CN115572568A - Low-activation-temperature polyurethane dispersion adhesive and preparation method thereof - Google Patents
Low-activation-temperature polyurethane dispersion adhesive and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- 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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- 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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- 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
- C08G18/28—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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- 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
- C08G18/28—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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- 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
- C08G18/28—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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 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
- C08G18/6655—Compounds of group C08G18/42 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
- C08G2170/00—Compositions for adhesives
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a low activation temperature polyurethane dispersion adhesive and a preparation method thereof. The preparation method comprises the following steps: 1) Mixing and reacting macromolecular polyol A, macromolecular polyol B and diisocyanate to obtain a polyurethane prepolymer; 2) And (3) reducing the viscosity of the prepolymer by using an organic solvent, adding a hydrophilic monomer, adding water for dispersion, adding a chain extender and a defoaming agent, and decompressing and pumping out the solvent to obtain the polyurethane dispersion adhesive. The polyurethane dispersion adhesive prepared by the method has lower activation temperature and higher initial adhesion, and can be applied to processing of cases, balls and textile materials, such as adhesion of thermolabile base materials such as synthetic leather, films and foams.
Description
Technical Field
The invention belongs to the technical field of waterborne polyurethane adhesives, and particularly relates to a low-activation-temperature polyurethane dispersion adhesive and a preparation method thereof.
Background
With the popularization of the green chemistry concept, water products are gradually replacing solvent products in the adhesive industry. The water-based polyurethane adhesive takes water as a solvent, polyurethane particles are dispersed in a continuous water phase, and compared with the solvent-based polyurethane adhesive, the water-based polyurethane adhesive has the advantages of no toxicity, no flammability, low VOCs emission, low cost and the like. The aqueous polyurethane adhesive has been widely applied in shoe making, automobiles, furniture and food packaging industries in recent years due to good chemical resistance, low temperature resistance, good flexibility and high bonding strength.
At present, common activation temperatures of polyurethane dispersion (PUD) adhesives on the market are 50-60 ℃, 80-100 ℃ and 130-150 ℃, and PUD adhesives with the activation temperature lower than 40 ℃ are rarely reported. In the bonding of temperature-sensitive base materials such as bags, textile composites and balls, the flexible materials such as foams, synthetic leather and films in the base materials can be damaged by overhigh temperature. Therefore, the development of the polyurethane dispersion adhesive with low activation temperature is very valuable and practical.
Chinese patent CN 109206569B obtains prepolymer by reacting polyol with polyisocyanate and dimethylolpropionic acid, then reacts with aromatic diol chain extender, and is emulsified by adding water to obtain polyurethane dispersion adhesive, the initial adhesion strength is measured to be 2.9N/mm, but the activation temperature is higher and needs 65 ℃. In Chinese patent CN 103254867A, PBA-2000, PPG-2000 and IPDI are mixed and reacted, then sulfonate type hydrophilic monomer is added for chain extension, and water dispersion is carried out to obtain the waterborne polyurethane adhesive with the lowest activation temperature of 40 ℃, but the peel strength is only 0.21N/mm, and the adhesive strength is smaller.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a low-activation-temperature polyurethane dispersion adhesive which can be activated at the temperature of below 40 ℃ and can also keep higher initial adhesion strength.
The invention also aims to provide a preparation method of the low activation temperature polyurethane dispersion adhesive.
The purpose of the invention is realized by the following technical scheme.
The invention utilizes two macromolecular polyols A and B with different crystallinity and different molecular weight as soft segment of polyurethane dispersion. The polyol A has weaker crystallization property and smaller molecular weight, and provides lower activation temperature for the PUD adhesive, so that the whole polyurethane molecular chain is easy to move and activate; the polyol B has stronger crystallization property and larger molecular weight, and provides high initial adhesion for the PUD adhesive. Reacting the polyol with diisocyanate to obtain a polyurethane prepolymer; reducing the viscosity of the prepolymer by using a solvent, adding a hydrophilic monomer for chain extension, and then adding deionized water for dispersion at a high speed; and finally adding a chain extender and a defoaming agent, and decompressing and pumping out the solvent to obtain the low-activation-temperature polyurethane dispersion adhesive.
A preparation method of a low activation temperature polyurethane dispersion adhesive comprises the following steps:
(1) Adding the macromolecular polyol A and the macromolecular polyol B into a reaction vessel, heating at 110-130 ℃ and pumping water and drying under the vacuum degree of 0.095-0.1MPa for 1-2h;
(2) Cooling the reaction system in the step (1) to below 60 ℃, adding diisocyanate and a catalyst, and reacting for 0.5-2.5h under the conditions of heating and stirring at 85-95 ℃ to obtain a polyurethane prepolymer;
(3) Cooling the reaction system in the step (2) to below 60 ℃, adding an organic solvent which is 1.5-2 times of the mass of the polyurethane prepolymer in the step (2), reducing the viscosity, adding a hydrophilic monomer for reacting for 10-30min, adding deionized water, and dispersing at a high speed for 20-30min;
(4) And (3) adding a chain extender into the reaction product obtained in the step (3) to react for 10-30min, adding a defoaming agent, heating at 40-65 ℃ and distilling under the vacuum degree of 0.06-0.1MPa to remove the organic solvent, thus obtaining the polyurethane dispersion adhesive with low activation temperature.
Further, the adding amount of each substance in percentage by mass of the total mass of the mixture is as follows:
macrodiol A:58.50 to 80.69 percent;
macrodiol B:0 to 25.07 percent;
diisocyanate: 12.92 to 16.04 percent;
hydrophilic monomer: 3.62 to 7.36 percent;
chain extender: 0.17-1.79%;
catalyst: 0.01 to 0.10 percent;
defoaming agent: 0.05 to 0.20 percent;
the addition amount of the substances accounts for 100 percent of the total mass of the mixture.
Further, the macrodiol A in the step (1) comprises one or more of polyethylene glycol adipate PEA, polybutylene adipate PBA, neopentyl glycol adipate PNA, polyhexamethylene glycol adipate PHA, polyhexamethylene glycol adipate PHNA, polybutylene adipate neopentyl glycol diol PBNA, polypropylene adipate PPA, polyethylene glycol PEG, polypropylene glycol PPG, polytetrahydrofuran ether glycol PTMG, polycaprolactone diol PCL and polycarbonate diol PCDL, the number average molecular weight of the macrodiol is 500-2000, and the crystallization property of the macrodiol A is weaker than that of the macrodiol B. Particularly preferred are the 1000 to 1500 molecular weight polyadipic acid-based polyester diols.
Further, the macrodiol B in the step (1) comprises one or more of polyethylene glycol adipate PEA, polybutylene adipate PBA, neopentyl glycol adipate PNA, polyhexamethylene glycol adipate PHA, polyhexamethylene glycol adipate PHNA, polybutylene glycol adipate PBNA, polypropylene glycol adipate PPA, polyethylene glycol PEG, polypropylene glycol PPG, polytetrahydrofuran ether glycol PTMG, polycaprolactone diol PCL and polycarbonate diol PCDL, the number average molecular weight of the macrodiol is 2000-6000, and the crystallization property of the macrodiol B is stronger than that of the macrodiol A. Particularly preferred are the poly-adipic polyester diols having molecular weights of 3000 to 4000.
Further, the diisocyanate in the step (2) comprises one or more of 4,4 '-diphenylmethane diisocyanate MDI, isophorone diisocyanate IPDI, toluene diisocyanate TDI, hexamethylene diisocyanate HDI, and 4,4' -dicyclohexylmethane diisocyanate HMDI. Particularly preferred is hexamethylene diisocyanate HDI, which has a good linear structure and is resistant to yellowing.
Further, the catalyst in the step (2) comprises one of dibutyltin dilaurate, stannous octoate and dibutyltin diacetate.
Further, the organic solvent in step (3) comprises one or more of acetone, butanone, methyl acetate and toluene.
Further, the hydrophilic monomer in the step (3) is one or more of the combination of diaminoethanesulfonic acid sodium salt AAS-Na, and the structural formula of the diaminoethanesulfonic acid sodium salt AAS-Na is:
wherein R is 1 Is one of aromatic hydrocarbon, alkane and alicyclic hydrocarbon;
further, the chain extender in the step (4) comprises one or more of ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, isophoronediamine, hydrazine hydrate and hydroxyethylethylenediamine.
Further, the defoaming agent in the step (4) is an organic silicon type defoaming agent, and comprises one of BYK-065, BYK-066 and BYK-141.
Further, the solid content of the low activation temperature polyurethane dispersion obtained in the step (4) is 20% to 60%, preferably 30% to 50%, without particular limitation.
Compared with the prior art, the invention has the following beneficial effects:
the polyurethane dispersion adhesive prepared by the invention has the advantages of high solid content, good stability, low activation temperature and high initial adhesion strength, and can be used for processing and bonding heat-labile base materials in bags, textiles and balls.
The preparation method provided by the invention is simple and efficient in synthesis and good in repeatability, the whole system is an aqueous system, and the preparation method is safe and environment-friendly and basically free of Volatile Organic Compounds (VOCs) emission.
Detailed Description
Embodiments of the present invention are further illustrated below, but the examples of the present invention are not limited thereto.
Solid content determination: weighing a certain amount of sample with mass m 0 Dried poly (propylene oxide)In the tetrafluoroethylene watch glass, the total mass of the sample and the watch glass is m 1 Spreading the emulsion on a watch glass, placing the watch glass in a constant-temperature blast oven with the temperature set to 60 ℃ for heating for 24h, taking out the watch glass, cooling to room temperature, weighing the watch glass, placing the watch glass in the oven for heating for 30min, weighing the watch glass until the difference value between two adjacent times of weighing is within 0.01g, and recording the total mass m of the dried glue film and the watch glass 2 . The PUD solids content is then:
measurement of viscosity: the viscosity of the polyurethane dispersion was measured using an NDJ-8S rotational viscometer with a # 1 spindle at 12 rpm.
Measurement of average particle diameter: the average particle size of the polyurethane dispersion was determined using a nanometer particle size analyzer model ZS Nano S, malvern instruments, uk.
And (3) measuring the adhesive property: referring to GB/T2791-1995, initial adhesion and final peel strength were determined by an AGS-X electronic universal tester. The PUDs are uniformly brushed on the surfaces of two pieces of PVC (130 mm multiplied by 25 mm) by a brush, and after heating and activating for 5min, the two pieces of PVC are bonded under the pressure of more than or equal to 1.2 MPa. The initial adhesion was measured after 5min of bonding and the final peel strength was measured after 24 h.
And (3) measuring the activation temperature: referring to European standard EN 12961. The heat activated adhesive generates adhesive force after being activated in a certain temperature range, and shows ideal T peeling strength, and the temperature range is called as an optimal activation temperature.
Example 1
73.46g of polybutylene adipate glycol PBA-1000 and 8.16g of polyhexamethylene adipate glycol PHA-3000 were put in a 500ml three-necked round-bottomed flask equipped with an electric stirrer, a condenser and a thermometer, and dehydrated at 120 ℃ under a vacuum of 0.1MPa for 2 hours. The temperature is reduced to 60 ℃, 14.73g of hexamethylene diisocyanate HDI and 0.01g of dibutyltin dilaurate catalyst are added, the temperature is increased to 90 ℃, the reaction is carried out for 1.5h, and the residual amount of-NCO is titrated by a di-n-butylamine method until the content of-NCO reaches 0.96wt%. The temperature is reduced to 60 ℃, and 150g of acetone is added for dissolution. The temperature of the system is controlled at 40 ℃, and 3.06g of ethylene diamino ethyl sodium sulfonate is added for reaction for 20min. 100g of deionized water is slowly added at the rotating speed of 800r/min and stirred for 20min. And adding 0.47g of hydroxyethyl ethylenediamine for chain extension for 30min, and adding a defoaming agent to obtain the white blue-emitting light dispersoid. And finally, under the conditions of 60 ℃ and 0.08MPa vacuum degree, decompressing and removing the acetone solvent to obtain the polyurethane dispersion adhesive PUD1.
Example 2
69.79g of polybutylene adipate diol PBA-1000 and 12.32g of polyhexamethylene adipate diol PHA-3000 were put into a 500ml three-necked round-bottomed flask equipped with an electric stirrer, a condenser and a thermometer, and dehydrated at 120 ℃ under a vacuum of 0.1MPa for 2 hours. And (3) cooling to 60 ℃, adding 14.28g of Hexamethylene Diisocyanate (HDI) and 0.01g of dibutyltin dilaurate catalyst, heating to 90 ℃, reacting for 1.5h, and titrating the residual amount of-NCO by a di-n-butylamine method until the content of-NCO reaches 0.93wt%. The temperature is reduced to 60 ℃, and 150g of acetone is added for dissolution. The temperature of the system is controlled at 40 ℃, and 3.06g of ethylene diamino ethyl sodium sulfonate is added for reaction for 20min. 100g of deionized water is slowly added at the rotating speed of 800r/min and stirred for 20min. And adding 0.44g of hydroxyethyl ethylenediamine for chain extension for 30min, and adding a defoaming agent to obtain the white blue-emitting light dispersoid. And finally, under the conditions of 60 ℃ and 0.08MPa vacuum degree, decompressing and removing the acetone solvent to prepare the polyurethane dispersion adhesive PUD2.
Example 3
66.07g of polybutylene adipate glycol PBA-1000 and 16.52g of polyhexamethylene adipate glycol PHA-3000 were put in a 500ml three-necked round-bottomed flask equipped with an electric stirrer, a condenser and a thermometer, and dehydrated at 120 ℃ under a vacuum of 0.1MPa for 2 hours. And (3) cooling to 60 ℃, adding 13.84g of Hexamethylene Diisocyanate (HDI) and 0.01g of dibutyltin dilaurate catalyst, heating to 90 ℃, reacting for 1.5h, and titrating the residual quantity of-NCO by a di-n-butylamine method until the content of-NCO reaches 0.90wt%. The temperature is reduced to 60 ℃, and 150g of acetone is added for dissolution. The temperature of the system is controlled at 40 ℃, and 3.06g of ethylene diamino ethyl sodium sulfonate is added for reaction for 20min. 100g of deionized water is slowly added at the rotating speed of 800r/min and stirred for 20min. And adding 0.41g of hydroxyethyl ethylenediamine for chain extension for 30min, and adding a defoaming agent to obtain the white blue-emitting light dispersoid. And finally, under the conditions of 60 ℃ and 0.08MPa vacuum degree, decompressing and removing the acetone solvent to prepare the polyurethane dispersion adhesive PUD3.
Example 4
62.31g of polybutylene adipate diol PBA-1000 and 20.77g of polyhexamethylene adipate diol PHA-3000 were put into a 500ml three-necked round-bottomed flask equipped with an electric stirrer, a condenser and a thermometer, and dehydrated at 120 ℃ under a vacuum of 0.1MPa for 2 hours. And (3) cooling to 60 ℃, adding 13.38g of Hexamethylene Diisocyanate (HDI) and 0.01g of dibutyltin dilaurate catalyst, heating to 90 ℃, reacting for 1.5h, and titrating the residual quantity of-NCO by a di-n-butylamine method until the content of-NCO reaches 0.87wt%. The temperature is reduced to 60 ℃, and 150g of acetone is added for dissolution. The temperature of the system is controlled at 40 ℃, and 3.06g of ethylene diamino ethyl sodium sulfonate is added for reaction for 20min. 100g of deionized water is slowly added at the rotating speed of 800r/min and stirred for 20min. And adding 0.39g of hydroxyethyl ethylenediamine for chain extension for 30min, and adding a defoaming agent to obtain the white blue-emitting light dispersoid. And finally, under the conditions of 60 ℃ and 0.08MPa vacuum degree, decompressing and removing the acetone solvent to obtain the polyurethane dispersion adhesive PUD4.
Example 5
58.50g of polybutylene adipate glycol PBA-1000 and 25.07g of polyhexamethylene adipate glycol PHA-3000 were put in a 500ml three-necked round-bottomed flask equipped with an electric stirrer, a condenser and a thermometer, and dehydrated at 120 ℃ under a vacuum of 0.1MPa for 2 hours. The temperature is reduced to 60 ℃, 12.92g of hexamethylene diisocyanate HDI and 0.01g of dibutyltin dilaurate catalyst are added, the temperature is increased to 90 ℃, the reaction is carried out for 1.5h, and the residual amount of-NCO is titrated by a di-n-butylamine method until the content of-NCO reaches 0.84wt%. The temperature is reduced to 60 ℃, and 150g of acetone is added for dissolution. The temperature of the system is controlled at 40 ℃, and 3.06g of ethylene diamino ethyl sodium sulfonate is added for reaction for 20min. 100g of deionized water is slowly added at the rotating speed of 800r/min and stirred for 20min. And (3) adding 0.36g of hydroxyethyl ethylenediamine for chain extension for 30min, and adding a defoaming agent to obtain a white bluish light dispersion. And finally, under the conditions of 60 ℃ and 0.08MPa vacuum degree, decompressing and removing the acetone solvent to obtain the polyurethane dispersion adhesive PUD5.
The implementation effect is as follows: the PUD sample of representative example 2 was subjected to an activation temperature test, and the initial tack force was measured as shown in Table 1 below.
TABLE 1
| Activation temperature (. Degree.C.) | 35 | 40 | 50 | 60 | 70 | 80 |
| Initial adhesion (N/mm) | 3.43 | 4.03 | 4.03 | 3.75 | 3.73 | 3.71 |
As can be seen from Table 1, the PUD adhesive of the examples of the present invention exhibits an ideal initial tack force of up to 4.03N/mm after heating at 40 ℃, indicating that the adhesive is fully activated at 40 ℃ and has a lower activation temperature.
The basic properties of the PUD samples prepared in the examples of the present invention are shown in table 2 below, where the initial tack and final peel strength were measured at an activation temperature of 40 ℃.
TABLE 2
The solid content of the polyurethane dispersion adhesive prepared in the embodiment is about 50%, and the polyurethane dispersion adhesive has high solid content; the viscosity of the polyurethane dispersion is below 300 mPas, and the viscosity is lower; the average particle size of the polyurethane dispersion adhesive was 200.5nm or less, indicating that the aqueous dispersion had good stability. The initial adhesion and the final peel strength of the polyurethane dispersion adhesive to PVC/PVC are respectively above 3.20N/mm and 5.96N/mm under the activation of 40 ℃, and the polyurethane dispersion adhesive has excellent adhesion performance. The aqueous polyurethane dispersion adhesive does not contain solvent, has no influence on the environment, and can meet the bonding requirements of heat-labile base materials such as textile composite materials and bags.
The above examples are only preferred embodiments of the present invention, which are intended to illustrate the present invention, but not to limit the present invention, and those skilled in the art should be able to make changes, substitutions, modifications, etc. without departing from the spirit of the present invention.
Claims (10)
1. A preparation method of a low activation temperature polyurethane dispersion adhesive is characterized by comprising the following steps:
(1) Adding the macromolecular polyol A and the macromolecular polyol B into a reaction vessel, heating at 110-130 ℃ and pumping water and drying under the vacuum degree of 0.095-0.1MPa for 1-2h;
(2) Cooling the reaction system in the step (1) to below 60 ℃, adding diisocyanate and a catalyst, and reacting for 0.5-2.5h under the conditions of heating and stirring at 85-95 ℃ to obtain a polyurethane prepolymer;
(3) Cooling the reaction system in the step (2) to below 60 ℃, adding an organic solvent which is 1.5-2 times of the mass of the polyurethane prepolymer in the step (2), reducing the viscosity, adding a hydrophilic monomer for reacting for 10-30min, adding deionized water, and dispersing at a high speed for 20-30min;
(4) And (3) adding a chain extender into the reaction product obtained in the step (3) to react for 10-30min, adding a defoaming agent, heating to 40-65 ℃, and distilling under the vacuum degree of 0.06-0.1MPa to remove the organic solvent to obtain the low-activation-temperature polyurethane dispersion adhesive.
2. The method for preparing the polyurethane adhesive with low activation temperature as claimed in claim 1, wherein the amount of each substance added is as follows, in percentage by mass, based on the total mass of the mixture:
macrodiol A:58.50 to 80.69 percent
Macrodiol B:0 to 25.07 percent
Diisocyanate: 12.92 to 16.04 percent
Hydrophilic monomer: 3.62 to 7.36 percent
Chain extender: 0.17-1.79%
Catalyst: 0.01 to 0.10 percent
Defoaming agent: 0.05 to 0.20 percent
The addition amount of the substances accounts for 100 percent of the total mass of the mixture.
3. The method for preparing a polyurethane dispersion adhesive with low activation temperature as claimed in claim 1, wherein in step (1), the macrodiol A comprises at least one of polyethylene glycol adipate diol PEA, polybutylene glycol adipate PBA, neopentyl glycol adipate diol PNA, polyhexamethylene glycol adipate PHA, polyhexamethylene glycol adipate PHNA, polybutylene glycol adipate neopentyl glycol diol PBNA, polypropylene glycol PPA, polytetrahydrofuran ether glycol PTMG, polycaprolactone diol PCL and polycarbonate diol PCDL; the number average molecular weight of the macroglycol is 500-2000, and the crystallization performance of the macroglycol A is weaker than that of the macroglycol B.
4. The method as claimed in claim 1, wherein in step (1), the macrodiol B comprises at least one of poly (ethylene adipate) glycol PEA, poly (butylene adipate) glycol PBA, poly (neopentyl adipate) glycol PNA, poly (hexanediol adipate) glycol PHA, poly (hexanediol adipate) neopentyl glycol PHNA, poly (butanediol neopentyl glycol adipate) PBNA, poly (propylene glycol adipate) glycol PPA, polyethylene glycol PEG, polypropylene glycol PPG, polytetrahydrofuran ether glycol PTMG, polycaprolactone diol PCL, and polycarbonate diol PCDL, the macrodiol has a number average molecular weight of 2000-6000, and the crystallization property of the macrodiol B is stronger than that of the macrodiol A.
5. The method of claim 1, wherein in step (2), the diisocyanate comprises at least one of 4,4 '-diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), toluene Diisocyanate (TDI), hexamethylene Diisocyanate (HDI), and 4,4' -dicyclohexylmethane diisocyanate (HMDI).
6. The method of claim 1, wherein in step (2), the catalyst comprises one of dibutyltin dilaurate, stannous octoate and dibutyltin diacetate.
7. The method for preparing the polyurethane dispersion adhesive with low activation temperature according to claim 1, wherein in the step (3), the organic solvent comprises one or more of acetone, butanone, methyl acetate and toluene; the hydrophilic monomer is one or more of the combination of diaminoethanesulfonic acid sodium salt AAS-Na, and the structural formula of the diaminoethanesulfonic acid sodium salt AAS-Na is as follows:
wherein R is 1 Is one of aromatic hydrocarbon, alkane and alicyclic hydrocarbon.
8. The method for preparing the polyurethane dispersion adhesive with the low activation temperature according to claim 1, wherein in the step (4), the chain extender comprises one or more of ethylenediamine, propylenediamine, butylenediamine, hexylenediamine, isophoronediamine, hydrazine hydrate and hydroxyethyl ethylenediamine; the defoaming agent is an organic silicon type defoaming agent and comprises one of BYK-065, BYK-066 or BYK-141.
9. The method for preparing the low activation temperature polyurethane dispersion adhesive according to claim 1, wherein in the step (4), the solid content of the obtained low activation temperature polyurethane dispersion is 20-60%.
10. The low activation temperature polyurethane dispersion adhesive prepared by the preparation method of any one of claims 1-9, wherein the activation temperature is lower than 40 ℃.
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| KR20050052833A (en) * | 2003-12-01 | 2005-06-07 | 애경화학 주식회사 | An aqueous hot-melt polyurethane adhesive and the method for preparing the same |
| EP2921541A1 (en) * | 2014-03-21 | 2015-09-23 | Henkel AG&Co. KGAA | Aqueous polyurethane dispersions |
| CN106978129A (en) * | 2017-03-16 | 2017-07-25 | 惠州市亨迪树脂制品有限公司 | A kind of high solids content double-component waterborne polyurethane adhesive with low-temperature activation and preparation method thereof |
| CN110818873A (en) * | 2019-11-20 | 2020-02-21 | 万华化学集团股份有限公司 | Waterborne polyurethane resin and preparation method and application thereof |
| CN112250832A (en) * | 2020-10-21 | 2021-01-22 | 万华化学集团股份有限公司 | Waterborne polyurethane resin and preparation method and application thereof |
| CN112812727A (en) * | 2021-01-20 | 2021-05-18 | 重庆中科力泰高分子材料股份有限公司 | Long-lasting viscous waterborne polyurethane adhesive and preparation method thereof |
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| KR20050052833A (en) * | 2003-12-01 | 2005-06-07 | 애경화학 주식회사 | An aqueous hot-melt polyurethane adhesive and the method for preparing the same |
| EP2921541A1 (en) * | 2014-03-21 | 2015-09-23 | Henkel AG&Co. KGAA | Aqueous polyurethane dispersions |
| CN106978129A (en) * | 2017-03-16 | 2017-07-25 | 惠州市亨迪树脂制品有限公司 | A kind of high solids content double-component waterborne polyurethane adhesive with low-temperature activation and preparation method thereof |
| CN110818873A (en) * | 2019-11-20 | 2020-02-21 | 万华化学集团股份有限公司 | Waterborne polyurethane resin and preparation method and application thereof |
| CN112250832A (en) * | 2020-10-21 | 2021-01-22 | 万华化学集团股份有限公司 | Waterborne polyurethane resin and preparation method and application thereof |
| CN112812727A (en) * | 2021-01-20 | 2021-05-18 | 重庆中科力泰高分子材料股份有限公司 | Long-lasting viscous waterborne polyurethane adhesive and preparation method thereof |
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