CN114591712A - Environment-friendly water-based laminating adhesive and preparation method thereof - Google Patents
Environment-friendly water-based laminating adhesive and preparation method thereof Download PDFInfo
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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
- C09J175/08—Polyurethanes from 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
- C09J11/04—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
- 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
- C09J11/08—Macromolecular additives
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/329—Phosphorus containing acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses an environment-friendly aqueous laminating adhesive and a preparation method thereof, and relates to the technical field of aqueous adhesives. The environment-friendly water-based laminating adhesive is prepared by preparing a polyurethane prepolymer from diphenylmethane diisocyanate and polypropylene glycol-2000 as raw materials, preparing a fluorine-containing hydrolysis-resistant block copolymer from dodecafluoroheptyl methacrylate, allyl propyl ether and hydroxyethyl methacrylate as raw materials, and adding water to adjust the solid content after the polyurethane prepolymer, the fluorine-containing hydrolysis-resistant block copolymer and a repair flame retardant are cured to obtain the environment-friendly water-based laminating adhesive. After the laminating adhesive meets flame and heat flow, the repairing flame retardant can form a compact carbon layer structure with good strength to cover the surface of a polyurethane carbon chain, so that the environment-friendly water-based laminating adhesive is prevented from being burnt and heated, and the repairing performance and the flame retardant performance of the environment-friendly water-based laminating adhesive are improved; the cured product of the polyurethane prepolymer and the fluorine-containing hydrolysis-resistant block copolymer has good thermal stability and weather resistance, and the environment-friendly water-based laminating adhesive with flame retardance, weather resistance and strong bonding force is obtained.
Description
Technical Field
The invention relates to the technical field of water-based adhesives, in particular to an environment-friendly water-based laminating adhesive and a preparation method thereof.
Background
The aqueous polyurethane adhesive is formed by dissolving or dispersing polyurethane in water, and the aqueous laminating adhesive is one of aqueous polyurethane adhesives and is generally used for laminating films. The paper-plastic laminating adhesive not only requires good adhesive force to the surface of a plastic film with non-polarity and low surface energy, but also requires good adhesive force to the surface of paper with polarity; but also must have good affinity for the ink, which places special demands on paper-plastic laminates. The water-based laminating adhesive takes water as a dispersion medium, and has the advantages of low production cost, little pollution, safe use and wide development prospect.
The invention patent of the publication No. CN110218536B discloses a water-based paper-plastic laminating adhesive and a preparation method thereof, and discloses a high vinyl acetate content emulsion paper-plastic laminating adhesive which is prepared by adopting a seed emulsion polymerization process, wherein monomers used in the seed emulsion polymerization process comprise a hard monomer, a soft monomer and a functional monomer, the hard monomer mainly comprises vinyl acetate and accounts for 80-90wt% of the hard monomer, and other hard monomers are selected from one or more of acrylonitrile, methyl methacrylate and methyl acrylate. However, the following technical problems exist: the laminating adhesive cannot form a flame-retardant structure on the surface of polyurethane after meeting flame and heat flow so as to achieve good flame-retardant performance and repair performance, and the later-stage bonding strength needs to be improved.
A solution is now proposed to address the technical drawback in this respect.
Disclosure of Invention
The invention aims to provide an environment-friendly water-based laminating adhesive and a preparation method thereof, which are used for solving the technical problems that in the prior art, the laminating adhesive cannot form a flame-retardant structure on the surface of polyurethane after encountering flame and heat flow so as to achieve good flame-retardant performance and repair performance, and the later-stage bonding strength needs to be improved.
The purpose of the invention can be realized by the following technical scheme:
an environment-friendly aqueous laminating adhesive is prepared by preparing a polyurethane prepolymer from raw materials of diphenylmethane diisocyanate and polypropylene glycol-2000, preparing a fluorine-containing hydrolysis-resistant block copolymer from raw materials of dodecafluoroheptyl methacrylate, allyl propyl ether and hydroxyethyl methacrylate, and adding water to adjust solid content after the polyurethane prepolymer, the fluorine-containing hydrolysis-resistant block copolymer and a repair flame retardant are cured to obtain the environment-friendly aqueous laminating adhesive;
the preparation method of the repair flame retardant comprises the following steps: adding perchloric acid and p-toluenesulfonic acid into a reaction kettle, uniformly mixing, adding flake graphite powder, dropwise adding 10wt% of potassium permanganate aqueous solution, keeping dropwise adding for 1-2 hours, keeping water bath at 50-60 ℃ for heat preservation, and continuously stirring for 45-70 min after the potassium permanganate aqueous solution is dropwise added; naturally cooling to room temperature, adding 30wt% of hydrogen peroxide to adjust the pH of the reaction system to 6-7, carrying out vacuum filtration, washing with ethanol, heating to 180-250 ℃, and carrying out heat preservation and drying for 4-6 hours to obtain expanded graphite; adding piperazine pyrophosphate into the expanded graphite, carrying out ball milling and crushing, and sieving with a sieve of 80-100 meshes.
In the repair flame retardant, the flake graphite powder is natural apparent graphite which is shaped like fish scales, belongs to a hexagonal system, is in a layered structure, and has good high temperature resistance, electric conduction, heat conduction, lubrication, plasticity and acid and alkali resistance. Due to the existence of carbon atoms at the plane edge and unpaired electrons in the crystalline flake graphite, the reactivity is high; perchloric acid is used as an intercalation agent, p-toluenesulfonic acid is used as a catalyst, potassium permanganate aqueous solution and hydrogen peroxide are used as oxidants, and perchloric acid is embedded between flake graphite layers to form expanded graphite with a graphite interlayer compound; because the piperazine pyrophosphate is a halogen-free flame retardant containing hyperbranched piperazine, the flame retardant can serve as a carbon source, an air source and an acid source at the same time, is favorable for reducing the moisture absorption of the expanded graphite, improving the water resistance and the migration resistance of the expanded graphite, can more quickly catalyze the char-forming reaction at high temperature, improves the char-forming capability of the char-forming agent, and is also favorable for improving the compactness of a carbon layer; after the environment-friendly water-based laminating adhesive meets flame and heat flow, moisture and low-molecular volatile substances volatilize, the expanded graphite expands under heating to form a worm-shaped carbon structure, the piperazine pyrophosphate is decomposed under heating to release ammonia, nitrogen and water vapor and form a glass-like substance, the expanded graphite has good fluidity and covers in a loose expanded carbon layer structure, the expanded graphite and the piperazine pyrophosphate are matched to form a compact carbon layer structure with good strength to cover on the surface of a polyurethane carbon chain, further combustion and heating of the environment-friendly water-based laminating adhesive are prevented, and the repair performance and the flame retardant performance of the environment-friendly water-based laminating adhesive are improved.
Further, the mass ratio of the crystalline flake graphite powder to the aqueous solution of p-toluenesulfonic acid and potassium permanganate is 1: 1.5-3: 0.6-1.5 g of flake graphite powder, 3.5-4.2 mL of perchloric acid is added into 1g of flake graphite powder, and the addition amount of piperazine pyrophosphate is 5-10% of the mass of the expanded graphite.
The preparation method of the environment-friendly water-based laminating adhesive comprises the following steps:
preparing a polyurethane prepolymer: adding raw materials of diphenylmethane diisocyanate and polypropylene glycol-2000 into a reaction kettle, adding a solvent N, N-dimethylformamide, heating to 60-80 ℃, mechanically stirring under the protection of nitrogen, reacting for 4-6 hours, standing to room temperature, filtering, and removing the solvent by means of reduced pressure concentration to obtain a polyurethane prepolymer;
the reaction principle of the polyurethane prepolymer is as follows:
preparing a fluorine-containing hydrolysis-resistant block copolymer: adding dodecafluoroheptyl methacrylate, allyl propyl ether and hydroxyethyl methacrylate into a reaction kettle, adding a solvent N, N-dimethylformamide, heating to 50-65 ℃, dropwise adding azodiisobutyronitrile into a dropping funnel to initiate reaction, keeping for 1-2 hours until dropwise adding is finished, keeping the temperature and stirring for reaction for 6-8 hours, standing to room temperature, filtering, and removing the solvent by decompression and concentration to obtain the fluorine-containing hydrolysis-resistant block copolymer;
and (3) crosslinking and curing: and mixing the polyurethane prepolymer with the fluorine-containing hydrolysis-resistant block copolymer according to the molar ratio of isocyanate groups to hydroxyl groups of 1: 1.5-1.7, adding a repair flame retardant, uniformly mixing, and adding water to adjust the solid content to 40-60% to obtain the environment-friendly water-based laminating adhesive.
The reaction principle of the preparation and crosslinking curing of the fluorine-containing hydrolysis-resistant block copolymer is as follows:
the fluorine-containing hydrolysis-resistant block copolymer is obtained by condensation polymerization of dodecafluoroheptyl methacrylate, allyl propyl ether and hydroxyethyl methacrylate under the action of an initiator, considering that the fluorine-containing polymer has good thermal stability, weather resistance, water and oil repellency, ether bonds can form hydrogen bonds in water to improve hydrophilicity, the dodecafluoroheptyl methacrylate contains a plurality of carbon-fluorine bonds, the allyl propyl ether contains the ether bonds, the condensation product has moderate hydrophile-lipophile, is not easy to hydrolyze, has good thermal stability and weather resistance, is cured with a polyurethane prepolymer after being well dispersed in water, and is dried to obtain the environment-friendly water-based laminating adhesive layer which is not easy to hydrolyze, flame retardant, weather resistant and strong in binding force.
Further, when the polyurethane prepolymer is prepared, the mass ratio of the diphenylmethane diisocyanate to the polypropylene glycol-2000 is 7.8-8.5: the dosage of the 1, N, N-dimethylformamide is 2-5 times of the mass of the diphenylmethane diisocyanate.
Further, when the fluorine-containing hydrolysis-resistant block copolymer is prepared, the mass ratio of the dodecafluoroheptyl methacrylate to the allyl propyl ether to the hydroxyethyl methacrylate is 0.3-0.5: 1: 0.6-0.8, the dosage of the azodiisobutyronitrile is 1-3% of the mass of the allyl propyl ether, and the dosage of the N, N-dimethylformamide is 1-3 times of the mass of the allyl propyl ether.
Furthermore, the using amount of the repairing flame retardant in crosslinking and curing is 0.6-1.5% of the mass of the polyurethane prepolymer.
The invention has the following beneficial effects:
1. the aqueous laminating adhesive is obtained by adding water to adjust the solid content after the polyurethane prepolymer, the fluorine-containing hydrolysis-resistant block copolymer and the repair flame retardant are cured, and the repair flame retardant can form a compact carbon layer structure with good strength to cover the surface of a polyurethane carbon chain after meeting flame and heat flow, so that the further combustion and heating of the environment-friendly aqueous laminating adhesive are prevented, and the repair performance and the flame retardant performance of the environment-friendly aqueous laminating adhesive are improved; the cured product of the polyurethane prepolymer and the fluorine-containing hydrolysis-resistant block copolymer has good thermal stability and weather resistance, the environment-friendly water-based laminating adhesive with flame retardance, weather resistance and strong bonding force is obtained, the initial bonding strength reaches 14.6-15.4N/mm, the later bonding strength reaches 22.2-23.4N/mm, and the flame retardance meets the FV-0 level requirement.
2. The repairing flame retardant is formed by embedding perchloric acid between flake graphite layers to form expanded graphite with a graphite interlayer compound; the piperazine pyrophosphate serves as a carbon source, an air source and an acid source at the same time, so that the moisture absorption of the expanded graphite is reduced, the water resistance and the mobility resistance of the expanded graphite are improved, and the carbonization reaction can be rapidly catalyzed at high temperature; the piperazine pyrophosphate is heated and decomposed to release ammonia gas, nitrogen gas and water vapor and form a glassy substance, has good fluidity and is covered in a loose expanded carbon layer structure.
3. The fluorine-containing hydrolysis-resistant block copolymer is obtained by condensation polymerization of dodecafluoroheptyl methacrylate, allyl propyl ether and hydroxyethyl methacrylate under the action of an initiator, considering that the fluorine-containing polymer has good thermal stability, weather resistance and water and oil repellency, ether bonds can form hydrogen bonds in water to improve hydrophilicity, the dodecafluoroheptyl methacrylate contains a plurality of carbon-fluorine bonds, the allyl propyl ether contains the ether bonds, and a condensation product is moderate in hydrophile and lipophile, not easy to hydrolyze, good in thermal stability and weather resistance.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a preparation method of an environment-friendly aqueous laminating adhesive, which comprises the following steps:
preparing a polyurethane prepolymer: adding 25kg of diphenylmethane diisocyanate and 3.13kg of polypropylene glycol-2000 into a reaction kettle, adding 65kg of N, N-dimethylformamide serving as a solvent, heating to 66 ℃, mechanically stirring under the protection of nitrogen for reaction for 5.2 hours, standing to room temperature, filtering, and removing the solvent by concentration under reduced pressure to obtain the polyurethane prepolymer.
Preparing a fluorine-containing hydrolysis-resistant block copolymer: adding 3.8kg of dodecafluoroheptyl methacrylate, 10kg of allyl propyl ether and 6.7kg of hydroxyethyl methacrylate into a reaction kettle, adding 25kg of solvent N, N-dimethylformamide, heating to 58 ℃, dropwise adding 0.17kg of azobisisobutyronitrile into a dropping funnel to initiate reaction, keeping the dropwise addition for 1.5 hours, keeping the temperature and stirring for reaction for 7 hours, standing to room temperature, filtering, and removing the solvent by concentration under reduced pressure to obtain the fluorine-containing hydrolysis-resistant block copolymer.
And (3) crosslinking and curing: mixing the polyurethane prepolymer and the fluorine-containing hydrolysis-resistant block copolymer according to the molar ratio of isocyanate group to hydroxyl group of 1:1.56, adding a repair flame retardant accounting for 0.9% of the mass of the polyurethane prepolymer, uniformly mixing, and adding water to adjust the solid content to 52% to obtain the environment-friendly water-based laminating adhesive.
The preparation method of the repair flame retardant comprises the following steps: adding 3.8L perchloric acid and 2.6kg p-toluenesulfonic acid into a reaction kettle, uniformly mixing, adding 1kg of crystalline flake graphite powder, dropwise adding 0.8kg of 10wt% potassium permanganate aqueous solution, keeping dropwise adding for 1.5 hours, preserving heat in a 53 ℃ water bath, and continuously stirring for 60min after the potassium permanganate aqueous solution is dropwise added; naturally cooling to room temperature, adding 30wt% of hydrogen peroxide to adjust the pH of the reaction system to 6.5, carrying out vacuum filtration, washing with ethanol, heating to 215 ℃, and carrying out heat preservation and drying for 5.5 hours to obtain expanded graphite; adding piperazine pyrophosphate with the mass of 6% into the expanded graphite, carrying out ball milling and crushing, and sieving with a 80-mesh sieve.
Example 2
The embodiment provides a preparation method of an environment-friendly water-based laminating adhesive, which comprises the following steps:
preparing a polyurethane prepolymer: adding 25kg of diphenylmethane diisocyanate and 3.05kg of polypropylene glycol-2000 as raw materials into a reaction kettle, adding 90kg of solvent N, N-dimethylformamide, heating to 75 ℃, mechanically stirring and reacting for 4.5 hours under the protection of nitrogen, standing to room temperature, filtering, and removing the solvent by reduced pressure concentration to obtain the polyurethane prepolymer.
Preparing a fluorine-containing hydrolysis-resistant block copolymer: adding 4.2kg of dodecafluoroheptyl methacrylate, 10kg of allyl propyl ether and 7.5kg of hydroxyethyl methacrylate into a reaction kettle, adding 18kg of solvent N, N-dimethylformamide, heating to 62 ℃, dropwise adding 0.25kg of azobisisobutyronitrile into a dropping funnel to initiate reaction, keeping the dropwise addition for 1.6 hours, keeping the temperature and stirring for reaction for 7.5 hours, standing to room temperature, filtering, and removing the solvent by concentration under reduced pressure to obtain the fluorine-containing hydrolysis-resistant block copolymer.
And (3) crosslinking and curing: mixing the polyurethane prepolymer and the fluorine-containing hydrolysis-resistant block copolymer according to the molar ratio of isocyanate group to hydroxyl group of 1:1.62, adding a repair flame retardant accounting for 1.1% of the mass of the polyurethane prepolymer, uniformly mixing, and adding water to adjust the solid content to 48% to obtain the environment-friendly water-based laminating adhesive.
The preparation method of the repair flame retardant comprises the following steps: adding 3.7L perchloric acid and 2.5kg p-toluenesulfonic acid into a reaction kettle, uniformly mixing, adding 1kg of crystalline flake graphite powder, dropwise adding 1.3kg of 10wt% potassium permanganate aqueous solution, keeping dropwise adding for 2 hours, preserving heat in a water bath at 57 ℃, and continuously stirring for 62min after the potassium permanganate aqueous solution is dropwise added; naturally cooling to room temperature, adding 30wt% of hydrogen peroxide to adjust the pH of the reaction system to 6.5, carrying out vacuum filtration, washing with ethanol, heating to 225 ℃, and carrying out heat preservation and drying for 4.5 hours to obtain expanded graphite; adding 7% by mass of piperazine pyrophosphate into the expanded graphite, carrying out ball milling and crushing, and sieving by a 90-mesh sieve.
Example 3
The embodiment provides a preparation method of an environment-friendly aqueous laminating adhesive, which comprises the following steps:
preparing a polyurethane prepolymer: adding 25kg of diphenylmethane diisocyanate and 3.16kg of polypropylene glycol-2000 as raw materials into a reaction kettle, adding 100kg of solvent N, N-dimethylformamide, heating to 76 ℃, mechanically stirring under the protection of nitrogen, reacting for 5.6 hours, standing to room temperature, filtering, and removing the solvent by concentration under reduced pressure to obtain the polyurethane prepolymer.
Preparing a fluorine-containing hydrolysis-resistant block copolymer: adding 4.2kg of dodecafluoroheptyl methacrylate, 10kg of allyl propyl ether and 7.8kg of hydroxyethyl methacrylate into a reaction kettle, adding 25kg of solvent N, N-dimethylformamide, heating to 63 ℃, dropwise adding 0.28kg of azobisisobutyronitrile into a dropping funnel to initiate reaction, keeping the dropwise addition for 2 hours, keeping the temperature and stirring for reaction for 7.6 hours, standing to room temperature, filtering, and removing the solvent by concentration under reduced pressure to obtain the fluorine-containing hydrolysis-resistant block copolymer.
And (3) crosslinking and curing: mixing the polyurethane prepolymer and the fluorine-containing hydrolysis-resistant block copolymer according to the molar ratio of isocyanate group to hydroxyl group of 1:1.67, adding a repair flame retardant accounting for 1.1% of the mass of the polyurethane prepolymer, uniformly mixing, and adding water to adjust the solid content to 56% to obtain the environment-friendly water-based laminating adhesive.
The preparation method of the repair flame retardant comprises the following steps: adding 3.9L perchloric acid and 1.9kg p-toluenesulfonic acid into a reaction kettle, uniformly mixing, adding 1kg of crystalline flake graphite powder, dropwise adding 1.4kg of 10wt% potassium permanganate aqueous solution, keeping dropwise adding for 1.8 hours, preserving heat in a 60 ℃ water bath, and continuously stirring for 62min after the potassium permanganate aqueous solution is dropwise added; naturally cooling to room temperature, adding 30wt% of hydrogen peroxide to adjust the pH of the reaction system to 7, carrying out vacuum filtration, washing with ethanol, heating to 218 ℃, and carrying out heat preservation and drying for 5.5 hours to obtain expanded graphite; adding piperazine pyrophosphate with the mass of 9% into the expanded graphite, carrying out ball milling and crushing, and sieving with a 100-mesh sieve.
Example 4
The embodiment provides a preparation method of an environment-friendly aqueous laminating adhesive, which comprises the following steps:
preparing a polyurethane prepolymer: adding 25kg of diphenylmethane diisocyanate and 2.94kg of polypropylene glycol-2000 as raw materials into a reaction kettle, adding 112.5kg of solvent N, N-dimethylformamide, heating to 78 ℃, mechanically stirring under the protection of nitrogen for reaction for 6 hours, standing to room temperature, filtering, and removing the solvent by reduced pressure concentration to obtain the polyurethane prepolymer.
Preparing a fluorine-containing hydrolysis-resistant block copolymer: adding 3.5kg of dodecafluoroheptyl methacrylate, 10kg of allyl propyl ether and 6.8kg of hydroxyethyl methacrylate into a reaction kettle, adding 28kg of solvent N, N-dimethylformamide, heating to 65 ℃, dropwise adding azobisisobutyronitrile into a dropping funnel to initiate reaction, keeping the dropwise adding for 2 hours, keeping the temperature and stirring for reaction for 7.8 hours, standing to room temperature, filtering, and removing the solvent by concentration under reduced pressure to obtain the fluorine-containing hydrolysis-resistant block copolymer.
And (3) crosslinking and curing: mixing the polyurethane prepolymer and the fluorine-containing hydrolysis-resistant block copolymer according to the molar ratio of isocyanate group to hydroxyl group of 1:1.64, adding a repair flame retardant accounting for 1.3% of the mass of the polyurethane prepolymer, uniformly mixing, and adding water to adjust the solid content to 57% to obtain the environment-friendly water-based laminating adhesive.
The preparation method of the repair flame retardant comprises the following steps: adding 3.7L perchloric acid and 2.7kg p-toluenesulfonic acid into a reaction kettle, uniformly mixing, adding 1kg of crystalline flake graphite powder, dropwise adding 0.8kg of 10wt% potassium permanganate aqueous solution, keeping dropwise adding for 2 hours, preserving heat in a water bath at 57 ℃, and continuously stirring for 62min after the potassium permanganate aqueous solution is dropwise added; naturally cooling to room temperature, adding 30wt% of hydrogen peroxide to adjust the pH value of the reaction system to 7, carrying out vacuum filtration, washing with ethanol, heating to 240 ℃, and carrying out heat preservation and drying for 5.5 hours to obtain expanded graphite; adding 7% by mass of piperazine pyrophosphate into the expanded graphite, carrying out ball milling and crushing, and sieving by using a 80-mesh sieve.
Example 5
The embodiment provides a preparation method of an environment-friendly aqueous laminating adhesive, which comprises the following steps:
preparing a polyurethane prepolymer: adding 25kg of diphenylmethane diisocyanate and 3.01kg of polypropylene glycol-2000 into a reaction kettle, adding 115kg of solvent N, N-dimethylformamide, heating to 78 ℃, mechanically stirring under the protection of nitrogen, reacting for 5.8 hours, standing to room temperature, filtering, and removing the solvent by concentration under reduced pressure to obtain the polyurethane prepolymer.
Preparing a fluorine-containing hydrolysis-resistant block copolymer: adding 4.8kg of dodecafluoroheptyl methacrylate, 10kg of allyl propyl ether and 6.6kg of hydroxyethyl methacrylate into a reaction kettle, adding 28kg of solvent N, N-dimethylformamide, heating to 65 ℃, dropwise adding 0.24kg of azobisisobutyronitrile into a dropping funnel to initiate reaction, keeping the dropwise addition for 2 hours, stirring and reacting for 8 hours under the condition of heat preservation, standing to room temperature, filtering, and removing the solvent by concentration under reduced pressure to obtain the fluorine-containing hydrolysis-resistant block copolymer.
And (3) crosslinking and curing: mixing the polyurethane prepolymer and the fluorine-containing hydrolysis-resistant block copolymer according to the molar ratio of isocyanate group to hydroxyl group of 1:1.68, adding a repair flame retardant accounting for 1.4% of the mass of the polyurethane prepolymer, uniformly mixing, and adding water to adjust the solid content to 60% to obtain the environment-friendly water-based laminating adhesive.
The preparation method of the repair flame retardant comprises the following steps: adding 4.1L perchloric acid and 2.5kg p-toluenesulfonic acid into a reaction kettle, uniformly mixing, adding 1kg of crystalline flake graphite powder, dropwise adding 1.4kg of 10wt% potassium permanganate aqueous solution, keeping dropwise adding for 1.8 hours, preserving heat in a 59 ℃ water bath, and continuously stirring for 65min after the potassium permanganate aqueous solution is dropwise added; naturally cooling to room temperature, adding 30wt% of hydrogen peroxide to adjust the pH of the reaction system to 7, carrying out vacuum filtration, washing with ethanol, heating to 240 ℃, and carrying out heat preservation and drying for 6 hours to obtain expanded graphite; adding piperazine pyrophosphate with the mass of 10% into the expanded graphite, carrying out ball milling and crushing, and sieving with a 100-mesh sieve.
Comparative example 1
This comparative example differs from example 5 in that no repair flame retardant was added.
Comparative example 2
This comparative example differs from example 5 in that dodecafluoroheptyl methacrylate was replaced with methacrylic acid in the preparation of the fluorine-containing hydrolysis-resistant block copolymer.
Comparative example 3
This comparative example differs from example 5 in that the fluorine-containing hydrolysis resistant block copolymer was prepared by replacing allyl propyl ether with n-butyl acrylate.
Performance testing
The initial bonding strength and the later bonding strength of the environment-friendly aqueous laminating adhesives prepared in the examples 1-5 and the comparative examples 1-3 are tested according to the standard GB/T19340-:
| test item | Initial bond Strength (N/mm) | Late stage bond Strength (N/mm) | Flame retardant properties |
| Example 1 | 14.6 | 22.2 | Meets the FV-0 grade requirement |
| Example 2 | 14.8 | 22.7 | Meets the FV-0 grade requirement |
| Example 3 | 14.9 | 22.9 | Meets the FV-0 grade requirement |
| Example 4 | 15.1 | 23.1 | Meets the FV-0 grade requirement |
| Example 5 | 15.4 | 23.4 | Meets the FV-0 grade requirement |
| Comparative example 1 | 14.1 | 20.8 | Flame combustion time of 15min, not meeting the FV-0 grade requirement |
| Comparative example 2 | 12.7 | 16.9 | Meets the FV-0 grade requirement |
| Comparative example 3 | 13.4 | 19.7 | Meets the FV-0 grade requirement |
From the table, the initial bonding strength and the later bonding strength of the environment-friendly water-based laminating adhesive prepared by the embodiment of the invention are superior to those of a comparative example, and the later bonding strength is obviously improved compared with the initial bonding strength, which shows that the environment-friendly water-based laminating adhesive can be quickly crystallized and adhered after bonding. In the comparative example 1, as the repair flame retardant is not added, a compact carbon layer structure with good strength cannot be formed to cover the surface of the polyurethane carbon chain, and the flame retardant property is obviously reduced; in the comparative example 2, the dodecafluoroheptyl methacrylate is replaced by methacrylic acid, so that the flame-retardant and weather-resistant water-based composite film adhesive layer cannot be obtained, and the later-stage bonding strength is also obviously reduced; comparative example 3 there was a slight decrease in both the early and late bond strengths due to the replacement of allyl propyl ether with n-butyl acrylate. The application range of the environment-friendly water-based laminating adhesive comprises but is not limited to plastic-plastic compounding (soft compounding between any two base materials in plastic films such as CPP, BOPP, PE, PET and the like) and aluminum-plastic compounding (soft compounding between aluminum foil and plastic films such as CPP, BOPP, PE, PET, PA and the like).
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the invention as defined in the following claims.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (6)
1. An environment-friendly aqueous laminating adhesive is characterized in that a polyurethane prepolymer is prepared from raw materials of diphenylmethane diisocyanate and polypropylene glycol-2000, a fluorine-containing hydrolysis-resistant block copolymer is prepared from raw materials of dodecafluoroheptyl methacrylate, allyl propyl ether and hydroxyethyl methacrylate, and the environment-friendly aqueous laminating adhesive is prepared by solidifying the polyurethane prepolymer, the fluorine-containing hydrolysis-resistant block copolymer and a repair flame retardant and then adding water to adjust the solid content;
the preparation method of the repair flame retardant comprises the following steps: adding perchloric acid and p-toluenesulfonic acid into a reaction kettle, uniformly mixing, adding flake graphite powder, dropwise adding 10wt% of potassium permanganate aqueous solution, keeping for 1-2 hours, preserving heat in a water bath at 50-60 ℃, and continuously stirring for 45-70 min after the potassium permanganate aqueous solution is dropwise added; naturally cooling to room temperature, adding 30wt% of hydrogen peroxide to adjust the pH of the reaction system to 6-7, carrying out vacuum filtration, washing with ethanol, heating to 180-250 ℃, and carrying out heat preservation and drying for 4-6 hours to obtain expanded graphite; adding piperazine pyrophosphate into the expanded graphite, carrying out ball milling and crushing, and sieving with a sieve of 80-100 meshes.
2. The environment-friendly aqueous laminating adhesive as claimed in claim 1, wherein the mass ratio of the crystalline flake graphite powder to the aqueous solution of p-toluenesulfonic acid and potassium permanganate is 1: 1.5-3: 0.6-1.5 g of flake graphite powder, 3.5-4.2 mL of perchloric acid is added into 1g of flake graphite powder, and the addition amount of piperazine pyrophosphate is 5-10% of the mass of the expanded graphite.
3. The preparation method of the environment-friendly water-based laminating adhesive is characterized by comprising the following steps of:
preparing a polyurethane prepolymer: adding raw materials of diphenylmethane diisocyanate and polypropylene glycol-2000 into a reaction kettle, adding a solvent of N, N-dimethylformamide, heating to 60-80 ℃, mechanically stirring and reacting for 4-6 hours under the protection of nitrogen, standing to room temperature, filtering, and removing the solvent by concentration under reduced pressure to obtain a polyurethane prepolymer;
preparing a fluorine-containing hydrolysis-resistant block copolymer: adding dodecafluoroheptyl methacrylate, allyl propyl ether and hydroxyethyl methacrylate into a reaction kettle, adding a solvent N, N-dimethylformamide, heating to 50-65 ℃, dropwise adding azodiisobutyronitrile into a dropping funnel to initiate reaction, keeping for 1-2 hours until dropwise adding is finished, keeping the temperature and stirring for reaction for 6-8 hours, standing to room temperature, filtering, and removing the solvent by decompression and concentration to obtain the fluorine-containing hydrolysis-resistant block copolymer;
and (3) crosslinking and curing: and mixing the polyurethane prepolymer with the fluorine-containing hydrolysis-resistant block copolymer according to the molar ratio of isocyanate groups to hydroxyl groups of 1: 1.5-1.7, adding a repair flame retardant, uniformly mixing, and adding water to adjust the solid content to 40-60% to obtain the environment-friendly water-based laminating adhesive.
4. The preparation method of the environment-friendly water-based laminating adhesive as claimed in claim 3, wherein when the polyurethane prepolymer is prepared, the mass ratio of the diphenylmethane diisocyanate to the polypropylene glycol-2000 is 7.8-8.5: the dosage of the 1, N, N-dimethylformamide is 2-5 times of the mass of the diphenylmethane diisocyanate.
5. The preparation method of the environment-friendly water-based laminating adhesive as claimed in claim 3, wherein in the preparation of the fluorine-containing hydrolysis-resistant block copolymer, the mass ratio of the dodecafluoroheptyl methacrylate to the allyl propyl ether to the hydroxyethyl methacrylate is 0.3-0.5: 1: 0.6-0.8, the amount of the azobisisobutyronitrile is 1-3% of the mass of the allyl propyl ether, and the amount of the N, N-dimethylformamide is 1-3 times of the mass of the allyl propyl ether.
6. The preparation method of the environment-friendly water-based laminating adhesive as claimed in claim 3, wherein the amount of the repairing flame retardant used in the crosslinking and curing process is 0.6-1.5% by mass of the polyurethane prepolymer.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115260970A (en) * | 2022-09-28 | 2022-11-01 | 江苏斯瑞达材料技术股份有限公司 | Acrylic acid composite glue with good weather resistance and humidity resistance and preparation method thereof |
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| CN102134463A (en) * | 2010-08-19 | 2011-07-27 | 北京高盟新材料股份有限公司 | Water-based dry-type complex film adhesive and preparation method thereof |
| JP2013112788A (en) * | 2011-11-30 | 2013-06-10 | Lintec Corp | Flame-retardant adhesive sheet |
| CN111777955A (en) * | 2020-07-30 | 2020-10-16 | 溧阳市双强装饰材料有限公司 | Environment-friendly water-based laminating adhesive and preparation method thereof |
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| CN102134463A (en) * | 2010-08-19 | 2011-07-27 | 北京高盟新材料股份有限公司 | Water-based dry-type complex film adhesive and preparation method thereof |
| JP2013112788A (en) * | 2011-11-30 | 2013-06-10 | Lintec Corp | Flame-retardant adhesive sheet |
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| CN115260970A (en) * | 2022-09-28 | 2022-11-01 | 江苏斯瑞达材料技术股份有限公司 | Acrylic acid composite glue with good weather resistance and humidity resistance and preparation method thereof |
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