CN112409912A - UV (ultraviolet) curing coating containing Y-type perfluoropolyether single-ended diol - Google Patents
UV (ultraviolet) curing coating containing Y-type perfluoropolyether single-ended diol Download PDFInfo
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- CN112409912A CN112409912A CN201910781493.XA CN201910781493A CN112409912A CN 112409912 A CN112409912 A CN 112409912A CN 201910781493 A CN201910781493 A CN 201910781493A CN 112409912 A CN112409912 A CN 112409912A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- 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
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
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- 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
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- Chemical & Material Sciences (AREA)
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- 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)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to an ultraviolet-curing fluorine-containing polyurethane acrylate coating, which comprises the following components in parts by weight: 5-20 parts of a fluorine-containing urethane acrylate oligomer; 140-300 parts of a diluent; 100-200 parts of a hardening agent; 3-5 parts of a photoinitiator. The invention synthesizes the fluorine-containing polyurethane acrylate polymer by introducing perfluoropolyether single-ended diol, and prepares the fluorine-containing polyurethane acrylate coating. The paint has excellent water resistance, oil resistance, high hardness and other performances.
Description
Technical Field
The invention relates to a UV curing coating, in particular to an antifouling coating containing Y-type perfluoropolyether single-ended diol.
Background
The garbage can is made of metal and plastic, and is widely used in streets and alleys due to the lightness and low price of the plastic. The plastic garbage can has the advantages of low cost, corrosion resistance, long service life, easiness in cleaning, simplicity in processing and the like, so that the plastic garbage can is increasingly widely applied, and grease adsorption is a difficult problem in cleaning the plastic garbage can. Therefore, the development of an antifouling paint is of great significance.
The perfluoropolyether alcohol is introduced into a UV curing system, the perfluoropolyether double-end alcohol is generally widely used, and the structure ensures that both ends of the perfluoropolyether are fixed in chain segments in a curing film, so that the perfluoropolyether is not beneficial to the free migration of fluorocarbon chain segments, as shown in the formula [2 ]. The single-end alcohol of the perfluoropolyether is introduced into the oligomer, only one end of the fluorocarbon chain segment of the perfluoropolyether is fixed due to the single-end structure, and the free fluorocarbon chain segment is easier to transition to the surface of a cured film. Compared with perfluoropolyether single-ended alcohol and perfluoropolyether single-ended diol, after the perfluoropolyether single-ended alcohol and the perfluoropolyether single-ended diol are introduced into the oligomer, only one end of each fluorocarbon chain is fixed, and the difference is that the perfluoropolyether single-ended diol is free and only has the fluorocarbon chain, as shown in the formula [3], and the oligomer corresponding to the perfluoropolyether single-ended alcohol also contains a hydrocarbon chain, as shown in the formula [4], so that the hydrophobicity and oleophobicity of the UV curing film are influenced.
The UV curing coating contains Y-type perfluoropolyether single-ended diol capable of improving antifouling performance, and compared with other UV antifouling coatings, the UV curing coating ensures the friction resistance and relatively improves the water-oil contact angle; the multifunctional acrylate is selected as a hardening agent, so that the hardness of the coating film is ensured. The preparation process and equipment of the fluorine-containing polyurethane acrylate oligomer are simple, convenient to operate, low in cost and easy for large-scale conversion and production.
Disclosure of Invention
Based on the above background, the present invention provides a low-cost UV curable coating with antifouling property.
The technical scheme adopted by the invention is as follows:
the high-hardness transparent friction-resistant easy-to-clean hydrophobic and oleophobic coating is characterized by comprising the following components in parts by weight:
5-20 parts of urethane acrylate oligomer,
140 to 300 portions of diluent,
100-200 parts of a hardener,
3-5 parts of a photoinitiator;
the preparation method of the FUA oligomer comprises the following steps: firstly, adding 6-10 parts of polyisocyanate, 0.2-1 part of catalyst and 100-200 parts of solvent into a container, dripping 20-80 parts of perfluoropolyether single-ended diol within 30min, slowly raising the temperature of the system to 60 ℃ in the dripping process, reacting for 5-7 h after the temperature is stable to obtain a fluorine-containing polyurethane oligomer 1 with an isocyanate group as a terminal group; secondly, adding 4-20 parts of carbon chain dihydric alcohol into the product obtained in the first step, and reacting for 5-7 h to obtain perfluoropolyether oligomer 2 with an isocyanate group as a terminal group; and thirdly, adding 3-4 parts of (methyl) acrylate into the product obtained in the second step, and reacting for 5-7 hours to obtain the fluorine-containing polyurethane acrylate oligomer.
And the preparation method of the coating comprises the step of uniformly mixing 5-20 parts of urethane acrylate oligomer, 140-300 parts of solvent, 100-200 parts of hardening agent and 3-5 parts of photoinitiator.
The perfluoropolyether single-ended diol is Y type, and the molecular formula is a compound shown in the following formula [1 ].
CF3O[CF(CF3)CF2O]x(CF2O)yCH2N(CH2CH2OH)2 [1]
The average molecular weight of the perfluoropolyether single-ended diol is 1000-4000.
The polyisocyanate is an aromatic polyisocyanate or an aliphatic polyisocyanate.
The catalyst is amine catalyst or organic metal catalyst.
Moreover, the solvent is a mixture of trichlorotrifluoroethane and acetone.
And the carbon chain dihydric alcohol is one or more of polyethylene glycol, polyglycerol, polycarbonate diol and polytetrahydrofuran diol.
The average molecular weight of the carbon chain diol is 400-2000.
The (meth) acrylate is HEA or HEMA.
Also, the diluent is isopropanol.
Also, the hardener is a tetrafunctional acrylate.
And, the photoinitiator is 819, 1173, TPO.
The invention has the advantages and positive effects that:
the fluorine-containing polyurethane acrylate coating disclosed by the invention contains a fluorine-containing component capable of improving antifouling performance, and polyether polyol capable of improving mechanical performance is added, and compared with other UV antifouling coatings, the fluorine-containing polyurethane acrylate coating ensures the friction resistance and relatively improves the water-oil contact angle; the multifunctional acrylate is selected as a hardening agent, so that the hardness of the coating film is ensured. The preparation process and equipment of the fluorine-containing polyurethane acrylate oligomer are simple, convenient to operate, low in cost and easy for large-scale conversion and production.
Detailed Description
The present invention will be specifically described below by way of examples. It is to be noted that the following examples are only intended to illustrate the present invention and should not be construed as limiting the scope of the present invention.
The method for preparing the antifouling coating from the UV curing coating comprises the following steps:
dripping the UV curing coating on a polycarbonate sheet (PC sheet) by a dropper, and rotationally coating on a spin coater at a rotating speed of 600r/min, an acceleration time of 5s, a uniform speed of 15s, a rotating speed of 2000r/min, an acceleration time of 5s and a uniform speed of 45 s; the UV curing lamp power was 1000W and the curing time was 45s, 15s intervals every 15 s.
The test criteria in the examples below are as follows
Contact angle: a contact angle tester JC2000D5 (water is ultrapure water and oil is n-hexadecane) is adopted;
pencil hardness: measuring the pencil hardness according to the method described in the national standard GB/T6739-;
and (3) friction resistance test: the contact angle was measured by rubbing the nonwoven fabric with 500g load for 1000 times.
Example 1:
(1) preparation of oligomer 1 terminated with isocyanate group: adding 9 parts of IPDI and 100 parts of trichlorotrifluoroethane/acetone into a three-neck flask according to the weight ratio, introducing nitrogen, and stirring; dripping 68 parts of perfluoropolyether single-ended diol and 0.3 part of dibutyltin dilaurate within 30min, heating to 60 ℃ while dripping and stirring, and reacting for 7 h;
(2) preparation of isocyanate-terminated oligomer 2: continuously dropwise adding 8 parts of polytetrahydrofuran diol in the reaction, introducing nitrogen, and reacting for 7 hours at 60 ℃;
(3) preparation of fluorine-containing urethane acrylate oligomer (FUA): and continuously dropwise adding 4 parts of HEMA in the reaction, introducing nitrogen, and reacting at 60 ℃ for 5 hours to obtain the fluorine-containing polyurethane acrylate oligomer (FUA).
(4) Preparing a UV-cured fluorine-containing polyurethane acrylate coating:
the UV FUA coating has the following index performances:
water contact angle 114.6 °
Oil contact angle 72.5 °
Pencil hardness 6H
Contact angle 111.9 degree after friction
Example 2:
(1) preparation of oligomer 1 terminated with isocyanate group: adding 9 parts of IPDI and 100 parts of fluorine solvent/acetone into a three-neck flask according to the weight ratio, introducing nitrogen, and stirring; dropwise adding 32 parts of perfluoropolyether single-ended diol and 0.2 part of dibutyltin dilaurate within 30min, heating to 60 ℃ while dropwise adding and stirring, and reacting for 7 h;
(2) preparation of isocyanate-terminated oligomer 2: continuously dropwise adding 10 parts of polycarbonate diol in the reaction, introducing nitrogen, and reacting at 60 ℃ for 7 hours;
(3) preparation of fluorine-containing urethane acrylate oligomer (FUA): and continuously dropwise adding 4 parts of HEMA in the reaction, introducing nitrogen, and reacting at 60 ℃ for 5 hours to obtain the fluorine-containing polyurethane acrylate oligomer (FUA).
(4) Preparing a UV-cured fluorine-containing polyurethane acrylate coating:
the UV FUA coating has the following index performances:
water contact angle 116.4 degree
Oil contact angle 74.3 °
Pencil hardness 6H
Contact angle after friction of 112.3 °
While only the preferred embodiments of the present invention have been described, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The ultraviolet-curing fluorine-containing polyurethane acrylate (FUA) coating is characterized by comprising the following components in parts by weight:
5-20 parts of urethane acrylate oligomer,
140 to 300 portions of diluent,
100-200 parts of a hardener,
3-5 parts of a photoinitiator;
the preparation method of the FUA oligomer comprises the following steps: firstly, adding 6-10 parts of polyisocyanate, 0.2-1 part of catalyst and 100-200 parts of solvent into a container, dripping 20-80 parts of perfluoropolyether single-ended diol within 30min, slowly raising the temperature of the system to 60 ℃ in the dripping process, reacting for 5-7 h after the temperature is stable to obtain a fluorine-containing polyurethane oligomer 1 with an isocyanate group as a terminal group; secondly, adding 4-20 parts of carbon chain dihydric alcohol into the product obtained in the first step, and reacting for 5-7 h to obtain perfluoropolyether oligomer 2 with an isocyanate group as a terminal group; and thirdly, adding 3-4 parts of (methyl) acrylate into the product obtained in the second step, and reacting for 5-7 hours to obtain the fluorine-containing polyurethane acrylate oligomer.
2. The UV-curable coating material according to claim 1, wherein the perfluoropolyether single-terminal diol is Y-type and is a compound represented by the following formula [1 ].
CF3O[CF(CF3)CF2O]x(CF2O)yCH2N(CH2CH2OH)2 [1]。
3. The UV-curable coating according to claim 1, wherein the perfluoropolyether single-ended diol has an average molecular weight of 1000 to 4000.
4. The UV-curable coating according to claim 1, wherein the carbon chain diol is one or more of polyethylene glycol, polyglycerol, polycarbonate diol and polytetrahydrofuran diol.
5. The UV-curable coating according to claim 1, wherein the carbon chain diol has an average molecular weight of 400 to 2000.
6. The UV-curable coating according to claim 1, wherein the hardener is a tetra-functional acrylate.
7. The UV-curable coating according to claim 1, wherein the diluent is isopropanol.
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CN201910781493.XA CN112409912A (en) | 2019-08-23 | 2019-08-23 | UV (ultraviolet) curing coating containing Y-type perfluoropolyether single-ended diol |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113755092A (en) * | 2021-09-09 | 2021-12-07 | 哈尔滨工业大学无锡新材料研究院 | Preparation method of ultraviolet/sunlight curable fluorine-containing coating |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113755092A (en) * | 2021-09-09 | 2021-12-07 | 哈尔滨工业大学无锡新材料研究院 | Preparation method of ultraviolet/sunlight curable fluorine-containing coating |
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Application publication date: 20210226 |