CN107955126B - Aqueous dispersion of polyurethane-polyurea polyol and preparation method thereof - Google Patents

Abstract

The invention relates to an aqueous dispersion of a polyurethane-polyurea polyol, which is prepared from the following raw materials: a) the chain extender containing two hydroxyl groups is one or more of a diamine chain extender and a polyamine chain extender; b) one or more of a diol and a polyol having a number average molecular weight greater than 500 and less than 20000 daltons; c) an isocyanate comprising one or more of a diisocyanate and a polyisocyanate; d) a hydrophilic compound component, the hydrophilic group of the hydrophilic compound is one or more of an ionic group, a potentially ionic group, and a nonionic group. The present invention can be applied to single/two-component coating resins.

Description

Aqueous dispersion of polyurethane-polyurea polyol and preparation method thereof

Technical Field

The invention relates to an aqueous dispersion of polyurethane-polyurea polyol and a preparation method thereof.

Background

The aqueous polyurethane dispersion takes water as a dispersion medium, is nontoxic, tasteless and noncombustible, and is an environment-friendly high polymer material. The polyurethane-polyurea polyol aqueous dispersion is aqueous polyurethane containing hydroxyl in the structure, can obtain good crosslinking effect by matching with an isocyanate curing agent, and has the performance reaching or even exceeding that of solvent type polyurethane resin. The current method for synthesizing the aqueous polyurethane-polyurea polyol dispersion adopts a mode of excessive capping of alcohol, including macromolecular alcohol or small molecular alcohol or amino alcohol, such as patents CN1278539A, CN102002166B and CN 103570915A, US2007123643A 1. Such dispersions, although different in their synthesis, share a common feature: these patents produce hydroxyl-terminated polyurethane-polyurea dispersions by end-capping with alcoholic compounds which contain a hydroxyl content of 0.4 to 1.5% by weight, but polyurethane-polyureas cannot be used in one-component systems, but only in two-component systems, due to the low end-capping molecular weight (less than 10000 daltons). When the dispersion is used as a two-component coating resin, the hydroxyl content of 0.4-1.5 wt% means that more expensive curing agents need to be added, and the application cost is high; while low molecules are detrimental to the storage stability of the dispersion. In addition, the molecular weight of the existing polyurethane-polyurea dispersoid is lower than 10000 daltons, and the mechanical property is lower, so the polyurethane-polyurea dispersoid cannot be used as a single-component coating resin.

Disclosure of Invention

The invention aims to provide a high molecular weight polyurethane-polyurea polyol aqueous dispersion which can be applied to single components and double components, and compared with the polyurethane-polyurea polyol aqueous dispersion in the prior art, the dispersion has higher hydroxyl content and larger molecular weight. Unlike the prior art dispersions which generally employ a capping process, the aqueous polyurethane-polyurea polyol dispersions of the present invention are obtained using a diamine chain extender or a polyamine chain extender containing two hydroxyl groups. The molecular weight of the dispersion is improved while the content of the hydroxyl is higher, and when the dispersion is used as a two-component coating, good crosslinking effect can be obtained by matching with less curing agent; when the dispersion is used as a single component, the dispersion can also meet the use requirement due to the large molecular weight of the dispersion.

In order to achieve the above object, the technical solution of the present invention is as follows:

an aqueous dispersion of a polyurethane-polyurea polyol, prepared using raw materials comprising:

a) the chain extender containing two hydroxyl groups is one or more of a diamine chain extender and a polyamine chain extender;

b) one or more of a diol and a polyol having a number average molecular weight greater than 500 and less than 20000 daltons;

c) an isocyanate comprising one or more of a diisocyanate and a polyisocyanate;

d) a hydrophilic compound component, the hydrophilic group of the hydrophilic compound is one or more of an ionic group, a potentially ionic group, and a nonionic group. Wherein the potentially ionic group is an ionizable functional group having reactivity with NCO, and is converted into a corresponding salt by adding a neutralizing agent.

The chain extender containing two hydroxyl groups is selected from one or more compounds shown in the following structural formula:

wherein R is₁Is alkyl or hydrogen, preferably hydrogen, methyl, ethyl, propyl, more preferably methyl; r₂The alkyl group is preferably an ethyl group or a propyl group, and more preferably an ethyl group. By using the chain extender, polyurethane polyurea dispersoid with higher hydroxyl content (0.43-0.75 wt%) and high molecular weight (15-25 ten thousand daltons) can be obtained at lower temperature.

The chain extender containing two hydroxyl groups is prepared from hydroxyl acrylate and diamine or polyamine containing primary amino,

preferably, the hydroxy acrylate is selected from one or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate, preferably one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate, more preferably hydroxyethyl methacrylate;

preferably, the primary amino group-containing diamine or polyamine is selected from one or more of primary aliphatic amines, primary alicyclic amines, secondary aliphatic amines and secondary alicyclic amines, preferably ethylenediamine, 1, 6-hexamethylenediamine, isophoronediamine, N- (2-hydroxyethyl) ethylenediamine, 1, 4-diaminocyclohexane, bis (4-aminocyclohexane) methane, adipic acid dihydrazide, one or more of diethylenetriamine, triethylenetetramine, hydrazine hydrate and polyetheramine, more preferably one or more of diethylenetriamine, N- (2-hydroxyethyl) ethylenediamine, diethylenetriamine, triethylenetetramine and hydrazine hydrate, still more preferably one or more of N- (2-hydroxyethyl) ethylenediamine and diethylenetriamine.

When the chain extender containing two hydroxyl groups is prepared, the reaction temperature of the hydroxyl acrylate and diamine or polyamine containing primary amino groups is 40-150 ℃, and preferably 80-120 ℃;

preferably, the molar ratio of the primary amino group in the primary amino group-containing diamine or polyamine to the C ═ C double bond contained in the acrylic acid moiety in the hydroxyl acrylate is 0.8 to 2.0:1, preferably 1.0 to 1.3: 1.

The amount of component a) is from 0.02 to 10% by weight, preferably from 2 to 8% by weight, based on the solids of the polyurethane-polyurea polyol dispersion;

the amount of component b) is 25 to 90 wt%, preferably 39 to 80 wt%;

the amount of component c) is 5 to 40 wt.%, preferably 10 to 35 wt.%;

the amount of component d) is 0.2 to 20 wt.%, preferably 1 to 10 wt.%.

The component b) is dihydric alcohol or polyhydric alcohol with hydroxyl functionality of 2-5 and number average molecular weight of more than 500 and no more than 15000 daltons; one or more of dihydric alcohol, trihydric alcohol and tetrahydric alcohol with the number average molecular weight of more than 500 and 8000 daltons are preferred; more preferably one or more of polyester dihydric alcohol, polycarbonate dihydric alcohol and polycaprolactone dihydric alcohol with the number average molecular weight of 1500-3000 daltons.

Preferred polyester diols are linear polyester diols, such as can be obtained by dehydration and condensation from carboxylic acids and/or anhydrides such as aliphatic, cycloaliphatic, aromatic dicarboxylic acids or their corresponding anhydrides and the like and diols by known means, examples of which include, but are not limited to, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonane dicarboxylic acid, decane dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexane dicarboxylic acid, maleic acid, fumaric acid, malonic acid, or mixtures thereof; examples of the dihydric alcohol include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1, 2-propanediol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, 2, 3-butanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 2-dimethyl-1, 3-propanediol, 1, 4-dihydroxycyclohexane, 1, 4-dimethylolcyclohexane, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, or a mixture thereof. Cycloaliphatic, aromatic di-hydroxy compounds are also suitable as diols for preparing the polyester. Also included are fatty acid-containing polyesters having an average OH functionality of about 2 and comprising the transesterification reaction product of castor oil with an oil other than castor oil.

The component b) is preferably a polyester diol containing isophthalic acid and/or terephthalic acid and/or adipic acid and neopentyl glycol, ethylene glycol, butanediol and/or hexanediol as structural components.

Preferably, by using homo-or copolymer diols of caprolactone as component b), which can be obtained by ring opening of lactones or mixtures of lactones with suitable di-hydroxy-functional diols having a number average molecular weight of 50 to 500. Wherein caprolactone such as-caprolactone, methyl-caprolactone and mixtures thereof, and dihydric alcohol such as the above-mentioned dihydric alcohol having a number average molecular weight of 50 to 500 are used as structural components of the polyester polyol. Preference is given to using linear polycaprolactone diols of 1, 4-butanediol, 1, 6-hexanediol, 2-dimethyl-1, 3-propanediol and/or mixtures thereof cyclo-caprolactone.

Preferably, polycarbonate diols prepared by using diols and carbonates are used as component b). The diol may be 1, 4-butanediol or 1, 6-hexanediol, and the carbonate may be diaryl carbonate or dialkyl carbonate. The diaryl carbonate comprises diphenyl carbonate and the dialkyl carbonate comprises dimethyl carbonate; preference is given to polycarbonates prepared by reacting 1, 6-hexanediol with dimethyl carbonate.

The component c) is isocyanate with the functionality of 1.5-5.0 and the NCO content of 7-55 wt%, and the isocyanate is selected from one or more of aliphatic, alicyclic, aromatic and araliphatic isocyanate; preferably, the component c) is an isocyanate having a functionality of 1.8 to 3.0 and an NCO content of 35.0 to 52.0 wt.%.

In a preferred embodiment, the aliphatic, cycloaliphatic, aromatic, araliphatic diisocyanate has the formula Y (NCO)₂Wherein Y represents a divalent aliphatic hydrocarbon group having 4 to 12 carbon atoms, a divalent alicyclic hydrocarbon group having 6 to 15 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms or a divalent araliphatic hydrocarbon group having 7 to 15 carbon atoms; such as one or more polyisocyanates containing carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups and/or biuret groups.

Component c) according to the invention is more preferably tetramethylene diisocyanate, methylpentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1, 4-cyclohexane diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, 4' -dicyclohexylpropane diisocyanate, 1, 4-phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4' -diphenylmethane diisocyanate, 2' -and 2,4' -diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, p-xylylene diisocyanate, p-isopropylidene diisocyanate and mixtures of these compounds; further preferred is one or more of 1, 6-hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate.

Preferably, in component d), the hydrophilic compound whose hydrophilic groups are potentially ionic groups is selected from one or more of the group consisting of dihydroxycarboxylic acid, trihydroxycarboxylic acid, diaminosulfonic acid, triamino sulfonic acid, diamine containing tertiary amino groups and/or diol, more preferably one or more of dihydroxypropionic acid, dimethylolpropionic acid, dimethylolbutyric acid, dimethylolacetic acid, dihydroxysuccinic acid, N- (2-aminoethyl) -2-aminoethanesulfonic acid, N- (3-aminopropyl) -3-aminopropanesulfonic acid, N- (2-aminoethyl) -3-aminopropanesulfonic acid, N-ethyldiethanolamine and N, N-dimethyldipropylenetriamine, further preferred is one or more of dimethylolpropionic acid and N, N-dimethyldipropylenetriamine;

preferably, in component d), the hydrophilic compound whose hydrophilic groups are ionic groups is selected from one or more of alkali metal, alkaline earth metal and/or ammonium salts of dihydroxycarboxylic acid, trihydroxycarboxylic acid, diaminosulphonic acid, triaminosulphonic acid and salts of diamines and/or diols containing tertiary amino groups; more preferably one or more of alkali metal salts, alkaline earth metal salts and/or ammonium salts of N- (2-aminoethyl) -2-aminoethanesulfonic acid, N- (3-aminopropyl) -3-aminoethanesulfonic acid, N- (2-aminoethyl) -3-aminopropanesulfonic acid, N-ethyldiethanolamine, organic acid salts of N, N-dimethylpropylenetriamine, and further preferably sodium N- (2-aminoethyl) -2-aminoethanesulfonate;

preferably, in said component d), the hydrophilic compound, the hydrophilic group of which is a non-ionic group, is selected from one or more of polyether monols, polyether diols, polyether polyols, such as homopolymers, copolymers and grafting products of styrene oxide, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin, such as dehydration condensation products of polyols or mixtures thereof, such as polyether diols or polyether polyols obtained by alkoxylation of diols, polyols, diamines, polyamines and monoalcohols.

Preferably, the hydrophilic compound containing nonionic groups in component d) is polyoxyethylene ether glycol, such as ethylene oxide homopolymer, ethylene glycol dehydration condensation product; or polyoxyethylene ether monoalcohols, the monoalcohols of which are, for example: saturated monoalcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols, nonanols, n-decanols, n-dodecanols, n-tetradecanols, n-hexadecanols, cyclohexanol, hydroxymethylcyclohexane and 3-ethyl-3-hydroxymethyloxoheterocycles; unsaturated alcohols, such as allyl alcohol, 1-dimethyl-allyl alcohol or oleyl alcohol; aromatic alcohols such as phenol, the isomeric cresols or hydroxymethylphenol; araliphatic alcohols such as benzyl alcohol, anisyl alcohol or cinnamyl alcohol; secondary monoamines, such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, di-N-butylamine, diisobutylamine, bis (2-ethylhexyl) -amine, N-methyl-and N-ethylcyclohexylamine or dicyclohexylamine; heterocyclic secondary amines such as morpholine, pyrrolidine, piperidineethylpyrazole and the like. Or polyoxyethylene ether polyol, such as glycerol, pentaerythritol and sugar as initiator, and one or two of propylene oxide and ethylene oxide as polymerization unit.

The number of ethylene oxide in the polyoxyethylene ether monohydric alcohol, the polyoxyethylene ether dihydric alcohol and the polyoxyethylene ether polyol is 4-200, the number average molecular weight is 200-9000 daltons, and the functionality of hydroxyl groups capable of reacting with NCO is 1-3; preferably, the number of the ethylene oxide is 12-75, the number average molecular weight is 600-3500 dalton, and the functionality of hydroxyl containing the hydroxyl capable of reacting with NCO is 1-2; further is the mono-or di-hydroxyl polyethoxy ether with the ethylene oxide number of 15-45 and the number average molecular weight of 800-2000 daltons.

Particularly preferred components d) include at least one of sodium N- (2-aminoethyl) -2-aminoethane sulfonate, dimethylolpropionic acid, YMR 120, MPEG-1200, PEG 2000.

The aqueous dispersion of polyurethane-polyurea polyol, the raw material further comprising at least one of the following components:

component e) dihydric alcohol and/or polyhydric alcohol which have the number average molecular weight of 62-500 daltons and can react with NCO;

component f) a chain extender having a number average molecular weight of less than 500 daltons, capable of reacting with NCO, which is one or more of a monoamine, a diamine and a polyamine; or

Component g), a neutralizing agent.

Component e) is selected from one or more of N-butanol, ethylene glycol, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 1, 4-dihydroxycyclohexane, 1, 4-dimethylolcyclohexane, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, N-substituted ethanolamine, glycerol, trimethylolpropane, trimethylolethane and pentaerythritol;

preferably one or more of 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, neopentyl glycol, 1, 4-cyclohexanedimethanol, glycerol and pentaerythritol;

more preferably one or more of 1, 2-propanediol and 1, 3-butanediol;

preferably, component e) is used in an amount of 0 to 8 wt.%, preferably 0 to 4 wt.%, based on the solids of the polyurethane-polyurea polyol dispersion.

Component f) is selected from one or more of diethanolamine, 1, 2-hexamethylenediamine, 1, 2-ethylenediamine, 1, 6-hexamethylenediamine, 1-amino-3, 3, 5-trimethyl-5-aminomethyl-cyclohexane, piperazine, ethanolamine and hydroxyethylethylenediamine;

preferably one or more of 1, 2-ethylenediamine, 1, 6-hexamethylenediamine, 1-amino-3, 3, 5-trimethyl-5-aminomethyl-cyclohexane (isophoronediamine) and hydroxyethylethylenediamine;

more preferably one or both of 1, 2-ethylenediamine and 1-amino-3, 3, 5-trimethyl-5-aminomethyl-cyclohexane;

preferably, component f) is used in an amount of 0 to 6 wt.%, preferably 0 to 3 wt.%, based on the solids of the polyurethane-polyurea polyol dispersion.

Component g) is selected from one or more of tertiary amine and inorganic base, or one or more of organic acid;

preferably, the tertiary amine is trialkylamine, each alkyl group of the trialkylamine preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and the tertiary amine is more preferably one or more of trimethylamine, triethylamine, methyldiethylamine, tripropylamine, triethanolamine, dimethylcyclohexylamine, N-methylmorpholine, diisopropylethylamine, and dimethylethanolamine; the tertiary amine is more preferably triethylamine;

the inorganic base is preferably one or more of sodium hydroxide, ammonia water and potassium hydroxide, and more preferably ammonia water;

the organic acid is preferably selected from one or more of formic acid, acetic acid, butyric acid and itaconic acid, more preferably from one or more of formic acid, acetic acid and butyric acid, and most preferably acetic acid;

preferably, component g) is used in an amount of 0 to 5 wt.%, preferably 0 to 1.5 wt.%, based on the solids of the polyurethane-polyurea polyol dispersion.

Component g) the molar ratio of neutralizing agent to acid groups is generally from 0.3 to 1.6:1, preferably from 0.7 to 1.1: 1. The acid groups may be neutralized before, during, or after the carbamation reaction. Preferably, the reaction is followed, typically at room temperature.

Preferably, suitable solvents for preparing the polyurethane-polyurea polyol dispersion include solvents having a boiling point below 100 ℃ at atmospheric pressure and which do not contain any functional groups reactive with isocyanates. Moreover, the solvent is preferably removable from the dispersion prepared by distillation under relatively mild conditions. Such solvents include acetone, methyl ethyl ketone, t-butyl methyl ether or tetrahydrofuran. Methyl ethyl ketone or acetone is preferably used as the solvent, and acetone is particularly preferred.

The present invention also provides a process for preparing said aqueous polyurethane-polyurea polyol dispersion, comprising the steps of:

1) putting the components b) and c) into a reaction kettle to react in a solvent to obtain an NCO-terminated prepolymer solution with the concentration of 70-100 wt%;

2) mixing the prepolymer solution with water;

3) adding the component a) into the mixture obtained in the step 2), and stirring for reaction;

4) removing part of the solvent or completely removing the solvent to obtain an aqueous dispersion of the polyurethane-polyurea polyol;

wherein when component d) contains hydroxyl groups, it is added during the preparation of the NCO prepolymer solution in step 1); when component d) contains amino groups, it is added after the preparation of the NCO prepolymer solution and before the prepolymer solution and water are mixed.

Further, the present invention provides another process for preparing said aqueous polyurethane-polyurea polyol dispersion, comprising the steps of:

1) putting the components b) and c) into a reaction kettle to react in a solvent to obtain an NCO-terminated prepolymer solution with the concentration of 70-100 wt%;

2) mixing the prepolymer solution with water;

3) adding the component a), and stirring for reaction;

4) removing part of the solvent or completely removing the solvent to obtain an aqueous dispersion of the polyurethane-polyurea polyol;

wherein when component d) contains hydroxyl groups, it is added during the preparation of the NCO prepolymer solution in step 1); when component d) contains amino groups, it is added after the preparation of the NCO prepolymer solution and before the prepolymer solution and water are mixed;

d) comprising a hydrophilic compound containing potentially ionic groups;

the component g) is added during the preparation of the prepolymer solution in step 1) or after the preparation of the NCO prepolymer solution and before the prepolymer solution and water are mixed.

The present invention also provides a further process for preparing said aqueous polyurethane-polyurea polyol dispersion, comprising the steps of:

1) putting the components b), c) and e) into a reaction kettle to react in a solvent to obtain an NCO-terminated prepolymer solution with the concentration of 70-100 wt%;

2) mixing the prepolymer solution with water;

3) adding the component a) and optional f), and stirring for reaction;

4) removing part of the solvent or completely removing the solvent to obtain an aqueous dispersion of the polyurethane-polyurea polyol;

wherein when component d) contains hydroxyl groups, it is added during the preparation of the NCO prepolymer solution in step 1); when component d) contains amino groups, it is added after the preparation of the NCO prepolymer solution and before the prepolymer solution and water are mixed;

when d) comprises a hydrophilic compound containing potentially ionic groups, component g) is added either during the preparation of the prepolymer solution in step 1) or after the preparation of the NCO prepolymer solution and before the prepolymer solution and water are mixed.

In this document, the meaning of a plurality is two or more than two.

The polyurethane-polyurea polyol aqueous dispersion provided in the present invention:

1) by introducing a diamine chain extender or a polyamine chain extender containing two hydroxyl groups, namely the component a), the aqueous dispersion of the polyurethane-polyurea polyol with the hydroxyl content of 0.43-0.75 wt% and the number average molecular weight of 150000-250000 is obtained, and the higher molecular weight can be used independently or matched with a curing agent to prepare the two-component polyurethane coating. When the coating is used for a single-component coating, excellent film forming property and mechanical strength can be provided; when used as a two-component coating, the coating also has excellent water resistance, acid and alkali resistance and alcohol resistance.

2) Because the component a) is amine, the high-hydroxyl-terminated polyurethane-polyurea polymer has high activity, can complete the introduction of high hydroxyl at normal temperature, and has simpler operation compared with the preparation of the hydroxyl-terminated polyurethane-polyurea polyol dispersion by using polyol for end capping.

Drawings

FIG. 1 shows the NMR spectrum of a chain extender I containing two hydroxyl groups prepared according to the method of example 1 of the present invention: (¹H NMR) graph.

FIG. 2 shows the NMR spectrum of a chain extender II containing two hydroxyl groups prepared according to the method of example 2 of the present invention (R) ((R))¹H NMR) graph.

FIG. 3 shows NMR spectra of chain extender III containing two hydroxyl groups prepared according to the method of example 3 of the present invention: (¹H NMR) graph.

Detailed Description

The following examples are further illustrative of the present invention and are presented only for the purpose of illustrating the invention in limited variation and are not to be construed as limiting the spirit of the invention.

The main materials used were:

polyol I having a number average molecular weight greater than 500 and less than 20000 daltons: poly (adipic acid-neopentyl glycol-hexanediol) diol, OH number 75mg KOH/g, CMA654, Wada Chemicals

Polyol II having a number average molecular weight greater than 500 and less than 20000 daltons: 1, 6-hexanediol poly (o-phthalate), OH number 56mg KOH/g, PH56, Spilamper

Polyol III having a number average molecular weight greater than 500 and less than 20000 daltons: polycarbonate diol, OH number 56mgKOH/g, CC2200, Colesine

Polyol iv having a number average molecular weight greater than 500 and less than 20000 daltons: polycaprolactone diol, OH value 56mgKOH/g, PLACCEL220, Japan xylonite

Polyol v with number average molecular weight greater than 500 and less than 20000 daltons: 1, 6-hexanediol polyadipate diol having an OH number of 37mg KOH/g, CMA3044, Wada Chemicals

Isocyanate I: dicyclohexylmethane diisocyanate (

HMDI, Wanhua chemistry)

Isocyanate II: isophorone diisocyanate (

IPDI, Wanhua chemistry)

Isocyanate III: hexamethylene diisocyanate (

HDI, Wanhua chemical)

Polyether I: difunctional polyether (Ymer120), trimethylolpropane polyethylene glycol monomethyl ether, having a number average molecular weight of 1000 daltons, boston

Polyether II: monofunctional polyether (MPEG-1200), polyethylene glycol monomethyl ether, having a number average molecular weight of 1200 daltons, petrochemical in Hunan

Polyether III: difunctional polyether (PEG-2000), polyethylene glycol, with a number average molecular weight of 2000 daltons, Hunan petrochemical

The synthesis process of the chain extender containing two hydroxyl groups, namely the preparation of the component a), is as follows, wherein the parameters are determined as follows:

OH content: measured according to phthalic anhydride method in GB/T-12008

Average particle size: the polyurethane dispersion was diluted with water to a concentration of 0.5% by weight, measured using Marvin Nano-ZS90

pH value: measurement with a Metrohm model 6173 PH meter

Determination of NCO: the content of-NCO in the polyurethane synthesis process is determined according to the chemical industry standard of the people's republic of China for determining the content of isocyanate groups in the polyurethane prepolymer HG/T2409-92.

And (3) measuring the molecular weight: a small amount of the emulsion was dissolved in tetrahydrofuran and measured by HP1100LCMSD liquid chromatography-mass spectrometer. The column model was PLGEL10MIXED2B X3 (PL corporation), the column temperature was 30 ℃, the mobile phase was tetrahydrofuran, the mobile phase velocity was 1.500mL/min, the standard was monodisperse polystyrene, and the detector was HP1047A differential refractometer (Agilent).

Yield of chain extender containing at least two hydroxyl groups: HPLC analysis (samples were made up to 4 mg/ml in tetrahydrofuran as solvent and tested at 40 ℃ C. at a flow rate of 1 ml/min).

Example 1

Synthesis of chain extender I containing two hydroxyl groups

Adding 218g of N- (2-hydroxyethyl) ethylenediamine and 260g of hydroxyethyl methacrylate into a 1000ml reaction bottle, stirring and heating to 80 ℃, keeping the temperature for reaction for 2 hours, increasing the temperature to 100 ℃, and continuing to keep the temperature for reaction for 2 hours. Discharging to obtain target product with content of about 95%, and the structural formula is shown in the specification¹The chemical shifts in H-NMR are shown in FIG. 1:

example 2

Synthesis of chain extender II containing two hydroxyl groups

200g of diethylenetriamine and 480g of hydroxyethyl methacrylate are added into a 1000ml reaction bottle, stirred and heated to 80 ℃, and the temperature is kept for reaction for 2 hours, raised to 100 ℃, and kept for reaction for 2 hours. Discharging to obtain target product with content of about 95%, and the structural formula is shown in the specification¹The chemical shifts in H-NMR are shown in FIG. 2:

example 3

Synthesis of chain extender III containing two hydroxyl groups

Adding 116g of ethylenediamine and 480g of hydroxyethyl methacrylate into a 1000ml reaction bottle, stirring and heating to 80 ℃, keeping the temperature for reaction for 2 hours, increasing the temperature to 100 ℃, and continuing to keep the temperature for reaction for 2 hours. Discharging to obtain target product with content of about 95%, and the structural formula is shown in the specification¹The chemical shifts in H-NMR are shown in FIG. 3: .

The following is a synthesis process for an aqueous dispersion of a polyurethane-polyurea polyol:

example 4

260g of dehydrated polyol I with number average molecular weight more than 500 and less than 20000 daltons, 80g of isocyanate I, 1.8g of dehydrated Ymer120, 45g of acetone and 6.5g of dimethylolpropionic acid were added to a 1L four-neck round bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 80-90 ℃ until NCO reached 1.75% and the concentration of the terminal NCO prepolymer solution was 89% by weight. Adding 250g of acetone for dilution and cooling to below 40 ℃ and adding 4.91g of triethylamine for about 5min, then dispersing the mixture by adding 570g of water, adding 15.0g of chain extender I containing two hydroxyl groups after dispersion, and continuing stirring and reacting for 15 min. After separation of the acetone by distillation, a solvent-free polyurethane polyol dispersion is obtained. It has a solids content of 44% by weight, an OH content of 0.6% by weight (based on solids), a mean particle diameter of 120nm, a pH of 8.0 and a number average molecular weight of 167502 for polyurethane polyureas.

Example 5

195g of dehydrated polyol II having a number average molecular weight of more than 500 and less than 20000 Dalton, 113.9g of isocyanate I, 75g of acetone, 12.4g of dimethylolpropionic acid, 12.11g of 1, 3-butanediol and 9.8g of triethylamine are introduced into a 1L four-necked round-bottomed flask equipped with a nitrogen inlet and outlet, and the mixture is stirred at 80 to 90 ℃ until an NCO content of 2.26% by weight and an NCO-terminated prepolymer solution concentration of 82% by weight are reached. Adding 250g of acetone for dilution, cooling to 40 ℃, adding 520g of water for dispersing the mixture, adding 10.0g of chain extender I containing two hydroxyl groups and 1g of 1, 2-ethylenediamine after dispersing, and continuing stirring for reaction for 15 min. After separation of the acetone by distillation, a solvent-free polyurethane polyol dispersion is obtained. It has a solids content of 35% by weight, an OH content of 0.75% by weight (based on solids), a mean particle diameter of 65nm, a pH value of 8.0 and a number-average molecular weight of 175168.

Example 6

195g of dehydrated polyol II having a number average molecular weight of more than 500 and less than 20000 Dalton, 113.9g of isocyanate I, 5.4g of dimethylolpropionic acid, 9.3g of 1, 3-butanediol, 35g of YMer120 are introduced into a 1L four-neck round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture is stirred at 80 to 90 ℃ until NCO reaches 3.2% by weight and the concentration of the terminal NCO prepolymer solution is 100% by weight. 325g of acetone is added for dilution and the temperature is reduced below 40 ℃ and 5.6g of triethylamine are added for about 5min, then the mixture is dispersed by adding 520g of water, after dispersion 30.0g of chain extender I containing two hydroxyl groups is added, and the reaction is continued for 15min with stirring. After separation of the acetone by distillation, a solvent-free polyurethane polyol dispersion is obtained. It has a solids content of 35% by weight, an OH content of 0.75% by weight (based on solids), a mean particle diameter of 85nm, a pH value of 8.1 and a number-average molecular weight of 168541.

Example 7

195g of dehydrated polyol II having a number average molecular weight of more than 500 and less than 20000 Dalton, 113.9g of isocyanate I, 75g of acetone, 5.4g of dimethylolpropionic acid, 10g of 1, 3-butanediol, 1.0g of MEPG-1200 were placed in a 1L four-necked round bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 80-90 ℃ until NCO reached 3.15% by weight and the concentration of the end NCO prepolymer solution was 82% by weight. 250g of acetone are added for dilution and the temperature is reduced below 40 ℃ and 5.6g of triethylamine are added for about 5min, then the mixture is dispersed by adding 520g of water, after dispersion 10.0g of chain extender I containing two hydroxyl groups and 11.5g of isophorone diamine are added, and the reaction is continued for 15min with stirring. After separation of the acetone by distillation, a solvent-free polyurethane polyol dispersion is obtained. It has a solids content of 35% by weight, an OH content of 0.75% by weight (based on solids), a mean particle diameter of 85nm, a pH value of 8.1 and a number-average molecular weight of 165140 for the polyurethane polyurea.

Example 8

260g of dehydrated polyol I having a number average molecular weight of more than 500 and less than 20000 Dalton, 51g of isocyanate III, 1.8g of dehydrated YMR 120, 45g of acetone and 6.5g of dimethylolpropionic acid were placed in a 1L four-neck round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 80-90 ℃ until NCO reached 1.88% by weight and the concentration of the terminal NCO prepolymer solution was 88% by weight. Adding 250g of acetone for dilution, cooling to below 40 ℃, adding 4.91g of triethylamine for about 5min, then dispersing the mixture by adding 570g of water, adding 15.0g of chain extender II containing two hydroxyl groups after dispersion, and continuing stirring for reaction for 15 min. After separation of the acetone by distillation, a solvent-free polyurethane polyol dispersion is obtained. It has a solids content of 44% by weight, an OH content of 0.43% by weight (based on solids), a mean particle diameter of 120nm, a pH of 8.0 and a number-average molecular weight of 171032.

Example 9

300g of dehydrated polyol I having a number average molecular weight of more than 500 and less than 20000 Dalton, 26.4g of isocyanate II, 41g of isocyanate III, 3.0g of dehydrated PEG2000, 45g of acetone were placed in a 1L four-necked round bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 80-90 ℃ until NCO reached 2.15 wt% and the concentration of the terminal NCO prepolymer solution was 90 wt%. Adding 400g of acetone for dilution, cooling to below 40 ℃, adding 5.0g of 50% solid content N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt aqueous solution, reacting at 40-45 ℃ for 15min, then dispersing the mixture by adding 540g of water, adding 15.0g of chain extender II containing two hydroxyl groups after dispersion, and continuing stirring and reacting for 15 min. After separation of the acetone by distillation, a solvent-free polyurethane polyol dispersion is obtained. It has a solids content of 40% by weight, an OH content of 0.58% by weight (based on solids), a mean particle diameter of 200nm, a pH value of 7.4 and a number-average molecular weight of 165412.

Example 10

The polyol II with the number average molecular weight of more than 500 and less than 20000 daltons in example 4 was replaced by the equivalent amount of polyol III, the rest being unchanged. It has a solids content of 35% by weight, an OH content of 0.75% by weight (based on solids), a mean particle diameter of 85nm, a pH value of 8.1 and a number-average molecular weight of 156221 for the polyurethane polyurea.

Example 11

The polyol II with the number average molecular weight of more than 500 and less than 20000 daltons in example 4 was replaced by the equivalent amount of polyol IV, the rest being unchanged. It has a solids content of 35 wt.%, an OH content of 0.75 wt.%, an average particle size of 73nm, a pH of 7.8 and a number average molecular weight of 170028.

Example 12

195g of polyol II from example 4, having a number average molecular weight of more than 500 and less than 20000 Dalton, were exchanged for 292.5g of polyol V, the remainder being unchanged. It has a solids content of 35% by weight, an OH content of 0.55% by weight (based on solids), a mean particle diameter of 105nm, a pH value of 7.9 and a number-average molecular weight of 155657 for the polyurethane polyurea.

Example 13

260g of dehydrated polyol I having a number average molecular weight of more than 500 and less than 20000 Dalton, 80g of isocyanate I, 1.8g of dehydrated Ymer120, 140g of acetone were added to a 1L four-neck round bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 80-90 ℃ until NCO reached 1.65% and the concentration of the terminal NCO prepolymer solution was 71% by weight. Adding 150g of acetone for dilution, cooling to below 40 ℃, adding 4.91g N, reacting with N-dimethyl dipropylenetriamine for about 10min, then adding 4g of acetic acid for neutralization for 5min, adding 570g of water to disperse the mixture, adding 15.0g of chain extender I containing two hydroxyl groups after dispersing, and continuing stirring for reacting for 15 min. After separation of the acetone by distillation, a solvent-free polyurethane polyol dispersion is obtained. It has a solids content of 44% by weight, an OH content of 0.6% by weight (based on solids), a mean particle diameter of 120nm, a pH value of 8.0 and a number-average molecular weight of 153684.

Example 14

190g of dehydrated polyol I, 80g of isocyanate I, 60g of dehydrated PEG-2000 and 45g of acetone were placed in a 1L four-necked round-bottomed flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 80 to 90 ℃ until NCO reached 1.45% and the concentration of the NCO-terminated prepolymer solution was 88% by weight. Adding 150g of acetone for dilution, cooling to below 40 ℃, adding 570g of water for dispersing the mixture, adding 15.0g of chain extender I containing two hydroxyl groups after dispersion, and continuing stirring for reaction for 15 min. After separation of the acetone by distillation, a solvent-free polyurethane polyol dispersion is obtained. It has a solids content of 35% by weight, an OH content of 0.6% by weight (based on solids), a mean particle diameter of 65nm, a pH value of 6.8 and a number-average molecular weight of 245821 for the polyurethane polyurea.

Comparative example 1

260g of dehydrated polyol I with number average molecular weight more than 500 and less than 20000 daltons, 51g of isocyanate III, 1.8g of dehydrated Ymer120, 45g of acetone and 6.5g of dimethylolpropionic acid are added to a 1L four-neck round-bottom flask equipped with a nitrogen inlet and outlet, the mixture is stirred at 80-90 ℃ until the NCO reaches 1.88%, 17.2g of trimethylolpropane and 60g of acetone are added, the temperature is raised to 70 ℃ and the reaction is continued until the total NCO content of the system is less than 0.1%, 250g of acetone is added to dilute and cool to below 40 ℃ and 4.91g of triethylamine is added for about 5min, and 570g of water is added to disperse the mixture. After separation of the acetone by distillation, a solvent-free polyurethane polyol dispersion is obtained. It has a solids content of 40% by weight, an OH content of 1.29% by weight (based on solids), an average particle diameter of 180nm, a pH value of 8.0 and a number-average molecular weight of the polyurethane polyurea of 8654.

Preparation of adhesive film

And pouring 50g of the dispersion on a 20 x 20cm glass plate, placing the glass plate on a flat table top, forming a film at 25 ℃, taking down the film after the film is dried, placing the film in a 70 ℃ oven, continuously drying for 4 hours, and testing the mechanical property of the adhesive film at 25 ℃.

Tensile strength and elongation: 10 mm. times.50 mm strips of the adhesive film were cut and stretched at a rate of 200mm/min using a GOTECH TCS 2000.

The mechanical properties of the emulsion are shown in the table I.

TABLE-emulsion mechanical and storage Properties

Comparative experimental example 1 differs from the examples of the present application mainly in that the polyurethane-polyurea polyol aqueous dispersion is prepared without using the chain extender containing two hydroxyl groups prepared in the present application, but using an excess of alcohol capping.

It can be seen from the table that the polyurethane-polyurea polyol aqueous dispersion based on the invention has excellent film forming property and storage stability, the mechanical strength of the film is high, and the polyurethane-polyurea polyol aqueous dispersion can be completely used as a one-component polyurethane coating resin to meet the use requirements, which is the characteristics and advantages that the end-capped polyurethane-polyurea polyol aqueous dispersion (comparative example 1) does not have.

Preparing a two-component coating:

100g of the dispersion of the above example are initially charged in a vessel, 0.1g of Byk 028 (German Bick chemistry) are added to adjust the dispersion rate to 800r/min for 15min of dispersion, and then 0.15g of Byk346 (German Bick chemistry), 0.1g of Tego 410 (German Digao), 1.5g of film-forming auxiliary (dipropylene glycol butyl ether, Dow chemistry), 0.5g of thickener(s) ((R) (1.5 g of

U601, 40 wt% aqueous solution, WANHUA chemical), 0.05g bactericide (BIT, Dow chemical) and 25g deionized water, continuously dispersing for 15min while maintaining the dispersion speed unchanged after the addition is finished, and finally adding a curing agent

68 (80 wt% solid content in propylene glycol methyl ether acetate), continuously dispersing for about 25min, and filtering with a 200-mesh filter screen to obtain the water-based dual-component wood coating.

Note: curing agent OH in Dispersion of the above examples

268 NCO 1:1.5 (molar ratio)

Table two test items

Table three test results

Note: represents OH in the dispersion and a curing agent

NCO in 68: 1.75 (molar ratio)

It can be seen from table three that the two-component coating prepared based on the polyurethane-polyurea polyol aqueous dispersion provided by the present invention has excellent hardness, outstanding water resistance and chemical resistance, and is significantly better than the end-capped polyurethane-polyurea polyol aqueous dispersion (comparative example 1) in various tests, and the end-capped polyurethane-polyurea polyol aqueous dispersion needs to increase the amount of the curing agent to be used, i.e., needs to add the curing agent to achieve the same resistance, so that the OH in the dispersion of the above example is OH in the curing agent

268 NCO ═ 1:1.75 (molar ratio) (see comparative example 1).

Claims (46)

1. An aqueous dispersion of a polyurethane-polyurea polyol, characterized in that it is prepared from raw materials comprising:

a) the chain extender containing two hydroxyl groups is one or more of a diamine chain extender and a polyamine chain extender;

b) one or more of a diol and a polyol having a number average molecular weight greater than 500 and less than 20000 daltons;

c) an isocyanate comprising one or more of a diisocyanate and a polyisocyanate;

d) a hydrophilic compound component, wherein the hydrophilic group of the hydrophilic compound is one or more of an ionic group, a potentially ionic group and a nonionic group; wherein the chain extender containing two hydroxyl groups is selected from one or more compounds shown in the following structural formula:

wherein R is₁Is alkyl or hydrogen; r₂Is an alkyl group.

2. The aqueous dispersion of a polyurethane-polyurea polyol according to claim 1, wherein R₁Hydrogen, methyl, ethyl, propyl; r₂Ethyl and propyl.

3. The aqueous dispersion of a polyurethane-polyurea polyol according to claim 2, wherein R₁Is methyl; r₂Is ethyl.

4. The aqueous dispersion of polyurethane-polyurea polyol according to claim 1, wherein the chain extender containing two hydroxyl groups is prepared from a hydroxy acrylate and a diamine or polyamine containing a primary amino group.

5. The aqueous polyurethane-polyurea polyol dispersion according to claim 4, wherein,

the hydroxyl acrylate is selected from one or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate;

the diamine or polyamine containing primary amino group is selected from one or more of aliphatic primary amine, alicyclic primary amine, aliphatic secondary amine and alicyclic secondary amine.

6. The aqueous polyurethane-polyurea polyol dispersion according to claim 5, wherein,

the hydroxyl acrylate is selected from one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate;

the diamine or polyamine containing primary amino group is selected from one or more of ethylenediamine, 1, 6-hexamethylenediamine, isophoronediamine, N- (2-hydroxyethyl) ethylenediamine, 1, 4-diaminocyclohexane, bis (4-aminocyclohexane) methane, adipic acid dihydrazide, diethylenetriamine, triethylenetetramine, hydrazine hydrate and polyetheramine.

7. The aqueous dispersion of polyurethane-polyurea polyol according to claim 6, wherein,

the hydroxyl acrylate is hydroxyethyl methacrylate;

the primary amino group-containing diamine or polyamine is selected from one or more of diethylenetriamine, N- (2-hydroxyethyl) ethylenediamine, diethylenetriamine, triethylenetetramine and hydrazine hydrate.

8. The aqueous dispersion of a polyurethane-polyurea polyol according to claim 7, wherein the primary amino group-containing diamine or polyamine is selected from one or more of N- (2-hydroxyethyl) ethylenediamine and diethylenetriamine.

9. The aqueous dispersion of a polyurethane-polyurea polyol according to claim 4, wherein the reaction temperature of the hydroxy acrylate with the primary amino group-containing diamine or polyamine is 40 to 150 ℃ when the chain extender containing two hydroxyl groups is prepared.

10. The aqueous dispersion of a polyurethane-polyurea polyol according to claim 9, wherein the reaction temperature of the hydroxy acrylate with the primary amino group-containing diamine or polyamine is from 80 to 120 ℃.

11. The aqueous dispersion of a polyurethane-polyurea polyol according to claim 9, wherein the molar ratio of the primary amino group in the primary amino group-containing diamine or polyamine to the C ═ C double bond contained in the acrylic acid moiety in the hydroxyl acrylate is 0.8 to 2.0: 1.

12. The aqueous dispersion of polyurethane-polyurea polyol according to claim 11, wherein,

the molar ratio of the primary amino group in the diamine or polyamine containing the primary amino group to the C ═ C double bond contained in the acrylic acid part in the hydroxyl acrylate is 1.0-1.3: 1.

13. The aqueous polyurethane-polyurea polyol dispersion according to claim 1, wherein the component a) is used in an amount of 0.02 to 10 wt.%, based on the solids of the polyurethane-polyurea polyol dispersion;

the amount of the component b) is 25-90 wt%;

the amount of the component c) is 5-40 wt%;

the amount of component d) is 0.2 to 20 wt%.

14. The aqueous polyurethane-polyurea polyol dispersion according to claim 13, wherein the component a) is used in an amount of 2 to 8 wt.%, based on the solids of the polyurethane-polyurea polyol dispersion;

the amount of the component b) is 39-80 wt%;

the amount of the component c) is 10-35 wt%;

the amount of component d) is 1 to 10 wt%.

15. The aqueous dispersion of polyurethane-polyurea polyols according to any of claims 1 to 14, wherein component b) is a diol or polyol having a hydroxyl functionality of 2 to 5 and a number average molecular weight of more than 500 and not more than 15000 daltons.

16. The aqueous dispersion of polyurethane-polyurea polyol according to claim 15, wherein component b) is one or more of diols, triols and tetrols having a number average molecular weight of greater than 500 and equal to 8000 daltons.

17. The aqueous polyurethane-polyurea polyol dispersion according to claim 16, wherein component b) is a polyester diol having a number average molecular weight of 1500 to 3000 daltons.

18. The aqueous dispersion of polyurethane-polyurea polyol according to claim 17, wherein component b) is one or more of polycarbonate diol and polycaprolactone diol having a number average molecular weight of 1500 to 3000 daltons.

19. The aqueous dispersion of a polyurethane-polyurea polyol according to any of claims 1 to 14, wherein component c) is an isocyanate having a functionality of 1.5 to 5.0 and an NCO-content of 7 to 55 wt.%, the isocyanate being selected from one or more of aliphatic, cycloaliphatic, aromatic and araliphatic isocyanates.

20. The aqueous polyurethane-polyurea polyol dispersion according to claim 19, wherein component c) is an isocyanate having a functionality of 1.8 to 3.0 and an NCO content of 35.0 to 52.0 wt.%.

21. An aqueous dispersion of a polyurethane-polyurea polyol according to claim 20, wherein component c) is selected from one or more of 1, 6-hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate.

22. The aqueous dispersion of polyurethane-polyurea polyols according to any of claims 1 to 14, characterized in that,

in the component d), the hydrophilic compound with the hydrophilic group as a potential ionic group is selected from one or more of dihydroxy carboxylic acid, trihydroxy carboxylic acid, diamino sulfonic acid, triamino sulfonic acid, diamine containing tertiary amino group and/or diol;

in the component d), the hydrophilic compound whose hydrophilic group is an ionic group is selected from one or more of alkali metal salts, alkaline earth metal salts and/or ammonium salts of dihydroxy carboxylic acids, trihydroxy carboxylic acids, diamino sulfonic acids, triamino sulfonic acids and salts of diamine and/or diol containing tertiary amino groups;

in the component d), the hydrophilic compound with the hydrophilic group being a nonionic group is selected from one or more of polyether monohydric alcohol, polyether dihydric alcohol and polyether glycol;

the number of ethylene oxide in the polyoxyethylene ether monohydric alcohol, the polyoxyethylene ether dihydric alcohol and the polyoxyethylene ether polyol is 4-200, the number average molecular weight is 200-9000 daltons, and the functionality of hydroxyl groups capable of reacting with NCO is 1-3.

23. The aqueous dispersion of a polyurethane-polyurea polyol according to claim 22, wherein,

in the component d), the hydrophilic compound with hydrophilic groups as potential ionic groups is selected from one or more of dihydroxypropionic acid, dimethylolpropionic acid, dimethylolbutyric acid, dimethylolacetic acid, dihydroxysuccinic acid, N- (2-aminoethyl) -2-aminoethanesulfonic acid, N- (3-aminopropyl) -3-aminopropanesulfonic acid, N- (2-aminoethyl) -3-aminopropanesulfonic acid, N-ethyldiethanolamine and N, N-dimethyldipropylenetriamine;

in the component d), the hydrophilic compound whose hydrophilic group is an ionic group is selected from one or more of alkali metal salts, alkaline earth metal salts and/or ammonium salts of N- (2-aminoethyl) -2-aminoethanesulfonic acid, N- (3-aminopropyl) -3-aminopropanesulfonic acid, N- (2-aminoethyl) -3-aminopropanesulfonic acid, and organic acid salts of N-ethyldiethanolamine, N-dimethyldipropylenetriamine;

in the component d), the hydrophilic compound with the hydrophilic group being a nonionic group is selected from one or more of polyoxyethylene ether monohydric alcohol, polyoxyethylene ether dihydric alcohol and polyoxyethylene ether polyol;

the polyoxyethylene ether monohydric alcohol, the polyoxyethylene ether dihydric alcohol and the polyoxyethylene ether polyol have the ethylene oxide number of 12-75, the number average molecular weight of 600-3500 daltons and the functionality of 1-2, wherein the hydroxyl can react with NCO.

24. The aqueous dispersion of a polyurethane-polyurea polyol according to claim 23, wherein,

in the component d), the hydrophilic compound with the hydrophilic group as a potential ionic group is selected from one or two of dimethylolpropionic acid and N, N-dimethyl dipropylenetriamine;

in the component d), the hydrophilic compound of which the hydrophilic group is an ionic group is N- (2-aminoethyl) -2-aminoethane sodium sulfonate;

wherein the polyoxyethylene ether monohydric alcohol, the polyoxyethylene ether dihydric alcohol and the polyoxyethylene ether polyol are mono-or di-hydroxyl polyethoxy ether with the ethylene oxide number of 15-45 and the number average molecular weight of 800-2000 daltons.

25. The aqueous dispersion of polyurethane-polyurea polyol according to any of claims 1 to 14, wherein the starting material further comprises at least one of the following components:

component e) dihydric alcohol and/or polyhydric alcohol which have the number average molecular weight of 62-500 daltons and can react with NCO;

component f) a chain extender having a number average molecular weight of less than 500 daltons, capable of reacting with NCO, which is one or more of a monoamine, a diamine and a polyamine; or

Component g), a neutralizing agent.

26. The aqueous dispersion of a polyurethane-polyurea polyol according to claim 25, wherein component e) is selected from one or more of N-butanol, ethylene glycol, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 1, 4-dihydroxycyclohexane, 1, 4-dimethylolcyclohexane, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, N-substituted ethanolamines, glycerol, trimethylolpropane, trimethylolethane and pentaerythritol.

27. The aqueous dispersion of a polyurethane-polyurea polyol according to claim 26, wherein component e) is selected from one or more of 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, neopentyl glycol, 1, 4-cyclohexanedimethanol, glycerol and pentaerythritol.

28. The aqueous dispersion of a polyurethane-polyurea polyol according to claim 27, wherein component e) is selected from one or more of 1, 2-propanediol and 1, 3-butanediol.

29. The aqueous polyurethane-polyurea polyol dispersion according to claim 26, wherein component e) is used in an amount of 0 to 8 wt% of the solids of the polyurethane-polyurea polyol dispersion.

30. The aqueous polyurethane-polyurea polyol dispersion according to claim 29, wherein component e) is used in an amount of 0 to 4 wt% of the solids of the polyurethane-polyurea polyol dispersion.

31. The aqueous dispersion of a polyurethane-polyurea polyol according to claim 25, wherein component f) is selected from one or more of diethanolamine, 1, 2-hexamethylenediamine, 1, 2-ethylenediamine, 1, 6-hexamethylenediamine, 1-amino-3, 3, 5-trimethyl-5-aminomethyl-cyclohexane, piperazine, ethanolamine and hydroxyethylethylenediamine.

32. The aqueous dispersion of a polyurethane-polyurea polyol according to claim 31, wherein component f) is selected from one or more of 1, 2-ethylenediamine, 1, 6-hexamethylenediamine, 1-amino-3, 3, 5-trimethyl-5-aminomethyl-cyclohexane and hydroxyethylethylenediamine.

33. The aqueous dispersion of a polyurethane-polyurea polyol according to claim 32, wherein component f) is selected from one or two of 1, 2-ethylenediamine and 1-amino-3, 3, 5-trimethyl-5-aminomethyl-cyclohexane.

34. The aqueous polyurethane-polyurea polyol dispersion according to claim 31, wherein component f) is used in an amount of 0 to 6 wt% based on the solids of the polyurethane-polyurea polyol dispersion.

35. The aqueous polyurethane-polyurea polyol dispersion according to claim 34, wherein component f) is used in an amount of 0 to 3 wt% based on the solids of the polyurethane-polyurea polyol dispersion.

36. The aqueous dispersion of a polyurethane-polyurea polyol according to claim 25, wherein component g) is selected from one or more of tertiary amines and inorganic bases, or one or more of organic acids.

37. The aqueous dispersion of a polyurethane-polyurea polyol according to claim 36, wherein the tertiary amine is a trialkylamine;

the inorganic base is one or more of sodium hydroxide, ammonia water and potassium hydroxide;

the organic acid is selected from one or more of formic acid, acetic acid, butyric acid and itaconic acid.

38. The aqueous dispersion of a polyurethane-polyurea polyol according to claim 37, wherein the trialkylamine has from 1 to 12 carbon atoms per alkyl group;

the inorganic base is ammonia water;

the organic acid is selected from one or more of formic acid, acetic acid and butyric acid.

39. The aqueous dispersion of a polyurethane-polyurea polyol according to claim 38, wherein the trialkylamine has from 1 to 6 carbon atoms per alkyl group;

the organic acid is acetic acid.

40. The aqueous dispersion of a polyurethane-polyurea polyol according to claim 39, wherein the tertiary amine is selected from one or more of trimethylamine, triethylamine, methyldiethylamine, tripropylamine, triethanolamine, dimethylcyclohexylamine, N-methylmorpholine, diisopropylethylamine, and dimethylethanolamine.

41. The aqueous dispersion of a polyurethane-polyurea polyol according to claim 40, wherein the tertiary amine is triethylamine.

42. The aqueous polyurethane-polyurea polyol dispersion according to claim 36, wherein component g) is used in an amount of 0 to 5 wt% based on the solids of the polyurethane-polyurea polyol dispersion.

43. The aqueous polyurethane-polyurea polyol dispersion according to claim 42, wherein component g) is used in an amount of 0 to 1.5 wt% based on the solids of the polyurethane-polyurea polyol dispersion.

44. A process for preparing an aqueous dispersion of a polyurethane-polyurea polyol according to any one of claims 1 to 24, comprising the following steps:

1) putting the components b) and c) into a reaction kettle to react in a solvent to obtain an NCO-terminated prepolymer solution with the concentration of 70-100 wt%;

2) mixing the prepolymer solution with water;

3) adding the component a) into the mixture obtained in the step 2), and stirring for reaction;

4) removing part of the solvent or completely removing the solvent to obtain an aqueous dispersion of the polyurethane-polyurea polyol;

wherein when component d) contains hydroxyl groups, it is added during the preparation of the NCO prepolymer solution in step 1); when component d) contains amino groups, it is added after the preparation of the NCO prepolymer solution and before the prepolymer solution and water are mixed.

45. A process for preparing an aqueous dispersion of a polyurethane-polyurea polyol according to any one of claims 25 to 43, comprising the steps of:

1) putting the components b) and c) into a reaction kettle to react in a solvent to obtain an NCO-terminated prepolymer solution with the concentration of 70-100 wt%;

2) mixing the prepolymer solution with water;

3) adding the component a), and stirring for reaction;

4) removing part of the solvent or completely removing the solvent to obtain an aqueous dispersion of the polyurethane-polyurea polyol;

wherein when component d) contains hydroxyl groups, it is added during the preparation of the NCO prepolymer solution in step 1); when component d) contains amino groups, it is added after the preparation of the NCO prepolymer solution and before the prepolymer solution and water are mixed;

d) comprising a hydrophilic compound containing potentially ionic groups;

the component g) is added during the preparation of the prepolymer solution in step 1) or after the preparation of the NCO prepolymer solution and before the prepolymer solution and water are mixed.

46. A process for preparing an aqueous dispersion of a polyurethane-polyurea polyol according to any one of claims 25 to 43, comprising the steps of:

1) putting the components b), c) and e) into a reaction kettle to react in a solvent to obtain an NCO-terminated prepolymer solution with the concentration of 70-100 wt%;

2) mixing the prepolymer solution with water;

3) adding the component a) and optional f), and stirring for reaction;

4) removing part of the solvent or completely removing the solvent to obtain an aqueous dispersion of the polyurethane-polyurea polyol;

wherein when component d) contains hydroxyl groups, it is added during the preparation of the NCO prepolymer solution in step 1); when component d) contains amino groups, it is added after the preparation of the NCO prepolymer solution and before the prepolymer solution and water are mixed;

when d) comprises a hydrophilic compound containing potentially ionic groups, component g) is added either during the preparation of the prepolymer solution in step 1) or after the preparation of the NCO prepolymer solution and before the prepolymer solution and water are mixed.

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