CN113929853A - Nano-material modified waterborne polyurethane resin and preparation method thereof - Google Patents
Nano-material modified waterborne polyurethane resin and preparation method thereof Download PDFInfo
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- CN113929853A CN113929853A CN202111126855.5A CN202111126855A CN113929853A CN 113929853 A CN113929853 A CN 113929853A CN 202111126855 A CN202111126855 A CN 202111126855A CN 113929853 A CN113929853 A CN 113929853A
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- polyurethane resin
- aqueous polyurethane
- nanomaterial
- chain extender
- nano
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 31
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000004970 Chain extender Substances 0.000 claims abstract description 15
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 11
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 11
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 10
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 5
- 229920003232 aliphatic polyester Polymers 0.000 claims abstract description 5
- 125000000129 anionic group Chemical group 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 229920000570 polyether Polymers 0.000 claims abstract description 5
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 3
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 3
- 229920005862 polyol Polymers 0.000 claims abstract description 3
- 150000003077 polyols Chemical class 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 3
- 150000002009 diols Chemical class 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229920000515 polycarbonate Polymers 0.000 claims description 9
- 239000004417 polycarbonate Substances 0.000 claims description 9
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical group OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 7
- 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 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- -1 alkali metal salt Chemical class 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 150000003384 small molecules Chemical group 0.000 claims description 3
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 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 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 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
- 230000009467 reduction Effects 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 150000003606 tin compounds Chemical class 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 150000003752 zinc compounds Chemical class 0.000 claims description 2
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 claims description 2
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 claims description 2
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 abstract description 25
- 239000004814 polyurethane Substances 0.000 abstract description 25
- 239000000839 emulsion Substances 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000010985 leather Substances 0.000 abstract description 3
- 239000003973 paint Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000011527 polyurethane coating Substances 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 239000002313 adhesive film Substances 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- 230000001804 emulsifying effect Effects 0.000 description 5
- STBLQDMGPBQTMI-UHFFFAOYSA-N heptane;isocyanic acid Chemical compound N=C=O.N=C=O.CCCCCCC STBLQDMGPBQTMI-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- ZDWQSEWVPQWLFV-UHFFFAOYSA-N C(CC)[Si](OC)(OC)OC.[O] Chemical compound C(CC)[Si](OC)(OC)OC.[O] ZDWQSEWVPQWLFV-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- 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
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Nanotechnology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the field of high molecular polymers, and particularly discloses a nano-material modified waterborne polyurethane resin and a preparation method thereof. The raw materials of the waterborne polyurethane comprise polyol, polyisocyanate, carbon nano tubes, nano silicon nitride, a first micromolecule chain extender, an anionic hydrophilic chain extender, a catalyst, a silane coupling agent, a salt forming agent and a second micromolecule chain extender; wherein, the polyalcohol is the combination of aliphatic polyester dihydric alcohol and polyether dihydric alcohol, and the silane coupling agent is gamma-glycidyl ether oxypropyl trimethoxy silane; the nano material modified aqueous polyurethane resin emulsion obtained by the invention has good stability and long storage time, and the coating film of the aqueous polyurethane resin has high strength and excellent water resistance, solvent resistance and heat resistance. Overcomes the defect of poor performance of the existing waterborne polyurethane coating film, and has important significance for expanding the application of waterborne polyurethane in the aspects of paint, adhesive and leather finishing agent.
Description
Technical Field
The invention relates to the field of high molecular polymers, and particularly discloses a nano-material modified waterborne polyurethane resin and a preparation method thereof.
Background
With the development of the synthesis technology of waterborne polyurethane, the performance of the waterborne polyurethane is continuously improved, and in recent years, the application field of the waterborne polyurethane is continuously expanded. At present, the application of the modified polyurethane in the fields of coatings, adhesives, leather finishing agents and the like is more and more extensive. However, compared with solvent-based polyurethanes, the conventional waterborne polyurethane has the defects of poor water resistance and solvent resistance, low strength, poor heat resistance and the like, which greatly affects the application of the waterborne polyurethane. Therefore, the performance defect of the waterborne polyurethane is overcome, and the development of the high-performance waterborne polyurethane is of great significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a nano-material modified waterborne polyurethane resin and a preparation method thereof.
In order to solve the technical problem, the technical scheme adopted by the invention is that the nano-material modified waterborne polyurethane resin comprises the following raw material components in parts by mass:
the polyalcohol is the combination of aliphatic polyester dihydric alcohol and polyether dihydric alcohol;
the silane coupling agent is gamma-glycidol ether oxygen propyl trimethoxy silane, and the structural formula is as follows:
the modified aqueous polyurethane resin as the nano material is further improved:
preferably, the aliphatic polyester diol is selected from one or two of polycarbonate diol and polycaprolactone diol, and the polyether diol is selected from polytetrahydrofuran diol.
Preferably, the polycarbonate diol, polycaprolactone diol, and polytetrahydrofuran diol have a number average molecular weight of 1000 or 2000.
Preferably, the polyisocyanate is selected from any one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexyl diisocyanate or a combination of two or more of the above.
Preferably, the first small molecular chain extender is any one or a combination of two or more of ethylene glycol, 1, 4-butanediol, 2-methyl-1, 3-propanediol and 1, 4-cyclohexanedimethanol.
Preferably, the second small molecule chain extender is one or a combination of two or more of ethylenediamine, 1, 4-cyclohexyldimethylamine and isophorone diamine.
Preferably, the anionic hydrophilic chain extender is dimethylolpropionic acid or dimethylolbutyric acid.
Preferably, the catalyst is selected from any one or a combination of two or more of organozinc compounds, organotin compounds, organic alkali metal salts, tertiary amines and salt compounds thereof.
Preferably, the organic zinc compound is selected from any one of zinc isooctanoate, zinc octoate and zinc acetylacetonate; the organic tin compound is selected from any one of dibutyl tin laurate and stannous octoate; the organic alkali metal salt is sodium acetate.
In order to solve the technical problem of the present invention, another technical solution is that the preparation method of the nanomaterial-modified aqueous polyurethane resin described in any one of the above, comprising the steps of:
s1, weighing raw materials in set parts by mass, adding the diisocyanate and the carbon nano tubes into the polyol, heating to 80-90 ℃, preserving heat for 2-3 hours, cooling to 40-50 ℃, adding the anionic hydrophilic chain extender and the first micromolecule chain extender, adding the catalyst, heating to 70-80 ℃, and preserving heat for 4-6 hours to obtain a first prepolymer;
s2, cooling the first prepolymer to 40-50 ℃, adding the silane coupling agent, preserving heat for 5-10 min, adding the viscosity reduction solvent, and adding the nano silicon nitride to obtain a second prepolymer;
s3, cooling the second prepolymer to 10-20 ℃, then adding the salt forming agent for neutralization, adding ice water and the second small molecular chain extender, and carrying out reduced pressure distillation to obtain the nano material modified waterborne polyurethane resin.
Wherein the viscosity reducing solvent is used for adjusting the concentration of the solution and is one or more of acetone, butanone, methyl ethyl ketone, N-methyl pyrrolidone and N, N-dimethylformamide, the addition amount can be added according to the reaction requirement, and the solvent is distilled and removed in the reduced pressure distillation stage.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the invention, the silane coupling agent gamma-glycidyl ether oxypropyl trimethoxysilane is added in the synthesis process, the silane coupling agent is silane containing three silicon oxygen bonds and epoxy functional groups, and a cross-linked network structure is formed in a waterborne polyurethane system due to slow hydrolysis of the silicon oxygen bonds, so that the cross-linked network structure can ensure relatively stable existence of the added nano material in emulsion particles while improving the strength and molecular weight of an adhesive film, thereby ensuring that the nano material is not easy to settle and aggregate.
2) The invention adds the carbon nano tube in the initial stage of the synthesis reaction, which obviously improves the dispersion effect of the carbon nano tube in the aqueous polyurethane system and obviously improves the strength, the wear resistance and the solvent resistance of the aqueous polyurethane adhesive film. Meanwhile, after the reaction is finished, the solvent is added to reduce the viscosity of the prepolymer, the nano silicon nitride is added, so that the good dispersion of the nano silicon nitride in the prepolymer with low viscosity can be effectively ensured, and the nano material can be uniformly distributed in particles of the waterborne polyurethane emulsion after the water is added for emulsification. The nano silicon nitride obviously improves the heat resistance and the strength of the waterborne polyurethane adhesive film. After the aqueous polyurethane is formed into a film, the strength, the water resistance, the solvent resistance and the heat resistance of the aqueous polyurethane resin can be greatly improved because the nano materials are uniformly distributed in emulsion particles.
3) The nano material modified aqueous polyurethane resin emulsion obtained by the invention has good stability and long storage time, and the coating film of the aqueous polyurethane resin has high strength and excellent water resistance, solvent resistance and heat resistance. Overcomes the defect of poor performance of the existing waterborne polyurethane coating film, and has important significance for expanding the application of waterborne polyurethane in the aspects of paint, adhesive and leather finishing agent.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to embodiments, and all other embodiments obtained by a person of ordinary skill in the art without any creative effort based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
Adding 30g of polycarbonate diol and 10g of polytetrahydrofuran diol into a three-neck flask, then adding 20g of toluene diisocyanate, 10g of dipropyl methane diisocyanate and 3g of carbon nano tubes, heating to 90 ℃, reacting for 2h, cooling to 50 ℃, adding 3g of dimethylolpropionic acid, 4g of 1, 4-cyclohexanedimethanol, 0.3g of stannous octoate and acetone, stirring, heating to 80 ℃, reacting for 5h, cooling to 45 ℃, adding acetone to reduce the system viscosity, adding 1g of nano silicon nitride and 1g of gamma-glycidyl ether oxypropyl trimethoxysilane, reacting for 10min, cooling to 10 ℃, adding 2.2g of triethylamine for neutralization, adding 100g of ice water for emulsifying and dispersing, adding 3g of ethylenediamine, extending the chain, continuing to emulsify and disperse, and then removing the acetone through reduced pressure distillation to obtain the modified waterborne polyurethane emulsion.
Example 2
Adding 30g of polycarbonate diol and 10g of polytetrahydrofuran diol into a three-neck flask, then adding 20g of toluene diisocyanate, 10g of dipropyl methane diisocyanate and 4g of carbon nano tubes, heating to 90 ℃, reacting for 2h, cooling to 50 ℃, adding 3g of dimethylolpropionic acid, 4g of 1, 4-cyclohexanedimethanol, 0.3g of stannous octoate and acetone, stirring, heating to 80 ℃, reacting for 5h, cooling to 45 ℃, adding acetone to reduce the system viscosity, adding 1g of nano silicon nitride and 1g of gamma-glycidyl ether oxypropyl trimethoxysilane, reacting for 10min, cooling to 10 ℃, adding 2.2g of triethylamine for neutralization, adding 100g of ice water for emulsifying and dispersing, adding 3g of ethylenediamine, extending the chain, continuing to emulsify and disperse, and then removing the acetone through reduced pressure distillation to obtain the modified waterborne polyurethane emulsion.
Example 3
Adding 30g of polycarbonate diol and 10g of polytetrahydrofuran diol into a three-neck flask, then adding 20g of toluene diisocyanate, 10g of dipropyl methane diisocyanate and 5g of carbon nano tube, heating to 90 ℃, reacting for 2h, cooling to 50 ℃, adding 3g of dimethylolpropionic acid, 4g of 1, 4-cyclohexanedimethanol, 0.3g of stannous octoate and acetone, stirring, heating to 80 ℃, reacting for 5h, cooling to 45 ℃, adding acetone to reduce the system viscosity, adding 1g of nano silicon nitride and 1g of gamma-glycidyl ether oxypropyl trimethoxysilane, reacting for 10min, cooling to 10 ℃, adding 2.2g of triethylamine for neutralization, adding 100g of ice water for emulsifying and dispersing, adding 3g of ethylenediamine, extending the chain, continuing to emulsify and disperse, and then removing the acetone through reduced pressure distillation to obtain the modified waterborne polyurethane emulsion.
Example 4
Adding 30g of polycarbonate diol and 10g of polytetrahydrofuran diol into a three-neck flask, then adding 20g of toluene diisocyanate, 10g of dipropyl methane diisocyanate and 5g of carbon nano tube, heating to 90 ℃, reacting for 2h, cooling to 50 ℃, adding 3g of dimethylolpropionic acid, 4g of 1, 4-cyclohexanedimethanol, 0.3g of stannous octoate and acetone, stirring, heating to 80 ℃, reacting for 5h, cooling to 45 ℃, adding acetone to reduce the system viscosity, adding 2g of nano silicon nitride and 1g of gamma-glycidyl ether oxypropyl trimethoxysilane, reacting for 10min, cooling to 10 ℃, adding 2.2g of triethylamine for neutralization, adding 100g of ice water for emulsifying and dispersing, adding 3g of ethylenediamine, extending the chain, continuing to emulsify and disperse, and then removing the acetone through reduced pressure distillation to obtain the modified waterborne polyurethane emulsion.
Example 5
Adding 30g of polycarbonate diol and 10g of polytetrahydrofuran diol into a three-neck flask, then adding 20g of toluene diisocyanate, 10g of dipropyl methane diisocyanate and 0g of carbon nano tube, heating to 90 ℃, reacting for 2h, cooling to 50 ℃, adding 3g of dimethylolpropionic acid, 4g of 1, 4-cyclohexanedimethanol, 0.3g of stannous octoate and acetone, stirring, heating to 80 ℃, reacting for 5h, cooling to 45 ℃, adding acetone to reduce the system viscosity, adding 0g of nano silicon nitride and 1g of gamma-glycidyl ether oxypropyl trimethoxysilane, reacting for 10min, cooling to 10 ℃, adding 2.2g of triethylamine for neutralization, adding 100g of ice water for emulsifying and dispersing, adding 3g of ethylenediamine, extending the chain, continuing to emulsify and disperse, and then removing the acetone through reduced pressure distillation to obtain the modified waterborne polyurethane emulsion.
And (3) performance detection:
the modified aqueous polyurethane resin emulsions obtained in examples 1 to 5 were examined for properties including appearance of the emulsion, solid content, strength, water resistance, and heat resistance. The modified aqueous polyurethane emulsion adhesive films obtained in examples 1 to 5 were subjected to a performance test.
TABLE 1 Performance results of modified aqueous polyurethane resin emulsions obtained in examples 1 to 5
As can be seen from Table 1, the tensile strength of the modified waterborne polyurethane resin coating films obtained in examples 1 to 4 is greater than 50MPa, and is obviously higher than that of example 5, which shows that the mechanical strength of the adhesive film added in the raw materials is high; the heat resistance of the modified waterborne polyurethane resin coating films obtained in the examples 1 to 4 is obviously better than that of the example 5, which shows that the heat resistance of the adhesive film is obviously improved; the water is dripped on the coating films of the modified waterborne polyurethane obtained in the examples 1 to 4 for 48 hours, and the abnormality is avoided, and the water is obviously better than that in the example 5; therefore, examples 1 to 4 obtained modified aqueous polyurethane resins significantly superior in tensile strength, water resistance and heat resistance to the aqueous polyurethane resin without the addition of the nanomaterial.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.
Claims (10)
1. The nano-material modified waterborne polyurethane resin is characterized by comprising the following raw material components in parts by mass:
the polyhydric alcohol is the combination of aliphatic polyester dihydric alcohol and polyether dihydric alcohol, and the silane coupling agent is gamma-glycidyl ether oxypropyl trimethoxy silane.
2. The nanomaterial-modified aqueous polyurethane resin according to claim 1, wherein the aliphatic polyester diol is one or two selected from polycarbonate diol and polycaprolactone diol, and the polyether diol is polytetrahydrofuran diol.
3. The nanomaterial-modified aqueous polyurethane resin according to claim 2, wherein the number average molecular weight of the polycarbonate diol, polycaprolactone diol, and polytetrahydrofuran diol is 1000 or 2000.
4. The nanomaterial-modified aqueous polyurethane resin according to claim 1, wherein the polyisocyanate is selected from any one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexyl diisocyanate, or a combination of two or more thereof.
5. The nanomaterial-modified aqueous polyurethane resin according to claim 1, wherein the first small-molecule chain extender is one or a combination of two or more of ethylene glycol, 1, 4-butanediol, 2-methyl-1, 3-propanediol, and 1, 4-cyclohexanedimethanol.
6. The nanomaterial-modified aqueous polyurethane resin according to claim 1, wherein the second small molecule chain extender is one or a combination of two or more selected from ethylenediamine, 1, 4-cyclohexyldimethylamine and isophoronediamine.
7. The nanomaterial-modified aqueous polyurethane resin according to claim 1, wherein the anionic hydrophilic chain extender is dimethylolpropionic acid or dimethylolbutyric acid.
8. The nanomaterial-modified aqueous polyurethane resin according to claim 1, wherein the catalyst is selected from any one or a combination of two or more of an organozinc compound, an organotin compound, an organic alkali metal salt, a tertiary amine, and a salt compound thereof.
9. The nanomaterial-modified aqueous polyurethane resin according to claim 1, wherein the organic zinc compound is selected from any one of zinc isooctanoate, zinc octanoate, and zinc acetylacetonate; the organic tin compound is selected from any one of dibutyl tin laurate and stannous octoate; the organic alkali metal salt is sodium acetate.
10. A method for preparing the nanomaterial-modified aqueous polyurethane resin according to any one of claims 1 to 9, comprising the steps of:
s1, weighing raw materials in set parts by mass, adding the diisocyanate and the carbon nano tubes into the polyol, heating to 80-90 ℃, preserving heat for 2-3 hours, cooling to 40-50 ℃, adding the anionic hydrophilic chain extender and the first micromolecule chain extender, adding the catalyst, heating to 70-80 ℃, and preserving heat for 4-6 hours to obtain a first prepolymer;
s2, cooling the first prepolymer to 40-50 ℃, adding the silane coupling agent, preserving heat for 5-10 min, adding the viscosity reduction solvent, and adding the nano silicon nitride to obtain a second prepolymer;
s3, cooling the second prepolymer to 10-20 ℃, then adding the salt forming agent for neutralization, adding ice water and the second small molecular chain extender, and carrying out reduced pressure distillation to obtain the nano material modified waterborne polyurethane resin.
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