CN109628051B - High-temperature-resistant three-component polyurethane adhesive and preparation method thereof - Google Patents
High-temperature-resistant three-component polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN109628051B CN109628051B CN201811601222.3A CN201811601222A CN109628051B CN 109628051 B CN109628051 B CN 109628051B CN 201811601222 A CN201811601222 A CN 201811601222A CN 109628051 B CN109628051 B CN 109628051B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/4833—Polyethers containing oxyethylene units
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
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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
- C09J11/04—Non-macromolecular additives inorganic
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention relates to a high-temperature-resistant three-component polyurethane adhesive and a preparation method thereof, belonging to the technical field of polyurethane. The high-temperature-resistant three-component polyurethane adhesive comprises a component A, a component B and a component C, wherein the mixing mass ratio is 50-200:100: 1-5; the component A consists of high-temperature resistant polyester polyol, a catalyst and a high-temperature resistant auxiliary agent; the component B is an isocyanate component obtained by modifying aliphatic diisocyanate or alicyclic diisocyanate and polyether polyol, and the mass fraction of isocyano is 12-20%; the component C is glycerol or trimethylolpropane; the high-temperature-resistant polyester polyol is prepared by esterification and polycondensation of alicyclic polybasic acid and alicyclic polyhydric alcohol. The high-temperature-resistant three-component polyurethane adhesive disclosed by the invention is low in viscosity, easy to glue, stable in bonding performance and capable of widening the high-temperature applicability of the polyurethane adhesive; the invention also provides a simple and feasible preparation method.
Description
Technical Field
The invention relates to a high-temperature-resistant three-component polyurethane adhesive and a preparation method thereof, belonging to the technical field of polyurethane.
Background
The polyurethane adhesive has a strong adhesive effect on most base materials with active hydrogen on the surfaces because the molecular structure contains high-activity polyisocyanate and high-polarity carbamate. In addition, the polyurethane adhesive also has the characteristics of adjustable toughness, simple and convenient bonding process, excellent low-temperature resistance, excellent stability and the like. The polyurethane adhesive has excellent adhesive property, so that the application field of the polyurethane adhesive is continuously expanded, and the polyurethane adhesive is particularly widely applied to the field of food packaging, the polyurethane adhesive is mainly matched with flexible packaging at present, and more than 90 percent of food packaging bags are formed by adhering the polyurethane adhesive according to statistics.
Different requirements on the adhesive can be met according to different contents of packaged objects, for example, in the field of food packaging, different requirements such as pasteurization, high temperature, cooking at 121 ℃, cooking at 135 ℃, microwave packaging, vacuum packaging and the like can be met according to different foods. When the polyurethane is exposed to the high-temperature and high-humidity environment for a long time, the carbamate group in the polyurethane is easy to hydrolyze, the molecular weight is reduced, and the bonding effect is poor; in addition, the polyurethane material has poor thermal oxidation resistance, and adhesive products in the environments are easy to yellow, so that the application and popularization of the adhesive are also limited.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant three-component polyurethane adhesive which is low in viscosity, easy to glue and stable in bonding performance, and widens the high-temperature applicability of the polyurethane adhesive; the invention also provides a simple and feasible preparation method.
The high-temperature-resistant three-component polyurethane adhesive comprises a component A, a component B and a component C, wherein the mixing mass ratio is 50-200:100: 1-5; the component A consists of high-temperature resistant polyester polyol, a catalyst and a high-temperature resistant auxiliary agent; the component B is an isocyanate component obtained by modifying aliphatic diisocyanate or alicyclic diisocyanate and polyether polyol, and the mass fraction of isocyano is 12-20%; the component C is multi-functionality glycerol or trimethylolpropane, and a cross-linked network structure of polyurethane is easily formed after molding, so that the high-temperature resistance is improved.
The high-temperature-resistant polyester polyol is prepared by esterification and polycondensation of alicyclic polybasic acid and alicyclic polyhydric alcohol.
Preferably, the molecular weight of the high temperature resistant polyester polyol is 200-1000.
The alicyclic polybasic acid is tetrahydrophthalic anhydride, tetrahydrophthalic acid, hexahydrophthalic anhydride, hexahydroisophthalic acid, 4-methyl hexahydrophthalic anhydride, 1, 2-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid or 1, 4-cyclohexanedicarboxylic acid; the alicyclic polyol is one or two of cyclohexane dimethanol or cyclohexanediol.
The catalyst is metal salt of transition metal tin and bismuth, and the addition amount is 0.05-1% of the polyester polyol.
The high-temperature resistant auxiliary agent comprises a high-temperature resistant antioxidant, an ultraviolet resistant absorbent, a hydrolysis resistant stabilizer, a nano auxiliary agent and the like, and the addition amount of the high-temperature resistant auxiliary agent is referred to the batch charge of the polyester polyol.
Wherein the high-temperature-resistant antioxidant is an antioxidant compounded by a hindered phenol main antioxidant and a phosphite ester auxiliary antioxidant, and the total addition amount is 1-5 per mill of the feeding amount of the polyester polyol. The hindered phenol antioxidant is 1010, 1076 or 1094, and the phosphite ester auxiliary antioxidant is triphenyl phosphite (TPP) or antioxidant 168.
Preferably, the uvioresistant absorbent can be a conventional light stabilizer, such as benzophenones, benzotriazoles and the like, and the addition amount is 1-3 per thousand of the charging amount of the polyester polyol.
Preferably, the hydrolysis-resistant stabilizer is an organosilane coupling agent KH550 or KH560, and the addition amount is 1-3% of the feeding amount of the polyester polyol.
Preferably, the nano additive is fumed silica, and the addition amount of the fumed silica is 0.3-1 per mill of the feeding amount of the polyester polyol.
Preferably, the aliphatic diisocyanate is Hexamethylene Diisocyanate (HDI).
Preferably, the cycloaliphatic diisocyanate is isophorone diisocyanate (IPDI) or dicyclohexylmethane diisocyanate (HMDI).
Preferably, the polyether polyol is a polyethylene glycol or polypropylene glycol polyol having a molecular weight of 400-1000.
The preparation method of the high-temperature-resistant three-component polyurethane adhesive comprises the following steps:
(1) preparation of component A:
placing alicyclic polyhydric alcohol, alicyclic polybasic acid and catalyst in a reactor, stirring, and carrying out esterification reaction at 140-200 ℃ under the protection of nitrogen; when the esterification water yield reaches 95 percent of the theoretical water yield, continuously heating to 240 ℃ at 220-; cooling the system to obtain high-temperature-resistant polyester polyol;
when the temperature of the high-temperature-resistant polyester polyol component is reduced to 120 ℃, opening the reaction kettle device, adding the high-temperature-resistant auxiliary agent, keeping the temperature of the system at 120 ℃, and continuously stirring for 2-8 hours until the system is clarified again;
thirdly, continuously cooling the system to 90-110 ℃, and discharging to obtain a component A;
(2) preparation of component B: adding polyether polyol into aliphatic diisocyanate or alicyclic diisocyanate at 50 ℃, reacting for 4h to detect the mass fraction of isocyanate in a system, and discharging materials to obtain a component B, wherein the mass fraction of isocyanate reaches 12-20% of a theoretical design value;
(3) and (3) stirring and mixing the component A, the component B and the component C at a high speed at room temperature, casting and coating on the surface of a corresponding packaging PET film through a machine or manually, laminating by hot pressing, and standing at 40 ℃ for 24 hours to obtain the high-temperature-resistant three-component polyurethane adhesive.
And (3) placing the bonded PET film for double-layer packaging in a 135 ℃ steam environment for 1 hour, and detecting the peel strength of the two layers of films to measure the high-temperature resistance of the adhesive.
According to the high-temperature-resistant three-component adhesive, the high-temperature-resistant monomer component is introduced into the component A, namely, the alicyclic dihydric alcohol and the acid monomer with rigid ring structures are introduced into the polyester polyol, so that the high-temperature rigidity and the hydrolysis resistance stability of the polyester polyol are integrally improved, and the structure is more stable; the component B adopts an aliphatic or alicyclic isocyanate structure, so that the yellowing resistance of the polyurethane adhesive can be obviously improved; meanwhile, micromolecular glycerol and trimethylolpropane of the component C are introduced, and the problems of high viscosity and difficult sizing of the traditional bi-component polyurethane adhesive can be effectively reduced by regulating and controlling the using amount of the component C.
Compared with the prior art, the invention has the following beneficial effects:
(1) the high-temperature-resistant three-component adhesive prepared by the invention not only keeps the comprehensive bonding performance of the conventional two-component polyurethane adhesive, but also has the advantages of low viscosity, easy gluing and controllable physical and mechanical properties, and also has excellent bonding strength in a long-time high-temperature or water boiling environment, thereby widening the high-temperature applicability of the polyurethane adhesive;
(2) the preparation method of the high-temperature-resistant three-component adhesive is simple and feasible, and is beneficial to industrial production.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
Example 1
Placing the tetrahydrophthalic anhydride/1, 2-cyclohexanediol with the molar ratio of 1/1.4 into a reactor, adding 10ppm of n-butyl titanate catalyst, uniformly stirring, and carrying out esterification reaction under the protection of nitrogen, wherein the temperature is programmed to rise from 140 ℃ to 200 ℃, and after 8 hours, the water yield of the system reaches 95% of the theoretical water blowing amount; continuously heating the system to 220 ℃, simultaneously applying vacuum, continuously dehydrating and dealcoholizing under the condition that the vacuum degree is controlled to be-0.06 MPa, wherein the use time is 10 hours, the acid value of the system is 2.0mgKOH/g, and the molecular weight reaches about 400; stopping vacuumizing the system, cooling to 120 ℃, sequentially adding 0.05 percent of catalyst stannous octoate, 0.5 thousandth of antioxidant 1010, 0.5 thousandth of antioxidant 168, 1 thousandth of ultraviolet-resistant absorbent UV-P, 1 thousandth of hydrolysis-resistant agent KH550 and 0.5 thousandth of fumed silica into the relatively high-temperature-resistant polyester polyol, continuously stirring uniformly until the system is clear and transparent, cooling to 90 ℃, and discharging to obtain a component A1.
50 g of polyethylene glycol (PEG400) with the molecular weight of 400 is put into 42 g of HDI at the temperature of 50 ℃, the system is heated to 80 ℃ to react for 4h, the mass fraction of isocyanate in the system is detected, the NCO percent of the system is measured to be 12.3 percent, and the temperature is reduced to 50 ℃ to discharge the material, thus obtaining the component B1.
Uniformly stirring 5.0 g of the component A1, 10 g of the component B1 and 0.1 g of glycerin at a high speed, coating the mixture on a flexible packaging PET film, carrying out hot pressing, vulcanizing and completely curing, and testing the peel strength of the flexible packaging PET film. The product is placed in a steam environment of 135 ℃ for 1 hour, and the peel strength can still reach 90 percent before testing.
Example 2
Placing the cyclohexane dicarboxylic acid/1, 3-cyclohexanediol with the molar ratio of 1/1.1 into a reactor, adding 100ppm of n-butyl titanate catalyst, uniformly stirring, and carrying out esterification reaction under the protection of nitrogen, wherein the temperature is programmed to rise from 140 ℃ to 200 ℃, and after 9 hours, the water yield of the system reaches 95% of the theoretical water blowing amount; continuously heating the system to 240 ℃, simultaneously applying vacuum, continuously dehydrating and dealcoholizing under the condition that the vacuum degree is controlled to be-0.1 MPa, wherein the use time is 6 hours, the acid value of the system is 1.0mgKOH/g, and the molecular weight reaches about 1000; stopping vacuumizing the system, cooling to 120 ℃, sequentially adding 0.4% of catalyst dibutyltin dilaurate, 2 thousandths of antioxidant 1076, 2 thousandths of antioxidant 168, 1 thousandths of ultraviolet-resistant absorbent UV-O, 3 thousandths of hydrolysis-resistant agent KH560 and 1 thousandths of fumed silica into the feeding amount of the high-temperature-resistant polyester polyol, continuously stirring uniformly until the system is clear and transparent, cooling to 90 ℃, and discharging to obtain a component A2.
100 g of polypropylene glycol (PPG400) with the molecular weight of 400 is put into 230 g of IPDI at the temperature of 50 ℃, the system is heated to 80 ℃ to react for 4h, the mass fraction of isocyanate in the system is detected, the NCO percent of the system is measured to be 19.4 percent, and the temperature is reduced to 50 ℃ to discharge the material, thus obtaining the component B2.
20 g of component A2, 10 g of component B2 and 0.5 g of trimethylolpropane are uniformly stirred at a high speed, coated on a flexible packaging PET film, hot-pressed, vulcanized and completely cured, and then the peel strength of the flexible packaging PET film is tested. The product is placed in a steam environment of 135 ℃ for 1 hour, and the peel strength can still reach 92 percent before testing.
Example 3
Putting hexahydro isophthalic acid/cyclohexane dimethanol in a molar ratio of 1/1.2 into a reactor, adding 50ppm of n-butyl titanate catalyst, uniformly stirring, and carrying out esterification reaction under the protection of nitrogen, wherein the temperature is programmed to rise from 140 ℃ to 200 ℃, and after 7 hours, the water yield of the system reaches 95% of the theoretical water blowing amount; continuously heating the system to 225 ℃, simultaneously applying vacuum, continuously dehydrating and dealcoholizing under the condition that the vacuum degree is controlled to be-0.1 MPa, wherein the use time is 6 hours, the acid value of the system is 1.0mgKOH/g, and the molecular weight reaches about 600; stopping vacuumizing the system, cooling to 120 ℃, sequentially adding 1% of catalyst bismuth octodecanoate, 4 thousandths of antioxidant 1094 and 1 thousandths of antioxidant TPP relative to the feeding amount of the high-temperature-resistant polyester polyol, 1 thousandth of ultraviolet-resistant absorbent UV-9, 3 thousandths of hydrolysis-resistant agent KH560 and 0.6 thousandth of fumed silica, continuously stirring uniformly until the system is clear and transparent, cooling to 90 ℃, and discharging to obtain a component A3.
100 g of 1000 molecular weight polypropylene glycol (PPG1000) is put into 140 g of HMDI at 50 ℃, the system is heated to 80 ℃ and reacted for 4h to detect the isocyanate mass fraction in the system, the NCO% of the system is measured to be 15.8%, and the temperature is reduced to 50 ℃ to discharge the material, thus obtaining the component B3.
10 g of component A3, 10 g of component B3 and 0.3 g of trimethylolpropane are uniformly stirred at a high speed, coated on a flexible packaging PET film, hot-pressed, vulcanized and completely cured, and then the peel strength of the flexible packaging PET film is tested. The product is placed in a steam environment at 135 ℃ for 1 hour, and the peel strength can still reach 93 percent before testing.
Example 4
Putting hexahydrophthalic anhydride/cyclohexanedimethanol into a reactor according to the molar ratio of 1/1.2, adding 50ppm of n-butyl titanate catalyst, uniformly stirring, and carrying out esterification reaction under the protection of nitrogen, namely, raising the temperature from 140 ℃ to 200 ℃ by a programmed temperature, wherein the water yield of the system reaches 95% of the theoretical water yield after 7 hours; continuously heating the system to 225 ℃, simultaneously applying vacuum, continuously dehydrating and dealcoholizing under the condition that the vacuum degree is controlled to be-0.1 MPa, wherein the use time is 6 hours, the acid value of the system is 1.0mgKOH/g, and the molecular weight reaches about 600; stopping vacuumizing the system, cooling to 120 ℃, sequentially adding 0.8% of catalyst bismuth isooctanoate, 3 thousandths of antioxidant 1094, 2 thousandths of antioxidant TPP, 1 thousandths of ultraviolet-resistant absorbent UV-9, 3 thousandths of hydrolysis-resistant agent KH560 and 0.6 thousandths of fumed silica (the addition amounts of the above additives are all relative to the total amount of hexahydro isophthalic acid/cyclohexane dimethanol) relative to the feeding amount of the high-temperature-resistant polyester polyol, continuously stirring uniformly until the system is clear and transparent, cooling to 90 ℃, and discharging to obtain a component A4.
100 g of 1000 molecular weight polypropylene glycol (PPG1000) is put into 140 g of HMDI at 50 ℃, the system is heated to 80 ℃ and reacted for 4h to detect the isocyanate mass fraction in the system, the NCO% of the system is measured to be 15.8%, and the temperature is reduced to 50 ℃ to discharge the material, thus obtaining the component B4.
10 g of component A4, 10 g of component B4 and 0.27 g of glycerin are uniformly stirred at a high speed, coated on a flexible packaging PET film, hot-pressed, vulcanized and completely cured, and then the peel strength of the flexible packaging PET film is tested. The product is placed in a steam environment of 135 ℃ for 1 hour, and the peel strength can still reach 94 percent before testing.
Comparative example 1
Putting adipic acid without a rigid annular structure and cyclohexanedimethanol with a molar ratio of 1/1.2 into a reactor, adding 50ppm (relative to the total amount of the adipic acid and the cyclohexanedimethanol) of n-butyl titanate catalyst, uniformly stirring, and carrying out esterification reaction under the protection of nitrogen, wherein the temperature programming is increased from 140 ℃ to 200 ℃, and after 5 hours, the water yield of the system reaches 97% of the theoretical water yield; continuously heating the system to 225 ℃, simultaneously applying vacuum, continuously dehydrating and dealcoholizing under the condition that the vacuum degree is controlled to be-0.1 MPa, wherein the use time is 5 hours, the acid value of the system is 1.0mgKOH/g, and the molecular weight reaches about 600; stopping vacuumizing the system, cooling to 120 ℃, supplementing 1 percent of catalyst stannous octoate, 4 thousandths of antioxidant 1094 and 1 thousandths of antioxidant TPP, 1 thousandths of ultraviolet-resistant absorbent UV-9, 3 thousandths of hydrolysis-resistant agent KH560 and 0.6 thousandths of fumed silica (the addition amounts of the above additives are all the total amount of the adipic acid/cyclohexanedimethanol), continuously stirring uniformly until the system is clear and transparent, cooling to 90 ℃, and discharging to obtain a component DA 1.
100 g of 1000 molecular weight polypropylene glycol (PPG1000) is put into 140 g of HMDI at 50 ℃, the system is heated to 80 ℃ and reacted for 4h, the isocyanate mass fraction in the system is detected, the NCO% of the system is measured to be 15.8%, and the temperature is reduced to 50 ℃ to discharge the material, thus obtaining the component DB 1.
100 g of component DA1, 100 g of component DB1 and 0.3 g of trimethylolpropane are uniformly stirred at a high speed, coated on a flexible packaging PET film, hot-pressed, vulcanized and completely cured, and then the peel strength of the flexible packaging PET film is tested. The product was placed in a steam environment at 135 ℃ for 1 hour, and the peel strength was reduced to 53% before the test.
Comparative example 2
Putting hexahydro isophthalic acid/cyclohexane dimethanol in a molar ratio of 1/1.2 into a reactor, adding 50ppm of n-butyl titanate catalyst, uniformly stirring, and carrying out esterification reaction under the protection of nitrogen, wherein the temperature is programmed to rise from 140 ℃ to 200 ℃, and after 7 hours, the water yield of the system reaches 95% of the theoretical water blowing amount; continuously heating the system to 225 ℃, simultaneously applying vacuum, continuously dehydrating and dealcoholizing under the condition that the vacuum degree is controlled to be-0.1 MPa, wherein the use time is 6 hours, the acid value of the system is 1.0mgKOH/g, and the molecular weight reaches about 600; stopping vacuumizing the system, cooling to 120 ℃, sequentially adding 1% of catalyst bismuth octodecanoate, 4 thousandths of antioxidant 1094 and 1 thousandth of antioxidant TPP relative to the feeding amount of the high-temperature-resistant polyester polyol, 1 thousandth of ultraviolet-resistant absorbent UV-9, 3 thousandths of hydrolysis-resistant agent KH560 and 0.6 thousandth of fumed silica, continuously stirring uniformly until the system is clear and transparent, cooling to 90 ℃, and discharging to obtain a component DA 2.
100 g of 1000 molecular weight polypropylene glycol (PPG1000) is put into 140 g of HMDI at 50 ℃, the system is heated to 80 ℃ and reacted for 4h, the isocyanate mass fraction in the system is detected, the NCO% of the system is measured to be 15.8%, and the temperature is reduced to 50 ℃ to discharge the material, thus obtaining the component DB 2.
10 g of component DA2, 10 g of component DB2 and 0.31 g of butanediol are uniformly stirred at a high speed, coated on a flexible packaging PET film, hot-pressed, vulcanized and completely cured, and then the peel strength of the flexible packaging PET film is tested. The product is placed in a steam environment of 135 ℃ for 1 hour, and the peel strength can still reach 74 percent before testing.
Claims (6)
1. A high-temperature-resistant three-component polyurethane adhesive is characterized in that: comprises a component A, a component B and a component C, and the mixing mass ratio is 50-200:100: 1-5; the component A consists of high-temperature resistant polyester polyol, a catalyst and a high-temperature resistant auxiliary agent; the component B is an isocyanate component obtained by modifying aliphatic diisocyanate or alicyclic diisocyanate and polyether polyol, and the mass fraction of isocyano is 12-20%; the component C is glycerol or trimethylolpropane;
the high-temperature resistant polyester polyol is prepared by esterification and polycondensation of alicyclic polybasic acid and alicyclic polyhydric alcohol;
the alicyclic polybasic acid is tetrahydrophthalic anhydride, tetrahydrophthalic acid, hexahydrophthalic anhydride, hexahydroisophthalic acid, 4-methyl hexahydrophthalic anhydride, 1, 2-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid or 1, 4-cyclohexanedicarboxylic acid;
the alicyclic polyol is one or two of cyclohexane dimethanol or cyclohexanediol;
the high-temperature resistant auxiliary agent comprises a high-temperature resistant antioxidant, an ultraviolet resistant absorbent, a hydrolysis resistant stabilizer and a nano auxiliary agent;
the preparation method of the high-temperature-resistant three-component polyurethane adhesive comprises the following steps:
(1) preparation of component A:
placing alicyclic polyhydric alcohol, alicyclic polybasic acid and catalyst in a reactor, stirring, and carrying out esterification reaction at 140-200 ℃ under the protection of nitrogen; when the esterification water yield reaches 95 percent of the theoretical water yield, continuously heating to the temperature of 220 ℃ and 240 ℃, and vacuumizing the reaction device; cooling the system to obtain high-temperature-resistant polyester polyol;
when the temperature of the high-temperature-resistant polyester polyol component is reduced to 120 ℃, opening the reaction kettle device, adding the high-temperature-resistant auxiliary agent, keeping the temperature of the system at 120 ℃, and continuously stirring for 2-8 hours until the system is clarified again;
thirdly, continuously cooling the system to 90-110 ℃, and discharging to obtain a component A;
(2) preparation of component B: adding polyether polyol into aliphatic diisocyanate or alicyclic diisocyanate at 50 ℃, reacting for 4h to detect the mass fraction of isocyanate in a system, and discharging materials to obtain a component B, wherein the mass fraction of isocyanate reaches 12-20% of a theoretical design value;
(3) and (3) stirring and mixing the component A, the component B and the component C at a high speed at room temperature, casting and coating on the surface of a corresponding packaging PET film through a machine or manually, laminating by hot pressing, and standing at 40 ℃ for 24 hours to obtain the high-temperature-resistant three-component polyurethane adhesive.
2. The high temperature resistant three-component polyurethane adhesive of claim 1, wherein: the catalyst is metal salt of transition metal tin and bismuth, and the addition amount is 0.05-1% of the mass of the polyester polyol.
3. The high temperature resistant three-component polyurethane adhesive of claim 1, wherein: the aliphatic diisocyanate is hexamethylene diisocyanate.
4. The high temperature resistant three-component polyurethane adhesive of claim 1, wherein: the alicyclic diisocyanate is isophorone diisocyanate or dicyclohexylmethane diisocyanate.
5. The high temperature resistant three-component polyurethane adhesive of claim 1, wherein: the polyether polyol is polyethylene glycol or polypropylene glycol polyol with the number average molecular weight of 400-1000.
6. The method for preparing the high-temperature-resistant three-component polyurethane adhesive according to claim 1, wherein the method comprises the following steps: in the step I, the dehydration and dealcoholization are carried out under the condition that the vacuum degree is controlled to be-0.04 to-0.1 MPa until the acid value of the system is less than 2mgKOH/g and the molecular weight is 200-1000, and the heating and the vacuum pumping are stopped.
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| CN111533891B (en) * | 2020-04-16 | 2023-01-13 | 上海炼升化工股份有限公司 | Polyester polyol for high-temperature-resistant adhesive and preparation method thereof |
| CN113292709A (en) * | 2021-05-24 | 2021-08-24 | 华大化学集团有限公司 | Polyurethane polyol for high-strength and high-gloss polyurethane and preparation process thereof |
| CN113214773B (en) * | 2021-06-08 | 2022-08-19 | 山西浩博瑞新材料有限公司 | High-temperature-resistant heat-insulating polyurethane sealant and preparation method thereof |
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