aqueous polyurethane emulsion of room-temperature self crosslinking characteristic.
Background technology
Current, the principal element of restriction aqueous polyurethane development is that time of drying is long, and weathering resistance, resistance to blocking and scratch resistance performance are not as good as solvent based coating.And the cross-linking modified mechanical property and the chemical resistance that can improve polyurethane aqueous dispersion body becomes the very important problem in aqueous polyurethane field.From American-European development trend, for improving the physical and mechanical properties of paint film, form crosslinking structure after emulsion room temperature or the film formation at low temp drying and become universal demand, have good water-fast, heat-resisting, resistance to acids and bases, resistance to soiling and physical strength by the crosslinked paint film that makes.These characteristics seem particularly important at coating industry.
For a long time, coating relates to the every aspect in people's productive life, is playing an important role aspect the maintenance protection such as woodenware, plastics, buildings, automobile.But the traditional coating industry extensively makes volatility or even toxic solvents such as vinyl acetic monomer, N-BUTYL ACETATE or benzene,toluene,xylene, and environmental pollution and HUMAN HEALTH all constitute a serious threat.Since the seventies and eighties in last century, initiated to be developed to most developed countries and developing country so far by western developed country, people more and more tend to the water-borne coatings of environmental protection safe in utilization.In general, water-borne coatings comprises aqueous alkide resin, aqueous polyester resin, aqueous epoxy resins, water-borne acrylic resin and waterborne polyurethane resin etc., wherein advantage such as waterborne polyurethane resin, snappiness big with its excellent abrasive, erosion resistance, chemical-resistant, hardness becomes the market focus rapidly, yet some technical problems of outwardness cause its industrialization to be made slow progress.
Aqueous polyurethane cold cross-linking system is generally bicomponent system, but bicomponent system uses very inconvenient, and linking agent must add when construction, and operation easier is big, difficult quality unanimity between each batch, and the problem of bicomponent system maximum is to use the phase ofer short duration.The high-temperature cross-linking system can obtain single-component package, but adopts high-temperature cross-linking that its Application Areas is very limited, and the high temperature energy consumption also is the economic factors that must consider.Therefore, the room-temperature self crosslinking product emulsion because of easy to use, energy-conservation, pollute less, the research and development focus that becomes water-borne coatings of many uses, a large amount of reports and patent have appearred.Wherein versatile and flexible and active higher characteristic becomes the bright spot of room-temperature self crosslinking emulsion exploitation to acetoacetyl with it.
Utilize the acetoacetyl response characteristic to prepare existing a lot of years history of cross-linking coating; but because many-sided problems such as raw material, technology; its Application Areas is limited to solvent based coating more; the research of water-borne coatings aspect also focuses mostly at aqueous alkide resin, water-borne acrylic resin etc., and its research in aqueous polyurethane seldom relates to.
Yi Shi Man begins one's study very early and utilizes the acetoacetyl crosslinking reaction to prepare method (the A Comparison of Catalyst forCrosslinking Acetoacetylated Resins via the Michael Reaction of solvent-borne type crosslinked polypropylene coating; Journal of Coating Technology; vol 61; No.770, March 1989).By selecting appropriate catalyst; in the acetoacetyl active methylene radical can with unsaturated acrylic double bond under room temperature environment, take place Michael reaction (as shown in the formula); so acetoacetyl content in the controlling polymers, double bond functional group's quantity just can be prepared the paint film of any cross-linking density in the adjustment acrylic compound.
Yi Shi Man in 1996 system has again reported diversified mechanism of crosslinking of acetoacetyl compound and the application in thermosetting coating (application of etheric acid based compound in thermosetting coating, " coatings industry ", 1996 the 1st phases) thereof.By rationally utilizing in the acetoacetyl two active centre-active methylene groups and ketone carbonyl, multiple cross-linked form can be introduced in the coating and can realize self-vulcanizing, as the reaction of acetoacetyl and amine, aldehyde and unsaturated double-bond etc.But this article does not relate to the acetoacetyl compound is applied to method in the water-base resin, does not more relate to the method that is applied to waterborne polyurethane resin.
Enter 21 century, disclosed Chinese patent CN1729262A of Yi Shi Man (2006) and U.S. Pat 6,683,132 (2004) have all been introduced the production technology of multiple cross-linked acetoacetyl Water-borne Alkyd Coatings.This invention realizes the excellent properties of coating by the oxidative cure of unsaturated carboxylic acid in acetoacetyl and polyamine reaction and the Synolac, and has clear superiority aspect tack-free time, time of drying.
The Cray Valley Chinese mugwort Berli card disclosed Chinese patent CN1628149A of company had introduced a kind of method of the acetoacetyl compound being introduced the bi-component waterborne resin in 2005; wherein the A component is the dispersible polymer that contains acetoacetyl-functional, and the B component is the aqueous dispersion of polyfunctional acrylic ester.During use both are mixed in proportion, acetoacetyl elder generation and acrylic double bond generation Michael reaction when film forming is solidified then by the UV-light regelate, obtain the cross-linked coating of wear resistance, chemical resistance excellence thus.But for the excellent more not research of aqueous polyurethane coating of over-all properties.ROHM AND HAAS has also been carried out big quantity research to acetoacetyl solidified water-borne coatings, but focuses mostly in water soluble acrylic acid coating, as U.S. Pat 5,616, and 764, US 5,548,024, US 5,525,662 etc.
In May, 2009, the disclosed Chinese patent CN101429270A of Hong Kong University of Science and Thchnology introduced a kind of preparation method who utilizes acetoacetyl to carry out the acrylic/polyurethane composite emulsion of crosslinking curing.Its preparation process was divided into for two steps, synthesized at first respectively and contained the ACRYLIC EMULSION of acetoacetyl and water dispersible base polyurethane prepolymer for use as, was scattered in performed polymer in the ACRYLIC EMULSION then and finishes chain extension to obtain the cross-linking type composite emulsion.Carry out compoundly owing to chosen urethane and ACRYLIC EMULSION, the paint film over-all properties is greatly improved, all performance excellences such as hardness, wear-resisting, anti-alcoholic solvent.But the method for using acetoacetyl to carry out the preparation of water-based polyaminoester emulsion is not seen and is mentioned.
The disclosed Chinese patent CN1422293A of Akzo Nobel N.V. in 2003 has introduced a kind of acetoacetyl compound that uses and has been solidifying agent; cation-type water-thinned dispersion with amino-functional is a matrix resin, prepares the method for cross-linked coating by the two-pack application techniques.The paint film that obtains of kind method has higher hardness and glossiness thus, and good water-fast, solvent resistance are arranged.But this patent does not overcome some drawbacks of two-component coating equally, and afterwards pot life problems, two components need accurate measurement etc. when using such as joining lacquer.
Summary of the invention
At the ubiquitous problem of current aqueous polyurethane coating, present inventor's proposition innovatively is incorporated into acetoacetyl crosslinking curing technology among the preparation method of polyaminoester emulsion.Therefore the present invention provides a kind of aqueous polyurethane emulsion preparation method with room-temperature self crosslinking characteristic, and described method comprises: mainly made by following raw material:
1) 100 mass parts oligomer diols;
2) 50～150 mass parts polyisocyanates;
3) 8～28 mass parts hydrophilic compounds or potential hydrophilic compounds;
4) 5～50 mass parts acetoacetyl compounds;
5) the many alkylol cpds of 1～20 mass parts small molecules;
6) 0.5～10 mass parts polyamine compound;
7) 1～21 mass parts ammonia or organic amine neutralizing agent; Selectively and
8) 0.01～0.1 mass parts polyurethane reaction catalyzer; Selectable and
9) 20～310 mass parts organic solvents.
In the method for the invention, polyurethane reaction catalyzer and organic solvent are not the components that must adopt among the preparation method of the present invention, described component is in preparation method of the present invention, can optionally add or not add, those skilled in the art can determine in conjunction with instruction of the present invention and this area general knowledge.
Employed polyisocyanates can extensively be taken from the commercially available various polyisocyanates product that aqueous polyurethane is produced that satisfies among the room-temperature self-crosslinking water-based polyurethane emulsion preparation method of the present invention, the present invention includes but be not limited to diphenylmethanediisocyanate (MDI), tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (H
12MDI), tetramethylxylylene diisocyanate (TMXDI) or hexamethylene diisocyanate trimer and derivative thereof, or their arbitrary composition.
As embodiment preferred, described MDI can be for pure 4, and 4 '-MDI also can be 4,4 '-MDI, 2,4 '-MDI and 2,2 '-MDI mixture of isomers, wherein 2, the content of 4 '-MDI is 45～99% in mass, 2, the content of 2 '-MDI is less than 2%, as the Wannate MDI-50 of Yantai Wanhua Polyurethane Co., Ltd.
As embodiment preferred, described TDI can be for pure 2, and 4-TDI also can be 2,4-TDI and 2,6-TDI mixture of isomers, wherein 2, the content of 4-TDI is 50～90% in mass, is generally about 80% or about 65%, i.e. common alleged TDI-80 or TDI-65 on the market.
Hexamethylene diisocyanate trimer described in the inventive method and derivative thereof, its structural formula is:
Wherein n is 1～5 integer, is preferably 1～3 integer.
Oligomer diol of the present invention can be the various oligomer diols of this area routine, the present invention includes but is not limited to polyether Glycols, polyester diol, PTMG, polycaprolactone glycol, polycarbonate diol, polyacrylate diol or polybutadiene diol or their arbitrary combination.
As embodiment preferred, described polyether Glycols is generally poly(propylene oxide) ether glycol or polyethylene oxide end capping polypropylene oxide ether glycol, it can adopt the method preparation of this area routine, for example can be the poly(propylene oxide) ether dibasic alcohol that adopts traditional alkali metal hydroxide catalysis to be produced, also can be the poly(propylene oxide) ether dibasic alcohol that adopts composition metal prussiate coordination catalysis to be produced.
Described PTMG includes but not limited to be the oligomer diol that adopts cationic catalyst catalysis tetrahydrofuran (THF) to be produced that cationic catalyst can be various ways such as perchloric acid, the vitriol oil, alkylsulphonic acid, heteropolyacid and Lewis acid.
Described polyester diol is for adopting organic dibasic acid or acid anhydrides and the small molecules dibasic alcohol oligomer diol by the condensation reaction preparation, organic dibasic acid can for Succinic Acid, pentanedioic acid, hexanodioic acid, terephthalic acid, m-phthalic acid, Tetra hydro Phthalic anhydride etc. wherein one or more, preferred hexanodioic acid; The small molecules dibasic alcohol can be ethylene glycol, 1, ammediol, 1, and 4-butyleneglycol, 1,6-hexylene glycol, glycol ether, neopentyl glycol, 1,4-hydroxymethyl-cyclohexanes etc. are preferably 1,4-butyleneglycol, 1,6-hexylene glycol or neopentyl glycol.
As embodiment preferred, oligomer diol molecular weight of the present invention is 500-3000 dalton, is preferably molecular weight 750-2500 dalton, more preferably 900-2200 dalton.
As embodiment preferred, the hydroxyl value of described oligomer diol is 35-225mgKOH/g, is preferably 45-145mgKOH/g, more preferably 51-125mgKOH/g.
Acetoacetyl compound of the present invention comprises acetoacetoxy groups and/or acetoacetyl amino-complex, and its structural formula is respectively
Wherein R is aromatic series, aliphatics, alicyclic alkanes or nitrogenous, oxygen, the equiatomic heterochain alkane of silicon residue; M, n are 1～7 integer and m+n≤8.
As embodiment preferred, acetoacetyl compound of the present invention includes but not limited to: N-(2-hydroxyethyl) aceto-acetamide, glycol monomethyl acetoacetyl ester, neopentyl glycol single acetoacetyl ester, TriMethylolPropane(TMP) single acetyl ethanoyl ester, TriMethylolPropane(TMP) diacetyl ethanoyl ester, tetramethylolmethane single acetyl acetoxyl ester, tetramethylolmethane diacetyl acetic acid base ester, tetramethylolmethane triacetyl acetoxyl ester, sorbyl alcohol triacetyl acetoxyl ester or sorbyl alcohol tetrem ethyl acetoacetic acid base ester etc. or their arbitrary composition;
As embodiment preferred further, described acetoacetyl compound is tetramethylolmethane single acetyl acetoxyl ester, tetramethylolmethane diacetyl acetic acid base ester or tetramethylolmethane triacetyl acetoxyl ester or their arbitrary composition.
Hydrophilic compounds structural formula of the present invention is:
As embodiment preferred, hydrophilic compounds of the present invention includes but not limited to 1,4-butyleneglycol-2-sodium sulfonate, 2,2-dimethylol propionic acid ammonium salt, 1, the 3-third diamino propyl sulfonic acid sodium or 2,2-dimethylolpropionic acid triethyl ammonium salts etc. or their arbitrary composition in addition, also comprise the various amino acid saltss that satisfy requirement of the present invention.
Potential hydrophilic compounds of the present invention is the compound that contains a carboxyl and two or more hydroxyl structures in the molecule simultaneously, the present invention includes as embodiment preferred but be not limited to 2, the 2-dimethylol propionic acid, 2, the 2-dimethylolpropionic acid, half ester compound that TriMethylolPropane(TMP), glycerine or diethanolamine and acid anhydrides generation ring-opening reaction obtain etc. or their arbitrary composition, further preferred 2, the 2-dimethylol propionic acid.
Among the preparation method of room-temperature self-crosslinking water-based polyurethane emulsion of the present invention, the many alcohol of described small molecules can how pure for this area various small molecules commonly used, as embodiment preferred, the many alcohol of described small molecules include but not limited to: ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,6-hexylene glycol, glycol ether, neopentyl glycol, 1,4-hydroxymethyl-cyclohexane, glycerol, TriMethylolPropane(TMP), thanomin, diethanolamine or trolamine or their arbitrary composition; As further preferred embodiment, the many alcohol of described small molecules are butyleneglycol.
In the inventive method, described polyamine compound can be this area various polyamine compounds commonly used, as embodiment preferred, the present invention includes but be not limited to hydrazine hydrate, quadrol, 1,3-propylene diamine, 1,4-butanediamine, 1,6-hexanediamine, isophorone diamine, 4,4 '-dicyclohexyl methyl hydride diamines or diethylenetriamine or their arbitrary composition; Further be preferably hydrazine hydrate or quadrol.
In the inventive method, described organic amine can be this area various organic amines commonly used, and as embodiment preferred, described organic amine is methylamine, thanomin, Isopropylamine, diethylamine, triethylamine or dimethylaminoethanol or their arbitrary composition.
In the inventive method, described catalyzer can be this area various catalyzer commonly used, and as embodiment preferred, catalyzer is dibutyl tin laurate, stannous octoate, triethylamine or triethylenediamine or their arbitrary composition;
In the inventive method, described organic solvent can be this area various organic solvents commonly used, and as embodiment preferred, described organic solvent is acetone or butanone or their combination.
As embodiment preferred; the preparation method of room-temperature self-crosslinking water-based polyurethane emulsion of the present invention comprises: with the oligomer diol of above-mentioned chemical dose; polyisocyanates; how pure small molecules is; hydrophilic compounds or potential hydrophilic compounds; with the acetoacetyl compound; selectively and organic solvent; selectively drop in the reactor with catalyzer; at 1～4 hour synthetic performed polymer of 60～90 ℃ of reactions with isocyanate terminated base; be cooled to subsequently and add ammonia or organic amine neutralization below 50 ℃; regulating the pH value is 8-10; and with said mixture dispersion and emulsion in water; add the polyamine compound then and carry out chain extension; decompression removes solvent, promptly gets anion aqueous room-temperature self crosslinking emulsion.
As embodiment preferred; the preparation method of room-temperature self-crosslinking water-based polyurethane emulsion of the present invention comprises: with above-mentioned stoichiometric polyisocyanates and oligomer diol; selectively add in the reaction vessel with catalyzer; feed drying nitrogen; start to stir also and be warming up to 70-80 ℃ gradually; after 2 hours reactant is cooled to 50-60 ℃; add stoichiometric hydrophilic compounds or potential hydrophilic compounds; how pure acetoacetyl compound and small molecules be; add an amount of organic solvent and adjust viscosity to 2000mPa.s; keep 60-70 ℃ of temperature of reaction; react and measure prepolymer NCO content after 2 hours; get final product stopped reaction with theoretical value deviation ± 5%; cool the temperature to below 40 ℃; add the neutralization of stoichiometric ammonia or organic amine; regulating the pH value is 8-10; use the high-shear dispersion machine; adding deionized water under quick stirring condition disperses; add stoichiometric polyamine compound immediately; organic solvent is removed in last underpressure distillation, promptly gets stable anion aqueous room-temperature self crosslinking emulsion.
The preparation method of room-temperature self-crosslinking water-based polyurethane emulsion of the present invention, when using ammonia or organic amine neutralizing agent, should guarantee to disperse back emulsion pH value between 8～10,, be shown below because hydrolysis reaction takes place the acetoacetoxy groups compound easily under acidic conditions:
And under alkaline condition, acetoacetoxy groups and ammonia/organic amine generate the enamine structure, can be in aqueous medium stable existence.
Have excellent water-fast, acid-alkali-corrosive-resisting and chemical-resistant behind the emulsion film forming of the inventive method preparation, have outstanding physical and mechanical propertiess such as hardness is big, elasticity is high, scratch resistance simultaneously.It is long time of drying to efficiently solve current water-borne coatings, and problems such as anti-solvent and resistance to marring difference have kept conventional urethane coating excellent abrasive simultaneously, weathering resistance, elasticity height, advantage such as hardness is big.
Embodiment
The present invention will be further described by following examples, but protection scope of the present invention not only is confined to embodiment, and the change that this field professional does technical solution of the present invention all should belong in protection scope of the present invention.
Embodiment 1
With 115 gram Wannate MDI-50 (Yantai Wanhua Polyurethane Co., Ltd, 2,4 '-MDI content 45-55%, 2,2 '-MDI content is less than 0.5%, all the other are 4,4 '-MDI, down with) and the poly(propylene oxide) ether glycol PPG1000 adding four-necked bottle of 150 gram molecular weights 1000, feed drying nitrogen, start stirring and be warming up to 70 ℃ gradually, after 2 hours reactant is cooled to 50 ℃, add 15 grams 2 in batches, the 2-dimethylol propionic acid, 10 grams 1,4-butyleneglycol and 16 gram tetramethylolmethane diacetyl acetic acid base esters keep temperature of reaction to continue reaction 2 hours for 60 ℃, add 140 gram acetone and reduce viscosity.The prepolymer temperature is reduced to below 30 ℃, add 11.5 gram triethylamines and mix, use the high-shear dispersion machine under quick stirring condition, to add deionized water and disperse, add 6.1 grams quadrol soluble in water immediately.Last underpressure distillation is removed acetone and is obtained stable room-temperature self-crosslinking water-based polyurethane emulsion.
Embodiment 2
The PTMG PTMEG1000 of 115 gram Wannate MDI-50 and 150 gram molecular weights 1000 is added four-necked bottle, feed drying nitrogen, start to stir also and be warming up to 70 ℃ gradually, after 2 hours reactant is cooled to 50 ℃, add 23 grams 1 in batches, 4-butyleneglycol-2-sodium sulfonate, 12 gram neopentyl glycol and 16 gram TriMethylolPropane(TMP) single acetyl acetoxyl esters keep temperature of reaction to continue reaction 2 hours for 60 ℃, add 140 gram acetone and reduce viscosity.The prepolymer temperature is reduced to below 30 ℃, and the ammoniacal liquor that adds 16 grams, 25% concentration mixes, and uses the high-shear dispersion machine to add deionized water under quick stirring condition and disperses, and adds 10.9 grams hexanediamine soluble in water immediately.Last underpressure distillation is removed acetone and is obtained stable room-temperature self-crosslinking water-based polyurethane emulsion.
Embodiment 3
The poly adipate succinic acid ester PBA1000 and 30 of 115 gram TDI-80,120 gram molecular weights 1000 is restrained the sodium sulfonate group glycol (by 5-sodium sulfo isophthalate, hexanodioic acid and 1, the 4-butyleneglycol makes by condensation reaction, hydroxyl value 112mgKOH/g) adds four-necked bottle, feed drying nitrogen, start to stir also and be warming up to 70 ℃ gradually, after 2 hours reactant is cooled to 50 ℃, add 12 gram neopentyl glycol and 16 gram tetramethylolmethane triacetyl acetoxyl esters in batches, keep temperature of reaction to continue reaction 2 hours for 60 ℃, add 100 gram acetone and reduce viscosity.The prepolymer temperature is reduced to below 30 ℃, and the ammoniacal liquor that adds 16 grams, 25% concentration mixes, and uses the high-shear dispersion machine to add deionized water under quick stirring condition and disperses, and adds 4.6 grams diethylenetriamine soluble in water immediately.Last underpressure distillation is removed acetone and is obtained stable room-temperature self-crosslinking water-based polyurethane emulsion.
Embodiment 4
The poly(propylene oxide) ether glycol PPG1000 and the 0.04 gram catalyzer dibutyl tin laurate of 115 gram IPDI, 150 gram molecular weights 1000 are added four-necked bottle, feed drying nitrogen, start to stir also and be warming up to 70 ℃ gradually, after 2 hours reactant is cooled to 50 ℃, add 15 grams 2,2-dimethylol propionic acid, 13 grams 1,4-butyleneglycol and 16 gram tetramethylolmethane single acetyl acetoxyl esters in batches, keep temperature of reaction to continue reaction 2 hours for 60 ℃, add 50 gram acetone and reduce viscosity.The prepolymer temperature is reduced to below 30 ℃, add 11.5 gram triethylamines and mix, use the high-shear dispersion machine under quick stirring condition, to add deionized water and disperse, add the hydrazine hydrate of 17 grams 30% immediately.Last underpressure distillation is removed acetone and is obtained stable room-temperature self-crosslinking water-based polyurethane emulsion.
Embodiment 5
With 125 gram H
12The PTMG PTMEG1000 of MDI, 150 gram molecular weights 1000 and 0.06 gram catalyzer dibutyl tin laurate add four-necked bottle, feed drying nitrogen, start to stir also and be warming up to 70 ℃ gradually, after 2 hours reactant is cooled to 50 ℃, add 15 grams 2,2-dimethylol propionic acid, 10 grams 1,4-butyleneglycol and 16 gram tetramethylolmethane diacetyl acetic acid base esters in batches, keep temperature of reaction to continue reaction 2 hours for 60 ℃, add 80 gram acetone and reduce viscosity.The prepolymer temperature is reduced to below 30 ℃, and the ammoniacal liquor that adds 16 grams, 25% concentration mixes, and uses the high-shear dispersion machine to add deionized water under quick stirring condition and disperses, and adds 16 grams isophorone diamine soluble in water immediately.Last underpressure distillation is removed acetone and is obtained stable room-temperature self-crosslinking water-based polyurethane emulsion.
Claims (15)
1. the preparation method of a room-temperature self-crosslinking water-based polyurethane emulsion is characterized in that, described method comprises that this emulsion is made by following raw material:
1) molecular weight of 100 mass parts is the daltonian oligomer diol of 500-3000;
2) 50～150 mass parts polyisocyanates;
3) 8～28 mass parts hydrophilic compounds or potential hydrophilic compounds;
4) 5～50 mass parts acetoacetyl compounds;
5) the many alkylol cpds of 1～20 mass parts small molecules;
6) 0.5～10 mass parts polyamine compound;
7) 1～21 mass parts ammonia or organic amine neutralizing agent; Selectively and
8) 0.01～0.1 mass parts polyurethane reaction catalyzer; Selectively and
9) 20～310 mass parts organic solvents,
Wherein said hydrophilic compounds is 1,4-butyleneglycol-2-sodium sulfonate, 2,2-dimethylol propionic acid ammonium, 1, the 3-third diamino propyl sulfonic acid sodium or 2,2-dimethylolpropionic acid triethyl ammonium or their arbitrary composition;
Described potential hydrophilic compounds is 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid, half ester compound that TriMethylolPropane(TMP), glycerine or diethanolamine and acid anhydrides generation ring-opening reaction obtain or their arbitrary composition;
Described acetoacetyl compound is N-(2-hydroxyethyl) aceto-acetamide, glycol monomethyl acetoacetyl ester, neopentyl glycol single acetoacetyl ester, TriMethylolPropane(TMP) single acetyl ethanoyl ester, TriMethylolPropane(TMP) diacetyl ethanoyl ester, tetramethylolmethane single acetyl acetoxyl ester, tetramethylolmethane diacetyl acetic acid base ester, tetramethylolmethane triacetyl acetoxyl ester, sorbyl alcohol triacetyl acetoxyl ester or sorbyl alcohol tetrem ethyl acetoacetic acid base ester or their arbitrary composition.
2. method according to claim 1, it is characterized in that, described polyisocyanates is diphenylmethanediisocyanate, tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, tetramethylxylylene diisocyanate or hexamethylene diisocyanate trimer or their arbitrary composition.
3. method according to claim 2 is characterized in that, described oligomer diol is a polyether Glycols, polyester diol, polycarbonate diol, polyacrylate diol or polybutadiene diol or their arbitrary composition.
4. method according to claim 3 is characterized in that, described oligomer diol molecular weight is 750-2500 dalton.
5. method according to claim 4 is characterized in that, described oligomer diol molecular weight is 900-2200 dalton.
6. method according to claim 4 is characterized in that, the hydroxyl value of described oligomer diol is 45～145mgKOH/g.
7. method according to claim 6 is characterized in that, the hydroxyl value of described oligomer diol is 51～125mgKOH/g.
8. method according to claim 6 is characterized in that, described acetoacetyl compound is tetramethylolmethane single acetyl acetoxyl ester, tetramethylolmethane diacetyl acetic acid base ester or tetramethylolmethane triacetyl acetoxyl ester or their arbitrary composition.
9. method according to claim 8, it is characterized in that, the many alcohol of described small molecules are ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,6-hexylene glycol, glycol ether, neopentyl glycol, 1,4-hydroxymethyl-cyclohexane, glycerol, TriMethylolPropane(TMP), diethanolamine or trolamine or their arbitrary composition.
10. method according to claim 9 is characterized in that, the many alcohol of described small molecules are butyleneglycol.
11. method according to claim 9 is characterized in that, described polyamine compound is hydrazine hydrate, quadrol, 1,3-propylene diamine, 1,4-butanediamine, 1,6-hexanediamine, isophorone diamine, 4,4 '-dicyclohexyl methyl hydride diamines or diethylenetriamine or their arbitrary composition.
12. method according to claim 11 is characterized in that, described polyamine compound is hydrazine hydrate or quadrol.
13. method according to claim 11 is characterized in that, described organic amine neutralizing agent is methylamine, thanomin, Isopropylamine, diethylamine, triethylamine or dimethylaminoethanol or their arbitrary composition; Catalyzer is dibutyl tin laurate, stannous octoate, triethylamine or triethylenediamine or their arbitrary composition; Described organic solvent is acetone or butanone.
14. according to the arbitrary described method of claim 1-13; it is characterized in that; described method comprises: with oligomer diol; polyisocyanates; how pure small molecules is; hydrophilic compounds or potential hydrophilic compounds; with the acetoacetyl compound; selectively and organic solvent; selectively drop in the reactor with catalyzer; at 1～4 hour synthetic performed polymer of 60～90 ℃ of reactions with isocyanate terminated base; be cooled to subsequently and add ammonia or the neutralization of organic amine neutralizing agent below 50 ℃; regulating the pH value is 8-10; and with said mixture dispersion and emulsion in water; add the polyamine compound then and carry out chain extension; decompression removes solvent, promptly gets anion aqueous room-temperature self crosslinking emulsion.
15. want each described method among the 1-13 according to right; it is characterized in that; described method comprises: with polyisocyanates and oligomer diol; selectively add in the reaction vessel with catalyzer; feed drying nitrogen; start to stir also and be warming up to 70-80 ℃ gradually; after 2 hours reactant is cooled to 50-60 ℃; add hydrophilic compounds or potential hydrophilic compounds then; how pure acetoacetyl compound and small molecules be; add an amount of organic solvent and adjust viscosity; keep 60-70 ℃ of temperature of reaction; react and measure prepolymer NCO content after 2 hours; cool the temperature to below 40 ℃; add the neutralization of stoichiometric ammonia or organic amine neutralizing agent, regulating the pH value is 8-10, uses the high-shear dispersion machine; adding deionized water under quick stirring condition disperses; add stoichiometric polyamine compound immediately, organic solvent is removed in last underpressure distillation, promptly gets stable anion aqueous room-temperature self crosslinking emulsion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910242639 CN101709108B (en) | 2009-12-11 | 2009-12-11 | Method for preparing room-temperature self-crosslinking water-based polyurethane emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910242639 CN101709108B (en) | 2009-12-11 | 2009-12-11 | Method for preparing room-temperature self-crosslinking water-based polyurethane emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101709108A CN101709108A (en) | 2010-05-19 |
| CN101709108B true CN101709108B (en) | 2011-10-26 |
Family
ID=42401918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910242639 Active CN101709108B (en) | 2009-12-11 | 2009-12-11 | Method for preparing room-temperature self-crosslinking water-based polyurethane emulsion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101709108B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948659B (en) * | 2010-09-17 | 2013-01-09 | 淄博奥德美高分子材料有限公司 | Aqueous polyurethane resin and preparation method thereof |
| CN102070768B (en) * | 2010-12-06 | 2012-10-03 | 安徽好思家涂料有限公司 | Water-soluble polyurethane for wood lacquer and preparation method thereof |
| CN102432800B (en) * | 2011-09-05 | 2013-05-08 | 惠州市汉诺新材料有限公司 | Water-oil dual-purpose dispersion agent as well as preparation method and application thereof |
| CN103055465B (en) * | 2011-10-18 | 2016-01-20 | 上海格伦化学科技有限公司 | A kind of oil-soluble formaldehyde scavenger and preparation method thereof |
| CN102659994A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院福建物质结构研究所 | Use of sulfonate-type polyol as chain extender for preparing polyurethane |
| CN107118638B (en) * | 2017-06-09 | 2019-04-23 | 天津昌海新材料科技发展有限公司 | Impervious high adhesiveness material of a kind of two-component for ceramic tile and preparation method thereof |
| EP3760657A4 (en) * | 2018-02-28 | 2021-12-01 | Tosoh Corporation | Hydrophilizing agent for production of self-emulsifying polyisocyanate composition, self-emulsifying polyisocyanate composition, coating material composition, and coating film |
| CN109337034B (en) * | 2018-09-26 | 2021-08-03 | 上海维凯光电新材料有限公司 | Polyurethane emulsion of composite multiple crosslinking system and synthetic method thereof |
| CN110003431B (en) * | 2019-04-16 | 2021-07-20 | 浙江新诺高分子材料有限公司 | Preparation method of dispersion emulsion of high-alkali-resistance aqueous polyurethane |
| CN111269391A (en) * | 2020-03-23 | 2020-06-12 | 泰安聚仁新材料有限公司 | Alkali-resistant water-based polyurethane aluminized protective coating material and preparation method thereof |
| CN112226193B (en) * | 2020-10-19 | 2021-10-15 | 惠州市道科包装材料有限公司 | Preparation method and application of water-based high-strength bi-component adhesive |
| CN112661647A (en) * | 2020-12-11 | 2021-04-16 | 江苏长能节能新材料科技有限公司 | Aldehyde removing agent and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5916960A (en) * | 1993-12-21 | 1999-06-29 | The Sherwin-Williams Company | Water-based, storage stable, self-curing coating composition |
| WO2002081525A1 (en) * | 2001-04-09 | 2002-10-17 | Eastman Chemical Company | Polyol latex compositions and condensation polymers formed therefrom |
| JP3961133B2 (en) * | 1998-11-04 | 2007-08-22 | 株式会社クラレ | Synthetic resin emulsion powder |
| CN100460434C (en) * | 2006-05-08 | 2009-02-11 | 北京科聚化工新材料有限公司 | Self-emulsifying water-thinned anion polyurethane emulsion and its prepn process |
-
2009
- 2009-12-11 CN CN 200910242639 patent/CN101709108B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5916960A (en) * | 1993-12-21 | 1999-06-29 | The Sherwin-Williams Company | Water-based, storage stable, self-curing coating composition |
| JP3961133B2 (en) * | 1998-11-04 | 2007-08-22 | 株式会社クラレ | Synthetic resin emulsion powder |
| WO2002081525A1 (en) * | 2001-04-09 | 2002-10-17 | Eastman Chemical Company | Polyol latex compositions and condensation polymers formed therefrom |
| CN100460434C (en) * | 2006-05-08 | 2009-02-11 | 北京科聚化工新材料有限公司 | Self-emulsifying water-thinned anion polyurethane emulsion and its prepn process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101709108A (en) | 2010-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101709108B (en) | Method for preparing room-temperature self-crosslinking water-based polyurethane emulsion | |
| CN102219886B (en) | Preparation method of aqueous polyurethane emulsion with high solid content | |
| CN101696262B (en) | Preparation method and application of modified polyurethane aqueous dispersions of polyisocyanate curing agents | |
| TW510916B (en) | Aqueous reacitve filler compositions | |
| JP3537955B2 (en) | Hyperbranched polyaspartate and method for its preparation | |
| CN109761834A (en) | A kind of preparation method and application of the dispersible polyaspartic ester resin of water and aqueous carbamide paint | |
| CA2649376C (en) | Oil based aqueous polyurethane dispersions | |
| CN104884493B (en) | Aqueous polyurethane resin dispersion and use of same | |
| KR20110029173A (en) | Aqueous polyurethane resin dispersion, manufacturing method for same, and paint composition containing same | |
| MXPA01009822A (en) | Self-crosslinking polyurethane, polyurethane polyurea or polyurea dispersions for sizing agents. | |
| JPH11152321A (en) | Urethane prepolymer, its production, and coating composition using it | |
| JPS62285910A (en) | Urethane group-containing polymer and its production and use | |
| CN102459383A (en) | Novel solvents for the production of polyutherane dispersions | |
| WO2010030544A1 (en) | Coating formulations and compositions based on polyamines, polyols and polyisocyanates, and processes of preparing and of using the same | |
| JPWO2008108346A1 (en) | Water-based polyurethane resin composition and coating composition using the same | |
| WO2006104094A1 (en) | Aqueous polyurethane resin composition and process for production thereof | |
| JP5596363B2 (en) | Aqueous dispersion of carbonyl group-containing urethane urea resin | |
| CN101418119B (en) | Method for preparing oxidative crosslinked starch modified waterborne polyurethane hybridization material | |
| CN101284900B (en) | Anionic waterborn polyurethane dispersion for wood lacquer and method for preparing same | |
| JPH01310773A (en) | Top coat finishing method | |
| JP2012193253A (en) | Highly hydrophilic aqueous polyurethane resin dispersion composition | |
| JPS5893761A (en) | Composition for one-pack type thermosetting polyurethane paint | |
| JP3629167B2 (en) | Two-component aqueous acrylic-urethane composition, adhesive and coating agent containing the composition | |
| JPH09286945A (en) | Binder for water-based printing ink | |
| CN107686548A (en) | The preparation method of water-based pure polyureas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: YANTAI WANHUA POLYURETHANE CO., LTD. GUANGDONG WAN Free format text: FORMER OWNER: YANTAI WANHUA POLYURETHANE CO., LTD. |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20110526 Address after: 102200, Beijing, Changping science and Technology Park Spark Street, No. 5, Beijing poly chemical new material Co., Ltd. Applicant after: Keju Chemical New Material Co., Ltd., Beijing Co-applicant after: Yantai Wanhua Polyurethane Co., Ltd. Co-applicant after: Guangdong Wanhua Rongwei Polyurethane Ltd. Co-applicant after: Ningbo Wanhua Rongwei Polyurethan Co., Ltd. Address before: 102200, Beijing, Changping science and Technology Park Spark Street, No. 5, Beijing poly chemical new material Co., Ltd. Applicant before: Keju Chemical New Material Co., Ltd., Beijing Co-applicant before: Yantai Wanhua Polyurethane Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 102200, Beijing, Changping science and Technology Park Spark Street, No. 5, Beijing poly chemical new material Co., Ltd. Patentee after: Keju Chemical New Material Co., Ltd., Beijing Patentee after: Wanhua Chemical Group Co., Ltd. Patentee after: Guangdong Wanhua Rongwei Polyurethane Ltd. Patentee after: Ningbo Wanhua Rongwei Polyurethan Co., Ltd. Address before: 102200, Beijing, Changping science and Technology Park Spark Street, No. 5, Beijing poly chemical new material Co., Ltd. Patentee before: Keju Chemical New Material Co., Ltd., Beijing Patentee before: Yantai Wanhua Polyurethane Co., Ltd. Patentee before: Guangdong Wanhua Rongwei Polyurethane Ltd. Patentee before: Ningbo Wanhua Rongwei Polyurethan Co., Ltd. |
|
| C56 | Change in the name or address of the patentee |
Owner name: WANHUA CHEMICAL (BEIJING) CO., LTD. Free format text: FORMER NAME: KEJU CHEMICAL NEW MATERIAL CO., LTD., BEIJING |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 102200, Beijing, Changping science and Technology Park Spark Street, No. 5, Beijing poly chemical new material Co., Ltd. Patentee after: Wanhua chemical (Beijing) Co., Ltd. Patentee after: Wanhua Chemical Group Co., Ltd. Patentee after: WANHUA CHEMICAL (FOSHAN) RONGWEI POLYURETHANE CO., LTD. Patentee after: WANHUA CHEMICAL (NINGBO) RONGWEI POLYURETHANE CO., LTD. Address before: 102200, Beijing, Changping science and Technology Park Spark Street, No. 5, Beijing poly chemical new material Co., Ltd. Patentee before: Keju Chemical New Material Co., Ltd., Beijing Patentee before: Wanhua Chemical Group Co., Ltd. Patentee before: Guangdong Wanhua Rongwei Polyurethane Ltd. Patentee before: Ningbo Wanhua Rongwei Polyurethan Co., Ltd. |