CN108841281B - Preparation method of rubber recovery powder modified fluorine-containing acrylate polymer coating - Google Patents
Preparation method of rubber recovery powder modified fluorine-containing acrylate polymer coating Download PDFInfo
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- CN108841281B CN108841281B CN201810667634.0A CN201810667634A CN108841281B CN 108841281 B CN108841281 B CN 108841281B CN 201810667634 A CN201810667634 A CN 201810667634A CN 108841281 B CN108841281 B CN 108841281B
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- containing acrylate
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- 238000000576 coating method Methods 0.000 title claims abstract description 53
- 239000011248 coating agent Substances 0.000 title claims abstract description 51
- 239000000843 powder Substances 0.000 title claims abstract description 35
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 30
- 238000011084 recovery Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 125000001153 fluoro group Chemical class F* 0.000 title 1
- 239000000463 material Substances 0.000 claims abstract description 42
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 32
- 239000011737 fluorine Substances 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000002221 fluorine Chemical class 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 claims description 3
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 10
- 230000032683 aging Effects 0.000 abstract description 7
- 230000003075 superhydrophobic effect Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000254137 Cicadidae Species 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 241000255777 Lepidoptera Species 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
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 229920001872 Spider silk Polymers 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000010316 high energy milling Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of a rubber recovery powder modified fluorine-containing acrylate polymer coating, which comprises the steps of dissolving an acrylate monomer and a fluorine-containing acrylate monomer in a first solvent according to a certain proportion to react to prepare a fluorine-containing acrylate polymer solution, crushing and grinding a clean rubber recovery material to prepare rubber recovery powder with the particle size of 70-2000 mu m, and mixing the fluorine-containing acrylate polymer solution, the rubber recovery powder and a second solvent according to a certain proportion to obtain the rubber recovery powder modified fluorine-containing acrylate polymer coating; the hydrophobic contact angle of the coating prepared by the coating is more than 150 degrees. The preparation method provided by the invention has the advantages that the rubber recovery powder is used for modifying the fluorine-containing acrylate polymer, the hydrophobic property of the fluorine-containing acrylate polymer is obviously improved, the fluorine-containing acrylate polymer has good high-temperature resistance, aging resistance, mechanical property and adhesion property, the preparation condition is simple, the process is controllable, the required equipment is common, the raw materials are easy to obtain and low in cost, the fluorine-containing acrylate polymer is suitable for industrial mass production, and the fluorine-containing acrylate polymer has strong market competitiveness.
Description
Technical Field
The invention relates to the technical field of paint preparation, and particularly relates to a preparation method of a rubber recycled powder modified fluorine-containing acrylate polymer paint.
Background
The behavior of wetting a solid surface with a liquid is a very important feature in the field of polymer chemistry, surface wettability can be expressed by a surface contact angle, and in nature, many biological materials exhibit excellent surface wettability such as lotus leaves, rice leaves, wings of butterflies, eyes of mosquitoes, moth eyes, wings of cicadas, rose petals, gecko feet, desert beetles, spider silks, fish scales, and the like, and the contact angle of a water drop on the surface of these materials is often more than 140 °. When the contact angle of a water droplet with a solid surface is greater than 150 °, the solid surface is referred to as a superhydrophobic surface.
Materials with superhydrophobic surfaces have a wide range of practical applications in everyday life, industry and agriculture. For example, on a transmission wire and an insulator of a power system, a material with a super-hydrophobic surface has a certain anti-icing effect, so that the damage of icing on the wire and the insulator can be reduced; on the shell of the ship, the material with the super-hydrophobic surface can reduce the water resistance, improve the navigation speed and play roles of preventing fouling and corrosion; on functional textiles, materials with superhydrophobic surfaces can also be made into waterproof and antifouling garments, and due to the above requirements of practical applications, research on superhydrophobic coating materials is receiving more and more attention.
In order to achieve superhydrophobicity of the coating material, the following two basic properties need to be satisfied: micro-nano multi-scale roughness structure of the solid surface and lower surface energy of the solid surface. Based on the two principles, various methods for preparing the super-hydrophobic coating exist at present, however, due to the problems of complicated preparation process, high raw material cost and production cost, difficulty in mass production and the like, the existing methods for preparing the super-hydrophobic coating material do not have the potential of industrial production, and most of the super-hydrophobic coating materials prepared by the methods have the defects of poor stability, mechanical strength and consistency.
In conclusion, on the basis of the existing research, by adopting appropriate raw materials and improving the preparation process, the super-hydrophobic coating material and the preparation method thereof, which have the advantages of simple and controllable preparation process, low raw material cost and production cost, high stability and mechanical strength of the obtained product and suitability for industrial batch production, are provided, and have important theoretical and practical significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a rubber recovery powder modified fluorine-containing acrylate polymer coating.
The invention adopts the following technical scheme:
a preparation method of a rubber reclaimed powder modified fluorine-containing acrylate polymer coating comprises the following steps:
s1, mixing the acrylate monomer and the fluorine-containing acrylate monomer according to the mass ratio of (2.5-20): 1, adding a catalyst, and heating to react to prepare a fluorine-containing acrylate polymer solution;
s2, crushing and grinding the clean reclaimed rubber material to obtain reclaimed rubber powder with the particle size of 70-2000 mu m;
s3, mixing the fluorine-containing acrylate polymer solution obtained in the step S1, the rubber recovery powder obtained in the step S2 and a second solvent according to a mass ratio of 1: (0.02-0.3): (3-10) mixing to obtain the product.
In the above technical solution, in step S1, the acrylate monomer is one or more of methyl methacrylate, butyl methacrylate, methacrylic acid and acrylic acid.
Further, in the above technical solution, the fluorine-containing acrylate monomer is one or more of hexafluorobutyl acrylate, hexafluorobutyl methacrylate and dodecafluoroheptyl methacrylate.
Further, in the above technical solution, the first solvent is one or more of toluene, xylene, butyl acetate, ethanol, tetrahydrofuran, and methyl ethyl ketone.
Preferably, in the above technical solution, in step S1, the mass ratio of the acrylate monomer, the fluorine-containing acrylate monomer, and the first solvent is 1: (0.08-0.3): (2-20).
Further preferably, in the above technical solution, in step S1, the catalyst is azobisisobutyronitrile or dibenzoyl peroxide.
Further, in the above technical means, the mass of the catalyst is 0.8 to 1% of the sum of the mass of the acrylate monomer and the mass of the fluorine-containing acrylate monomer.
Still further preferably, in the above technical solution, in step S1, the reaction temperature is 60 to 90 ℃.
Further, in the technical scheme, the reaction time is 4-12 h;
further, in the above technical solution, the reaction is protected by an inert gas, preferably a nitrogen atmosphere.
In the technical scheme, the step S2 specifically comprises two steps of crushing the rubber reclaimed material into rubber particles with the particle size of 6-12mm and high-energy grinding the rubber particles into rubber reclaimed powder with the particle size of 70-2000 mu m; preferably, the temperature of the high energy milling process is less than 30 ℃.
Preferably, in the above technical solution, in step S2, the particle size of the rubber recovery powder is 180-400 μm.
In the above technical solution, in step S3, the second solvent is one or more of toluene, xylene, butyl acetate, ethanol, tetrahydrofuran, and methyl ethyl ketone.
Further, in the above technical solution, the fluoroacrylate polymer solution, the rubber recovery powder, and the second solvent are mixed in a mass ratio of 1: (0.03-0.2): (4.5-8).
According to another aspect of the present invention, there is provided a coating material prepared by the above-mentioned preparation method.
According to another aspect of the invention, the super-hydrophobic coating material is prepared by the preparation method or the coating, and the hydrophobic contact angle of the super-hydrophobic coating material is more than 150 degrees.
The invention has the advantages that:
(1) according to the preparation method provided by the invention, the rubber recovery powder is utilized to modify the fluorine-containing acrylate polymer, so that the prepared coating material is excellent in hydrophobic property, stable in performance, good in high temperature resistance, aging resistance and mechanical property, and obviously superior to the fluorine-containing acrylate polymer coating in comprehensive performance;
(2) according to the preparation method provided by the invention, the rubber recovery powder is used for modifying the fluorine-containing acrylate polymer, and the rubber recovery powder is used for molding the multi-scale rough structure on the surface of the super-hydrophobic coating material, so that the adhesion performance of the coating material is greatly improved, and the waste rubber material is recycled, so that the environmental pollution can be effectively reduced, the raw material cost can be greatly reduced, the preparation method is suitable for industrial mass production, and has strong market competitiveness;
(3) the preparation method of the rubber recovery powder modified fluorine-containing acrylate polymer coating provided by the invention has the advantages of simple conditions and controllable process, the required equipment is common equipment, the adopted raw materials are easy to obtain and low in price, the production efficiency is high, the large-scale industrial production is suitable, the prepared coating is suitable for various base materials, the comprehensive performance of the coating obtained by coating is excellent, the application prospect is wide, and the theoretical and practical significance is great.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to specific examples.
The following examples are intended only to further illustrate the present invention and should not be construed as limiting the invention. Modifications or substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and scope of the invention.
Unless otherwise specified, the test reagents and materials used in the examples of the present invention are commercially available.
Unless otherwise specified, the technical means used in the examples of the present invention are conventional means well known to those skilled in the art.
Examples
The embodiment of the invention provides a preparation method of a rubber recovery powder modified fluorine-containing acrylate polymer coating, which comprises the following specific steps:
s1, mixing the acrylate monomer and the fluorine-containing acrylate monomer according to the mass ratio of (2.5-20): 1, adding a catalyst, and heating to react to prepare a fluorine-containing acrylate polymer solution;
specifically, the acrylate monomer is one or more of methyl methacrylate, butyl methacrylate, methacrylic acid and acrylic acid;
specifically, the fluorine-containing acrylate monomer is one or more of hexafluorobutyl acrylate, hexafluorobutyl methacrylate and dodecafluoroheptyl methacrylate;
specifically, the first solvent is one or more of toluene, xylene, butyl acetate, ethanol, tetrahydrofuran and methyl ethyl ketone;
preferably, the mass ratio of the acrylate monomer, the fluorine-containing acrylate monomer and the first solvent is 1: (0.08-0.3): (2-20);
specifically, the catalyst is azobisisobutyronitrile or dibenzoyl peroxide;
in detail, the mass of the catalyst is 0.8-1% of the sum of the mass of the acrylate monomer and the mass of the fluorine-containing acrylate monomer;
specifically, the reaction temperature is 60-90 ℃;
specifically, the reaction time is 4-12 h;
in detail, the reaction is protected by inert gas, preferably nitrogen atmosphere;
s2, crushing and grinding the clean reclaimed rubber material to obtain reclaimed rubber powder with the particle size of 70-2000 mu m;
specifically, the method comprises two steps of crushing the rubber reclaimed material into rubber particles with the particle size of 6-12mm and high-energy grinding the rubber particles into rubber reclaimed powder with the particle size of 70-2000 mu m;
in detail, in the step of high-energy grinding the rubber particles, the temperature of the high-energy grinding process is less than 30 ℃;
preferably, the particle size of the rubber recovery powder is 180-400 μm;
s3, mixing the fluorine-containing acrylate polymer solution obtained in the step S1, the rubber recovery powder obtained in the step S2 and a second solvent according to a mass ratio of 1: (0.02-0.3): (3-10) mixing to obtain the product.
Specifically, the second solvent is one or more of toluene, xylene, butyl acetate, ethanol, tetrahydrofuran, and methyl ethyl ketone.
In detail, the fluorine-containing acrylate polymer solution, the rubber recovery powder and the second solvent are mixed in a mass ratio of 1: (0.03-0.2): (4.5-8).
The test of preparing the rubber recovery powder modified fluorine-containing acrylate polymer coating by using different test raw materials and different process parameters is compared in the embodiment of the invention, and the specific test conditions are shown in the following tables 1 and 2.
TABLE 1 comparative table of test materials used in examples of the present invention
TABLE 2 comparison table of test conditions used in the examples of the present invention
Meanwhile, the coatings prepared in the above examples were applied to various substrates, and the properties thereof were tested.
According to the national standard GB/T9286-1998 grid test for paint films of colored paint and varnish, the adhesion of the super-hydrophobic coating material on the surfaces of a glass plate, a polycarbonate plate, a polymethyl methacrylate plate, a polyvinyl chloride plate, an aluminum plate and a stainless steel plate is tested by adopting a grid marking method; the pencil hardness of the super-hydrophobic coating material is tested according to the national standard GB/T6739-; the contact angle of the water drop on the surface of the super-hydrophobic coating material and the contact angle of the coating material after aging at a high temperature of 130 ℃ for 30 days were tested, and the results of the test data are shown in table 3 below.
Table 3 results of performance testing of the coatings prepared in the examples of the present invention
Comparing the test conditions in tables 1 and 2 and the results in table 3, it can be seen that the rubber recycling powder modified fluorine-containing acrylate polymer coating has the best adhesion with polymethyl methacrylate and polyvinyl chloride base materials, and the coating corresponding to example 3 has the best combination property; because the boiling points of tetrahydrofuran and methyl ethyl ketone are lower, the molecular weight of the synthesized polymer is likely to be smaller, so that the adhesion force between the synthesized polymer and a base material is reduced; the more the hard monomer methyl methacrylate is used in the raw materials, the higher the hardness of the final coating is; the more dodecafluoroheptyl methacrylate, the higher the fluorine content of the monomer, the better the ageing resistance of the final coating.
Comparing and analyzing the results in table 3, it can be seen that the preparation method provided by the embodiment of the present invention modifies the fluoroacrylate polymer by using the rubber recovery powder, the prepared coating material has excellent hydrophobic property, stable performance, good high temperature resistance, aging resistance and mechanical property, the comprehensive performance is obviously superior to that of the fluoroacrylate polymer coating (the results of comparative example 6 and other embodiments), the rubber recovery powder is used to mold the multi-scale rough structure on the surface of the superhydrophobic coating material, the adhesion property of the coating material is greatly improved, the coating material has good adhesion, good hardness and excellent hydrophobic property (contact angle > 150 °) on the surfaces of various substrates such as glass plate, polycarbonate plate, polymethylmethacrylate plate, polyvinyl chloride plate, aluminum plate and stainless steel plate, the practical requirements are satisfied, and after aging for 30 days at a high temperature of 130 ℃, the coating material still has super-hydrophobicity, so the prepared super-hydrophobic coating material has good high temperature resistance and aging resistance, and the service life is long; meanwhile, the waste rubber material is recycled, so that the environmental pollution can be effectively reduced, the raw material cost can be greatly reduced, the method is suitable for industrial mass production, and the market competitiveness is strong; the preparation method has the advantages of simple conditions, controllable process, common equipment, easily-obtained and cheap raw materials, high production efficiency and suitability for large-scale industrial production, the prepared coating is suitable for various substrates, and the coating obtained by coating has excellent comprehensive performance, wide application prospect and great theoretical and practical significance.
Finally, the above is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present 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 (8)
1. A preparation method of a rubber reclaimed powder modified fluorine-containing acrylate polymer coating is characterized by comprising the following steps:
s1, mixing the acrylate monomer and the fluorine-containing acrylate monomer according to the mass ratio of (2.5-20): 1, adding a catalyst, and heating to react to prepare a fluorine-containing acrylate polymer solution;
s2, crushing and grinding the clean reclaimed rubber material to obtain reclaimed rubber powder with the particle size of 70-200 mu m;
s3, mixing the fluorine-containing acrylate polymer solution obtained in the step S1, the rubber recovery powder obtained in the step S2 and a second solvent according to a mass ratio of 1: (0.02-0.3): (3-10) mixing to obtain the product;
in step S1, the acrylate monomer is one or more of methyl methacrylate, butyl methacrylate, methacrylic acid and acrylic acid, the fluorine-containing acrylate monomer is one or more of hexafluorobutyl acrylate, hexafluorobutyl methacrylate and dodecafluoroheptyl methacrylate, the first solvent is one or more of toluene, xylene, butyl acetate, ethanol, tetrahydrofuran and methyl ethyl ketone, and the mass ratio of the acrylate monomer, the fluorine-containing acrylate monomer and the first solvent is 1: (0.08-0.3): (2-20), the catalyst is azobisisobutyronitrile or dibenzoyl peroxide, and the mass of the catalyst is 0.8-1% of the sum of the mass of the acrylate monomer and the mass of the fluorine-containing acrylate monomer.
2. The production method according to claim 1, wherein, in step S1,
the reaction temperature is 60-90 ℃;
and/or the reaction time is 4-12 h;
and/or the reaction is protected by inert gas.
3. The method of claim 2, wherein in step S1, the reaction is protected with a nitrogen atmosphere.
4. The preparation method according to claim 1, wherein the step S2 specifically comprises two steps of crushing the reclaimed rubber into rubber particles of 6-12mm and high-energy grinding the rubber particles into rubber reclaimed powder with the particle size of 70-200 μm, wherein the temperature of the high-energy grinding process is less than 30 ℃.
5. The method as claimed in claim 4, wherein in step S2, the particle size of the rubber recovery powder is 180-400 μm.
6. The production method according to any one of claim 1, wherein, in step S3,
the second solvent is one or more of toluene, xylene, butyl acetate, ethanol, tetrahydrofuran and methyl ethyl ketone;
and/or the fluorine-containing acrylate polymer solution, the rubber recovery powder and the second solvent are mixed according to a mass ratio of 1: (0.03-0.2): (4.5-8).
7. A coating material produced by the production method according to any one of claims 1 to 6.
8. An ultrahydrophobic coating material made with the coating of claim 7, the ultrahydrophobic coating material having a hydrophobic contact angle greater than 150 °.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1136059A (en) * | 1995-04-03 | 1996-11-20 | 株式会社格林太尔 | Coating material for interior or exterior coating of buiding and process for manufacturing thereof |
| JP2000313839A (en) * | 1999-04-28 | 2000-11-14 | Toagosei Co Ltd | Fluororubber based coating composition |
| CN103865372A (en) * | 2014-04-08 | 2014-06-18 | 中山职业技术学院 | Preparation method of fluorine-containing acrylic acid super-hydrophobic coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1136059A (en) * | 1995-04-03 | 1996-11-20 | 株式会社格林太尔 | Coating material for interior or exterior coating of buiding and process for manufacturing thereof |
| JP2000313839A (en) * | 1999-04-28 | 2000-11-14 | Toagosei Co Ltd | Fluororubber based coating composition |
| CN103865372A (en) * | 2014-04-08 | 2014-06-18 | 中山职业技术学院 | Preparation method of fluorine-containing acrylic acid super-hydrophobic coating |
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