CN106752606B - A kind of aqueous fluorine silica acrylic acid coating and preparation method thereof - Google Patents
A kind of aqueous fluorine silica acrylic acid coating and preparation method thereof Download PDFInfo
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- CN106752606B CN106752606B CN201611028286.XA CN201611028286A CN106752606B CN 106752606 B CN106752606 B CN 106752606B CN 201611028286 A CN201611028286 A CN 201611028286A CN 106752606 B CN106752606 B CN 106752606B
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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
- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
The present invention provides a kind of aqueous fluorine silica acrylic acid coating and preparation method thereof, aqueous fluorine silica acrylic acid coating includes fluoro-acrylate copolymer lotion and polysiloxane pre polymers body, and the mass ratio of fluoro-acrylate copolymer lotion and polysiloxane pre polymers body is 2~6: 1；The preparation method of aqueous fluorine silica acrylic acid coating is the following steps are included: be mixed to get mixture by 2~6: 1 mass ratio for fluoro-acrylate copolymer lotion and siloxanes performed polymer；The mixture is coated uniformly on substrate, the dry 30min under room temperature, then at 60~120 DEG C of 1~3h of solidification.Aqueous fluorine silica acrylic acid coating of the invention has many advantages, such as that weather-proof, rub resistance, hydrophobicity are strong and more environmentally-friendly；Preparation method of the invention has the advantages that simple process, condition are easily-controllable.
Description
Technical field
The present invention relates to functional form acrylic resin synthesis field more particularly to a kind of aqueous fluorine silica acrylic acid coating and its
Preparation method.
Background technique
As the raising and social industrial expansion, green environmental friendly coatings of people's environmental consciousness become entire coating industry
Development trend, wherein water paint has energy saving, and volatile organic matter (VOC) is few, at low cost, non-ignitable, is easy to storage and transportation, nothing
Toxicity, it is non-stimulated, the advantages that small is injured caused by coating personnel, becomes one of the main direction of development of environment-friendly type coating.Mesh
Before, the research emphasis of low pollution, high performance water paint mainly exists: (1) research and preparation of novel film forming polymer；(2)
The optimization of formulation for coating material and technique.
Fluorine silica acrylic acid coating mainly based on organic solvent type, causes serious pollution to the environment.Originally the aqueous fluorine silicon that please be prepare
Acrylic coating, VOC is few, environmentally protective.The country is about preparing aqueous fluorine silicone acrylic resin to select containing reactive functionality
Organic fluorine monomer and siloxanyl monomers based on, be prepared with acrylic ester monomer by emulsion free-radical polymerization method.By
It is easy hydrolytic crosslinking in siloxanyl monomers, is precipitated in the form of gel, to influence emulsion intercalation method, and causes raw material
Waste.Although the patent delivered is mainly to inhibit the hydrolysis of siloxanyl monomers by the way that polyalcohol is added, polyalcohol
Introducing the water resistance that can make film and hydrophobicity reduces, so that the comprehensive performance of film reduces.Organosilicon product is with polysiloxanes
It is silicon oxygen chain link for its basic structural unit, is connected with various organic groups on silicon atom.It is made from it in structure it is found that organosilicon
Material has the characteristics of inorganic polymer and organic polymer, good weatherability, oxidative resistance, electrical insulating property, thermal stability concurrently
Deng.But the single organic silicon coating used as coating hardness, flexibility and in terms of relatively have much difficulty in healing weighing apparatus, it is organic
Silicon coating haves the shortcomings that matter is crisp, toughness is poor, and in complicated working environment, coating is easy to appear crackle, corrugation cortex etc.
Phenomenon.In addition, common are the wear-resisting stiffened coating of machine silicon during the preparation process, diluent is mainly based on organic solvent, environment
Pollution is big.Acrylic resin have filming performance it is good, cheap, colour retention is good, it is resistance to ultraviolet the advantages that, but its there are cold
The disadvantages of crisp heat is glutinous, stain resistant and poor water resistance.
Therefore, it is necessary to invent one kind aqueous fluorine silica acrylic acid coating of good performance and preparation method thereof.
Summary of the invention
The technical problems to be solved by the present invention are: providing one kind aqueous fluorine silica acrylic acid coating of good performance and its system
Preparation Method.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention are as follows:
The present invention provides a kind of aqueous fluorine silica acrylic acid ester paint, including fluoro-acrylate copolymer lotion and poly- silicon oxygen
The mass ratio of alkane performed polymer, fluoro-acrylate copolymer lotion and polysiloxane pre polymers body is 2~6: 1；
The fluoro-acrylate copolymer lotion includes the raw material of following parts by weight:
The polysiloxane pre polymers body includes the raw material of following parts by weight:
The pH value of the aqueous hydrochloric acid solution is 4.0.
The present invention also provides a kind of preparation methods of above-mentioned aqueous fluorine silica acrylic acid coating, comprising the following steps:
Fluoro-acrylate copolymer lotion and siloxanes performed polymer are mixed to get mixture by 2~6: 1 mass ratio；
The mixture is coated uniformly on substrate, the dry 30min under room temperature, then at 60~120 DEG C of solidifications 1~
3h。
The beneficial effects of the present invention are: by introducing Organic fluoride and silicon materials in raw material in preparing for acrylic coating,
Introduce crosslinkable groups in the strand of fluoro-acrylate copolymer lotion and polysiloxane pre polymers body respectively, as hydroxyl,
Carboxyl, epoxy group and alcoxyl silicon substrate increase the crosslink density of film in film forming procedure, so that film good mechanical properties,
So that aqueous fluorine silica acrylic acid coating has many advantages, such as that weather-proof, antifriction scrape along hydrophobicity is strong；The aqueous fluorine silica acrylic acid of the present invention applies
Volatile organic matter (VOC) content in material reduces, more environmentally-friendly；The preparation method of the aqueous fluorine silica acrylic acid of the present invention pass through by
Aqueous fluorine-containing acrylic resin is blended to use with polysiloxane pre polymers body, can be reduced in environmental change and be answered caused by coating
Power；Preparation method simple process of the invention, condition are easily-controllable.
Specific embodiment
In order to describe the technical content, the structural feature, the achieved object and the effect of this invention in detail, below in conjunction with embodiment
It is explained in detail.
The most critical design of the present invention is: by synthesis fluoro-acrylate copolymer lotion and polysiloxane pre polymers
During body, crosslinkable groups, such as hydroxyl, carboxyl, epoxy group and alcoxyl silicon substrate are introduced in its strand respectively, so that
Aqueous fluorine silica acrylic acid coating property is good.
The present invention provides a kind of aqueous fluorine silica acrylic acid coating, including fluoro-acrylate copolymer lotion and polysiloxanes
The mass ratio of performed polymer, fluoro-acrylate copolymer lotion and polysiloxane pre polymers body is 2~6: 1；
The fluoro-acrylate copolymer lotion includes the raw material of following parts by weight:
The polysiloxane pre polymers body includes the raw material of following parts by weight:
The pH value of the aqueous hydrochloric acid solution is 4.0.
The principle of the present invention: pass through the process in synthesis fluoro-acrylate copolymer lotion and polysiloxane pre polymers body
In, crosslinkable groups, such as hydroxyl, carboxyl, epoxy group and alcoxyl silicon substrate are introduced in its strand respectively, so that aqueous fluorine silicon
Acrylic coating is functional；The present invention is contracted with the hydrolysis of the emulsion free-radical polymerization of acrylic ester monomer and siloxanyl monomers
It closes and separately carries out, then again mix polysiloxane pre polymers body aqueous solution with fluoro-acrylate copolymer lotion, hot setting
Prepare film.Paint film defect problem caused by introducing so as to avoid polyalcohol also avoids silicon during emulsion polymerization
Agglomerate gel caused by hydrolytic crosslinking between oxygen alkane monomer.
As can be seen from the above description, the beneficial effects of the present invention are: by being introduced in preparing in raw material for acrylic coating
Organic fluoride and silicon materials, introducing in the strand of fluoro-acrylate copolymer lotion and polysiloxane pre polymers body can hand over respectively
Symbasis group, if hydroxyl, carboxyl, epoxy group and alcoxyl silicon substrate increase the crosslink density of film in film forming procedure, so that applying
Film dynamic performance is good, so that aqueous fluorine silica acrylic acid coating has many advantages, such as that weather-proof, antifriction scrape along hydrophobicity is strong；Water of the present invention
Property fluorine silica acrylic acid coating in VOC content reduce, it is more environmentally-friendly.
Further, the acrylic ester monomer is acrylic acid, glycidyl methacrylate, methyl methacrylate
Ester, butyl acrylate, hydroxy-ethyl acrylate or butyl methacrylate it is one or more.
Further, organic fluorine monomer is trifluoroethyl methacrylate, Hexafluorobutyl mathacrylate or methyl
The combination of one or more of perluorooctyl acrylate.
Further, the initiator is the combination of one or more of ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate.
Further, the emulsifier is that conventional emulsifier is compounded with reactive emulsifier with any mass ratio；It is described normal
Rule emulsifier is the one or more of lauryl sodium sulfate, octyl phenol polyoxyethylene ether or nonylphenol polyoxyethylene ether；It is described
Reactive emulsifier is allyl octyl phenol polyoxyethylene ether, 3- allyloxy -2- hydroxyl -1- propane sulfonic acid sodium or allyloxy
Nonylphenol polyoxyethylene ether ammonium sulfate it is one or more.
Seen from the above description, it can be avoided using reactive emulsifier since emulsifier excess bring negatively affects.
Further, pH buffer is the one or more of sodium bicarbonate, sodium carbonate or sodium acetate.
Further, the siloxanyl monomers are ethyl orthosilicate, methyltrimethoxysilane, phenyltrimethoxysila,e
Or γ-glycidyl ether oxygen propyl trimethoxy silicane is one or more.
A kind of preparation method of above-mentioned aqueous fluorine silica acrylic acid coating, comprising the following steps:
Fluoro-acrylate copolymer lotion and siloxanes performed polymer are mixed to get mixture by 2~6: 1 mass ratio；
The mixture is coated uniformly on substrate, the dry 30min under room temperature, then at 60~120 DEG C of solidifications 1~
3h。
As can be seen from the above description, the beneficial effects of the present invention are: the preparation side of the aqueous fluorine silica acrylic acid coating of the present invention
Method can reduce coating institute by the way that aqueous fluorine-containing acrylic resin and polysiloxane pre polymers body to be blended to use in environmental change
The stress of generation；Preparation method simple process of the invention, condition are easily-controllable.
Further, the fluoro-acrylate copolymer lotion synthetic method the following steps are included:
Step 1: acrylic monomer and organic fluorine monomer are mixed into obtain monomer mixed solution；Emulsifier and pH buffer is molten
Solution stirs and is added the monomer mixed solution in deionized water, obtain pre-emulsion；Initiator deionized water dissolving must be caused
Agent solution；
Step 2: the pre-emulsion of 1/4~1/3 total weight parts and the initiator solution of 1/3~1/2 total weight parts being stirred mixed
The first mixed liquor is closed to obtain, the pre-emulsion of surplus is mixed into obtain the second mixed liquor with the initiator solution of surplus；Heat described first
Lotion of the mixed liquor into first mixed liquor keeps the temperature 0~20min after generating blue light, and control drips described second in 2h
Mixed liquor；
Step 3: after first mixed liquor is all mixed with second mixed liquor, being warming up to 65~90 DEG C, heat preservation 2
~4h is cooled to 45 DEG C hereinafter, discharging is filtered, and adjusting pH value to 7.0 obtains the fluoro-acrylate copolymer lotion.
Further, the siloxanes performed polymer the preparation method comprises the following steps: by aqueous hydrochloric acid solution, chlorination tetra-n-butyl ammonium and going
After mixing, siloxanyl monomers are added in ionized water, and after 1~3h of stirring obtains uniform solution at 25~40 DEG C, the reaction was continued 1~
4h is up to polysiloxane pre polymers body.
Embodiment 1
By 1.2g lauryl sodium sulfate, 1.2g allyl octyl phenol polyoxyethylene ether, 0.15g sodium bicarbonate 65.0g
After completely dissolution, monomer mixed solution is added dropwise while stirring, and (monomer mixed solution includes: 1.8g acrylic acid, 5.0g propylene to deionized water
Sour hydroxyl ethyl ester, 30.0g methyl methacrylate, 22.0g butyl acrylate, ten trifluoro monooctyl ester of 8.0g methacrylic acid), sufficiently stir
Mix to obtain pre-emulsion；It is stand-by that the ammonium persulfate of 0.3g with 25.0g deionized water dissolving is obtained into initiator solution；
Blender is being housed, in the four-hole boiling flask of nitrogen conduit and dropping funel, 1/4~1/3 total weight is added in condenser pipe
The pre-emulsion (in mass, similarly hereinafter) of part, the initiator solution of 1/3~1/2 total weight parts stir evenly to obtain the first mixing
Liquid is heated to 78 DEG C, keeps the temperature 20min after the lotion in the first mixed liquor has blue light generation, starts the pre-emulsion that surplus is added dropwise
The second mixed liquor formed with the initiator solution of surplus, control drip in 2h；
After completion of dropwise addition, 80 DEG C are warming up to, keeps the temperature 3h, after monomer sufficiently reacts, is cooled to 45 DEG C hereinafter, discharging, is used
200 mesh sub-sieves are filtered, and adjust pH value to 7.0 to get fluoro-acrylate copolymer lotion with ammonium hydroxide；
After mixing by 70.0g deionized water, 3mL aqueous hydrochloric acid solution, 0.1g chlorination tetra-n-butyl ammonium curing accelerator,
25.0g ethyl orthosilicate, 5.0g phenyltrimethoxysila,e, γ-glycidyl ether oxygen propyl trimethoxy silicon of 0.5g is added
Alkane (KH560), after stirring 2h obtains uniform solution at 25 DEG C, the reaction was continued 3h is up to polysiloxane pre polymers body；
Mixture is obtained after fluoro-acrylate copolymer lotion is compounded with polysiloxane pre polymers body 5:1 in mass ratio, it will
After mixture is coated uniformly on substrate, dry 30min, is then warming up to 60 DEG C of 2~3h of solidification again under room temperature.
The film main performance test method of the aqueous fluorine silica acrylic acid coating of the present embodiment and it the results are shown in Table 1；This implementation
Middle fluoro-acrylate copolymer lotion and the performance test results of polysiloxane pre polymers body film are shown in Table 2.
Embodiment 2
By the 3- allyloxy -2- hydroxyl -1- propane sulfonic acid sodium of 1.2g, 1.2g allyl octyl phenol polyoxyethylene ether,
After completely dissolution with 65.0g deionized water, monomer mixed solution is added dropwise while stirring, and (monomer mixed solution includes: 0.15g sodium bicarbonate
3.0g glycidyl methacrylate, 30.0g methyl methacrylate, 22.0g butyl acrylate, 8.0g methacrylic acid six
Fluorine butyl ester), it is sufficiently stirred and prepares pre-emulsion.The ammonium persulfate of 0.3g is obtained initiator solution with 25.0g deionized water dissolving to wait for
With；
Blender is being housed, in the four-hole boiling flask of nitrogen conduit and dropping funel, 1/4~1/3 total weight is added in condenser pipe
The pre-emulsion (in mass, similarly hereinafter) of part, the initiator solution of 1/3~1/2 total weight parts stir evenly to obtain the first mixed liquor,
78 DEG C are heated to, keeps the temperature 20min after the lotion in the first mixed liquor has blue light generation, starts to be added dropwise the pre-emulsion of surplus and remaining
Second mixed liquor of the initiator solution composition of amount, control drip in 2h；
After completion of dropwise addition, 80 DEG C are warming up to, keeps the temperature 3h, after monomer sufficiently reacts, is cooled to 45 DEG C hereinafter, discharging, is used
200 mesh sub-sieves are filtered, and adjust pH value to 7.0 to get fluoro-acrylate copolymer lotion with ammonium hydroxide；
70.0g deionized water, 3.0mL aqueous hydrochloric acid solution, 0.1g chlorination tetra-n-butyl ammonium curing accelerator are uniformly mixed
Afterwards, it is added 25.0g methyltrimethoxysilane, 5.0g phenyltrimethoxysila,e, 0.5g KH560, stirring 2h is obtained at 25 DEG C
After uniform solution, the reaction was continued 4h is up to polysiloxane pre polymers body；
Mixture is obtained after fluoro-acrylate copolymer lotion is compounded with polysiloxane pre polymers body 5:1 in mass ratio, it will
After mixture is coated uniformly on substrate, dry 30min, is then warming up to 60 DEG C of 2~3h of solidification again under room temperature.
The film main performance test method of the aqueous fluorine silica acrylic acid coating of the present embodiment and it the results are shown in Table 1；This implementation
Middle fluoro-acrylate copolymer lotion and the performance test results of polysiloxane pre polymers body film are shown in Table 2.
Embodiment 3
By 1.2g nonylphenol polyoxyethylene ether, 1.2g allyloxy nonylphenol polyoxyethylene ether ammonium sulfate, 0.15g bicarbonate
After completely dissolution with 65.0g deionized water, monomer mixed solution is added dropwise while stirring, and (monomer mixed solution includes: 3.0g methyl-prop to sodium
Olefin(e) acid ethylene oxidic ester, 30.0g methyl methacrylate, 22.0g butyl acrylate, 8.0g Hexafluorobutyl mathacrylate), it fills
Stirring is divided to prepare pre-emulsion.It is stand-by that the ammonium persulfate of 0.3g with 25.0g deionized water dissolving is obtained into initiator solution；
Blender is being housed, in the four-hole boiling flask of nitrogen conduit and dropping funel, 1/4~1/3 total weight is added in condenser pipe
The pre-emulsion (in mass, similarly hereinafter) of part, the initiator solution of 1/3~1/2 total weight parts stir evenly to obtain the first mixed liquor,
75 DEG C are heated to, keeps the temperature 20min after the lotion in the first mixed liquor has blue light generation, starts to be added dropwise the pre-emulsion of surplus and remaining
Second mixed liquor of the initiator solution composition of amount, control drip in 2h；
After completion of dropwise addition, 80 DEG C are warming up to, keeps the temperature 3h, after monomer sufficiently reacts, is cooled to 45 DEG C hereinafter, discharging, is used
200 mesh sub-sieves are filtered, and adjust pH value to 7.0 or so to get fluoro-acrylate copolymer lotion with ammonium hydroxide；
70.0g deionized water, 3.0mL aqueous hydrochloric acid solution, 0.1g chlorination tetra-n-butyl ammonium curing accelerator are uniformly mixed
Afterwards, 15.0g methyltrimethoxysilane is added, 15.0g ethyl orthosilicate, the KH560 of 0.5g, stirring 1h is obtained uniform at 35 DEG C
After solution, the reaction was continued 3h is up to polysiloxane pre polymers body；
Mixture is obtained after fluoro-acrylate copolymer lotion is compounded with polysiloxane pre polymers body 3:1 in mass ratio, it will
After mixture is coated uniformly on substrate, dry 30min, is then warming up to 60 DEG C of 2~3h of solidification again under room temperature.
The film main performance test method of the aqueous fluorine silica acrylic acid coating of the present embodiment and it the results are shown in Table 1；This implementation
Middle fluoro-acrylate copolymer lotion and the performance test results of polysiloxane pre polymers body film are shown in Table 2.
Embodiment 4
By 1.2g nonylphenol polyoxyethylene ether, 1.2g allyloxy nonylphenol polyoxyethylene ether ammonium sulfate, 0.15g bicarbonate
After completely dissolution with 65.0g deionized water, monomer mixed solution is added dropwise while stirring, and (monomer mixed solution includes: 3.0g methyl-prop to sodium
Olefin(e) acid ethylene oxidic ester, 30.0g methyl methacrylate, 22.0g butyl acrylate, 8.0g Hexafluorobutyl mathacrylate), it fills
Stirring is divided to prepare pre-emulsion.It is stand-by that the ammonium persulfate of 0.3g with 25.0g deionized water dissolving is obtained into initiator solution；
Blender is being housed, in the four-hole boiling flask of nitrogen conduit and dropping funel, 1/4~1/3 total weight is added in condenser pipe
The pre-emulsion (in mass, similarly hereinafter) of part, the initiator solution of 1/3~1/2 total weight parts stir evenly to obtain the first mixed liquor,
78 DEG C are heated to, keeps the temperature 20min after the lotion in the first mixed liquor has blue light generation, starts to be added dropwise the pre-emulsion of surplus and remaining
Second mixed liquor of the initiator solution composition of amount, control drip in 2h；
After completion of dropwise addition, 80 DEG C are warming up to, keeps the temperature 3h, after monomer sufficiently reacts, is cooled to 45 DEG C hereinafter, discharging, is used
200 mesh sub-sieves are filtered, and adjust pH value to 7.0 to get fluoro-acrylate copolymer lotion with ammonium hydroxide；
70.0g deionized water, 3.0mL aqueous hydrochloric acid solution, 0.1g chlorination tetra-n-butyl ammonium curing accelerator are uniformly mixed
Afterwards, 15.0g methyltrimethoxysilane, 10.0g ethyl orthosilicate is added, 5.0g phenyltrimethoxysila,e stirs at 25 DEG C
After 2h obtains uniform solution, the reaction was continued 3h is up to polysiloxane pre polymers body；
Mixture is obtained after fluoro-acrylate copolymer lotion is compounded with polysiloxane pre polymers body 4:1 in mass ratio, it will
After mixture is coated uniformly on substrate, dry 30min, is then warming up to 80 DEG C of 2~3h of solidification again under room temperature.
The film main performance test method of the aqueous fluorine silica acrylic acid coating of the present embodiment and it the results are shown in Table 1；This implementation
Middle fluoro-acrylate copolymer lotion and the performance test results of polysiloxane pre polymers body film are shown in Table 2.
Embodiment 5
By 1.2g octyl phenol polyoxyethylene ether, 1.2g allyloxy nonylphenol polyoxyethylene ether ammonium sulfate, 0.15g bicarbonate
Sodium with 65.0g deionized water after completely dissolution, while stirring be added dropwise monomer mixed solution (monomer mixed solution includes: 3.0g acrylic acid,
30.0g methyl methacrylate, 22.0g butyl acrylate, 8.0g Hexafluorobutyl mathacrylate), it is sufficiently stirred and prepares pre- cream
Liquid.It is stand-by that the ammonium persulfate of 0.3g with 25.0g deionized water dissolving is obtained into initiator solution；
Blender is being housed, in the four-hole boiling flask of nitrogen conduit and dropping funel, 1/4~1/3 total weight is added in condenser pipe
The pre-emulsion (in mass, similarly hereinafter) of part, the initiator solution of 1/3~1/2 total weight parts stir evenly to obtain the first mixed liquor,
80 DEG C are heated to, keeps the temperature 20min after the lotion in the first mixed liquor has blue light generation, starts to be added dropwise the pre-emulsion of surplus and remaining
Second mixed liquor of the initiator solution composition of amount, control drip in 2h；
After completion of dropwise addition, 82 DEG C are warming up to, keeps the temperature 3h, after monomer sufficiently reacts, is cooled to 45 DEG C hereinafter, discharging, is used
200 mesh sub-sieves are filtered, and adjust pH value to 7.0 to get fluoro-acrylate copolymer lotion with ammonium hydroxide；
70.0g deionized water, 3.0mL aqueous hydrochloric acid solution, 0.1g chlorination tetra-n-butyl ammonium curing accelerator are uniformly mixed
Afterwards, 15.0g methyltrimethoxysilane, 10.0g ethyl orthosilicate is added, 5.0g phenyltrimethoxysila,e stirs at 25 DEG C
After 2h obtains uniform solution, the reaction was continued 4h is up to polysiloxane pre polymers body；
Mixture is obtained after fluoro-acrylate copolymer lotion is compounded with polysiloxane pre polymers body 6:1 in mass ratio, it will
After mixture is coated uniformly on substrate, dry 30min, is then warming up to 120 DEG C of 2~3h of solidification again under room temperature.
The film main performance test method of the aqueous fluorine silica acrylic acid coating of the present embodiment and it the results are shown in Table 1；This implementation
Middle fluoro-acrylate copolymer lotion and the performance test results of polysiloxane pre polymers body film are shown in Table 2.
The film main performance of the aqueous fluorine silica acrylic acid coating of table 1
The performance test of table 2 fluoro-acrylate copolymer lotion and polysiloxane pre polymers body film
Remarks: the inner painting film preparation of table 2 explanation: fluoro-acrylate copolymer lotion and polysiloxane pre polymers body difference is equal
Even to be coated on substrate, dry 30min, is then warming up to 80 DEG C of solidification 3h again under room temperature.
In conclusion aqueous fluorine silica acrylic acid coating provided by the invention and preparation method thereof, by acrylic coating
Prepare and introduce Organic fluoride and silicon materials in raw material, respectively in point of fluorine-containing copolymer emulsion and polysiloxane pre polymers body
Crosslinkable groups are introduced in subchain, as hydroxyl, carboxyl, epoxy group and alcoxyl silicon substrate increase the friendship of film in film forming procedure
Join density, so that film good mechanical properties, so that aqueous fluorine silica acrylic acid coating has weather-proof, antifriction scrape along hydrophobicity is strong etc.
Advantage；VOC content in the aqueous fluorine silica acrylic acid coating of the present invention reduces, more environmentally-friendly；The aqueous fluorine silica acrylic acid of the present invention
Preparation method can be reduced by the way that aqueous fluorine-containing acrylic resin and polysiloxane pre polymers body to be blended to use in environmental change
Stress caused by coating；Preparation method simple process of the invention, condition are easily-controllable.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification is applied directly or indirectly in other relevant technical fields,
Similarly it is included within the scope of the present invention.
Claims (9)
1. a kind of aqueous fluorine silica acrylic acid coating, which is characterized in that pre- by fluoro-acrylate copolymer lotion and polysiloxanes
The mass ratio of aggressiveness composition, fluoro-acrylate copolymer lotion and polysiloxane pre polymers body is 2~6: 1；
The fluoro-acrylate copolymer lotion includes the raw material of following parts by weight:
The polysiloxane pre polymers body is made of the raw material of following parts by weight:
The pH value of the aqueous hydrochloric acid solution is 4.0；
The acrylic ester monomer contain one of acrylic acid, glycidyl methacrylate and hydroxy-ethyl acrylate or
It is a variety of.
2. aqueous fluorine silica acrylic acid coating according to claim 1, which is characterized in that organic fluorine monomer is methyl-prop
The combination of one or more of ten trifluoro monooctyl ester of olefin(e) acid trifluoro ethyl ester, Hexafluorobutyl mathacrylate or methacrylic acid.
3. aqueous fluorine silica acrylic acid coating according to claim 1, which is characterized in that the initiator be ammonium persulfate,
The combination of one or more of potassium peroxydisulfate or sodium peroxydisulfate.
4. aqueous fluorine silica acrylic acid coating according to claim 1, which is characterized in that the emulsifier is conventional emulsifier
It is compounded with reactive emulsifier with any mass ratio；The conventional emulsifier is lauryl sodium sulfate, octylphenol polyethylene ethylene oxide
Ether or nonylphenol polyoxyethylene ether it is one or more；The reactive emulsifier is allyl octyl phenol polyoxyethylene ether, 3-
Allyloxy -2- hydroxyl -1- propane sulfonic acid sodium or allyloxy nonylphenol polyoxyethylene ether ammonium sulfate it is one or more.
5. aqueous fluorine silica acrylic acid coating according to claim 1, which is characterized in that pH buffer is sodium bicarbonate, carbon
Sour sodium or sodium acetate it is one or more.
6. aqueous fluorine silica acrylic acid coating according to claim 1, which is characterized in that the siloxanyl monomers are positive silicic acid
Ethyl ester, methyltrimethoxysilane, phenyltrimethoxysila,e or γ-glycidyl ether oxygen propyl trimethoxy silicane one kind
Or it is a variety of.
7. a kind of preparation method of aqueous fluorine silica acrylic acid coating described in -6 any one according to claim 1, feature exist
In, comprising the following steps:
Fluoro-acrylate copolymer lotion and polysiloxane pre polymers body are mixed to get mixture by 2~6: 1 mass ratio；
The mixture is coated uniformly on substrate, the dry 30min under room temperature, then at 60~120 DEG C of 1~3h of solidification.
8. the preparation method of aqueous fluorine silica acrylic acid coating according to claim 7, which is characterized in that the fluorine-containing propene
The synthetic method of acid ester copolymer lotion the following steps are included:
Step 1: acrylic ester monomer and organic fluorine monomer are mixed into obtain monomer mixed solution；Emulsifier and pH buffer are dissolved
In deionized water, the monomer mixed solution is stirred and be added, pre-emulsion is obtained；Initiator is obtained into initiator with deionized water dissolving
Solution；
Step 2: the initiator solution of the pre-emulsion of 1/4~1/3 total weight parts and 1/3~1/2 total weight parts is stirred
The pre-emulsion of surplus is mixed to obtain the second mixed liquor with the initiator solution of surplus by the first mixed liquor；Heat first mixing
Lotion of the liquid into first mixed liquor keeps the temperature 0~20min after generating blue light, and control drips second mixing in 2h
Liquid；
Step 3: after first mixed liquor all mix with second mixed liquor, 65~90 DEG C are warming up to, keep the temperature 2~
4h is cooled to 45 DEG C hereinafter, discharging is filtered, and adjusting pH value to 7.0 obtains the fluoro-acrylate copolymer lotion.
9. the preparation method of aqueous fluorine silica acrylic acid coating according to claim 7, which is characterized in that the polysiloxanes
Performed polymer the preparation method comprises the following steps: after mixing by aqueous hydrochloric acid solution, chlorination tetra-n-butyl ammonium and deionized water, siloxanes is added
Monomer, after 1~3h of stirring obtains uniform solution at 25~40 DEG C, the reaction was continued 1~4h is up to polysiloxane pre polymers body.
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| CN107603393A (en) * | 2017-10-10 | 2018-01-19 | 临汾铁环漆业有限公司 | A kind of method for protecting water-borne acrylic coatings adhesive force |
| CN108300080A (en) * | 2017-10-12 | 2018-07-20 | 广东华兹卜新材料科技有限公司 | A kind of fluorine-containing aqueous multicolor finish and preparation method thereof |
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