CN113201111A - Fluorine-containing polyurethane acrylate resin, preparation method and application thereof - Google Patents
Fluorine-containing polyurethane acrylate resin, preparation method and application thereof Download PDFInfo
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- CN113201111A CN113201111A CN202110685954.0A CN202110685954A CN113201111A CN 113201111 A CN113201111 A CN 113201111A CN 202110685954 A CN202110685954 A CN 202110685954A CN 113201111 A CN113201111 A CN 113201111A
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- fluorine
- acrylate resin
- polyurethane acrylate
- containing polyurethane
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 51
- 239000011737 fluorine Substances 0.000 title claims abstract description 51
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000004814 polyurethane Substances 0.000 title claims abstract description 36
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 36
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000004321 preservation Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 150000002009 diols Chemical class 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 239000003112 inhibitor Substances 0.000 claims abstract description 11
- 239000004417 polycarbonate Substances 0.000 claims abstract description 11
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 7
- 239000012948 isocyanate Substances 0.000 claims abstract description 7
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 229920000570 polyether Polymers 0.000 claims abstract description 7
- 239000010702 perfluoropolyether Substances 0.000 claims description 12
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 7
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 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 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002537 cosmetic Substances 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 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 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 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 3
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 abstract description 3
- 238000000016 photochemical curing Methods 0.000 abstract description 3
- 239000010959 steel Substances 0.000 abstract description 3
- 210000002268 wool Anatomy 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 9
- 239000012467 final product Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 150000002221 fluorine Chemical class 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SOGFHWHHBILCSX-UHFFFAOYSA-J prop-2-enoate silicon(4+) Chemical compound [Si+4].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C SOGFHWHHBILCSX-UHFFFAOYSA-J 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
- C08G18/44—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
- C08G18/28—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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
-
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- 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
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the field of photocuring materials, in particular to a preparation method of fluorine-containing polyurethane acrylate resin, which comprises the following steps: placing fluorine-containing polyether alcohol, polycarbonate diol, isocyanate and a catalyst in a reaction container, heating to 60-75 ℃ under the protection of dry air, and reacting for 1-3 hours under heat preservation until the theoretical value of NC 0% is reached to obtain a chain segment fluorine-containing NCO terminated prepolymer; and adding a polymerization inhibitor and a hydroxyl-containing multifunctional acrylate monomer into the obtained NCO-terminated prepolymer, carrying out heat preservation reaction at 85-90 ℃ for 3-4 h, and obtaining the fluorine-containing polyurethane acrylate resin after NCO is completely consumed. The invention provides a fluorinated polyurethane acrylate resin which can solve the system compatibility and has the functions of fingerprint resistance, doodling resistance and steel wool resistance; the invention also provides a preparation method and application of the fluorine-containing polyurethane acrylate resin, which have simple steps and meet the requirements.
Description
Technical Field
The invention relates to the field of photocuring materials, in particular to a fluorine-containing polyurethane acrylate resin, a preparation method and application thereof.
Background
As a novel rapid forming means, the application of the photocuring technology in a plurality of fields of coatings is continuously improved, recently, along with the continuous expansion of some functional requirements of people on fingerprint resistance, doodling resistance and steel wool resistance of surfaces of electronic products such as mobile phones, notebooks and the like, some fluorine-containing and silicon-containing modified polyurethane acrylates play important roles due to special functional groups and structures thereof.
At present, the main method for solving the technical requirements is to add some fluorine-containing and silicon acrylate auxiliary agents and wear-resistant organic and inorganic powders into some high-functionality urethane acrylates, but the addition of such auxiliary agents is always due to the compatibility problem of the auxiliary agents and the surface migration effect of fluorine-containing elements, and even due to the sedimentation caused by the system compatibility problem due to the addition of the inorganic powders, the required performance of the product cannot be achieved.
Disclosure of Invention
In order to solve the technical problems, the invention provides the fluorine-containing polyurethane acrylate resin which can solve the system compatibility and has the advantages of fingerprint resistance, doodling resistance and steel wool resistance.
The invention also provides a preparation method and application of the fluorine-containing polyurethane acrylate resin, which have simple steps and meet the requirements.
The invention adopts the following technical scheme:
a preparation method of fluorine-containing polyurethane acrylate resin comprises the following steps:
placing fluorine-containing polyether alcohol, polycarbonate diol, isocyanate and a catalyst in a reaction container, heating to 60-75 ℃ under the protection of dry air, and reacting for 1-3 hours under heat preservation until the theoretical value of NC 0% is reached to obtain a chain segment fluorine-containing NCO terminated prepolymer;
and adding a polymerization inhibitor and a hydroxyl-containing multifunctional acrylate monomer into the obtained NCO-terminated prepolymer, carrying out heat preservation reaction at 85-90 ℃ for 3-4 h, and obtaining the fluorine-containing polyurethane acrylate resin after NCO is completely consumed.
The technical scheme is further improved in that the fluorine-containing polyether alcohol is hydroxyl-terminated perfluoropolyether alcohol, the molecular weight of the hydroxyl-terminated perfluoropolyether alcohol is 1000-5000, and the hydroxyl-terminated perfluoropolyether alcohol is PFPE-OH-1000, 1600, 3000 and the like.
The technical proposal is further improved in that the structural formula of the perfluoro polyether alcohol containing terminal hydroxyl is as follows:
the technical proposal is further improved in that the polycarbonate diol is one or more of T5650E, T5650J, T5651 or T5652 in the series of the Asahi chemical industry PCDL.
The technical proposal is further improved in that the isocyanate is TDI, IPDI, HDI, HMDI, HDI biuret or HDI tripolymer; the catalyst is one of dibutyltin dilaurate, stannous octoate or organic bismuth.
The technical proposal is further improved in that the polymerization inhibitor is one of MEHQ and HQ.
The technical proposal is further improved in that the hydroxyl-containing multifunctional acrylate monomer is one or two groups of pentaerythritol triacrylate and dipentaerythritol pentaester.
The fluorine-containing polyurethane acrylate resin is prepared by the preparation method.
The technical scheme is further improved in that the number average molecular weight of the fluorinated polyurethane acrylate resin is 2000-5000.
An application of the fluorine-containing polyurethane acrylate resin in cosmetic packaging, high-grade ink or 3C electronic products.
The invention has the beneficial effects that:
the invention introduces fluorine element into polyurethane chain segment through reaction of perfluoropolyether alcohol and polyisocyanate, and then uses hydroxyl-containing acrylate with high functionality to carry out end capping to prepare a series of fluorine-containing polyurethane acrylate.
Detailed Description
In order to further illustrate the invention, the following examples are set forth, but are not to be construed as limiting the scope of the invention.
A preparation method of fluorine-containing polyurethane acrylate resin comprises the following steps:
placing fluorine-containing polyether alcohol, polycarbonate diol, isocyanate and a catalyst in a reaction container, heating to 60-75 ℃ under the protection of dry air, and reacting for 1-3 hours under heat preservation until the theoretical value of NC 0% is reached to obtain a chain segment fluorine-containing NCO terminated prepolymer;
and adding a polymerization inhibitor and a hydroxyl-containing multifunctional acrylate monomer into the obtained NCO-terminated prepolymer, carrying out heat preservation reaction at 85-90 ℃ for 3-4 h, and obtaining the fluorine-containing polyurethane acrylate resin after NCO is completely consumed.
Further, the fluorine-containing polyether alcohol is hydroxyl-terminated perfluoropolyether alcohol, and the molecular weight of the hydroxyl-terminated perfluoropolyether alcohol is 1000-5000.
Further, the structural formula of the hydroxyl-terminated perfluoropolyether alcohol is as follows:
further, the polycarbonate diol is one or more of T5650E, T5650J, T5651 or T5652 in the Asahi chemical formula PCDL series.
Further, the isocyanate is TDI, IPDI, HDI, HMDI, HDI biuret, or HDI trimer; the catalyst is one of dibutyltin dilaurate, stannous octoate or organic bismuth.
Further, the polymerization inhibitor is one of MEHQ and HQ.
Further, the hydroxyl-containing multifunctional acrylate monomer is one or two of pentaerythritol triacrylate and dipentaerythritol pentaester.
A fluorine-containing polyurethane acrylate resin prepared by the above preparation method; the number average molecular weight of the fluorinated polyurethane acrylate resin is 2000-5000.
The application of the fluorine-containing polyurethane acrylate resin is applied to cosmetic packaging, high-grade ink or 3C electronic products; the application of the fluorine-containing polyurethane acrylate resin of the present invention is not limited to the above-mentioned fields.
Example 1
Placing 50g of fluoropolyether alcohol PFPE-1000, 75g of polycarbonate diol T5651, 33.6g of hexamethylene diisocyanate and 0.1g of catalyst into a reaction container, heating to 60-75 ℃ under the protection of dry air, preserving heat for reaction for 1-3 hours, obtaining a segmented fluorine-containing NCO terminated prepolymer when NC 0% reaches the initial half, and carrying out the next step;
adding 1g of polymerization inhibitor MEHQ and 110g of pentaerythritol triacrylate into the obtained NCO-terminated prepolymer, heating to 85-90 ℃, and carrying out heat preservation reaction for 3-4 h to obtain a final product after NCO is completely consumed.
Example 2
Placing 30g of fluoropolyether alcohol PFPE-1000, 85g of polycarbonate diol T5651, 33.6g of hexamethylene diisocyanate and 0.1g of catalyst into a reaction container, heating to 60-75 ℃ under the protection of dry air, preserving heat for reaction for 1-3 hours, obtaining a segmented fluorine-containing NCO terminated prepolymer when NC 0% reaches the initial half, and carrying out the next step;
adding 1g of polymerization inhibitor MEHQ and 200g of dipentaerythritol pentaacrylate into the obtained NCO-terminated prepolymer, heating to 85-90 ℃, reacting for 3-4 hours in a heat preservation manner, and obtaining a final product after NCO is completely consumed.
Example 3
Placing 20g of fluoropolyether alcohol PFPE-1000, 90g of polycarbonate diol T5651, 33.6g of hexamethylene diisocyanate and 0.1g of catalyst into a reaction container, heating to 60-75 ℃ under the protection of dry air, preserving heat for reaction for 1-3 hours, obtaining a segmented fluorine-containing NCO terminated prepolymer when NC 0% reaches the initial half, and carrying out the next step;
adding 1g of polymerization inhibitor MEHQ, 55g of pentaerythritol triacrylate and 100g of dipentaerythritol pentaacrylate into the obtained NCO-terminated prepolymer, heating to 85-90 ℃, carrying out heat preservation reaction for 3-4 h, and obtaining a final product after NCO is completely consumed.
Example 4
Placing 40g of fluoropolyether alcohol PFPE-1600, 175g of polycarbonate diol T5652, 33.6g of hexamethylene diisocyanate and 0.1g of catalyst in a reaction container, heating to 60-75 ℃ under the protection of dry air, carrying out heat preservation reaction for 1-3 hours, obtaining a segmented fluorine-containing NCO terminated prepolymer when NC 0% reaches the initial half, and carrying out the next step;
adding 1g of polymerization inhibitor MEHQ and 200g of dipentaerythritol pentaacrylate into the obtained NCO-terminated prepolymer, heating to 85-90 ℃, reacting for 3-4 hours in a heat preservation manner, and obtaining a final product after NCO is completely consumed.
The invention introduces fluorine element into polyurethane chain segment through reaction of perfluoropolyether alcohol and polyisocyanate, and then uses hydroxyl-containing acrylate with high functionality to carry out end capping to prepare a series of fluorine-containing polyurethane acrylate.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of fluorine-containing polyurethane acrylate resin is characterized by comprising the following steps:
placing fluorine-containing polyether alcohol, polycarbonate diol, isocyanate and a catalyst in a reaction container, heating to 60-75 ℃ under the protection of dry air, and reacting for 1-3 hours under heat preservation until the theoretical value of NC 0% is reached to obtain a chain segment fluorine-containing NCO terminated prepolymer;
and adding a polymerization inhibitor and a hydroxyl-containing multifunctional acrylate monomer into the obtained NCO-terminated prepolymer, carrying out heat preservation reaction at 85-90 ℃ for 3-4 h, and obtaining the fluorine-containing polyurethane acrylate resin after NCO is completely consumed.
2. The method for preparing fluorine-containing polyurethane acrylate resin according to claim 1, wherein the fluorine-containing polyether alcohol is hydroxyl-terminated perfluoropolyether alcohol, and the molecular weight of the hydroxyl-terminated perfluoropolyether alcohol is 1000 to 5000.
3. The method of claim 2, wherein the hydroxyl terminated perfluoropolyether alcohol has the following structural formula:
4. the method of claim 1, wherein the polycarbonate diol is one or more of T5650E, T5650J, T5651 and T5652 in the Asahi-PCDL series.
5. The method of preparing the fluorine-containing polyurethane acrylate resin according to claim 1, wherein the isocyanate is TDI, IPDI, HDI, HMDI, HDI biuret, or HDI trimer; the catalyst is one of dibutyltin dilaurate, stannous octoate or organic bismuth.
6. The method of preparing a fluorine-containing polyurethane acrylate resin according to claim 1, wherein the polymerization inhibitor is one of MEHQ and HQ.
7. The method for preparing a fluorine-containing urethane acrylate resin according to claim 1, wherein the hydroxyl group-containing multifunctional acrylate monomer is one or two of pentaerythritol triacrylate and dipentaerythritol pentaester.
8. A fluorine-containing polyurethane acrylate resin, wherein the fluorine-containing polyurethane acrylate resin is obtained using the production method according to any one of claims 1 to 7.
9. The fluorine-containing polyurethane acrylate resin according to claim 8, wherein the number average molecular weight of the fluorine-containing polyurethane acrylate resin is 2000 to 5000.
10. The application of the fluorine-containing polyurethane acrylate resin is characterized in that the fluorine-containing polyurethane acrylate resin is applied to cosmetic packaging, high-grade ink or 3C electronic products.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110685954.0A CN113201111A (en) | 2021-06-21 | 2021-06-21 | Fluorine-containing polyurethane acrylate resin, preparation method and application thereof |
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| CN202110685954.0A CN113201111A (en) | 2021-06-21 | 2021-06-21 | Fluorine-containing polyurethane acrylate resin, preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104204018A (en) * | 2011-11-30 | 2014-12-10 | 涂层国外知识产权有限公司 | Coating composition |
| CN111511790A (en) * | 2017-12-26 | 2020-08-07 | 阿克佐诺贝尔国际涂料股份有限公司 | Fluorinated polyacrylate coating compositions, method for their preparation and their use |
| CN112574390A (en) * | 2021-03-01 | 2021-03-30 | 太仓中化环保化工有限公司 | High-wear-resistance UV resin with anti-fingerprint function and preparation method thereof |
-
2021
- 2021-06-21 CN CN202110685954.0A patent/CN113201111A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104204018A (en) * | 2011-11-30 | 2014-12-10 | 涂层国外知识产权有限公司 | Coating composition |
| CN111511790A (en) * | 2017-12-26 | 2020-08-07 | 阿克佐诺贝尔国际涂料股份有限公司 | Fluorinated polyacrylate coating compositions, method for their preparation and their use |
| CN112574390A (en) * | 2021-03-01 | 2021-03-30 | 太仓中化环保化工有限公司 | High-wear-resistance UV resin with anti-fingerprint function and preparation method thereof |
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