CN116606623A - Preparation method of polyurethane adhesive, polyurethane adhesive and application of polyurethane adhesive in production of high-temperature-resistant steaming packaging film - Google Patents
Preparation method of polyurethane adhesive, polyurethane adhesive and application of polyurethane adhesive in production of high-temperature-resistant steaming packaging film Download PDFInfo
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- CN116606623A CN116606623A CN202310876304.3A CN202310876304A CN116606623A CN 116606623 A CN116606623 A CN 116606623A CN 202310876304 A CN202310876304 A CN 202310876304A CN 116606623 A CN116606623 A CN 116606623A
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- China
- Prior art keywords
- polyurethane adhesive
- activated carbon
- epoxy
- set temperature
- reacting
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 84
- 239000000853 adhesive Substances 0.000 title claims abstract description 83
- 239000004814 polyurethane Substances 0.000 title claims abstract description 67
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000010025 steaming Methods 0.000 title claims abstract description 19
- 239000012785 packaging film Substances 0.000 title claims abstract description 17
- 229920006280 packaging film Polymers 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 196
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 66
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229940105325 3-dimethylaminopropylamine Drugs 0.000 claims abstract description 51
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000006185 dispersion Substances 0.000 claims abstract description 24
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 22
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 claims abstract description 19
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003822 epoxy resin Substances 0.000 claims abstract description 15
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 claims abstract description 15
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 claims abstract description 15
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 15
- 229960002216 methylparaben Drugs 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims description 83
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 73
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- 238000001914 filtration Methods 0.000 claims description 55
- 239000008367 deionised water Substances 0.000 claims description 54
- 229910021641 deionized water Inorganic materials 0.000 claims description 54
- 238000002156 mixing Methods 0.000 claims description 48
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 44
- 238000001816 cooling Methods 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 32
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 28
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 22
- 238000009835 boiling Methods 0.000 claims description 18
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 18
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 17
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 16
- FPXVXEIZGKLUIX-UHFFFAOYSA-M ethanol;hexadecyl(trimethyl)azanium;bromide Chemical compound [Br-].CCO.CCCCCCCCCCCCCCCC[N+](C)(C)C FPXVXEIZGKLUIX-UHFFFAOYSA-M 0.000 claims description 13
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 9
- 230000010355 oscillation Effects 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000011127 biaxially oriented polypropylene Substances 0.000 claims description 3
- 229920006378 biaxially oriented polypropylene Polymers 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- 150000002009 diols Chemical class 0.000 abstract description 15
- 125000003700 epoxy group Chemical group 0.000 abstract description 7
- 230000007062 hydrolysis Effects 0.000 abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000012948 isocyanate Substances 0.000 abstract description 4
- 150000002513 isocyanates Chemical class 0.000 abstract description 4
- 125000003277 amino group Chemical group 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 3
- WDGCBNTXZHJTHJ-UHFFFAOYSA-N 2h-1,3-oxazol-2-id-4-one Chemical group O=C1CO[C-]=N1 WDGCBNTXZHJTHJ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 description 24
- 238000001556 precipitation Methods 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 230000008569 process Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229920005862 polyol Polymers 0.000 description 11
- 229920000728 polyester Polymers 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 150000003077 polyols Chemical class 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 7
- 239000004925 Acrylic resin Substances 0.000 description 6
- 239000002313 adhesive film Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- AUABZJZJXPSZCN-UHFFFAOYSA-N 2-(dimethylamino)phenol Chemical compound CN(C)C1=CC=CC=C1O AUABZJZJXPSZCN-UHFFFAOYSA-N 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- HMSLTVNEKMTVKK-UHFFFAOYSA-N 3-(1-ethenylcyclohexa-2,4-dien-1-yl)prop-2-enoic acid Chemical class C=CC1(CC=CC=C1)C=CC(=O)O HMSLTVNEKMTVKK-UHFFFAOYSA-N 0.000 description 4
- -1 small-molecule polyol Chemical class 0.000 description 4
- WOAWYKPABZNBBV-UHFFFAOYSA-N 2-[bis(hydroxymethyl)amino]acetic acid Chemical class OCN(CO)CC(O)=O WOAWYKPABZNBBV-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010411 cooking Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 238000007719 peel strength test Methods 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 241000218378 Magnolia Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- VHDPPDRSCMVFAV-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH+](C)C VHDPPDRSCMVFAV-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical class OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 238000010998 test method Methods 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
-
- 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
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
-
- 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
-
- 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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the field of adhesives, in particular to a preparation method of a polyurethane adhesive, the polyurethane adhesive and application of the polyurethane adhesive in production of high-temperature-resistant steaming packaging films. The preparation method of the polyurethane adhesive comprises the following steps: loading 3-dimethylaminopropylamine by using active carbon, and modifying the surface of the active carbon to introduce amino groups to obtain surface modified active carbon; epoxy groups are introduced by modifying polycaprolactone diol with epoxy bromopropane and react with isocyanate to generate an oxazolidone structure, excessive isocyanate continuously reacts with polycaprolactone diol, 1, 4-butanediol, trimethylolpropane, epoxy resin and methyl parahydroxybenzoate, and after the reaction is finished, surface modified activated carbon dispersion liquid is added, and the mixture is uniformly mixed to obtain the polyurethane adhesive. The polyurethane adhesive prepared by the invention has good heat resistance and hydrolysis resistance, is used in a steaming-resistant packaging film, and still has good adhesive property after steaming at high temperature.
Description
Technical Field
The invention relates to the field of adhesives, in particular to a preparation method of a polyurethane adhesive, the polyurethane adhesive and application of the polyurethane adhesive in production of high-temperature-resistant steaming packaging films.
Background
The high-temperature-resistant steaming packaging film is a flexible packaging film for food, and has the advantages of durable packaging, stable storage, high-temperature-resistant steaming and boiling, and the like. When the high-temperature-resistant steaming packaging film is a composite film, the performance of the packaging film is not only related to the material for preparing the packaging film, but also closely related to the performance of the adhesive used for preparing the composite film. The polyurethane adhesive has high transparency and good adhesion performance to most substrate materials, and becomes a main adhesive for producing composite films.
Chinese patent CN112048278B discloses a steaming-resistant double-component solvent-free polyurethane compound adhesive film and a preparation method thereof, wherein component A is prepared into high-temperature-resistant polyester diol by introducing small molecular alcohol containing lateral methyl and aromatic dibasic acid into a system, viscosity is reduced by adding polyether diol, hydrolysis resistance is improved, nano filler is added to further improve heat resistance of the polyester diol, component B is prepared by modifying high-temperature-resistant polyester by castor oil, compatibility of the polyester diol and the polyether diol is improved, and simultaneously, a hydrolysis-resistant modifier is added to improve hydrolysis resistance of an adhesive film, and the two components are mixed and cured when the adhesive film is used, so that the steaming-resistant double-component solvent-free polyurethane compound adhesive film can be obtained, but the two components are uniformly mixed and cured when the adhesive film is used, and the peeling strength of the compound adhesive film prepared after curing is still to be improved; chinese patent CN109370500B discloses a polyurethane adhesive and a preparation method thereof, wherein the polyurethane adhesive comprises a component A and a component B, wherein the component A is obtained by reacting an oligomer resin a prepared by reacting small-molecule polybasic acid with small-molecule polyol through polyester and then chain-extending the obtained by reacting the oligomer resin B prepared by reacting small-molecule polybasic acid with small-molecule polyol through polyester and polyisocyanate, hyperbranched polymer, nano material, coupling agent, defoamer and flatting agent are added after the reaction of the oligomer resin B prepared by reacting small-molecule polybasic acid with small-molecule polyol and polyisocyanate, the component B is obtained after the uniform mixing, and the two components are uniformly mixed according to a certain proportion when in use, so that the polyurethane adhesive is obtained, but the adhesive can be cured just by uniformly mixing before use, and the peeling strength of the adhesive after high-temperature steaming is obviously reduced.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a polyurethane adhesive, the polyurethane adhesive and application of the polyurethane adhesive in production of a high-temperature-resistant steaming packaging film, solves the problem of large difference of peel strength of the polyurethane adhesive before and after steaming, and improves the peel strength of the polyurethane adhesive at room temperature.
In order to achieve the above purpose, the invention provides a preparation method of a polyurethane adhesive, which comprises the following steps:
(1) Mixing 3-dimethylaminopropylamine with ethanol, stirring, adding pretreated activated carbon, continuously stirring, heating to a set temperature, stirring, filtering, washing and drying to obtain activated carbon loaded with 3-dimethylaminopropylamine;
(2) Dropwise adding gamma-aminopropyl triethoxysilane into an ethanol water solution, carrying out ultrasonic treatment, stirring, dropwise adding hexadecyl trimethyl ammonium bromide ethanol solution, adding activated carbon loaded with 3-dimethylaminopropylamine after the dropwise adding is finished, reacting, cooling, filtering, washing and drying to obtain surface modified activated carbon;
(3) Mixing PCL (polycaprolactone diol) and N, N-dimethylformamide, cooling to a set temperature, adding cesium carbonate and epoxybromopropane, stirring, reacting, filtering, purifying and drying after the reaction to obtain epoxy-terminated polycaprolactone;
(4) Adding 2,4, 6-tris (dimethylaminomethyl) phenol into epoxy-terminated polycaprolactone, stirring, heating to a first set temperature under the inert gas atmosphere, dropwise adding diphenylmethane diisocyanate, reacting at the first set temperature, cooling to a second set temperature after the reaction, adding diphenylmethane diisocyanate and PCL, reacting at the second set temperature, adding 1, 4-butanediol and trimethylolpropane, heating to a third set temperature, reacting, adding epoxy resin and ethyl acetate, reacting at a fourth set temperature, adding methylparaben after the reaction, maintaining the fourth set temperature for reaction, cooling, adding surface modified activated carbon dispersion, and mixing to obtain the polyurethane adhesive.
Preferably, in the step (1): the mass ratio of the 3-dimethylaminopropylamine to the ethanol to the pretreated activated carbon is (10-20): (50-70): 5, a step of; the temperature was set at 60 ℃.
Preferably, the pretreated activated carbon is prepared by the steps of: and (3) washing the activated carbon with deionized water for several times, mixing with the deionized water, boiling, filtering, drying, grinding and sieving to obtain the pretreated activated carbon.
Preferably, the mass ratio of the active carbon to the deionized water is 5: (200-300); boiling comprises boiling at 100deg.C for 3 times, each for 20min.
Preferably, in the step (2): the mass ratio of the ethanol aqueous solution, the gamma-aminopropyl triethoxysilane, the cetyl trimethyl ammonium bromide ethanol solution and the 3-dimethylaminopropylamine loaded active carbon is 100: (0.5-2.5): 5:5, a step of; the reaction condition is 65-75 ℃ for 5-8h.
Preferably, in the cetyl trimethyl ammonium bromide ethanol solution, cetyl trimethyl ammonium bromide is used as a solute, ethanol is used as a solvent, and the mass ratio of the cetyl trimethyl ammonium bromide to the ethanol is 1:9.
preferably, in the step (3): the mass ratio of PCL, N-dimethylformamide, cesium carbonate and epoxybromopropane is (110-150): (340-420): (48-52): (35.5-37.5); the set temperature is 0-2 ℃, and the reaction condition is that the reaction is carried out for 24-26 hours at the set temperature.
Preferably, the PCL comprises PCL400.
Preferably, the purification comprises the steps of rotary evaporation and concentration of the filtrate, precipitation by adding deionized water, filtration, dissolution of the obtained filter residue by tetrahydrofuran, precipitation by adding deionized water, filtration, repeated dissolution of the filter residue by tetrahydrofuran, precipitation by adding deionized water, and filtration for three times.
Preferably, in the step (4): the preparation method of the surface modified activated carbon dispersion liquid comprises the following steps: mixing the surface modified activated carbon with ethyl acetate, and performing ultrasonic treatment to obtain a surface modified activated carbon dispersion liquid; wherein the mass ratio of the surface modified activated carbon to the ethyl acetate is 5:25, ultrasonic conditions are: ultrasonic oscillation is carried out for 10-20min at the frequency of 20-40 kHz.
Preferably, in the step (4): the mass ratio of the epoxy-terminated polycaprolactone, 2,4, 6-tris (dimethylaminomethyl) phenol, diphenylmethane diisocyanate, PCL, 1, 4-butanediol, trimethylolpropane, epoxy resin, ethyl acetate, methyl p-hydroxybenzoate and surface-modified activated carbon dispersion liquid is (120-280): (11-16): (975-1000): (1000-2000): (90-120): 80: (50-170): (200-220): 125: (210-270), wherein the mass ratio of the diphenylmethane diisocyanate added in the two steps is as follows: 250: (725-750).
Preferably, in the step (4): the first set temperature is 150-170 ℃, and the reaction time is 60-120min; the second set temperature is 75 ℃, and the reaction time is 2 hours; the third set temperature is 85 ℃, and the reaction time is 2 hours; the fourth set temperature is 80 ℃ and the reaction time is 2h.
Preferably, the epoxy-terminated polycaprolactone and PCL1000 are dehydrated under the following conditions: dehydrating at 120 ℃ for 1h at a stirring speed of 180 r/min.
Preferably, the PCL includes any one of PCL1000 (average molecular weight of polycaprolactone diol is 1000), PCL2000 (average molecular weight of polycaprolactone diol is 2000).
Preferably, the invention discloses a polyurethane adhesive prepared by the preparation method of the polyurethane adhesive.
Preferably, the invention discloses a method for producing a high-temperature steaming and boiling resistant packaging film by adopting the polyurethane adhesive, which comprises the following steps:
and (3) respectively and uniformly coating the polyurethane adhesive on the BOPP film, compounding by using an aluminum foil film, and curing to obtain the high-temperature-resistant steaming packaging film.
Compared with the prior art, the invention has the beneficial effects that:
1. firstly, pretreating activated carbon, loading 3-dimethylaminopropylamine on the pretreated activated carbon, modifying the surface of the activated carbon by using gamma-aminopropyl triethoxysilane, introducing amino groups on the surface of the activated carbon, reacting with epoxy groups and isocyanate groups as a cross-linking agent to increase the compatibility of the activated carbon, loading 3-dimethylaminopropylamine in pore channels in the activated carbon, and desorbing the activated carbon into an adhesive system after the activated carbon is heated, wherein the 3-dimethylaminopropylamine has a tertiary amine structure, so that the 3-dimethylaminopropylamine can react with carboxyl groups of hydrolysis broken chains in a neutralization manner, and the hydrolysis of polyester can be inhibited; in order to ensure that the adhesive still has good bonding performance after being heated, the system contains unreacted epoxy groups, and 3-dimethylaminopropylamine has amino groups capable of reacting with the epoxy groups at room temperature, so that activated carbon is required to be used for adsorbing the adhesive into a pore canal to prevent the adhesive from reacting with the epoxy groups to form a crosslinking curing system, so that the bonding strength of the crosslinking agent is reduced;
2. Modifying polyester diol, converting terminal hydroxyl into epoxy group and then reacting with isocyanate group to generate oxazolidone structure, improving heat resistance and hydrolysis resistance of polyurethane adhesive; the excessive isocyanate groups are blocked by methyl p-hydroxybenzoate, and are deblocked at 120 ℃ to regenerate isocyanate groups, so that the isocyanate groups can react with the heated and desorbed 3-dimethylaminopropylamine and free epoxy groups in the system to generate a new crosslinking system, thereby ensuring that the adhesive has higher peel strength after high-temperature cooking.
Drawings
FIG. 1 is a flow chart of a process for preparing the polyurethane adhesive of the present invention;
FIG. 2 is a schematic illustration of the reaction of the present invention to prepare an epoxy-capped polyester diol;
FIG. 3 is a reaction scheme showing the reaction of an epoxy-capped polycaprolactone with an isocyanate;
FIG. 4 is a bar graph showing the peel strength test results of composite films 1-7 prepared in example 6 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
Example 1
The embodiment discloses a preparation method of a polyurethane adhesive, which comprises the following steps:
(1) Washing the activated carbon with deionized water for 3 times, and mixing the activated carbon with deionized water according to a ratio of 5:200, boiling for 3 times at 100 ℃ for 20min each time, filtering, drying for 12h at 100 ℃, grinding, and sieving with a 600-mesh sieve to obtain pretreated activated carbon; uniformly mixing 3-dimethylaminopropylamine and ethanol, uniformly stirring at a stirring speed of 150r/min at room temperature, adding pretreated activated carbon, continuously stirring at room temperature for 4 hours, heating to 60 ℃ in a water bath, stirring for 1 hour, filtering, washing with deionized water, and drying at 70 ℃ for 4 hours to obtain activated carbon loaded with 3-dimethylaminopropylamine, wherein the mass ratio of 3-dimethylaminopropylamine to ethanol to pretreated activated carbon is: 10:50:5, a step of;
(2) Dropwise adding gamma-aminopropyl triethoxysilane into 95wt% ethanol water solution at room temperature, completely dropwise adding the gamma-aminopropyl triethoxysilane within 10min, carrying out ultrasonic treatment at a frequency of 20kHz for 15min, stirring at a stirring speed of 150r/min for 4h, dropwise adding cetyltrimethylammonium bromide ethanol solution within 30min, adding active carbon loaded with 3-dimethylaminopropylamine after dropwise adding, heating to 65 ℃ in a water bath for reaction for 8h, cooling to room temperature after reaction, filtering, washing with deionized water, and drying at 70 ℃ for 8h to obtain surface modified active carbon, wherein the mass ratio of 95wt% ethanol water solution, gamma-aminopropyl triethoxysilane, cetyltrimethylammonium bromide ethanol solution and active carbon loaded with 3-dimethylaminopropylamine is as follows: 100:0.5:5: the mass ratio of the cetyl trimethyl ammonium bromide to the ethanol in the cetyl trimethyl ammonium bromide ethanol solution is as follows: 1:9, a step of performing the process;
(3) Uniformly mixing PCL400 and N, N-dimethylformamide, cooling to 2 ℃ in an ice water bath, adding cesium carbonate and epoxybromopropane, uniformly stirring at a stirring speed of 150r/min, maintaining the temperature for reacting for 24 hours, filtering, collecting filtrate, rotationally evaporating and concentrating, adding deionized water for precipitation, filtering, dissolving the obtained filter residues by tetrahydrofuran, adding deionized water for precipitation, filtering, repeatedly dissolving, adding deionized water for precipitation, and vacuum drying at 50 ℃ for 12 hours after the filtering process is performed three times to obtain the epoxy-terminated polycaprolactone, wherein the mass ratio of PCL400 to N, N-dimethylformamide to cesium carbonate to epoxybromopropane is: 110:340:48:35.5;
(4) Mixing the surface modified activated carbon with ethyl acetate according to a ratio of 5: ultrasonic oscillation is carried out for 20min at the frequency of 20kHz in the mass ratio of 25 to obtain surface modified activated carbon dispersion liquid; dehydrating epoxy-terminated polycaprolactone and PCL1000 at a stirring speed of 180r/min for 1h at 120 ℃ to obtain dehydrated epoxy-terminated polycaprolactone and dehydrated PCL1000, adding 2,4, 6-tris (dimethylaminomethyl) phenol into the dehydrated epoxy-terminated polycaprolactone, stirring uniformly, introducing nitrogen, heating to 150 ℃, increasing the stirring speed to 500r/min, dropwise adding diphenylmethane diisocyanate, dropwise adding the mixture in 90min, carrying out heat preservation reaction for 120min, cooling to 75 ℃ at a cooling speed of 2 ℃/min after the reaction is finished, adding diphenylmethane diisocyanate and dehydrated PCL1000, reacting at 75 ℃ for 2h, adding 1, 4-butanediol and trimethylolpropane, heating to 85 ℃, reacting for 2h, adding epoxy resin and ethyl acetate, reacting at 80 ℃ for 1h, adding methylparaben, blocking the epoxy-terminated polyol, maintaining the reaction for 2h, cooling to room temperature, adding surface-modified active carbon dispersion liquid, and uniformly mixing to obtain polyurethane adhesive, wherein the epoxy-terminated polycaprolactone, the 2,4, 6-dimethylaminophenol, the surface-modified polyol, the surface-modified dimethylol, the styrene-1-glycol, the surface-modified dimethylol, the modified dimethylol-1000-formaldehyde resin and the modified PCL-modified styrene-1, the surface-modified styrene-1-butadiene-acrylate resin are obtained by mixing. 120:11:975:1000:120:80:50:200:125:210, the mass ratio of the diphenylmethane diisocyanate added twice is as follows: 250:725.
Example 2
The embodiment discloses a preparation method of a polyurethane adhesive, which comprises the following steps:
(1) Washing the activated carbon with deionized water for 3 times, and mixing the activated carbon with deionized water according to a ratio of 5:250, boiling for 3 times at 100 ℃ for 20min each time, filtering, drying for 11h at 105 ℃, grinding, and sieving with a 600-mesh sieve to obtain pretreated activated carbon; uniformly mixing 3-dimethylaminopropylamine and ethanol, uniformly stirring at a stirring speed of 150r/min at room temperature, adding pretreated activated carbon, continuously stirring at room temperature for 5 hours, heating to 60 ℃ in a water bath, stirring for 1 hour, filtering, washing with deionized water, and drying at 75 ℃ for 3 hours to obtain activated carbon loaded with 3-dimethylaminopropylamine, wherein the mass ratio of 3-dimethylaminopropylamine to ethanol to pretreated activated carbon is: 15:60:5, a step of;
(2) Dropwise adding gamma-aminopropyl triethoxysilane into 95wt% ethanol water solution at room temperature, after dropwise adding, ultrasonic treatment is carried out for 10min at the frequency of 30kHz, stirring is carried out for 5h at the stirring speed of 150r/min, then dropwise adding cetyltrimethylammonium bromide ethanol solution, after dropwise adding is completed within 30min, adding active carbon loaded with 3-dimethylaminopropylamine, heating in a water bath to 70 ℃ for reacting for 6.5h, cooling to room temperature after reacting, filtering, washing with deionized water, drying for 7h at 75 ℃ to obtain surface modified active carbon, wherein the mass ratio of 95wt% ethanol water solution, gamma-aminopropyl triethoxysilane, cetyltrimethylammonium bromide ethanol solution and active carbon loaded with 3-dimethylaminopropylamine is as follows: 100:1:5: the mass ratio of the cetyl trimethyl ammonium bromide to the ethanol in the cetyl trimethyl ammonium bromide ethanol solution is as follows: 1:9, a step of performing the process;
(3) Uniformly mixing PCL400 and N, N-dimethylformamide, cooling to 1 ℃ in an ice water bath, adding cesium carbonate and epoxybromopropane, uniformly stirring at a stirring speed of 150r/min, maintaining the temperature for reacting for 25 hours, filtering, collecting filtrate, rotationally evaporating and concentrating, adding deionized water for precipitation, filtering, dissolving the obtained filter residues by tetrahydrofuran, adding deionized water for precipitation, filtering, repeatedly dissolving, adding deionized water for precipitation, and vacuum drying at 55 ℃ for 11 hours after the filtering process is performed three times to obtain the epoxy-terminated polycaprolactone, wherein the mass ratio of PCL400 to N, N-dimethylformamide to cesium carbonate to epoxybromopropane is: 120:360:49:36;
(4) Mixing the surface modified activated carbon with ethyl acetate according to a ratio of 5: ultrasonic oscillation is carried out for 15min at the frequency of 30kHz in the mass ratio of 25, so as to obtain surface modified activated carbon dispersion liquid; dehydrating epoxy-terminated polycaprolactone and PCL1000 at a stirring speed of 180r/min for 1h at 120 ℃ to obtain dehydrated epoxy-terminated polycaprolactone and dehydrated PCL1000, adding 2,4, 6-tris (dimethylaminomethyl) phenol into the dehydrated epoxy-terminated polycaprolactone, stirring uniformly, introducing nitrogen, heating to 155 ℃, increasing the stirring speed to 500r/min, dropwise adding diphenylmethane diisocyanate, dropwise adding the mixture in 90min, carrying out heat preservation reaction for 105min, cooling to 75 ℃ at a cooling speed of 2 ℃/min after the reaction is finished, adding diphenylmethane diisocyanate and dehydrated PCL1000, reacting at 75 ℃ for 2h, adding 1, 4-butanediol and trimethylolpropane, heating to 85 ℃, reacting for 2h, adding epoxy resin and ethyl acetate, reacting at 80 ℃ for 1h, adding methylparaben, blocking the epoxy-terminated polyol, maintaining the reaction for 2h, cooling to room temperature, adding surface-modified active carbon dispersion liquid, and uniformly mixing to obtain polyurethane adhesive, wherein the epoxy-terminated polycaprolactone, the 2,4, 6-dimethylaminophenol, the surface-modified epoxy-4-trimethylolpropane, the surface-modified styrene-1-glycol, the surface-modified styrene-1-acrylate resin and the modified PCL1000 are prepared by the following steps of reacting the epoxy-terminated polycaprolactone, the epoxy-4-dimethylether and the surface-modified styrene-1-acrylate resin with the modified PCL resin: 160:12:1000:1000:120:80:75:200:125:225, the mass ratio of the diphenylmethane diisocyanate added in two times is as follows: 250:750.
Example 3
The embodiment discloses a preparation method of a polyurethane adhesive, which comprises the following steps:
(1) Washing the activated carbon with deionized water for 3 times, and mixing the activated carbon with deionized water according to a ratio of 5:250, boiling for 3 times at 100 ℃ for 20min each time, filtering, drying for 11h at 105 ℃, grinding, and sieving with a 600-mesh sieve to obtain pretreated activated carbon; uniformly mixing 3-dimethylaminopropylamine and ethanol, uniformly stirring at a stirring speed of 150r/min at room temperature, adding pretreated activated carbon, continuously stirring at room temperature for 5 hours, heating to 60 ℃ in a water bath, stirring for 1 hour, filtering, washing with deionized water, and drying at 75 ℃ for 3 hours to obtain activated carbon loaded with 3-dimethylaminopropylamine, wherein the mass ratio of 3-dimethylaminopropylamine to ethanol to pretreated activated carbon is: 15:60:5, a step of;
(2) Dropwise adding gamma-aminopropyl triethoxysilane into 95wt% ethanol water solution at room temperature, after dropwise adding, ultrasonic treatment is carried out for 10min at the frequency of 30kHz, stirring is carried out for 5h at the stirring speed of 150r/min, then dropwise adding cetyltrimethylammonium bromide ethanol solution, after dropwise adding is completed within 30min, adding active carbon loaded with 3-dimethylaminopropylamine, heating in a water bath to 70 ℃ for reacting for 6.5h, cooling to room temperature after reacting, filtering, washing with deionized water, drying for 7h at 75 ℃ to obtain surface modified active carbon, wherein the mass ratio of 95wt% ethanol water solution, gamma-aminopropyl triethoxysilane, cetyltrimethylammonium bromide ethanol solution and active carbon loaded with 3-dimethylaminopropylamine is as follows: 100:1.5:5: the mass ratio of the cetyl trimethyl ammonium bromide to the ethanol in the cetyl trimethyl ammonium bromide ethanol solution is as follows: 1:9, a step of performing the process;
(3) Uniformly mixing PCL400 and N, N-dimethylformamide, cooling to 1 ℃ in an ice water bath, adding cesium carbonate and epoxybromopropane, uniformly stirring at a stirring speed of 150r/min, maintaining the temperature for reacting for 25 hours, filtering, collecting filtrate, rotationally evaporating and concentrating, adding deionized water for precipitation, filtering, dissolving the obtained filter residues by tetrahydrofuran, adding deionized water for precipitation, filtering, repeatedly dissolving, adding deionized water for precipitation, and vacuum drying at 55 ℃ for 11 hours after the filtering process is performed three times to obtain the epoxy-terminated polycaprolactone, wherein the mass ratio of PCL400 to N, N-dimethylformamide to cesium carbonate to epoxybromopropane is: 130:380:50:36.5;
(4) Mixing the surface modified activated carbon with ethyl acetate according to a ratio of 5: ultrasonic oscillation is carried out for 15min at the frequency of 30kHz in the mass ratio of 25, so as to obtain surface modified activated carbon dispersion liquid; dehydrating epoxy-terminated polycaprolactone and PCL1000 at a stirring speed of 180r/min for 1h at 120 ℃ to obtain dehydrated epoxy-terminated polycaprolactone and dehydrated PCL1000, adding 2,4, 6-tris (dimethylaminomethyl) phenol into the dehydrated epoxy-terminated polycaprolactone, stirring uniformly, introducing nitrogen, heating to 160 ℃, increasing the stirring speed to 500r/min, dropwise adding diphenylmethane diisocyanate, dropwise adding the mixture in 90min, carrying out heat preservation reaction for 90min, cooling to 75 ℃ at a cooling speed of 2 ℃/min after the reaction is finished, adding diphenylmethane diisocyanate and dehydrated PCL1000, reacting at 75 ℃ for 2h, adding 1, 4-butanediol and trimethylolpropane, heating to 85 ℃, reacting for 2h, adding epoxy resin and ethyl acetate, reacting at 80 ℃ for 1h, adding methylparaben, blocking the epoxy-terminated polyol, maintaining the reaction for 2h, cooling to room temperature, adding surface-modified active carbon dispersion liquid, and uniformly mixing to obtain polyurethane adhesive, wherein the epoxy-terminated polycaprolactone, the 2,4, 6-dimethylaminophenol, the surface-modified polyol, the surface-modified dimethylol, the styrene-1-glycol, the surface-modified dimethylol, the modified dimethylol-1000-formaldehyde resin and the modified PCL-modified styrene-1, the surface-modified styrene-1-butadiene-acrylate resin are obtained by mixing. 200:13.5:1000:1000:110:80:96:200:125:240, the mass ratio of the diphenylmethane diisocyanate added in two times is as follows: 250:750.
Example 4
The embodiment discloses a preparation method of a polyurethane adhesive, which comprises the following steps:
(1) Washing the activated carbon with deionized water for 3 times, and mixing the activated carbon with deionized water according to a ratio of 5:250, boiling for 3 times at 100 ℃ for 20min each time, filtering, drying for 11h at 105 ℃, grinding, and sieving with a 600-mesh sieve to obtain pretreated activated carbon; uniformly mixing 3-dimethylaminopropylamine and ethanol, uniformly stirring at a stirring speed of 150r/min at room temperature, adding pretreated activated carbon, continuously stirring at room temperature for 5 hours, heating to 60 ℃ in a water bath, stirring for 1 hour, filtering, washing with deionized water, and drying at 75 ℃ for 3 hours to obtain activated carbon loaded with 3-dimethylaminopropylamine, wherein the mass ratio of 3-dimethylaminopropylamine to ethanol to pretreated activated carbon is: 15:60:5, a step of;
(2) Dropwise adding gamma-aminopropyl triethoxysilane into 95wt% ethanol water solution at room temperature, after dropwise adding, ultrasonic treatment is carried out for 10min at the frequency of 30kHz, stirring is carried out for 5h at the stirring speed of 150r/min, then dropwise adding cetyltrimethylammonium bromide ethanol solution, after dropwise adding is completed within 30min, adding active carbon loaded with 3-dimethylaminopropylamine, heating in a water bath to 70 ℃ for reacting for 6.5h, cooling to room temperature after reacting, filtering, washing with deionized water, drying for 7h at 75 ℃ to obtain surface modified active carbon, wherein the mass ratio of 95wt% ethanol water solution, gamma-aminopropyl triethoxysilane, cetyltrimethylammonium bromide ethanol solution and active carbon loaded with 3-dimethylaminopropylamine is as follows: 100:2:5: the mass ratio of the cetyl trimethyl ammonium bromide to the ethanol in the cetyl trimethyl ammonium bromide ethanol solution is as follows: 1:9, a step of performing the process;
(3) Uniformly mixing PCL400 and N, N-dimethylformamide, cooling to 1 ℃ in an ice water bath, adding cesium carbonate and epoxybromopropane, uniformly stirring at a stirring speed of 150r/min, maintaining the temperature for reacting for 25 hours, filtering, collecting filtrate, rotationally evaporating and concentrating, adding deionized water for precipitation, filtering, dissolving the obtained filter residues by tetrahydrofuran, adding deionized water for precipitation, filtering, repeatedly dissolving, adding deionized water for precipitation, and vacuum drying at 55 ℃ for 11 hours after the filtering process is performed three times to obtain the epoxy-terminated polycaprolactone, wherein the mass ratio of PCL400 to N, N-dimethylformamide to cesium carbonate to epoxybromopropane is: 140:400:51:37, respectively;
(4) Mixing the surface modified activated carbon with ethyl acetate according to a ratio of 5: ultrasonic oscillation is carried out for 15min at the frequency of 30kHz in the mass ratio of 25, so as to obtain surface modified activated carbon dispersion liquid; dehydrating epoxy-terminated polycaprolactone and PCL2000 at a stirring speed of 180r/min for 1h at 120 ℃ to obtain dehydrated epoxy-terminated polycaprolactone and dehydrated PCL2000, adding 2,4, 6-tris (dimethylaminomethyl) phenol into the dehydrated epoxy-terminated polycaprolactone, stirring uniformly, introducing nitrogen, heating to 165 ℃, increasing the stirring speed to 500r/min, dropwise adding diphenylmethane diisocyanate, dropwise adding the mixture in 90min, carrying out heat preservation reaction for 75min, cooling to 75 ℃ at a cooling speed of 2 ℃/min after the reaction is finished, adding diphenylmethane diisocyanate and dehydrated PCL2000, reacting at 75 ℃ for 2h, adding 1, 4-butanediol and trimethylolpropane, heating to 85 ℃, reacting for 2h, adding epoxy resin and ethyl acetate, reacting at 80 ℃ for 1h, adding methylparaben, blocking the epoxy-terminated polyol, maintaining the reaction for 2h, cooling to room temperature, adding surface-modified active carbon dispersion liquid, and uniformly mixing to obtain polyurethane adhesive, wherein the epoxy-terminated polycaprolactone, the 2,4, 6-dimethylaminophenol, the surface-modified dimethylol, the styrene-4-epoxy-4-hydroxy-styrene, the surface-modified styrene-1, the surface-modified dimethylol-2-4-hydroxy-2-methyl-2-hydroxy-4-methyl-2-methyl-hydroxy-2-methyl-4-hydroxy-methyl-2-methyl-ketone, and the modified PCL-hydroxy-1-hydroxy-4-hydroxy-methyl 2-hydroxy-terminated epoxy-methyl) respectively. 240:15:1000:2000:100:80:170:220:125:255, the mass ratio of the diphenylmethane diisocyanate added twice is as follows: 250:750.
Example 5
The embodiment discloses a preparation method of a polyurethane adhesive, which comprises the following steps:
(1) Washing the activated carbon with deionized water for 3 times, and mixing the activated carbon with deionized water according to a ratio of 5:300, boiling for 3 times at 100 ℃ for 20min each time, filtering, drying for 10h at 110 ℃, grinding, and sieving with a 600-mesh sieve to obtain pretreated activated carbon; uniformly mixing 3-dimethylaminopropylamine and ethanol, uniformly stirring at a stirring speed of 150r/min at room temperature, adding pretreated activated carbon, continuously stirring at room temperature for 6 hours, heating to 60 ℃ in a water bath, stirring for 1 hour, filtering, washing with deionized water, and drying at 80 ℃ for 2 hours to obtain activated carbon loaded with 3-dimethylaminopropylamine, wherein the mass ratio of 3-dimethylaminopropylamine to ethanol to pretreated activated carbon is: 20:70:5, a step of;
(2) Dropwise adding gamma-aminopropyl triethoxysilane into 95wt% ethanol water solution at room temperature, after dropwise adding, ultrasonic treatment is carried out for 5min at the frequency of 40kHz, stirring is carried out for 6h at the stirring speed of 150r/min, then dropwise adding cetyltrimethylammonium bromide ethanol solution, after dropwise adding is completed within 30min, adding active carbon loaded with 3-dimethylaminopropylamine, heating to 75 ℃ in water bath for reacting for 5h, cooling to room temperature after reacting, filtering, washing with deionized water, and drying for 6h at 80 ℃ to obtain surface modified active carbon, wherein the mass ratio of 95wt% ethanol water solution, gamma-aminopropyl triethoxysilane, cetyltrimethylammonium bromide ethanol solution and active carbon loaded with 3-dimethylaminopropylamine is as follows: 100:2.5:5: the mass ratio of the cetyl trimethyl ammonium bromide to the ethanol in the cetyl trimethyl ammonium bromide ethanol solution is as follows: 1:9, a step of performing the process;
(3) Uniformly mixing PCL400 and N, N-dimethylformamide, cooling to 0 ℃ in an ice water bath, adding cesium carbonate and epoxybromopropane, uniformly stirring at a stirring speed of 150r/min, maintaining the temperature for reaction for 26 hours, filtering, collecting filtrate, rotationally evaporating and concentrating, adding deionized water for precipitation, filtering, dissolving the obtained filter residues with tetrahydrofuran, adding deionized water for precipitation, filtering, repeatedly dissolving, adding deionized water for precipitation, and vacuum drying at 60 ℃ for 10 hours after the filtering process is performed three times to obtain the epoxy-terminated polycaprolactone, wherein the mass ratio of PCL400 to N, N-dimethylformamide to cesium carbonate to epoxybromopropane is: 150:420:52:37.5;
(4) Mixing the surface modified activated carbon with ethyl acetate according to a ratio of 5: ultrasonic oscillation is carried out for 10min at the frequency of 40kHz in the mass ratio of 25, so as to obtain surface modified activated carbon dispersion liquid; dehydrating epoxy-terminated polycaprolactone and PCL1000 at a stirring speed of 180r/min for 1h at 120 ℃ to obtain dehydrated epoxy-terminated polycaprolactone and dehydrated PCL1000, adding 2,4, 6-tris (dimethylaminomethyl) phenol into the dehydrated epoxy-terminated polycaprolactone, stirring uniformly, introducing nitrogen, heating to 170 ℃, increasing the stirring speed to 500r/min, dropwise adding diphenylmethane diisocyanate, dropwise adding the mixture in 90min, carrying out heat preservation reaction for 60min, cooling to 75 ℃ at a cooling speed of 2 ℃/min after the reaction is finished, adding diphenylmethane diisocyanate and dehydrated PCL1000, reacting at 75 ℃ for 2h, adding 1, 4-butanediol and trimethylolpropane, heating to 85 ℃, reacting for 2h, adding epoxy resin and ethyl acetate, reacting at 80 ℃ for 1h, adding methylparaben, blocking the epoxy-terminated polyol, maintaining the reaction for 2h, cooling to room temperature, adding surface-modified active carbon dispersion liquid, and uniformly mixing to obtain polyurethane adhesive, wherein the epoxy-terminated polycaprolactone, the 2,4, 6-dimethylaminophenol, the surface-modified epoxy-4-trimethylolpropane, the surface-modified styrene-1-glycol, the surface-modified styrene-1-acrylate resin and the modified PCL1000 are prepared by the following steps of reacting the epoxy-terminated polycaprolactone, the epoxy-4-dimethylether and the surface-modified styrene-1-acrylate resin with the modified PCL. 280:16:1000:1000:90:80:150:200:125:270, the mass ratio of the diphenylmethane diisocyanate added twice is as follows: 250:750.
Comparative example 1
The comparative example discloses a preparation method of a polyurethane adhesive, which comprises the following steps:
(1) Washing the activated carbon with deionized water for 3 times, and mixing the activated carbon with deionized water according to a ratio of 5:250, boiling for 3 times at 100 ℃ for 20min each time, filtering, drying for 11h at 105 ℃, grinding, and sieving with a 600-mesh sieve to obtain pretreated activated carbon;
(2) Dropwise adding gamma-aminopropyl triethoxysilane into 95wt% ethanol water solution at room temperature, after dropwise adding, carrying out ultrasonic treatment for 10min at the frequency of 30kHz, stirring for 5h at the stirring speed of 150r/min, dropwise adding cetyltrimethylammonium bromide ethanol solution, after dropwise adding, dropwise adding pretreated activated carbon, heating to 70 ℃ in a water bath to react for 6.5h, cooling to room temperature after reacting, filtering, washing with deionized water, and drying for 7h at the temperature of 75 ℃ to obtain surface modified activated carbon, wherein the mass ratio of 95wt% ethanol water solution, gamma-aminopropyl triethoxysilane, cetyltrimethylammonium bromide ethanol solution and pretreated activated carbon is as follows: 100:1:5: the mass ratio of the cetyl trimethyl ammonium bromide to the ethanol in the cetyl trimethyl ammonium bromide ethanol solution is as follows: 1:9, a step of performing the process;
(3) Uniformly mixing PCL400 and N, N-dimethylformamide, cooling to 1 ℃ in an ice water bath, adding cesium carbonate and epoxybromopropane, uniformly stirring at a stirring speed of 150r/min, maintaining the temperature for reacting for 25 hours, filtering, collecting filtrate, rotationally evaporating and concentrating, adding deionized water for precipitation, filtering, dissolving the obtained filter residues by tetrahydrofuran, adding deionized water for precipitation, filtering, repeatedly dissolving, adding deionized water for precipitation, and vacuum drying at 55 ℃ for 11 hours after the filtering process is performed three times to obtain the epoxy-terminated polycaprolactone, wherein the mass ratio of PCL400 to N, N-dimethylformamide to cesium carbonate to epoxybromopropane is: 120:360:49:36;
(4) Mixing the surface modified activated carbon with ethyl acetate according to a ratio of 5: ultrasonic oscillation is carried out for 15min at the frequency of 30kHz in the mass ratio of 25, so as to obtain surface modified activated carbon dispersion liquid; dehydrating epoxy-terminated polycaprolactone and PCL1000 at a stirring speed of 180r/min for 1h at 120 ℃ to obtain dehydrated epoxy-terminated polycaprolactone and dehydrated PCL1000, adding 2,4, 6-tris (dimethylaminomethyl) phenol into the dehydrated epoxy-terminated polycaprolactone, stirring uniformly, introducing nitrogen, heating to 155 ℃, increasing the stirring speed to 500r/min, dropwise adding diphenylmethane diisocyanate, dropwise adding in 90min, carrying out heat preservation reaction for 105min, cooling to 75 ℃ at a cooling speed of 2 ℃/min after the reaction is finished, adding diphenylmethane diisocyanate and dehydrated PCL1000, reacting at 75 ℃ for 2h, adding 1, 4-butanediol and trimethylolpropane, heating to 85 ℃, reacting for 2h, adding epoxy resin and ethyl acetate, reacting at 80 ℃ for 1h, adding methylparaben, maintaining at 80 ℃ for 2h, cooling to room temperature, adding surface-modified active carbon dispersion liquid, 3-dimethylaminopropylamine, and uniformly mixing to obtain polyurethane adhesive, wherein the epoxy-terminated polycaprolactone, the epoxy-4, 6-dimethylaminopropane, the surface-modified dimethylolpropane, the surface-modified dimethylolglycinate and the PCL1000 are prepared by the following steps of dispersing epoxy-terminated polyol, the epoxy-4-dimethylolglycinate, the dimethylolglycinate and the dimethylolglycinate: 160:12:1000:1000:120:80:75:200:125:200:25, the mass ratio of the diphenylmethane diisocyanate added in two times is as follows: 250:750.
Comparative example 2
The comparative example discloses a preparation method of a polyurethane adhesive, which comprises the following steps:
(1) Washing the activated carbon with deionized water for 3 times, and mixing the activated carbon with deionized water according to a ratio of 5:250, boiling for 3 times at 100 ℃ for 20min each time, filtering, drying for 11h at 105 ℃, grinding, and sieving with a 600-mesh sieve to obtain pretreated activated carbon; uniformly mixing 3-dimethylaminopropylamine and ethanol, uniformly stirring at a stirring speed of 150r/min at room temperature, adding pretreated activated carbon, continuously stirring at room temperature for 5 hours, heating to 60 ℃ in a water bath, stirring for 1 hour, filtering, washing with deionized water, and drying at 75 ℃ for 3 hours to obtain activated carbon loaded with 3-dimethylaminopropylamine, wherein the mass ratio of 3-dimethylaminopropylamine to ethanol to pretreated activated carbon is: 15:60:5, a step of;
(2) Dropwise adding gamma-aminopropyl triethoxysilane into 95wt% ethanol water solution at room temperature, after dropwise adding, ultrasonic treatment is carried out for 10min at the frequency of 30kHz, stirring is carried out for 5h at the stirring speed of 150r/min, then dropwise adding cetyltrimethylammonium bromide ethanol solution, after dropwise adding is completed within 30min, adding active carbon loaded with 3-dimethylaminopropylamine, heating in a water bath to 70 ℃ for reacting for 6.5h, cooling to room temperature after reacting, filtering, washing with deionized water, drying for 7h at 75 ℃ to obtain surface modified active carbon, wherein the mass ratio of 95wt% ethanol water solution, gamma-aminopropyl triethoxysilane, cetyltrimethylammonium bromide ethanol solution and active carbon loaded with 3-dimethylaminopropylamine is as follows: 100:1:5: the mass ratio of the cetyl trimethyl ammonium bromide to the ethanol in the cetyl trimethyl ammonium bromide ethanol solution is as follows: 1:9, a step of performing the process;
(3) Mixing the surface modified activated carbon with ethyl acetate according to a ratio of 5: ultrasonic oscillation is carried out for 15min at the frequency of 30kHz in the mass ratio of 25, so as to obtain surface modified activated carbon dispersion liquid; dehydrating PCL1000 at a stirring speed of 180r/min at 120 ℃ for 1h to obtain dehydrated PCL1000, uniformly mixing diphenylmethane diisocyanate and dehydrated PCL1000, reacting at 75 ℃ for 2h, adding 1, 4-butanediol and trimethylolpropane, heating to 85 ℃, reacting for 2h, adding epoxy resin and ethyl acetate, reacting at 80 ℃ for 1h, adding methyl parahydroxybenzoate for end capping, maintaining at 80 ℃ for 2h, reacting, cooling to room temperature, adding surface modified activated carbon dispersion liquid, and uniformly mixing to obtain the polyurethane adhesive, wherein the mass ratio of diphenylmethane diisocyanate, PCL1000, 1, 4-butanediol, trimethylolpropane, epoxy resin, ethyl acetate, methyl parahydroxybenzoate and surface modified activated carbon dispersion liquid is as follows: 1000:1400:120:80:130:200:125:200.
example 6
The embodiment discloses a method for producing a high-temperature steaming and boiling resistant packaging film by adopting a polyurethane adhesive, which comprises the following steps:
the polyurethane adhesives prepared in examples 1-5 and comparative examples 1-2 were uniformly coated on BOPP films, respectively, and compounded with aluminum foil films to prepare a double-layer composite structure, which was cooked at 50deg.C The mixture is treated for 96 hours to obtain a high-temperature resistant steaming and boiling packaging film which is recorded as a composite film 1-7, wherein the coating amount of the polyurethane adhesive is 5g/m 2 。
The activated carbon in the comparative examples of all the above examples is from Shanghai Hainou carbon Co., ltd, model HNACB-200; 3-dimethylaminopropylamine from Jinan century to chemical industry Co., ltd, CAS number 109-55-7; gamma-aminopropyl triethoxysilane is available from Shanghai Ala Biochemical technologies Co., ltd, CAS number 919-30-2; cetyl dimethyl ammonium bromide is available from Hailading Biochemical technologies Co., ltd, CAS number 57-09-0; polycaprolactone diols were from Hunan polykernel chemical materials Co., ltd, with accession numbers 2044 (molecular weight 400), 2102 (molecular weight 1000), 2202 (molecular weight 2000); cesium carbonate is from Shanghai Michelson Biochemical technologies Co., ltd, with CAS number 534-17-8; the epibromohydrin is from the Wuhan Kano technology Co., ltd, with the CAS number of 3132-64-7; tetrahydrofuran is from Shanghai Jizhui Biochemical technology Co., ltd, CAS number 123-75-1; diphenylmethane diisocyanate from Shanghai Michelia Biochemical technology Co., ltd., CAS number 101-68-8;2,4, 6-tris (dimethylaminomethyl) phenol was from the scientific and technological company, calif. Beijing, with a CAS number of 90-72-2; 1.4-butanediol from Shanghai Jizhui Biochemical technology Co., ltd., CAS number 110-63-4; trimethylolpropane is from the scientific and technological company of Bajingbailing, with CAS number of 77-99-6; methyl parahydroxybenzoate was obtained from Nanjing chemical reagent Co., ltd, CAS number 99-76-3; epoxy was from the Jiangyin Wan Qian chemical strength supplier, model E44 (6101).
Test examples
Test one: heat resistance test: the heat resistance of the composite films 1 to 7 was tested according to GB/T10004-2008 "composite Plastic film for packaging, bag Dry method composite, extrusion composite", and the composite films were subjected to digestion at 135℃for 40 minutes, and examined for the presence of obvious bubbles and deformation, and the test results are shown in Table 1.
As can be seen from Table 1, the polyurethane adhesive bonding composite films 1-7 prepared by the invention have good heat resistance, and have no more bubbles and large deformation after being steamed at 135 ℃ for 40 min.
And II, testing: peel strength test: the peel strength of the composite films 1 to 7 was measured according to GB/T10004-2008 "composite Plastic film for packaging, bag Dry method composite, extrusion composite" and GB/T8808-2002 "Soft composite Plastic Material peeling test method", and the peel strengths before and after boiling at 135℃for 40 minutes were measured, and the test results are shown in Table 2.
As can be seen from Table 2, the polyurethane adhesive prepared by the invention has better peel strength for bonding the composite films 1-7, and the composite films 1-3 show that the 180 DEG peel strength of the composite films is increased along with the increase of the contents of the epoxy-terminated polycaprolactone and the epoxy resin before and after cooking, the 180 DEG peel strength of the composite films is reduced because the 180 DEG peel strength of the adhesive is increased when the polycaprolactone diol with the molecular weight of 2000 is selected, the flexibility is better because the molecular chain of the polycaprolactone diol with the larger molecular weight is longer, the contained ester bonds are more, the bonding effect is better, and the 180 DEG peel strength of the composite films 2 and 6 is reduced because the 3-dimethylaminopropylamine is crosslinked with the epoxy resin when the 3-dimethylaminopropylamine is directly added into the polyurethane adhesive, and the 180 DEG peel strength of the adhesive is reduced, and the 180 DEG peel strength of the isocyanate in the adhesive after cooking is not reduced enough to form a crosslinked system though the adhesive is not reduced; as can be seen from the composite film 2 and the composite film 7, the 180-degree peel strength of the adhesive is increased because the system does not contain the rigid group of oxazolidone, and the 180-degree peel strength of the adhesive is reduced because the adhesive does not contain oxazolidone, and the heat resistance of the adhesive is reduced.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the polyurethane adhesive is characterized by comprising the following steps of:
(1) Mixing 3-dimethylaminopropylamine with ethanol, stirring, adding pretreated activated carbon, continuously stirring, heating to a set temperature, stirring, filtering, washing and drying to obtain activated carbon loaded with 3-dimethylaminopropylamine;
(2) Dropwise adding gamma-aminopropyl triethoxysilane into an ethanol water solution, carrying out ultrasonic treatment, stirring, dropwise adding hexadecyl trimethyl ammonium bromide ethanol solution, adding activated carbon loaded with 3-dimethylaminopropylamine after the dropwise adding is finished, reacting, cooling, filtering, washing and drying to obtain surface modified activated carbon;
(3) Mixing PCL and N, N-dimethylformamide, cooling to a set temperature, adding cesium carbonate and epoxy bromopropane, stirring, reacting, filtering, purifying and drying after the reaction to obtain epoxy-terminated polycaprolactone;
(4) Adding 2,4, 6-tris (dimethylaminomethyl) phenol into epoxy-terminated polycaprolactone, stirring, heating to a first set temperature under the inert gas atmosphere, dropwise adding diphenylmethane diisocyanate, reacting at the first set temperature, cooling to a second set temperature after the reaction, adding diphenylmethane diisocyanate and PCL, reacting at the second set temperature, adding 1, 4-butanediol and trimethylolpropane, heating to a third set temperature, reacting, adding epoxy resin and ethyl acetate, reacting at a fourth set temperature, adding methylparaben after the reaction, maintaining the fourth set temperature for reaction, cooling, adding surface modified activated carbon dispersion, and mixing to obtain the polyurethane adhesive.
2. The method for preparing a polyurethane adhesive according to claim 1, wherein in the step (1): the mass ratio of the 3-dimethylaminopropylamine to the ethanol to the pretreated activated carbon is (10-20): (50-70): 5, a step of; setting the temperature to be 60 ℃; wherein, the pretreatment activated carbon is prepared by the following steps: washing the activated carbon with deionized water, mixing the washed activated carbon with the deionized water, boiling, filtering, drying, grinding and sieving to obtain pretreated activated carbon, wherein the mass ratio of the activated carbon to the deionized water is 5: (200-300); boiling comprises boiling at 100deg.C for 3 times, each for 20min.
3. The method for preparing a polyurethane adhesive according to claim 1, wherein in the step (2): the mass ratio of the ethanol aqueous solution, the gamma-aminopropyl triethoxysilane, the cetyl trimethyl ammonium bromide ethanol solution and the 3-dimethylaminopropylamine loaded active carbon is 100: (0.5-2.5): 5:5, a step of; the reaction condition is 65-75 ℃ for 5-8h; in the cetyl trimethyl ammonium bromide ethanol solution, cetyl trimethyl ammonium bromide is used as a solute, ethanol is used as a solvent, and the mass ratio of the cetyl trimethyl ammonium bromide to the ethanol is 1:9.
4. the method for preparing a polyurethane adhesive according to claim 1, wherein in the step (3): the mass ratio of PCL, N-dimethylformamide, cesium carbonate and epoxybromopropane is (110-150): (340-420): (48-52): (35.5-37.5); setting the temperature to be 0-2 ℃, and reacting for 24-26 hours at the set temperature; the PCL includes PCL400.
5. The method for preparing a polyurethane adhesive according to claim 1, wherein in the step (4): the preparation method of the surface modified activated carbon dispersion liquid comprises the following steps: mixing the surface modified activated carbon with ethyl acetate, and performing ultrasonic treatment to obtain a surface modified activated carbon dispersion liquid; wherein the mass ratio of the surface modified activated carbon to the ethyl acetate is 5:25, ultrasonic conditions are: ultrasonic oscillation is carried out for 10-20min at the frequency of 20-40 kHz.
6. The method for preparing a polyurethane adhesive according to claim 1, wherein in the step (4): the mass ratio of the epoxy-terminated polycaprolactone, 2,4, 6-tris (dimethylaminomethyl) phenol, diphenylmethane diisocyanate, PCL, 1, 4-butanediol, trimethylolpropane, epoxy resin, ethyl acetate, methyl p-hydroxybenzoate and surface-modified activated carbon dispersion liquid is (120-280): (11-16): (975-1000): (1000-2000): (90-120): 80: (50-170): (200-220): 125: (210-270), wherein the mass ratio of the diphenylmethane diisocyanate added in the two steps is 250: (725-750).
7. The method for preparing a polyurethane adhesive according to claim 1, wherein in the step (4): the first set temperature is 150-170 ℃, and the reaction time is 60-120min; the second set temperature is 75 ℃, and the reaction time is 2 hours; the third set temperature is 85 ℃, and the reaction time is 2 hours; the fourth set temperature is 80 ℃ and the reaction time is 2h.
8. The method for preparing a polyurethane adhesive according to claim 1, wherein in the step (4): the epoxy-terminated polycaprolactone and PCL are dehydrated, and the conditions of the dehydration are as follows: dehydrating at 120 ℃ for 1h at a stirring speed of 180 r/min; the PCL comprises any one of PCL1000 and PCL 2000.
9. A polyurethane adhesive prepared by the method for preparing a polyurethane adhesive according to any one of claims 1 to 8.
10. A method for producing a retort resistant packaging film using the polyurethane adhesive of claim 9, comprising the steps of:
and uniformly coating the polyurethane adhesive on a BOPP film, compounding with an aluminum foil film, and curing to obtain the high-temperature-resistant steaming packaging film.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040082753A1 (en) * | 2001-03-06 | 2004-04-29 | Sanderson John R. | Purification of propylene oxide |
| CN102936210A (en) * | 2012-11-15 | 2013-02-20 | 中南林业科技大学 | 2,4-toluene diisocyanate and preparation method and application thereof |
| CN104163906A (en) * | 2014-03-07 | 2014-11-26 | 华东理工大学 | Catalyst for use in trimerization of isocyanate and cyclization reaction of isocyanate and epoxy and application thereof |
| US20170051103A1 (en) * | 2014-05-05 | 2017-02-23 | Resinate Materials Group, Inc. | Improved recycle-content polyester polyols |
| CN110563913A (en) * | 2019-08-30 | 2019-12-13 | 山东一诺威聚氨酯股份有限公司 | High heat-resistant thermoplastic polyurethane elastomer and preparation method thereof |
| CN115873225A (en) * | 2022-12-29 | 2023-03-31 | 广州市白云化工实业有限公司 | Polyester epoxy diluent, epoxy adhesive and preparation method thereof |
-
2023
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040082753A1 (en) * | 2001-03-06 | 2004-04-29 | Sanderson John R. | Purification of propylene oxide |
| CN102936210A (en) * | 2012-11-15 | 2013-02-20 | 中南林业科技大学 | 2,4-toluene diisocyanate and preparation method and application thereof |
| CN104163906A (en) * | 2014-03-07 | 2014-11-26 | 华东理工大学 | Catalyst for use in trimerization of isocyanate and cyclization reaction of isocyanate and epoxy and application thereof |
| US20170051103A1 (en) * | 2014-05-05 | 2017-02-23 | Resinate Materials Group, Inc. | Improved recycle-content polyester polyols |
| CN110563913A (en) * | 2019-08-30 | 2019-12-13 | 山东一诺威聚氨酯股份有限公司 | High heat-resistant thermoplastic polyurethane elastomer and preparation method thereof |
| CN115873225A (en) * | 2022-12-29 | 2023-03-31 | 广州市白云化工实业有限公司 | Polyester epoxy diluent, epoxy adhesive and preparation method thereof |
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