CN107216460B - Perfluoropolyether fluorine-based fluorosilane with multiple hydrolysis active end groups and application - Google Patents

Perfluoropolyether fluorine-based fluorosilane with multiple hydrolysis active end groups and application Download PDF

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CN107216460B
CN107216460B CN201710347429.1A CN201710347429A CN107216460B CN 107216460 B CN107216460 B CN 107216460B CN 201710347429 A CN201710347429 A CN 201710347429A CN 107216460 B CN107216460 B CN 107216460B
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perfluoropolyether
fluorosilane
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vinyl
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CN107216460A (en
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徐涛
吴克安
闵律平
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Sinochem Environmental Protection Chemicals Taicang Co Ltd
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
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Abstract

The invention relates to a perfluoropolyether fluorine-based silane with multiple hydrolysis active end groups and application thereof, wherein the molecular chain tail end of the perfluoropolyether fluorine-based silane has at least 4 hydrolysis active functional groups, and the perfluoropolyether fluorine-based silane is applied to the field of coatings, so that the water contact angle and the oil contact angle of a paint film of the coating can be obviously improved, and meanwhile, the graffiti resistance of the paint film is also improved. On the other hand, the introduction of multi-hydrolysis active end groups at the tail end of the perfluoropoly-fluoroether-based fluorosilane molecular chain can obviously improve the adhesive force between the perfluoropoly-fluoroether-based fluorosilane molecular chain and a paint film, and finally improve the anti-fouling durability of the paint film.

Description

Perfluoropolyether fluorine-based fluorosilane with multiple hydrolysis active end groups and application
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a perfluoropolyether fluorosilane with multiple hydrolysis active end groups and application thereof.
Background
The surface of materials such as ceramics, glass and metals contains a large amount of polar functional group hydroxyl (-OH), so that water drops, oil stains, fingerprints, oil and fat, cosmetics and other pollutants are very easily adhered to the surface of the materials, and the appearance and the transparency of the materials are seriously reduced. Particularly, when the materials are applied to the surfaces of touch screens, displays and cameras of electronic products such as mobile phones, cameras and computers, optical lenses of glasses for myopia, hyperopia and labor protection, front windshields and rearview mirrors of automobiles, high-rise building glass and display windows, stainless steel handrails of stairs, sanitary ceramics, shower rooms and the like, the surfaces are urgently required to be kept clean all the time along with the continuous improvement of the living standard of human beings. It is thought that the quality of the end products and the living standards of people will be seriously affected if effective methods are not used to improve the water, oil and dirt repellency of these surfaces.
At present, the water, oil and dirt resistance of the surface of the materials is generally improved by coating the surface of the materials with low-surface-energy coatings. From the technical point of view, the hydrophobic and oleophobic function of the material surface is realized by two main ways, namely adding a low surface energy substance on the material surface; secondly, a rough structure is constructed on the surface of the material. A more rapid and efficient method is to add low surface energy substances to the coating.
Compared with fluorocarbon compounds, perfluoropolyether (PFPE) has better degradability, extremely low surface energy and can resist the adhesion of water and oil stains; PFPE is grafted on an alkoxy silane end group to prepare the perfluoropolyether group fluorosilane, the alkoxy silane containing the hydrolysis active end functional group can perform condensation reaction with hydroxyl (-OH), so that the perfluoropolyether group fluorosilane can be grafted on the surfaces of materials such as ceramics, glass and metal, and the waterproof, oilproof and antifouling performances of the surfaces are improved, and the technologies are disclosed in patents of CN201610182551.3, CN201610031538.8, CN201510679557.7, CN201310686998.0, CN102686685 and the like. However, in practical use, the perfluoropolyether-based fluorosilane is required to have not only good water-proof, oil-proof and stain-proof properties, but also excellent wear resistance, so that the treated surface has lasting water-proof, oil-proof and stain-proof properties.
In response to such practical needs, patents CN201510993283.9 and CN201510679557.7 and CN201610031538.8 disclose a method of grafting 2 to 3 alkoxysilane functions simultaneously at the end of the perfluoropolyether molecular chain, which improves the abrasion resistance of the coating to some extent. Patent CN104769009 discloses a method for simultaneously grafting 4 alkoxysilane functions onto the end of a perfluoropolyether molecular chain, wherein the treated surface has extremely low surface tension and excellent wear resistance, however, the raw materials for preparing the compound are not easily available, flammable and explosive, and the number of terminal groups with hydrolytic activity is small.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the perfluoropolyether fluorine-based fluorosilane with multiple hydrolysis active end groups and the application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a perfluoropolyether group fluorosilane with multiple hydrolysis active end groups has a structural formula shown as I,
Figure BDA0001295241020000021
wherein,
a. b and c are natural numbers, 50 ≧ c ≧ b > a and c ≧ 4, and the order of existence of each repeating unit with a, b, and c bracketed by a bracket is arbitrary in the formula;
g is a natural number, and 3 ≧ g > 0;
Rfis a monovalent perfluoropolyether group;
x is a divalent organic group having 2 to 10 carbon atoms and does not contain a nitrogen atom;
y is a divalent alkyl group;
R1is an alkoxy substituent on a silicon atom;
R2is an alkyl substituent on a silicon atom.
According to the invention, R isfIs F (C)dF2dO)e-, wherein d and e are natural numbers.
Preferably, said R isfIs F (C)3F6O)e-or F (C)4F8O)e-, where 50 ≧ e ≧ 3.
More preferably, said RfIs F (CF)2CF2CF2O)e-、F(CFCF3CF2O)e-or F (CF)2CF2CF2CF2O)e-, where 50 ≧ e ≧ 3.
According to the invention, X is CmHnF2m-nOiWherein m, n and i are natural numbers, and 20 ≧ m ≧ 2, 40 ≧ n ≧ 1 and 10 ≧ i ≧ 1.
Preferably, said X is-CF2CF2CH2OCjH2j-，-CF2CF2CF2CH2OCjH2j-or-CF (CF)3)CH2OCjH2j-, where j is a natural number, and 10 ≧ j ≧ 3.
According to the invention, Y is-CqH2qWherein q is a natural number and 10. gtoreq.gtoreq.2.
According to the invention, R is1Is methoxy, ethoxy or propoxy.
According to the invention, R is2Is methyl, ethyl, propyl or butyl.
The invention adopts another technical scheme that: the application of the perfluoropolyether-based fluorosilane with multiple hydrolysis active end groups in coating.
In the invention, all the raw materials can be obtained by commercial purchase and/or known means, and meet the requirements of standard chemical products when not particularly stated.
The prior art is referred to in the art for techniques not mentioned in the present invention.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
the molecular chain end of the perfluoropoly-fluorine-ether-based fluorosilane provided by the invention has at least 4 hydrolysis active functional groups, so that the adhesion force of a PFPE chain and a base material is greatly improved, and when the PFPE chain is applied to the field of paint, the water contact angle and the oil contact angle of a paint film of the paint can be obviously improved, and meanwhile, the graffiti resistance of the paint film is also improved. On the other hand, the introduction of multi-hydrolysis active end groups at the tail end of the molecular chain of the perfluoropolyether group fluorosilane can obviously improve the adhesion of the molecular chain of the perfluoropolyether group fluorosilane to a paint film, and finally improve the anti-fouling durability of the paint film. The surfaces of ceramics, glass, metal and the like are treated by the paint, and have super water-proof, oil-proof and antifouling performances.
Drawings
FIG. 1 is H of perfluoropolyether-based fluorosilane prepared in example 11NMR spectrum analysis.
Detailed Description
The perfluoropolyether group fluorosilane can be prepared by the following method:
(1) carrying out addition reaction on vinyl-terminated perfluoropolyether and dialkoxy hydrosilane in the presence of a fluorine-containing solvent and a catalyst to prepare perfluoropolyether fluorosilane;
(2) carrying out hydrolysis reaction on the perfluoropolyether-based fluorosilane prepared in the step (1) to prepare a perfluoropolyether-based fluorosilane hydrolysate;
(3) reacting the perfluoropolyether-based fluorosilane hydrolysate prepared in the step (2) with polyvinyl silicone oil in the presence of an alkaline catalyst to prepare vinyl perfluoropolyether-based fluorosilicone oil;
(4) carrying out addition reaction on the vinyl perfluoropolyether-based fluorosilicone oil prepared in the step (3) and trialkoxy hydrosilane in the presence of a fluorine-containing solvent and a catalyst to prepare the perfluoropolyether-based fluorosilicone;
wherein the structural formula of the vinyl-terminated perfluoropolyether is shown as a formula II,
RfCF2CF2CF2CH2OCj-2H2j-4CH＝CH2
Ⅱ，
r in the structural formula shown in the formula IIfA monovalent perfluoropolyether group, j is a natural number, j is not less than 10 and not less than 3,
or the structural formula of the end vinyl perfluoropolyether is shown as a formula III,
RfCF2CF2CH2OCj-2H2j-4CH＝CH2
Ⅲ，
r in the structural formula shown in the formula IIIfA monovalent perfluoropolyether group, j is a natural number, j is not less than 10 and not less than 3,
or the structural formula of the end vinyl perfluoropolyether is shown as the formula IV,
RfCF(CF3)CH2OCj-2H2j-4CH＝CH2
Ⅳ，
r in the structural formula shown in the formula IVfIs a monovalent perfluoropolyether group, j is a natural number, and j is not less than 10 and not less than 3.
Preferably, R in the structural formula shown in the formula IIfIs F- (CF)2CF2CF2CF2O)e-, in which e isA natural number of 50 ≧ e ≧ 3.
Preferably, R in the structural formula shown in the formula IIIfIs F- (CF)2CF2CF2O)e-, where e is a natural number, and 50. gtoreq.e.gtoreq.3.
Preferably, R in the structural formula shown in the formula IVfIs F- (CFCF)3CF2O)e-, where e is a natural number, and 50. gtoreq.e.gtoreq.3.
The vinyl-terminated perfluoropolyethers of the invention can be prepared by reducing an alcohol (R) from a perfluoropolyetherfCH2OH) and allyl bromide under alkaline conditions, and the specific synthetic method refers to a patent US6958191, and the adopted raw material perfluoropolyether reduced alcohol is provided by Taicang chemical environmental protection chemical company Limited.
Preferably, in the step (1), the fluorine-containing solvent is one or a mixture of several of methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, 1,1,1,3, 3-pentafluorobutane, perfluorohexane, perfluoroheptane, perfluorooctane, trifluorotoluene, m-ditrifluorotoluene, hexafluoro-p-xylene, and hexafluoro-m-xylene.
Preferably, in step (1), the catalyst is a Karstedt-type platinum catalyst or a Speir-type platinum catalyst. More preferably, the mass content of the platinum element in the actual reaction system is 5-20 ppm. Specifically, Karstedt type platinum catalyst (VM-23, Zhejiang thoroughfare Jian orange organosilicon materials Co., Ltd.) is selected.
Preferably, in step (1), the dialkoxy hydrosilane is selected from one or more of methyldimethoxysilane, methyldiethoxysilane, methyldipropoxysilane, ethyldimethoxysilane, ethyldiethoxysilane, ethyldipropoxysilane, propyldimethoxysilane, propyldiethoxysilane, propyldipropoxysilane, and the like.
Preferably, in the step (1), the vinyl-terminated perfluoropolyether and the dialkoxy hydrosilane are in an equimolar ratio, and the addition amount of the fluorine-containing solvent accounts for 20-80% of the total reaction system.
Preferably, the addition reaction in the step (1) is carried out under the protection of nitrogen and at the temperature of 30-150 ℃.
Specifically, the specific implementation manner of step (1) is as follows: the method comprises the steps of reacting vinyl-terminated perfluoropolyether, dialkoxy hydrosilane, a fluorine-containing solvent and a catalyst at 30-150 ℃ for 10-14 hours under the protection of nitrogen, then vacuumizing, and removing low boiling point for 0.5-1.5 hours under the pressure of 0.1-5 KPa to prepare the perfluoropolyether-based fluorosilane.
Preferably, the hydrolysis reaction in the step (2) is carried out at 70-90 ℃.
Specifically, the specific implementation manner of step (2) is as follows: and (2) washing the perfluoropolyether-based fluorosilane prepared in the step (1) with water, heating to 70-90 ℃, reacting for 3-5 hours, cooling, standing, layering, collecting lower-layer viscous liquid, repeatedly washing with water, heating, reacting for 2-4 times, and removing low boiling point for 0.5-1.5 hours under the pressure of 0.1-5 KPa to prepare the perfluoropolyether-based fluorosilane hydrolysate.
More specifically, in step (2), the volume of water added per water washing is approximately the same as the volume of the viscous liquid.
Preferably, in the step (3), the alkaline catalyst is one or a mixture of potassium hydroxide, sodium hydroxide and lithium hydroxide.
Preferably, in the step (3), the structural formula of the polyvinyl silicone oil is shown as formula V,
Figure BDA0001295241020000051
wherein b and c are natural numbers, and 50 ≧ c ≧ b, and c ≧ 4.
More preferably, the polyvinyl silicone oil can be prepared by the ring-opening polymerization reaction of octamethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane and hexamethyldisiloxane under the catalysis of potassium hydroxide, and is also commercially available. The viscosity is 50-50000 mPas, and the molar content of vinyl is 2-10 mmol/g.
Preferably, the reaction in the step (3) is carried out under the protection of nitrogen and at the temperature of 50-150 ℃.
Specifically, the specific implementation manner of step (3) is as follows: uniformly mixing the perfluoropolyether-based fluorosilane hydrolysate prepared in the step (2), polyvinyl silicone oil and an alkaline catalyst, reacting for 3-5 hours at 50-150 ℃ under the protection of nitrogen, vacuumizing, and removing low boiling point for 0.5-1.5 hours under the pressure of 0.1-5 KPa to prepare the vinyl perfluoropolyether-based fluorosilane oil.
Preferably, in the step (4), the fluorine-containing solvent is one or a mixture of several of methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, 1,1,1,3, 3-pentafluorobutane, perfluorohexane, perfluoroheptane, perfluorooctane, trifluorotoluene, m-ditrifluorotoluene, hexafluoro-p-xylene, and hexafluoro-m-xylene.
Preferably, in step (4), the catalyst is a Karstedt-type platinum catalyst or a Speir-type platinum catalyst. More preferably, the mass content of the platinum element in the actual reaction system is 5-20 ppm. Specifically, Karstedt type platinum catalyst (VM-23, Zhejiang thoroughfare Jian orange organosilicon materials Co., Ltd.) is selected.
Preferably, in the step (4), the trialkoxyhydrosilane is selected from one or more of trimethoxy silane, triethoxy silane, tripropoxy silane and other compounds.
Preferably, in the step (4), the vinyl group (Si-CH ═ CH) in the vinyl perfluoropolyether-based fluorosilicone oil2) And hydrosilyl (Si-H) in trialkoxy hydrosilyl is in an equal molar ratio, and the fluorine-containing solvent accounts for 20-80% of the total reaction system.
Preferably, the addition reaction in the step (4) is carried out under the protection of nitrogen and at the temperature of 30-150 ℃.
Specifically, the specific implementation manner of step (4) is as follows: and (3) reacting the vinyl perfluoropolyether-based fluorosilicone oil prepared in the step (3), a fluorine-containing solvent, trialkoxyhydrosilane and a catalyst at 50-150 ℃ for 3-5 hours under the protection of nitrogen, vacuumizing, and removing low boiling point for 0.5-1.5 hours under the pressure of 0.1-5 KPa to prepare the perfluoropolyether-based fluorosilicone.
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the following examples. The raw materials used in the examples are commercially available.
Example 1
This example provides a perfluoropolyfluoroether-based fluorosilane having multiple hydrolytically active end groups, the structure of which is represented by the general formula i, wherein a is 1, b is 4, c is 4, d is 3, e is 9, g is 3, and X is CFCF3CH2OCH2CH2CH2，Y＝CH2CH2CH2，R1＝OC2H5Having the formula shown below:
Figure BDA0001295241020000061
the perfluoropolyether group fluorosilane of the present example is prepared by the following steps:
(1) 100.0g of terminal vinyl perfluoropolyether (molecular weight 1684g/mol, provided by Taicang chemical environmental protection chemical Co., Ltd.) with a reflux condenser, nitrogen purge, strong stirring and temperature control device is added into a four-neck flask with a structure general formula of F (CFCF)3CF2O)9CFCF3CH2OCH2CH＝CH2) Uniformly stirring 6.3g of methyldimethoxysilane and 110.0g of m-benzotrifluoride at room temperature, adding 1g of Karstedt type platinum catalyst VM-23 (the Pt content is 3000ppm, and the Pt is provided by Zhejiang thoroughfare Jian orange organosilicon materials Co., Ltd.), gradually heating to 80 ℃, then carrying out heat preservation reaction for 8 hours, and finally removing low boiling for 2 hours under the vacuum degree of 0.2KPa to obtain the product perfluoropolyether-based fluorosilane;
(2) cooling the perfluoropolyether-based fluorosilane prepared in the step (1) to room temperature, gradually adding pure water with the same volume under the stirring condition, washing with water, slowly heating to 80 ℃ and carrying out heat preservation reaction for about 4 hours, cooling, standing, layering and collecting lower-layer viscous liquid, repeating the washing, heating and reaction operations for 3 times on the lower-layer viscous liquid, and finally removing low boiling for about 1 hour under the vacuum degree of 0.2KPa to prepare perfluoropolyether-based fluorosilane hydrolysate;
(3) mixing the perfluoropolyether-based fluorosilane hydrolysate prepared in the step (2), 47.7g of polyvinyl silicone oil (the structural formula of which is in accordance with the general formula shown in the formula V, wherein b is 4, and c is 4; prepared by reacting octamethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane and hexamethyldisiloxane in equal molar ratio for 4 hours under the catalysis of potassium hydroxide for ring-opening polymerization at 130 ℃, and finally dehydrating at 100KPa for 0.5 hour for refining) and 0.1g of potassium hydroxide, reacting for 4 hours under the protection of nitrogen within the temperature range of 140 ℃, slowly vacuumizing, and removing low boiling for about 1 hour under the pressure of 0.2KPa to prepare the vinyl perfluoropolyether-based fluorosilane oil;
(4) and (3) reacting the vinyl perfluoropolyether-based fluorosilicone oil prepared in the step (3), 200g of m-ditrifluorotoluene, 39.0g of trialkoxyhydrosilane and 2g of Karstedt type platinum catalyst VM-23 at 80 ℃ for 12 hours under the protection of nitrogen, slowly vacuumizing, and finally removing low boiling for about 1 hour under the pressure of 0.2KPa to prepare the target product of the perfluoropolyether-based fluorosilicone (marked as PFPE-FS-1).
Nuclear magnetic H of product PFPE-FS-1 Compound1NMR analysis, H of PFPE-FS-11The results of NMR analysis are shown in FIG. 1, and it is understood from FIG. 1 that:
chemical shift peaks around 0ppm attributed to the pendent Si-CH groups of the organosilicon chains3The proton in (1);
a chemical shift peak around 0.5ppm belonging to C linked to triethoxysilicaneH 2Si(OC2H5)3A proton at the alpha position;
the chemical shift peak near 1.2ppm belongs to triethoxysilicane Si-O-CH2-CH 3The proton of (a);
disordered chemical shift peaks in the range of 1.3-1.4 ppm belong to polysiloxane main chain side group SiCH 2CH 2The proton of (a);
disordered chemical shift peaks in the range of 3.3-3.9 ppm belong to triethoxysilicane Si-O-CH 2-CH3And two methylene groups R close to the perfluoropolyether molecular chainf-CH 2-O-CH 2Of (c) is added.
Example 2
This example provides a perfluoropolyfluoroether-based fluorosilane having multiple hydrolytically active end groups, the structure of which is represented by the general formula i, wherein a is 1, b is 4, c is 4, d is 3, e is 20, g is 3, and X is CFCF3CH2OCH2CH2CH2，Y＝CH2CH2CH2，R1＝OC2H5。
This example perfluoropolyether-based fluorosilane was prepared according to the method and procedure of example 1, except that: the specification of the vinyl-terminated perfluoropolyether in the formula is changed as follows: the molecular weight is 3510g/mol, and the molecular weight is provided by Taicang Zhonghua environmental protection chemical company, and the structural general formula is as follows: f (CFCF)3CF2O)20CFCF3CH2OCH2CH＝CH2The corresponding mass is replaced with 209 g.
The perfluoropolyether fluorosilicone of this example is identified as PFPE-FS-2.
Example 3
This example provides a perfluoropolyfluoroether-based fluorosilane having multiple hydrolytically active end groups, the structure of which is represented by the general formula i, wherein a is 1, b is 4, c is 4, d is 3, e is 30, g is 3, and X is CFCF3CH2OCH2CH2CH2，Y＝CH2CH2CH2，R1＝OC2H5。
This example perfluoropolyether-based fluorosilane was prepared according to the method and procedure of example 1, except that: the specification of the vinyl-terminated perfluoropolyether in the formula is changed as follows: the molecular weight is 5170g/mol, which is provided by Taicang Zhonghua environmental protection chemical company, and the structural general formula is as follows: f (CFCF)3CF2O)30CFCF3CH2OCH2CH＝CH2The corresponding mass is replaced with 307 g.
The perfluoropolyether fluorosilicone of this example is identified as PFPE-FS-3.
Comparative example
This comparative example provides a perfluoropolyether-based fluorosilane, preparation thereofThe method comprises the following steps: 100.0g of methyl ester based perfluoropolyether (molecular weight of 3332g/mol, provided by Taicang chemical environmental protection Co., Ltd.) having a general structural formula of F (CFCF) was added to a four-neck flask equipped with a reflux condenser, nitrogen purge, strong stirring and temperature control device3CF2O)19CFCF3COOCH3) Then 13.1g of aminopropyltriethoxysilane is slowly dripped at room temperature, and the dripping is finished within 1 hour; gradually heating to 80 ℃, then carrying out heat preservation reaction for 8 hours, and finally removing low boiling for 2 hours under the vacuum degree of 0.2KPa to obtain the product of the perfluoropolyether fluorosilane (marked as PFPE-FS-4). The structural formula of the perfluoropolyether group fluorosilane (PFPE-FS-4) is shown as follows,
Figure BDA0001295241020000081
preparation of the coating
The perfluoropolyether group fluorosilane is applied to preparing a coating, and the coating can be selected from the following formula: 100 parts of organic silicon resin; 0.01-10 parts of perfluoropolyether fluorosilane; 10-10000 parts of a diluting solvent; 0.01-5 parts of curing catalyst by weight.
The silicone resin may be polymerized by Si (R)3O)qR4 (4-q)One or more of them are subjected to condensation reaction, wherein R is3Is H, CH3、C2H5、C3H7Or C4H9，R4Is CH3、C2H5、C3H7Or C4H9And q is 1, 2, 3 or 4.
Preferably, the structural formula of the organic silicon resin is shown as II,
Figure BDA0001295241020000082
wherein,
R3is H, CH3、C2H5、C3H7Or C4H9；
R4Is CH3、C2H5、C3H7Or C4H9；
W1、W2R can be independently selected4 3SiO or R3；
k1、k2、k3Is a natural number, and k1>k2>k3，100>k1+k2+k3>10。
The dilution solvent may be an alcohol solvent. Such as methanol, ethanol and isopropanol.
The curing catalyst can be one or a combination of more of organic acid and inorganic acid, and specifically, the curing catalyst is one or a combination of more of acetic acid, hydrochloric acid, phosphoric acid and nitric acid.
Specifically, the perfluoropolyether group fluorosilane of examples 1 to 3 and the comparative example was used for preparing a coating.
The preparation of the coating comprises the following steps: stirring and mixing 500 parts by mass of organic silicon glass resin (SI-101 with the solid content of 30 percent and the diluting solvent of ethanol provided by san pont chemical company, laiyang), 0.5 part by mass of perfluoropolyether fluorosilane (PFPE-FS-1) and 4500 parts by mass of ethanol uniformly at room temperature, gradually adding 2 parts by mass of concentrated hydrochloric acid (with the mass concentration of 36 percent), and stirring and mixing uniformly to obtain the coating sample FSC-1.
According to the method and procedure shown in the coating sample FSC-1, PFPE-FS-1 in the formulation of FSC-1 was replaced by 0.1 part, 0.2 part, 1.0 part and 10 parts by mass to prepare coating samples FSC-2, FSC-3, FSC-4 and FSC-5, respectively, and the rest was the same as the preparation method of FSC-1.
Test pieces FSC-6, FSC-7 and FSC-8 were prepared by replacing perfluoropolyether-based fluorosilane in the formulation of FSC-1 with PFPE-FS-2, PFPE-FS-3 and PFPE-FS-4, respectively, according to the procedure and procedure shown in coating sample FSC-1, and otherwise identical to the procedure for preparing FSC-1.
Coating sample FSC-0 was prepared according to the procedure and procedure shown for coating sample FSC-1, without using perfluoropolyether-based fluorosilane (PFPE-FS-1) in the FSC-1 formulation, otherwise as for FSC-1.
Preparation of paint films
The surface of a glass slide (76.2X 25.4X 1.2mm) is cleaned by ethanol, and then a coating sample FSC-0 is uniformly sprayed on the glass slide by a w71 type spray gun, wherein the spraying amount is 1.5kg/m2. And standing the paint film for 24 hours at room temperature, and then putting the paint film into a 100 ℃ oven to be cured for 1 hour at high temperature to finally prepare the test piece FSS-0.
According to the method and procedure shown in the test piece FSS-0, FSC-0 was replaced with FSC-1, FSC-2, FSC-3, FSC-4, FSC-5, FSC-6, FSC-7 and FSC-8, and test pieces FSS-1, FSS-2, FSS-3, FSS-4, FSS-5, FSS-6, FSS-7 and FSS-8 were prepared, respectively, and the other methods were the same as the preparation method of FSS-0.
Performance testing of the paint films
Evaluation of scrawling resistance: after graffiti is made on the surfaces of paint films FSS-0, FSS-1, FSS-2, FSS-3 and FSF-4 by using a high-power oil black marking pen (red, blue and black), and the paint films are dried for 4 hours at room temperature, the stains on the surfaces of the paint films are wiped by using a dry paper towel, and whether stains are left on the surfaces of the paint films is observed. The hierarchical labeling was performed according to the following criteria:
level 1: means that stains can be easily wiped off and that no residue remains inside the paint film;
and 2, stage: indicating that the stain can be wiped off, but is laborious and has no residue inside the paint film;
and 3, level: indicating that stains can be wiped off, but there is ink bleeding inside the paint film;
4, level: indicating that the stain was not wiped off.
Contact angle test method: the test pieces FSS-0, FSS-1, FSS-2, FSS-3 and FSF-4 without any abrasion were placed on a contact angle meter (model: DSA30, supplied by Kluyvers, Germany) with deionized water and dodecane as the test medium and a test droplet volume of 4. mu.L, and the contact angle values were recorded for 3 droplets and the arithmetic mean of the 3 test data was taken.
Evaluation of Friction durability: fixing test pieces FSS-0, FSS-1, FSS-2, FSS-3 and FSF-4 on an abrasion resistance tester (ESIDA-NM-002, available from Shimada instruments Co., Ltd., Shenzhen), and binding polypropylene non-woven fabric (model: B95, Jiangxi Haorui industrial materials Co., Ltd.) on a contact head friction probe; applying 500g of test load above the probe, wherein the test stroke is 20mm, and the sample speed is 10 times/min; after the abrasion test was performed for 20 minutes, the experiment was stopped and the contact angle of the surface was lost.
The results of the graffiti resistance, contact angle, and abrasion durability tests are shown in table 1.
TABLE 1
Figure BDA0001295241020000101
As can be seen from the comparison of examples FSS-1 to 7 (except FSS-5) and FSS-0 of Table 1: the perfluoro poly-fluorine-ether-based fluorosilane is introduced into the organic silicon resin coating, so that the water contact angle and the oil contact angle of the coating can be obviously improved, and meanwhile, the graffiti resistance of a paint film is also improved; comparison of examples FSS-1 to 7 with FSS-8 shows that: the contact angle between water and dodecane is basically unchanged before and after the test piece FSS-1-7 is abraded, and the FSS-8 is greatly changed, so that the adhesion force between a perfluoropolyether molecular chain and a paint film can be remarkably improved by introducing multiple hydrolysis active end groups at the tail end of perfluoropolyether, and the anti-fouling durability of the paint film is finally improved; by comparing FSS-5 with FSS-1-4 in the examples, it can be seen that the addition amount of the perfluoropolyether group fluorosilane in the organic silicon resin coating is not easy to be too high, otherwise, the adhesion of a paint film is influenced.
The present invention is described in detail in order to make those skilled in the art understand the content and practice the invention, and the invention is not limited to the above embodiments, and all equivalent changes or modifications made according to the spirit of the invention should be covered by the scope of the invention.

Claims (10)

1. A perfluoropolyether group fluorine silane with multiple hydrolysis active end groups is characterized in that: the structural formula of the perfluoropolyether group fluorosilane is shown as I,
Figure FDA0002650810580000011
wherein,
a. b and c are natural numbers, 50 ≧ c ≧ b > a and c ≧ 4, and the order of existence of each repeating unit with a, b, and c bracketed by a bracket is arbitrary in the formula;
g is a natural number, and 3 ≧ g > 0;
Rfis a monovalent perfluoropolyether group;
x is a divalent organic group having 2 to 10 carbon atoms and does not contain a nitrogen atom;
y is a divalent alkyl group;
R1is an alkoxy substituent on a silicon atom;
R2is an alkyl substituent on a silicon atom;
the preparation method of the perfluoropolyether group fluorosilane comprises the following steps:
(1) carrying out addition reaction on vinyl-terminated perfluoropolyether and dialkoxy hydrosilane in the presence of a fluorine-containing solvent and a catalyst to prepare perfluoropolyether fluorosilane;
(2) carrying out hydrolysis reaction on the perfluoropolyether-based fluorosilane prepared in the step (1) to prepare a perfluoropolyether-based fluorosilane hydrolysate;
(3) reacting the perfluoropolyether-based fluorosilane hydrolysate prepared in the step (2) with polyvinyl silicone oil in the presence of an alkaline catalyst to prepare vinyl perfluoropolyether-based fluorosilicone oil;
(4) carrying out addition reaction on the vinyl perfluoropolyether-based fluorosilicone oil prepared in the step (3) and trialkoxy hydrosilane in the presence of a fluorine-containing solvent and a catalyst to prepare the perfluoropolyether-based fluorosilicone;
wherein the structural formula of the vinyl-terminated perfluoropolyether is shown as a formula II,
RfCF2CF2CF2CH2OCj-2H2j-4CH＝CH2 Ⅱ，
or the structural formula of the end vinyl perfluoropolyether is shown as a formula III,
RfCF2CF2CH2OCj-2H2j-4CH＝CH2 Ⅲ，
or the structural formula of the end vinyl perfluoropolyether is shown as the formula IV,
RfCF(CF3)CH2OCj-2H2j-4CH＝CH2 Ⅳ，
in the formulas II, III and IV, j is a natural number, and j is larger than or equal to 10 and larger than or equal to 3.
2. The perfluoropolyether-based fluorosilane having multiple hydrolytically active end groups of claim 1, wherein: the R isfIs F (C)dF2dO)e-, wherein d and e are natural numbers.
3. The perfluoropolyether-based fluorosilane having multiple hydrolytically active end groups of claim 2, wherein: the R isfIs F (C)3F6O)e-or F (C)4F8O)e-, where 50 ≧ e ≧ 3.
4. The perfluoropolyether-based fluorosilane having multiple hydrolytically active end groups of claim 3, wherein: the R isfIs F (CF)2CF2CF2O)e-、F(CFCF3CF2O)e-or F (CF)2CF2CF2CF2O)e-, where 50 ≧ e ≧ 3.
5. The perfluoropolyether-based fluorosilane having multiple hydrolytically active end groups of claim 1, wherein: x is CmHnF2m-nOiWherein m, n and i are natural numbers, and 20 ≧ m ≧ 2, 40 ≧ n ≧ 1 and 10 ≧ i ≧ 1.
6. The perfluoropolyether-based fluorosilane having multiple hydrolytically active end groups of claim 5, wherein: said X is-CF2CF2CH2OCjH2j-，-CF2CF2CF2CH2OCjH2j-or-CF (CF)3)CH2OCjH2j-, where j is a natural number, and 10 ≧ j ≧ 3.
7. The perfluoropolyether-based fluorosilane having multiple hydrolytically active end groups of claim 1, wherein: y is-CqH2qWherein q is a natural number and 10. gtoreq.gtoreq.2.
8. The perfluoropolyether-based fluorosilane having multiple hydrolytically active end groups of claim 1, wherein: the R is1Is methoxy, ethoxy or propoxy.
9. The perfluoropolyether-based fluorosilane having multiple hydrolytically active end groups of claim 1, wherein: the R is2Is methyl, ethyl, propyl or butyl.
10. Use of the perfluoropolyether-based fluorosilane having multiple hydrolytically active end groups according to any one of claims 1-9 in coatings.
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