CN113061240B - Precursor and preparation method thereof, super-amphiphobic coating material and preparation method thereof, and super-amphiphobic coating - Google Patents

Precursor and preparation method thereof, super-amphiphobic coating material and preparation method thereof, and super-amphiphobic coating Download PDF

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CN113061240B
CN113061240B CN202110373662.3A CN202110373662A CN113061240B CN 113061240 B CN113061240 B CN 113061240B CN 202110373662 A CN202110373662 A CN 202110373662A CN 113061240 B CN113061240 B CN 113061240B
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刘栋
张希
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Tianjin Chengke Yihua Technology Co ltd
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Abstract

The invention provides a precursor and a preparation method thereof, a super-amphiphobic coating material and a preparation method thereof, and a super-amphiphobic coating, wherein an intermediate product is formed by polymerizing a derivative of perfluoropolyether and epsilon-caprolactone, and the precursor prepared by the intermediate product and isocyanate methyl triethoxy silicon has a low surface energy functional group, and meanwhile, as a terminal group contains 6 ethoxy groups, the precursor can participate in chemical reactions such as hydrolysis-polycondensation and the like with most organic silicon sources as a co-precursor, and can be used for methods such as a sol-gel method, a coprecipitation method and the like to prepare various functional materials, particularly for preparing the super-amphiphobic material with low surface energy, so as to reduce the final surface energy of the materials and form a main chain with a more stable structure.

Description

Precursor and preparation method thereof, super-amphiphobic coating material and preparation method thereof, and super-amphiphobic coating
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to a precursor and a preparation method thereof, a super-amphiphobic coating material obtained from the precursor and a preparation method thereof, and a super-amphiphobic coating.
Background
The precursor is often found in material preparation methods such as a sol-gel method, a coprecipitation method and the like, and is a prototype sample of a target product of a synthetic material, namely, a preceding-stage product of the target product can be realized through certain steps. The functional materials such as the super-amphiphobic material, the silicon dioxide aerogel heat-insulating material, the photocatalytic degradation material, the sound absorption material and the like are prepared by using an organic silicon source as a precursor. The precursor can be selected from common chemical raw materials and can also be automatically synthesized according to a target product, the former has the advantage of low cost, and the latter can improve the functionality of the target product or make up for the defects of traditional materials. For example 201610017971.6' a visible light-responsive TiO 2 Preparation method of precursor and obtained TiO 2 The precursor and the catalyst are synthesized by common chemical raw material titanate, and the synthesized precursor solves the problem of common TiO 2 The problem of no response under visible light; for example 202010253246.5, a grid-shaped porous precursor material, a preparation method thereof and an anode material are invented, and the anode material prepared by the precursor has high rate capability, high activation rate of the energy storage material and improved capacity.
At present, materials taking silicon-oxygen 'Si-O' as a main chain are prepared and synthesized by adopting an organic silicon source as a precursor in the early stage, such as methyltrimethoxysilane, triethoxysilane and the like, which are common and characterized in that the materials contain methoxy or ethoxy and the like which are easy to hydrolyze to form end groups of unsaturated bonds, and can be condensed into the main chain in a solvent system. Has the advantages of low cost and belonging to common chemical raw materials. The defects are that the molecular weight is small, the functional characteristics are not possessed, the material can only be used as a common main chain, and the modification and modification of the material characteristics are all from modification of a branched chain after the main chain is formed by polycondensation.
From the basic theory of solid wettability (Wenzel model and Cassie model), it can be known that the following two factors are mainly involved in the wettability of the solid material surface: surface free energy and surface roughness. Therefore, at present, the main technical routes for researching and preparing the super-amphiphobic coating at home and abroad are divided into two routes, one is to construct a nanoscale rough surface on the surface of a base material by etching or other electrochemical methods, and the other is to modify a material by using a substance with low surface energy to reduce the surface energy of the coating. The former is limited by the method and difficult to produce on a large scale, and the latter is the main preparation and production means at present. At present, the main chain of the super-amphiphobic material mostly takes carbon chains, silicon chains and metal oxides as main materials, but because substances with low surface energy modify the main chain by methods of substitution, chain initiation, post addition and the like, the modified material has the defects of poor mechanical friction resistance, long modification link period and high cost of a modifier, particularly a fluorine-containing modifier, the cost of the super-amphiphobic coating cannot be reduced, and the popularization of the super-amphiphobic coating is limited.
Disclosure of Invention
In view of the above, the present invention provides a precursor and a preparation method thereof, which solve the problems of the existing precursor, wherein the precursor contains a perfluoropolyether derivative, so that a chain structure or a net structure formed when the precursor is used as a silicon source to prepare a final target product is more stable and has lower surface energy.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a precursor is a polycaprolactone precursor terminated by fluoropolyether triethoxysilane, and has a chemical molecular formula as follows:
Figure BDA0003010319340000021
wherein PFxXeN is
Figure BDA0003010319340000022
Furthermore, in the PFxPEN, x is more than 0 and less than or equal to 5, and x is preferably 1 or 2; n is more than 0 and less than or equal to 10, and n is preferably 2, 5 or 10.
A preparation method of a precursor comprises the following steps:
s1, dispersing hexafluoropropylene oxide in an aprotic solvent, adding an alkali metal fluoride inorganic salt serving as a catalyst, and carrying out anionic polymerization until the hexafluoropropylene oxide is subjected to ring opening; the reaction formula is as follows:
Figure BDA0003010319340000031
s2, injecting the solution obtained in the step S1 into a prepared mixed solvent of trifluoroethanol and low-carbon alcohol for reaction, and drying a product after the reaction to obtain a derivative of perfluoropolyether; the reaction formula is as follows (the mixed solvent in the reaction formula takes trifluoroethanol and ethanol as an example):
CF 3 CF 2 CF 2 O - +CF 3 CH 2 OH+CH 3 CH 2 OH→HOCH 2 -CF 2 -O-(CF 2 -CF 2 -O) x -CF 2 -CH 2 OH
HOCH 2 -CF 2 -O-(CF 2 -CF 2 -O) x -CF 2 -CH 2 OH is the general formula of the derivative of the perfluoropolyether, wherein x is more than 0 and less than or equal to 5, and 1 and 2 are optimized;
s3, dissolving a derivative of perfluoropolyether in a sufficient tetrahydrofuran or polyalcohol solvent system, adding epsilon-caprolactone and a catalyst for reaction, and performing rotary evaporation or drying on a product after the reaction to obtain an intermediate product with a certain polymerization degree; the reaction formula is as follows (in the reaction formula, sn (Oct) is used as a catalyst) 2 For example):
Figure BDA0003010319340000032
the intermediate product, excluding the two-terminal-H moieties, is denoted PFxPEn for simplicity as follows:
Figure BDA0003010319340000033
wherein n is more than 0 and less than or equal to 10, preferably 2, 5 and 10;
s4, dissolving the intermediate product and isocyanate methyl triethoxysilane in a low carbon alcohol, low carbon ketone or straight chain low carbon ether solvent, adding a catalyst, carrying out an amino addition reaction, and drying after the reaction is finished to obtain solid powder, namely the target product of the polycaprolactone precursor terminated by the fluoropolyether triethoxysilane. The reaction formula is as follows:
Figure BDA0003010319340000041
Figure BDA0003010319340000042
namely the target product of polycaprolactone precursor terminated by fluoropolyether triethoxysilane.
Further, in the S1, the aprotic solvent is diglyme, acetonitrile or dimethylformamide, and the alkali metal fluoride inorganic salt is lithium fluoride, sodium fluoride or potassium fluoride;
in the S2, the lower alcohol is methanol, ethanol or propanol;
in the S3, the polyalcohol is ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, neopentyl glycol, glycerol or hexanediol, and the catalyst is stannous isooctanoate or dibutyltin dilaurate;
in S4, the catalyst is stannous isooctanoate or dibutyltin dilaurate.
Further, in the S1, the molar ratio of hexafluoropropylene oxide, the aprotic solvent, and the alkali metal fluoride inorganic salt is (1 to 5): (5-30): (1-5);
in the S2, in the mixed solvent of the trifluoroethanol and the lower alcohol, the molar ratio of the trifluoroethanol to the lower alcohol is 1;
in S3, the molar ratio of the derivative of the perfluoropolyether to the tetrahydrofuran or the polyol solvent is (1-5): (10-100), the mole ratio of epsilon-caprolactone to the derivative of perfluoropolyether is (1-20): (1-5);
in the S4, the molar ratio of the intermediate product to the isocyanate methyl triethoxysilane is 1: (2 to 10), preferably 1.
Further, the reaction conditions in the S1 are that the reaction is carried out for 2 to 5 hours under normal pressure at the temperature of between 20 and 30 ℃ until the hexafluoropropylene oxide is completely opened;
the reaction condition in the S2 is that the reaction is carried out for 1 to 3 hours under normal pressure at the temperature of between 20 and 30 ℃; the longer the reaction time, the greater the degree of polymerization of x;
the reaction condition in the S3 is that the reaction is carried out for 2 to 6 hours under the condition of stirring at the normal pressure at the temperature of between 30 and 50 ℃;
the reaction condition in the S4 is that the reaction is carried out for 10 to 24 hours under the condition of stirring at the normal pressure and at the temperature of 25 ℃.
The invention also provides the application of the precursor, and the application of the fluorine-containing polyether triethoxysilane terminated polycaprolactone precursor in preparing a super-amphiphobic coating. The super-amphiphobic material with low surface energy is prepared by the low surface functional group, the final surface energy of the material can be reduced, and a main chain with a more stable structure is formed.
The invention also aims to provide a super-amphiphobic coating material and a preparation method thereof, and aims to solve the problems that the modified material has poor mechanical friction resistance, long modification link period and high cost of a modifier, particularly a fluorine-containing modifier, caused by the fact that the main chain of the existing super-amphiphobic material is modified by methods such as substitution, chain initiation, post addition and the like in the preparation process.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a super-amphiphobic coating material comprises a silicon-oxygen-silicon network structure material prepared by hydrolysis-polycondensation reaction of a precursor, a mixed solvent of butyl acetate and low carbon alcohol and a resin adhesive; the mass ratio of the silicon-oxygen-silicon network structure material to the mixed solvent of butyl acetate and lower alcohol is (1-5): (20-100), the mass of the resin binder is not more than 20% of the total mass.
Further, the silicon-oxygen-silicon network structure material is prepared by dispersing the precursor in a mixed solvent of alcohol and ionic liquid, and hydrolyzing and polycondensing under the catalysis of weak organic acid.
The chain polycondensation formula of the silicon-oxygen-silicon network structure material is as follows:
Figure BDA0003010319340000061
a preparation method of a super-amphiphobic coating material comprises the following steps:
s1, drying the ionic liquid in vacuum, removing water in air adsorbed by the ionic liquid, wherein the ionic liquid is alcohol: ionic liquid = (1 to 2): (1-5) adding alcohol into the ionic liquid, and uniformly mixing to obtain a mixed solvent of the alcohol and the ionic liquid;
s2, dispersing the precursor in the mixed solvent of the alcohol and the ionic liquid, adding an organic weak acid serving as a catalyst, and performing hydrolysis-polycondensation reaction; the reaction formula is as follows:
Figure BDA0003010319340000062
s3, after the hydrolysis-polycondensation reaction is finished, rapidly heating to 60-100 ℃ under a vacuum condition, keeping the temperature and maintaining the vacuum for a certain time, and then rapidly reducing the surface tension of the mixed phase by utilizing the characteristics of the ionic liquid to fix the polycaprolactone structure; slowly cooling to room temperature, introducing air, recovering internal and external pressure, and removing mixed liquid phase to obtain white powder, namely the silicon-oxygen-silicon net structure material;
and S4, uniformly dispersing the silicon-oxygen-silicon network structure material in a mixed solvent of butyl acetate and low-carbon alcohol, adding a resin adhesive, and uniformly mixing to obtain the super-amphiphobic coating material.
Further, in the S1, the ionic liquid is 1-alkyl-3-methylimidazole tetrafluoroborate or 1-alkyl-3-methylimidazole hexafluorophosphate, and the alcohol is methanol, ethanol, propanol or isopropanol;
in the S2, the organic weak acid is dilute oxalic acid or citric acid;
in S4, the lower alcohol is methanol, ethanol or propanol.
Further, in the S1, the number of alkyl groups of the ionic liquid is 2 to 7.
Further, in S4, the resin binder is an acrylic resin.
Further, in the S2, the mass ratio of the precursor, the weak organic acid, and the mixed solvent is (1 to 3): (1-2): (100-200);
in the S4, the mass ratio of butyl acetate to low-carbon alcohol is 1: (1-10), the mass ratio of the silicon-oxygen-silicon network structure material to the mixed solvent of butyl acetate and low carbon alcohol is (1-5): (20 to 100), and the mass of the resin binder is not more than 20% of the total mass.
Further, the ionic liquid in S1 is dried in vacuum at 80 ℃ for 72h in a vacuum drying oven.
Further, the reaction condition in S2 is that the reaction is carried out for 30min to 120min under normal temperature and normal pressure by stirring;
in the step S3, the rapid temperature rise under the vacuum condition is specifically that under the condition that the vacuum degree is 10 mbar-8 mbar, the temperature rise rate is 3 ℃/S-5 ℃/S to 60 ℃ -100 ℃, and the temperature is kept and the vacuum is maintained for 1 min-5 min.
The invention also provides a super-amphiphobic coating which is formed by coating the super-amphiphobic coating material on the surface of a base material and then curing.
The super-amphiphobic coating is characterized in that a liquid obtained by uniformly mixing a silicon-oxygen-silicon network structure material, a mixed solvent of butyl acetate and low-carbon alcohol and a resin adhesive is injected into a spray gun, an oil-free air compressor is used for spraying, and the super-amphiphobic coating is obtained after the liquid is naturally cured on the surface of an object to be sprayed for 1-2 hours.
Compared with the prior art, the precursor and the preparation method thereof, the super-amphiphobic coating material and the preparation method thereof, and the super-amphiphobic coating have the following advantages:
(1) The precursor is prepared by polymerizing perfluoropolyether derivatives and epsilon-caprolactone to form an intermediate product and synthesizing the intermediate product and isocyanate methyl triethoxy silicon, has a low-surface-energy fluoridation functional group structure, is terminated by triethoxy silane and contains-CF 2 -O-(CF 2 -CF 2 -O) x -CF 2 The structure is a precursor with low local chain segment surface energy, and can reduce the surface energy of the whole material when other materials are prepared;
(2) The precursor provided by the invention has 6 ethoxy-CH terminal groups 2 CH 2 OH can be rapidly hydrolyzed in a liquid phase reaction, and can be widely used for preparing various functional materials by a sol-gel method and a coprecipitation method, so that a chain structure or a net structure formed by the materials is more stable and has lower surface energy.
Compared with the prior art, the super-amphiphobic coating material, the preparation method thereof and the super-amphiphobic coating have the following advantages:
(1) Compared with the conventional method for reducing the surface tension of the main chain by replacing modified silicon chains and carbon chains with functional groups, the method adopts polycaprolactone terminated by fluoropolyether triethoxysilane as a precursor, and uses the PF of the precursor x PE n The structure of the functional group with low surface energy is adopted, and the structure of the ionic liquid medium firm chain is adopted, so that the super-amphiphobic coating is prepared without introducing the functional group with low surface energy, the modification link is omitted, the production cost is saved, and the reaction period is shortened;
(2) By the precursor itself containing "-CF 2 -O-(CF 2 -CF 2 -O) x -CF 2 -”The low surface structure is introduced to the main chain instead of the modification process, so that the overall structure is more stable, and the macro expression is that the mechanical friction resistance of the coating is greatly improved;
(3) The mixed solvent of alcohol and ionic liquid used in the method can be repeatedly used, no waste liquid discharge exists, and the method is economical and environment-friendly.
Drawings
FIG. 1 is a Fourier infrared projection spectrum of a precursor prepared in examples 1,2 and 3 according to the present invention;
FIG. 2 is a representation of XPS spectrum vs. C1s fine spectrum of a precursor prepared in example 1 according to the present invention;
FIG. 3 is a representation of XPS spectra versus C1s fine spectra of a precursor prepared according to example 3 of the present invention;
FIG. 4 is a schematic view of the spatial structure of the Si-O-Si network material according to the present invention;
FIG. 5 is a graph of the static contact angle of the liquid of the super-amphiphobic coating material prepared in examples 4 to 6 of the present invention with respect to water when the liquid is sprayed on the surface of several different substrates to form the double-amphiphobic coating;
FIG. 6 is a graph of the static contact angle of the super-amphiphobic coating liquid prepared in examples 4 to 6 of the present invention to n-hexadecane, formed by spraying the super-amphiphobic coating liquid on the surface of several different substrates;
FIG. 7 is a transmission electron microscope photograph of ethyl orthosilicate in comparative example 1 in comparative experiment 1;
FIG. 8 is a transmission electron microscope photograph of a Si-O-Si chain structure obtained by hydrolytic polycondensation of tetraethoxysilane in comparative example 1 in comparative experiment 1;
FIG. 9 is a transmission electron microscope photograph of a precursor prepared by the precursor preparation method of the present invention in comparative experiment 1;
FIG. 10 is a transmission electron microscope image of Si-O-Si silicon-oxygen network structure formed by hydrolytic polycondensation of the precursor of the present invention in comparative experiment 1.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, were all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The invention is described in detail below with reference to embodiments and the accompanying drawings.
The preparation of the precursor comprises the following steps:
s1, dispersing hexafluoropropylene oxide in an aprotic solvent such as diglyme, acetonitrile or dimethylformamide, adding an alkali metal fluoride inorganic salt such as lithium fluoride, sodium fluoride or potassium fluoride serving as a catalyst, and reacting at the temperature of 20-30 ℃ under normal pressure for 2-5 hours until the hexafluoropropylene oxide is completely subjected to ring opening; wherein the mol ratio of the hexafluoropropylene oxide, the aprotic solvent and the alkali metal fluoride inorganic salt is (1-5): (5-30): (1-5);
s2, injecting the solution obtained in the step S1 into a pre-prepared mixed solvent of trifluoroethanol and low-carbon alcohol for reaction (the molar ratio of the trifluoroethanol to the low-carbon alcohol is 1, the low-carbon alcohol is methanol, ethanol or propanol), wherein the amount of the substance of the mixed solvent of the trifluoroethanol and the low-carbon alcohol is not less than that of the substance of hexafluoropropylene oxide, namely the excessive amount of the substance of the mixed solvent of the trifluoroethanol and the low-carbon alcohol is ensured; reacting for 1-3 hours at 20-30 ℃ under normal pressure, and performing rotary evaporation or drying on a product after reaction to obtain a perfluoropolyether derivative;
s3, dissolving a derivative of perfluoropolyether in a sufficient amount of tetrahydrofuran or a polyol solvent system (the polyol is ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, neopentyl glycol, glycerol or hexanediol), adding epsilon-caprolactone and a catalyst (the catalyst is stannous isooctanoate or dibutyltin dilaurate), stirring at the temperature of 30-50 ℃ under normal pressure for reaction for 2-6 hours, and carrying out rotary evaporation or drying on a product after the reaction to obtain an intermediate product with a certain polymerization degree; wherein the mol ratio of the derivative of the perfluoropolyether to the tetrahydrofuran or the polyalcohol solvent is (1-5): (10-100), the mole ratio of epsilon-caprolactone to the derivative of perfluoropolyether is (1-20): (1-5);
s4, dissolving the intermediate product and isocyanate methyl triethoxysilane in a low carbon alcohol, low carbon ketone or straight chain low carbon ether solvent, adding stannous isooctanoate or dibutyltin dilaurate as a catalyst, stirring and reacting at the normal pressure for 10-24 hours at 25 ℃, opening C = N double bonds under the catalysis of the catalyst, performing amine addition reaction, and realizing the end capping of the two ends of the intermediate product by the isocyanate methyl triethoxysilane, wherein the molar ratio of the intermediate product to the isocyanate methyl triethoxysilane is 1: (2 to 10), preferably 1; and after the reaction is finished, drying to obtain solid powder, namely the target product of the polycaprolactone precursor terminated by the fluoropolyether triethoxysilane.
Example 1
1. Weighing 16.6g of hexafluoropropylene oxide and 2.6g of lithium fluoride, sequentially dispersing in 130g of diglyme, and stirring and reacting for 2.5 hours at the temperature of 25 ℃ under normal pressure;
2. fully mixing 20g of trifluoroethanol and 20g of ethanol to prepare a mixed solvent of the trifluoroethanol and the lower alcohol, further slowly pouring the product obtained in the step 1 into the mixed solvent of the trifluoroethanol and the lower alcohol, fully stirring at the temperature of 25 ℃ and normal pressure for reaction for 1 hour, stopping the reaction, volatilizing the solvent by using a rotary evaporator to obtain HOCH 2 -CF 2 -O-CF 2 -CF 2 -O-CF 2 -CH 2 29.2 g of OH powder;
3. 14.7g of the powder obtained in step 2 was weighed and dissolved in 100g of 1, 2-propanediol solution, and 22.8g of epsilon-caprolactone monomer was added to the mixed solution as Sn (Oct) 2 As a catalyst, stirring at constant speed for reaction for 3 hours at normal pressure at the temperature of 35 ℃, and performing rotary evaporation to obtain 37.5g of an intermediate product H-PF 1 PE 2 -H；
4. 37.5g of the intermediate product H-PF were added in total 1 PE 2 -H and 60g of isocyanate methyltriethoxysilane were dissolved together in an excess propanol solvent, and an amine addition reaction was sufficiently carried out by stirring with dibutyltin dilaurate at 25 ℃ under normal pressure for 12 hours, and finally the solvent was dried to obtain 59.2g of a precursor.
Example 2
1. Placing 83g of hexafluoropropylene oxide and 50g of sodium fluoride in 700g of dimethylformamide, and stirring and reacting for 3 hours at 20 ℃ under normal pressure;
2. 150g of trifluoroethanolMixing with 150g ethanol to obtain mixed solvent of trifluoroethanol and lower alcohol, further slowly pouring the product obtained in step 1 into the mixed solvent of trifluoroethanol and lower alcohol, stirring at 20 deg.C under normal pressure for 2 hr, stopping reaction, and volatilizing solvent to obtain HOCH 2 -CF 2 -O-[CF 2 -CF 2 -O] 2 -CF 2 -CH 2 102g of OH powder;
3. weighing 41g of the powder obtained in the step 2, dissolving the powder in 300g of tetrahydrofuran, adding 45g of epsilon-caprolactone monomer into the mixed solution, taking DY-12 as a catalyst, reacting for 3.5 hours at a constant speed under normal pressure at the temperature of 40 ℃, and performing rotary evaporation to obtain 86g of an intermediate product H-PF 2 PE 2 -H；
4. The total of 86g of intermediate H-PF 1 PE 2 dissolving-H and 90g of isocyanate methyl triethoxysilane in an excessive propanol solvent, stirring for 20 hours under normal pressure at 25 ℃ under the catalysis of DY-12, and finally drying the solvent to obtain 130g of a precursor.
Example 3
1. 332g of hexafluoropropylene oxide and 210g of potassium fluoride are weighed and sequentially dispersed in 4kg of diglyme, and stirred at the temperature of 20 ℃ for reaction for 4 hours;
2. fully mixing 200g of trifluoroethanol and 200g of ethanol to prepare a mixed solvent of the trifluoroethanol and the lower alcohol, further slowly pouring the product obtained in the step 1 into the mixed solvent of the trifluoroethanol and the lower alcohol, fully stirring at the temperature of 30 ℃ and normal pressure for reaction for 3 hours, stopping the reaction, volatilizing the solvent by using a rotary evaporator to obtain HOCH 2 -CF 2 -O-[CF 2 -CF 2 -O] 4 -CF 2 -CH 2 320g of OH powder;
3. 64.2g of the powder obtained in step 2 was weighed and dissolved in 500g of 1, 4-butanediol solution, and 228g of epsilon-caprolactone monomer was added to the mixed solution as Sn (Oct) 2 As a catalyst, stirring and reacting at constant speed for 5.5 hours at the temperature of 45 ℃ and normal pressure, and performing rotary evaporation to obtain 292.2g of intermediate product H-PF 4 PE 10 -H；
4. 292.2g of the intermediate product H-PF were added in total 1 PE 2 -H and 65 g of isocyanatomethyltriethoxysilane were dissolved together in an excess of propanol solvent, and the amino addition reaction was carried out by stirring with dibutyltin dilaurate at 25 ℃ under normal pressure for 15 hours, and finally the solvent was dried to obtain 336g of the precursor.
The precursors obtained in examples 1,2 and 3 were tested:
wherein, FIG. 1 is a Fourier infrared projection spectrum of the precursors obtained in examples 1,2 and 3, and it can be known from FIG. 1 that the products obtained in the three examples are all 1069cm -1 At position of 801cm -1 At a distance of 456cm -1 The distinctive peaks are respectively represented by the asymmetric stretching vibration, the bending vibration and the swinging vibration of Si-O-Si, which indicates that the triethoxy silane terminated polycaprolactone is formed, the two ends of the precursor have stable Si-O-Si main chain end groups, and the length is 1202cm -1 And at 1145cm -1 Typical peak positions of C-F functional groups appear as-CF 2 、-CF 3 The stretching vibration shows that the perfluoropolyether derivative stably exists in the prepared precursor, so that the precursor has a low-surface-energy fluoridation functional group structure.
FIGS. 2 and 3 are C1s fine spectra obtained by XPS spectrum scanning of the products obtained in examples 1 and 3, respectively, and the C1s characteristic peaks are divided into 5, C-Si at 283.5 eV-283.7 eV, C-C at 284.60eV, C-O/C = O at 287.1 eV-287.4 eV, and C-CF at 290.4 eV-290.6 eV 2 and-CF at 292.4eV to 292.7eV 3 The characteristic peaks prove that the synthesis and preparation of the precursor are successful and achieve the expected purpose.
The preparation of the super-amphiphobic coating comprises the following steps:
s1, fully drying the ionic liquid in a vacuum drying oven at 80 ℃ for 72 hours to remove the water in the air adsorbed by the ionic liquid, wherein the mass ratio of alcohol: ionic liquid = (1 to 2): (1-5) adding alcohol into the ionic liquid according to the proportion, and uniformly mixing to obtain a mixed solvent of the alcohol and the ionic liquid;
wherein the ionic liquid is 1-alkyl-3-methylimidazole tetrafluoroborate or 1-alkyl-3-methylimidazole hexafluorophosphate, and the number of alkyl groups of the ionic liquid is 2-7; the alcohol is methanol, ethanol, propanol or isopropanol;
s2, dispersing the precursor into a mixed solvent of alcohol and ionic liquid, adding organic weak acid such as dilute oxalic acid or citric acid as a catalyst, stirring and reacting for 30-120 min at normal temperature and normal pressure, and performing hydrolysis-polycondensation reaction; the mass ratio of the precursor, the organic weak acid and the mixed solvent is (1-3): (1-2): (100-200);
s3, after the hydrolysis-polycondensation reaction is finished, rapidly increasing the temperature to 60-100 ℃ at the temperature rise rate of 3-5 ℃/S under the condition that the vacuum degree is 10-8 mbar, keeping the temperature and the vacuum for 1-5 min, and rapidly reducing the surface tension of the mixed phase by utilizing the characteristics of ionic liquid to fix the polycaprolactone structure; slowly cooling to room temperature, introducing air, recovering internal and external pressure, and removing mixed liquid phase by using centrifugal equipment to obtain white powder, namely the silicon-oxygen-silicon network structure material (as shown in figure 4, a space structure schematic diagram of the silicon-oxygen-silicon network structure material);
s4, uniformly dispersing the silicon-oxygen-silicon network structure material in a mixed solvent of butyl acetate and low-carbon alcohol (the mass ratio of the butyl acetate to the low-carbon alcohol is 1 (1-10), the low-carbon alcohol is methanol, ethanol or propanol), adding a resin adhesive such as acrylic resin, and uniformly mixing to obtain the super-amphiphobic coating material; wherein the mass ratio of the silicon-oxygen-silicon network structure material to the mixed solvent of butyl acetate and low carbon alcohol is (1-5): (20-100), the mass of the resin binder does not exceed 20% of the total mass;
and S5, injecting the liquid of the super-amphiphobic coating material after uniformly mixing the silicon-oxygen-silicon network structure material, the mixed solvent of butyl acetate and low-carbon alcohol and the resin adhesive into a spray gun, spraying by using an oil-free air compressor, and naturally curing the liquid on the surface of the object to be sprayed for 1-2 hours to form a transparent coating, namely the super-amphiphobic coating.
Example 4
1. 300g of 1-alkyl-3-methylimidazolium tetrafluoroborate ([ C ]) were preliminarily prepared 2-7 mim]BF 4 ) Drying in 80 deg.C vacuum drying oven for 72 hr to completely remove adsorbed water in air, and injecting 200g ethanol into ionic liquid by peristaltic pump to form mixture of alcohol and ionic liquidSynthesizing a solvent;
2. taking 150g of mixed solvent of alcohol and ionic liquid, weighing 2g of the precursor obtained in the embodiment 1, putting the precursor and 2g of 0.001mol/L diluted oxalic acid prepared in advance into the mixed solvent of the alcohol and the ionic liquid, and stirring at high speed for 50min;
3. putting the mixed liquid into a vacuum high-temperature furnace with the vacuum degree of 8mbar, rapidly increasing the temperature to 100 ℃ at the heating rate of 5 ℃/s, and keeping the temperature and the vacuum for 2min;
4. slowly cooling to room temperature, gradually introducing air, recovering internal and external pressure, and removing mixed liquid phase by centrifugal equipment to obtain white powder 1.92g.
5. Completely putting 1.92g of powder into a mixed solvent of 25g of butyl acetate and 25g of ethanol, then adding 5g of acrylic resin with the brand number of BD-6010, and fully mixing to obtain a super-amphiphobic coating material liquid;
6. injecting the liquid of the super-amphiphobic coating material into a spray gun, spraying the stone by using an oil-free air compressor, and forming a micro-surface coating with a nano structure after the surface of the stone is completely dried, namely the super-amphiphobic coating.
Example 5
1. 500g of 1-alkyl-3-methylimidazolium hexafluorophosphate ([ C ] in advance 2-7 mim]PF 6 ) Placing in a vacuum drying oven at 80 deg.C, drying for 72 hr to completely remove adsorbed water in air, and injecting 100g propanol into ionic liquid with peristaltic pump to form mixed solvent of alcohol and ionic liquid;
2. taking 180g of mixed solvent of alcohol and ionic liquid, weighing 10g of the precursor obtained in the embodiment 2, putting the precursor and 15g of 0.001mol/L diluted oxalic acid prepared in advance into the mixed solvent of the alcohol and the ionic liquid, and stirring at high speed for 30min;
3. putting the mixed liquid into a vacuum high-temperature furnace with the vacuum degree of 10mbar, rapidly increasing the temperature to 80 ℃ at the heating rate of 3 ℃/s, and preserving the heat and the vacuum for 3min;
4. slowly cooling to room temperature, gradually introducing air, recovering internal and external pressure, and removing mixed liquid phase by centrifugal equipment to obtain white powder 9.8g.
5. Completely putting 9.8g of powder into a mixed solvent of 50g of butyl acetate and 350g of ethanol, then adding 55g of acrylic resin with the trademark of T802-50A, and fully mixing to obtain a super-amphiphobic coating material liquid;
6. injecting the liquid of the super-amphiphobic coating material into a spray gun, spraying the cement board by using an oil-free air compressor, and forming the micro-surface coating with the nano structure after the surface of the cement board is completely dried, namely the super-amphiphobic coating.
Example 6
1. 100g of 1-alkyl-3-methylimidazolium hexafluorophosphate ([ C ] was preliminarily prepared 2-7 mim]PF 6 ) Placing in a vacuum drying oven at 80 deg.C, drying for 72 hr to completely remove adsorbed water in air, and injecting 100g methanol into ionic liquid with peristaltic pump to form mixed solvent of alcohol and ionic liquid;
2. taking 200g of mixed solvent of alcohol and ionic liquid, weighing 30g of the precursor obtained in the embodiment 3, putting the precursor and 10g of pre-prepared 0.001mol/L citric acid into the mixed solvent of alcohol and ionic liquid, and stirring at high speed for 80min;
3. putting the mixed liquid into a vacuum high-temperature furnace with the vacuum degree of 9mbar, rapidly increasing the temperature to 60 ℃ at the heating rate of 4 ℃/s, and preserving the heat and vacuum for 1min;
4. slowly cooling to room temperature, gradually introducing air, recovering internal and external pressure, and removing mixed liquid phase by centrifugal equipment to obtain 29.9g of white powder;
5. putting 29.9g of powder into a mixed solvent of 200g of butyl acetate and 800g of methanol, then adding 100g of acrylic resin with the brand number of T802-50A, and fully mixing to obtain a super-amphiphobic coating material liquid;
6. injecting the super-amphiphobic coating material liquid into a spray gun, spraying the glass by using an oil-free air compressor, and forming a nano-structure micro-surface coating after the surface of the glass is completely dried, namely the super-amphiphobic coating.
Test of the Performance of the Superamphiphobic coating
The super-amphiphobic coating material liquid prepared in examples 4 to 6 was sprayed onto several different substrate surfaces to form super-amphiphobic coatings. FIG. 5 shows the static contact angles of the surfaces of several substrates after being spray-dried with the super-hydrophobic coating to water, which indicates that the static contact angles with water are all over 150 degrees, and the substrate belongs to the super-hydrophobic coating; FIG. 6 is a static contact angle diagram of n-hexadecane on the surfaces of several substrates after being sprayed and dried with the super-amphiphobic coating, and the static contact angles with n-hexadecane are all over 150 degrees, and the substrates belong to the super-oleophobic coating. The coating is super-hydrophobic and super-oleophobic and is a super-amphiphobic coating.
Comparative experiment 1
Comparative example 1 adopts ethyl orthosilicate as a precursor, a Si-O-Si chain structure is obtained by hydrolytic polycondensation, as shown in fig. 7, a transmission electron microscope image of the precursor is made of ethyl orthosilicate, fig. 8 is a transmission electron microscope image of the Si-O-Si chain structure is made of ethyl orthosilicate by hydrolytic polycondensation, under a transmission electron microscope with 30 ten thousand times magnification, a common silicon source precursor represented by ethyl orthosilicate is formed, only a chain and net structure is formed by simple hydrolytic polycondensation as a super-hydrophobic main chain, and the introduction of a low surface energy functional group can be realized by performing secondary modification on the main chain, so that the introduction of the low surface energy functional group can be easily caused by loss of mechanical friction through a conventional synthetic method, that is, the low surface energy functional group introduced by grafting the main chain is easily lost by replacing the reaction, and the super-hydrophobic performance is finally lost without the low surface functional group on the main chain.
FIG. 9 is a transmission electron microscope image of a precursor with a low surface energy functional group structure prepared by the precursor preparation method of the present invention, FIG. 10 is a transmission electron microscope image of a Si-O-Si silicon-oxygen network structure with a low surface energy structure formed by hydrolytic polycondensation of the precursor of the present invention, and the precursor of the present invention is a low surface energy functional group-CF with fluoropolyether 2 -O-(CF 2 -CF 2 -O) x -CF 2 A precursor with a structure of Si-O-Si silicon-oxygen network structure, which is terminated by triethoxysilane and can be formed by hydrolytic polycondensation, a super-hydrophobic main chain formed by normal hydrolytic polycondensation is provided with a low-surface-energy substance (a light ring-shaped structure under an electron microscope), so that the super-amphiphobic can be realized without carrying out secondary modification on the main chain, and simultaneously, the self structure of the main chain cannot be subjected to macroscopic mechanical friction to leadResulting in loss of the super-amphiphobic properties.
Comparative experiment 2
Control 1 is a commercially available super-amphiphobic coating of a certain brand, control 2 is a super-amphiphobic coating prepared by hydrolytic condensation of ethyl orthosilicate and modification with hexamethyldisilazane, and the coatings prepared in examples 4 to 6 were subjected to scrub resistance tests in sequence, referring to the test method for characterizing the mechanical rubbing resistance of the coating in the current "scrub resistance test of architectural coatings" GB/T9266, and the results are given in table 1 below, for example:
TABLE 1 comparison of the mechanical friction resistance of the super-amphiphobic coating
Group number Washing 1000 times Washing 2000 times Wash 5000 times Brushing 10000 times
Control group 1 Super-amphiphobic Super-amphiphobic Loss of /
Control group 2 Super-amphiphobic Loss of / /
Example 4 Super-amphiphobic Super-amphiphobic Super-amphiphobic Super-amphiphobic
Example 5 Super-amphiphobic Super-amphiphobic Super-amphiphobic Super-amphiphobic
Example 6 Super-amphiphobic Super-amphiphobic Super-amphiphobic Super-amphiphobic
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, so that any modifications, equivalents, improvements and the like, which are within the spirit and principle of the present invention, should be included in the scope of the present invention.

Claims (14)

1. A precursor, characterized by: the precursor is a polycaprolactone precursor terminated by fluoropolyether triethoxysilane, and the chemical molecular formula of the precursor is as follows:
Figure FDA0003808492800000011
wherein PFxXeN is
Figure FDA0003808492800000012
In the PFxPEN, x is more than 0 and less than or equal to 5; n is more than 0 and less than or equal to 10.
2. A precursor according to claim 1, wherein: in the PFxPEN, x is 1,2, n is 2, 5 and 10.
3. A method for preparing the precursor according to claim 1, wherein: the preparation method of the precursor comprises the following steps:
s1, dispersing hexafluoropropylene oxide in an aprotic solvent, adding an alkali metal fluoride inorganic salt serving as a catalyst, and carrying out anionic polymerization until the hexafluoropropylene oxide is subjected to ring opening;
s2, injecting the solution obtained in the step S1 into a prepared mixed solvent of trifluoroethanol and low-carbon alcohol for reaction, and drying a product after the reaction to obtain a derivative of perfluoropolyether;
s3, dissolving a derivative of perfluoropolyether in a sufficient tetrahydrofuran or polyalcohol solvent system, adding epsilon-caprolactone and a catalyst for reaction, and performing rotary evaporation or drying on a product after the reaction to obtain an intermediate product with a certain polymerization degree;
s4, dissolving the intermediate product and isocyanate methyl triethoxysilane in a low carbon alcohol, low carbon ketone or straight chain low carbon ether solvent, adding a catalyst, carrying out an amino addition reaction, and after the reaction is finished, drying to obtain solid powder, namely the target product of the polycaprolactone precursor terminated by the fluoropolyether triethoxysilane.
4. A method for producing a precursor according to claim 3, characterized in that:
in the S1, the aprotic solvent is diethylene glycol dimethyl ether, acetonitrile or dimethylformamide, and the alkali metal fluoride inorganic salt is lithium fluoride, sodium fluoride or potassium fluoride; in the S2, the lower alcohol is methanol, ethanol or propanol; in the S3, the polyalcohol is ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, neopentyl glycol, glycerol or hexanediol, and the catalyst is stannous isooctanoate or dibutyltin dilaurate; in the S4, the low-carbon pure material is methanol, ethanol or propanol, the low-carbon ketone is acetone or butanone, the straight-chain low-carbon ether is ethyl ether, and the catalyst is stannous isooctanoate or dibutyltin dilaurate.
5. A method for producing a precursor according to claim 3, characterized in that: in the S1, the mol ratio of the hexafluoropropylene oxide, the aprotic solvent and the alkali metal fluoride inorganic salt is (1-5): (5-30): (1-5); in the S2, in the mixed solvent of the trifluoroethanol and the lower alcohol, the molar ratio of the trifluoroethanol to the lower alcohol is 1; in the S3, the molar ratio of the derivative of the perfluoropolyether to the tetrahydrofuran or the polyol solvent is (1-5): (10-100), the mole ratio of epsilon-caprolactone to the derivative of perfluoropolyether is (1-20): (1-5); in S4, the molar ratio of the intermediate product to the isocyanate methyl triethoxysilane is 1: (2-10).
6. The method for producing a precursor according to claim 3, characterized in that: the molar ratio of intermediate to isocyanate methyltriethoxysilane was 1.
7. A method for producing a precursor according to claim 3, characterized in that:
the reaction conditions in the S1 are that the reaction is carried out for 2 to 5 hours under normal pressure at the temperature of between 20 and 30 ℃;
the reaction condition in the S2 is that the reaction is carried out for 1 to 3 hours under normal pressure at the temperature of between 20 and 30 ℃;
the reaction condition in the S3 is that the reaction is carried out for 2 to 6 hours under the condition of stirring at the normal pressure at the temperature of between 30 and 50 ℃;
the reaction condition in S4 is that the reaction is carried out for 10 to 24 hours under the condition of normal pressure stirring at the temperature of 25 ℃.
8. Use of a precursor according to claim 1 or 2, characterized in that: the application of the fluorine-containing polyether triethoxysilane-terminated polycaprolactone precursor in preparing a super-amphiphobic coating.
9. A super-amphiphobic coating material is characterized in that: comprises a silicon-oxygen-silicon network structure material prepared by hydrolysis-polycondensation reaction of the precursor of claim 1 or 2, a mixed solvent of butyl acetate and lower alcohol, and a resin adhesive; the mass ratio of the silicon-oxygen-silicon network structure material to the mixed solvent of butyl acetate and low carbon alcohol is (1-5): (20-100), the mass of the resin binder is not more than 20% of the total mass.
10. A method for preparing the super-amphiphobic coating material according to claim 9, characterized in that: the method comprises the following steps:
s1, drying the ionic liquid in vacuum, removing water in air adsorbed by the ionic liquid, and preparing an alcoholic solution according to the mass ratio: ionic liquid = (1 to 2): (1-5) adding an alcohol solution into the ionic liquid, and uniformly stirring to obtain a mixed solvent;
s2, dispersing the precursor of claim 1 or 2 in the mixed solvent, and adding an organic weak acid serving as a catalyst to perform hydrolysis-polycondensation reaction;
s3, after the hydrolysis-polycondensation reaction is finished, rapidly heating to 60-100 ℃ under a vacuum condition, slowly cooling to room temperature after heat preservation and vacuum preservation for a certain time, introducing air, recovering internal and external pressure, and removing a mixed liquid phase to obtain white powder, namely the silicon-oxygen-silicon reticular structure material;
and S4, uniformly dispersing the silicon-oxygen-silicon network structure material in a mixed solvent of butyl acetate and low-carbon alcohol, adding a resin adhesive, and uniformly mixing to obtain the super-amphiphobic coating material.
11. The method for preparing the super-amphiphobic coating material according to claim 10, characterized in that:
in the S1, the ionic liquid is 1-alkyl-3-methylimidazole tetrafluoroborate or 1-alkyl-3-methylimidazole hexafluorophosphate, and the alcoholic solution is methanol, ethanol, propanol or isopropanol; in the S2, the organic weak acid is dilute oxalic acid or citric acid; in S4, the lower alcohol is methanol, ethanol or propanol.
12. The method for preparing the super-amphiphobic coating material according to claim 10, characterized in that: in S2, the mass ratio of the precursor, the weak organic acid and the mixed solvent is (1-3): (1-2): (100-200); in the S4, the mass ratio of butyl acetate to low-carbon alcohol is 1: (1-10).
13. The preparation method of the super-amphiphobic coating material according to claim 10, characterized by comprising the following steps: the reaction condition in the S2 is that the mixture is stirred and reacts for 30-120 min at normal temperature and normal pressure; in the step S3, the rapid temperature rise under the vacuum condition is specifically that under the condition that the vacuum degree is 10 mbar-8 mbar, the temperature rise rate is 3 ℃/S-5 ℃/S to 60 ℃ -100 ℃, and the temperature is kept and the vacuum is maintained for 1 min-5 min.
14. A super-amphiphobic coating is characterized in that: the super-amphiphobic coating material is formed by coating the super-amphiphobic coating material of claim 9 on the surface of a substrate and then curing.
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