CN109942806A - Perfluoropolyether-modified dendritic silicon alkane derivatives and its preparation method and application - Google Patents
Perfluoropolyether-modified dendritic silicon alkane derivatives and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of perfluoropolyether-modified dendritic silicon alkane derivatives, and the structural formula of the perfluoropolyether-modified dendritic is as shown in following formula 1, formula 2:Formula 1
Description
Technical field
The invention belongs to technical field of polymer materials, more particularly to a kind of perfluoropolyether-modified dendroid silane are derivative
Object and its preparation method and application.
Background technique
The optical modules such as optical mirror slip, eyeglass, prism, reflecting mirror, touch screen and health care utensil are when in use
It is easy to be polluted by finger mark, skin oil and fat, sweat, cosmetics etc..This spot, which once adheres to, to be difficult to be removed, and is adhered to
The optical module of spot easily causes various problems.If the visual field can be interfered for example, dirt is adhered on the surface of eyeglass,
Appearance is set to be deteriorated；If dirt, identity decline, to the operability of the display with touch screen are adhered in the surface of display
Generate adverse effect.For above situation, such spot and stain usually are reduced by being surface-treated to component at present
Influence, one of the most common is the coupling technology of glass and silane.Have and organic material simultaneously in silane coupled agent molecule
There are the organo-functional group and reactivity alkoxy grp (such as methoxyl group, ethyoxyl) of good affinity.By in glass surface
Form silane coupling agent coating, on the one hand, hydrolytic condensation occurs for the moisture in the alkoxy and air in silane coupled agent molecule
Reaction is converted to siloxanes to form coating；On the other hand, silane coupling agent can form chemistry with glass or metal surface
And secondary or physical bond, to generate durable tough and tensile coating.Raising with consumer to the experience requirements of the optical modules such as touch screen,
The requirement of glass surface treatment technology is also higher and higher, do not require nothing more than the surface-treated layer to be formed with excellent water and oil repellant,
The performances such as antifouling also require coating to have brilliant wearability, uvioresistant and acid and alkali-resistance etc., common silane coupling agent
These requirements can not be met simultaneously at all.
Fluorine containing silane compound is (to can be the perfluor alkane of low molecular weight containing fluoro-containing group simultaneously in a kind of molecular structure
The holo-fluorine polyester of base or high molecular weight) and hydrolyzable alkoxy silane molecule.Fluorine containing silane compound is for substrate
When surface treatment, it is capable of providing excellent water and oil repellant and soil resistance etc..Wherein, alkoxysilane-modified functional perfluoro is poly-
Ether (english abbreviation PFPE, the same below) has been achieved with immense success as the application of glass surface anti-fingerprint coating (AFC).It is this
Coating had both had the characteristic of fluoropolymer-containing oleophobic and low-friction coefficient, it may have the hydrophobic and wear properties of siloxanes.
The combination of PFPE polymer and alkoxy silane makes product obtain better rub resistance and UV durability.Wherein, alcoxyl
The active end of base silane will be reacted by hydrolysis and condensation reaction with surface, be adjusted to substrate surface structural arrangement, this
Excellent connection provides durability required for touch-screen applications；The low surface surface Neng Shi of PFPE polymer has from clear
Clean ability and good stroke of sense of touch；The product has excellent wearability, and surface cleaning ability can be made to keep longer time.To the greatest extent
Existing alkoxysilane-modified PFPE anti-fingerprint coating product is managed to succeed on the market, but as client is to including
The requirement of performance including first contact angle, wearability etc. is higher and higher, and the product based on the prior art is no longer satisfied portion
Divide the anti-fingerprint demand of high-end applications.
Summary of the invention
The purpose of the present invention is to provide a kind of perfluoropolyether-modified dendritic silicon alkane derivatives and preparation method thereof, purports
It is not able to satisfy high-end applications product in the existing material first contact angle as glass surface anti-fingerprint coating of solution, wear-resisting property
The problem of demand.
Another object of the present invention is to provide a kind of applications of perfluoropolyether-modified dendritic silicon alkane derivatives.
For achieving the above object, The technical solution adopted by the invention is as follows:
One aspect of the present invention provides a kind of perfluoropolyether-modified dendritic silicon alkane derivatives, described perfluoropolyether-modified
The structural formula of dendritic is as shown in following formula 1, formula 2:
Wherein, m, n are respectively selected from 1~40 integer, and m+n=20~60, m/n=0.3~3；L is 0 or 1；With silicon original
The connected terminal methoxy group of son can be replaced the alkoxy that carbon atom number is 2~5.
Correspondingly, a kind of preparation method of perfluoropolyether-modified dendritic silicon alkane derivatives, includes the following steps:
Perfluoropolyether-modified dendritic intermediate as shown in following formula 3 and/or formula 4 is prepared respectively, wherein m,
N is respectively selected from 1~40 integer, and m+n=20~60, m/n=0.3~3；L is 0 or 1,
Under nitrogen or oxygen protection, among dendritic perfluoropolyether-modified shown in formula 3 and/or formula 4
Body and 1,3- bis--(benzotrifluoride), the mixing of tri-alkoxy hydrogen silane, is added catalyst, reacts 4- under conditions of 40-116 DEG C
For 24 hours, compound shown in preparation formula 1 and/or formula 2, wherein the alkoxy in the tri-alkoxy hydrogen silane is selected from carbon atom number
1~5 alkoxy.
And above-mentioned perfluoropolyether-modified dendritic silicon alkane derivatives are in the application in anti-fingerprint coating material field.
Perfluoropolyether-modified dendritic silicon alkane derivatives provided by the invention (contain containing PFPE chain, linking group simultaneously
Phenyl group) and three kinds of structural units of silane end, when it forms coating such as anti-fingerprint coating, PFPE chain, linking group and silicon
Alkane end is respectively formed functional layer, transition zone and bonded layer structure.Wherein, the functional layer is mainly made of PFPE, is had
The good advantage of hydrophobic oleophobic, lubricity is the functional part that anti-fingerprint coating plays anti-fingerprint effect.Silane in the bonded layer
The alkoxy of upper connection occurs hydrolysis-condensation reaction and is formed with hydrophily and the preferable siloxane layer of brittleness.The transition zone is used
In connecting the functional layer and the bonded layer, the function of the functional layer and the bonded layer is finally realized.The present invention is with 5-
The group that bromomethyl-Resorcinol allyl ether reaction obtains is as transition layer structure, on the one hand, the transition of specific structure
Layer has the biggish linking group of volume, and when being rubbed, transition zone can give full play to the function of dissipation frictional energy,
It is transmitted to the active force of bonded layer from transition zone to decay rapidly, reduces the probability of bonding damage layer, it is wear-resisting to improve coating
Ability；On the other hand, transition layer structure provided by the invention has dendritic structure, can introduce more reactive group, leads to
The reactive group activity for crossing specific structure introducing is high, to be conducive to improve the introducing quantity of alkoxy silane, improves bonded layer
Stability, further increase coating abrasive resistance.In addition, the present invention improves the hydrophobicity of linking group by MOLECULE DESIGN
(using 5- bromomethyl-Resorcinol allyl ether as raw material reaction obtain group be used as linking group), increase transition
It can be further improved the hydrophobicity of coating while thickness is spent.To sum up, perfluoropolyether-modified dendritic silicon provided by the invention
Alkane derivatives have excellent anti-fingerprint, refuse the performances such as oily, antifouling, are more importantly, with excellent abrasive resistance and dredge
Aqueous energy (water repellent), can be used as all kinds of glass panel anti-fingerprint coatings, especially also be able to satisfy the high height of confrontation fingerprint demand
Hold the requirement of application product.
The preparation method of perfluoropolyether-modified dendritic silicon alkane derivatives provided by the invention, first prepares with specific knot
The perfluoropolyether-modified dendritic intermediate of structure, is then prepared by silicon hydrogenation.This method not only item
Part is mild, and process is simple, and controllability is strong.
Perfluoropolyether-modified dendritic silicon alkane derivatives provided by the invention as anti-fingerprint coating material in application,
It with the performances such as excellent anti-fingerprint, water and oil repellant, antifouling, is more importantly that there is excellent abrasive resistance, can be used as
All kinds of glass panel anti-fingerprint coatings are particularly suitable for applying as the anti-fingerprint of the high-end applications product high to anti-fingerprint demand
Layer.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
A kind of perfluoropolyether-modified dendritic silicon alkane derivatives, the knot of the perfluoropolyether-modified dendritic
Structure formula is as shown in following formula 1, formula 2:
Wherein, m, n are respectively selected from 1~40 integer, and m+n=20~60, m/n=0.3~3；L is 0 or 1；And and silicon
The connected terminal methoxy group of atom can be replaced the alkoxy that carbon atom number is 2~5.
Perfluoropolyether-modified dendritic silicon alkane derivatives provided in an embodiment of the present invention, simultaneously containing PFPE chain, connection
Group (containing phenyl group) and three kinds of structural units of silane end, when it forms coating such as anti-fingerprint coating, PFPE chain, linker
Group and silane end are respectively formed functional layer, transition zone and bonded layer structure.Wherein, the functional layer is mainly by PFPE structure
At, have the advantages that hydrophobic oleophobic, lubricity are good, be anti-fingerprint coating play anti-fingerprint effect functional part.The bonding
The alkoxy connected on silane in layer occurs hydrolysis-condensation reaction and is formed with hydrophily and the preferable siloxane layer of brittleness.It is described
Transition zone finally realizes the function of the functional layer and the bonded layer for connecting the functional layer and the bonded layer.
Inventor has found that when using perfluoropolyether-modified silane derivative as coating material, when coating table
When face is rubbed, active force is transmitted to transition zone from functional layer, then passes to bonded layer from transition zone.And works as and be transmitted to bonding
When the power of layer is sufficiently large, the destruction of unrepairable occurs for bonded layer.In view of this, the embodiment of the present invention is with 5- bromomethyl -1,3-
Benzenediol allyl ether reacts the group obtained as transition layer structure as raw material, on the one hand, the transition zone of specific structure, tool
There is the biggish linking group of volume, when being rubbed, transition zone can give full play to the function of dissipation frictional energy, thus fast
Speed decaying is transmitted to the active force of bonded layer from transition zone, reduces the probability of bonding damage layer, improves coating abrasive resistance；Separately
On the one hand, transition layer structure provided in an embodiment of the present invention has dendritic structure, can introduce more reactive group, leads to
The reactive group activity for crossing specific structure introducing is high, to be conducive to improve the introducing quantity of alkoxy silane, improves bonded layer
Stability, further increase coating abrasive resistance.In addition, the embodiment of the present invention improves linking group by MOLECULE DESIGN
Hydrophobicity (group that reaction obtains using 5- bromomethyl-Resorcinol allyl ether as raw material is as linking group), is increasing
It can be further improved the hydrophobicity of coating while adding transition region thickness.To sum up, perfluoropolyether-modified tree provided by the invention
Dendritic silane derivative has excellent anti-fingerprint, refuses the performances such as oily, antifouling, be more importantly, has excellent wear-resisting energy
Power and hydrophobic performance (water repellent), can be used as all kinds of glass panel anti-fingerprint coatings, especially also be able to satisfy confrontation fingerprint demand
The requirement of high high-end applications product.
In the embodiment of the present invention, in perfluoropolyether-modified dendritic silicon alkane derivatives structure, in perfluoropolyether alcohol, m, n
It is respectively selected from 1~40 integer, and m+n=20~60, m/n=0.3~3.Suitable molecular structure is conducive to improve material
Hydrophobic oleophobic activity and lubricity.Silicon atom quantity is 2-8 in perfluoropolyether-modified dendritic silicon alkane derivatives structure, silicon
Atom number increases, and can improve the wearability of product；And the dendroid knot of perfluoropolyether-modified dendritic silicon alkane derivatives
Structure assigns the better wear-resisting property of product and lower coefficient of friction.In addition, the embodiment of the present invention is connected by ehter bond (C-O-C)
Binding groups and functional group are connect, than there is better stability and wear-resisting property by amido bond (- C (O)-NH-) connection.Into
One step, as another embodiment, it is 2~5 that the terminal methoxy group being connected with silicon atom, which could alternatively be carbon atom number,
Alkoxy, such as ethyoxyl, propoxyl group, butoxy.It should be appreciated that in the embodiment of the present invention, the end alkane being connected with silicon atom
The carbochain of oxygroup be not easy it is too long, if carbochain is too long, be used as coating material when, after being bonded with substrate, strand freedom degree is larger,
Coating stability lowers.As preferred embodiment, the end alkoxy group being connected with silicon atom is selected from methoxy or ethoxy.Specifically
Preferably, the end alkyl being connected with silicon atom is methoxy or ethoxy.It is worth noting that, perfluor of the embodiment of the present invention is poly-
In the modified dendritic silicon alkane derivatives structure of ether, m/n=0.3~3 meet the perfluoropolyether-modified branch of the proportional region
Shape silane derivative has excellent wear-resisting property.
Perfluoropolyether-modified dendritic silicon alkane derivatives provided in an embodiment of the present invention are obtained by following methods preparation
?.
And the embodiment of the invention provides a kind of preparation method of perfluoropolyether-modified dendritic silicon alkane derivatives,
Include the following steps:
S01. perfluoropolyether-modified dendritic intermediate as shown in following formula 3 and/or formula 4 is prepared respectively,
In, m, n are respectively selected from 1~40 integer, and m+n=20~60, m/n=0.3~3；L is 0 or 1；
S02. under nitrogen or oxygen protection, by dendritic perfluoropolyether-modified shown in formula 3 and/or formula 4
Intermediate and 1,3- bis--(benzotrifluoride), the mixing of tri-alkoxy hydrogen silane, is added catalyst, anti-under conditions of 40-116 DEG C
4-24h is answered, compound shown in shown formula 1 and/or formula 2 is prepared, wherein the alkoxy in the tri-alkoxy hydrogen silane is selected from carbon
The alkoxy that atomicity is 1~5.
The preparation method of perfluoropolyether-modified dendritic silicon alkane derivatives provided in an embodiment of the present invention, first preparing has
The perfluoropolyether-modified dendritic intermediate of specific structure, is then prepared by silicon hydrogenation.This method
Not only mild condition, and process is simple, and controllability is strong.
Specifically, it is poly- to prepare dendroid perfluoropolyether-modified as shown in equation 3 above and/or formula 4 in above-mentioned steps S01
Close object intermediate.Herein, it should be understood that the perfluoropolyether-modified dendritic intermediate can be 3 shownization of formula
Object is closed, at this point, compound shown in formula 1 is prepared after step S02；In the perfluoropolyether-modified dendritic
Mesosome can be compound shown in formula 4, at this point, compound shown in formula 2 is prepared after step S02；Certainly, the perfluor
Polyether-modified dendritic intermediate can be the mixing simultaneously containing compound shown in compound shown in formula 3 and formula 4
Object, at this point, the mixture of compound shown in compound shown in formula 1 and formula 2 is prepared after step S02.
It is different according to the value of l in the embodiment of the present invention, the preparation method of compound shown in formula 3, formula 4 difference.
As a kind of specific preferred embodiment, as l=0, perfluoropolyether-modified branch shown in formula 3 and/or formula 4
The preparation method of shaped polymer intermediate the following steps are included:
S111. 5- bromomethyl -1,3 benzenediol, allyl bromide, bromoallylene are dissolved in organic solvent, potassium hydroxide and/or hydrogen is added
The aqueous solution and phase transfer catalyst of sodium oxide molybdena after mixed processing, react 4-12h under conditions of 40-66 DEG C, are evaporated under reduced pressure
Afterwards, washing layering collects upper solution and handles to obtain 5- bromomethyl -1,3- benzene diallyl ether through revolving；
S112. 5- bromomethyl -1,3- benzene diallyl ether, perfluoropolyether alcohol, 1,3- bis--(benzotrifluoride), phase transfer are urged
After the mixing of the aqueous solution of agent and potassium hydroxide and/or sodium hydroxide, 4-12h is reacted under the conditions of 40-110 DEG C, is washed to down
When layer pH value of solution is 7, lower layer's solution is collected, after revolving processing plus washing is washed with organic solvent, lower layer's dope is collected,
It is concentrated under reduced pressure to give compound shown in formula 3 and/or formula 4.
Specifically, in above-mentioned steps S111,5- bromomethyl -1,3 benzenediol, allyl bromide, bromoallylene hydroxide ion effect
Under, reaction generates 5- bromomethyl -1,3- benzene diallyl ether.5- bromomethyl -1,3- benzene diallyl ether, allyl bromide, bromoallylene are organic examination
Agent has preferable solubility in organic solvent, and the embodiment of the present invention is for dissolving 5- bromomethyl -1,3 benzenediol, allyl
The organic solvent of bromine is selected from least one of tetrahydrofuran, dioxane, fluorine-containing organic solvent.In the embodiment of the present invention, hydrogen
Oxygen radical ion to the generation of reaction, control reaction rate, improves products collection efficiency and purity, influence is very big as catalysts.
But hydroxide such as sodium hydroxide or potassium hydroxide are inorganic matter, and solubility property in organic solvent is bad, anti-in order to promote
It should occur, in the embodiment of the present invention, add phase transfer catalyst to promote the progress of reaction.
Preferably, the phase transfer catalyst is selected from benzyltriethylammoinium chloride, tetrabutylammonium bromide, tetrabutyl chlorination
Ammonium, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride
At least one of.The preferred phase transfer catalyst, well can effectively shift the hydroxide ion in aqueous solution
Into organic system, promote the generation of reaction, and guarantees suitable reaction rate.It is further preferred that the phase transfer catalysis (PTC)
The additive amount of agent is that the 0.5-10% of big (5- bromomethyl -1, the 3 benzenediol) quality of raw material middle-molecular-weihydroxyethyl is advisable, and additive amount is too low
The conversion and reaction time for being unfavorable for reaction extend, the trouble of the excessively high raising for bringing cost and post-processing.
Preferably, the aqueous solution of the potassium hydroxide and/or sodium hydroxide is the quality of potassium hydroxide and/or sodium hydroxide
Percentage composition is the aqueous solution of 30-50%.The mass percentage of suitable potassium hydroxide and/or sodium hydroxide, on the one hand, can
To guarantee the concentration of suitable hydroxide ion, be conducive to the reaction for being catalyzed 5- bromomethyl -1,3 benzenediol, allyl bromide, bromoallylene；It is another
Aspect, the concentration of suitable potassium hydroxide and/or sodium hydroxide are conducive to the transfer efficiency of phase transfer catalyst, thus more preferably
Ground controls reaction rate.
The reaction condition of -1,3 benzenediol of 5- of embodiment of the present invention bromomethyl, allyl bromide, bromoallylene are as follows: anti-under the conditions of 40-110 DEG C
Answer 4-12h.If reaction temperature is too low and/or the reaction time is too short, raw material cannot convert completely very well；If reaction temperature is excessively high
And/or the reaction time is too long, and more side reactions can occur, influence product yield.Inventor is the study found that in the reaction item
Preferable yield is obtained under part.
After reaction, 5- bromomethyl -1,3- benzene diallyl ether is generated, but in reaction system, in addition to product 5- bromomethyl -
1,3- benzene diallyl ether also contains raw material, reaction medium, complicated component.If directly entering following step as raw material
The reaction of S112, then not only bad for the progress of reaction, and obtained product yield is low, purity is low, is unfavorable for isolating and purifying,
It eventually leads to and is difficult to obtain expected final product.In view of this, after the completion of reaction, the embodiment of the present invention carries out reaction system
Then purification process is washed, stratification specifically, first solvent, especially organic solvent are taken out in vacuum distillation, collect
Upper solution, at this point, other issuable big polarity in potassium hydroxide, sodium hydroxide and reaction process in reaction system
Impurity removal.Further, the upper solution of collection is subjected to revolving processing, removes low-boiling-point substance, the mainly complete original of unreacted
Expect issuable low polar impurity in component and reaction process.The temperature of processing is rotated, 5- bromomethyl -1,3- benzene diene is lower than
The boiling point of propyl ether.
In above-mentioned steps S112,5- bromomethyl -1,3- benzene diallyl ether, perfluoropolyether alcohol are dissolved in fluorocarbon solvent,
Under the action of hydroxide ion, 5- bromomethyl -1,3- benzene diallyl ether, the reaction of perfluoropolyether alcohol prepare the formula 3 and/or formula of l=0
Compound shown in 4.
In the embodiment of the present invention, select fluorocarbon solvent as reaction medium, the fluorocarbon solvent that specifically can choose includes 1,
3- bis--(benzotrifluoride), perfluor benzene, hydrofluoroether and perfluoro alkane etc., preferably 1,3- bis--(benzotrifluoride).
In the embodiment of the present invention, hydroxide ion to the generation of reaction, control reaction rate, is mentioned as catalysts
High product yield and purity influence very big.But hydroxide such as sodium hydroxide or potassium hydroxide are inorganic matter, in organic solvent
Solubility property it is bad, in order to promote reaction, in the embodiment of the present invention, add phase transfer catalyst promote reaction into
Row.
Preferably, the phase transfer catalyst is selected from benzyltriethylammoinium chloride, tetrabutylammonium bromide, tetrabutyl chlorination
Ammonium, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride
At least one of.The preferred phase transfer catalyst, well can effectively shift the hydroxide ion in aqueous solution
Into organic system, promote the generation of reaction, and guarantees suitable reaction rate.It is further preferred that the phase transfer catalysis (PTC)
The additive amount of agent is the 0.5-10% of big reaction raw materials (5- bromomethyl -1,3- benzene diallyl ether) quality of molecular weight.If described
The additive amount of phase transfer catalyst is too low, and the conversion and reaction time for being unfavorable for reaction extend；The mistake of the phase transfer catalyst
Height brings the raising of cost, while post-processing trouble.
Preferably, the aqueous solution of the potassium hydroxide and/or sodium hydroxide is the quality of potassium hydroxide and/or sodium hydroxide
Percentage composition is the aqueous solution of 30-50%.The mass percentage of suitable potassium hydroxide and/or sodium hydroxide, on the one hand, can
To guarantee the concentration of suitable hydroxide ion, be conducive to the reaction for being catalyzed 5- bromomethyl -1,3 benzenediol, allyl bromide, bromoallylene；It is another
Aspect, the concentration of suitable potassium hydroxide and/or sodium hydroxide are conducive to the transfer efficiency of phase transfer catalyst, thus more preferably
Ground controls reaction rate.
The reaction condition of 5- bromomethyl -1,3- benzene of embodiment of the present invention diallyl ether, perfluoropolyether alcohol are as follows: 40-110 DEG C of item
4-12h is reacted under part.If reaction temperature is too low and/or time too short raw material cannot convert completely very well；If reaction temperature is excessively high
And/or more side reactions can then occur for overlong time, influence product yield.
After reaction, reaction system is washed, be washed to lower layer's pH value of solution be 7 when, remove water-solubility impurity, receive
Collect lower layer's solution, revolving is handled, removes low-boiling-point substance (using product boiling point as standard), finally, using washing organic solvent
It is washed, removes unreacted raw material, collected lower layer's dope, be concentrated under reduced pressure to give shown in l=0 up-to-date style 3 and/or formula 4
Compound.Preferably, the washing is selected from least one of petroleum ether, n-hexane, methyl tertiary butyl ether(MTBE) with organic solvent.
As another specific preferred embodiment, as l=1, perfluoropolyether-modified tree shown in formula 3 and/or formula 4
The preparation method of dendritic polymer intermediate the following steps are included:
S211. 1,3 benzenediol of 5- bromomethyl is dissolved in organic solvent, the water of potassium hydroxide and/or sodium hydroxide is added
Solution and phase transfer catalyst, back flow reaction 4-12h；It is added allyl bromide, bromoallylene, the reaction was continued 4-12h, after vacuum distillation, washing point
Layer collects upper solution and handles to obtain 5,5'- ((5- (bromomethyl) -1,3- phenylene) bis- (oxygroups)) bis- (methylenes through revolving
Base)) two (bis- (allyloxy) benzene of 1,3-)；
S212. by 5,5'- ((5- (bromomethyl) -1,3- phenylene) bis- (oxygroups)) bis- (methylene)) two (bis- (alkene of 1,3-
Propoxyl group) benzene), perfluoropolyether alcohol, 1,3- bis--(benzotrifluoride), phase transfer catalyst and potassium hydroxide and/or sodium hydroxide
Aqueous solution mixing after, react 4-12h under the conditions of 40-110 DEG C, be washed to lower layer's pH value of solution be 7 when, collect lower layer's solution, rotation
After steaming processing plus washing is washed with organic solvent, is collected lower layer's dope, is concentrated under reduced pressure to give shown in formula 3 and/or formula 4
Compound.
Specifically, for 5- bromomethyl -1,3 benzenediol under the action of hydroxide ion, first itself is poly- in above-mentioned steps S211
Closing is in dendroid trimer；Then with allyl bromide, bromoallylene under the catalysis of hydroxide ion, reaction obtains 5,5'- ((5- (bromine first
Base) -1,3- phenylene) bis- (oxygroups)) bis- (methylene)) two (bis- (allyloxy) benzene of 1,3-).5- bromomethyl -1,3- benzene diene
Propyl ether, allyl bromide, bromoallylene are organic reagent, have preferable solubility in organic solvent, the embodiment of the present invention is for dissolving 5- bromine
Methyl-1,3 benzenediols, allyl bromide, bromoallylene organic solvent in tetrahydrofuran, dioxane, fluorine-containing organic solvent at least one
Kind.In the embodiment of the present invention, hydroxide ion is as catalysts, to the generation of reaction, control reaction rate, raising product
Yield and purity influence very big.But hydroxide such as sodium hydroxide or potassium hydroxide are inorganic matter, dissolution in organic solvent
Performance is bad, in order to promote reaction, in the embodiment of the present invention, adds phase transfer catalyst to promote the progress of reaction.
Preferably, the phase transfer catalyst is selected from benzyltriethylammoinium chloride, tetrabutylammonium bromide, tetrabutyl chlorination
Ammonium, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride
At least one of.The preferred phase transfer catalyst, well can effectively shift the hydroxide ion in aqueous solution
Into organic system, promote the generation of reaction, and guarantees suitable reaction rate.It is further preferred that the phase transfer catalysis (PTC)
The additive amount of agent is the 0.5-10% of big raw material (5- bromomethyl -1, the 3- benzene diallyl ether) quality of molecular weight, and additive amount is too low
The conversion and reaction time for being unfavorable for reaction extend, the trouble of the excessively high raising for bringing cost and post-processing.
Preferably, the aqueous solution of the potassium hydroxide and/or sodium hydroxide is the quality of potassium hydroxide and/or sodium hydroxide
Percentage composition is the aqueous solution of 30-50%.The mass percentage of suitable potassium hydroxide and/or sodium hydroxide, on the one hand, can
To guarantee the concentration of suitable hydroxide ion, be conducive to the reaction for being catalyzed 5- bromomethyl -1,3 benzenediol, allyl bromide, bromoallylene；It is another
Aspect, the concentration of suitable potassium hydroxide and/or sodium hydroxide are conducive to the transfer efficiency of phase transfer catalyst, thus more preferably
Ground controls reaction rate.
The self-polymerization of 1,3 benzenediol of 5- of embodiment of the present invention bromomethyl, dendroid tripolymer, allyl bromide, bromoallylene are returning
It is carried out under stream reaction condition, reaction time 4-12h.Reaction terminates generation 5,5'-, and ((5- (bromomethyl) -1,3- phenylene) is double
(oxygroup)) bis- (methylene)) two (1,3- bis- (allyloxy) benzene), but in reaction system, in addition to product, also contain raw material, anti-
Answer medium, complicated component.If directly enter the reaction of following step S212 as raw material, not only bad for reaction into
Row, and obtained product yield is low, purity is low, is unfavorable for isolating and purifying, and eventually leads to and is difficult to obtain expected final product.Have
In consideration of it, after the completion of reaction, the embodiment of the present invention carries out purification process to reaction system, specifically, first vacuum distillation is taken out
Solvent, especially organic solvent, are then washed, stratification, upper solution are collected, at this point, the hydrogen-oxygen in reaction system
Change other issuable big polar impurity removals in potassium, sodium hydroxide and reaction process.Further, by the upper layer of collection
Solution carries out revolving processing, removes low-boiling-point substance, mainly issuable low in the complete raw material components of unreacted and reaction process
Polar impurity.The temperature of processing is rotated, is lower than 5,5'- ((5- (bromomethyl) -1,3- phenylene) bis- (oxygroups)) bis- (methylene))
The boiling point of two (bis- (allyloxy) benzene of 1,3-).
In above-mentioned steps S212, by 5,5'- ((5- (bromomethyl) -1,3- phenylene) bis- (oxygroups)) bis- (methylene)) two
(1,3- bis- (allyloxy) benzene), perfluoropolyether alcohol are dissolved in fluorocarbon solvent, under the action of hydroxide ion, 5,5'- ((5-
(bromomethyl) -1,3- phenylene) bis- (oxygroups)) bis- (methylene)) two (bis- (allyloxy) benzene of 1,3-), the reaction of perfluoropolyether alcohol
Prepare compound shown in the formula 3 and/or formula 4 of l=1.
In the embodiment of the present invention, select fluorocarbon solvent as reaction medium.The fluorocarbon solvent that can choose includes 1,3- bis--
(benzotrifluoride), perfluor benzene, hydrofluoroether and perfluoro alkane etc., preferably 1,3- bis--(benzotrifluoride).
In the embodiment of the present invention, hydroxide ion to the generation of reaction, control reaction rate, is mentioned as catalysts
High product yield and purity influence very big.But hydroxide such as sodium hydroxide or potassium hydroxide are inorganic matter, in organic solvent
Solubility property it is bad, in order to promote reaction, in the embodiment of the present invention, add phase transfer catalyst promote reaction into
Row.
Preferably, the phase transfer catalyst is selected from benzyltriethylammoinium chloride, tetrabutylammonium bromide, tetrabutyl chlorination
Ammonium, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride
At least one of.The preferred phase transfer catalyst, well can effectively shift the hydroxide ion in aqueous solution
Into organic system, promote the generation of reaction, and guarantees suitable reaction rate.It is further preferred that the phase transfer catalysis (PTC)
The additive amount of agent is the big raw material 5,5'- ((5- (bromomethyl) -1,3- phenylene) bis- (oxygroups)) bis- (methylene) of molecular weight) two
The 0.5-10% of (1,3- bis- (allyloxy) benzene) quality, the too low conversion for being unfavorable for reaction of additive amount and reaction time extend,
The trouble of the excessively high raising for bringing cost and post-processing.
Preferably, the aqueous solution of the potassium hydroxide and/or sodium hydroxide is the quality of potassium hydroxide and/or sodium hydroxide
Percentage composition is the aqueous solution of 30-50%.The mass percentage of suitable potassium hydroxide and/or sodium hydroxide, on the one hand, can
To guarantee the concentration of suitable hydroxide ion, be conducive to the reaction for being catalyzed 5- bromomethyl -1,3 benzenediol, allyl bromide, bromoallylene；It is another
Aspect, the concentration of suitable potassium hydroxide and/or sodium hydroxide are conducive to the transfer efficiency of phase transfer catalyst, thus more preferably
Ground controls reaction rate.
Preferably, the perfluoropolyether alcohol, m, n are respectively selected from 1~40 integer, and m+n=20~60, m/n=0.3~
3。
5,5'- of the embodiment of the present invention ((5- (bromomethyl) -1,3- phenylene) bis- (oxygroups)) bis- (methylene)) two (1,3-
Bis- (allyloxy) benzene), the reaction condition of perfluoropolyether alcohol are as follows: 4-12h is reacted under the conditions of 40-110 DEG C.When reaction temperature is too low
Between too short raw material cannot convert very well completely, more side reactions can then occur for the excessively high overlong time of reaction temperature, influence product
Yield.
After reaction, reaction system is washed, be washed to lower layer's pH value of solution be 7 when, remove water-solubility impurity, receive
Collect lower layer's solution, revolving is handled, removes low-boiling-point substance (using product boiling point as standard), finally, using washing organic solvent
It is washed, removes unreacted raw material, collected lower layer's dope, be concentrated under reduced pressure to give shown in l=0 up-to-date style 3 and/or formula 4
Compound.Preferably, the washing is selected from least one of petroleum ether, n-hexane, methyl tertiary butyl ether(MTBE) with organic solvent.
In above-mentioned steps S02, under nitrogen or oxygen protection, by tree perfluoropolyether-modified shown in formula 3 and/or formula 4
Dendritic polymer intermediate, fluorocarbon solvent (reaction medium) are mixed with tri-alkoxy hydrogen silane, and silicon occurs under the action of catalyst
Compound shown in hydrogenation, preparation formula 1 and/or formula 2.
In the embodiment of the present invention, the alkoxy in the tri-alkoxy hydrogen silane is selected from the alcoxyl that carbon atom number is 1~5
Base, such as ethyoxyl, propoxyl group, butoxy.It should be appreciated that in the embodiment of the present invention, the end alkoxy group being connected with silicon atom
Carbochain be not easy it is too long, if carbochain is too long, be used as coating material when, after being bonded with substrate, strand freedom degree is larger, coating
Stability lowers.As preferred embodiment, the end alkoxy group being connected with silicon atom is selected from methoxy or ethoxy.
In the embodiment of the present invention, it is preferred that the reaction medium is selected from 1,3- bis--(benzotrifluoride), perfluor benzene, hydrofluoroether
With the fluorocarbon solvents such as perfluoro alkane；Most preferably, the reaction medium is 1,3- bis--(benzotrifluoride).The embodiment of the present invention 1,
3- bis--(benzotrifluoride) and perfluoropolyether-modified dendritic intermediate ratio are 1~5:1 of mass ratio, at this point, dissolution
It is functional.The content of 1,3-, bis--(benzotrifluoride) is too low to be unfavorable for dissolving, and 1,3-, bis--(benzotrifluoride) contains
It measures excessively high formation waste and post-processing needs more energy consumptions.
Preferably, the catalyst is selected from chloroplatinic acid catalyst, blocks this Taide catalyst, platinum catalyst, palladium catalyst, rhodium
At least one of complex compound catalyst.Preferred catalyst not only contributes in perfluoropolyether-modified dendritic
Silicon hydrogenation between mesosome and trimethoxy hydrogen silane, and reaction efficiency is high, and product purity is high, is easy to pass through post-processing
Purifying.It is further preferred that the quality of the catalyst is the 20-120ppm of the reaction system gross mass, catalytic amount mistake
Low to make reaction not exclusively, catalytic amount is excessively high to cause increased costs and coloured product to deepen purity reduction.
The silicon hydrogenation condition of the embodiment of the present invention are as follows: react 4-24h under conditions of 40-116 DEG C.Reaction temperature mistake
Low time too short raw material cannot convert completely very well, and more side reactions can then occur for the excessively high overlong time of reaction temperature, influence
Product yield.
It is worth noting that, the perfluoropolyether-modified dendritic intermediate of the embodiment of the present invention has multiple reactions
Center can connect multiple alkoxy silanes, to be conducive to increase bonded layer intensity, improve coating abrasion performance.
And the embodiment of the invention also provides a kind of above-mentioned perfluoropolyether-modified dendritic silicon alkane derivatives or above-mentioned
Application of the perfluoropolyether-modified dendritic silicon alkane derivatives that method prepares in anti-fingerprint coating material field.
Perfluoropolyether-modified dendritic silicon alkane derivatives provided in an embodiment of the present invention are as anti-fingerprint coating material
It in application, having the performances such as excellent anti-fingerprint, water and oil repellant, antifouling, is more importantly that there is excellent abrasive resistance,
It can be used as all kinds of glass panel anti-fingerprint coatings, be particularly suitable for as the high-end applications product high to anti-fingerprint demand
Anti-fingerprint coating.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of perfluoropolyether-modified dendritic silicon alkane derivatives, the knot of the perfluoropolyether-modified dendritic
Structure formula is shown below and (is named as S-1):
Wherein, m, n are respectively selected from 1~40 integer, and m+n=20~60, m/n=0.3~3；L is 0.
The preparation method of above compound the following steps are included:
S11. the synthesis of perfluoropolyether-modified dendrimers intermediate
Thermometer, agitating device, condensing unit are housed at one, add 202g5- bromine first in vacuum distillation apparatus four-hole boiling flask
Base -1,3 benzenediol, 250g allyl bromide, bromoallylene, 1000g THF (tetrahydrofuran), 20g phase transfer catalyst TBAB (tetrabutyl phosphonium bromide
Ammonium), 40% sodium hydrate aqueous solution of 250g, mixing is heated to 66 DEG C of reaction 4h, and vacuum distillation removes solvent, adds 500g
Water agitator treating 30min, stratification take 45 DEG C of removal low-boiling-point substances of upper solution Rotary Evaporators to obtain colourless liquid 5- bromine first
Base -1,3- benzene diallyl ether 270g.
At one equipped with thermometer, agitating device, in condensing unit three-necked flask plus 150g 5- bromomethyl -1,3- benzene two
Allyl ether, 2000g (molecular weight of perfluoropolyether alcohol is 4000) perfluoropolyether alcohol, 4000g1,3- bis--(benzotrifluoride), 20g phase
40% sodium hydroxide solution of transfer catalyst TBAB and 100g, mixing are heated to 110 DEG C of reaction 10h, and 1000g water is added
Agitator treating 30min, stratification, once to pH value of solution=7, lower layer's solution rotating evaporimeter removes lower layer's solution repeated washing
Low-boiling-point substance adds 200g petroleum ether (90-120 DEG C) agitator treating 20min, stratification, 45 DEG C of rotary evaporations of lower layer's viscous product
Instrument oil pump is concentrated under reduced pressure 2h and obtains colorless and transparent following formula intermediate 2050g, wherein m, n are respectively selected from 1~40 integer, l 0.
S12. based on the corresponding perfluoropolyether methoxy silane synthesis of midbody compound
Under nitrogen protection at one equipped with thermometer, agitating device, in condensing unit three-necked flask by above formula intermediate
500g, dry 1,3- bis--(benzotrifluoride) 1500g, the clarification of trimethoxy hydrogen silane 72g stirring and dissolving, are heated to 116 DEG C,
This Taide catalyst toluene solution of the card of 21g 5000ppm is added dropwise, is reacted for 24 hours under nitrogen environment, Rotary Evaporators are concentrated under reduced pressure
Removal low-boiling-point substance obtains structure flaxen Perfluoropolyether silanes 501g as shown in S-1.1H NMR (400MHz, CDCl3): δ 0.58
(t 4H), 1.8 (m 4H), 3.55 (s 18H), 3.69 (s 2H), 3.94 (t 4H), 4.63 (s 2H), 6.21-6.26 (m
3H)。
Embodiment 2
A kind of perfluoropolyether-modified dendritic silicon alkane derivatives, the knot of the perfluoropolyether-modified dendritic
Structure formula is shown below and (is named as S-2):
Wherein, m, n are respectively selected from 1~40 integer, and m+n=20~60, m/n=0.3~3；L is 0.
The preparation method of above compound the following steps are included:
S21. the synthesis of perfluoropolyether-modified dendrimers intermediate
One equipped with thermometer, agitating device, condensing unit, in vacuum distillation apparatus four-hole boiling flask plus 202g5- bromine first
Base -1,3 benzenediol, 250g allyl bromide, bromoallylene, 1000g THF, 20g phase transfer catalyst 40% sodium hydroxide of TBAB, 250g are water-soluble
Liquid, mixing are heated to 66 DEG C of reaction 4h, are evaporated under reduced pressure and remove solvent, add 500g water agitator treating 30min, stratification,
45 DEG C of removal low-boiling-point substances of upper solution Rotary Evaporators are taken to obtain colourless liquid 5- bromomethyl -1,3- benzene diallyl ether 270g.
At one equipped with thermometer, agitating device, in condensing unit three-necked flask plus 30g 5- bromomethyl -1,3- benzene diene
Propyl ether, 200g (molecular weight of perfluoropolyether alcohol is 4000) perfluoropolyether alcohol, 600g1,3- bis--(benzotrifluoride), 2g phase transfer
40% sodium hydroxide solution of catalyst TBAB and 10g, mixing are heated to 110 DEG C of reaction 10h, and the stirring of 100g water is added and washes
30min is washed, stratification, for lower layer's solution repeated washing once to pH value of solution=7, lower layer's solution rotating evaporimeter removes low boiling
Object adds 20g petroleum ether (90-120 DEG C) agitator treating 20min, stratification, 45 DEG C of Rotary Evaporators oil pumps of lower layer's viscous product
2h is concentrated under reduced pressure and obtains colorless and transparent intermediate 206g, wherein m, n are respectively selected from 1~40 integer, and m+n=20~60, m/n
=0.3~3；L is 0.
S22. the corresponding methoxy silane synthesis based on midbody compound
Under nitrogen protection at one equipped with thermometer, agitating device, in condensing unit three-necked flask by compound B (n=0)
50g, dry 1,3- bis--(benzotrifluoride) 150g, trimethoxy hydrogen silane 10g stirring and dissolving are clarified, and are heated under nitrogen environment
To 116 DEG C, this Taide catalyst toluene solution of the card of 3g 5000ppm is added dropwise, is reacted for 24 hours under nitrogen environment, Rotary Evaporators subtract
Pressure concentration removal low-boiling-point substance obtains structure flaxen Perfluoropolyether silanes 49g as shown in S-2.1H NMR (400MHz, CDCl3):
δ 0.58 (t 8H), 1.8 (m 8H), 3.55 (s 36H), 3.69 (s 4H), 3.94 (t 8H), 4.63 (s 4H), 6.21-6.26
(m 6H)。
Embodiment 3
A kind of perfluoropolyether-modified dendritic silicon alkane derivatives, the knot of the perfluoropolyether-modified dendritic
Structure formula is shown below and (is named as S-3):
Wherein, m, n are respectively selected from 1~40 integer, and m+n=20~60, m/n=0.3~3；L is 1.
The preparation method of above compound the following steps are included:
S31. the synthesis of perfluoropolyether-modified intermediate polymer of getting one's things ready (l=1)
Add 202g 5- in the three-necked flask that one is equipped with thermometer, agitating device, condensing unit, vacuum distillation apparatus
1,3 benzenediol of bromomethyl, 40% sodium hydrate aqueous solution of 500g THF, 600g, 20g phase transfer catalyst are heated with stirring to back
Stream reaction 12h.Into above-mentioned reaction solution plus allyl bromide, bromoallylene 240-480g, the reaction was continued 12h, vacuum distillation is removed low-boiling-point substance, is added
200g water agitator treating 30min, stratification take upper solution Rotary Evaporators removal low-boiling-point substance to obtain colourless liquid 5,5'-
((5- (bromomethyl) -1,3- phenylene) bis- (oxygroups)) bis- (methylene)) two (bis- (allyloxy) benzene of 1,3-) 210g.
At one equipped with thermometer, agitating device, in condensing unit three-necked flask plus 32.4g5,5'- ((5- (bromomethyl)-
1,3- phenylene) bis- (oxygroups)) bis- (methylene)) two (1,3- bis- (allyloxy) benzene), the 400g (molecular weight of perfluoropolyether alcohol
For 4000) perfluoropolyether alcohol, 1200g1,3- bis--(benzotrifluoride), 10g phase transfer catalyst TBAB and 20g40% sodium hydroxide
Solution, mixing are heated to 110 DEG C of reaction 10h, and 100g water agitator treating 30min, stratification is added, and lower layer's solution repeats
It washed once to pH value of solution=7, lower layer's solution rotating evaporimeter removes low-boiling-point substance, (90-120 DEG C) stirring of 20g petroleum ether is added to wash
20min, stratification are washed, 45 DEG C of Rotary Evaporators oil pumps of lower layer's viscous product are concentrated under reduced pressure 2h and obtain colorless and transparent following formula intermediate
A 403g, wherein m, n are respectively selected from 1~40 integer, and m+n=20~60, m/n=0.3~3；L is 1.
S32. the synthesis of perfluoropolyether methoxy silane is corresponded to based on midbody compound
Under nitrogen protection at one equipped with thermometer, agitating device, in condensing unit three-necked flask by compound A (n=1)
50g, dry 1,3- bis--(benzotrifluoride) 150g, trimethoxy hydrogen silane 20g stirring and dissolving are clarified, and are heated under nitrogen environment
To 116 DEG C, this Taide catalyst toluene solution of the card of 4g5000ppm is added dropwise, is reacted for 24 hours under nitrogen environment, Rotary Evaporators subtract
Pressure concentration removal low-boiling-point substance obtains structure flaxen Perfluoropolyether silanes 51g as shown in S-3.1H NMR (400MHz, CDCl3):
δ 0.58 (t 8H), 1.8 (m 8H), 3.55 (s 36H), 3.69 (s 2H), 3.94 (t 4H), 4.61 (s 4H), 4.63 (s
2H), 6.21-6.26 (m 9H).
Embodiment 4
A kind of perfluoropolyether-modified dendritic silicon alkane derivatives, the knot of the perfluoropolyether-modified dendritic
Structure formula is shown below and (is named as S-4):
Wherein, m, n are respectively selected from 1~40 integer, and m+n=20~60, m/n=0.3~3；L is 1.
The preparation method of above compound the following steps are included:
S41. the synthesis of perfluoropolyether-modified intermediate polymer of getting one's things ready
Add 202g 5- in the three-necked flask that one is equipped with thermometer, agitating device, condensing unit, vacuum distillation apparatus
1,3 benzenediol of bromomethyl, 40% sodium hydrate aqueous solution of 500g THF, 600g, 20g phase transfer catalyst are heated with stirring to back
Stream reaction 12h.Into above-mentioned reaction solution plus allyl bromide, bromoallylene 240-480g, the reaction was continued 12h, vacuum distillation is removed low-boiling-point substance, is added
200g water agitator treating 30min, stratification take upper solution Rotary Evaporators removal low-boiling-point substance to obtain colourless liquid 5,5'-
((5- (bromomethyl) -1,3- phenylene) bis- (oxygroups)) bis- (methylene)) two (bis- (allyloxy) benzene of 1,3-) 210g.
At one equipped with thermometer, agitating device, in condensing unit three-necked flask plus 64.8g 5,5'- ((5- (bromine first
Base) -1,3- phenylene) bis- (oxygroups)) bis- (methylene)) and two (bis- (allyloxy) benzene of 1,3-), 400g (point of perfluoropolyether alcohol
Son amount is 4000) perfluoropolyether alcohol, 1200g1,3- bis--(benzotrifluoride), 10g phase transfer catalyst TBAB and 40g40% hydrogen-oxygen
Change sodium solution, mixing is heated to 116 DEG C of reaction 12h, and 100g water agitator treating 30min, stratification, lower layer's solution is added
Once to pH value of solution=7, lower layer's solution rotating evaporimeter removes low-boiling-point substance, 50g petroleum ether (90-120 DEG C) is added to stir repeated washing
Washing 20min, stratification are mixed, 45 DEG C of Rotary Evaporators oil pumps of lower layer's viscous product are concentrated under reduced pressure 2h and obtain colorless and transparent intermediate
406g, wherein m, n are respectively selected from 1~40 integer, and m+n=20~60, m/n=0.3~3；L is 1.
S42. the synthesis of perfluoropolyether methoxy silane is corresponded to based on midbody compound
Under nitrogen protection at one equipped with thermometer, agitating device, in condensing unit three-necked flask by compound B (n=1)
50g, dry 1,3- bis--(benzotrifluoride) 200g, trimethoxy hydrogen silane 40g stirring and dissolving are clarified, and are heated under nitrogen environment
To 116 DEG C, this Taide catalyst toluene solution of the card of 6g 5000ppm is added dropwise, is reacted for 24 hours under nitrogen environment, Rotary Evaporators subtract
Pressure concentration removal low-boiling-point substance obtains structure flaxen Perfluoropolyether silanes 53g as shown in S-4.1H NMR (400MHz, CDCl3):
δ 0.58 (t 16H), 1.8 (m 16H), 3.55 (s 72H), 3.69 (s 4H), 3.94 (t 8H), 4.61 (s 8H), 4.63 (s
4H), 6.21-6.26 (m 18H).
Comparative example 1
A kind of perfluoropolyether-modified silane derivative, structural formula are shown below and (are named as S-C1):
The perfluoropolyether-modified silane derivative (AFC) of embodiment 1-4, comparative example is tested for the property, test side
Method is as follows:
1. glass surface pre-processes: to chemically strengthening glass surface (gorilla glass, Corning Incorporated's production, thickness 0.7
Millimeter) spraying AFC medicament before, using atmospheric plasma generator to surface carry out plasma.
2. medicament coating and baking processing: the AFC sample synthesized in above-described embodiment and comparative example is dissolved in hydrofluoroether
In (Novec HFE7200,3M company), the AFC solution that concentration is 20% (weight) is obtained.It is dilute with Novec 7200 again before spraying
It is interpreted into the liquid medicine of 0.1% (solid content).Use commercial spraying equipment (the spray head medicament flow velocity: 70 for being furnished with two-fluid spray nozzle
Mm/second) by (dosing 60-80g/m on liquid medicine even application to substrate surface2).30 points are toasted at 150 DEG C again
Clock is formed by curing AFC coating, carries out performance evaluation test after being cooled to room temperature.
3. evaluating abrasion resistance: being measured with contact angle measurement (DSA, Kruss company, water-bed 1 μ L of size) with above-mentioned implementation
The Static water contact angles for the surface covering that substrate surface in example and comparative example after AFC sample treatment is formed.
Firstly, with contact angle measurement measurement surface covering, there are no contact any object after its formation as initial evaluation
Static water contact angles before body (Rubbing number zero), as first contact angle.
Then, it is evaluated by friction durability of the steel wool friction test to surface-treated layer.Condition: steel wool mill
Head (No. 0000,5 millimeters × 10 millimeters × 10 millimeters of size)；Load 1000g；140 mm/second of friction velocity.Every friction 1000
It is secondary, measure a Static water contact angles (degree).When the measured value of contact angle is less than 100 degree, stop evaluation.
Shown in test result figure the following table 1.
Table 1
Seen from table 1 above, compared to comparative example, AFC provided by the invention has excellent anti-fingerprint, refuses oily, antifouling etc.
Performance is more importantly to have excellent abrasive resistance and hydrophobic performance (water repellent), can be used as the anti-finger of all kinds of glass panels
Line coating is especially also able to satisfy the requirement of the high high-end applications product of confrontation fingerprint demand.
Comparing embodiment 1 and embodiment 3, embodiment 2 and embodiment 4 are it is found that embodiment 3 is used for bonding compared with embodiment 1
The alkoxy quantity that alkoxy quantity is more, embodiment 4 is compared with embodiment 2 for bonding is more, finally obtained AFC, and embodiment 3 is relatively real
The crocking resistance for applying example 1 is good, and embodiment 4 is good compared with the crocking resistance of embodiment 2.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of perfluoropolyether-modified dendritic silicon alkane derivatives, which is characterized in that the perfluoropolyether-modified dendroid
The structural formula of polymer is as shown in following formula 1, formula 2:
Wherein, m, n are respectively selected from 1~40 integer, and m+n=20~60, m/n=0.3~3；L is 0 or 1；And and silicon atom
Connected terminal methoxy group can be replaced the alkoxy that carbon atom number is 2~5.
2. perfluoropolyether-modified dendritic silicon alkane derivatives as described in claim 1, which is characterized in that be connected with silicon atom
Terminal methoxy group replace with ethyoxyl.
3. a kind of preparation method of perfluoropolyether-modified dendritic silicon alkane derivatives, which comprises the steps of:
Perfluoropolyether-modified dendritic intermediate as shown in following formula 3 and/or formula 4 is prepared respectively, wherein m, n points
Not Xuan Zi 1~40 integer, and m+n=20~60, m/n=0.3~3；L is 0 or 1,
Under nitrogen or oxygen protection, by dendritic intermediate perfluoropolyether-modified shown in formula 3 and/or formula 4 with
1,3- bis--(benzotrifluoride), the mixing of tri-alkoxy hydrogen silane, are added catalyst, react 4-24h under conditions of 40-116 DEG C,
Prepare compound shown in formula 1 shown in claims 1 or 2 and/or formula 2, wherein the alkoxy choosing in the tri-alkoxy hydrogen silane
The alkoxy for being 1~5 from carbon atom number.
4. the preparation method of perfluoropolyether-modified dendritic silicon alkane derivatives as claimed in claim 3, which is characterized in that institute
It states tri-alkoxy hydrogen silane and is selected from trimethoxy hydrogen silane or triethoxy hydrogen silane.
5. the preparation method of perfluoropolyether-modified dendritic silicon alkane derivatives as claimed in claim 3, which is characterized in that institute
State catalyst selected from chloroplatinic acid catalyst, block this Taide catalyst, platinum catalyst, palladium catalyst, in rhodium complex catalysts
It is at least one.
6. the preparation method of perfluoropolyether-modified dendritic silicon alkane derivatives as claimed in claim 5, which is characterized in that institute
The quality for stating catalyst is the 20-120ppm of the reaction system gross mass.
7. special such as the preparation method of the described in any item perfluoropolyether-modified dendritic silicon alkane derivatives of claim 3-6
Sign is, the formula 3, formula 4 the preparation method comprises the following steps:
As l=0, comprising the following steps:
5- bromomethyl -1,3 benzenediol, allyl bromide, bromoallylene are dissolved in organic solvent, the water of potassium hydroxide and/or sodium hydroxide is added
Solution and phase transfer catalyst, mixing are evaporated under reduced pressure and are washed at layering after reacting 4-12h under conditions of 40-66 DEG C
Reason collects upper solution and handles to obtain 5- bromomethyl -1,3- benzene diallyl ether through revolving；
By 5- bromomethyl -1,3- benzene diallyl ether, perfluoropolyether alcohol 1,3- bis--(benzotrifluoride), phase transfer catalyst and hydrogen-oxygen
Change the aqueous solution of potassium and/or sodium hydroxide, mixing, after reacting 4-12h under the conditions of 40-110 DEG C, being washed to lower layer's pH value of solution is
7, lower layer's solution is collected, revolving processing adds washing to be washed with organic solvent, lower layer's dope collected, through being concentrated under reduced pressure
To compound shown in formula 3 and/or formula 4；Or
As l=1, comprising the following steps:
1,3 benzenediol of 5- bromomethyl is dissolved in organic solvent, be added the aqueous solution of potassium hydroxide and/or sodium hydroxide with mutually turn
Shifting catalyst, back flow reaction 4-12h；It is added allyl bromide, bromoallylene, after the reaction was continued 4-12h, after being evaporated under reduced pressure and washing layering, receives
Collection upper solution handles to obtain 5,5'- ((5- (bromomethyl) -1,3- phenylene) bis- (oxygroups)) bis- (methylene) through revolving) two
(bis- (allyloxy) benzene of 1,3-)；
By 5,5'- ((5- (bromomethyl) -1,3- phenylene) bis- (oxygroups)) bis- (methylene)) two (bis- (allyloxy) benzene of 1,3-)
Perfluoropolyether alcohol 1, the aqueous solution of 3- bis--(benzotrifluoride) phase transfer catalyst and potassium hydroxide and/or sodium hydroxide, mixing,
After reacting 4-12h under the conditions of 40-110 DEG C, being washed to lower layer's pH value of solution is 7, collects lower layer's solution, adds washing after revolving processing
It is washed with organic solvent, collects lower layer's dope, be concentrated under reduced pressure to give compound shown in formula 3 and/or formula 4.
8. the preparation method of perfluoropolyether-modified dendritic silicon alkane derivatives as claimed in claim 7, which is characterized in that institute
State phase transfer catalyst be selected from benzyltriethylammoinium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate,
At least one of tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride；And/or
The organic solvent is selected from least one of tetrahydrofuran, dioxane, fluorine-containing organic solvent；And/or
The washing is selected from least one of petroleum ether, n-hexane, methyl tertiary butyl ether(MTBE) with organic solvent.
9. the preparation method of perfluoropolyether-modified dendritic silicon alkane derivatives as claimed in claim 7, which is characterized in that institute
It is 30-50% that the aqueous solution for stating potassium hydroxide and/or sodium hydroxide, which is the mass percentage of potassium hydroxide and/or sodium hydroxide,
Aqueous solution.
10. a kind of perfluoropolyether-modified any one of dendritic silicon alkane derivatives or claim 3-9 as claimed in claim 1 or 2
Application of the perfluoropolyether-modified dendritic silicon alkane derivatives that the method prepares in anti-fingerprint coating material field.
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| CN110483826A (en) * | 2019-08-23 | 2019-11-22 | 山东师范大学 | A kind of polyurethane of surface grafting polysiloxanes nanometer film, preparation method and application |
| CN111116899A (en) * | 2019-12-30 | 2020-05-08 | 深圳德诚达光电材料有限公司 | Preparation method of glass anti-slip agent |
| CN115746287A (en) * | 2023-01-10 | 2023-03-07 | 苏州东杏表面技术有限公司 | Perfluoropolyether silane compound containing benzene ring structure, preparation method thereof, surface treating agent based on compound and film |
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