CN105801618A - Preparation method of fluorine-containing super-hydro-oleophobic agent - Google Patents
Preparation method of fluorine-containing super-hydro-oleophobic agent Download PDFInfo
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- CN105801618A CN105801618A CN201610289480.7A CN201610289480A CN105801618A CN 105801618 A CN105801618 A CN 105801618A CN 201610289480 A CN201610289480 A CN 201610289480A CN 105801618 A CN105801618 A CN 105801618A
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- fluorine
- anhydride
- preparation
- containing super
- oleophobic agent
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
Abstract
The invention discloses a preparation method of a fluorine-containing super-hydro-oleophobic agent. The method comprises the following steps of: (1) synthesis of perfluoropropyl carbonyl-alkyl carbonyl alkenyl ether, namely mixing perfluorinated propylene acyl halide and alkyl alkenyl carboxylic acid in the presence of nitrogen, reacting anhydrous aluminum chloride at a room temperature for 24 hours under the action of a catalyst, and carrying out filtration and reduced pressure distillation to remove unreacted alkyl alkenyl carboxylic acid, thereby obtaining perfluorinated alkyl alkenyl anhydride; and (2) synthesis of the fluorine-containing super-hydro-oleophobic agent, namely adding the perfluorinated alkyl alkenyl anhydride and triethoxysilane to a solvent for stirred reaction in the presence of nitrogen, and carrying out filtration and reduced pressure distillation to remove the solvent, thereby obtaining perfluorinated anhydride alkyl triethoxy silane. The prepared fluorine-containing super-hydro-oleophobic agent containing an anhydride structure can be dissolved into a conventional chemical solvent, and is relatively good in chemical temperature property, friction resistance, hydro-oleophobicity and the like.
Description
Technical field
The present invention relates to technical field of surface, refer in particular to a kind of fluorine-containing super-hydrophobic oleophobic agent
Preparation method.
Background technology
When being contaminated by perspiration or sebum liquid such as product surfaces such as mobile phone, flat board, bathrooms, no
Only affect the outward appearance of product, it is also possible to serviceability is impacted, as do not processed for a long time,
Can cause product surface that a certain degree of corrosion occurs.Therefore, described product surface need to be carried out
Process, to solve the problems such as perishable and easy contamination.
Fluoropolymer have high heat stability, chemical inertness, weatherability, low-friction coefficient,
Low-refraction, low-surface-energy, excellent hydrophobic and lyophobic property, radiation resistance and resistance to ag(e)ing etc. are combined
Close performance, be widely used in petrochemical industry, Aero-Space, electronic apparatus, building, machinery etc.
Numerous areas.But, in prior art, fluoropolymer is in preparation method and serviceability etc.
There is problem more or less in aspect.
Publication No. CN102643303A discloses the preparation method of a kind of fluoride anti-fingerprint agent, its
Reaction is not required to use catalyst, but employs Carbimide. alkyl three second of hypertoxicity in preparation process
To consersion unit, TMOS, as raw material, not only requires that height also increases danger.Publication No.
CN104629571A discloses the preparation method of a kind of fluoride anti-fingerprint agent, through fluoride anti-fingerprint agent
Glass after process and water contact angle are just 116 °, and contact angle is less.Disclosed in " science "
Carbochain is the longest, and fluorine atom is the most, and hydrophobicity is the best, but, in prior art, fluorine-containing anti-corruption
Losing anti-fingerprint material is all the alkoxy silane containing short fluorocarbon chain, and hydrophobic performance is poor.
In prior art, almost all of fluorine-containing Water-and-oil repellant is in use used dilute
Release agent and be fluorinated solution, HFE-254, HFE-458 as conventional in market or ring fluorine ethers
Deng, above-mentioned solvent is the most expensive, and has toxicity, volatile, and severe corrosive etc. lacks
Point.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of fluorine-containing super-hydrophobic oleophobic agent, the party
Fluorine-containing super-hydrophobic oleophobic agent containing acid anhydride structure prepared by method, can be dissolved in the chemical solvent of routine,
And chemical temperatures, rub resistance and hydro-oleophobicity etc. are preferable.
For reaching above-mentioned purpose, the solution of the present invention is:
The preparation method of a kind of fluorine-containing super-hydrophobic oleophobic agent, comprises the following steps:
One, the synthesis of perfluoro propyl carbonyl-alkyl carbonyl alkene ether: under nitrogen protection, by perfluor
Propiono halogenide and the mixing of alkylalkenyl carboxylic acid, anhydrous Aluminum chloride is as room under catalyst action
24h is reacted under the conditions of temperature；Filtering, decompression is distilled off unreacted alkylalkenyl carboxylic acid,
Perfluoroalkyl thiazolinyl anhydride；
Two, the synthesis of fluorine-containing super-hydrophobic oleophobic agent: under nitrogen protection, by perfluoroalkyl thiazolinyl
Anhydride and triethoxysilane add stirring reaction in solvent；Filtering, decompression is distilled off solvent,
Obtain perfluor anhydride alkyl triethoxysilane.
Further, perfluoro propionyl halogenide and alkylalkenyl carboxylic acid according to mol ratio are
1:1-1:1.2 reacts.
Further, catalyst anhydrous Aluminum chlorideConsumptionDivide for perfluoroalkyl base halides quality
The 0.5 2 ‰ of number.
Further, in step one and step 2 during decompression distillation, system pressure is
-0.1—0.07MPa。
Further, double-component perfluoroalkyl thiazolinyl anhydride and triethoxysilane according to mol ratio are
1:1-1:1.1 reacts.
Further, in the building-up process of perfluor anhydride alkyl triethoxysilane, the solvent of use
For the one in chloroform and ether or both arbitrarily mix.
Further, in the building-up process of perfluor anhydride alkyl triethoxysilane, reaction temperature is
50-70℃。
Further, in the building-up process of perfluor anhydride alkyl triethoxysilane, the response time is
24-48h。
Further, in the building-up process of double-component perfluor anhydride alkyl triethoxysilane, eluting
Agent is the mixture of chloroform and ether, and mixed volume is than for chloroform: ether=1:1 1:2.
After using such scheme, the synthetic route of the present invention is:
Wherein: m, n in perfluoro propionyl halogenide and alkylalkenyl carboxylic acid structure formula are
Integer, wherein m is the integer of 1 to 12, and n is the integer of 2 to 16；R is F, Cl,
The halogens such as Br and I, wherein preferably F or Cl, Et is writing a Chinese character in simplified form of ethanol ethanol, chemistry
Formula is C2H5OH。
Synthesis technique of the present invention is simple, and productivity is high, and production cost is relatively low, beneficially industrialization
Produce.The fluorine-containing super-hydrophobic oleophobic agent that the present invention obtains contains acid anhydride structure, can be dissolved in the change of routine
Learning solvent, be applied to anticorrosive, anti-fingerprint and oil-stain-preventing surface processes, the base material being suitable for is moulded
Material, kirsite, copper alloy, rustless steel, ironcasting and glass, product has super after treatment
Hydro-oleophobicity, the feature such as friction resistant durability, salt fog resistance and ultraviolet aging resistance.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment one
A kind of preparation method of fluorine-containing super-hydrophobic oleophobic agent, synthesis step is as follows:
One, the synthesis of perfluoro propyl-thiazolinyl anhydride
Under nitrogen protection, it is that 1:1 adds by five fluorine propiono fluorine and octenyl carboxylic acid according to mol ratio
Enter in two mouthfuls of flasks, at 0.5 ‰ anhydrous Aluminum chlorides as under room temperature condition under catalyst action
Reaction 24h；Filtering, decompression is distilled off unreacted octenyl carboxylic acid, obtains five fluoropropyls pungent
Thiazolinyl anhydride.
Two, the synthesis of fluorine-containing super-hydrophobic oleophobic agent
Under nitrogen protection, by five fluoropropyl octenyl anhydride and triethoxysilane according to mole
Ratio joins in the reaction vessel containing ether for 1:1.1, stirring reaction 24h at 50 DEG C；
Filtering, decompression is distilled off solvent, obtains five fluoropropyl octyl group anhydride triethoxysilanes.
Embodiment two
A kind of preparation method of fluorine-containing super-hydrophobic oleophobic agent, synthesis step is as follows:
One, the synthesis of perfluoro propyl-thiazolinyl anhydride
Under nitrogen protection, it is 1:1.1 by seven fluorine propiono iodine and cyclobutenyl carboxylic acid according to mol ratio
Join in two mouthfuls of flasks, at 1 ‰ anhydrous Aluminum chlorides as under room temperature condition under catalyst action
Reaction 24h；Filtering, decompression is distilled off unreacted acrylic carboxylic acid, obtains heptafluoropropyl fourth
Thiazolinyl anhydride.
Two, the synthesis of fluorine-containing super-hydrophobic oleophobic agent
Under nitrogen protection, by heptafluoropropyl cyclobutenyl anhydride and triethoxysilane according to mole
Ratio joins in the reaction vessel containing ether for 1:1.1, stirring reaction 24h at 50 DEG C；
Filtering, decompression is distilled off solvent, obtains heptafluoropropyl butyl anhydride triethoxysilane.
Embodiment three
A kind of preparation method of fluorine-containing super-hydrophobic oleophobic agent, synthesis step is as follows:
One, the synthesis of perfluoro propyl-thiazolinyl anhydride
Under nitrogen protection, by ten trifluoropropyl acid iodides and hexenyl carboxylic acid according to mol ratio it is
1:1.1 joins in two mouthfuls of flasks, at 1 ‰ anhydrous Aluminum chlorides as room temperature under catalyst action
Under the conditions of react 24h；Filtering, decompression is distilled off unreacted acrylic carboxylic acid, obtains 13
Fluoropropyl hexenyl anhydride.
Two, the synthesis of fluorine-containing super-hydrophobic oleophobic agent
Under nitrogen protection, by ten trifluoro propyl hexenyl anhydride and triethoxysilane according to rubbing
You join in the reaction vessel containing chloroform for 1:1 by ratio, stirring reaction 48h at 60 DEG C；
Filtering, decompression is distilled off solvent, obtains ten trifluoro propyl hexyl anhydride triethoxysilanes.
Embodiment four
A kind of preparation method of fluorine-containing super-hydrophobic oleophobic agent, synthesis step is as follows:
One, the synthesis of perfluoro propyl-thiazolinyl anhydride
Under nitrogen protection, it is 1:1 by 17 fluorine propiono fluorine and octenyl carboxylic acid according to mol ratio
Join in two mouthfuls of flasks, at 1.5 ‰ anhydrous Aluminum chlorides as room temperature condition under catalyst action
Lower reaction 24h；Filtering, decompression is distilled off unreacted acrylic carboxylic acid, obtains 17 fluorine third
Base octenyl anhydride.
Two, the synthesis of fluorine-containing super-hydrophobic oleophobic agent
Under nitrogen protection, by ten heptafluoropropyl octenyl anhydride and triethoxysilane according to rubbing
You join in the reaction vessel containing chloroform for 1:1 by ratio, stirring reaction 48h at 60 DEG C；
Filtering, decompression is distilled off solvent, obtains ten heptafluoropropyl octyl group anhydride triethoxysilanes.
The foregoing is only the preferred embodiments of the present invention, not the restriction to this case design, all
The equivalent variations done according to the design key of this case, each falls within the protection domain of this case.
Claims (9)
1. the preparation method of a fluorine-containing super-hydrophobic oleophobic agent, it is characterised in that include following
Step:
One, the synthesis of perfluoro propyl carbonyl-alkyl carbonyl alkene ether: under nitrogen protection, by perfluor
Propiono halogenide and the mixing of alkylalkenyl carboxylic acid, anhydrous Aluminum chloride is as room under catalyst action
24h is reacted under the conditions of temperature；Filtering, decompression is distilled off unreacted alkylalkenyl carboxylic acid,
Perfluoroalkyl thiazolinyl anhydride；
Two, the synthesis of fluorine-containing super-hydrophobic oleophobic agent: under nitrogen protection, by perfluoroalkyl thiazolinyl
Anhydride and triethoxysilane add stirring reaction in solvent；Filtering, decompression is distilled off solvent,
Obtain perfluor anhydride alkyl triethoxysilane.
The preparation method of a kind of fluorine-containing super-hydrophobic oleophobic agent the most as claimed in claim 1, its
Being characterised by, perfluoro propionyl halogenide and alkylalkenyl carboxylic acid according to mol ratio are
1:1-1:1.2 reacts.
The preparation method of a kind of fluorine-containing super-hydrophobic oleophobic agent the most as claimed in claim 1, its
Being characterised by, catalyst anhydrous Aluminum chloride consumption is perfluoroalkyl base halides mass fraction
0.5-2 ‰.
The preparation method of a kind of fluorine-containing super-hydrophobic oleophobic agent the most as claimed in claim 1, its
Being characterised by, in step one and step 2 during decompression distillation, system pressure is
-0.1—0.07MPa。
The preparation method of a kind of fluorine-containing super-hydrophobic oleophobic agent the most as claimed in claim 1, its
Being characterised by, double-component perfluoroalkyl thiazolinyl anhydride and triethoxysilane are 1 according to mol ratio:
1-1:1.1 reacts.
The preparation method of a kind of fluorine-containing super-hydrophobic oleophobic agent the most as claimed in claim 1, its
Being characterised by, in the building-up process of perfluor anhydride alkyl triethoxysilane, the solvent of use is
One in chloroform and ether or both arbitrarily mix.
The preparation method of a kind of fluorine-containing super-hydrophobic oleophobic agent the most as claimed in claim 1, its
Being characterised by, in the building-up process of perfluor anhydride alkyl triethoxysilane, reaction temperature is
50-70℃。
The preparation method of a kind of fluorine-containing super-hydrophobic oleophobic agent the most as claimed in claim 1, its
Being characterised by, in the building-up process of perfluor anhydride alkyl triethoxysilane, the response time is
24-48h。
The preparation method of a kind of fluorine-containing super-hydrophobic oleophobic agent the most as claimed in claim 1, its
It is characterised by, in the building-up process of double-component perfluor anhydride alkyl triethoxysilane, eluant
For chloroform and the mixture of ether, mixed volume is than for chloroform: ether=1:1 1:2.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610289480.7A CN105801618A (en) | 2016-05-04 | 2016-05-04 | Preparation method of fluorine-containing super-hydro-oleophobic agent |
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| CN201610289480.7A CN105801618A (en) | 2016-05-04 | 2016-05-04 | Preparation method of fluorine-containing super-hydro-oleophobic agent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822672A (en) * | 2018-07-06 | 2018-11-16 | 天津市建筑材料科学研究院有限公司 | A kind of oil rub resistance spray |
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| JPH02169067A (en) * | 1988-12-20 | 1990-06-29 | Natoko Paint Kk | Formation of coating film |
| CN102070662A (en) * | 2010-12-25 | 2011-05-25 | 锦州惠发天合化学有限公司 | Preparation method of fluorine-silicon surfactant |
| CN102643303A (en) * | 2012-04-13 | 2012-08-22 | 阜新恒通氟化学有限公司 | Preparation method of fluoride anti-fingerprint agent |
| CN103665022A (en) * | 2013-12-13 | 2014-03-26 | 江南大学 | Method for synthesizing novel perfluoropolyether alkoxysilane applied to anti-fingerprint paint |
| CN104292251A (en) * | 2014-09-12 | 2015-01-21 | 苏州大学 | Water-proofing agent as well as preparation method and application thereof |
-
2016
- 2016-05-04 CN CN201610289480.7A patent/CN105801618A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02169067A (en) * | 1988-12-20 | 1990-06-29 | Natoko Paint Kk | Formation of coating film |
| CN102070662A (en) * | 2010-12-25 | 2011-05-25 | 锦州惠发天合化学有限公司 | Preparation method of fluorine-silicon surfactant |
| CN102643303A (en) * | 2012-04-13 | 2012-08-22 | 阜新恒通氟化学有限公司 | Preparation method of fluoride anti-fingerprint agent |
| CN103665022A (en) * | 2013-12-13 | 2014-03-26 | 江南大学 | Method for synthesizing novel perfluoropolyether alkoxysilane applied to anti-fingerprint paint |
| CN104292251A (en) * | 2014-09-12 | 2015-01-21 | 苏州大学 | Water-proofing agent as well as preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822672A (en) * | 2018-07-06 | 2018-11-16 | 天津市建筑材料科学研究院有限公司 | A kind of oil rub resistance spray |
| CN108822672B (en) * | 2018-07-06 | 2020-08-07 | 天津市建筑材料科学研究院有限公司 | Anti-oil stain spray |
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Address after: The North Industrial Zone of Jimei Tianfeng road Xiamen City, Fujian province 361021 No. 69 Applicant after: Xiamen Jian Lin health home Limited by Share Ltd Address before: The North Industrial Zone of Jimei Tianfeng road Xiamen City, Fujian province 361021 No. 69 Applicant before: Xiamen Runner Industrial Corporation |
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Application publication date: 20160727 |