CN108047940A - A kind of Thief zone high durable environment friendly silicon fluorine emulsion and preparation method thereof - Google Patents
A kind of Thief zone high durable environment friendly silicon fluorine emulsion and preparation method thereof Download PDFInfo
- Publication number
- CN108047940A CN108047940A CN201711419999.3A CN201711419999A CN108047940A CN 108047940 A CN108047940 A CN 108047940A CN 201711419999 A CN201711419999 A CN 201711419999A CN 108047940 A CN108047940 A CN 108047940A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- environment friendly
- emulsion
- liquid
- thief zone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- 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
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plant Pathology (AREA)
- Silicon Polymers (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of Thief zone high durable environment friendly silicon fluorine emulsion, consisting of 30~50wt% of small molecule silane, 10~20wt% of fluorine alkyl siloxanes, 0.5~3wt% of silicon fluoride modifying titanium dioxide, 1~3wt% of composite organic emulsifier, 0.5~1.5wt% of fluorine-containing surfactant, 3~5wt% of Ludox, surplus are deionized water.In addition the preparation method of above-mentioned Thief zone high durable environment friendly silicon fluorine emulsion is also disclosed.The present invention not only ensure that product had good, lasting hydrophobic oleophobic anti-pollution function, but also product is made to have excellent permeability and weatherability, while will not also change the appearance and its gas permeability of substrate surface；And preparation process is simple, safety and environmental protection free from extraneous odour, can be widely used for the water proof anti-soil of the base materials such as concrete, stone material, GRC.
Description
Technical field
The present invention relates to substrate surface protection technology field more particularly to a kind of Thief zone high durable environment friendly silicon fluorine emulsions
And preparation method thereof.
Background technology
Concrete, stone material, GRC etc. are porous material, inside there is various capillaries, hole etc., particularly its
Surface is generally relatively rough, and dust, pollutant and vehicle exhaust in air etc. can all be deposited in substrate surface.In water
Under help, pollutant can be entered along capillary, hole etc. inside base material, and leaves spot on surface.In this way, it not only influences
Appearance, and be difficult to remove, especially for ornamental clear-water concrete or GRC components, the antifouling of surface is even more outstanding
To be important.
Surfacecti proteon most efficient method, exactly prevents base material from being contacted with water and other harmful substances, is exactly specifically logical
It crosses and forms one of lasting protective layer in substrate surface and certain depth and realize.In recent years, since organosilicon material is with excellent
Different hydrophobicity and high temperature degradation resistance, thus it is widely used in the surfacecti proteon of base material.But the protective layer formed still can not
Realize lasting surface soiling effect, this is because under long-term outdoors sunlight irradiation, the molecule segment of surface protecting layer according to
It so can be by ultraviolet damage so that hydrophobic properties of the surface decline, and surface soiling ability declines；In addition, the surface of the prior art is prevented
In watch box system, mostly using organic solvent, thus can bring smell, toxicity, it is volatile and inflammable and explosive the defects of and harm.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide it is a kind of suitable for porous substrate surface, have
The environment friendly silicon fluorine emulsion of high osmosis high-weatherability after brushing or spraying to substrate surface, does not change substrate surface color,
Lasting hydrophobic oleophobic performance is played simultaneously and there is excellent anti-fouling effect, and environment-protective no-smell safe to use.The present invention
Another object be the preparation method that above-mentioned Thief zone high durable environment friendly silicon fluorine emulsion is provided.
The purpose of the present invention is achieved by the following technical programs：
A kind of Thief zone high durable environment friendly silicon fluorine emulsion provided by the invention, consisting of：Small molecule silane 30~
50wt%, 10~20wt% of fluorine alkyl siloxanes, 0.5~3wt% of silicon fluoride modifying titanium dioxide, composite organic emulsifier 1
~3wt%, 0.5~1.5wt% of fluorine-containing surfactant, 3~5wt% of Ludox, surplus are deionized water；Wherein,
The structural formula of the small molecule silane is CnH2n+1-Si(OR1)m-R3-m, wherein, R1For methyl or ethyl, 4≤n≤
8,1≤m≤3, n, m are integer, and R is the saturated alkane that carbon number is 1~6；
The structural formula of the fluorine alkyl siloxanes is：Rf-(CH2)n-Si(OR1)3, wherein, R1For methyl or ethyl, RfFor
CmF2m+1Or C6F5, 0≤n≤3,1≤m≤13, n, m are integer.
Further, the grain size of silicon fluoride modifying titanium dioxide of the present invention is 10~100nm.
Further, composite organic emulsifier of the present invention is by alkylphenol polyoxyethylene ether OP series, dodecyl
Sodium sulfonate, Sorbitan acid alcohol aliphatic ester span series, fatty alcohol polyoxyethylene ether peregal series, AEO series, nonyl phenol
At least two kinds compoundings in polyoxyethylene ether NP series, sorbitan fatty acid ester polyoxyethylene ether Tween series are formed.
In said program, fluorine-containing surfactant of the present invention is by anionic type fluorocarbon surfactant, cationic
Fluorocarbon surfactant, amphoteric ion fluorocarbon surfactant, non-ionic fluorocarbon surfactant, siliceous fluoro-carbon surface active
One kind or its combination in agent.The Ludox is 10~100nm of grain size, the Nano-meter SiO_2 of concentration 30%2Aqueous dispersions.
Another object of the present invention is achieved by the following technical programs：
The preparation method of above-mentioned Thief zone high durable environment friendly silicon fluorine emulsion provided by the invention, comprises the following steps：
(1) preparation of silane emulsion
It by the small molecule silane, is uniformly mixed with composite organic emulsifier, portions of de-ionized water, obtains silane breast
Liquid；
(2) preparation of fluorine alkyl siloxanes lotion
By the fluorine alkyl siloxanes, it is uniformly mixed with fluorine-containing surfactant, remaining deionized water, obtains fluoroalkyl silicon
Oxygen alkane lotion；
(3) by the silane emulsion and fluorine alkyl siloxanes lotion after mixing, it is modified dioxy with Ludox, silicon fluoride
Change titanium to be uniformly mixed to get to Thief zone high durable environment friendly silicon fluorine emulsion.
Further, in step (1) described in preparation method of the present invention, the composite organic emulsifier adds in two times,
I.e.：
The composite organic emulsifier of the small molecule silane and 50~70wt%, at 25~60 DEG C stir 30~
90min is uniformly mixed, and A liquid is made；
The remaining composite organic emulsifier is added in the deionized water of 30~70wt%, is stirred at 25~60 DEG C
B liquid is made in 30~90min；
Then, the A liquid is added dropwise under stirring in B liquid, after being added dropwise to complete, it is 5 to adjust solution system pH value
~7,30~90min is stirred under the conditions of 25~60 DEG C, mixing speed is 1000~3000r/min, silane emulsion is made.
Further, in step (2) described in preparation method of the present invention, the fluorine-containing surfactant adds in two times, i.e.,：
By the fluorine alkyl siloxanes, the fluorine-containing surfactant with 50~70wt%, at 25~60 DEG C stir 30~
90min is uniformly mixed, and C liquid is made；
The remaining fluorine-containing surfactant is added in remaining deionized water, and 30~90min is stirred at 25~60 DEG C,
D liquid is made；
Then, the C liquid is added dropwise under stirring in D liquid, after being added dropwise to complete, it is 5 to adjust solution system pH value
~7,30~90min is stirred under the conditions of 25~60 DEG C, mixing speed is 1000~3000r/min, fluorine alkyl siloxanes are made
Lotion.
Further, in step (3) described in preparation method of the present invention, the silane emulsion exists with fluorine alkyl siloxanes lotion
After stirring 30~90min at 25~60 DEG C, the stirring condition is kept, sequentially adds Ludox, silicon fluoride modifying titanium dioxide
It is uniformly mixed.
The invention has the advantages that：
(1) Thief zone high durable environment friendly silicon fluorine emulsion of the present invention has the excellent resistance to height that organosilicon material possesses
Low temperature properties, resistance to ag(e)ing and hydrophobicity (contact angle of water is 137 °~146 °)；Simultaneously as the introducing of organic fluorine material and assign
Excellent properties, the pollutants such as water, oil such as coating oil resistant, solvent resistant, chemical stabilization and lower surface energy has been given to be difficult to be attached on
Surface, so as to good resistance to soiling.
(2) Thief zone high durable environment friendly silicon fluorine emulsion of the present invention, due to being made of micromolecular compound, even if
In the concrete article of high grade still there is good permeability (C50 concrete, penetration depth up to 4.5~5.4mm), can have
Effect is penetrated into inside base material, and with base material with chemical bonds, formed with organosilicon material in substrate surface and certain depth and
Containing the netted three-dimensional waterproof and oilproof stain-proofing layer based on fluorocarbon chain, avoided so as to which moisture is persistently effectively prevented to enter internal
Pollution；Meanwhile and will not be in the closed film of Surface Creation, therefore the appearance color and gas permeability of base material are not influenced.
(3) silicon fluoride modifying titanium dioxide has preferable dispersiveness and compatibility in this system, its introducing assigns
Coating excellent UV resistant performance, further improves the ageing-resistant ability of coating, while helps to improve dredging for coating
Water oleophobic performance.Also, the introducing of silicon fluoride modifying titanium dioxide causes coating to have photocatalytic activity, being capable of photocatalytic degradation
Organic pollution possesses certain sterilizing function, can effectively inhibit the growths such as microorganism, moss.
(4) Ludox is entrained in this system, and silica bodily form net structure is formed after curing so that and coating is not afraid of soda acid,
Improve coating performance.
(5) Thief zone high durable environment friendly silicon fluorine emulsion of the present invention, performance are stablized, and storage stability is good, puts at room temperature
12 months are put without obvious sediment or reunion.
(6) simple production process of the present invention, it is easy to use；And product system is emulsion-type, and organic solvent is not required, from
And avoid using caused by organic solvent smell, toxicity, volatility and it is inflammable and explosive dangerous the problems such as, safety collar
Free from extraneous odour is protected, can be widely applied in the surfacecti proteon of concrete, stone material, GRC etc..
Below in conjunction with embodiment, the present invention is described in further detail.
Specific embodiment
A kind of Thief zone high durable environment friendly silicon fluorine emulsion of the embodiment of the present invention is mainly by small molecule silane, fluoroalkyl
The complex that siloxanes, silicon fluoride modifying titanium dioxide, composite organic emulsifier, fluorine-containing surfactant, Ludox are formed
System.Wherein,
Silicon fluoride modifying titanium dioxide is made using the method described in the patent No. 201410669702.9, that is, passes through Hydrolysis of Titanium
The synthetically prepared TiO 2 sol solution of alkoxide；Then it is grafted fluorine richness alkyl silane in titanium dioxide surface and obtains silicon fluoride
Modifying titanium dioxide nano material.In the embodiment of the present invention, silicon fluoride modifying titanium dioxide is ground to grain size as 10~100nm.
Ludox is 10~100nm of grain size, the Nano-meter SiO_2 of concentration 30%2Aqueous dispersions.
Embodiment one：
A kind of Thief zone high durable environment friendly silicon fluorine emulsion of the present embodiment, its step are as follows：
(1) preparation of silane emulsion
Trimethoxysilane 30g, composite organic emulsifier 0.6g (OP10 and each 0.3g of NP10) are weighed, is poured into
Heating water bath stirs 30min with the speed of 1000r/min, A liquid is made to 25 DEG C in container；
It weighs composite organic emulsifier 0.4g (OP10 and each 0.2g of NP10) to be added in 19g deionized waters, at 25 DEG C
Under, 30min is stirred with the speed of 1000r/min, B liquid is made；
Then, by above-mentioned A liquid under the stirring of 1000r/min, B is slowly dropped into the speed of 0.1~0.3mL/s
In liquid；After being added dropwise to complete, phosphoric acid is used to adjust solution system pH value as 5~7, then in 25 DEG C, mixing speed 1000r/min
Under the conditions of stir 30min, be made silane emulsion；
(2) preparation of fluorine alkyl siloxanes lotion
Ten trifluoro octyl group trimethoxy silane 10g, perfluoroalkyl polyethers 0.25g are weighed, heating water bath in container is poured into and arrives
25 DEG C, 30min is stirred with the speed of 1000r/min, C liquid is made；
Perfluoroalkyl polyethers 0.25g is weighed, is added in 36g deionized waters, at 25 DEG C, with the speed of 1000r/min
30min is stirred, D liquid is made；
Then, by above-mentioned C liquid under the stirring of 1000r/min, D is slowly dropped into the speed of 0.1~0.3mL/s
In liquid；After being added dropwise to complete, phosphoric acid is used to adjust solution system pH value as 5~7, then at 25 DEG C, mixing speed 1000r/min
Under the conditions of stir 30min, fluorine alkyl siloxanes lotions is made；
(3) by above-mentioned silane emulsion, mix with fluorine alkyl siloxanes lotion, stirred under 25 DEG C, 1000r/min speed
After 30min；Keep above-mentioned stirring condition, sequentially add Ludox 3g, silicon fluoride modifying titanium dioxide 0.5g be uniformly mixed to get
To Thief zone high durable environment friendly silicon fluorine emulsion.
Embodiment two：
A kind of Thief zone high durable environment friendly silicon fluorine emulsion of the present embodiment, its step are as follows：
(1) preparation of silane emulsion
Weigh isobutyl triethoxy silane 40g, (dodecyl sodium sulfate and span20 are each by composite organic emulsifier 2g
1g), heating water bath in container is poured into, to 35 DEG C, to stir 40min with the speed of 1500r/min, A liquid is made；
It weighs composite organic emulsifier 1g (dodecyl sodium sulfate and each 0.5g of span20) and is added to 22g deionized waters
In, at 30 DEG C, 35min is stirred with the speed of 2000r/min, B liquid is made；
Then, by above-mentioned A liquid under the stirring of 3000r/min, B is slowly dropped into the speed of 0.1~0.3mL/s
In liquid；After being added dropwise to complete, phosphoric acid is used to adjust solution system pH value as 5~7, then at 35 DEG C, mixing speed 1000r/min
Under the conditions of stir 60min, be made silane emulsion；
(2) preparation of fluorine alkyl siloxanes lotion
Tridecafluoro-n-octyltriethoxysilane 13g, perfluoroalkyl betain 0.5g are weighed, heating water bath in container is poured into and arrives
40 DEG C, 60min is stirred with the speed of 2000r/min, C liquid is made；
Perfluoroalkyl betain 0.5g is weighed, is added in 15g deionized waters, at 45 DEG C, with the speed of 1500r/min
30min is stirred, D liquid is made；
Then, by above-mentioned C liquid under the stirring of 2000r/min, D is slowly dropped into the speed of 0.1~0.3mL/s
In liquid；After being added dropwise to complete, phosphoric acid is used to adjust solution system pH value as 5~7, then at 35 DEG C, mixing speed 1500r/min
Under the conditions of stir 40min, fluorine alkyl siloxanes lotions is made；
(3) by above-mentioned silane emulsion, mix with fluorine alkyl siloxanes lotion, stirred under 35 DEG C, 1500r/min speed
After 70min；Keep above-mentioned stirring condition, sequentially add Ludox 4g, silicon fluoride modifying titanium dioxide 2g be uniformly mixed to get to
Thief zone high durable environment friendly silicon fluorine emulsion.
Embodiment three：
A kind of Thief zone high durable environment friendly silicon fluorine emulsion of the present embodiment, its step are as follows：
(1) preparation of silane emulsion
Octyltri-ethoxysilane 50g, composite organic emulsifier 1g (peregal 15 and each 0.5g of AEO9) are weighed, is poured into
Heating water bath stirs 90min with the speed of 1500r/min, A liquid is made to 45 DEG C in container；
Composite organic emulsifier 0.5g (peregal 15 and each 0.25g of AEO9) is weighed to be added in 14g deionized waters,
At 35 DEG C, 70min is stirred with the speed of 2000r/min, B liquid is made；
Then, by above-mentioned A liquid under the stirring of 1000r/min, B is slowly dropped into the speed of 0.1~0.3mL/s
In liquid；After being added dropwise to complete, phosphoric acid is used to adjust solution system pH value as 5~7, then at 60 DEG C, mixing speed 1500r/min
Under the conditions of stir 60min, be made silane emulsion；
(2) preparation of fluorine alkyl siloxanes lotion
15 fluorine nonyl trimethoxy silane 15g, full-fluorine octyl sulfuryl fluoride 1g are weighed, pours into container heating water bath to 25
DEG C, 80min is stirred with the speed of 2000r/min, C liquid is made；
Full-fluorine octyl sulfuryl fluoride 0.5g is weighed, is added in 10.5g deionized waters, at 45 DEG C, with the speed of 1500r/min
Degree stirring 40min, is made D liquid；
Then, by above-mentioned C liquid under the stirring of 1500r/min, D is slowly dropped into the speed of 0.1~0.3mL/s
In liquid；After being added dropwise to complete, phosphoric acid is used to adjust solution system pH value as 5~7, then at 25 DEG C, mixing speed 3000r/min
Under the conditions of stir 40min, fluorine alkyl siloxanes lotions is made；
(3) by above-mentioned silane emulsion, mix with fluorine alkyl siloxanes lotion, stirred under 30 DEG C, 1500r/min speed
After 30min；Keep above-mentioned stirring condition, sequentially add Ludox 5g, silicon fluoride modifying titanium dioxide 2.5g be uniformly mixed to get
To Thief zone high durable environment friendly silicon fluorine emulsion.
Example IV：
A kind of Thief zone high durable environment friendly silicon fluorine emulsion of the present embodiment, its step are as follows：
(1) preparation of silane emulsion
Octyl group trimethoxy silane 50g, composite organic emulsifier 1g (Tween40 and each 0.5g of OP13) are weighed, is poured into
Heating water bath stirs 70min with the speed of 1500r/min, A liquid is made to 45 DEG C in container；
It weighs composite organic emulsifier 1g (Tween40 and each 0.5g of OP13) to be added in 13g deionized waters, at 35 DEG C
Under, 70min is stirred with the speed of 1800r/min, B liquid is made；
Then, by above-mentioned A liquid under the stirring of 1000r/min, B is slowly dropped into the speed of 0.1~0.3mL/s
In liquid；After being added dropwise to complete, phosphoric acid is used to adjust solution system pH value as 5~7, then at 35 DEG C, mixing speed 1500r/min
Under the conditions of stir 80min, be made silane emulsion；
(2) preparation of fluorine alkyl siloxanes lotion
It weighs 15 fluorine nonyl triethoxysilane 17g, perfluoroalkyl poly ether phosphate 1g and pours into heating water bath in container
To 40 DEG C, 40min is stirred with the speed of 1000r/min, C liquid is made；
Perfluoroalkyl poly ether phosphate 0.5g is weighed, is added in 10g deionized waters, at 50 DEG C, with 2000r/min's
Speed stirs 30min, and D liquid is made；
Then, by above-mentioned C liquid under the stirring of 2000r/min, D is slowly dropped into the speed of 0.1~0.3mL/s
In liquid；After being added dropwise to complete, phosphoric acid is used to adjust solution system pH value as 5~7, then at 45 DEG C, mixing speed 2000r/min
Under the conditions of stir 30min, fluorine alkyl siloxanes lotions is made；
(3) by above-mentioned silane emulsion, mix with fluorine alkyl siloxanes lotion, stirred under 50 DEG C, 2500r/min speed
After 60min；Keep above-mentioned stirring condition, sequentially add Ludox 3.5g, silicon fluoride modifying titanium dioxide 3g be uniformly mixed to get
To Thief zone high durable environment friendly silicon fluorine emulsion.
Embodiment five：
A kind of Thief zone high durable environment friendly silicon fluorine emulsion of the present embodiment, its step are as follows：
(1) preparation of silane emulsion
Weigh isobutyl triethoxy silane 40g, composite organic emulsifier 1.5g (dodecyl sodium sulfate 1g and NP10
Emulsifier 0.5g), it pours into heating water bath in container and, to 45 DEG C, 40min is stirred with the speed of 2000r/min, A liquid is made；
It weighs composite organic emulsifier 1.5g (dodecyl sodium sulfate 1g and NP10 emulsifier 0.5g) and is added to 20g
In ionized water, at 35 DEG C, 30min is stirred with the speed of 1500r/min, B liquid is made；
Then, by above-mentioned A liquid under the stirring of 1500r/min, B is slowly dropped into the speed of 0.1~0.3mL/s
In liquid；After being added dropwise to complete, phosphoric acid is used to adjust solution system pH value as 5~7, then at 60 DEG C, mixing speed 2200r/min
Under the conditions of stir 90min, be made silane emulsion；
(2) preparation of fluorine alkyl siloxanes lotion
17 fluorine decyl trimethoxy silane 20g, perfluoroalkyl acrylate 1g are weighed, heating water bath in container is poured into and arrives
60 DEG C, 80min is stirred with the speed of 1500r/min, C liquid is made；
Perfluoroalkyl acrylate 0.5g is weighed, is added in 11.5g deionized waters, at 45 DEG C, with 1500r/min's
Speed stirs 30min, and D liquid is made；
Then, by above-mentioned C liquid under the stirring of 1000r/min, D is slowly dropped into the speed of 0.1~0.3mL/s
In liquid；After being added dropwise to complete, phosphoric acid is used to adjust solution system pH value as 5~7, then at 55 DEG C, mixing speed 1500r/min
Under the conditions of stir 50min, fluorine alkyl siloxanes lotions is made；
(3) by above-mentioned silane emulsion, mix with fluorine alkyl siloxanes lotion, stirred under 45 DEG C, 1500r/min speed
After 40min；Above-mentioned stirring condition is kept, sequentially adds Ludox 2.5g, silicon fluoride modifying titanium dioxide 1.5g is uniformly mixed, i.e.,
Obtain Thief zone high durable environment friendly silicon fluorine emulsion.
Embodiment six：
A kind of Thief zone high durable environment friendly silicon fluorine emulsion of the present embodiment, its step are as follows：
(1) preparation of silane emulsion
Weigh octyltri-ethoxysilane 35g, composite organic emulsifier 1.5g (15 breasts of OP10 emulsifiers 1g and peregal
Agent 0.5g), it pours into heating water bath in container and, to 55 DEG C, 60min is stirred with the speed of 2500r/min, A liquid is made；
Weigh composite organic emulsifier 1g (15 emulsifier 0.5g of OP10 emulsifiers 1g and peregal) be added to 20g go from
In sub- water, at 45 DEG C, 40min is stirred with the speed of 2500r/min, B liquid is made；
Then, by above-mentioned A liquid under the stirring of 1500r/min, B is slowly dropped into the speed of 0.1~0.3mL/s
In liquid；After being added dropwise to complete, phosphoric acid is used to adjust solution system pH value as 5~7, then at 50 DEG C, mixing speed 1200r/min
Under the conditions of stir 70min, be made silane emulsion；
(2) preparation of fluorine alkyl siloxanes lotion
17 fluorine decyl triethoxysilane 20g, fluorinated polyether siloxanes 1g are weighed, pour into container heating water bath to 45
DEG C, 70min is stirred with the speed of 1500r/min, C liquid is made；
Fluorinated polyether siloxanes 0.5g is weighed, is added in 16g deionized waters, at 45 DEG C, with the speed of 1500r/min
30min is stirred, D liquid is made；
Then, by above-mentioned C liquid under the stirring of 1200r/min, D is slowly dropped into the speed of 0.1~0.3mL/s
In liquid；After being added dropwise to complete, phosphoric acid is used to adjust solution system pH value as 5~7, then at 55 DEG C, mixing speed 1500r/min
Under the conditions of stir 45min, fluorine alkyl siloxanes lotions is made；
(3) by above-mentioned silane emulsion, mix with fluorine alkyl siloxanes lotion, stirred under 45 DEG C, 1500r/min speed
After 40min；Keep above-mentioned stirring condition, sequentially add Ludox 3g, silicon fluoride modifying titanium dioxide 2g be uniformly mixed to get to
Thief zone high durable environment friendly silicon fluorine emulsion.
Thief zone high durable environment friendly silicon fluorine emulsion made from various embodiments of the present invention, the test result of barrier propterty is such as
Shown in table 1.
The barrier propterty of Thief zone high durable environment friendly silicon fluorine emulsion made from 1 various embodiments of the present invention of table
Claims (9)
1. a kind of Thief zone high durable environment friendly silicon fluorine emulsion, it is characterised in that form and be：30~50wt% of small molecule silane, fluorine
10~20wt% of alkylsiloxane, 0.5~3wt% of silicon fluoride modifying titanium dioxide, 1~3wt% of composite organic emulsifier, contain
0.5~1.5wt% of fluorine surfactant, 3~5wt% of Ludox, surplus are deionized water；Wherein,
The structural formula of the small molecule silane is CnH2n+1-Si(OR1)m-R3-m, wherein, R1For methyl or ethyl, 4≤n≤8,1≤
M≤3, n, m are integer, and R is the saturated alkane that carbon number is 1~6；
The structural formula of the fluorine alkyl siloxanes is：Rf-(CH2)n-Si(OR1)3, wherein, R1For methyl or ethyl, RfFor CmF2m+1
Or C6F5, 0≤n≤3,1≤m≤13, n, m are integer.
2. Thief zone high durable environment friendly silicon fluorine emulsion according to claim 1, it is characterised in that：The silicon fluoride is modified
The grain size of titanium dioxide is 10~100nm.
3. Thief zone high durable environment friendly silicon fluorine emulsion according to claim 1, it is characterised in that：The composite organic
Emulsifier is by alkylphenol polyoxyethylene ether OP series, dodecyl sodium sulfate, Sorbitan acid alcohol aliphatic ester span series, fat
Fat alcohol polyoxyethylene ether peregal series, AEO series, nonylphenol polyoxyethylene ether NP series, sorbitan fatty acid ester gather
At least two kinds compoundings in ethylene oxide ether Tween series are formed.
4. Thief zone high durable environment friendly silicon fluorine emulsion according to claim 1, it is characterised in that：The fluorochemical surface is lived
Property agent is by anionic type fluorocarbon surfactant, cationic fluorocarbon surfactant, amphoteric ion fluorocarbon surfactant, non-
Ionic fluorocarbon surfactant, one kind in siliceous fluorocarbon surfactant or its combination.
5. Thief zone high durable environment friendly silicon fluorine emulsion according to claim 1, it is characterised in that：The Ludox is grain
The Nano-meter SiO_2 of 10~100nm of footpath, concentration 30%2Aqueous dispersions.
6. the preparation method of one of the claim 1-5 Thief zone high durable environment friendly silicon fluorine emulsions, it is characterised in that including
Following steps：
(1) preparation of silane emulsion
By the small molecule silane, it is uniformly mixed with composite organic emulsifier, portions of de-ionized water, obtains silane emulsion；
(2) preparation of fluorine alkyl siloxanes lotion
By the fluorine alkyl siloxanes, it is uniformly mixed with fluorine-containing surfactant, remaining deionized water, obtains fluorine alkyl siloxanes
Lotion；
(3) by the silane emulsion and fluorine alkyl siloxanes lotion after mixing, with Ludox, silicon fluoride modifying titanium dioxide
It is uniformly mixed to get to Thief zone high durable environment friendly silicon fluorine emulsion.
7. the preparation method of Thief zone high durable environment friendly silicon fluorine emulsion according to claim 6, it is characterised in that：It is described
In step (1), the composite organic emulsifier adds in two times, i.e.,：
The composite organic emulsifier of the small molecule silane and 50~70wt%, 30~90min of stirring is mixed at 25~60 DEG C
Close uniform, obtained A liquid；
The remaining composite organic emulsifier is added in the deionized water of 30~70wt%, stir 30 at 25~60 DEG C~
B liquid is made in 90min；
Then, the A liquid is added dropwise under stirring in B liquid, after being added dropwise to complete, it is 5~7 to adjust solution system pH value,
30~90min is stirred under the conditions of 25~60 DEG C, mixing speed is 1000~3000r/min, silane emulsion is made.
8. the preparation method of the Thief zone high durable environment friendly silicon fluorine emulsion according to claim 6 or 7, it is characterised in that：
In the step (2), the fluorine-containing surfactant adds in two times, i.e.,：
By the fluorine alkyl siloxanes, the fluorine-containing surfactant with 50~70wt% stirs 30~90min at 25~60 DEG C
It is uniformly mixed, C liquid is made；
The remaining fluorine-containing surfactant is added in remaining deionized water, and 30~90min is stirred at 25~60 DEG C, is made
D liquid；
Then, the C liquid is added dropwise under stirring in D liquid, after being added dropwise to complete, it is 5~7 to adjust solution system pH value,
30~90min is stirred under the conditions of 25~60 DEG C, mixing speed is 1000~3000r/min, fluorine alkyl siloxanes lotion is made.
9. the preparation method of Thief zone high durable environment friendly silicon fluorine emulsion according to claim 6, it is characterised in that：It is described
In step (3), after the silane emulsion stirs 30~90min with fluorine alkyl siloxanes lotion at 25~60 DEG C, described in holding
Stirring condition sequentially adds Ludox, silicon fluoride modifying titanium dioxide is uniformly mixed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711419999.3A CN108047940B (en) | 2017-12-25 | 2017-12-25 | High-permeability high-weather-resistance environment-friendly type silicon-fluorine emulsion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711419999.3A CN108047940B (en) | 2017-12-25 | 2017-12-25 | High-permeability high-weather-resistance environment-friendly type silicon-fluorine emulsion and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108047940A true CN108047940A (en) | 2018-05-18 |
| CN108047940B CN108047940B (en) | 2020-06-30 |
Family
ID=62131774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711419999.3A Active CN108047940B (en) | 2017-12-25 | 2017-12-25 | High-permeability high-weather-resistance environment-friendly type silicon-fluorine emulsion and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108047940B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109021819A (en) * | 2018-07-03 | 2018-12-18 | 南京米福新材料科技有限公司 | A kind of fluorine silicon resin waterproof draws toner and preparation method thereof |
| CN109082151A (en) * | 2018-05-23 | 2018-12-25 | 南京超润新材料科技有限公司 | A kind of aqueous super-amphiphobic silica solution and its preparation method and application |
| CN111234697A (en) * | 2018-06-26 | 2020-06-05 | 王春林 | Halogen-free flame-retardant silane water-based paint and preparation and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020026881A1 (en) * | 2000-03-03 | 2002-03-07 | Resource Development L.L.C. | Physiologically acceptable and non-corrosive silicone compositions, methods of making and using them to render surfaces water and soil repellent |
| CN102219551A (en) * | 2011-04-27 | 2011-10-19 | 河南省交通科学技术研究院有限公司 | Organic silicon waterproof agent with respiratory function and preparation method thereof |
| CN102585073A (en) * | 2012-01-16 | 2012-07-18 | 中山大学 | Fluorine silicon-modified acrylic ester emulsion and preparation method thereof |
| CN103275616A (en) * | 2013-06-06 | 2013-09-04 | 江苏博特新材料有限公司 | Environment-friendly water-based nano coating material used for concrete protection, and preparation method thereof |
| CN104403374A (en) * | 2014-11-20 | 2015-03-11 | 广州乾程化工科技发展有限公司 | Fluorinated silane modified titanium dioxide nanometer material as well as preparation method and application thereof |
| CN105198274A (en) * | 2015-08-17 | 2015-12-30 | 华南农业大学 | Fluoroalkyl-modified composite organosilicon water-proofing agent and preparing method and application thereof |
-
2017
- 2017-12-25 CN CN201711419999.3A patent/CN108047940B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020026881A1 (en) * | 2000-03-03 | 2002-03-07 | Resource Development L.L.C. | Physiologically acceptable and non-corrosive silicone compositions, methods of making and using them to render surfaces water and soil repellent |
| CN102219551A (en) * | 2011-04-27 | 2011-10-19 | 河南省交通科学技术研究院有限公司 | Organic silicon waterproof agent with respiratory function and preparation method thereof |
| CN102585073A (en) * | 2012-01-16 | 2012-07-18 | 中山大学 | Fluorine silicon-modified acrylic ester emulsion and preparation method thereof |
| CN103275616A (en) * | 2013-06-06 | 2013-09-04 | 江苏博特新材料有限公司 | Environment-friendly water-based nano coating material used for concrete protection, and preparation method thereof |
| CN104403374A (en) * | 2014-11-20 | 2015-03-11 | 广州乾程化工科技发展有限公司 | Fluorinated silane modified titanium dioxide nanometer material as well as preparation method and application thereof |
| CN105198274A (en) * | 2015-08-17 | 2015-12-30 | 华南农业大学 | Fluoroalkyl-modified composite organosilicon water-proofing agent and preparing method and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109082151A (en) * | 2018-05-23 | 2018-12-25 | 南京超润新材料科技有限公司 | A kind of aqueous super-amphiphobic silica solution and its preparation method and application |
| CN111234697A (en) * | 2018-06-26 | 2020-06-05 | 王春林 | Halogen-free flame-retardant silane water-based paint and preparation and application thereof |
| CN111269658A (en) * | 2018-06-26 | 2020-06-12 | 王春林 | Halogen-free flame-retardant silane water-based paint and preparation and application thereof |
| CN111286270A (en) * | 2018-06-26 | 2020-06-16 | 王春林 | Halogen-free flame-retardant silane water-based paint and preparation and application thereof |
| CN111363475A (en) * | 2018-06-26 | 2020-07-03 | 王春林 | Halogen-free flame-retardant silane water-based paint and preparation and application thereof |
| CN109021819A (en) * | 2018-07-03 | 2018-12-18 | 南京米福新材料科技有限公司 | A kind of fluorine silicon resin waterproof draws toner and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108047940B (en) | 2020-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108047940A (en) | A kind of Thief zone high durable environment friendly silicon fluorine emulsion and preparation method thereof | |
| CN108047938A (en) | A kind of high soil resistance fluosilicic lotion and preparation method thereof | |
| CN104403374B (en) | A kind of silicon fluoride modifying titanium dioxide nano material and its preparation method and application | |
| CN103290674B (en) | A kind of processing method and treatment fluid preparing floride-free super-hydrophobic cotton fabric | |
| CN104356792B (en) | Water-based stone nano-protector and preparation method thereof | |
| JP3522424B2 (en) | Aqueous organopolysiloxane-containing composition and method for producing the same | |
| CN106675395B (en) | A kind of building surface permeable organic silicon protective agent and preparation method thereof | |
| CN108864907B (en) | Water-based interior wall coating and preparation method thereof | |
| JP2004502017A (en) | Organosilicon water repellent composition | |
| KR101830289B1 (en) | Aqueous emulsions of alkylalkoxysilanes | |
| CN115043612B (en) | Breathable permeable concrete protective agent and preparation method thereof | |
| CN101805205B (en) | Organic silicon compound liquid for protecting stone material and application method thereof | |
| CN107022080A (en) | A kind of preparation method of novel silicon alkanes plural gel waterproof material | |
| CN106634078B (en) | A kind of nuclear case structure hybridization colloidal sol and its preparation and application with photocatalysis characteristic | |
| CN110183246B (en) | Self-crosslinking alkylalkoxysilane impregnant | |
| KR20180091925A (en) | Coating compositions and methods of treatment | |
| CN107207884A (en) | Weather-proof, antimycotic, anti-coloring pollution coating and the method being applied on timber, masonry material or other porous materials | |
| KR101273757B1 (en) | Fluorocarbon-grafted polysiloxanes | |
| CN106082773A (en) | A kind of ground waterproofing agent of organosilicon and preparation method thereof | |
| CN101422774B (en) | Preparation method of enamel surface coatings with hydrophobic effect | |
| CN106833368A (en) | A kind of preparation method of waterborne organic silicon stone protectant | |
| CN109337493A (en) | A kind of Environment-friendlyinternal internal wall paint and preparation method thereof | |
| CN103571327B (en) | Methyl silicate stone protectant and manufacture method | |
| CN104177126A (en) | Preparation method and application of emulsion type superhydrophobic protective agent for stone | |
| CN108047941A (en) | A kind of Thief zone high durable fluosilicic protective liquid and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |