CN111978909B - Reactive polyurethane hot melt adhesive for low-temperature coating and preparation method thereof - Google Patents
Reactive polyurethane hot melt adhesive for low-temperature coating and preparation method thereof Download PDFInfo
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- CN111978909B CN111978909B CN202010934903.2A CN202010934903A CN111978909B CN 111978909 B CN111978909 B CN 111978909B CN 202010934903 A CN202010934903 A CN 202010934903A CN 111978909 B CN111978909 B CN 111978909B
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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
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
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- 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
- C08G18/48—Polyethers
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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 reactive polyurethane hot melt adhesive for low-temperature coating and a preparation method thereof, wherein the reactive polyurethane hot melt adhesive for low-temperature coating is prepared from the following raw materials in parts by weight: 10-35 parts of isocyanate, 10-70 parts of aliphatic polyester dihydric alcohol, 20-50 parts of polyether dihydric alcohol, 5-20 parts of aromatic polyester dihydric alcohol, 0.05-0.5 part of antioxidant, 0.01-0.1 part of stabilizer, 0.05-0.5 part of catalyst and 0.1-5 parts of adhesion promoter. The invention has better fluidity and lower viscosity at lower temperature, and ensures the later bonding force.
Description
Technical Field
The invention relates to the field of reactive polyurethane hot melt adhesives, in particular to a reactive polyurethane hot melt adhesive for low-temperature (the low temperature is 80-90 ℃) coating and a preparation method thereof.
Background
Reactive polyurethane hot melt adhesives, also known as moisture-curing hot melt adhesives, are polyurethane hot melt adhesives containing isocyanate groups. When gluing, the reactive polyurethane hot melt adhesive is heated and melted into fluid to be coated on an adherend, and after the adherend is attached, the adhesive layer generates initial adhesive force due to cooling and solidification; the active isocyanate group in the adhesive layer reacts with moisture in the air, moisture attached to the surface of an adherend and an active hydrogen group to generate chemical crosslinking curing, so that the performances such as adhesive force, temperature resistance and the like are obviously improved. The reactive polyurethane hot melt adhesive has the characteristics of no solvent, good initial viscosity, rapid curing and the like of common polyurethane hot melt adhesives, has the advantages of solvent resistance, temperature resistance, creep resistance and the like of reactive adhesives, and is developed rapidly in recent years. However, the existing reaction type polyurethane hot melt adhesive also has the problems of high melting temperature, high melting viscosity, high initial adhesion and bonding force, short positioning time and the like.
In the field of woodworking cladding application, some used film materials are thin and do not resist high temperature, and if the adhesive used for bonding has high glue melting temperature, high viscosity and poor fluidity, the bonding is difficult, and even the problems of film deformation, bulging and the like occur.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the reactive polyurethane hot melt adhesive for low-temperature coating and the preparation method thereof, and tackifying resins such as EVA (ethylene-vinyl acetate copolymer), TPU (thermoplastic polyurethane elastomer), acrylic resin and the like are not added in the system, so that the reactive polyurethane hot melt adhesive has better fluidity and lower viscosity at lower temperature, and the later-stage adhesive force is ensured.
The purpose of the invention is realized by the following technical scheme:
a reactive polyurethane hot melt adhesive for low-temperature coating is prepared from the following raw materials in parts by weight:
preferably, the isocyanate is one or a mixture of several of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and diphenylmethane-4, 4-diisocyanate.
Preferably, the aliphatic polyester diol is one or a mixture of more of poly adipic acid-1, 6 hexanediol ester diol, poly adipic acid-1, 4 butanediol ester diol, poly adipic acid-neopentyl glycol ester diol, poly adipic acid-diethylene glycol-neopentyl glycol ester diol and poly adipic acid-hexanediol-neopentyl glycol ester diol.
Preferably, the polyether glycol mainly contains propylene oxide, and the relative molecular weight of the polyether glycol is 1000-5000.
Preferably, the aromatic polyester diol is one or a mixture of several of poly (diethylene glycol phthalate) diol, poly (1, 6-hexanediol phthalate) diol, poly (neopentyl glycol terephthalate) diol, poly (phthalic anhydride) -neopentyl glycol ester diol, poly (phthalic anhydride) -diethylene glycol diol and poly (isophthalic acid) neopentyl glycol ester diol.
Preferably, the antioxidant is one or a mixture of several of antioxidant 1076, antioxidant 1035, antioxidant 245 and antioxidant 1010.
Preferably, the stabilizer is one or a mixture of several of phosphoric acid, benzoyl chloride, benzoic acid and nonanoic acid.
Preferably, the catalyst is one or a mixture of dibutyltin dilaurate, stannous octoate, tetramethylethylenediamine, triethylenediamine and dimorpholinyl triethyl ether.
Preferably, the adhesion promoter is one or a mixture of silane coupling agent A-172, silane coupling agent KH550, silane coupling agent KH560 and silane coupling agent KH 570.
A preparation method of a reactive polyurethane hot melt adhesive for low-temperature coating comprises the following steps:
step 1, weighing isocyanate, aliphatic polyester dihydric alcohol, polyether dihydric alcohol, aromatic polyester dihydric alcohol, an antioxidant, a stabilizer, a catalyst and an adhesion promoter according to the formula of the reactive polyurethane hot melt adhesive for low-temperature coating;
step 2, adding the aliphatic polyester diol, the polyether diol, the aromatic polyester diol, the antioxidant and the stabilizer into a reaction kettle, keeping the temperature between 100 and 140 ℃ and the pressure between-0.085 and-0.095 MPa, and stirring and dehydrating for 1 to 4 hours;
step 3, stopping heating, adding the isocyanate when the temperature in the reaction kettle is reduced to 90-100 ℃, stirring and reacting for 1 hour at the temperature of 90-100 ℃, and keeping the vacuum degree between-0.06 MPa and-0.095 MPa;
step 4, adding the adhesion promoter and the catalyst into the reaction kettle, stirring and reacting for 30-50 minutes at 90-100 ℃, and keeping the vacuum degree at-0.08 MPa to-0.095 MPa;
and 5, closing stirring, defoaming for 10-20 min, filtering, and discharging to obtain the reactive polyurethane hot melt adhesive for low-temperature coating.
According to the technical scheme provided by the invention, tackifying resins such as EVA (ethylene vinyl acetate), TPU (thermoplastic polyurethane), acrylic resin and the like are not added into the low-temperature coating reaction type polyurethane hot melt adhesive, so that the low-temperature coating reaction type polyurethane hot melt adhesive has good fluidity, low viscosity and good later-stage adhesive force at a low temperature, meets the adhesive requirements of thin film materials and non-high-temperature-resistant film materials, and has a good adhesive effect.
Detailed Description
The technical solutions in the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The reactive polyurethane hot melt adhesive for low-temperature coating and the preparation method thereof provided by the invention are described in detail below. Details which are not described in detail in the embodiments of the invention belong to the prior art which is known to a person skilled in the art.
A reactive polyurethane hot melt adhesive for low-temperature coating is prepared from the following raw materials in parts by weight:
specifically, the reactive polyurethane hot melt adhesive for low-temperature coating may include the following embodiments:
(1) the isocyanate is one or a mixture of more of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and diphenylmethane-4, 4-diisocyanate.
(2) The aliphatic polyester diol is one or a mixture of more of poly adipic acid-1, 6 hexanediol ester diol, poly adipic acid-1, 4 butanediol ester diol, poly adipic acid-neopentyl glycol ester diol, poly adipic acid-diethylene glycol-neopentyl glycol ester diol and poly adipic acid-hexanediol-neopentyl glycol ester diol.
(3) The polyether glycol takes propylene oxide as a main body, and the relative molecular weight is 1000-5000.
(4) The aromatic polyester diol is one or a mixture of more of poly phthalic anhydride diethylene glycol, poly phthalic acid-1, 6-hexanediol, poly phthalic acid neopentyl glycol, poly terephthalic acid-neopentyl glycol, poly phthalic anhydride-diethylene glycol, poly isophthalic acid neopentyl glycol, and poly adipic acid-phthalic acid-diethylene glycol-ethylene glycol.
(5) The antioxidant is one or more of antioxidant 1076, antioxidant 1035, antioxidant 245 and antioxidant 1010.
(6) The stabilizer is one or a mixture of more of phosphoric acid, benzoyl chloride, benzoic acid and nonanoic acid.
(7) The catalyst is one or a mixture of dibutyltin dilaurate, stannous octoate, tetramethylethylenediamine, triethylenediamine and dimorpholintriethylether.
(8) The adhesion promoter is one or a mixture of silane coupling agent A-172, silane coupling agent KH550, silane coupling agent KH560 and silane coupling agent KH 570.
Further, the preparation method of the reactive polyurethane hot melt adhesive for low-temperature coating can comprise the following steps:
step 1, weighing isocyanate, aliphatic polyester dihydric alcohol, polyether dihydric alcohol, aromatic polyester dihydric alcohol, an antioxidant, a stabilizer, a catalyst and an adhesion promoter according to the formula of the reactive polyurethane hot melt adhesive for low-temperature coating.
And 2, adding the aliphatic polyester diol, the polyether diol, the aromatic polyester diol, the antioxidant and the stabilizer into a reaction kettle, keeping the temperature between 100 and 140 ℃ and the pressure between-0.085 and-0.095 MPa, and stirring and dehydrating for 1 to 4 hours.
And 3, stopping heating, adding the isocyanate when the temperature in the reaction kettle is reduced to 90-100 ℃, stirring and reacting for 1 hour at the temperature of 90-100 ℃, and keeping the vacuum degree between-0.06 MPa and-0.095 MPa.
And 4, adding the adhesion promoter and the catalyst into the reaction kettle, stirring and reacting for 30-50 minutes at the temperature of 90-100 ℃, and keeping the vacuum degree at-0.08 MPa to-0.095 MPa.
And 5, closing stirring, defoaming for 10-20 min, filtering, discharging, and packaging in vacuum or nitrogen to obtain the reactive polyurethane hot melt adhesive for low-temperature coating.
The reactive polyurethane hot melt adhesive for low-temperature coating provided by the invention at least has the following advantages:
(1) according to the reactive polyurethane hot melt adhesive for low-temperature coating, tackifying resins such as EVA (ethylene vinyl acetate), TPU (thermoplastic polyurethane), acrylic resin and the like are not added, so that the viscosity of the hot melt adhesive is reduced, and the hot melt adhesive can be melted and used at a lower temperature.
(2) According to the reactive polyurethane hot melt adhesive for low-temperature coating, tackifying resins such as EVA (ethylene vinyl acetate), TPU (thermoplastic polyurethane), acrylic resin and the like are not added, so that the wetting capacity of the hot melt adhesive can be ensured, and the hot melt adhesive has good later-stage bonding force.
In conclusion, the embodiment of the invention does not add tackifying resins such as EVA, TPU, acrylic resin and the like in the system, has better fluidity and lower viscosity at lower temperature, and ensures the later-stage adhesive force.
In order to more clearly show the technical scheme and the technical effects provided by the present invention, the reactive polyurethane hot melt adhesive for low-temperature coating and the preparation method thereof provided by the present invention are described in detail with specific embodiments below.
Example 1
The preparation method of the reactive polyurethane hot melt adhesive for low-temperature coating can comprise the following steps:
step 1, weighing 12kg of diphenylmethane-4, 4-diisocyanate, 20kg of poly adipic acid-neopentyl glycol ester diol, 5kg of poly adipic acid-1, 6 hexanediol ester diol, 20kg of polyether diol, 9kg of poly phthalic anhydride diethylene glycol ester diol, 10100.05kg of antioxidant, 0.01kg of phosphoric acid, 0.05kg of dibutyltin dilaurate and KH-5500.5 kg of silane coupling agent. The polyether diol used in the examples of the present invention had a number average molecular weight of 2000, the poly (adipic acid-neopentyl glycol) ester diol had a number average molecular weight of 2000, the poly (phthalic anhydride diethylene glycol) ester diol had a number average molecular weight of 1000, and the poly (adipic acid-1, 6-hexanediol ester diol) had a number average molecular weight of 2000.
And 2, adding the poly adipic acid-neopentyl glycol ester diol, the poly adipic acid-1, 6 hexanediol ester diol, polyether diol, poly phthalic anhydride diethylene glycol ester diol, an antioxidant 1010 and phosphoric acid into a reaction kettle, keeping the temperature between 120 and 130 ℃ and the pressure between-0.085 and-0.095 MPa, and stirring and dehydrating for 2 hours.
And 3, stopping heating, adding the diphenylmethane-4, 4-diisocyanate when the temperature in the reaction kettle is reduced to 90-100 ℃, stirring and reacting for 1 hour at the temperature of 90-100 ℃, and keeping the vacuum degree between-0.06 MPa and-0.095 MPa.
And 4, adding the dibutyltin dilaurate and a silane coupling agent KH-550 into the reaction kettle, stirring and reacting for 40 minutes at the temperature of between 90 and 100 ℃, and keeping the vacuum degree between-0.08 MPa and-0.095 MPa.
And 5, closing stirring, defoaming for 10min, filtering, discharging, and packaging in vacuum or nitrogen to obtain the reactive polyurethane hot melt adhesive for low-temperature coating.
Example 2
The preparation method of the reactive polyurethane hot melt adhesive for low-temperature coating can comprise the following steps:
step 1, weighing 16kg of diphenylmethane-4, 4-diisocyanate, 8kg of poly adipic acid-diethylene glycol-neopentyl glycol ester glycol, 5kg of poly adipic acid-1, 4-butanediol ester glycol, 30kg of polyether diol, 5kg of poly adipic acid-phthalic acid-diethylene glycol-ethylene glycol ester glycol, 10350.05 kg of antioxidant, 0.01kg of a mixture of phosphoric acid and benzoic acid, 0.1kg of dimorpholintriethyl ether and 0-1720.5 kg of silane coupling agent A. The polyether diol used in the examples of the present invention had a number average molecular weight of 1000, a number average molecular weight of 3500 for poly (diethylene glycol-neopentyl glycol) adipate, a number average molecular weight of 3000 for poly (1, 4-butylene glycol) adipate, a number average molecular weight of 5500 for poly (diethylene glycol-ethylene glycol) adipate, and a weight ratio of 1:1 for phosphoric acid and benzoic acid.
And 2, adding the mixture of the poly adipic acid-diethylene glycol-neopentyl glycol ester diol, the poly adipic acid-1, 4-butanediol ester diol, the polyether diol, the poly adipic acid-phthalic acid-diethylene glycol-ethylene glycol ester diol, the antioxidant 1035, the phosphoric acid and the benzoic acid into a reaction kettle, keeping the temperature between 120 and 130 ℃ and the pressure between-0.085 and-0.095 MPa, and stirring and dehydrating for 2 hours.
And 3, stopping heating, adding the diphenylmethane-4, 4-diisocyanate when the temperature in the reaction kettle is reduced to 90-100 ℃, stirring and reacting for 1 hour at the temperature of 90-100 ℃, and keeping the vacuum degree between-0.06 MPa and-0.095 MPa.
And 4, adding the dimorpholinyl triethyl ether and the silane coupling agent A-172 into the reaction kettle, stirring and reacting for 40 minutes at the temperature of between 90 and 100 ℃, and keeping the vacuum degree between-0.08 MPa and-0.095 MPa.
And 5, closing stirring, defoaming for 10min, filtering, discharging, and packaging in vacuum or nitrogen to obtain the reactive polyurethane hot melt adhesive for low-temperature coating.
Example 3
A preparation method of the reactive polyurethane hot melt adhesive for low-temperature coating can comprise the following steps:
step 1, weighing 18kg of diphenylmethane-4, 4-diisocyanate, 20kg of poly adipic acid-neopentyl glycol ester diol, 4kg of poly adipic acid-1, 6 hexanediol ester diol, 1kg of poly adipic acid-1, 4 butanediol ester diol, 20kg of polyether diol, 10kg of poly phthalic anhydride diethylene glycol ester diol, 10100.05kg of antioxidant, 0.01kg of phosphoric acid, 0.1kg of dibutyltin dilaurate and KH-5600.5 kg of silane coupling agent. The polyether diol used in the examples of the present invention had a number average molecular weight of 1000, a number average molecular weight of 3000 for poly (adipic acid-neopentyl glycol) diol, a number average molecular weight of 1000 for poly (phthalic anhydride diethylene glycol) diol, a molecular weight of 2000 for poly (adipic acid-1, 6 hexanediol) diol, and a molecular weight of 3000 for poly (adipic acid-1, 4 butanediol) diol.
Step 2, adding poly adipic acid-neopentyl glycol ester diol, poly adipic acid-1, 6 hexanediol ester diol, poly adipic acid-1, 4 butanediol ester diol, polyether diol, poly phthalic anhydride diethylene glycol ester diol, an antioxidant 1010 and phosphoric acid into a reaction kettle, keeping the temperature between 120 and 130 ℃ and the pressure between-0.085 and-0.095 MPa, and stirring and dehydrating for 2 hours.
And 3, stopping heating, adding the diphenylmethane-4, 4-diisocyanate when the temperature in the reaction kettle is reduced to 90-100 ℃, stirring and reacting for 1 hour at the temperature of 90-100 ℃, and keeping the vacuum degree between-0.06 MPa and-0.095 MPa.
And 4, adding the dibutyltin dilaurate and a silane coupling agent KH-560 into the reaction kettle, stirring and reacting for 40 minutes at the temperature of between 90 and 100 ℃, and keeping the vacuum degree between-0.08 MPa and-0.095 MPa.
And 5, closing stirring, defoaming for 10min, filtering, discharging, and packaging in vacuum or nitrogen to obtain the reactive polyurethane hot melt adhesive for low-temperature coating.
Example 4
The preparation method of the reactive polyurethane hot melt adhesive for low-temperature coating can comprise the following steps:
step 1, weighing 14kg of diphenylmethane-4, 4-diisocyanate, 22kg of poly adipic acid-diethylene glycol-neopentyl glycol ester diol, 4kg of poly adipic acid-1, 4-butanediol ester diol, 20kg of polyether diol, 10kg of poly phthalic anhydride diethylene glycol ester diol, 10100.05kg of antioxidant, 0.01kg of phosphoric acid, 0.1kg of dibutyltin dilaurate and KH-5700.5 kg of silane coupling agent. The polyether diol used in the examples of the present invention had a number average molecular weight of 2000, a number average molecular weight of 3000 for poly (diethylene glycol-neopentyl glycol) adipate diol (diethylene glycol/neopentyl glycol molar ratio of 1:3), a number average molecular weight of 1000 for poly (diethylene glycol phthalate) diol, and a number average molecular weight of 3000 for poly (1, 4-butylene glycol) adipate diol.
And 2, adding the poly adipic acid-diethylene glycol-neopentyl glycol ester diol, the poly adipic acid-1, 4-butanediol ester diol, polyether diol, poly phthalic anhydride diethylene glycol ester diol, an antioxidant 1010 and phosphoric acid into a reaction kettle, keeping the temperature between 120 and 130 ℃ and the pressure between-0.085 and-0.095 MPa, and stirring and dehydrating for 2 hours.
And 3, stopping heating, adding the diphenylmethane-4, 4-diisocyanate when the temperature in the reaction kettle is reduced to 90-100 ℃, stirring and reacting for 1 hour at the temperature of 90-100 ℃, and keeping the vacuum degree between-0.06 MPa and-0.095 MPa.
And 4, adding the dibutyltin dilaurate and a silane coupling agent KH-570 into the reaction kettle, stirring and reacting for 40 minutes at the temperature of between 90 and 100 ℃, and keeping the vacuum degree between-0.08 MPa and-0.095 MPa.
And 5, closing stirring, defoaming for 10min, filtering, discharging, and packaging in vacuum or nitrogen to obtain the reactive polyurethane hot melt adhesive for low-temperature coating.
Test method and results
The following performance tests were carried out on the low-temperature coating reactive polyurethane hot melt adhesives prepared in examples 1 to 4 of the present invention:
(1) and (3) viscosity testing: the viscosities of the low-temperature coating reactive polyurethane hot melt adhesives prepared in examples 1 to 4 of the present invention at 80 ℃, 90 ℃ and 120 ℃ were measured using an NDJ-1C rotational viscometer, respectively. If the viscosity of the adhesive at 80 ℃ is less than 60000mpa.s, the adhesive is considered to be capable of adhesive bonding at 80 ℃.
(2) And (3) later-stage bonding force test: using a wood-plastic plate as a test substrate and a 14-filament-thick PVC film with a dyne value of 32-34 as a test film, the reactive polyurethane hot melt adhesives for low temperature coating prepared in the embodiments 1-4 of the present invention were heated to 80-90 ℃ to melt into fluid form at a temperature of 50g/m2Coating the sizing amount on a test membrane material, attaching a prepared test base material, and pressing and attaching the veneers by using the same pressure; on the facing, a 25mm wide PVC film was cut, and the peel strength after curing for 24 hours was measured at 180 ℃ in an environment at a temperature of 25 ℃ and a humidity of 45%.
The test results are shown in table 1 below:
TABLE 1
As can be seen from table 1: the viscosity of the reactive polyurethane hot melt adhesive for low-temperature coating prepared in the embodiments 1 to 4 is less than 60000mPa.s at 80 ℃, so that the reactive polyurethane hot melt adhesive can be applied by melting at 80-90 ℃. After sizing and curing, the film with the thickness of 14 filaments cannot deform and bulge, has good later-stage bonding force, and cannot be pulled open after curing for 24 hours. The invention can be used at lower temperature, and meets the market demand.
In conclusion, the embodiment of the invention does not add tackifying resins such as EVA, TPU, acrylic resin and the like in the system, has better fluidity and lower viscosity at lower temperature, and ensures the later-stage adhesive force.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. The reactive polyurethane hot melt adhesive for low-temperature coating is characterized by being prepared from the following raw materials in parts by weight:
10-35 parts of isocyanate,
10-70 parts of aliphatic polyester diol,
20-50 parts of polyether glycol,
5 to 20 parts of aromatic polyester diol,
0.05 to 0.5 portion of antioxidant,
0.01 to 0.1 part of a stabilizer,
0.05 to 0.5 portion of catalyst,
0.1-5 parts of an adhesion promoter;
wherein the aromatic polyester dihydric alcohol is one or a mixture of more of poly phthalic anhydride diethylene glycol ester glycol, poly phthalic acid-1, 6-hexanediol ester glycol, poly phthalic acid neopentyl glycol ester glycol, poly terephthalic acid-neopentyl glycol ester glycol, poly phthalic anhydride-diethylene glycol ester glycol and poly isophthalic acid neopentyl glycol ester glycol.
2. The reactive polyurethane hot melt adhesive for low-temperature coating according to claim 1, wherein the isocyanate is one or a mixture of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and diphenylmethane-4, 4-diisocyanate.
3. The reactive polyurethane hot melt adhesive for low-temperature coating according to claim 1 or 2, wherein the aliphatic polyester diol is one or more selected from the group consisting of poly (1, 6-hexanediol adipate diol), poly (1, 4-butanediol adipate diol), poly (neopentyl glycol adipate diol), poly (diethylene glycol adipate diol) and poly (hexanediol adipate diol) neopentyl glycol ester diol.
4. The reactive polyurethane hot melt adhesive for low-temperature coating according to claim 1 or 2, wherein the polyether diol mainly comprises propylene oxide and has a relative molecular weight of 1000-5000.
5. The reactive polyurethane hot melt adhesive for low-temperature coating according to claim 1 or 2, wherein the antioxidant is one or a mixture of several of antioxidant 1076, antioxidant 1035, antioxidant 245 and antioxidant 1010.
6. The reactive polyurethane hot melt adhesive for low-temperature coating according to claim 1 or 2, wherein the stabilizer is one or a mixture of phosphoric acid, benzoyl chloride, benzoic acid and nonanoic acid.
7. The reactive polyurethane hot melt adhesive for low-temperature coating according to claim 1 or 2, wherein the catalyst is one or a mixture of dibutyltin dilaurate, stannous octoate, tetramethylethylenediamine, triethylenediamine and dimorpholintriethylether.
8. The reactive polyurethane hot melt adhesive for low-temperature coating according to claim 1 or 2, wherein the adhesion promoter is one or a mixture of silane coupling agent A-172, silane coupling agent KH550, silane coupling agent KH560 and silane coupling agent KH 570.
9. A preparation method of a reactive polyurethane hot melt adhesive for low-temperature coating is characterized by comprising the following steps:
step 1, weighing isocyanate, aliphatic polyester dihydric alcohol, polyether dihydric alcohol, aromatic polyester dihydric alcohol, an antioxidant, a stabilizer, a catalyst and an adhesion promoter according to the formula of the reactive polyurethane hot melt adhesive for low-temperature coating in any one of the claims 1 to 8;
step 2, adding the aliphatic polyester diol, the polyether diol, the aromatic polyester diol, the antioxidant and the stabilizer into a reaction kettle, keeping the temperature between 100 and 140 ℃ and the pressure between-0.085 and-0.095 MPa, and stirring and dehydrating for 1 to 4 hours;
step 3, stopping heating, adding the isocyanate when the temperature in the reaction kettle is reduced to 90-100 ℃, stirring and reacting for 1 hour at the temperature of 90-100 ℃, and keeping the vacuum degree between-0.06 MPa and-0.095 MPa;
step 4, adding the adhesion promoter and the catalyst into the reaction kettle, stirring and reacting for 30-50 minutes at 90-100 ℃, and keeping the vacuum degree at-0.08 MPa to-0.095 MPa;
and 5, closing stirring, defoaming for 10-20 min, filtering and discharging to obtain the reactive polyurethane hot melt adhesive for low-temperature coating as claimed in any one of claims 1-8.
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