CN113461896B

CN113461896B - Waterborne polyurethane resin and preparation method and application thereof

Info

Publication number: CN113461896B
Application number: CN202010241476.XA
Authority: CN
Inventors: 周操; 纪学顺; 胡海东; 韩克�; 刘姗; 晋云全; 孙家宽
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2020-03-31
Filing date: 2020-03-31
Publication date: 2022-08-05
Anticipated expiration: 2040-03-31
Also published as: CN113461896A

Abstract

The invention provides a novel aqueous polyurethane resin and a preparation method and application thereof, wherein the novel aqueous polyurethane resin comprises the following raw materials: the polyurethane-modified polyurethane resin comprises polyisocyanate with at least two isocyanate groups, macromolecular polyol with at least two groups capable of reacting with isocyanate, a monofunctional component which is reactive to isocyanate and contains a polyethoxy chain segment, a catalyst, a sulfonic acid type hydrophilic chain extender containing active hydrogen, an amine chain extender, an amine containing a urethane bond and an amine end-capping agent. The novel waterborne polyurethane resin has excellent comprehensive properties (high solid content and good construction performance), has good initial adhesive performance when being used as an adhesive, and has the advantages of good heat resistance, excellent mechanical properties, good storage stability and easy realization of the preparation process.

Description

Waterborne polyurethane resin and preparation method and application thereof

Technical Field

The invention belongs to the technical field of waterborne polyurethane resin, and particularly relates to novel polyurethane resin and a preparation method and application thereof.

Background

The waterborne polyurethane adhesive is an adhesive which takes water as a dispersing medium to replace an organic solvent, is safe to use, is non-toxic and harmless, and does not pollute the environment. Compared with an oily adhesive, the aqueous polyurethane adhesive still has the problems of poor initial viscosity, poor adhesive strength and the like, and the aqueous polyurethane adhesive is low in solid content, so that the drying speed is slow, and the construction viscosity is high due to high solid content; these drawbacks severely limit the application and dissemination of waterborne polyurethane adhesives. Therefore, the waterborne polyurethane adhesive is modified to improve the comprehensive performance of the waterborne polyurethane adhesive, improve the application effect of the waterborne polyurethane adhesive, expand the application range of the waterborne polyurethane adhesive and become a hotspot of the research of the polyurethane industry at present.

In the synthesis of aqueous polyurethane adhesives, it is generally necessary to increase the rate of tack build, i.e., initial tack (early strength), as much as possible. The prior art generally adopts the following schemes to improve initial viscosity:

the hard segment content in polyurethane is reduced, for example, Chinese patent CN107267107A introduces a preparation method of environment-friendly water-based polyurethane adhesive, the hard segment content is lower, the method can improve the initial viscosity and simultaneously reduce the heat resistance of resin;

secondly, the content of the urethane in the resin is increased and the content of the carbamido is reduced by increasing the content of the alcohol chain extender and reducing the content of the amine chain extender, but the scheme brings the defects of overlarge dispersion viscosity, low reaction efficiency and the like, for example, the scheme is used in Chinese patent CN101235264A to synthesize the aqueous polyurethane adhesive, and the aqueous polyurethane adhesive has the defects of large dispersion viscosity, high emulsion slag content and the like;

and thirdly, the molecular weight of the polyurethane is reduced, and then the molecular weight is increased by matching with another component, for example, two components are required to be used in the process of using the epoxy modified two-component polyurethane introduced in Chemistry and addition (2012 and 05), the two components are required to be used in a short time after preparation, and the diluent also has the problems of environmental pollution and safety in the process of transportation.

Therefore, a competitive new waterborne polyurethane adhesive which can achieve better initial adhesion performance and effectively avoid the above problems is a problem to be solved.

Disclosure of Invention

The invention aims to provide a novel aqueous polyurethane resin, a preparation method and application thereof, aiming at the problems of the existing aqueous emulsion for the adhesive. The waterborne polyurethane has excellent comprehensive properties (high solid content and good construction performance), has good initial adhesion performance, good heat resistance, excellent mechanical property and good storage stability when used as an adhesive, and the preparation process is easy to realize.

In order to achieve the purpose, the invention provides a novel waterborne polyurethane resin which is prepared by reacting the following raw materials:

s1) a polyisocyanate having at least two isocyanate groups;

s2) a macropolyol having at least two groups capable of reacting with isocyanate;

s3) a monofunctional isocyanate-reactive component containing polyethoxy segments;

s4) a catalyst;

s5) sulfonic acid type hydrophilic chain extender containing active hydrogen;

s6) an amine chain extender;

s7) amines containing urethane linkages having the formula:

，

wherein X is 1 or 2, y is 0 or 1; r ₁ 、R ₂ 、R ₃ Is C1-C20 alkylene selected from substituted or unsubstituted straight chain alkylene, substituted or unsubstituted cyclic alkylene;

s8) amine blocking agents.

In the invention, the novel waterborne polyurethane resin comprises the following raw materials in parts by weight:

component S1)15 to 50 parts by weight, preferably 26 to 37 parts by weight;

component S2)150-300 parts by weight, preferably 200-240 parts by weight;

component S3)1 to 15 parts by weight, preferably 3 to 7 parts by weight;

component S4) accounts for 50-150ppm of S1-S3;

component S5)1 to 10 parts by weight, preferably 3 to 5 parts by weight;

component S6)0.1 to 10 parts by weight, preferably 0.2 to 3.5 parts by weight;

component S7) in an amount of 0.1 to 14 parts by weight, preferably 0.19 to 5.3 parts by weight.

Component S8) in an amount of 0.04 to 4.00 parts by weight, preferably 0.09 to 0.25 part by weight.

In the present invention, the component S1) is a polyisocyanate having at least two isocyanate groups, selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate, preferably selected from one or two of isophorone diisocyanate and hexamethylene diisocyanate.

In the invention, the component S2) is macromolecular polyol with at least two groups capable of reacting with isocyanate, which is selected from polyether diol and/or polyester diol, and the average molecular weight of the macromolecular polyol is 500-3000 g/mol, preferably 1500-2000 g/mol; preferably one or more selected from the group consisting of polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polytetrahydrofuran ether glycol, polycaprolactone diol, polycarbonate diol, polyethylene adipate diol, 1, 4-butanediol adipate diol, neopentyl glycol adipate diol, 1, 6-hexanediol adipate diol, and neopentyl glycol adipate 1, 6-hexanediol adipate diol, more preferably one or two selected from the group consisting of 1, 4-butanediol adipate diol, and 1, 6-hexanediol adipate diol.

In the invention, the component S3) is a monofunctional component which is reactive to isocyanate and contains polyethoxy chain segments, and the molecular weight of the component S3) is 500-3000 g/mol; preferably a polyoxyalkylene ether comprising at least one hydroxyl group and the polymerized units of said polyoxyalkylene ether are propylene oxide and/or ethylene oxide, more preferably ethylene oxide; wherein the number of ethylene oxide units in each molecule of the polyoxyalkylene ether is preferably 4 to 200, more preferably 12 to 75; further, the component S3 is preferably Tego Chemie

D-3403, Ymer N120 from Perstrop, Inc., and MPEG1200 from Letian, Korea, Inc., more preferably MPEG1200 from Letian, Korea.

In the present invention, the component S4) is a catalyst selected from 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, and preferably bismuth neodecanoate.

In the invention, the component S5) is a sulfonic acid type hydrophilic chain extender containing active hydrogen, which is selected from one or more of sodium 2- (2-aminoethyl) aminoethane sulfonate, sodium 2- (2-aminoethyl) aminopropane sulfonate, sodium 1, 4-butanediol-2-sulfonate and sodium 1, 2-dihydroxy-3-propane sulfonate, and is preferably sodium 2- (2-aminoethyl) aminoethane sulfonate.

In the invention, the component S6) is an amine chain extender, which is selected from one or more of ethylenediamine, hexamethylenediamine, pentamethylenediamine, hydroxyethylethylenediamine, isophoronediamine, bisaminopolyetheramine, and 4, 4-diphenylmethanediamine, and is preferably selected from one or two of hydroxyethylethylenediamine and isophoronediamine.

In the present invention, the component S7) contains an amine having a urethane bond, wherein R is represented by the formula ₁ 、 R ₂ 、R ₃ Which may be the same or different, preferably R ₁ 、R ₂ The same; optionally the alkylene group may also contain up to 1 heteroatom selected from oxygen, nitrogen or sulphur.

Preferably, said R is ₁ 、R ₂ 、R ₃ Is C1-C5 alkylene, more preferably R ₁ 、R ₂ 、R ₃ Substituted or unsubstituted straight chain alkylene of C1-C5;

more preferably, said R ₃ Substituted straight chain alkylene of C1-C5;

more preferably, the substituted linear alkylene group, wherein the substituents are selected from methyl, ethyl or propyl;

further, the component S7) is preferably selected from 2-hydroxypropyl (2- ((2-aminoethyl) amino) ethyl) carbamate (HPAA) and/or 2-hydroxybutyl (2- ((2-aminoethyl) amino) ethyl) carbamate (HBAA), the corresponding structural formulae of which are respectively:

in the present invention, the component S8) is an amine-based capping agent selected from one or more of diethanolamine, N-methylethanolamine and ethanolamine, preferably diethanolamine.

According to the novel aqueous polyurethane resin provided by the invention, preferably, the raw materials for preparing the aqueous polyurethane resin also comprise an organic solvent which does not contain a group capable of reacting with isocyanate; more preferably, the organic solvent is selected from acetone and/or butanone, and further preferably acetone.

According to the novel aqueous polyurethane resin provided by the invention, preferably, the raw material also comprises water, and the product is an aqueous dispersion of a polyurethane resin polymer.

Another object of the present invention is to provide a method for preparing the aqueous polyurethane resin, comprising the steps of:

(1) component S1), component S2) and component S3) are catalyzed by component S4) to prepare a diisocyanate-terminated prepolymer;

(2) adding an organic solvent into the diisocyanate-terminated prepolymer prepared in the step (1) for dissolving and diluting to obtain a diluted prepolymer;

(3) adding the component S5), the component S6) and the component S7) into the diluted prepolymer obtained in the step (2), and performing chain extension reaction at 40-50 ℃ for 15-25 min to obtain a chain-extended prepolymer;

(4) adding a component S8 into the chain-extended prepolymer obtained in the step (3), carrying out end-capping reaction at 40-50 ℃ for 5-10 min, and then adding water to disperse to obtain a waterborne polyurethane coarse emulsion;

(5) and (4) removing the organic solvent from the aqueous polyurethane crude emulsion obtained in the step (4) to obtain the novel aqueous polyurethane resin.

The preparation method of the invention, in the step (1), the reaction process conditions for preparing the diisocyanate-terminated prepolymer comprise: the reaction temperature is 75-85 ℃; the reaction was stopped by the time the NCO of the reaction system reached the theoretical value. Herein, NCO is defined as the mass fraction of isocyanate groups in a sample, expressed in%, calculated as:

wherein M is _NCO 、M _OH Respectively the molar weight and the mol of isocyanate and hydroxyl in all the raw materials of the sample;

m is sample mass, g;

42 is the molar mass of NCO, g/mol.

Preferably, the reaction system in step (1) further comprises an organic solvent for dissolving each reaction component, wherein the organic solvent is an organic solvent free of a group reactive with isocyanate, preferably acetone and/or butanone, and more preferably acetone; further, the amount of the organic solvent is 0.05 to 0.4 times, preferably 0.08 to 0.2 times of the total weight of the components S1 to S3.

In the preparation method of the invention, in the step (2), the organic solvent is an organic solvent which does not contain a group reactive with isocyanate, preferably acetone and/or butanone, and more preferably acetone; further, the organic solvent is used in an amount of 1.0 to 2.1 times, preferably 1.4 to 2.0 times, the total weight of the components S1), S2), S3). In the step (1) and the step (2), the organic solvents may be the same or different, and preferably, they are the same.

Preferably, in the step (2), the diisocyanate-terminated prepolymer is dissolved and diluted by an organic solvent; the dissolving and diluting conditions comprise: the temperature is 50-60 ℃, and the time is 5-10 min.

In the preparation method of the invention, in the step (3), the chain extension reaction process conditions include: the reaction temperature is 40-50 ℃, and the reaction time is 15-25 min;

preferably, in the step (3), the component S5), the component S6) and the component S7) are diluted with water before use, the amount of water is not particularly required, and the raw materials can be dissolved, and is preferably 3 to 5 times of the sum of the mass of the components S5, S6 and S7.

In the preparation method, in the step (4), the end-capping reaction process conditions include: the reaction temperature is 40-50 ℃, and the reaction time is 5-10 min;

preferably, in the step (4), the component S8) is diluted with water before use, the amount of the water is not particularly required, and the raw material can be dissolved, and is preferably 3-5 times of the mass of the component S8);

preferably, in the step (4), water is added for dispersion, the amount of the water is not specifically required, and the aqueous polyurethane coarse emulsion is allowed to reach the solid content required by the aqueous polyurethane resin product.

In the preparation method of the present invention, step (5), the manner of removing the organic solvent is a conventional operation, and is not particularly limited, and preferably, distillation under reduced pressure is used. The removed organic solvent includes the organic solvent optionally used for dissolving each reaction component in the step (1) and the organic solvent added for dissolving and diluting the diisocyanate terminated prepolymer in the step (2).

In the invention, the solid content of the novel waterborne polyurethane resin prepared by the method is 40-57 wt%, preferably 45-55 wt%.

In the invention, the average particle size of the novel waterborne polyurethane resin is 120-250 nm, preferably 140-200 nm; molecular weight of 1X 10 ⁵ ～1×10 ⁶ g/mol。

The invention also provides the application of the novel aqueous polyurethane resin or the novel aqueous polyurethane resin prepared by the preparation method as an adhesive.

According to the application provided by the invention, the novel waterborne polyurethane resin is preferably applied to the fields of shoe glue, plastic uptake glue, laminating glue and automotive interior glue.

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

the invention uses a special amine chain extender with carbamate groups on the side chain, which forms urea groups with isocyanate groups to be grafted to a polyurethane main chain to form polyurethane-polyurea and simultaneously introduces the carbamate groups on the side chain of the polyurethane-polyurea. The ratio of the urethane group to the urea group generated by the amine chain extender is at least 2:1, and compared with the common amine chain extender, the urethane/urea group chain extender can obtain high-proportion urethane/urea groups, so that the initial viscosity of a polyurethane product is improved. In addition, the molecular weight of the polyurethane is greatly improved after the amine chain extender is adopted for reaction, and the polyurethane resin still has good heat resistance and humidity resistance. In addition, because the amine chain extender has higher reaction activity and can react with isocyanate at the temperature of 40-50 ℃, the prepolymer can be diluted by a large amount of organic solvents such as acetone, and compared with the traditional method for improving the carbamate by increasing the proportion of the alcohol chain extender and the amine chain extender, the method has higher reaction efficiency, lower dispersion viscosity and lower content of generated emulsion slag.

(2) The waterborne polyurethane prepared by the method has the advantages that the molecular chain containing the carbamate is introduced on the side group, the movement energy of the molecular chain is low, the movement can be carried out at a low temperature, when the resin is coated on the surface of a base material, the molecular chain starts to move firstly because the glass transition temperature of the molecular chain is low, and the carbamate bond on the molecular chain can form a hydrogen bond with the surface of the base material, so that the adhesive force is improved.

(3) The hydrophilicity of the waterborne polyurethane resin provided by the invention is mainly realized by sulfonic acid type hydrophilic chain extenders (such as sodium sulfamate) containing active hydrogen, neutralization is not needed, odor and VOC (volatile organic compounds) brought by neutralizers with low boiling points such as triethylamine are avoided, and the waterborne polyurethane resin is good in environmental protection performance.

(4) The invention has simple production process, convenient operation, safety and no toxicity.

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.

The embodiment of the invention has the following main raw material sources:

1、

(Isophor)Ketone diisocyanate having an NCO content of about 37.8%, wanhua chemical group ltd);

(1, 6-hexamethylene diisocyanate, NCO content about 50%, Vanhua chemical group Co., Ltd.);

(4, 4' -dicyclohexylmethane diisocyanate, NCO content about 32%, Vanhua chemical group Co., Ltd.);

2. PBA-2000 (poly 1, 4-butanediol adipate diol, hydroxyl value of 56mgKOH/g, number average molecular weight 2000, functionality of 2, dawsonia macrochemical);

PBA-3000 (poly 1, 4-butanediol adipate diol, hydroxyl value of 37.4mgKOH/g, number average molecular weight of 3000, functionality of 2, dawski chemistry);

PHA-2000 (poly 1, 6-hexanediol adipate diol with a hydroxyl number of 56mgKOH/g, a number average molecular weight of 2000, a functionality of 2, dahlia macrochemistry);

3. MPEG1200 (polyethylene glycol monomethyl ether, hydroxyl number 46.75mgKOH/g, number average molecular weight 1200, functionality 1, clonidine, korea);

4. an organic bismuth catalyst (bismuth neodecanoate, advanced chemical company, usa);

5. organic solvents (acetone, nibowanghua);

6、

a95 (sodium 2- (2-aminoethyl) tauride, 51 + -2% solids aqueous solution, amine number 260 + -20 mgKOH/g, EVONIK, Germany);

7. IPDA (Isophorone diamine, Vanhua chemical group Ltd.);

hydroxyethylethylenediamine (Yangzhitin-Pasteur, Inc.);

8. DEOA (diethanolamine, raisin-basf llc);

9. 2-hydroxypropyl (2- ((2-aminoethyl) amino) ethyl) carbamate (HPAA): adding 303g of 1, 4-bis-BOC-1, 4,7 triazaheptane into a four-neck flask with a condensing tube and a thermometer, heating to 90 ℃ under the condition of introducing nitrogen, dropwise adding 102g of propylene carbonate within 2H, preserving the heat at 100 ℃ for 4H after the dropwise adding is finished until the amine value is less than 0.2%, adding 400g of deionized water after the reaction is finished, heating to 100 ℃ for refluxing for 4-5H, distilling to remove distilled water, separating and purifying to obtain the compound, wherein the hydrogen spectrum data of the compound are a (1.18ppm, d,3H), b (2.66ppm, m,6H), c (3.28ppm, t,2H), d (3.99ppm, m,1H), e (4.11ppm, m,1H), f (4.36ppm, 1H);

10. 2-hydroxybutyl (2- ((2-aminoethyl) amino) ethyl) carbamate (HBAA): 303g of 1, 4-bis-BOC-1, 4,7 triazaheptane is added into a four-neck flask with a condenser and a thermometer, the flask is heated to 90 ℃ under the condition of introducing nitrogen, 116g of butylene carbonate is added dropwise within 2H, the temperature is kept at 100 ℃ for 4H after the dropwise addition is finished until the amine value is less than 0.2%, 400g of deionized water is added after the reaction is finished and the flask is heated to 100 ℃ for reflux for 4-5H, distilled water is removed by distillation, and the product is obtained by separation and purification, and the hydrogen spectrum data of the product are a (0.9ppm, t,3H), b (1.48ppm, m,2H), c (2.66ppm, m,6H), d (3.28ppm, m,2H), e (3.81ppm, m,1H), f (4.11ppm, m,1H), g (4.36ppm, m, 1H).

Example 1

(1) 32g of a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was placed in the flask

5g

200g PHA-2000, 7g MPEG1200, 100ppm of organic bismuth catalyst and 21g of acetone as raw materials, and reacting at 75 ℃, sampling and monitoring the NCO of the system in the reaction process until the NCO reaches 3.49 percent of a theoretical value, and generating a diisocyanate-terminated prepolymer;

(2) cooling to about 60 ℃, adding 341g of acetone, and stirring for 5min to obtain a diluted diisocyanate-terminated prepolymer;

(3) mixing 14g ofHPAA and 5g

Diluting 0.2g of hydroxyethyl ethylenediamine with 77g of deionized water, adding the diluted solution into a reaction system at the temperature of 45 ℃, and stirring the solution to perform chain extension reaction for 20min to obtain a chain-extended prepolymer;

(4) diluting 0.64g of diethanolamine by 3g of deionized water, adding the diluted solution into a reaction system, and carrying out end capping reaction for 5min at 45 ℃; adding 257g of water under the condition of shearing dispersion, and obtaining the aqueous polyurethane crude emulsion after shearing dispersion;

(5) distilling the crude emulsion under reduced pressure to remove the solvent acetone to prepare a novel milky blue-light-evident waterborne polyurethane emulsion-1 (namely the novel waterborne polyurethane resin of the invention);

the resin had a particle size of 160nm and a molecular weight of 120000g/moL, the emulsion had a solid content of 45 wt% and the emulsion had a residue content of 50ppm (residue content is the weight ratio of the residue remaining on the filter to the emulsion weight, the emulsion formed after acetone removal from the emulsion by a rotary evaporator was filtered through a 100 mesh filter).

Comparative example 1

(1) A diisocyanate-terminated prepolymer was prepared in the same manner as in step (1) of example 1;

(2) the temperature was reduced to about 60 ℃ and 6.3g of 1, 4-butanediol and 100g of acetone were added and reacted, it being found that after 5h of reaction, the NCO remained 0.4% (theoretical 0.02%);

(3) mixing 5g

Diluting with 20g of deionized water, adding the diluted solution into a reaction system at 45 ℃, and stirring the solution to perform chain extension reaction for 20 min;

(4) diluting 0.64g of diethanolamine by 3g of deionized water, adding the diluted solution into a reaction system, and carrying out end capping reaction for 5min at 45 ℃; adding 257g of water under the condition of shearing dispersion, and obtaining the aqueous polyurethane crude emulsion after shearing dispersion (the dispersion viscosity is found to be larger);

(5) distilling the crude emulsion under reduced pressure to remove the solvent acetone, wherein the content of emulsion residues is high, and preparing aqueous polyurethane emulsion;

the solid content of the emulsion is 45 wt%, the slag content is 260ppm, the particle size of the resin is 160nm, and the molecular weight is 110000g/moL L.

Comparative example 2

(3) 7g of hydroxyethylethylenediamine and 5g

Diluting with 48g of deionized water, adding the diluted solution into a reaction system at 45 ℃, and stirring the solution to perform chain extension reaction for 20 min;

(4) diluting 0.64g of diethanolamine by 3g of deionized water, adding the diluted solution into a reaction system, and carrying out end capping reaction for 5min at 45 ℃; adding 257g of water under the condition of shearing dispersion, and obtaining the aqueous polyurethane coarse emulsion after shearing dispersion;

(5) distilling the crude emulsion under reduced pressure to remove solvent acetone to obtain aqueous polyurethane emulsion;

the emulsion had a solid content of 45 wt%, a slag content of 60ppm, a resin particle size of 150nm and a molecular weight of 130000 g/moL.

Comparative example 3

32g of a four-necked flask equipped with a reflux condenser, a thermometer and a mechanical stirrer was charged into the flask

5g

200g PHA-2000, 7g MPEG1200, 14g HPAA, and the raw material of 100ppm of organobismuth catalyst, 21g acetone, at 75 ℃ reaction, found that after the reaction for 1 hour, gel was formed.

Example 2

(1) To a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was added 5g

25g

230g of PBA-2000, 3g of MPEG1200, 150ppm of organic bismuth catalyst and 53g of acetone as raw materials, and reacting at 85 ℃, sampling and monitoring NCO of a system in the reaction process until NCO reaches 1.37 percent of a theoretical value, and generating a diisocyanate-terminated prepolymer;

(2) cooling to about 50 ℃, adding 526g of acetone, and stirring for 10min to obtain a diluted diisocyanate-terminated prepolymer;

(3) 2g of hydroxyethylethylenediamine, 0.5g of HPAA and 3g of

Diluting with 16.5g of deionized water, adding the diluted solution into a reaction system at 40 ℃, and stirring the solution to perform chain extension reaction for 25 min;

(4) diluting 0.23g of diethanolamine by 1g of deionized water, adding the diluted solution into a reaction system, and carrying out end capping reaction for 10min at 40 ℃; adding 300g of water under the condition of shearing dispersion, and obtaining the aqueous polyurethane crude emulsion after shearing dispersion;

(5) distilling the crude emulsion under reduced pressure to remove the solvent acetone to prepare a novel milky blue-light-evident waterborne polyurethane emulsion-2;

the particle size of the resin is 140nm, the molecular weight is 110000g/moL, the solid content of the emulsion is 50 wt%, and the slag content is 65 ppm.

Example 3

(1) To a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was added 8g

18g

240g of PBA-3000, 5g of MPEG1200, 50ppm of organic bismuth catalyst and 22g of acetone as raw materials, and reacting at 80 ℃, sampling and monitoring NCO of a system in the reaction process until NCO reaches 1.75 percent of a theoretical value, and generating a diisocyanate-terminated prepolymer;

(2) cooling to about 55 ℃, adding 450g of acetone, and stirring for 8min to obtain a diluted diisocyanate-terminated prepolymer;

(3) 1.5g of hydroxyethylethylenediamine, 3.2g of HBAA and 4g of

Diluting with 25.1g of deionized water, adding the mixture into a reaction system at 50 ℃, and stirring the mixture to perform chain extension reaction for 15 min;

(4) diluting 0.4g of diethanolamine by 1.6g of deionized water, adding the diluted solution into a reaction system, and carrying out end capping reaction for 10min at 50 ℃; adding 320g of water into the end-capping reagent under the condition of shearing dispersion, and obtaining the aqueous polyurethane crude emulsion after shearing dispersion;

(5) distilling the crude emulsion under reduced pressure to remove the solvent acetone to prepare novel milky white blue-light-evident waterborne polyurethane emulsion-3;

the resin had a particle size of 150nm and a molecular weight of 115000g/moL, the emulsion had a solids content of 40 wt% and a residue content of 45 ppm.

Example 4

(1) Into a four-necked flask equipped with a reflux condenser, a thermometer and a mechanical stirrer were charged 35g

230g of PBA-2000, 5.5g of MPEG1200, an organic bismuth catalyst with 200ppm of raw materials and 23g of acetone are reacted at 80 ℃, and NCO of a system is sampled and monitored in the reaction process until NCO reaches 2.61 percent of a theoretical value, so that a diisocyanate-terminated prepolymer is generated;

(2) cooling to about 60 ℃, adding 460g of acetone, and stirring for 5min to obtain a diluted diisocyanate-terminated prepolymer;

(3) 3.5g of hydroxyethylethylenediamine, 3g of HBAA and 5g of

Diluting with 46g of deionized water, adding the diluted solution into a reaction system at 48 ℃, and stirring the solution to perform chain extension reaction for 18 min;

(4) diluting 0.6g of diethanolamine by 2.4g of deionized water, adding the diluted solution into a reaction system, and carrying out end capping reaction for 8min at 48 ℃; adding 297g of water under the condition of shearing dispersion, and obtaining the aqueous polyurethane coarse emulsion after shearing dispersion;

(5) distilling the crude emulsion under reduced pressure to remove the solvent acetone to prepare novel milky white blue-light-evident waterborne polyurethane emulsion-4;

the resin had a particle size of 200nm, a molecular weight of 135000g/moL, an emulsion having a solids content of 45 wt% and a residue content of 70 ppm.

Example 5

(1) To a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was added 23g

10g

100g of PBA-2000, 130g of PHA-2000, 4g of MPEG1200, 100ppm of organic bismuth catalyst and 24g of acetone as raw materials, and reacting at 80 ℃, wherein NCO of the system is sampled and monitored in the reaction process until the NCO reaches 1.88 percent of a theoretical value, and a diisocyanate-terminated prepolymer is generated;

(2) cooling to about 60 ℃, adding 400g of acetone, and stirring for 5min to obtain a diluted diisocyanate-terminated prepolymer;

(3) 1g of hydroxyethylethylenediamine, 3g of HBAA and 5g of

Diluting with 45g of deionized water, adding the diluted solution into a reaction system at 50 ℃, and stirring the solution to perform chain extension reaction for 15 min;

(4) diluting 0.7g of diethanolamine by 3.5g of deionized water, adding the diluted solution into a reaction system, and carrying out end capping reaction for 8min at 50 ℃; adding 250g of water under the condition of shearing dispersion, and obtaining the aqueous polyurethane crude emulsion after shearing dispersion;

(5) distilling the crude emulsion under reduced pressure to remove the solvent acetone to prepare novel milky white blue-light-evident waterborne polyurethane emulsion-5;

the resin had a particle size of 140nm, a molecular weight of 105000g/moL, an emulsion having a solid content of 55 wt% and a residue content of 49 ppm.

Preparation of the adhesive:

100g of the aqueous polyurethane emulsion obtained in each of the examples and comparative examples, 0.05g of BYK024 (Beck chemical) were mixed and stirred at 500rpm for 5min, 0.2g of Tego245 (digao) was added thereto, further stirred for 5min, then 0.15g of Vesmody U604 (Vasmy chemical) was added thereto, and then stirred at 600rpm for 10 min.

Preparation of a sample:

the following materials were compounded to prepare composite samples:

composite material	Substrate 1	Base material 2
			A	Rubber composition	Rubber composition
B	Canvas	Canvas
			C	PVC	PVC

The specific process is as follows: firstly, treating a base material 1 (rubber) and a base material 2 (rubber) by using ethanol, and then airing for later use; each of the above adhesive dispersions was first applied thinly to the above-mentioned strips of the substrate 1 and the substrate 2 having a width of 2.5cm and a length of 15cm using a brush and dried in an oven at 65 ℃ for 5min, and then taken out30kg/cm ² And pressing for 10S to obtain the composite material A.

Composite materials B and C were prepared in the same manner.

Testing the peel strength of the composite:

the peel strength was measured with a GOTECH tensile machine at a peel rate of 200 mm/min.

1-initial strength (i.e. initial tack): and after pressing, directly testing the peel strength of the laminated board by a tensile machine.

2-late strength: after the test piece was left at room temperature for 24 hours, the peel strength was measured.

The test results are shown in Table 1.

TABLE 1 Peel Strength of the composites

As can be seen from Table 1, the initial tack of the composite material prepared based on the aqueous polyurethane resin provided by the present invention is significantly improved.

Testing of the heat resistance of the composite:

1-initial heat resistance: the prepared test piece is hung with a weight of 500 g and placed in an oven at 80 ℃, and the length of the test piece pulled apart within 30 minutes is tested.

2-late heat resistance: the prepared test piece is placed at room temperature for 3 days, a weight of 1 kg is hung, the test piece is placed in a 70 ℃ oven, and the length of the test piece pulled open within 24 hours is tested.

3-moisture and heat resistance: the prepared test piece is placed at room temperature for 3 days, a weight of 500 g is hung, and the test piece is placed in an oven with the temperature of 70 ℃ and the humidity of 95 percent to test the pulling length of the test piece within 24 hours.

The test results are shown in Table 2.

TABLE 2 Heat and moisture resistance of the composites

As can be seen from Table 2, compared with the aqueous polyurethane resin of the comparative example, the composite material prepared based on the aqueous polyurethane resin provided by the invention has significantly improved initial heat resistance and wet heat resistance.

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. The waterborne polyurethane resin is characterized by being prepared by reacting the following raw materials:

s1) a polyisocyanate having at least two isocyanate groups;

s4) a catalyst;

s5) sulfonic acid type hydrophilic chain extender containing active hydrogen;

s6) an amine chain extender;

s7) amines containing urethane linkages having the formula:

，

wherein X =1 or 2, y =0 or 1; r ₁ 、R ₂ 、R ₃ Is C1-C20 alkylene selected from substituted or unsubstituted straight chain alkylene, substituted or unsubstituted cyclic alkylene;

s8) amine blocking agents.

2. The aqueous polyurethane resin according to claim 1, wherein the amount of each component in the raw materials is:

component S1)15-50 parts by weight;

component S2)150-300 parts by weight;

1-15 parts by weight of component S3);

component S4) accounts for 50-150ppm of S1-S3;

1-10 parts by weight of component S5);

0.1 to 10 parts by weight of the component S6);

0.1 to 14 parts by weight of the component S7);

component S8)0.04-4.00 parts by weight.

3. The aqueous polyurethane resin according to claim 2, wherein the amount of each component in the raw materials is:

component S1) 26 to 37 parts by weight;

component S2) 200 and 240 parts by weight;

component S3) 3-7 parts by weight;

component S4) accounts for 50-150ppm of S1-S3;

component S5) 3-5 parts by weight;

0.2 to 3.5 parts by weight of the component S6);

0.19 to 5.3 parts by weight of the component S7);

component S8) 0.09-0.25 part by weight.

4. The aqueous polyurethane resin according to claim 1, wherein the component S7) contains an amine having a urethane bond, and R is represented by the following structural formula ₁ 、R ₂ 、R ₃ May be the same or different.

5. The aqueous polyurethane resin according to claim 4, wherein R is ₁ 、R ₂ The same is true.

6. The aqueous polyurethane resin according to claim 4, wherein R is ₁ 、R ₂ 、R ₃ The alkylene group optionally contains up to 1 heteroatom selected from oxygen, nitrogen or sulfur.

7. The aqueous polyurethane resin according to claim 4, wherein R is ₁ 、R ₂ 、R ₃ Is C1-C5 alkylene.

8. The aqueous polyurethane resin according to claim 7, wherein R is ₁ 、R ₂ 、R ₃ Is a substituted or unsubstituted straight chain alkylene group of C1-C5.

9. The aqueous polyurethane resin according to claim 8, wherein R is ₃ Is a substituted linear alkylene group of C1-C5, wherein the substituents are selected from methyl, ethyl or propyl.

10. The aqueous polyurethane resin according to claim 4, wherein the component S7) is selected from 2-hydroxypropyl (2- ((2-aminoethyl) amino) ethyl) carbamate and/or 2-hydroxybutyl (2- ((2-aminoethyl) amino) ethyl) carbamate, the corresponding structural formulae of which are respectively:

。

11. the aqueous polyurethane resin according to claim 1, wherein the component S1) is a polyisocyanate having at least two isocyanate groups, selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane diisocyanate;

the component S2) is macromolecular polyol with at least two groups capable of reacting with isocyanate, and is selected from polyether diol and/or polyester diol, and the average molecular weight of the macromolecular polyol is 500-3000 g/mol;

the component S3) is a component which is reactive to isocyanate, has single functionality and contains polyethoxy chain segments, and the molecular weight of the component S3) is 500-3000 g/mol;

the component S4), a catalyst selected from 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 component S5) is a sulfonic acid type hydrophilic chain extender containing active hydrogen, which is selected from one or more of 2- (2-aminoethyl) aminoethanesulfonic acid sodium salt, 2- (2-aminoethyl) aminopropanesulfonic acid sodium salt, 1, 4-butanediol-2-sulfonic acid sodium salt and 1, 2-dihydroxy-3-propanesulfonic acid sodium salt;

the component S6) is amine chain extender which is selected from one or more of ethylenediamine, hexamethylenediamine, pentamethylenediamine, hydroxyethyl ethylenediamine, isophorone diamine, diamino polyether amine and 4, 4-diphenylmethane diamine;

the component S8) is amine-type end capping agent selected from one or more of diethanolamine, N-methylethanolamine and ethanolamine.

12. The aqueous polyurethane resin according to claim 11, wherein the polyisocyanate having at least two isocyanate groups of component S1) is one or two selected from isophorone diisocyanate and hexamethylene diisocyanate.

13. The aqueous polyurethane resin according to claim 11, wherein the component S2), wherein the polyether diol and/or polyester diol has an average molecular weight of 1500-2000 g/mol.

14. The aqueous polyurethane resin according to claim 11, wherein the component S2) is one or more macropolyol having at least two groups reactive with isocyanate selected from the group consisting of polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polytetrahydrofuran ether glycol, polycaprolactone diol, polycarbonate diol, polyethylene adipate diol, 1, 4-butanediol adipate diol, neopentyl glycol adipate diol, 1, 6-hexanediol adipate diol, and neopentyl glycol adipate 1, 6-hexanediol adipate diol.

15. The aqueous polyurethane resin according to claim 14, wherein the component S2) is a macropolyol having at least two groups reactive with isocyanate, and is one or both of a 1, 4-butanediol adipate diol and a 1, 6-hexanediol adipate diol.

16. The aqueous polyurethane resin according to claim 11, wherein the component S3) is a monofunctional isocyanate-reactive component containing a polyethoxy segment and is a polyoxyalkylene ether containing at least one hydroxyl group, and the polymerized units of the polyoxyalkylene ether are propylene oxide and/or ethylene oxide.

17. The aqueous polyurethane resin according to claim 16, wherein the polymerized unit of the polyoxyalkylene ether is ethylene oxide.

18. The aqueous polyurethane resin according to claim 16, wherein the number of ethylene oxide units per molecule of the polyoxyalkylene ether is 4 to 200.

19. The aqueous polyurethane resin according to claim 18, wherein the number of ethylene oxide units per molecule of the polyoxyalkylene ether is 12 to 75.

20. The aqueous polyurethane resin according to claim 11, wherein the component S3 is one or more of Tegomer D-3403 from Tego Chemie, Inc., Ymer N120 from Pertrop, Inc., and MPEG1200 from Korea Letian, Inc.

21. The aqueous polyurethane resin according to claim 11, wherein the component S4) catalyst is bismuth neodecanoate.

22. The aqueous polyurethane resin according to claim 11, wherein the sulfonic acid type hydrophilic chain extender containing active hydrogen of component S5) is sodium 2- (2-aminoethyl) tauride.

23. The aqueous polyurethane resin according to claim 11, wherein the amine chain extender of component S6) is one or two selected from the group consisting of hydroxyethylethylenediamine and isophoronediamine.

24. The aqueous polyurethane resin according to claim 11, wherein the amine-based blocking agent of component S8) is diethanolamine.

25. A method for producing the aqueous polyurethane resin according to any one of claims 1 to 24, characterized by comprising the steps of:

(5) and (4) removing the organic solvent from the aqueous polyurethane crude emulsion obtained in the step (4) to obtain the aqueous polyurethane resin.

26. The method according to claim 25, wherein in the step (1), the reaction for preparing the diisocyanate-terminated prepolymer is carried out at a reaction temperature of 75 to 85 ℃ and is stopped when NCO in the reaction system reaches a theoretical value; and/or

The reaction system in the step (1) contains an organic solvent, wherein the organic solvent is an organic solvent which does not contain a group capable of reacting with isocyanate;

the dosage of the organic solvent is 0.05-0.4 time of the total weight of the components S1-S3.

27. The method of claim 26, wherein the organic solvent is acetone and/or butanone.

28. The method of claim 26, wherein the organic solvent is used in an amount of 0.08 to 0.2 times the total weight of the components S1 to S3.

29. The method according to claim 25, wherein in the step (2), the organic solvent is an organic solvent containing no group reactive with isocyanate;

the dosage of the organic solvent is 1.0 to 2.1 times of the total weight of the components S1), S2) and S3); and/or

The dissolving and diluting conditions are that the temperature is 50-60 ℃ and the time is 5-10 min.

30. The method of claim 29, wherein the organic solvent is acetone and/or butanone;

the dosage of the organic solvent is 1.4 to 2.0 times of the total weight of the components S1), S2) and S3).

31. The preparation method of claim 25, wherein in the step (3), the chain extension reaction is carried out at a temperature of 40-50 ℃ for 15-25 min.

32. The preparation method of claim 25, wherein in the step (4), the end-capping reaction is carried out at a temperature of 40 to 50 ℃ for 5 to 10 min.

33. Use of the aqueous polyurethane resin of any one of claims 1 to 24 or the aqueous polyurethane resin prepared by the process of any one of claims 25 to 32 as an adhesive.