CN109679056B

CN109679056B - Self-crosslinking polyurethane-polyurea water dispersion and preparation method and application thereof

Info

Publication number: CN109679056B
Application number: CN201811353949.4A
Authority: CN
Inventors: 曹玉阳; 晋云全; 纪学顺; 李英卓; 刘云玲; 尹逊迪
Original assignee: Wanhua Chemical Group Co Ltd; Wanhua Chemical Ningbo Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd; Wanhua Chemical Ningbo Co Ltd
Priority date: 2018-11-14
Filing date: 2018-11-14
Publication date: 2021-06-25
Anticipated expiration: 2038-11-14
Also published as: CN109679056A

Abstract

The present invention provides an aqueous self-crosslinking polyurethane-polyurea dispersion prepared by a) at least one silicone component; b) at least one polyol having a functionality of 2 to 4 and a number average molecular weight of 500 to 5000 g/mole; c) one or more polyols having a number average molecular weight above 62 and less than 500 g/mole; d) at least one polyethoxy component having a number average molecular weight of from 500 g/mole to 10000 g/mole, which is different from component b) which is reactive toward isocyanates; e) at least one polyisocyanate component; f) monoamino compounds f1) and polyamino compounds f2) which are free of sulfonate and/or carboxylate groups and differ from component a), polyamino compounds f3) which carry sulfonate and/or carboxylate groups; g) one or more antioxidants are reacted and dispersed in water. The invention also relates to a method for producing said dispersions and to the use thereof.

Description

Self-crosslinking polyurethane-polyurea water dispersion and preparation method and application thereof

Technical Field

The invention relates to the technical field of chemical additives, in particular to a self-crosslinking polyurethane-polyurea aqueous dispersion, a preparation method thereof and application thereof in a glass fiber impregnating compound.

Background

The impregnating compound is an indispensable industrial consumable in glass fiber production, is the most key technology for embodying the inherent quality of glass fibers, can effectively improve the defects and surface properties of the glass fibers, improves the application range of the glass fibers, ensures the quality of the glass fibers and greatly depends on the impregnating compound, and cannot produce high-quality and various glass fiber products without good guarantee of the impregnating compound, so that the impregnating compound is the basis for developing and applying the glass fiber products.

The glass fiber impregnating compound generally comprises a film forming agent, a coupling agent, an antistatic agent and the like. The film forming agent is an important component in the impregnating compound, and the amount of the film forming agent in the impregnating compound is the largest. The film forming agent is used for bonding the glass fiber monofilaments into strands during drawing and winding, and plays roles in protecting the glass fibers and improving the properties of the glass fibers such as stiffness, chopping property, impregnation rate and the like in subsequent processing procedures.

The polyurethane-polyurea aqueous dispersion has excellent performance, high strength after film forming, good toughness and good elasticity, is applied to a glass fiber impregnating compound, has excellent bonding performance and film forming property compared with other types of resin, can effectively protect glass fiber, has strong polarity, can be well combined with most matrix resin, is assisted by an efficient coupling agent, can better solve the problem of interface combination, can meet most requirements of glass fiber production, and can be used as a main film forming agent of the glass fiber impregnating compound.

At present, the injection molding temperature of materials such as nylon 66 is above 280 ℃, and the prepared coating often generates yellowing in a long-time high-temperature environment, which is undesirable, and limits the application range and application efficiency of the glass fiber impregnating agent which takes polyurethane-polyurea water dispersion as a main film-forming agent.

The prior art discloses a variety of stabilizers and additives that reduce the thermal yellowing of film formers, which have limited use in aqueous systems.

US-a 5216078 discloses a stabilizer which significantly reduces the thermal yellowing of the product. However, this system is only suitable for solvent-containing systems and not for aqueous systems.

Disclosure of Invention

The object of the present invention is to provide a self-crosslinking polyurethane-polyurea dispersion. Compared with the prior art, the following properties are improved: the adhesive force is better; the high-temperature yellowing resistance of the adhesive film is improved, the adhesive film still has excellent high-temperature yellowing resistance under the condition of 280 ℃ for a long time, and the effect is more obvious by matching the composite antioxidant.

In order to achieve the above object, the present invention provides a high-solid content polyurethane-polyurea aqueous dispersion prepared by reacting and dispersing in water raw materials comprising:

a) at least one siloxane component which additionally has at least two amino groups or at least two hydroxyl groups or at least one amino group and one hydroxyl group and the silicon-bonded groups contain at least two methoxy and/or ethoxy groups;

b) at least one polyol having a functionality of 2 to 4 and a number average molecular weight of 500 to 5000 g/mole;

c) one or more polyols having a number average molecular weight above 62 and less than 500 g/mole;

d) at least one isocyanate-reactive, monofunctional polyethoxy component having a number average molecular weight of from 500 g/mole to 10000 g/mole;

e) at least one polyisocyanate component;

f) monoamino compounds f1) which differ from component a), and polyamino compounds f2) which are free of sulfonate and/or carboxylate groups, and polyamino compounds f3) which carry sulfonate and/or carboxylate groups, the amino groups being selected from primary and/or secondary amino groups;

g) one or more antioxidants.

Preferably, the component f3) carries sulfonate groups and represents less than 1% by weight of the solids of the aqueous polyurethane-polyurea dispersion, and the average amino functionality of the component f) is from 1.30 to 1.75 and the equivalent ratio between NCO groups in the NCO prepolymer and the total amount of isocyanate-reactive amino and hydroxyl groups of the component f) is from 0.70 to 0.95.

Preferably, the solid content of the polyurethane-polyurea water dispersion is 40-60 wt%, preferably 45-55 wt%; the amount of component a) used in the present invention is 0.02 to 5% by weight, preferably 0.02 to 2% by weight, based on the weight of the solid parts of the aqueous polyurethane-polyurea dispersion; the amount of the component b) is 20-90 wt%, preferably 50-80 wt%; the amount of the component c) is 0.1 to 10wt%, preferably 0.1 to 8 wt%; the amount of the component d) is 0.5 to 8wt%, preferably 2 to 4.5 wt%; the amount of the component e) is 5-40 wt%, preferably 12-33 wt%; the amount of f1) in the component mixed amine f) is 0.1-10 wt%, preferably 1-5.5 wt%, the amount of f2) is 1-10 wt%, preferably 2-9 wt%, and the amount of f3) is 0.1-1 wt%; the amount of component g) is 0.01 to 2 wt.%, preferably 0.3 to 1.2 wt.%.

The silicone component of component a) imparts to the polyurethane or polyurethane-urea side chains a siloxane group containing at least two NCO reactive functional groups selected from one or more of a hydroxyl group, a primary amino group, a secondary amino group. The component a) is preferably a siloxane having at least two primary and/or secondary amino groups. Suitable examples include, but are not limited to, N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, N- β - (aminoethyl) - γ -aminopropyltriethoxysilane, N- (β -aminoethyl) - γ -aminopropylmethyldimethoxysilane, 1, 3-bis (aminopropyl) tetramethyldisiloxane, and the like, more preferably N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, N- β - (aminoethyl) - γ -aminopropyltriethoxysilane, N- (β -aminoethyl) - γ -aminopropylmethyldimethoxysilane.

The component b) is one or more of dihydric alcohol, trihydric alcohol and tetrahydric alcohol with the number average molecular weight of 500-5000 g/mol; preferably, the functionality with the number average molecular weight of 1000-3000 g/mol is one or more of difunctional or higher functional polyether polyol, polyester polyol, polycarbonate polyol and polycaprolactone polyol.

Preferably, the polyester polyol is a linear polyester diol or a slightly branched polyester diol, for example obtainable by dehydration and condensation from a carboxylic acid and/or anhydride such as an aliphatic, alicyclic, aromatic dicarboxylic or polycarboxylic acid or the corresponding anhydride thereof and a polyhydric alcohol by known means, examples of said carboxylic acid or anhydride including, but not limited to, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, maleic acid, fumaric acid, malonic acid, trimellitic acid, phthalic anhydride, trimellitic anhydride, succinic anhydride or mixtures thereof; examples of such polyols include, but are not limited to, 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, 1, 4-dihydroxycyclohexane, 1, 4-dimethylolcyclohexane, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, or mixtures thereof. Preference is given to polyester polyols which contain isophthalic acid and/or terephthalic acid and/or adipic acid, and neopentyl glycol, ethylene glycol, butanediol and/or hexanediol as structural components.

Suitable polyester polyols are linear polyester diols or slightly branched polyester diols, such as may be obtained by dehydration and condensation from carboxylic acids and/or anhydrides such as aliphatic, cycloaliphatic, aromatic dicarboxylic or polycarboxylic acids or their corresponding anhydrides and the like and polyols 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, nonanedicarboxylic acid, decanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, maleic acid, fumaric acid, malonic acid, trimellitic acid, phthalic anhydride, trimellitic anhydride, succinic anhydride or mixtures thereof; examples of such polyols include, but are not limited to, 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, 1, 4-dihydroxycyclohexane, 1, 4-dimethylolcyclohexane, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, or mixtures thereof. Preference is given to polyester polyols which contain isophthalic acid and/or terephthalic acid and/or adipic acid, and neopentyl glycol, ethylene glycol, butanediol and/or hexanediol as structural components.

Component b) according to the invention is preferably a phthalic anhydride polyester polyol having a number average molecular weight of from 500 g/mol to 5000 g/mol; particularly preferred is a phthalic anhydride polyester polyol having a number average molecular weight of 500 g/mole to 5000 g/mole; the phthalic anhydride polyester polyol is a copolymer of phthalic anhydride and one or more of diethylene glycol and 1, 6-hexanediol neopentyl glycol.

The component c) is selected from 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, neopentyl glycol, 1, 4-dihydroxycyclohexane, 1, 4-dimethylolcyclohexane, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, neopentyl glycol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol and 2-ethyl-1.3-hexanediol; one or more of 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, and neopentyl glycol are preferred.

The component d) is a polyethoxy component which is reactive toward isocyanates and has a number average molecular weight of from 500 g/mol to 10000 g/mol, such as polyethoxy monoalkyl ethers, a polyfunctional polyether polyol, such as homopolymers, copolymers and graft products of styrene oxide, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin, dehydration condensation products of polyols or mixtures thereof, products obtained by alkoxylation of diols, diamines and monoalcohols, which is different from component b).

Preferably, the component d) is polyethoxy ether with the number average molecular weight of 500-8000 g/mol and the number of ethylene oxide groups of 4-200, more preferably polyethoxy ether with the number average molecular weight of 500-3000 g/mol and the number of ethylene oxide groups of 12-75.

The component e) is one or more of aromatic, aliphatic and cycloaliphatic polyisocyanates, preferably one or more of aromatic, aliphatic and cycloaliphatic polyisocyanates having at least two isocyanate groups.

Preferably, said component e) is a diisocyanate 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. Suitable diisocyanates may be tetramethylene diisocyanate, methylpentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1, 4-cyclohexane diisocyanate, isophorone diisocyanate ester, 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.

The component e) according to the invention may also comprise small amounts of higher-functional polyisocyanates known per se in polyurethane chemistry or modified polyisocyanates containing, for example, carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups and/or biuret groups. Hexamethylene diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate and toluene diisocyanate are preferred.

The aqueous dispersions of the invention are based on polymers which contain ionic or potentially ionic groups for hydrophilization, which groups are capable of rendering the aqueous dispersion cationic or anionic in nature. Sulfonate and carboxylate groups are preferred. In addition, those which can be converted into the above-mentioned ionic groups or potential ionic groups by neutralization to form salts can also be used. Hydrophilic groups are introduced into the polymer via component f 3).

The component f1) is preferably a primary and/or secondary monoamine, more preferably an aminoalcohol, i.e. a compound containing both amino and hydroxyl groups in the molecule, such as one or more of ethanolamine, N-methylethanolamine, diethanolamine and 2-propanolamine.

The component f2) is preferably a primary and/or secondary diamine with a number average molecular weight of 60-500 g/mol, more preferably one or two of ethylenediamine, 1, 2-diaminopropane, 1, 4-diaminobutane, 1, 6-hexamethylenediamine, 2-methylpentane-1, 5-diamine, isophoronediamine, N- (2-hydroxyethyl) -ethylenediamine, 4-diaminodicyclohexylmethane, piperazine and diethylenetriamine; one or both of N- (2-hydroxyethyl) -ethylenediamine and isophoronediamine are particularly preferred.

The component f3) is particularly preferably one or more of N- (2-aminoethyl) -2-aminoethanesulfonic acid, N- (3-aminopropyl) -3-aminopropanesulfonic acid, N- (2-aminoethyl) -3-aminopropanesulfonic acid and alkali metal and/or ammonium salts thereof.

The average amino functionality of the mixture f) is from 1.30 to 1.75 and the equivalent ratio between the NCO groups in the NCO prepolymer and the total amount of isocyanate-reactive amino and hydroxyl groups of the mixture e) is from 0.7 to 0.95.

The component g) is preferably a composite antioxidant containing hindered phenol and phosphite antioxidant, for example, the composite antioxidant comprises 20-60 wt% of hindered phenol and 40-80 wt% of phosphite antioxidant, preferably comprises 35-45wt% of hindered phenol antioxidant and 55-65wt% of phosphite antioxidant, and more preferably comprises 40wt% of hindered phenol antioxidant and 60 wt% of phosphite antioxidant.

The invention also provides a process for preparing the aqueous polyurethane-polyurea dispersion, comprising the following steps:

1) putting the components b), c), d) and e) and a solvent into a reaction kettle for reaction under the protection of inert gas by one-step or multi-step (for example, two-step or three-step) reaction, and obtaining a prepolymer of the terminal isocyanate after the reaction is finished (preferably, the reaction is carried out until the NCO% reaches 1.5-6 wt%, and further 1.7-5.5 wt%);

2) adding a solvent into the obtained prepolymer of the isocyanate-terminated prepolymer for dilution, and then adding a component g);

3) adding the mixture f) diluted by water and a) diluted by a solvent to carry out chain extension reaction;

4) mixing with water, and partially or completely removing the solvent to obtain a polyurethane-polyurea water dispersion;

preferably, in the step 1), the components b), c), d), e) and the solvent are put into a reaction kettle under the protection of inert gas to react at 80-90 ℃; in the step 2), the component g) is added at 40-50 ℃.

The component f) diluted with water in the step 3) is the component f) diluted with 2 to 8 times, preferably 4 to 6 times of water, and the component a) diluted with a solvent is the component a) diluted with 2 to 8 times, preferably 4 to 6 times of a solvent (such as acetone); wherein the reaction time in the step 3) is 10-30 minutes, preferably 15-25 minutes; the reaction temperature is 15-60 ℃, preferably 20-60 ℃ or further preferably 35-45 ℃; preferably, the equivalent ratio of NCO groups in the isocyanate-terminated prepolymer to the total amount of isocyanate-reactive amino and hydroxyl groups of mixture f) is from 0.70 to 0.95.

The solvent is a water-soluble solvent which does not contain any groups reactive with isocyanates and which can be removed from the dispersion prepared by distillation.

The solvent may be selected from one or more of acetone, methyl ethyl ketone, t-butyl methyl ether and tetrahydrofuran, preferably methyl ethyl ketone or acetone, and particularly preferably acetone.

The aqueous dispersions have a solids content of from 10 to 70%, preferably from 25 to 65% and particularly preferably from 45 to 60%. The amount of water used in step 4) is such that the aqueous dispersion has a solids content of from 10 to 70%, preferably from 25 to 65% and particularly preferably from 45 to 60%.

In general, the dispersion obtained has an average particle diameter of 260-310nm, pH of 6.8 to 7.3, preferably 6.9 to 7.2, as determined by laser correlation in the dispersed phase, an average amino functionality: 1.50-1.70, prepolymer NCO group/(amino + hydroxyl) 0.70-0.95.

The polyurethane-polyurea water dispersion has higher strength, better adhesive force, film forming property and yellowing resistance, and can be used in the field of glass fiber composite materials.

The aqueous polyurethane-polyurea dispersions of the invention have the following characteristics:

(1) the self-crosslinking group is introduced into the chain segment, so that the adhesive force on the surface of the base material is improved, and the high-temperature yellowing resistance is improved.

(2) By introducing the monofunctional polyether and the monofunctional monoamine, the emulsion with very low molecular weight is obtained, the stability of the aqueous dispersion is favorably improved, the high-temperature yellowing resistance of the adhesive film is improved, the adhesive film still has excellent high-temperature yellowing resistance even at 280 ℃, and the effect is more obvious by matching the composite antioxidant.

Detailed Description

The materials used were:

polyester polyol I: 1, 6-hexanediol poly (phthalate), OH 56mg KOH/g, designation PH56, manufactured by Nanjing Jinling Spiral chemical company.

Polyester polyol II: polyethylene-diethylene glycol phthalate having an OH number of 56mg KOH/g, under the designation PD56, manufactured by Nanjing Jinlingstapane chemical company.

Polyester polyol III: 1, 6-hexanediol neopentyl glycol phthalate diol phthalate, OH 56mg KOH/g, designation PHN56, Nanjing Jinling Spandex chemical company.

MPEG-1200: monofunctional polyethers, polyethylene glycol monomethyl ether, having a number average molecular weight of 1200 daltons, a petrochemical in Hunan.

Polyisocyanate I IPDI isophorone diisocyanate, Van der Chemicals.

Compound antioxidant: 60% of diphenyl diisoproylether diphosphite, the designation JPP-100, North City chemical and 40% of hindered phenol antioxidant, the designation Irganox1010, Basff.

The parameters in the following examples were determined as follows:

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

Determination of the 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.

Example 1

200g of dehydrated polyester polyol I (component b)), 91g of polyisocyanate I (component e)), 8.5g of dehydrated MPEG-1200 (component d)), and 40g of acetone were charged into a 1L four-necked round-bottomed flask equipped with a nitrogen inlet/outlet, and the mixture was stirred at 80 to 90 ℃ until the-NCO content reached 7.56% by weight. 16.0g of neopentyl glycol (component c)) and 20g of acetone are added with cooling, and the reaction is continued with stirring while increasing the temperature to 75 ℃ until NCO reaches 3.46% by weight. The temperature is reduced, 360g of acetone is added for dilution, the temperature is reduced to 50 ℃, 2g A-95(N- (2-aminoethyl) -2-aminoethanesulfonic acid, component f3)), 15.3g of IPDA (component f2)), 87g of water diluted solution and 20g of acetone solution dissolved with 2.2g N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane (component a)) are added respectively with stirring, the reaction is carried out for 10min with stirring, 14g of 50% diethanolamine (component f1)) aqueous solution is added, the reaction is carried out for 10min with stirring, 1.6g of composite antioxidant is added, the mixture is stirred uniformly, and 270g of deionized water is added with rapid stirring for dispersion. After separation of the acetone again by distillation, a solvent-free aqueous polyurethane-polyurea dispersion is obtained. It has a solids content of 55% by weight, an average particle diameter of 296nm, determined by laser correlation in the disperse phase, and a pH of 6.9.

Average amino functionality: 1.61.

prepolymer NCO group/(amino + hydroxy) ═ 0.74.

Example 2

215g of dehydrated polyester polyol I, 86.1g of polyisocyanate I, 8g of dehydrated MPEG-1200 and 41g of acetone were put into a 1L four-necked round-bottomed flask equipped with a nitrogen inlet/outlet, and the mixture was stirred at 80 to 90 ℃ until the-NCO reached 6.59% by weight. 14.8g of 1, 4-butanediol and 20g of acetone are added with cooling, the reaction is continued with stirring while the temperature is raised to 75 ℃ until the NCO has reached 2.40% by weight. And cooling, adding 360g of acetone for dilution, cooling to 50 ℃, adding 2g A-95 g of IPDA, 8.2g of IPDA, 60g of water diluted solution and 20g of acetone dissolved solution dissolved with 2.39g N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane respectively under stirring, reacting for 10min under stirring, then adding 12.4g of aqueous solution of diethanolamine with the concentration of 50%, reacting for 10min under stirring, adding 1.72g of composite antioxidant, stirring uniformly, and adding 270g of deionized water under rapid stirring for dispersion. After separation of the acetone again by distillation, a solvent-free aqueous polyurethane-polyurea dispersion is obtained. It has a solids content of 50% by weight, an average particle diameter of 304nm, determined by laser correlation in the disperse phase, and a pH of 7.0.

Average amino functionality: 1.52.

prepolymer NCO group/(amino + hydroxy) ═ 0.74.

Example 3

80g of dehydrated polyester polyol I, 105g of dehydrated polyester polyol II, 75.4g of polyisocyanate I, 12g of dehydrated MPEG-1200 and 35.6g of acetone were placed in a 1L four-necked round-bottomed flask equipped with a nitrogen inlet/outlet, and the mixture was stirred at 80 to 90 ℃ until 4.65% by weight of-NCO was obtained. 15.0g of neopentyl glycol and 14.8g of acetone are added with cooling, and the reaction is continued with stirring while the temperature is increased to 75 ℃ until NCO reaches 2.29% by weight. Reducing the temperature, adding 308g of acetone for dilution, reducing the temperature to 50 ℃, respectively adding 1g A-95 g of IPDA, 8.45g of water diluted solution and 100g of acetone solution dissolved with 0.72g N-beta- (aminoethyl) -gamma-aminopropyltriethoxysilane 5g of acetone solution under stirring, reacting for 10min under stirring, then adding 7.2g of aqueous solution of diethanolamine with the concentration of 50%, reacting for 10min under stirring, adding 1.5g of composite antioxidant, stirring uniformly, and adding 365g of deionized water under rapid stirring for dispersion. After separation of the acetone again by distillation, a solvent-free aqueous polyurethane-polyurea dispersion is obtained. It has a solids content of 55% by weight, an average particle diameter of 271nm as determined by laser correlation in the dispersed phase, and a pH of 7.0.

Average amino functionality: 1.62.

prepolymer NCO group/(amino + hydroxy) ═ 0.91.

Example 4

92g of dehydrated polyester polyol I, 70g of dehydrated polyester polyol II, 68g of polyisocyanate I, 11.2g of dehydrated MPEG-1200 and 32.4g of acetone were placed in a 1L four-necked round-bottomed flask equipped with a nitrogen inlet/outlet, and the mixture was stirred at 80 to 90 ℃ until 4.85% by weight of-NCO was obtained. 9.8g of neopentyl glycol and 13g of acetone are added with cooling, the reaction is continued with stirring while the temperature is increased to 75 ℃ until NCO reaches 3.24% by weight. Reducing the temperature, adding 308g of acetone for dilution, reducing the temperature to 50 ℃, respectively adding 1.3g A-95 g of hydroxyethyl ethylenediamine, 7.35g of IPDA, 71g of water diluted solution and 50g of acetone solution dissolved with 1.5g N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane into the mixture under stirring, reacting for 10min under stirring, then adding 9.4g of 50% aqueous solution of diethanolamine, reacting for 10min under stirring, adding 1.4g of composite antioxidant, stirring uniformly, and adding 210g of deionized water under rapid stirring for dispersion. After separation of the acetone again by distillation, a solvent-free aqueous polyurethane-polyurea dispersion is obtained. It has a solids content of 50% by weight, an average particle diameter in the disperse phase, determined by laser correlation, of 277nm, and a pH of 6.9.

Average amino functionality: 1.66.

prepolymer NCO group/(amino + hydroxy) ═ 0.72.

Example 5

232g of dehydrated polyester polyol I, 80g of polyisocyanate I, 10g of dehydrated MPEG-1200 and 41.5g of acetone were charged into a 1L four-necked round-bottomed flask equipped with a nitrogen inlet/outlet, and the mixture was stirred at 80 to 90 ℃ until 5.39% by weight of-NCO was reached. 11.9g of neopentyl glycol and 17.3g of acetone were added while cooling, and the reaction was continued with stirring while heating to 75 ℃ until NCO reached 2.58% by weight. And cooling, adding 356g of acetone for dilution, cooling to 50 ℃, adding 2.1g A-95 g of IPDA, 72g of water diluted solution and 50g of acetone solution dissolved with 3.2g N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane respectively under stirring, reacting for 10min under stirring, then adding 12.5g of aqueous solution of diethanolamine with the concentration of 50%, reacting for 10min under stirring, adding 1.73g of composite antioxidant, uniformly stirring, and adding 352g of deionized water under rapid stirring for dispersion. After separation of the acetone again by distillation, a solvent-free aqueous polyurethane-polyurea dispersion is obtained. It has a solids content of 50% by weight, an average particle diameter of 287nm, determined by laser correlation in the disperse phase, and a pH of 7.2.

Average amino functionality: 1.56.

prepolymer NCO group/(amino + hydroxy) ═ 0.75.

Example 6

150g of dehydrated polyester polyol I, 92g of polyisocyanate I, 8g of dehydrated MPEG-1200, and 34g of acetone were put into a 1L four-necked round-bottomed flask equipped with a nitrogen inlet/outlet, and the mixture was stirred at 80 to 90 ℃ until the-NCO reached 10.17% by weight. 22.6g of neopentyl glycol and 20g of acetone are added with cooling, the reaction is continued with stirring while the temperature is increased to 75 ℃ until NCO reaches 2.88% by weight. The temperature is reduced, 287g of acetone is added for dilution, the temperature is reduced to 50 ℃, 2g A-95 g of IPDA, 9.87g of IPDA, 80g of water diluted solution and 5g of acetone dissolved with 5.4g N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane are added respectively for dissolution under stirring, the reaction is carried out for 10min under stirring, then 7.8g of diethanolamine aqueous solution with the concentration of 50 percent is added, the reaction is carried out for 10min under stirring, 3.0g of composite antioxidant is added, the stirring is carried out uniformly, 352g of deionized water is added for dispersion under rapid stirring. After separation of the acetone again by distillation, a solvent-free aqueous polyurethane-polyurea dispersion is obtained. It has a solids content of 48% by weight, an average particle diameter of 297nm determined by laser correlation in the disperse phase, and a pH of 7.0.

Average amino functionality: 1.70.

prepolymer NCO group/(amino + hydroxy) ═ 0.81.

Example 7

400g of dehydrated polyester polyol III, 73g of polyisocyanate I, 15g of dehydrated MPEG-1200, 0.8g of 1, 4-butanediol and 51g of acetone were placed in a 1L four-necked round-bottomed flask equipped with a nitrogen inlet/outlet, and the mixture was stirred at 80 to 90 ℃ until the-NCO content reached 1.78 wt%. Cooling, adding 718g of acetone for dilution, cooling to 50 ℃, adding 1.7g A-95 g of IPDA, 66g of water diluted solution and 5g of acetone solution dissolved with 1.7g N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane respectively under stirring, reacting for 10min under stirring, then adding 13.1g of aqueous solution of diethanolamine with the concentration of 50%, reacting for 10min under stirring, adding 1.7g of composite antioxidant, stirring uniformly, and adding 352g of deionized water under rapid stirring for dispersion. After separation of the acetone again by distillation, a solvent-free aqueous polyurethane-polyurea dispersion is obtained. It has a solids content of 50% by weight and a mean particle diameter pH of 263nm, determined by laser correlation in the disperse phase, of 7.2.

Average amino functionality: 1.55.

prepolymer NCO group/(amino + hydroxy) ═ 0.70.

Comparative example 1

185g of dehydrated polyester polyol I, 87g of polyisocyanate I, 8.7g of dehydrated MPEG-1200 and 37.4g of acetone were put into a 1L four-necked round-bottomed flask equipped with a nitrogen inlet/outlet, and the mixture was stirred at 80 to 90 ℃ until the-NCO reached 7.70% by weight. 18.0g of neopentyl glycol and 15.5g of acetone are added with cooling, and the reaction is continued with stirring while the temperature is increased to 75 ℃ until the NCO has reached 2.75% by weight. Cooling, adding 330g of acetone for dilution, cooling to 50 ℃, adding 1.5g of A-95, 11.6g of IPDA, 85g of water diluted solution and 50g of acetone solution dissolved with 1.3g N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane respectively under stirring, reacting for 10min under stirring, then adding 3.7g of diethanolamine aqueous solution with the concentration of 50%, reacting for 10min under stirring, adding 1.6g of composite antioxidant, stirring uniformly, and adding 270g of deionized water under rapid stirring for dispersion. After separation of the acetone again by distillation, a solvent-free aqueous polyurethane-polyurea dispersion is obtained. It has a solids content of 58% by weight,in the dispersed phase By laser correlationAverage particle size at 293nm, pH 7.0.

Average amino functionality: 1.82.

prepolymer NCO group/(amino + hydroxy) ═ 1.15.

Comparative example 2

The 50% diethanolamine solution of example 4, having a solids content of 50% by weight, has an average particle size of 292nm, determined by laser correlation in the dispersed phase, and a pH of 7.0.

Average amino functionality: 2.

prepolymer NCO group/(amino + hydroxy) ═ 1.18.

Comparative example 3

175g of dehydrated polyester polyol I, 76.5g of polyisocyanate I, 8.5g of dehydrated MPEG-1200, and 32g of acetone were put into a 1L four-necked round-bottomed flask equipped with a nitrogen inlet/outlet, and the mixture was stirred at 80 to 90 ℃ until the-NCO content reached 4.3% by weight. 12g of 1, 4-butanediol and 16.5g of acetone are added with cooling, the reaction is continued with stirring while the temperature is raised to 75 ℃ until the NCO has reached 2.92% by weight. The temperature is reduced, 294g of acetone is added for dilution, the temperature is reduced to 50 ℃, 2.4g of A-95, 4.2g of hydroxyethyl ethylenediamine, 4.87g of IPDA, 60g of water diluted solution and 50g of acetone solution dissolved with 0.7g N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane are added respectively under stirring, the reaction is carried out for 10min under stirring, then 14.7g of diethanolamine aqueous solution with the concentration of 50 percent is added, the reaction is carried out for 10min under stirring, 1.4g of composite antioxidant is added, the mixture is stirred uniformly, and 234g of deionized water is added under rapid stirring for dispersion. After separation of the acetone again by distillation, a solvent-free aqueous polyurethane-polyurea dispersion is obtained. It has a solids content of 50% by weight, an average particle diameter of 287nm, determined by laser correlation in the disperse phase, and a pH of 7.9.

Average amino functionality: 1.51.

prepolymer NCO group/(amino + hydroxy) ═ 0.55.

Comparative example 4

232g of dehydrated polyester polyol I, 80g of polyisocyanate I, 10g of dehydrated MPEG-1200 and 41.5g of acetone were charged into a 1L four-necked round-bottomed flask equipped with a nitrogen inlet/outlet, and the mixture was stirred at 80 to 90 ℃ until 5.39% by weight of-NCO was reached. 11.9g of neopentyl glycol and 17.3g of acetone were added while cooling, and the reaction was continued with stirring while heating to 75 ℃ until NCO reached 2.58% by weight. Cooling, adding 356g acetone to dilute and cool to 50 ℃, adding 2.1g A-95, 12g IPDA and 72g water diluted solution under stirring, reacting for 10min under stirring, then adding 12.5g 50% diethanolamine aqueous solution, reacting for 10min under stirring, adding 1.73g composite antioxidant, stirring uniformly, and adding 352g deionized water under rapid stirring for dispersion. After separation of the acetone again by distillation, a solvent-free aqueous polyurethane-polyurea dispersion is obtained. It has a solids content of 50% by weight, an average particle diameter of 268nm, determined by laser correlation in the disperse phase, and a pH of 7.3.

Average amino functionality: 1.56.

prepolymer NCO group/(amino + hydroxy) ═ 0.75.

Comparative example 5

192g of dehydrated polyester polyol I, 71.5g of polyisocyanate I, 10g of dehydrated MPEG-1200 and 46g of acetone were put into a 1L four-necked round-bottomed flask equipped with a nitrogen inlet/outlet, and the mixture was stirred at 80 to 90 ℃ until 5.90% by weight of-NCO was reached. 9.8g of neopentyl glycol and 15.3g of acetone are added with cooling, and the reaction is continued with stirring while the temperature is increased to 75 ℃ until the NCO reaches 3.02% by weight. Reducing the temperature, adding 308g of acetone for dilution, reducing the temperature to 50 ℃, respectively adding 1.7g of A-95, 6.8g of IPDA and 43g of water diluted solution and 90g of acetone solution dissolved with 9g N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane under stirring, reacting for 10min under stirring, then adding 10.7g of diethanolamine aqueous solution with the concentration of 50%, reacting for 10min under stirring, adding 1.5g of composite antioxidant, stirring uniformly, and adding 332g of deionized water under rapid stirring for dispersion. After separation of the acetone again by distillation, a solvent-free aqueous polyurethane-polyurea dispersion is obtained. It has a solids content of 50% by weight, an average particle diameter of 385nm, determined by laser correlation in the disperse phase, and a pH of 7.2.

Average amino functionality: 1.62.

prepolymer NCO group/(amino + hydroxy) ═ 0.77.

Glass fiber impregnating compound formula table

The test method for the yellowing condition of the adhesive film in the following comparative table is as follows:

firstly, diluting the water dispersion to 45% of solid content, pouring 50g of the water dispersion onto a 20 x 20cm glass plate, placing the glass plate on a flat table top for film formation at 25 ℃, taking down the glass plate after the film formation is dried, placing the glass plate in a 70 ℃ oven, continuously drying the glass plate for 4 hours, cutting the glass plate into 4 x 4cm, placing the glass plate in a 280 ℃ oven for baking for 30 minutes, and visually observing the yellowing condition of a glue film.

The test method for the yellowing of the paint films in the following comparative tables is as follows:

the adhesion of the dispersion on glass was tested using the percent-cell test method, with the lower the rating, the better the performance.

the prepared glass fiber impregnating compound is coated on a tinplate test board with the wet layer thickness of 20 mu m, the test board is placed at room temperature and dried for 30min, the color measurement is carried out according to a CIELAB method, then the test board is baked for 30min in an oven at 280 ℃, the color measurement is carried out according to the CIELAB method, the b value measured by an unbaked sample plate is subtracted from the measured b value, the delta b value is obtained, and the higher the delta b value is, the more serious the yellowing of a paint film is.

And (3) testing results:

as can be seen from the examples and the comparative examples, the polyurethane-polyurea water dispersion film-forming agent provided by the invention has excellent high-temperature yellowing resistance and stability, and the performances of all aspects in the formula of the examples are better than those of the comparative examples in all tests.

Claims

1. An aqueous self-crosslinking polyurethane-polyurea dispersion prepared by reacting and dispersing in water reaction starting materials comprising:

a) at least one silicone component further having at least two amino groups or at least two hydroxyl groups or at least one amino group and one hydroxyl group, and the silicon-attached group contains at least two methoxy and/or ethoxy groups;

c) one or more polyols having a number average molecular weight above 62 g/mole and less than 500 g/mole;

d) at least one polyethoxylate ether component having a number average molecular weight of from 500 g/mole to 10000 g/mole which is different from component b) reactive toward isocyanates;

e) at least one polyisocyanate component;

f) monoamino compounds f1) and polyamino compounds f2) which are free of sulfonate and/or carboxylate groups and which are different from component a), and polyamino compounds f3) which carry sulfonate and/or carboxylate groups, the amino groups being selected from primary and/or secondary amino groups;

g) one or more antioxidants;

said component f3) carrying sulfonate groups and representing a proportion of less than 1% by weight based on the solids of the aqueous polyurethane-polyurea dispersion, and the average amino functionality of the mixture f) being from 1.30 to 1.75;

the self-crosslinking aqueous polyurethane-polyurea dispersion is prepared by the following steps:

1) putting the components b), c), d), e) and a solvent into a reaction kettle for reaction under the protection of inert gas by one-step or multi-step reaction to obtain a prepolymer of the terminal isocyanate;

the equivalent ratio of NCO groups in the isocyanate-terminated prepolymer to the total amount of isocyanate-reactive amino and hydroxyl groups of mixture f) is from 0.70 to 0.95.

2. The aqueous polyurethane-polyurea dispersion according to claim 1, wherein the aqueous polyurethane-polyurea dispersion has a solids content of 45% to 60%; said component a) being from 0.02 to 5% by weight, based on the weight of the solids of the aqueous polyurethane-polyurea dispersion, of the solids of the aqueous polyurethane-urea dispersion; the amount of the component b) is 20-90 wt%; the amount of the component c) is 0.1-10 wt%; the amount of the component d) is 0.5-8 wt%; the amount of the component e) is 5-40 wt%; the dosage of f1) in the mixture f) is 0.1-10 wt%, the dosage of f2) is 1-10 wt%, and the dosage of f3) is 0.1-1 wt%; the amount of component g) is 0.01 to 2 wt%.

3. The aqueous polyurethane-polyurea dispersion according to claim 2, wherein the aqueous polyurethane-polyurea dispersion has a solids content of 45% to 60%; said component a) being from 0.02 to 2% by weight, based on the weight of the solids of the aqueous polyurethane-polyurea dispersion, of the solids of the aqueous polyurethane-urea dispersion; the amount of the component b) is 50-80 wt%; the amount of the component c) is 0.1-8 wt%; the amount of the component d) is 2-4.5 wt%; the amount of the component e) is 12-33 wt%; the dosage of f1) in the mixture f) is 1-5.5 wt%, and the dosage of f2) is 2-9 wt%; the amount of component g) is 0.3 to 1.2 wt%.

4. The aqueous polyurethane-polyurea dispersion according to any of claims 1 to 3, wherein component a) is a siloxane component which additionally has at least two amino groups or at least two hydroxyl groups or at least one amino group and one hydroxyl group and the groups bonded to silicon contain at least two methoxy and/or ethoxy groups; and/or

The component b) is one or more of dihydric alcohol, trihydric alcohol and tetrahydric alcohol with the number average molecular weight of 500-5000 g/mol; and/or

The component c) is selected from one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 3-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 and 2-ethyl-1.3-hexanediol; and/or

The component d) is polyethoxy ether with the number average molecular weight of 500-8000 g/mol and the number of ethylene oxide groups of 4-200; and/or

The component e) is one or more of aromatic, aliphatic and alicyclic polyisocyanates; and/or

The component f1) is one or two of diethylamine, ethanolamine or diethanolamine; and/or

The component f2) is polyamine with the number average molecular weight of 60-500 g/mol; and/or

The component f3) is one or more of N- (2-aminoethyl) -2-aminoethanesulfonic acid, N- (3-aminopropyl) -3-aminopropanesulfonic acid, N- (2-aminoethyl) -3-aminopropanesulfonic acid and alkali metal salts and/or ammonium salts thereof; and/or

The component g) is one or more composite antioxidants containing hindered phenols and phosphite antioxidants.

5. The aqueous polyurethane-polyurea dispersion according to claim 4, wherein component a) is a siloxane having at least two amino groups; and/or

The component b) is one or more of polyether polyol, polyester polyol, polycarbonate polyol and polycaprolactone polyol with the number average molecular weight of 1000-3000 g/mol and the functionality of difunctional or higher; and/or

The component c) is selected from one or more of 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, neopentyl glycol and 1, 4-cyclohexanedimethanol; and/or

The component d) is polyethoxy ether with the number average molecular weight of 500-3000 g/mol and the number of ethylene oxide of 12-75; and/or

The component e) is one or more of cycloaliphatic polyisocyanates having two isocyanate groups; and/or

The component f2) is one or two of 1, 2-ethylenediamine, 1, 4-diaminobutane, 1, 6-hexamethylenediamine, N- (2-hydroxyethyl) -ethylenediamine, isophoronediamine, 4-diaminodicyclohexylmethane and piperazine; and/or

The component g) is a composite antioxidant containing 35-45wt% of hindered phenol antioxidant and 55-65wt% of phosphite antioxidant.

6. The aqueous polyurethane-polyurea dispersion according to claim 5, wherein component a) is N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, N- β - (aminoethyl) - γ -aminopropyltriethoxysilane, N- (β -aminoethyl) - γ -aminopropylmethyldimethoxysilane or 1, 3-bis (aminopropyl) tetramethyldisiloxane; and/or

The component f2) is one or two of N- (2-hydroxyethyl) -ethylenediamine and isophorone diamine.

7. The aqueous polyurethane-polyurea dispersion according to claim 6, wherein component a) is N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, N- β - (aminoethyl) - γ -aminopropyltriethoxysilane or N- (β -aminoethyl) - γ -aminopropylmethyldimethoxysilane.

8. The aqueous polyurethane-polyurea dispersion according to any of claims 1 to 3, wherein the aqueous polyurethane-polyurea dispersion has an average particle diameter of 260-310nm, a pH of 6.8 to 7.3, an average amino functionality: 1.50-1.70.

9. The aqueous polyurethane-polyurea dispersion according to claim 8, wherein the aqueous polyurethane-polyurea dispersion has a pH of 6.9 to 7.2.

10. A process for preparing an aqueous polyurethane-polyurea dispersion according to any of claims 1 to 9, comprising the following steps:

4) mixing with water, and partially or completely removing the solvent to obtain the polyurethane-polyurea aqueous dispersion.

11. The method as claimed in claim 10, wherein in the step 1), the components b), c), d), e) and the solvent are put into a reaction kettle under the protection of inert gas to react at 80-90 ℃; in the step 2), adding the component g) at 40-50 ℃; in the step 3), the chain extension reaction is carried out at the temperature of 20-60 ℃.

12. The process of claim 11, wherein the equivalent ratio of NCO groups in the isocyanate-terminated prepolymer to the total amount of isocyanate-reactive amino and hydroxyl groups of mixture f) is from 0.70 to 0.95.

13. The process according to any one of claims 10 to 12, wherein the water-diluted mixture f) is obtained by dilution with 2 to 8 times the mass of water based on the mass of the mixture f), and the solvent-diluted component a) is obtained by dilution with 1 to 20 times the mass of solvent based on the mass of the component a); wherein the reaction time in the step 3) is 10-30 minutes; wherein the solvent is a water-soluble solvent which does not contain any groups reactive with isocyanates and which can be removed from the dispersion prepared by distillation.

14. The method according to claim 13, wherein the water-diluted mixture f) is obtained by diluting with 4-6 times of water based on the mass of the mixture f), and the solvent-diluted component a) is obtained by diluting with 5-20 times of solvent based on the mass of the component a); wherein the reaction time in the step 3) is 15-20 minutes; wherein the solvent is a water-soluble solvent which does not contain any groups reactive with isocyanates and which can be removed from the dispersion prepared by distillation.

15. The process of claim 13, wherein the solvent is selected from one or more of acetone, methyl ethyl ketone, t-butyl methyl ether, and tetrahydrofuran.

16. The method of claim 15, wherein the solvent is selected from methyl ethyl ketone or acetone.

17. The method of claim 16, wherein the solvent is selected from acetone.

18. Use of the aqueous self-crosslinking polyurethane-polyurea dispersion according to any of claims 1 to 9 for impregnating glass fibers.