CN102822220B - Aqueous anionic polyurethane dispersions - Google Patents
Aqueous anionic polyurethane dispersions Download PDFInfo
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- CN102822220B CN102822220B CN201180017821.0A CN201180017821A CN102822220B CN 102822220 B CN102822220 B CN 102822220B CN 201180017821 A CN201180017821 A CN 201180017821A CN 102822220 B CN102822220 B CN 102822220B
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
Aqueous anionic polyurethane dispersions based on specific hydrophobic polyols are useful as filming agents for fhe coating of rigid surfaces like metal, plastics, glass and wood and provide coatings with excellent durability, adhesion, hydrolyfic and alkali/acid resistance and hardness.
Description
The present invention relates to the water-based anionic polyurethane dispersion based on concrete hydrophobicity polyvalent alcohol, and relate to their purposes as membrane-forming agent, for for example rigid surface of metal, plastics, glass and timber is applied.
Aqueous dispersion of the present invention provide there is IMAGE, the coating of binding property, resistance to hydrolysis and acidproof/alkalescence and hardness.
Background technology
The surface of the many manufacture goods manufacture goods of leather, plastics, timber and preparation of metals (for example by) need to be processed; object is to make this surface more even; or avoid passing in time or contact atmosphere and worn and torn in protection surface; and/or improve some character attractive in appearance, for example higher or lower opacity, softness or hard sense of touch and color etc.
Conventionally, obtain these effects by applying film-forming polymer (coating), nowadays in various film-forming polymer, solvent borne polyurethane is well-known and comes into one's own in coating field, has outstanding chemical resistant properties and resistance to mechanical film because they can produce.
Similarly, owing to being discharged into environment about reduction, particularly the Regulation Policy of the low VOC in work area comes into one's own gradually, and nowadays the aqueous dispersion of urethane has also played corresponding uses.
In the time considering that the urethane of use dispersion form applies, produce some problems, reason is that their dispersive abilities in water need to comprise hydrophilic segment, this hydrophilic segment has reduced weather resistance and the stability to hydrolysis of film inherently.
Known in the art unsaturated group is incorporated into and in urethane, causes the Cross-linked of film and therefore can improve chemical resistance of coating; Unfortunately, be present in yellowing that shortcoming relevant in urethane is film and the strong oxidizing condition of needs for Cross-linked to unsaturated group.
US 2003/0191273 has described and has used the aqueous dispersion of the urethane based on Marlamid as application composition; The coating of preparing from these dispersions it is said there is good pendulum-rocker hardness, the good anti-heel marking and high glossiness.
US 2008/0194757 has described the polyurethane composition of water-dispersion, and this polyurethane composition contains urea acid (nurate) compound with long chain alkyl group as polyisocyanate component; Described composition is stated to be coat film good binding property, water resisting property, weathering resistance, erosion resistance, water-repellancy and grease proofness is provided.
Be surprisedly, nowadays find to obtain the aqueous dispersion of anionic polyurethane, the aqueous dispersion of this anionic polyurethane can make durable membranes on rigid substrate, have outstanding binding property, chemical resistant properties and hardness by be incorporated into specific hydrophobicity polyvalent alcohol in urethane, and described specific hydrophobicity polyvalent alcohol is by making fatty alcohol react to obtain with aromatics diglycidylether.
Summary of the invention
The invention provides the aqueous dispersion containing the anionic polyurethane of 20 to 50 % by weight, obtain described aqueous dispersion by following steps: in water, disperse, and extend the anionic prepolymer of neutralization with polyamines, this anionic prepolymer is containing the hydroxy-acid group of 5 to 125meq/100g dry weights, and by making one or more aliphatic polyisocyanates, cycloaliphatic polyisocyanate or aromatic polyisocyanate react to prepare with the mixture (P) of polyvalent alcohol, the mixture (P) of described polyvalent alcohol comprises following component I), II), III), IV) and V):
I) one or more hydrophobicity polyvalent alcohols of 4 to 90 % by weight, the molar average hydroxy functionality of described hydrophobicity polyvalent alcohol is 2 to 3, hydroxyl value is 350 to 40(mg KOH/g), and by making alcohol roh react to obtain with aromatics diglycidylether, wherein R is the saturated C of branching or straight chain
4-C
30alkyl chain, is preferably the saturated C of branching or straight chain
6-C
22alkyl chain, or R is the saturated C of branching or straight chain
4-C
10alkyl phenyl group, wherein said aromatics diglycidylether has following chemical formula (I):
Wherein R
1be group (i):
Wherein R
2, R
3each is Me, Et or H independently;
Or R
1be optionally by one or more alkyl groups, be preferably the phenylene that methyl group replaces;
Or R
1be optionally by one or more alkyl groups, be preferably the biphenylene that methyl group replaces;
Or R
1be group (ii):
II) one or more anionics of 1 to 10 % by weight or potential anionic polyvalent alcohol, it has two or more isocyanate group is had to reactive group and at least one carboxyl or carboxylic acid ester groups;
III) one or more linear polycarbonate glycol of 0 to 95 % by weight, its molecular weight is 500 to 3000;
IV) one or more linear polyesters glycol of 0 to 95 % by weight, its molecular weight is 500 to 4,000;
V) one or more polyoxyalkylene diols of 0 to 95 % by weight, described polyoxyalkylene diols is selected from poly-(oxygen base propylidene) glycol and poly-(oxygen base tetramethylene) glycol,
The ratio of the mixture (P) of polyisocyanates and polyvalent alcohol is: the ratio of the summation of all reactivity-OH groups that the mixture (P) of the isocyanate group NCO of described polyisocyanates and described polyvalent alcohol comprises is between 1.2 and 2.3.
According to another aspect, the present invention relates to use aforesaid water-based anionic polyurethane dispersion for the preparation of application composition.
Detailed Description Of The Invention
In one embodiment, component I), II), III), IV) and V) amount at least 95 % by weight of mixture that account for polyvalent alcohol, the mixture of described polyvalent alcohol also comprises other non-ionic polyol of 0 to 5 % by weight, and the molecular weight of described other non-ionic polyol is lower than 1000 and contain two or more oh groups; The example of available non-ionic polyol is: glycerol, tetramethylolmethane, neopentyl glycol, butyleneglycol, 1,4-cyclohexanedimethanol, TriMethylolPropane(TMP) and their derivative, for example propoxylation TriMethylolPropane(TMP), polyfunctional poly divinyl and polyester polyol.
In a preferred embodiment, component I), II), III), IV) and V) amount to 100 % by weight of mixture (P) of the polyvalent alcohol that accounts for prepolymer; In preferred embodiment, component I), II), III) and IV) amount to 100 % by weight of the mixture that accounts for polyvalent alcohol.
Hydrophobicity polyvalent alcohol I) not containing epoxide group, be preferably 5 to 75 % by weight of the mixture of polyvalent alcohol.
Preferably, in the aromatics diglycidylether of chemical formula (I), R
1be group (i), wherein R
2, R
3it is methyl group.
The average N CO functionality of operable polyisocyanates is between 2.0 and 2.3, and preferably aliphatic series or cycloaliphatic polyisocyanate.
The example of available polyisocyanates is 4,4 '-dicyclohexyl-methane-vulcabond, 1-isocyanate group-3-(isocyanatomethyl)-3,5,5-trimethyl-cyclohexane (or isophorone diisocyanate), 1,4-fourth vulcabond, hexamethylene diisocyanate and their mixture.
Most preferred polyisocyanates is 4,4 '-dicyclohexyl-methane-vulcabond, 1-isocyanic ester-3-isocyanic ester-methyl-3,5,5-trimethyl-cyclohexane (or isophorone diisocyanate) and hexamethylene diisocyanate and their mixture.
Pass through vulcabond, for example 1, hexamethylene-diisocyanate, isophorone diisocyanate, 4, the part trimerizing of 4'-dicyclohexyl methane diisocyanate and composition thereof, biuretized, urethane or allophanic acid esterification, or by aforementioned vulcabond is mixed obtain average N CO functionality higher than 2 polyisocyanates with the product of their trimerizing, biuretized, urethane or allophanic acid esterification.
The component I I of the mixture (P) of polyvalent alcohol) carboxylic acid that preferably replaced by two methylol groups in position 2, for example dimethylol propionic acid, dimethylolpropionic acid or their mixture.
To component I I in the mixture of polyvalent alcohol) amount select, to obtain the prepolymer containing 5 to 125meq/100g dry weight COOH groups; Most preferably, described value is between 20 and 60.
Can be obtaining polycarbonate by the dealcoholization condensation reaction of low molecular weight diols and dialkyl carbonate, obtain polycarbonate by the dephenolize condensation reaction of low molecular weight diols and dipheryl carbonate base ester or obtain the component III of the mixture (P) to polyvalent alcohol in the option of polycarbonate by the de-glycol condensation reaction of low molecular weight diols and alkylene carbonates or dialkyl carbonate) select.
The example of described low molecular weight diols comprises BDO, 1,5-PD, 1,6-hexylene glycol, ethylene glycol, propylene glycol, 3-methyl isophthalic acid, 5-pentanediol, neopentyl glycol, glycol ether, Isosorbide-5-Nitrae-cyclohexanediol and 1,4 cyclohexane dimethanol etc.The example of described dialkyl carbonate comprises methylcarbonate and diethyl carbonate.The example of carbonic acid two alkylene esters is carbonic acid diethylidene esters.
A more preferred example of polycarbonate diol is poly-(the carbonic acid hexa-methylene ester) glycol obtaining by the condensation reaction of 1,6-hexylene glycol and dialkyl carbonate.
Preferably, the number-average molecular weight of described polycarbonate diol is 800 to 2000.
The component I V of the mixture (P) of polyvalent alcohol) can be selected from and react the polyester obtaining by acid, ester, acid anhydride or acyl halide with glycol.
For example, toxilic acid, succsinic acid, hexanodioic acid, suberic acid, sebacic acid, phthalic acid, terephthalic acid and m-phthalic acid, and acyl halide, acid anhydride and the ester of their possible correspondences can be for the preparation of described polyester.
The example of suitable glycol is ethylene glycol, BDO, 1,3-PD, 1,2-PD, neopentyl glycol, tetramethylene glycol, glycol ether, 1,6-hexylene glycol, 1,5-PD; The aklylene glycol replacing, for example 2，2-dimethyl-1，3-propanediol; Ring glycol, for example Isosorbide-5-Nitrae-cyclohexanediol and 1,4 cyclohexane dimethanol and aromatic diol; These glycol react with aliphatic dicarboxylic acid, cycloaliphatic dicarboxylic acid or aromatic dicarboxylic acid or react with the alkyl ester of low-molecular-weight alcohol or react with the compound that can form ester bond, to obtain the polymkeric substance of lower molecular weight, preferably, the fusing point of described lower molecular weight polymkeric substance is lower than approximately 80 ° of C.
Can also use hydroxy-end capped polycaprolactone.
Preferably, the number-average molecular weight of polyester glycol is 800 to 3,000.
One preferred embodiment in, polyester glycol is selected from the polyester based on hexanodioic acid and/or phthalic acid and 1,6-hexylene glycol, ethylene glycol, glycol ether, neopentyl glycol, BDO or their mixtures.
According to one preferred embodiment, the polyvalent alcohol of mixture (P) is containing coming from the unit of poly-(oxygen base ethylidene) glycol.
The aqueous dispersion of anionic polyurethane of the present invention can be prepared by following steps: i) with ratio as defined above, polyisocyanates is reacted with the mixture (P) of polyvalent alcohol; Ii) prepolymer obtaining is dispersed in water; Iii) in obtained dispersion, add polyamine (chain extension agent) that it is reacted until all isocyanate group disappear.
Preferably, between 40 and 110 ° of C temperature, the in the situation that of organic solvent or ORGANIC SOLVENT MIXTURES existence, carry out step I); But find to use hydrophobicity polyvalent alcohol I) reduced the viscosity of reaction mixture, thereby, advantageously reduced synthetic in the required amount of solvent and the total flow of VOC.
Suitable solvent is common solvent, for example N-Methyl pyrrolidone, N-ethyl pyrrolidone, dipropylene glycol dimethyl ether, ethyl acetate, butylacetate, ethylene glycol monomethyl ether acetate or ethylene glycol monoethyl ether acetate, 1-methoxy-propyl 2-acetic ester, 3-methoxyl group-n-butylacetic acid ester, acetone, 2-butanone, 4-methyl-2 pentanone, pimelinketone, , contain especially aromatic ester, the mixture of carbonic ether, for example methylcarbonate, diethyl carbonate, carbonic acid 1, 2-ethyl and carbonic acid 1, the sub-propyl ester of 2-, lactone, for example [β]-propiolactone, [γ]-butyrolactone, [ε]-caprolactone and [ε]-methyl caprolactone, also has following solvent, for example propylene glycol diacetate, diethylene glycol dimethyl ether, Diethylene Glycol ethyl ether acetic ester, any required mixture of Diethylene Glycol butyl ether acetic ester and N-methyl caprolactam or described solvent.Preferred solvent is N-ethyl pyrrolidone and dipropylene glycol dimethyl ether.
Conventionally to step I) prepolymer that obtains neutralizes while finishing, preferably uses tertiary amine as N-alkyl morpholine, trialkylamine, dialkyl group alkanolamine, alkyl two alkanolamines, trialkanolamine and their mixture, at the temperature lower than 90 ° of C, carry out.
Triethylamine, dimethylethanolamine and N-methylmorpholine are particularly suitable for this scope.
Neutralization operation can, in the time that reactions steps i) finishes, be carried out in water-less environment, or is distributed in water and (in step I process i), carries out at prepolymer subsequently.
Carry out step I i), in the time of mechanical stirring, preferably in the situation that emulsifying agent exists, prepolymer is poured in water, vice versa.
Emulsifying agent can be selected from nonionic surface active agent, aniorfic surfactant and cationic surfactant; Preferably, described emulsifying agent is nonionic surface active agent.
Step I ii) in preferably aliphatic tertiary amine or aliphatic secondary amine of polyamines.
Step I ii) in can use the mixture of polyamines.
The example of suitable polyamines is hydrazine, quadrol, piperazine, 1,5-pentamethylene diamine, 1,6-bis-hexanediamines, isophorone diamine, diethylenetriamine, 2-methyl isophthalic acid, 5-pentamethylene diamine and 4,4 '-methylene radical-bis--hexahydroaniline.
Determining step iii) temperature and the amount of time length and polyamines, roll into a ball and obtain meticulous, stable and polyurethane dispersions uniformly to exhaust the dissociateive NCO being present in prepolymer, this is well-known in the art.
Can be by step I ii) process in or at step I ii) distillation while finishing removes the organic solvent that may exist.
The step I ii of the inventive method) can be by infiltrate polyamines in the dispersion of prepolymer, and remain on and stir and get off to carry out lower than the temperature of 40 ° of C.
The Brookfield of anionic polyurethane aqueous dispersion of the present invention
viscosity conventionally 50 and 2000mPa*s between.
In order to prepare application composition, anion-type water-thinned polyurethane dispersion can be mixed with linking agent, binding agent (being preferably acrylic adhesive) and/or other additives, thereby for example further improve their coating property, film forming ability, and reduce or increase opacity to avoid producing " orange peel " effect or " flake " effect and foaming.
The example that can join the additive in application composition is, flow agent, wetting agent, weighting agent, pigment, wax, tensio-active agent, thickening material, coalescing agent, rust-preventive agent etc.
Can make the anionic polyurethane of aqueous dispersion of the present invention crosslinked with any linking agent well known by persons skilled in the art, described linking agent be for example to dispersible in the polyisocyanates of water, polyisocyanates, polyaziridine, carbodiimide, epoxy silane and the trimeric cyanamide of end-blocking.
With the dry weight basis of dispersion, the add-on of linking agent is conventionally between 1 and 10%.
Crosslinked is useful, resistance to mechanicalness and chemical resistant properties that can reinforcing membrane.
Film forming anionic polyurethane aqueous dispersion of the present invention and the application composition that contains described film forming anionic polyurethane aqueous dispersion are preferred for finish rigid substrate, for example plastics (as polycarbonate, ABS and PVC), timber, glass and metal (for example, aluminium, steel, galvanized iron and galvanized steel: GA, GL, GI and EGI).
The material that is coated with the film obtaining by aqueous dispersion of the present invention can be for vehicle interior, with finish instrument or car door inner side, can be used for electronic product, for example mobile phone,
with
can be used for the metallic surface such as counter body or housing of TV set, and for rolling up coating.
In following examples, record the synthetic of hydrophobicity polyvalent alcohol and according to the preparation of aqueous dispersion of the present invention.
Be that 25 ° of C and angle are under the condition of 90 °, to measure the particle diameter of dispersion by the laser correlation spectrum (LCS) with Coulter N4 Plus instrument in temperature.
Embodiment
Listed material below using in embodiment hereinafter described:
Polyvalent alcohol 1: the glycol, 1 based on polyester, the adipic acid ester-phthalic ester of 6-hexylene glycol, molecular weight is 1000g/mol
Polyvalent alcohol 2: the glycol based on polycarbonate, poly-(carbonic acid hexa-methylene ester) glycol, molecular weight is 1000g/mol
H-polyvalent alcohol 5: cocounut oil diglycollic amide, molecular weight is 213g/mol
H-polyvalent alcohol 6: oleic acid diethyl amide, molecular weight is 269.7g/mol
DGEBA: the diglycidylether of dihydroxyphenyl propane, molecular weight is 380g/mol
DMPA: dimethylol propionic acid, molecular weight is 134,2g/mol
Alcohol C6: n-hexyl alcohol, molecular weight is 102g/mol
Alcohol C12: n-dodecanol, molecular weight is 186g/mol
Alcohol C20: line style C20 monohydroxy-alcohol, molecular weight is 298g/mol
NMP:N-methyl-pyrrolidone
NMP:N-ethyl-pyrrolidone
IPDI: isophorone diisocyanate, molecular weight is 222g/mol
HMDI:4,4 '-dicyclohexyl-methane-vulcabond, molecular weight is 262g/mol
TEA: triethylamine, molecular weight is 101,15g/mol
DEA: diethanolamine, molecular weight is 105,14g/mol
HH: hydrazine hydrate, 24.36% aqueous solution, molecular weight is 32,04g/mol
ADD: wetting agent Byk 346
Embodiment 1.1-1.3
Embodiment 1.1-1.3 has described the preparation process of the hydrophobicity polyvalent alcohol based on DGEBA.
Embodiment 1.1
Synthesizing of H-polyvalent alcohol 1.
Under nitrogen atmosphere, by 140.6g(1.363mol) alcohol C6 join in the reactor that thermometer, mechanical stirrer and condenser are housed, and be heated to 65 ° of C.Under the stirring of 65 ° of C, add 40% the KOH of 0.40g.
Then add 259.4g(0.682mol) DGEBA, reaction mixture is heated to 120 ° of C and maintains approximately 4 hours in this temperature, until epoxide group all disappears.
In this embodiment and all other embodiment, all establishing criteria ASTM D1652-04 determines the titration of epoxide group.
Transform once reach completely epoxy, reaction mixture is cooled to 80 ° of C and adds 85% the phosphoric acid of 0.35g, obtaining H-polyvalent alcohol 1(molecular weight is 586g/mol).OH number is 191mg KOH/g.
Embodiment 1.2
Synthesizing of H-polyvalent alcohol 2.
According to the process of embodiment 1.1, by 186.0g(1 mole) alcohol C12 join in reactor, be heated to 70 ° of C, then add the KOH of 0.75g 40%.
Then add 190.0g(0.5mol) DGEBA, reaction mixture is heated to 120 ° of C, and maintains this temperature until epoxide group disappears (approximately 4 hours).
Then reaction mixture is cooled to 80 ° of C and adds 85% the phosphoric acid of 0.65g, obtaining H-polyvalent alcohol 2(molecular weight is 752g/mol).OH number is 149mg KOH/g.
Embodiment 1.3
Synthesizing of H-polyvalent alcohol 3.
According to the process of embodiment 1.1, by 326.0g(1 mole) alcohol C20 join in reactor, be heated to 100 DEG C, then add the KOH of 0.80g 40%.
Then add 190.0g(0.5mol) DGEBA, reaction mixture is heated to 130 DEG C, and maintains this temperature until epoxide group disappears (approximately 12 hours).
Then reaction mixture is cooled to 120 DEG C and add 85% the phosphoric acid of 0.80g, obtains H-polyvalent alcohol 3.OH number is 108mg KOH/g.
Embodiment 1.4
Synthesizing of H-polyvalent alcohol 4.
Embodiment 1.4 has described according to prior art and has prepared the hydrophobicity polyvalent alcohol (H-polyvalent alcohol 4) based on IPDI.
Under nitrogen atmosphere and room temperature, the NEP of 135.1g alcohol C6,432.0g is joined in the reactor that is provided with thermometer, agitator and condenser.
When mixture after approximately 30 minutes, under agitation adds the IPDI of 293.9g 40 ° of C homogenizing.
Then reaction mixture is heated to 80 ° of C, reaction is carried out under 90 ° of C, until the content of NCO group equals 6.45% in prepolymer.
In this embodiment and all other embodiment, all establishing criteria method ASTM D2572 determines the titration of remaining isocyanate base.
Prepolymer is cooled to 80 ° of C, and under agitation slowly adds the DEA of 138.8g.
The solid residue content of the polyvalent alcohol (H-polyvalent alcohol 4) obtaining is 75 % by weight (molecular weight 429.7).OH number is 261mg KOH/g.
Embodiment 2.1
Prepare aqueous dispersion of the present invention.
According to embodiment 1.1, the H-polyvalent alcohol 1 of the polyvalent alcohol of 138.7g 2 and 26.6g, the DMPA of 20.9g and the NMP of 80g are joined in reactor.When mixture after approximately 30 minutes, under agitation adds the HMDI of 155.6g 40 ° of C homogenizing.
Then keep 30 minutes by reaction mixture heating, and at 60 ° of C.
React at 95-100 ° of C, until the theoretical value (approximately 1 hour) that in prepolymer, the content of NCO group equals 5.07%.
Then prepolymer is cooled to approximately 75 ° of C, and under agitation adds the neutralizing agent TEA of 14.9g.
After approximately 10 minutes and at the internal temperature of 65 ° of C, at violent stirring and the temperature lower than 35 ° of C, prepolymer is dispersed in softening water.In the temperature lower than 35 ° of C, as described in Table 1, add the aqueous solution of the diamines HH(24.36% of 47.8g) carry out increment.
In the polyurethane dispersions obtaining, add wetting agent ADD, then filter with 150 μ m canvas, make solid residue content reach 35 % by weight.The dispersion obtaining is limpid and stable.
Embodiment 2.2-2.4
Prepare other aqueous dispersion of the present invention.
According to the process as described in embodiment 2.1, the composition of having changed as shown in table 1, unit is gram.
Embodiment 2.5(comparative example)
According to the process as described in embodiment 2.1, do not use any hydrophobicity polyvalent alcohol, use the composition recording as table 1.
Embodiment 2.6-2.10(comparative example)
Other aqueous dispersion of preparation prior art.
The Verbose Listing of composition and their amount are recorded in table 1.
Under nitrogen atmosphere and room temperature, polyvalent alcohol 1 or polyvalent alcohol 2 and H-polyvalent alcohol 4, H-polyvalent alcohol 5 or H-polyvalent alcohol 6, DMPA and NMP are joined in the reactor that is provided with thermometer, agitator and condenser.
When mixture after approximately 30 minutes, under agitation adds HMDI 40 ° of C homogenizing.
Then keep 30 minutes by reaction mixture heating, and at 60 ° of C.
React at 95-100 ° of C, until the content of NCO group equals theoretical value (approximately 1 hour) in prepolymer.
Then prepolymer is cooled to approximately 75 ° of C, and under agitation adds neutralizing agent TEA.
After approximately 10 minutes and at the internal temperature of 65 ° of C, at violent stirring and the temperature lower than 35 ° of C, prepolymer is dispersed in softening water.At the temperature lower than 35 ° of C, add the chain extension agent HH described in table 1 to carry out increment.
In the polyurethane dispersions obtaining, add wetting agent ADD, then filter with 150 μ m canvas, make solid residue content reach 35 % by weight.The dispersion obtaining is limpid and stable.
Application Example
In Application Example, show the result comparison using between the coating that two kinds of dispersions according to the present invention of coating and use that prior art dispersion is processed process.
To having applied the glass of polyurethane dispersions or the machinery of metal base, physics and chemical property compare.
Use portable protractor PGX to measure the contact angle on the aluminium base applying.Integration pump provides accurate water droplet with 0.5 μ l stepping (step), and built-in camera catches independent water droplet image, the static contact angle when determining " balance ".
Table 1
* comparative example
Measure the standard method of test of organic coating hardness by fork damping test according to standard method ASTM D4366-95() on glass baseplate, measure the hardness of film.
By the surperficial resistance of the cold liquid of standard method UNIEN12720() at resistance to hydrolysis and the resistance to ethanol of mensuration film on glass.
At the temperature of 55 ° of C, by the glass specimen of coating being immersed in alkalescence or acidic solution to (1%NaOH or 5%HCl) 2 minutes, assess its chemical resistant properties (NaOH, HCl).Represent result by following standard: 0=is the poorest, coating is damaged, 5=is best, not impact.
Measure fusible standard method of test by standard method ASTM D3359-09(by adhesive tape test) determine the binding property on metal base (aluminum and zinc galvinized steel).Represent result by following standard: 0=is the poorest, coating is damaged, 5=is best, not impact.
The results are shown in table 2.
Can find that, with respect to every other embodiment, the contact angle of embodiment 2.4 significantly increases, show that coating hydrophobicity is higher.
The dispersion that does not use any hydrophobicity polyvalent alcohol to prepare with respect to those, the base material that is coated with the dispersion of embodiment 2.2 and 2.4 has doubly better resistance to ethanol of 6-7, with respect to according to the dispersion of prior art, the base material that is coated with the dispersion of embodiment 2.2 and 2.4 even has better resistance to ethanol.
According to the anti-H of coating of the present invention
2o (resistance to hydrolysis) is good.
Table 2
* comparative example
* wetting conditions: plate is immersed in water to 4 hours, carries out binding property test in 2 minutes after taking out.
In addition,, with respect to the base material of preparing according to the dispersion of prior art, the base material that is coated with the dispersion of embodiment 2.2 and 2.4 demonstrates good hardness and on aluminium base and steel substrate, all has outstanding binding property.
In the time considering alkali resistance and acid resistance, the alkali resistance showing by coating prepared by dispersion of the present invention is identical with prior art coating with acid resistance or be better than prior art.
Claims (10)
1. aqueous dispersion, the anionic polyurethane that this aqueous dispersion contains 20 to 50 % by weight, obtain described aqueous dispersion by following steps: in water, disperse, and carry out the anionic prepolymer of increment neutralization with polyamines, this anionic prepolymer is containing the hydroxy-acid group of 5 to 125meq/100g dry weights, and by making one or more aliphatic polyisocyanates, prepared by the reacting of the mixture (P) of cycloaliphatic polyisocyanate or aromatic polyisocyanate and polyvalent alcohol, the mixture (P) of described polyvalent alcohol comprises following I), II), III), IV) and V):
I) one or more hydrophobicity polyvalent alcohols of 4 to 90 % by weight, the molar average hydroxy functionality of described hydrophobicity polyvalent alcohol is 2 to 3, hydroxyl value is 350 to 40, and by making alcohol roh react to obtain with aromatics diglycidylether, wherein R is the saturated C of branching or straight chain
4-C
30alkyl chain, or R is the saturated C of branching or straight chain
4-C
10alkyl phenyl group, wherein said aromatics diglycidylether has following chemical formula (I):
Wherein R
1group (i):
R
2, R
3each is Me, Et or H independently;
Or R
1it is the phenylene optionally being replaced by one or more alkyl groups;
Or R
1it is the biphenylene optionally being replaced by one or more alkyl groups;
Or R
1group (ii):
II) one or more anionics of 1 to 10 % by weight or potential anionic polyvalent alcohol, it has two or more isocyanate group is had to reactive group and at least one carboxyl or carboxylic acid ester groups;
III) one or more linear polycarbonate glycol of 0 to 95 % by weight, its molecular weight is 500 to 3000;
IV) one or more linear polyesters glycol of 0 to 95 % by weight, its molecular weight is 500 to 4,000;
V) one or more polyoxyalkylene diols of 0 to 95 % by weight, described polyoxyalkylene diols is selected from poly-(oxygen base propylidene) glycol and poly-(oxygen base tetramethylene) glycol,
The ratio of the mixture (P) of polyisocyanates and polyvalent alcohol is: the ratio of the summation of all reactivity-OH groups that the mixture (P) of the isocyanate group NCO of described polyisocyanates and described polyvalent alcohol comprises is between 1.2 and 2.3.
2. aqueous dispersion as claimed in claim 1, it is characterized in that, described component I), II), III), IV) and V) amount at least 95 % by weight of mixture that account for polyvalent alcohol, the mixture of described polyvalent alcohol also comprises other non-ionic polyol of 0 to 5 % by weight, and the molecular weight of described other non-ionic polyol is lower than 1000 and contain two or more oh groups.
3. aqueous dispersion as claimed in claim 2, is characterized in that, described component I), II), III), IV) and V) amount to 100 % by weight of mixture (P) of the polyvalent alcohol that accounts for prepolymer.
4. aqueous dispersion as claimed in claim 3, is characterized in that, described component I), II), III) and IV) amount to 100 % by weight of mixture that account for polyvalent alcohol.
5. aqueous dispersion as claimed in claim 1, it is characterized in that, one or more hydrophobicity polyvalent alcohols I that the mixture (P) of described polyvalent alcohol comprises 5 to 75 % by weight), it is by making alcohol roh react to obtain, and wherein R is the saturated C of branching or straight chain
6-C
22alkyl chain, and R
1group (i):
6. aqueous dispersion as claimed in claim 5, is characterized in that, described R
2, R
3me.
7. aqueous dispersion as claimed in claim 1, is characterized in that, the aliphatic polyisocyanate from one or more average N CO functionality between 2.0 and 2.3 or cycloaliphatic polyisocyanate are prepared the anionic prepolymer of described neutralization.
8. aqueous dispersion as claimed in claim 1, is characterized in that, the component I I of the mixture (P) of described polyvalent alcohol) be dimethylol propionic acid, dimethylolpropionic acid or their mixture; The component III of the mixture (P) of described polyvalent alcohol) be that number-average molecular weight is poly-(carbonic acid hexa-methylene ester) glycol of 800 to 2000; The component I V of the mixture (P) of described polyvalent alcohol) be selected from based on hexanodioic acid and/or phthalic acid and 1,6-hexylene glycol, ethylene glycol, glycol ether, neopentyl glycol, 1, the polyester of 4-butyleneglycol and their mixture, and number-average molecular weight is 800 to 3000.
9. the aqueous dispersion described in aforementioned any one claim, is characterized in that, the mixture (P) of described polyvalent alcohol is containing the unit that comes from poly-(oxygen base ethylidene) glycol.
10. use as claimed in any one of claims 1-9 wherein aqueous dispersion for the preparation of application composition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITVA2010A000033A IT1399424B1 (en) | 2010-04-08 | 2010-04-08 | AQUEOUS DISPERSIONS OF ANIONIC POLYURETHANE |
| ITVA2010A000033 | 2010-04-08 | ||
| PCT/EP2011/055337 WO2011124602A1 (en) | 2010-04-08 | 2011-04-06 | Aqueous anionic polyurethane dispersions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102822220A CN102822220A (en) | 2012-12-12 |
| CN102822220B true CN102822220B (en) | 2014-10-29 |
Family
ID=43034686
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180017821.0A Active CN102822220B (en) | 2010-04-08 | 2011-04-06 | Aqueous anionic polyurethane dispersions |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP2556097A1 (en) |
| KR (1) | KR101791283B1 (en) |
| CN (1) | CN102822220B (en) |
| IT (1) | IT1399424B1 (en) |
| WO (1) | WO2011124602A1 (en) |
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| EP2937368A1 (en) * | 2014-04-24 | 2015-10-28 | BASF Coatings GmbH | Aqueous two component coating compositions and coatings produced from the same having high erosion resistance |
| CN104592882B (en) * | 2015-01-30 | 2017-07-04 | 雅图高新材料有限公司 | Automobile single-component water-based plain color paint and its preparation technology |
| CN106189764A (en) * | 2015-10-30 | 2016-12-07 | 丹阳市日月漆业有限公司 | A kind of coating and its preparation method and application |
| CN106189766A (en) * | 2015-10-30 | 2016-12-07 | 丹阳市日月漆业有限公司 | Coating and its preparation method and application |
| CN106189765A (en) * | 2015-10-30 | 2016-12-07 | 丹阳市日月漆业有限公司 | A kind of water-based mono-component plastic coating and its preparation method and application |
| CN106167671A (en) * | 2015-10-30 | 2016-11-30 | 丹阳市日月漆业有限公司 | Water-based mono-component plastic coating and its preparation method and application |
| CN106189767A (en) * | 2015-10-30 | 2016-12-07 | 丹阳市日月漆业有限公司 | A kind of water paint and its preparation method and application |
| CN108659651A (en) * | 2018-03-08 | 2018-10-16 | 河北晨阳工贸集团有限公司 | Natural gas heating outer wall pipeline environment-protective water paint and preparation method thereof |
| CN110330620B (en) * | 2019-08-02 | 2021-08-24 | 山西省应用化学研究所(有限公司) | Waterborne polyurethane ink binder for plastic film and preparation method thereof |
| JP2024505993A (en) * | 2021-06-08 | 2024-02-08 | Dic株式会社 | Cationic urethane resin composition |
| EP4426763A1 (en) | 2021-11-05 | 2024-09-11 | Hempel A/S | Water based coating composition for wind blades |
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| US2700030A (en) * | 1951-12-21 | 1955-01-18 | Ciba Ltd | Manufacture of an etherification product of a poly-glycidyl ether of a polyoxy compound with a higher monohydric alcohol |
| CN1275995C (en) * | 2002-04-05 | 2006-09-20 | 拜尔公司 | Polyurethane dispersion based on fatty acid dialkyl alochol amide |
| CN101553534A (en) * | 2006-12-25 | 2009-10-07 | 日本聚氨酯工业株式会社 | Aqueous polyurethane resin emulsion coating composition and method for producing the same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4569966A (en) * | 1984-04-19 | 1986-02-11 | Ppg Industries, Inc. | Polymeric microparticles |
| JP2002284838A (en) | 2001-03-26 | 2002-10-03 | Nicca Chemical Co Ltd | Aqueous dispersion of hydroxyl group-containing acrylic/ urethane copolymer, two-pack aqueous acrylic/urethane composition, and coating material and adhesive containing the composition |
| US7241504B2 (en) | 2003-01-17 | 2007-07-10 | The United States Of America As Represented By The Secretary Of The Navy | Diols formed by ring-opening of epoxies |
| US20080194757A1 (en) | 2004-10-05 | 2008-08-14 | Adeka Corporation | Water-Dispersed Polyurethane Composition |
| JP5053718B2 (en) | 2007-06-05 | 2012-10-17 | 株式会社Ａｄｅｋａ | Solvent-free aqueous polyurethane resin composition and method for producing the same |
-
2010
- 2010-04-08 IT ITVA2010A000033A patent/IT1399424B1/en active
-
2011
- 2011-04-06 KR KR1020127027572A patent/KR101791283B1/en active IP Right Grant
- 2011-04-06 EP EP11715460A patent/EP2556097A1/en not_active Withdrawn
- 2011-04-06 WO PCT/EP2011/055337 patent/WO2011124602A1/en active Application Filing
- 2011-04-06 CN CN201180017821.0A patent/CN102822220B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2700030A (en) * | 1951-12-21 | 1955-01-18 | Ciba Ltd | Manufacture of an etherification product of a poly-glycidyl ether of a polyoxy compound with a higher monohydric alcohol |
| CN1275995C (en) * | 2002-04-05 | 2006-09-20 | 拜尔公司 | Polyurethane dispersion based on fatty acid dialkyl alochol amide |
| CN101553534A (en) * | 2006-12-25 | 2009-10-07 | 日本聚氨酯工业株式会社 | Aqueous polyurethane resin emulsion coating composition and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| ITVA20100033A1 (en) | 2011-10-09 |
| KR20130040833A (en) | 2013-04-24 |
| IT1399424B1 (en) | 2013-04-16 |
| WO2011124602A1 (en) | 2011-10-13 |
| CN102822220A (en) | 2012-12-12 |
| KR101791283B1 (en) | 2017-10-27 |
| EP2556097A1 (en) | 2013-02-13 |
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