CN111154448A - High-modulus reactive polyurethane hot melt adhesive and preparation method thereof - Google Patents
High-modulus reactive polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
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- CN111154448A CN111154448A CN202010011987.2A CN202010011987A CN111154448A CN 111154448 A CN111154448 A CN 111154448A CN 202010011987 A CN202010011987 A CN 202010011987A CN 111154448 A CN111154448 A CN 111154448A
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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
-
- 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
-
- 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
-
- 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
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
Abstract
The invention discloses a high-modulus reactive polyurethane hot melt adhesive, which is particularly used for bonding polar materials, such as plastics of PC, PA, TPU, PMMA, ABS, PET and the like, and also used for bonding materials of glass, aluminum, stainless steel and the like, and consists of a polyester polyol mixture, an antioxidant, isocyanate, a catalyst, an adhesion promoter and a defoaming agent, wherein the polyester polyol and the antioxidant are heated, melted and dehydrated at high temperature, the isocyanate compound is added, the temperature of a polymer is controlled, the catalyst and the adhesion promoter are added after polymerization reaction is finished, the mixture is uniformly stirred and dispersed, and finally the defoaming agent is added for full vacuum defoaming, so that the high-modulus reactive polyurethane hot melt adhesive is obtained; the reactive polyurethane hot melt adhesive has good adhesion to narrow frames, is particularly suitable for assembly of a pipeline structure of modern industrial electronic products, has high initial strength, high curing speed, high modulus, simple production and preparation process and easy industrial production aiming at adhesion of polar materials.
Description
Technical Field
The invention relates to the technical field of preparation of single-component moisture-curing polyurethane adhesives, in particular to a high-modulus reactive polyurethane hot melt adhesive and a preparation method thereof.
Background
The reactive polyurethane hot melt adhesive is divided into a closed polyurethane hot melt adhesive and a moisture-curable polyurethane hot melt adhesive, and the former has high dissociation temperature (generally higher than 100 ℃) of a sealing agent, so that an adhesive layer can be foamed, and the reactive polyurethane hot melt adhesive is only used for maintenance treatment; the moisture-curable polyurethane hot melt adhesive has the characteristics of a hot melt adhesive and a reactive adhesive, has the characteristics of low application temperature compared with the traditional hot melt adhesive, high bonding strength after curing, water resistance, heat resistance, chemical resistance and the like, and can show excellent bonding performance to substrates containing active hydrogen such as wood, ceramics, fabrics and the like and smooth substrates such as metal, glass, plastic, rubber and the like.
With the rapid development of the electronic industry, a large number of large-screen and portable handheld electronic products such as mobile phones, tablet computers and the like appear, the frame design of the electronic products is narrower and narrower, the screen and the frame, the front cover and the rear cover and the frame need to be structurally bonded in the production line of the electronic equipment, the requirements on the initial strength, the rapid curing and the final bonding strength of the adhesive are higher, and with the increasing demands on various electronic products and the development trend that the electronic products are thinner, lighter and more beautiful, the requirements on the production assembly line of the products are higher and higher.
At present, the initial adhesive strength of the existing products in the market at the early stage is generally about 0.3MPa (10-minute shear strength of PMMA-PMMA), the strength is less than 0.5MPa, the rapid positioning and bonding cannot be effectively realized, the preset bonding effect can be achieved only under the condition of long-time pressure maintaining, the cost is increased, the efficiency is also reduced, and after the products are completely cured, as most of electronic products are mainly narrow frames, the consumption of adhesives is low (the cross-sectional area of the bearing is small), but the volume of the fixed materials is large, the infirm phenomenon of bonding representation is easily caused, and a glue line with proper melt viscosity is researched and prepared to ensure the glue applying speed, no gel, good fluidity and uniform and superfine (below 1 millimeter) glue lines are formed; the adhesive has high initial adhesion strength and can be quickly cured; reactive polyurethane hot melt adhesives which have high modulus and high cohesive strength after curing are the development targets in the future.
Disclosure of Invention
The invention mainly aims to provide a high-modulus reactive polyurethane hot melt adhesive and a preparation method thereof, which are used for solving the problems in the background art.
In order to achieve the purpose, the invention adopts the technical scheme that:
a high-modulus reaction type polyurethane hot melt adhesive is prepared from the following raw materials in percentage by mass: 70-85% of polyester polyol mixture, 0.05-0.5% of antioxidant, 15-25% of isocyanate compound, 0.1-1.0% of catalyst, 0.1-1.0% of adhesion promoter and 0.1-0.5% of defoaming agent.
Preferably, the mass percentage of the isocyanate group of the reactive polyurethane hot melt adhesive is between 1% and 4%.
Preferably, the polyester polyol is synthesized by one of PA (phosphatidic acid), SA (sialic acid), AA (adipic acid), TPA (terephthalic acid), DDDA (lauric acid) and one of BDO (butanediol), HDO (hexanediol), NPG (neopentyl glycol), MPD (3-methyl-1, 5 pentanediol), EG (ethylene glycol), MPG (1,2 propanediol), DEG (diethylene glycol) or a mixture thereof; wherein, the molecular weight of the polyester polyol is between 500-6500 liquid polyester polyol and solid polyester polyol, and the solid polyester polyol is crystalline polyester polyol or amorphous polyester polyol.
Preferably, the polyester polyol mixture consists of 24-64% of liquid polyester polyol, 24-40% of crystalline polyester polyol and 12-36% of amorphous polyester polyol in percentage by mass.
Preferably, the antioxidant is one or a mixture of any more of 2, 6-di-tert-butyl-p-cresol, β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester, tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tris (2, 4-di-tert-butylphenyl) phosphite and β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid isooctyl ester.
Preferably, the isocyanate compound is an aromatic diisocyanate, and comprises one or a mixture of any several of toluene diisocyanate, diphenylmethane diisocyanate and carbodiimide-modified diphenylmethane diisocyanate.
Preferably, the catalyst is one or a mixture of any more of dioctyltin dithiolate, dibutyltin mercaptide and 2, 2-dimorpholinyl diethyl ether.
Preferably, the adhesion promoter is one or a mixture of any more of A-1170, A-187 and A-189 of the Mylar material.
Preferably, the defoaming agent is a BYK-A535 type defoaming agent.
A preparation method of a high-modulus reactive polyurethane hot melt adhesive comprises the following steps:
s1, selecting raw materials according to the mass percentage; wherein, the liquid polyester polyol 24-64%, the crystalline polyester polyol 24-40%, the amorphous polyester polyol 12-36%, the antioxidant 0.05-0.5%, the isocyanate compound 15-25%, the catalyst 0.1-1.0%, the adhesion promoter 0.1-1.0%, and the defoaming agent 0.1-0.5%;
s2, uniformly stirring and mixing the polyester polyol mixture and the antioxidant, heating to 150-160 ℃, stirring and dehydrating for 2 hours under the full vacuum condition until the mass percentage of the water content of the raw materials in the kettle is lower than 0.03%, filling dry inert gas (nitrogen or argon) and breaking vacuum;
s3, cooling to 100 ℃ in the atmosphere of dry inert gas (nitrogen or argon), adding an isocyanate compound, rapidly and uniformly stirring, and controlling the temperature to be between 100 ℃ and 110 ℃ to carry out full vacuum stirring reaction for 1 hour;
s4, adding a catalyst and an adhesion promoter under the condition of constant temperature of 110 ℃, stirring for 30 minutes in full vacuum, and filling dry inert gas (nitrogen or argon) to break the vacuum;
s5, keeping the temperature at 110 ℃ under the atmosphere of dry inert gas (nitrogen or argon), adding a defoaming agent, and stirring in vacuum for 30 minutes to defoam;
s6, discharging at a constant temperature of 110 ℃ to obtain the high-modulus reactive polyurethane hot melt adhesive.
Compared with the prior art, the invention has the following beneficial effects: the high-modulus reactive polyurethane hot melt adhesive is prepared by heating polyester polyol and an antioxidant at a high temperature, melting and dehydrating, adding an isocyanate compound, controlling the temperature of a polymer, adding a catalyst and an adhesion promoter after the polymerization reaction is finished, uniformly stirring and dispersing, and finally adding a defoaming agent for full vacuum defoaming.
Detailed Description
The following description is given by way of specific detection methods and specific embodiments, and the examples are given for the purpose of illustration only and are not intended to limit the present invention.
The test method is as follows:
(1) and (3) viscosity detection:
the viscosity of the gel samples at spindle # 27 was tested by means of a Brookfield DV viscometer according to the test method GB/T2794-.
(2) Initial adhesion shear strength adhesion test:
according to the test method GB/T8165-. The initial tack shear strength was measured in a universal tester for 10 minutes. The test was carried out on a universal tester at a speed of 5mm/min, and the maximum adhesive strength at which the part bond failed was measured and recorded.
(3) Elastic modulus test after full cure:
according to the test method of GB/T3321-.
(4) Shear strength adhesion test after complete curing:
according to the test method GB/T8165-.
Preparation of the samples in the examples:
example 1:
heating a reaction kettle to a constant temperature of 160 ℃, adding 40g of polydiethylene glycol phthalate glycol with the molecular weight of 1600, 20g of neopentyl glycol phthalate glycol with the molecular weight of 3200, 20g of polybutylene adipate glycol with the molecular weight of 3750 and 0.1g of β - (3, 5-di-tert-butyl-4-hydroxyphenyl) isooctyl propionate, stirring and mixing uniformly, stirring and dehydrating for 2 hours under the full vacuum condition of 160 ℃ until the mass percentage of the water content of the raw materials in the kettle is lower than 0.03%, filling dry nitrogen to break vacuum, cooling to 100 ℃ under the nitrogen atmosphere, adding 19g of pure MDI (diphenylmethane diisocyanate), stirring uniformly rapidly, controlling the temperature to be 110 ℃ and stirring and reacting for 1 hour under the full vacuum condition, filling nitrogen to break vacuum, adding 0.3g of dioctyl tin dithiol and 0.5g of A-1170 under the constant temperature of 110 ℃ and stirring for 30 minutes, filling nitrogen to break vacuum, adding 0.1g of BYK-A535 under the nitrogen atmosphere, stirring for 30 minutes under the full vacuum condition, filling the nitrogen to break vacuum, sealing and discharging and defoaming.
Example 2:
heating a reaction kettle to a constant temperature of 160 ℃, adding 35g of polyhexamethylene phthalate glycol with the molecular weight of 1000, 15g of poly neopentyl glycol adipate glycol with the molecular weight of 3200, 15g of polyhexamethylene adipate glycol with the molecular weight of 3000, 10g of polyhexamethylene suberate glycol with the molecular weight of 3750 and 0.1g of β - (3, 5-di-tert-butyl-4-hydroxyphenyl) isooctyl propionate, uniformly stirring and dehydrating for 2 hours at 160 ℃ under the full vacuum condition until the mass percentage of the water content of the raw materials in the kettle is lower than 0.03%, filling dry nitrogen to break the vacuum, cooling to 100 ℃ under the nitrogen atmosphere, adding 24g of pure MDI (diphenylmethane diisocyanate), rapidly stirring uniformly, controlling the temperature to be 110 ℃ under the full vacuum stirring reaction for 1 hour, filling the nitrogen to break the vacuum, adding 0.3g of dioctyltin disulfide and 0.5g of A-187 under the constant temperature of 110 ℃, filling the nitrogen to be vacuum stirred for 30 minutes, filling the nitrogen to break the vacuum, adding 0.1g of BYK-535 under the constant temperature under the nitrogen atmosphere, stirring for 30 minutes, filling the vacuum, sealing and packaging under the constant temperature and vacuum reaction conditions of 110 ℃ to prepare the polyurethane.
Example 3:
heating a reaction kettle to a constant temperature of 150 ℃, adding 20g of polyethylene glycol phthalate with the molecular weight of 3000, adding 24g of poly (3-methyl-1, 5-pentanediol) glycol adipate with the molecular weight of 2000, 10g of poly (neopentyl glycol adipate) glycol diol with the molecular weight of 2600, 25g of polycaprolactone diol with the molecular weight of 4000, 5g of poly (dodecanedioic acid hexanediol) glycol adipate with the molecular weight of 3750 and 0.1g of β - (3, 5-di-tert-butyl-4-hydroxyphenyl) isooctyl propionate, stirring and uniformly under the condition of full vacuum at 150 ℃, dehydrating for 2 hours until the mass percentage of the water content of the raw materials in the kettle is lower than 0.03%, filling dry nitrogen to break the vacuum, cooling to 100 ℃ under the nitrogen atmosphere, adding 15g of pure MD (diphenylmethane diisocyanate), stirring uniformly rapidly, stirring under the condition of full vacuum at 105 ℃, stirring for 1 hour, filling the nitrogen to break the vacuum, adding 0.3g of mercaptan and 0.5g of dibutyltin A-187, stirring under the condition of full vacuum at the constant temperature of 110 ℃, filling the nitrogen to break the vacuum, packaging under the condition of full vacuum, discharging, and discharging the polyurethane.
Example 4:
heating a reaction kettle to a constant temperature of 150 ℃, adding 39g of polyethylene glycol phthalate glycol with the molecular weight of 2000, 15g of polyhexamethylene glycol terephthalate with the molecular weight of 2600, 25g of polyhexamethylene glycol adipate with the molecular weight of 3750 and 0.1g of β - (3, 5-di-tert-butyl-4-hydroxyphenyl) isooctyl propionate, stirring and mixing uniformly, stirring and dehydrating for 2 hours under the full vacuum condition of 150 ℃ until the mass percentage of the water content of the raw materials in the kettle is lower than 0.03%, filling dry nitrogen to break vacuum, cooling to 100 ℃ under the nitrogen atmosphere, adding 20g of modified liquefied MDI (diphenylmethane diisocyanate), stirring uniformly rapidly, controlling the temperature to be 100 ℃ and stirring and reacting for 1 hour under the full vacuum condition, filling nitrogen to break vacuum, adding 0.3g of 2, 2-dimorpholinyl diethyl ether and 0.5g of A-189 to stir for 30 minutes under the constant temperature of 110 ℃, filling nitrogen to break vacuum, adding 0.1g of BYK-A535, stirring for 30 minutes under the constant temperature, filling nitrogen to break vacuum, packaging under the constant temperature and sealing and discharging.
Example 5:
heating a reaction kettle to a constant temperature of 160 ℃, adding 20g of poly sebacic acid-3-methyl-1, 5-pentanediol ester diol with the molecular weight of 2000, 10g of poly neopentyl glycol hexanediol phthalate with the molecular weight of 2000, 25g of poly hexanediol terephthalate with the molecular weight of 3200, 25g of poly butanediol adipate with the molecular weight of 4000, 5g of poly hexanediol suberate diol with the molecular weight of 4000 and 0.1g of β - (3, 5-di-tert-butyl-4-hydroxyphenyl) isooctyl propionate, stirring and mixing uniformly, stirring and dehydrating for 2 hours under the condition of full vacuum at 160 ℃ until the mass percentage content of the raw material in the kettle is lower than 0.03%, filling dry nitrogen to break the vacuum, cooling to 100 ℃ under the nitrogen atmosphere, adding 15g of pure MDI (diphenylmethane diisocyanate), stirring uniformly rapidly, controlling the temperature to fully stir and react for 1 hour under the condition of 110 ℃, filling the nitrogen to break the vacuum, adding 0.2g of 2-dimorpholinodiethyl ether, 0.1g of dibutyltin thiol, 1170A-1170A to stir and packaging under the conditions of full vacuum, filling the nitrogen to break the vacuum and vacuum, stirring and discharging under the conditions of full vacuum, filling the nitrogen to break the vacuum, stirring and sealing and discharging under the condition of vacuum, adding the ByK, stirring, sealing, stirring, sealing, and discharging under the vacuum, and.
Comparative example 1:
heating the reaction kettle to a constant temperature of 120 ℃, adding 44.2g of polyoxypropylene ether diol with molecular weight of 2000, 20g of polyhexamethylene adipate diol with molecular weight of 3500 and 20g of acrylic thermoplastic resin with molecular weight of 60000, uniformly stirring, keeping the temperature of 120 ℃, and vacuumizing and dehydrating for 2 hours. Then the temperature is reduced to 80 ℃, 15g of pure MDI (diphenylmethane diisocyanate) is added, and the reaction is carried out for 2 hours at the constant temperature of 80 ℃. And finally, adding 0.3g of dimorpholinodiethyl ether and 0.5g of gamma-glycidyl ether oxypropyl trimethoxy silane, uniformly stirring, and defoaming in vacuum until no bubbles exist to prepare the reactive polyurethane hot melt adhesive.
The data results of sampling and testing of the high modulus reactive polyurethane hot melt adhesives prepared in examples 1 to 5, comparative example 1 and the commercially available reactive polyurethane hot melt adhesive are shown in table 1.
TABLE 1
The elastic modulus of the reactive polyurethane hot melt adhesive is generally higher than that of related products sold in the market, and the initial adhesion strength is high within 10 minutes, so that the production efficiency of modern factories is improved.
The above description is only exemplary of the present invention and should not be taken as limiting the invention, as any modification, equivalent replacement or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A high-modulus reactive polyurethane hot melt adhesive is characterized in that: the reactive polyurethane hot melt adhesive is prepared from the following raw materials in percentage by mass: 70-85% of polyester polyol mixture, 0.05-0.5% of antioxidant, 15-25% of isocyanate compound, 0.1-1.0% of catalyst, 0.1-1.0% of adhesion promoter and 0.1-0.5% of defoaming agent.
2. The high-modulus reactive polyurethane hot melt adhesive according to claim 1, wherein: the mass percentage of isocyanate groups of the reactive polyurethane hot melt adhesive is between 1 and 4 percent.
3. The high-modulus reactive polyurethane hot melt adhesive according to claim 1, wherein: the polyester polyol is synthesized by one of PA (phosphatidic acid), SA (sialic acid), AA (adipic acid), TPA (terephthalic acid) and DDDA (lauric acid) and one of BDO (butanediol), HDO (hexanediol), NPG (neopentyl glycol), MPD (3-methyl-1, 5 pentanediol), EG (ethylene glycol), MPG (1,2 propanediol), DEG (diethylene glycol) or a mixture of the two; wherein, the molecular weight of the polyester polyol is between 500-6500 liquid polyester polyol and solid polyester polyol, and the solid polyester polyol is crystalline polyester polyol or amorphous polyester polyol.
4. The high-modulus reactive polyurethane hot melt adhesive according to claim 3, wherein: the polyester polyol mixture consists of 24-64% of liquid polyester polyol, 24-40% of crystalline polyester polyol and 12-36% of amorphous polyester polyol in percentage by mass.
5. The high-modulus reactive polyurethane hot melt adhesive according to claim 1, wherein the antioxidant is one or a mixture of any more of 2, 6-di-tert-butyl-p-cresol, β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester, tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tris (2, 4-di-tert-butylphenyl) phosphite and β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid isooctyl ester.
6. The high-modulus reactive polyurethane hot melt adhesive according to claim 1, wherein: the isocyanate compound is aromatic diisocyanate and comprises one or a mixture of any more of toluene diisocyanate, diphenylmethane diisocyanate and carbodiimide modified diphenylmethane diisocyanate.
7. The high-modulus reactive polyurethane hot melt adhesive according to claim 1, wherein: the catalyst is one or a mixture of any more of dioctyl tin dithiolate, dibutyltin mercaptide and 2, 2-dimorpholinyl diethyl ether.
8. The high-modulus reactive polyurethane hot melt adhesive according to claim 1, wherein: the adhesion promoter is one or a mixture of any more of A-1170, A-187 and A-189 of the new material.
9. The high-modulus reactive polyurethane hot melt adhesive according to claim 1, wherein: the defoaming agent is a BYK-A535 type defoaming agent.
10. The preparation method of the high-modulus reactive polyurethane hot melt adhesive according to claim 1, wherein the preparation method comprises the following steps: the method comprises the following steps:
s1, selecting raw materials according to the mass percentage; wherein, the liquid polyester polyol 24-64%, the crystalline polyester polyol 24-40%, the amorphous polyester polyol 12-36%, the antioxidant 0.05-0.5%, the isocyanate compound 15-25%, the catalyst 0.1-1.0%, the adhesion promoter 0.1-1.0%, and the defoaming agent 0.1-0.5%;
s2, uniformly stirring and mixing the polyester polyol mixture and the antioxidant, heating to 150-160 ℃, stirring and dehydrating for 2 hours under the full vacuum condition until the mass percentage of the water content of the raw materials in the kettle is lower than 0.03%, filling dry inert gas (nitrogen or argon) and breaking vacuum;
s3, cooling to 100 ℃ in the atmosphere of dry inert gas (nitrogen or argon), adding an isocyanate compound, rapidly and uniformly stirring, and controlling the temperature to be between 100 ℃ and 110 ℃ to carry out full vacuum stirring reaction for 1 hour;
s4, adding a catalyst and an adhesion promoter under the condition of constant temperature of 110 ℃, stirring for 30 minutes in full vacuum, and filling dry inert gas (nitrogen or argon) to break the vacuum;
s5, keeping the temperature at 110 ℃ under the atmosphere of dry inert gas (nitrogen or argon), adding a defoaming agent, and stirring in vacuum for 30 minutes to defoam;
s6, discharging at a constant temperature of 110 ℃ to obtain the high-modulus reactive polyurethane hot melt adhesive.
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