CN105884811A - Method for preparing perfluorinated polyether di-alkoxy silane - Google Patents
Method for preparing perfluorinated polyether di-alkoxy silane Download PDFInfo
- Publication number
- CN105884811A CN105884811A CN201410835343.XA CN201410835343A CN105884811A CN 105884811 A CN105884811 A CN 105884811A CN 201410835343 A CN201410835343 A CN 201410835343A CN 105884811 A CN105884811 A CN 105884811A
- Authority
- CN
- China
- Prior art keywords
- pfpe
- allyl amine
- trimethoxy silane
- solvent
- reacted
- 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.)
- Pending
Links
Abstract
The invention aims at providing a method for preparing perfluorinated polyether di-alkoxy silane. The method is characterized by including the following steps that 1, perfluorinated alkyl polyether di-acyl fluorine and allyl amine are added into a reaction vessel in the molar ratio of 1:(1-1.2), a solvent and alkali are added, the mixture is stirred overnight under the room temperature condition, filtering is carried out, the solvent is removed in a reduced pressure distillation mode, separation is carried out through a silica gel column, an eluent is prepared from petroleum ether and ethyl acetate in the ratio of 6:1, and products are obtained; 2, a certain quantity of the products in the step 1 and a catalyst are added into a reaction kettle, sealing and nitrogen protection are carried out, the reaction kettle is placed into an oil bath and heated to be at the assigned temperature, the stirring reaction is carried out for 48 hours, and the reaction kettle is cooled to be at the room temperature after the reaction; the solvent of the product obtained in the step 2 is removed in a reduced-pressure distillation mode, recrystallization is carried out through methylbenzene, and the product is obtained. The product obtained with the method is applied to anti-fingerprint coatings, has the advantages that fingerprints are reduced, cleaning is easy, and abrasion is resistant, and is suitable for base materials such as glass, plastic, metal and films.
Description
Technical field
The present invention relates to a kind of by perfluoroalkyl polyethers two acyl fluorides, allyl amine and the reaction of trimethoxy silane, obtain
The synthetic method of the effective ingredient PFPE dialkoxy silicane of a kind of modified anti-fingerprint paint, belongs to chemical materials neck
Territory.
Background technology
Antifouling paint easy to clean, is the exploitation focus of functional paint in recent years, is widely applied to building materials, ceramic tile, floor
And glass, as done the surfaces such as construction equipment, mobile phone component, all kinds of touch screen and eyeglass, it is that a kind of coating one layer is hydrophobic
Oleophobic low-friction coefficient, the functional paint of surface blot wear-resisting, easy to clean.Fluorine material has the attribute of its uniqueness, as
Chemical stability, temperature tolerance, low-friction coefficient and low surface tension etc..Wherein, PFPE is commercially applied the widest
General.The functionalization of PFPE main chain, makes these materials can apply to coating, or modified becoming can change porous
Material with non-porous surface of bottom material character.The surface obtaining a resistance to dirt with long-term wear properties is to be faced
Challenge.Perfluoroether anti-fingerprint paint has a resistant coating of PFPE (PFPE) functional structure, and has oleophobic and low
The characteristic of coefficient of friction, also has the hydrophobic of alkoxy silane and wear properties.The active end of alkoxy silane is by hydrolysis
React with surface with condensation reaction, it is possible to substrate surface structural arrangement is adjusted.This excellent bonding provide tactile
Touch the durability required for panel type display application.Its good anti-wear performance makes the time that the holding of surface cleaning ability is longer.
This surface source easy to clean can in the low surface of alkoxy silane functional PFPE polymer, it is possible to forms one
Low surface tension layer or stain-proofing layer.
Based on fluoro-containing coating, there is above-described feature, market occurred multiple fluorine-containing coat material, as DOW CORNING,
The companies such as Ha Weisi all release the fluoro-containing coating of all kinds of brand.The present invention is then with perfluoroether as polymerized unit, and its chemistry is steady
Qualitative, temperature tolerance, low-friction coefficient and low surface tension etc. are with the obvious advantage, and application prospect is the most wide.
Summary of the invention
It is an object of the invention to be reacted with trimethoxy silane by perfluoroalkyl polyethers two acyl fluorides, allyl amine, it is provided that one
Plant the preparation method of the effective ingredient PFPE dialkoxy silicane of modified anti-fingerprint paint.
The technical scheme provided according to the present invention, described one is by perfluoroalkyl polyethers two acyl fluorides, allyl amine and front three
TMOS reacts, and obtains the new method of the effective ingredient PFPE dialkoxy silicane of a kind of modified anti-fingerprint paint
Feature is, including following synthesis step:
(1) preparation of PFPE diallyl amide
It is 1: 1～1.2 to join in reaction vessel by perfluoroalkyl polyethers two acyl fluorides and allyl amine according to mol ratio, adds
A certain amount of solvent and alkali, be stirred overnight at ambient temperature.Filtering, decompression is distilled off solvent, and silicagel column separates,
Eluant is petroleum ether: ethyl acetate=6: 1, i.e. obtains described product after removing solvent.The reaction equation of described step
For:
Wherein p/q=1-3
Described solvent is ether, Isosorbide-5-Nitrae-dioxane and toluene.
The consumption of described allyl amine is 2～2.4 times of perfluoroalkyl polyethers two acyl fluorides consumption.
Described reaction temperature is room temperature.
The described response time is 12 hours.
Described alkali is sodium hydroxide, sodium carbonate, sodium bicarbonate, triethylamine.
(2) PFPE diallyl amide and trimethoxy silane Si-H addition reaction
Joining in reactor by a certain amount of above-mentioned steps product and catalyst, seal, nitrogen is protected, and is put by reactor
In oil bath, it is warming up to assigned temperature, stirring reaction 48 hours.It is cooled to room temperature.
Product at reduced pressure above-mentioned steps obtained is distilled off solvent, then purifies with re crystallization from toluene, i.e. obtains product.
The reaction equation of described step is:
Described alkoxy silane consumption is 2 times of moles.
Described solvent is dichloroethanes.
Described catalyst is chloroplatinic acid.
Described catalyst amount is 5mol%.
Described reaction temperature is 60～80 DEG C.
The described response time is 36～48 hours.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.
The synthetic route of the method for the invention is:
Wherein p/q=1-3.
Embodiment one: one is reacted with trimethoxy silane obtained one by perfluoroalkyl polyethers two acyl fluorides, allyl amine
The preparation method of the effective ingredient PFPE dialkoxy silicane of modified anti-fingerprint paint, comprises the following steps:
(1) in 250mL round-bottomed flask, 10.6134g (0.1mmol) is added
(p/q=1), 11.4mg (0.2mmol) allyl amine, 100mL ether, it is stirred overnight at ambient temperature.Reaction knot
Shu Hou, filters, and removes solvent with Rotary Evaporators, and silicagel column separates, and eluant is petroleum ether: ethyl acetate=6: 1,
I.e. obtaining described product after removing solvent, productivity is 47%.
(2) in 100mL reactor, 5.3104g (0.05mmol) above-mentioned steps product, 12.2mg (0.1 are added
Mmol) trimethoxy silane, 10mg (5mol%) chloroplatinic acid, 50mL dichloroethanes, seal, nitrogen is protected,
Reactor is placed in oil bath, is warming up to 60 DEG C, stirring reaction 48 hours.Question response quickly cools down reactor after terminating
To room temperature.Product at reduced pressure above-mentioned steps obtained is distilled off solvent, then purifies with recrystallization, i.e. obtains product,
Productivity is 51%.Reaction equation is:
Embodiment two: one is reacted with trimethoxy silane obtained one by perfluoroalkyl polyethers two acyl fluorides, allyl amine
The preparation method of the effective ingredient PFPE dialkoxy silicane of modified anti-fingerprint paint, comprises the following steps:
(1) in 250mL round-bottomed flask, 10.6134g (0.1mmol) is added
(p/q=1), 11.4mg (0.2mmol) allyl amine, 100mL1,4-dioxane, it is stirred overnight at ambient temperature.
After reaction terminates, filtering, remove solvent with Rotary Evaporators, silicagel column separates, and eluant is petroleum ether: ethyl acetate
=6: 1, i.e. obtain described product after removing solvent, productivity is 36%.
(2) in 100mL reactor, 5.3104g (0.05mmol) above-mentioned steps product, 12.2mg (0.1 are added
Mmol) trimethoxy silane, 10mg (5mol%) chloroplatinic acid, 50mL dichloroethanes, seal, nitrogen is protected,
Reactor is placed in oil bath, is warming up to 60 DEG C, stirring reaction 48 hours.Question response quickly cools down reactor after terminating
To room temperature.Product at reduced pressure above-mentioned steps obtained is distilled off solvent, then purifies with recrystallization, i.e. obtains product,
Productivity is 49%.Reaction equation is:
Embodiment three: one is reacted with trimethoxy silane obtained one by perfluoroalkyl polyethers two acyl fluorides, allyl amine
The preparation method of the effective ingredient PFPE dialkoxy silicane of modified anti-fingerprint paint, comprises the following steps:
(1) in 250mL round-bottomed flask, 10.6134g (0.1mmol) is added
(p/q=1), 11.4mg (0.2mmol) allyl amine, 100mL toluene, it is stirred overnight at ambient temperature.Reaction knot
Shu Hou, filters, and removes solvent with Rotary Evaporators, and silicagel column separates, and eluant is petroleum ether: ethyl acetate=6: 1,
I.e. obtaining described product after removing solvent, productivity is 58%.
(2) in 100mL reactor, 5.3104g (0.05mmol) above-mentioned steps product, 12.2mg (0.1 are added
Mmol) trimethoxy silane, 10mg (5mol%) chloroplatinic acid, 50mL dichloroethanes, seal, nitrogen is protected,
Reactor is placed in oil bath, is warming up to 60 DEG C, stirring reaction 48 hours.Question response quickly cools down reactor after terminating
To room temperature.Product at reduced pressure above-mentioned steps obtained is distilled off solvent, then purifies with recrystallization, i.e. obtains product,
Productivity is 54%.Reaction equation is:
Embodiment four: one is reacted with trimethoxy silane obtained one by perfluoroalkyl polyethers two acyl fluorides, allyl amine
The preparation method of the effective ingredient PFPE dialkoxy silicane of modified anti-fingerprint paint, comprises the following steps:
(1) in 250mL round-bottomed flask, 10.5936g (0.1mmol) is added
(p/q=2), 11.4mg (0.2mmol) allyl amine, 100mL toluene, it is stirred overnight at ambient temperature.Reaction knot
Shu Hou, filters, and removes solvent with Rotary Evaporators, and silicagel column separates, and eluant is petroleum ether: ethyl acetate=6: 1,
I.e. obtaining described product after removing solvent, productivity is 57%.
(2) in 100mL reactor, 5.3005g (0.05mmol) above-mentioned steps product, 12.2mg (0.1 are added
Mmol) trimethoxy silane, 10mg (5mol%) chloroplatinic acid, 50mL dichloroethanes, seal, nitrogen is protected,
Reactor is placed in oil bath, is warming up to 60 DEG C, stirring reaction 48 hours.Question response quickly cools down reactor after terminating
To room temperature.Product at reduced pressure above-mentioned steps obtained is distilled off solvent, then purifies with recrystallization, i.e. obtains product,
Productivity is 56%.Reaction equation is:
Embodiment five: one is reacted with trimethoxy silane obtained one by perfluoroalkyl polyethers two acyl fluorides, allyl amine
The preparation method of the effective ingredient PFPE dialkoxy silicane of modified anti-fingerprint paint, comprises the following steps:
(1) in 250mL round-bottomed flask, 10.5870g (0.1mmol) is added
(p/q=3), 11.4mg (0.2mmol) allyl amine, 100mL toluene, it is stirred overnight at ambient temperature.Reaction knot
Shu Hou, filters, and removes solvent with Rotary Evaporators, and silicagel column separates, and eluant is petroleum ether: ethyl acetate=6: 1,
I.e. obtaining described product after removing solvent, productivity is 55%.
(2) in 100mL reactor, 5.2972g (0.05mmol) above-mentioned steps product, 12.2mg (0.1 are added
Mmol) trimethoxy silane, 10mg (5mol%) chloroplatinic acid, 50mL dichloroethanes, seal, nitrogen is protected,
Reactor is placed in oil bath, is warming up to 60 DEG C, stirring reaction 48 hours.Question response quickly cools down reactor after terminating
To room temperature.Product at reduced pressure above-mentioned steps obtained is distilled off solvent, then purifies with recrystallization, i.e. obtains product,
Productivity is 64%.Reaction equation is:
Claims (9)
1. one kind is reacted with trimethoxy silane by perfluoroalkyl polyethers two acyl fluorides, allyl amine, obtains a kind of modified anti-fingerprint
The feature of the new method of the effective ingredient PFPE dialkoxy silicane of coating is, including following synthesis step:
(1) preparation of PFPE diallyl amide
It is 1: 1～1.2 to join in reaction vessel by perfluoroalkyl polyethers two acyl fluorides and allyl amine according to mol ratio, adds certain
The solvent of amount and alkali, be stirred overnight at ambient temperature.Filtering, decompression is distilled off solvent, and silicagel column separates, eluant
For petroleum ether: ethyl acetate=6: 1, after removing solvent, i.e. obtain described product.
(2) PFPE diallyl amide and trimethoxy silane Si-H addition reaction
Joining in reactor by a certain amount of above-mentioned steps product and catalyst, seal, nitrogen is protected, and reactor is placed in oil
In bath, it is warming up to assigned temperature, stirring reaction 48 hours.Question response quickly cools down reactor to room temperature after terminating.By above-mentioned step
Suddenly the product at reduced pressure obtained is distilled off solvent, then purifies with re crystallization from toluene, i.e. obtains product.
2. one as claimed in claim 1 is reacted with trimethoxy silane by perfluoroalkyl polyethers two acyl fluorides, allyl amine,
To the new method of the effective ingredient PFPE dialkoxy silicane of a kind of modified anti-fingerprint paint, it is characterized in that: synthetic route is:
Wherein p/q=1-3.
3. one as claimed in claim 1 is reacted with trimethoxy silane by perfluoroalkyl polyethers two acyl fluorides, allyl amine,
To the new method of the effective ingredient PFPE dialkoxy silicane of a kind of modified anti-fingerprint paint, it is characterized in that: described solvent is
Ether, Isosorbide-5-Nitrae-dioxane, toluene.
4. one as claimed in claim 1 is reacted with trimethoxy silane by perfluoroalkyl polyethers two acyl fluorides, allyl amine,
To the new method of the effective ingredient PFPE dialkoxy silicane of a kind of modified anti-fingerprint paint, it is characterized in that: the described first step
Two kinds of reaction raw materials rate of charges are 1: 1～1.2, and second step reaction raw materials rate of charge is 1: 1.
5. one as claimed in claim 1 is reacted with trimethoxy silane by perfluoroalkyl polyethers two acyl fluorides, allyl amine,
To the new method of the effective ingredient PFPE dialkoxy silicane of a kind of modified anti-fingerprint paint, it is characterized in that: described reaction temperature
Degree is first step room temperature before this, and second step is 60～80 DEG C.
6. one as claimed in claim 1 is reacted with trimethoxy silane by perfluoroalkyl polyethers two acyl fluorides, allyl amine,
To the new method of the effective ingredient PFPE dialkoxy silicane of a kind of modified anti-fingerprint paint, it is characterized in that: during described reaction
Between the first step be 12 hours, second step is 36～48 hours.
7. one as claimed in claim 1 is reacted with trimethoxy silane by perfluoroalkyl polyethers two acyl fluorides, allyl amine,
To the new method of the effective ingredient PFPE dialkoxy silicane of a kind of modified anti-fingerprint paint, it is characterized in that: perfluoroalkyl ethers acyl
In fluorine, polymerized unit ratio is 1-3.
8. one as claimed in claim 1 is reacted with trimethoxy silane by perfluoroalkyl polyethers two acyl fluorides, allyl amine,
To the new method of the effective ingredient PFPE dialkoxy silicane of a kind of modified anti-fingerprint paint, it is characterized in that: urge used by the first step
Agent is chloroplatinic acid, and consumption is 5mol%.
9. one as claimed in claim 1 is reacted with trimethoxy silane by perfluoroalkyl polyethers two acyl fluorides, allyl amine,
To the new method of the effective ingredient PFPE dialkoxy silicane of a kind of modified anti-fingerprint paint, it is characterized in that: alkali used is hydrogen
Sodium oxide, sodium carbonate, sodium bicarbonate, triethylamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410835343.XA CN105884811A (en) | 2014-12-24 | 2014-12-24 | Method for preparing perfluorinated polyether di-alkoxy silane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410835343.XA CN105884811A (en) | 2014-12-24 | 2014-12-24 | Method for preparing perfluorinated polyether di-alkoxy silane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105884811A true CN105884811A (en) | 2016-08-24 |
Family
ID=56701099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410835343.XA Pending CN105884811A (en) | 2014-12-24 | 2014-12-24 | Method for preparing perfluorinated polyether di-alkoxy silane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105884811A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112028750A (en) * | 2020-08-27 | 2020-12-04 | 上海应用技术大学 | Perfluoroalkyl ether and preparation and application thereof |
| US10920014B2 (en) | 2017-07-07 | 2021-02-16 | Samsung Electronics Co., Ltd. | Compounds, compositions including the same, and layered structures and devices prepared from the compositions |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402618C (en) * | 2001-11-08 | 2008-07-16 | 3M创新有限公司 | Coating composition comprising a fluorochemical polyether silane partial condensate and use thereof |
| CN101657493A (en) * | 2007-04-16 | 2010-02-24 | 3M创新有限公司 | Perfluoroelastomer composition and sealing material |
| CN103665022A (en) * | 2013-12-13 | 2014-03-26 | 江南大学 | Method for synthesizing novel perfluoropolyether alkoxysilane applied to anti-fingerprint paint |
-
2014
- 2014-12-24 CN CN201410835343.XA patent/CN105884811A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402618C (en) * | 2001-11-08 | 2008-07-16 | 3M创新有限公司 | Coating composition comprising a fluorochemical polyether silane partial condensate and use thereof |
| CN101657493A (en) * | 2007-04-16 | 2010-02-24 | 3M创新有限公司 | Perfluoroelastomer composition and sealing material |
| CN103665022A (en) * | 2013-12-13 | 2014-03-26 | 江南大学 | Method for synthesizing novel perfluoropolyether alkoxysilane applied to anti-fingerprint paint |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10920014B2 (en) | 2017-07-07 | 2021-02-16 | Samsung Electronics Co., Ltd. | Compounds, compositions including the same, and layered structures and devices prepared from the compositions |
| CN112028750A (en) * | 2020-08-27 | 2020-12-04 | 上海应用技术大学 | Perfluoroalkyl ether and preparation and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103665022A (en) | Method for synthesizing novel perfluoropolyether alkoxysilane applied to anti-fingerprint paint | |
| US10696848B2 (en) | Fluorinated ether compound, coating liquid, article and novel compounds | |
| US10233331B2 (en) | Fluorinated ether composition, method for its production, coating liquid, substrate having surface-treated layer and method for its production | |
| CN105331259B (en) | Fluorochemical surface treating agent and the product handled with it | |
| KR20180044282A (en) | Fluorine-containing ether compound, fluorine-containing ether composition, coating solution, and article | |
| US11525031B2 (en) | Fluorinated ether compound, fluorinated ether composition, coating liquid, article and its production method | |
| JP6127438B2 (en) | Fluorinated ether composition, substrate having surface layer formed from the composition, and method for producing the same | |
| KR101969187B1 (en) | Fluorine-containing ether composition, method for producing same, coating fluid, and method for manufacturing substrate having surface-treated layer | |
| JPWO2019049753A1 (en) | Fluorine-containing ether compounds, compositions and articles | |
| TW201439221A (en) | Perfluoropolyether-modified polysilazane, making method, surface treating agent, and treated article | |
| CN103087324A (en) | Fluorooxyalkylene group-containing polymer composition, surface treatment agent containing the composition, and article and optical article treated with the surface treatment agent | |
| US20200002567A1 (en) | Silane compound containing perfluoro (poly ) ether group | |
| JP2022089886A (en) | Fluorine-containing ether compound, fluorine-containing ether composition, coating liquid, article and manufacturing method therefor | |
| TW201617420A (en) | Base material surface treatment agent including phosphate compound containing perfluoropolyether group | |
| JP6690675B2 (en) | Compound, composition, surface treatment agent, article and method for producing compound | |
| TW201634612A (en) | Fluorine-containing agent and article treated by the same | |
| KR20180132845A (en) | Compositions comprising perfluoro (poly) ether-modified amide silane compounds | |
| WO2018203491A2 (en) | Manufacturing method for fluorine-containing ether compound, and fluorine-containing ether compound | |
| CN105884811A (en) | Method for preparing perfluorinated polyether di-alkoxy silane | |
| CN113912834A (en) | Preparation method of perfluoropolyether siloxane product and application of perfluoropolyether siloxane product in anti-fingerprint coating and anti-fingerprint coating | |
| JP2016060816A (en) | Coating film forming composition and method for producing the same, and coating film | |
| JP2017137510A (en) | Method for producing fluorine-containing ether compound | |
| CN108440593B (en) | Anti-fingerprint compound and preparation method and application thereof | |
| WO2018221520A1 (en) | Fluorinated ether composition for vapor deposition, and article with vapor-deposited film and production method therefor | |
| CN108976253A (en) | A kind of fluorine silicon waterproof oil-repellent agent and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160824 |
|
| RJ01 | Rejection of invention patent application after publication |