CN115160970B - Preparation method of water-based polyurethane heat-sealing adhesive - Google Patents
Preparation method of water-based polyurethane heat-sealing adhesive Download PDFInfo
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- CN115160970B CN115160970B CN202210718730.XA CN202210718730A CN115160970B CN 115160970 B CN115160970 B CN 115160970B CN 202210718730 A CN202210718730 A CN 202210718730A CN 115160970 B CN115160970 B CN 115160970B
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- chain extender
- hydrophilic chain
- aqueous polyurethane
- heat
- sulfonate
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 50
- 239000004814 polyurethane Substances 0.000 title claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000012945 sealing adhesive Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000004970 Chain extender Substances 0.000 claims abstract description 52
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 38
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 26
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 25
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 24
- 229920000554 ionomer Polymers 0.000 claims abstract description 24
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 238000007789 sealing Methods 0.000 claims abstract description 23
- 239000000839 emulsion Substances 0.000 claims abstract description 18
- 229920000728 polyester Polymers 0.000 claims abstract description 17
- 150000002009 diols Chemical class 0.000 claims abstract description 16
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 16
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 16
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003292 glue Substances 0.000 claims abstract description 14
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 13
- -1 polyol sulfonate Chemical class 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 11
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 9
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- MLQUDRXSWPSUAB-UHFFFAOYSA-N ethane-1,2-diamine;ethanesulfonic acid Chemical compound NCCN.CCS(O)(=O)=O MLQUDRXSWPSUAB-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 229920005906 polyester polyol Polymers 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 229920001748 polybutylene Polymers 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 3
- 239000012948 isocyanate Substances 0.000 abstract description 3
- 150000002513 isocyanates Chemical class 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 13
- 239000004743 Polypropylene Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 229920001155 polypropylene Polymers 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 3
- INJAHHABQHQOMY-UHFFFAOYSA-N 2-(dihydroxymethyl)butanoic acid Chemical compound CCC(C(O)O)C(O)=O INJAHHABQHQOMY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- MVXNTIQDKVZTKW-UHFFFAOYSA-N 1,4-dioxane-2-sulfonic acid Chemical compound O1C(COCC1)S(=O)(=O)O MVXNTIQDKVZTKW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0809—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups
- C08G18/0814—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups containing ammonium groups or groups forming them
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5072—Polyethers having heteroatoms other than oxygen containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sealing Material Composition (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a preparation method of water-based polyurethane heat-sealing glue, which comprises the following steps: reacting polyester diol, epoxidized polybutadiene resin and polyisocyanate to generate polyurethane prepolymer; acetone is added to reduce the viscosity of the prepolymer, and then a sulfonate hydrophilic chain extender is added; adding diethylenetriamine to obtain an ionomer; adding water into the ionomer to obtain aqueous polyurethane emulsion, adding carboxylate hydrophilic chain extender into the aqueous polyurethane emulsion, and removing acetone to obtain the aqueous polyurethane heat-sealing glue. The polyurethane prepolymer has active group NCO in isocyanate and carbonyl in an epoxidized polybutadiene resin structure, so that the heat sealing strength is improved; in the preparation process, the sulfonate hydrophilic chain extender is added for chain extension, so that the dispersibility and stability of the obtained ionomers can be improved, and the formed water-based polyurethane heat-sealing adhesive has more excellent performance.
Description
Technical Field
The invention relates to the technical field of food and medicine blister packaging, in particular to a preparation method of water-based polyurethane heat-sealing glue.
Background
The blister package has very wide application and is a main package form in the fields of food, health care products, medicines and the like. In the medicine package, medicine is placed in the blister of plastic hard sheet formed by suction moulding, and then heat-sealed with aluminium foil coated with heat-sealing glue so as to protect medicine. Wherein the blister package is made of polyvinyl chloride sheet material for the most part, and the covering material of the blister package is basically aluminum foil, and the heat sealing glue coated on the aluminum foil is commonly called VC agent. However, since chlorine exists in polyvinyl chloride, the material has a certain pollution to the environment when being treated as solid waste after being used, and thus many researchers are working to find other alternative materials.
Polypropylene materials have been of interest to researchers because of the absence of elemental chlorine, but because of the non-polarity of polypropylene materials, heat seal strength is insufficient for heat sealing polypropylene materials if existing VC agents are still used.
Disclosure of Invention
The invention aims to provide a preparation method of water-based polyurethane heat-sealing glue, which aims to realize effective heat-sealing strength of polypropylene when a polypropylene material is used as a foaming base material of a blister package and the heat-sealing strength of the conventional VC agent is insufficient.
The invention is realized by the following technical scheme:
the invention aims to provide a preparation method of water-based polyurethane heat-sealing glue, which comprises the following steps:
reacting polyester diol, epoxidized polybutadiene resin and polyisocyanate to generate polyurethane prepolymer;
acetone is added to reduce the viscosity of the prepolymer, and then a sulfonate hydrophilic chain extender is added;
adding diethylenetriamine to obtain an ionomer;
adding water into the ionomer to obtain aqueous polyurethane emulsion;
and adding a carboxylate hydrophilic chain extender into the aqueous polyurethane emulsion, and removing acetone to obtain the aqueous polyurethane heat-sealing adhesive.
In an alternative embodiment, the mass ratio of the polyester polyol, the epoxidized polybutadiene resin, and the polyisocyanate is 30 to 40: 8-12: 20-30 parts.
In an alternative embodiment, the polyester diol is any one of polyethylene adipate, polybutylene adipate, and polyhexamethylene adipate.
In an alternative embodiment, the epoxidized polybutadiene resin has a number average molecular weight of 1000 to 1800g/mol; the hydroxyl content of the epoxidized polybutadiene resin is 5-8wt%.
In an alternative embodiment, the polyisocyanate is any one of hexamethylene diisocyanate, 2, 4-toluene diisocyanate.
In an alternative embodiment, the carboxylate hydrophilic chain extender is any one of dimethylolpropionic acid, dimethylolbutyric acid and carboxyl-containing half-ester diol, and the mass part of the carboxylate hydrophilic chain extender is 2-4:30-40 compared with the mass part of the polyester diol.
In an alternative embodiment, the sulfonate hydrophilic chain extender is any one of ethylenediamine-based ethanesulfonate, ethylenedihydroxyethanesulfonate, dihydroxypolyoxy polyol sulfonate.
In an alternative embodiment, the mass ratio of sulfonate hydrophilic chain extender to carboxylate hydrophilic chain extender is from 0.5 to 0.8:1;
the mass ratio of the diethylenetriamine to the sulfonate hydrophilic chain extender is 0.2-0.6:1.
In an alternative embodiment, the method comprises the steps of:
adding polyester diol, epoxidized polybutadiene resin and polyisocyanate into a reactor, and reacting for 2-4 hours at 40-60 ℃ to generate polyurethane prepolymer;
adding acetone to reduce the viscosity of the prepolymer, adding a sulfonate hydrophilic chain extender into a reactor, and reacting for 2-4 hours at 40-60 ℃;
cooling to below 50 ℃, adding diethylenetriamine for neutralization to obtain an ionomer;
adding water into the ionomer, and stirring for 1-2 minutes under high shear to obtain aqueous polyurethane emulsion;
and adding a carboxylate hydrophilic chain extender into the aqueous polyurethane emulsion, and distilling under reduced pressure to remove acetone to obtain the aqueous polyurethane heat-sealing adhesive.
Compared with the prior art, the invention has the following advantages and beneficial effects:
in the embodiment of the invention, the polyurethane prepolymer generated by utilizing the reaction of polyester diol, epoxidized polybutadiene resin and polyisocyanate has active group NCO in isocyanate and carbonyl in the structure of the epoxidized polybutadiene resin, and when the water-based polyurethane heat-seal adhesive is coated on an aluminum foil and is heat-sealed with a polypropylene material, the heat-seal strength is improved; in the preparation process, the sulfonate hydrophilic chain extender is used for chain extension, and the dispersibility and stability of the obtained ionomers can be improved due to the strong hydrophilicity of sulfonic acid groups in the sulfonate hydrophilic chain extender and the neutralization process, so that the carboxylate hydrophilic chain extender is more beneficial to chain extension, the solid content of the formed water-based polyurethane heat-sealing adhesive is more excellent, and the cohesiveness is better. The heat-sealing adhesive obtained by the embodiment of the invention overcomes the defect of insufficient heat-sealing strength when the conventional VC adhesive is used for heat-sealing polypropylene materials.
Detailed Description
For the purpose of making apparent the objects, technical solutions and advantages of the present invention, the present invention will be further described in detail with reference to the following examples and the accompanying drawings, wherein the exemplary embodiments of the present invention and the descriptions thereof are for illustrating the present invention only and are not to be construed as limiting the present invention.
A preparation method of water-based polyurethane heat-seal adhesive comprises the following steps:
reacting polyester diol, epoxidized polybutadiene resin and polyisocyanate to generate polyurethane prepolymer;
acetone is added to reduce the viscosity of the prepolymer, and then a sulfonate hydrophilic chain extender is added;
adding diethylenetriamine to obtain an ionomer;
adding water into the ionomer to obtain aqueous polyurethane emulsion;
and adding a carboxylate hydrophilic chain extender into the aqueous polyurethane emulsion, and removing acetone to obtain the aqueous polyurethane heat-sealing adhesive.
Further, the mass ratio of the polyester polyol, the epoxidized polybutadiene resin and the polyisocyanate is 30-40: 8-12: 20-30 parts.
Further, the polyester diol is any one of polyethylene glycol adipate, polybutylene adipate and polyhexamethylene glycol adipate.
Further, the epoxidized polybutadiene resin has a number average molecular weight of 1000 to 1800g/mol; the hydroxyl content of the epoxidized polybutadiene resin is 5-8wt%.
Further, the polyisocyanate is any one of hexamethylene diisocyanate and 2, 4-toluene diisocyanate.
Further, the carboxylate hydrophilic chain extender is any one of dimethylolpropionic acid, dimethylolbutyric acid and carboxyl-containing half-ester dihydric alcohol, and the mass part of the carboxylate hydrophilic chain extender is 2-4:30-40 compared with the mass part of the polyester dihydric alcohol.
Further, the sulfonate hydrophilic chain extender is any one of ethylenediamine ethanesulfonate, ethylenedioxyethanesulfonate and dihydroxypolyoxy polyol sulfonate; the mass part of the sulfonate hydrophilic chain extender is 2-4:30-40 compared with the mass part of the polyester diol.
Further, the mass ratio of the sulfonate hydrophilic chain extender to the carboxylate hydrophilic chain extender is 0.5-0.8:1;
the mass ratio of the diethylenetriamine to the sulfonate hydrophilic chain extender is 0.2-0.6:1.
Further, the method comprises the following steps:
adding polyester diol, epoxidized polybutadiene resin and polyisocyanate into a reactor, and reacting for 2-4 hours at 40-60 ℃ to generate polyurethane prepolymer;
adding acetone to reduce the viscosity of the prepolymer, adding a sulfonate hydrophilic chain extender into a reactor, and reacting for 2-4 hours at 40-60 ℃;
cooling to below 50 ℃, adding diethylenetriamine for neutralization to obtain an ionomer;
adding water into the ionomer, and stirring for 1-2 minutes under high shear to obtain aqueous polyurethane emulsion;
and adding a carboxylate hydrophilic chain extender into the aqueous polyurethane emulsion, and distilling under reduced pressure to remove acetone to obtain the aqueous polyurethane heat-sealing adhesive.
The polyurethane prepolymer generated by the reaction of polyester diol, epoxidized polybutadiene resin and polyisocyanate has active groups NCO in isocyanate and carbonyl in the structure of the epoxidized polybutadiene resin, and when the aqueous polyurethane heat-sealing adhesive is coated on aluminum foil and heat-sealed with polypropylene materials, the reactivity of polypropylene and the aluminum foil is improved due to the existence of the two active groups and the polar structure of the formed polyurethane prepolymer, and the heat-sealing strength is improved. Meanwhile, olefin structural units in the epoxidized polybutadiene resin structure have a certain modification effect on the polypropylene material and a certain effect on reducing the initial heat sealing temperature. The addition of acetone can reduce the viscosity of the prepolymer; adding a sulfonate hydrophilic chain extender to carry out chain extension, neutralizing by using diethylenetriamine to form an ionomer, then emulsifying, and finally carrying out chain extension by using a carboxylate hydrophilic chain extender to form the water-based polyurethane heat-sealing adhesive. In the preparation process, the sulfonate hydrophilic chain extender is used for chain extension, and the dispersibility and stability of the obtained ionomers can be improved due to the strong hydrophilicity of sulfonic acid groups in the sulfonate hydrophilic chain extender and the neutralization process, so that the chain extension of the carboxylate hydrophilic chain extender is facilitated, the solid content of the formed water-based polyurethane heat-sealing adhesive is more excellent, and the cohesiveness is better; and the sulfonate hydrophilic chain extender is firstly used to reduce the dosage of the neutralizing agent diethylenetriamine.
The following is a detailed description of specific examples.
1) Examples:
a preparation method of water-based polyurethane heat-sealing glue, wherein the raw material compositions of examples 1-6 are shown in the following table 1:
table 1 raw material composition tables of examples 1 to 6
Example 7:
a preparation method of water-based polyurethane heat-sealing glue is different from example 1 in that the polyester diol adopts polyhexamethylene adipate, and the rest is the same as example 1.
Example 8:
a preparation method of an aqueous polyurethane heat-sealing adhesive is different from example 1 in that 2, 4-toluene diisocyanate is adopted as polyisocyanate, and the rest is the same as example 1.
Example 9:
a preparation method of water-based polyurethane heat-sealing glue is different from example 1 in that dihydroxypolyoxypolyhydric alcohol sulfonate is adopted as sulfonate hydrophilic chain extender, and the rest is the same as example 1.
Example 10:
a preparation method of water-based polyurethane heat-sealing glue is different from example 1 in that a carboxylate hydrophilic chain extender adopts carboxyl-containing half-ester dihydric alcohol, and the rest is the same as example 1.
The preparation process of each of the above examples 1 to 6 is: according to the formula of each case, adding polyethylene glycol adipate, epoxidized polybutadiene resin and polyethylene glycol adipate into a reactor, and reacting for 2 hours at 40 ℃ to generate polyurethane prepolymer; adding acetone to reduce the viscosity of the prepolymer, and then adding ethylenediamine ethanesulfonate into a reactor to react for 2 hours at 40 ℃; cooling to 50 ℃, adding diethylenetriamine for neutralization to obtain an ionomer; adding water into the ionomer, and stirring for 1 min under high shear to obtain aqueous polyurethane emulsion; and adding carboxylate hydrophilic chain extender dihydroxymethyl butyric acid into the aqueous polyurethane emulsion, and distilling under reduced pressure to remove acetone to obtain the aqueous polyurethane heat-sealing adhesive.
For examples 7 to 10, the raw materials were adjusted according to the respective formulations.
2) Comparative example
A preparation method of water-based polyurethane heat-sealing glue, wherein the raw material compositions of comparative examples 1 to 6 are shown in the following table 2:
table 2 raw material composition tables of comparative examples 1 to 6
The preparation process of the above comparative examples 1 to 6 is: according to the formula of each case, adding polyethylene glycol adipate, epoxidized polybutadiene resin and polyethylene glycol adipate into a reactor, and reacting for 2 hours at 40 ℃ to generate polyurethane prepolymer; adding acetone to reduce the viscosity of the prepolymer, and then adding ethylenediamine ethanesulfonate into a reactor to react for 2 hours at 40 ℃; cooling to 50 ℃, adding diethylenetriamine for neutralization to obtain an ionomer; adding water into the ionomer, and stirring for 1 min under high shear to obtain aqueous polyurethane emulsion; and adding carboxylate hydrophilic chain extender dihydroxymethyl butyric acid into the aqueous polyurethane emulsion, and distilling under reduced pressure to remove acetone to obtain the aqueous polyurethane heat-sealing adhesive.
Comparative example 7: the difference from example 1 is that dimethylolbutyric acid is added before the formation of the ionomers and ethylenediamine-based ethanesulfonate is added after the formation of the ionomers.
3) Test case
The heat-seal adhesives obtained in examples 1 to 10 and comparative examples 1 to 7 were subjected to performance tests, and the test results are shown in tables 3 and 4, respectively.
The heat-seal adhesives obtained in examples 1 to 10 and comparative examples 1 to 7 were coated on a hard aluminum foil having a thickness of 0.02. Mu.m, and heat-sealed with a polypropylene sheet on a heat sealer after baking at a heat-seal temperature of 170℃for 5 seconds, and the heat-seal strength was measured, and the results are shown in tables 3 and 4, respectively.
TABLE 3 results of Heat seal Performance test for examples 1-10
Table 4 results of Heat seal Performance test of comparative examples 1 to 7
From the above examples and comparative examples, the performances of the heat-seal adhesives obtained in examples 1 to 10 all meet the use requirements, and the heat-seal strength meets the requirements and is superior to the existing heat-seal adhesives; and the heat-sealing adhesives of examples 1 to 10 can meet the requirement by heat-sealing at 170 ℃. When the proportions of the neutralizing agent, the carboxylate chain extender and the sulfonate chain extender of each comparative example were adjusted, the obtained heat-seal adhesive was poor in performance. Comparing example 1 with comparative example 7, it is known that the order of addition of the carboxylate and sulfonate chain extenders has some effect on the performance of the heat seal. When the carboxylate chain extender is added first and then the sulfonate chain extender is added, the performance of the heat-seal adhesive satisfies the use requirements, but is inferior to that of example 1.
The methods, processes, apparatuses, etc. not mentioned in the present application are all available and can be performed by using existing methods or existing methods, and are not described herein.
The foregoing detailed description of the invention has been presented for purposes of illustration and description, and it should be understood that the invention is not limited to the particular embodiments disclosed, but is intended to cover all modifications, equivalents, alternatives, and improvements within the spirit and principles of the invention.
Claims (4)
1. The preparation method of the water-based polyurethane heat-sealing adhesive is characterized by comprising the following steps of:
reacting polyester diol, epoxidized polybutadiene resin and polyisocyanate to generate polyurethane prepolymer;
acetone is added to reduce the viscosity of the prepolymer, and then a sulfonate hydrophilic chain extender is added;
adding diethylenetriamine to obtain an ionomer;
adding water into the ionomer to obtain aqueous polyurethane emulsion;
adding a carboxylate hydrophilic chain extender into the aqueous polyurethane emulsion, and removing acetone to obtain aqueous polyurethane heat-sealing glue;
the number average molecular weight of the epoxidized polybutadiene resin is 1000-1800 g/mol; the hydroxyl content of the epoxidized polybutadiene resin is 5-8wt%;
the mass ratio of the polyester polyol to the epoxidized polybutadiene resin to the polyisocyanate is 30-40: 8-12: 20-30 parts;
the mass part of the carboxylate hydrophilic chain extender is 2-4:30-40 compared with the mass part of the polyester diol;
the mass ratio of the sulfonate hydrophilic chain extender to the carboxylate hydrophilic chain extender is 0.5-0.8:1;
the mass ratio of the diethylenetriamine to the sulfonate hydrophilic chain extender is 0.2-0.6:1;
the carboxylate hydrophilic chain extender is any one of dimethylolpropionic acid, dimethylolbutyric acid and carboxyl-containing half-ester dihydric alcohol;
the sulfonate hydrophilic chain extender is any one of ethylenediamine ethanesulfonate, ethylenediamine ethanesulfonate and dihydroxyl polyoxylated polyol sulfonate.
2. The method for preparing the aqueous polyurethane heat-sealing glue according to claim 1, wherein the polyester diol is any one of polyethylene glycol adipate, polybutylene glycol adipate and polyhexamethylene glycol adipate.
3. The method for preparing an aqueous polyurethane heat-sealing adhesive according to claim 1, wherein the polyisocyanate is any one of hexamethylene diisocyanate and 2, 4-toluene diisocyanate.
4. The method for preparing the aqueous polyurethane heat-sealing adhesive as claimed in claim 1, which is characterized by comprising the following steps:
adding polyester diol, epoxidized polybutadiene resin and polyisocyanate into a reactor, and reacting for 2-4 hours at 40-60 ℃ to generate polyurethane prepolymer;
adding acetone to reduce the viscosity of the prepolymer, adding a sulfonate hydrophilic chain extender into a reactor, and reacting for 2-4 hours at 40-60 ℃;
cooling to below 50 ℃, adding diethylenetriamine for neutralization to obtain an ionomer;
adding water into the ionomers, and stirring for 1-2 minutes under high shear to obtain aqueous polyurethane emulsion;
and adding a carboxylate hydrophilic chain extender into the aqueous polyurethane emulsion, and distilling under reduced pressure to remove acetone to obtain the aqueous polyurethane heat-sealing adhesive.
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| CN102827571A (en) * | 2012-09-28 | 2012-12-19 | 广东多正化工科技有限公司 | Preparation method of water-based polyurethane adhesive |
| CN111500245A (en) * | 2020-04-22 | 2020-08-07 | 乐凯胶片股份有限公司 | Solvent-free polyurethane adhesive for solar back panel and preparation method thereof |
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| CN102827571A (en) * | 2012-09-28 | 2012-12-19 | 广东多正化工科技有限公司 | Preparation method of water-based polyurethane adhesive |
| CN111500245A (en) * | 2020-04-22 | 2020-08-07 | 乐凯胶片股份有限公司 | Solvent-free polyurethane adhesive for solar back panel and preparation method thereof |
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