CN113480965A - High-toughness polyurethane amine-aldehyde resin glue - Google Patents
High-toughness polyurethane amine-aldehyde resin glue Download PDFInfo
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- CN113480965A CN113480965A CN202110831989.0A CN202110831989A CN113480965A CN 113480965 A CN113480965 A CN 113480965A CN 202110831989 A CN202110831989 A CN 202110831989A CN 113480965 A CN113480965 A CN 113480965A
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- polyurethane
- urea
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- glue
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 61
- 239000004814 polyurethane Substances 0.000 title claims abstract description 61
- 239000003292 glue Substances 0.000 title claims abstract description 47
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000003822 epoxy resin Substances 0.000 claims abstract description 23
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000012745 toughening agent Substances 0.000 claims abstract description 15
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical class OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims abstract description 12
- 239000003085 diluting agent Substances 0.000 claims abstract description 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 11
- 239000005011 phenolic resin Substances 0.000 claims abstract description 11
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 11
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 7
- 229920005862 polyol Polymers 0.000 claims abstract description 7
- 150000003077 polyols Chemical class 0.000 claims abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 22
- 239000004202 carbamide Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000853 adhesive Substances 0.000 claims description 15
- 230000001070 adhesive effect Effects 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 8
- 239000005060 rubber Substances 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008098 formaldehyde solution Substances 0.000 claims description 6
- 230000005484 gravity Effects 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- XNINAOUGJUYOQX-UHFFFAOYSA-N 2-cyanobutanoic acid Chemical compound CCC(C#N)C(O)=O XNINAOUGJUYOQX-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 230000010933 acylation Effects 0.000 claims description 3
- 238000005917 acylation reaction Methods 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 150000008430 aromatic amides Chemical class 0.000 claims description 3
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 3
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical group 0.000 claims description 3
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 claims description 3
- 229950005308 oxymethurea Drugs 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 6
- 238000004026 adhesive bonding Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 238000010073 coating (rubber) Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
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
-
- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- 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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- 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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09J161/32—Modified amine-aldehyde condensates
-
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
- C09J187/00—Adhesives based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09J187/005—Block or graft polymers not provided for in groups C09J101/00 - C09J185/04
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses high-toughness polyurethane amine-aldehyde resin glue which mainly comprises the following components: polyurethane, oligomer polyol, diisocyanate, a solvent, ethyl acetate, modified epoxy resin, a curing agent, a toughening agent, a diluent, a filler, thermoplastic phenolic resin and modified urea-formaldehyde resin, and comprises six steps. According to the preparation method of the high-toughness polyurethane amine-aldehyde resin glue, the modified epoxy resin prepared by adding the active toughening agent and the diluent into the epoxy resin can effectively improve the toughening effect and the extensibility, can improve the process, increase the wettability to an adherend and improve the bonding effect, and meanwhile, the polyurethane main agent is added with the ethyl acetate solvent to be mixed with the modified urea-formaldehyde resin for reaction, so that the low-temperature resistance can be effectively improved, the bonding strength is improved, the use is convenient, the practical performance of the polyurethane amine-aldehyde resin glue is improved, and the practicability and the excellence of the proportioning scheme are ensured.
Description
Technical Field
The invention relates to the technical field of glue, in particular to high-toughness polyurethane amine-aldehyde resin glue.
Background
The glue is an intermediate for connecting two materials, mostly appears as a water agent, belongs to the fine chemical engineering class, is various in types, is mainly classified by a bonding material, a physical form, a hardening method and a material of an adherend, does not exist independently, and can play a bonding role only by being coated between two objects, and common materials include instant glue, epoxy resin bonding class, anaerobic glue, UV glue (ultraviolet light curing class), hot melt glue, pressure sensitive glue, latex and the like.
In the use of glue, the excessive rubber coating volume can make the polymer in the glue crowded together each other, just can not produce fine pulling force between the polymer, and simultaneously, moisture between the polymer is also difficult for volatilizing, this is why in the bonding process "the glued membrane is thicker, the bonding efficiency of glue is worse", the rubber coating volume is too much, what the glue played greatly is "filling effect" rather than bonding effect, what the bonding between the object was leaned on is not the cohesive force of glue, but "cohesion" of glue, consequently need use high tenacity polyurethane amine-aldehyde resin glue to improve the result of use, so as to reach the user demand.
Disclosure of Invention
The invention aims to provide high-toughness polyurethane amine-aldehyde resin glue to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
the high-toughness polyurethane amine-aldehyde resin glue mainly comprises the following components: polyurethane, oligomer polyol, diisocyanate, a solvent, ethyl acetate, modified epoxy resin, a curing agent, a toughening agent, a diluent, a filler, thermoplastic phenolic resin and modified urea-formaldehyde resin, and is characterized in that: the method comprises the following six steps:
the method comprises the following steps: introducing a polyurethane main agent, oligomer polyol and excessive diisocyanate into a stirring container for mixing reaction to prepare an isocyanate group-terminated prepolymer, adding diamine for chain extension and crosslinking to form a urea chain and a biuret knot in the chain extension and crosslinking processes, and adding polyoxypropylene glycol for reaction to prepare an NCO group-containing prepolymer to form a polyurethane main agent;
step two: diluting the prepared polyurethane main agent by adding a proper amount of water, adding a solvent, stirring, adding a curing agent into the diluted polyurethane main agent, and fully stirring to obtain polyurethane glue;
step three: introducing an epoxy resin main agent and a curing agent into a stirring container, carrying out mixing reaction, then adding a toughening agent for carrying out curing reaction, improving brittleness, stirring and mixing to obtain an adhesive, then adding a diluent, reducing the viscosity of the adhesive, improving manufacturability, and simultaneously adding a filler for mixing reaction to obtain a modified epoxy resin adhesive;
step four: introducing a phenol solution and a formaldehyde solution into a test tube, carrying out oscillation operation, and generating thermoplastic phenolic resin through polycondensation under the action of an acidic or alkaline catalyst;
step five: the urea, the melamine, the polyvinyl alcohol, the sodium hydroxide solution 30% and the ammonium chloride solution 20% are obtained and are introduced into a reaction kettle for mixing reaction to obtain the modified urea-formaldehyde resin.
Step six: the prepared polyurethane glue, the modified epoxy resin adhesive and the modified urea-formaldehyde resin are introduced into a reaction kettle for stirring reaction, and the temperature is controlled to be 40 ℃ to prepare the polyurethane amine-aldehyde resin glue.
Further, the molecular weight of the polyoxypropylene glycol is 2000 and 1000, the solvent is composed of ethyl acetate, the water content in the solvent is not more than 300PPM, the curing agent is composed of aromatic amide and generated by acylation of anhydride and aromatic amine, the specific gravity of the curing agent is 1.2, the specific gravity of the polyurethane main agent is 1.15, the prepared polyurethane glue is yellow transparent liquid, 5 parts of the polyurethane main agent is matched with 1 part of the curing agent according to the weight ratio, and 8 parts of the ethyl acetate is matched at the same time.
Further, the relative molecular weight of the modified epoxy resin is generally 400-7000, the viscosity is 16-55 Pa.s, the toughening agent is an active toughening agent and is prepared by mixing and reacting low-molecular polysulfone, liquid butyronitrile, liquid carboxyl butyronitrile and other rubbers, the diluent is prepared by mixing and reacting acetone, toluene and ethyl acetate, and the filler is prepared by mixing and reacting glass fiber, talcum powder and titanium dioxide.
Further, 5g of chemically pure phenol and 3.5mL of chemically pure formaldehyde solution (with the density of about 1.1g/cm3 and the concentration of 37-40%) are added into a 25X 200mm test tube, 2mL of chemically pure concentrated hydrochloric acid is added, a rubber plug with a straight glass tube length of 300mm is plugged after uniform oscillation, the test tube is fixed on an iron stand and is placed in a water bath at 85-95 ℃ for heating, after a moment, violent reaction occurs in the test tube, heating is continued after the reaction until pink solid resin is generated, the solid resin is taken out, and the thermoplastic phenolic resin is obtained after washing with water.
Further, the urea is fed for three times, the adding amount of the urea for the first time is 40% of the total amount, the adding amount of the urea for the second time is 50% of the total amount, the adding amount of the urea for the third time is 10% of the total amount, the melamine is added in the first reaction stage process, the polyvinyl alcohol is added in the second reaction stage process, the dimethylol urea is favorably generated, and the content of the free urea is controlled to be about 10%.
Compared with the prior art, the invention has the beneficial effects that: the preparation method of the high-toughness polyurethane amine-aldehyde resin glue is characterized in that modified epoxy resin prepared by adding the active toughening agent and the diluent into the epoxy resin can effectively improve the toughening effect and the extensibility, can improve the process, increase the wettability to an adherend, improve the bonding effect, simultaneously add the ethyl acetate solvent through the polyurethane main agent, and through mixed reaction with the modified urea-formaldehyde resin, can effectively improve the low-temperature resistance, improve the bonding strength, is convenient to use, improves the practical performance of the polyurethane amine-aldehyde resin glue, and ensures the practicability and the excellence of the proportioning scheme.
Drawings
FIG. 1 is a schematic specification of a polyurethane glue of the present invention;
FIG. 2 is a schematic diagram showing the formulation of the polyurethane glue of the present invention;
fig. 3 is a schematic diagram of a preparation process of the high-toughness polyurethane amine-aldehyde resin glue.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "upper", "lower", "inner", "outer", "front", "rear", "both ends", "one end", "the other end", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it is to be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "disposed," "connected," and the like are to be construed broadly, such as "connected," which may be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Example 1
Referring to fig. 1-3, the present invention provides an embodiment: the high-toughness polyurethane amine-aldehyde resin glue mainly comprises the following components: polyurethane, oligomer polyol, diisocyanate, a solvent, ethyl acetate, modified epoxy resin, a curing agent, a toughening agent, a diluent, a filler, thermoplastic phenolic resin and modified urea-formaldehyde resin, and is characterized in that: the method comprises the following six steps:
the method comprises the following steps: introducing a polyurethane main agent, oligomer polyol and excessive diisocyanate into a stirring container for mixing reaction to prepare an isocyanate group-terminated prepolymer, adding diamine for chain extension and crosslinking to form a urea chain and a biuret knot in the chain extension and crosslinking processes, and adding polyoxypropylene glycol for reaction to prepare an NCO group-containing prepolymer to form a polyurethane main agent;
step two: diluting the prepared polyurethane main agent by adding a proper amount of water, adding a solvent, stirring, adding a curing agent into the diluted polyurethane main agent, and fully stirring to obtain polyurethane glue;
step three: introducing an epoxy resin main agent and a curing agent into a stirring container, carrying out mixing reaction, then adding a toughening agent for carrying out curing reaction, improving brittleness, stirring and mixing to obtain an adhesive, then adding a diluent, reducing the viscosity of the adhesive, improving manufacturability, and simultaneously adding a filler for mixing reaction to obtain a modified epoxy resin adhesive;
step four: introducing a phenol solution and a formaldehyde solution into a test tube, carrying out oscillation operation, and generating thermoplastic phenolic resin through polycondensation under the action of an acidic or alkaline catalyst;
step five: the formaldehyde, the urea, the melamine, the polyvinyl alcohol, the sodium hydroxide solution 30% and the ammonium chloride solution 20% are obtained and are introduced into a reaction kettle to be mixed and reacted to obtain the modified urea-formaldehyde resin.
Step six: the prepared polyurethane glue, the modified epoxy resin adhesive and the modified urea-formaldehyde resin are introduced into a reaction kettle for stirring reaction, and the temperature is controlled to be 40 ℃ to prepare the polyurethane amine-aldehyde resin glue.
Further, the molecular weight of the polyoxypropylene glycol is 2000 and 1000, the solvent comprises ethyl acetate, the water content in the solvent is not more than 300PPM, the curing agent comprises aromatic amide and is generated by acylation of anhydride and aromatic amine, the specific gravity of the curing agent is 1.2, the solid content of the curing agent is 60-65%, the specific gravity of the polyurethane main agent is 1.15, the solid content of the polyurethane is 75-75%, the prepared polyurethane glue is yellow transparent liquid, 5 parts of the polyurethane main agent is prepared into 1 part of the curing agent according to the weight ratio, 8 parts of ethyl acetate is prepared at the same time, the prepared polyurethane glue is stored in a closed container, the viscosity can be increased for about 1-2 days without obvious increase, the room temperature curing can be realized, for reactive polyurethane glue, if the room temperature curing needs a long time, a catalyst can be added to promote the curing, and in order to shorten the curing time, a heating method is adopted, the heating is not only beneficial to the curing of the adhesive, but also beneficial to accelerating the reaction of NCO groups in the adhesive and active hydrogen groups on the surface of a substrate, the heating can soften the adhesive layer so as to increase the infiltration on the surface of the substrate and facilitate the molecular motion, the polyurethane prepolymer containing NCO end groups reacts with alcohol containing epoxy groups to generate polyurethane with end epoxy groups, the crosslinking curing is completed through the reaction of the epoxy groups and amine, polyurea containing amino functional groups is adopted to prepare the adhesive layer which is polyurethane, the mechanical processing performance and the wetting performance can be effectively improved, the initial adhesion effect after compounding is increased, the adhesive has good transparency and elasticity, the chemical resistance and the high shear strength can be simultaneously improved, no odor exists, the service life is prolonged, and the better environmental protection performance is realized.
Further, the relative molecular weight of the modified epoxy resin is generally 400-7000, the viscosity is 16-55 Pa.s, the toughening agent is an active toughening agent and is prepared by mixing and reacting rubbers such as low-molecular polysulfone, liquid butyronitrile, liquid carboxyl butyronitrile and the like, the diluent is prepared by mixing and reacting acetone, toluene and ethyl acetate, the filler is prepared by mixing and reacting glass fiber, talcum powder and titanium dioxide, the modified epoxy resin can be added into liquid carboxyl butyronitrile rubber for toughening, the adding amount is 11-12%, wherein the content of acrylonitrile in the liquid carboxyl butyronitrile rubber is controlled to be 20-28%, 30% of silicon dioxide is added for curing for 2 hours at 120 ℃, the strength can be prevented from being reduced, meanwhile, the liquid chloroprene hydroxyethyl methacrylate copolymer is added for toughening, the shear strength and the impact strength can be improved, and 100 parts of epoxy resin and 100 parts of chloroprene hydroxyethyl methacrylate copolymer are used for toughening, 20 portions of poly (n-butyl acrylate) and a synchronous method are used for synthesizing an interpenetrating network system of the poly (n-butyl acrylate) and the poly (n-butyl acrylate), and 28 portions of phthalic anhydride and a proper amount of azodiisobutyronitrile are added simultaneously, so that the impact strength can be improved by 1.4 times.
Further, 5g of chemically pure phenol and 3.5mL of chemically pure formaldehyde solution (with the density of about 1.1g/cm3 and the concentration of 37-40%) are added into a 25X 200mm test tube, 2mL of chemically pure concentrated hydrochloric acid is added, a rubber plug with a straight glass tube length of 300mm is plugged after uniform oscillation, the test tube is fixed on an iron stand and is placed in a water bath at 85-95 ℃ for heating, after 30min heating, violent reaction can occur in the test tube, after reaction, heating is continued to generate viscous liquid, the liquid becomes brittle solid after cooling, the solid can be partially dissolved in alcohol and acetone but is not dissolved in alkaline aqueous solution, heating is continued again until pink solid resin is generated, the solid resin is taken out by using an iron wire hook, corrosion is avoided, and the thermoplastic phenolic resin is obtained after water washing.
Further, introducing formaldehyde into a reaction kettle, then feeding urea for three times, wherein the adding amount of the urea for the first time is 40% of the total amount, the adding amount of the urea for the second time is 50% of the total amount, the adding amount of the melamine is 10% of the total amount for the third time, the adding of the polyvinyl alcohol is performed in the first reaction stage process, the generation of dimethylol urea is facilitated, the content of free urea is controlled to be about 10%, when the required viscosity is reached, the pH value is adjusted to be neutral or slightly alkaline by using sodium hydroxide, and the mixture is cooled to be below 40 ℃ to be discharged, so that the transparent or milky viscous solution is obtained.
Example 2
Firstly, a preparation process flow of thermoplastic phenolic resin comprises the following steps:
adding formaldehyde into a reactor, dropwise adding sodium hydroxide while stirring to adjust the pH value to 8.5-8.8, then adding a first batch of urea, slowly raising the temperature to 45-50 ℃, reacting for 12min at the temperature, adding melamine to react for 30min, controlling the reaction temperature to be about 80 ℃, then dropwise adding an ammonium chloride solution by using a dropper to adjust the pH value to 5.5-5.8, then adding polyvinyl alcohol to react for a period of time, then adding a second batch of urea, adjusting the reaction temperature to be 86 ℃, preserving the temperature for about 80min, adding sodium hydroxide to adjust the pH value to 8-9 when the required viscosity is reached, then adding a third batch of urea to react for 40min, adjusting the pH value to be in a neutral or slightly alkaline state, then cooling to below 30 ℃ and discharging to prepare a transparent or milky viscous solution, adjusting the pH value to 7.2-8.0, taking 1-2 g of a solid content (48 +/-2)%, drying a sample at the constant temperature of 110 ℃ for 3h, the modified unmodified glue bonding test piece is soaked in hot water at 63 ℃ for 2 hours, the shear strength is 7.1MPa and 4.3MPa, the viscosity is high, the modified unmodified glue bonding test piece is convenient to use for a plurality of base materials, the modified unmodified glue bonding test piece can be matched with other materials for use, fuel and pigment can be colored at will, the solubility is good, and the hardness is high.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (5)
1. The high-toughness polyurethane amine-aldehyde resin glue mainly comprises the following components: polyurethane, oligomer polyol, diisocyanate, a solvent, ethyl acetate, modified epoxy resin, a curing agent, a toughening agent, a diluent, a filler, thermoplastic phenolic resin and modified urea-formaldehyde resin, and is characterized in that: the method comprises the following six steps:
the method comprises the following steps: introducing a polyurethane main agent, oligomer polyol and excessive diisocyanate into a stirring container for mixing reaction to prepare an isocyanate group-terminated prepolymer, adding diamine for chain extension and crosslinking to form a urea chain and a biuret knot in the chain extension and crosslinking processes, and adding polyoxypropylene glycol for reaction to prepare an NCO group-containing prepolymer to form a polyurethane main agent;
step two: diluting the prepared polyurethane main agent by adding a proper amount of water, adding a solvent, stirring, adding a curing agent into the diluted polyurethane main agent, and fully stirring to obtain polyurethane glue;
step three: introducing an epoxy resin main agent and a curing agent into a stirring container, carrying out mixing reaction, then adding a toughening agent for carrying out curing reaction, improving brittleness, stirring and mixing to obtain an adhesive, then adding a diluent, reducing the viscosity of the adhesive, improving manufacturability, and simultaneously adding a filler for mixing reaction to obtain a modified epoxy resin adhesive;
step four: introducing a phenol solution and a formaldehyde solution into a test tube, carrying out oscillation operation, and generating thermoplastic phenolic resin through polycondensation under the action of an acidic or alkaline catalyst;
step five: the urea, the melamine, the polyvinyl alcohol, the sodium hydroxide solution 30% and the ammonium chloride solution 20% are obtained and are introduced into a reaction kettle to be mixed and reacted to obtain the modified urea-formaldehyde resin;
step six: the prepared polyurethane glue, the modified epoxy resin adhesive and the modified urea-formaldehyde resin are introduced into a reaction kettle for stirring reaction, and the temperature is controlled to be 40 ℃ to prepare the polyurethane amine-aldehyde resin glue.
2. The high-toughness polyurethane amine-aldehyde resin glue according to claim 1, wherein: the molecular weight of the polyoxypropylene glycol is 2000 and 1000, the solvent is composed of ethyl acetate, the water content in the solvent is not more than 300PPM, the curing agent is composed of aromatic amide and generated by acylation of anhydride and aromatic amine, the specific gravity of the curing agent is 1.2, the specific gravity of the polyurethane main agent is 1.15, the prepared polyurethane glue is yellow transparent liquid, 5 parts of the polyurethane main agent is matched with 1 part of the curing agent according to the weight ratio, and 8 parts of the ethyl acetate is matched at the same time.
3. The high-toughness polyurethane amine-aldehyde resin glue according to claim 1, wherein: the modified epoxy resin is generally 400-7000 in relative molecular weight, 16-55 Pa.s in viscosity, the toughening agent is an active toughening agent and is prepared by mixing and reacting low-molecular polysulfone, liquid butyronitrile, liquid carboxyl butyronitrile and other rubbers, the diluent is prepared by mixing and reacting acetone, toluene and ethyl acetate, and the filler is prepared by mixing and reacting glass fiber, talcum powder and titanium dioxide.
4. The high-toughness polyurethane amine-aldehyde resin glue according to claim 1, wherein: 5g of chemically pure phenol and 3.5mL of chemically pure formaldehyde solution (with the density of about 1.1g/cm3 and the concentration of 37-40%) are added into a 25X 200mm test tube, 2mL of chemically pure concentrated hydrochloric acid is added, a rubber plug with a straight glass tube length of 300mm is plugged after uniform oscillation, the test tube is fixed on an iron support, the test tube is placed in a water bath at 85-95 ℃ for heating, after a moment, violent reaction occurs in the test tube, heating is continued after the reaction until pink solid resin is generated, the solid resin is taken out, and the thermoplastic phenolic resin is obtained after washing with water.
5. The high-toughness polyurethane amine-aldehyde resin glue according to claim 1, wherein: the urea is fed for three times, the adding amount of the urea for the first time is 40 percent of the total amount, the adding amount of the urea for the second time is 50 percent of the total amount, the adding amount of the urea for the third time is 10 percent of the total amount, the melamine is added in the process of the first reaction stage, the polyvinyl alcohol is added in the process of the second reaction stage, the dimethylol urea is favorably generated, and the content of the free urea is controlled to be about 10 percent.
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