WO2003059982A1 - Dispersions de polyurethanne aqueuses utilisees en tant qu'adhesifs et revetements et leur preparation - Google Patents

Dispersions de polyurethanne aqueuses utilisees en tant qu'adhesifs et revetements et leur preparation Download PDF

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Publication number
WO2003059982A1
WO2003059982A1 PCT/CN2003/000051 CN0300051W WO03059982A1 WO 2003059982 A1 WO2003059982 A1 WO 2003059982A1 CN 0300051 W CN0300051 W CN 0300051W WO 03059982 A1 WO03059982 A1 WO 03059982A1
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Prior art keywords
aqueous polyurethane
prepolymer
polyurethane dispersion
water
acid
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PCT/CN2003/000051
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English (en)
Chinese (zh)
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Youlu Duan
Hexian Zou
Gang Duan
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Youlu Duan
Hexian Zou
Gang Duan
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Priority to AU2003203332A priority Critical patent/AU2003203332A1/en
Publication of WO2003059982A1 publication Critical patent/WO2003059982A1/fr

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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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80

Definitions

  • Aqueous polyurethane dispersion used as adhesive and coating and preparation thereof used as adhesive and coating and preparation thereof
  • the present invention relates to an organic polymer material, that is, an aqueous polyurethane dispersion liquid that can be used as an adhesive and a coating, and a method for preparing the same.
  • Aqueous polyurethane dispersions can be used as adhesives and coatings.
  • Aqueous polyurethane dispersions are prepared by a four-step process: 1) The excess polyisocyanate is reacted with a polyol and a diol (or diamine) with a carboxyl group to form an isocyanate. Tailed prepolymer; 2) neutralization of the prepolymer; 3) dispersion of the neutralized prepolymer in water; 4) chain extension to form an aqueous polycyanate.
  • 1,6-hexyl diisocyanate (HDI) is widely used to prepare water-based polyurethane adhesives and coatings.
  • the first step is to use isophorone diisocyanate (IPDI) and dihydroxymethylpropionic acid (DMPA) to generate Isocyanate-terminated adduct.
  • IPDI isophorone diisocyanate
  • DMPA dihydroxymethylpropionic acid
  • the second step HDI and polyester diol are reacted with the adduct produced in the first step to form a prepolymer, which is then neutralized and dispersed in water and reacts with water to extend the chain to form an aqueous polyurethane dispersion.
  • the disadvantages of this method are: (1) the two-step method for preparing the prepolymer increases the number of process steps and complicates the process; (2) a large amount of solvent (N-fluorenyl-2- Pyrrolidone, that is, NMP); (3) The aqueous polyurethane dispersion prepared can only be used as a coating and is not suitable as an adhesive.
  • US patent 2 USP. 4,870,129 (Wolfgang Henhin et al.) Invented a water-based polyamic acid adhesive prepared based on a mixture of HDI and IPDI, which has a low activation temperature and good adhesion properties.
  • the water-based polyurethane amine adhesive products Dispercoll U-53 and U-54 developed by Bayer are the best water-based polyurethane adhesive products in the world today.
  • Urethane adhesive but diisocyanates with aromatic rings, such as tetramethylene diphenyl diisocyanate (TMXDI), toluene diisocyanate (TDI), and methylene diphenyl diisocyanate (MDI) are excluded from the third A kind of diisocyanate.
  • TXDI tetramethylene diphenyl diisocyanate
  • TDI toluene diisocyanate
  • MDI methylene diphenyl diisocyanate
  • German patent 4 DE.4109477A1 (Hans et al.) Discloses a two-component aqueous polyurethane decomposition solution based on a mixture of TMXDI and other diisocyanates.
  • the weight of TMXDI should be at least 30%, preferably at least 30%. 50%.
  • this type of water-based polyurethane can be prepared by a solvent-free or low-solvent process, but the water-based polyurethane prepared in its experimental example has poor performance, and the surface of the resulting film is sticky. Only after reacting with the curing agent can it be made into a non-sticky film , Can only be used as an adhesive for flexible packaging composite film.
  • HDI is a diisocyanate widely used in the preparation of aqueous polyurethane dispersions.
  • HDI-based aqueous polyurethane dispersions can be used as coatings, and their films are soft and high in strength.
  • Aqueous polyurethane dispersions cannot be successfully prepared using HDI alone; (2) Prepolymers are prepared by two-step method using two diisocyanates of HDI and IPDI, and then neutralized, dispersed and diffused to successfully prepare aqueous polyamic acid coatings, but A large number of solvents must be used to prepare its prepolymer; (3) TMXDI, and its mixture with other diisocyanates, can be used to prepare aqueous polyurethane dispersions using a solvent-free or solvent-free process. The film is sticky, or the strength is not high enough to be suitable as a coating.
  • the present invention will provide a new mixed system of three or more isocyanates composed of HDI, TMXDI and other diisoesters to prepare aqueous polyurethane aqueous dispersions.
  • This new system will overcome the above-mentioned shortcomings. Summary of invention
  • the invention provides a new water-based polyurethane aqueous dispersion.
  • the new water-based polyurethane dispersion is composed of
  • This new water-based polyurethane dispersion has both good adhesive properties, can be used as an adhesive, and good film-forming properties.
  • the film has good mechanical properties and can be used as a coating.
  • this new ternary or higher ternary isocyanate mixed system it is also possible to prepare a new nano aqueous polyurethane dispersion.
  • the aqueous polyurethane dispersion of the present invention is composed of the reaction product of the following components:
  • An isocyanate composition composed of at least three different isocyanates composed of HDI, TMXDI and other polyisocyanates, wherein the weight percentages of the three isocyanates are 1-98: 1 to 98: 1 to 98;
  • a hydroxycarboxylic acid whose molecular formula is: (HO) xR (COOH) y, where R represents a straight or branched hydrocarbon group containing 1-12 carbon atoms, and X and Y represent the number of 1-3 ;
  • An organic polyhydroxy compound including a polyester polyol, a polyether polyol, a sulfonic-type polypolyol, a poly (lipid-ether) polyol, or a physical mixture of the above-mentioned polyols;
  • a chain extender which may be a polyamine compound or a mixture of polyamines, a hydrazine compound, water, or a mixture thereof.
  • the properties of the aqueous polyurethane dispersion of the present invention are better than those of the best commercial water-based polyurethane products, Bayer's Dispercoll U-53 and U-54, and their bonding temperature resistance is better than U-53 and U- 54 high 30. Above C, its film-forming properties are better than U-53 and U-54, and its film's tensile strength is also better than U-53 and U-54.
  • the aqueous polyurethane dispersion of the present invention can be used both as an adhesive and as a paint.
  • the present invention also provides a method for preparing a ternary and more than ternary isocyanate-based aqueous polyurethane dispersion such as HDI, TMXDI, and other isocyanates, including the following steps:
  • This neutralization reaction can be performed before the prepolymer is formed, or it can be performed simultaneously with the prepolymerization reaction, or after the prepolymerization reaction is completed and the prepolymer is dispersed in water, or a neutralizing agent can be added to the water to react with The chain extension and chain termination reactions proceed simultaneously.
  • the method for preparing an aqueous polyurethane dispersion does not require the step of recovering the organic solvent by distillation.
  • Another feature of the method for preparing an aqueous polyurethane dispersion of the present invention is that the neutralization reaction can be performed before preparing the prepolymer.
  • the method of the present invention can also prepare nano-aqueous polyurethane with a particle size less than 100 nanometers, which is smaller than that of Dispercoll U of Bayer -54 (particle size about 200 nm) is smaller than 1/2.
  • polyurethane in the present invention is defined as a polymer containing a urethane group, and also includes a polymer containing a urea group in addition to a carbamate group.
  • the aqueous polyurethane dispersion of the present invention is composed of three or more polyisocyanates, such as HDI, TMXDI, and other polyisocyanates. In the presence of a small amount or no organic solvent, it can be used with polyols, hydroxycarboxylic compounds, and may also contain It is prepared by reacting small molecule diols to form a prepolymer, and then dispersing it in water to extend the chain into a polymer. This new water-based polyurethane dispersion is compared with Bayer's water-based polyurethane dispersion products Dispercoll U-53 and U-54 based on a mixture of HDI and IPDI.
  • Bayer's process includes vacuum distillation recovery from an aqueous polyurethane dispersion.
  • Organic solvent step, and the process of the present invention omits the step of distilling and recovering the organic solvent.
  • the present invention can also prepare a nano-aqueous polyurethane dispersion with a particle size of less than 100 nanometers, which is also smaller than Dispercoll U-54 (particle size is about 200 nm).
  • polyisocyanate of the aqueous polyurethane dispersion of the present invention in addition to 1,6-hexyl diisocyanate (HDI) and tetramethylphenyl difluorenyl diisocyanate (TMXDI), other polyisocyanates may be aliphatic, or It can be aromatic or a mixture of aliphatic and aromatic polyisocyanates.
  • HDI 1,6-hexyl diisocyanate
  • TMXDI tetramethylphenyl difluorenyl diisocyanate
  • Suitable aliphatic diisocyanates are isophorone diisocyanate (IPDI), cyclopentyl diisocyanate, cyclohexyl diisocyanate, fluorenyl cyclohexyl diisocyanate, dicyclohexyl dioxane diisocyanate (H, 2 MDI ), 1,4-tetrafluorenyl diisocyanate, 2,2,4-trifluorenyl-1,6-hexyl diisocyanate, 1,12-twelve Alkyl diisocyanate.
  • IPDI isophorone diisocyanate
  • H fluorenyl cyclohexyl diisocyanate
  • H, 2 MDI dicyclohexyl dioxane diisocyanate
  • 1,4-tetrafluorenyl diisocyanate 2,2,4-trifluorenyl-1,6-hexyl diisocyanate
  • aromatic diisocyanates examples include benzene diisocyanate, terphenylene diisocyanate (TDI), diphenylbenzene diisocyanate, biphenyl diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate (MDI).
  • TDI terphenylene diisocyanate
  • diphenylbenzene diisocyanate diphenylbenzene diisocyanate
  • biphenyl diisocyanate naphthalene diisocyanate
  • MDI diphenylmethane diisocyanate
  • a better ternary combination is HDI and TMXDI with IPDI, or with H 12 MDI, or with MDI, or with TDI.
  • the best ternary combinations are HDI, TMXDI and IPDI, or HDI, TMXDI and MDI (or TDI).
  • Suitable monoisocyanates include methyl isocyanate, ethyl isocyanate, octadecyl isocyanate and the like.
  • Suitable polyisocyanates include modified diisocyanates with isocyanate groups greater than 2, such as trimers of HDI, IPDI, TDI and the like. In addition, the modified polyisocyanate may contain groups such as urethane, biuret, and the like.
  • the polyol compound suitable for preparing the aqueous polyurethane dispersion of the present invention has a number average molecular weight from 400 to 10,000, and a molecular weight from 400 to 3000 is even better.
  • These high molecular weight polyols include:
  • Polyester polyols are prepared by reacting polyhydric compounds, preferably diols, possibly by adding triols, and polyvalent carboxylic compounds, more preferably dicarboxylic acids.
  • polycarboxylic acids In addition to these polycarboxylic acids, corresponding hepatic carboxylic acid compounds, or small molecular alcohol esters of these polycarboxylic acids, and mixtures thereof can also be used to prepare these polyester polyols.
  • These polycarboxylic acid compounds may be aliphatic, alicyclic, aromatic, and / or heterocyclic. They may be unsaturated and / or substituted with halogen or the like.
  • carboxylic acids examples include succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, trimellitic acid, terbium phthalate, tetrahydrophthalic anhydride, hexahydrophthalic anhydride , Tetrachlorophthalic anhydride, bridging tetrahydrophthalic acid ⁇ f, glutamic anhydride, maleic acid, maleic anhydride, trans-butenedioic acid, dimers and trimers of fatty acids, for example, can be mixed with fatty acids Dimer and trimer of oleic acid, difluorenyl terephthalate and diethylene terephthalate.
  • Suitable polyhydric alcohol compounds include ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol , Neopentyl glycol, diethylene glycol, 2-fluorenyl-1,3-propanediol, 2,2-difluorenyl-1,3-propanediol, various isomers of dihydroxyfluorenyl cyclohexane, Glycerol and trimethylolpropane.
  • Polylactone polyols such as polymers of caprolactone initiated with the above-mentioned polyols.
  • Polyhydroxyl-containing polycarbonate such as the product of the aforementioned reaction of a polyol compound for the preparation of polyester polyols with phosgene and a diaryl carbonate. Also suitable are the reaction products of the aforementioned low molecular weight oligomers of polyesters or polylactones with phosgene, diaryl carbonates or cyclic carbonates.
  • the polyhydric alcohol compound is preferably a dihydric alcohol compound, such as 1,3-propanediol, 1,4-butanediol, 1,4-dioxohydroxycyclohexane, 1,6-hexanedione Alcohol, diethylene glycol, triethylene glycol or tetraethylene glycol.
  • the diaryl carbonate includes diphenyl carbonate, cyclic carbonate such as ethylene or propylene, and the like.
  • Polyether polyols including polymers which are reacted with alkyl epoxy compounds initiated by compounds containing active hydrogen. These epoxy compounds include propylene oxide, butylene oxide, styrene epoxy, tetrahydrofuran, 3-chloro-1,2-propylene oxide, or a mixture of these epoxy compounds. If the weight content of ethylene oxide in the polyether does not exceed 10%, a certain proportion of ethylene oxide may be used. However, polyether polyols containing no ethylene epoxy are more suitable for use.
  • Compounds containing at least one active hydrogen atom to initiate this reaction include water, methanol, ethanol, 1,2,6-hexanetriol, in addition to those polyol compounds suitable for the preparation of polyester polyols as described above, 1 , 2,4-butanetriol, tris-hydroxyethane, pentaerythritol, mannitol, sorbitol, fluorenyl rations, sucrose, phenol, isononylbenzene, resorcinol, hydroquinone, 1 1,1,1- or 1,1,2-tri (hydrocarbylphenyl) ethane.
  • Polyether polyols started with amine-containing compounds can also be used, but used less often.
  • Suitable amine-based compounds include ethylenediamine, diethylenetriamine, triethylenetetramine, 1,6-hexamethylenediamine, piperazine, and 2,5-difluorenylpiperidine.
  • Phenol and acetol resins can also be used as starting compounds.
  • the preferred starting compounds for the preparation of polyether polyols are compounds containing only hydroxyl groups, followed by compounds containing tertiary amines, followed by compounds containing NH groups that react with isocyanates.
  • Polythioether glycols including 2,2'-dihydroxydiethylsulfide self-condensates, and polycondensates with other diols, dicarboxylic acids, formaldehyde, aminocarboxylic acids, or amino alcohols.
  • Polymeric polyols of the sulfonic type can be prepared from dicarboxylic acids, sulfonic acid diols, and sulfonic acid dicarboxylic acids.
  • a better sulfonic polymer polyol is prepared by the condensation reaction of sodium 5-ophthalate isophthalic acid, adipic acid and 1,4-butanediol, and / or diethylene glycol.
  • monoalcohols and higher polyols can also be used to prepare the isocyanate-terminated prepolymers of the present invention.
  • the ratio of the unit alcohol and the polyol should ensure that the average number of isocyanate groups of the prepolymer formed is equal to or less than two. Suitable examples include methanol, ethanol, n-propanol, isopropanol, hexanol, Octanol, Glycerol, Trimethylolpropane, 1,2,4-butanetriol, 1,2,6-hexanetriol, and mixtures thereof.
  • hydrophilic group that is, an anionic group, a cationic group, or no
  • Suitable hydrophilic components contain at least one (preferably at least two) isocyanate groups, or groups that are reactive with isocyanates, and contain at least one hydrophilic group or one potentially hydrophilic group.
  • Examples of compounds that can be used to embed potential ionic groups include aliphatic hydroxycarboxylic acids, aliphatic or aromatic amine (primary or secondary amine) carboxylic acids, aliphatic hydroxysulfonic acids, aliphatic or aromatic Group amine (primary or secondary amine) sulfonic acid.
  • the molecular weight of these acids is preferably less than 400.
  • the preferred anionic group embedded in the polyurethane is a carboxylic acid group and a hydroxy acid of the following general formula:
  • the hydroxycarboxylic acid is a 2,2-dihydroxyfluorenyl alkyl acid represented by the following formula
  • R 1 represents hydrogen or an alkyl group having 1 to 9 carbon atoms.
  • examples of these compounds are 2,2-dihydroxyfluorenylacetic acid, 2,2-dihydroxyfluorenylpropionic acid, 2,2-dihydroxyfluorenylbutanoic acid, and 2,2-dihydroxyfluorenylvaleric acid.
  • DMPA 2,2-dihydroxyamidinopropionic acid
  • the carboxylic acid group can be treated with a neutralizing agent to transform into a hydrophilic anionic group.
  • Neutralizing agents include alkali metal salts, ammonia, primary amines, swollen amines, and preferably tertiary amines.
  • Suitable alkali metal salts are sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate. It is better to use volatile organic amines, preferably tertiary amine compounds.
  • Suitable amine compounds are trimethylamine, triethylamine, triisopropylamine, tributylamine, N, N-dimethylcyclohexylamine, N, N-dioctadecylamine, ⁇ , ⁇ - Dimethylaniline, N-fluorenylmorpholine, N-ethylmorpholine, N-fluorenylpiperazine, N-fluorenylpyrrolidine, N-fluorenylpyridine, N, N-difluorenylethanolamine, N, N-Dimethylethanolamine, Triethanolamine, N-methyldiethanolamine, dimethylpropanolamine, 2-methoxyethyldiamine, N-hydroxyethylpyridine, 2- (2-dimethylethyl) (Oxyamine) ethanol or 5-diethylamine-2-fluorenone.
  • the most preferred tertiary amines are those which do not contain isocyanate-reactive groups.
  • the carboxylic acid in the hydroxycarboxylic acid can be neutralized and then reacted with isocyanate to be embedded in the structure of the prepolymer.
  • the hydroxyl group of the hydroxycarboxylic acid can also be reacted with the polyhydric alcohol and isocyanate to form a prepolymer with a carboxylic acid group, and then the alkali metal salt or a tertiary amine compound can be used to neutralize the carboxylic acid group in the prepolymer.
  • Neutralization of carboxylic acid groups can also be partially Before the prepolymer is formed, and partly after the prepolymer is formed. The neutralized prepolymer is relatively easy to disperse in water.
  • the addition of a neutralizing agent will cause a sharp increase in the viscosity of the prepolymer.
  • the neutralizing agent can be mixed with water, and the unneutralized or The partially neutralized prepolymer is dispersed in this neutralizer-containing water.
  • the amount of the neutralizing agent is 100% to 120% of the carboxylic acid equivalent.
  • a small molecular weight diol may also be mixed with a polyhydric alcohol to prepare an isocyanate-terminated prepolymer. It is usually an aliphatic diol with a molecular weight from 60 to 400. Examples of small molecular weight diols are ethylene glycol, 1,3-propanediol, 1,4-butanediol or 1,6-hexanediol. The most commonly used is 1,4-butanediol. Small molecular weight diols can increase the strength, water resistance, and temperature resistance of polyurethanes.
  • the isocyanate-terminated prepolymer is prepared by reacting an excess of isocyanate with the above-mentioned active hydrogen-containing compound.
  • the equivalent ratio of NCO in isocyanate to OH containing active hydrogen is 1-4.0: 1.0.
  • the weight percentage of isocyanate groups in the resulting prepolymer is 1% to 10%.
  • the weight ratio of the polyhydric alcohol, the hydroxycarboxylic acid compound, and the small molecular weight diol is 50-98: 1-10: 0-20.
  • the prepolymer preparation temperature is 25 ° C to 120 ° C, and the reaction time is 1 to 20 hours. The better reaction temperature is from 60'C to 100 ° C.
  • the reaction temperature is lower than 25 ° C, the reaction time is too long, and the resulting prepolymer has a high viscosity, which is difficult to handle and difficult to disperse in water.
  • co-solvents can also be used to reduce the viscosity of the prepolymer, but adding too much organic solvent will cause environmental protection, safety and health issues.
  • a reaction temperature higher than 12CTC may cause side reactions, such as the reaction of isocyanate groups with carboxyl groups, the reaction of isocyanates with hydrogen on the amino group, etc., resulting in changes in the properties of the prepolymer and the resulting water Changes in the properties of polyurethane dispersions.
  • a small amount of catalyst can be used to accelerate the synthesis of the prepolymer.
  • the amount of the catalyst is 0.05% to 2.0% of the total weight of the prepolymer, and more preferably 0.1% to 0.2%.
  • a commonly used catalyst is dibutyltin dilaurate.
  • the prepolymer can also be prepared in the presence of cosolvents, which must be volatile organic compounds that do not contain active hydrogen. Adding a co-solvent can reduce the viscosity of the prepolymer and make the synthesis reaction of the prepolymer more uniform.
  • cosolvents include organic solvents such as ketones, esters, ethers and ketoesters. The more commonly used co-solvents are acetone and N-fluorenyl-2-pyrrolidone (NMP).
  • the amount of co-solvent is generally 0% to 5% by weight of the prepolymer, that is, the weight content of the organic solvent in the resulting aqueous polyurethane dispersion does not exceed 2% (calculated based on 40% solids content).
  • an external emulsifier containing no active hydrogen can also be used to increase the water-dispersing ability of the prepolymer and to improve the film-forming properties of the resulting aqueous polyurethane dispersion.
  • the additional dispersant may be anionic, cationic, or non-ionic, depending on the ionic characteristics of the aqueous polyurethane dispersion.
  • Added emulsification Agents, dispersants and surfactants can be added to the prepolymer or water before dispersing in water, or to the resulting aqueous polyurethane dispersion. If necessary, defoaming and leveling agents can also be added. Thickeners can also be added to adjust the viscosity of the aqueous polyurethane.
  • the isocyanate group-terminated prepolymer can be dispersed in distilled or deionized water with stirring.
  • the amount of water used to prepare a stable aqueous polyurethane dispersion is 80% to 40% of the total weight of the resulting aqueous polyurethane dispersion, and more preferably 65% to 50%.
  • Water can be added to the prepolymer for dispersion, or the prepolymer can be added to water for dispersion, or the prepolymer stream and water stream can be continuously dispersed in the line through a high-speed dispersion device.
  • the temperature of the prepolymer before dispersing is generally 35 ° C to 110 ° C.
  • the preferred temperature is 45 ° C. C to 90 ° C, preferably 70 ° C to 80 ° C.
  • the temperature of the water used for dispersion is 25 ° C to 90 ° C, preferably room temperature or 60-70 ° C.
  • a chain extender is added to the dispersion of this prepolymer.
  • the chain extender may be a known alcohol-based chain extender, but an amine or hydroxylamine-based chain extender is preferred.
  • the chain extender can be added to the water before the prepolymer is dispersed, at the same time, or after the dispersion.
  • the amine chain extender is a polyamine or a mixture of polyamines.
  • the average functionality of the amine chain extender that is, the number of amine nitrogen atoms per molecule, should be about 1.8 to 6.0, more preferably 2.0 to 4.0, and most preferably 2.0 to 3.0.
  • the required functionality can be achieved by mixing polyamines. For example, a functionality of 2.5 can be obtained using a mixture of equal moles of diamine and triamine.
  • Suitable amine chain extenders are hydrocarbon polyamine compounds having 2 to 6 amine genes, where the amines are primary or secondary amines. It may be aromatic, aliphatic, or alicyclic amine, and generally has 1-30 carbon atoms, more preferably 2-15 carbon atoms, and most preferably 2-10 carbon atoms.
  • polyamines examples include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N- (2-piperazineethyl) ethylenediamine, ⁇ , ⁇ '-bis- (2-aminoethyl ) Pyrazine, ⁇ , ⁇ , ⁇ '-tris (2-aminoethyl) ethylenediamine, ⁇ - [ ⁇ - (2-aminoethyl) -2-aminoethyl] -N'-(2 -Piperazineethyl) -ethylenediamine, N- (2-aminoethylene-N '-(2-piperazineethyl) amine, N, N-bis (2-piperazineethyl) amine, poly Ethyleneimine, iminodiamine guanidine, melamine, N- (2-aminoethyl) -1,3-propanediamine, 3,3'-diaminobenzidine, 2,4,6-
  • IPDA isophorone diamine
  • bis (4-aminocyclohexyl) pinene bis (4-amino-3) -Fluorenylcyclohexyl) methane
  • 1,6-hexanediamine 1,6-hexanediamine
  • ethylenediamine diethylenetriamine
  • triethylenetetramine 1,6-hexanediamine
  • tetraethylenepentamine 1,6-hexanediamine
  • hydrazine as a chain extender Also better.
  • the amount of chain extender used depends on the number of ending isocyanate groups in the prepolymer.
  • the equivalent ratio of the terminal isocyanate group in the prepolymer and the isocyanate active group in the chain extender is 1.0: 0.6 to 1.0: 1.1, A better ratio is 1.0: 0.8 to 1.0: 0.98.
  • Water can also act as a chain extender.
  • the isocyanate group at the end of the prepolymer reacts with water to form an amine, which emits carbon dioxide.
  • the resulting amine reacts with another isocyanate group to form a urea bond, and the prepolymer chain grows into a polymer.
  • This chain extension reaction releases a large amount of carbon dioxide, causing the dispersion to form a foam, and ammonia water must be added to neutralize it, and a defoamer must be added to obtain a stable aqueous polyurethane dispersion.
  • the reaction between the prepolymer dispersed in water and the chain extender is generally performed in the range of 5-9 ° C, and it is preferably performed in the range of 20-80 ° C, and preferably in the range of 30-60'C.
  • the reaction Conditions are generally carried out until the isocyanate groups of the prepolymer are substantially completely reacted.
  • the final product is an aqueous polyurethane dispersion of stable colloidal particles. Its particle size is generally less than 1.0 micron, such as 0.01 to 1.0 micron, preferably less than 0.5 micron, and most preferably 0.01 to 0.3 micron.
  • the composition and preparation method of the aqueous polyurethane dispersion of the present invention can prepare a nano-aqueous polyurethane dispersion with a particle size of less than 100 nanometers (0.1 micron). Nano-aqueous polyurethane dispersion has good storage stability, good adhesion properties and good film-forming properties.
  • the aqueous polyurethane dispersion of the present invention generally has a solid content of 20% to 60%, and a better solid content of 35% to 50%.
  • the pH of the aqueous polyurethane dispersion of the present invention depends on its ionic type, and is anionic, cationic, or non-ionic. Generally, the aqueous polyurethane dispersion of the present invention is anionic, and its pH is 6-10, more preferably 7-9.5, and most preferably 7.5-9.5.
  • the viscosity of the aqueous polyurethane aqueous dispersion of the present invention is 10-10,000 centipoise, preferably 100-1,000 centipoise.
  • Thickeners can be used to adjust the viscosity of aqueous polyurethanes.
  • Typical thickeners are polyurethane dispersions, acrylic polymer emulsions, or aqueous cellulose dispersions.
  • the aqueous polyurethane dispersion of the present invention has good compatibility with other aqueous polymers, and their blends can improve certain properties of the aqueous polyurethane and reduce its cost.
  • suitable waterborne polymers to be blended with are: polyacrylate emulsion, polystyrene-acrylate emulsion, polyvinyl acetate emulsion, polyethylene-vinyl acetate emulsion, polyvinyl chloride emulsion, synthetic rubber emulsion, natural Rubber latex, etc.
  • aqueous polyurethane dispersion of the present invention can be used as a single component in many cases.
  • water-dispersible curing agents can be added. Suitable curing agents include water-dispersible polyisocyanates, water-dispersible polyisocyanates, polycarbodiimides, polyaziridines, and water-based epoxy resins. The amount of this curing agent is generally 1% to 20% of the total weight of the two components, and more preferably 3% to 7%.
  • the aqueous polyurethane of the present invention can be used as an adhesive, an adhesive, a coating, a primer and a varnish.
  • Available in various Such substrates include paper, wood, leather, metal, ceramics, cement, cloth, natural rubber, synthetic polymer materials, etc. Can be applied by brush, spray or roller.
  • aqueous polyurethane dispersion of the present invention can also be modified by adding various additives.
  • additives include surfactants, defoamers, coalescents, fungicides, bactericides, plasticizers, thickeners, fillers, active pigments, UV stabilizers, flavorants, water-dispersible waxes, oils, Flame retardants and the like and mixtures thereof.
  • the measurement method of the mechanical properties of the adhesive temperature resistance properties is as follows:
  • Test sample preparation is the same as peel strength. Use a paper cutter to cut the sample into 50 X 25mm strips, and the glue area on one end is 25 X 25mm. Separate the uncoated 25 x 25mm composite PVC at the other end at 180 degrees. Hang one end with 100 g of missing code on the other end and hang the other end in a blast oven. From room temperature to 125 'C, the heating rate is 25. C / hour. Record the temperature at which the sample is pulled apart. If the sample is not pulled up to 125 ° C, record the peeling of the adhesive surface.
  • aqueous polyurethane dispersion was poured into a glass mold, dried at room temperature overnight, demoulded, left for 7 days, and the film was cut into dumbbell-shaped samples with a knife. Its thickness is controlled at 0.5-1.0mm. Using Intron, the stress-strain properties were measured at a speed of 5 cm / min, and the yield strength, tensile strength, and elongation were recorded. Preferred embodiment The following examples further illustrate the present invention, but the present invention is not limited to these examples. Unless otherwise specified, the proportions and percentages used in the examples are all weight ratios.
  • Example 1-2 the proportions and percentages used in the examples are all weight ratios.
  • Examples 1 and 2 illustrate a prepolymer synthesized in one step by reacting a mixture of three diisocyanates composed of HDI and two ring-shaped diisocyanates (IPDI and TMXDI) in the presence of a small amount of solvent with DMPA and polyester diol.
  • IPDI and TMXDI ring-shaped diisocyanates
  • the resulting neutralized isocyanate-terminated prepolymer was dispersed in 450 g of water with rapid stirring, and then a solution of 12.9 g of EDA in 22 g of water was slowly added. The dispersion was stirred at 60-65 ° C for 2 hours to obtain a stable, translucent, aqueous polyurethane dispersion with the following properties:
  • Viscosity centipoise
  • the neutralized isocyanate-terminated prepolymer was dispersed in 529 g of water with rapid stirring, and then a solution of 7.6 g of EDA in 30 g of water was slowly added. This dispersion was stirred at 60-65 ° C for 2 hours to obtain a stable aqueous polyurethane dispersion with properties such as Down:
  • Viscosity centipoise
  • Examples 3 and 4 illustrate the use of a mixture of three diisocyanates, such as HDI, IPDI, and TMXDI, in the presence of a small amount of solvent (acetone), with triethylamine, 1,4-butanediol, DMPA, and polyesterdiol to form Prepolymer, which is dispersed in water, and the aqueous polyurethane dispersion produced by chain extension with diamine has better adhesive properties and better film-forming properties than Bayer's aqueous polyurethane products Dispercoll U-53 and U-54
  • Example 5 (Comparative Example) The properties of Dispercoll U-53 and U-54 were measured and compared with the aqueous polyurethane dispersion liquid phase prepared in Examples 3 and 4.
  • U-53 and U-54 are products based on US Patent No. 4,870,129. They are a sulfonic acid-based aqueous polyurethane dispersion and are considered to be the best commercially available aqueous polyurethane dispersion adhesive products since the 1990s.
  • Example 3
  • Dispercoll U-53 and U-54 were measured.
  • a PVC / PVC adhesion test sample was prepared on the PVC coated with U-53 and U-54 by heat activated composite. Test its adhesive properties. Films were prepared by casting U-53 and U-54 in glass plate molds, and their mechanical properties were tested.
  • Dispercoll U-53 and U-54 Bayer's water-based polyurethane products, based on US patent 2 USR 4,870,129, use HDI and IPDI with polyester diols in a large amount of acetone (the total weight of the final aqueous polyurethane dispersion 40- 80% acetone) was used to prepare the prepolymer, and a sulfonate aliphatic diamine was used as a chain extender and a sulfonate ion group was introduced.
  • the prepared aqueous polyurethane dispersion contains a large amount of acetone, and a vacuum distillation method is required to reduce the acetone content in the final product to less than 1%. All test results are shown in Table 1.
  • Example 6 illustrates the use of a mixture of HDI, IPDI, and TMXDI in the absence of an organic solvent to react with a poly (ester-ether) glycol and other aqueous polyurethane dispersions.
  • Agent Compared with US patent 7 USP. 5,891,580 (Ficke et al.), This patent uses a mixture of 2,4-TDI and 2,6-TDI with polyether glycol, etc., in an aqueous polyurethane dispersion prepared in the presence of a large amount of acetone. It contains a large amount of acetone, and the water-based polyurethane product can be obtained after the acetone is distilled off. The product can be used as an adhesive for flexible packaging composite films.
  • Viscosity centipoise
  • Example 7 illustrates that an aqueous polyurethane dispersion prepared by using a mixture of HDI, IPDI, and TMXDI in the presence of a solvent without reacting with polyether glycol, etc., has good film-forming properties, and the film has good mechanical properties. It can be used as coating and can be used to make medical gloves and condoms.
  • Viscosity centipoise
  • Example 8 illustrates that an aqueous polyurethane dispersion prepared by using a mixture of HDI, H, 2 MDI, and TMXDI with polyether glycol, etc., is a good coating.
  • Viscosity centipoise
  • Example 9 shows that a mixture of HDI, TMXDI, and TDI is used in the presence of a small amount of solvent to react with a polyether diol and other aqueous polyurethane dispersions, which can be used as fabric treating agents.
  • Viscosity centipoise
  • Example 10 illustrates that a mixture of HDI, TMXDI and MDI can be used to react with polyether glycol and the like in the presence of a small amount of organic solvent to obtain a stable aqueous polyurethane dispersion.
  • Viscosity centipoise
  • This dispersion has good adhesive properties on surface-treated polypropylene, polyethylene and polyester films, and can be used as an adhesive for flexible packaging composite films.
  • This aqueous polyurethane dispersion also has good adhesion properties to fabrics, fibers, leather, etc.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne des matières à macromolécules organiques, c'est-à-dire, des dispersions de polyuréthanne aqueuses, leur utilisations en tant qu'adhésifs et revêtements et leur préparation. Lesdites dispersions de polyuréthanne aqueuses sont préparées par un procédé dans lequel on utilise ou pas un solvant organique et un mélange d'au moins trois polyisocyanates se composant de diisocyanate de 1,6-hexane (HDI), de diisocyanate de tétraméthylxylène (TMXDI) et d'autres polyisocyanates. Lesdites dispersions sont des dispersions de polyuréthanne aqueuses à l'échelle nanométrique. Ces nouvelles dispersions de polyuréthanne aqueuses possèdent non seulement d'excellentes propriétés en tant qu'adhésifs, mais également de bonnes propriétés filmogènes pour la formation d'un film possédant d'excellentes propriétés mécaniques, ce qui permet leur utilisation en tant que revêtements.
PCT/CN2003/000051 2002-01-18 2003-01-20 Dispersions de polyurethanne aqueuses utilisees en tant qu'adhesifs et revetements et leur preparation WO2003059982A1 (fr)

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CNB021105855A CN100497429C (zh) 2002-01-18 2002-01-18 用作胶粘剂和涂料的水性聚氨酯分散液及其制备

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* Cited by examiner, † Cited by third party
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EP3770226A4 (fr) * 2018-03-30 2022-01-19 Baoshan Iron & Steel Co., Ltd. Revêtement isolant auto-adhésif hydrosoluble respectueux de l'environnement pour de l'acier au silicium

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* Cited by examiner, † Cited by third party
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CN100358930C (zh) * 2005-10-11 2008-01-02 东华大学 一种用于人造毛皮底布涂层的复合乳液的制备方法及应用
CN100500777C (zh) * 2006-06-13 2009-06-17 大连科盾防腐新材料有限公司 一种聚氨酯导静电防腐涂料
CN101235264A (zh) * 2007-01-30 2008-08-06 中国科学院福建物质结构研究所 一种水性聚氨酯胶粘剂及其制备方法
CN100575436C (zh) * 2007-10-11 2009-12-30 同济大学 一种含碳纳米管水性聚氨酯导电涂料及其制备方法
CN101649039B (zh) * 2008-08-15 2012-05-02 段友芦 高固体含量、低活化温度的水性聚氨酯分散液,制备方法及其用途
CN101899277B (zh) * 2010-04-30 2013-01-09 华烁科技股份有限公司 一种rfid天线基材用水性聚氨酯胶粘剂
CN101845269B (zh) * 2010-05-31 2012-05-30 淄博永麒化工技术开发有限公司 Pvc防护手套用水性聚氨酯涂饰剂及其制备方法
CN102492113B (zh) * 2011-12-01 2013-10-09 山西省应用化学研究所 一种基于hdi-tdi的水性聚氨酯胶粘剂的制备方法
CN102876271A (zh) * 2012-09-26 2013-01-16 苏州汾湖电梯有限公司 观光电梯用玻璃粘合剂及其制备方法
CN105925165A (zh) * 2016-04-29 2016-09-07 李强 一种高分子水性聚氨酯涂料及其制备方法
CN106117509A (zh) * 2016-08-01 2016-11-16 旭川化学（苏州）有限公司 一种耐增塑剂单组份水性聚氨酯树脂及其制备方法
CN107353394B (zh) * 2017-08-23 2022-10-28 黄山联固新材料科技有限公司 一种涂料、聚氨酯及其制备方法
CN108219103B (zh) * 2018-01-15 2019-12-24 广州昊毅新材料科技股份有限公司 水性聚氨酯树脂及其制备方法与应用
CN117757414B (zh) * 2024-02-22 2024-05-28 上海蒂姆新材料科技有限公司 一种汽车折边胶用双组分胶粘剂及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4617349A (en) * 1984-11-02 1986-10-14 Takeda Chemical Industries, Ltd. Urethane resin compositions
EP0576485B1 (fr) * 1991-03-22 1996-06-05 Henkel KGaA Dispersions de polymeres appropries a des systemes reactifs, procede pour leur preparation et utilisation
US5608000A (en) * 1993-09-24 1997-03-04 H. B. Fuller Licensing & Financing, Inc. Aqueous polyurethane dispersion adhesive compositions with improved heat resistance
US6147155A (en) * 1999-06-08 2000-11-14 Bayer Corporation Aqueous polyurethane dispersions containing non-cyclic diisocyanates and a process for their preparation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4617349A (en) * 1984-11-02 1986-10-14 Takeda Chemical Industries, Ltd. Urethane resin compositions
EP0576485B1 (fr) * 1991-03-22 1996-06-05 Henkel KGaA Dispersions de polymeres appropries a des systemes reactifs, procede pour leur preparation et utilisation
US5608000A (en) * 1993-09-24 1997-03-04 H. B. Fuller Licensing & Financing, Inc. Aqueous polyurethane dispersion adhesive compositions with improved heat resistance
US6147155A (en) * 1999-06-08 2000-11-14 Bayer Corporation Aqueous polyurethane dispersions containing non-cyclic diisocyanates and a process for their preparation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3770226A4 (fr) * 2018-03-30 2022-01-19 Baoshan Iron & Steel Co., Ltd. Revêtement isolant auto-adhésif hydrosoluble respectueux de l'environnement pour de l'acier au silicium

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