CN111234759A - Moisture-curing polyurethane hot melt adhesive and preparation method and application thereof - Google Patents
Moisture-curing polyurethane hot melt adhesive and preparation method and application thereof Download PDFInfo
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- CN111234759A CN111234759A CN202010149895.0A CN202010149895A CN111234759A CN 111234759 A CN111234759 A CN 111234759A CN 202010149895 A CN202010149895 A CN 202010149895A CN 111234759 A CN111234759 A CN 111234759A
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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
-
- 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
- C08G18/4266—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
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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
- C08G18/44—Polycarbonates
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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
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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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
Abstract
The invention discloses a moisture-curing polyurethane hot melt adhesive and a preparation method and application thereof, belonging to the technical field of adhesives. The moisture-curing polyurethane hot melt adhesive comprises the following components in parts by mass: 22.9-48.99% of polycarbonate diol, 10-30% of polycaprolactone, 10-30% of non-crystalline polyester polyol, 1-2% of chain extender, 10-30% of isocyanate monomer, 0.01-0.1% of catalyst and 0-5% of functional assistant, wherein the sum of the mass fractions of the components is 100%. The moisture-curing polyurethane hot melt adhesive is based on polycarbonate and is matched with part of polycaprolactone, polyester polyol, a chain extender, a coupling agent, a flatting agent and a catalyst, so that the hot melt adhesive for floors, which has excellent moisture and heat resistance, good bonding strength after curing and low bonding strength attenuation, can be prepared, and is suitable for bonding processing of floor base materials such as glass magnesium boards, wood-plastic base materials, stone-plastic base materials and the like.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a moisture-curing polyurethane hot melt adhesive and a preparation method and application thereof.
Background
At present, moisture-curable polyurethane hot melt adhesives (PUR) are prepared by taking polyurethane prepolymers with isocyanate groups as end groups as main bodies and adding various additives which do not react with the main bodies, such as thermoplastic resins, fillers and the like. The moisture-curing polyurethane hot melt adhesive can be heated and melted on equipment by using special construction equipment, and can have higher bonding strength to substrates containing active hydrogen or water absorption, such as metal, wood, rubber, fiber, wood, leather, plastic and the like, by blade coating, roller coating or spot coating gluing.
In addition, the glass magnesium board (commonly called as magnesium oxide board) is a magnesium cementing material with stable performance, which is prepared by preparing and adding a modifier in a ternary system of magnesium oxide, magnesium chloride and water, a novel non-combustible decorative material which is compounded by taking a medium-alkaline glass fiber net as a reinforcing material and taking a light material as a filler, has the advantages of fire resistance, water resistance, moisture resistance, insect prevention, tastelessness, no freezing, corrosion, cracking, changing, non-combustion, high strength, light weight, convenient construction, nailability, sawability, cohesiveness and convenient decoration, and can be compounded with various heat-insulating materials to prepare a composite heat-insulating board.
When the glass magnesium board is used for manufacturing a floor, a base material such as bark, a Polyvinyl Chloride (PVC) sheet and the like is generally adhered to the glass magnesium board by using an adhesive such as a moisture-curing polyurethane hot melt adhesive, so that the adhesive is required to have good heat resistance, humidity resistance and the like, and in order to quickly test the heat resistance, humidity resistance and the like of the adhesive, the processed floor can be generally subjected to a boiling-water resistance test under the test condition that the problems of glue opening, swelling and the like are observed after the floor is boiled for 5-6 hours by using boiling water. However, the moisture-curing polyurethane hot melt adhesive sold on the market at present has the problem of poor moisture and heat resistance, and floor materials obtained by bonding the moisture-curing polyurethane hot melt adhesive are boiled in boiling water for 1-2 hours to cause the problems of glue failure, swelling and the like, so that the adhesives such as the moisture-curing polyurethane hot melt adhesive sold on the market at present are difficult to pass a boiling-resistant test, and cannot meet the requirements of customers.
Disclosure of Invention
An embodiment of the present invention is directed to provide a moisture-curable polyurethane hot melt adhesive, so as to solve the problems set forth in the above background art.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
the moisture-curing polyurethane hot melt adhesive comprises the following components in parts by mass: 22.9-48.99% of polycarbonate diol, 10-30% of polycaprolactone, 10-30% of noncrystalline polyester polyol, 1-2% of chain extender, 10-30% of isocyanate monomer, 0.01-0.1% of catalyst and 0-5% of functional assistant, wherein the sum of the mass fractions of the components is 100%.
As a preferable scheme of the embodiment of the invention, the moisture-curing polyurethane hot melt adhesive comprises the following components in percentage by mass: 30-35% of polycarbonate diol, 19-23% of polycaprolactone, 20-25% of noncrystalline polyester polyol, 1.6-2% of chain extender, 20-21.4% of isocyanate monomer, 0.05-0.1% of catalyst and 0.95-5% of functional assistant, wherein the sum of the mass fractions of the components is 100%.
As another preferable mode of the embodiment of the present invention, the polycarbonate diol is one or more of a polymer of 3-methyl-1, 5-pentanediol and 1, 6-hexanediol, a polymer of 1, 4-butanediol and 1, 5-pentanediol, a polymer of 3-methyl-1, 5-pentanediol and 1, 4-butanediol; the polycarbonate diol has an average molecular weight of 1000 to 3000. Preferably, the polycarbonate diol is a polymer of 3-methyl-1, 5-pentanediol and 1, 6-hexanediol.
As another preferable scheme of the embodiment of the invention, the average molecular weight of the polycaprolactone is 1000-4000.
As another preferable mode of the embodiment of the present invention, the non-crystalline polyester polyol is one or more of a polymer of 3-methyl-1, 5-pentanediol with 1, 6-adipic acid, a polymer of 3-methyl-1, 5-pentanediol with terephthalic acid, a polymer of 3-methyl-1, 5-pentanediol with isophthalic acid, a polymer of 3-methyl-1, 5-pentanediol with terephthalic acid and 1, 6-adipic acid, and a polymer of poly-3-methyl-1, 5-pentanediol with sebacic acid; the average molecular weight of the non-crystalline polyester polyol is 1000-4000. Preferably, the non-crystalline polyester polyol is a polymer of 3-methyl-1, 5-pentanediol and isophthalic acid.
As another preferable scheme of the embodiment of the invention, the chain extender is one or more of 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol and 3-methyl-1, 5-pentanediol. Preferably, the chain extender is 3-methyl-1, 5-pentanediol.
As another preferable scheme of the embodiment of the invention, the isocyanate monomer is diphenylmethane diisocyanate; the catalyst is one or more of dimorpholinyl diethyl ether, dimorpholinyl triethyl ether, stannous octoate and dibutyltin dilaurate; the functional auxiliary agent is a silane coupling agent and/or an acrylate leveling agent. Preferably, the catalyst is dimorpholinodiethylether; the silane coupling agent is gamma-glycidol ether oxygen propyl trimethoxy silane.
Another object of an embodiment of the present invention is to provide a preparation method of the moisture-curable polyurethane hot melt adhesive, which includes the following steps:
weighing polycarbonate diol, polycaprolactone, non-crystalline polyester polyol, a chain extender, an isocyanate monomer, a catalyst and a functional auxiliary agent according to the mass fraction for later use;
placing the polycarbonate diol, polycaprolactone and amorphous polyester polyol at the temperature of 120-140 ℃ for vacuum stirring to obtain a mixture A;
placing the mixture A and the chain extender at the temperature of 60-80 ℃ for vacuum stirring to obtain a mixture B;
under a protective atmosphere, mixing the mixture B with the isocyanate monomer, and reacting at 70-80 ℃ to obtain a mixture C;
and mixing and polymerizing the mixture C, the catalyst and the functional auxiliary agent at 70-80 ℃, and filtering to obtain the moisture-curing polyurethane hot melt adhesive.
The embodiment of the invention also aims to provide the moisture-curing polyurethane hot melt adhesive prepared by the preparation method.
The invention also aims to provide application of the moisture-curing polyurethane hot melt adhesive in bonding floor substrates.
Another purpose of the embodiments of the present invention is to provide the following advantages compared with the prior art:
the moisture-curing polyurethane hot melt adhesive provided by the embodiment of the invention is based on polycarbonate, and is matched with part of polycaprolactone, polyester polyol, a chain extender, a coupling agent, a leveling agent and a catalyst, so that the hot melt adhesive for floors, which has excellent weather resistance (namely excellent humidity resistance, boiling resistance, aging resistance and chemical stability), good bonding strength after curing and insusceptible bonding strength attenuation, can be prepared, and is suitable for bonding processing of floor base materials such as glass magnesium boards, wood-plastic base materials, stone-plastic base materials and the like.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
Example 1
The embodiment provides a moisture-curing polyurethane hot melt adhesive, and a preparation method of the moisture-curing polyurethane hot melt adhesive comprises the following steps:
(1) weighing 30kg of polycarbonate diol, 23kg of polycaprolactone, 24kg of non-crystalline polyester polyol, 2kg of chain extender, 20kg of isocyanate monomer, 0.05kg of catalyst and 0.95kg of functional auxiliary agent for later use; wherein the polycarbonate diol is a polymer of 3-methyl-1, 5-pentanediol and 1, 6-hexanediol, and has an average molecular weight of 3000; the average molecular weight of polycaprolactone is 2000; the non-crystalline polyester polyol is a polymer of 3-methyl-1, 5-pentanediol and isophthalic acid, and has an average molecular weight of 2000; the chain extender is 3-methyl-1, 5-pentanediol; the isocyanate monomer is diphenylmethane diisocyanate, and a commercially available product MDI-100 can be selected; the catalyst is dimorpholinyl diethyl ether; the functional assistant is 0.45kg of silane coupling agent and 0.5kg of acrylate flatting agent, specifically, the silane coupling agent can be a commercial product KH-560 (gamma-glycidyl ether oxypropyl trimethoxy silane), and the acrylate flatting agent can be a commercial product KOOLY-1606 in the Sankorea chemical industry.
(2) Placing the polycarbonate diol, polycaprolactone and amorphous polyester polyol into a reaction kettle, heating to 130 ℃, vacuumizing, and stirring at the rotating speed of 50rpm to obtain a mixture A.
(3) And (3) cooling the temperature of the reaction kettle to 70 ℃, adding the chain extender which is dehydrated by the molecular sieve and has the water content of less than 500ppm and the mixture A, and stirring the mixture A in vacuum at the rotating speed of 50rpm to obtain a mixture B.
(4) And adding the molten liquid isocyanate monomer and the mixture B under the protection atmosphere of nitrogen, stirring and mixing at the rotating speed of 30rpm, vacuumizing, increasing the stirring rotating speed to 50rpm, and heating to 110 ℃ for reacting for 2.3 hours to obtain a mixture C.
(5) And when the NCO content of the mixture C reaches a theoretical value, adding the catalyst and the functional auxiliary agent, stirring and mixing the mixture C and the catalyst and the functional auxiliary agent at the rotating speed of 50rpm for 30min, stopping stirring, continuously vacuumizing, breaking vacuum after complete defoaming, starting unloading, adding a filtering device during unloading, wherein the filtering device can adopt a filtering screen with more than 150 meshes, and filtering to obtain the moisture-curing polyurethane hot melt adhesive.
Example 2
The embodiment provides a moisture-curing polyurethane hot melt adhesive, and a preparation method of the moisture-curing polyurethane hot melt adhesive comprises the following steps:
(1) weighing 35kg of polycarbonate diol, 21kg of polycaprolactone, 20kg of non-crystalline polyester polyol, 1.6kg of chain extender, 21.4kg of isocyanate monomer, 0.05kg of catalyst and 0.95kg of functional auxiliary agent for later use; wherein the polycarbonate diol is a polymer of 1, 4-butanediol and 1, 5-pentanediol, and has an average molecular weight of 3000; the average molecular weight of polycaprolactone is 3000; the non-crystalline polyester polyol is a polymer of 3-methyl-1, 5-pentanediol and 1, 6-adipic acid, and has an average molecular weight of 1000; the chain extender is 1, 4-butanediol; the isocyanate monomer is diphenylmethane diisocyanate, and a commercially available product MDI-100 can be selected; the catalyst is dimorpholinyl diethyl ether; the functional assistant is 0.45kg of silane coupling agent and 0.5kg of acrylate flatting agent, specifically, the silane coupling agent can be a commercial product KH-560 (gamma-glycidyl ether oxypropyl trimethoxy silane), and the acrylate flatting agent can be a commercial product KOOLY-1606 in the Sankorea chemical industry.
(2) Placing the polycarbonate diol, polycaprolactone and amorphous polyester polyol into a reaction kettle, heating to 130 ℃, vacuumizing, and stirring at the rotating speed of 50rpm to obtain a mixture A.
(3) And (3) cooling the temperature of the reaction kettle to 70 ℃, adding the chain extender which is dehydrated by the molecular sieve and has the water content of less than 500ppm and the mixture A, and stirring the mixture A in vacuum at the rotating speed of 50rpm to obtain a mixture B.
(4) And adding the molten liquid isocyanate monomer and the mixture B under the protection atmosphere of nitrogen, stirring and mixing at the rotating speed of 30rpm, vacuumizing, increasing the stirring rotating speed to 50rpm, and heating to 110 ℃ for reacting for 2.3 hours to obtain a mixture C.
(5) And when the NCO content of the mixture C reaches a theoretical value, adding the catalyst and the functional auxiliary agent, stirring and mixing the mixture C and the catalyst and the functional auxiliary agent at the rotating speed of 50rpm for 30min, stopping stirring, continuously vacuumizing, breaking vacuum after complete defoaming, starting unloading, adding a filtering device during unloading, wherein the filtering device can adopt a filtering screen with more than 150 meshes, and filtering to obtain the moisture-curing polyurethane hot melt adhesive.
Example 3
The embodiment provides a moisture-curing polyurethane hot melt adhesive, and a preparation method of the moisture-curing polyurethane hot melt adhesive comprises the following steps:
(1) weighing 32kg of polycarbonate diol, 19kg of polycaprolactone, 25kg of non-crystalline polyester polyol, 1.6kg of chain extender, 21.4kg of isocyanate monomer, 0.05kg of catalyst and 0.95kg of functional auxiliary agent for later use; wherein the polycarbonate diol is a polymer of 3-methyl-1, 5-pentanediol and 1, 4-butanediol, and has an average molecular weight of 2000; the average molecular weight of polycaprolactone is 1000; the non-crystalline polyester polyol is a polymer of 3-methyl-1, 5-pentanediol and terephthalic acid, and the average molecular weight of the non-crystalline polyester polyol is 4000; the chain extender is 1, 4-butanediol; the isocyanate monomer is diphenylmethane diisocyanate, and a commercially available product MDI-100 can be selected; the catalyst is dimorpholinyl diethyl ether; the functional assistant is 0.5kg of silane coupling agent and 0.45kg of acrylate flatting agent, specifically, the silane coupling agent can be a commercial product KH-560 (gamma-glycidyl ether oxypropyl trimethoxy silane), and the acrylate flatting agent can be a commercial product KOOLY-1606 in the Sankorea chemical industry.
(2) Placing the polycarbonate diol, polycaprolactone and amorphous polyester polyol into a reaction kettle, heating to 130 ℃, vacuumizing, and stirring at the rotating speed of 50rpm to obtain a mixture A.
(3) And (3) cooling the temperature of the reaction kettle to 70 ℃, adding the chain extender which is dehydrated by the molecular sieve and has the water content of less than 500ppm and the mixture A, and stirring the mixture A in vacuum at the rotating speed of 50rpm to obtain a mixture B.
(4) And adding the molten liquid isocyanate monomer and the mixture B under the protection atmosphere of nitrogen, stirring and mixing at the rotating speed of 30rpm, vacuumizing, increasing the stirring rotating speed to 50rpm, and heating to 110 ℃ for reacting for 2.3 hours to obtain a mixture C.
(5) And when the NCO content of the mixture C reaches a theoretical value, adding the catalyst and the functional auxiliary agent, stirring and mixing the mixture C and the catalyst and the functional auxiliary agent at the rotating speed of 50rpm for 30min, stopping stirring, continuously vacuumizing, breaking vacuum after complete defoaming, starting unloading, adding a filtering device during unloading, wherein the filtering device can adopt a filtering screen with more than 150 meshes, and filtering to obtain the moisture-curing polyurethane hot melt adhesive.
Example 4
The embodiment provides a moisture-curing polyurethane hot melt adhesive, and a preparation method of the moisture-curing polyurethane hot melt adhesive comprises the following steps:
(1) weighing 48.99kg of polycarbonate diol, 30kg of polycaprolactone, 10kg of non-crystalline polyester polyol, 1kg of chain extender, 10kg of isocyanate monomer and 0.01kg of catalyst for later use; wherein the polycarbonate diol is a mixture of a polymer of 1, 5-pentanediol and 1, 6-hexanediol and a polymer of 1, 4-butanediol and 1, 5-pentanediol, and has an average molecular weight of 1000; the average molecular weight of polycaprolactone is 4000; the non-crystalline polyester polyol is a polymer of 3-methyl-1, 5-pentanediol and 1, 6-adipic acid and a mixture of 3-methyl-1, 5-pentanediol and polymers of terephthalic acid and 1, 6-adipic acid, and has an average molecular weight of 3000; the chain extender is a mixture of 1, 5-pentanediol and 1, 6-hexanediol; the isocyanate monomer is diphenylmethane diisocyanate, and a commercially available product MDI-100 can be selected; the catalyst is a mixture of dimorpholinyl triethyl ether and stannous octoate.
(2) Placing the polycarbonate diol, polycaprolactone and amorphous polyester polyol into a reaction kettle, heating to 120 ℃, vacuumizing, and stirring at the rotating speed of 50rpm to obtain a mixture A.
(3) And (3) cooling the temperature of the reaction kettle to 60 ℃, adding the chain extender which is dehydrated by the molecular sieve and has the water content of less than 500ppm and the mixture A, and stirring the mixture A in vacuum at the rotating speed of 50rpm to obtain a mixture B.
(4) And adding the molten liquid isocyanate monomer and the mixture B under the protection atmosphere of nitrogen, stirring and mixing at the rotating speed of 30rpm, vacuumizing, increasing the stirring rotating speed to 50rpm, and heating to 100 ℃ to react for 2.5 hours to obtain a mixture C.
(5) And when the NCO content of the mixture C reaches a theoretical value, adding the catalyst and the functional auxiliary agent, stirring and mixing the mixture C and the catalyst and the functional auxiliary agent at the rotating speed of 50rpm for 30min, stopping stirring, continuously vacuumizing, breaking vacuum after complete defoaming, starting unloading, adding a filtering device during unloading, wherein the filtering device can adopt a filtering screen with more than 150 meshes, and filtering to obtain the moisture-curing polyurethane hot melt adhesive.
Example 5
The embodiment provides a moisture-curing polyurethane hot melt adhesive, and a preparation method of the moisture-curing polyurethane hot melt adhesive comprises the following steps:
(1) weighing 22.9kg of polycarbonate diol, 10kg of polycaprolactone, 30kg of non-crystalline polyester polyol, 2kg of chain extender, 30kg of isocyanate monomer, 0.1kg of catalyst and 5kg of functional auxiliary agent for later use; wherein the polycarbonate diol is a mixture of a polymer of 1, 5-pentanediol and 1, 6-hexanediol, a polymer of 1, 4-butanediol and 1, 5-pentanediol, and a polymer of 3-methyl-1, 5-pentanediol and 1, 4-butanediol, and has an average molecular weight of 3000; the average molecular weight of polycaprolactone is 2000; the non-crystalline polyester polyol is a mixture of a polymer of 3-methyl-1, 5-pentanediol and isophthalic acid, a polymer of 3-methyl-1, 5-pentanediol and terephthalic acid and 1, 6-adipic acid, and a polymer of poly-3-methyl-1, 5-pentanediol and sebacic acid, and has an average molecular weight of 2000; the chain extender is a mixture of 1, 6-hexanediol, neopentyl glycol and 3-methyl-1, 5-pentanediol; the isocyanate monomer is diphenylmethane diisocyanate, and a commercially available product MDI-100 can be selected; the catalyst is a mixture of dimorpholinyl triethyl ether, stannous octoate and dibutyltin dilaurate; the functional assistant is 2kg of silane coupling agent and 3kg of acrylate flatting agent, specifically, the silane coupling agent can be selected from KH-560 (gamma-glycidyl ether oxypropyl trimethoxy silane) which is a commercially available product, and the acrylate flatting agent can be selected from KOOLY-1606 which is a commercially available product in the chemical industry of Santa Clara.
(2) Placing the polycarbonate diol, polycaprolactone and amorphous polyester polyol into a reaction kettle, heating to 140 ℃, vacuumizing, and stirring at the rotating speed of 50rpm to obtain a mixture A.
(3) And (3) cooling the temperature of the reaction kettle to 80 ℃, adding the chain extender which is dehydrated by the molecular sieve and has the water content of less than 500ppm and the mixture A, and stirring the mixture A in vacuum at the rotating speed of 50rpm to obtain a mixture B.
(4) And adding the molten liquid isocyanate monomer and the mixture B under the protection atmosphere of nitrogen, stirring and mixing at the rotating speed of 30rpm, vacuumizing, increasing the stirring rotating speed to 50rpm, and heating to 120 ℃ for reacting for 2 hours to obtain a mixture C.
(5) And when the NCO content of the mixture C reaches a theoretical value, adding the catalyst and the functional auxiliary agent, stirring and mixing the mixture C and the catalyst and the functional auxiliary agent at the rotating speed of 50rpm for 30min, stopping stirring, continuously vacuumizing, breaking vacuum after complete defoaming, starting unloading, adding a filtering device during unloading, wherein the filtering device can adopt a filtering screen with more than 150 meshes, and filtering to obtain the moisture-curing polyurethane hot melt adhesive.
Comparative example 1
This comparative example provides a moisture-curing polyurethane hot melt adhesive commercially available from hangao.
Comparative example 2
This comparative example provides another weatherable moisture-curing polyurethane hot melt adhesive.
The moisture-curing polyurethane hot melt adhesives provided in the embodiments 1 to 3 and the comparative examples 1 to 2 are respectively used for wood-plastic board bonding PVC, stone-plastic board bonding PVC and glass magnesium board bonding PVC, and after curing the test samples obtained by corresponding bonding at 25 ℃/24 hours, the bonding performance test is carried out (refer to the GB 245908 standard of wood-plastic floors), and the test results are shown in the following table 1.
TABLE 1
As can be seen from Table 1, the substrates of examples 1-3 and comparative examples 1-2 can be completely destroyed after wood-plastic plate bonding PVC, stone-plastic plate bonding PVC and glass magnesium plate bonding PVC are cured at 25 ℃/24 hours, which shows that the basic bonding performance of the moisture-curing polyurethane hot melt adhesives is not obviously different under the same conditions.
The moisture-curing polyurethane hot melt adhesives provided in the above examples 1 to 3 and comparative examples 1 to 2 are respectively used for wood-plastic board bonding PVC, stone-plastic board bonding PVC and glass magnesium board bonding PVC, the test samples obtained by corresponding bonding are cured at 25 ℃/24 hours, and are aged at 100 ℃ for 7, and then the bonding performance test is performed (refer to the GB 245908 standard of wood-plastic floor), and the test results are shown in the following table 2.
TABLE 2
As can be seen from table 2, after the bonded test piece is cured at 25 ℃/24 hours and then aged at 100 ℃ for 7 days, the bonding strength of the moisture-curable polyurethane hot melt adhesive provided in comparative example 1 has been reduced, and the moisture-curable polyurethane hot melt adhesives provided in embodiments 1 to 3 of the present invention still have good bonding strength and can still completely destroy the substrate, which indicates that the moisture-curable polyurethane hot melt adhesives provided in embodiments 1 to 3 of the present invention have good aging resistance.
The moisture-curable polyurethane hot melt adhesives provided in the above examples 1 to 3 and comparative examples 1 to 2 were used for wood-plastic board bonding PVC, stone-plastic board bonding PVC, and glass magnesium board bonding PVC, respectively, and the test samples obtained by the corresponding bonding were cured at 25 ℃/24 hours, and boiled in water at 100 ℃ for 6 hours, and then the bonding condition of the test samples was observed, and the test results are shown in table 3 below.
TABLE 3
As can be seen from Table 3, after the bonded test piece is cured at a temperature of 25 ℃/24 hours and then boiled in water at a temperature of 100 ℃ for 6 hours, three substrates bonded by the moisture-curing polyurethane hot melt adhesives provided in comparative examples 1-2 have a phenomenon of glue failure, while three substrates bonded by the moisture-curing polyurethane hot melt adhesives provided in examples 1-3 of the present invention have no phenomenon of glue failure, which indicates that the moisture-curing polyurethane hot melt adhesives provided in examples 1-3 of the present invention have good boiling resistance.
In summary, compared with the existing commercially available moisture-curable polyurethane hot melt, the moisture-curable polyurethane hot melt provided by the embodiment of the invention has better bonding strength to the wood-plastic board, the stone-plastic board, the glass magnesium board and other base materials, and the base materials bonded by the moisture-curable polyurethane hot melt can pass high-temperature aging and boiling resistance tests, which shows that the moisture-curable polyurethane hot melt provided by the embodiment of the invention not only has better bonding strength, but also has better weather resistance.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. The moisture-curing polyurethane hot melt adhesive is characterized by comprising the following components in parts by mass: 22.9-48.99% of polycarbonate diol, 10-30% of polycaprolactone, 10-30% of non-crystalline polyester polyol, 1-2% of chain extender, 10-30% of isocyanate monomer, 0.01-0.1% of catalyst and 0-5% of functional assistant, wherein the sum of the mass fractions of the components is 100%.
2. The moisture-curing polyurethane hot melt adhesive as claimed in claim 1, wherein the moisture-curing polyurethane hot melt adhesive comprises the following components in percentage by mass: 30-35% of polycarbonate diol, 19-23% of polycaprolactone, 20-25% of non-crystalline polyester polyol, 1.6-2% of chain extender, 20-21.4% of isocyanate monomer, 0.05-0.1% of catalyst and 0.95-5% of functional assistant, wherein the sum of the mass fractions of the components is 100%.
3. The moisture-curable polyurethane hot melt adhesive according to claim 1 or 2, wherein the polycarbonate diol is one or more of a polymer of 3-methyl-1, 5-pentanediol and 1, 6-hexanediol, a polymer of 1, 4-butanediol and 1, 5-pentanediol, a polymer of 3-methyl-1, 5-pentanediol and 1, 4-butanediol; the polycarbonate diol has an average molecular weight of 1000 to 3000.
4. The moisture-curable polyurethane hot melt adhesive according to claim 1 or 2, wherein the average molecular weight of the polycaprolactone is 1000-4000.
5. The moisture-curable polyurethane hot melt adhesive according to claim 1 or 2, wherein the non-crystalline polyester polyol is one or more of a polymer of 3-methyl-1, 5-pentanediol and 1, 6-adipic acid, a polymer of 3-methyl-1, 5-pentanediol and terephthalic acid, a polymer of 3-methyl-1, 5-pentanediol and isophthalic acid, a polymer of 3-methyl-1, 5-pentanediol and terephthalic acid and 1, 6-adipic acid, and a polymer of poly-3-methyl-1, 5-pentanediol and sebacic acid; the average molecular weight of the non-crystalline polyester polyol is 1000-4000.
6. The moisture-curing polyurethane hot melt adhesive according to claim 1 or 2, wherein the chain extender is one or more of 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, and 3-methyl-1, 5-pentanediol.
7. The moisture-curable polyurethane hot melt adhesive according to claim 1 or 2, wherein the isocyanate monomer is diphenylmethane diisocyanate; the catalyst is one or more of dimorpholinyl diethyl ether, dimorpholinyl triethyl ether, stannous octoate and dibutyltin dilaurate; the functional auxiliary agent is a silane coupling agent and/or an acrylate leveling agent.
8. A preparation method of the moisture-curing polyurethane hot melt adhesive as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
weighing polycarbonate diol, polycaprolactone, non-crystalline polyester polyol, a chain extender, an isocyanate monomer, a catalyst and a functional auxiliary agent according to the mass fraction for later use;
placing the polycarbonate diol, polycaprolactone and amorphous polyester polyol at the temperature of 120-140 ℃ for vacuum stirring to obtain a mixture A;
placing the mixture A and the chain extender at the temperature of 60-80 ℃ for vacuum stirring to obtain a mixture B;
under a protective atmosphere, mixing the mixture B with the isocyanate monomer, and reacting at 70-80 ℃ to obtain a mixture C;
and mixing and polymerizing the mixture C, the catalyst and the functional auxiliary agent at 70-80 ℃, and filtering to obtain the moisture-curing polyurethane hot melt adhesive.
9. A moisture-curing polyurethane hot melt adhesive prepared by the preparation method as claimed in claim 8.
10. Use of the moisture-curable polyurethane hot melt adhesive according to any one of claims 1 to 7 and 9 for bonding floor substrates.
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Cited By (1)
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