CN115975578A - Polyurethane adhesive and preparation method thereof, aluminum plastic film and preparation method thereof - Google Patents

Polyurethane adhesive and preparation method thereof, aluminum plastic film and preparation method thereof Download PDF

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CN115975578A
CN115975578A CN202211629141.0A CN202211629141A CN115975578A CN 115975578 A CN115975578 A CN 115975578A CN 202211629141 A CN202211629141 A CN 202211629141A CN 115975578 A CN115975578 A CN 115975578A
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parts
polyurethane
hydroxyl
polyurethane adhesive
polyol
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袁功道
胡湘
赵志荣
徐秋春
戴晓兵
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Jiangxi Shengwei Material Co ltd
Zhuhai Smoothway Electronic Materials Co Ltd
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Jiangxi Shengwei Material Co ltd
Zhuhai Smoothway Electronic Materials Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to the technical field of adhesives, and discloses a polyurethane adhesive and a preparation method thereof, an aluminum plastic film and a preparation method thereof. The polyurethane adhesive is prepared from 20-70 parts of polyester polyol containing terminal hydroxyl, 10-20 parts of polyurethane polymer, 5-50 parts of polyisocyanate, 1-10 parts of oxazoline grafted acrylic resin and 0-5 parts of assistant. The Tg of the polyester polyol containing the terminal hydroxyl is-20 to 20 ℃, and the Tg of the polyurethane polymer is 40 to 100 ℃. The preparation raw material of the polyurethane polymer comprises polymeric polyol, wherein the polymeric polyol comprises polyol with a main chain of polyester, polyether or polyolefin and a functionality of 2-3. The polyurethane adhesive adopted by the invention has better adhesive force to various base materials, so that the prepared aluminum-plastic film has higher peel strength and better humidity resistance and boiling resistance.

Description

Polyurethane adhesive and preparation method thereof, aluminum plastic film and preparation method thereof
Technical Field
The invention relates to the technical field of adhesives, in particular to a polyurethane adhesive and a preparation method thereof, and an aluminum plastic film and a preparation method thereof.
Background
The composite film material has the advantages of high strength, good air tightness, water resistance, refraction, heat sealing resistance and the like, and is widely applied to the industries of food, beverage, medicine, electronics, pesticide, cosmetics and the like. The performance of the composite membrane material is not only related to the properties of the composite membrane itself, but also depends on the performance of the adhesive for compounding the composite membrane. The polyurethane adhesive has excellent comprehensive performance and is widely applied to composite film materials.
For example, soft package lithium batteries are widely used in the 3C and power energy storage fields, and have many advantages compared with cylindrical and square lithium batteries, such as flexibility in design, lightness and thinness, small internal resistance, safety, many cycle times, high energy density, and the like, but are limited by factors such as raw materials, manufacturing equipment, processes, and the like, the performance and yield of an aluminum-plastic film are not far from the requirements of specific battery manufacturers, and especially on power batteries with extremely high requirements on safety performance, the quality guarantee period of the battery of not less than 10 years puts extremely high requirements on the quality and performance stability of the aluminum-plastic film.
The polyurethane adhesive has good adhesive force to aluminum foil and nylon, can well bond a nylon film and the aluminum foil after being prepared into bi-component glue, the peel strength of an aluminum-plastic film prepared by curing can reach more than 5N/15mm, and the aluminum-plastic film has good moisture and heat resistance, but the common polyurethane adhesive on the market at the present stage can be baked in a double-85 oven for 48 hours without white lines and delamination, but most of the polyurethane adhesive can not resist baking in the double-85 oven for 168 hours, and the polyurethane adhesive for the aluminum-plastic film which can resist boiling of water at 75 ℃ for more than 7 days is rare.
Therefore, how to improve the moist heat resistance and the boiling resistance of the polyurethane adhesive is a difficult problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a polyurethane adhesive and a preparation method thereof, wherein the polyurethane adhesive has better humidity resistance and boiling resistance, and meets the use requirement of the polyurethane adhesive for an aluminum plastic film.
In order to achieve the above object, a first aspect of the present invention provides a polyurethane adhesive, which comprises, by mass, 20 to 70 parts of hydroxyl-terminated polyester polyol, 10 to 20 parts of polyurethane polymer, 5 to 50 parts of polyisocyanate, 1 to 10 parts of oxazoline grafted acrylic resin, and 0 to 5 parts of auxiliary agent, wherein the hydroxyl-terminated polyester polyol has a Tg of-20 to 20 ℃, the polyurethane polymer has a Tg of 40 to 100 ℃, and the polyurethane polymer comprises a polymeric polyol, wherein the polymeric polyol comprises a polyol having a polyester, polyether, or polyolefin as a main chain and having a functionality of 2 to 3.
In the polyurethane adhesive adopted by the invention, the low-Tg hydroxyl-terminated polyester polyol and the high-Tg polyurethane polymer are used as main bonding agents, and the adhesive formed by curing the low-Tg hydroxyl-terminated polyester polyol and the high-Tg polyurethane polymer with polyisocyanate has better adhesive force on various substrates, such as wood, metal, clinker, paper, leather, textiles, glass and the like. Therefore, the cured aluminum-plastic film used as the adhesive for the aluminum foil and the nylon film has higher peel strength and can ensure that the prepared aluminum-plastic film has higher punching depth performance. In addition, the preparation raw materials of the polyurethane polymer select the polyol with the main chain of polyester, polyether or polyolefin and the functionality of 2-3 as the polymeric polyol, so that the boiling resistance of the polyurethane adhesive can be improved, and the moisture and heat resistance and the boiling resistance of the polyurethane adhesive can be further improved by combining the oxazoline grafted acrylic resin which has strong reaction activity with the carboxyl in the hydroxyl-terminated polyester polyol.
In some technical schemes, the average molecular weight of the polyester polyol containing the terminal hydroxyl is 500-60000, the hydroxyl value is 2-50 mgKOH/g, the acid value is 0.5-30 mgKOH/g, and the raw materials for preparing the polyester polyol containing the terminal hydroxyl comprise 10-50 parts by mass of aliphatic dibasic acid, 5-30 parts by mass of aromatic dicarboxylic acid or anhydride, 30-70 parts by mass of polyol with the average functionality of 2-3.5 and 0-5 parts by mass of catalyst.
In some technical schemes, the average molecular weight of the polyurethane polymer is 500-50000, the hydroxyl value is 2-50 mgKOH/g, and the preparation raw materials of the polyurethane polymer comprise, by mass, 5-60 parts of isocyanate, 5-40 parts of polymeric polyol with the average molecular weight of 500-6000, 0-10 parts of aliphatic monohydric alcohol or dihydric alcohol and 0.5-15 parts of polyamine with the molecular weight of less than 500.
In some technical schemes, the polyisocyanate is aromatic polyisocyanate monomer, or the polyisocyanate is aromatic polyisocyanate copolymer, the content of the aromatic polyisocyanate in the copolymer is 5-20%, and the average functionality is 2-6.
In some embodiments, the total molar amount of-OH in the hydroxyl-terminated polyester polyol and the polyurethane polymer is m, the molar amount of-NCO in the polyisocyanate is n, and m/n is 1 to 30.
In some embodiments, the preparation raw material further comprises a solvent, wherein the solvent is at least one of cyclohexane, acetone, butanone, ethanol, isopropanol and ethyl acetate, and the auxiliary agent comprises a catalyst and/or a promoter.
The second aspect of the present invention provides a preparation method of a polyurethane adhesive, comprising the steps of:
(1) Preparing polyester polyol containing terminal hydroxyl;
(2) Preparing a polyurethane polymer;
(3) Mixing the hydroxyl-terminated polyester polyol, the polyurethane polymer, the auxiliary agent and the solvent to obtain a mixture;
(4) And stirring and mixing the mixture, the polyisocyanate and the modified acrylic resin.
The preparation method of the polyurethane adhesive is simple and the production cost is controllable.
The third aspect of the invention provides an aluminum-plastic film, which comprises an aluminum substrate and a nylon film adhered to the aluminum substrate by an adhesive, wherein the adhesive is the polyurethane adhesive or the polyurethane adhesive prepared by the preparation method of the polyurethane adhesive. The aluminum plastic film disclosed by the invention has better humidity resistance and boiling resistance by adopting a special adhesive.
The fourth aspect of the invention provides a method for preparing an aluminum-plastic film, which comprises the following steps: and compounding a nylon film on the aluminum substrate by sequentially adopting gravure coating and hot pressing modes of the polyurethane adhesive, and curing.
In some technical schemes, the gluing amount of the gravure coating is 15-25 g/m 2 Drying the coated film by an oven and drying the film by adopting a sectional temperature control program.
In some technical schemes, the temperature of the hot pressing is 80-100 ℃, and the pressure is 0.05-0.08 MPa.
In some technical schemes, the curing temperature is 55-100 ℃, and the curing time is 1-7 d.
Detailed Description
The polyurethane adhesive is a two-component system, and forms an adhesive through the reaction of an adhesive main agent and a curing agent. The polyurethane adhesive of the invention can be used for adhering a nylon film on an aluminum substrate to prepare an aluminum plastic film.
Meanwhile, the preparation method of the aluminum-plastic film can comprise the following steps: and (3) compounding a nylon film on the aluminum substrate by sequentially adopting a gravure coating and hot pressing mode by using a polyurethane adhesive, and then curing. Wherein the coating amount of the gravure coating is 15-25 g/m 2 Drying the coated film by an oven and drying the film by adopting a sectional temperature control program, preferably, the sectional temperature control program can be 70-90-70 ℃. The temperature of the hot pressing is80-100 ℃ and the pressure is 0.05-0.08 MPa. The temperature of the aging is 55 to 100 ℃, preferably 65 to 90 ℃, and more preferably 70 to 80 ℃. The aging time is 1 to 7 days, preferably 3 to 7 days, and more preferably 5 to 7 days. The thickness of the aluminum matrix is preferably 30 to 50 μm and corona treated before coating with the polyurethane adhesive.
The bonding main agent of the polyurethane adhesive comprises, by mass, 20-70 parts of hydroxyl-terminated polyester polyol and 10-20 parts of polyurethane polymer.
The mass parts of the hydroxyl-terminated polyester polyol can be, but are not limited to, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts and 70 parts. The Tg of the hydroxyl-terminated polyester polyol is-20 to 20 ℃, preferably-20 to 10 ℃, more preferably-10 to 10 ℃. The hydroxyl-terminated polyester polyol has an average molecular weight of 500 to 60000, preferably 1000 to 50000, and more preferably 5000 to 30000. The hydroxyl value of the hydroxyl-terminated polyester polyol is 2 to 50mgKOH/g, preferably 2 to 30mgKOH/g, and more preferably 5 to 20mgKOH/g. The acid value of the hydroxyl-terminated polyester polyol is 0.5 to 30mgKOH/g, preferably 0.5 to 20mgKOH/g, and more preferably 0.5 to 10mgKOH/g.
The preparation raw materials of the polyester polyol containing the terminal hydroxyl comprise 10 to 50 parts of aliphatic dibasic acid, 5 to 30 parts of aromatic dicarboxylic acid or anhydride, 30 to 70 parts of polyhydric alcohol with the average functionality of 2 to 3.5 and 0 to 5 parts of catalyst in parts by mass. The aliphatic dibasic acid is preferably 10 to 40 parts, more preferably 20 to 45 parts, and the aliphatic dibasic acid includes but is not limited to adipic acid and sebacic acid. The aromatic dicarboxylic acid or anhydride is preferably 5 to 20 parts, more preferably 10 to 20 parts, and the aromatic dicarboxylic acid includes, but is not limited to, phthalic acid and isophthalic acid. Anhydrides include, but are not limited to, phthalic anhydride. The polyol is preferably 30 to 60 parts, more preferably 35 to 55 parts, and includes, but is not limited to, neopentyl glycol, propylene glycol, ethylene glycol, diethylene glycol, or modified bisphenol a. The catalyst is preferably 1 to 5 parts, more preferably 1 to 3 parts, and the catalyst includes, but is not limited to, sodium hydroxide, lithium hydroxide, lead oxide, organotin, organotitanium or organozinc, and the use of a basic catalyst is preferred.
The mass parts of the polyurethane polymer may be, but are not limited to, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts. The Tg of the polyurethane polymer is from 40 to 100 deg.C, preferably from 50 to 90 deg.C, more preferably from 60 to 80 deg.C. The average molecular weight of the polyurethane polymer is from 500 to 50000, preferably from 1000 to 40000, more preferably from 5000 to 30000. The hydroxyl value of the polyurethane polymer is 2 to 50mgKOH/g, preferably 2 to 30mgKOH/g, and more preferably 5 to 20mgKOH/g. The polyurethane polymer has a residual isocyanate monomer content of less than 5%, preferably less than 2%, more preferably less than 0.5%.
The preparation raw materials of the polyurethane polymer comprise, by mass, 5-60 parts of isocyanate, 5-40 parts of polymeric polyol with the average molecular weight of 500-6000, 0-10 parts of aliphatic monohydric alcohol or dihydric alcohol and 0.5-15 parts of polyamine with the molecular weight of less than 500. The mass fraction of isocyanate is preferably 20 to 40%, and the isocyanate may be a mono-isocyanate or a diisocyanate. Diisocyanates include, but are not limited to, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, or tetramethylene diisocyanate. The mass portion of the polymeric polyol is preferably 10-30%, the preparation raw material of the polyurethane polymer comprises the polymeric polyol, and the polymeric polyol comprises the polyol with a main chain of polyester, polyether or polyolefin and a functionality of 2-3. The polymeric polyol preferably has a molecular weight of 500 to 2500 and a functionality of 1.8 to 4. Preferably, the polymeric polyol is a polyol having a polyester as a backbone. The aliphatic monohydric alcohol or dihydric alcohol is preferably 5 to 10 parts by mass. The aliphatic monohydric alcohol is aliphatic monohydric alcohol with 1-18 carbon atoms, and preferably ethanol, n-butanol, ethylene glycol monobutyl ether or 1-octanol. Glycols include, but are not limited to, neopentyl glycol, propylene glycol, ethylene glycol or diethylene glycol. The proportion of the polyamine is preferably 5 to 15, and the polyamine is used as a chain extender including, but not limited to, hydrazine, ethylenediamine or isophoronediamine. A solvent may also be added when preparing the polyurethane polymer, and the solvent may be, but is not limited to, acetone, butanone, cyclohexane, toluene, xylene, or ethyl acetate.
The curing agent of the polyurethane adhesive of the present invention is polyisocyanate, and the mass part of the polyisocyanate is 5 to 50 parts, and the mass part of the polyisocyanate can be, but is not limited to, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, and 50 parts. The polyisocyanate is an aromatic polyisocyanate monomer, or the polyisocyanate is an aromatic polyisocyanate copolymer, the content of the aromatic polyisocyanate in the copolymer is 5-20%, and the average functionality is 2-6. As an example, the curing agent is HDI biuret, HDI trimer, IPDI trimer, TDI trimer or TDI-TMP prepolymer.
The preparation raw materials of the polyurethane adhesive comprise hydroxyl-terminated polyester polyol and-OH in a polyurethane polymer, wherein the molar total amount of-NCO in the polyisocyanate is m, the molar amount of-NCO in the polyisocyanate is n, m/n is 1-30, preferably 1-20, more preferably 1.
The preparation raw material of the polyurethane adhesive of the present invention further includes 1-10 parts of oxazoline grafted acrylic resin, and the parts by mass of the oxazoline grafted acrylic resin may be, but are not limited to, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, and 10 parts. The grafting ratio of the oxazoline grafted acrylic resin can be 40%, WS-500 (water-based oxazoline grafted acrylic resin) of ECOPROS can be selected, the temperature can be raised to 95 ℃, the water is pumped out by using a vacuum pump under negative pressure, and then propylene glycol methyl ether is added to dilute the solvent-based oxazoline grafted acrylic resin with 20% solid content.
The raw materials for preparing the polyurethane adhesive also comprise 40-60 parts of solvent, and the parts by weight of the solvent can be, but are not limited to, 40 parts, 45 parts, 50 parts, 55 parts and 60 parts by way of example. The solvent may be, but not limited to, a low boiling point solvent such as cyclohexane, acetone, methyl ethyl ketone, ethanol, isopropanol or ethyl acetate, and preferably is a miscible solvent of two or more of the above, wherein the water content of the solvent should be less than 500ppm.
The preparation raw materials of the polyurethane adhesive also comprise 0-5 parts of an auxiliary agent, and the auxiliary agent can be, by way of example and not limitation, 0, 1, 2, 3, 4 and 5 parts by mass. The auxiliary agent comprises a catalyst and/or a promoter. The catalyst can be but is not limited to an organotin drier T12, and the adhesion promoter can be but is not limited to a silane coupling agent KH560.
The polyurethane adhesive is colorless or light yellow transparent liquid in appearance, has the viscosity of 100-3000 mPa.s, the solid content of 30-50 percent, the pH value of 7.0-8.5, the hydroxyl value (solid part) of 5-20 mgKOH/g, the acid value of 2-10 mgKOH/g and the activation period of more than 6 h.
The preparation method of the polyurethane adhesive comprises the following steps:
(1) Preparing hydroxyl-terminated polyester polyol;
(2) Preparing a polyurethane polymer;
(3) Mixing the hydroxyl-terminated polyester polyol, the polyurethane polymer, the auxiliary agent and the solvent to obtain a mixture;
(4) And stirring and mixing the mixture, the polyisocyanate and the modified acrylic resin.
Wherein, the preparation of the hydroxyl-terminated polyester polyol in the step (1) comprises the following steps: under the protection of nitrogen, adding polyol into a reaction kettle, heating to 110-150 ℃, adding carboxylic acid, anhydride and a catalyst after the polyol is completely molten, heating to 200-250 ℃, and removing water generated by esterification reaction through a water removal device. The esterification or transesterification reaction of this reaction may be carried out simultaneously. After the water is removed, the hydroxyl value is detected to be 5-20 mg KOH/g, and the acid value is less than 2mg KOH/g, and then the material can be discharged.
Step (2) preparation of polyurethane polymer comprising: putting polymeric polyol, aliphatic monohydric alcohol or dihydric alcohol into a reaction kettle under the protection of nitrogen, heating to 100-120 ℃ for reaction, and removing water generated by esterification through vacuum. Adding isocyanate, heating for reaction, adding dihydric alcohol with carboxyl and solvent, reducing the temperature to 80-90 ℃, keeping the reaction until the residual NCO content is about 2%, and then reducing the temperature to 60 ℃. Adding enough solvent into the prepolymer under the condition of strong stirring, and slowly adding the diluted polyamine after the prepolymer is completely dispersed. The remaining NCO was reacted completely by back-extension until no NCO was detected by IR spectroscopy, cooled to 30 ℃ and the discharge filtered.
To better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples. It should be noted that the following implementation of the method is a further explanation of the present invention, and should not be taken as a limitation of the present invention.
(1) Preparation of hydroxyl-terminated polyester polyols
(1) Preparation of hydroxyl-terminated polyester polyol A1
2326g of 1,4-cyclohexanedimethanol, 1140g of diethylene glycol, 20.5g of trimethylolpropane and 8g of dibutyltin oxide were accurately weighed and charged together into a 10-L four-necked flask. And introducing nitrogen, raising the reaction temperature to 130 ℃ at the speed of 1 ℃/min, adding 335g of terephthalic acid and 505g of isophthalic acid after reactants are completely dissolved, raising the temperature to 220 ℃ at the speed of 2 ℃/min, and continuously removing water generated in the esterification reaction in the process of raising the temperature. When the esterified water is not obviously discharged, preserving the heat for 2 hours, adding 2887g of adipic acid and 8.6g of antioxidant 1010, continuously heating to 250 ℃ for reaction, and continuously discharging the esterified water until the hydroxyl value is detected to be 5-20 mg KOH/g, the acid value is less than 2mg KOH/g, and discharging the material, wherein the Tg is-20 ℃.
(2) Preparation of hydroxyl-terminated polyester polyol A2
2326g of 1,4-cyclohexanedimethanol, 1140g of diethylene glycol and 8g of dibutyltin oxide were accurately weighed and charged together into a 10-L four-necked flask. And introducing nitrogen, raising the reaction temperature to 130 ℃ at the speed of 1 ℃/min, adding 390g of terephthalic acid and 780g of phthalic acid after reactants are completely dissolved, raising the temperature to 220 ℃ at the speed of 2 ℃/min, and continuously removing water generated in the esterification reaction in the process of raising the temperature. Keeping the temperature for 2 hours when the esterified water is not obviously discharged, adding 2500g of adipic acid and 6.6g of antioxidant 1010, continuously heating to 250 ℃ for reaction, and continuously discharging the esterified water until the hydroxyl value is detected to be 5-20 mg KOH/g, the acid value is less than 2mg KOH/g, and then discharging, wherein the Tg is-20 ℃.
(3) Preparation of hydroxyl-terminated polyester polyol A3
800g of neopentyl glycol, 1500g of 1, 3-propanediol, 20.5g of trimethylolpropane and 8g of dibutyltin oxide were accurately weighed and charged together in a 10L four-necked flask. And introducing nitrogen, raising the reaction temperature to 130 ℃ at the speed of 1 ℃/min, adding 138g of terephthalic acid and 700g of isophthalic acid after reactants are completely dissolved, raising the temperature to 220 ℃ at the speed of 2 ℃/min, and continuously removing water generated in the esterification reaction in the process of raising the temperature. When the esterified water is not obviously discharged, preserving the heat for 2 hours, adding 2887g of adipic acid and 6.6g of antioxidant 1010, continuously heating to 250 ℃ for reaction, and continuously discharging the esterified water until the hydroxyl value is detected to be 5-20 mg KOH/g, the acid value is less than 2mg KOH/g, and discharging the product, wherein the Tg is-20 ℃.
(2) Preparation of polyurethane polymers
(1) Preparation of polyurethane Polymer B1
100g of polyester polyol having an average molecular weight of 2000 and 9.7g of neopentyl glycol were put into a reaction vessel and heated to 105 ℃ under a nitrogen atmosphere, and moisture was removed by vacuum. After cooling to 80 ℃ and further 105g of HDI and heating to 95 ℃ for 1h, 13g of dimethylolpropionic acid and 86g of ethyl acetate were added and the temperature was lowered to 85 ℃ and the reaction was maintained for 3h until the residual NCO content was about 2%, the temperature was further lowered to 60 ℃. Adding 200g of ethyl acetate into the prepolymer under strong stirring, slowly adding a mixture of 4g of ethylenediamine and 30g of butanone after the prepolymer is completely dispersed, and completely reacting the reserved NCO through chain extension until NCO is no longer detected by an IR (infrared) spectrum and the hydroxyl value is 5-20 mg KOH/g, cooling to 30 ℃, filtering and discharging, wherein the Tg is 50-70 ℃.
(2) Preparation of polyurethane Polymer B2
100g of polyester polyol having an average molecular weight of 2000 and 9.7g of neopentyl glycol were put into a reaction vessel and heated to 105 ℃ under a nitrogen atmosphere, and moisture was removed by vacuum. After cooling to 80 ℃ and further 138g of IPDI and heating to 95 ℃ for 1h, 13g of dimethylolpropionic acid and 86g of ethyl acetate were added, the temperature was lowered to 85 ℃ and the reaction was continued for 3h until the residual NCO content was about 2%, and the temperature was further lowered to 60 ℃. Adding 200g of ethyl acetate into the prepolymer under strong stirring, slowly adding a mixture of 4g of ethylenediamine and 30g of butanone after the prepolymer is completely dispersed, and completely reacting the reserved NCO through chain extension until NCO is no longer detected by an IR (infrared) spectrum and the hydroxyl value is 5-20 mg KOH/g, cooling to 30 ℃, filtering and discharging, wherein the Tg is 50-70 ℃.
(3) Preparation of polyurethane Polymer B3
150g of a polyester polyol having an average molecular weight of 2000 and 9.7g of propylene glycol were put into a reaction vessel under a nitrogen gas atmosphere, heated to 105 ℃ and then the water was removed by vacuum. Cooling to 80 ℃, adding 112g of toluene diisocyanate, heating to 90 ℃, reacting for 2h, adding 13g of dimethylolpropionic acid and 100g of ethyl acetate, cooling to 85 ℃, keeping the reaction for 3h until the residual content of NCO is about 2%, and continuously cooling to 60 ℃. Adding 200g of ethyl acetate into the prepolymer under strong stirring, slowly adding a mixture of 3g of isophorone diamine and 30g of butanone after the prepolymer is completely dispersed, and completely reacting the reserved NCO through chain extension until NCO is no longer detected by IR (infrared) spectroscopy, cooling to 30 ℃ when the hydroxyl value is 5-20 mg KOH/g, filtering and discharging, wherein the Tg is 50-70 ℃.
(4) Preparation of polyurethane Polymer B4
100g of a polyacetal polyol having an average molecular weight of 2000 and 9.7g of neopentyl glycol were put into a reaction vessel and heated to 105 ℃ under a nitrogen atmosphere, and moisture was removed by vacuum evacuation. After a further 105g of HDI and heating to 130 ℃ for 1h, 13g of dimethylolpropionic acid and 86g of ethyl acetate were added, the temperature was lowered to 85 ℃ and the reaction was held for 3h until the residual NCO content was approximately 2%, and the temperature was further lowered to 60 ℃. And adding 200g of ethyl acetate into the prepolymer under strong stirring, slowly adding a mixture of 4g of ethylenediamine and 30g of butanone after the prepolymer is completely dispersed, and completely reacting the reserved NCO through chain extension until NCO is no longer detected by an IR (infrared) spectrum and the hydroxyl value is 5-20 mg KOH/g, cooling to 30 ℃, filtering and discharging.
Example 1
This example is a polyurethane adhesive, which is prepared from 1400g of hydroxyl-terminated polyester polyol a, 60g of polyurethane polymer B, 115g of TDI-TMP polymer, 10g of oxazoline grafted acrylic resin, 400g of butanone, 400g of ethyl acetate, 560 g of KH, and 0.7g of T12.
Example 2
This example is a polyurethane adhesive, which is prepared from 1350g of hydroxyl-terminated polyester polyol a, 100g of polyurethane polymer B, 115g of TDI-TMP polymer, 13g of oxazoline grafted acrylic resin, 400g of butanone, 400g of ethyl acetate, 560 g of KH, and 0.7g of T12.
Example 3
This example is a polyurethane adhesive, which is prepared from 1400g of hydroxyl-terminated polyester polyol a, 60g of polyurethane polymer B, 115g of TDI-TMP polymer, 10g of oxazoline grafted acrylic resin, 400g of butanone, 400g of ethyl acetate, 560 g of KH, and 0.7g of T12.
Example 4
This example is a polyurethane adhesive, which is prepared from 1400g of hydroxyl-terminated polyester polyol a, 60g of polyurethane polymer B, 115g of TDI-TMP polymer, 10g of oxazoline grafted acrylic resin, 400g of butanone, 400g of ethyl acetate, 560 g of KH, and 0.7g of T12.
Example 5
This example is a polyurethane adhesive, which is prepared from 2400g of hydroxyl-terminated polyester polyol a, 60g of polyurethane polymer B, 115g of TDI-TMP polymer, 10g of oxazoline grafted acrylic resin, 400g of butanone, 400g of ethyl acetate, 560 g of KH, and 0.7g of T12.
Example 6
This example is a polyurethane adhesive, and the raw materials for its preparation include 3400g of hydroxyl-terminated polyester polyol a, 60g of polyurethane polymer B, 115g of TDI-TMP polymer, 10g of oxazoline grafted acrylic resin, 400g of butanone, 400g of ethyl acetate, 560 g of KH, and 0.7g of T12.
Comparative example 1
This example is a polyurethane adhesive, which is prepared from a hydroxyl-terminated polyester polyol A1410g, a polyurethane polymer B2 g, TDI-TMP polymer 115g, butanone 400g, ethyl acetate 400g, KH560 g, and T12.7 g.
Comparative example 2
The embodiment is a polyurethane adhesive, and the preparation raw materials comprise 1400g of hydroxyl-terminated polyester polyol A, 60g of polyurethane polymer B, 115g of TDI-TMP polymer, 10g of oxazoline grafted acrylic resin, 400g of butanone, 400g of ethyl acetate, 560 g of KH, and 0.7g of T12.
The polyurethane adhesives of examples 1 to 6 and comparative examples 1 to 2 were used to attach nylon films to aluminum substrates, respectively, to prepare aluminum-plastic films. Cutting the aluminum-plastic film into sample strips of 15mm by 230mm by using a cutter, and testing the peel strength by using a tensile machine; the specimens were immersed in 75 ℃ water and boiled for 7d to observe delamination. And (3) punching each aluminum-plastic film into a rectangular aluminum-plastic shell with the length of 65mm, the width of 50mm and the depth of 4mm by using a shell punching machine, putting the rectangular aluminum-plastic shell into a double-85 oven, and baking the rectangular aluminum-plastic shell for 168 hours to observe white lines and layering conditions, wherein the test results are shown in table 1.
Wherein, the peel strength test is carried out according to the standard of GB/T2792-2014 test method for the peel strength of the adhesive tape, the stretching speed is (100 +/-50) mm/min, and the stretching direction and the part which is not peeled form a T shape.
The boiling resistance test adopts a HWS12 type electric heating constant temperature water bath kettle, the temperature is set to be 75 ℃ for boiling a sample strip for 7d, the layering situation is observed after the 1 st day, the 3 rd day and the 7 th day respectively, if the sample strip is not layered, the peeling strength is tested according to the standard of GB/T2792-2014 adhesive tape peeling strength test method, the stretching speed is (100 +/-50) mm/min, and the stretching direction and the un-peeled part are in a T shape.
The damp and heat resistance test is to put the aluminum plastic film after the shell punching molding into a double 85 oven, and test Cab according to the part 2 of the test method of GB/T2423.3-2006 Electrical and electronic product environmental test: the constant weight damp-heat test was conducted according to the standard, and the presence or absence of white lines and delamination were observed after the 1 st, 3 rd and 7 th days, respectively.
Table a test result of the performance of each embodiment
Figure BDA0003996590900000111
The results in table 1 show that the polyurethane adhesive of the present invention has high peel strength, and the raw materials for preparing the polyurethane adhesive have oxazoline grafted acrylic resin, and the polyurethane adhesive is prepared by using the polyol with a main chain of polyester, polyether or polyolefin and a functionality of 2 to 3 as the polymeric polyol, so that the polyurethane adhesive has good moist heat resistance and boiling resistance, thereby satisfying the high performance requirement of the aluminum plastic film.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it is not limited to the embodiments, and those skilled in the art should understand that the technical solutions of the present invention can be modified or substituted with equivalents without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. The polyurethane adhesive is characterized by comprising, by mass, 20-70 parts of hydroxyl-terminated polyester polyol, 10-20 parts of polyurethane polymer, 5-50 parts of polyisocyanate, 1-10 parts of oxazoline grafted acrylic resin and 0-5 parts of auxiliary agent, wherein the Tg of the hydroxyl-terminated polyester polyol is-20 ℃, the Tg of the polyurethane polymer is 40-100 ℃, and the raw material for preparing the polyurethane polymer comprises polymeric polyol, wherein the polymeric polyol comprises polyol with a main chain of polyester, polyether or polyolefin and a functionality of 2-3.
2. The polyurethane adhesive according to claim 1, wherein the hydroxyl-terminated polyester polyol has an average molecular weight of 500 to 60000, a hydroxyl value of 2 to 50mgKOH/g, and an acid value of 0.5 to 30mgKOH/g, and the hydroxyl-terminated polyester polyol is prepared from, in parts by mass, 10 to 50 parts of an aliphatic dibasic acid, 5 to 30 parts of an aromatic dibasic acid or anhydride, 30 to 70 parts of a polyol having an average functionality of 2 to 3.5, and 0 to 5 parts of a catalyst.
3. The polyurethane adhesive according to claim 1, wherein the polyurethane polymer has an average molecular weight of 500-50000 and a hydroxyl value of 2-50 mgKOH/g, and the polyurethane polymer is prepared from 5-60 parts by mass of isocyanate, 5-40 parts by mass of a polymeric polyol having an average molecular weight of 500-6000, 0-10 parts by mass of an aliphatic monohydric or dihydric alcohol, and 0.5-15 parts by mass of a polyamine having a molecular weight of less than 500.
4. The polyurethane adhesive of claim 1, wherein the polyisocyanate is an aromatic polyisocyanate monomer, or the polyisocyanate is an aromatic polyisocyanate copolymer and the aromatic polyisocyanate content in the copolymer is 5 to 20%, and the average functionality is 2 to 6.
5. The polyurethane adhesive of claim 1, wherein the hydroxyl-terminated polyester polyol and the polyurethane polymer have a total molar amount of-OH in m, the polyisocyanate has a molar amount of-NCO in n, and m/n is 1 to 30.
6. The polyurethane adhesive of claim 1, wherein the raw materials further comprise a solvent, the solvent is at least one of cyclohexane, acetone, butanone, ethanol, isopropanol and ethyl acetate, and the auxiliary agent comprises a catalyst and/or an accelerator.
7. The method for preparing the polyurethane adhesive according to any one of claims 1 to 6, comprising the steps of:
(1) Preparing polyester polyol containing terminal hydroxyl;
(2) Preparing a polyurethane polymer;
(3) Mixing the hydroxyl-terminated polyester polyol, the polyurethane polymer, the auxiliary agent and the solvent to obtain a mixture;
(4) And stirring and mixing the mixture, the polyisocyanate and the modified acrylic resin.
8. An aluminum-plastic film comprising an aluminum substrate and a nylon film adhered to the aluminum substrate with an adhesive, wherein the adhesive is the polyurethane adhesive according to any one of claims 1 to 6 or the polyurethane adhesive prepared by the method of claim 7.
9. The method for preparing an aluminum-plastic film according to claim 8, comprising the steps of: and compounding a nylon film on the aluminum substrate by sequentially adopting gravure coating and hot pressing modes of the polyurethane adhesive, and curing.
10. The method for producing an aluminum-plastic film according to claim 9, comprising at least one of the following features (1) to (3):
(1) the glue applying amount of the gravure coating is 15-25 g/m 2 Drying the coated film by an oven and drying the coated film by adopting a sectional temperature control program;
(2) the temperature of the hot pressing is 80-100 ℃, and the pressure is 0.05-0.08 MPa;
(3) the curing temperature is 55-100 ℃, and the curing time is 1-7 d.
CN202211629141.0A 2022-12-13 2022-12-13 Polyurethane adhesive and preparation method thereof, aluminum plastic film and preparation method thereof Pending CN115975578A (en)

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