CN105524552B - A kind of high performance organo-silicon fluorine nano paint and its application - Google Patents
A kind of high performance organo-silicon fluorine nano paint and its application Download PDFInfo
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- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
- C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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Abstract
The present invention provides a kind of high performance organo-silicon fluorine nano paints, including raw material composition as follows by mass percentage: perfluoropolyether silicone resin 0.1 ~ 5%；Fluorine-containing cage modle polysilsesquioxane 0.01 ~ 1%；Solvent 90 ~ 99.84%；Additive 0.05 ~ 4%；The organic silicon-fluorine coating that organic silicon-fluorine nano paint is prepared in the present invention has excellent hydrophobic anti-pollution, fingerprint resistance energy and durability.
Description
Technical field
The invention belongs to organic silicon-fluorine technical field of coatings, apply more particularly, to a kind of high performance organo-silicon fluorine nanometer
Material and its application.
Background technique
The hard materials such as external wall, glass, electronic component, automobile, ceramics often connect in actual production application
Various media are touched, wherein just including water, organic solvent, sweat stain, dust etc., all the safe handling of material and performance attractive in appearance are caused
It influences.Such as on pcb board and most of electronic component, moisture, acidity or alkaline gas, grease stain in air and environment etc.
It will cause material to cause to deliquesce, corrode and pollute respectively, influence product electrical property and safe handling；In touch display screen curtain and greatly
On the organic/inorganic glass material of part (including mobile phone screen, computer, television screen, show window, skyscraper glass, automobile gear
Wind glass and rearview mirror, eyeglass etc.), due to the deposition of greasy dirt (including fingerprint, sweat stain), dust and moisture content, cause visual
Performance decline and influence beauty, impact properties of product；Steel and other metal products, are easily oxidized corruption in the environment
Erosion；In ceramic product, spot easily deposits its surface and is difficult to clean.In order to overcome or alleviated by above-mentioned material product these lack
Point, what application was most at present is to coat one layer or a few coatings in these product subsurfaces and be protected, and wherein to be coated with
Machine fluosilicic class coating effect is the most excellent.
Use fluorine containing silane processing substrate make product have grease proofing, antifouling, waterproof and it is anti-pollution glass, ceramics,
It is applied on electronic component and optical element, such as United States Patent (USP) NO.5,274,159, No.6,200,884, No.3.646,
085, No.3,950,588 is prepared using fluorinated alkoxysilanes (including fluor alkaline silane and Perfluoropolyether silanes etc.)
Coating composition forms monolayer or very thin coating on substrate, to reach moisture-proof, grease proofing, anti-pollution, dust-fast, resistant
The performances such as dirt, anti-fingerprint attachment；But after the organic silicon-fluorine compound of such monolayer film forming, wear-resisting property and durability
Can it is poor, often with environment (glass, ceramics, external wall and automobile surface layer) contact when it is easy to fall off, thus prospect of the application by
To restriction.
Summary of the invention
The present invention provides a kind of high performance organo-silicon fluorine nanometer painting according to the deficiency in current organic silicon-fluorine coating technology
Material.
Another object of the present invention is to provide the preparation method and application of above-mentioned organic silicon-fluorine nano paint.
Technical purpose of the invention is achieved through the following technical solutions:
The present invention provides a kind of high performance organo-silicon fluorine nano paints, including raw material group as follows by mass percentage
At:
The perfluoropolyether silicone resin comprises the following structure one of formula:
R1For alkyl, H, acyloxy or ketoxime base；R2For the alkyl of methyl, ethyl, phenyl or C3~6；R3For H, methyl or second
Base；Q is the link group, including C3H6Or C2H4NHC3H6；
A is 1,2 or 3；B is 1 or 2；M is 2 or 3, and n is 2 or 3.
HPFO is perfluoropolyether group, and perfluoropolyether group molecular weight is 500~10000, and includes in following structural formula
Any one:
(a)CF3CF2CF2O(CF(CF3)CF2O)nCF(CF3Wherein n is 1~30 to)-,；
(b)CF3O(CF2CF2O)m′(CF2O)n′, wherein m ', n ' are 1~50, and wherein m '/n ' is 0.2~25；
(c)CF3CF2O(CF2CF2O)n″CF2, wherein n " is 1~50；
(d)CF3CF(CF3)O(CF(CF3)CF2O)n″′CF(CF3Wherein n " ' is 1~30 to)-,；
Wherein shown in fluorine-containing cage modle polysilsesquioxane structural formula such as formula (I) or formula (II):
RfFor C containing fluoroalkylYF2Y+1C2H4-；Y is any one natural number in 1~8, and X includes hydroxyl or alkoxy.
Preferably, the synthesis of the perfluoropolyether silicone resin is as follows:
By per-fluoro polyether compound and reactive organic silicon compound containing active group, after separating-purifying, obtain complete
Perfluoroalkyl polyether silicone resin, the per-fluoro polyether compound containing active group includes HPFO-COOCH3、HPFO-CH2CH=
CH2, HPFO-OH or HPFO-C (O) F, the organo-silicon compound include hydrogen blocking silicone silicone oil, aminoethylaminopropyl front three
Oxysilane, aminoethylaminopropyl methyl dimethoxysilane, isocyanatopropyl triethoxysilane or γ-glycidyl ether oxygen
Propyl trimethoxy silicane.
Preferably, when X is hydroxyl, the preparation method of fluorine-containing cage modle polysilsesquioxane includes following step in the Formula II
It is rapid:
S1. by RfSi (OEt)3Catalysis reaction is carried out in alcohols solvent, is generated
S2. products therefrom in S1 is purified, is added in fluoride solvent and dissolves, catalyst reaction is then added；
S3. will in S2 catalysis reaction after product be added 4-n-butyl ammonium hydrogen sulfate reaction, then be added hexafluoroisopropanol and
The mixed solvent of water, is stirred to react, and the fluorine-containing cage modle polysilsesquioxane of the Formula II is obtained after purification.
Preferably, reaction temperature is 40~50 DEG C in the S2, and the reaction time is 55~65min in the S1；The S3
Then middle reaction is cooled to room temperature the mixing that hexafluoroisopropanol and water is added to be first warming up to 75~85 DEG C of 25~35min of reaction
Solvent.
Reaction of the present invention is as follows:
The three-dimensional dimension of fluorine-containing cage modle polysilsesquioxane (F-POSS) is within the scope of nanoscale in the present invention, is
Typical Nano compound has nanoparticle small-size effect, surface and interfacial effect, quantum size effect, maroscopic quantity
Sub- tunnel-effect, to have stronger comprehensive performance.The F-POSS that the present invention voluntarily synthesizes is divided into again without active group and band
Two classes of active group；The raw material for synthesizing F-POSS includes CF3CH2CH2Si(OR)3、C3F7CH2CH2Si(OR)3、
C2F5CH2CH2Si(OR)3、C6F13CH2CH2Si(OR)3、C8F17CH2CH2Si(OR)3Deng in alcohols solvent (ethyl alcohol, isopropanol etc.)
In, catalysis reaction obtains under alkaline condition, as shown below,
Wherein Rf=-CH2CH2CF3
-CH2CH2CF2CF3
-CH2CH2CF2CF2CF3
-CH2CH2CF2CF2CF2CF2CF2CF3
-CH2CH2CF2CF2CF2CF2CF2CF2CF2CF3
It is synthesized with reaction active groups F-POSS, as shown below,
Wherein, reaction dissolvent is fluoride solvent, and b is acidic catalyst trifluoromethane sulfonic acid (CF3SO3H), c is tetra-n-butyl
Ammonium hydrogen sulfate (NBut4HSO4), d is (CF3)2CH2OH/H2O mixed solvent.
With reaction active groups F-POSS synthesis step specifically:
F-POSS after purification is added in fluoride solvent and is dissolved, 45 DEG C is warming up to, suitable acidic catalyst (three is added
Methyl fluoride sulfonic acid etc.), reaction stops after sixty minutes；Then appropriate 4-n-butyl ammonium hydrogen sulfate is added, is quickly risen after being sufficiently stirred
Temperature reacts 30 minutes to 80 DEG C, is cooled to room temperature (or 25 DEG C), is rapidly added enough hexafluoroisopropanol/water mixed solvents, accelerates
Stirring rate, sufficiently reaction 70min, obtain double fluorinated hydroxy polysilsesquioxanes after separating-purifying.
Preferably, the RfIncluding CF3CH2CH2-、C3F7CH2CH2-、C6F13CH2CH2Or C8F17CH2CH2-。
Preferably, the mass percent of the perfluoropolyether silicone resin is 0.01~1%, poly- times of the fluorine-containing cage modle
The mass percent of half siloxanes is 0.01~0.5%.
Preferably, the mass percent of the perfluoropolyether silicone resin is 0.01~0.5%, and the fluorine-containing cage modle is poly-
The mass percent of silsesquioxane is 0.02~0.15%.
Particularly, solvent of the present invention is as general dissolution purposes, the solvent fluoride solvent and non-fluorine-containing molten
Agent, the fluoride solvent include nona-fluoro butyl group methyl ether, nona-fluoro butyl group ether, perflexane, perfluorocyclohexane, perfluoro-methyl hexamethylene
One or more mixing of alkane, perfluorotoluene, PF 5070,1,3- bis- (trifluoromethyl) benzene, perfluor -2- butyl tetrahydrofuran
Object, the non-fluoride solvent include propylene glycol monomethyl ether acetate, glycol monoethyl ether, methyl ethyl ketone, methanol, ethyl alcohol, isopropanol,
One of tetrahydrofuran, ethyl acetate, toluene or dimethylbenzene are a variety of.
Particularly, additive of the present invention can according to need adds respectively, and the additive includes coupling agent, anti-painting
One of crow agent, scratch resistance agent, catalyst are a variety of.
Compared with the existing technology, the invention has the following advantages:
Organic silicon-fluorine coating provided by the invention, using simple manufacture craft, in base coating direct spraying, dip-coating, rolling
After the processing such as brush, curing molding obtains organic silicon-fluorine coating, can improve mechanical endurance energy and durability.It can be used for building outer
The materials such as wall, solar battery, automobile, pcb board, ceramics, electronic component need grease proofing, moisture-proof (water), anti-pollution, anti-corrosion
The performances such as erosion, rub resistance, lubrication, while also having the performance of anti-fingerprint deposition, it can be used for the application of " finger print safety " coating.
Detailed description of the invention
Steel wool frictional behaviour test result is used in Fig. 1 embodiment of the present invention.
Fig. 2 is that steel wool frictional behaviour test result is used in comparative example.
Pure cotton cloth/non-woven fabrics frictional behaviour test result is used in Fig. 3 embodiment of the present invention.
Fig. 4 is that pure cotton cloth/non-woven fabrics frictional behaviour test result is used in comparative example.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that the present embodiment is served only for pair
The present invention is further described, but should not be understood as limiting the scope of the invention, with perfluoropolyether siloxanes and contains
The nano coating of fluorine cage modle polysilsesquioxane (F-POSS) preparation belongs to the scope of the present invention, which is skilled in technique
Personnel can make some nonessential modifications and adaptations according to the content of aforementioned present invention.
Unless stated otherwise, the present invention uses reagent, method and apparatus for the art conventional reagent, method and are set
It is standby.
Perfluoropolyether silicone compounds are sealed using containing active group (vinyl, hydroxyl, methyl esters etc.) in the present embodiment
End per-fluoro polyether compound is primary raw material, is obtained with reactive organic silicon compound (Si―H addition reaction, hydrolytic condensation etc.), through separating
After purification, it is used to prepare organic silicon-fluorine nano paint.It is perfluoropolyether about the sealing end per-fluoro polyether compound containing active group
Methyl esters, structural formula HPFO-COOCH3；Allyl capped perfluoropolyether, structural formula HPFO-CH2CH=CH2, terminal hydroxy group perfluor
Polyether structure formula is HPFO-OH；Or perfluoropolyether acyl fluorides structural formula is HPFO-C (O) F；
Organo-silicon compound are hydrogen blocking silicone silicone oil, aminoethyl amino propyl trimethoxy silane, aminoethylaminopropyl
Methyl dimethoxysilane .KH560 or isocyanatopropyl triethoxysilane.
Perfluoropolyether raw material is purchased from SOLVAY Su Wei, Sanming, Fujian Province Hai Sifu Chemical Co., Ltd., too in the present embodiment
The enterprises such as Cang Zhonghua environmental protective chemical industry Co., Ltd, organic silicon raw material purchased from Sinopharm Chemical Reagent Co., Ltd., Aladdin,
Gelest company etc..
The synthesis of perfluoropolyether silicone resin in Examples 1 to 3, those skilled in the art are according to specific perfluoropolyether
Silicone resin structural formula selects corresponding raw material can be obtained referring to the prior art.
Embodiment 1:
Perfluoropolyether silicone resin F1, molecular structural formula are as follows:
Wherein m=10~50, n=5~100.
Synthetic method is according to general per-fluoro polyether compound and organo-silicon compound hydrosilylation conditioned response.
The synthesis of fluorine-containing cage modle polysilsesquioxane (F-POSS), molecular structure are as follows:
It is by perfluoro capryl trimethoxy silane (C8F17CH2CH2Si(OCH3)3, perfluoro capryl triethoxysilane
C8F17CH2CH2Si(OCH2CH3)3Reaction obtains, Rf representative-CH2CH2C8F17Group.
With reaction active groups F-POSS synthesis step specifically:
Perfluoro capryl polysilsesquioxane after purification is added in fluoride solvent and is dissolved, is warming up to 45 DEG C, is added appropriate
Acidic catalyst (trifluoromethane sulfonic acid etc.), reaction stop after sixty minutes；Then appropriate 4-n-butyl ammonium hydrogen sulfate is added, fills
Point stirring after be rapidly heated to 80 DEG C, react 30 minutes, be cooled to room temperature (or 25 DEG C), be rapidly added enough hexafluoroisopropanols/
Water mixed solvent accelerates stirring rate, sufficiently reaction 70min, and double fluorinated hydroxy polysilsesquioxanes are obtained after separating-purifying.
The design of organic silicon-fluorine nano paint formula is as follows:
| Substance | Content (mass fraction %) |
| Perfluoropolyether silicone resin F1 | 0.15% |
| Fluorine-containing cage modle polysilsesquioxane (F-POSS) | 0.02% |
| Solvent | 99.78% |
| Additive (auxiliary agent) | 0.05% |
Wherein, solvent be nona-fluoro butyl group ether, nona-fluoro butyl group methyl ether, perfluorooctane, propylene glycol methyl ether acetate, ethyl alcohol,
Glycol monoethyl ether, water, ethyl alcohol, ether, acetone, n,N-Dimethylformamide, hexafluoro butanol, HF-7100, HF-7200, HFE-
7300 mixture；
Additive is by taking catalyst (dibutyl tin dilaurate), co-catalyst (aluminium acetylacetonate) as an example in the present embodiment,
Other auxiliary agents can also be added as needed in those skilled in the art.
Embodiment 2
Perfluoropolyether silicone resin F2 synthesis, molecular structure are as follows:
Wherein R1 is methyl, ethyl；R2 is methyl；R3 is H；A=2 or 3.
Fluorine-containing cage modle polysilsesquioxane (F-POSS), molecular structure is as follows:
It is by perfluoro hexyl trimethoxy silane (C6F13CH2CH2Si(OCH3)3, perfluoro hexyl triethoxysilane
C6F13CH2CH2Si(OCH2CH3)3Reaction obtains, RfFor-CH2CH2C6F13。
The design of organic silicon-fluorine nano paint formula is as follows:
| Substance | Content (mass fraction %) |
| Perfluoropolyether silicone resin F2 | 0.20% |
| Fluorine-containing cage modle polysilsesquioxane (F-POSS) | 0.10% |
| Solvent | 99.65% |
| Additive (auxiliary agent) | 0.05% |
Wherein, solvent is the same as the identical of embodiment 1；Additive is identical with embodiment 1.
Embodiment 3
The synthesis of perfluoropolyether silicone resin F3, molecular structural formula are as follows:
Wherein n=5~100.
The band fluorine-containing cage modle polysilsesquioxane (F-POSS) of active reactive group, molecular structure is as follows:
Wherein RfFor-CH2CH2C6F13Or-CH2CH2C8F17, TfGroup is condensed for trifluoromethane sulfonic acid.
The design of organic silicon-fluorine nano paint formula is as follows:
Wherein, solvent is the same as the identical of embodiment 1；Additive is identical with embodiment 1.
Comparative example 1
The preparation method is the same as that of Example 1, the difference is that perfluoropolyether silicone resin F1 is not used,
Fluorine-containing cage modle polysilsesquioxane (F-POSS), organic silicon-fluorine nano paint formula are not added in comparative example 1
It designs as follows:
| Substance | Content (mass fraction) |
| Perfluoropolyether silicone resin F1 | 0.25% |
| Mixed solvent | 99.6% |
| Additive (auxiliary agent) | 0.15% |
Solvent is identical with embodiment 1；Additive is identical with embodiment 1.
Comparative example 2
Organic silicon-fluorine nano paint is prepared with heptadecafluorodecyl triethoxysilane (F17), molecular structural formula is as follows:
The design of organic silicon-fluorine nano paint formula is as follows:
| Substance | Content (mass fraction) |
| Heptadecafluorodecyl triethoxysilane F17 | 0.5% |
| Mixed solvent | 99.2% |
| Additive (auxiliary agent) | 0.3% |
Solvent is identical with embodiment 1；Additive is identical with embodiment 1.
Comparative example 3:
Using heptadecafluorodecyl triethoxysilane (F17) and fluorine-containing cage modle polysilsesquioxane used in Example 1
It is matched, preparation method and raw material proportioning are the same as embodiment 1, specific formula design such as following table.
The design of organic silicon-fluorine nano paint formula is as follows:
| Substance | Content (mass fraction) |
| Heptadecafluorodecyl triethoxysilane F17 | 0.5% |
| Fluorine-containing cage modle polysilsesquioxane (F-POSS) | 0.05% |
| Mixed solvent | 99.25% |
| Additive (auxiliary agent) | 0.2% |
Solvent is identical with embodiment 1；Additive is identical with embodiment 1.
By prepared organic silicon-fluorine nano paint in embodiment and comparative example using the side such as dip-coating, spraying, wiping
Formula is coated on the substrate surfaces such as glass, ceramics, metal, testing coating correlated performance after forming and hardening.
Organic silicon-fluorine nano coating prepares (lower for for glass baseplate):
(1) cleaning glass and corona treatment:
After glass is used ethyl alcohol, acetone soak, supersonic wave cleaning machine is cleaned, after drying at 60 DEG C at low temperature plasma
Reason, after wiping out spot, deionized water cleaning, room temperature is dried；Glass surface and water contact angle are tested, reaching 10 °, the following are most
It is excellent.
(2) organic silicon-fluorine coating coats
Using modes such as dip-coating, spraying, roller coating, blade coating, wipings, organic silicon-fluorine nano paint is coated on substrate surface,
It is placed at room temperature for 20 minutes.
(3) organic silicon-fluorine nano coating forming and hardening
Coating meron is placed in the following conditions curing molding: the 1. 2. 3. room 120 DEG C of * 30min 85 DEG C of * 85%RH*2hrs
Warm * 48hrs or more.
Organic silicon-fluorine nano coating performance detection tests contact angle respectively, slides the property such as angle, soil resistance, hardness, rub resistance
Energy.
(1) contact angle (water & hexadecane) is tested: 2 μ L deionized waters of drop or hexadecane in the substrate surface processed,
Test contact angle.(test equipment: dynamic/Static Contact angle tester)
(2) slide angle or roll angle test: 7 μ L deionized waters of drop are in horizontal positioned substrate surface, then slowly inclination
Sample determines the smallest angle value when drop slides/rolls.(test equipment: dynamic/Static Contact angle tester).
(3) permanent pen is tested
It is drawn lines on sample surfaces with permanent pen, then observes ink traces variation and wiping removes complexity:
| 0 grade | Ink does not have trace |
| 1 grade | Discontinuous droplet-like is presented in ink, can be wiped easily with non-woven fabrics |
| 2 grades | Semicontinuous shape is presented in ink, and trace is fuzzy, and non-woven fabrics can be wiped easily |
| 3 grades | Ink traces are clear, wiped with non-woven fabrics difficulty |
(4) anti-fingerprint performance test
Sample surfaces are stained with fingerprint or imitated fingerprint mixed solvent, then wipe fingerprint with dry paper handkerchief, monitor fingerprint
In substrate surface adhesion condition and wiping difficulty or ease situation
(5) hardness test
Use pencil hardness instrument testing coating hardness.
(6) dynamic friction coefficient is tested
It is dynamic using the test of 50cm/min wiping speed in horizontal coating sample with non-dust cloth (10mm*30mm) weight bearing 100g
State friction coefficient μ
(7) crocking resistance is tested
After the certain number in different medium friction substrate surface, test and situation of change before and after water contact angle connect with water
Feeler attenuation rate is defined as organic silicon-fluorine coating final abrasion resistance when reaching 10%, while also testing when contact angle is 100 °
Rubbing number.
1. resistance to pure cotton cloth/non-woven fabrics frictional behaviour test
Test condition: 1kg pressure, rub rate 8000mm/min, friction area 10mm*50mm
2. the 0000# of resistance to steel wool frictional behaviour is tested
Test condition: 1kg pressure, rub rate 8000mm/min, friction area 10mm*50mm
Test data is as follows in embodiment:
1. substrate initial performance test result such as table 1
2. 0000# steel wool and pure cotton cloth/non-woven fabrics frictional behaviour test result
1. 0000# steel wool frictional behaviour is tested, as illustrated in fig. 1 and 2:
With the 0000# of resistance to steel wool Rubbing number at 100 ° of water contact angle
2. pure cotton cloth/non-woven fabrics frictional behaviour test, as shown in Figures 3 and 4:
With the Rubbing number of resistance to non-woven fabrics at 100 ° of water contact angle
It is compared by embodiment measured data and comparative example it is found that organic silicon-fluorine nano paint has excellent dredge in the present invention
Water anti-pollution, fingerprint resistance energy, durability (crocking resistance) etc..
The present invention has been described by exemplary approach herein, it should be understood that the term is intended to substantially have
Descriptive word, rather than restrictive word.Obviously, according to teaching content above, many modification shapes of the invention
Formula or deformation type are possible.The present invention can be implemented with the specific mode in Claims scope that is different from.
Claims (8)
1. a kind of high performance organo-silicon fluorine nano paint, which is characterized in that including raw material composition as follows by mass percentage:
The perfluoropolyether silicone resin comprises the following structure one of formula:
R1For alkyl, H, acyloxy or ketoxime base；R2For the alkyl of methyl, ethyl, phenyl or C3~6；R3For H, methyl or ethyl；Q
For the link group, including C3H6Or C2H4NHC3H6；
A is 1,2 or 3；B is 1 or 2；M is 2 or 3, and n is 2 or 3；
HPFO is perfluoropolyether group, and perfluoropolyether group molecular weight is 500~10000, and includes appointing in following structural formula
It anticipates one kind:
(a)CF3CF2CF2O(CF(CF3)CF2O)nCF(CF3Wherein n is 1~30 to)-,；
(b)CF3O(CF2CF2O) m ' (CF2O) n '-, wherein m ', n ' are 1~50, and wherein m '/n ' is 0.2~25；
(c)CF3CF2O(CF2CF2O)n″CF2, wherein n " is 1~50；
(d)CF3CF(CF3)O(CF(CF3)CF2O)n″′CF(CF3Wherein n " ' is 1~30 to)-,；
Wherein shown in fluorine-containing cage modle polysilsesquioxane structural formula such as formula (I) or formula (II):
The Rf is CF3CH2CH2-、C3F7CH2CH2-、C6F13CH2CH2Or C8F17CH2CH2, X includes hydroxyl or alkoxy,
The Tf is that trifluoromethane sulfonic acid is condensed group.
2. high performance organo-silicon fluorine nano paint according to claim 1, which is characterized in that the perfluoropolyether siloxanes
The synthesis of resin is as follows:
By per-fluoro polyether compound and reactive organic silicon compound containing active group, after separating-purifying, it is poly- to obtain perfluor
Ether silicone resin, the per-fluoro polyether compound containing active group include HPFO-COOCH3, HPFO-CH2CH=CH2,
HPFO-OH or HPFO-C (O) F, the organo-silicon compound include hydrogen blocking silicone silicone oil, aminoethylaminopropyl trimethoxy
Silane, aminoethylaminopropyl methyl dimethoxysilane, isocyanatopropyl triethoxysilane or γ-glycidyl ether oxygen propyl
Trimethoxy silane.
3. high performance organo-silicon fluorine nano paint according to claim 1, which is characterized in that when X is hydroxyl, the formula
The preparation method of fluorine-containing cage modle polysilsesquioxane includes the following steps: in II
S1. by RfSi (OEt)3Catalysis reaction is carried out in alcohols solvent, is generated
S2. products therefrom in S1 is purified, is added in fluoride solvent and dissolves, catalyst reaction is then added；
S3. will 4-n-butyl ammonium hydrogen sulfate reaction is added in product after catalysis reaction in S2, hexafluoroisopropanol and water is then added
Mixed solvent is stirred to react, and the fluorine-containing cage modle polysilsesquioxane is obtained after purification.
4. high performance organo-silicon fluorine nano paint according to claim 3, which is characterized in that reaction temperature is in the S2
40~50 DEG C, the reaction time is 55~65min in the S1；
In the S3 then reaction is cooled to room temperature addition hexafluoroisopropanol to be first warming up to 75~85 DEG C of 25~35min of reaction
With the mixed solvent of water.
5. high performance organo-silicon fluorine nano paint according to claim 1, which is characterized in that the solvent is fluoride solvent
With non-fluoride solvent, the fluoride solvent includes nona-fluoro butyl group methyl ether, nona-fluoro butyl group ether, perflexane, perfluorocyclohexane, complete
Methyl fluoride hexamethylene, perfluorotoluene, PF 5070,1,3- bis- (trifluoromethyl) benzene, perfluor -2- butyl tetrahydrofuran one kind or
A variety of mixtures, the non-fluoride solvent include propylene glycol monomethyl ether acetate, glycol monoethyl ether, methyl ethyl ketone, methanol, second
One of alcohol, isopropanol, tetrahydrofuran, ethyl acetate, toluene or dimethylbenzene are a variety of；The additive include coupling agent,
Anti-graffiti dose, scratch resistance agent, one of catalyst or a variety of.
6. high performance organo-silicon fluorine nano paint described in a kind of claim 1 to 5 any one claim prepare it is organic
Application in fluosilicic coating.
7. application according to claim 6, which is characterized in that after the coating is coated on substrate, curing molding, i.e.,
Obtain the organic silicon-fluorine coating；The coating processes are spraying, dip-coating, spin coating or vacuum deposition.
8. application according to claim 6, which is characterized in that the organic silicon-fluorine nano paint is used to prepare " fingerprint peace
Coating entirely ".
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