CN117285900A - Polyurethane adhesive for flexible package and preparation method thereof - Google Patents
Polyurethane adhesive for flexible package and preparation method thereof Download PDFInfo
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- CN117285900A CN117285900A CN202311212135.XA CN202311212135A CN117285900A CN 117285900 A CN117285900 A CN 117285900A CN 202311212135 A CN202311212135 A CN 202311212135A CN 117285900 A CN117285900 A CN 117285900A
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- China
- Prior art keywords
- polyurethane adhesive
- rosin
- flexible packaging
- preparation
- eso
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- 239000000853 adhesive Substances 0.000 title claims abstract description 105
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 105
- 239000004814 polyurethane Substances 0.000 title claims abstract description 85
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 55
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 55
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 55
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229920000728 polyester Polymers 0.000 claims abstract description 42
- 229920005862 polyol Polymers 0.000 claims abstract description 33
- 150000003077 polyols Chemical class 0.000 claims abstract description 33
- 238000009459 flexible packaging Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 16
- 239000003549 soybean oil Substances 0.000 claims abstract description 16
- 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 abstract description 11
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 11
- 239000001361 adipic acid Substances 0.000 claims abstract description 10
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 7
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 7
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000002131 composite material Substances 0.000 abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 238000009835 boiling Methods 0.000 abstract description 13
- 238000007789 sealing Methods 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 24
- 238000012360 testing method Methods 0.000 description 16
- 239000000523 sample Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 239000002028 Biomass Substances 0.000 description 8
- 230000006378 damage Effects 0.000 description 8
- 229920005906 polyester polyol Polymers 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012940 solvent-free polyurethane adhesive Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- KKADPXVIOXHVKN-UHFFFAOYSA-N 4-hydroxyphenylpyruvic acid Chemical compound OC(=O)C(=O)CC1=CC=C(O)C=C1 KKADPXVIOXHVKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000004668 long chain fatty acids Chemical group 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- 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
-
- 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
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- 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
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
-
- 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
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
- C09J2400/16—Metal
- C09J2400/163—Metal in the substrate
-
- 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
- C09J2423/00—Presence of polyolefin
- C09J2423/10—Presence of homo or copolymers of propene
- C09J2423/106—Presence of homo or copolymers of propene in the substrate
-
- 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
- C09J2467/00—Presence of polyester
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a polyurethane adhesive for flexible packaging and a preparation method thereof. A preparation method of a polyurethane adhesive for flexible packaging comprises the following steps: (1) Preparing polyester PET-A by adopting 1, 6-adipic acid, ethylene glycol and diethylene glycol; preparing polyester PET-B by adopting 1, 6-adipic acid, phthalic anhydride, ethylene glycol and neopentyl glycol; preparing bio-based polyol ESO/Rosin by adopting Rosin and epoxidized soybean oil; (2) Preparing polyurethane prepolymer pre-PU-A by adopting PET-A and diphenylmethane diisocyanate; (3) Mixing ESO/Rosin and PET-B as a component B, pre-PU-A as a component A, and mixing A, B to obtain the polyurethane adhesive PU/ER for flexible packaging. The invention does not use toxic and harmful reagent, has simple preparation process and low energy consumption; the bio-based bi-component polyurethane adhesive prepared from rosin and epoxidized soybean oil has higher hydrophobicity, and successfully improves the bonding strength before and after water boiling and the heat sealing strength of the composite film.
Description
Technical Field
The invention relates to the technical field of polyurethane adhesives, in particular to a polyurethane adhesive for flexible packaging and a preparation method thereof.
Background
The steaming-resistant flexible packaging composite film is widely favored as a convenient and sanitary food package because the steaming-resistant flexible packaging composite film can greatly prolong the quality guarantee period of food and retain the original flavor of the food. At present, most adhesives used for compounding a steaming-resistant film are solvent polyurethane adhesives, the adhesives are easy to hydrolyze under high-temperature and high-humidity environments to cause the peeling force to be reduced, and the composite film is layered or a steaming bag is broken seriously, so that the adhesives are required to be modified to improve the water-resistant performance of the adhesives.
Patent CN202111607212.2 discloses a polyol component of a flexible bi-component polyurethane adhesive for flexible packaging composite films and a preparation method thereof, the prepared polyurethane adhesive uses ethyl acetate as an ester solvent, and the ethyl acetate has micro toxicity and generates a certain harm to the body in the discharging process. The polyurethane adhesive synthesized by the prior art is solvent type, can bring a large amount of Volatile Organic Compound (VOC) emission in the use process, and damages the physical health of constructors while damaging the environment; in addition, the polyurethane adhesive is mainly derived from petrochemical products, biomass is not added as a synthesis raw material, so that the raw material price is increased, the cost is increased rapidly, the synthesis reaction temperature is high, and the energy consumption is high.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the polyurethane adhesive for flexible packaging and the preparation method thereof, and the prepared bio-based adhesive is a solvent-free bi-component polyurethane adhesive, does not add any volatile organic solvent, avoids the emission of the solvent in the use process, can effectively reduce the harm to the environment and human bodies, has no solvent residue after solidification, and reduces the influence of the solvent on the performance of the adhesive; the compounding process does not need drying treatment, and the energy consumption caused by solvent volatilization can be effectively reduced.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a preparation method of a polyurethane adhesive for flexible packaging, which comprises the following steps:
(1) Preparation of polyester PET-A: mixing 1, 6-Adipic Acid (AA), ethylene Glycol (EG) and diethylene glycol (DEG), placing the mixture in a reaction vessel, stirring, and reacting to obtain polyester PET-A;
preparation of polyester PET-B: mixing 1, 6-Adipic Acid (AA), phthalic Anhydride (PA), ethylene Glycol (EG) and neopentyl glycol (NPG) in a reaction vessel, stirring and reacting to obtain polyester PET-B;
preparation of biobased polyol ESO/Rosin: rosin (Rosin), epoxidized Soybean Oil (ESO) and a catalyst are placed in a reaction vessel to react to prepare bio-based polyol ESO/Rosin;
(2) Placing the polyester PET-A prepared in the step (1) and diphenylmethane diisocyanate into a reaction container, and reacting to generate a polyurethane prepolymer pre-PU-A;
(3) Mixing the bio-based polyol ESO/Rosin and the polyester PET-B as a component B of the polyurethane adhesive, taking the polyurethane prepolymer pre-PU-A as a component A of the polyurethane adhesive, and mixing A, B to prepare the polyurethane adhesive PU/ER (epoxy Rosin polyurethane adhesive) for flexible packaging.
Preferably, in the step (1), the molar ratio of the 1, 6-adipic acid, the ethylene glycol and the diethylene glycol is 6:3:3-6:5:5.
Preferably, in the step (1), the preparation reaction temperature of the polyester PET-A is 180-260 ℃ and the reaction time is 1-3 hours; further preferably, the preparation reaction temperature of the polyester PET-A is 200-240 ℃ and the reaction time is 1.5-2.5 h.
Preferably, in the step (1), a catalyst is added in the preparation reaction process of the polyester PET-A; further preferably, the catalyst is tetrabutyl titanate; still more preferably, the catalyst is added in an amount of 0.003 to 0.005% by mass of the total mass of the material.
Preferably, in the step (1), after the preparation reaction of the polyester PET-A, the device is started to heat and vacuum pump to 110-130 ℃ in the reaction container, and the negative pressure is maintained for 1-3 hours to remove the moisture in the polyester PET-A.
Preferably, in the step (1), the molar ratio of the 1, 6-adipic acid, phthalic anhydride, ethylene glycol and neopentyl glycol is 4:0.5:6:2-6:2:6:2.
Preferably, in the step (1), the preparation reaction temperature of the polyester PET-B is 180-260 ℃ and the reaction time is 1-3 h; further preferably, the preparation reaction temperature of the polyester PET-B is 200-240 ℃ and the reaction time is 1.5-2.5 h.
Preferably, in the step (1), a catalyst is added in the preparation reaction process of the polyester PET-B; further preferably, the catalyst is tetrabutyl titanate; still more preferably, the catalyst is added in an amount of 0.003 to 0.005% by mass of the total mass of the material.
Preferably, in the step (1), after the preparation reaction of the polyester PET-B, the device is started to heat and vacuum pump to 110-130 ℃ in the reaction container, and the negative pressure is maintained for 1-3 hours to remove the moisture in the polyester PET-B.
Preferably, in the step (1), the mol ratio of the rosin to the epoxidized soybean oil is 0.5:1-2:1; further preferably, the mol ratio of the rosin to the epoxidized soybean oil is 0.8:1-2:1; still further preferably, the molar ratio of the rosin to the epoxidized soybean oil is 1:1 to 2:1; still more preferably, the molar ratio of the rosin to the epoxidized soybean oil is 1.2:1 to 1.8:1.
Preferably, in the step (1), the preparation reaction temperature of the bio-based polyol ESO/Rosin is 120-160 ℃; further preferably, the preparation reaction temperature of the bio-based polyol ESO/Rosin is 130-150 ℃.
Preferably, in the step (1), a catalyst is added during the preparation reaction of the bio-based polyol ESO/Rosin; further preferably, the catalyst is Triethylamine (TEA).
Preferably, in the step (1), after the preparation reaction of the bio-based polyol ESO/Rosin, the device is started to heat and vacuum pump to 110-130 ℃ and negative pressure in the reaction vessel, and the reaction vessel is kept for 1-3 hours to remove the moisture and the catalyst in the bio-based polyol ESO/Rosin.
Preferably, in the step (2), the mass fraction of isocyanate groups of the polyurethane prepolymer pre-PU-A is 13% -17%; further preferably, the polyurethane prepolymer pre-PU-A has an isocyanate group mass fraction of 16% -17%.
Preferably, in step (2), the temperature at which the polyester PET-A is reacted with diphenylmethane diisocyanate is from 70 to 80 ℃.
Preferably, in the step (3), the addition amount of the bio-based polyol ESO/Rosin is 10% -60% of the mass of the polyester PET-B; further preferably, the amount of the bio-based polyol ESO/Rosin added is 10 to 40% by mass of the polyester PET-B.
Preferably, in the step (3), the A, B two components are mixed according to the molar ratio of isocyanate groups to hydroxyl groups of 2:1-3:1; further preferably, the A, B two components are mixed at a molar ratio of isocyanate groups to hydroxyl groups of 2.5:1.
The invention provides a polyurethane adhesive for flexible packages, which is prepared by the preparation method of the polyurethane adhesive for flexible packages.
Compared with the prior art, the invention has the beneficial effects that:
in the preparation method of the polyurethane adhesive for flexible packaging, two different polyesters PET-A and PET-B are synthesized through monomer molecular structure design; the bio-based polyol ESO/Rosin is synthesized by taking Rosin (Rosin) and Epoxidized Soybean Oil (ESO) as raw materials through a ring-opening esterification reaction, then the bio-based polyol is introduced into a solvent-free polyurethane adhesive structure, a long chain fatty acid structure of vegetable oil base and a rigid tricyclic phenanthrene skeleton structure of Rosin are introduced into the polyurethane adhesive through hydroxyl and isocyanate reaction, and the bio-based solvent-free adhesive with the adhesive strength before and after boiling and the heat sealing strength of a composite film meeting the use requirements of national standard GB/T41168-2021 is successfully obtained by utilizing the high adhesive force of the Rosin to a packaging film substrate and the hydrophobicity of an epoxidized soybean oil aliphatic long chain. The application of renewable biological resources successfully reduces the dependence of polyurethane adhesives on petroleum raw materials, reduces the synthesis cost and reduces the harm of traditional polyurethane adhesives to the environment and human bodies.
The invention does not use toxic and harmful reagent, and has simple preparation process and low energy consumption. The bio-based double-component polyurethane adhesive prepared by feeding rosin and epoxidized soybean oil in a certain molar ratio has higher hydrophobicity, successfully improves the bonding strength before and after water boiling and the heat sealing strength of a composite film, and has the peeling force of RCPP/Al layers far higher than the requirements of national standard GB/T41168-2021 (peeling force after water boiling is more than or equal to 2.0N) after water boiling.
Drawings
FIG. 1 is a schematic diagram of a synthetic route of a polyurethane adhesive for flexible packaging according to an embodiment of the present invention;
FIG. 2 is a schematic view of a flexible package composite film structure;
FIG. 3 is a tensile stress-strain curve of the adhesive of example 1;
FIG. 4 is a graph showing the change in adhesive strength and heat seal strength before and after boiling in water of the composite packaging films of the adhesives of examples and comparative examples;
FIG. 5 is the surface water contact angle of the adhesives of examples and comparative examples;
fig. 6 is an infrared spectrum of the adhesives of examples and comparative examples.
Detailed Description
The following describes the invention in more detail. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The experimental methods in the following examples, unless otherwise specified, are conventional, and the experimental materials used in the following examples, unless otherwise specified, are commercially available.
The synthesis route of the bio-based solvent-free polyurethane adhesive is shown in figure 1, and is specifically as follows:
a) The polyester PET-A and the polyester PET-B are synthesized by adopting the same preparation process except different raw materials. The corresponding raw materials are respectively added into a four-neck flask, a reaction device is built, stirring is started, the temperature is heated to 220 ℃ from room temperature, and the temperature of a top thermometer is kept to be 100+/-2 ℃. And (3) when the temperature reaches 220 ℃, adding a proper amount of tetrabutyl titanate into the flask, and preserving the heat for 2 hours. The vacuum in the flask was then increased gradually at a rate of-0.01 Mpa/30 min. Sampling at intervals for testing the acid value and the hydroxyl value, stopping the reaction after the test result is qualified, and discharging after cooling.
b) An amount of the polyester PET-A prepared in step a was charged into a 500ml four-necked flask. The apparatus was turned on to heat and vacuum pump the flask to an ambient temperature of 120℃and a pressure of-0.1 MPa for a period of time to remove the water from the polyester polyol. The heating was turned off and the temperature of the polyester PET-A was reduced to 60 ℃. By presetting different contents omega NCO The amount of the corresponding diphenylmethane diisocyanate (MDI) was calculated and added to the flask, maintaining the reaction temperature at 75 ℃. The isocyanate group mass fraction (mass fraction of isocyanate groups in the sample, expressed as ω) of the reaction product was tested by sampling at regular intervals NCO ) Wait for omega NCO Stopping the reaction after reaching the theoretical value and tending to be stable to obtain the prepolymer pre-PU-A, and sealing and preserving for later use.
c) The reaction device is built, a stirring rod, a temperature control and a reflux condenser are assembled on a 500ml four-neck flask. A quantity of Rosin (Rosin) and Epoxidized Soybean Oil (ESO) were added to a 500ml four-necked flask, and an appropriate amount of Triethylamine (TEA) was added as a catalyst, and the temperature was raised to 140 ℃. And testing the acid value of the product in the bottle at fixed time intervals by adopting a chemical titration method, and stopping the reaction after the acid value in the reaction kettle is unchanged. The apparatus was heated and vacuum pumped to 120℃and-0.1 MPa in the flask and held for a period of time to remove water and TEA from the polyester polyol to obtain the bio-based polyol ESO/Rosin.
d) Mixing different PET-B mass fractions of bio-based polyol ESO/Rosin with PET-B as a component B of the polyurethane adhesive, taking a prepolymer pre-PU-A as a component A of the polyurethane adhesive, and mixing an AB component with a certain R (-NCO/-OH) ratio to prepare an epoxy Rosin polyurethane adhesive (PU/ER) for film compounding.
By presetting omega of polyurethane prepolymers NCO Based on the PET-A addition of polyester and the hydroxyl number, the theoretical addition of MDI can be calculated. When no side reaction occurs, the quantitative relation among the variables is shown as the following formula:
wherein m is the theoretical added mass (g), ω of MDI required per 100g of polyester polyol NCO Isocyanate group mass fraction (%), OH of the synthesized prepolymer v Is the hydroxyl number (mg KOH/g) of the polyester polyol.
Example 1
The embodiment provides a preparation method of a polyurethane adhesive, which specifically comprises the following steps:
a) Polyester PET-A preparation: the metered corresponding raw materials AA, EG, DEG are added into a four-neck flask according to the mol ratio of 6:3.6:3.6, a reaction device is built, stirring is started, the mixture is heated to 220 ℃ from room temperature, and the temperature of a top thermometer is kept to be 100+/-2 ℃. After the temperature reached 220 ℃, 0.004% tetrabutyl titanate was added to the flask, and the temperature was kept for 2 hours. The vacuum in the flask was then increased stepwise at a rate of-0.01 MPa/30 min. Samples were taken at intervals to test acid and hydroxyl numbers. Stopping the reaction after the result to be tested is qualified, and discharging after cooling.
The polyester PET-B and the polyester PET-A are synthesized by adopting the same preparation process, and the molar ratio of the raw materials is AA to EG to NPG=5.5 to 0.5 to 6 to 2.
b) 200g of the polyester PET-A prepared in step a was charged into a 500ml four-necked flask. The apparatus was turned on to heat and vacuum pump the flask to an internal environment of 120℃and-0.1 MPa for 2 hours to remove the water from the polyester polyol. The heating was turned off and the temperature of the polyester PET-A was reduced to 60 ℃. Preparation of 16% omega NCO Content of polyurethane prepolymer: 276.9g of diphenylmethane diisocyanate (MDI) was added to the flask by calculation, maintaining the reaction temperature at 75 ℃. Sampling and testing the isocyanate matrix content fraction of the reaction product at fixed intervals until omega NCO Stopping the reaction after reaching a theoretical value and tending to be stable, sealing and preserving for standby, and recording a polyurethane prepolymer sample as pre-PU-A.
c) The reaction device is built, a stirring rod, a temperature control and a reflux condenser are assembled on a 500ml four-neck flask. Rosin (Rosin) and Epoxidized Soybean Oil (ESO) were added to two 500ml four-necked flasks at molar ratios of 2:1 and 1:1, and an appropriate amount of Triethylamine (TEA) was added as a catalyst and heated to 140 ℃. And testing the acid value of the product in the bottle at fixed time intervals by adopting a chemical titration method, and stopping the reaction after the acid value in the reaction kettle is unchanged. The apparatus was heated and vacuum pumped to 120℃and-0.1 MPa in the flask and held for 2 hours to remove water and TEA from the polyester polyol to obtain polyols ESO/Rosin-1 (ER 1) and ESO/Rosin-2 (ER 2) prepared based on natural renewable raw materials.
d) The preparation method comprises the steps of mixing a bio-based polyol ESO/Rosin-1 (ER 1) ESO/Rosin-2 (ER 2) with PET-B in a mass fraction of 10% to obtain a polyurethane adhesive B component, mixing a prepolymer pre-PU-A as a polyurethane adhesive A component and mixing A, B components with an R value (-NCO/-OH mole ratio) of 2.5 to prepare the epoxy Rosin polyurethane adhesive (PU/ER) for film compounding.
The adhesive has a certain relation between the adhesive strength and the mechanical property. And observing a composite film damage mode after the peeling test, wherein the polyurethane adhesive damage mode of the ER1 is interface damage, and the adhesive is peeled from the surface of the aluminum foil. The polyurethane adhesive added with ER2 has a cohesive failure mode, and the peeled adhesive is distributed on the surfaces of the aluminum foil and the RCPP, so that the adhesive strength is related to the cohesive force of the adhesive. The tensile strength test results of the biomass-based adhesive are shown in fig. 3. As the proportion of rosin increases, the tensile strength and elongation at break of the adhesive decrease. This may be that after adding an excessive amount of rosin, ER1 contains a lot of free rosin which does not participate in the reaction, which damages the structure and regularity of the adhesive and also increases the rigidity of the adhesive, resulting in a decrease in the adhesive strength and elongation at break.
Example 2
In the preparation method of the polyurethane adhesive of the present embodiment, reference is made to the embodiment 1, but in the step (a) of the present embodiment, the raw material ratio of the polyester PET-a is AA: EG: deg=6:4.8:4.8, polyester PET-B was prepared with a raw material ratio AA: PA: EG: npg=5:1:6:2. Step (b) omega NCO =17% MDI addition was 324.6g. Step (c) adds Rosin (Rosin) and Epoxidized Soybean Oil (ESO) in a molar ratio of only 2:1. Step (d) mixing 10%, 20%, 40% and 60% of bio-based polyol ESO/Rosin-1 (ER 1) with PET-B to obtain a polyurethane adhesive B component, mixing a prepolymer pre-PU-A to obtain a polyurethane adhesive A component, and mixing A, B components with an R value of 2.5 to obtain an epoxy Rosin polyurethane adhesive (PU/ER) for film compounding.
Example 3
The preparation method of the polyurethane adhesive provided in this example refers to example 2, but in this example, step (b) is kept for 3 hours to remove water, step (c) Rosin (Rosin) and Epoxidized Soybean Oil (ESO) are fed in a molar ratio of 1:1, and the sample is recorded as ER2; the added amount of the bio-based polyol ESO/Rosin-2 in the step (d) is 10%, 20%, 40% and 60% of the mass fraction of the PET-B.
Comparative example 1
This example provides a method for preparing a polyurethane adhesive with reference to example 1, but in this comparative example step (d), the bio-based polyol ER was not added, and the prepared adhesive was used as a control group PU-control.
The composite film is tested for stripping force, heat sealing strength and steaming resistance according to the related standard test method of GB/T41168-2021 composite film and bag steamed by plastic and aluminum foil for food packaging, and the test instrument is a tensile machine of XLW type of Jinan optical-mechanical and electrical technology Co. The specific method comprises the following steps:
cutting the prepared composite film into 15mm multiplied by 200mm sample strips, respectively carrying out T-type peeling force test on the RCPP layer and the PET layer of the composite film on a tensile machine, recording test data, testing each sample 5 times under the same condition, and taking the average value of the 5 times as a test result.
And (3) taking a 15.0+/-0.1 mm sample with the length of 100+/-1 mm from the direction perpendicular to the heat sealing part of the composite film pressed by the heat sealing tester, opening 180 degrees by taking the heat sealing part as the center, clamping two ends of the sample on two clamps of the tester, and enabling the axis of the sample to coincide with the central lines of the upper clamp and the lower clamp and to be required to be appropriate in tightness. The distance between the clamps is 50mm, the test speed is 300+/-20 mm/min, and the maximum load of the sample during fracture is read. Each sample was tested 5 times under the same conditions, and the average of the 5 tests was taken as the heat seal strength test result.
And placing the boiling bag in a boiling pot filled with boiling water, continuously heating for 30min, taking out the boiling bag, observing the appearance of the product, and testing the sample according to a peeling force test method after the sample is completely cooled.
FIG. 4 is a graph showing the adhesive strength and heat seal strength of the biomass polyurethane adhesive prepared based on ER1 before and after the film is boiled in combination, wherein PU/ER1-1, PU/ER1-2, PU/ER1-3 and PU/ER1-4 respectively show that the amount of bio-based polyol in example 2 is 10%, 20%, 40% and 60% of PET-B mass fraction, and the peeling force of the inner layer and the outer layer of the composite film is increased along with the increase of ER1 mass fraction because the interface interaction between the adhesive and the aluminum foil surface is enhanced due to free rosin contained in the bio-polyol. When the ER1 addition reaches 40% of the PET-B mass, the RCPP/Al layer stripping force of the PU/ER1-3 reaches the maximum value of 10.87N, and the addition of ER1 is continuously increased, so that the RCPP/Al layer stripping force is not increased any more. The PET/Al layer of the outer layer shows the same trend as that of the inner layer, the peeling force of the PET/Al layer of the PU/ER1-2 reaches the maximum value of 7.25N, the addition amount of the ER1 is continuously increased, and the peeling force of the PET/Al layer is less in change. In addition, the heat seal strength of the composite film prepared by the adhesive containing ER1 is higher than that of the control sample. After water boiling, the peeling force of the RCPP layer of the PU/ER1 adhesive is respectively 4.53N, 3.77N, 3.97N and 4.07N which are far higher than the requirements of the national standard GB/T41168-2021 (the peeling force after water boiling is more than or equal to 2.0N). The peel force of the RCPP/Al layers of the composite films prepared by the PU/ER1-2, the PU/ER1-3 and the PU/ER1-4 is lower than that of the composite film prepared by the control sample by 4.37N along with the increase of the addition amount of the ER 1. This is because the unreacted complete rosin in ER1 contains hydrophilic groups, carboxyl groups. Under the conditions of high temperature and high humidity and the mass fraction of rosin is higher, hydrophilic groups of the rosin can be corroded by moisture to reduce the hydrogen bonding effect on a substrate.
FIG. 5 shows the surface water contact angles of adhesives with different contents of biomass polyol (ER 2), wherein PU/ER2-1, PU/ER2-2, PU/ER2-3 and PU/ER2-4 respectively show that the amount of the biomass polyol in the example 3 is 10%, 20%, 40% and 60% of the mass fraction of PET-B, and the polyurethane adhesives have higher hydrophobicity and the contact angle of the adhesives without biomass polyol is 98.0 degrees. As the mass fraction of ER2 increases, the adhesive contact angle increases and then decreases. This is due to the higher ESO ratio in ER2, increased aliphatic long chains in the adhesive, and increased adhesive hydrophobicity. However, as the mass fraction of ER2 continues to increase, hydrophilic groups introduced by unreacted rosin increase, and the hydrophobicity of the adhesive decreases. All samples have static water contact angles in the range of 98-106 degrees, namely the polyurethane adhesive prepared from the biomass-based polyol has good hydrophobicity.
The infrared spectrograms of the polyurethane adhesives added with different polyol groups are respectively shown in fig. 6, and PU/ER1 and PU/ER2 in fig. 6 are the materials prepared in the example 1. Polyurethane adhesives with added biomass polyols have similar characteristic peaks and functional groups as adhesives prepared from polyester polyols. 3340cm -1 The positions are the stretching vibration peaks of N-H in urethane bonds of the polyurethane adhesive, 2950 cm and 2860cm -1 Is a methylene C-H absorption peak, 1730cm -1 C=O stretching vibration peak of ester group at 1650cm -1 At C=O stretching vibration peak of allophanate, 1130cm -1 The stretching vibration peak of ether bond C-O-C. The adhesive is 2270cm -1 NCO characteristic peaks are observed, which indicates that-NCO groups are not completely reacted in the curing process, and the NCO groups can react with active hydrogen on the surface of a substrate to form chemical crosslinking, so that the bonding strength is improved. In addition, NCO in the adhesive reacts with water penetrating into the adhesive to form urea bond during water boiling, and the water-heat resistance of the adhesive can be effectively enhanced when the content is low and the integral structure of the adhesive is not damagedCan be used.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, and yet fall within the scope of the invention.
Claims (10)
1. The preparation method of the polyurethane adhesive for the flexible package is characterized by comprising the following steps of:
(1) Preparation of polyester PET-A: mixing 1, 6-adipic acid, ethylene glycol and diethylene glycol, placing the mixture in a reaction vessel, stirring, and reacting to generate polyester PET-A;
preparation of polyester PET-B: mixing 1, 6-adipic acid, phthalic anhydride, ethylene glycol and neopentyl glycol, placing the mixture in a reaction vessel, stirring, and reacting to generate polyester PET-B;
preparation of biobased polyol ESO/Rosin: placing Rosin, epoxidized soybean oil and a catalyst in a reaction container, and reacting to obtain bio-based polyol ESO/Rosin;
(2) Placing the polyester PET-A prepared in the step (1) and diphenylmethane diisocyanate into a reaction container, and reacting to generate a polyurethane prepolymer pre-PU-A;
(3) Mixing the bio-based polyol ESO/Rosin and the polyester PET-B as a component B of the polyurethane adhesive, taking the polyurethane prepolymer pre-PU-A as a component A of the polyurethane adhesive, and mixing A, B to prepare the polyurethane adhesive PU/ER for flexible packaging.
2. The method for preparing a polyurethane adhesive for flexible packaging according to claim 1, wherein in the step (1), the molar ratio of 1, 6-adipic acid, ethylene glycol and diethylene glycol is 6:3:3-6:5:5.
3. The method for preparing polyurethane adhesive for flexible package according to claim 2, wherein in the step (1), the preparation reaction temperature of the polyester PET-a is 180-260 ℃ and the reaction time is 1-3 hours.
4. The method for preparing a polyurethane adhesive for flexible packaging according to claim 1, wherein in the step (1), the molar ratio of 1, 6-adipic acid, phthalic anhydride, ethylene glycol and neopentyl glycol is 4:0.5:6:2-6:2:6:2.
5. The method for preparing a polyurethane adhesive for flexible packaging according to claim 1, wherein in the step (1), the molar ratio of rosin to epoxidized soybean oil is 0.5:1-2:1.
6. The method for producing a polyurethane adhesive for flexible packaging according to claim 5, wherein in the step (1), the bio-based polyol ESO/Rosin is produced at a reaction temperature of 120 to 160 ℃.
7. The method for preparing a polyurethane adhesive for flexible packaging according to claim 1, wherein in the step (2), the mass fraction of isocyanate groups of the polyurethane prepolymer pre-PU-a is 13% to 17%.
8. The method for producing a polyurethane adhesive for flexible packaging according to claim 1, wherein in the step (3), the bio-based polyol ESO/Rosin is added in an amount of 10 to 60% by mass of the polyester PET-B.
9. The method for preparing a polyurethane adhesive for flexible packaging according to claim 1, wherein in the step (3), the A, B two components are mixed according to a molar ratio of isocyanate groups to hydroxyl groups of 2:1-3:1.
10. A polyurethane adhesive for flexible packaging, characterized in that it is prepared by the method for preparing a polyurethane adhesive for flexible packaging according to any one of claims 1 to 9.
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