CN110818873B - Waterborne polyurethane resin and preparation method and application thereof - Google Patents
Waterborne polyurethane resin and preparation method and application thereof Download PDFInfo
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- CN110818873B CN110818873B CN201911143047.2A CN201911143047A CN110818873B CN 110818873 B CN110818873 B CN 110818873B CN 201911143047 A CN201911143047 A CN 201911143047A CN 110818873 B CN110818873 B CN 110818873B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6622—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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Abstract
The invention belongs to the technical field of waterborne polyurethane resin, and particularly relates to waterborne polyurethane resin and a preparation method and application thereof, wherein the waterborne polyurethane resin is prepared from the following raw materials: A) a diisocyanate-terminated prepolymer; B) an organic solvent that dissolves the diluted diisocyanate-terminated prepolymer; C) a chain extender; the isocyanate-terminated diisocyanate prepolymer contains polyethylene adipate diethylene glycol and higher molecular weight polyadipate ester which are used in a synergistic manner. The resin obtained by the invention has excellent comprehensive properties including high solid content and good construction performance, and the prepared adhesive has excellent heat resistance and high bonding strength, and the preparation process is easy to realize.
Description
Technical Field
The invention belongs to the technical field of waterborne polyurethane adhesive resin, and particularly relates to a low-cost high-performance waterborne 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. Due to its excellent adhesion and environmental protection advantages, the aqueous polyurethane adhesive is widely used in various fields such as cold-bonded shoes, vulcanized rubber, absorbent plastic, automotive interior adhesive, compound adhesive, etc., and for the application properties of the aqueous polyurethane adhesive, the following properties are required: 1) excellent bonding strength; 2) proper initial heat resistance and later heat resistance; 3) hydrolytic stability; in addition to these three properties, low cost is a very significant advantage as market competition is more and more stressed.
In order to reduce the cost of the waterborne polyurethane adhesive, the waterborne polyurethane adhesive is usually obtained by modifying waterborne polyurethane. Chinese patent CN 201611038559 discloses a preparation method of a sulfonic acid type waterborne polyurethane adhesive, which comprises the steps of preparing a waterborne polyurethane prepolymer by taking dihydroxypropionic acid and 2, 4-diaminosulfonic acid sodium sulfonate as hydrophilic chain extenders, and then uniformly mixing a high-molecular emulsion ethylene-vinyl acetate and deionized water for emulsifying to obtain the sulfonic acid type waterborne polyurethane adhesive with solid content of 50 percent for shoes. Because the vinyl acetate and the polyurethane are blended, the blending stability of the vinyl acetate and the polyurethane is insufficient, the storage stability of the emulsion is poor, and the initial strength is established slowly.
Chinese patent CN 201811129301 discloses a preparation method of an acrylate modified waterborne polyurethane adhesive, which comprises the steps of firstly reacting polyether polyol with polyisocyanate to obtain a waterborne polyurethane prepolymer, reacting the waterborne polyurethane prepolymer with an acrylic acid monomer or a methacrylic acid monomer under the action of an emulsifier and an initiator to prepare waterborne polyurethane acrylic acid, and obtaining emulsion.
Therefore, how to develop the waterborne polyurethane resin with excellent comprehensive performance, simple production process and lower cost is a major problem which is urgently needed to be overcome in the adhesive industry at present.
Disclosure of Invention
The invention aims to provide the waterborne polyurethane resin and the preparation method and application thereof, aiming at the problems of the existing waterborne emulsion for the adhesive, the waterborne polyurethane resin has excellent comprehensive performance and lower cost, and the prepared adhesive has good heat resistance, excellent mechanical property, good storage stability and easy realization of the preparation process.
In order to achieve the above object, the present invention provides an aqueous polyurethane resin, which is prepared by a raw material reaction (polyurethane reaction) comprising:
A) a diisocyanate terminated prepolymer prepared by the following components:
a1, at least one diisocyanate, added in an amount of 7.0% to 12.0% by weight, preferably 8.5% to 10.0% by weight;
a2, at least two of polyethylene adipate glycol and polyadipate glycol, wherein the addition amount of the at least two of the polyethylene adipate glycol and the polyadipate glycol accounts for 80.0wt% -90.0wt%, preferably 85.0wt% -88.0wt%, and the molar ratio of the polyethylene adipate glycol to the polyadipate glycol is preferably 1: 0.5-3, more preferably 1: 1-1.5, and more preferably 1: 1.1-1.4;
a3, at least one monofunctional and/or difunctional component reactive toward isocyanates containing polyethoxy segments having a molecular weight of 3000g/mol at 500-;
a4, at least one catalyst, in an amount of 0.001 to 0.02 wt.%, preferably 0.002 to 0.01 wt.%;
B) at least one low boiling organic solvent that dissolves the diluted diisocyanate-terminated prepolymer;
C) the chain extender comprises the following components:
c1, at least one sulfonic acid type hydrophilic chain extender containing active hydrogen, the adding amount accounts for 0.3-3wt%, preferably 0.4-1.1 wt%;
optionally c2, at least one (preferably two) diamine small chain extenders containing active hydrogen, having a molecular weight of 59-200g/mol, added in an amount of 0.3-1.5wt%, preferably 0.6-1.2 wt%;
the wt% is based on the total weight of component A) and component C);
wherein the sum of components A) and C) is from 95.5 to 99.4 parts by weight, component C) from 0.6 to 4.5 parts by weight, and component B) is used in an amount of from 0.8 to 5 times, preferably from 1 to 2 times, the total mass of components A) and C) based on 100 parts by weight.
According to the aqueous polyurethane resin provided by the invention, preferably, the diisocyanate-terminated prepolymer of component A) is prepared by adopting the following raw material reaction:
a1, diisocyanate, preferably one or more selected from toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate, more preferably selected from hexamethylene diisocyanate;
a2, poly (diethylene adipate) glycol and one or more poly (butylene adipate) glycol and poly (adipate) glycol selected from the group consisting of poly (ethylene adipate) glycol, poly (1, 4-butylene glycol), poly (neopentyl glycol adipate) glycol, poly (1, 6-hexanediol adipate) glycol and poly (neopentyl glycol adipate) 1, 6-hexanediol glycol, more preferably comprises (1) poly (ethylene adipate) glycol having a molecular weight of 1000-2000 g/mol; and (2) poly adipic acid 1, 4-butanediol glycol ester dihydric alcohol with the molecular weight of 2000-4000g/mol and/or poly adipic acid 1, 6-hexanediol glycol ester dihydric alcohol with the molecular weight of 2000-4000 g/mol;
a3, isocyanate-reactive, monofunctional, polyethoxy segment-containing component having a molecular weight of 500-4000g/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; component a3 is preferably from Tego Chemie
D-3403, Ymer N120 from Perstrop, MPEG3000, MPEG2200, MPEG4000, and MPEG1200 from Korea Letian, more preferably MPEG2200 and MPEG1200 from Korea Letian;
a4, a catalyst which can be one or more of tertiary amine catalyst, organic acid tin salt and organic acid bismuth salt; preferably one or more selected from triethylamine, 1, 4-diazabicyclo- [2,2,2] -octane, dibutyltin oxide, tin dioctoate, dibutyltin dilaurate, tin bis- (2-ethylhexanoate), bismuth neodecanoate and bismuth 2-ethylhexanoate, more preferably bismuth neodecanoate.
According to the aqueous polyurethane resin provided by the invention, in component C), preferably, the sulfonic acid type hydrophilic chain extender C1 containing active hydrogen 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-propanesulfonate, and is more preferably sodium 2- (2-aminoethyl) aminoethane sulfonate.
Preferably, in the amine chain extender C2 of component C), the small molecule diamine chain extender containing active hydrogen has a molecular weight of 59 to 200g/mol, preferably one or more selected from the group consisting of ethylenediamine, hexamethylenediamine, pentamethylenediamine, hydroxyethylethylenediamine, isophoronediamine, 4-diphenylmethanediamine and diethanolamine, more preferably two or more selected from the group consisting of hydroxyethylethylenediamine, hexamethylenediamine and isophoronediamine.
The aqueous polyurethane resin provided according to the present invention preferably contains, based on 100 parts by weight of the total weight of components A) and C),
a1 is used in an amount of 7 to 12 parts, for example, 8 parts, 10 parts, 12 parts, more preferably 8.5 to 10 parts;
a2 is used in an amount of 80 to 90 parts, for example, 80 parts, 85 parts, 90 parts, more preferably 85 to 88 parts;
a3 is used in an amount of 1 to 4 parts, for example, 1.0 part, 2.5 parts, 3.3 parts, more preferably 1.5 to 3.5 parts;
a4 is used in an amount of 0.001 to 0.02 parts, for example, 0.002 parts, 0.008 parts, 0.012 parts, 0.015 parts, 0.02 parts, more preferably 0.002 to 0.01 parts;
the amount of the sulfonic acid type hydrophilic chain extender c1 containing active hydrogen is 0.3 to 3 parts, for example, 0.5 part, 0.8 part, 1.0 part, 1.2 parts, 1.5 parts and 2.8 parts, and more preferably 0.4 to 1.1 parts;
the amount of the active hydrogen-containing micromolecule diamine chain extender c2 is 0.3-1.5 parts, such as 0.3 part, 0.4 part, 0.6 part, 0.8 part, 1 part, 1.2 parts and 1.5 parts, and more preferably 0.6-1.2 parts;
preferably, the molar ratio of component a1 to component a2 is (1.0-2.0): 1, more preferably (1.3-1.6): 1;
the component B) is 100-200 parts by weight, for example 100 parts by weight, 120 parts by weight, 150 parts by weight, 170 parts by weight, 185 parts by weight, 200 parts by weight.
Preferably, the organic solvent B) is selected from acetone and/or butanone, more preferably acetone.
Another object of the present invention is to provide a method for preparing the aqueous polyurethane resin, comprising the steps of:
(1) preparing a diisocyanate-terminated prepolymer using components a1-a 4;
(2) dissolving and diluting the diisocyanate-terminated prepolymer obtained in the step (1) by using a component B) to obtain a diluted diisocyanate-terminated prepolymer;
(3) diluting component C) with water to obtain an aqueous solution of component C); contacting the product obtained in the step (2) with the aqueous solution of the component C) to carry out chain extension reaction, and adding deionized water to the obtained product under the condition of high-speed shearing to disperse to obtain a waterborne polyurethane coarse emulsion;
(4) and (4) distilling the emulsion obtained in the step (3) under reduced pressure to remove the component B), thus obtaining the waterborne polyurethane emulsion.
According to the preparation method provided by the present invention, preferably, in the step (1), the reaction process conditions for preparing the diisocyanate-terminated prepolymer include: 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, MNCO、MOHRespectively 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, in step (2), the diisocyanate-terminated prepolymer is subjected to dilution by dissolving using component B) under conditions including: the temperature is 50-60 deg.C, and the time is 5-10 min; the component B) is an organic solvent selected from acetone and/or butanone, preferably acetone; the amount of the organic solvent added is 1 to 2 times the sum of the parts by weight of the components A) and C).
Preferably, in the step (3), the chain extension reaction process conditions comprise: the reaction temperature is 45-50 ℃, and the reaction time is 15-25 min; more preferably, the water in the aqueous solution of the component C) is used in an amount of 3 to 5 times of the mass of the component C); the aqueous solution of the component C) may be an aqueous solution comprising a mixture of the amine chain extender C2 and the sulfonic acid type hydrophilic chain extender C1 containing active hydrogen, which is diluted with deionized water to obtain a mixture of the component C1 and the component C2.
In some examples, in step (4), the solvent removal manner is vacuum distillation, and the solvent to be removed here mainly refers to the organic solvent used for dissolving and diluting the diisocyanate-terminated prepolymer obtained in step (1) in step (2).
The solid content of the waterborne polyurethane is 45-55%, preferably 48-50%. The average particle size of the aqueous polyurethane resin is 150-250nm, preferably 170-200 nm. The number average molecular weight of the polyurethane obtained (measured by gel permeation chromatography) is generally in the range of 20000 to 60000.
The invention also provides the application of the waterborne polyurethane resin or the waterborne polyurethane resin prepared by the preparation method as an adhesive.
According to the application provided by the invention, the waterborne polyurethane is preferably applied to the fields of shoe glue, plastic uptake glue, laminating glue and automotive interior glue.
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 low-boiling-point neutralizers such as triethylamine are avoided, and the waterborne polyurethane resin is good in environmental protection performance. In some preferred embodiments, the sulfonic acid type hydrophilic chain extender containing active hydrogen uses sodium sulfamate, which belongs to strong acid and strong base salt, and is not easy to hydrolyze, so that the product has better water resistance. The addition of the poly-adipic acid diethylene glycol as the macrodiol in the polyurethane synthesis stage reduces the cost, improves the low-temperature film-forming property of the resin, increases the compatibility between soft and hard sections, and improves the ionic mechanical stability of the emulsion. Meanwhile, the addition of the adipic acid glycol ester with larger molecular weight is beneficial to the crystallization of the resin, and the initial strength and the initial heat resistance of the resin are obviously improved. The addition of the high molecular weight monofunctional hydrophilic agent contributes to the storage stability and mechanical stability of the emulsion, and also contributes to the crystallization of the resin, so that the mechanical stability of the emulsion, the initial peel strength and the initial heat resistance of the emulsion can be greatly improved.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
(1) the waterborne polyurethane resin provided by the invention has excellent comprehensive performance by adjusting the types and components as reaction raw materials;
(2) in a preferred embodiment, the synergistic use of the polydiethylene glycol adipate and the polyhexamethylene glycol adipate can reduce the cost, obtain the aqueous polyurethane adhesive with excellent comprehensive performance, and play a positive role in the mechanical stability, the activation temperature and the film forming property of the resin;
(3) the addition of the high molecular weight monofunctional hydrophilic reagent not only improves the low-temperature storage and mechanical stability of the emulsion, but also improves the initial peel strength and initial heat resistance of the resin;
(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 raw material sources are as follows:
1、
HMDI (dicyclohexylmethane diisocyanate, NCO content about 32.0%, Vanhua Chemicals 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);
PBA3000 (poly 1, 4-butanediol adipate diol, hydroxyl value of 37.4mgKOH/g, number average molecular weight of 3000, functionality of 2, dawski chem);
PHA-2000 (poly 1, 6-hexanediol adipate diol, hydroxyl value of 56mgKOH/g, number average molecular weight of 2000, functionality of 2, dahlia macrochemistry);
CMA-654 (poly (neopentyl glycol adipate) hexanediol adipate diol, hydroxyl value of 74.8mgKOH/g, number average molecular weight of about 1500, functionality of 2, large chemistry of Tahitian China);
CMB-54 (polyethylene glycol adipate diol with hydroxyl value of 56mgKOH/g, number average molecular weight of about 2000, functionality of 2, large chemistry of Nitzschia);
3. MPEG1200 (polyethylene glycol monomethyl ether, hydroxyl number 46.75mgKOH/g, number average molecular weight 1200, functionality 1, clonidine, korea);
MPEG2200 (polyethylene glycol monomethyl ether, hydroxyl number 25.5mgKOH/g, number average molecular weight 2200, functionality 1, glatiramer);
4. an organic bismuth catalyst (bismuth neodecanoate, advanced chemical company, usa);
5. organic solvents (acetone, nibowanghua);
6、
a95 (sodium 2- (2-aminoethyl) tauride, solid content 51 + -2% aqueous solution, amine number 260 + -20 mgKOH/g, EVONIK, Germany);
7. IPDA (Isophorone diamine, Vanhua chemical group Ltd.);
hydroxyethylethylenediamine (Yangzhitin-Pasteur, Inc.);
hexamethylenediamine (HDA, Vanhua chemical group, Inc.);
ethylenediamine (EDA, avastin reagent).
Example 1: (PBA3000 spelling CMB-54. MPEG1200)
(1) Into a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was placed 35g
HDI, 210g of PBA-3000 (poly 1, 4-butylene adipate glycol), 142.5g of CMB-54 (poly diethylene adipate glycol), 6g of MPEG1200, 30ppm of an organic bismuth catalyst and 39g of acetone, and reacting at 80 ℃ to generate a diisocyanate-terminated prepolymer;
(2) sampling and monitoring NCO of a system in the reaction process until the NCO reaches below 1.25 percent of a theoretical value, cooling to about 60 ℃, adding 680g of acetone, and stirring for 5min to obtain a diluted diisocyanate-terminated prepolymer;
(3) 1g of hydroxyethylethylenediamine, 2g of HDA and 4g of
A95 is diluted by 28g of deionized water, added into the reaction system at 45 ℃ and stirred for chain extension reaction for 20 min; adding 429g of water under the condition of shearing dispersion, and obtaining the aqueous polyurethane emulsion after shearing dispersion;
(4) distilling the crude emulsion under reduced pressure to remove the solvent acetone to obtain milky white waterborne polyurethane emulsion with obvious blue light; the solid content is 48 wt%, and the particle size is 170 nm. The molecular weight of the obtained resin is 34000, and a gel permeation chromatography method is adopted as a molecular weight testing method.
Example 2: (PBA2000 spelling CMB-54. MPEG2200)
(1) 32g of a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was placed in the flask
HDI, 142.5g PBA-2000, 142.5g CMB-54, 8g MPEG1200, 30ppm of organic bismuth catalyst and 32.5g acetone, and reacting at 80 ℃ to generate a diisocyanate-terminated prepolymer;
(2) sampling and monitoring NCO of a system in the reaction process until the NCO reaches below 1.08 percent of a theoretical value, cooling to about 60 ℃, adding 680g of acetone, and stirring for 5min to obtain a diluted diisocyanate-terminated prepolymer;
(3) 1g of hydroxyethylethylenediamine, 1g of HDA and 2.5g of
A95 is diluted by 18g of deionized water, added into the reaction system at 45 ℃ and stirred for chain extension reaction for 20 min; adding 327g of water under the condition of shearing dispersion, and obtaining the aqueous polyurethane emulsion after shearing dispersion;
(4) distilling the crude emulsion under reduced pressure to remove the solvent acetone to prepare milky white aqueous polyurethane emulsion with obvious blue light; the solid content was 50 wt%, and the particle size was 185 nm. The molecular weight of the obtained resin is 53000, and the molecular weight test method adopts a gel permeation chromatography method.
Example 3: (PBA3000 spelling CMB-54. MPEG2200)
(1) Into a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was placed 35g
HDI, 210g PBA-3000, 142.5g CMB-54, 11g MPEG2200, 30ppm organic bismuth catalyst and 39.8g acetone are reacted at 80 ℃ to generate a diisocyanate terminated prepolymer;
(2) sampling and monitoring NCO of a system in the reaction process until the NCO reaches below 1.23 percent of a theoretical value, cooling to about 60 ℃, adding 688g of acetone, and stirring for 5min to obtain a diluted diisocyanate-terminated prepolymer;
(3) 1g of hydroxyethylethylenediamine, 3g of HDA and 2g of HDA
A95 is diluted by 24g of deionized water, added into the reaction system at 45 ℃ and stirred for chain extension reaction for 20 min; adding 436g of water under the condition of shearing dispersion, and obtaining aqueous polyurethane emulsion after shearing dispersion;
(4) distilling the crude emulsion under reduced pressure to remove the solvent acetone to prepare milky white aqueous polyurethane emulsion with obvious blue light; the solid content is 48 wt%, and the particle size is 180 nm. The molecular weight of the obtained resin is 46000, and the molecular weight test method adopts a gel permeation chromatography method.
Example 4: (different molar ratios PBA3000 splicing CMB-54. MPEG2200)
(1) 31g of a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged into the flask
HDI, 142.5g PBA-3000, 142.5g CMB-54, 11g MPEG2200, 30ppm organobismuth catalyst, 32.7g of acetone at 80 ℃ to form a diisocyanate-terminated prepolymer;
(2) sampling and monitoring NCO of a system in the reaction process, cooling to about 60 ℃ when the NCO reaches below 1.47% of a theoretical value, adding 621g of acetone, and stirring for 5min to obtain a diluted diisocyanate-terminated prepolymer;
(3) 1g of hydroxyethylethylenediamine, 3g of HDA and 1.5g of
A95 is diluted by 22g deionized water, added into the reaction system at 45 ℃ and stirred for chain extension reaction for 20 min; adding 331g of water under the condition of shearing dispersion, and obtaining aqueous polyurethane emulsion after shearing dispersion;
(4) distilling the crude emulsion under reduced pressure to remove the solvent acetone to prepare milky white aqueous polyurethane emulsion with obvious blue light; the solid content is 50 wt%, and the particle size is 200 nm. The molecular weight of the obtained resin is 21000, and a gel permeation chromatography method is adopted as a molecular weight testing method.
Example 5: (PHA3000 spelling CMB-54. MPEG2200)
(1) Into a four-necked flask equipped with a reflux condenser, a thermometer and a mechanical stirrer were charged 35g
HDI, 210g PHA-3000, 142.5g CMB-54, 11g MPEG2200, 30ppm of organic bismuth catalyst and 39.8g of acetone are reacted at 80 ℃ to generate a diisocyanate-terminated prepolymer;
(2) sampling and monitoring NCO of a system in the reaction process until the NCO reaches below 1.23 percent of a theoretical value, cooling to about 60 ℃, adding 688g of acetone, and stirring for 5min to obtain a diluted diisocyanate-terminated prepolymer;
(3) 1g of hydroxyethylethylenediamine, 3g of HDA and 2g of
A95 is diluted by 24g of deionized water, added into the reaction system at 45 ℃ and stirred for chain extension reaction for 20 min; 436g of water were added under shear dispersion conditions,shearing and dispersing to obtain a waterborne polyurethane emulsion;
(4) distilling the crude emulsion under reduced pressure to remove the solvent acetone to prepare milky white aqueous polyurethane emulsion with obvious blue light; the solid content of the product is 48 wt%, and the particle size is 195 nm. The molecular weight of the obtained resin is 37000, and the molecular weight test method adopts a gel permeation chromatography method.
Comparative example 1: (PBA3000, plus CMA-654, MPEG2200)
(1) Into a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged 40g
HDI, 210g PBA-3000, 142.5g CMA-654, 11g MPEG2200, 30ppm organic bismuth catalyst and 40.3g acetone, and reacting at 80 ℃ to generate a diisocyanate-terminated prepolymer;
(2) sampling and monitoring NCO of a system in the reaction process until the NCO reaches below 1.33 percent of a theoretical value, cooling to about 60 ℃, adding 597g of acetone, and stirring for 5min to obtain a diluted diisocyanate-terminated prepolymer;
(3) 1g of hydroxyethylethylenediamine, 3g of HDA and 3g of HDA
A95 is diluted by 28g of deionized water, added into the reaction system at 45 ℃ and stirred for chain extension reaction for 20 min; adding 499g of water under the condition of shearing dispersion, and obtaining the aqueous polyurethane emulsion after shearing dispersion;
(4) distilling the crude emulsion under reduced pressure to remove the solvent acetone to prepare milky white aqueous polyurethane emulsion with obvious blue light; the solid content was 45 wt%, and the particle size was 160 nm.
Comparative example 2: (HMDI, PBA300, CMB-54, MPEG2200)
(1) Into a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged 54g
HMDI, 210g PBA-3000, 142.5g CMB-54, 11g MPEG2200, 30ppm organobismuth catalyst, 41.75g acetone, 80Reacting at the temperature of DEG C to generate a diisocyanate-terminated prepolymer;
(2) sampling and monitoring NCO of a system in the reaction process until the NCO reaches below 1.14 percent of a theoretical value, cooling to about 60 ℃, adding 721g of acetone, and stirring for 5min to obtain a diluted diisocyanate-terminated prepolymer;
(3) 1g of hydroxyethylethylenediamine, 2g of HDA and 3g of
A95 is diluted by 24g of deionized water, added into the reaction system at 45 ℃ and stirred for chain extension reaction for 20 min; adding 455g of water under the condition of shearing dispersion, and obtaining the aqueous polyurethane emulsion after shearing dispersion;
(4) distilling the crude emulsion under reduced pressure to remove the solvent acetone to prepare milky white aqueous polyurethane emulsion with obvious blue light; the solid content of the powder is 48 wt%, and the particle size is 200 nm.
Comparative example 3: (IPDI, EDA type)
(1) 58g of a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged into the flask
IPDI, 210g PBA-3000, 142.5g CMB-54, 11g MPEG2200, 30ppm organic bismuth catalyst and 42.1g acetone, and reacting at 80 ℃ to generate a diisocyanate terminated prepolymer;
(2) sampling and monitoring NCO of a system in the reaction process until the NCO reaches below 2.12 percent of a theoretical value, cooling to about 60 ℃, adding 728g of acetone, and stirring for 5min to obtain a diluted diisocyanate-terminated prepolymer;
(3) 1.5g of hydroxyethylethylenediamine, 1g of EDA and 5g of EDA
Diluting A95 and 6g IPDA with 54g deionized water, adding into the reaction system at 45 ℃, and stirring for chain extension reaction for 20 min; adding 400g of water under the condition of shearing dispersion, and obtaining the aqueous polyurethane emulsion after shearing dispersion;
(4) distilling the crude emulsion under reduced pressure to remove the solvent acetone to prepare milky white aqueous polyurethane emulsion with obvious blue light; the solid content is 50 wt%, and the particle size is 180 nm.
Preparation of the adhesive:
100g of the aqueous dispersion from each of the examples and comparative examples, 0.05g of BYK024 (Beck chemistry) were mixed and stirred at 500rpm for 5min, 0.2g of Tego245 (digan) was added and stirred for a further 5min, then 0.15g of Vesmody U604 (VasHua chemistry) was added and stirred at 600rpm for 10 min.
Preparation of a sample:
the following materials were compounded to prepare composite samples:
| composite material | Substrate 1 | Substrate 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 5 minutes, and then taken out and press-fitted at 30kg/cm2 for 10 seconds to prepare a composite material a.
Composite materials B and C were prepared in the same manner.
Testing of 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: 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 strength of the composite material prepared based on the aqueous polyurethane resin provided by the present invention is significantly improved compared to the aqueous polyurethane resin prepared from HMDI, EDA and CMA-654. Compared with the resin prepared by using PBA2000 as the macrodiol in example 2 and the resin prepared by using MPEG1200 as the nonionic hydrophilic group in example 1, the waterborne polyurethane resin prepared based on PBA3000 and MPEG2200 has better initial strength.
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 out 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, (1) compared with the aqueous polyurethane resin prepared by adopting CMA-654 in the comparative example 1, the composite material prepared by the aqueous polyurethane resin prepared on the basis of CMB-54 provided by the invention has obviously improved initial heat resistance and damp-heat resistance. Using H in comparison with comparative example 212For the waterborne polyurethane resin prepared from MDI, the composite material prepared from the waterborne polyurethane resin provided by the invention has obviously improved heat resistance in the initial stage and the later stage. (2) The resins prepared in example 3 using PBA3000 and MPEG2200 both had better initial heat resistance and wet heat resistance than the resins obtained in the other examples.
Adhesion test after high temperature treatment:
the aqueous polyurethane resin emulsion prepared by the method is placed for 72 hours at the temperature of 70 ℃. The effect of the resin emulsion on peel strength on a rubber substrate after storage at high temperature was observed. The results are shown in Table 3.
TABLE 3 peel strength of adhesive on rubber substrate after storage at high temperature
As is apparent from table 3, based on the aqueous urethane resin provided herein, the peel strength did not change significantly when stored at high temperature for 3 days, which indicates that the aqueous urethane resin of the present application has excellent storage stability.
Compared with other examples, the heat resistance, the damp heat resistance, the bonding strength and the high-temperature storage stability of the sample are obviously better than those of other examples under the condition that the MPEG2200 is added as the monofunctional nonionic hydrophilic agent, the CMB-54 and the PBA3000 are in proper molar ratio, and the hexamethylene diamine is used as the diamine chain extender.
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 (21)
1. The waterborne polyurethane resin is prepared by reacting the following raw materials:
A) a diisocyanate-terminated prepolymer prepared by the following components:
a1, at least one diisocyanate, wherein the diisocyanate is hexamethylene diisocyanate and is added in an amount of 7.0-12.0 wt%;
a2, at least two of poly (diethylene glycol adipate) glycol and poly (adipate) glycol, wherein the addition amount of the poly (diethylene glycol adipate) glycol and the poly (adipate) glycol accounts for 80.0-90.0 wt%, and the molar ratio of the poly (diethylene glycol adipate) glycol to the poly (adipate) glycol is 1: 0.5-3; the polyadipate diol is selected from one or two of polyadipate-1, 4-butanediol diol ester diol and polyadipate-1, 6-hexanediol diol ester diol;
a3, at least one monofunctional isocyanate-reactive component containing polyethoxy segments having a molecular weight of 500-4000g/mol, the amount added being from 1 to 4% by weight;
a4, at least one catalyst, the adding amount of which is 0.001-0.02 wt%;
B) at least one low boiling organic solvent that dissolves the diluted diisocyanate-terminated prepolymer;
C) the chain extender comprises the following components:
c1, at least one sulfonic acid type hydrophilic chain extender containing active hydrogen, the adding amount accounts for 0.3 to 3 weight percent;
optionally c2, at least one diamine small molecular chain extender containing active hydrogen, the molecular weight is 59-200g/mol, and the adding amount accounts for 0.3-1.5 wt%;
the wt% is based on the total weight of component A) and component C);
wherein the total of the components A) and C) is calculated by 100 parts by weight, wherein the component A) is 95.5-99.4 parts by weight, the component C) is 0.6-4.5 parts by weight, and the amount of the component B) is 0.8-5 times of the total mass of the components A) and C).
2. The aqueous polyurethane resin according to claim 1,
A) a diisocyanate-terminated prepolymer prepared by the following components:
a1, hexamethylene diisocyanate, the addition amount of which accounts for 8.5-10.0 wt%;
a2, at least two of polyethylene glycol adipate glycol and polyadipate glycol, wherein the addition amount of the polyethylene glycol adipate glycol and the polyadipate glycol accounts for 85.0wt% -88.0wt%, and the molar ratio of the polyethylene glycol adipate glycol to the polyadipate glycol is 1: 1-1.5;
a3, at least one monofunctional isocyanate-reactive component containing polyethoxy segments having a molecular weight of 2000-3000g/mol, the addition amount of which is from 1.5 to 3.5% by weight;
a4, at least one catalyst, the adding amount of which is 0.002-0.01 wt%;
C) the chain extender comprises the following components:
c1, at least one sulfonic acid type hydrophilic chain extender containing active hydrogen, the adding amount accounts for 0.4 to 1.1 weight percent;
optionally c2, at least one diamine small molecular chain extender containing active hydrogen, the molecular weight is 59-200g/mol, and the adding amount is 0.6-1.2 wt%;
the wt% is based on the total weight of component A) and component C);
the amount of component B) is 1-2 times the total mass of components A) and C).
3. The aqueous polyurethane resin according to claim 2, wherein the molar ratio of the polyethylene adipate glycol to the polyadipate glycol is 1:1.1 to 1.4.
4. The aqueous polyurethane resin according to claim 1, wherein the diisocyanate-terminated prepolymer of component a) is prepared by reacting raw materials comprising:
a1, hexamethylene diisocyanate;
a2, poly (diethylene glycol adipate) and one or two poly (adipate) diols selected from poly (1, 4-butylene glycol adipate) diol and poly (1, 6-hexanediol adipate) diol;
a3, an isocyanate-reactive, monofunctional, polyethoxy segment-containing component having a molecular weight of 500-3000 g/mol;
a4, and the catalyst is one or more selected from tertiary amine catalysts, organic acid tin salts and organic acid bismuth salts.
5. The aqueous polyurethane resin according to any one of claims 1 to 3, wherein,
a2 includes (1) polydiethylene adipate having a molecular weight of 1000-2000 g/mol; and (2) poly adipic acid-1, 4-butanediol ester dihydric alcohol with the molecular weight of 2000-4000g/mol and/or poly adipic acid-1, 6-hexanediol ester dihydric alcohol with the molecular weight of 2000-4000 g/mol;
a3 is a polyoxyalkylene ether containing one hydroxyl group and the polymerized units of the polyoxyalkylene ether are propylene oxide and ethylene oxide or ethylene oxide;
a4 the catalyst is 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.
6. The aqueous polyurethane resin according to claim 5,
a3, wherein the polymerization unit of the polyoxyalkylene ether is ethylene oxide;
a4, catalyst selected from bismuth neodecanoate.
7. The aqueous polyurethane resin according to claim 6, wherein the number of ethylene oxide units in each molecule of the polyoxyalkylene ether is 4 to 200.
8. The aqueous polyurethane resin according to claim 7, wherein the number of ethylene oxide units per molecule of the polyoxyalkylene ether is 12 to 75.
9. The aqueous polyurethane resin according to any one of claims 1 to 3, wherein in component C), the sulfonic acid type hydrophilic chain extender C1 containing active hydrogen is selected from one or more of sodium 2- (2-aminoethyl) tauride, sodium 2- (2-aminoethyl) aminopropanesulfonate, sodium 1, 4-butanediol-2-sulfonate and sodium 1, 2-dihydroxy-3-propanesulfonate; and/or
In the amine chain extender C2 of the component C), the molecular weight of the micromolecule diamine chain extender containing active hydrogen is 59-200g/mol, and the micromolecule diamine chain extender is selected from one or more of ethylenediamine, hexamethylenediamine, pentamethylenediamine, hydroxyethyl ethylenediamine, isophoronediamine and 4, 4-diphenylmethane diamine.
10. The aqueous polyurethane resin according to claim 9, wherein in component C), the sulfonic acid type hydrophilic chain extender C1 containing active hydrogen is sodium 2- (2-aminoethyl) aminoethane sulfonate; and/or
In the amine chain extender C2 of the component C), the small molecular diamine chain extender containing active hydrogen is selected from two or more of hydroxyethyl ethylenediamine, hexamethylenediamine and isophorone diamine.
11. The aqueous polyurethane resin according to any one of claims 1 to 3, wherein the molar ratio of component a1 to component a2 is (1.0-2.0): 1.
12. the aqueous polyurethane resin according to claim 11, wherein the molar ratio of component a1 to component a2 is (1.3-1.6): 1.
13. the aqueous polyurethane resin according to any one of claims 1 to 3, wherein the organic solvent B) is selected from acetone and/or butanone.
14. The aqueous polyurethane resin according to claim 13, wherein the organic solvent B) is selected from acetone.
15. The aqueous polyurethane resin according to any one of claims 1 to 3, wherein the solid content of the aqueous polyurethane is 45 to 55%; the average particle size of the aqueous polyurethane resin was 150-250 nm.
16. The aqueous polyurethane resin according to claim 15, wherein the solid content of the aqueous polyurethane is 48 to 50%; the average particle size of the aqueous polyurethane resin was 170-200 nm.
17. A method for producing the aqueous polyurethane resin according to any one of claims 1 to 16, comprising the steps of:
(1) preparing a diisocyanate-terminated prepolymer using components a1-a 4;
(2) dissolving and diluting the diisocyanate-terminated prepolymer obtained in the step (1) by using a component B) to obtain a diluted diisocyanate-terminated prepolymer;
(3) diluting component C) with water to obtain an aqueous solution of component C); contacting the product obtained in the step (2) with the aqueous solution of the component C) to carry out chain extension reaction, and adding deionized water to the obtained product under the condition of high-speed shearing to disperse to obtain a waterborne polyurethane coarse emulsion;
(4) and (4) distilling the emulsion obtained in the step (3) under reduced pressure to remove the component B), thus obtaining the waterborne polyurethane emulsion.
18. The method of claim 17, wherein in the step (1), the reaction process conditions for preparing the diisocyanate-terminated prepolymer include: the reaction temperature is 75-85 ℃; stopping the reaction until the NCO of the reaction system reaches a theoretical value; and/or
In the step (2), the diisocyanate-terminated prepolymer is dissolved and diluted by the component B), and the dissolving and diluting conditions comprise: the temperature is 50-60 deg.C, and the time is 5-10 min; and/or
In the step (3), the chain extension reaction process conditions comprise: the reaction temperature is 45-50 ℃, and the reaction time is 15-25 min.
19. The method according to claim 18, wherein the water is used in an amount of 3 to 5 times the mass of the component C) in the aqueous solution of the component C) in the step (3).
20. Use of the aqueous polyurethane resin according to any one of claims 1 to 16 or the aqueous polyurethane resin obtained by the preparation method according to any one of claims 17 to 19 as an adhesive.
21. Use according to claim 20, as an adhesive in the shoe glue field, the blister glue field, the laminating glue field and the automotive interior glue field.
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| CN112250832B (en) * | 2020-10-21 | 2023-05-26 | 万华化学集团股份有限公司 | Water-based polyurethane resin and preparation method and application thereof |
| CN113336664A (en) * | 2021-05-07 | 2021-09-03 | 广安摩珈生物科技有限公司 | Bio-based waterborne polyurethane resin and preparation method and application thereof |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001074921A1 (en) * | 2000-03-30 | 2001-10-11 | Crompton Corporation | Sulfonate-containing polyurethane dispersions via non-solvent process |
| CN101665675A (en) * | 2009-09-22 | 2010-03-10 | 烟台华大化学工业有限公司 | Method for preparing aqueous polyurethane adhesive and superfine fiber synthetic leather |
| CN102690404A (en) * | 2011-02-18 | 2012-09-26 | 中国石油化工股份有限公司 | Nonionic waterborne polyurethane dispersoid and preparation method thereof |
| CN102936480A (en) * | 2012-11-08 | 2013-02-20 | 无锡市万力粘合材料有限公司 | Waterborne polyurethane adhesive for fabric and preparation method thereof |
| CN103030775A (en) * | 2012-12-14 | 2013-04-10 | 广州宏昌胶粘带厂 | Waterborne polyurethane emulsion for making waterproof strip and preparation method thereof |
| CN103254867A (en) * | 2013-04-26 | 2013-08-21 | 巨石集团有限公司 | Preparation method of sulfonic acid type waterborne polyurethane adhesive |
| CN104031225A (en) * | 2013-03-06 | 2014-09-10 | 万华化学集团股份有限公司 | Aqueous polyurethane dispersoid for synthetic leather adhesive and preparation method thereof |
| CN106497492A (en) * | 2016-11-13 | 2017-03-15 | 嘉兴德扬生物科技有限公司 | A kind of waterborne polyurethane adhesive for shoes with high solid content and preparation method thereof |
| CN109608605A (en) * | 2017-12-19 | 2019-04-12 | 传化智联股份有限公司 | A kind of ion-non-ion aqueous polyurethane dispersion preparation |
| CN109679059A (en) * | 2018-12-11 | 2019-04-26 | 万华化学集团股份有限公司 | A kind of polyurethane-polyurea water dispersion and the preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109206569B (en) * | 2017-07-03 | 2021-01-19 | 比亚迪股份有限公司 | Waterborne polyurethane, waterborne polyurethane adhesive and preparation method thereof |
-
2019
- 2019-11-20 CN CN201911143047.2A patent/CN110818873B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001074921A1 (en) * | 2000-03-30 | 2001-10-11 | Crompton Corporation | Sulfonate-containing polyurethane dispersions via non-solvent process |
| CN101665675A (en) * | 2009-09-22 | 2010-03-10 | 烟台华大化学工业有限公司 | Method for preparing aqueous polyurethane adhesive and superfine fiber synthetic leather |
| CN102690404A (en) * | 2011-02-18 | 2012-09-26 | 中国石油化工股份有限公司 | Nonionic waterborne polyurethane dispersoid and preparation method thereof |
| CN102936480A (en) * | 2012-11-08 | 2013-02-20 | 无锡市万力粘合材料有限公司 | Waterborne polyurethane adhesive for fabric and preparation method thereof |
| CN103030775A (en) * | 2012-12-14 | 2013-04-10 | 广州宏昌胶粘带厂 | Waterborne polyurethane emulsion for making waterproof strip and preparation method thereof |
| CN104031225A (en) * | 2013-03-06 | 2014-09-10 | 万华化学集团股份有限公司 | Aqueous polyurethane dispersoid for synthetic leather adhesive and preparation method thereof |
| CN103254867A (en) * | 2013-04-26 | 2013-08-21 | 巨石集团有限公司 | Preparation method of sulfonic acid type waterborne polyurethane adhesive |
| CN106497492A (en) * | 2016-11-13 | 2017-03-15 | 嘉兴德扬生物科技有限公司 | A kind of waterborne polyurethane adhesive for shoes with high solid content and preparation method thereof |
| CN109608605A (en) * | 2017-12-19 | 2019-04-12 | 传化智联股份有限公司 | A kind of ion-non-ion aqueous polyurethane dispersion preparation |
| CN109679059A (en) * | 2018-12-11 | 2019-04-26 | 万华化学集团股份有限公司 | A kind of polyurethane-polyurea water dispersion and the preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| PPS基磺酸型水性聚氨酯的合成及其性能;许戈文等;《粘接》;20151231;第29-33页 * |
| 磺酸盐型水性聚氨酯的合成与性能研究;鲍俊杰等;《中国胶黏剂》;20081231;第17卷(第12期);第32-35页 * |
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