CN114957616B - Fluorine-containing hydroxyl resin and preparation method and application thereof - Google Patents

Fluorine-containing hydroxyl resin and preparation method and application thereof Download PDF

Info

Publication number
CN114957616B
CN114957616B CN202210777410.1A CN202210777410A CN114957616B CN 114957616 B CN114957616 B CN 114957616B CN 202210777410 A CN202210777410 A CN 202210777410A CN 114957616 B CN114957616 B CN 114957616B
Authority
CN
China
Prior art keywords
fluorine
resin
containing hydroxyl
fluorohydroxy
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.)
Active
Application number
CN202210777410.1A
Other languages
Chinese (zh)
Other versions
CN114957616A (en
Inventor
马晓阳
陈之善
梁伟健
侯文俊
黎家强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingyuan Hi Tech Huayuan Science And Technology Collaborative Innovation Research Institute Co ltd
Original Assignee
Qingyuan Hi Tech Huayuan Science And Technology Collaborative Innovation Research Institute Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Qingyuan Hi Tech Huayuan Science And Technology Collaborative Innovation Research Institute Co ltd filed Critical Qingyuan Hi Tech Huayuan Science And Technology Collaborative Innovation Research Institute Co ltd
Priority to CN202210777410.1A priority Critical patent/CN114957616B/en
Publication of CN114957616A publication Critical patent/CN114957616A/en
Application granted granted Critical
Publication of CN114957616B publication Critical patent/CN114957616B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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

Abstract

The invention discloses a fluorine-containing hydroxyl resin, 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 enrichment effect of fluorine; meanwhile, triglycidyl isocyanurate has a triazine ring rigid structure, so that the prepared coating has good hardness and high normal-temperature drying speed; the paint prepared by using the fluorine-containing hydroxyl resin has good glossiness, transparency, hydrophobicity, quick drying property and higher hardness, can meet the finishing paint coating requirements in the fields of automobile manufacturing and maintenance, rail trains, large-scale vehicles, wind power blades and the like, and has wide market prospect.

Description

Fluorine-containing hydroxyl resin and preparation method and application thereof
Technical Field
The invention relates to the field of fine chemical synthesis, in particular to fluorine-containing hydroxyl resin, and a preparation method and application thereof.
Background
The double-component polyurethane coating takes hydroxyl resin and polyisocyanate curing agent as main film forming substances, belongs to high-end coating varieties, has excellent decorative and durable protectiveness, is widely applied to the coating protection in the fields of automobile manufacturing and maintenance, rail trains, large vehicles, engineering machinery and the like, and is popular in the market. The hydrophobic coating has good antifouling and self-cleaning properties, can be applied to the fields of anti-icing, anti-fog, anti-corrosion, dust removal and the like, and has good market prospect; current schemes for preparing hydrophobic coating materials can be divided into two categories: firstly, the structure of the surface micro-nano structure is realized by sol-gel, chemical vapor deposition, layer-by-layer self-assembly, etching and other methods according to the lotus leaf effect, but the micro-nano structure obtained by the methods has excellent super-hydrophobic performance, but the light absorption and scattering on the surface of the coating are serious, a transparent coating cannot be obtained, and the application of the hydrophobic coating is limited; the other scheme is to reduce the surface energy of the coating and improve the hydrophobic property of the coating by introducing elements such as fluorine, silicon and the like, but the scheme can obtain the transparent polyurethane coating, but has the problems of low drying speed, high-temperature baking, poor hardness, low glossiness and the like, and limits the application field of the transparent polyurethane coating.
CN202010249169.6 is prepared by copolymerizing (methyl) acrylic ester monomers containing silicon and fluorine elements with other acrylic acid monomers, introducing the silicon and fluorine elements into polyurethane through free radical polymerization, and enabling the fluorine elements and the silicon elements to exist on a side chain of a polymer in a stable covalent bond mode, 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 slower than the price, and high-temperature baking is needed to realize the drying. CN202010358266.9 provides a superhydrophobic coating agent, a transparent superhydrophobic coating, and preparation methods and applications thereof, the superhydrophobic coating agent comprising polymer microspheres, a fluoropolymer and a polymer crosslinking agent dispersed in a solvent; the super-hydrophobic coating agent does not need to use inorganic filler, can form 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 and a rolling angle of less than 10 degrees, and has visible light transmittance of 83-95%. However, the coating needs to be baked at 120 ℃ to be dried, and the indexes such as glossiness, hardness and the like are not clear, so that the use of the polymer microsphere can lead to low glossiness of the coating, which limits the application field of the coating.
Therefore, it is a hot spot of current research to develop a polyurethane coating material having not only good hydrophobicity but also good gloss and transparency.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the fluorine-containing hydroxyl resin, and the paint prepared by using the fluorine-containing hydroxyl resin has the advantages of good hydrophobicity, high glossiness and high transparency.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a fluorine-containing hydroxyl resin comprising the following components: fluorine-containing monohydric alcohol, long-chain anhydride, epoxy resin and catalyst; the molar ratio of the fluorine-containing monohydric alcohol to the long-chain 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 in the invention have chemical reaction, so that the fluorine-containing structural unit in the fluorine-containing monohydric alcohol can be connected with a long chain with stronger mobility, and when the fluorine-containing monohydric alcohol is applied to a coating, the fluorine-containing group is easier to gather to 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, the fluorohydroxy resin can be provided with a hard core, so that the coating has good hardness and higher normal-temperature drying speed when the fluorohydroxy resin is applied to the coating; on the other hand, triglycidyl isocyanurate and fluorine-containing monohydric alcohol and long-chain anhydride act together to ensure that the fluorine-containing hydroxyl resin has high fluorine content, realizes the hydrophobicity of a coating by virtue of the enrichment effect of fluorine, and overcomes the problems that the conventional hydrophobic polyurethane coating technology improves the hydrophobicity by introducing silicon-fluorine-containing nano particles, but causes the transparency of the coating to be poor, the glossiness to be low and the like, so that the coating has better hydrophobicity, glossiness and transparency.
The inventors have further found that by using the above-described molar ratio of the components, the hydrophobicity, gloss, and transparency of the coating can be more effectively improved.
Preferably, the molar ratio of the fluorine-containing monohydric alcohol, the long-chain anhydride and the epoxy resin is 3:3:1, the inventor finds through experiments that the fluorine-containing monohydric alcohol, long-chain anhydride and epoxy resin can improve the hydrophobicity, glossiness and transparency of the paint best 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 anhydride comprises at least one of succinic anhydride, glutaric anhydride, 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% -0.04%.
Preferably, the fluorohydroxy 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 10-30% 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 fluorine-containing hydroxyl resin, comprising the steps of: mixing and heating fluorine-containing monohydric alcohol and long-chain anhydride for a period of time, adding epoxy resin and catalyst into the mixture, continuously reacting for a period of time at high temperature, and then adding solvent 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 1-5h.
More preferably, the temperature of the mixed heating of the fluorine-containing monohydric alcohol and the long-chain anhydride is 115-125 ℃ and the heating time is 2-3h.
Preferably, the heating temperature after the addition of the epoxy resin and the catalyst is 120-140 ℃.
More preferably, the heating temperature after the addition of the epoxy resin and catalyst is 125-135 ℃.
Preferably, the reaction time is 3 to 5 hours after the addition of the epoxy resin and the catalyst.
After the epoxy resin and the catalyst were added, the end of the reaction was determined from the acidity value of the mixed solution, and when the acidity value of the mixed solution was less than 2mg KOH/g, the end of the reaction was determined.
The invention also provides application of the fluorine-containing hydroxyl resin in 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 first component 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, butanone, methyl isobutyl ketone, 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 can be endowed with high fluorine content by adding fluorine-containing monohydric alcohol, long-chain anhydride and triglycidyl isocyanurate in a specific molar ratio, and realize the hydrophobicity of the prepared coating through the enrichment effect of fluorine; meanwhile, triglycidyl isocyanurate has a triazine ring rigid structure, so that the prepared coating has good hardness and high normal-temperature drying speed; the paint prepared by using the fluorine-containing hydroxyl resin has good glossiness, transparency, hydrophobicity, quick drying property and higher hardness, can meet the finishing paint coating requirements in the fields of automobile manufacturing and maintenance, rail trains, large-scale vehicles, wind power blades and the like, and has wide market prospect.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
Example 1
An embodiment of the present invention relates to a method for preparing a fluorine-containing hydroxyl resin, which comprises: firstly, adding 3mol (1391.4 g) of perfluorooctyl ethanol and 3mol (300.3) of succinic anhydride into a reaction kettle, and reacting for 3 hours at the temperature of 110 ℃; then adding 1mol (297.3 g) of triglycidyl isocyanurate and 0.22g of stannous octoate, reacting for 3 hours at 140 ℃, adding 221g of n-butyl acetate for dilution when the acid value reaches 1.8mg KOH/g, and obtaining the fluorine-containing hydroxyl resin; the fluorine-containing hydroxyl resin had a solid content of 90.1%, a viscosity of 17650 mPa.s and a hydroxyl content of 2.6%.
Example 2
The preparation method of the fluorine-containing hydroxyl resin comprises the following steps: firstly, adding 3mol (1092.3 g) of perfluorohexyl ethanol and 3mol (342.3) of glutaric anhydride into a reaction kettle, and reacting for 2 hours at 130 ℃; then adding 1mol (297.3 g) of triglycidyl isocyanurate and 1.29g of dibutyl tin dilaurate, reacting for 5 hours at 120 ℃, enabling the acid value to reach 1.7mg KOH/g, adding 852g of amyl acetate, and diluting to obtain the fluorine-containing hydroxyl resin; the fluorine-containing hydroxyl resin had a solid content of 70.2%, a viscosity of 3820 mPas and a hydroxyl content of 3.0%.
Example 3
The preparation method of the fluorine-containing hydroxyl resin comprises the following steps: firstly, adding 3mol (792.3 g) of perfluorobutyl alcohol and 3mol (384.3) of adipic anhydride into a reaction kettle, and reacting for 3 hours at 120 ℃; then adding 1mol (297.3 g) of triglycidyl isocyanurate and 0.55g of dibutyl tin dilaurate, reacting for 4 hours at 130 ℃, enabling the acid value to reach 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 6640 mPas and a hydroxyl content of 3.5%.
Example 4
The preparation method of the fluorine-containing hydroxyl resin comprises the following steps: firstly, adding 3mol (504 g) of hexafluoroisopropanol and 3mol (300.3) of succinic anhydride into a reaction kettle, and reacting for 3 hours at 115 ℃; then adding 1mol (297.3 g) of triglycidyl isocyanurate and 0.35g of stannous octoate, reacting for 3 hours at 135 ℃, enabling the acid value to reach 1.9mgKOH/g, adding 367g of n-butyl acetate, and diluting to obtain the fluorine-containing hydroxyl resin; the fluorine-containing hydroxyl resin had a solid content of 75.3%, a viscosity of 5890 mPa.s and a hydroxyl content of 4.6%.
Example 5
The preparation method of the fluorine-containing hydroxyl resin comprises the following steps: firstly, adding 3mol (696.3 g) of octafluoropentanol and 3mol (300.3) of succinic anhydride into a reaction kettle, and reacting for 2 hours at 125 ℃; then adding 1mol (297.3 g) of triglycidyl isocyanurate and 0.35g of stannous octoate, reacting for 4 hours at 130 ℃, enabling the acid value to reach 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 had a solid content of 85.1%, a viscosity of 9830 mPas and a hydroxyl content of 3.9%.
Example 6
This embodiment differs from embodiment 1 only in that: the molar ratio of the perfluorooctyl alcohol, the succinic anhydride and the triglycidyl isocyanurate is 1:1:1.
example 7
This embodiment differs from embodiment 1 only in that: the molar ratio of the perfluorooctyl alcohol, the succinic anhydride and the triglycidyl isocyanurate is 1:1:3.
comparative example 1
A comparative example of a fluorohydroxy resin according to the present invention differs from example 1 only in that: the epoxy resin described in this comparative example was bisphenol a type epoxy resin E51.
Comparative example 2
This comparative example differs from example 1 only in that: the molar ratio of the perfluorooctyl alcohol, the succinic anhydride and the triglycidyl isocyanurate is 4:5:1.
the fluorohydroxyl-containing resins of examples 1-7 and comparative examples 1-2 were prepared into hydrophobic polyurethane coatings, the components of which and parts by weight are shown in the following table 1, wherein the mass ratio of the components a and b is 2:1.
TABLE 1
Effect example
The hydrophobic polyurethane paint samples 1 to 9 (examples 1 to 7 correspond to samples 1 to 7, comparative examples 1 to 2 correspond to samples 8 and 9) obtained in the experimental examples were tested for construction viscosity by using GB/T1723 to 93, for tack-free time by using GB/T1728 to 1979, for dry time by using GB/T1728 to 1979, for hardness by using GB/T6739 to 2006, for glossiness by using GB/T9754 to 2007, for light transmittance by using GB/T1721 to 2008, for water contact angle by using gram Lv Shi contact angle meter DSA25, and the results are shown in Table 2 below.
TABLE 2
The results are shown in Table 2 for the hydrophobic polyurethane coatings prepared in examples 1-5 of the present invention: (1) The product has excellent quick surface drying and real drying performance, can finish drying at normal temperature, and is suitable for application requirements in the fields of automobile repair, railway vehicles, engineering machinery and the like; (2) The pencil hardness reaches H, and most application requirements including automobile manufacturing can be met; (3) The contact angles are all over 110 degrees, so that the higher level of hydrophobicity of the transparent coating is achieved; (4) The transparent performance is excellent, the glossiness reaches more than 95, the decorative performance 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 because a triazine ring structure is not introduced, and the hardness of the coating is also poor; comparative example 2 was not reacted in an optimized ratio, and the drying speed, hardness, gloss, transparency and water contact angle of the coating were all reduced.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been 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 to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.

Claims (7)

1. The application of fluorine-containing hydroxyl resin in preparing hydrophobic polyurethane paint is characterized in that the hydrophobic polyurethane paint comprises a component A and a component B, and the weight ratio of the component A to the component B is 2:1, a step of; 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; 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;
the fluorine-containing hydroxyl resin comprises the following components: fluorine-containing monohydric alcohol, long-chain anhydride, epoxy resin and catalyst; the molar ratio of the fluorine-containing monohydric alcohol to the long-chain anhydride to the epoxy resin is 3:3:1, a step of; the epoxy resin is triglycidyl isocyanurate.
2. The use of a fluorohydroxy resin according to claim 1 for preparing a hydrophobic polyurethane coating, wherein said fluoromonol comprises at least one of perfluorooctyl ethanol, perfluorohexyl ethanol, perfluorobutyl ethanol, hexafluoroisopropanol, octafluoropentanol.
3. Use of a fluorohydroxy resin according to claim 1 for the preparation of hydrophobic polyurethane coatings, wherein the long-chain anhydride comprises at least one of succinic anhydride, glutaric anhydride, adipic anhydride.
4. Use of a fluorohydroxy resin according to claim 1 for the preparation of hydrophobic polyurethane coatings, wherein the catalyst comprises at least one of stannous octoate, dibutyl tin dilaurate.
5. Use of a fluorohydroxy resin according to claim 1 for the preparation of hydrophobic polyurethane coatings, wherein the fluorohydroxy resin further comprises a solvent.
6. The use of a fluorohydroxy resin according to claim 5 for preparing a hydrophobic polyurethane coating, wherein said solvent comprises at least one of n-butyl acetate, amyl acetate, propylene glycol methyl ether acetate, methyl isobutyl ketone, methyl amyl ketone.
7. Use of the fluorohydroxy resin according to any one of claims 1 to 6 for preparing hydrophobic polyurethane coatings, characterized in that the preparation method of the fluorohydroxy resin comprises the following steps: mixing and heating fluorine-containing monohydric alcohol and long-chain anhydride, then adding epoxy resin and catalyst into the mixture, continuously heating the mixture until the acidity value of the mixed solution is less than 2mg KOH/g, and adding a solvent for dilution to obtain the fluorine-containing hydroxyl resin.
CN202210777410.1A 2022-06-28 2022-06-28 Fluorine-containing hydroxyl resin and preparation method and application thereof Active CN114957616B (en)

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 CN114957616A (en) 2022-08-30
CN114957616B true 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)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

Citations (5)

* Cited by examiner, † Cited by third party
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
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

Also Published As

Publication number Publication date
CN114957616A (en) 2022-08-30

Similar Documents

Publication Publication Date Title
CN114957616B (en) Fluorine-containing hydroxyl resin and preparation method and application thereof
US7476707B2 (en) Preparation of high solid polyester polyol/silica nanocomposite resin with low viscosity and related nanocomposite coatings
CN105199511A (en) Varnish for stainless steel substrate and preparation method and application of varnish
CN102492338A (en) Elastic heat-insulation fluorocarbon coating and preparation method and use method thereof
CN110684440A (en) Anticorrosive tough coating for outdoor communication tower and preparation method thereof
WO2014102166A1 (en) A coating composition, a preparation method therefore, and use 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
CN111732892A (en) Household nano self-cleaning coating and preparation method thereof
CN112552497B (en) High-hydroxyl-value polyester resin for extinction type powder coating and preparation method and application thereof
CN112521591B (en) Polyester resin with lasting high temperature resistance and excellent hardness for powder coating and preparation method thereof
WO2015152050A1 (en) Anti-fogging agent composition, anti-fogging article and manufacturing method thereof
CN108531047B (en) Water-based epoxy resin fire-resistant paint, preparation method and application thereof
CN102417786A (en) Nano-modified man-made stone surface composite functional coating material
CN108129974B (en) Polysiloxane finish paint for rolling stock and preparation method thereof
CN112300393A (en) Polysiloxane resins, coating compositions containing them and their use
CN109180925B (en) Hydroxyl polyester resin for high-gloss powder coating and preparation method and application thereof
CN114426797B (en) Super-wear-resistant PAE polyurea aviation coating
CN108467647A (en) A kind of automatically cleaning reflective heat-insulation paint and preparation method thereof
CN110982396B (en) High-corrosion-resistance color plate coil coating
JP2016113535A (en) Coating composition and coated article
CN113637354A (en) High-reflectivity water-based ink for photovoltaic module backboard glass
CN113214709A (en) Water-based fluorocarbon paint for preparing paint film
CN103073980B (en) There is the no-solvent type elastic metallic paint preparation method of high-heating radiation
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