CN112708101B - Preparation method of thermoplastic polyurethane elastomer for reactive hot melt adhesive - Google Patents
Preparation method of thermoplastic polyurethane elastomer for reactive hot melt adhesive Download PDFInfo
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- CN112708101B CN112708101B CN202011572899.6A CN202011572899A CN112708101B CN 112708101 B CN112708101 B CN 112708101B CN 202011572899 A CN202011572899 A CN 202011572899A CN 112708101 B CN112708101 B CN 112708101B
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
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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
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8125—Unsaturated isocyanates or isothiocyanates having two or more isocyanate or isothiocyanate groups
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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
- 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
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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
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a preparation method of a thermoplastic polyurethane elastomer for a reactive hot melt adhesive. Adding 50-80 parts of polyester polyol and 5-10 parts of dihydroxy polybutadiene into a reaction kettle, controlling the temperature at 115 ℃ and 120 ℃, controlling the vacuum degree to be less than or equal to 0.095MPa, and dehydrating for 2-3h in vacuum; after dehydration treatment, cooling the mixture in the previous step to 78-82 ℃, adding 10-40 parts of polyisocyanate, 0-0.5 part of catalyst, 0-1.0 part of antioxidant and 0-1.0 part of anti-yellowing agent into the reaction kettle, stirring at 80-150r/min, uniformly mixing, and stirring and reacting at 80-85 ℃ and under the vacuum degree of less than or equal to 0.095MPa at 80-150r/min for 3 hours; obtaining a thermoplastic polyurethane elastomer for the reactive hot melt adhesive; and packaging and sealing the thermoplastic polyurethane elastomer used for the reactive hot melt adhesive in the last step under the protection of nitrogen to obtain a finished product. The thermoplastic polyurethane elastomer prepared by the invention can improve the initial adhesion strength of the reactive polyurethane hot melt adhesive, increase the melt viscosity, improve the cohesive force, has excellent compatibility and can meet the market demands at home and abroad.
Description
Technical Field
The invention relates to the field of chemical materials, in particular to a preparation method of a thermoplastic polyurethane elastomer for a reactive polyurethane hot melt adhesive (HMPUR), which is used for improving the initial adhesion strength, increasing the melt viscosity and improving the cohesion and compatibility of polyurethane.
Background
In spite of the development of the adhesive industry in recent years, the reactive polyurethane hot melt adhesive is one of the fastest growing adhesive varieties. This is not only due to their excellent properties, but also because such hot melt adhesives can provide the user with excellent environmental friendliness. The adhesive strength of the reactive polyurethane hot melt adhesive is different from that of the common hot melt adhesive, the reactive polyurethane hot melt adhesive contains isocyanate-terminated (NCO) polyurethane prepolymer, and the isocyanate-terminated (NCO) polyurethane prepolymer can react with moisture or active hydrogen substances in the air or on an adherend to form a partially crosslinked reticular structure, so that the adhesive strength, chemical resistance, heat resistance, hydrolysis resistance and other properties of the reactive polyurethane hot melt adhesive are superior to those of the common hot melt adhesive. Meanwhile, the adhesive has the thermoplastic cold setting property of common hot melt adhesive, is simple and convenient to bond, and has the characteristics of polyurethane adhesive such as wide range of joinable objects, large property adjustability, good surface compatibility on paint surfaces and the like. 100 percent of solid content, no solvent and environmental protection. These have led to the widespread use of these hot melt adhesives in various applications, such as the automotive industry, the footwear industry, textiles, the wood industry, the electronics industry, book binding, and the like.
Although single-component HMPURs do exist, the PUR prepolymers, the main component, do not satisfy the industrial requirements of use. Particularly, the initial viscosity is poor, and the workpiece is often fixed by a temporary clamp after glue application and butt joint until the PUR is primarily cured to generate a certain bonding force, which is very inconvenient. Therefore, the existing HMPUR product can modify the HMPUR product and increase the initial adhesion of the HMPUR product. The main method currently used for such modification is to add a tackifier resin, a thermoplastic elastomer, and the like thereto.
The tackifying resins for modification generally include natural resins such as rosin resins, terpene phenolic resins, and the like, and various petroleum resins, and the thermoplastic elastomers include EVA, EAA, acrylic resins, thermoplastic polyurethane elastomers TPU, and the like. These are all used to improve the initial tack properties of HMPURs and have a similar problem: the small molecular weight model has poor effect, and when the addition amount is more, the initial adhesion strength can be even reduced; the type compatibility with large molecular weight is poor, the HMPUR is easy to precipitate, the use temperature of the HMPUR is greatly increased sometimes, and the production of users is inconvenient. The thermoplastic polyurethane elastomer has the advantages of natural compatibility due to the structure similar to that of the PUR, and in order to give consideration to initial adhesion strength and compatibility, the thermoplastic polyurethane elastomer for the HMPUR on the market mostly adopts a model with small molecular weight, easy compatibility and high crystallization speed, and the initial adhesion strength is improved to the maximum as soon as possible by accelerating the crystallization speed of the HMPUR, so that the initial adhesion strength is improved in a phase-change manner. However, this will cause the open time of HMPUR to be greatly shortened, and eliminate the advantage that the open time can be freely adjusted, thereby limiting the flexibility and application range of HMPUR.
Disclosure of Invention
Therefore, the invention provides a preparation method of a thermoplastic polyurethane elastomer for a reactive polyurethane hot melt adhesive, which solves the technical problems that the initial adhesion strength of the reactive polyurethane hot melt adhesive is insufficient, the tackifying capability and compatibility of improved tackifying resin and the thermoplastic elastomer are difficult to be considered, and the performances such as use temperature, opening time and the like are adversely affected.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a preparation method of a thermoplastic polyurethane elastomer for a reactive hot melt adhesive, which comprises the following steps of:
step one, adding 50-80 parts of polyester polyol and 5-10 parts of dihydroxy polybutadiene into a reaction kettle, controlling the temperature to be 115-120 ℃, controlling the vacuum degree to be less than or equal to 0.095MPa, and dehydrating for 2-3h in vacuum to obtain a mixture;
step two, after dehydration treatment, cooling the mixture obtained in the step one to 78-82 ℃, adding 10-40 parts of polyisocyanate, 0-0.5 part of catalyst, 0-1.0 part of antioxidant and 0-1.0 part of yellowing resistant agent into a reaction kettle, stirring at 80-150r/min, uniformly mixing, and stirring and reacting at 80-85 ℃ and under the vacuum degree of less than or equal to 0.095MPa at 80-150r/min for 3 hours; obtaining a thermoplastic polyurethane elastomer for the reactive polyurethane hot melt adhesive;
and step three, packaging and sealing the thermoplastic polyurethane elastomer for the reactive polyurethane hot melt adhesive in the step two under the protection of nitrogen to obtain a finished product of the thermoplastic polyurethane elastomer for the reactive polyurethane hot melt adhesive.
Further, in the first step, the polyester polyol is a mixture containing 5 to 30% of amorphous polyester polyol, 20 to 60% of liquid polyester polyol and 10 to 50% of crystalline polyester polyol.
Further, the amorphous polyester polyol is prepared by reacting a reactant 1 with a reactant 2; wherein reactant 1 is one or both of neopentyl glycol or hexanediol; reactant 2 is either or both phthalic acid or phthalic anhydride.
Further, the liquid polyester polyol is prepared by reacting a reactant 3 with a reactant 4;
the viscosity of the liquid polyester polyol is more than 10Pa.s at 80 ℃;
wherein, the reactant 3 is one or more of neopentyl glycol, hexanediol or butanediol; reactant 4 is one or more of adipic acid, phthalic acid, terephthalic acid or isophthalic acid.
Further, the crystalline polyester polyol is prepared by reacting a reactant 5 with a reactant 6;
the crystalline polyester polyol is prepared from 40 to 120 ℃;
wherein, the reactant 5 is one or more of ethylene glycol, hexanediol or butanediol; reactant 6 is one or more of adipic acid, sebacic acid or terephthalic acid.
Further, in the first step, the hydroxyl-terminated polybutadiene component has a hydroxyl value of 20-50mgKOH/g and a viscosity of 3-10Pa.s at 40 ℃.
Further, in the second step, the polyisocyanate component is dimer acid diisocyanate (DDI).
Further, in the second step, the catalyst is one or more of lead octoate, tin octoate or zinc octoate.
In the second step, the antioxidant is any one of 2, 6-di-tert-butyl-p-cresol, antioxidant 1010 and antioxidant 1076.
In the second step, the yellowing-resistant agent is any one of 2-hydroxy-4-methylbenzophenone, 2- (2 '-hydroxy-3', 5 '-di-tert-butyl) phenyl-5-chlorobenzotriazole, 2- (2' -hydroxy-3 ', 5-di-tert-amyl) phenylbenzotriazole, 2- (2' -hydroxy-3 ', 5' -di-tert-octyl) phenylbenzotriazole and 2-hydroxy-4-n-octoxybenzophenone.
The invention has the following advantages:
according to the invention, by introducing the liquid telechelic polymer hydroxyl-terminated polybutadiene into the formula, good melting property and bonding property are provided under the condition of controlling the molecular weight of the product to be at a lower level.
The invention uses dimer acid diisocyanate (DDI) with excellent compatibility and reaction activity with hydroxyl-terminated polybutadiene to replace common diphenylmethane diisocyanate (MDI), and uses lead octoate, tin octoate and zinc octoate as catalysts, thereby not only ensuring the reaction activity of DDI, but also ensuring the compatibility of DDI and HMPUR.
Therefore, the thermoplastic polyurethane elastomer prepared by the invention can improve the initial adhesion strength of the reactive polyurethane hot melt adhesive, increase the melt viscosity, improve the cohesive force, has excellent compatibility and can meet the market demands at home and abroad.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Producing high-viscosity liquid polyester polyol by polyester polyol P-5 Qingdao Xinyutian chemical industry Co., Ltd;
the polyester polyol 356T is a crystalline polyester polyol produced by Qingdao Xinyutian chemical Co., Ltd;
polyester polyol Dynacoll7130 wins Chuangdegusai to produce amorphous polyether polyol;
polyester polyol 224 a Yao polyurethane plastic product factory in Taizhou produced high viscosity liquid polyester polyol;
polyester polyol P-153 Yao in Taizhou polyurethane plastic product factories to produce amorphous polyester polyol;
the polyester polyol P-40 Yao and Tanzhou polyurethane plastic product factory produces high-viscosity liquid polyester polyol;
the polyester polyol CMA-2066 Wanhua chemical group GmbH produces crystalline polyester polyol;
polyester polyol CMA-66 Wanhua chemical group GmbH produces crystalline polyester polyol.
Example 1
Step one, adding 80kg of polyester polyol and 5kg of dihydroxy polybutadiene into a reaction kettle, wherein the polyester polyol is formed by mixing P-540 kg of polyester polyol, 356T 25kg of polyester polyol and 713015 kg of Dynacoll polyester polyol, controlling the temperature to be 120 ℃, the vacuum degree to be less than or equal to 0.095MPa, and carrying out vacuum dehydration for 2-3h to obtain a mixture;
step two, after dehydration treatment, cooling the mixture obtained in the step one to 80 ℃, adding 15kg of dimer acid diisocyanate, 0.5kg of zinc octoate, 10101.0 kg of antioxidant and 1.0kg of 2-hydroxy-4-methylbenzophenone into the reaction kettle, stirring at 90r/min, uniformly mixing, and stirring and reacting at 85 ℃ and under the vacuum degree of less than or equal to 0.095MPa at 90r/min for 3 hours; obtaining a thermoplastic polyurethane elastomer for the reactive polyurethane hot melt adhesive;
and step three, packaging and sealing the thermoplastic polyurethane elastomer obtained in the step two under the protection of nitrogen to isolate oxygen and water vapor, so as to obtain a finished product A of the thermoplastic polyurethane elastomer for the reactive polyurethane hot melt adhesive.
Example 2
Step one, adding 60kg of polyester polyol and 10kg of dihydroxy polybutadiene into a reaction kettle, wherein the polyester polyol is formed by mixing P-530 kg of polyester polyol, 356T 28kg of polyester polyol and 713012 kg of Dynacoll polyester polyol, controlling the temperature to be 120 ℃, and dehydrating for 2-3 hours in vacuum under the vacuum degree of less than or equal to 0.095MPa to obtain a mixture;
step two, after dehydration treatment, cooling the mixture obtained in the step one to 80 ℃, adding 30kg of dimer acid diisocyanate, 0.5kg of zinc octoate, 10101.0 kg of antioxidant and 1.0kg of 2-hydroxy-4-methylbenzophenone into the reaction kettle, stirring and mixing uniformly at 100r/min, and stirring and reacting for 3 hours at the temperature of 85 ℃ and the vacuum degree of less than or equal to 0.095MPa at 100 r/min; obtaining a thermoplastic polyurethane elastomer for the reactive polyurethane hot melt adhesive;
and step three, packaging and sealing the thermoplastic polyurethane elastomer obtained in the step two under the protection of nitrogen to isolate oxygen and water vapor, so as to obtain a finished product B of the thermoplastic polyurethane elastomer for the reactive polyurethane hot melt adhesive.
Example 3
Step one, adding 80kg of polyester polyol and 5kg of dihydroxy polybutadiene into a reaction kettle, wherein the polyester polyol is formed by mixing 22438 kg of polyester polyol, CMA-206625 kg of polyester polyol and P-15317 kg of polyester polyol, controlling the temperature to be 120 ℃, and the vacuum degree to be less than or equal to 0.095MPa, and dehydrating for 2-3 hours in vacuum to obtain a mixture;
step two, after dehydration treatment, cooling the mixture obtained in the step one to 80 ℃, adding 15kg of dimer acid diisocyanate, 0.5kg of zinc octoate, 10101.0 kg of antioxidant and 1.0kg of 2-hydroxy-4-methylbenzophenone into the reaction kettle, stirring and mixing uniformly at 100r/min, and stirring and reacting for 3 hours at 85 ℃ and under the vacuum degree of less than or equal to 0.095MPa at 100 r/min; obtaining a thermoplastic polyurethane elastomer for the reactive polyurethane hot melt adhesive;
and step three, packaging and sealing the thermoplastic polyurethane elastomer obtained in the step two under the protection of nitrogen to isolate oxygen and water vapor, so as to obtain a finished product C of the thermoplastic polyurethane elastomer for the reactive polyurethane hot melt adhesive.
Example 4
Step one, adding 60kg of polyester polyol and 10kg of dihydroxy polybutadiene into a reaction kettle, wherein the polyester polyol is formed by mixing 22432 kg of polyester polyol, CMA-206626 kg of polyester polyol and P-15312 kg of polyester polyol, controlling the temperature to be 120 ℃, the vacuum degree to be less than or equal to 0.095MPa, and dehydrating in vacuum for 2-3 hours to obtain a mixture;
step two, after dehydration treatment, cooling the mixture obtained in the step one to 80 ℃, adding 30kg of dimer acid diisocyanate, 0.5kg of zinc octoate, 10101.0 kg of antioxidant and 1.0kg of 2-hydroxy-4-methylbenzophenone into the reaction kettle, stirring and mixing uniformly at 100r/min, and stirring and reacting for 3 hours at the temperature of 85 ℃ and the vacuum degree of less than or equal to 0.095MPa at 100 r/min; obtaining a thermoplastic polyurethane elastomer for the reactive polyurethane hot melt adhesive;
and step three, packaging and sealing the thermoplastic polyurethane elastomer obtained in the step two under the protection of nitrogen to isolate oxygen and water vapor, so as to obtain a finished product D of the thermoplastic polyurethane elastomer for the reactive polyurethane hot melt adhesive.
Example 5
Step one, adding 60kg of polyester polyol and 10kg of dihydroxy polybutadiene into a reaction kettle, wherein the polyester polyol is formed by mixing P-4032 kg of polyester polyol, CMA-6627kg of polyester polyol and P-15312 kg of polyester polyol, controlling the temperature to be 120 ℃, and dehydrating for 2-3 hours under the vacuum degree of less than or equal to 0.095MPa to obtain a mixture;
step two, after dehydration treatment, cooling the mixture obtained in the step one to 80 ℃, adding 30kg of dimer acid diisocyanate, 0.5kg of zinc octoate, 10101.0 kg of antioxidant and 1.0kg of 2-hydroxy-4-methylbenzophenone into the reaction kettle, stirring at 100r/min, uniformly mixing, stirring at 100r/min at 85 ℃ and under the vacuum degree of less than or equal to 0.095MPa, and reacting for 3 hours; obtaining a thermoplastic polyurethane elastomer for the reactive polyurethane hot melt adhesive;
and step three, packaging and sealing the thermoplastic polyurethane elastomer obtained in the step two under the protection of nitrogen to isolate oxygen and water vapor, so as to obtain a finished product E of the thermoplastic polyurethane elastomer for the reactive polyurethane hot melt adhesive.
Example of Experimental examination
The finished products A-E of the thermoplastic polyurethane elastomer for the reactive polyurethane hot melt adhesive prepared according to the invention are compared and tested with the following experiments by selecting the Pearlbond 539 and Pearlbond 500 of Lubrizol in the United states.
1. Melt index
The determination is carried out by a melt index meter, the determination process of which is ISO 1133-1-2011 determination of melt Mass Flow Rate (MFR) and melt volume flow rate (MVR) of thermoplastics, taking a melt mass flow rate of 2.16kg at 170 ℃.
2. Melt viscosity
The measurement is carried out using a rotational viscometer at 130 ℃ and the measurement procedure is carried out according to ISO 1133-1-2011 "determination of melt Mass Flow Rate (MFR) and melt volume flow rate (MVR) of thermoplastics".
3. Melting Point
Measured by differential scanning calorimetry.
4. Initial adhesion strength
According to the standard of GBT 528-.
5. Open time
According to GBT13477.5-2002, part 5 of the building sealant test method __: determination of tack free time standard, a 0.1mm film of glue is applied to a smooth plate using an applicator and the time from application of the glue layer to lack of tack is recorded.
6. Compatibility
Adding 1-15% of thermoplastic elastomer by weight into the same polyurethane hot melt adhesive prepolymer at 120 ℃, stirring until the thermoplastic elastomer is completely and uniformly mixed, coating a 0.5mm adhesive film on a smooth flat plate by using a coater, observing the condition of the adhesive film after cooling, and recording the addition amount of the thermoplastic elastomer when the adhesive film is cooled and the thermoplastic elastomer is caked and separated out.
TABLE 1 comparative test results
From experimental test results, the compatibility and initial adhesion strength of the thermoplastic polyurethane elastomer and the reactive polyurethane hot melt adhesive prepolymer prepared by the method are better than those of the Pearlbond series, and the opening time of the reactive polyurethane hot melt adhesive is not influenced like the Pearlbond 539.
Therefore, the thermoplastic polyurethane elastomer prepared by the invention can improve the initial adhesion strength, increase the melt viscosity, improve the cohesive force and has excellent compatibility when being used for the reactive polyurethane hot melt adhesive, thereby having wide market application prospect at home and abroad.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (7)
1. A preparation method of thermoplastic polyurethane elastomer for reactive hot melt adhesive is characterized in that,
the method comprises the following steps of:
step one, adding 50-80 parts of polyester polyol and 5-10 parts of dihydroxy polybutadiene into a reaction kettle, controlling the temperature at 115 ℃ and 120 ℃, controlling the vacuum degree to be less than or equal to 0.095MPa, and dehydrating for 2-3 hours in vacuum to obtain a mixture;
step two, after dehydration treatment, cooling the mixture obtained in the step one to 78-82 ℃, adding 10-40 parts of polyisocyanate, 0-0.5 part of catalyst, 0-1.0 part of antioxidant and 0-1.0 part of yellowing resistant agent into the reaction kettle, stirring at 80-150r/min, uniformly mixing, and stirring and reacting at 80-85 ℃ and under the vacuum degree of less than or equal to 0.095MPa at 80-150r/min for 3 hours; obtaining a thermoplastic polyurethane elastomer for the reactive polyurethane hot melt adhesive;
step three, packaging and sealing the thermoplastic polyurethane elastomer for the reactive hot melt adhesive in the step two under the protection of nitrogen to obtain a finished product of the thermoplastic polyurethane elastomer for the reactive hot melt adhesive;
in the first step, the polyester polyol is a mixture of 5-30% of amorphous polyester polyol, 20-60% of liquid polyester polyol and 10-50% of crystalline polyester polyol;
in the first step, the hydroxyl value of the dihydroxy polybutadiene is selected to be 20-50mgKOH/g, and the viscosity is 3-10Pa.s at 40 ℃;
in the second step, the polyisocyanate is dimer acid diisocyanate.
2. The method for preparing a thermoplastic polyurethane elastomer for reactive hot melt adhesives as claimed in claim 1,
the amorphous polyester polyol is prepared by reacting a reactant 1 with a reactant 2;
wherein, the reactant 1 is one or two of neopentyl glycol and hexanediol; reactant 2 is one or two of phthalic acid and phthalic anhydride.
3. The method for preparing a thermoplastic polyurethane elastomer for reactive hot melt adhesives according to claim 1,
the liquid polyester polyol is prepared by reacting a reactant 3 with a reactant 4;
the viscosity of the liquid polyester polyol is more than 10Pa.s at 80 ℃;
wherein, the reactant 3 is one or more of neopentyl glycol, hexanediol or butanediol; reactant 4 is one or more of adipic acid, phthalic acid, terephthalic acid or isophthalic acid.
4. The method for preparing a thermoplastic polyurethane elastomer for reactive hot melt adhesives according to claim 1,
the crystalline polyester polyol is prepared by reacting a reactant 5 with a reactant 6;
wherein, the reactant 5 is one or more of ethylene glycol, hexanediol or butanediol; reactant 6 is one or more of adipic acid, sebacic acid or terephthalic acid.
5. The method for preparing a thermoplastic polyurethane elastomer for reactive hot melt adhesives as claimed in claim 1,
in the second step, the catalyst is one or more of lead octoate, tin octoate or zinc octoate.
6. The method for preparing a thermoplastic polyurethane elastomer for reactive hot melt adhesives according to claim 1,
in the second step, the antioxidant is any one of 2, 6-di-tert-butyl-p-cresol, antioxidant 1010 or antioxidant 1076.
7. The method for preparing a thermoplastic polyurethane elastomer for reactive hot melt adhesives according to claim 1,
in the second step, the yellowing-resistant agent is any one of 2-hydroxy-4-methylbenzophenone, 2- (2 '-hydroxy-3', 5 '-di-tert-butyl) phenyl-5-chlorobenzotriazole, 2- (2' -hydroxy-3 ', 5-di-tert-amyl) phenylbenzotriazole, 2- (2' -hydroxy-3 ', 5' -di-tert-octyl) phenylbenzotriazole or 2-hydroxy-4-n-octoxy benzophenone.
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| CN107163895A (en) * | 2017-06-09 | 2017-09-15 | 南通恒华粘合材料科技有限公司 | Paper-plastic stick monocomponent polyurethane thermosol and preparation method thereof |
| CN111647132B (en) * | 2020-06-09 | 2022-01-07 | 上海华峰超纤科技股份有限公司 | Preparation method and application of low-elasticity polyurethane resin |
| CN111849408A (en) * | 2020-06-22 | 2020-10-30 | 上海回天新材料有限公司 | Moisture-curing polyurethane hot melt adhesive with high initial adhesion strength and preparation method thereof |
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2020
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