CN118291076A - Double-component solvent-free polyurethane adhesive and preparation method thereof - Google Patents
Double-component solvent-free polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN118291076A CN118291076A CN202410333766.5A CN202410333766A CN118291076A CN 118291076 A CN118291076 A CN 118291076A CN 202410333766 A CN202410333766 A CN 202410333766A CN 118291076 A CN118291076 A CN 118291076A
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- component
- polyurethane adhesive
- free polyurethane
- polyol
- solvent
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- 239000012940 solvent-free polyurethane adhesive Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920005862 polyol Polymers 0.000 claims abstract description 63
- 150000003077 polyols Chemical class 0.000 claims abstract description 63
- 239000003607 modifier Substances 0.000 claims abstract description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 11
- 239000012948 isocyanate Substances 0.000 claims abstract description 10
- 239000004970 Chain extender Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 23
- 229920005906 polyester polyol Polymers 0.000 claims description 19
- 238000001723 curing Methods 0.000 claims description 18
- 239000004359 castor oil Substances 0.000 claims description 17
- 235000019438 castor oil Nutrition 0.000 claims description 17
- 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 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 230000001276 controlling effect Effects 0.000 claims description 15
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 15
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 15
- 238000004321 preservation Methods 0.000 claims description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000160 oxazolidinyl group Chemical group 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- -1 polymethylene Polymers 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 28
- 230000001070 adhesive effect Effects 0.000 abstract description 28
- 229920002635 polyurethane Polymers 0.000 description 15
- 239000004814 polyurethane Substances 0.000 description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- UPIKAIAOTXEAAZ-UHFFFAOYSA-N 2-(1,3-oxazolidin-3-yl)ethanol Chemical compound OCCN1CCOC1 UPIKAIAOTXEAAZ-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 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 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000009459 flexible packaging Methods 0.000 description 2
- 239000012939 laminating adhesive Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DZARITHRMKPIQB-UHFFFAOYSA-N 2-(2-propan-2-yl-1,3-oxazolidin-3-yl)ethanol Chemical compound CC(C)C1OCCN1CCO DZARITHRMKPIQB-UHFFFAOYSA-N 0.000 description 1
- CYMHAQCMKNVHPA-UHFFFAOYSA-N 3-butyl-2-heptan-3-yl-1,3-oxazolidine Chemical compound CCCCC(CC)C1OCCN1CCCC CYMHAQCMKNVHPA-UHFFFAOYSA-N 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004839 Moisture curing adhesive Substances 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004823 Reactive adhesive Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 244000290333 Vanilla fragrans Species 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007306 turnover Effects 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The application discloses a two-component solvent-free polyurethane adhesive and a preparation method thereof, and relates to the technical field of adhesives. The application discloses a preparation method of a two-component solvent-free polyurethane adhesive, which comprises the following steps: in nitrogen atmosphere, blending and reacting polyol, isocyanate curing agent and phosphoric acid to obtain a component A; in a nitrogen atmosphere, blending and reacting the polyol and the latent curing agent to obtain a component B; and (3) blending the component A, the component B, the chain extender, the modifier and the catalyst to obtain the two-component solvent-free polyurethane adhesive. The adhesive prepared by the application has the advantages of high initial adhesion, high adhesive strength and good heat resistance.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a two-component solvent-free polyurethane adhesive and a preparation method thereof.
Background
Polyurethane is a generic term for polymeric compounds containing repeating urethane or isocyanate groups, which are polymerized from materials containing di-isocyanate and dihydroxy groups. Polyurethane adhesives are becoming an indispensable adhesive product in life and industry due to their high adhesive strength and good water and medium resistance. The earliest polyurethane adhesives were mainly of the solvent type, in which a prepolymer was formed by adding a suitable solvent (ethyl acetate, butanone, etc.), glycol and diisocyanate to the adhesive, and adding a chain extender to the solvent for polymerization, and finally evaporating the solvent on a drying tunnel. However, the organic solvent type adhesive has the problem of volatilization of an organic solvent, on one hand, the solvent is wasted, and on the other hand, the adhesive has the problems of pollution caused by volatilization of the organic solvent, flammability and explosion safety, so that the polyurethane adhesive is developed to a sol-free adhesive from the aspects of safety, environmental protection and high performance. The first generation polyurethane solvent-free adhesive is a single-component moisture-curing adhesive, has the characteristics of large molecular weight, high viscosity and the like, but needs higher operation temperature, and has the byproduct carbon dioxide emission in the curing process, so that the composite film is easy to foam, and needs humidifying equipment when in use; the second-generation polyurethane solvent-free adhesive is a double-component reactive adhesive and has the characteristics of small molecular weight, low viscosity and low operating temperature of the product, but the defects of easy migration of components into a film, pollution to food and reduction of heat sealing strength are overcome because more free diisocyanate is added in the components to reduce the viscosity.
In addition, with the rapid development of the electronic commerce industry, the development of general non-printing packaging is promoted, and the production and turnover periods are faster and faster, so that the performance of the laminating adhesive is more highly required. However, the existing two-component polyurethane adhesive has long curing time and low heat resistance. In order to solve the technical problems, the invention provides a two-component polyurethane adhesive, which has low viscosity after being fully mixed so as to ensure that the adhesive wets a coated substrate and can be quickly cured in the post curing process after compounding, thereby providing enough bonding strength so that a composite film can be cut and bagged.
Disclosure of Invention
The invention aims to provide a two-component solvent-free polyurethane adhesive and a preparation method thereof, which solve the following technical problems:
the existing two-component polyurethane adhesive has long curing time and low heat resistance.
The aim of the invention can be achieved by the following technical scheme:
a preparation method of a two-component solvent-free polyurethane adhesive comprises the following steps:
a1: in nitrogen atmosphere, adding the first polyol composition into a reaction kettle A, controlling the temperature to be 60-80 ℃, adding an isocyanate curing agent, carrying out heat preservation reaction for 3-6h, adding phosphoric acid, carrying out heat preservation stirring for 10-30min, and obtaining a component A;
a2: adding the polyol composition II into the reaction kettle B in nitrogen atmosphere, controlling the temperature to be 30-35 ℃, adding the latent curing agent, and carrying out heat preservation and stirring for 0.5-1h to obtain a component B;
A3: and (3) blending the component A, the component B, the chain extender, the modifier and the catalyst to obtain the two-component solvent-free polyurethane adhesive.
As a further aspect of the invention: the first polyol composition A1 is obtained by mixing 10-40 parts by weight of castor oil modified polyol component I, 10-30 parts by weight of polyether polyol component I and 5-20 parts by weight of polyester polyol component I; the mass ratio of the polyol composition I, the isocyanate curing agent and the phosphoric acid is 1:1.5-2.5:0.015-0.07.
As a further aspect of the invention: the first polyol composition in A1 is the first polyol composition after vacuum dehydration; the vacuum dehydration comprises the following specific steps: vacuumizing the first polyol composition at 100-120 deg.c to vacuum degree below-0.092 MPa and dewatering for 1-3 hr while stirring.
As a further aspect of the invention: the first castor oil modified polyol component is castor oil modified polyol, the functionality of the castor oil modified polyol is 2-3.5, the average hydroxyl value is 50-400mgKOH/g, and the castor oil modified polyol is any one of Polycin series products of Vanilla specialty Chemicals Co., ltd (Vertellus) and Savex (China) Severe series products of Basf Co.
As a further aspect of the invention: the isocyanate curing agent is any one of 2, 6-toluene diisocyanate, 2, 4-toluene diisocyanate, isophorone diisocyanate, 4' -diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate.
As a further aspect of the invention: the second polyol composition in A2 is obtained by mixing 10-50 parts by weight of castor oil modified polyol component II and 20-60 parts by weight of polyester polyol component II; the mass ratio of the polyol composition II to the latent curing agent is 100:0.1-2.
As a further aspect of the invention: the polyol composition II in the A2 is the polyol composition II after vacuum dehydration; the vacuum dehydration comprises the following specific steps: vacuumizing the polyol composition II to a vacuum degree below-0.092 MPa at 100-120 ℃ and dehydrating for 1-3h under stirring.
As a further aspect of the invention: the second castor oil modified polyol component is castor oil modified polyol with the functionality of 2-3.5 and the average hydroxyl value of 50-400mgKOH/g, and is any one of Polycin series products of Vanile specialty Chemicals Co., ltd (Vertellus) and Savex (China) Severe series products of Basf.
As a further aspect of the invention: the polyether polyol is any one of polyethylene glycol Polyether (PEG), polytetramethylene ether glycol (PTMEG) and polypropylene glycol (PPG); the polyether polyol has a functionality of 2-3, an average hydroxyl value of 50-400mgKOH/g and an average molecular weight of 300-3000g/mol.
As a further aspect of the invention: the polyester polyol is any one of aromatic polyester polyol, aliphatic polyester polyol and dimer acid polyester polyol; the polyester polyol has an average functionality of 2 to 3, an average hydroxyl value of 50to 300mgKOH/g and an average molecular weight of 500to 5000g/mol.
As a further aspect of the invention: the polyester polyol is adipic acid polyester polyol, the average functionality is 2-2.5, the average hydroxyl value is 50-200mgKOH/g, and the average molecular weight is 500-2000g/mol.
As a further aspect of the invention: the latent catalyst is an oxazolidine curing agent.
As a further aspect of the invention: the oxazolidine curing agent is one or more of 1-4, 2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine, 3-hydroxyethyl-1, 3-oxazolidine and 3-butyl-2- (1-ethylpentyl) oxazolidine which are mixed according to any ratio.
As a further aspect of the invention: the preparation method of the modifier comprises the following steps: adding nano montmorillonite and deionized water into a reaction bottle, dispersing uniformly, adding gamma-glycidol ether oxypropyl trimethoxy silane, regulating the pH to 4-6, controlling the temperature to 70-80 ℃, preserving the temperature for 3-6h under stirring, filtering, extracting with toluene, and drying to obtain the modifier.
As a further aspect of the invention: the mass ratio of the nano montmorillonite to the deionized water to the gamma-glycidyl ether oxypropyl trimethoxy silane is 10:100-200:1-5.
As a further aspect of the invention: the catalyst in A3 is dibutyl tin dilaurate; the chain extender is 1, 4-butanediol; component A: component B: the mass ratio of the chain extender to the modifier to the catalyst is 100:50-80:10-20:1-10:1-2.
A two-component solvent-free polyurethane adhesive is prepared by any one of the preparation methods.
The invention has the beneficial effects that:
The application takes gamma-glycidoxypropyl trimethoxy silane as raw material to carry out organic modification on nano montmorillonite, and the gamma-glycidoxypropyl trimethoxy silane enters the interlayer of the montmorillonite and carries out chemical bonding with hydroxyl on the surface of the montmorillonite to obtain the modifier. The application takes isocyanate end-capped prepolymer as a component A and hydroxyl end-capped prepolymer as a component B, and the component A, the component B, the modifier and the chain extender 1, 4-butanediol are mixed to obtain the double-component solvent-free polyurethane adhesive. The polyurethane adhesive prepared by the application has the characteristics of good heat resistance, low curing shrinkage and good flexibility, and is widely applied in the field of flexible packaging.
The application adds polyester polyol, polyether polyol and castor oil modified polyol as polyol components in polyurethane adhesive. Wherein, the ether group in the polyether polyol is easy to rotate, and the prepared prepolymer has good flexibility and water resistance; the polyester polyol contains a rigid ester-based structure to give the material good mechanical properties.
The application adds montmorillonite modified by silane coupling agent as modifier, isocyanate reacts with hydroxyl on the surface of nano montmorillonite, long-chain organic matter is grafted on the surface of nano montmorillonite, and polyurethane adhesive crosslinked with montmorillonite is prepared by in-situ polymerization, thus achieving the purpose of reinforcing and toughening the adhesive. The modifier is uniformly dispersed in the polyurethane adhesive, so that the crystallization tendency of a polyurethane hard segment is destroyed, the molecular motion of polyurethane resin is not facilitated, the viscosity of a system is reduced, the flexibility of a molecular chain is increased, the viscosity is reduced, and the problems of high viscosity and poor fluidity of a polyester prepolymer caused by adding polyester polyol into the existing material are solved. According to the application, the modifier and the phosphoric acid are added into the raw materials of the polyurethane adhesive composition at the same time, so that the initial adhesion, heat resistance and hydrolytic stability of the adhesive are effectively improved; and the epoxy group of the modifier acts with phosphoric acid, so that the problem that the viscosity of the system is improved due to crystallization tendency of the organic matters caused by the fact that the epoxy group and the adhesive participate in the curing reaction due to the fact that the organic matters with the epoxy group are directly added in the prior art is effectively avoided.
Detailed Description
The following description will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation method of the modifier of the embodiment 1 comprises the following steps: adding 10g of nano montmorillonite and 100mL of deionized water into a reaction bottle, dispersing uniformly, adding 1g of gamma-glycidoxypropyl trimethoxysilane, regulating the pH to 4, controlling the temperature to 70 ℃, preserving the heat for 3h under the stirring condition, filtering, extracting with toluene, and drying to obtain the modifier.
The preparation method of the modifier of the embodiment 2 comprises the following steps: adding 10g of nano montmorillonite and 150mL of deionized water into a reaction bottle, dispersing uniformly, adding 3g of gamma-glycidoxypropyl trimethoxysilane, regulating the pH to 4, controlling the temperature to 75 ℃, preserving the heat for 3h under the stirring condition, filtering, extracting with toluene, and drying to obtain the modifier.
The preparation method of the modifier of the embodiment 3 comprises the following steps: adding 10g of nano montmorillonite and 200mL of deionized water into a reaction bottle, dispersing uniformly, adding 5g of gamma-glycidoxypropyl trimethoxysilane, regulating the pH to 4, controlling the temperature to 80 ℃, preserving the heat for 6h under the stirring condition, filtering, extracting with toluene, and drying to obtain the modifier.
Example 4a method for preparing a two-component solvent-free polyurethane adhesive comprising the steps of:
A1: 20g of castor oil modified polyol (Polycin T400 produced by Van Taruus specialty Chemicals Co., ltd.), 30g of polyether polyol (PPG 2000), 10g of polyester polyol (L3211 produced by Shanghai Cru chemical Co., ltd.) are added into a reaction bottle A, the temperature is controlled to 120 ℃, the mixture is vacuumized to a vacuum degree of-0.092 MPa, and dehydrated for 1 hour under stirring to obtain a polyol composition I;
a2: in a nitrogen atmosphere, adding 60g of a polyol composition I into a reaction kettle A, controlling the temperature to be 60 ℃, adding 90g of 4,4' -diphenylmethane diisocyanate, carrying out heat preservation reaction for 6 hours until the-NCO content is lower than 15%, adding 2g of phosphoric acid, carrying out heat preservation stirring for 30 minutes, and obtaining an isocyanate functional group (NCO) -terminated prepolymer component A;
A3: 49g of castor oil modified polyol (Polycin T400 produced by Van Taurus specialty Chemicals Co., ltd.) and 49g of polyester polyol (L3211 produced by Shanghai Cru chemical Co., ltd.) are added into a reaction bottle B, the temperature is controlled at 120 ℃, the vacuum degree is pumped to-0.092 MPa, and dehydration is carried out for 1 hour under stirring to obtain a polyol composition II;
A4: in a nitrogen atmosphere, adding 98g of a polyol composition II into a reaction kettle B, controlling the temperature to be 35 ℃, adding 1.5g of 3-hydroxyethyl-1, 3-oxazolidine, and stirring for 1h under heat preservation to prepare a hydroxyl (OH) -terminated polyol prepolymer;
A5: 100g A parts, 50 parts g B parts, 10g of 1, 4-butanediol, 10g of the modifier prepared in example 1 and 2g of dibutyltin dilaurate are blended to obtain the two-component solvent-free polyurethane adhesive.
Example 5a method for preparing a two-component solvent-free polyurethane adhesive comprising the steps of:
A1: 20g of castor oil modified polyol (Polycin T400 produced by Van Taruus specialty Chemicals Co., ltd.), 30g of polyether polyol (PPG 2000), 10g of polyester polyol (L3211 produced by Shanghai Cru chemical Co., ltd.) are added into a reaction bottle A, the temperature is controlled to 120 ℃, the mixture is vacuumized to a vacuum degree of-0.092 MPa, and dehydrated for 1 hour under stirring to obtain a polyol composition I;
a2: in a nitrogen atmosphere, adding 60g of a polyol composition I into a reaction kettle A, controlling the temperature to be 60 ℃, adding 90g of 4,4' -diphenylmethane diisocyanate, carrying out heat preservation reaction for 6 hours until the-NCO content is lower than 15%, adding 2g of phosphoric acid, carrying out heat preservation stirring for 30 minutes, and obtaining an isocyanate functional group (NCO) -terminated prepolymer component A;
A3: 49g of castor oil modified polyol (Polycin T400 produced by Van Taurus specialty Chemicals Co., ltd.) and 49g of polyester polyol (L3211 produced by Shanghai Cru chemical Co., ltd.) are added into a reaction bottle B, the temperature is controlled at 120 ℃, the vacuum degree is pumped to-0.092 MPa, and dehydration is carried out for 1 hour under stirring to obtain a polyol composition II;
A4: in a nitrogen atmosphere, adding 98g of a polyol composition II into a reaction kettle B, controlling the temperature to be 35 ℃, adding 1.5g of 3-hydroxyethyl-1, 3-oxazolidine, and stirring for 1h under heat preservation to prepare a hydroxyl (OH) -terminated polyol prepolymer;
A5: 100g A parts, 50 parts g B parts, 10g of 1, 4-butanediol, 10g of the modifier prepared in example 2 and 2g of dibutyltin dilaurate are blended to obtain the two-component solvent-free polyurethane adhesive.
Example 6 a method for preparing a two-component solvent-free polyurethane adhesive comprising the steps of:
A1: 20g of castor oil modified polyol (Polycin T400 produced by Van Taruus specialty Chemicals Co., ltd.), 30g of polyether polyol (PPG 2000), 10g of polyester polyol (L3211 produced by Shanghai Cru chemical Co., ltd.) are added into a reaction bottle A, the temperature is controlled to 120 ℃, the mixture is vacuumized to a vacuum degree of-0.092 MPa, and dehydrated for 1 hour under stirring to obtain a polyol composition I;
a2: in a nitrogen atmosphere, adding 60g of a polyol composition I into a reaction kettle A, controlling the temperature to be 60 ℃, adding 90g of 4,4' -diphenylmethane diisocyanate, carrying out heat preservation reaction for 6 hours until the-NCO content is lower than 15%, adding 2g of phosphoric acid, carrying out heat preservation stirring for 30 minutes, and obtaining an isocyanate functional group (NCO) -terminated prepolymer component A;
A3: 49g of castor oil modified polyol (Polycin T400 produced by Van Taurus specialty Chemicals Co., ltd.) and 49g of polyester polyol (L3211 produced by Shanghai Cru chemical Co., ltd.) are added into a reaction bottle B, the temperature is controlled at 120 ℃, the vacuum degree is pumped to-0.092 MPa, and dehydration is carried out for 1 hour under stirring to obtain a polyol composition II;
A4: in a nitrogen atmosphere, adding 98g of a polyol composition II into a reaction kettle B, controlling the temperature to be 35 ℃, adding 1.5g of 3-hydroxyethyl-1, 3-oxazolidine, and stirring for 1h under heat preservation to prepare a hydroxyl (OH) -terminated polyol prepolymer;
A5: 100g A parts, 50 parts g B parts, 10g of 1, 4-butanediol, 10g of the modifier prepared in example 3 and 2g of dibutyltin dilaurate are blended to obtain the two-component solvent-free polyurethane adhesive.
Comparative example 1 was compared with example 4, and only the modifier prepared in example 1 added in example 4 was replaced with nano montmorillonite in equal amount, and the remaining components and preparation method were completely identical to those of example 4.
Comparative example 2 was compared with example 4, and only the phosphoric acid added in example 4 was deleted, and the remaining components and preparation method were completely identical to those of example 4.
Comparative example 3 comparative example 1 compared with example 4, only the modifier prepared in example 1 added in example 4 was replaced with gamma-glycidoxypropyl trimethoxysilane in equal amount, and the remaining components and preparation method were completely identical to those of example 4.
And (3) performance detection:
(1) Peel strength: the test is carried out according to GB/T8808-1988 soft composite plastic material peeling test method, the PE/PE composite film is bonded, the measuring speed is 300mm/min, and the test result is shown in Table 1;
(2) Hardness: detection is carried out according to GB/T2411-2008 'hardness of indentation (Shore hardness) measured by a durometer for plastics and hard rubber', and the detection results are shown in Table 1;
(3) Water absorption rate: the samples prepared in examples 4-6 and comparative examples 1-3 were weighed and placed in deionized water, immersed for 24 hours at room temperature, then the surface water stain was wiped off, weighed again, and the water absorption η was calculated:
water absorption η= [ (m 1-m 0)/m 0] ×100%
Wherein, eta-water absorption rate,%; m 0-weight of sample before water absorption, mg; m 1-weight of sample after water absorption, mg; the detection results are shown in Table 1;
(4) Viscosity: detection is carried out according to GB/T2794-1995 adhesive viscosity determination, and the detection results are shown in Table 1;
table 1: examples 4-6, comparative examples 1-3 Performance test data statistics
As shown in Table 1, the two-component solvent-free polyurethane adhesive prepared by the application is applied to the flexible packaging industry as a laminating adhesive, has good water resistance and high initial adhesion strength, can realize quick solidification, and shortens the production period.
The foregoing describes one embodiment of the present invention in detail, but the description is only a preferred embodiment of the present invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.
Claims (9)
1. The preparation method of the two-component solvent-free polyurethane adhesive is characterized by comprising the following steps of:
a1: in nitrogen atmosphere, adding the first polyol composition into a reaction kettle A, controlling the temperature to be 60-80 ℃, adding an isocyanate curing agent, carrying out heat preservation reaction for 3-6h, adding phosphoric acid, carrying out heat preservation stirring for 10-30min, and obtaining a component A;
a2: adding the polyol composition II into the reaction kettle B in nitrogen atmosphere, controlling the temperature to be 30-35 ℃, adding the latent curing agent, and carrying out heat preservation and stirring for 0.5-1h to obtain a component B;
A3: and (3) blending the component A, the component B, the chain extender, the modifier and the catalyst to obtain the two-component solvent-free polyurethane adhesive.
2. The method for preparing a two-component solvent-free polyurethane adhesive according to claim 1, wherein the first polyol composition A1 is obtained by mixing 10-40 parts by weight of castor oil modified polyol component A, 10-30 parts by weight of polyether polyol component A and 5-20 parts by weight of polyester polyol component A; the mass ratio of the polyol composition I, the isocyanate curing agent and the phosphoric acid is 1:1.5-2.5:0.015-0.07.
3. The method for preparing a two-component solvent-free polyurethane adhesive according to claim 1, wherein the isocyanate curing agent is any one of 2, 6-toluene diisocyanate, 2, 4-toluene diisocyanate, isophorone diisocyanate, 4' -diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate.
4. The method for preparing a two-component solvent-free polyurethane adhesive according to claim 1, wherein the polyol composition II in A2 is obtained by mixing 10-50 parts by weight of castor oil modified polyol component II and 20-60 parts by weight of polyester polyol component II; the mass ratio of the polyol composition II to the latent curing agent is 100:0.1-2.
5. The method for preparing a two-component solvent-free polyurethane adhesive according to claim 1, wherein the latent catalyst is an oxazolidine curing agent.
6. The method for preparing the two-component solvent-free polyurethane adhesive according to claim 1, wherein the preparation method of the modifier comprises the following steps: adding nano montmorillonite and deionized water into a reaction bottle, dispersing uniformly, adding gamma-glycidol ether oxypropyl trimethoxy silane, regulating the pH to 4-6, controlling the temperature to 70-80 ℃, preserving the temperature for 3-6h under stirring, filtering, extracting with toluene, and drying to obtain the modifier.
7. The preparation method of the two-component solvent-free polyurethane adhesive according to claim 6, which is characterized in that the mass ratio of nano montmorillonite to deionized water to gamma-glycidoxypropyl trimethoxy silane is 10:100-200:1-5.
8. The method for preparing a two-component solvent-free polyurethane adhesive according to claim 1, wherein the catalyst in A3 is dibutyl tin dilaurate; the chain extender is 1, 4-butanediol; component A: component B: the mass ratio of the chain extender to the modifier to the catalyst is 100:50-80:10-20:1-10:1-2.
9. A two-component solvent-free polyurethane adhesive, characterized in that it is produced by the production method according to any one of claims 1 to 8.
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