CN116376420B - Fluorine-containing coating and preparation method and application thereof - Google Patents
Fluorine-containing coating and preparation method and application thereof Download PDFInfo
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- CN116376420B CN116376420B CN202310421429.7A CN202310421429A CN116376420B CN 116376420 B CN116376420 B CN 116376420B CN 202310421429 A CN202310421429 A CN 202310421429A CN 116376420 B CN116376420 B CN 116376420B
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- 239000011737 fluorine Substances 0.000 title claims abstract description 89
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 89
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000000576 coating method Methods 0.000 title claims abstract description 57
- 239000011248 coating agent Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 47
- 239000011347 resin Substances 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 34
- 239000000945 filler Substances 0.000 claims abstract description 31
- 239000013530 defoamer Substances 0.000 claims abstract description 28
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 26
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 42
- 239000003973 paint Substances 0.000 claims description 36
- VLSRKCIBHNJFHA-UHFFFAOYSA-N 2-(trifluoromethyl)prop-2-enoic acid Chemical compound OC(=O)C(=C)C(F)(F)F VLSRKCIBHNJFHA-UHFFFAOYSA-N 0.000 claims description 24
- 229920001843 polymethylhydrosiloxane Polymers 0.000 claims description 23
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000008096 xylene Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 9
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000005871 repellent Substances 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 230000002209 hydrophobic effect Effects 0.000 abstract description 6
- 230000003373 anti-fouling effect Effects 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 67
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000010276 construction Methods 0.000 description 6
- 125000001153 fluoro group Chemical group F* 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical group [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011414 polymer cement Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 238000004383 yellowing 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
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a fluorine-containing coating, a preparation method and application thereof, wherein the fluorine-containing coating comprises the following preparation raw materials in parts by weight: 35-60 parts of polyurethane resin, 6-10 parts of fluorine-containing modified resin, 10-18 parts of polyacrylate resin, 8-15 parts of solvent, 15-24 parts of filler, 0.1-0.3 part of defoamer and 0.2-0.5 part of flatting agent. According to the invention, the fluorine-containing modified resin is prepared and synthesized, and when the fluorine-containing coating is cured to form a film, the fluorine-containing modified resin participates in the crosslinking curing reaction of the film-forming resin, so that the cured coating film has the characteristic of low surface energy, and has excellent water resistance, hydrophobic and antifouling properties and good toughness.
Description
Technical Field
The invention belongs to the technical field of building waterproof paint, and particularly relates to a fluorine-containing paint, and a preparation method and application thereof.
Background
In construction engineering, waterproof paint is a widely used material. Traditional waterproof paint is mainly made of asphalt, polymer emulsion and other materials. These coatings have good waterproof properties, but suffer from disadvantages such as easy aging, easy cracking, and difficult construction. In order to overcome the disadvantages of the conventional waterproof coatings, some novel waterproof coatings, such as two-component coatings based on epoxy resins and polyurethane, are presented. The coating has excellent weather resistance, chemical resistance and wear resistance, can be used indoors and outdoors, and is suitable for various substrates such as concrete, metal, wood and the like. However, the building waterproof paint on the current market still has some problems such as high construction difficulty, uneven coating, poor hydrophobicity of the coating, non-durable water resistance and the like. The fluorine atoms and the organic silicon have the advantages of small surface tension, high mechanical strength, aging resistance, yellowing resistance, good water resistance and the like, so that the fluorine-silicon modified resin or the fluorine-containing organic silicon-containing modifier is added into the waterproof paint to modify the waterproof paint, but after the organic silicon is added, the toughness of a part of the waterproof paint is sacrificed, and the workability is poor.
Disclosure of Invention
The present invention is directed to a fluorine-containing coating that overcomes at least one of the problems and deficiencies set forth in the background art discussed above.
The invention also provides a preparation method of the fluorine-containing paint.
The invention also provides application of the fluorine-containing paint.
The invention provides a fluorine-containing coating, which comprises the following preparation raw materials in parts by weight: 35-60 parts of polyurethane resin, 6-10 parts of fluorine-containing modified resin, 10-18 parts of polyacrylate resin, 8-15 parts of solvent, 15-24 parts of filler, 0.1-0.3 part of defoamer and 0.2-0.5 part of flatting agent;
the structural formula of the fluorine-containing modified resin is as follows:
Wherein n has a value of 75 to 125.
According to one of the technical schemes of the fluorine-containing paint, the invention at least comprises the following steps of
The beneficial effects are that:
the fluorine-containing modified resin is added into the polyurethane waterproof paint to prepare the fluorine-containing paint, and the fluorine-containing paint can be used for building waterproof, has good construction performance, and the cured coating film has the characteristic of low surface energy and has excellent waterproof performance and hydrophobic antifouling performance.
The fluorine-containing modified resin contains a large number of active carboxyl groups, can react with hydroxyl groups in polyurethane resin and polyacrylate resin to participate in the curing reaction of the resin, so that a fluorosilicone polymer is introduced into a coating film, the hydrophobic property of the coating film is improved, and further excellent stain resistance and waterproof property are achieved.
The polyacrylate resin is added, so that the toughness of a coating film can be improved, and the construction performance is excellent.
In some embodiments of the present invention, the method for preparing the fluorine-containing modified resin comprises the steps of: and mixing polymethylhydrosiloxane and a catalyst under nitrogen atmosphere, and dropwise adding trifluoro methacrylic acid for heating reflux reaction.
The invention leads the trifluoro-methacrylic acid to be introduced into the side chain of the polymethyl hydrosiloxane by the reaction of the active hydrogen in the polymethyl hydrosiloxane and the double bond in the trifluoro-methacrylic acid, thus forming the fluorine-containing modified resin with active carboxyl groups.
In some embodiments of the present invention, the preparation method of the fluorine-containing modified resin specifically includes the following steps: dissolving polymethylhydrosiloxane in xylene solvent, introducing nitrogen for protection, adding catalyst, mixing uniformly, dripping xylene solution with trifluoro methacrylic acid, heating and carrying out reflux reaction.
In some embodiments of the invention, the mass ratio of the polymethylhydrosiloxane to the trifluoromethyl acrylic acid is 1:8-12.
In some embodiments of the invention, the catalyst is a platinum-gold-containing catalyst.
In some embodiments of the invention, the heating temperature is 80 ℃ to 100 ℃.
In some embodiments of the invention, the heating is at a temperature of 85 ℃ to 98 ℃.
The invention controls the heating temperature to make the solvent in the reaction reflux, and brings out the raw materials or water generated in the reaction, so that the fluorine-containing modified resin remains water, and the coating performance is affected when the coating is cured.
In some embodiments of the invention, the reaction time is 18h to 24h.
In some embodiments of the invention, the reaction time is 19h to 23h.
In some embodiments of the invention, the solvent is at least one of xylene, butyl acetate, and dimethyl carbonate.
In some embodiments of the invention, the filler is at least one of talc, calcium carbonate, kaolin, and quartz powder.
In some embodiments of the invention, the leveling agent is a polyurethane leveling agent.
In some embodiments of the invention, the polyurethane leveling agent is one of BYK-3450, BYK-307 and EFKA 4320.
In some embodiments of the invention, the defoamer is one of BYK-066, BYK-164 and TEGO Foamex 840.
The second aspect of the present invention provides a method for producing a fluorine-containing paint, comprising the steps of: and mixing the polyurethane resin, the fluorine-containing modified resin, the polyacrylate resin, the solvent, the filler, the defoaming agent and the leveling agent.
In a third aspect, the invention provides the use of a fluorine-containing coating for the preparation of a water-repellent coating for buildings.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
According to the invention, polyurethane resin and polyacrylate resin are used as film forming substances, and fluorine-containing modified resin with carboxyl groups participates in the curing reaction of the film forming substances, so that the coating has excellent construction performance, low surface energy and excellent water resistance and hydrophobic antifouling performance.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
In the description of the present invention, the descriptions of the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Specific embodiments of the present invention are described in detail below.
The platinum-containing gold catalyst used in the invention is Karstedt's catalyst.
The polyurethane resin used in the invention is purchased from Dongguan Baojing chemical industry Co., ltd, and the brand is MR-918.
The polyacrylate resin used in the invention is purchased from Xiamen love kinetic energy released in material chemical industry Co., ltd, and the brand number is CRAYVALLAC A-72-A2-60.
Example 1
The embodiment is a fluorine-containing coating, which comprises the following preparation raw materials in parts by weight: 45 parts of polyurethane resin, 8 parts of fluorine-containing modified resin, 17 parts of polyacrylate resin, 12 parts of solvent, 18 parts of filler, 0.1 part of defoamer and 0.3 part of flatting agent.
The structural formula of the fluorine-containing modified resin of this embodiment is:
the preparation method of the fluorine-containing modified resin of the embodiment comprises the following steps:
s1, 10 parts of polymethylhydrosiloxane is dissolved in 20 parts of dimethylbenzene, nitrogen is introduced to discharge oxygen, 0.2 part of Karstedt catalyst is added, and the mixture is uniformly mixed;
S2, mixing 75 parts of dimethylbenzene and 60 parts of trifluoromethyl acrylic acid, then dropwise adding the mixture into the solution in the step S1 for 30min, heating to 90 ℃, and carrying out reflux reaction for 20h;
s3, after the reaction is finished, the reactant is rotationally evaporated to remove the dimethylbenzene.
The solvent in this example was xylene.
The filler in this example is calcium carbonate.
The defoamer of this example was BYK-066.
The leveling agent in this example is BYK-3450.
The mass ratio of the polymethylhydrosiloxane to the trifluoromethyl acrylic acid in this example was 1:6.
The preparation of the fluorine-containing paint of the embodiment comprises the following steps: and uniformly mixing and stirring the polyurethane resin, the fluorine-containing modified resin, the polyacrylate resin, the solvent, the filler, the defoamer and the flatting agent in parts by weight to obtain the fluorine-containing coating.
Example 2
The embodiment is a fluorine-containing coating, which comprises the following preparation raw materials in parts by weight: 49 parts of polyurethane resin, 6 parts of fluorine-containing modified resin, 15 parts of polyacrylate resin, 12 parts of solvent, 18 parts of filler, 0.1 part of defoamer and 0.3 part of flatting agent.
The structural formula of the fluorine-containing modified resin of this embodiment is:
the preparation method of the fluorine-containing modified resin of the embodiment comprises the following steps:
s1, 10 parts of polymethylhydrosiloxane is dissolved in 20 parts of dimethylbenzene, nitrogen is introduced to discharge oxygen, 0.2 part of Karstedt catalyst is added, and the mixture is uniformly mixed;
S2, mixing 75 parts of dimethylbenzene and 60 parts of trifluoromethyl acrylic acid, then dropwise adding the mixture into the solution in the step S1 for 30min, heating to 90 ℃, and carrying out reflux reaction for 20h;
s3, after the reaction is finished, the reactant is rotationally evaporated to remove the dimethylbenzene.
The solvent in this example was xylene.
The filler in this example is calcium carbonate.
The defoamer of this example was BYK-066.
The leveling agent in this example is BYK-3450.
The mass ratio of the polymethylhydrosiloxane to the trifluoromethyl acrylic acid in this example was 1:6.
The preparation of the fluorine-containing paint of the embodiment comprises the following steps: and uniformly mixing and stirring the polyurethane resin, the fluorine-containing modified resin, the polyacrylate resin, the solvent, the filler, the defoamer and the flatting agent in parts by weight to obtain the fluorine-containing coating.
Example 3
The embodiment is a fluorine-containing coating, which comprises the following preparation raw materials in parts by weight: 45 parts of polyurethane resin, 10 parts of fluorine-containing modified resin, 15 parts of polyacrylate resin, 12 parts of solvent, 18 parts of filler, 0.1 part of defoamer and 0.3 part of flatting agent.
The structural formula of the fluorine-containing modified resin of this embodiment is:
the preparation method of the fluorine-containing modified resin of the embodiment comprises the following steps:
s1, 10 parts of polymethylhydrosiloxane is dissolved in 20 parts of dimethylbenzene, nitrogen is introduced to discharge oxygen, 0.2 part of Karstedt catalyst is added, and the mixture is uniformly mixed;
S2, mixing 75 parts of dimethylbenzene and 60 parts of trifluoromethyl acrylic acid, then dropwise adding the mixture into the solution in the step S1 for 30min, heating to 90 ℃, and carrying out reflux reaction for 20h;
s3, after the reaction is finished, the reactant is rotationally evaporated to remove the dimethylbenzene.
The solvent in this example was xylene.
The filler in this embodiment is quartz powder.
The defoamer of this example is TEGO Foamex 840.
The leveling agent in this embodiment is EFKA4320.
The mass ratio of the polymethylhydrosiloxane to the trifluoromethyl acrylic acid in this example was 1:6.
The preparation of the fluorine-containing paint of the embodiment comprises the following steps: and uniformly mixing and stirring the polyurethane resin, the fluorine-containing modified resin, the polyacrylate resin, the solvent, the filler, the defoamer and the flatting agent in parts by weight to obtain the fluorine-containing coating.
Comparative example 1
The comparative example, without adding fluorine-containing modified resin, prepares waterproof coating, and comprises the following preparation raw materials in parts by weight: 48 parts of polyurethane resin, 17 parts of polyacrylate resin, 10 parts of solvent, 25 parts of filler, 0.1 part of defoamer and 0.3 part of flatting agent.
The solvent of this comparative example was xylene.
The filler of this comparative example is calcium carbonate.
The defoamer of this comparative example was BYK-066.
The leveling agent of this comparative example was BYK-3450.
The preparation of the waterproof paint of the comparative example comprises the following steps: and uniformly mixing and stirring the polyurethane resin, the polyacrylate resin, the solvent, the filler, the defoamer and the flatting agent in parts by weight to obtain the waterproof coating.
Comparative example 2
The comparative example is a fluorine-containing coating, which comprises the following preparation raw materials in parts by weight: 48 parts of polyurethane resin, 4 parts of fluorine-containing modified resin, 13 parts of polyacrylate resin, 10 parts of solvent, 25 parts of filler, 0.1 part of defoamer and 0.3 part of flatting agent.
The structural formula of the fluorine-containing modified resin of the comparative example is:
the preparation method of the fluorine-containing modified resin of the comparative example comprises the following steps:
s1, 10 parts of polymethylhydrosiloxane is dissolved in 20 parts of dimethylbenzene, nitrogen is introduced to discharge oxygen, 0.2 part of Karstedt catalyst is added, and the mixture is uniformly mixed;
S2, mixing 75 parts of dimethylbenzene and 40 parts of trifluoromethyl acrylic acid, then dropwise adding the mixture into the solution in the step S1 for 30min, heating to 90 ℃, and carrying out reflux reaction for 20h;
s3, after the reaction is finished, the reactant is rotationally evaporated to remove the dimethylbenzene.
The solvent of this comparative example was xylene.
The filler of this comparative example is calcium carbonate.
The defoamer of this comparative example was BYK-066.
The leveling agent of this comparative example was BYK-3450.
The mass ratio of the polymethylhydrosiloxane to the trifluoromethyl acrylic acid in the comparative example is 1:4.
The preparation of the fluorine-containing paint of the comparative example comprises the following steps: and uniformly mixing and stirring the polyurethane resin, the fluorine-containing modified resin, the polyacrylate resin, the solvent, the filler, the defoamer and the flatting agent in parts by weight to obtain the fluorine-containing coating.
Comparative example 3
The comparative example is a fluorine-containing coating, which comprises the following preparation raw materials in parts by weight: 45 parts of polyurethane resin, 8 parts of fluorine-containing modified resin, 17 parts of polyacrylate resin, 12 parts of solvent, 18 parts of filler, 0.1 part of defoamer and 0.3 part of flatting agent.
The structural formula of the fluorine-containing modified resin of the comparative example is:
the preparation method of the fluorine-containing modified resin of the comparative example comprises the following steps:
s1, 10 parts of polymethylhydrosiloxane is dissolved in 20 parts of dimethylbenzene, nitrogen is introduced to discharge oxygen, 0.2 part of Karstedt catalyst is added, and the mixture is uniformly mixed;
S2, mixing 75 parts of dimethylbenzene and 60 parts of trifluoromethyl acrylic acid, then dropwise adding the mixture into the solution in the step S1 for 30min, heating to 70 ℃, and carrying out reflux reaction for 16h;
s3, after the reaction is finished, the reactant is rotationally evaporated to remove the dimethylbenzene.
The solvent of this comparative example was xylene.
The filler of this comparative example is calcium carbonate.
The defoamer of this comparative example was BYK-066.
The leveling agent of this comparative example was BYK-3450.
The mass ratio of the polymethylhydrosiloxane to the trifluoromethyl acrylic acid in the comparative example is 1:6.
The preparation of the fluorine-containing paint of the comparative example comprises the following steps: and uniformly mixing and stirring the polyurethane resin, the fluorine-containing modified resin, the polyacrylate resin, the solvent, the filler, the defoamer and the flatting agent in parts by weight to obtain the fluorine-containing coating.
Comparative example 4
According to the comparative example, fluorine-containing modified resin is not added, and trifluoromethyl acrylic acid is directly added for modification, so that the waterproof coating is prepared from the following preparation raw materials in parts by weight: 45 parts of polyurethane resin, 8 parts of trifluoromethyl acrylic acid, 17 parts of polyacrylate resin, 12 parts of solvent, 18 parts of filler, 0.1 part of defoamer and 0.3 part of flatting agent.
The solvent of this comparative example was xylene.
The filler of this comparative example is calcium carbonate.
The defoamer of this comparative example was BYK-066.
The leveling agent of this comparative example was BYK-3450.
The preparation of the waterproof paint of the comparative example comprises the following steps: and uniformly mixing and stirring the polyurethane resin, the trifluoromethyl acrylic acid, the polyacrylate resin, the solvent, the filler, the defoamer and the flatting agent in parts by weight to obtain the waterproof coating.
Comparative example 5
In the comparative example, fluorine-containing modified resin is not added, methyl hydrogen siloxane is directly added for modification to prepare the waterproof coating, and the waterproof coating comprises the following preparation raw materials in parts by weight: 45 parts of polyurethane resin, 8 parts of polymethylhydrosiloxane, 17 parts of polyacrylate resin, 12 parts of solvent, 18 parts of filler, 0.1 part of defoamer and 0.3 part of flatting agent.
The solvent of this comparative example was xylene.
The filler of this comparative example is calcium carbonate.
The defoamer of this comparative example was BYK-066.
The leveling agent of this comparative example was BYK-3450.
The preparation of the waterproof paint of the comparative example comprises the following steps: and uniformly mixing and stirring the polyurethane resin, the polymethylhydrosiloxane, the polyacrylate resin, the solvent, the filler, the defoamer and the flatting agent in parts by weight to obtain the waterproof coating.
The fluorine-containing paints obtained in examples 1 to 3 and comparative examples 1 to 5 were subjected to water-impermeable property and water absorption test, the water-impermeable property test being specifically referred to GB/T23445-2009 polymer cement waterproof paint, the test pressure being 0.3MPa, to maintain the water-impermeable property as good as the pressing time is longer. The water absorption test is referred to GB/T19250-2013 polyurethane waterproof paint, and the result is shown in Table 1.
The fluorine-containing paints obtained in examples 1 to 3 and comparative examples 1 to 5 were subjected to a stain resistance test, which was conducted with reference to the 5.5 immersion A method test of the GB/T9780-2013 building paint coating stain resistance test method, and the results are shown in Table 2.
The fluorine-containing paints obtained in examples 1 to 3 and comparative examples 1 to 5 were subjected to tensile property test, and the tensile property test was conducted in 9 with reference to the GB/T16777-2008 building waterproof paint test method, and the results are shown in Table 3.
Table 1 results of the test of water-impermeable property and water-absorption rate of the fluorine-containing paints of examples 1 to 3 and comparative examples 1 to 5
| - | Pressurized watertight time/min | Water absorption/% |
| Example 1 | 120 | 0.7 |
| Example 2 | 116 | 0.8 |
| Example 3 | 118 | 0.7 |
| Comparative example 1 | 48 | 8.5 |
| Comparative example 2 | 102 | 5.7 |
| Comparative example 3 | 94 | 6.4 |
| Comparative example 4 | 97 | 4.8 |
| Comparative example 5 | 81 | 3.9 |
Table 2 results of the fouling resistance test of the fluorine-containing paints of examples 1 to 3 and comparative examples 1 to 5
TABLE 3 tensile test results for the fluorine-containing paints of examples 1 to 3 and comparative examples 1 to 5
| - | Elongation at break/% |
| Example 1 | 514 |
| Example 2 | 523 |
| Example 3 | 483 |
| Comparative example 1 | 519 |
| Comparative example 2 | 427 |
| Comparative example 3 | 458 |
| Comparative example 4 | 431 |
| Comparative example 5 | 405 |
The difference between comparative example 1 and example 1 is that the fluorine-containing modified resin provided by the present invention is not added, and as seen from Table 3, the elongation at break is similar to that of example 1, mainly, no silicone resin is added in the coating film, and the main film forming substance is relatively increased, so that the toughness is somewhat increased, but as seen from tables 1 and 2, the waterproof coating material prepared in comparative example 1 has low water-proof time under pressurization and water absorption, and at the same time has low water contact angle, low water repellency and poor anti-fouling property.
Comparative example 2 is different from example 1 in that the amount of fluorine-containing modified resin is reduced while the mass ratio of polymethylhydrosiloxane to trifluoromethylacrylic acid is increased, and as can be seen from tables 1, 2 and 3, the fluorine-containing coating material prepared in comparative example 2 is inferior in water resistance, stain resistance and toughness, and is poor in water resistance and hydrophobic stain resistance mainly due to insufficient surface energy caused by the reduction of fluorine atoms in the coating film.
The difference between comparative example 3 and example 1 is that the heating reaction temperature and reaction time in the preparation method of fluorine-containing modified resin are reduced, and as can be seen from tables 1, 2 and 3, the fluorine-containing coating prepared in comparative example 3 is poor in water resistance, stain resistance and toughness, and mainly because the heating reaction temperature is too low, the solvent reflux in the reaction is small, the moisture in the reaction cannot be removed in time, residues are caused, and the reaction time is insufficient to completely introduce the trifluoromethyl acrylic acid into the polymethylhydrosiloxane.
Comparative example 4 is different from example 1 in that the modification is performed by directly adding the trifluoromethyl acrylic acid, and as can be seen from table 2, the stain resistance of the waterproof coating prepared in comparative example 4 is improved, and mainly because a certain amount of fluorine atoms are introduced into the coating after the addition of the trifluoromethyl acrylic acid, the surface energy of the coating is reduced, but as can be seen from tables 1 and 3, the pressurized water-impermeable time and the water absorption rate are not high, and at the same time the elongation at break of the coating is low, and the waterproof and workability are poor.
Comparative example 5 is different from example 1 in that the direct addition polymerization of methyl hydrogen siloxane was modified, and as can be seen from tables 1,2 and 3, the waterproof coating material prepared in comparative example 5 was poor in both water resistance and stain resistance, particularly in tensile properties, and further in workability.
In summary, the polyurethane resin and the polyacrylate resin are taken as film forming substances, and the fluorine-containing modified resin with carboxyl groups participates in the curing reaction of the film forming substances, so that the coating has excellent workability, low surface energy and excellent water resistance and hydrophobic antifouling performance.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (6)
1. The fluorine-containing coating is characterized by comprising the following preparation raw materials in parts by weight: 35-60 parts of polyurethane resin, 6-10 parts of fluorine-containing modified resin, 10-18 parts of polyacrylate resin, 8-15 parts of solvent, 15-24 parts of filler, 0.1-0.3 part of defoamer and 0.2-0.5 part of flatting agent;
the structural formula of the fluorine-containing modified resin is as follows:
；
Wherein n has a value of 75-125;
The preparation method of the fluorine-containing modified resin comprises the following steps: mixing polymethylhydrosiloxane and a catalyst in nitrogen atmosphere, and dropwise adding trifluoro methacrylic acid for heating reflux reaction;
the mass ratio of the polymethylhydrosiloxane to the trifluoromethyl acrylic acid is 1:5-9;
The heating temperature is 80-100 ℃;
The reaction time is 18-24 h.
2. The fluorine-containing paint according to claim 1, wherein the solvent is at least one of xylene, butyl acetate and dimethyl carbonate.
3. The fluorine-containing paint according to claim 1, wherein the filler is at least one of talc, calcium carbonate, kaolin and quartz powder.
4. A fluorine-containing coating according to claim 1, characterised in that the levelling agent is a polyurethane levelling agent.
5. A method of producing a fluorine-containing paint according to any one of claims 1 to 4, comprising the steps of: and mixing the polyurethane resin, the fluorine-containing modified resin, the polyacrylate resin, the solvent, the filler, the defoaming agent and the leveling agent.
6. Use of a fluorine-containing coating according to any of claims 1 to 4 for the preparation of a water-repellent coating for buildings.
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