CN107459641A - A kind of preparation method of perfluoropolyether-modified allyloxy body - Google Patents
A kind of preparation method of perfluoropolyether-modified allyloxy body Download PDFInfo
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- CN107459641A CN107459641A CN201710761841.8A CN201710761841A CN107459641A CN 107459641 A CN107459641 A CN 107459641A CN 201710761841 A CN201710761841 A CN 201710761841A CN 107459641 A CN107459641 A CN 107459641A
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- perfluoropolyether
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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Abstract
The present invention relates to a kind of preparation method of perfluoropolyether-modified allyloxy body, specially, by holo-fluorine polyester acyl fluorides and allyl compound in the presence of phase transfer catalyst Y, fluoride salt MF and non-protonic solvent, react and perfluoropolyether-modified allyloxy body is made.The present invention provides preparation method and simplifies manufacturing process, and raw material availability is high, product not facile hydrolysis, it is not necessary to through column chromatography, reduce cost, yield is up to 94.7%, is produced beneficial to mass production, has larger application value.
Description
Technical field
The present invention relates to the synthesis of holo-fluorine polyester silane compound intermediate, especially a kind of perfluoropolyether-modified allyl
The preparation method of epoxide body.
Background technology
As a kind of very important intermediate, it has been obtained for extensively perfluoropolyether-modified allyloxy body class compound
General application.For current this kind of compound mainly for the preparation of perfluoropolyether-modified silane compound, it is highly resistance to that the latter can form tool
Scratch resistance, preferable smoothness and outstanding waterproof/oiliness, the film of anti-stain characteristic, stain-proofing layer and display as optical component
The anti-finger print layer of device.
Those skilled in the art has attempted a variety of methods to obtain this kind of important intermediate.For example, WO2011/
A kind of preparation method of perfluoropolyether-modified allyloxy body is elaborated in 059430, this method is using PFPE acyl fluorides as starting
Raw material, in such as NaBH4, diborane complex and LiAlH4Deng carrying out being reduced into PFPE alcohol in the presence of reducing agent；Mixture
Again through column chromatography purification process, the higher PFPE alcohol of purity is obtained；Exist afterwards in alkaline matters such as inorganic or organic bases
It is lower generation fluorine sodium alkoxide, then with Br-CH2CH=CH2Reaction obtains PFPE alcohol.But the reduction of this method PFPE alcohol is not
Thoroughly, and there is accessory substance to need column chromatography, consume eluant, eluent, cost is high, is unfavorable for mass production production；Deposited in alkaline matter
In PFPE alcohol and Br-CH2CH=CH2Reaction carries out Williamson ether synthesis, and it belongs to reversible reaction.The fluorine sodium alkoxide of generation is easy
Hydrolysis, therefore need constantly to remove the water of generation in course of reaction, otherwise reaction conversion ratio is extremely low.WO2015/087902 is disclosed
Scheme in, PFPE acyl fluorides and alcohols are esterified first, are then PFPE alcohol with sodium borohydride reduction, finally in alkalescence
The aqueous solution and phase transfer catalyst are present, with Br-CH2CH=CH2Reaction generation target product.Although the program improves perfluor
The problem of reduction of polyethers acyl fluorides is not thorough, and fluorine sodium alkoxide conversion ratio is low, but allyl bromide, bromoallylene easily hydrolyzes life in alkaline aqueous solution
Into pungent allyl alcohol, therefore allyl bromide, bromoallylene need to be excessive a lot, just can guarantee that reactant conversion is more complete.
The content of the invention
To overcome, existing perfluoropolyether-modified allyloxy preparation is complicated, cost is higher, conversion ratio is low, raw material
Consume the technological deficiency such as big.Inventor has finally found out one kind and has prepared perfluoropolyether-modified allyloxy by studying for a long period of time
The method of body.
This method reaction expression：
Wherein, M is monovalent metal group, and X is leaving group；Y is phase transfer catalyst, and MF is fluoride salt.
Preparation method provided by the invention makees phase transfer catalyst using quaternary ammonium salt, and reaction introduces fluorine to polymer phase simultaneously
Compound salt generation of reactive material [F (CF2CF2O)m(CF2O)nCF2O-M+], it further can then react with allyl compound
To prepare perfluoropolyether-modified allyloxy body.
Specific preparation process comprises the following steps：
(1) nitrogen blowing and non-protonic solvent and fluoride salt and phase transfer catalyst are added into reactor, unlatching is stirred
Mixing obtains suspension；
(2) PFPE acyl fluorides and allyl compound are added into step (1) reactor；
(3) at a temperature of 0.3~5.0MPa pressure and 50~100 DEG C, it is sufficiently stirred 12~18h of reaction；
(4) reactant mixture is filtered, washs and produce the perfluoropolyether-modified allyloxy body by reaction after terminating.
Wherein, step (1) described non-protonic solvent is selected from：Methyl iso-butyl ketone (MIBK), cyclohexanone, diethylene glycol dimethyl ether,
One or more in methyl triglyme, methyl tetraethylene glycol dimethyl ether and tetrahydrofuran.
Wherein, the mass ratio of PFPE acyl fluorides and non-protonic solvent is 1：1~2.
Wherein, PFPE acyl fluorides and the mol ratio of fluoride salt and phase transfer catalyst are 1：1.2~2.0：0.1~
0.18。
Wherein, the mol ratio of step (2) the PFPE acyl fluorides and allyl compound is 1：1.3~2.0.
Wherein, in the washing described in step (4), deionized water, acetone or the two mixing are used.
In above-mentioned preparation method, reaction pressure is unfavorable for phase-transfer-catalyzed reactions less than 0.3MPa, but reaction pressure is higher than
5.0MPa then requires too high to the material of reaction vessel, is unfavorable for producing, comprehensive consideration, reaction pressure 0.3~5.0MPa of scope,
It is preferred that pressure is 1.2~3.0MPa.
In above-mentioned preparation method, when reaction temperature is less than 50 DEG C, reaction carries out slow, need to extend the reaction time, take compared with
Long.Reaction temperature is higher than 100 DEG C, and reaction is violent, is unfavorable for controlling course of reaction.Therefore at a temperature of 50~100 DEG C, it is sufficiently stirred anti-
Answer 12~18h.
Concrete scheme is as follows：
A kind of preparation method of perfluoropolyether-modified allyloxy body, described preparation method is, by holo-fluorine polyester acyl
Fluorine in the presence of phase transfer catalyst Y, fluoride salt MF and non-protonic solvent, reacts and perfluor is made with allyl compound
Polyether-modified allyloxy body, reaction expression are as follows：
Wherein, m, n are numeral independently, are more than 0, less than 200 integer, it is preferred that m, n are more than 10,
Less than 100 integer；
Any one of X in Cl, Br, I；R1 is selected from H ,-CH2-、-CH2CH2- in any one；R2 be selected from H ,-
CH=CH2In any one.
Further, reaction expression is as follows：
Wherein, m, n are numeral independently, are more than 0, less than 200 integer, it is preferred that m, n are more than 10,
Less than 100 integer.
Further, at a temperature of the condition of described reaction is 0.3~5.0MPa pressure and 50~100 DEG C, stirring is anti-
Answer 12~18h.
Further, described allyl compound is CH2=CHCH2-Cl、CH2=CHCH2-I、CH2=CH-CH
(CH2Br)-CH=CH2、CH2=CH-CH (CH2CH2Br)-CH=CH2In any one.
Further, described phase transfer catalyst is 4-butyl ammonium hydrogen sulfate, benzyltriethylammoinium chloride, tetraethyl chlorine
Change at least one of ammonium, tetraethylammonium bromide.
Further, described fluoride salt is at least one of AgF, NaF, CsF.
Further, described preparation method step is as follows：
(1) nitrogen blowing and non-protonic solvent, fluoride salt and phase transfer catalyst are added into reactor, opens stirring
Suspension is made；
(2) PFPE acyl fluorides and allyl compound are added into the reactor of step (1)；
(3) at a temperature of 0.3~5.0MPa pressure and 50~100 DEG C, 12~18h of stirring reaction；
(4) reactant mixture is filtered, washed by reaction after terminating, and produces the perfluoropolyether-modified allyloxy
Body.
Further, in the step (1), non-protonic solvent is selected from：Methyl iso-butyl ketone (MIBK), cyclohexanone, diethylene glycol
One or more in dimethyl ether, methyl triglyme, methyl tetraethylene glycol dimethyl ether, tetrahydrofuran.
Further, in the step (2), the quality of PFPE acyl fluorides and non-protonic solvent in the step (1)
Than for 1：1~1：2.
Further, PFPE acyl fluorides and fluoride salt and phase transfer catalysis (PTC) in the step (1) in the step (2)
The mol ratio of agent is 1：(1.2~2.0)：(0.1~0.18)；
Optional, the mol ratio of PFPE acyl fluorides and allyl compound is 1 in the step (2)：1.3~1：2.0；
Optional, in the step (4), washing uses deionized water, acetone or the mixed solution of the two.
Beneficial effect：The present invention provides preparation method and simplifies manufacturing process, and raw material availability is high, product not facile hydrolysis, no
Need through column chromatography, reduce cost, yield is up to 94.7%, is produced beneficial to mass production, has huge application value.
Embodiment
Technical solution of the present invention is further elaborated with reference to embodiment.Unreceipted particular technique or bar in embodiment
Part person, carried out according to the technology described by document in the art or condition or according to product description.Agents useful for same or instrument
The unreceipted production firm person of device, being can be by the conventional products of acquisition purchased in market.
Embodiment 1
In the 5L stainless steel cauldrons with stirring, the diethylene glycol diformazan that 2000g is dried is added under a nitrogen atmosphere
Ether, 40.5g KF, 14g benzyltriethylammoinium chloride, stir 0.5h.It is subsequently added into 92.5g Br-CH2CH=CH2, slowly
2000g PFPEs acyl fluorides (mean molecule quantity 4000) is added dropwise.Nitrogen pressurizes, and holding reacting kettle inner pressure is 1.5Mpa, makes anti-
Mixture is answered to react 18h at 65 DEG C.Analyzed according to the IR of gained reaction product, from-C (=0) F functional groups'
1890cm-1Absworption peak is wholly absent (conversion ratio 100%).Reactant mixture is filtered to remove solid, filtrate with 2000g go from
Son washing is washed once twice, then with 500g acetone, and volatile ingredient is finally distilled off under reduced pressure, thus obtains PFPE
Modified allyloxy body 1982g, yield is about 94.7%.Product not facile hydrolysis, it is not necessary to through column chromatography, reduce into
This.Being analyzed to identify structure through H-NMR is：
F(CF2CF2O)m(CF2O)nCF2O-CH2CH=CH2
1H-NMR data are as follows：
δ4.0-4.1(O-CH2 CH=CH 2 )2H
δ4.9-5.2(O-CH2CH=CH 2)2H
δ5.7-5.9(O-CH2CH=CH2)1H
Embodiment 2
In the 5L stainless steel cauldrons with stirring, the diethylene glycol diformazan that 2000g is dried is added under a nitrogen atmosphere
Ether, 40.5g KF, 14g benzyltriethylammoinium chloride, stir 0.5h.It is subsequently added into 140g CH2=CH-CH (CH2Br)-CH
=CH2, 2000g PFPEs acyl fluorides (mean molecule quantity 4000) is slowly added dropwise.Nitrogen pressurizes, and holding reacting kettle inner pressure is
1.5Mpa, reactant mixture is set to react 15h at 65 DEG C.Analyzed according to the IR of gained reaction product, from-C (=0) F official
The 1890cm of energy base-1Absworption peak is wholly absent (conversion ratio 100%).Reactant mixture is filtered to remove solid, and filtrate is used
2000g deionizations are washed twice, then washed once with 500g acetone, and volatile ingredient is finally distilled off under reduced pressure, thus
To perfluoropolyether-modified allyloxy body 1991g, yield is about 93.0%.Product not facile hydrolysis, it is not necessary to through column chromatography,
Reduce cost.Being analyzed to identify structure through H-NMR is：
F(CF2CF2O)m(CF2O)nCF2O-CH2CH (CH=CH2)2
1H-NMR data are as follows：
δ1.9-2.1[O-CH2CH(CH=CH2)2]1H
δ3.8-4.0[O-CH 2CH (CH=CH2)2]2H
δ4.8-5.1[O-CH2CH (CH=CH 2)2]4H
δ5.7-5.9[O-CH2CH(CH=CH2)2]2H
Embodiment 3
In the 5L stainless steel cauldrons with stirring, under a nitrogen atmosphere add 2000g dry methyl iso-butyl ketone (MIBK),
30g NaF, 20g 4-butyl ammonium hydrogen sulfate, stir 0.5h.It is subsequently added into 130g I-CH2CH=CH2, 2000g is slowly added dropwise
PFPE acyl fluorides (mean molecule quantity 4000).Nitrogen pressurizes, and holding reacting kettle inner pressure is 0.3Mpa, reactant mixture is existed
12h is reacted at 100 DEG C.Analyzed according to the IR of gained reaction product, in the 1890cm from-C (=0) F functional groups-1Absworption peak is complete
It totally disappeared mistake (conversion ratio 100%).Reactant mixture is filtered to remove solid, and filtrate is washed twice with 2000g deionizations, then is used
500g acetone is washed once, and volatile ingredient is finally distilled off under reduced pressure, thus obtains perfluoropolyether-modified allyloxy body
1985g, yield are about 93.1%.Product not facile hydrolysis, it is not necessary to through column chromatography, reduce cost.It is true through H-NMR analyses
Recognizing structure is：
F(CF2CF2O)m(CF2O)nCF2O-CH2CH=CH2
1H-NMR data are as follows：
δ4.0-4.1(O-CH2 CH=CH 2 )2H
δ4.9-5.2(O-CH 2 CH=CH2 )2H
δ5.7-5.9(O-CH 2 CH=CH 2 )1H
Embodiment 4
In the 5L stainless steel cauldrons with stirring, under a nitrogen atmosphere add 2000g dry tetrahydrofuran,
40.5g KF, 14g tetraethylammonium bromide, stir 0.5h.It is subsequently added into 92.5g Br-CH2CH=CH2, be slowly added dropwise
2000g PFPEs acyl fluorides (mean molecule quantity 4000).Nitrogen pressurizes, and holding reacting kettle inner pressure is 5Mpa, mixes reaction
Thing reacts 18h at 50 DEG C.Analyzed according to the IR of gained reaction product, in the 1890cm from-C (=0) F functional groups-1Absorb
Peak is wholly absent (conversion ratio 100%).Reactant mixture is filtered to remove solid, and filtrate is washed twice with 2000g deionizations,
Washed once with 500g acetone again, volatile ingredient is finally distilled off under reduced pressure, thus obtain perfluoropolyether-modified allyl oxygen
Matrix 1977g, yield are about 94.5%.Product not facile hydrolysis, it is not necessary to through column chromatography, reduce cost.Through H-NMR points
Analysis confirms that structure is：
F(CF2CF2O)m(CF2O)nCF2O-CH2CH=CH2
1H-NMR data are as follows：
δ4.0-4.1(O-CH2 CH=CH 2 )2H
δ4.9-5.2(O-CH 2 CH=CH2 )2H
δ5.7-5.9(O-CH 2 CH=CH 2 )1H
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art is not departing from the principle and objective of the present invention
In the case of above-described embodiment can be changed within the scope of the invention, change, replace and modification.
Claims (10)
- A kind of 1. preparation method of perfluoropolyether-modified allyloxy body, it is characterised in that：Described preparation method is, by perfluor Polyether-based acyl fluorides in the presence of phase transfer catalyst Y, fluoride salt MF and non-protonic solvent, reacts with allyl compound Perfluoropolyether-modified allyloxy body is made, reaction expression is as follows：Wherein, m, n are numeral independently, are more than 0, less than 200 integer, it is preferred that m, n be more than 10,100 with Under integer；Any one of X in Cl, Br, I；R1 is selected from H ,-CH2-、-CH2CH2- in any one；R2 is selected from H ,-CH= CH2In any one.
- 2. the preparation method of perfluoropolyether-modified allyloxy body according to claim 1, it is characterised in that：Reaction expression It is as follows：Wherein, m, n are numeral independently, are more than 0, less than 200 integer, it is preferred that m, n be more than 10,100 with Under integer.
- 3. the preparation method of perfluoropolyether-modified allyloxy body according to claim 1, it is characterised in that：Described is anti- At a temperature of the condition answered is 0.3~5.0MPa pressure and 50~100 DEG C, 12~18h of stirring reaction.
- 4. the preparation method of perfluoropolyether-modified allyloxy body according to claim 1, it is characterised in that：Described alkene Compound is CH2=CHCH2-Cl、CH2=CHCH2-I、CH2=CH-CH (CH2Br)-CH=CH2、CH2=CH-CH (CH2CH2Br)-CH=CH2In any one.
- 5. the preparation method of perfluoropolyether-modified allyloxy body according to claim 1, it is characterised in that：Described phase Transfer catalyst be 4-butyl ammonium hydrogen sulfate, benzyltriethylammoinium chloride, etamon chloride, in tetraethylammonium bromide at least It is a kind of.
- 6. the preparation method of perfluoropolyether-modified allyloxy body according to claim 1, it is characterised in that：Described fluorine Compound salt is at least one of AgF, NaF, CsF.
- 7. the preparation method of perfluoropolyether-modified allyloxy body according to claim 1, it is characterised in that：Described system Preparation Method step is as follows：(1) nitrogen blowing and non-protonic solvent, fluoride salt and phase transfer catalyst are added into reactor, opens stirring and be made Suspension；(2) PFPE acyl fluorides and allyl compound are added into the reactor of step (1)；(3) at a temperature of 0.3~5.0MPa pressure and 50~100 DEG C, 12~18h of stirring reaction；(4) reactant mixture is filtered, washed by reaction after terminating, and produces the perfluoropolyether-modified allyloxy body.
- 8. the preparation method of perfluoropolyether-modified allyloxy body according to claim 6, it is characterised in that：The step (1) in, non-protonic solvent is selected from：Methyl iso-butyl ketone (MIBK), cyclohexanone, diethylene glycol dimethyl ether, methyl triglyme, first One or more in base tetraethylene glycol dimethyl ether, tetrahydrofuran.
- 9. the preparation method of perfluoropolyether-modified allyloxy body according to claim 6, it is characterised in that：The step (2) in, the mass ratio of PFPE acyl fluorides and non-protonic solvent in the step (1) is 1：1~1：2.
- 10. the preparation method of perfluoropolyether-modified allyloxy body according to claim 6, it is characterised in that：The step Suddenly PFPE acyl fluorides and the mol ratio of fluoride salt and phase transfer catalyst in the step (1) are 1 in (2)：(1.2~ 2.0)：(0.1~0.18)；Optional, the mol ratio of PFPE acyl fluorides and allyl compound is 1 in the step (2)：1.3~1：2.0；Optional, in the step (4), washing uses deionized water, acetone or the mixed solution of the two.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102307851A (en) * | 2008-12-11 | 2012-01-04 | 3M创新有限公司 | Amide-linked perfluoropolyether thiol compounds and processes for their preparation and use |
| CN102666759A (en) * | 2009-11-11 | 2012-09-12 | 依视路国际集团（光学总公司） | Surface treatment composition, process for producing the same, and surface-treated article |
| WO2015087902A1 (en) * | 2013-12-13 | 2015-06-18 | 旭硝子株式会社 | Fluorine-containing ether composition, method for producing same, coating liquid, base material having surface treatment layer, and method for producing same |
| CN106085227A (en) * | 2016-06-21 | 2016-11-09 | 衢州氟硅技术研究院 | A kind of preparation method of high-performance anti-fingerprint agent |
-
2017
- 2017-08-30 CN CN201710761841.8A patent/CN107459641B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102307851A (en) * | 2008-12-11 | 2012-01-04 | 3M创新有限公司 | Amide-linked perfluoropolyether thiol compounds and processes for their preparation and use |
| CN102666759A (en) * | 2009-11-11 | 2012-09-12 | 依视路国际集团（光学总公司） | Surface treatment composition, process for producing the same, and surface-treated article |
| WO2015087902A1 (en) * | 2013-12-13 | 2015-06-18 | 旭硝子株式会社 | Fluorine-containing ether composition, method for producing same, coating liquid, base material having surface treatment layer, and method for producing same |
| CN106085227A (en) * | 2016-06-21 | 2016-11-09 | 衢州氟硅技术研究院 | A kind of preparation method of high-performance anti-fingerprint agent |
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