CN111019079B

CN111019079B - Aqueous dispersion of polyurethane or polyurethane urea and preparation method and application thereof

Info

Publication number: CN111019079B
Application number: CN201911329913.7A
Authority: CN
Inventors: 邢庆达; 纪学顺; 王震; 晋云全; 朱文辉; 刘云玲; 尹逊迪; 王少鹏; 于丽
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2019-12-20
Filing date: 2019-12-20
Publication date: 2022-02-18
Anticipated expiration: 2039-12-20
Also published as: CN111019079A

Abstract

The invention relates to the technical field of polyurethane aqueous dispersion, in particular to an aqueous dispersion of polyurethane or polyurethane urea, a preparation method and application thereof, wherein the polyurethane or polyurethane urea is a reaction product prepared from the following raw materials: a) a polyol having Mn ≥ 1000 and a functionality of 2-4, b) an isocyanate having at least two isocyanate groups, optionally c) a monofunctional nonionically hydrophilicizing compound having at least one NCO-reactive functional group, d) a hydrophilicizing compound having one or more of an ionic group, a potentially ionic group and a nonionic group and having 2-3 NCO-reactive functional groups, e) a long carbon chain hydroxy fatty acid, f) a small molecule blocking agent having a single amino group, optionally g) a low molecular compound having 2 or more NCO-reactive amino groups. The aqueous dispersion can ensure the flexibility of resin and can improve the adhesive force of aqueous slurry on nylon fabric.

Description

Aqueous dispersion of polyurethane or polyurethane urea and preparation method and application thereof

Technical Field

The invention relates to the technical field of polyurethane aqueous dispersion, in particular to polyurethane or polyurethane urea aqueous dispersion and a preparation method and application thereof.

Background

The aqueous glue has the characteristics of no organic solvent, no harm to human bodies, environmental friendliness and the like, and is gradually applied to various fields of textiles, woodware, metals, buildings and the like as a glue. Among them, the water-based paint used for the textile coating is required to have the characteristics of high adhesion, high flexibility, water washing resistance, dryness, yellowing resistance and the like due to the particularity of the base material of the textile coating.

In textile materials, the nylon fabric has low surface energy, so that the water-based paint needing to be coated is difficult to meet the requirements of high adhesion and high flexibility.

In addition, the fastness of water-based coatings for nylon fabrics has been an industry challenge. The water-based coating for nylon fabric in the market at present mainly comprises water-based acrylic resin and organic silicon resin, however, the water-based acrylic resin has the defects of hot adhesion, cold brittleness, water washing resistance and yellowing, and the organic silicon resin is expensive and limits the wide application of the organic silicon resin.

For example, patent document CN 108997918A discloses that a silicon-modified two-component aqueous polyurethane resin obtained by introducing an aqueous silicone resin into an aqueous hydroxyl resin, although the surface tension of the polyurethane resin is reduced to some extent, is used in floor paints and road finishes to improve the water resistance thereof. However, silicone resins are expensive and not suitable for wide application and popularization.

For example, patent document CN 104975521 a discloses that by grafting polyethylene glycol hydrophilic polyether into a polyurethane segment, the wetting permeability of an aqueous slurry to a nylon fabric is improved by utilizing the hydrophilic permeability of polyethylene glycol, thereby improving the adhesion. However, polyethylene glycol has high hydrophilicity, and causes the water resistance of the coating to be reduced, so that the use requirement cannot be met.

Therefore, how to balance the high adhesion and high flexibility of the water-based coating used on the nylon fabric becomes a key direction of research.

Disclosure of Invention

The invention aims to provide a polyurethane or polyurethane urea aqueous dispersion, a preparation method and application thereof, aiming at the problems of the existing water-based paint in the coating of nylon fabric.

In order to achieve the purpose, the technical scheme of the invention is as follows:

in one aspect, there is provided an aqueous dispersion of a polyurethane or polyurethaneurea, the polyurethane or polyurethaneurea in the aqueous dispersion being the reaction product made from starting materials comprising:

a) polyol with Mn more than or equal to 1000g/mol and functionality of 2-4,

b) an isocyanate having at least two isocyanate groups,

optionally c) monofunctional nonionically hydrophilicizing compounds containing at least one NCO-reactive functional group,

d) a hydrophilic compound containing one or more of an ionic group, a potentially ionic group and a non-ionic group and containing 2 to 3 NCO-reactive functional groups,

e) a long carbon chain of a hydroxy fatty acid,

f) small molecule blocking agents containing a single amino group (e.g., primary or secondary),

optionally, g) (e.g. different from component d)) low molecular weight compounds containing 2 and more NCO-reactive amino groups.

In some examples, the polyurethane or polyurethaneurea is a reaction product made from raw materials comprising:

a) polyol with Mn more than or equal to 1000g/mol and functionality of 2-4,

b) an isocyanate having at least two isocyanate groups,

c) monofunctional nonionically hydrophilicizing compounds having at least one NCO-reactive functional group,

e) a long carbon chain of a hydroxy fatty acid,

a) polyol with Mn more than or equal to 1000g/mol and functionality of 2-4,

b) an isocyanate having at least two isocyanate groups,

e) a long carbon chain of a hydroxy fatty acid,

g) (e.g., other than component d) low molecular weight compounds containing 2 and more NCO-reactive amino groups.

a) polyol with Mn more than or equal to 1000g/mol and functionality of 2-4,

b) an isocyanate having at least two isocyanate groups,

e) a long carbon chain of a hydroxy fatty acid,

f) small molecule capping agents containing a single amino group (e.g., a primary or secondary amino group).

According to the aqueous dispersions provided by the present invention, in some preferred embodiments, the NCO-reactive functional groups are selected from the group consisting of hydroxyl, primary amino (-NH), and₂) And a secondary amino (-NH-).

In some preferred embodiments, the NCO-reactive amino group is a primary amino group (-NH)₂) And/or a secondary amino (-NH-).

In some examples, the aqueous dispersions provided according to the invention are those in which the following components are used, based on 100 parts by weight of the total amount of polyurethane or polyurethane urea in the aqueous dispersion:

component a) is 60 to 90 parts by weight (e.g., 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight), preferably 70 to 85 parts by weight;

component b) is 7 to 25 parts by weight (e.g., 8 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, 22 parts by weight), preferably 10 to 20 parts by weight;

component c) is 0 to 5 parts by weight (e.g., 0.1 parts by weight, 0.4 parts by weight, 0.8 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 4 parts by weight, 4.5 parts by weight), preferably 0.5 to 3 parts by weight;

component d) is 0.5 to 5 parts by weight (e.g., 0.8 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3.5 parts by weight, 4 parts by weight), preferably 0.5 to 3 parts by weight;

component e) is 0.5 to 5 parts by weight (e.g., 0.8 parts by weight, 1.2 parts by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight), preferably 1 to 5 parts by weight;

component f) is 0.1 to 3 parts by weight (e.g., 0.2 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1.2 parts by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight), preferably 0.1 to 1 part by weight;

component g) is 0 to 8 parts by weight (e.g., 0.5 parts by weight, 1.5 parts by weight, 2 parts by weight, 4 parts by weight, 6 parts by weight), preferably 1 to 5 parts by weight.

In some examples, component a) is selected from one or more amorphous (at room temperature) polyester polyols having a number average molecular weight Mn of 1000-.

Suitable polyester polyols are linear polyester diols or slightly branched polyester diols, which can be obtained, for example, by dehydration and condensation of carboxylic acids and/or anhydrides (e.g., aliphatic dicarboxylic or polycarboxylic acids or their corresponding anhydrides, cycloaliphatic dicarboxylic or polycarboxylic acids or their corresponding anhydrides, aromatic dicarboxylic or polycarboxylic acids or their corresponding anhydrides) and polyols by known means. Wherein, examples of the carboxylic acid and/or anhydride include, but are not limited to, one or more of 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, trimellitic acid, phthalic anhydride, trimellitic anhydride, and succinic anhydride; examples of such polyols include, but are not limited to, one or more of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, 2, 3-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2-dimethyl-1, 3-propanediol, neopentyl glycol, 1, 4-dihydroxycyclohexane, 1, 4-dimethylolcyclohexane, 1, 8-octanediol, 1, 10-decanediol, and 1, 12-dodecanediol. Optionally, during the preparation of the polyester polyol, a polyol having a higher functionality may be added; polyols having a higher functionality, for example, trimethylolpropane, glycerol or pentaerythritol. Cycloaliphatic dihydroxy compounds and/or polyhydroxy compounds, aromatic dihydroxy compounds and/or polyhydroxy compounds are also suitable as polyols for preparing the polyester polyols. Preferably, the polyester polyol is prepared by using one or more of adipic acid, isophthalic acid and terephthalic acid as a carboxylic acid raw material and one or more of neopentyl glycol, diethylene glycol, 2-methyl-1, 3-propanediol and hexanediol as a polyol raw material.

The polyester polyols may also be homopolymers or copolymers of lactones, which may be obtained by ring-opening polymerization of lactones or mixtures of lactones with suitable difunctional or higher-functional low molecular weight polyols. Lactones such as butyrolactone, epsilon-caprolactone, methyl-epsilon-caprolactone, and the like; the low molecular weight polyol of di-or higher functionality is used as the polyol raw material for preparing the polyester polyol as described above. It is preferable to prepare a linear polyester polyol by ring-opening reaction of epsilon-caprolactone with one or more of 1, 4-butanediol, 1, 6-hexanediol and 2, 2-dimethyl-1, 3-propanediol as a polyol.

The polyester polyol may also be a polycarbonate having hydroxyl groups prepared by using a diol and a carbonate, as component a). The diol may be 1, 4-butanediol or 1, 6-hexanediol, and the carbonate may be diaryl carbonate or dialkyl carbonate. The diaryl carbonate may be diphenyl carbonate and the dialkyl carbonate may be dimethyl carbonate. The polycarbonates are preferably prepared by reacting 1, 6-hexanediol with dimethyl carbonate.

In accordance with the aqueous dispersions provided herein, in some examples, component b) is a diisocyanate and/or a polyisocyanate.

In some examples, the polyisocyanate is selected from one or more of aliphatic polyisocyanates, cycloaliphatic polyisocyanates, and aromatic polyisocyanates.

In the present invention, the diisocyanate has the general structural formula, for example, Y (NCO)₂In the formula, Y represents a divalent aliphatic hydrocarbon group of C4-C12, a divalent alicyclic hydrocarbon group of C6-C15, a divalent aromatic hydrocarbon group of C6-C15 or a divalent araliphatic hydrocarbon group of C7-C15. In some examples, the diisocyanate is selected from one or more of aliphatic diisocyanates, cycloaliphatic diisocyanates and aromatic diisocyanates, preferably from aliphatic diisocyanates and/or cycloaliphatic diisocyanates.

In some preferred embodiments, the diisocyanate is selected from one or more of tetramethylene diisocyanate, pentamethylene 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, and p-xylylene diisocyanate.

In some preferred embodiments, component b) is a mixture of hexamethylene diisocyanate and 1, 4-cyclohexane diisocyanate, a mixture of hexamethylene diisocyanate and isophorone diisocyanate, a mixture of hexamethylene diisocyanate and 4,4' -dicyclohexylmethane diisocyanate or a mixture of hexamethylene diisocyanate and 4,4' -dicyclohexylpropane diisocyanate, more preferably a mixture of hexamethylene diisocyanate and 1, 4-cyclohexane diisocyanate, a mixture of hexamethylene diisocyanate and isophorone diisocyanate or a mixture of hexamethylene diisocyanate and 4,4' -dicyclohexylmethane diisocyanate.

In some preferred embodiments, the hexamethylene diisocyanate in component b) comprises 50 to 100 wt% (e.g., 60 wt%, 80 wt%, 95 wt%), more preferably 70 to 100 wt%, of the total weight of component b).

In some examples, component c) is a monofunctional polyethoxy ether having a number average molecular weight of 200-; the number of ethylene oxide contained in each molecule is 4 to 200 (for example, the number of ethylene oxide contained in each molecule of monofunctional polyethoxy ether is 10, 20, 50, 100, 150), preferably 12 to 75.

Examples of initiators for making the monofunctional polyethoxy ether include, but are not limited to, saturated monoalcohols (e.g., methanol, ethanol, N-propanol, isopropanol, N-butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols, nonanols, N-decanol, N-dodecanol, N-tetradecanol, N-hexadecanol, cyclohexanol, hydroxymethylcyclohexane, or 3-ethyl-3-hydroxymethyloxoheterocycle), unsaturated alcohols (e.g., allyl alcohol, 1-dimethyl-allyl alcohol, or oleyl alcohol), aromatic alcohols (e.g., phenol, the isomeric cresols, the isomeric hydroxymethylphenol), araliphatic alcohols (e.g., benzyl alcohol, anisyl alcohol, or cinnamyl alcohol), secondary monoamines (e.g., dimethylamine, diethylamine, dipropylamine, diisopropylamine, di-N-butylamine, diisobutylamine, bis (2-ethylhexyl) -amine, N-methylcyclohexylamine, N-methyl cyclohexylamine, N-butanol, and N-butanol, N-ethylcyclohexylamine or dicyclohexylamine), heterocyclic secondary amines (e.g., morpholine, pyrrolidine, piperidineethylpyrazole); preferred starters are saturated monoalcohols having up to 4 carbon atoms, more preferably methanol as starter. The polymerized units of the monofunctional polyethoxy ether (or polyoxyalkylene ether) may be, for example, propylene oxide and/or ethylene oxide, preferably ethylene oxide. Wherein, the number of the ethylene oxide contained in each molecule of the monofunctional polyethoxy ether is 4-200, and preferably 12-75.

In some preferred embodiments, component c) is selected from polyethylene glycol monomethyl ethers having a number average molecular weight of 500 to 3000 and an ethylene oxide number of 12 to 75.

According to the aqueous dispersions provided by the present invention, in some examples, component d) is selected from one or more of hydrophilic compounds containing ionic groups and containing 2 to 3 NCO-reactive functional groups, hydrophilic compounds containing potentially ionic groups and containing 2 to 3 NCO-reactive functional groups, and hydrophilic compounds containing nonionic groups and containing 2 to 3 NCO-reactive functional groups.

In some preferred embodiments, the hydrophilic compound containing a potentially ionic group and 2-3 NCO-reactive functional groups is selected from one or more of dimethylolpropionic acid, dimethylolbutyric acid, dimethylolacetic acid, dihydroxysuccinic acid, N- (2-aminoethyl) -2-aminoethanesulfonic acid, N- (3-aminopropyl) -3-aminopropanesulfonic acid and N- (2-aminoethyl) -3-aminopropanesulfonic acid.

The hydrophilic compound containing an ionic group and containing 2 to 3 NCO-reactive functional groups may be a salt corresponding to the hydrophilic compound containing a potentially ionic group and containing 2 to 3 NCO-reactive functional groups. These salts may be alkali metal, alkaline earth metal or ammonium salts thereof. In some preferred embodiments, the hydrophilic compound containing an ionic group and 2-3 NCO-reactive functional groups is selected from one or more of dimethylolpropionate, dimethylolbutyrate, dimethylolacetate, dihydroxysuccinate, N- (2-aminoethyl) -2-aminoethanesulfonate, N- (3-aminopropyl) -3-aminopropanesulfonate and N- (2-aminoethyl) -3-aminopropanesulfonate; more preferably selected from the group consisting of alkali metal salts of dimethylolpropionic acid, alkaline earth metal salts of dimethylolpropionic acid, ammonium salts of dimethylolpropionic acid, alkali metal salts of dimethylolbutyric acid, alkaline earth metal salts of dimethylolbutyric acid, ammonium salts of dimethylolbutyric acid, alkali metal salts of dimethylolacetic acid, alkaline earth metal salts of dimethylolacetic acid, ammonium salts of dimethylolacetic acid, alkali metal salts of dihydroxysuccinic acid, alkaline earth metal salts of dihydroxysuccinic acid, ammonium salts of dihydroxysuccinic acid, alkali metal salts of N- (2-aminoethyl) -2-aminoethanesulfonic acid, alkaline earth metal salts of N- (2-aminoethyl) -2-aminoethanesulfonic acid, ammonium salts of N- (2-aminoethyl) -2-aminoethanesulfonic acid, alkali metal salts of N- (3-aminopropyl) -2-aminoethanesulfonic acid, alkali metal salts of dimethylolpropionic acid, ammonium salts of dimethylolbutyric acid, alkali metal salts of dimethylolbutyric acid, salts of succinic acid, salts of dimethylolbutyric acid, salts of succinic acid, salts of esters, Alkaline earth metal salts of N- (3-aminopropyl) -2-aminoethanesulfonic acid, ammonium salts of N- (3-aminopropyl) -2-aminoethanesulfonic acid, alkali metal salts of N- (3-aminopropyl) -3-aminopropanesulfonic acid, alkaline earth metal salts of N- (3-aminopropyl) -3-aminopropanesulfonic acid, one or more of an ammonium salt of N- (3-aminopropyl) -3-aminopropanesulfonic acid, an alkali metal salt of N- (2-aminoethyl) -3-aminopropanesulfonic acid, an alkaline earth metal salt of N- (2-aminoethyl) -3-aminopropanesulfonic acid, and an ammonium salt of N- (2-aminoethyl) -3-aminopropanesulfonic acid.

In some preferred embodiments, the hydrophilic compound containing a nonionic group and 2 to 3 NCO-reactive functional groups is a polyoxyethylene ether (or polyethoxy ether); the number average molecular weight of the polyoxyethylene ether is 200-8000, and more preferably 500-3000; the number of ethylene oxide contained in each polyoxyethylene ether molecule is 4 to 200, and more preferably 12 to 75.

In some preferred embodiments, component d) is selected from one or more of sodium N- (2-aminoethyl) -2-aminoethane sulfonate, dimethylolpropionic acid, and polyoxyethylene ether.

According to the aqueous dispersion provided by the present invention, in some examples, component e) is a hydroxy fatty acid comprising one hydroxyl group and one carboxyl group and having a carbon number of 12 or more, preferably one or more selected from 12-hydroxystearic acid, 6-hydroxyoctadecanoic acid, 3-hydroxyoctadecanoic acid, castor oil, 2-hydroxydodecanoic acid, 2-hydroxytetradecanoic acid, 2-hydroxyhexadecanoic acid, and 2-hydroxystearic acid, and more preferably 12-hydroxystearic acid.

In some examples, the ratio of the total moles of NCO-reactive amino groups contained in component f) to the total moles of NCO groups contained in component b) is from 1:126 to 1:4 (e.g., 1:100, 1:60, 1:50, 1:25, 1:20, 1:15, 1:10, 1: 4.5).

In some examples, component f) has a number average molecular weight of 300 or less. In some preferred embodiments, component f) is selected from one or more of methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methyl-N-propylamine, diethyl (methyl) aminopropylamine, morpholine, piperidine, 2-amino-2-methyl-1-propanol and diethanolamine, more preferably from 2-amino-2-methyl-1-propanol and/or diethanolamine.

In accordance with the aqueous dispersions provided herein, in some examples, component g) has a number average molecular weight of 300 or less. In some examples, component g) is selected from one or more of ethylenediamine, hydroxyethylethylenediamine, 1, 3-propylenediamine, 1, 2-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, 1, 6-hexylenediamine, and isophoronediamine; preferably selected from ethylenediamine and/or isophoronediamine.

In some examples, the aqueous dispersions provided according to the present invention have a surface tension of 20 to 50dyne/cm (e.g., 22dyne/cm, 24dyne/cm, 28dyne/cm, 30dyne/cm, 35dyne/cm, 40dyne/cm, 48dyne/cm), preferably 25 to 45 dyne/cm.

In some examples, the aqueous dispersion has a solids content of 25 to 60 wt% (e.g., 28 wt%, 35 wt%, 45 wt%, 50 wt%), preferably 30 to 55 wt%.

In some examples, the aqueous dispersion has a pH of 4 to 11 (e.g., 6, 8, 9), preferably 5 to 10.

In some examples, the aqueous dispersion has an average particle size of 80 to 600nm (e.g., 100nm, 200nm, 300nm, 450nm, 550nm), preferably 150 to 400 nm.

The aqueous dispersion prepared by the invention adopts amorphous polyester polyol as a soft segment, so that the softness of resin in the aqueous dispersion can be ensured, and better hand feeling can be obtained. The long carbon chain hydroxyl fatty acid containing single hydroxyl can enable the molecular chain end of polyurethane or polyurethane urea to be linked with a long carbon chain tail, so that the surface tension of the polyurethane emulsion can be obviously reduced, and the adhesive force of the aqueous slurry on the nylon fabric with low surface tension is improved; in addition, carboxyl in long carbon chain hydroxyl fatty acid can improve the crosslinking action of polyurethane or polyurethane urea and a curing agent in the aqueous dispersion, and can further improve the adhesive force of the aqueous sizing agent on the nylon fabric. Meanwhile, the blocking effect of the micromolecule blocking agent containing single amino can effectively control the molecular weight of polyurethane or polyurethane urea within a reasonable range (for example, the theoretical design molecular weight is 30000-48000g/mol), and also can enhance the wettability of resin to a base material and promote the adhesive force.

In another aspect, there is provided a process for the preparation of an aqueous dispersion of a polyurethane or polyurethaneurea as described above, comprising the steps of:

1) under the protection of inert gas, mixing the component a), the component b), the component e) and the optional component c) with a solvent according to a ratio, and then carrying out polymerization reaction until the content of isocyanate in a reaction mixture of a system reaches or is slightly lower than a theoretical calculated value to obtain an isocyanate-terminated prepolymer I;

2) adding the solvent to dilute the prepolymer I of the isocyanate-terminated prepolymer and cooling the system, adding the component d), the component f) and optionally the component g) to perform chain extension reaction to obtain a prepolymer II of the isocyanate-terminated prepolymer; neutralizing the obtained isocyanate-terminated prepolymer II with a neutralizing agent, then adding water for dispersing or dispersing in water, optionally adding a component g) for further chain extension reaction for 5min after the dispersion is finished, and optionally partially or completely removing the solvent by a distillation mode during or after the dispersion to obtain the aqueous polyurethane or polyurethane-urea dispersion; wherein component d) is a hydrophilic compound containing a potentially ionic group and containing 2-3 NCO-reactive functional groups;

or, 1) under the protection of inert gas, mixing the component a), the component b), the component e) and the optional component c) with a solvent according to the proportion, and then carrying out polymerization reaction until the content of isocyanate in a reaction mixture of a system reaches or is slightly lower than a theoretical calculated value to obtain an isocyanate-terminated prepolymer I;

2) adding the solvent to dilute the prepolymer I of the isocyanate-terminated prepolymer and cooling the system, adding the component d), the component f) and optionally the component g) to perform chain extension reaction to obtain a prepolymer II of the isocyanate-terminated prepolymer; then adding water for dispersing or dispersing the polyurethane or polyurethane urea in water, and optionally adding a component g) for further chain extension reaction for 5min after the dispersion is finished to obtain the aqueous dispersion of polyurethane or polyurethane urea; wherein the component d) is a hydrophilic compound containing ionic or nonionic groups and containing 2 to 3 NCO-reactive functional groups.

In some examples, the method of preparing the aqueous dispersion of polyurethane or polyurethaneurea comprises the steps of:

2) mixing the prepolymer I of the obtained isocyanate-terminated prepolymer with the solvent, diluting, cooling the system, adding the component d), the component f) and optionally the component g) for chain extension reaction to obtain a prepolymer II of the isocyanate-terminated prepolymer; then adding water for dispersing or dispersing the polyurethane or polyurethane urea in water, and optionally adding a component g) for further chain extension reaction for 5min after the dispersion is finished to obtain the aqueous dispersion of polyurethane or polyurethane urea; wherein the component d) is a hydrophilic compound containing ionic or nonionic groups and containing 2 to 3 NCO-reactive functional groups.

According to the process for the preparation of the aqueous dispersions of polyurethanes or polyurethane-ureas provided by the invention, the system can, in some cases, be diluted by adding a solvent, the solvent being removed partly or completely by a distillation operation during or after the dispersion. For example, a water-miscible solvent inert to isocyanate groups may optionally be added for dilution during the reaction. Suitable solvents may be one or more of acetone, methyl isobutyl ketone, butanone, tetrahydrofuran, dioxane, acetonitrile, dipropylene glycol dimethyl ether and 1-methyl-2-pyrrolidone, preferably selected from acetone and/or butanone, more preferably acetone.

The solvent may be added not only at the beginning of the preparation but also during the polymerization, before or after the chain extension reaction.

According to the method for producing an aqueous dispersion of polyurethane or polyurethane-urea provided by the present invention, in some examples, in step 1), the solvent is added in an amount of 0.02 to 0.4 times, preferably 0.05 to 0.3 times the total solid fraction of the raw material components added in step 1).

According to the method for producing an aqueous dispersion of polyurethane or polyurethane-urea provided by the present invention, in some examples, in step 2), the solvent to be diluted is added in an amount of 0.6 to 3 times, preferably 0.8 to 2 times, the total solid fraction of the raw material components added in step 1) and step 2).

During the preparation of aqueous dispersions of polyurethanes or polyurethane-ureas, the degree of conversion is usually monitored by tracking the NCO content of the reaction mixture in the system. For this purpose, spectroscopic measurements (for example, determination of infrared or near-infrared spectra, refractive index) and chemopotentiometric titrations (for example, chemical titrations via removal of a sample) can be selected, preference being given to chemopotentiometric titrations.

Optionally, a catalyst may also be added during the preparation of the aqueous polyurethane or polyurethane-urea dispersion. Conventional catalysts may be those known to one of ordinary skill in the art for accelerating the reaction of-NCO with-OH. For example, one or more of triethylamine, 1, 4-diazabicyclo- [2,2,2] -octane, dibutyltin oxide, tin dioctoate, dibutyltin dilaurate, tin bis- (2-ethylhexanoate), bismuth neodecanoate, and bismuth 2-ethylhexanoate. The catalyst is preferably bismuth neodecanoate or bismuth 2-ethylhexanoate, more preferably bismuth neodecanoate.

According to the method for preparing an aqueous dispersion of polyurethane or polyurethane-urea provided by the present invention, in some examples, the process conditions of the polymerization reaction of step 1) include: the reaction temperature is 50-100 ℃, and preferably 70-80 ℃.

According to the preparation method of the aqueous dispersion of polyurethane or polyurethane-urea provided by the invention, in some examples, the temperature of the chain extension reaction in the step 2) is generally 10-100 ℃, and preferably 25-60 ℃.

In a further aspect, there is provided the use of an aqueous dispersion of a polyurethane or polyurethaneurea as described above or obtained by the preparation process as described above, on nylon fabric. The process of applying said aqueous polyurethane or polyurethane urea dispersion as an aqueous slurry to nylon fabrics is well known to the person skilled in the art and will not be described in detail here.

Compared with the prior art, the technical scheme of the invention has the following beneficial effects:

the polyurethane or polyurethane urea aqueous dispersion has lower surface tension, and can improve the adhesive force of aqueous slurry on nylon fabric with low surface tension; in addition, carboxyl in long carbon chain hydroxyl fatty acid can improve the crosslinking action of polyurethane or polyurethane urea and a curing agent in the aqueous dispersion, and can further improve the adhesive force of the aqueous sizing agent on the nylon fabric; meanwhile, the blocking effect of the small molecule blocking agent containing single amino ensures that the molecular weight of polyurethane or polyurethane urea is controlled, the wettability of resin to a base material can be enhanced, and the adhesive force is improved.

The polyurethane or polyurethane urea aqueous dispersion has excellent comprehensive performance, can meet the requirements of high adhesive force and high flexibility, and is safe and environment-friendly.

The preparation method of the polyurethane or polyurethane urea aqueous dispersion is simple and easy to realize; when the modified nylon is applied to nylon fabrics, good application performance can be obtained (for example, the adhesive force on the nylon fabrics is improved, and the requirements of adhesive force and flexibility are met).

Detailed Description

In order that the technical features and contents of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.

Information on the main raw materials used in the first and second examples and comparative examples

PNA2000, amorphous polyester diol, OH value 56mg KOH/g, nicotineak chemical industries, ltd;

PNA1000, amorphous polyester diol, OH value 112mg KOH/g, nicotineak chemical industries, ltd;

CMB54, amorphous polyester diol, OH 56mg KOH/g, taihua chemical industries, ltd;

WHP307, amorphous polyester diol, OH number 37.5mg KOH/g, Vanhua chemical group GmbH.

4, 4-dicyclohexylmethane diisocyanate, Vanhua chemical group, Inc.;

hexamethylene diisocyanate, Vanhua chemical group, Inc.

MPEG-1200 (monomethylpolyoxyethylene ether, Mn ═ 1200) available from korean agro chemical co;

MPEG-520 (monomethyl polyoxyethylene ether, Mn 520) available from Korea agricultural chemical Co., Ltd.

Sodium N- (2-aminoethyl) -2-aminoethane sulfonate (Vestamin A95, 50% aqueous solution by mass concentration), the industrial group won and created in Germany.

12-Hydroxystearic acid, Cia-chemical industries, Ltd.

AMP-95 (2-amino-2-methyl-1-propanol) at 95% concentration, Dow chemical;

diethanolamine, Yangzhitin-Pasteur Limited company.

Ethylenediamine, technical grade, winnings petrifaction-basf llc;

isophorone diamine, technical grade, Vanhua chemical group, Inc.;

hydroxyethylethylene diamine, technical grade, Wanhua chemical group, Inc.;

a801, thickener, Vanhua chemical group, Inc.;

u505, thickener, Vanhua chemical group, Inc.;

CX-100, aziridine curing agent, Disemann;

TPU adhesive tape: width 1cm, shanghai zeki industries, inc.

Second, main testing method

The prepared polyurethane or polyurethane urea aqueous dispersion is used for coating and preparing a fabric coating on a fabric, and the construction process comprises the following steps: preparing aqueous slurry according to the construction formula shown in table 1, and then coating on the fabric; coating the 20D nylon yarn fabric with a circular knife to obtain water-based slurry, and drying at 160 deg.C for 1min, wherein the coating amount is 2-8g/m²。

And taking out the 20D nylon yarn fabric coated with the water-based slurry in a scraping manner, cooling, performing performance test and subsequently attaching a seal strip on the fabric, wherein the attached seal strip is a TPU adhesive tape, hot-pressing the TPU adhesive tape at 120 ℃ for 30s, and cooling to test an obtained strip sample.

1. And (3) testing the adhesive force: the bonding fastness of the to-be-tested bonding strip sample prepared according to the construction process is tested by using a tensile machine (GS-2000-D, high-speed rail detection instrument (Dongguan) Co., Ltd.); the test results are presented by data on the strip strength (in N/mm).

2. Flexibility test: drying the 20D nylon yarn fabric coated with the water-based slurry in a scraping manner, and then kneading by hand to judge the softness; grading is carried out according to 1-5 points, 5 points represent the best, and 0 point represents the worst.

3. And (3) testing the anti-adhesion property: drying the 20D nylon yarn fabric coated with the water-based slurry in a scraping manner, and then carrying out hot pressing on the fabric for 24 hours at the temperature of 80 ℃ by using a 5kg weight to judge whether the fabric is bonded; grading is carried out according to 1-5 points, 5 points represent the best, and 0 point represents the worst.

4. And (3) testing washing fastness: and (3) drying the 20D nylon yarn fabric coated with the water-based slurry in a scraping manner, washing the dried fabric for 1 hour at 40 ℃ by a washing machine, drying the fabric into a cycle, and judging whether the fabric is bonded or not and whether the fabric falls off or not by the cycle.

TABLE 1 construction formulation for aqueous sizing used in preparing fabrics

In the formulations of Table 1, the amounts of the components are based on 100% by weight of the aqueous polyurethane or polyurethane urea dispersion.

Example 1

1) Adding 210g of dehydrated PNA2000, 84g of CMB54, 5.88g of MPEG-1200, 10g of 12-hydroxystearic acid, 0.1g of bismuth neodecanoate, 47.6g of hexamethylene diisocyanate and 35.7g of acetone into a 1L four-neck round-bottom flask with a nitrogen inlet and outlet, stirring at 70-80 ℃ for reaction, and stopping the reaction until the NCO content in the reaction system reaches 2.50 wt% to obtain isocyanate-terminated prepolymer I;

2) adding 528g of acetone into the system for dilution, reducing the temperature, keeping the temperature of the system at 43-50 ℃, adding 4.9g A95, 13.5g of isophorone diamine and 1.4g of AMP-95 for chain extension reaction for 15min, and obtaining an isocyanate-terminated prepolymer II; then 625g of water is added under high-speed stirring to disperse the obtained reaction product, and 0.8g of ethylenediamine is added after the dispersion is finished and the stirring is continued for 5 min. After separation of the acetone again by distillation, a solvent-free aqueous polyurethane or polyurethane urea dispersion is obtained with a theoretical design molecular weight of 35722g/mol, a solids content of 40% by weight, an average particle diameter of 218nm, a pH of 8.2 and a surface tension of 30 dyne/cm.

Example 2

1) Adding 210g of dehydrated PNA2000, 84g of CMB54, 5.88g of MPEG-1200, 1.9g of 2-hydroxystearic acid, 0.1g of bismuth neodecanoate, 47.6g of hexamethylene diisocyanate and 137.4g of acetone into a 1L four-neck round-bottom flask with a nitrogen inlet and outlet, stirring at 70-80 ℃ for reaction, and stopping the reaction until the NCO content in the reaction system reaches 2.33 wt% to obtain isocyanate-terminated prepolymer I;

2) adding 1122g of acetone into the system for dilution, cooling, keeping the temperature of the system at 43-50 ℃, adding 19g A95 and 11.5g of AMP-95 for chain extension reaction for 15min, and obtaining an isocyanate-terminated prepolymer II; the resulting reaction product was then dispersed by the addition of 625g of water under high speed stirring. After separation of the acetone again by distillation, a solvent-free aqueous polyurethane or polyurethane urea dispersion is obtained with a theoretical design molecular weight of 41120g/mol, a solids content of 40% by weight, an average particle diameter of 157nm, a pH of 8.0 and a surface tension of 50 dyne/cm.

Example 3

1) Adding 210g of dehydrated PNA2000, 84g of CMB54, 20g of MPEG-1200, 20g of 12-hydroxystearic acid, 0.1g of bismuth neodecanoate, 47.6g of hexamethylene diisocyanate and 7.6g of acetone into a 1L four-neck round-bottom flask with a nitrogen inlet and outlet, stirring at 70-80 ℃ for reaction, and stopping the reaction until the NCO content in the reaction system reaches 2.04 wt% to obtain isocyanate-terminated prepolymer I;

2) adding 236.4g of acetone into the system for dilution, reducing the temperature, keeping the temperature of the system at 43-50 ℃, adding 2g A95, 10g of isophorone diamine and 0.4g of AMP-95 for chain extension reaction for 15min, and obtaining an isocyanate-terminated prepolymer II; the resulting reaction product was then dispersed by the addition of 625g of water under high speed stirring. After separation of the acetone again by distillation, a solvent-free aqueous polyurethane or polyurethane urea dispersion is obtained, having a theoretical design molecular weight of 33618g/mol, a solids content of 40% by weight, an average particle diameter of 251nm, a pH value of 8.0 and a surface tension of 20 dyne/cm.

Example 4

1) Adding 125g of dehydrated PNA2000, 6g of MPEG-520, 8g of 12-hydroxystearic acid, 0.05g of bismuth neodecanoate, 40g of hexamethylene diisocyanate and 17.9g of acetone into a 1L four-neck round-bottom flask with a nitrogen inlet and outlet, stirring at 70-80 ℃ for reaction, and stopping the reaction until the NCO content in the reaction system reaches 6.68 wt% to obtain isocyanate-terminated prepolymer I;

2) adding 289.7g of acetone into the system for dilution, cooling, keeping the temperature of the system at 43-50 ℃, adding 10g A95, 16.5g of isophorone diamine and 2g of diethanol amine for chain extension reaction for 15min, and obtaining a prepolymer II of the isocyanate end; the resulting reaction product was then dispersed by adding 450g of water under high speed stirring. After separation of the acetone again by distillation, a solvent-free aqueous dispersion of polyurethane or polyurethane urea is obtained, having a theoretical design molecular weight of 37800g/mol, a solids content of 40% by weight, an average particle diameter of 189nm, a pH of 8.0 and a surface tension of 35 dyne/cm.

Example 5

1) 590g of dehydrated WHP307, 5.88g of MPEG-1200, 5g of 12-hydroxystearic acid, 0.19g of bismuth neodecanoate, 45g of hexamethylene diisocyanate and 64.6g of acetone are added into a 1L four-mouth round-bottom flask with a nitrogen inlet and outlet, and stirred at 70-80 ℃ for reaction, and the reaction is terminated until the NCO content in the reaction system reaches 0.71 wt%, so as to obtain isocyanate-terminated prepolymer I;

2) adding 913.2g of acetone into the system for dilution, cooling, keeping the temperature of the system at 43-50 ℃, adding 5g A95 and 1.4g of AMP-95 for chain extension reaction for 15min to obtain an isocyanate-terminated prepolymer II; the resulting reaction product was then dispersed by adding 1064g of water with high speed stirring. After separation of the acetone again by distillation, a solvent-free aqueous polyurethane or polyurethane urea dispersion is obtained, with a theoretical design molecular weight of 45217g/mol, with a solids content of 40% by weight, an average particle diameter of 390nm and a pH of 8.0. The surface tension was 39 dyne/cm.

Example 6

1) Adding 50g of dehydrated PNA1000, 110g of CMB54, 6g of MPEG-1200, 10g of 12-hydroxystearic acid, 0.07g of bismuth neodecanoate, 40g of hexamethylene diisocyanate, 25g of 4, 4-dicyclohexylmethane diisocyanate and 24.1g of acetone into a 1L four-neck round-bottom flask with a nitrogen inlet and a nitrogen outlet, stirring at 70-80 ℃ for reaction, and stopping the reaction until the NCO content in the reaction system reaches 6.63 wt% to obtain isocyanate-terminated prepolymer I;

2) adding 363.2g of acetone into the system for dilution, cooling, keeping the temperature of the system at 43-50 ℃, adding 5g A95 g, 12g of hydroxyethyl ethylenediamine and 1.4g of AMP-95 for chain extension reaction for 15min to obtain an isocyanate-terminated prepolymer II; then 426g of water is added under high-speed stirring to disperse the obtained reaction product, and 2g of ethylenediamine is added after the dispersion is finished to continue stirring for 5 min. After separation of the acetone again by distillation, a solvent-free aqueous polyurethane or polyurethane urea dispersion is obtained with a theoretical design molecular weight of 34550g/mol, a solids content of 40% by weight, an average particle diameter of 185nm, a pH of 8.0 and a surface tension of 43 dyne/cm.

Comparative example 1

1) Adding 210g of dehydrated PNA2000, 84g of CMB54, 5.88g of polyethylene glycol monomethyl ether, 0.1g of bismuth neodecanoate, 47.6g of hexamethylene diisocyanate and 35.7g of acetone into a 1L four-mouth round-bottom flask with a nitrogen inlet and outlet, stirring at 70-80 ℃ for reaction, and stopping the reaction until the NCO content in the reaction system reaches 2.94 wt% to obtain isocyanate-terminated prepolymer I;

2) adding 514g of acetone into the system for dilution, reducing the temperature, keeping the temperature of the system at 43-50 ℃, adding 4.9g A95, 13.5g of isophorone diamine and 1.4g of AMP-95 for chain extension reaction for 15min, and obtaining an isocyanate-terminated prepolymer II; then 625g of water is added under high-speed stirring to disperse the obtained reaction product, and 0.8g of ethylenediamine is added after the dispersion is finished and the stirring is continued for 5 min. After separation of the acetone again by distillation, a solvent-free aqueous polyurethane or polyurethane urea dispersion is obtained, with a theoretical design molecular weight of 42081g/mol, a solids content of 40% by weight, an average particle diameter of 213nm, a pH of 8.0 and a surface tension of 55 dyne/cm.

Comparative example 2

1) Adding 210g of dehydrated PNA2000, 84g of CMB54, 5.88g of polyethylene glycol monomethyl ether, 10g of 12-hydroxystearic acid, 0.1g of bismuth neodecanoate, 47.6g of hexamethylene diisocyanate and 35.7g of acetone into a 1L four-neck round-bottom flask with a nitrogen inlet and outlet, stirring at 70-80 ℃ for reaction, and stopping the reaction until the NCO content in the reaction system reaches 2.50 wt% to obtain an isocyanate-terminated prepolymer I;

2) adding 526g of acetone into the system for dilution, reducing the temperature, keeping the temperature of the system at 43-50 ℃, adding 4.9g A95 and 13.5g of isophorone diamine for chain extension reaction for 15min, and obtaining an isocyanate-terminated prepolymer II; then 625g of water is added under high-speed stirring to disperse the obtained reaction product, and 0.8g of ethylenediamine is added after the dispersion is finished and the stirring is continued for 5 min. After separation of the acetone again by distillation, a solvent-free aqueous polyurethane or polyurethane urea dispersion is obtained with a theoretical design molecular weight of 57780g/mol, a solids content of 40% by weight, an average particle diameter of 195nm, a pH value of 8.0 and a surface tension of 45 dyne/cm.

Comparative example 3

1) Adding 150g of dehydrated PNA2000, 84g of CMB54, 5.88g of polyethylene glycol monomethyl ether, 30g of 12-hydroxystearic acid, 0.1g of bismuth neodecanoate, 53g of HDI and 32.3g of acetone into a 1L four-neck round-bottom flask with a nitrogen inlet and outlet, stirring at 70-80 ℃ for reaction, and stopping the reaction until the NCO content in the reaction system reaches 3.46 wt% to obtain isocyanate-terminated prepolymer I;

2) adding 480g of acetone into the system for dilution, cooling, keeping the temperature of the system at 43-50 ℃, adding 3g A95 and 17g of AMP-95 for chain extension reaction for 15min, and obtaining an isocyanate-terminated prepolymer II; then 575g of water is added under high-speed stirring to disperse the obtained reaction product, and 1g of ethylenediamine is added after the dispersion is finished to continue stirring for 5 min. Finally, storage-stable polyurethane emulsions are not obtained.

The aqueous dispersion emulsions prepared in each example and comparative example were used to prepare coatings for use on fabrics according to the aqueous slurry formulations provided in table 1 and tested for performance. The results of the performance tests obtained are shown in table 2.

Table 2 performance test results for fabric coatings

Backup note: in the scoring criteria, 5 was the best and 0 was the worst.

As can be seen from the test results of table 1:

compared with the examples 1 to 6 of the invention, the aqueous dispersion of polyurethane or polyurethane urea obtained in comparative example 1 has higher surface tension because the component e) is not added, so that the strength of the strip is lower, and the strip falls off after washing; in comparative example 2, since component f) was not added, although the surface tension of the resulting aqueous dispersion of polyurethane or polyurethane urea was not increased, the molecular weight of the aqueous dispersion was increased because no molecular capping was carried out with component f), so that the strip strength was also low, washing-off occurred, and the anti-sticking hand was poor; in comparative example 3, a stable aqueous polyurethane emulsion could not be obtained due to the addition of excessive amounts of component e) and component f); it is stated that not only the selection of the raw material components used is required to achieve a product having both high adhesion and high flexibility, but also the amounts of component e) and component f) are controlled within a reasonable range, not the more the better.

In conclusion, the aqueous sizing agent prepared from the aqueous polyurethane emulsion prepared by the invention and used for the surface of the nylon fabric has higher adhesive strength and flexibility, can realize both high adhesive force and high flexibility, and can keep good washing fastness and anti-sticking hand feeling.

Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims

1. An aqueous dispersion of a polyurethane or polyurethaneurea, wherein the polyurethane or polyurethaneurea in the aqueous dispersion is a reaction product prepared from raw materials comprising:

a) polyol with Mn more than or equal to 1000g/mol and functionality of 2-4,

b) an isocyanate having at least two isocyanate groups,

e) a long carbon chain hydroxy fatty acid which is a hydroxy fatty acid containing one hydroxyl group and one carboxyl group and has a carbon number of more than or equal to 12,

f) a small molecule end capping agent containing a single amino group, the number average molecular weight of which is less than or equal to 300;

optionally, g) low-molecular compounds containing 2 and more NCO-reactive amino groups and having a number-average molecular weight of 300 or less; the NCO-reactive functional group is selected from one or more of a hydroxyl group, a primary amino group and a secondary amino group;

the NCO-reactive amino group is a primary amino group and/or a secondary amino group;

wherein the total amount of polyurethane or polyurethane urea in the aqueous dispersion is 100 parts by weight, and the use amount of each component is as follows:

component a) is 60 to 90 parts by weight;

the component b) is 7 to 25 weight parts;

the component c) is 0 to 5 weight parts;

0.5 to 5 parts by weight of component d);

0.5 to 5 parts by weight of component e);

0.1 to 3 parts by weight of component f);

the component g) is 0 to 8 weight parts.

2. The aqueous dispersion according to claim 1, wherein the following components are used, based on 100 parts by weight of the total amount of polyurethane or polyurethane urea in the aqueous dispersion:

the component a) accounts for 70 to 85 weight parts;

10-20 parts by weight of component b);

0.5 to 3 parts by weight of component c);

0.5 to 3 parts by weight of component d);

the component e) is 1 to 5 weight parts;

the component f) is 0.1 to 1 weight part;

the component g) is 1 to 5 weight portions.

3. The aqueous dispersion according to claim 1 or 2, characterized in that component a) is selected from one or more of the group consisting of amorphous polyester polyols having a Mn of 1000-; and/or

The component c) is monofunctional polyethoxy ether with a number average molecular weight of 200-8000; the number of ethylene oxide contained in each molecule is 4-200.

4. The aqueous dispersion according to claim 3, wherein component a) is selected from one or more of the group consisting of amorphous polyester polyols having a Mn of 1000 and 5000g/mol and a functionality of 2 to 4; and/or

Component c) is a monofunctional polyethoxy ether having a number average molecular weight of 500-3000; the number of ethylene oxide contained in each molecule is 12-75.

5. The aqueous dispersion according to claim 4, wherein component a) is selected from one or more of the group consisting of amorphous polyester diols having Mn of 1000 and 5000 g/mol; and/or

The component c) is selected from polyethylene glycol monomethyl ether with the number average molecular weight of 500-3000 and the number of ethylene oxide of 12-75.

6. Aqueous dispersion according to any of claims 1 to 2,4 to 5, characterised in that component b) is a diisocyanate and/or a polyisocyanate.

7. The aqueous dispersion according to claim 6, wherein the polyisocyanate is selected from one or more of aliphatic polyisocyanates, cycloaliphatic polyisocyanates and aromatic polyisocyanates;

the diisocyanate is selected from one or more of aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate.

8. The aqueous dispersion according to claim 7, wherein the diisocyanate is selected from the group consisting of aliphatic diisocyanates and/or cycloaliphatic diisocyanates.

9. The aqueous dispersion according to claim 7, wherein the diisocyanate is selected from one or more of the group consisting of tetramethylene diisocyanate, pentamethylene 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 and p-xylylene diisocyanate.

10. The aqueous dispersion according to claim 6, wherein component b) is a mixture of hexamethylene diisocyanate and 1, 4-cyclohexane diisocyanate, a mixture of hexamethylene diisocyanate and isophorone diisocyanate, a mixture of hexamethylene diisocyanate and 4,4 '-dicyclohexylmethane diisocyanate or a mixture of hexamethylene diisocyanate and 4,4' -dicyclohexylpropane diisocyanate.

11. The aqueous dispersion according to claim 10, wherein component b) is a mixture of hexamethylene diisocyanate and 1, 4-cyclohexane diisocyanate, a mixture of hexamethylene diisocyanate and isophorone diisocyanate or a mixture of hexamethylene diisocyanate and 4,4' -dicyclohexylmethane diisocyanate.

12. The aqueous dispersion according to claim 10, wherein the hexamethylene diisocyanate in component b) comprises 50 to 100% by weight of the total weight of component b).

13. The aqueous dispersion according to claim 12, wherein the hexamethylene diisocyanate in component b) comprises 70 to 100% by weight of the total weight of component b).

14. Aqueous dispersion according to any of claims 1 to 2,4 to 5, 7 to 13, characterised in that component d) is selected from one or more of hydrophilic compounds containing ionic groups and containing 2 to 3 NCO-reactive functional groups, hydrophilic compounds containing potentially ionic groups and containing 2 to 3 NCO-reactive functional groups and hydrophilic compounds containing non-ionic groups and containing 2 to 3 NCO-reactive functional groups.

15. The aqueous dispersion according to claim 14, characterised in that the hydrophilic compounds containing potentially ionic groups and containing 2 to 3 NCO-reactive functional groups are selected from one or more of dimethylolpropionic acid, dimethylolbutyric acid, dimethylolacetic acid, dihydroxysuccinic acid, N- (2-aminoethyl) -2-aminoethanesulfonic acid, N- (3-aminopropyl) -3-aminopropanesulphonic acid and N- (2-aminoethyl) -3-aminopropanesulphonic acid;

the hydrophilic compound containing ionic groups and 2-3 NCO reactive functional groups is selected from one or more of dimethylolpropionate, dimethylolbutyrate, dimethylolacetate, dihydroxysuccinate, N- (2-aminoethyl) -2-aminoethanesulfonate, N- (3-aminopropyl) -3-aminopropanesulfonate and N- (2-aminoethyl) -3-aminopropanesulfonate;

the hydrophilic compound containing nonionic groups and 2-3 NCO reactive functional groups is polyoxyethylene ether; the number average molecular weight of the polyoxyethylene ether is 200-8000; the number of ethylene oxide contained in each polyoxyethylene ether molecule is 4-200.

16. Aqueous dispersion according to claim 15, characterised in that the hydrophilic compounds containing ionic groups and containing 2 to 3 NCO-reactive functional groups are selected from the group consisting of alkali metal salts of dimethylolpropionic acid, alkaline earth metal salts of dimethylolpropionic acid, ammonium salts of dimethylolpropionic acid, alkali metal salts of dimethylolbutyric acid, alkaline earth metal salts of dimethylolbutyric acid, ammonium salts of dimethylolbutyric acid, alkali metal salts of dimethylolacetic acid, alkaline earth metal salts of dimethylolacetic acid, ammonium salts of dimethylolacetic acid, alkali metal salts of dihydroxysuccinic acid, alkaline earth metal salts of dihydroxysuccinic acid, ammonium salts of dihydroxysuccinic acid, alkali metal salts of N- (2-aminoethyl) -2-aminoethanesulfonic acid, alkaline earth metal salts of N- (2-aminoethyl) -2-aminoethanesulfonic acid, salts of N- (2-aminoethanesulfonic acid, salts of L-butyric acid, salts of L-esters of L-carboxylic acid, L-carboxylic acid L-, Ammonium salt of N- (2-aminoethyl) -2-aminoethanesulfonic acid, alkali metal salt of N- (3-aminopropyl) -2-aminoethanesulfonic acid, alkaline earth metal salt of N- (3-aminopropyl) -2-aminoethanesulfonic acid, ammonium salt of N- (3-aminopropyl) -2-aminoethanesulfonic acid, alkali metal salt of N- (3-aminopropyl) -3-aminopropanesulfonic acid, alkaline earth metal salt of N- (3-aminopropyl) -3-aminopropanesulfonic acid, ammonium salt of N- (3-aminopropyl) -3-aminopropanesulfonic acid, alkali metal salt of N- (2-aminoethyl) -3-aminopropanesulfonic acid, alkaline earth metal salt of N- (2-aminoethyl) -3-aminopropanesulfonic acid and N- (2-aminopropyl) -2-aminoethanesulfonic acid -one or more of the ammonium salts of aminoethyl) -3-aminopropanesulfonic acid;

the hydrophilic compound containing nonionic groups and 2-3 NCO reactive functional groups is polyoxyethylene ether; the number average molecular weight of the polyoxyethylene ether is 500-3000; the number of ethylene oxide contained in each polyoxyethylene ether molecule is 12-75.

17. The aqueous dispersion according to claim 14, wherein component d) is selected from one or more of the group consisting of sodium N- (2-aminoethyl) -2-aminoethane sulfonate, dimethylolpropionic acid and polyoxyethylene ether.

18. An aqueous dispersion according to any of claims 1 to 2,4 to 5, 7 to 13, 15 to 17, characterised in that component e) is selected from one or more of 12-hydroxystearic acid, 6-hydroxyoctadecanoic acid, 3-hydroxyoctadecanoic acid, 2-hydroxydodecanoic acid, 2-hydroxytetradecanoic acid, 2-hydroxyhexadecanoic acid and 2-hydroxystearic acid.

19. The aqueous dispersion of claim 18, wherein component e) is 12-hydroxystearic acid.

20. The aqueous dispersion according to any of claims 1 to 2,4 to 5, 7 to 13, 15 to 17 and 19, wherein the ratio of the total number of moles of NCO-reactive amino groups contained in component f) to the total number of moles of NCO groups contained in component b) is from 1:126 to 1:4.

21. The aqueous dispersion according to any of claims 1-2, 4-5, 7-13, 15-17, 19, wherein component f) is selected from one or more of methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methyl-N-propylamine, diethyl (methyl) aminopropylamine, morpholine, piperidine, 2-amino-2-methyl-1-propanol and diethanolamine.

22. The aqueous dispersion according to claim 21, wherein component f) is selected from 2-amino-2-methyl-1-propanol and/or diethanolamine.

23. An aqueous dispersion according to any of claims 1-2, 4-5, 7-13, 15-17, 19, 22, characterised in that component g) is selected from one or more of ethylenediamine, hydroxyethylethylenediamine, 1, 3-propylenediamine, 1, 2-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, 1, 6-hexylenediamine and isophoronediamine.

24. The aqueous dispersion according to claim 23, wherein component g) is selected from ethylenediamine and/or isophoronediamine.

25. The aqueous dispersion according to any of claims 1-2, 4-5, 7-13, 15-17, 19, 22, 24, wherein the aqueous dispersion has a surface tension of 20-50 dyne/cm;

the solids content of the aqueous dispersion is 25 to 60 wt%;

the pH value of the aqueous dispersion is 4-11;

the average particle size of the aqueous dispersion is 80-600 nm.

26. The aqueous dispersion of claim 25, wherein the aqueous dispersion has a surface tension of 25 to 45 dyne/cm;

the solids content of the aqueous dispersion is 30 to 55 wt%;

the pH value of the aqueous dispersion is 5-10;

the average particle size of the aqueous dispersion is 150-400 nm.

27. A process for the preparation of an aqueous dispersion of a polyurethane or polyurethaneurea according to any one of claims 1 to 26, comprising the steps of:

2) adding the solvent to dilute the prepolymer I of the isocyanate-terminated prepolymer and cooling the system, adding the component d), the component f) and optionally the component g) to perform chain extension reaction to obtain a prepolymer II of the isocyanate-terminated prepolymer; neutralizing the obtained isocyanate-terminated prepolymer II with a neutralizing agent, then adding water for dispersing or dispersing the isocyanate-terminated prepolymer II in the water, and optionally adding a component g) for further chain extension reaction for 5min after the dispersion is finished to obtain the aqueous dispersion of polyurethane or polyurethane urea; wherein component d) is a hydrophilic compound containing a potentially ionic group and containing 2-3 NCO-reactive functional groups;

28. The method of preparing an aqueous dispersion of a polyurethane or polyurethane urea of claim 27, wherein the solvent is selected from one or more of acetone, methyl isobutyl ketone, butanone, tetrahydrofuran, dioxane, acetonitrile, dipropylene glycol dimethyl ether, and 1-methyl-2-pyrrolidone;

in the step 1), the adding amount of the solvent is 0.02-0.4 time of the total solid parts of the raw material components added in the step 1);

in the step 2), the adding amount of the solvent for dilution is 0.6-3 times of the total solid parts of the raw material components added in the step 1) and the step 2).

29. The process for the preparation of an aqueous dispersion of a polyurethane or polyurethane urea according to claim 28, characterised in that the solvent is selected from acetone and/or butanone;

in the step 1), the adding amount of the solvent is 0.05 to 0.3 time of the total solid part of the raw material components added in the step 1);

in the step 2), the adding amount of the solvent for dilution is 0.8-2 times of the total solid parts of the raw material components added in the step 1) and the step 2).

30. The method of preparing an aqueous dispersion of a polyurethane or polyurethaneurea as claimed in claim 29, wherein the solvent is acetone.

31. Use of an aqueous dispersion of a polyurethane or polyurethaneurea according to any one of claims 1 to 26 or of a polyurethane or polyurethaneurea obtained by the process according to any one of claims 27 to 30 for nylon fabrics.