CN114621670B

CN114621670B - Aqueous polyurethane-urea dispersions, method for the production and use thereof

Info

Publication number: CN114621670B
Application number: CN202011471191.1A
Authority: CN
Inventors: 晋云全; 王萃萃; 王震; 周操; 曹玉阳; 纪学顺
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2020-12-14
Filing date: 2020-12-14
Publication date: 2023-05-30
Anticipated expiration: 2040-12-14
Also published as: CN114621670A

Abstract

The invention discloses a polyurethane-urea dispersoid and a preparation method thereof, wherein the polyurethane-urea dispersoid is prepared by the reaction of the following components: a) at least one component containing at least one group reactive with isocyanates and at least one double bond, wherein the beta position of the double bond contains an electron-withdrawing group, b) at least one component containing at least one group reactive with isocyanates and at least one conjugated double bond, c) an unsaturated diolefin containing bridged structures, d) at least one macromolecular diol and/or polyol, e) at least one di-and/or polyisocyanate component, f) at least one diol or polyol having a molecular weight of 40-400, g) at least one component having sulfonate and/or carboxylate and/or polyethoxy groups, which additionally has at least one hydroxyl or amino group reactive with isocyanates, h) optionally one compound which is a mono-amino and/or diamino-and/or triamino-group.

Description

Aqueous polyurethane-urea dispersions, method for the production and use thereof

Technical Field

The invention relates to aqueous polyurethane-urea dispersions, to a method for the production thereof and to the use thereof.

Background

Since aqueous polyurethane-urea dispersions have excellent paintability, excellent initial adhesion and peel strength, and outstanding resistance, they have been widely used in the fields of paints, sealants, adhesives, and the like. Two-component formulation systems, however, have been widely studied because of their ability to provide excellent resistance. However, two-component systems suffer from the problem of shorter activation times, one-component systems do not suffer from the disadvantage of longer activation times, but since in order to achieve the later resistance, one-component polyurethane-polyurea dispersions need to ensure sufficiently large molecular weights, but with the consequent problems of poor leveling and poor film formation.

The DA reaction (Diels-Alder reaction) is a reversible reaction that reacts between a dienyl and a dienophile at lower temperatures to achieve an increase in molecular weight and degree of crosslinking, and at high temperatures reversible reactions occur, resulting in a decrease in molecular weight and a decrease in degree of crosslinking. The excellent leveling effect is endowed again, and the DA reaction is widely applied to the field of self-repairing.

Publication CN201910835463.0 proposes the use of furfuryl alcohol and maleimide to prepare diols containing a DA reactive structural monomer, and then to prepare polyurethanes which have excellent self-healing effects. However, the diol containing the DA-reactive monomer used in the patent is in a chain, so that mobility is inhibited, the reaction of DA has larger steric hindrance, and the reaction efficiency is lower. CN202010288909 uses maleimide and tetrahydrofuran containing disulfide bonds to prepare polyurethanes containing DA-reactive monomers, providing excellent self-healing effects. But disulfide-bonded tetrahydrofuran has a large odor and is limited in use. The patent 201910355537.2 uses maleimide modified cellulose mixed with polyurethane emulsion to prepare self-healing polyurethane.

At present, most DA (DA) reactive monomers mainly synthesize components containing one DA reactive group, and then graft the components to polymers containing the other DA reactive monomer by a physical blending or chemical grafting method, so that the process is complicated.

In the research of the inventor, the monomer with DA structure, such as alpha-furyl alcohol and maleimide structure, can be directly grafted at the tail end of polyurethane prepolymer, the preparation method is simple, and the monomer is compounded with norbornadiene derivative with bridged ring structure to prepare the polyurethane dispersion containing DA reaction monomer, so that the polyurethane dispersion can provide excellent resistance and hardness at normal temperature and excellent leveling and activating effect under high temperature conditions, and has wide application on the surface of hard base materials such as woodware, metal and the like.

Disclosure of Invention

The invention aims at providing a polyurethane-urea dispersion with DA reactive groups and the use thereof. The DA monomer is firstly connected to the tail end of polyurethane in a chemical grafting mode, can generate ring-opening reaction at different temperatures, is simultaneously assisted with another DA reaction monomer with high rigidity, and finally realizes excellent resistance and hardness at normal temperature and excellent leveling and activating effect at high temperature. The problem that the balance between resistance and leveling of the traditional polyurethane-urea dispersion is difficult to realize is solved. Can be used as an adhesive and a coating, and can be widely applied to the fields of plastics, metals, woodware, inorganic materials and the like.

It is a further object of the present invention to provide a process for preparing polyurethane-polyurea dispersions having DA-reactive groups, which is simple and easy to carry out.

In order to achieve the above object, the present invention has the following technical scheme:

an aqueous polyurethane-urea dispersion, the polyurethane or polyurethane polyurea contained in said aqueous polyurethane-urea dispersion being the reaction product resulting from the reaction of components comprising:

a) At least one component comprising at least one group reactive with isocyanates and at least one double bond, wherein the beta position of the double bond comprises an electron withdrawing group,

b) At least one component comprising at least one group reactive with isocyanate and at least one conjugated double bond,

c) An unsaturated diolefin containing a bridged ring structure,

d) At least one macrodiol and/or polyol,

e) At least one di-and/or polyisocyanate component,

f) At least one dihydric or polyhydric alcohol having a molecular weight of 40 to 400,

g) At least one component having sulfonate and/or carboxylate and/or polyethoxy groups, which additionally has at least one hydroxyl or amino group reactive with isocyanate and thus incorporates sulfonate and/or carboxylate and/or polyethoxy structural units into the polyurethane segment,

h) An optional one is a mono-and/or di-and/or tri-amino-compound.

In the present invention,

component a) is 0.5 to 3 wt.%, preferably 0.6 to 1.3 wt.% of the solids of the aqueous polyurethane-urea dispersion; component b) is 0.01 to 5 wt.%, preferably 1 to 2.3 wt.% of the solids of the aqueous polyurethane-urea dispersion; component c) is 0.01 to 10 wt.%, preferably 1.5 to 6 wt.% of the solids of the aqueous polyurethane-urea dispersion; component d) is 15 to 50 wt.%, preferably 23 to 32 wt.% of the solids of the aqueous polyurethane-urea dispersion; component e) is 25 to 50 wt.%, preferably 29 to 39 wt.% of the solids of the aqueous polyurethane-urea dispersion; component f) is 15 to 40% by weight, preferably 18 to 37% by weight, of the solids of the aqueous polyurethane-urea dispersion; component g) is 0.1 to 10 wt.%, preferably 0.9 to 4 wt.% of the solids of the aqueous polyurethane or polyurethane-urea dispersion; component h) is 0 to 10% by weight, preferably 0.3 to 1.4% by weight, based on the solids of the aqueous polyurethane or polyurethane-urea dispersion. .

In the present invention, component a) has the structural formula

Wherein R represents H or hydroxy.

In the present invention, component b) is selected from the group consisting of alpha-furyl alcohol having the formula

Wherein n represents 1,2, 3

Preferably, component b) is selected from one or more of α -furyl alcohol, α -furyl propanol, more preferably α -furyl alcohol, α -furyl alcohol.

In the present invention, component C) is selected from the group consisting of substituted derivatives of unsaturated dienes containing bridged ring structures, such as norbornadiene, suitable compounds may be aziridinyl-1- (bicyclo [2, 1] -hept-2, 5-diene) -2-one (A), tert-butoxynorbornadiene (B), methyl bicyclo [2, 1] -hept-2, 5-diene-2-carboxylate (C), preferably aziridinyl-1- (bicyclo [2, 1] -hept-2, 5-diene) -2-one, of the formula:

wherein R is:

A：

B：

C：

preferably

In the invention, the component d) is a polyol with a number average molecular weight of 500-15000, and the functionality of the polyol is 2-5; preferably diols and/or triols and/or tetraols having a number average molecular weight of 600 to 8000; more preferably, the polyester or polyether glycol having a number average molecular weight of 1000 to 2000 and a functionality of 2.

Suitable polyester polyols may be obtained, for example, by dehydration condensation of carboxylic acids and/or anhydrides such as aliphatic, cycloaliphatic, aromatic dicarboxylic or polycarboxylic acids or their corresponding anhydrides, for example 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, phthalic anhydride or mixtures thereof, with polyols; examples of the polyhydric alcohol may be 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, 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 adipic acid, and polyester polyols of neopentyl glycol, ethylene glycol, butanediol, hexanediol as structural components.

The polyester polyols may also be homopolymers or copolymers of lactones, which may be obtained by ring opening of mixtures of lactones or lactones with suitable di-and/or higher functional low molecular weight polyols. Wherein the lactone is selected from the group consisting of butyrolactone, epsilon-caprolactone, methyl-epsilon-caprolactone, and mixtures thereof, and the polyol is selected from the group consisting of low molecular weight polyols as described above as structural components of the polyester polyol. Preference is given to using linear polyester polyols of 1, 4-butanediol, 1, 6-hexanediol, 2-dimethyl-1, 3-propanediol or mixtures thereof for ring opening epsilon-caprolactone.

Polycarbonates having hydroxyl groups prepared by transesterification using diols and carbonates are also suitable for the present invention. The diol may be 1, 4-butanediol, 1, 6-hexanediol, and the carbonate may be diaryl carbonate, dialkyl carbonate. The diaryl carbonate comprises diphenyl carbonate and the dialkyl carbonate comprises dimethyl carbonate; polycarbonates prepared by reacting 1, 6-hexanediol with dimethyl carbonate are preferred.

Suitable polyether diols may be glycol dehydration products, such as ethylene glycol, propylene glycol, butylene glycol, 1, 6-hexanediol, and the like, preferably polyethylene glycol, propylene glycol dehydration products of one or both of polyethylene glycol and polypropylene glycol, polypropylene oxide propylene ether glycol, polyoxyethylene-propylene ether block-forging glycols.

The polyether glycol can also be one or two of EO and PO ring-opened products under the condition of a catalyst, such as polyoxyethylene ether glycol, polyoxypropylene ether glycol and polyoxyethylene-propenyl ether embedded forging glycol.

The polyether glycol shown can also be a tetrahydrofuran ring-opening product, wherein the initiator can be ethylene glycol, propylene glycol, butanediol, hexanediol and the like, and polytetrahydrofuran glycol prepared by ring-opening butanediol is preferred.

The polyether glycol shown is preferably a polyoxyethylene ether glycol.

More suitable diols are polycarbonate diols, polyadipic acid-neopentyl glycol ester diols, polyoxyethylene ether diols.

In the present invention, said component e) is selected from isocyanates having a functionality of 1.5 to 5.0 and an nco content of 7 to 55wt%, said isocyanates being selected from one or more of aliphatic, alicyclic, aromatic and araliphatic isocyanates; preferably, the functionality is 1.8 to 3.0, and the NCO content is 35.0 to 52.0wt%; more preferably diisocyanate Y (NCO) ₂ Wherein Y represents two having 4 to 12 carbon atomsA divalent aliphatic hydrocarbon group, 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. Particularly preferred are one or more of 1, 6-hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate.

In the context of the present invention, the component f) may be one or more of ethylene glycol, di-, tri-, tetraethylene glycol, 1, 2-propanediol, di-, tri-, tetrapropylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, 2, 3-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, trimethylolpropane, trimethylolethane, pentaerythritol, 2-dimethyl-1, 3-propanediol, 1, 4-dihydroxycyclohexane, 1, 4-dimethylolcyclohexane, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol or mixtures thereof, preferably 1, 3-propanediol, 1, 4-butanediol, neopentyl glycol.

Suitable components f) also start to be alcoholates of glycerides, for example soybean oil alcoholates, castor oil alcoholates, preferably soybean oil alcoholates having a hydroxyl number of 290-300.

Component g) shown is more preferably one or more of soybean oil alcoholysis, neopentyl glycol, 1, 4-butanediol with a hydroxyl number of 290-300

In the present invention, the component g) provides hydrophilicity as a hydrophilic group while providing chain extension or chain termination. Suitable hydrophilic groups may be nonionic groups, ionic groups, and potentially ionic groups.

Suitable hydrophilic compounds may be: ring-opened homo-or copolymers of ethylene oxide, styrene oxide, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin; dehydration condensation products of di-and/or polyols or mixtures thereof. Wherein the number of ethylene oxide in each molecule is 4 to 200, preferably 12 to 75. Polyethoxyethers having a number average molecular weight of 200 to 8000 and an ethylene oxide number of 4 to 200 are preferred, and 1-2 functionality having a number average molecular weight of 400 to 3000 and an ethylene oxide number of 9 to 75 are more preferred. Particularly preferred are polyethylene glycol monomethyl ether having a number average molecular weight of 500 to 2000 and an ethylene oxide number of 12 to 48.

Suitable components g) also include one or more of N- (2-aminoethyl) -2-aminoethane sulfonate, dimethylolpropionate.

More suitable components g) are one or both of dimethylolpropionate and polyethylene glycol monomethyl ether.

Wherein the dimethylolpropionate is obtained by partially or completely neutralizing the carboxyl group in dimethylolpropionic acid with a neutralizing agent. Examples of suitable neutralizing agents are, for example, one or more of primary, secondary, and tertiary amines, including, but not limited to, one or more of ethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, morpholine, N-methylmorpholine, N-methyldiethanolamine, triethylamine, dimethylcyclohexylamine, ethyldiisopropylamine, and the like. Triethylamine is preferred.

In general, a neutralizing agent is added such that the degree of neutralization is at least 50%, preferably at least 65%, and not more than 150%, based on the carboxylic acid introduced. The neutralization degree is particularly preferably 80 to 105%.

In the present invention, the optional component h) acts as a chain extender to achieve higher molecular weights or a capping agent to control molecular weight build-up, suitable components h) may be compounds containing 1 to 3 NCO-reactive functional groups including one or more of hydroxyl, primary amino, secondary amino; preferably, when component h) is a compound containing from 2 to 3 NCO-reactive functional groups, at least two of which are primary or secondary amino groups. Such as aliphatic and/or cycloaliphatic primary di-or triamines (e.g., 1, 2-ethylenediamine, 1, 6-hexamethylenediamine, 1-amino-3, 5-trimethyl-5-aminomethylcyclohexane (isophoronediamine), piperazine, 1, 4-diaminocyclohexane, bis- (4-aminocyclohexyl) methane, and diethylenetriamine). Amino alcohols, i.e. compounds containing amino and hydroxyl groups in one molecule, such as 1, 3-diamino-2-propanol, N- (2-hydroxyethyl) ethylenediamine, N-bis (2-hydroxyethyl) ethylenediamine and 2-propanolamine, are also possible. Suitable components h) are compounds containing 1 NCO-reactive functional group for controlling the molecular weight, such as ethanolamine, diethanolamine, dipropanolamine, etc., preferably diethanolamine, and mixtures of the above-mentioned compounds.

In the context of the present invention, the components h) mentioned are preferably isophoronediamine, N- (2-hydroxyethyl) ethylenediamine, 1, 6-hexamethylenediamine, diethanolamine and mixtures thereof. Isophoronediamine is more preferred.

The aqueous polyurethane-urea dispersions according to the invention have a solids content of 30 to 50% by weight, preferably 35 to 45% by weight. The pH of the dispersion is from 5 to 11, preferably from 7.2 to 10. The average particle diameter is usually 15 to 550nm, preferably 25 to 120nm.

The invention aims at obtaining polyurethane-polyurea dispersoids with DA reactive groups by directly grafting maleimide and furfuryl alcohol as DA reactive monomers onto polyurethane segments. The DA reactive functional group is used for reversible DA reaction, and the polyurethane chain segment is subjected to ring forming-ring opening reaction at different temperatures, so that the molecular weight is reduced at higher construction temperature due to the ring opening reaction, the coating film is more easily leveled and wetted, the ring forming reaction occurs after the temperature is cooled down, the molecular weight is increased, the excellent hardness and the crosslinking degree are provided, and the resistance is provided. In addition, the norbornadiene derivative with a high rigidity bridged ring structure and smaller molecular weight is externally added to react with DA monomer obtained by high-temperature ring opening to synergistically increase the molecular weight, improve the rigidity and increase the hardness and the resistance of a paint film. Can be used as an adhesive and a coating, and can be widely applied to the fields of hard base materials such as plastics, metals, woodware, inorganic materials and the like.

The invention also provides a process for the preparation of the aqueous polyurethane-urea dispersion described above by reacting components b), d), e), g) in one or more steps to form an isocyanate-terminated prepolymer, then reacting the prepolymer with component f), component a) to a theoretical value, cooling to 30 to 50 ℃, adding component c), dispersing or dissolving with water, where optionally component h) is added after dispersion; wherein component g) can be added in the first step or in the second step; optionally a solvent inert to the isocyanate, which is added during the initial and/or during the reaction to reduce the viscosity and can be partially or completely removed by distillation during or after the dispersion, is optionally added with further functional auxiliaries to impart specific properties, such as anti-yellowing auxiliaries, anti-uv auxiliaries, hydrolysis auxiliaries, etc.

Suitable solvents are acetone, methyl isobutyl ketone, butanone, tetrahydrofuran, dioxane, acetonitrile, dipropylene glycol dimethyl ether, 1-methyl-2-pyrrolidone, etc., which may be added not only at the beginning of the preparation but also during the reaction or after the end. It is also possible to add it batchwise. Acetone and butanone are preferred, and acetone is more preferred.

The preparation of the aqueous polyurethane-urea dispersions according to the invention can be carried out in one or more stages in homogeneous phase or, in the case of multistage reactions, partly in the disperse phase. The complete or partial polymerization is followed by a dispersing, emulsifying or dissolving step. Optionally, the polyaddition or modification can be carried out further afterwards in the disperse phase.

The ratio of the NCO molar amount of the isocyanate used to prepare the aqueous polyurethane-urea dispersion of the present invention to the sum of the molar amounts of hydroxyl and amino groups is from 1.08 to 2.0:1, preferably 1.15-1.70:1.

conventional catalysts, which are known to those skilled in the art for accelerating the reaction of NCO with OH, may be used. For example, triethylamine, 1, 4-diazabicyclo- [2, 2] -octane, dibutyl tin oxide, tin dioctanoate or dibutyl tin dilaurate, tin bis- (2-ethylhexanoate), bismuth neodecanoate, bismuth 2-ethylhexanoate, and the like. Bismuth neodecanoate and bismuth 2-ethylhexanoate are preferable, and bismuth neodecanoate is more preferable. The catalyst may be added before the polymerization reaction starts or during the polymerization.

Compared with the existing aqueous polyurethane-urea adhesive, the DA reaction monomer adopted by the invention has the advantages of high reaction speed, high safety and simple process, is suitable for large-scale manufacture, solves the problem that the existing single-component polyurethane-urea dispersion is difficult to balance in the aspects of resistance and leveling, and can realize the purposes of high Wen Liuping effect, good low-temperature resistance and high hardness without adding a high-boiling-point solvent. Can be used as an adhesive and a coating (providing the performances of bonding, surface treatment and surface protection), and the base material is in the field of hard base materials such as plastics, metals, woodware, inorganic materials and the like.

May also be used with auxiliary substances and additives known in the coating or adhesive arts. Such as emulsion agents, light stabilizers (e.g., UV absorbers and sterically Hindered Amines (HALS)), as well as antioxidants, fillers, anti-settling agents, defoamers and/or wetting agents, flow regulators, reactive diluents, plasticizers, neutralizing agents, catalysts, co-solvents, thickeners, pigments, dyes, matting agents, tackifiers (lockers), and the like.

Detailed Description

The present invention will be described in further detail with reference to the following examples, but the scope of the present invention is not limited to these examples.

The main raw materials used are as follows:

diol I: soybean oil alcoholysis, OH number = 299mg KOH/g, wanhua chemistry

Dihydric alcohol II: polyadipic acid-neopentyl glycol ester diol, OH number=112 mg KOH/g, wanhua chemistry

Diol III: polycarbonate diol, OH number=56 mg KOH/g, basf

Diol VI: polyoxyethylene ether, OH value=112 mg KOH/g, wanhua chemistry

Isocyanate I: hexamethylene diisocyanate [ ]

HDI, wanhua chemistry

Isocyanate II: isophorone diisocyanate [ ]

IPDI, wanhua chemistry

Isocyanate III: dicyclohexylmethane diisocyanate [ ]

HMDI, wanhua chemistry

Polyether I: polyethylene glycol monomethyl ether having an average molecular weight of 1200g/mol (Korean Letian)

Polyether II: polyethylene glycol monomethyl ether having an average molecular weight of 520g/mol, (Han Nong chemistry)

7-t-Butoxynorbornadiene (CAS NO 877-06-5) Shanghai Michael chemical Co., ltd

Bicyclo [2, 1] -hept-2, 5-diene-2-carboxylic acid methyl ester (CAS NO 3604-36-2) Honest Joy Holdings Limited

Aziridinyl-1- (bicyclo [ 2.2.1 ] -hept-2.5-dien) -2-one (CAS NO 253333-54-9) Chemstep

Particle size was determined by a Markov laser particle sizer Nano-S90.

Example 1

99g of dehydrated diol II, 9.36g of DMPA (2, 2-dimethylolpropionic acid), 120g of HMDI, 6g of alpha-furylmethanol, 0.08g of bismuth 2-ethylhexanoate, 17g of acetone were charged into a 1L four-necked round bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 70 to 90℃until the NCO reached 7.6% by weight. 59.92g of diol I, 0.06g of bismuth 2-ethylhexanoate, 4g of maleimide and 29g of acetone are added, until the NCO reaches 0.6% by weight, 412g of acetone are added, the temperature is reduced to 40℃after dilution, 12g of aziridinyl-1- (bicyclo [2, 1] -hept-2, 5-dien) -2-one are added, and 7g of triethylamine are added for neutralization for 5min. 553g of water was added to disperse the mixture. After separation of the acetone by distillation, 0.89g of emulsifier LCN407, 0.03g of defoamer were added. An aqueous solvent-free polyurethane-urea dispersion was obtained having a solids content of 35% by weight and an average particle diameter of 45nm and a pH value of 8.0.

Example 2

88g of dehydrated diol III, 6g of DMPA, 120g of IPDI, 4g of alpha-furyl alcohol, 0.06g of bismuth 2-ethylhexanoate, 17g of acetone are added to a 1L four-necked round bottom flask equipped with a nitrogen inlet and outlet, and the mixture is stirred at 70-90 ℃ until the NCO reaches 14.66wt%. 123g of diol I, 3g of maleimide, 8.3g of polyether 1, 0.06g of bismuth 2-ethylhexanoate and 29g of acetone are added, until NCO reaches 1% by weight, 472g of acetone are added, and after dilution, 6g of methyl bicyclo [2, 1] -hept-2, 5-diene-2-carboxylate are added. Then, 4.5g of triethylamine was added thereto to neutralize the mixture for 5 minutes. 582g of water was added to disperse the mixture. The chain extension was continued for 5min with the addition of 5g of IPDA. After separation of the acetone by distillation, 0.89g of emulsifier LCN407, 0.03g of defoamer were added. An aqueous solvent-free polyurethane-urea dispersion was obtained having a solids content of 38% by weight and an average particle diameter of 75 nm, pH 8.1.

Example 3

88g of dehydrated diol II, 2g of DMPA, 134g of HDI, 10g of alpha-furyl methanol, 25g of diol-VI, 0.06g of bismuth 2-ethylhexanoate and 17g of acetone are added into a 1L four-necked round bottom flask with a nitrogen inlet and outlet, and the mixture is stirred at 70-90 ℃ until NCO reaches 17.2wt%. 150g of diol I, 7g of NPG, 3g of maleimide, 2.3g of polyether II, 0.06g of bismuth 2-ethylhexanoate and 29g of acetone are added, until the NCO reaction reaches 1.1% by weight, 582g of acetone are added, the mixture is diluted, the temperature is reduced to 40℃and 25g of 7-tert-butoxynorbornadiene are added. 1.2g of triethylamine was added thereto to neutralize the mixture for 5 minutes. 514g of water was added to disperse the mixture. After separation of the acetone by distillation, 0.89g of emulsifier LCN407, 0.03g of defoamer were added. An aqueous solvent-free polyurethane-urea dispersion was obtained having a solids content of 40% by weight and an average particle diameter of 120nm and a pH value of 7.7.

Example 4

76g of dehydrated diol III, 5g of DMPA, 124g of HMDI, 6g of alpha-furylmethanol, 0.06g of bismuth 2-ethylhexanoate, 12g of diol VI, 17g of acetone were added to a 1L four port round bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 70-90℃until the NCO reached 11.4wt%. 87g of diol I, 4g of maleimide, 2g of BDO, 0.05g of bismuth 2-ethylhexanoate and 29g of acetone are added, until the NCO reaction reaches 0.8% by weight, 422g of acetone are added, the reaction mixture is diluted and reduced to 40℃after which 5g of aziridinyl-1- (bicyclo [2, 1] -hept-2, 5-dien) -2-one are added. 3.75g of triethylamine was added thereto to neutralize the mixture for 5 minutes. 512g of water was added to disperse the mixture. 1g of IPDA was added and chain-extended for 5min, after separation of the acetone by distillation, 0.8g of emulsifier LCN407, 0.02g of defoamer were added. An aqueous solvent-free polyurethane-urea dispersion was obtained having a solids content of 38% by weight and an average particle diameter of 65nm and a pH value of 8.3.

Comparative example 1

99g of dehydrated diol II, 9.36g of DMPA, 120g of HMDI, 6g of alpha-furylmethanol, 0.08g of bismuth 2-ethylhexanoate, 17g of acetone were added to a 1L four port round bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 70 to 90℃until the NCO reached 7.6% by weight. 59.92g of diol I, 0.06g of bismuth 2-ethylhexanoate, 4g of maleimide and 29g of acetone are added, the reaction is continued until 0.6 wt.% of acetone is added, after dilution is opened, the temperature is reduced to 40℃and 7g of triethylamine are added for neutralization for 5min. 553g of water were added to disperse the mixture. After separation of the acetone by distillation, 0.89g of emulsifier LCN407, 0.03g of defoamer were added. An aqueous solvent-free polyurethane-urea dispersion was obtained having a solids content of 35% by weight and an average particle diameter of 45nm and a pH value of 7.3.

Comparative example 2

99g of dehydrated diol II, 9.36g of DMPA, 120g of HMDI, 0.08g of bismuth 2-ethylhexanoate, and 17g of acetone were added to a 1L four port round bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 70 to 90℃until the NCO reached 8.8% by weight. 59.92g of diol I, 0.06g of bismuth 2-ethylhexanoate, 29g of acetone are added, the reaction is continued until 1.0% by weight, 402g of acetone are added, after dilution is opened, the temperature is reduced to 40℃and 12g of aziridinyl-1- (bicyclo [2, 1] -hept-2, 5-diene) are added, followed by 7g of triethylamine for neutralization for 5min. 608g of water are added to disperse the mixture. After separation of the acetone by distillation, 0.89g of emulsifier LCN407, 0.03g of defoamer were added. An aqueous solvent-free polyurethane-urea dispersion was obtained having a solids content of 35% by weight and an average particle diameter of 45nm and a pH value of 8.5.

Application example (Metal high-gloss varnish)

The formulation of the metallic high gloss varnish is shown in the following table 1, and the preparation method thereof comprises the following steps: the components in table 1 are added in sequence under stirring at 1500r/min at room temperature according to the weight portion ratio, the mixture is stirred for 15-30 minutes until the components are completely dispersed, then a wire rod is adopted to scrape a coating film of 0.2 mu m on polished tinplate, after the mixture is dried at normal temperature, the mixture is baked for 2 minutes at 100 ℃, and the result is shown as 2.

TABLE 1 composition of raw materials in parts by weight

Evaluation results (acetic acid resistance, ethanol resistance, alkali resistance, water resistance)

Acetic acid resistance test: dripping edible vinegar on the surface of the coating film, standing at normal temperature for 1h, and observing the change of the coating film

Ethanol resistance test: dropping 50wt% ethanol/water solution onto the surface of paint film, standing at normal temperature for 1 hr, and observing the change of paint film

Alkali resistance test: dripping 50g/L sodium bicarbonate aqueous solution on the surface of a paint film, standing for 1h at normal temperature, and observing the change of the paint film

And (3) water resistance test: deionized water with the conductivity lower than 2 mu S/cm and at 40 ℃ is prepared, the template is placed in water in a mode of 15-20 degrees relative to the vertical direction, more than three fourths of the template is kept below the water surface, after one day, the template is taken out and placed between constant temperature and humidity (25 ℃ and relative humidity of 60-70%) for 24 hours, and whether the paint film turns white or not and whether the whitening can be recovered or not is observed.

Gloss is tested according to GB/T9754-2007 (85 DEG), leveling effect can be judged by gloss, and the higher the gloss, the better the leveling.

TQC pendulum hardness, SPO500.

It can be seen from the table that the polyurethane dispersion prepared using the present invention has excellent gloss and resistance when applied to the field of metallic paint, and that in comparative example 1, in comparison with comparative example 1/2, the gloss can be substantially balanced but the hardness is low because norbornadiene having a high rigidity bridged ring structure is not added, as compared with the formulation in which furfuryl alcohol and maleimide are only added. However, the addition of only norbornadiene having a highly rigid bridged ring structure does not allow the hardness to be increased because of the absence of DA groups capable of reacting with the norbornadiene.

This demonstrates that the DA monomer of this patent opens the ring formed by the DA monomer at higher construction temperatures, and that the lower molecular weight imparts excellent leveling and wetting to the coating film. After the temperature drops, the ring-opened DA monomer re-rings, increasing the molecular weight, imparting hardness and resistance. In addition, the hardness and resistance of the coating film can be further increased under the condition of adding norbornadiene with a high-rigidity bridged ring structure.

Claims

1. An aqueous polyurethane-urea dispersion, characterized in that the polyurethane polyurea contained in the aqueous polyurethane-urea dispersion is a reaction product obtained by a reaction comprising:

c) An unsaturated diolefin containing a bridged ring structure,

d) At least one macrodiol and/or polyol,

e) At least one of the components of the polyisocyanate,

g) At least one component having sulfonate and/or carboxylate and/or polyethoxy groups, which additionally has at least one amino group reactive with isocyanate and thus incorporates sulfonate and/or carboxylate and/or polyethoxy structural units into the polyurethane segment,

h) Optionally one is a mono-and/or di-and/or tri-amino-compound;

the structural formula of the component a) is as follows

Wherein R represents H or hydroxy; component b) is selected from alpha-furyl alcohol, and has the structural formula shown in the specification

Wherein n represents 1,2, 3; component C) is selected from aziridinyl-1- (bicyclo [2, 1] -hept-2, 5-diene) -2-one (A), tert-butoxynorbornadiene (B), methyl bicyclo [2, 1] -hept-2, 5-diene-2-carboxylate (C); component a) is 0.5 to 3% by weight of the solids of the aqueous polyurethane-urea dispersion; component b) is 0.01 to 5% by weight of the solids of the aqueous polyurethane-urea dispersion; component c) is 0.01 to 10% by weight of the solids of the aqueous polyurethane-urea dispersion; component d) is 15 to 50% by weight of the solids of the aqueous polyurethane-urea dispersion; component e) is 25 to 50% by weight of the solids of the aqueous polyurethane-urea dispersion; component f) is 15-40% by weight of the solids of the aqueous polyurethane-urea dispersion; component g) is 0.1 to 10% by weight of the solids of the aqueous polyurethane-urea dispersion; component h) is 0 to 10% by weight of the solids of the aqueous polyurethane-urea dispersion.

2. The aqueous polyurethane-urea dispersion according to claim 1, characterized in that component a) is 0.6 to 1.3% by weight of the solids of the aqueous polyurethane-urea dispersion; component b) is 1 to 2.3% by weight of the solids of the aqueous polyurethane-urea dispersion; component c) is 1.5 to 6% by weight of the solids of the aqueous polyurethane-urea dispersion; component d) is 23-32% by weight of the solids of the aqueous polyurethane-urea dispersion; component e) is 29 to 39% by weight of the solids of the aqueous polyurethane-urea dispersion; component f) is 18 to 37% by weight of the solids of the aqueous polyurethane-urea dispersion; component g) is 0.9 to 4% by weight of the solids of the aqueous polyurethane-urea dispersion; component h) is 0.3 to 1.4% by weight of the solids of the aqueous polyurethane-urea dispersion.

3. The aqueous polyurethane-urea dispersion according to claim 1, characterized in that,

component b) is selected from one or more of alpha-furyl methanol, alpha-furyl ethanol and alpha-furyl propanol.

4. An aqueous polyurethane-urea dispersion according to any of claims 1 to 3 in which component c) is selected from aziridinyl-1- (bicyclo [2, 1] -hept-2, 5-dien) -2-one.

5. An aqueous polyurethane-urea dispersion according to any of claims 1 to 3 in which component d) is a diol or polyol having a hydroxyl functionality of from 2 to 5 and a number average molecular weight of from 500 to 15000 daltons.

6. The aqueous polyurethane-urea dispersion according to claim 5, wherein component d) is one or more of diols, triols and tetrols having a number average molecular weight of greater than 600 and equal to 8000 daltons.

7. The aqueous polyurethane-urea dispersion according to claim 5, wherein component d) is one or more of polyester diols and polyether diols having a number average molecular weight of from 1000 to 2000 daltons.

8. An aqueous polyurethane-urea dispersion according to any of claims 1 to 3 in which component e) is selected from isocyanates having a functionality of from 1.5 to 5.0 and an nco content of from 7 to 55% by weight, selected from one or more of aliphatic, cycloaliphatic, aromatic and araliphatic isocyanates.

9. The aqueous polyurethane-urea dispersion according to claim 8, wherein the isocyanate is selected from one or more of 1, 6-hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate.

10. An aqueous polyurethane-urea dispersion according to any of claims 1-3 in which component f) is selected from one or more of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, trimethylolpropane, trimethylolethane, pentaerythritol, soybean oil alcoholysis.

11. An aqueous polyurethane-urea dispersion according to any of claims 1 to 3 in which component g) is selected from the group consisting of the use of one or more of N- (2-aminoethyl) -2-aminoethane sulfonate, dimethylol propionate, polyethylene glycol monomethyl ether; and/or, the component h) is one or more selected from isophorone diamine, N- (2-hydroxyethyl) ethylene diamine, 1, 6-hexamethylenediamine and diethanolamine.

12. The process for the preparation of an aqueous polyurethane-urea dispersion according to any one of claims 1 to 11, characterized in that components b), d), e), g) are reacted in one or more steps to form an isocyanate-terminated prepolymer, which prepolymer is then reacted with component f), component a) to a theoretical value, cooled to 30 to 50 ℃, component c) is added, dispersed or dissolved with water, wherein optionally component h) is added after dispersion; wherein component g) is added in the first or second step; optionally a solvent inert to the isocyanate which is added at the beginning and/or during the reaction to reduce the viscosity and can be removed partially or completely by distillation during or after the dispersion.

13. Use of an aqueous polyurethane-urea dispersion according to any one of claims 1 to 11 or an aqueous polyurethane-urea dispersion prepared according to the method of claim 12 or a formulation of polyurethane-urea with other emulsions as an adhesive or coating, the substrate being a plastic, wood, inorganic material.