CN107129557A - A kind of fluorine-containing automatically cleaning polymer and its application in hydrophobic anti-pollution paint - Google Patents
A kind of fluorine-containing automatically cleaning polymer and its application in hydrophobic anti-pollution paint Download PDFInfo
- Publication number
- CN107129557A CN107129557A CN201710265247.XA CN201710265247A CN107129557A CN 107129557 A CN107129557 A CN 107129557A CN 201710265247 A CN201710265247 A CN 201710265247A CN 107129557 A CN107129557 A CN 107129557A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- reaction
- automatically cleaning
- acrylate
- polymer
- 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
- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
-
- 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
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy 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
- C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
-
- 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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
-
- 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
-
- 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
- C09D5/1687—Use of special additives
-
- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Paints Or Removers (AREA)
- Detergent Compositions (AREA)
Abstract
The invention discloses a kind of fluorine-containing automatically cleaning polymer and its application in hydrophobic anti-pollution paint, the preparation method of the fluorine-containing automatically cleaning polymer comprises the following steps：In a solvent, the acrylate containing epoxide group, the acrylate containing siloxane group, the acrylate containing hydroxyl are added, initiator is added, nitrogen is passed through, is reacted, after system becomes sticky, stop reaction, be made containing epoxide group, siloxane group, hydroxyl polymer；In a solvent, add after obtained reaction product, PFPE acyl fluorides and acid binding agent, 12~24h of reaction, fluorine-containing automatically cleaning polymer is made.Each step reaction yield is higher in Inventive polymers preparation process, using the method for simple free radical polyalcohol and radical reaction, technique is simple, introduces epoxide group and improves wearability, the hydrophobic anti-pollution paint that simultaneously prepared by the present invention uses more stable siloxane group, more conducively stores.
Description
Technical field
The invention belongs to self-cleaning coating field, and in particular to a kind of fluorine-containing automatically cleaning polymer and its hydrophobic anti-soil apply
Application in material.
Background technology
In recent years, imitation " lotus leaf effect " prepares the hydrophobic anti-pollution layer of glass base and received significant attention.Hydrophobic anti-pollution layer
It is typically characterised by：Water (liquid) pearl can be quickly rolled off from hydrophobic surface, and the pollutants such as the dust on surface have been taken away while tumbling,
Play the effect of automatically cleaning anti-soil.The application of current touch-screen and building glass is more and more extensive, touch-screen pole in use
Easy fingerprints and greasy dirt, building glass are easier by dust and oil pollution exposed to outdoor, and these glass baseplates are dirty
After dye, usage experience is substantially reduced, and is not easy to cleaning, and especially building glass cleaning difficulty is bigger.Therefore, research prepares one
Kind wearability is good, and hydrophobic performance is excellent, and method is simple, and self-cleaning coating with low cost is significant.
The key for preparing the hydrophobic anti-pollution layer of glass base is the hydro-oleophobicity and wearability for improving coating.Influence is hydrophobic
Two principal elements of oleophobic performance：First, the roughness on surface, second, the surface tension or surface-element of material surface
Composition, and material surface chemical constitution.Based on the two factors, there are three kinds to preparing glass primary surface anti-pollution layer at present
Method.First, it is combined coarse structure in glass surface construction Nano/micron.Second, with the material modification glass of low-surface-energy
Glass surface.3rd, two methods are combined, first using the material modification micro-and nano-particles of low-surface-energy, first method
With the third method due to introducing micro-and nano-particles, surface roughness is considerably increased, hydrophobic properties of the surface are greatly improved,
It even can reach super-hydrophobic, wear-resisting sex chromosome mosaicism can not be solved, so laboratory stage is rested on mostly, though second method
A part of hydrophobic effect is so sacrificed, but the material and glass substrate surface formation chemical bond by low-surface-energy are so as to significantly
Wearability is improved, while this method and because cost is low, construction method is simple, therefore, application is widely used.
PFPE is at normal temperatures the transparent oily liquids of colorless and odorless.It is instead of in PFPE molecule with fluorine atom
Hydrogen atom.The electronegativity of fluorine atom is bigger than the electronegativity of hydrogen atom so that intermolecular attraction is smaller, carbon skeleton outer layer row
Row are even closer, and then can effectively prevent the exposure of carbon atom and carbochain, therefore with smaller surface tension, compared to it
His fluorine-containing material, perfluoropolyether segment has more preferable compliance, and the automatic cleaning coating prepared using PFPE has lower
Coefficient of friction, effect is more smooth and wear-resisting.Therefore self-cleaning coating is prepared using PFPE using quite varied.
Such as current Daikin company prepares glass using alkoxysilane-modified functionalized perfluoropolyethers (PFPE)
The hydrophobic anti-pollution paint of glass base.Dakin and Dow corning companies are prepared for PFPE alkylsiloxane by Si―H addition reaction and dredged
Water anti-pollution paint.Only have one end to carry on a silicon atom, the silicon atom in above-mentioned hydrophobic anti-pollution paint molecule and be connected to silicon
Oxyalkyl group.Other hydrophobic anti-pollution paints are also mostly using such structure on the market.
Existing self-cleaning coating preparation process is complicated, and each step reaction yield is not high.The hydrophobic anti-soil prepared is applied
On the one hand siloxy group easily hydrolyzes in the strand of material, is unfavorable for storage, another aspect quantity is on the low side, cause individual molecule and
The chemical bonding site that glass surface occurs is less, therefore wearability is not enough.
The content of the invention
In order to overcome existing self-cleaning coating wearability not enough, preparation method is complicated, and the high shortcoming of cost is of the invention
Primary and foremost purpose is to provide a kind of fluorine-containing automatically cleaning polymer, be using free-radical polymerized method be made containing siloxy group,
The copolymer of epoxide group, hydroxyl, then adds fluorine-containing material, and wearability and the good glass base automatically cleaning of hydrophobic performance is made
Polymer.
Another object of the present invention is to provide application of the above-mentioned fluorine-containing automatically cleaning polymer in hydrophobic anti-pollution paint.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of fluorine-containing automatically cleaning polymer, comprises the following steps：
(1) in a solvent, the acrylate containing epoxide group, the acrylate containing siloxane group are added, is contained
The acrylate of hydroxyl, adds initiator, is passed through nitrogen, is reacted, after system becomes sticky, stop reaction, be made containing
Epoxide group, siloxane group, the polymer of hydroxyl；
(2) in a solvent, add after reaction product, PFPE acyl fluorides and the acid binding agent of step (1), 12~24h of reaction,
Fluorine-containing automatically cleaning polymer is made.
The preferred butanone of described solvent, benzotrifluoride, ethyl acetate, tetrahydrofuran, chloroform, 1,1,2 trichorotrifluoroethanes
At least one of or the electronics fluorination liquids of 3M Novec 7200.
Acrylate containing epoxide group described in step (1) has following general structure：
R is carbon number 1-10 alkyl；
The acrylate containing siloxane group has following general structure：
R is carbon number 1-10 alkyl；
The acrylate containing hydroxyl has following general structure：
R is carbon number 1-10 alkyl.
The preferred azo-initiator of initiator described in step (1), particularly preferred AIBN (azodiisobutyronitrile) or azo
Two different heptonitriles (ABVN)；
The duration for being passed through nitrogen is no less than 0.5 hour；It is preferred that 0.5~1 hour；
The reaction of step (1) is carried out at 70~80 DEG C；
The acrylate containing epoxide group described in step (1), the acrylate containing siloxane group are with containing
The mol ratio of the acrylate of hydroxyl is 1:(2-5):(2-4), preferably 1:2:2.
PFPE acyl fluorides described in step (2) has following general structure：
N is 3-15, preferably 8；
In step (2), the mol ratio of the reaction product of step (1), PFPE acyl fluorides and acid binding agent is 1.0:(0.4-
0.5):(0.4-0.5), preferably 1.0:0.4:0.4；
Reaction described in step (2) is carried out at -20~20 DEG C；Preferably 0 DEG C of reaction temperature.
Fluorine-containing automatically cleaning polymer can be used for preparing hydrophobic anti-pollution paint as made from the above method.Specifically
Catalyst and crosslinking agent are added in fluorine-containing automatically cleaning polymer, is mixed, hydrophobic anti-pollution paint is made.
The preferred enclosed type sulfonic acid catalyst of described catalyst, particularly preferred U.S. Jin Shi catalyst K-Pure CXC-
1614；The consumption of catalyst accounts for the 0.1-0.5% of hydrophobic anti-pollution paint quality, preferably accounts for 0.2%.
The preferred diethylenetriamine of described crosslinking agent, phthalic anhydride, hexahydrophthalic acid anhydride or methyl hexahydrobenzene two
Formic anhydride, particularly preferred methyl hexahydrophthalic acid anhydride；The consumption of crosslinking agent accounts for the 1-10% of hydrophobic anti-pollution paint quality, preferably
Account for 5%.
In use, by above-mentioned hydrophobic anti-pollution paint dissolving in a solvent, being sprayed on glass substrate surface, being in temperature
A period of time is toasted under 120~150 DEG C (being preferably 150 DEG C)；
In the solvent, the mass fraction in hydrophobic anti-pollution paint is 0.5~1%, preferably 0.5%.
The present invention has the following advantages and effect relative to prior art：
1st, in the structure of fluorine-containing automatically cleaning polymer of the invention, on the one hand the acrylate of hydroxyl participates in film forming, another
Aspect provides binding site to PFPE acyl fluorides, and hydroxyl and acyl fluorides radical reaction activity very well, substantially increase perfluor and gathered
The grafting rate of ether, and the content of fluorine can be adjusted by the content for the acrylate for adjusting hydroxyl；Epoxide group draws
Enter one side film-forming, can also equally improve the adhesive property with base material；Silica in the acrylate of silicone-containing base
Silanol is formed after alkyl group hydrolysis, wearability can be further improved with glass surface formation chemical bond.
2nd, have compared to other automatic cleaning coating materials, on fluorine-containing automatically cleaning polymer molecular chain prepared by the present invention multiple
Siloxane group, multiple epoxide groups, the hydrophobic anti-pollution layer of formation and the cohesive force of substrate surface are stronger, and anti-wear performance is more
Plus it is excellent, while the coating production high conversion rate that the present invention is provided, technique is simple, it is with low cost.The silicon that the present invention is used
Oxygen alkane coupling agent is more stablized, and is easy to storage.
3rd, each step reaction yield is higher in Inventive polymers preparation process, using simple free radical polyalcohol and base
The method of group's reaction, technique is simple, introduces epoxide group and improves wearability, while hydrophobic anti-pollution paint prepared by the present invention
Using more stable siloxane group, more conducively store.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
A kind of fluorine-containing automatically cleaning polymer, is made by following steps：
(1) raw material is prepared by following molfraction：40 parts of hydroxyethyl methacrylates, 30 parts of 3- [three (1- methylethoxies
Base) silicon substrate] propyl methacrylate (IPSMA), 10 parts of GMAs, 1% initiator A IBN；
The structural formula of hydroxyethyl methacrylate is as follows：
The structural formula of 3- [three (1- methyl ethoxies) silicon substrates] propyl methacrylate (IPSMA) is as follows：
The structural formula of GMA is as follows：
(2) above-mentioned reactant is put into reaction bulb, with benzotrifluoride, ethyl acetate, tetrahydrofuran, chloroform, 1,1,2 three
At least one of chloro-trifluoro-ethane or the electronics fluorination liquids of 3M Novec TM HFE 7200, butanone are solvent, are passed through nitrogen, drum
30min is steeped, reaction bulb is sealed with stop-leak compound, in 75 DEG C of oil bath stirring reaction 12h, system becomes sticky, terminating reaction；Rotary evaporation
Solvent is removed, is then slowly added drop-wise to polymer in methanol solution, polymer forms precipitation in methanol solution, so repeatedly
Several times, then obtained polymer samples are placed in 25 DEG C of vacuum drying chamber and are dried in vacuo 5h.Obtain the ternary trackless
Copolymer, yield is more than 95%.
(3) with 1,1,2 trichorotrifluoroethane is solvent, first throws above-mentioned 80 parts of ternary trackless copolymers and 40 parts of triethylamines
Enter in reaction bulb, in the ice bath that reaction bulb is placed in 0 DEG C, the PFPE acyl fluorides that 40 parts of n values are 8 is slowly added dropwise into reaction bulb
Sealed after solution, completion of dropping with stop-leak compound after reaction bulb, reaction 18h, terminating reaction.After reaction terminating, first by reaction solution from
The heart, removes solid impurity, takes to be hanged supernatant liquor and does, precipitation among methanol is then slowly added drop-wise to, so repeatedly in first
Precipitated in alcohol several times, (appropriate sodium acid carbonate auxiliary adjustment pH can also be added until showing neutrality after lower sediment dissolving
Value), the lower sediment being collected into dissolving is added into anhydrous sodium sulfate dried overnight.Most rear overhang is dry to obtain fluorine-containing automatically cleaning polymerization
Thing.The conversion ratio of step reaction is 99%.Described number is molfraction.
Above-mentioned fluorine-containing automatically cleaning polymer is used to prepare hydrophobic anti-pollution paint, according to the mass fraction, fluorine-containing by 94.8 parts
Automatically cleaning polymer, 5 parts of crosslinking agent methyl hexahydrophthalic acid anhydrides and 0.2 part of catalyst K-Pure CXC-1614 mixing, are made
Automatic cleaning coating material.
In use, above-mentioned automatic cleaning coating material is dissolved in solvent, mass concentration is 0.5%,；It is sprayed on glass
Substrate surface, a period of time is toasted in the case where temperature is 150 DEG C.
Embodiment 2
A kind of fluorine-containing automatically cleaning polymer, is made by following steps：
(1) raw material is prepared by following molfraction：40 parts of hydroxyethyl methacrylates, 40 parts of 3- [three (1- methylethoxies
Base) silicon substrate] propyl methacrylate (IPSMA), 10 parts of GMAs, 1% initiator A IBN；
(2) above-mentioned reactant is put into reaction bulb, with benzotrifluoride, ethyl acetate, tetrahydrofuran, chloroform, 1,1,2 three
At least one of chloro-trifluoro-ethane or the electronics fluorination liquids of 3M Novec TM HFE 7200, butanone are solvent, are passed through nitrogen, drum
30min is steeped, reaction bulb is sealed with stop-leak compound, in 75 DEG C of oil bath stirring reaction 12h, system becomes sticky, terminating reaction；Rotary evaporation
Solvent is removed, is then slowly added drop-wise to polymer in methanol solution, polymer forms precipitation in methanol solution, so repeatedly
Several times, then obtained polymer samples are placed in 25 DEG C of vacuum drying chamber and are dried in vacuo 5h.Obtain the ternary trackless
Copolymer, yield is more than 95%.
(3) with 1,1,2 trichorotrifluoroethane is solvent, first throws above-mentioned 90 parts of ternary trackless copolymers and 40 parts of triethylamines
Enter in reaction bulb, in the ice bath that reaction bulb is placed in 0 DEG C, the PFPE acyl fluorides that 40 parts of n values are 8 is slowly added dropwise into reaction bulb
Sealed after solution, completion of dropping with stop-leak compound after reaction bulb, reaction 18h, terminating reaction.After reaction terminating, first by reaction solution from
The heart, removes solid impurity, takes to be hanged supernatant liquor and does, precipitation among methanol is then slowly added drop-wise to, so repeatedly in first
Precipitated in alcohol several times, (appropriate sodium acid carbonate auxiliary adjustment pH can also be added until showing neutrality after lower sediment dissolving
Value), the lower sediment being collected into dissolving is added into anhydrous sodium sulfate dried overnight.Most rear overhang is dry to obtain fluorine-containing automatically cleaning polymerization
Thing.The conversion ratio of step reaction is 99%.Described number is molfraction.
Above-mentioned fluorine-containing automatically cleaning polymer is used to prepare hydrophobic anti-pollution paint, according to the mass fraction, fluorine-containing by 94.8 parts
Automatically cleaning polymer, 5 parts of crosslinking agent methyl hexahydrophthalic acid anhydrides and 0.2 part of catalyst K-Pure CXC-1614 mixing, are made
Automatic cleaning coating material.
In use, above-mentioned automatic cleaning coating material is dissolved in solvent, mass concentration is 0.5%,；It is sprayed on glass
Substrate surface, a period of time is toasted in the case where temperature is 150 DEG C.
Embodiment 3
A kind of fluorine-containing automatically cleaning polymer, is made by following steps：
(1) raw material is prepared by following molfraction：40 parts of hydroxyethyl methacrylates, 50 parts of 3- [three (1- methylethoxies
Base) silicon substrate] propyl methacrylate (IPSMA), 10 parts of GMAs, 1% initiator A IBN；
(2) above-mentioned reactant is put into reaction bulb, with benzotrifluoride, ethyl acetate, tetrahydrofuran, chloroform, 1,1,2 three
At least one of chloro-trifluoro-ethane or the electronics fluorination liquids of 3M Novec TM HFE 7200, butanone are solvent, are passed through nitrogen, drum
30min is steeped, reaction bulb is sealed with stop-leak compound, in 75 DEG C of oil bath stirring reaction 12h, system becomes sticky, terminating reaction；Rotary evaporation
Solvent is removed, is then slowly added drop-wise to polymer in methanol solution, polymer forms precipitation in methanol solution, so repeatedly
Several times, then obtained polymer samples are placed in 25 DEG C of vacuum drying chamber and are dried in vacuo 5h.Obtain the ternary trackless
Copolymer, yield is more than 95%.
(3) with 1,1,2 trichorotrifluoroethane is solvent, first by above-mentioned 100 parts of ternary trackless copolymers and 40 parts of triethylamines
Put into reaction bulb, in the ice bath that reaction bulb is placed in 0 DEG C, the PFPE acyl that 40 parts of n values are 8 is slowly added dropwise into reaction bulb
Sealed after fluorine solution, completion of dropping with stop-leak compound after reaction bulb, reaction 18h, terminating reaction.After reaction terminating, first by reaction solution
Centrifugation, removes solid impurity, takes to be hanged supernatant liquor and does, is then slowly added drop-wise to precipitation among methanol, so exists repeatedly
Precipitated in methanol several times, (appropriate sodium acid carbonate auxiliary adjustment can also be added until showing neutrality after lower sediment dissolving
PH value), the lower sediment being collected into dissolving is added into anhydrous sodium sulfate dried overnight.Dry most rear overhang is to obtain fluorine-containing automatically cleaning to gather
Compound.The conversion ratio of step reaction is 99%.Described number is molfraction.
Above-mentioned fluorine-containing automatically cleaning polymer is used to prepare hydrophobic anti-pollution paint, according to the mass fraction, fluorine-containing by 94.8 parts
Automatically cleaning polymer, 5 parts of crosslinking agent methyl hexahydrophthalic acid anhydrides and 0.2 part of catalyst K-Pure CXC-1614 mixing, are made
Automatic cleaning coating material.
In use, above-mentioned automatic cleaning coating material is dissolved in solvent, mass concentration is 0.5%,；It is sprayed on glass
Substrate surface, a period of time is toasted in the case where temperature is 150 DEG C.
Embodiment 4
A kind of fluorine-containing automatically cleaning polymer, is made by following steps：
(1) raw material is prepared by following molfraction：40 parts of hydroxyethyl methacrylates, 40 parts of 3- [three (1- methylethoxies
Base) silicon substrate] propyl methacrylate (IPSMA), 20 parts of GMAs, 1% initiator A IBN；
(2) above-mentioned reactant is put into reaction bulb, with benzotrifluoride, ethyl acetate, tetrahydrofuran, chloroform, 1,1,2 three
At least one of chloro-trifluoro-ethane or the electronics fluorination liquids of 3M Novec TM HFE 7200, butanone are solvent, are passed through nitrogen, drum
30min is steeped, reaction bulb is sealed with stop-leak compound, in 75 DEG C of oil bath stirring reaction 12h, system becomes sticky, terminating reaction；Rotary evaporation
Solvent is removed, is then slowly added drop-wise to polymer in methanol solution, polymer forms precipitation in methanol solution, so repeatedly
Several times, then obtained polymer samples are placed in 25 DEG C of vacuum drying chamber and are dried in vacuo 5h.Obtain the ternary trackless
Copolymer, yield is more than 95%.
(3) with 1,1,2 trichorotrifluoroethane is solvent, first by above-mentioned 100 parts of ternary trackless copolymers and 40 parts of triethylamines
Put into reaction bulb, in the ice bath that reaction bulb is placed in 0 DEG C, the PFPE acyl that 40 parts of n values are 8 is slowly added dropwise into reaction bulb
Sealed after fluorine solution, completion of dropping with stop-leak compound after reaction bulb, reaction 18h, terminating reaction.After reaction terminating, first by reaction solution
Centrifugation, removes solid impurity, takes to be hanged supernatant liquor and does, is then slowly added drop-wise to precipitation among methanol, so exists repeatedly
Precipitated in methanol several times, (appropriate sodium acid carbonate auxiliary adjustment can also be added until showing neutrality after lower sediment dissolving
PH value), the lower sediment being collected into dissolving is added into anhydrous sodium sulfate dried overnight.Dry most rear overhang is to obtain fluorine-containing automatically cleaning to gather
Compound.The conversion ratio of step reaction is 99%.Described number is molfraction.
Above-mentioned fluorine-containing automatically cleaning polymer is used to prepare hydrophobic anti-pollution paint, according to the mass fraction, fluorine-containing by 94.8 parts
Automatically cleaning polymer, 5 parts of crosslinking agent methyl hexahydrophthalic acid anhydrides and 0.2 part of catalyst K-Pure CXC-1614 mixing, are made
Automatic cleaning coating material.
In use, above-mentioned automatic cleaning coating material is dissolved in solvent, mass concentration is 0.5%,；It is sprayed on glass
Substrate surface, a period of time is toasted in the case where temperature is 150 DEG C.
Embodiment 5
A kind of fluorine-containing automatically cleaning polymer, is made by following steps：
(1) raw material is prepared by following molfraction：40 parts of hydroxyethyl methacrylates, 40 parts of 3- [three (1- methylethoxies
Base) silicon substrate] propyl methacrylate (IPSMA), 10 parts of GMAs, 1% initiator A IBN；
(2) above-mentioned reactant is put into reaction bulb, with benzotrifluoride, ethyl acetate, tetrahydrofuran, chloroform, 1,1,2 three
At least one of chloro-trifluoro-ethane or the electronics fluorination liquids of 3M Novec TM HFE 7200, butanone are solvent, are passed through nitrogen, drum
30min is steeped, reaction bulb is sealed with stop-leak compound, in 75 DEG C of oil bath stirring reaction 12h, system becomes sticky, terminating reaction；Rotary evaporation
Solvent is removed, is then slowly added drop-wise to polymer in methanol solution, polymer forms precipitation in methanol solution, so repeatedly
Several times, then obtained polymer samples are placed in 25 DEG C of vacuum drying chamber and are dried in vacuo 5h.Obtain the ternary trackless
Copolymer, yield is more than 95%.
(3) with 1,1,2 trichorotrifluoroethane is solvent, first throws above-mentioned 90 parts of ternary trackless copolymers and 40 parts of triethylamines
Enter in reaction bulb, in the ice bath that reaction bulb is placed in 0 DEG C, the PFPE acyl fluorides that 40 parts of n values are 8 is slowly added dropwise into reaction bulb
Sealed after solution, completion of dropping with stop-leak compound after reaction bulb, reaction 18h, terminating reaction.After reaction terminating, first by reaction solution from
The heart, removes solid impurity, takes to be hanged supernatant liquor and does, precipitation among methanol is then slowly added drop-wise to, so repeatedly in first
Precipitated in alcohol several times, (appropriate sodium acid carbonate auxiliary adjustment pH can also be added until showing neutrality after lower sediment dissolving
Value), the lower sediment being collected into dissolving is added into anhydrous sodium sulfate dried overnight.Most rear overhang is dry to obtain fluorine-containing automatically cleaning polymerization
Thing.The conversion ratio of step reaction is 99%.Described number is molfraction.
Above-mentioned fluorine-containing automatically cleaning polymer is used to prepare hydrophobic anti-pollution paint, according to the mass fraction, fluorine-containing by 89.8 parts
Automatically cleaning polymer, 10 parts of crosslinking agent methyl hexahydrophthalic acid anhydrides and 0.2 part of catalyst K-Pure CXC-1614 mixing, system
Derived from cleaning coating material.
In use, above-mentioned automatic cleaning coating material is dissolved in solvent, mass concentration is 0.5%,；It is sprayed on glass
Substrate surface, a period of time is toasted in the case where temperature is 150 DEG C.
Coating constructed by the five kinds of hydrophobic anti-pollution paints obtained to embodiment 1~5 carries out contact angle test and wear-resisting survey
Examination
Hydrophobicity is tested
The hydrophobicity of coating is determined using JC2000D2 types contact angle tester.Using distilled water as probe liquid, drop amount is big
Small is 5 μ L, determines the Static water contact angles (water contact angle, abbreviation WCA) of coating surface, and same sample determines 3
Individual diverse location, averages.
Wearability test
Using the NM-1 abrasion wear test machines of Shanghai Pu Shen chemical machineries Co., Ltd, glass to be tested is fixed on experiment
On the testing stand of machine.Using steel wool as friction medium, reciprocating friction stroke 10cm loads 1kg.Rub after different number of times
Water contact angle it is as shown in the table.
The coating abrasion performance constructed by coating obtained in five embodiments is relatively good, wherein the hydrophobicity of embodiment 4
Can be optimal, while wearability is also relatively good, relatively good hydrophobic performance still can be kept after being rubbed by 5000 times.Therefore,
When GMA, hydroxyethyl methacrylate, 3- [three (1- methyl ethoxies) silicon substrates] propyl methyl
Acid esters (IPSMA) mole be 1:2:2, the mass fraction of crosslinking agent methyl hexahydrophthalic acid anhydride is in hydrophobic anti-pollution paint
Prepared hydrophobic anti-pollution paint wearability and hydrophobic when 5%, catalyst K-Pure CXC-1614 mass fraction are 0.2%
Performance is optimal.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of fluorine-containing automatically cleaning polymer, it is characterised in that comprise the following steps：
(1) in a solvent, the acrylate containing epoxide group, the acrylate containing siloxane group are added, contains hydroxyl
Acrylate, add initiator, be passed through nitrogen, reacted, after system becomes sticky, stop reaction, be made containing epoxy
Group, siloxane group, the polymer of hydroxyl；
(2) in a solvent, add after reaction product, PFPE acyl fluorides and the acid binding agent of step (1), 12~24h of reaction, be made
Fluorine-containing automatically cleaning polymer；
The acrylate containing epoxide group described in step (1), the acrylate containing siloxane group are with containing hydroxyl
Acrylate mol ratio be 1:(2-5):(2-4)；
In step (2), the mol ratio of the reaction product of the step (1), PFPE acyl fluorides and acid binding agent is 1.0:(0.4-
0.5):(0.4-0.5)。
2. preparation method according to claim 1, it is characterised in that：The acrylate containing epoxide group has such as
Lower general structure：
R is carbon number 1-10 alkyl.
3. preparation method according to claim 1, it is characterised in that：The acrylate containing siloxane group has
Following general structure：
R is carbon number 1-10 alkyl.
4. preparation method according to claim 1, it is characterised in that：The acrylate containing hydroxyl has following knot
Structure formula：
R is carbon number 1-10 alkyl.
5. preparation method according to claim 1, it is characterised in that：Initiator described in step (1) triggers for azo
Agent.
6. preparation method according to claim 1, it is characterised in that：
The reaction of step (1) is carried out at 70~80 DEG C；
Reaction described in step (2) is carried out at -20~20 DEG C.
7. a kind of fluorine-containing automatically cleaning polymer, it is characterised in that：It is to be made as the method described in claim any one of 1-6.
8. application of the fluorine-containing automatically cleaning polymer in hydrophobic anti-pollution paint is prepared described in claim 7.
9. application according to claim 8, it is characterised in that：It is that catalyst and friendship are added in fluorine-containing automatically cleaning polymer
Join agent, mix, hydrophobic anti-pollution paint is made；
The consumption of catalyst accounts for the 0.1-0.5% of hydrophobic anti-pollution paint quality；
The consumption of crosslinking agent accounts for the 1-10% of hydrophobic anti-pollution paint quality.
10. application according to claim 9, it is characterised in that：
Described catalyst is enclosed type sulfonic acid catalyst；
Described crosslinking agent is diethylenetriamine, phthalic anhydride, hexahydrophthalic acid anhydride or methyl hexahydrophthalic acid anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710265247.XA CN107129557B (en) | 2017-04-21 | 2017-04-21 | A kind of fluorine-containing automatically cleaning polymer and its application in hydrophobic anti-pollution paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710265247.XA CN107129557B (en) | 2017-04-21 | 2017-04-21 | A kind of fluorine-containing automatically cleaning polymer and its application in hydrophobic anti-pollution paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107129557A true CN107129557A (en) | 2017-09-05 |
| CN107129557B CN107129557B (en) | 2019-03-22 |
Family
ID=59715284
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710265247.XA Active CN107129557B (en) | 2017-04-21 | 2017-04-21 | A kind of fluorine-containing automatically cleaning polymer and its application in hydrophobic anti-pollution paint |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107129557B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112159506A (en) * | 2020-08-19 | 2021-01-01 | 浙江巨化技术中心有限公司 | Preparation method of multi-anchor brush-shaped perfluoropolyether anti-fingerprint agent |
| CN113583231A (en) * | 2021-07-09 | 2021-11-02 | 东华大学 | Preparation method of perfluoropolyether siloxane compound and fingerprint resisting agent |
| CN116217916A (en) * | 2023-02-07 | 2023-06-06 | 湖南天氟新材料有限公司 | Y-type perfluoropolyether modified acrylic ester, antifouling paint, preparation method and application |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09143274A (en) * | 1995-11-27 | 1997-06-03 | Kao Corp | New fluorine-containing polyether |
| WO2005123646A2 (en) * | 2004-06-17 | 2005-12-29 | Surface Secure Limited | Fluoroorganic compounds and anti-fouling treatments |
| CN1914183A (en) * | 2004-01-30 | 2007-02-14 | 3M创新有限公司 | Perfluoropolyether benzotriazole derivatives and use thereof as coatings |
| CN101824274A (en) * | 2010-05-14 | 2010-09-08 | 上海长悦涂料有限公司 | UV (Ultraviolet) curing type anti-contamination paint |
| CN103642382A (en) * | 2013-11-25 | 2014-03-19 | 中国科学院长春应用化学研究所 | Ultraviolet light curing anti-fouling paint and preparation method thereof |
| CN104876823A (en) * | 2015-05-05 | 2015-09-02 | 湖南晟通纳米新材料有限公司 | Synthetic method of polymerizable total-fluorine polyether monomer |
| CN105693949A (en) * | 2016-03-25 | 2016-06-22 | 中科院广州化学有限公司南雄材料生产基地 | Fluorine-containing anti-fingerprint oil polymer and preparation thereof, and application of polymer in field of super-amphiphobic materials |
| CN105694646A (en) * | 2016-03-15 | 2016-06-22 | 衢州氟硅技术研究院 | Fluorine-containing composition for surface treatment of porous base material |
| CN105778693A (en) * | 2016-03-10 | 2016-07-20 | 中科院广州化学有限公司南雄材料生产基地 | Self-cleaning coating material polymer and preparation method and application thereof |
| CN105801797A (en) * | 2016-03-25 | 2016-07-27 | 中科院广州化学有限公司南雄材料生产基地 | Fluorine-containing super-hydrophobic self-cleaning anti-fouling coating and preparation method and application thereof |
| CN106565944A (en) * | 2016-06-08 | 2017-04-19 | 中国石油化工股份有限公司 | Fluorine-containing hydrophobic coating and preparation and application thereof |
-
2017
- 2017-04-21 CN CN201710265247.XA patent/CN107129557B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09143274A (en) * | 1995-11-27 | 1997-06-03 | Kao Corp | New fluorine-containing polyether |
| CN1914183A (en) * | 2004-01-30 | 2007-02-14 | 3M创新有限公司 | Perfluoropolyether benzotriazole derivatives and use thereof as coatings |
| WO2005123646A2 (en) * | 2004-06-17 | 2005-12-29 | Surface Secure Limited | Fluoroorganic compounds and anti-fouling treatments |
| CN101824274A (en) * | 2010-05-14 | 2010-09-08 | 上海长悦涂料有限公司 | UV (Ultraviolet) curing type anti-contamination paint |
| CN103642382A (en) * | 2013-11-25 | 2014-03-19 | 中国科学院长春应用化学研究所 | Ultraviolet light curing anti-fouling paint and preparation method thereof |
| CN104876823A (en) * | 2015-05-05 | 2015-09-02 | 湖南晟通纳米新材料有限公司 | Synthetic method of polymerizable total-fluorine polyether monomer |
| CN105778693A (en) * | 2016-03-10 | 2016-07-20 | 中科院广州化学有限公司南雄材料生产基地 | Self-cleaning coating material polymer and preparation method and application thereof |
| CN105694646A (en) * | 2016-03-15 | 2016-06-22 | 衢州氟硅技术研究院 | Fluorine-containing composition for surface treatment of porous base material |
| CN105693949A (en) * | 2016-03-25 | 2016-06-22 | 中科院广州化学有限公司南雄材料生产基地 | Fluorine-containing anti-fingerprint oil polymer and preparation thereof, and application of polymer in field of super-amphiphobic materials |
| CN105801797A (en) * | 2016-03-25 | 2016-07-27 | 中科院广州化学有限公司南雄材料生产基地 | Fluorine-containing super-hydrophobic self-cleaning anti-fouling coating and preparation method and application thereof |
| CN106565944A (en) * | 2016-06-08 | 2017-04-19 | 中国石油化工股份有限公司 | Fluorine-containing hydrophobic coating and preparation and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112159506A (en) * | 2020-08-19 | 2021-01-01 | 浙江巨化技术中心有限公司 | Preparation method of multi-anchor brush-shaped perfluoropolyether anti-fingerprint agent |
| CN112159506B (en) * | 2020-08-19 | 2023-01-10 | 浙江巨化技术中心有限公司 | Preparation method of multi-anchor brush-shaped perfluoropolyether anti-fingerprint agent |
| CN113583231A (en) * | 2021-07-09 | 2021-11-02 | 东华大学 | Preparation method of perfluoropolyether siloxane compound and fingerprint resisting agent |
| CN116217916A (en) * | 2023-02-07 | 2023-06-06 | 湖南天氟新材料有限公司 | Y-type perfluoropolyether modified acrylic ester, antifouling paint, preparation method and application |
| CN116217916B (en) * | 2023-02-07 | 2023-09-05 | 湖南天氟新材料有限公司 | Y-type perfluoropolyether modified acrylic ester, antifouling paint, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107129557B (en) | 2019-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101875707B (en) | Fluorin-containing POSS acrylate polymer, preparation method thereof and paint | |
| KR940004199B1 (en) | Oil and water repellent coating compositions | |
| CN105331259B (en) | Fluorochemical surface treating agent and the product handled with it | |
| EP2641944B1 (en) | Fluorine-based surface treating agent for vapor deposition and article finished with the surface treating agent by vapor deposition | |
| CN102993782B (en) | Preparation method of polyurethane acrylate oligomer surface modified silica | |
| CN105693949B (en) | Fluorine-containing anti-fingerprint oil polymer and preparation and the application in super-amphiphobic material field | |
| CN107129557B (en) | A kind of fluorine-containing automatically cleaning polymer and its application in hydrophobic anti-pollution paint | |
| CN113788942B (en) | Preparation method of perfluoropolyether siloxane product and application of perfluoropolyether siloxane product in super-hydrophobic anti-fingerprint coating | |
| CN111944087B (en) | Fluorosilicone hybrid water-based acrylate emulsion and preparation method and application thereof | |
| CN106497302B (en) | Photocatalytic self-cleaning parents' network marine anti-pollution coating and preparation method thereof | |
| CN111057231B (en) | High-wear-resistance perfluoropolyether type fingerprint-resistant agent and preparation method thereof | |
| CN102977291A (en) | Cross-linkable fluorine-containing polymer, and its application in preparation of super-amphiphobic surfaces | |
| CN105778693A (en) | Self-cleaning coating material polymer and preparation method and application thereof | |
| EP3715399A1 (en) | Fluoropolyether-group-containing polymer, surface treatment agent, and article | |
| CN103724558A (en) | Inorganic/organic fluorine-containing microspheres with strawberry-shaped structures as well as preparation method and application thereof | |
| CN102964546A (en) | Water-dispersible ultraviolet crosslinking fluorine-containing polymer and application thereof | |
| CN106752233B (en) | A kind of UV solidification multifunctional anti-soil agent | |
| Ling et al. | Synthesis, modification and characterization of core–shell fluoroacrylate copolymer latexes | |
| CN103665280A (en) | Multifunctional fluorine-containing microsphere as well as preparation method and application thereof | |
| CN103601891B (en) | A kind of crosslinkable fluorine silicon resin and preparation thereof and application on super two thin material | |
| CN102199263B (en) | Amphiphobic fluoro-containing crosslinkable block copolymer and preparation method and application thereof | |
| TWI644942B (en) | Surface treatment agent | |
| CN105801797A (en) | Fluorine-containing super-hydrophobic self-cleaning anti-fouling coating and preparation method and application thereof | |
| CN113912834B (en) | Preparation method of perfluoropolyether siloxane product and application of perfluoropolyether siloxane product in anti-fingerprint coating and anti-fingerprint coating | |
| WO2022062288A1 (en) | Aniline anhydride, preparation method therefor, and polyaminoacid graft chain |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200617 Address after: 512400 No.3 comprehensive building, Ping'an 1st Road, industrial transfer park, Dalingshan (Nanxiong), Dongguan, Nanxiong City, Shaoguan City, Guangdong Province Co-patentee after: CAS GUANGZHOU CHEMISTRY Co.,Ltd. Patentee after: Guoke Guanghua (Nanxiong) New Materials Research Institute Co.,Ltd. Address before: 512400 Guangdong city of Shaoguan province Nanxiong City Abas Industrial Park (Guangdong Nanxiong fine chemical base) Co-patentee before: CAS GUANGZHOU CHEMISTRY Co.,Ltd. Patentee before: NANXIONG MATERIAL PRODUCTION BASE OF CHINESE ACADEMY OF SCIENCES GUANGZHOU CHEMICAL Co.,Ltd. |
|
| TR01 | Transfer of patent right |