Perfluoropolyether aminosilane compound, composition, preparation method and application thereof

Abstract

The present invention discloses a perfluoropolyether aminosilane compound, a composition, a preparation method and an application thereof, wherein the chemical structural formula is as follows: #imgabs0# wherein Rf is a perfluoropolyether group; X1 and X2 are independently divalent organic groups; R 1 and R 3 are independently hydrogen, phenyl or C1-20 alkyl, and R 1 and R 3 are not hydrogen, phenyl or C1-20 alkyl at the same time; R 2 and R 4 Separately, Y-SiT 1 j T 2 3‑j ; Wherein Y is a divalent organic group; T 1 is an alkoxy group, a hydroxy group or a group that can be hydrolyzed to a hydroxy group; T 2 The surface coating formed by the perfluoropolyether aminosilane compound of the present invention has high surface sliding property (dynamic friction coefficient is less than 0.04), high friction durability (especially rubber friction resistance), and excellent alkali resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of surface treatment, and in particular relates to a perfluoropolyether aminosilane compound, a composition, a preparation method and an application thereof. Background Art

[0002] In the prior art, when a perfluoropolyether-modified silane compound is used for the surface treatment of a substrate, it can provide excellent water repellency, oil repellency, antifouling properties, etc. The surface treatment layer obtained by the surface treatment agent containing the perfluoropolyether-modified silane compound is applied to a variety of substrates such as glass, plastic, fiber, and building materials as a so-called functional film. The hydrolyzable group connected by the Si at the end of the perfluoropolyether reacts with the surface active group of the substrate to form a Si-O-Si bond. At the same time, the perfluoropolyether chain is arranged in a directional manner on the surface of the substrate, thereby forming a firm surface film layer, giving the substrate excellent smoothness, wear resistance, weather resistance, and anti-fingerprint properties. As a surface treatment agent, the scope of use of perfluoropolyether-modified silane compounds is no longer limited to the field of electronic products such as touch screens, and has gradually been promoted and applied to home furnishing fields such as bathrooms and kitchenware, and at the same time, the wear resistance of the products is also increasingly required.

[0003] Existing surface treatment agents and products currently used in the market generally have good wear resistance to steel wool, generally able to withstand more than 5,000 or even tens of thousands of wears, but the wear resistance to rubber is not sufficient, which is manifested in the thinning of the surface film of the substrate after friction, or even partial shedding. At the same time, the products used in the market generally have poor alkali resistance, especially in a strong alkaline environment, the surface film is easily corroded and shed, mainly due to the reaction of Si-O-Si bonds with strong alkalis such as sodium hydroxide. Summary of the invention

[0004] The technical problem to be solved by the present invention is to overcome the shortcomings and defects mentioned in the above background technology, and to provide a perfluoropolyether aminosilane compound, a composition and a preparation method and application thereof to improve wear resistance, especially eraser wear resistance, and improve alkali resistance simultaneously.

[0005] In order to solve the above technical problems, the technical solution proposed by the present invention is:

[0006] A perfluoropolyether aminosilane compound, the chemical structure of which is as follows:

[0007]

[0008] Wherein Rf is a perfluoropolyether group;

[0009] X1 and X2 are independently divalent organic groups;

[0010] R 1 and R 3are independently hydrogen, phenyl or C1-20 alkyl, and R 1 and R 3 are not hydrogen, phenyl or C1-20 alkyl at the same time;

[0011] R 2 and R 4 Separately -Y-SiT 1 j T 2 3-j ;

[0012] Wherein Y is a divalent organic group;

[0013] T 1 is an alkoxy group, a hydroxy group, or a group that can be hydrolyzed to a hydroxy group;

[0014] T 2 is hydrogen, phenyl or C1-20 alkyl;

[0015] j in R 2 and R 4 are independent of each other and are integers between 0 and 3; R 2 The sum of j and R 4 The sum of j in is not less than 1;

[0016] a and b are independently 0 or 1.

[0017] Preferably, wherein Rf is F(CF2) m -(OC4F8) r -(OC3F6) s -(OC2F4) p -(OCF2) q -OC(Z)F-(CF2) t -, wherein r, s, p and q are independently and are integers between 0 and 100, the sum of r, s, p and q is not less than 1, each repeating unit with r, s, p and q and enclosed in brackets is straight chain or branched, and the order and quantity of each repeating unit in the formula are arbitrary, m and t are integers between 0 and 30, and Z is F or CF3.

[0018] Preferably, Rf is the following formula: CF3-(OC2F2) p -(OCF2) q -OCF2-, wherein the sum of p and q is an integer between 10 and 200; or, Rf is the following formula: F(CF2) m -(OC4F8) r -(OC3F6) s -(OC2F4) p -(OCF2) q-OC(Z)F-(CF2) t - , wherein m is an integer between 1 and 16, t is an integer between 0 and 2, p and q are each independently an integer between 1 and 200, and the sum of r, s, p and q is an integer between 10 and 200.

[0019] Preferably, X1 and X2 do not have any groups; or, X1 and X2 are independently -(R 5 ) e -X3-(R 6 ) g -, where R 5 and R 6 are independently C1-6 alkylene or substituted alkylene, e and g are independently 0 or 1, X3 is -O-, S-, -(CH2) k -、-CH=CH-、-O(CH2) k O-, -O(CH2O) k 、-(CF2) k -, -Het-, -Ar- or substituted -Ar-, k is independently an integer between 2 and 100 each time it appears, -Het- is an organic compound containing a heteroatom ring, and -Ar- is an organic compound having aromatic properties.

[0020] Preferably, Y is a C1-6 alkyl group; and / or,

[0021] T 1 Alkoxy OT 3 , where T 3 is a substituted or unsubstituted C1-3 alkyl group.

[0022] Preferably, the perfluoropolyether aminosilane compound is selected from the following structural formula:

[0023]

[0024] .

[0025] Preferably, the perfluoropolyether aminosilane compound is selected from the following structural formula:

[0026]

[0027] .

[0028] The present invention also provides a method for preparing the perfluoropolyether aminosilane compound, comprising the following steps:

[0029] Step 1, reacting a perfluoropolyether alcohol with an organic sulfonic acid compound in the presence of a solvent and a base to obtain a perfluoropolyether sulfonate; the perfluoropolyether alcohol has a structural formula of Rf-CH2OH;

[0030] Step 2, reacting a perfluoropolyether sulfonate with an iminodicarboxylate compound in the presence of a solvent and a base to obtain a perfluoropolyether aminodicarboxylate; the iminodicarboxylate compound has the structural formula:

[0031]

[0032] Where R 7 and R 8 Each is independently a C1-6 alkyl or a phenyl;

[0033] Step 3, heating and hydrolyzing the perfluoropolyether aminodicarboxylate under strong alkaline conditions and then acidifying to obtain perfluoropolyether aminodicarboxylic acid;

[0034] Step 4: reacting the perfluoropolyether amino dicarboxylic acid with an acyl halide reagent to generate a perfluoropolyether amino diacyl halide, and then reacting the perfluoropolyether amino dicarboxylic acid with an aminosilane coupling agent to obtain the perfluoropolyether aminosilane compound.

[0035] The present invention also provides a surface treatment composition, comprising a mixture of one or more of the perfluoropolyether aminosilane compounds and an organic solvent.

[0036] The present invention also provides an application of the surface treatment composition, which is used to form a coating on the surface of a substrate by coating, spraying or vapor deposition.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] The surface coating formed by the perfluoropolyether aminosilane compound and the substrate not only has good hydrophobicity, oleophobicity and smoothness, but also has enhanced adhesion to the substrate after hydrolysis due to the number of hydrolyzable siloxane groups at the molecular ends being greater than two, and the degree of self-crosslinking between molecules being increased, thus having good steel wool abrasion resistance, especially eraser abrasion resistance.

[0039] The perfluoropolyether aminosilane compound of the present invention has an increased degree of crosslinking between molecules (because the number of hydrolyzable siloxane groups at the molecular end is greater than two), resulting in a denser -Si-O-Si- network at the bottom of the treatment layer, which can delay the corrosion of the -Si-O-Si- network by human sweat and alkaline solution. On the other hand, the connecting group between the terminal siloxane and the perfluoropolyether chain contains a basic tertiary amine ( ) structure, which can not only effectively catalyze the hydrolysis condensation reaction of the siloxane at the end of the perfluoropolyether chain and the surface of the substrate, improve the degree of cross-linking, and increase the adhesion between the perfluoropolyether silane molecules and the substrate, thereby improving the wear resistance, but also can prevent the destruction of the -Si-O-Si- bonds in the coating by human sweat and alkali solution to a certain extent. The surface treatment layer formed thereby has good alkali resistance.

[0040] Therefore, the surface coating formed by the perfluoropolyether aminosilane compound of the present invention has high surface sliding property (dynamic friction coefficient is less than 0.04), high friction durability (especially rubber friction resistance), and excellent alkali resistance.

[0041] The perfluoropolyether aminosiloxane surface treatment agent of the present invention can be applied to the antifouling treatment of the surfaces of glass, resin, metal, ceramic, wood, ceramic, stone, leather, etc., and can be used as the antifouling coating of optical articles such as car navigation systems, mobile phones, computers, digital cameras, glasses lenses, camera lenses, filter sunglasses, liquid crystal displays, plasma displays, touch panel displays, etc. It can also be used as the antifouling coating of sanitary products such as bathtubs and washstands; the antifouling coating of window glass or tempered glass, headlight covers, etc. of cars, trams, airplanes, etc., and the anti-oil coating of kitchen building materials. It is particularly suitable for anti-fingerprint materials for display screens of smart phones, tablets or computers, and car central control screens. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0043] Figure 1 is the hydrogen nuclear magnetic resonance spectrum of the perfluoropolyether aminodicarboxylic acid compound (Q3) in Synthesis Example 1;

[0044] Figure 2 is the hydrogen nuclear magnetic resonance spectrum of the perfluoropolyether aminosilane compound (A1) in Synthesis Example 1;

[0045] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of the perfluoropolyether silane compound (A2) in Synthesis Example 2. DETAILED DESCRIPTION

[0046] In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively and meticulously below in conjunction with the accompanying drawings and preferred embodiments of the present invention, but the protection scope of the present invention is not limited to the following specific embodiments.

[0047] Unless otherwise defined, all professional terms used below have the same meanings as those generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0048] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0049] The perfluoropolyether aminosilane compound of some specific embodiments of the present invention has the following chemical structural formula (1):

[0050] (1)

[0051] In formula (1), Rf is F(CF2) m -(OC4F8) r -(OC3F6) s -(OC2F4) p -(OCF2) q -OC(Z)F-(CF2) t -, wherein r, s, p and q are independently and are integers between 0 and 100, the sum of r, s, p and q is not less than 1, each repeating unit with r, s, p and q and enclosed in brackets can be linear or branched, and the order and quantity of each repeating unit in the formula are arbitrary, m and t are integers between 0 and 30, and Z is F or CF3.

[0052] X1 and X2 are independently divalent organic groups;

[0053] R 1 and R 3 are independently hydrogen, phenyl or C1-20 alkyl, and R 1 and R 3 are not hydrogen, phenyl or C1-20 alkyl at the same time;

[0054] R 2 and R 4 Separately -Y-SiT 1 j T 2 3-j ;

[0055] Wherein Y is a divalent organic group, preferably a C1-6 alkyl group;

[0056] T 1 is an alkoxy group, a hydroxy group or a group that can be hydrolyzed to a hydroxy group, T 1 Preferably, alkoxy OT 3 , where T 3is a substituted or unsubstituted C1-3 alkyl group, preferably T 3 It is methyl, ethyl, propyl and isopropyl.

[0057] T 2 is hydrogen, phenyl or C1-20 alkyl;

[0058] j in R 2 and R 4 are independent of each other and are integers between 0 and 3, R 2 The sum of j and R 4 The sum of j in is not less than 1;

[0059] a and b are independent and can be 0 or 1.

[0060] In some specific embodiments, the above Rf can also be the following formula (2):

[0061] CF3-(OC2F2) p -(OCF2) q -OCF2-(2)

[0062] Wherein the sum of p and q is an integer between 10 and 200;

[0063] Alternatively, the above Rf is the following formula (3):

[0064] F(CF2) m -(OC4F8) r -(OC3F6) s -(OC2F4) p -(OCF2) q -OC(Z)F-(CF2) t -(3)

[0065] Wherein m is an integer between 1 and 16, t is an integer between 0 and 2, p and q are independently integers between 1 and 200, and the sum of r, s, p and q is an integer between 10 and 200. The order and number of the repeating units with r, s, p and q enclosed in parentheses are arbitrary in the formula.

[0066] In some specific embodiments, in the above formula, X1 and X2 may not have any groups, or may be independently -(R 5 ) e -X3-(R 6 ) g -, where R 5 and R 6 are independently C1-6 alkylene or substituted alkylene, e and g are independently 0 or 1, X3 is -O-, S-, -(CH2) k-、-CH=CH-、-O(CH2) k O-, -O(CH2O) k 、-(CF2) k -, -Het-, -Ar- or substituted -Ar-, k is independently an integer between 2 and 100 each time it appears, -Het- is an organic compound containing a heteroatom ring, and -Ar- is an organic compound having aromatic properties.

[0067] In the structure of the perfluoropolyether aminosilane compound (AF molecule) of some embodiments of the present invention, the tertiary amine ( ) structure plays a pivotal role between the fluorine chain (Rf) and the amide silane. On the one hand, it increases the spatial span of the terminal siloxane end group, which increases the probability of combining with Si-OH on the glass surface and cross-linking between AF molecules, increasing the degree of entanglement. Secondly, it increases the intra-chain strength at the end of the AF molecule, which is beneficial to the stability of the molecular chemical structure. On the other hand, the number of terminal branches itself is greater than 2, which makes it easier to form a dense Si-O-Si cross-linked network, thereby improving the rubber friction performance and alkali resistance.

[0068] The tertiary amines of some embodiments of the present invention ( ) structures are all connected to alkyl groups and have strong alkalinity. If N is connected to a carbonyl group to form an amide structure, the inductive effect of the carbonyl group will reduce the electron cloud density on N, making the alkalinity not as good as that of a tertiary amine connected to an alkyl group, which will affect its catalytic hydrolysis and condensation of the terminal siloxane.

[0069] The AF molecules of some embodiments of the present invention have an amide bond (-CON-) after the tertiary amine, which can make the AF molecules easier to orient, the fluorine chain is easier to stretch during curing, and the initial contact angle is high. While the two amide bonds have an orientation effect, the two amide bonds are two independent side chains, which makes the molecule as a whole more stable and less likely to expose the bottom film layer (between the silane network and the amide bond), which is beneficial to wear resistance. At the same time, the position of the amide bond is also very important. If the amide bond is between the fluorine chain and the tertiary amine, the mobility of the connecting group between the amide bond and the tertiary amine will be enhanced, the molecule as a whole will be easy to swing after curing, and the bottom film layer (between the silane network and the amide bond) will be more easily exposed, affecting the wear resistance, especially the abrasion resistance of the eraser.

[0070] In addition, tertiary amines ( ) structure before the amide bond, the tertiary amine in the bottom film after film formation ( ) structure tends to the outside of the film layer, and it has a certain alkalinity, which can prevent the amide bond from being hydrolyzed by the alkali solution when rubbed with alkali solution, and prevent the Si-O-Si network from being destroyed by the alkali solution. If the amide bond is directly exposed on the outside of the film layer, it will be detrimental to the alkali resistance.

[0071] In summary, the number of hydrolyzable siloxane groups at the end of the compound of the present invention is greater than two, which can improve the rubber friction performance and alkali resistance; the tertiary amine structure and the two independent amides' double branches not only ensure the orientation effect of the amide bond, but also increase the stability within the molecule and improve the degree of entanglement between molecules, so that the bottom film layer is not easily exposed and the wear resistance is improved; the tertiary amine bond is located between the two amide bonds and the fluorine chain, which can prevent the amide bond and the Si-O-Si network from being alkaline hydrolyzed after film formation, thereby improving the alkali resistance.

[0072] In some specific embodiments of the present invention, the preparation method of the perfluoropolyether silane compound comprises the following steps:

[0073] Step 1: reacting perfluoropolyether alcohol with an organic sulfonic acid compound in the presence of a solvent and a base, and obtaining perfluoropolyether sulfonate through post-treatment and purification.

[0074] The structural formula of the perfluoropolyether alcohol is Rf-CH2OH.

[0075] In some specific embodiments, the organic sulfonic acid compound can be one or a mixture of p-toluenesulfonic acid, p-toluenesulfonic anhydride, p-toluenesulfonyl chloride, methanesulfonic acid, methanesulfonyl chloride, methanesulfonic anhydride, trifluoromethanesulfonic acid, trifluoromethanesulfonyl chloride, and trifluoromethanesulfonic anhydride.

[0076] In some specific embodiments, the base is at least one of sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, triethylamine, diisopropylethylamine, and pyridine.

[0077] Step 2: reacting a perfluoropolyether sulfonate with an iminodicarboxylate compound in the presence of a solvent and a base, and purifying the resultant product by post-treatment to obtain a perfluoropolyether aminodicarboxylate of structural formula (4).

[0078] (4)

[0079] Where Rf is F(CF2) m -(OC4F8) r -(OC3F6) s -(OC2F4) p -(OCF2) q -OC(Z)F-(CF2) t -, m, r, s, p, q and t are the same as defined above. 7 and R 8 Each of the above is independently a C1-6 alkyl group or a phenyl group. X1 and X2 are as defined above.

[0080] The structural formula of the iminodicarboxylate compound is as follows (5):

[0081] (5)

[0082] Where R 7 and R 8 , the definitions of X1 and X2 are the same as above.

[0083] In some specific embodiments, the iminodicarboxylate compound can be specifically exemplified by diethyl iminodiacetate, di-tert-butyl iminodiacetate, diethyl 3,3'-iminodipropionate, iminodicarboxylic acid (tert-butyl methyl) ester, or includes but is not limited to the following structural formula:

[0084] , , .

[0085] In some specific embodiments, the base is at least one of sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, triethylamine, diisopropylethylamine, and pyridine.

[0086] Step 3: The perfluoropolyether amino dicarboxylate is heated and hydrolyzed under strong alkaline conditions and then acidified to obtain perfluoropolyether amino dicarboxylic acid, the structural formula of which is shown in (6).

[0087] (6)

[0088] In some specific embodiments, the strong base is an inorganic base, including at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide.

[0089] In some specific embodiments, the acid is an inorganic acid, including at least one of hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid.

[0090] Step 4: react the above perfluoropolyether amino dicarboxylic acid with an acyl halide reagent to generate a corresponding perfluoropolyether amino diacyl halide, and then react with an aminosilane coupling agent, and obtain a perfluoropolyether amino silane compound through post-treatment.

[0091] In some specific embodiments, the acyl chloride reagent is (COC1)2, SOC12, POC13, PC15 or SOBr2, preferably (COCl)2, SOCl2.

[0092] In some specific embodiments, the aminosilane coupling agent includes but is not limited to: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(phenylamino)propyltrimethoxysilane, di(3-trimethoxysilylpropyl)amine, one or a mixture of more than one.

[0093] The solvent described in the above steps is a fluorinated organic solvent capable of dissolving perfluoropolyether, including but not limited to: perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, bis(trifluoromethyl)benzene), C6F 13 CH2CH3 (ASAHIKLIN (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd., 3,3-pentafluorobutane (HFC-365mfc), HCFC-225 (ASAHIKLIN (registered trademark) AK225 manufactured by Asahi Glass Co., Ltd.)), perfluoropropyl methyl ether (3M Company's Novel (trade name) 7000), perfluorobutyl methyl ether (3M Company's Novel (trade name) 7100), perfluorobutyl ethyl ether (3M Company's Novel (trade name) 7200), perfluorohexyl methyl ether (3M Novel (trade name) 7300), or CF3CH2OCF2CHF2 (ASAHIKLIN (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.), etc. These solvents can be used alone or in combination of two or more as a mixture.

[0094] In some specific embodiments, the perfluoropolyether aminosilane compound described in step 4 may have a structural formula as shown in (7)-(8):

[0095] (7)

[0096] (8)

[0097] Wherein, Rf, X1 and X2 are defined the same as above.

[0098] Since perfluoropolyether alcohol is expensive, the molecular weight of the perfluoropolyether aminosilane compound of the present invention is greatly increased based on the raw material perfluoropolyether alcohol, so the yield of the obtained perfluoropolyether silane product is high, which can effectively increase the output.

[0099] The perfluoropolyether aminosiloxane compound obtained by the present invention is suitable for use in a surface treatment agent. The surface treatment agent may comprise a mixture of one or more of the above-mentioned perfluoropolyether-based silane compounds of the present invention and an organic solvent capable of dissolving the compound. In some specific embodiments, examples of the organic solvent include fluorine-containing solvents, such as fluorine-containing alkanes, fluorine-containing haloalkanes, fluorine-containing aromatic hydrocarbons and, for example, hydrofluoroethers, etc., and may also be a combination of different solvents.

[0100] In some specific embodiments, the above-mentioned perfluoropolyether aminosilane surface treatment agent can be a single component of compound (7)-(8), or a combination of compounds (7)-(8).

[0101] When the composition composed of the above compounds (7)-(8) is used as a surface treatment agent, the mass fraction of compound (7) is 0%-100%, preferably 20%-60%; the mass fraction of compound (8) is 0%-100%, preferably 30%-50%.

[0102] The composition composed of the perfluoropolyether aminosilane compound of the present invention can adjust the steel wool resistance and rubber friction resistance of the surface treatment agent by adjusting the ratio of each structure of the perfluoropolyether aminosilane compound. For example, in the following Example 7, compound A1: compound B2: compound C1 = 3:4:3, the dynamic friction coefficient is the lowest, and the steel wool resistance and rubber friction resistance are the best.

[0103] The perfluoropolyether aminosilane compound of the present invention can be selected in different concentrations according to the different coating methods adopted. During wet coating, the surface treatment agent is diluted to a concentration dilution with a solid content of 0.04wt%-0.5wt%. Then, it is coated or sprayed on a plasma-treated substrate for baking, and the film is obtained after cooling, wherein the baking temperature is 80-150°C, the baking time is 10-60min, and the final cooling temperature is room temperature. When the vapor deposition method is adopted, the perfluoropolyether aminosiloxane compound is first diluted with the above-mentioned fluorine-containing solvent to a liquid with a solid content of about 20%, and then the liquid is prepared into pills, which are loaded on the substrate deposited with SiO2 through a vapor deposition machine to form a uniform surface coating.

[0104] Synthesis example 1

[0105] The perfluoropolyether silane compound A1 was synthesized according to the following steps:

[0106] Step 1:

[0107] In a 250 mL single-mouth round-bottom flask equipped with a magnetic stirrer, add 50 g of CF3 (OCF2CF2) with an average composition of p (OCF2) q Perfluoropolyether alcohol (the sum of p and q is 38, the number average molecular weight is 3500, purchased from SOLVAY), 50 mL of 1,3-di(trifluoromethyl)benzene, 4.4 g of triethylamine, 8 g of trifluoromethanesulfonic anhydride were added dropwise under ice bath, and stirred at room temperature for 3 h after addition. After extraction with water and methanol, 51.3 g of light yellow transparent product was obtained by vacuum distillation, which is perfluoropolyether trifluoromethanesulfonate compound (Q1): CF3(OCF2CF2) p (OCF2) q OCF2CH2OSO2CF3.

[0108] Step 2:

[0109] In a 250 mL single-mouth round-bottom flask equipped with a magnetic stirrer, 51 g of the perfluoropolyether trifluoromethanesulfonate compound obtained in step 1, 50 mL of Novel 7200, 5.5 g of diisopropylethylamine and 5.4 g of diethyl iminodiacetate were added. After the addition, the temperature was raised to 60 ° C and refluxed for 6 h. After extraction with methanol, 50.2 g of a light yellow transparent product was obtained by vacuum distillation, which is the perfluoropolyether aminodicarboxylate compound (Q2): CF3 (OCF2CF2) p (OCF2) q OCF2CH2N(CH2COOCH2CH3)2.

[0110] The characteristic H chemical shift of the newly added structure was identified by NMR spectrometer as follows

[0111]

[0112] Step 3:

[0113] In a 500mL single-mouth round-bottom flask equipped with a magnetic stirrer, 50g of the perfluoropolyether aminodicarboxylate compound obtained in step 2 and 50mL of a 20wt% potassium hydroxide aqueous solution were added, the temperature was raised to 100°C and refluxed for reaction for 5h, the temperature was lowered to room temperature, 50mL of Novel 7200 and 10mL of tetrahydrofuran were added, and the mixture was acidified with 10wt% hydrochloric acid. The lower fluorine phase was removed and extracted three times with 0.1M dilute hydrochloric acid, and the product was distilled under reduced pressure to obtain 48.5g of a colorless and transparent product, which was a perfluoropolyether aminodicarboxylic acid compound (Q3): CF3(OCF2CF2) p (OCF2) q OCF2CH2N(CH2COOH)2.

[0114] The H NMR spectrum of the perfluoropolyether aminodicarboxylic acid compound (Q3) is as follows: Figure 1 shown.

[0115] The characteristic H chemical shift of the newly added structure was identified by NMR spectrometer as follows

[0116]

[0117] Step 4:

[0118] In a 100 mL single-mouth round-bottom flask equipped with a magnetic stirrer, 9.5 g of the perfluoropolyether aminodicarboxylic acid compound (Q3) obtained in step 3, 15 mL of 1,3-di(trifluoromethyl)benzene, 0.5 g of oxalyl chloride and 0.1 mL of N,N-dimethylformamide were added, and the temperature was raised to 45°C for reaction for 5 h. After cooling to room temperature, the mixture was slowly added dropwise to a 250 mL single-mouth round-bottom flask containing 5 mL of 1,3-di(trifluoromethyl)benzene, 2.4 g of diisopropylethylamine and 2.7 g of di(3-trimethoxysilylpropyl)amine. The mixture was stirred at room temperature for reaction for 3 hours, 30 mL of perfluorohexane was added, and the mixture was extracted three times with 20 mL of methanol. The product was distilled under reduced pressure to obtain 11.0 g of a colorless to light yellow transparent product, which was a perfluoropolyether aminosilane compound (A1), and its structural formula is shown below.

[0119] (A1)

[0120] Where Rf is CF3(OCF2CF2) p (OCF2) q OCF2-, the sum of p and q is 38.

[0121] The nuclear magnetic resonance hydrogen spectrum of the perfluoropolyether silane compound (A1) is as follows Figure 2 shown.

[0122] The characteristic H chemical shift of the newly added structure was identified by NMR spectrometer as follows

[0123]

[0124] Synthesis example 2

[0125] The perfluoropolyether silane compound A2 was synthesized according to the following method:

[0126] In a 100 mL single-mouth round-bottom flask equipped with a magnetic stirrer, 9.5 g of the perfluoropolyether aminodicarboxylic acid compound (Q3) obtained in step 3 of Synthesis Example 1, 15 mL of 1,3-di(trifluoromethyl)benzene, 0.5 g of oxalyl chloride and 0.1 mL of N,N-dimethylformamide were added, and the temperature was raised to 45°C for reaction for 5 h. After cooling to room temperature, 5 mL of 1,3-di(trifluoromethyl)benzene solution containing 2.4 g of diisopropylethylamine and 0.9 g of di(3-trimethoxysilylpropyl)amine was slowly added dropwise to the reaction system, and the mixture was stirred at room temperature for reaction for 3 hours. Then, 5 mL of 1,3-di(trifluoromethyl)benzene solution containing 0.95 g of 3-aminopropyltrimethoxysilane was added dropwise to the reaction system, and the mixture was stirred at room temperature for reaction for 3 hours. 30 mL of perfluorohexane was added, and the mixture was extracted three times with 20 mL of methanol. The mixture was distilled under reduced pressure to obtain 10.5 g of a colorless to pale yellow transparent product, which was a perfluoropolyether silane compound (A2).

[0127] (A2)

[0128] Where Rf is CF3(OCF2CF2) p (OCF2) q OCF2-, the sum of p and q is 38.

[0129] The H NMR spectrum of the perfluoropolyether silane compound (A2) is as follows: Figure 3 shown.

[0130] The characteristic H chemical shift of the newly added structure was identified by NMR spectrometer as follows

[0131]

[0132] Synthesis example 3

[0133] The perfluoropolyether silane compound B1 was synthesized according to the following steps:

[0134] Step 1:

[0135] In a 250 mL single-necked round-bottom flask equipped with a magnetic stirrer, add 30 g of CF3 (OCF2CF2) with an average composition of p (OCF2) q Perfluoropolyether alcohol (the sum of p and q is 53, the number average molecular weight is 4900, purchased from SOLVAY), 30 mL of 1,3-di(trifluoromethyl)benzene, 1.9 g of pyridine, 2.4 g of p-toluenesulfonyl chloride dissolved in 1,3-di(trifluoromethyl)benzene solution were added dropwise under ice bath, and stirred at room temperature for 3 h after addition. After extraction with water and methanol, 30.5 g of colorless and transparent product was obtained by vacuum distillation, which is perfluoropolyether p-toluenesulfonate compound (M1): CF3(OCF2CF2) p (OCF2) q OCF2CH2OSO2C7H7.

[0136] Step 2:

[0137] In a 250 mL single-mouth round-bottom flask equipped with a magnetic stirrer, 30 g of the perfluoropolyether p-toluenesulfonate compound obtained in step 1, 30 mL of 1,3-di(trifluoromethyl)benzene, 3.5 g of anhydrous potassium carbonate and 2.4 g of diethyl iminodiacetate were added. After the addition, the temperature was raised to 90 ° C and refluxed for 6 h. After extraction with dilute hydrochloric acid and methanol, 29.5 g of a light yellow transparent product was obtained by vacuum distillation, which is the perfluoropolyether aminodicarboxylate compound (M2): CF3 (OCF2CF2) p (OCF2) q OCF2CH2N(CH2COOCH2CH3)2.

[0138] The characteristic H chemical shift of the newly added structure was identified by NMR spectrometer as follows

[0139]

[0140] Step 3:

[0141] In a 500mL single-mouth round-bottom flask equipped with a magnetic stirrer, 29g of the perfluoropolyether aminodicarboxylate compound obtained in step 2 and 30mL of a 20wt% potassium hydroxide aqueous solution were added, the temperature was raised to 100°C and refluxed for reaction for 5h, then cooled to room temperature, 40mL of Novel 7200 and 10mL of tetrahydrofuran were added, and the mixture was acidified with 10wt% hydrochloric acid. The lower fluorine phase was removed and extracted three times with 0.1M dilute hydrochloric acid, and 28.2g of a colorless and transparent product was obtained by vacuum distillation, namely, the perfluoropolyether aminodicarboxylic acid compound (M3): CF3(OCF2CF2) p (OCF2) q OCF2CH2N(CH2COOH)2.

[0142] The characteristic H chemical shift of the newly added structure was identified by NMR spectrometer as follows

[0143]

[0144] Step 4:

[0145] In a 100 mL single-mouth round-bottom flask equipped with a magnetic stirrer, 9 g of the perfluoropolyether aminodicarboxylic acid compound (M3) obtained in step 3, 15 mL of 1,3-di(trifluoromethyl)benzene, 0.4 g of oxalyl chloride and 0.1 mL of N,N-dimethylformamide were added, and the temperature was raised to 45°C for reaction for 5 h. After cooling to room temperature, the mixture was slowly added dropwise to a 250 mL single-mouth round-bottom flask containing 5 mL of 1,3-di(trifluoromethyl)benzene, 1.9 g of diisopropylethylamine and 1.8 g of di(3-trimethoxysilylpropyl)amine. The mixture was stirred at room temperature for reaction for 3 hours, 30 mL of perfluorohexane was added, and the mixture was extracted three times with 20 mL of methanol. The product was distilled under reduced pressure to obtain 9.9 g of a colorless to light yellow transparent product, which was a perfluoropolyether silane compound (B1), and its structural formula is shown below.

[0146] (B1)

[0147] Where Rf is CF3(OCF2CF2) p (OCF2) q OCF2-, the sum of p and q is 53.

[0148] The characteristic H chemical shift of the newly added structure was identified by NMR spectrometer as follows

[0149]

[0150] Synthesis example 4

[0151] The perfluoropolyether silane compound B2 was synthesized according to the following method:

[0152] In a 100 mL single-mouth round-bottom flask equipped with a magnetic stirrer, 9 g of the perfluoropolyether aminodicarboxylic acid compound (M3) obtained in step 3 of Synthesis Example 4, 15 mL of 1,3-di(trifluoromethyl)benzene, 0.4 g of oxalyl chloride and 0.1 mL of N,N-dimethylformamide were added, and the temperature was raised to 45°C for reaction for 5 h. After cooling to room temperature, 5 mL of 1,3-di(trifluoromethyl)benzene solution containing 1.7 g of diisopropylethylamine and 0.6 g of di(3-trimethoxysilylpropyl)amine was slowly added dropwise to the reaction system, and the mixture was stirred at room temperature for 3 hours. Then, 5 mL of 1,3-di(trifluoromethyl)benzene solution containing 0.7 g of 3-aminopropyltrimethoxysilane was added dropwise to the reaction system, and the mixture was stirred at room temperature for 3 hours. 30 mL of perfluorohexane was added, and the mixture was extracted three times with 20 mL of methanol. The mixture was distilled under reduced pressure to obtain 9.7 g of a colorless to light yellow transparent product, which was a perfluoropolyether silane compound (B2).

[0153] (B2)

[0154] Where Rf is CF3(OCF2CF2) p (OCF2) q OCF2-, the sum of p and q is 53.

[0155] The characteristic H chemical shift of the newly added structure was identified by NMR spectrometer as follows

[0156]

[0157] Synthesis example 5

[0158] The average composition is CF3(OCF2CF2) p (OCF2) q Perfluoropolyether alcohol of OCF2CH2OH (the sum of p and q is 22, the number average molecular weight is 2000, purchased from SOLVAY Company), and perfluoropolyether silane compound C was synthesized according to the steps of Synthesis Example 1 1, .

[0159] (C1)

[0160] Where Rf is CF3(OCF2CF2) p (OCF2) q OCF2-, the sum of p and q is 22.

[0161] The characteristic H chemical shift of the newly added structure was identified by NMR spectrometer as follows

[0162]

[0163] Compounds A1, A2, B1, B2, and C1 obtained in Synthesis Examples 1-5 were mixed with hydrofluoroether (3M Company, Novec 7200) to a mass concentration of 20% to prepare surface treatment agents (1)-(5).

[0164] Examples 1-3

[0165] Surface treatment agents (1), (2) and (5) were dissolved in hydrofluoroether (3M Company, Novec HFE7200) at a mass concentration of 0.25% to prepare surface treatment agents (6), (7) and (8), and the corresponding mass concentration of silane compound was 0.05%. Using a commercially available spray coating device, surface treatment agents (6), (7) and (8) were uniformly sprayed on the chemically strengthened glass at a flow rate of 50 mg / sec and a conveyor line speed of 13 mm / sec. Prior to coating, the surface of the chemically strengthened glass was subjected to plasma treatment. Then, the chemically strengthened glass with the spray-treated film was placed at 60% humidity and 60°C for 1 hour for curing to form a surface treatment layer.

[0166] Example 4

[0167] The surface treatment agent (1) and the surface treatment agent (2) were mixed at a mass ratio of 1:4 to obtain a surface treatment agent (9), which was then used to form a surface treatment layer in the same manner as described in Example 1.

[0168] Comparative Examples 1-3

[0169] Control surface treatment agent 1: Optool UD509 (Produced by Daikin Industries, Ltd.);

[0170] Comparative surface treatment agent 2: SURECO 2120X (Produced by Asahi Glass Co., Ltd.)

[0171] Control surface treatment agent 3: GT-320X (produced by Guangzhou Youer Material Technology Co., Ltd.).

[0172] A surface treatment layer was formed in the same manner as in Example 1 except that the commercially available comparative surface treatment agents 1, 2, and 3 were used.

[0173] Embodiment 5-6

[0174] The surface treatment agents (3) and (4) are deposited onto the chemically strengthened glass by vacuum deposition. -3 Pa, firstly, silicon dioxide is deposited on the chemically strengthened glass with a thickness of 10nm by electron beam deposition to form a silicon dioxide film, and then the aforementioned surface treatment agent is deposited on each piece of chemically strengthened glass with a thickness of about 8-10nm by vacuum deposition. Then, the chemically strengthened glass with the deposited film is placed in an environment of 60% humidity and 25°C for 2 hours for curing to form a surface treatment layer.

[0175] Example 7

[0176] Surface treatment agents (1), (4) and (5) were mixed at a mass ratio of 3:4:3 to obtain surface treatment agent (10), which was then treated in the same manner as in Example 6 to obtain a surface treatment layer.

[0177] Comparative Examples 4-6

[0178] The surface treatment layer was formed in the same manner as in Example 5 except that the commercially available reference surface treatment agents 1, 2, and 3 (see Comparative Examples 1-3) were used instead of the surface treatment agents (3) and (4).

[0179] Next, the surface treatment layer formed on the surface of the substrate was evaluated by the following method. The results are shown in Table 1-5.

[0180] The surfaces of the glass substrate samples produced by coating and baking the samples of the above-mentioned embodiments and comparative examples were measured using a contact angle meter (CA80, manufactured by Guangdong Beidou Precision Instrument Co., Ltd.) to measure the contact angles of the surface treatment layer to water and n-hexadecane.

[0181] The dynamic friction coefficient of the relative public paper (Daboai) was tested using a friction coefficient meter (Jinan Labthink Dynamic and Static Friction Tester, MXD-02) under the following conditions.

[0182] Contact area: 20mm×20mm;

[0183] Load: 200g;

[0184] Line speed: 100mm / min;

[0185] Stroke: 50mm.

[0186] The water contact angle of the surface treatment layer after rubbing was evaluated using a friction tester (ZJ-339-GSR, Shenzhen Zhijia Instrument Equipment Co., Ltd.) under the following conditions.

[0187] (1) Resistance to steel wool wear

[0188] After every 3,000 back and forth strokes, measure the water contact angle (the evaluation is terminated when the water contact angle is less than 100 degrees or 20,000 frictions have been performed).

[0189] Steel wool: BONSTAR#0000;

[0190] Load: 1kg / cm 2 ;

[0191] Travel distance: 40mm;

[0192] Moving speed: 60rpm.

[0193] After every 2,000 back and forth strokes, measure the water contact angle (the evaluation is terminated when the water contact angle is less than 100 degrees or 12,000 frictions have been performed).

[0194] Eraser: Minoan MB006004, 6.0mm;

[0195] Load: kg;

[0196] Travel distance: 40mm;

[0197] Moving speed: 40rpm.

[0198] The silicone rubber plug SR-51 manufactured by Tigers Polymer Corporation was processed into a cylindrical shape with a diameter of 1 cm and a thickness of 1 cm. The surface of the silicone rubber product (diameter 1 cm) was covered with cotton paper impregnated with artificial sweat of the composition shown below and used as a friction piece. The friction test was conducted on the surface-treated glass substrate, and the water drop angle was tested every 1000 back and forth times. The evaluation was terminated when the water drop angle was less than 100 degrees or 7000 times.

[0199] Load: 500g;

[0200] Travel distance: 40mm;

[0201] Moving speed: 40rpm.

[0202] Composition of artificial sweat

[0203] Anhydrous disodium hydrogen phosphate: 2g;

[0204] Sodium chloride: 20g;

[0205] 85% lactic acid: 2g;

[0206] Histidine hydrochloride: 5g;

[0207] Distilled water: 1Kg.

[0208] 4. Alkali resistance test evaluation

[0209] Test conditions: At 25°C, soak the surface-treated glass substrate sample in a 2wt% sodium hydroxide solution (pH=13.7). Take it out every 3 hours after cleaning and test the water contact angle of the surface. The evaluation will be terminated when the contact angle is lower than 100° or exceeds 18 hours.

[0210] The test results of hydrophobicity, oleophobicity and slipperiness are shown in Table 1 below.

[0211] Table 1

[0212]

[0213] The steel wool wear resistance is shown in Table 2.

[0214] Table 2

[0215]

[0216] The eraser wear resistance is shown in Table 3.

[0217] Table 3

[0218]

[0219] The wear resistance to human sweat is shown in Table 4.

[0220] Table 4

[0221]

[0222] The alkali resistance is shown in Table 5.

[0223] Table 5

[0224]

[0225] It can be seen from Tables 1, 2, 3, 4 and 5 that the target compound prepared according to the present invention and the composition formed by compounding the target compound have significantly better friction resistance than similar products on the market when sprayed on the substrate at a lower concentration, especially better resistance to rubber wear. At the same time, the target compound prepared according to the present invention and the composition formed by compounding the target compound formed by the present invention on the substrate have significantly better alkali resistance than similar products on the market. It can be considered that this is because the number of hydrolyzable siloxane groups at the molecular end of the target compound of the present invention is greater than two, and the film has a high degree of crosslinking; on the other hand, the tertiary amine ( ) structure has a certain alkalinity, which can catalyze the hydrolysis condensation reaction between the terminal siloxane group and the surface of the substrate. In addition, the alkaline group can inhibit the destruction of the -Si-O-Si- bond in the coating by human sweat and alkali solution to a certain extent, so the film has good alkali resistance.

[0226] The above is only a preferred embodiment of the present invention and does not limit the present invention in any form. Therefore, any simple modification, equivalent change and modification made to the above embodiment according to the technical essence of the present invention without departing from the content of the technical solution of the present invention shall fall within the scope of protection of the technical solution of the present invention.

Claims

1. A perfluoropolyether aminosilane compound, characterized in that: Its chemical structure is as follows: Wherein Rf is a perfluoropolyether group; X1 and X2 are independently divalent organic groups; R 1 and R 3 are independently hydrogen, phenyl or C1-20 alkyl, and R 1 and R 3 are not hydrogen, phenyl or C1-20 alkyl at the same time; R 2 and R 4 Separately -Y-SiT 1 j T 2 3-j ; Wherein Y is a divalent organic group; T 1 is an alkoxy group, a hydroxy group, or a group that can be hydrolyzed to a hydroxy group; T 2 is hydrogen, phenyl or C1-20 alkyl; j in R 2 and R 4 are independent of each other and are integers between 0 and 3; R 2 The sum of j and R 4 The sum of j in is not less than 1; a and b are independently 0 or 1.

2. The perfluoropolyether aminosilane compound according to claim 1, characterized in that: Where Rf is F(CF2) m -(OC4F8) r -(OC3F6) s -(OC2F4) p -(OCF2) q -OC(Z)F-(CF2) t -, wherein r, s, p and q are independently and are integers between 0 and 100, the sum of r, s, p and q is not less than 1, each repeating unit with r, s, p and q and enclosed in brackets is straight chain or branched, and the order and quantity of each repeating unit in the formula are arbitrary, m and t are integers between 0 and 30, and Z is F or CF3.

3. The perfluoropolyether aminosilane compound according to claim 2, characterized in that: Rf is the following formula: CF3-(OC2F2) p -(OCF2) q -OCF2-, wherein the sum of p and q is an integer between 10 and 200; or, Rf is the following formula: F(CF2) m -(OC4F8) r -(OC3F6) s -(OC2F4) p -(OCF2) q -OC(Z)F-(CF2) t - , wherein m is an integer between 1 and 16, t is an integer between 0 and 2, p and q are each independently an integer between 1 and 200, and the sum of r, s, p and q is an integer between 10 and 200.

4. The perfluoropolyether aminosilane compound according to any one of claims 1 to 3, characterized in that: X1 and X2 are independently -(R 5 ) e -X3-(R 6 ) g -, where R 5 and R 6 are independently C1-6 alkylene or substituted alkylene, e and g are independently 0 or 1, X3 is -O-, S-, -(CH2) k -、-CH=CH-、-O(CH2) k O-, -O(CH2O) k 、-(CF2) k -, -Het-, -Ar- or substituted -Ar-, k is independently an integer between 2 and 100 each time it appears, -Het- is an organic compound containing a heteroatom ring, and -Ar- is an organic compound having aromatic properties.

5. The perfluoropolyether aminosilane compound according to any one of claims 1 to 3, characterized in that: Y is a C1-6 alkyl group; and / or, T 1 Alkoxy OT 3 , where T 3 is a substituted or unsubstituted C1-3 alkyl group.

6. The perfluoropolyether aminosilane compound according to claim 4, characterized in that The perfluoropolyether aminosilane compound is selected from the following structural formula: 。 7. The perfluoropolyether aminosilane compound according to claim 6, characterized in that The perfluoropolyether aminosilane compound is selected from the following structural formula: 。 8. A method for preparing the perfluoropolyether aminosilane compound according to any one of claims 1 to 7, characterized in that: The steps include: Step 1, reacting a perfluoropolyether alcohol with an organic sulfonic acid compound in the presence of a solvent and a base to obtain a perfluoropolyether sulfonate; the perfluoropolyether alcohol has a structural formula of Rf-CH2OH; Step 2, reacting a perfluoropolyether sulfonate with an iminodicarboxylate compound in the presence of a solvent and a base to obtain a perfluoropolyether aminodicarboxylate; the iminodicarboxylate compound has the structural formula: Where R 7 and R 8 Each is independently a C1-6 alkyl or a phenyl; Step 3, heating and hydrolyzing the perfluoropolyether aminodicarboxylate under strong alkaline conditions and then acidifying to obtain perfluoropolyether aminodicarboxylic acid; Step 4: reacting the perfluoropolyether amino dicarboxylic acid with an acyl halide reagent to generate a perfluoropolyether amino diacyl halide, and then reacting the perfluoropolyether amino dicarboxylic acid with an aminosilane coupling agent to obtain the perfluoropolyether aminosilane compound.

9. A surface treatment composition, characterized in that A mixture comprising one or more of the perfluoropolyether aminosilane compounds according to any one of claims 1 to 7 and an organic solvent.

10. An application of the surface treatment composition according to claim 9, characterized in that: The coating is formed on the surface of the substrate by coating, spraying or vapor deposition.

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