CN102822220A - Aqueous anionic polyurethane dispersions - Google Patents
Aqueous anionic polyurethane dispersions Download PDFInfo
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- CN102822220A CN102822220A CN2011800178210A CN201180017821A CN102822220A CN 102822220 A CN102822220 A CN 102822220A CN 2011800178210 A CN2011800178210 A CN 2011800178210A CN 201180017821 A CN201180017821 A CN 201180017821A CN 102822220 A CN102822220 A CN 102822220A
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- 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
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- 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
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (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 water-based anionic polyurethane dispersion, and relate to their purposes, be used for the for example rigid surface of metal, plastics, glass and timber is applied as membrane-forming agent based on concrete hydrophobicity polyvalent alcohol.
Aqueous dispersion of the present invention provide have IMAGE, the coating of binding property, resistance to hydrolysis and acidproof/alkalescence and hardness.
Background technology
The surface of many manufacturing goods (the manufacturing goods that for example prepared by leather, plastics, timber and metal) need be handled; Purpose is to make this surface more even; Perhaps protect the surface to avoid passing in time or contact atmosphere and worn and torn; And/or improve some character attractive in appearance, for example higher or lower opacity, softness or hard sense of touch and color etc.
Usually; Obtain these effects through applying film-forming polymer (coating); Nowadays in various film-forming polymer, solvent borne polyurethane is to come into one's own as everyone knows and in the coating field, has outstanding chemical resistant properties and anti-mechanical film because they can produce.
Likewise, owing to be discharged into environment about reduction, particularly the Regulation Policy of the low VOC in the work area comes into one's own gradually, and nowadays the aqueous dispersion of urethane has also played corresponding uses.
When the urethane of considering use dispersion-s form applies, produced some problems, reason is that their dispersive abilities in water need comprise hydrophilic segment, this hydrophilic segment has reduced the weather resistance and the stability to hydrolysis of film inherently.
Known in the art unsaturated group is incorporated into crosslinkedization that cause film in the urethane and therefore can improves chemical resistance of coating; Unfortunately, be present in yellowing and the strong oxidizing condition of needs that shortcoming relevant in the urethane is a film with unsaturated group and be used for crosslinkedization.
US 2003/0191273 has described the aqueous dispersion that uses based on the urethane of Marlamid as application composition; It is said from the coating of these dispersion-ss preparation have good pendulum-rocker hardness, good anti-heel marking property and high glossiness.
US 2008/0194757 has described the polyurethane composition of water-dispersion, and this polyurethane composition contains sour (nurate) compound of the urea with long chain alkyl group as polyisocyanate component; Said compsn is stated to be coat film good binding property, water resisting property, weathering resistance, erosion resistance, water-repellancy and grease proofness is provided.
Surprisedly be; 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 through in urethane, being incorporated into specific hydrophobic property polyvalent alcohol, and said specific hydrophobic property polyvalent alcohol obtains through making Fatty Alcohol(C12-C14 and C12-C18) and aromatics diglycidylether react.
Summary of the invention
The invention provides the aqueous dispersion of the anionic polyurethane that contains 20 to 50 weight %; Obtain said aqueous dispersion through following steps: in water, disperse; And extend neutral anionic prepolymer with polyamines; This anionic prepolymer contains the hydroxy-acid group of 5 to 125meq/100g dry weights; And through making mixture (P) reaction of one or more aliphatic polyisocyanates, cycloaliphatic polyisocyanate or aromatic polyisocyanate and polyvalent alcohol prepare, the mixture of said polyvalent alcohol (P) comprises following component I), II), III), IV) and V):
I) one or more hydrophobicity polyvalent alcohols of 4 to 90 weight %; The molar average hydroxy functionality of said hydrophobicity polyvalent alcohol is 2 to 3; Hydroxyl value is 350 to 40 (mg KOH/g), and obtains through making alcohol roh and aromatics diglycidylether react, and 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, perhaps R is the saturated C of branching or straight chain
4-C
10The alkyl phenyl group, wherein said aromatics diglycidylether has following chemical formula (I):
R wherein
1Be group (i):
R wherein
2, R
3Each is Me, Et or H independently;
Perhaps R
1Be to be preferably the substituted phenylene of methyl group randomly by one or more alkyl groups;
Perhaps R
1Be to be preferably the substituted biphenylene of methyl group randomly by one or more alkyl groups;
Perhaps R
1Be group (ii):
II) one or more anionics of 1 to 10 weight % or potential anionic polyvalent alcohol, it has two or more NCO is had reactive group and at least one carboxyl or carboxylic acid ester groups;
III) one or more linear polycarbonate glycol of 0 to 95 weight %, its molecular weight is 500 to 3000;
IV) one or more linear polyesters glycol of 0 to 95 weight %, its molecular weight is 500 to 4,000;
V) one or more polyoxyalkylene diols of 0 to 95 weight %, said polyoxyalkylene diols are selected from gathers (oxygen base propylidene) two pure and mild gathering (oxygen base tetramethylene) glycol,
The ratio of the mixture of POLYMETHYLENE POLYPHENYLISOCYANATE and polyvalent alcohol (P) is: the ratio of the summation of all reactivities-OH group that the mixture (P) of the isocyanate group NCO of said POLYMETHYLENE POLYPHENYLISOCYANATE and said 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 to be used to prepare application composition.
Detailed Description Of The Invention
In one embodiment; Component I), IV III II))) and V) amount at least 95 weight % of the mixture that accounts for polyvalent alcohol; The mixture of said polyvalent alcohol also comprises other non-ionic polyol of 0 to 5 weight %, and the molecular weight of said other non-ionic polyol is lower than 1000 and contain two or more oh groups; The example of available non-ionic polyol is: USP Kosher, tetramethylolmethane, NSC 6366, butyleneglycol, 1; 4-cyclohexanedimethanol, TriMethylolPropane(TMP) and their verivate, for example propoxylation TriMethylolPropane(TMP), polyfunctional poly divinyl and polyester polyol.
In preferred embodiment, component I), IV III II))) and V) amount to 100 weight % of the mixture (P) of the polyvalent alcohol that accounts for prepolymer; In preferred embodiment, component I), III II)) and IV) amount to 100 weight % of the mixture that accounts for polyvalent alcohol.
Hydrophobicity polyvalent alcohol I) do not contain epoxide group, be preferably 5 to 75 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 POLYMETHYLENE POLYPHENYLISOCYANATE is between 2.0 and 2.3, and preferably aliphatic or cycloaliphatic polyisocyanate.
The example of available POLYMETHYLENE POLYPHENYLISOCYANATE is 4; 4 '-dicyclohexyl-methane-vulcabond, 1-NCO-3-(isocyanatomethyl)-3; 5; 5-trimethyl-cyclohexane (or isophorone diisocyanate), 1,4-fourth vulcabond, hexamethylene diisocyanate and their mixture.
Most preferred POLYMETHYLENE POLYPHENYLISOCYANATE 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 perhaps are higher than 2 POLYMETHYLENE POLYPHENYLISOCYANATE through making aforementioned vulcabond mix with the product of their trimerizing, biuretized, urethane or allophanic acid esterification to obtain average N CO functionality.
The component I I of the mixture of polyvalent alcohol (P)) preferably in the position 2 by two substituted carboxylic acids of methylol groups, for example dimethylol propionic acid, dimethylolpropionic acid or their mixture.
To component I I in the mixture of polyvalent alcohol) amount select, to obtain containing the prepolymer of 5 to 125meq/100g dry weight COOH groups; Most preferably, said value is between 20 and 60.
Can obtain polycarbonate, the dephenolize condensation reaction through low molecular weight diols and dipheryl carbonate base ester at dealcoholization condensation reaction and obtain polycarbonate or the component III of taking off in the option that the glycol condensation reaction obtains polycarbonate through low molecular weight diols and alkylene carbonates or dialkyl carbonate the mixture (P) of polyvalent alcohol through low molecular weight diols and dialkyl carbonate) select.
The example of said low molecular weight diols comprises 1,4-butyleneglycol, 1,5-pentanediol, 1,6-pinakon, terepthaloyl moietie, Ucar 35,3-methyl isophthalic acid, 5-pentanediol, NSC 6366, glycol ether, 1,4-cyclohexanediol and 1,4 cyclohexane dimethanol etc.The example of said 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 through 1, and the condensation reaction of 6-pinakon and dialkyl carbonate obtains gathers (carbonic acid hexa-methylene ester) glycol.
Preferably, the number-average molecular weight of said polycarbonate diol is 800 to 2000.
The component I V of the mixture of polyvalent alcohol (P)) can be selected from the polyester that obtains through acid, ester, acid anhydride or acyl halide and glycol reaction.
For example, toxilic acid, succsinic acid, hexanodioic acid, suberic acid, sebacic acid, phthalic acid, terephthalic acid and m-phthalic acid, and their possible corresponding acyl halide, acid anhydride and esters can be used to prepare said polyester.
The example of suitable glycol is a terepthaloyl moietie, 1,4-butyleneglycol, 1, ammediol, 1,2-Ucar 35, NSC 6366, tetramethylene glycol, glycol ether, 1,6-pinakon, 1,5-pentanediol; Substituted aklylene glycol, for example 2; The ring glycol, for example 1,4-cyclohexanediol and 1,4 cyclohexane dimethanol and aromatic diol; These glycol and aliphatic dicarboxylic acid, cycloaliphatic dicarboxylic acid or aromatic dicarboxylic acid reaction are perhaps reacted with the alkyl ester reaction of low-molecular-weight alcohol or with the compound that can form ester bond; To obtain the polymkeric substance of lower molecular weight; Preferably, the fusing point of said lower molecular weight polymkeric substance is lower than about 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 based on hexanodioic acid and/or phthalic acid and 1,6-pinakon, terepthaloyl moietie, glycol ether, NSC 6366,1, the polyester of 4-butyleneglycol or their mixtures.
According to one preferred embodiment, the polyvalent alcohol of mixture (P) does not contain and comes from the unit that gathers (oxygen base ethylidene) glycol.
The aqueous dispersion of anionic polyurethane of the present invention can prepare through following steps: i) make the mixture (P) of POLYMETHYLENE POLYPHENYLISOCYANATE and polyvalent alcohol react with as above defined ratio; Ii) the prepolymer that obtains is dispersed in the water; Iii) in resulting dispersion-s, adding polyamine (chain extension agent) makes it react until all NCO disappearances.
Preferably between 40 and 110 ° of C temperature, under the situation of organic solvent or ORGANIC SOLVENT MIXTURES existence, carry out step I); Yet find to use hydrophobicity polyvalent alcohol I) reduced the viscosity of reaction mixture, thereby, advantageously reduced the amount of solvent required in synthetic and the total flow of VOC.
Suitable solvent is a common solvent; For example N-Methyl pyrrolidone, N-ethyl pyrrolidone, dipropylene glycol dimethyl ether, ETHYLE ACETATE, butylacetate, ethylene glycol monomethyl ether acetate or ethylene glycol monoethyl ether acetate, 1-methoxy-propyl 2-acetic ester, 3-methoxyl group-just-butylacetic acid ester, acetone, 2-butanone, 4-methyl-2 pentanone, pimelinketone; The mixture that contains aromatic ester, carbonic ether especially; For example methylcarbonate, diethyl carbonate, carbonic acid 1; 2-ethyl and carbonic acid 1; The inferior propyl ester of 2-, lactone, for example [β]-propiolactone, [γ]-GBL, [ε]-caprolactone and [ε]-methyl caprolactone; Also has following solvent, for example any required mixture of propylene glycol diacetate, diethylene glycol dimethyl ether, Diethylene Glycol ethyl ether acetic ester, Diethylene Glycol butyl ether acetic ester and N-methyl caprolactam or said solvent.Preferred solvent is N-ethyl pyrrolidone and dipropylene glycol dimethyl ether.
Usually to step I) prepolymer that obtains when finishing neutralizes, and preferably uses tertiary amine such as N-alkyl morpholine, trialkylamine, dialkyl group alkanolamine, alkyl two alkanolamines, trialkanolamine and their mixture, under the temperature that is lower than 90 ° of C, carry out.
Triethylamine, dimethylethanolamine and N-methylmorpholine are particularly suitable for this scope.
Neutralization operation can be at reactions step i) when finishing, in water-less environment, carry out, perhaps, subsequently prepolymer carries out in being distributed to the process of (step I i) in the water.
Carry out step I i), when mechanical stirring, preferably under the situation that emulsifying agent exists, prepolymer is poured in the water, vice versa.
Emulsifying agent can be selected from non-ionics, aniorfic surfactant and cationic surfactant; Preferably, said emulsifying agent is a non-ionics.
The polyamines of step I in ii) be aliphatic tertiary amine or aliphatic secondary amine preferably.
Step I can be used the mixture of polyamines in ii).
The example of suitable polyamines is hydrazine, quadrol, piperazine, 1,5-pentamethylene diamine, 1,6-two hexanediamines, isophorone diamine, NSC 446,2-methyl isophthalic acid, 5-pentamethylene diamine and 4,4 '-methylene radical-two-hexahydroaniline.
Confirm the step I temperature ii) and the amount of time length and polyamines, be present in the free NCO group in the prepolymer and obtain meticulous, stable and uniform polyurethane dispersions that this is well-known in the art to exhaust.
Can remove the organic solvent that possibly exist through the distillation in step I process ii) or when step I ii) finishes.
The step I of the inventive method ii) can be through infiltrating polyamines in the dispersion-s of prepolymer, and remain on the temperature that stirs and be lower than 40 ° of C and get off to carry out.
The Brookfield of anionic polyurethane aqueous dispersion of the present invention
viscosity usually 50 and 2000mPa*s between.
In order to prepare application composition; Can the anion-type water-thinned polyurethane dispersion-s be mixed with linking agent, sticker (being preferably acrylic adhesive) and/or other additives; Thereby the coating property of further improving them for example; Film forming ability, and reduce or increase opacity to avoid producing perhaps " flake " effect and the foaming of " orange peel " effect.
The example that can join the additive in the 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, said linking agent for example be the POLYMETHYLENE POLYPHENYLISOCYANATE that can be scattered in water, end capped POLYMETHYLENE POLYPHENYLISOCYANATE, XA 1007, carbodiimide, epoxy silane and trimeric cyanamide.
With the dry weight basis of dispersion-s, the add-on of linking agent is usually between 1 and 10%.
Crosslinked is useful, anti-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 said film forming anionic polyurethane aqueous dispersion are preferred for the finish rigid substrate; For example plastics (like polycarbonate, ABS and PVC), timber, glass and metal (for example, aluminium, steel, zinced iron and galvanized steel: GA, GL, GI and EGI).
The material that is coated with the film that obtains through aqueous dispersion of the present invention can be used for vehicle interior; Inboard with finish instrument or car door; Can be used for electronic product; For example mobile phone,
and
can be used for the metallic surface such as counter body or housing of TV set, and are used for the volume coating.
In following examples, write down the synthetic of hydrophobicity polyvalent alcohol and according to the preparation of aqueous dispersion of the present invention.
Laser correlation spectrum (LCS) through having Coulter N4 Plus instrument is that 25 ° of C and angle are to measure the particle diameter of dispersion-s under 90 ° the condition in temperature.
Embodiment
Listed material below using among the said hereinafter embodiment:
Polyvalent alcohol 1: based on the glycol, 1 of polyester, the adipic acid ester-phthalic ester of 6-pinakon, molecular weight are 1000g/mol
Polyvalent alcohol 2: based on the glycol of polycarbonate, gather (carbonic acid hexa-methylene ester) glycol, molecular weight is 1000g/mol
H-polyvalent alcohol 5: cocounut oil diglycollic amide, molecular weight are 213g/mol
H-polyvalent alcohol 6: oleic acid diethyl amide, molecular weight are 269.7g/mol
DGEBA: the diglycidylether of dihydroxyphenyl propane, molecular weight are 380g/mol
DMPA: dimethylol propionic acid, molecular weight are 134,2g/mol
Alcohol C6: n-hexyl alcohol, molecular weight are 102g/mol
Alcohol C12: n-dodecanol, molecular weight are 186g/mol
Alcohol C20: line style C20 monohydroxy-alcohol, molecular weight are 298g/mol
NMP:N-methyl-pyrrolidone
NMP:N-ethyl-pyrrolidone
IPDI: isophorone diisocyanate, molecular weight are 222g/mol
HMDI:4,4 '-dicyclohexyl-methane-vulcabond, molecular weight are 262g/mol
TEA: triethylamine, molecular weight are 101,15g/mol
DEA: diethylolamine, molecular weight are 105,14g/mol
HH: Hydrazine Hydrate 80,24.36% aqueous solution, molecular weight are 32,04g/mol
ADD: wetting agent Byk 346
Embodiment 1.1-1.3
Embodiment 1.1-1.3 has described the preparation process based on the hydrophobicity polyvalent alcohol of DGEBA.
Embodiment 1.1
Synthesizing of H-polyvalent alcohol 1.
Under nitrogen atmosphere, the pure C6 of 140.6g (1.363mol) is joined in the reactor drum that TM, mechanical stirrer and condensing surface are housed, and be heated to 65 ° of C.40% of adding 0.40g KOH under the stirring of 65 ° of C.
Add 259.4g (0.682mol) DGEBA then, reaction mixture is heated to 120 ° of C and in this temperature maintenance about 4 hours, all disappear up to epoxide group.
All establishing criteria ASTM D1652-04 confirms the titration of epoxide group in this embodiment and all other embodiment.
Transform in case reached completely epoxy, reaction mixture is cooled to 80 ° of C and adds 85% the phosphoric acid of 0.35g, obtain H-polyvalent alcohol 1 (molecular weight is 586g/mol).The OH number is 191mg KOH/g.
Embodiment 1.2
Synthesizing of H-polyvalent alcohol 2.
According to the process of embodiment 1.1, the pure C12 of 186.0g (1 mole) is joined in the reactor drum, be heated to 70 ° of C, add the KOH of 0.75g 40% then.
Add 190.0g (0.5mol) DGEBA then, reaction mixture is heated to 120 ° of C, and maintain this temperature until epoxide group disappearance (about 4 hours).
Then reaction mixture is cooled to 80 ° of C and adds 85% the phosphoric acid of 0.65g, obtain H-polyvalent alcohol 2 (molecular weight is 752g/mol).The OH number is 149mg KOH/g.
Embodiment 1.3
Synthesizing of H-polyvalent alcohol 3.
According to the process of embodiment 1.1, the pure C20 of 326.0g (1 mole) is joined in the reactor drum, be heated to 100 ℃, add the KOH of 0.80g 40% then.
Add 190.0g (0.5mol) DGEBA then, reaction mixture is heated to 130 ℃, and maintain this temperature until epoxide group disappearance (about 12 hours).
Then reaction mixture is cooled to 120 ℃ and add 85% the phosphoric acid of 0.80g, obtains H-polyvalent alcohol 3.The OH number is 108mg KOH/g.
Embodiment 1.4
Synthesizing of H-polyvalent alcohol 4.
Embodiment 1.4 has described according to the hydrophobicity polyvalent alcohol (H-polyvalent alcohol 4) of prior art for preparing based on IPDI.
Under nitrogen atmosphere and room temperature, the NEP of 135.1g alcohol C6,432.0g is joined in the reactor drum that is provided with TM, whisking appliance and condensing surface.
When mixture after about 30 minutes, under agitation adds the IPDI of 293.9g 40 ° of C homogenizing.
Then reaction mixture is heated to 80 ° of C, is reflected under 90 ° of C and carries out, the content of NCO group equals 6.45% in prepolymer.
All establishing criteria method ASTM D2572 confirms the titration of remaining isocyanate base in this embodiment and all other embodiment.
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 that obtains (H-polyvalent alcohol 4) is 75 weight % (molecular weight 429.7).The OH number is 261mg KOH/g.
Embodiment 2.1
Prepare aqueous dispersion of the present invention.
According to embodiment 1.1, the polyvalent alcohol 2 of 138.7g and H-polyvalent alcohol 1, the DMPA of 20.9g and the NMP of 80g of 26.6g are joined in the reactor drum.When mixture after about 30 minutes, under agitation adds the HMDI of 155.6g 40 ° of C homogenizing.
Kept 30 minutes then with the reaction mixture heating, and at 60 ° of C.
React the theoretical value (about 1 hour) that the content of NCO group equals 5.07% in prepolymer at 95-100 ° of C.
Then prepolymer is cooled to about 75 ° of C, and under agitation adds the neutralizing agent TEA of 14.9g.
After about 10 minutes and at the internal temperature of 65 ° of C, violent stirring be lower than under the temperature of 35 ° of C, make prepolymer be dispersed in the softening water.In the temperature that is lower than 35 ° of C, as described in Table 1, the diamines HH (24.36% the aqueous solution) that adds 47.8g carries out increment.
In the polyurethane dispersions that obtains, add wetting agent ADD, filter with 150 μ m canvas then, make solid residue content reach 35 weight %.The dispersion-s that obtains is limpid and stable.
Embodiment 2.2-2.4
Prepare other aqueous dispersion of the present invention.
According to like embodiment 2.1 described processes, the composition of having changed as shown in table 1, unit are grams.
Embodiment 2.5 (comparative example)
According to like embodiment 2.1 described processes, do not use any hydrophobicity polyvalent alcohol, used the composition that writes down like 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 the 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 drum that is provided with TM, whisking appliance and condensing surface.
When mixture after about 30 minutes, under agitation adds HMDI 40 ° of C homogenizing.
Kept 30 minutes then with the reaction mixture heating, and at 60 ° of C.
React at 95-100 ° of C, the content of NCO group equals theoretical value (about 1 hour) in prepolymer.
Then prepolymer is cooled to about 75 ° of C, and under agitation adds neutralizing agent TEA.
After about 10 minutes and at the internal temperature of 65 ° of C, violent stirring be lower than under the temperature of 35 ° of C, make prepolymer be dispersed in the softening water.Under the temperature that is lower than 35 ° of C, the described chain extension agent HH of adding table 1 carries out increment.
In the polyurethane dispersions that obtains, add wetting agent ADD, filter with 150 μ m canvas then, make solid residue content reach 35 weight %.The dispersion-s that obtains is limpid and stable.
The application implementation example
In the application implementation example, shown result's comparison of using between prior art dispersion-s coating of handling and the coating of using two kinds of dispersion-ss according to the present invention to handle.
The glass that applied polyurethane dispersions or machinery, physics and the chemical property of metal base are compared.
Use portable protractor PGX that the contact angle on the aluminium base that applies is measured.Integration pump provides accurate water droplet with 0.5 μ l stepping (step), in the camera built independent water droplet image is caught the static contact angle when confirming " balance ".
Table 1
* comparative example
On glass baseplate, measured the hardness of film according to standard method ASTM D4366-95 (measuring the standard method of test of organic coating hardness through the fork damping test).
Through resistance to hydrolysis and the anti-ethanol property of standard method UNIEN12720 (the surperficial resistance of cold liquid) at mensuration film on glass.
Under the temperature of 55 ° of C,, assess its chemical resistant properties (NaOH, HCl) through the glass specimen that applies being immersed in alkalescence or the acidic solution (1%NaOH or 5%HCl) 2 minutes.Come ecbatic through following standard: 0=is the poorest, coating is damaged, best, the not influence of 5=.
Confirmed the binding property on the metal base (aluminum and zinc galvinized steel) through standard method ASTM D3359-09 (measuring fusible standard method of test) through adhesive tape test.Come ecbatic through following standard: 0=is the poorest, coating is damaged, best, the not influence of 5=.
The result is shown in Table 2.
Can find that with respect to every other embodiment, the contact angle of embodiment 2.4 significantly increases, show that the coating hydrophobicity is higher.
Do not use the dispersion-s of any hydrophobicity polyvalent alcohol preparation with respect to those; The base material that is coated with the dispersion-s of embodiment 2.2 and 2.4 has the doubly better anti-ethanol property of 6-7; With respect to dispersion-s according to prior art, be coated with embodiment 2.2 and 2.4 dispersion-s base material in addition have better anti-ethanol property.
Anti-H according to coating of the present invention
2O property (resistance to hydrolysis) is good.
Table 2
* comparative example
* wetting conditions: plate is immersed in the water 4 hours, after taking out, carries out binding property in 2 minutes and test.
In addition, with respect to the base material that the dispersion-s according to prior art prepares, the base material that is coated with the dispersion-s of embodiment 2.2 and 2.4 demonstrates good hardness and on aluminium base and steel substrate, all has outstanding binding property.
When considering alkali resistance with acid resistance, the alkali resistance that the coating for preparing with dispersion-s of the present invention shows is identical with the prior art coating with acid resistance or be superior to prior art.
Claims (10)
1. aqueous dispersion; This aqueous dispersion contains the anionic polyurethane of 20 to 50 weight %; Obtain said aqueous dispersion through following steps: in water, disperse; And come increment neutral anionic prepolymer with polyamines; This anionic prepolymer contains the hydroxy-acid group of 5 to 125meq/100g dry weights, and through making the reaction of mixture (P) of one or more aliphatic polyisocyanates, cycloaliphatic polyisocyanate or aromatic polyisocyanate and polyvalent alcohol prepare, the mixture of said polyvalent alcohol (P) comprises following I), II), III), IV) and V):
I) one or more hydrophobicity polyvalent alcohols of 4 to 90 weight %; The molar average hydroxy functionality of said hydrophobicity polyvalent alcohol is 2 to 3; Hydroxyl value is 350 to 40, and obtains through making alcohol roh and aromatics diglycidylether react, and wherein R is the saturated C of branching or straight chain
4-C
30Alkyl chain, perhaps R is the saturated C of branching or straight chain
4-C
10The alkyl phenyl group, wherein said aromatics diglycidylether has following chemical formula (I):
R wherein
1Be group (i):
R
2, R
3Each is Me, Et or H independently;
Perhaps R
1Be can be randomly by the substituted phenylene of one or more alkyl groups;
Perhaps R
1Be can be randomly by the substituted biphenylene of one or more alkyl groups;
Perhaps R
1Be group (ii):
II) one or more anionics of 1 to 10 weight % or potential anionic polyvalent alcohol, it has two or more NCO is had reactive group and at least one carboxyl or carboxylic acid ester groups;
III) one or more linear polycarbonate glycol of 0 to 95 weight %, its molecular weight is 500 to 3000;
IV) one or more linear polyesters glycol of 0 to 95 weight %, its molecular weight is 500 to 4,000;
V) one or more polyoxyalkylene diols of 0 to 95 weight %, said polyoxyalkylene diols are selected from gathers (oxygen base propylidene) two pure and mild gathering (oxygen base tetramethylene) glycol,
The ratio of the mixture of POLYMETHYLENE POLYPHENYLISOCYANATE and polyvalent alcohol (P) is: the ratio of the summation of all reactivities-OH group that the mixture (P) of the isocyanate group NCO of said POLYMETHYLENE POLYPHENYLISOCYANATE and said polyvalent alcohol comprises is between 1.2 and 2.3.
2. aqueous dispersion as claimed in claim 1; It is characterized in that; Said component I), IV III II))) and V) amount at least 95 weight % of the mixture that accounts for polyvalent alcohol; The mixture of said polyvalent alcohol also comprises other non-ionic polyol of 0 to 5 weight %, and the molecular weight of said 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, said component I), II), III), IV) and V) amount to 100 weight % of the mixture (P) of the polyvalent alcohol account for prepolymer.
4. aqueous dispersion as claimed in claim 3 is characterized in that, said component I), II), III) and IV) amount to 100 weight % of the mixture account for polyvalent alcohol.
5. aqueous dispersion as claimed in claim 1 is characterized in that, the mixture of said polyvalent alcohol (P) comprises one or more hydrophobicity polyvalent alcohols I of 5 to 75 weight %), it obtains through making alcohol roh react, and wherein R is the saturated C of branching or straight chain
6-C
22Alkyl chain, and R
1Be group (i):
6. aqueous dispersion as claimed in claim 5 is characterized in that, said R
2, R
3Be Me.
7. aqueous dispersion as claimed in claim 1 is characterized in that, prepares said neutral anionic prepolymer from the aliphatic polyisocyanate or the cycloaliphatic polyisocyanate of one or more average N CO functionality between 2.0 and 2.3.
8. aqueous dispersion as claimed in claim 1 is characterized in that, the component I I of the mixture of said polyvalent alcohol (P)) be dimethylol propionic acid, dimethylolpropionic acid or their mixture; The component III of the mixture of said polyvalent alcohol (P)) be number-average molecular weight be 800 to 2000 gather (carbonic acid hexa-methylene ester) glycol; The component I V of the mixture of said polyvalent alcohol (P)) be selected from based on hexanodioic acid and/or phthalic acid and 1,6-pinakon, terepthaloyl moietie, glycol ether, NSC 6366,1, the polyester of 4-butyleneglycol and their mixture, and number-average molecular weight is 800 to 3000.
9. as the aqueous dispersion described in aforementioned each claim, it is characterized in that the mixture of said polyvalent alcohol (P) does not contain and comes from the unit that gathers (oxygen base ethylidene) glycol.
10.) use is used to prepare application composition like each described aqueous dispersion in the claim 1 to 9.
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 true CN102822220A (en) | 2012-12-12 |
| CN102822220B 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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| CN104592882A (en) * | 2015-01-30 | 2015-05-06 | 广东雅图化工有限公司 | One-component water-based solid color paint for car and preparation process of the one-component water-based solid color paint |
| 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 |
| 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 |
| 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 |
| 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 |
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| CN106232662A (en) * | 2014-04-24 | 2016-12-14 | 巴斯夫涂料有限公司 | Aqueous bi-component coating compositions and high corrosion resistance coating prepared therefrom |
| 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 |
| CN110330620A (en) * | 2019-08-02 | 2019-10-15 | 山西省应用化学研究所(有限公司) | Plastic film water-based polyurethane ink binder and preparation method thereof |
| WO2022257008A1 (en) * | 2021-06-08 | 2022-12-15 | Dic Corporation | Cationic urethane resin composition |
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| WO2023079078A1 (en) | 2021-11-05 | 2023-05-11 | Hempel A/S | Water based coating composition for wind blades |
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2010
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- 2011-04-06 CN CN201180017821.0A patent/CN102822220B/en active Active
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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 |
| US4569966A (en) * | 1984-04-19 | 1986-02-11 | Ppg Industries, Inc. | Polymeric microparticles |
| CN1275995C (en) * | 2002-04-05 | 2006-09-20 | 拜尔公司 | Polyurethane dispersion based on fatty acid dialkyl alochol amide |
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| CN106232662A (en) * | 2014-04-24 | 2016-12-14 | 巴斯夫涂料有限公司 | Aqueous bi-component coating compositions and high corrosion resistance coating prepared therefrom |
| 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 |
| CN104592882A (en) * | 2015-01-30 | 2015-05-06 | 广东雅图化工有限公司 | One-component water-based solid color paint for car and preparation process of the one-component water-based solid color paint |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN110330620A (en) * | 2019-08-02 | 2019-10-15 | 山西省应用化学研究所(有限公司) | Plastic film water-based polyurethane ink binder 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 |
| WO2022257008A1 (en) * | 2021-06-08 | 2022-12-15 | Dic Corporation | Cationic urethane resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102822220B (en) | 2014-10-29 |
| EP2556097A1 (en) | 2013-02-13 |
| ITVA20100033A1 (en) | 2011-10-09 |
| KR101791283B1 (en) | 2017-10-27 |
| IT1399424B1 (en) | 2013-04-16 |
| WO2011124602A1 (en) | 2011-10-13 |
| KR20130040833A (en) | 2013-04-24 |
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