CN105462425A - Fluorocarbon paint high in fluorine content and preparation method thereof - Google Patents
Fluorocarbon paint high in fluorine content and preparation method thereof Download PDFInfo
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- CN105462425A CN105462425A CN201511031651.8A CN201511031651A CN105462425A CN 105462425 A CN105462425 A CN 105462425A CN 201511031651 A CN201511031651 A CN 201511031651A CN 105462425 A CN105462425 A CN 105462425A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
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- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
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Abstract
The invention relates to fluorocarbon paint high in fluorine content and a preparation method thereof. The fluorocarbon paint is prepared from 35-40 parts of fluorine-containing monomers, 15-30 parts of non-fluoric monomers, 3-5 parts of fluorochemicals, 5-25 parts of pigment, 0.2-1 part of preservatives, 1-5 parts of antifreeze agent, 0.5-2 parts of emulgator, 0.2-1 part of thickener, 5-10 parts of auxiliaries, 0.2-1 part of surfactant and 50-80 parts of water. The preparation method of the fluorocarbon paint high in fluorine content includes the steps that the fluorine-containing monomers, the non-fluoric monomers and the fluorochemicals are mixed and polymerized to be mixed and stirred with other ingredients, and accordingly the paint is prepared. The fluorocarbon paint is high in fluorine content and has outstanding performance.
Description
Technical field
The present invention relates to fluorocarbon coating field, particularly high fluorine content F-C paint of one and preparation method thereof.
Background technology
From nineteen eighty-two Japan AGC company be proposed trifluorochloroethylene (CTFE) and alkane alkene ether synthesis fluorocarbon resin (FEVE) since, fluorocarbon coating with its excellent performance progressively by coating circle is approved.China is the nineties in last century, taken the lead in succeeding in developing trifluorochloroethylene-vinyl acetate copolymer by the Dalian Wu in nation, Changshu that shakes, and realize industrialization, after this F-C paint is widely used, facilitate the formulation of relevant Industry Policy and fluorocarbon coating standard, and promote the application of normal temperature solidifying fluorine-carbon coating in high-performance long-acting anticorrosive coating field.
2004, China revised railroad industry standard TB/T1527 " railway steel bridge protection application ", first fluorocarbon coating is introduced steel bridge protection system, for the application of fluorocarbon coating in railway steel bridge provides foundation.
The fluorine content of F-C paint determines the quality of F-C paint, the fluorine content index defining F-C paint in TB/T1527 standard wants >=15%, here fluorine content refers to the fluorine content produced in the raw materials used fluorine resin of fluorocarbon coating, namely detect the fluorine content of the fluoro-resin adopted, but not dissolve the fluorine content of solvend.
There is the weathering resistance of certain fluorine content guarantee F-C paint, main flow FEVE fluoro-resin in the market, theoretical fluorine content is generally 23%, the fluorine content of expensive goods is generally 25%, and consider in fluoro coatings preparation process, particularly also to add many auxiliary agents in colored paint preparation process, therefore on market, its fluorine content of fluorine carbon is lower, Ministry of Railways TB/T1527 standard and Japan require it is all 15% for the fluorine content of F-C paint, HG/T3792 standard defines the Oil repellent index of 18%, the F-C paint that market is high-end, generally can only reach the fluorine content of 20%.
When F-C paint fluorine content reaches more than 25%, F-C paint coating all can have more excellent performance in weathering resistance, self-cleaning etc., therefore, improves the fluorine content of F-C paint, is an important directions of F-C paint industry research and development.
Summary of the invention
The object of the present invention is to provide a kind of novel fluoro-carbon paint and preparation method thereof, F-C paint of a kind of high fluorine content and preparation method thereof is particularly provided.
The main component of high fluorine content F-C paint of the present invention is:
Described fluorochemicals is hydrofluoride or small molecules fluorine cpd;
Described hydrofluoride can be one or more in alkaline metal fluoride cpd, alkaline-earth metal fluoride, Mercury difluoride, silver fluoride, antimonic fluoride, cobaltous fluoride;
Described small molecules fluorochemical can be one or more in sulfur tetrafluoride, boron trifluoride, tetrafluorosilane.
Described fluorochemical monomer is fluorinated acrylate, is preferably one or more in vinylformic acid five fluorine ethyl ester, methacrylic acid five fluorine ethyl ester, trifluoromethyl acrylate ethyl ester, trifluoroethyl methacrylate, vinylformic acid trifluoro ethyl ester, trifluoromethyl acrylate methyl esters.
Described non-fluorochemical monomer is one or more in vinylformic acid, vinyl ether, vinyl-acetic ester, ethylene glycol monoallyl ether.
Described antifreezing agent is ethylene glycol or glycerol.
Described auxiliary agent is one or more in superfine heavy calcium carbonate, barium sulfate, talcum powder.
The preparation method of high fluorine content F-C paint of the present invention is:
A. in without water receptacle by fluorochemical monomer and non-fluorochemical monomer mixing and stirring after, in system, add fluorochemicals, stir under 200 ~ 400r/min rotating speed;
B. add emulsifying agent in the mixture obtained in a, under 600 ~ 800r/min rotating speed, control temperature control temperature 40 ~ 90 DEG C, stirs 10 ~ 16h, obtains fluoropolymer seed resin;
C. in fluoropolymer seed resin, add sanitas, thickening material, antifreezing agent, pigment, stir under 600 ~ 800r/min rotating speed;
D. in system, add tensio-active agent and water, add auxiliary agent after being stirred to homogeneous latex emulsion shape, adjustment rotating speed 1300 ~ 1500r/min is stirred to fineness lower than 100um.
High fluorine content F-C paint of the present invention, after testing, Oil repellent can reach more than 28%, has excellent performance, especially in weathering resistance and antifouling property, has had larger lifting.
High fluorine content F-C paint of the present invention, fluorochemicals is with the addition of in the polymerization process of fluoropolymer seed tree, utilize small molecules fluorochemicals in the course of the polymerization process to the replacement of the H on c h bond in polymkeric substance, improve resin fluorine content, simultaneously, due to the high bond energy of C-F key, the F-C paint obtained is made to have excellent weathering resistance, meanwhile, because agitation grinding is to the granularity of below 100um, make F-C paint coating have lower surface energy, thus there is excellent print resistance.
Embodiment
Below in conjunction with specific embodiment, high fluorine content F-C paint of the present invention and preparation method thereof is described further.
Embodiment 1
Mass fraction proportioning feeding according to following:
A. in without water receptacle by vinylformic acid five fluorine ethyl ester and vinylformic acid mixing and stirring after, in system, add Sodium Fluoride, stir under 300r/min rotating speed;
B. add emulsifying agent in the mixture obtained in a, under 800r/min rotating speed, control temperature control temperature 50 DEG C, stirs 16h, obtains fluoropolymer seed resin;
C. in fluoropolymer seed resin, add sanitas, thickening material, ethylene glycol, pigment, stir under 800r/min rotating speed;
D. in system, add tensio-active agent and water, add talcum powder after being stirred to homogeneous latex emulsion shape, adjustment rotating speed 1500r/min is stirred to fineness and obtains F-C paint 1-1 lower than 100um.
Embodiment 2
Mass fraction proportioning feeding according to following:
A. in without water receptacle by methacrylic acid five fluorine ethyl ester vinyl ether mixing and stirring after, in system, add silver fluoride, stir under 400r/min rotating speed;
B. add emulsifying agent in the mixture obtained in a, under 600r/min rotating speed, control temperature control temperature 40 DEG C, stirs 14h, obtains fluoropolymer seed resin;
C. in fluoropolymer seed resin, add sanitas, thickening material, propylene glycol, pigment, stir under 800r/min rotating speed;
D. in system, add tensio-active agent and water, add barium sulfate after being stirred to homogeneous latex emulsion shape, adjustment rotating speed 1300r/min is stirred to fineness and obtains F-C paint 1-2 lower than 100um.
Embodiment 3
Mass fraction proportioning feeding according to following:
A. in without water receptacle by vinylformic acid trifluoro ethyl ester and vinyl-acetic ester mixing and stirring after, in system, add boron trifluoride, stir under 200r/min rotating speed;
B. add emulsifying agent in the mixture obtained in a, under 800r/min rotating speed, control temperature control temperature 90 DEG C, stirs 10h, obtains fluoropolymer seed resin;
C. in fluoropolymer seed resin, add sanitas, thickening material, ethylene glycol, pigment, stir under 800r/min rotating speed;
D. in system, add tensio-active agent and water, add superfine heavy calcium carbonate after being stirred to homogeneous latex emulsion shape, adjustment rotating speed 1500r/min is stirred to fineness lower than 100um, obtains F-C paint 1-3.
Embodiment 4
Mass fraction proportioning feeding according to following:
A. in without water receptacle by trifluoromethyl acrylate methyl esters and ethylene glycol monoallyl ether mixing and stirring after, in system, add cobaltous fluoride, stir under 200r/min rotating speed;
B. add emulsifying agent in the mixture obtained in a, under 800r/min rotating speed, control temperature control temperature 40 DEG C, stirs 16h, obtains fluoropolymer seed resin;
C. in fluoropolymer seed resin, add sanitas, thickening material, propylene glycol, pigment, stir under 800r/min rotating speed;
D. in system, add tensio-active agent and water, add barium sulfate after being stirred to homogeneous latex emulsion shape, adjustment rotating speed 1500r/min is stirred to fineness lower than 100um, obtains F-C paint 1-4.
F-C paint fluorine content is tested:
| F-C paint | Fluorine content |
| 1-1 | 29％ |
| 1-2 | 28％ |
| 1-3 | 31％ |
| 1-4 | 29％ |
F-C paint performance test:
| F-C paint | VOC g/L | Weathering resistance | Chemical resistant properties | Tack-free h | Application property |
| 1-1 | ≤80 | Excellent | Excellent | 2～3 | Easily |
| 1-2 | ≤80 | Excellent | Excellent | 2～3 | Easily |
| 1-3 | ≤80 | Excellent | Excellent | 2～3 | Easily |
| 1-4 | ≤80 | Excellent | Excellent | 2～3 | Easily |
Be enumerated above the specific embodiment of the present invention, but the present invention is not only confined to above embodiment, in the ken that one skilled in the relevant art possesses, many variations can also be made to it.
Claims (7)
1. a high fluorine content F-C paint, main component and mass fraction thereof are:
Fluorochemical monomer 35 ~ 40
Non-fluorochemical monomer 15 ~ 30
Fluorochemicals 3 ~ 5
Pigment 5 ~ 25
Sanitas 0.2 ~ 1
Antifreezing agent 1 ~ 5
Emulsifying agent 0.5 ~ 2
Thickening material 0.2 ~ 1
Auxiliary agent 5 ~ 10
Tensio-active agent 0.2 ~ 1
Water 50 ~ 80.
2. high fluorine content F-C paint according to claim 1, is characterized in that: described fluorochemicals is hydrofluoride or small molecules fluorine cpd;
Described hydrofluoride can be one or more in alkaline metal fluoride cpd, alkaline-earth metal fluoride, Mercury difluoride, silver fluoride, antimonic fluoride, cobaltous fluoride;
Described small molecules fluorochemical can be one or more in sulfur tetrafluoride, boron trifluoride, tetrafluorosilane.
3. high fluorine content F-C paint according to claim 1, it is characterized in that: described fluorochemical monomer is fluorinated acrylate, described fluorinated acrylate can be one or more in vinylformic acid five fluorine ethyl ester, methacrylic acid five fluorine ethyl ester, trifluoromethyl acrylate ethyl ester, trifluoroethyl methacrylate, vinylformic acid trifluoro ethyl ester, trifluoromethyl acrylate methyl esters.
4. high fluorine content F-C paint according to claim 1, is characterized in that: described non-fluorochemical monomer is one or more in vinylformic acid, vinyl ether, vinyl-acetic ester, ethylene glycol monoallyl ether.
5. high fluorine content F-C paint according to claim 1, is characterized in that: described antifreezing agent is ethylene glycol or glycerol.
6. high fluorine content F-C paint according to claim 1, is characterized in that: described auxiliary agent is one or more in superfine heavy calcium carbonate, barium sulfate, talcum powder.
7. the preparation method of high fluorine content F-C paint according to claim 1, its preparation process is:
A. in without water receptacle by fluorochemical monomer and non-fluorochemical monomer mixing and stirring after, in system, add fluorochemicals, stir under 200 ~ 400r/min rotating speed;
B. add emulsifying agent in the mixture obtained in a, under 600 ~ 800r/min rotating speed, control temperature control temperature 40 ~ 90 DEG C, stirs 10 ~ 16h, obtains fluoropolymer seed resin;
C. add in fluoropolymer seed resin sanitas, thickening material, antifreezing agent, pigment, stir under 600 ~ 800r/min rotating speed;
D. in system, add tensio-active agent and water, add auxiliary agent after being stirred to homogeneous latex emulsion shape, adjustment rotating speed 1300 ~ 1500r/min is stirred to fineness lower than 100um.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511031651.8A CN105462425A (en) | 2015-12-31 | 2015-12-31 | Fluorocarbon paint high in fluorine content and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511031651.8A CN105462425A (en) | 2015-12-31 | 2015-12-31 | Fluorocarbon paint high in fluorine content and preparation method thereof |
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| CN105462425A true CN105462425A (en) | 2016-04-06 |
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| CN201511031651.8A Pending CN105462425A (en) | 2015-12-31 | 2015-12-31 | Fluorocarbon paint high in fluorine content and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106010076A (en) * | 2016-06-02 | 2016-10-12 | 南京福臻再生资源科技股份有限公司 | High temperature resistant silicon-fluorine paint and preparation method thereof |
| CN106010075A (en) * | 2016-06-02 | 2016-10-12 | 南京福臻再生资源科技股份有限公司 | High temperature resistant enameled wire and preparation method thereof |
Citations (4)
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| CN1401713A (en) * | 2002-09-05 | 2003-03-12 | 上海一宁建筑材料有限公司 | Water fluorine-carbon nanapaint and producing process thereof |
| CN101457114A (en) * | 2008-12-30 | 2009-06-17 | 江阴国联化工有限公司 | Method for preparing hydrophilic fluorine carbon metal paint |
| CN102911568A (en) * | 2012-11-08 | 2013-02-06 | 湘阴县利康士涂料有限公司 | Aqueous fluorine carbon coating material and preparation technology thereof |
| CN103113507A (en) * | 2013-02-20 | 2013-05-22 | 华东理工大学 | Method for preparing water-borne fluorine-containing emulsion and water-borne fluorine-containing coating |
-
2015
- 2015-12-31 CN CN201511031651.8A patent/CN105462425A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401713A (en) * | 2002-09-05 | 2003-03-12 | 上海一宁建筑材料有限公司 | Water fluorine-carbon nanapaint and producing process thereof |
| CN101457114A (en) * | 2008-12-30 | 2009-06-17 | 江阴国联化工有限公司 | Method for preparing hydrophilic fluorine carbon metal paint |
| CN102911568A (en) * | 2012-11-08 | 2013-02-06 | 湘阴县利康士涂料有限公司 | Aqueous fluorine carbon coating material and preparation technology thereof |
| CN103113507A (en) * | 2013-02-20 | 2013-05-22 | 华东理工大学 | Method for preparing water-borne fluorine-containing emulsion and water-borne fluorine-containing coating |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106010076A (en) * | 2016-06-02 | 2016-10-12 | 南京福臻再生资源科技股份有限公司 | High temperature resistant silicon-fluorine paint and preparation method thereof |
| CN106010075A (en) * | 2016-06-02 | 2016-10-12 | 南京福臻再生资源科技股份有限公司 | High temperature resistant enameled wire and preparation method thereof |
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| C41 | Transfer of patent application or patent right or utility model | ||
| CB03 | Change of inventor or designer information |
Inventor after: Qi Shougang Inventor after: Sun Chong Inventor after: Mao Shangwu Inventor after: Gao Xueqing Inventor after: Wang Jingjing Inventor after: Cheng Qin Inventor after: Jiu Liang Inventor after: Li Ping Inventor after: Zhu Manli Inventor after: Yu Li Inventor before: Qi Shougang Inventor before: Gao Xueqing Inventor before: Sun Chong |
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Effective date of registration: 20160425 Address after: Shogun East Gulou District of Nanjing city of Jiangsu Province, No. 199 210028 Applicant after: Qi Shougang Applicant after: Sun Chong Applicant after: Mao Shangwu Applicant after: Gao Xueqing Applicant after: Wang Jingjing Applicant after: Cheng Qin Applicant after: Jiu Liang Applicant after: Li Ping Applicant after: Zhu Manli Applicant after: Yu Li Address before: 210000, 399, Xin Xin Road, Zhongshan Science Park, Liuhe District, Nanjing, Jiangsu, Nanjing Applicant before: Qi Shougang Applicant before: Gao Xueqing Applicant before: Sun Chong |
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