CN114957616A - Fluorine-containing hydroxyl resin and preparation method and application thereof - Google Patents
Fluorine-containing hydroxyl resin and preparation method and application thereof Download PDFInfo
- Publication number
- CN114957616A CN114957616A CN202210777410.1A CN202210777410A CN114957616A CN 114957616 A CN114957616 A CN 114957616A CN 202210777410 A CN202210777410 A CN 202210777410A CN 114957616 A CN114957616 A CN 114957616A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- resin
- containing hydroxyl
- coating
- anhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 72
- 239000011737 fluorine Substances 0.000 title claims abstract description 72
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229920005989 resin Polymers 0.000 title claims abstract description 50
- 239000011347 resin Substances 0.000 title claims abstract description 50
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000011527 polyurethane coating Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000003822 epoxy resin Substances 0.000 claims description 16
- 230000002209 hydrophobic effect Effects 0.000 claims description 16
- 229920000647 polyepoxide Polymers 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 8
- 229940014800 succinic anhydride Drugs 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- JDIJDQNYSUHWJJ-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecan-2-ol Chemical compound FC(F)(F)C(F)(O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JDIJDQNYSUHWJJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 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 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- 229940072049 amyl acetate Drugs 0.000 claims description 4
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 4
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 4
- GPAMBYNRXCUNML-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctan-2-ol Chemical compound FC(F)(F)C(F)(O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F GPAMBYNRXCUNML-UHFFFAOYSA-N 0.000 claims description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 3
- KUGBQWBWWNPMIT-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoropentan-1-ol Chemical compound CC(F)(F)C(F)(F)C(F)(F)C(O)(F)F KUGBQWBWWNPMIT-UHFFFAOYSA-N 0.000 claims description 3
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 claims description 3
- JCMNMOBHVPONLD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohexan-1-ol Chemical compound OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F JCMNMOBHVPONLD-UHFFFAOYSA-N 0.000 claims description 3
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 40
- 238000000576 coating method Methods 0.000 abstract description 37
- 238000001035 drying Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract description 4
- 238000012423 maintenance Methods 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000005002 finish coating Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 6
- 230000003075 superhydrophobic effect Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical compound [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 fluoro-hydroxyl group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000008096 xylene 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3236—Heterocylic compounds
- C08G59/3245—Heterocylic compounds containing only nitrogen as a heteroatom
-
- 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
- C08G18/58—Epoxy resins
- C08G18/584—Epoxy resins having nitrogen
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/423—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof containing an atom other than oxygen belonging to a functional groups to C08G59/42, carbon and hydrogen
-
- 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
- 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
- C08G2150/00—Compositions for coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a fluorine-containing hydroxyl resin and a preparation method and application thereof, belonging to the field of fine chemical synthesis. According to the invention, by adding the fluorine-containing monohydric alcohol, the long-chain anhydride and the triglycidyl isocyanurate in a specific molar ratio, the fluorine-containing hydroxyl resin has high fluorine content, and the hydrophobicity of the prepared coating is realized through the fluorine enrichment effect; meanwhile, triglycidyl isocyanurate has a rigid triazine ring structure, so that the prepared coating has good hardness and high normal-temperature drying speed; the coating prepared by the fluorine-containing hydroxyl resin has good glossiness, transparency, hydrophobicity, quick drying property and higher hardness, can meet the requirements of finish coating in the fields of automobile manufacturing and maintenance, rail trains, large vehicles, wind power blades and the like, and has wide market prospect.
Description
Technical Field
The invention relates to the field of fine chemical synthesis, and in particular relates to a fluorine-containing hydroxyl resin and a preparation method and application thereof.
Background
The two-component polyurethane coating is prepared by taking hydroxyl resin and a polyisocyanate curing agent as main film forming substances, belongs to a high-end coating variety, has excellent decoration and durable protection, is widely applied to coating protection in the fields of automobile manufacturing and maintenance, rail trains, large vehicles, engineering machinery and the like, and is deeply welcomed by the market. The hydrophobic coating has good antifouling and self-cleaning performances, can be applied to the fields of anti-icing, anti-fogging, anticorrosion, dust removal and the like, and has good market prospect; the current protocols for preparing hydrophobic coating materials can be divided into two categories: firstly, the structure of a surface micro-nano structure is carried out by imitating a lotus leaf effect, and can be realized by sol-gel, chemical vapor deposition, layer-by-layer self-assembly, etching and other methods, but the micro-nano structure obtained by the methods has excellent super-hydrophobic performance, but all the methods can cause serious light absorption and scattering on the surface of a coating, so that a transparent coating cannot be obtained, and the application of the hydrophobic coating is limited; the other scheme is that the surface energy of the coating is reduced by introducing elements such as fluorine, silicon and the like, and the hydrophobic property of the coating is improved, and the transparent polyurethane coating can be obtained by the scheme, but the problems of low drying speed, high-temperature baking requirement, poor hardness, low glossiness and the like exist, and the application field of the transparent polyurethane coating is limited.
CN202010249169.6 is copolymerized with other acrylic monomers by (methyl) acrylate monomers containing silicon and fluorine elements, the silicon and the fluorine elements are introduced into polyurethane by free radical polymerization, and the fluorine elements and the silicon elements exist in a side chain of a polymer in a form of stable covalent bonds, so that the surface energy of the material is reduced, and the hydrophobicity of a polyurethane coating is improved; however, the water contact angle of the polyurethane coating prepared by the technical scheme is only 99-102 degrees, and the hydrophobicity is general; the pencil hardness of the coating only reaches HB, and the requirements of the fields of automobile manufacturing and the like cannot be met; the drying speed of the coating is also relatively slow, and high-temperature baking is needed to realize drying. CN202010358266.9 provides a super-hydrophobic coating agent, a transparent super-hydrophobic coating, a preparation method and an application thereof, wherein the super-hydrophobic coating agent comprises polymer microspheres, fluorine-containing polymer and a polymer cross-linking agent which are dispersed in a solvent; the super-hydrophobic coating agent does not need to use inorganic filler, can form a stable transparent super-hydrophobic coating on various base materials, has good adhesion with the base materials, has a contact angle of more than 150 degrees, a rolling angle of less than 10 degrees and a visible light transmittance of 83-95 percent. However, the coating needs to be baked at 120 ℃ for drying, indexes such as glossiness and hardness are not clear, and the use of the polymer microspheres can cause low glossiness of the coating, so that the application field of the coating is limited.
Therefore, the development of a polyurethane coating material having not only good hydrophobicity but also good gloss and transparency is a hot spot of current research.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the fluorine-containing hydroxyl resin, and the coating prepared by using the fluorine-containing hydroxyl resin has the advantages of good hydrophobicity, high glossiness and high transparency.
In order to achieve the purpose, the invention adopts the technical scheme that: a fluorine-containing hydroxyl resin comprising the following components: fluorine-containing monohydric alcohol, long-chain acid anhydride, epoxy resin and catalyst; the molar ratio of the fluorine-containing monohydric alcohol to the long-chain acid anhydride to the epoxy resin is 1-3: 1-3: 1-3; the epoxy resin is triglycidyl isocyanurate.
The fluorine-containing monohydric alcohol and the long-chain anhydride are subjected to chemical reaction, so that the fluorine-containing structural units in the fluorine-containing monohydric alcohol are connected with the long chain with strong mobility, and when the fluorine-containing structural units are applied to the coating, the fluorine-containing groups are more easily gathered on the surface of the coating through chain segment movement in the curing process of the coating, so that the hydrophobicity of the coating is enhanced.
By adding triglycidyl isocyanurate containing a plurality of epoxy groups and having a triazine ring rigid structure, on one hand, a hard core can be provided for the fluorine-containing hydroxyl resin, so that when the resin is applied to a coating, the coating has good hardness and higher normal-temperature drying speed; on the other hand, the triglycidyl isocyanurate, the fluorine-containing monohydric alcohol and the long-chain anhydride act together, so that the fluorine-containing hydroxyl resin has high fluorine content, the hydrophobicity of the coating is realized through the fluorine enrichment effect, the problems that the transparency of the coating is poor, the glossiness is low and the like due to the fact that the hydrophobicity of the conventional hydrophobic polyurethane coating technology is improved by introducing the silicon-fluorine-containing nano particles are solved, and the coating has better hydrophobicity, glossiness and transparency.
The inventors have further found that by using the above components in the above molar ratio, the hydrophobicity, gloss and transparency of the coating can be more effectively improved.
Preferably, the molar ratio of the fluorine-containing monohydric alcohol to the long-chain acid anhydride to the epoxy resin is 3: 3: the inventor finds out through experiments that the fluorine-containing monohydric alcohol, the long-chain acid anhydride and the epoxy resin can improve the hydrophobicity, the glossiness and the transparency of the coating to the best extent at the molar ratio.
Preferably, the fluorine-containing monohydric alcohol comprises at least one of perfluorooctyl ethanol, perfluorohexyl ethanol, perfluorobutyl ethanol, hexafluoroisopropanol, octafluoropentanol.
Preferably, the long-chain acid anhydride comprises at least one of succinic anhydride, glutaric anhydride, and adipic anhydride.
Preferably, the catalyst comprises at least one of stannous octoate, dibutyl tin dilaurate.
Preferably, the weight percentage of the catalyst is 0.01% -0.05%.
More preferably, the weight percentage of the catalyst is 0.02% to 0.04%.
Preferably, the fluorine-containing hydroxyl resin further comprises a solvent.
More preferably, the solvent comprises at least one of n-butyl acetate, amyl acetate, propylene glycol methyl ether acetate, methyl isobutyl ketone, methyl amyl ketone.
Preferably, the solvent is present in an amount of 10 to 30% by weight.
More preferably, the weight percentage of the solvent is preferably 15-25%.
Another object of the present invention is to provide a method for preparing the resin containing a fluoro-hydroxyl group, comprising the steps of: and mixing and heating the fluorine-containing monohydric alcohol and the long-chain anhydride for a period of time, adding the epoxy resin and the catalyst into the mixture, continuously reacting the mixture for a period of time at a high temperature, and then adding the solvent into the mixture for dilution to obtain the fluorine-containing hydroxyl resin.
Preferably, the temperature for mixing and heating the fluorine-containing monohydric alcohol and the long-chain anhydride is 110-130 ℃, and the heating time is 1-5 h.
More preferably, the temperature for mixing and heating the fluorine-containing monohydric alcohol and the long-chain anhydride is 115-125 ℃, and the heating time is 2-3 h.
Preferably, the heating temperature after the addition of the epoxy resin and the catalyst is 120-140 ℃.
More preferably, the heating temperature is 125-135 ℃ after the addition of the epoxy resin and the catalyst.
Preferably, the reaction time is 3 to 5 hours after the epoxy resin and the catalyst are added.
It should be noted that, after the epoxy resin and the catalyst are added, the reaction is determined by the acidity value of the mixed solution, and when the acidity value of the mixed solution is less than 2mg KOH/g, the reaction is finished.
The invention also provides application of the fluorine-containing hydroxyl resin in the hydrophobic polyurethane coating.
Preferably, the hydrophobic polyurethane coating comprises a component a and a component b.
Preferably, the weight ratio of the component A to the component B is 2: 1.
preferably, the component A comprises the following components in parts by weight: 65-85 parts of fluorine-containing hydroxyl resin, 15-30 parts of organic solvent, 0.01-0.04 part of catalyst and 0.01-0.1 part of flatting agent.
More preferably, the component A comprises the following components in parts by weight: 70-80 parts of fluorine-containing hydroxyl resin, 20-25 parts of organic solvent, 0.02-0.03 part of catalyst and 0.02-0.05 part of flatting agent.
Preferably, the component B comprises the following components in parts by weight: 37-65 parts of polyisocyanate curing agent and 35-63 parts of organic solvent.
More preferably, the component B comprises the following components in parts by weight: 40-60 parts of curing agent and 40-60 parts of organic solvent.
Most preferably, the polyisocyanate curing agent is a hexamethylene diisocyanate trimer curing agent.
Preferably, the organic solvent comprises at least one of xylene, trimethylbenzene, ethyl acetate, sec-butyl acetate, n-butyl acetate, amyl acetate, propylene glycol methyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone.
Preferably, the catalyst is dibutyl tin dilaurate.
Preferably, the leveling agent is an organosilicon leveling agent, an organic fluorine leveling agent or an acrylate leveling agent.
The invention has the beneficial effects that: the invention provides a fluorine-containing hydroxyl resin, which has high fluorine content by adding fluorine-containing monohydric alcohol, long-chain acid anhydride and triglycidyl isocyanurate in a specific molar ratio, and realizes the hydrophobicity of the prepared coating through the fluorine enrichment effect; meanwhile, triglycidyl isocyanurate has a rigid triazine ring structure, so that the prepared coating has good hardness and high normal-temperature drying speed; the coating prepared by the fluorine-containing hydroxyl resin has good glossiness, transparency, hydrophobicity, quick drying property and higher hardness, can meet the requirements of finish coating in the fields of automobile manufacturing and maintenance, rail trains, large vehicles, wind power blades and the like, and has wide market prospect.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
In an embodiment of the present invention, a method for preparing a fluorine-containing hydroxy resin includes: firstly, 3mol (1391.4g) of perfluorooctyl ethanol and 3mol (300.3) of succinic anhydride are added into a reaction kettle and react for 3 hours at the temperature of 110 ℃; then adding 1mol (297.3g) of triglycidyl isocyanurate and 0.22g of stannous octoate, reacting for 3 hours at 140 ℃, adding 221g of n-butyl acetate when the acid value reaches 1.8mg KOH/g, and diluting to obtain the fluorine-containing hydroxyl resin; the fluorine-containing hydroxyl resin has the solid content of 90.1 percent, the viscosity of 17650mPa & s and the hydroxyl content of 2.6 percent.
Example 2
The preparation method of the resin containing the fluorine hydroxyl group in the embodiment comprises the following steps: firstly, adding 3mol (1092.3g) of perfluorohexylethanol and 3mol (342.3) of glutaric anhydride into a reaction kettle, and reacting for 2 hours at 130 ℃; then adding 1mol (297.3g) of triglycidyl isocyanurate and 1.29g of dibutyl tin dilaurate, reacting at 120 ℃ for 5 hours until the acid value reaches 1.7mg KOH/g, adding 852g of amyl acetate, and diluting to obtain the fluorine-containing hydroxyl resin; the fluorine-containing hydroxyl resin has a solid content of 70.2%, a viscosity of 3820mPa & s and a hydroxyl content of 3.0%.
Example 3
The preparation method of the resin containing the fluorine hydroxyl group in the embodiment comprises the following steps: firstly, adding 3mol (792.3g) of perfluorobutyl ethanol and 3mol (384.3) of adipic anhydride into a reaction kettle, and reacting for 3 hours at 120 ℃; then adding 1mol (297.3g) of triglycidyl isocyanurate and 0.55g of dibutyl tin dilaurate, reacting for 4 hours at 130 ℃ until the acid value reaches 1.5mgKOH/g, adding 368g of propylene glycol methyl ether acetate, and diluting to obtain the fluorine-containing hydroxyl resin; the fluorine-containing hydroxyl resin has a solid content of 80.2%, a viscosity of 6640mPa · s and a hydroxyl content of 3.5%.
Example 4
The preparation method of the resin containing the fluorine hydroxyl group in the embodiment comprises the following steps: firstly, adding 3mol (504g) of hexafluoroisopropanol and 3mol (300.3) of succinic anhydride into a reaction kettle, and reacting for 3 hours at 115 ℃; then adding 1mol (297.3g) of triglycidyl isocyanurate and 0.35g of stannous octoate, reacting for 3 hours at 135 ℃ until the acid value reaches 1.9mgKOH/g, adding 367g of n-butyl acetate, and diluting to obtain the fluorine-containing hydroxyl resin; the fluorine-containing hydroxyl resin has a solid content of 75.3%, a viscosity of 5890mPa · s and a hydroxyl content of 4.6%.
Example 5
The preparation method of the resin containing the fluorine hydroxyl group in the embodiment comprises the following steps: firstly, adding 3mol (696.3g) of octafluoropentanol and 3mol (300.3) of succinic anhydride into a reaction kettle, and reacting for 2 hours at 125 ℃; then adding 1mol (297.3g) of triglycidyl isocyanurate and 0.35g of stannous octoate, reacting for 4 hours at 130 ℃ until the acid value reaches 1.8mgKOH/g, adding 128g of methyl isobutyl ketone and 100g of methyl amyl ketone, and diluting to obtain the fluorine-containing hydroxyl resin; the fluorine-containing hydroxyl resin has the solid content of 85.1 percent, the viscosity of 9830mPa & s and the hydroxyl content of 3.9 percent.
Example 6
This example differs from example 1 only in that: the molar ratio of the perfluorooctyl ethanol to the succinic anhydride to the triglycidyl isocyanurate is 1: 1: 1.
example 7
This example differs from example 1 only in that: the molar ratio of the perfluorooctyl ethanol to the succinic anhydride to the triglycidyl isocyanurate is 1: 1: 3.
comparative example 1
A comparative example of a fluorinated hydroxyl resin of the present invention differs from example 1 only in that: the epoxy resin used in this comparative example was bisphenol A epoxy resin E51.
Comparative example 2
This comparative example differs from example 1 only in that: the mol ratio of the perfluorooctyl ethanol to the succinic anhydride to the triglycidyl isocyanurate is 4: 5: 1.
the fluorine-containing hydroxyl resin of the embodiments 1-7 and the comparative examples 1-2 is prepared into a hydrophobic polyurethane coating, the components and the parts by weight of the components of the hydrophobic polyurethane coating are shown in the following table 1, wherein the mass ratio of the component A to the component B is 2: 1.
TABLE 1
Examples of effects
Samples 1 to 9 (samples 1 to 7 corresponding to examples 1 to 7 and samples 8 and 9 corresponding to comparative examples 1 to 2) of the hydrophobic polyurethane coatings obtained in the experimental examples were tested for the construction viscosity by GB/T1723 to 93, the tack time by GB/T1728 to 1979, the hardness by GB/T6739 to 2006, the gloss by GB/T9754 to 2007, the light transmittance by GB/T1721 to 2008, and the water contact angle by DSA25, and the results are shown in the following Table 2.
TABLE 2
Results the hydrophobic polyurethane coatings prepared in inventive examples 1-5 are shown in table 2: (1) the paint has excellent quick surface drying and actual drying performances, can be dried at normal temperature, and is suitable for the application requirements in the fields of automobile repair, railway vehicles, engineering machinery and the like; (2) the pencil hardness reaches H, and can meet most application requirements including automobile manufacturing; (3) the contact angles are all over 110 degrees, and the higher level of the hydrophobicity of the transparent coating is achieved; (4) the transparency is excellent, the glossiness reaches more than 95, the decoration is very ideal, and the technical problems of poor transparency and low glossiness of the existing hydrophobic polyurethane coating are solved; in the comparative example 1, the surface drying time and the actual drying time of the system are greatly prolonged and the hardness of the coating is poor because a triazine ring structure is not introduced; comparative example 2 the reaction was not carried out in an optimized ratio, and the drying speed, hardness, gloss, transparency and water contact angle of the coating were all decreased.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A fluorine-containing hydroxyl resin, which is characterized by comprising the following components: fluorine-containing monohydric alcohol, long-chain acid anhydride, epoxy resin and catalyst; the molar ratio of the fluorine-containing monohydric alcohol to the long-chain acid anhydride to the epoxy resin is 1-3: 1-3: 1-3; the epoxy resin is triglycidyl isocyanurate.
2. The fluorohydroxy resin according to claim 1, wherein the molar ratio of the fluorine-containing monohydric alcohol, the long-chain acid anhydride and the epoxy resin is 3: 3: 1.
3. the fluorine-containing hydroxyl resin according to claim 1, wherein the fluorine-containing monohydric alcohol comprises at least one of perfluorooctylethanol, perfluorohexylethanol, perfluorobutylethanol, hexafluoroisopropanol, octafluoropentanol.
4. The fluorohydroxy resin of claim 1, wherein the long-chain anhydride comprises at least one of succinic anhydride, glutaric anhydride, and adipic anhydride.
5. The fluorohydroxy resin of claim 1, wherein the catalyst comprises at least one of stannous octoate, dibutyl tin dilaurate.
6. The fluorine-containing hydroxyl resin according to claim 1, further comprising a solvent;
preferably, the solvent comprises at least one of n-butyl acetate, amyl acetate, propylene glycol methyl ether acetate, methyl isobutyl ketone, methyl amyl ketone.
7. The method for producing a fluorohydroxy resin according to any one of claims 1 to 6, comprising the steps of: and mixing and heating the fluorine-containing monohydric alcohol and the long-chain anhydride, adding the epoxy resin and the catalyst into the mixture, continuously heating the mixture until the acidity value of the mixed solution is less than 2mg KOH/g, and adding the solvent into the mixture for dilution to obtain the fluorine-containing hydroxyl resin.
8. Use of a fluorohydroxy resin according to any one of claims 1-6 for the preparation of a hydrophobic polyurethane coating.
9. Use of a fluorohydroxy resin according to claim 8 in a hydrophobic polyurethane coating, wherein said hydrophobic polyurethane coating comprises a component A and a component B, said component A and component B being present in a weight ratio of 2: 1.
10. use of a fluorohydroxy resin according to claim 9 in hydrophobic polyurethane coatings, wherein the a component comprises the following components in parts by weight: 65-85 parts of fluorine-containing hydroxyl resin, 15-30 parts of organic solvent, 0.01-0.04 part of catalyst and 0.01-0.1 part of flatting agent; the component B comprises the following components in parts by weight: 37-65 parts of polyisocyanate curing agent and 35-63 parts of organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210777410.1A CN114957616B (en) | 2022-06-28 | 2022-06-28 | Fluorine-containing hydroxyl resin and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210777410.1A CN114957616B (en) | 2022-06-28 | 2022-06-28 | Fluorine-containing hydroxyl resin and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114957616A true CN114957616A (en) | 2022-08-30 |
| CN114957616B CN114957616B (en) | 2023-11-28 |
Family
ID=82966845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210777410.1A Active CN114957616B (en) | 2022-06-28 | 2022-06-28 | Fluorine-containing hydroxyl resin and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114957616B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115979428A (en) * | 2022-12-16 | 2023-04-18 | 无锡鑫巨宏智能科技有限公司 | Protective cover for infrared body temperature detector and preparation method thereof |
| CN116463022A (en) * | 2023-04-19 | 2023-07-21 | 淄博市交通建设发展中心 | High weather-resistant water-based modified polyacrylic acid bridge concrete protective coating |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006040471A1 (en) * | 2006-08-29 | 2008-03-06 | Krüger, Alfred | se of an epoxy-functional adduct prepared from triglycidyl iscyanurate or triglycidyl trimellitate as a crosslinker or hardener for carboxy-functional polyesters suitable for producing powder coatings |
| CN106432703A (en) * | 2016-09-26 | 2017-02-22 | 华南理工大学 | Hydroxyl polyester resin with high solid content and preparation method and application thereof |
| CN111825627A (en) * | 2020-07-28 | 2020-10-27 | 清远高新华园科技协同创新研究院有限公司 | Preparation method of high-solid-content hydroxyl resin |
| CN112321799A (en) * | 2020-11-04 | 2021-02-05 | 黄山新佳精细材料有限公司 | Epoxy resin for high-hardness and low-temperature curing type powder coating and preparation method thereof |
| CN112457762A (en) * | 2020-12-10 | 2021-03-09 | 中国科学院长春应用化学研究所 | High-adhesion fluorine-containing hydrophobic polyurethane transparent protective coating and preparation and use methods thereof |
-
2022
- 2022-06-28 CN CN202210777410.1A patent/CN114957616B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006040471A1 (en) * | 2006-08-29 | 2008-03-06 | Krüger, Alfred | se of an epoxy-functional adduct prepared from triglycidyl iscyanurate or triglycidyl trimellitate as a crosslinker or hardener for carboxy-functional polyesters suitable for producing powder coatings |
| CN106432703A (en) * | 2016-09-26 | 2017-02-22 | 华南理工大学 | Hydroxyl polyester resin with high solid content and preparation method and application thereof |
| CN111825627A (en) * | 2020-07-28 | 2020-10-27 | 清远高新华园科技协同创新研究院有限公司 | Preparation method of high-solid-content hydroxyl resin |
| CN112321799A (en) * | 2020-11-04 | 2021-02-05 | 黄山新佳精细材料有限公司 | Epoxy resin for high-hardness and low-temperature curing type powder coating and preparation method thereof |
| CN112457762A (en) * | 2020-12-10 | 2021-03-09 | 中国科学院长春应用化学研究所 | High-adhesion fluorine-containing hydrophobic polyurethane transparent protective coating and preparation and use methods thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115979428A (en) * | 2022-12-16 | 2023-04-18 | 无锡鑫巨宏智能科技有限公司 | Protective cover for infrared body temperature detector and preparation method thereof |
| CN115979428B (en) * | 2022-12-16 | 2023-10-10 | 无锡鑫巨宏智能科技有限公司 | Protective cover for infrared body temperature detector and preparation method thereof |
| CN116463022A (en) * | 2023-04-19 | 2023-07-21 | 淄博市交通建设发展中心 | High weather-resistant water-based modified polyacrylic acid bridge concrete protective coating |
| CN116463022B (en) * | 2023-04-19 | 2024-01-30 | 淄博市交通建设发展中心 | High weather-resistant water-based modified polyacrylic acid bridge concrete protective coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114957616B (en) | 2023-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114957616B (en) | Fluorine-containing hydroxyl resin and preparation method and application thereof | |
| CN111393588A (en) | Fluorine-silicon modified acrylic resin and preparation method and application thereof | |
| CN104530974A (en) | Anti-icing paint, as well as preparation and application thereof | |
| CN111269626B (en) | Preparation method of epoxy acrylic polysiloxane self-cleaning coating | |
| CN104530975A (en) | Frost prevention coating and preparation method and application thereof | |
| CN105199511A (en) | Varnish for stainless steel substrate and preparation method and application of varnish | |
| CN110684440A (en) | Anticorrosive tough coating for outdoor communication tower and preparation method thereof | |
| CN101864166A (en) | Method for preparing organic-silane-modified acrylic polyurethane ultraviolet curing prepolymer | |
| WO2014102166A9 (en) | A coating composition, a preparation method therefore, and use thereof | |
| CN102492338A (en) | Elastic heat-insulation fluorocarbon coating and preparation method and use method thereof | |
| CN108841322B (en) | Low surface energy coating and preparation method thereof | |
| CN111647149A (en) | Polyester resin with excellent wear resistance and chemical resistance for powder and preparation method thereof | |
| CN114921179A (en) | Environment-friendly high-temperature-resistant coating, preparation method and application thereof | |
| CN113801572B (en) | Super-hydrophobic and high-stability nano ceramic coating and application method thereof | |
| CN102876150A (en) | High weather resistant anti-pasting and doodling-proof water-based paint and preparing method thereof | |
| CN111732892A (en) | Household nano self-cleaning coating and preparation method thereof | |
| CN110003788B (en) | Water-based single-component nano-modified self-crosslinking weather-resistant finish paint | |
| CN112552497B (en) | High-hydroxyl-value polyester resin for extinction type powder coating and preparation method and application thereof | |
| CN108531047B (en) | Water-based epoxy resin fire-resistant paint, preparation method and application thereof | |
| CN108129974B (en) | Polysiloxane finish paint for rolling stock and preparation method thereof | |
| CN116355476B (en) | Heat-insulating paint for building and preparation method thereof | |
| CN112521591A (en) | Polyester resin with lasting high temperature resistance and excellent hardness for powder coating and preparation method thereof | |
| CN112300393A (en) | Polysiloxane resins, coating compositions containing them and their use | |
| CN108467647A (en) | A kind of automatically cleaning reflective heat-insulation paint and preparation method thereof | |
| CN112694836A (en) | Waterproof coating for high-speed rail and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |