CN107501541A - A kind of fluorinated polyether siloxanes and preparation method thereof - Google Patents
A kind of fluorinated polyether siloxanes and preparation method thereof Download PDFInfo
- Publication number
- CN107501541A CN107501541A CN201710648167.2A CN201710648167A CN107501541A CN 107501541 A CN107501541 A CN 107501541A CN 201710648167 A CN201710648167 A CN 201710648167A CN 107501541 A CN107501541 A CN 107501541A
- Authority
- CN
- China
- Prior art keywords
- group
- pfpe
- polyether
- fluoro
- conhch
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
- C08G65/33351—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group acyclic
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a kind of fluorinated polyether siloxanes and preparation method thereof, fluorinated polyether siloxanes following formula a1Or a2Represent：PFPE‑CONHCR1(CH2OCONHCH2CH2OCOCHR2CH2N(CH2CH2CH2Si(OR)3)2)2 (a1)；{[PFPE‑CONHCH2CH2]N[CONHCH2CH2OCOCHR2'CH2N(CH2CH2CH2Si(OR')3)2]CH2}2 (a2).Wherein, R1, R2 and R2' independently represent H or CH3, R and R' independently represent C1~4Alkyl, PFPE is monovalence multi-fluoro polyether group.Fluorinated polyether siloxanes and the base material cohesive force of the present invention are strong, adhesion strength is good, and preparation method raw material is easy to get, preparation process is easily controlled.
Description
Technical field
The present invention relates to a kind of fluorinated polyether siloxanes and preparation method thereof.
Background technology
The transparent optical device (such as mobile phone glass screen) of touch type electronic display device, is often contacted, easily with finger
Polluted by fingerprint, sweat, greasy dirt etc., and dirt is difficult to remove once being formed in the case of without using solvent, uses solvent
There is the danger of damage display device again；On the other hand, dirt has an effect on the visual sense of display device.In order to prevent dirt to display
It may be damaged during the pollution of part and removal dirt to caused by device, surface of the exploitation with antifouling, easy dirt-removing functions applies
Layer is just significant.
To achieve these goals, researcher has been developed for a variety of fluorinated siloxane antifouling products.Utilize siloxanes
The hydrolytic condensation of group is formed with base material and is chemically crosslinked, and improves coating cohesive force；Have using the fluorination of bonding on the siloxane
Machine group provides anti-fouling effect.
3M companies disclose the synthesis of more fluorinated polyether siloxanes and application patent (such as CN1998813320.2,
CN200480025773.X, CN200780030231.5 etc.), but point of the multi-fluoro polyether group of above-mentioned fluorinated polyether siloxanes
Son amount is relatively low, strand is short, compound coat is not shown sufficient oil repellent and lubricity.However, improve merely more
The molecular weight of perfluoroalkyl polyether group, increase its strand, although improving oil repellent and lubricity, due to siloxy group phase
Amount is reduced, have impact on the adhesion strength of coating, lasting anti-fouling effect declines.
Patent CN201110286992.5 is disclosed by the fluorine-containing alkylen polymers of a terminal hydrolysis and two terminal hydrolysis
The composition of the fluorine-containing alkylen polymers of property, the phase of water-disintegrable siloxane group is also further improved by more si-h bond compounds
To amount, because water-disintegrable siloxane group relative quantity is lifted, said composition has preferable marresistance, and lasting anti-fouling effect carries
Rise.However, in order to obtain the compound of more siloxane groups, the fluorine-containing alkylen polymers with terminal hydrolysis group
Building-up process in need to use more si-h bond compounds, due to active group more be difficult to control reaction, easily produce by-product
Thing；Secondly, siloxane group is all bonded on more si-h bond groups, due to space obstacle, makes these hydrolyzable groups be difficult to fill
The raw hydrolytic crosslinking of distribution, have impact on the adhesion strength with base material on the contrary；In addition, more si-h bond compounds described in patent are mostly
Non- conventional material, raw material is not easy to obtain and cost is high, is unfavorable for industrialized production.
The content of the invention
Present invention aims at solve above-mentioned technical problem present in prior art, there is provided a kind of fluorinated polyether siloxanes
And preparation method thereof, fluorinated polyether siloxanes its keep multi-fluoro polyether group Molecule amount it is higher in the case of, improve silica
The relative quantity of groups, maintains the space operation free degree of siloxane group, and there is preparation method raw material to be easy to get, prepare
The advantages of process is easily controlled.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that：
A kind of fluorinated polyether siloxanes, it is characterised in that：There is one or two monovalence multi-fluoro polyether base in each molecule
Group and four-Si (OR)3The alkoxysilyl group of expression, fluorinated polyether siloxanes following formula a1Or a2Represent：
PFPE-CONHCR1(CH2OCONHCH2CH2OCOCHR2CH2N(CH2CH2CH2Si(OR)3)2)2 (a1)
{[PFPE-CONHCH2CH2]N[CONHCH2CH2OCOCHR2'CH2N(CH2CH2CH2Si(OR')3)2]CH2}2 (a2)
Wherein, R1, R2 and R2' independently represent H or CH3, R and R' independently represent C1~4Alkyl, PFPE- is
Monovalence multi-fluoro polyether group；In formula a1Or a2In, all containing only one in four siloxane groups, with per molecule in per molecule
The fluorinated polyether siloxanes of siloxane group is compared, and the relative quantity of siloxane group substantially increases；In addition, siloxane group is logical
Transition long-chain (CH2OCONHCH2CH2OCOCHR2CH2Or CONHCH2CH2OCOCHR2'CH2) be connected with multi-fluoro polyether end group, with
Siloxane group is bonded directly to same group and compared, and the space operation free degree of siloxane group is protected in the structure
Hold, beneficial to the full cross-linked solidification of these hydrolyzable groups, therefore, the compound can strengthen the adhesion strength with base material, enter
And improve it and form the wearability of coating and antifouling persistence.
Further, monovalence multi-fluoro polyether group PFPE- is preferably F (CF (CF3)CF2O)nCF(CF3)-, n is 14 to 50
Integer, when n is less than 14, because multi-fluoro polyether group Molecule chain is shorter, antifouling property declines, it is difficult to reaches requirement, works as n
During more than 50, the performance of compound is difficult to further be lifted, but due to multi-fluoro polyether group relative quantity rise make the compound into
This increase, in addition, the decline of siloxane group relative quantity may influence the adhesion strength of coating and base material, and then make wearability and
Antifouling persistence reduces；R and R' is preferably CH3, coating is easily solidified, with R and R' carbon number in siloxane group
Increase, the hydrolysing activity of siloxane group can decline.
The preparation method of fluorinated polyether siloxanes, it is characterised in that comprise the following steps：
(1)：Multi-fluoro polyether list methyl formate reacts with polyfunctionality amino-compound, prepares the amidatioon production of multi-fluoro polyether
Thing；
(2)：The amidated products and the unsaturated monomer containing isocyanate groups of the multi-fluoro polyether prepared in step (1) are anti-
Answer, prepare the product containing double bond of multi-fluoro polyether；
(3)：The product containing double bond of the multi-fluoro polyether prepared in step (2) and double (3- (trialkoxysilyl) propyl group)
Amine reacts, formula a1Or a2The fluorinated polyether siloxanes of expression：
PFPE-CONHCR1(CH2OCONHCH2CH2OCOCHR2CH2N(CH2CH2CH2Si(OR)3)2)2 (a1)
{[PFPE-CONHCH2CH2]N[CONHCH2CH2OCOCHR2'CH2N(CH2CH2CH2Si(OR')3)2]CH2}2 (a2)
Wherein, R1, R2 and R2' independently represent H or CH3, R and R' independently represent C1~4Alkyl, PFPE- is
Monovalence multi-fluoro polyether group.
Further, multi-fluoro polyether list formic acid esters is preferably F (CF (CF3)CF2O)nCF(CF3)COOCH3, n is 14 to 50
Integer；Polyfunctionality amino-compound is preferably 2- amino-1,3-propanediols, AMPD and three second
Alkenyl tetramine.
Further, the unsaturated monomer containing isocyanate groups is acrylic acid isocyano group ethyl ester and methacrylic acid isocyano group
Ethyl ester.
Further, double (3- (trialkoxysilyl) propyl group) amine are preferably double (3- (trimethoxysilyl) third
Base) amine.
The present invention is by adopting the above-described technical solution, have the advantages that：
(1) the invention provides a kind of fluorinated polyether siloxanes, it is keeping the higher feelings of multi-fluoro polyether group Molecule amount
Under condition, the relative quantity of siloxane group is improved, maintains the space operation free degree of siloxane group, is handed over beneficial to abundant
Connection solidification.
(2) preparation method of fluorinated polyether siloxanes provided by the invention, raw material is easy to get and cost is relatively low, preparation process
It is easily controlled, beneficial to industrialized production.
(3) fluorinated polyether siloxanes provided by the invention, its coating and base material cohesive force are strong, adhesion strength is good；Coating
Good antifouling effect, ink on coating can be existed with rapid desufflation to the contact angle of water more than 113 °, to the contact angle of mineral oil
More than 74 °；Dirt on coating easily removes, inviolateness residual；Wearability and antifouling persistence are good, can be subjected to more than 6000 times
Circulation friction.
Embodiment
A kind of fluorinated polyether siloxanes of the present invention, there is one or two monovalence multi-fluoro polyether group and four in each molecule
Individual-Si (OR)3The alkoxysilyl group of expression, fluorinated polyether siloxanes can use following formula a1Or a2Represent：
PFPE-CONHCR1(CH2OCONHCH2CH2OCOCHR2CH2N(CH2CH2CH2Si(OR)3)2)2 (a1)
{[PFPE-CONHCH2CH2]N[CONHCH2CH2OCOCHR2'CH2N(CH2CH2CH2Si(OR')3)2]CH2}2 (a2)
Wherein, R1, R2 and R2' independently represent H or CH3, R and R' independently represent C1~4Alkyl, PFPE- is
Monovalence multi-fluoro polyether group.
In formula a1Or a2In, all containing an only siloxane group in four siloxane groups, with per molecule in per molecule
Fluorinated polyether siloxanes compare, the relative quantity of siloxane group substantially increases；In addition, siloxane group is by transition long-chain
(CH2OCONHCH2CH2OCOCHR2CH2Or CONHCH2CH2OCOCHR2'CH2) be connected with multi-fluoro polyether end group, with siloxane group
It is bonded directly to same group to compare, the space operation free degree of siloxane group is kept in the structure, beneficial to these
The full cross-linked solidification of hydrolyzable groups, therefore, the compound can strengthen the adhesion strength with base material, and then improve its formation
The wearability of coating and antifouling persistence.
Monovalence multi-fluoro polyether group PFPE- is preferably F (CF (CF3)CF2O)nCF(CF3)-, n is 14 to 50 integer, works as n
During less than 14, because multi-fluoro polyether group Molecule chain is shorter, antifouling property declines, it is difficult to reaches requirement, when n is more than 50
When, the performance of compound is difficult to further be lifted, but makes compound cost increase because multi-fluoro polyether group relative quantity rises,
In addition, the decline of siloxane group relative quantity may influence the adhesion strength of coating and base material, and then make wearability and antifouling hold
Long property reduces.As R and R' carbon number increase in siloxane group, the hydrolysing activity of siloxane group can decline, in order to
Coating is set easily to solidify, R and R' are preferably CH3。
The preparation method of fluorinated polyether siloxanes, comprises the following steps：
(1)：Multi-fluoro polyether list methyl formate reacts with polyfunctionality amino-compound, prepares the amidatioon production of multi-fluoro polyether
Thing.Polyfunctionality amino-compound is organic compound or a molecule containing 1~2 primary amine groups and 2 hydroxyls in a molecule
In the organic compound containing 1~2 primary amine groups and 2 secondary amino groups, wherein preferably 2- amino-1,3-propanediols, 2- amino-
2- methyl isophthalic acids, ammediol and triethylene tetraamine etc..When reactant is Shanbo's amines, mole dosage can gather for polyfluoro
1~1.2 times of ether list formic acid esters, so that the reaction of multi-fluoro polyether monoesters is complete；When reactant is double primary amino-compounds, with multi-fluoro polyether
The mole dosage of methyl esters is preferably controlled in 1:2.Reaction is preferably carried out under nitrogen protection, and selects suitable reaction temperature, instead
Answer degree to be tracked using FTIR, disappeared with ester group absworption peak for reaction end.After reaction, appropriate method purification production is selected
Thing, preferably product is dissolved in ethyl tert-butyl ether (ETBE), and adds appropriate HCl/water solution, stratification after stirring, remove water
Phase, organic phase is washed with deionized to neutrality, then with drier (such as magnesium sulfate) drying process, finally removes solvent and carried
Pure products.Following product can be obtained：PFPE-CONHCR1(CH2OH)2Or (PFPE-CONHCH2CH2NHCH2)2Deng, wherein, R1 is
H or CH3。
(2)：Then the amidated products with the multi-fluoro polyether obtained in step (1) and the unsaturation containing isocyanate groups
Monomer reaction, prepare the product containing double bond of multi-fluoro polyether.Unsaturated monomer containing isocyanate groups is acrylic acid isocyano group second
Ester and isocyanatoethyl.Wherein, hydroxyl or the mol ratio of secondary amine group and isocyanate groups are preferably 1:
1.In order to prevent double bond from polymerizeing in the reaction, appropriate polymerization inhibitor, such as hydroquinones are preferably added to；To prevent reaction excessively
Acutely, isocyanate compound is preferably added using dropwise addition mode.Reaction is preferably carried out under nitrogen protection, and is selected suitably
Reaction temperature, the extent of reaction can be tracked using FTIR, be disappeared with isocyanate groups absworption peak for reaction end.It can obtain
Following product：PFPE-CONHCR1(CH2OCONHCH2CH2OCOCR2=CH2)2Or [(PFPE-CONHCH2CH2)N
(CONHCH2CH2OCOCR2'=CH2)CH2]2Deng, wherein, R1, R2 and R2' independently represent H or CH3。
(3)：The finally product containing double bond with the multi-fluoro polyether obtained in step (2) and double (3- (tri-alkoxy monosilanes
Base) propyl group) amine reaction, both mol ratios are preferably 1:2, double (3- (trialkoxysilyl) propyl group) amine are preferably double
(3- (trimethoxysilyl) propyl group) amine, reaction are preferably carried out under nitrogen protection, formula a1Or a2The fluorination of expression gathers
Ether siloxanes：
PFPE-CONHCR1(CH2OCONHCH2CH2OCOCHR2CH2N(CH2CH2CH2Si(OR)3)2)2(a1)
{[PFPE-CONHCH2CH2]N[CONHCH2CH2OCOCHR2'CH2N(CH2CH2CH2Si(OR')3)2]CH2}2(a2)
Wherein, R1, R2 and R2' independently represent H or CH3, R and R' independently represent C1~4Alkyl, PFPE- is
Monovalence multi-fluoro polyether group.
(1) the invention provides a kind of fluorinated polyether siloxanes, it is keeping the higher feelings of multi-fluoro polyether group Molecule amount
Under condition, the relative quantity of siloxane group is improved, maintains the space operation free degree of siloxane group, is handed over beneficial to abundant
Connection solidification.
(2) preparation method of fluorinated polyether siloxanes provided by the invention, raw material is easy to get and cost is relatively low, preparation process
It is easily controlled, beneficial to industrialized production.
(3) fluorinated polyether siloxanes provided by the invention, its coating and base material cohesive force are strong, adhesion strength is good；Coating
Good antifouling effect, ink on coating can be existed with rapid desufflation to the contact angle of water more than 113 °, to the contact angle of mineral oil
More than 74 °；Dirt on coating easily removes, inviolateness residual；Wearability and antifouling persistence are good, can be subjected to more than 6000 times
Circulation friction.
Embodiment 1 (fluorinated polyether silicone compounds a synthesis --- a-1)
Step (1)：By 103.16g (about 0.02mol) multi-fluoro polyether list methyl formate F (CF (CF3)CF2O)nCF(CF3)
COOCH3, n=30 and 2.18g (about 0.024mol) 2- amino-1,3-propanediols are added in reaction bulb, under nitrogen protection, risen
Warm to 75 DEG C, stirring reaction 20h.FTIR is analyzed to identify ester group absworption peak (about 1790cm-1) disappear, and there is the acid amides in product
Base absworption peak (about 1710cm-1).Product is dissolved in 100g ethyl tert-butyl ether (ETBE)s, and adds 10ml 1mol/L HCl/water
Solution, stir 10 minutes, be then stored at room temperature liquid separation, remove aqueous phase.Organic phase is being washed with deionized to neutrality, then is using sulphur
Sour magnesium drying process, then steams solvent with Rotary Evaporators, obtained product F (CF (CF3)CF2O)nCF(CF3)CONHCH
(CH2OH)2, n=30.
Step (2)：By the product obtained in 78.26g (about 0.015mol) step (1) and 0.04g hydroquinones polymerization inhibitors
Add in reaction bulb, stirring is opened, under nitrogen protection, in the 30 minutes acrylic acid isocyano group second by 4.25g (about 0.03mol)
Ester is added dropwise in reaction bulb, then raises temperature to 80 DEG C, reacts 8h.FTIR analysis shows isocyanate groups absworption peaks disappear completely
Lose, obtain product F (CF (CF3)CF2O)nCF(CF3)CONHCH(CH2OCONHCH2CH2OOCCH=CH2)2, n=30.
Step (3)：The product obtained in 54.99g (about 0.01mol) step (2) is added into reaction bulb, opens stirring,
Under nitrogen protection, in 6.83g (about 0.02mol) double (3- (trimethoxysilyl) propyl group) amine are added dropwise in 30 minutes
In reaction bulb, 60 DEG C are then raised temperature to, reacts 10h.Obtain target product F (CF (CF3)CF2O)nCF(CF3)CONHCH
(CH2OCONHCH2CH2OOCCH2CH2N(CH2CH2CH2Si(OCH3)3)2)2, n=30.
Embodiment 2 (fluorinated polyether silicone compounds a synthesis --- a-2)
Step (1)：Except multi-fluoro polyether list methyl formate 50.04g (about 0.02mol) F (CF (CF3)CF2O)nCF
(CF3)COOCH3, n=14 is substituted, 2- amino-1,3-propanediols 2.52g (about 0.024mol) 2- amino-2-methyls -1,3-
Outside propane diols substitutes, remaining is identical with (1) the step of embodiment 1, obtained product F (CF (CF3)CF2O)nCF(CF3)CONHC
(CH2OH)2CH3, n=14.
Step (2)：In addition to multi-fluoro polyether dihydric alcohol is substituted with 38.63g (about 0.015mol) products obtained in the previous step, its
It is remaining identical with (2) the step of embodiment 1, obtain product F (CF (CF3)CF2O)nCF(CF3)CONHC
(CH2OCONHCH2CH2OOCCH=CH2)2CH3, n=14.
Step (3)：In addition to multi-fluoro polyether containing double bond is replaced with 28.57g (about 0.01mol) product obtained in the previous step, its
It is remaining identical with (3) the step of embodiment 1, obtain product F (CF (CF3)CF2O)nCF(CF3)CONHC
(CH2OCONHCH2CH2OOCCH2CH2N(CH2CH2CH2Si(OCH3)3)2)2CH3, n=14.
Embodiment 3 (fluorinated polyether silicone compounds a synthesis --- a-3)
Step (1)：Except multi-fluoro polyether list methyl formate 169.56g (about 0.02mol) F (CF (CF3)CF2O)nCF
(CF3)COOCH3, n=50 replacements are outer, and remaining is identical with (1) the step of embodiment 1, obtained product F (CF (CF3)CF2O)nCF
(CF3)CONHCH(CH2OH)2, n=50.
Step (2)：Except multi-fluoro polyether dihydric alcohol 128.06g (about 0.015mol) product replacements obtained in the previous step, third
Olefin(e) acid isocyano group ethyl ester is replaced outside with 4.66g isocyanatoethyl, and remaining is identical with (2) the step of embodiment 1,
Obtain product F (CF (CF3)CF2O)nCF(CF3)CONHCH(CH2OCONHCH2CH2OOCC(CH3)=CH2)2, n=50.
Step (3)：Except multi-fluoro polyether containing double bond replaces with 88.47g (about 0.01mol) product obtained in the previous step, in addition to, its
It is remaining identical with (3) the step of embodiment 1, obtain product F (CF (CF3)CF2O)nCF(CF3)CONHCH
(CH2OCONHCH2CH2OOCCH(CH3)CH2N(CH2CH2CH2Si(OCH3)3)2)2, n=50.
Embodiment 4 (fluorinated polyether silicone compounds a synthesis --- a-4)
Step (1)：Except multi-fluoro polyether list methyl formate 123.08g (about 0.02mol) F (CF (CF3)CF2O)nCF
(CF3)COOCH3, n=36 is substituted, outside triethylene tetraamine of the 2- amino-1,3-propanediols with 1.46g (0.01mol), and remaining is same
The step of embodiment 1 (1), is identical, obtained product (F (CF (CF3)CF2O)nCF(CF3)CONHCH2CH2NHCH2)2, n=36.
Step (2)：The product and 0.04g hydroquinones polymerization inhibitors that will be obtained in 92.93g (about 0.0075mol) previous step
Add in reaction bulb, stirring is opened, under nitrogen protection, in 30 minutes acrylic acid isocyano groups by 2.12g (about 0.015mol)
Ethyl ester is added dropwise in reaction bulb, then raises temperature to 80 DEG C, reacts 8h.Infrared analysis shows that isocyanate groups absworption peak disappears completely
Lose, obtain product (F (CF (CF3)CF2O)nCF(CF3)CONHCH2CH2N(CONHCH2CH2OOCCH=CH2)CH2)2, n=36.
Step (3)：The product obtained in 63.36g (about 0.005mol) previous step is added into reaction bulb, opens stirring,
Under nitrogen protection, in 3.42g (about 0.01mol) double (3- (trimethoxysilyl) propyl group) amine are added dropwise in 30 minutes
In reaction bulb, 60 DEG C are then raised temperature to, reacts 10h.Obtain target product (F (CF (CF3)CF2O)nCF(CF3)CONHCH2CH2N
(CONHCH2CH2OOCCH2CH2N(CH2CH2CH2Si(OCH3)3)2)CH2)2, n=36.
Comparative example 1 (fluorinated polyether silicone compounds b synthesis --- b-1)
By equimolar than F (CF (CF3)CF2O)nCF(CF3)COOCH3, n=30 and NH2CH2CH2CH2Si(OCH3)3
Amidation process prepare.Reaction is carried out under nitrogen protection, and 85 DEG C of reaction 5h, obtained target product is F (CF (CF3)
CF2O)nCF(CF3)CONHCH2CH2CH2Si(OCH3)3, n=30.
Comparative example 2 (fluorinated polyether silicone compounds b synthesis --- b-2)
It is 1 by mol ratio:2 CH3OCOCF2O(CF2O)11~13(CF2CF2O)11~13CF2COOCH3With
NH2CH2CH2CH2Si(OCH3)3Amidation process prepare.Reaction is carried out under nitrogen protection, 85 DEG C of reaction 5h, obtained mesh
Marking product is3(H3CO)SiCH2CH2CH2NHCOCF2O(CF2O)11~13(CF2CF2O)11~13CF2CONHCH2CH2CH2Si(OCH3)3。
Comparative example 3 (fluorinated polyether silicone compounds A synthesis --- A-1)
Except multi-fluoro polyether list methyl formate 36.76g (about 0.02mol) F (CF (CF3)CF2O)nCF(CF3)COOCH3,
Outside n=10 is substituted, remaining is identical with embodiment 1.
Sample preparation
The fluorinated siloxane compound 0.1g that embodiment 1~4 and comparative example 1~3 obtain is dissolved in 99.9g perfluoro butyls
In vinyl ethers, nonpolluting coating spray coating liquor is configured to.Spray coating liquor is sprayed on mobile phone glass screen, and solidified at 120 DEG C
0.5h, form nonpolluting coating.
Method of testing
1st, contact angle is tested
Mobile phone glass screen Jing Guo antifouling process is subjected to deionized water (W) and white mineral oil (O) with contact angle instrument
Contact angle test.Parallel determination 5 times, averages.Contact angle is bigger, and surface energy is smaller.
2nd, antipollution assessment
Oil pen tests：A line is drawn on mobile phone glass screen film with oil pen, then examines ink traces change
Change, and evaluated with following standard.
E：Ink rapid desufflation
F：Ink portions shrink
NG：Ink does not shrink substantially
3rd, dirt ease of removal is evaluated
The red oil-based dye that mass fraction is 3% is prepared, after picking sufficient amount with finger, by finger in mobile phone glass screen
Holding 5 seconds is forced with 1Kgf on film, then applies 1Kgf pressure to non-dust cloth and wipes fingerprint back and forth 5 times, with following
Standard is evaluated.
E：Do not leave stain
F：Leave a small number of stains
NG：Leave most stains
4th, the evaluation of wearability
Tested using wear resistant instrument, with steel wool (BONSTAR#0000,12mm diameter) on mobile phone glass screen film
With 1Kgf load force, the horizontal friction treatment of 1800mm/min wiping speed, 2000 circulations are handled respectively and 5000 are followed
Ring (each circulation steel wool moves back and forth respectively once).It is easy that contact angle, antifouling property and dirt are evaluated and tested after friction treatment as described above
Removal.
Table 1
The specific embodiment of the present invention is these are only, but the technical characteristic of the present invention is not limited thereto.It is any with this hair
Based on bright, to solve essentially identical technical problem, essentially identical technique effect is realized, made simple change, etc.
With replacement or modification etc., all it is covered by among protection scope of the present invention.
Claims (6)
- A kind of 1. fluorinated polyether siloxanes, it is characterised in that：There is one or two monovalence multi-fluoro polyether group in each molecule With four-Si (OR)3The alkoxysilyl group of expression, the fluorinated polyether siloxanes following formula a1Or a2Represent：PFPE-CONHCR1(CH2OCONHCH2CH2OCOCHR2CH2N(CH2CH2CH2Si(OR)3)2)2(a1){[PFPE- CONHCH2CH2]N[CONHCH2CH2OCOCHR2'CH2N(CH2CH2CH2Si(OR')3)2]CH2}2(a2) wherein, R1, R2 and R2' points It is not independent to represent H or CH3, R and R' independently represent C1~4Alkyl, PFPE- is monovalence multi-fluoro polyether group.
- A kind of 2. fluorinated polyether siloxanes according to claim 1, it is characterised in that：The monovalence multi-fluoro polyether group PFPE- is preferably F (CF (CF3)CF2O)nCF(CF3)-, n is 14 to 50 integer；The R and R' are preferably CH3。
- 3. use the preparation method of fluorinated polyether siloxanes as claimed in claim 1, it is characterised in that comprise the following steps：(1)：Multi-fluoro polyether list methyl formate reacts with polyfunctionality amino-compound, prepares the amidated products of multi-fluoro polyether；(2)：The amidated products of the multi-fluoro polyether prepared in step (1) react with the unsaturated monomer containing isocyanate groups, Prepare the product containing double bond of multi-fluoro polyether；(3)：The product containing double bond of the multi-fluoro polyether prepared in step (2) and double (3- (trialkoxysilyl) propyl group) amine are anti- Should, formula a1Or a2The fluorinated polyether siloxanes of expression：PFPE-CONHCR1(CH2OCONHCH2CH2OCOCHR2CH2N(CH2CH2CH2Si(OR)3)2)2(a1){[PFPE- CONHCH2CH2]N[CONHCH2CH2OCOCHR2'CH2N(CH2CH2CH2Si(OR')3)2]CH2}2(a2) wherein, R1, R2 and R2' points It is not independent to represent H or CH3, R and R' independently represent C1~4Alkyl, PFPE- is monovalence multi-fluoro polyether group.
- 4. the preparation method of fluorinated polyether siloxanes according to claim 3, it is characterised in that：The multi-fluoro polyether list first Acid esters is preferably F (CF (CF3)CF2O)nCF(CF3)COOCH3, n is 14 to 50 integer；The polyfunctionality amino-compound Preferably 2- amino-1,3-propanediols, AMPD and triethylene tetraamine.
- 5. the preparation method of fluorinated polyether siloxanes according to claim 3, it is characterised in that：It is described to contain NCO The unsaturated monomer of group is acrylic acid isocyano group ethyl ester and isocyanatoethyl.
- 6. the preparation method of fluorinated polyether siloxanes according to claim 3, it is characterised in that：Double (3- (three alcoxyls Base silicyl) propyl group) preferably double (3- (trimethoxysilyl) propyl group) amine of amine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710648167.2A CN107501541A (en) | 2017-08-01 | 2017-08-01 | A kind of fluorinated polyether siloxanes and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710648167.2A CN107501541A (en) | 2017-08-01 | 2017-08-01 | A kind of fluorinated polyether siloxanes and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107501541A true CN107501541A (en) | 2017-12-22 |
Family
ID=60690277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710648167.2A Pending CN107501541A (en) | 2017-08-01 | 2017-08-01 | A kind of fluorinated polyether siloxanes and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107501541A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369840A (en) * | 2018-09-19 | 2019-02-22 | 衢州氟硅技术研究院 | A kind of fluorinated polyether containing hydrolyzable groups |
| CN109651941A (en) * | 2018-12-13 | 2019-04-19 | 苏州东杏表面技术有限公司 | One kind is based on double open coats of organic-silicon-modified wear-resisting type and preparation method thereof |
| WO2019163282A1 (en) * | 2017-12-27 | 2019-08-29 | Ａｇｃ株式会社 | Fluorine-containing ether compound, fluorine-containing ether composition, coating liquid, article and production method thereof |
| KR20210124408A (en) * | 2019-03-29 | 2021-10-14 | 다이킨 고교 가부시키가이샤 | Fluoropolyether group-containing compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1849359A (en) * | 2003-09-08 | 2006-10-18 | 3M创新有限公司 | Fluorinated polyether isocyanate derived silane compositions |
| CN1902249A (en) * | 2003-12-05 | 2007-01-24 | 3M创新有限公司 | Coating compositions with perfluoropolyetherisocyanate derived silane and alkoxysilanes |
| CN106700810A (en) * | 2016-12-28 | 2017-05-24 | 衢州氟硅技术研究院 | Surface anti-dirty treatment composition containing tetrafluoroethylene derived hydrofluorother |
-
2017
- 2017-08-01 CN CN201710648167.2A patent/CN107501541A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1849359A (en) * | 2003-09-08 | 2006-10-18 | 3M创新有限公司 | Fluorinated polyether isocyanate derived silane compositions |
| CN1902249A (en) * | 2003-12-05 | 2007-01-24 | 3M创新有限公司 | Coating compositions with perfluoropolyetherisocyanate derived silane and alkoxysilanes |
| CN106700810A (en) * | 2016-12-28 | 2017-05-24 | 衢州氟硅技术研究院 | Surface anti-dirty treatment composition containing tetrafluoroethylene derived hydrofluorother |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7180665B2 (en) | 2017-12-27 | 2022-11-30 | Ａｇｃ株式会社 | Fluorine-containing ether compound, fluorine-containing ether composition, coating liquid, article, and method for producing the same |
| WO2019163282A1 (en) * | 2017-12-27 | 2019-08-29 | Ａｇｃ株式会社 | Fluorine-containing ether compound, fluorine-containing ether composition, coating liquid, article and production method thereof |
| CN111511802A (en) * | 2017-12-27 | 2020-08-07 | Ａｇｃ株式会社 | Fluorine-containing ether compound, fluorine-containing ether composition, coating liquid, article, and method for producing same |
| JPWO2019163282A1 (en) * | 2017-12-27 | 2020-12-17 | Ａｇｃ株式会社 | Fluorine-containing ether compound, fluorine-containing ether composition, coating liquid, article and its manufacturing method |
| CN109369840B (en) * | 2018-09-19 | 2021-01-08 | 衢州氟硅技术研究院 | Fluorinated polyether containing hydrolyzable group |
| CN109369840A (en) * | 2018-09-19 | 2019-02-22 | 衢州氟硅技术研究院 | A kind of fluorinated polyether containing hydrolyzable groups |
| CN109651941A (en) * | 2018-12-13 | 2019-04-19 | 苏州东杏表面技术有限公司 | One kind is based on double open coats of organic-silicon-modified wear-resisting type and preparation method thereof |
| KR20210124408A (en) * | 2019-03-29 | 2021-10-14 | 다이킨 고교 가부시키가이샤 | Fluoropolyether group-containing compound |
| CN113677739A (en) * | 2019-03-29 | 2021-11-19 | 大金工业株式会社 | Compound containing fluoropolyether group |
| US20220002587A1 (en) * | 2019-03-29 | 2022-01-06 | Daikin Industries, Ltd. | Fluoropolyether group-containing compound |
| KR102608756B1 (en) | 2019-03-29 | 2023-12-04 | 다이킨 고교 가부시키가이샤 | Compounds containing fluoropolyether groups |
| CN113677739B (en) * | 2019-03-29 | 2024-02-09 | 大金工业株式会社 | Compound containing fluoropolyether group |
| US11912888B2 (en) * | 2019-03-29 | 2024-02-27 | Daikin Industries, Ltd. | Fluoropolyether group-containing compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107501541A (en) | A kind of fluorinated polyether siloxanes and preparation method thereof | |
| CN107603474B (en) | Composition for antifouling coating of transparent optical device | |
| CN106085227B (en) | A kind of preparation method of high-performance anti-fingerprint agent | |
| US9771384B2 (en) | Fluorochemical surface treating agent and article treated therewith | |
| US8147954B2 (en) | Per-fluoro polyether compound, antifouling coating composition and film containing same | |
| CN107698768A (en) | A kind of preparation method of high-performance anti-fingerprint agent | |
| EP2927290B1 (en) | Fluorochemical coating composition and article treated therewith | |
| EP2154176B1 (en) | Perfluoroether moiety-containing polymer and a surface treating agent comprising the same | |
| EP2157120A1 (en) | Fluorine-containing surface treating agent and an article surface-treated therewith | |
| CN111057231B (en) | High-wear-resistance perfluoropolyether type fingerprint-resistant agent and preparation method thereof | |
| CN106700810B (en) | A kind of surface soiling treatment compositions comprising the derivative hydrofluoroether of tetrafluoroethene | |
| JP2014005353A (en) | Perfluoropolyether-modified silane compound, antifouling coating composition, antifouling coating and article having the coating | |
| TWI767203B (en) | Fluoropolyether group-containing compound | |
| CN113583231A (en) | Preparation method of perfluoropolyether siloxane compound and fingerprint resisting agent | |
| CN113321623B (en) | Six-functionality-degree fluorine-containing photocuring anti-fouling additive and application thereof | |
| CN109988504B (en) | Surface treatment composition containing fluorinated polyether siloxane | |
| CN113912834A (en) | Preparation method of perfluoropolyether siloxane product and application of perfluoropolyether siloxane product in anti-fingerprint coating and anti-fingerprint coating | |
| KR102504014B1 (en) | Fluorooxyalkylene group-containing polymer modified phosphonic acid derivative, surface treatment agent comprising said derivative, and product and optical product treated with said surface treatment agent | |
| CN105111877A (en) | Spray-type surface antifouling treatment composition | |
| CN113045970A (en) | Coating composition and article provided with coating | |
| KR101085050B1 (en) | UV curing per-fluoro polyether compound, antifouling coating composition and film containing same | |
| CN109929114B (en) | Fluorinated polyether siloxane and preparation method and application thereof | |
| EP3981823A1 (en) | Fluoropolyether group-containing polymer and production method therefor | |
| US20230137488A1 (en) | Curable composition | |
| CN113387898B (en) | Ten-functionality fluorine-containing photocuring anti-fouling additive and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | 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: 20171222 |
|
| RJ01 | Rejection of invention patent application after publication |