Perfluoropolyether siloxane compound and preparation method thereof

Abstract

The invention relates to a perfluoropolyether-based siloxane compound with a single-ended four-claw structure, in particular to a perfluoropolyether-based silane compound Rf-PFPE-CH2-O-Z '-[CO-N-(Y-SiR1jR23-j) 2] 2 as shown in a formula (3) and a preparation method of the perfluoropolyether-based silane compound Rf-PFPE-CH2-O-Z'-[CO-N-(Y-SiR1jR23-j) 2] 2. The perfluoropolyether-based silane compound provided by the invention can be used as a surface treating agent for substrates such as glass, so that the substrates such as glass treated by the perfluoropolyether-based silane compound have excellent antifouling and smooth properties, and are especially excellent in wear resistance.

Description

Technical Field

[0001] The present invention relates to a compound used as a surface treatment agent and a preparation method thereof, in particular to a silane compound containing a perfluoropolyether group and a preparation method thereof. Background Art

[0002] With the rapid popularization of smart phones, tablet computers and car central control devices around the world, the demand for touch-type electronic display devices has increased dramatically. When consumers touch the display panel with their fingers to operate, it is easy to form contamination such as wrinkles, sweat, and oil. Once the dirt is formed, it is difficult to remove without using solvents, which affects the visual sense of the display device. Using solvents also has the risk of damaging the display device. On the other hand, when performing touch operations, the screen is required to provide excellent surface sliding properties, and dirt contamination will also affect the surface activity. In order to form a functional film with better slipperiness and prevent the adhesion of fingerprints and other dirt on the surface of the substrate, the researchers used a fluorine-containing polymer compound with high lubricity and high water and oil repellency.

[0003] It is known in the prior art that when a perfluoropolyether-based silane compound is used to treat a substrate, a film layer with properties such as hydrophobicity, oleophobicity, antifouling, low friction coefficient and durability can be formed on its surface. On the one hand, this is due to the low surface energy characteristics of the perfluoropolyether in the molecule, and on the other hand, the siloxane group in the molecule can undergo a dehydration condensation reaction on the surface of the substrate to form a chemical bond and bond. The surface treatment agent containing the composition is evenly dispersed on the substrate by spraying or vapor deposition, and a film layer with protective function can be formed by heating and curing. Since the film layer is only a few nanometers and transparent, it will not affect the surface appearance and light transmittance of the substrate.

[0004] With the continuous expansion of the application field of perfluoropolyether silane compounds and the continuous changes in display substrates, the difficulty of surface treatment is also increasing, especially the long-term wear resistance has been severely challenged. It is urgent to develop products with stronger wear resistance and substrate adaptability. Summary of the invention

[0005] The present invention aims to provide a novel perfluoropolyether-based silane compound and a preparation method thereof. The perfluoropolyether-based silane compound has a four-claw structure at one end, and the treated substrate has excellent antifouling and slippery properties, and the wear resistance is particularly excellent.

[0006] In one aspect, the present invention provides a perfluoropolyether-based siloxane compound represented by formula (1):

[0007] R-PFPE-Z1-[X-NQ k T 2-k ]2(1)

[0008] Where R is R f or Z1-[Y-NQ kT 2-k ]2 represents a group, R f Represents C 1～16 PFPE represents a divalent perfluoropolyether group; Z1 represents a trivalent organic group; X represents a carbonyl group, a sulfonyl group or an acid anhydride;

[0009] T, independently at each occurrence, is a hydroxyl group, a hydrolyzable group, or a hydrocarbon group;

[0010] Q is independent at each occurrence, which is -Y-SiR 1 j R 2 3-j ;

[0011] Y is independently present at each occurrence and is a divalent organic group;

[0012] R 1 is, independently at each occurrence, an alkoxy group, a hydroxy group, or a group that can be hydrolyzed to a hydroxy group;

[0013] R 2 Each occurrence is independently a hydrocarbon group or Q′;

[0014] Q′ has the same meaning as Q;

[0015] j in each Q and Q' is independently an integer selected from 0 to 3, and the sum of j is at least 1;

[0016] k is independently 1 or 2.

[0017] On the other hand, the present invention provides a perfluoropolyether-based siloxane compound represented by formula (2):

[0018] R-PFPE-CH2-OZ′-[CO-NQ k T 2-k ]2(2)

[0019] Where R is R f or CH2-OZ′-[CO-NQ k T 2-k ]2 represents a group, R f Represents C 1～16 PFPE represents a divalent perfluoropolyether group; Z′ represents a trivalent organic group;

[0020] T, independently at each occurrence, is a hydroxyl group, a hydrolyzable group, or a hydrocarbon group;

[0021] Q is independent at each occurrence, which is -Y-SiR 1 j R 2 3-j ;

[0022] Y is independently present at each occurrence and is a divalent organic group;

[0023] R 1 is, independently at each occurrence, an alkoxy group, a hydroxy group, or a group that can be hydrolyzed to a hydroxy group;

[0024] R 2 Each occurrence is independently a hydrocarbon group or Q′;

[0025] Q′ has the same meaning as Q;

[0026] j in each Q and Q' is independently an integer selected from 0 to 3, and the sum of j is at least 1;

[0027] k is independently 1 or 2.

[0028] In another aspect, the present invention provides a perfluoropolyether-based silane compound represented by formula (3):

[0029] R f -PFPE-CH2-OZ′-[CO-N-(Y-SiR 1 j R 2 3-j )2]2(3)

[0030] In the formula, R f Represents C 1～16 PFPE stands for divalent perfluoropolyether group (OC4F8) p -(OC3F6) q -(OC2F4) r -(OCF2) s -OC(Z)F-(CF2) t -, wherein p, q, r and s are integers of 0 to 200 respectively, the sum of p, q, r and s is at least 1, the order and number of the repeating units with p, q, r and s enclosed in parentheses are arbitrary in the formula, t is an integer of 0 to 30, Z is F or CF3; Z' represents a trivalent organic group, preferably Z' is CH2(CH2) a CH, a is an integer of 1 to 9; Y represents a divalent organic group, preferably Y is (CH2) b , b is an integer from 1 to 6; R 1 is an alkoxy group, a hydroxy group or a group that can be hydrolyzed to a hydroxy group; R 2 C 1～6 An alkyl group or a phenyl group; j is an integer from 1 to 3.

[0031] Furthermore, j is 3.

[0032] Furthermore, Z' is CH2CH2CH or CH2(CH2)3CH.

[0033] Furthermore, Y is (CH2)3.

[0034] Further, R f CF3; PFPE is (OC2F4) r (OCF2) s OCF2, wherein r and s are integers of 0 to 200 respectively, the sum of r and s is at least 1, and the order of the repeating units enclosed in brackets marked with r and s in the formula is arbitrary; preferably, the sum of r and s is 20-100.

[0035] The present invention also provides a method for preparing a perfluoropolyether-based silane compound of formula (3), wherein R f -PFPE-CH2-OZ′-[CO-N-(Y-SiR 1 j R 2 3-j )2]2(3)

[0036] include:

[0037] Step (1): R f -PFPE-CH2-OH reacts with excess X1CH2(CH2) in the presence of solvent 1,3-di(trifluoromethyl)benzene and strong base potassium hydroxide a-1 The etherification reaction of CH2X2 generates R f -PFPE-CH2-OCH2(CH2) a-1 CH2X2;

[0038] Step (2): R f -PFPE-CH2-OCH2(CH2) a-1 CH2X2 reacts with di-tert-butyl malonate CH2[COOC(CH3)3]2 in the presence of anhydrous tetrahydrofuran and a superbase sodium hydride to generate R f -PFPE-CH2-OCH2(CH2) a CH[COOC(CH3)3]2;

[0039] Step (3): R f -PFPE-CH2-OCH2(CH2) a The hydrolysis and acidification reaction of CH[COOC(CH3)3]2 generates dicarboxylic acid compound R f -PFPE-CH2-OCH2(CH2) a CH(COOH)2;

[0040] Step (4): Dicarboxylic acid compound R f -PFPE-CH2-OCH2(CH2) a CH(COOH)2 reacts with acyl chloride reagent and aminosilane coupling agent NH-(Y-SiR 1 j R 2 3-j )2 to generate a perfluoropolyether-based silane compound of formula (3);

[0041] Among them, R f Represents C 1～16 PFPE stands for divalent perfluoropolyether group (OC4F8) p -(OC3F6) q -(OC2F4)r-(OCF2)s-OC(Z)F-(CF2) t -, wherein p, q, r and s are integers of 0 to 200 respectively, the sum of p, q, r and s is at least 1, the order and number of the repeating units with p, q, r and s enclosed in parentheses are arbitrary in the formula, t is an integer of 0 to 30, Z is F or CF3; Z' represents a trivalent organic group, preferably Z' is CH2(CH2) a CH, a is an integer of 1 to 9; Y represents a divalent organic group, preferably Y is (CH2) b , b is an integer from 1 to 6; R 1 is an alkoxy group, a hydroxy group or a group that can be hydrolyzed to a hydroxy group; R 2 C 1～6 alkyl or phenyl; j is an integer from 1 to 3; in step (1), X1 and X2 are independently Br or Cl.

[0042] Furthermore, in formula (3), R f CF3; PFPE is (OC2F4) r (OCF2) s OCF2, wherein r and s are integers of 0 to 200 respectively, the sum of r and s is at least 1, and the order of the repeating units enclosed in brackets marked with r and s is arbitrary in the formula; preferably, the sum of r and s is 20-100; n is 3; Z′ is CH2CH2CH or CH2(CH2)3CH; Y is (CH2)3; in step (1), X1 and X2 are both Br.

[0043] Further, the acyl halide reagent in step (4) is oxalyl chloride, and the aminosilane coupling agent NH-(Y-SiR 1 j R 2 3-j )2 is bis(3-trimethoxysilylpropyl)amine.

[0044] The present invention has the following beneficial effects due to the adoption of the above technical solution:

[0045] The substrate treated with the perfluoropolyether-based siloxane compound of the present invention has a contact angle of more than 115° to water; the surface of the substrate treated with the perfluoropolyether-based siloxane compound of the present invention has good antifouling performance and good smooth feel; the perfluoropolyether-based siloxane compound of the present invention has a four-claw structure at one end, and compared with the perfluoropolyether-based siloxane compound with a two-claw structure at one end, the wear resistance is greatly improved. DETAILED DESCRIPTION

[0046] In order to facilitate the understanding of the present invention, in order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention are described in detail below. In the following description, many specific details are set forth so as to fully understand the present invention, and the preferred embodiments of the present invention are given. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thoroughly understood. The present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present invention, so the present invention is not limited to the specific embodiments disclosed below. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the present invention. The terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0047] The present invention provides a perfluoropolyether-based siloxane compound represented by formula (1):

[0048] R-PFPE-Z1-[X-NQ k T 2-k ]twenty one)

[0049] In the above formula, PFPE represents a divalent perfluoropolyether group (OC4F8) p -(OC3F6) q -(OC2F4)r-(OCF2) s -OC(Z)F-(CF2) t -, where p, q, r and s are respectively integers greater than 0 and less than 200, the sum of p, q, r and s is at least 1, the order and quantity of the individual repeating units containing p, q, r and s and enclosed in brackets are arbitrary in the formula, t is an integer greater than 0 and less than 30, and Z is F or CF3.

[0050] The preferred PFPE is (OC2F4) r(OCF2) s OCF2, wherein r and s are integers of 0 to 200 respectively, the sum of r and s is at least 1, and the order of the repeating units enclosed in brackets marked with r and s in the formula is arbitrary; preferably, the sum of r and s is 20-100.

[0051] In the above formula (1), Z1 represents a trivalent organic group, preferably Z1 is CH2OCH2(CH2) a CH, a is an integer of 1 to 9. Furthermore, Z1 is CH2OCH2CH2CH or CH2OCH2(CH2)3CH.

[0052] In the above formula (1), X represents a carbonyl group, a sulfonyl group or an acid anhydride;

[0053] In the above formula (1), T is independently selected from hydroxyl, hydrolyzable group or hydrocarbon group at each occurrence; preferably, T is independently selected from hydroxyl, -O(R 7 ), C 1-12 Alkyl, C 2-12 Alkenyl, C 2-12 Alkynyl and phenyl, R 7 C 1-12 More preferably, each occurrence of T is independently hydroxyl, or -O(R 7 ), R 7 C 1-12 alkyl.

[0054] In the above formula (1), Q is independently -Y-SiR 1 j R 2 3-j , wherein Y is independently present at each occurrence and is a divalent organic group; R 1 Each occurrence is independently an alkoxy group, a hydroxy group or a group that can be hydrolyzed to a hydroxy group; preferably, R 1 For-OR 3 , where R 3 is substituted or unsubstituted C 1-3 Alkyl, preferably, R 3 is methyl; wherein R 2 Each time it appears, it is independent and is C 1-22 Alkyl or Q'; wherein Q' has the same meaning as Q; j in each Q and Q' is independently an integer selected from 0 to 3, and the sum of j is 1 or more; k is independently 1 or 2, preferably k is 2.

[0055] In the above formula (1), R is f or Z1-[Y-NQ k T 2-k]2 represents a group, R f Represents C 1～16 R is C 1～16 When the fluoroalkyl group is a fluoroalkyl group, R-PFPE- represents a monofunctional perfluoropolyether group; R is Z1-[Y-NQ k T 2-k ]2 indicates that the perfluoropolyether group is difunctional. Considering the product performance, it is preferably a monofunctional perfluoropolyether group, or a monofunctional and difunctional mixed perfluoropolyether group. When R-PFPE- indicates a monofunctional perfluoropolyether group, R is preferably CF3.

[0056] According to some preferred embodiments, the perfluoropolyether-based silane compound represented by the aforementioned formula (1) has a number average molecular weight of 500 to 10,000, preferably 1,000 to 8,000, and more preferably 3,000 to 7,500.

[0057] The perfluoropolyether-based silane compound represented by the above formula (1) can be f -PFPE-Z1-(X-OH)2 (where R is R f , that is, C 1～16 It is prepared by reacting (fluoroalkyl) or (HO-X)2-Z1-PFPE-Z1-(X-OH)2 with an acyl halide reagent and an aminosilane coupling agent.

[0058] According to some preferred embodiments, the acyl halide reagent is an acyl halide, a thionyl halide or a phosphorus oxyhalide, preferably an acyl chloride, sulfuryl chloride, phosphorus oxychloride, more preferably an acyl chloride, and most preferably oxalyl chloride.

[0059] According to some preferred embodiments, the aminosilane coupling agent is HNQ k T 2-k , where Q is -Y-SiR 1 j R 2 3-j , wherein Y is a divalent organic group; R 1 is an alkoxy group, a hydroxy group or a group that can be hydrolyzed to a hydroxy group; preferably, R 1 For-OR 3 , where R 3 is substituted or unsubstituted C 1-3 Alkyl, preferably, R 3 is methyl, ethyl, propyl or isopropyl; wherein R 2 C 1-22alkyl or Q'; wherein Q' has the same meaning as Q; j is independently selected from an integer from 0 to 3 in each Q and Q', and the sum of j is greater than 1; k is independently selected from 1 or 2, preferably k is 2; T is a hydroxyl group, a hydrolyzable group or a hydrocarbon group; preferably, T is selected from a hydroxyl group, -O(R 7 ), C 1-12 Alkyl, C 2-12 Alkenyl, C 2-12 Alkynyl and phenyl, R 7 C 1-12 More preferably, T is hydroxy or -O(R 7 ), R 7 C 1-12 alkyl.

[0060] According to some preferred embodiments, the present invention provides a perfluoropolyether-based siloxane compound represented by the following formula (2):

[0061] R-PFPE-CH2-OZ′-[CO-NQ k T 2-k ]twenty two)

[0062] In the above formula, PFPE represents a divalent perfluoropolyether group (OC4F8) p -(OC3F6) q -(OC2F4)r-(OCF2) s -OC(Z)F-(CF2) t -, where p, q, r and s are respectively integers greater than 0 and less than 200, the sum of p, q, r and s is at least 1, the order and quantity of the individual repeating units containing p, q, r and s and enclosed in brackets are arbitrary in the formula, t is an integer greater than 0 and less than 30, and Z is F or CF3.

[0063] The preferred PFPE is (OC2F4) r (OCF2) s OCF2, wherein r and s are integers of 0 to 200 respectively, the sum of r and s is at least 1, and the order of the repeating units enclosed in brackets marked with r and s in the formula is arbitrary; preferably, the sum of r and s is 20-100.

[0064] In the above formula (2), Z' represents a trivalent organic group, preferably CH2(CH2) a CH, a is an integer of 1 to 9. Furthermore, Z' is CH2CH2CH or CH2(CH2)3CH.

[0065] In the above formula (2), T is independently selected from hydroxyl, a hydrolyzable group or a hydrocarbon group at each occurrence; preferably, T is independently selected from hydroxyl, -O(R7 ), C 1-12 Alkyl, C 2-12 Alkenyl, C 2-12 Alkynyl and phenyl, R 7 C 1-12 More preferably, each occurrence of T is independently hydroxyl, or -O(R 7 ), R 7 C 1-12 alkyl.

[0066] In the above formula (2), Q is independently present at each occurrence and is -Y-SiR 1 j R 2 3-j , wherein Y is independently present at each occurrence and is a divalent organic group; R 1 Each occurrence is independently an alkoxy group, a hydroxy group or a group that can be hydrolyzed to a hydroxy group; preferably, R 1 For-OR 3 , where R 3 is substituted or unsubstituted C 1-3 Alkyl, preferably, R 3 is methyl; wherein R 2 Each time it appears, it is independent and is C 1-22 Alkyl or Q'; wherein Q' has the same meaning as Q; j in each Q and Q' is independently an integer selected from 0 to 3, and the sum of j is 1 or more; k is independently 1 or 2, preferably k is 2.

[0067] In the above formula (2), R is f or CH2-OZ′-[CO-NQ k T 2-k ]2 represents a group, R f Represents C 1～16 R is C 1～16 When the fluoroalkyl group is a fluoroalkyl group, R-PFPE- represents a monofunctional perfluoropolyether group; R is CH2-OZ′-[CO-NQ k T 2-k ]2 indicates that the perfluoropolyether group is difunctional. Considering the product performance, it is preferably a monofunctional perfluoropolyether group, or a monofunctional and difunctional mixed perfluoropolyether group. When R-PFPE- indicates a monofunctional perfluoropolyether group, R is preferably CF3.

[0068] According to some preferred embodiments, the perfluoropolyether-based silane compound represented by the aforementioned formula (2) has a number average molecular weight of 500 to 10,000, preferably 1,000 to 8,000, and more preferably 3,000 to 7,500.

[0069] The perfluoropolyether-based silane compound represented by the above formula (2) can be f -PFPE-Z1-(COOH)2 (where R is R f , that is, C 1～16 It is prepared by reacting (fluoroalkyl) or (HOOC)2-Z1-PFPE-Z1-(COOH)2 with an acyl halide reagent and an aminosilane coupling agent.

[0070] According to some preferred embodiments, the acyl halide reagent is an acyl halide, a thionyl halide or a phosphorus oxyhalide, preferably an acyl chloride, sulfuryl chloride, phosphorus oxychloride, more preferably an acyl chloride, and most preferably oxalyl chloride.

[0071] According to some preferred embodiments, the aminosilane coupling agent is HNQ k T 2-k , where Q is -Y-SiR 1 j R 2 3-j , wherein Y is a divalent organic group; R 1 is an alkoxy group, a hydroxy group or a group that can be hydrolyzed to a hydroxy group; preferably, R 1 For-OR 3 , where R 3 is substituted or unsubstituted C 1-3 Alkyl, preferably, R 3 is methyl, ethyl, propyl or isopropyl; wherein R 2 C 1-22 alkyl or Q'; wherein Q' has the same meaning as Q; j is independently selected from an integer from 0 to 3 in each Q and Q', and the sum of j is greater than 1; k is independently selected from 1 or 2, preferably k is 2; T is a hydroxyl group, a hydrolyzable group or a hydrocarbon group; preferably, T is selected from a hydroxyl group, -O(R 7 ), C 1-12 Alkyl, C 2-12 Alkenyl, C 2-12 Alkynyl and phenyl, R 7 C 1-12 More preferably, T is hydroxy or -O(R 7 ), R 7 C 1-12 alkyl.

[0072] According to some preferred embodiments, R f -PFPE-Z1-(COOH)2 (Bifunctional (HOOC)2-Z1-PFPE-Z1-(COOH)2 Preparation Method and Monofunctional R f The preparation method of -PFPE-Z1-(COOH)2 is the same, and the preparation process is described by taking a single functional group as an example) including:

[0073] Step (1): R f -PFPE-CH2-OH reacts with excess dihalogenated compound X1CH2R in the presence of solvent and strong base h The etherification reaction of CH2X2 generates R f -PFPE-CH2-OCH2R h CH2X2;

[0074] Step (2): R f -PFPE-CH2-OCH2R h The nucleophilic substitution reaction of CH2X2 with di-tert-butyl malonate CH2[COOC(CH3)3]2 in the presence of anhydrous solvent and superbase generates R f -PFPE-CH2-OCH2R h CH2CH[COOC(CH3)3]2;

[0075] Step (3): R f -PFPE-CH2-OCH2R h The hydrolysis and acidification reaction of CH2CH[COOC(CH3)3]2 generates dicarboxylic acid compound R f -PFPE-CH2-OCH2R h CH2CH(COOH)2.

[0076] According to some preferred embodiments, in the aforementioned step (1), X1 and X2 are independently Br or Cl; and it is particularly preferred that both X1 and X2 are Br. h is a valent or divalent organic group, such as phenylene, alkylene (CH2) a-1 (a is an integer) etc. X1CH2R h The dihalogenated compound represented by CH2X2 includes 1,2-dibromoethane, 1,3-dibromopropane, dibromohexane, etc., and 1,4-dibromobutane and 1,2-dibromoethane are particularly preferred.

[0077] The base described in the aforementioned step (1) is selected from an inorganic base or an organic base; the inorganic base is preferably selected from at least one of LiOH, NaOH, KOH, K2CO3, Na2CO3, Cs2CO3, t-BuOK; the organic base is preferably selected from at least one of DIPEA, DBU, 1,1,3,3-tetramethylguanidine. More preferably, the base is selected from at least one of sodium hydroxide and potassium hydroxide; potassium hydroxide is particularly preferred.

[0078] The solvent in the aforementioned step (1) is at least one selected from 1,3-di(trifluoromethyl)benzene, hydrofluoroether 7200, diethylene glycol dimethyl ether, etc., and is particularly preferably 1,3-di(trifluoromethyl)benzene.

[0079] The anhydrous solvent in the aforementioned step (2) is selected from furan, ethers, etc., and is particularly preferably anhydrous tetrahydrofuran. The superbase is potassium hydride, sodium hydride, etc., and is particularly preferably sodium hydride.

[0080] The hydrolysis in the aforementioned step (3) needs to be carried out under strong alkaline conditions, which can be selected from sodium hydroxide, potassium hydroxide, etc. The acidification needs to be carried out under strong acid conditions, which can be selected from inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid.

[0081] According to some preferred embodiments, the present invention provides a perfluoropolyether-based siloxane compound represented by the following formula (3):

[0082] R f -PFPE-CH2-OZ′-[CO-N-(Y-SiR 1 j R 2 3-j )2]2(3)

[0083] In the above formula, PFPE represents a divalent perfluoropolyether group (OC4F8) p -(OC3F6) q -(OC2F4)r-(OCF2)s-OC(Z)F-(CF2) t -, where p, q, r and s are respectively integers greater than 0 and less than 200, the sum of p, q, r and s is at least 1, the order and quantity of the individual repeating units containing p, q, r and s and enclosed in brackets are arbitrary in the formula, t is an integer greater than 0 and less than 30, and Z is F or CF3.

[0084] The preferred PFPE is (OC2F4) r (OCF2) s OCF2, wherein r and s are integers of 0 to 200 respectively, the sum of r and s is at least 1, and the order of the repeating units enclosed in brackets marked with r and s in the formula is arbitrary; preferably, the sum of r and s is 20-100.

[0085] In the above formula (3), Z' represents a trivalent organic group, preferably Z' is CH2(CH2) a CH, a is an integer of 1 to 9. Furthermore, Z' is CH2CH2CH or CH2(CH2)3CH.

[0086] In the above formula (3), R f Represents C 1～16 A fluoroalkyl group is particularly preferred, with CF3 being particularly preferred.

[0087] In the above formula (3), Y represents a divalent organic group, and preferably Y is (CH2) b, b is an integer from 1 to 6; (CH2)3 is particularly preferred.

[0088] In the above formula (3), R 1 is an alkoxy group, a hydroxy group or a group that can be hydrolyzed to a hydroxy group; preferably, R 1 For-OR 3 , where R 3 is substituted or unsubstituted C 1-3 Alkyl, preferably, R 3 R is methyl. 2 C 1～6 j is an integer of 1 to 3, and j is particularly preferably 3.

[0089] According to some preferred embodiments, the perfluoropolyether-based silane compound represented by the aforementioned formula (3) has a number average molecular weight of 500 to 10,000, preferably 1,000 to 8,000, and more preferably 3,000 to 7,500.

[0090] According to some preferred embodiments, the present invention provides a method for preparing a silane compound containing a perfluoropolyether group represented by the aforementioned formula (3),

[0091] R f -PFPE-CH2-OZ′-[CO-N-(Y-SiR 1 n R 2 3-n )2]2(3)

[0092] include:

[0093] Step (1): R f -PFPE-CH2-OH reacts with excess X1CH2(CH2) in the presence of solvent 1,3-di(trifluoromethyl)benzene and strong base potassium hydroxide a-1 The etherification reaction of CH2X2 generates R f -PFPE-CH2-OCH2(CH2) a-1 CH2X2;

[0094] Step (2): R f -PFPE-CH2-OCH2(CH2) a-1 CH2X2 reacts with di-tert-butyl malonate CH2[COOC(CH3)3]2 in the presence of anhydrous tetrahydrofuran superbase sodium hydride to generate R f -PFPE-CH2-OCH2(CH2) a CH[COOC(CH3)3]2;

[0095] Step (3): R f-PFPE-CH2-OCH2(CH2) a The hydrolysis and acidification reaction of CH[COOC(CH3)3]2 generates dicarboxylic acid compound R f -PFPE-CH2-OCH2(CH2) a CH(COOH)2;

[0096] Step (4): Dicarboxylic acid compound R f -PFPE-CH2-OCH2(CH2) a CH(COOH)2 reacts with acyl chloride reagent and aminosilane coupling agent NH-(Y-SiR 1 n R 2 3-n )2 to generate a perfluoropolyether-based silane compound of formula (3);

[0097] In the above steps, R f Represents C 1～16 PFPE stands for divalent perfluoropolyether group (OC4F8) p -(OC3F6) q -(OC2F4)r-(OCF2)s-OC(Z)F-(CF2) t -, wherein p, q, r and s are integers of 0 to 200 respectively, the sum of p, q, r and s is at least 1, the order and number of the repeating units with p, q, r and s enclosed in parentheses are arbitrary in the formula, t is an integer of 0 to 30, Z is F or CF3; Z' represents a trivalent organic group, preferably Z' is CH2(CH2) a CH, a is an integer of 1 to 9; Y represents a divalent organic group, preferably Y is (CH2) b , b is an integer from 1 to 6; R 1 is an alkoxy group, a hydroxy group or a group that can be hydrolyzed to a hydroxy group; R 2 C 1～6 alkyl or phenyl; n is an integer of 1 to 3; in step (1), X1 and X2 are independently Br or Cl.

[0098] In the above steps, preferably, R in formula (3) f CF3; PFPE is (OC2F4) r (OCF2) sOCF2, wherein r and s are integers of 0 to 200 respectively, the sum of r and s is at least 1, and the order of the repeating units enclosed in brackets marked with r and s is arbitrary in the formula; preferably, the sum of r and s is 20-100; n is 3; Z′ is CH2CH2CH or CH2(CH2)3CH; Y is (CH2)3; in step (1), X1 and X2 are both Br.

[0099] The hydrolysis in the aforementioned step (3) needs to be carried out under strong alkaline conditions, which can be selected from sodium hydroxide, potassium hydroxide, etc., and potassium hydroxide is particularly preferred. The acidification needs to be carried out under strong acid conditions, which can be selected from inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid, and hydrochloric acid is particularly preferred.

[0100] In the above step (4), according to some preferred embodiments, the acyl halide reagent is an acyl halide, a thionyl halide or a phosphoryl halide, preferably an acyl chloride, a sulfuryl chloride, a phosphoryl chloride, more preferably an acyl chloride, and most preferably oxalyl chloride. The aminosilane coupling agent is HNQ k T 2-k , where Q is -Y-SiR 1 j R 2 3-j , wherein Y is a divalent organic group; R 1 is an alkoxy group, a hydroxy group or a group that can be hydrolyzed to a hydroxy group; preferably, R 1 For-OR 3 , where R 3 is substituted or unsubstituted C 1-3 Alkyl, preferably, R 3 is methyl, ethyl, propyl or isopropyl; wherein R 2 C 1-22 alkyl or Q'; wherein Q' has the same meaning as Q; j is independently selected from an integer from 0 to 3 in each Q and Q', and the sum of j is greater than 1; k is independently selected from 1 or 2, preferably k is 2; T is a hydroxyl group, a hydrolyzable group or a hydrocarbon group; preferably, T is selected from a hydroxyl group, -O(R 7 ), C 1-12 Alkyl, C 2-12 Alkenyl, C 2-12 Alkynyl and phenyl, R 7 C 1-12 More preferably, T is hydroxy or -O(R 7 ), R 7 C 1-12 The aminosilane coupling agent is more preferably di(3-trimethoxysilylpropyl)amine.

[0101] Synthesis example 1

[0102] Step (1): Add 20 g of CF3 (OCF2CF2) with an average composition into a 100 ml three-necked flask with stirring. r (OCF2) s OCF2CH2OH perfluoropolyether modified alcohol (r+s is 35-50, number average molecular weight is 4000-5000), 30ml1,3-di(trifluoromethyl)benzene, 4g50wt% potassium hydroxide solution, stirred at room temperature for 2h, then 15g1,4-dibromobutane and 1gtetrabutylammonium bromide were added to the reaction bottle in sequence, stirred at 60°C for 10h, after the reaction was completed, water extraction and reduced pressure distillation were performed to obtain 19.8g of colorless oily transparent product, which is bromine perfluoropolyether compound (M11)CF3(OCF2CF2) r (OCF2) s OCF2CH2OCH2CH2CH2CH2CH2Br.

[0103] Step (2): Add 5g of sodium hydride and 20ml of anhydrous tetrahydrofuran to a three-necked flask equipped with a stirrer, slowly add a mixed solution of 20g of di-tert-butyl malonate CH[COOC(CH3)3]2 and 10ml of anhydrous tetrahydrofuran at room temperature, and stir for 2h; then slowly add it to a three-necked flask containing 19.6g of compound M11 obtained in step 1 and 30ml of 1,3-di(trifluoromethyl)benzene, heat to 60°C, and stir for 5h. After the reaction is completed, extract with water and distill under reduced pressure to obtain 19g of a colorless oily transparent product, which is a diester-based perfluoropolyether compound (M21)CF3(OCF2CF2) r (OCF2) s OCF2CH2OCH2CH2CH2CH2CH[COOC(CH3)3]2.

[0104] Step (3): 19 g of the compound M21 obtained in step 2, 30 ml of 1,3-di(trifluoromethyl)benzene and 10 g of a 20 wt% potassium hydroxide solution were added to a three-necked flask equipped with a stirrer, and the temperature was raised to 100°C and stirred for 5 hours. After the reaction was completed, the temperature was lowered to room temperature, 10 g of 36.5 wt% concentrated hydrochloric acid was added to adjust the pH to acidic, and 17.6 g of a colorless oily transparent product was obtained by water extraction and reduced pressure distillation, namely, the dicarboxyl perfluoropolyether compound (M31) CF3 (OCF2CF2) r (OCF2) s OCF2CH2OCH2CH2CH2CH2CH(COOH)2.

[0105] Step (4): In a three-necked flask equipped with a stirring device and a dropping funnel, 17.6 g of compound M31 obtained in step 3, 20 ml of 1,3-di(trifluoromethyl)benzene and 2 ml of oxalyl chloride ((COOCl)2) were added, and 0.5 ml of N,N-dimethylformamide (DMF) dissolved in 5 ml of 1,3-di(trifluoromethyl)benzene was slowly added via a dropping funnel. The temperature was then raised to 50°C and stirred for 3 h. After cooling to room temperature, it was slowly added dropwise to a three-necked flask containing a mixed solution of 15 ml of 1,3-di(trifluoromethyl)benzene, 10 ml of diisopropylethylamine and 15 ml of di(3-trimethoxysilylpropyl)amine, and stirred at room temperature for 4 h. Add 50 ml of perfluorooctane, extract repeatedly three times with 35 ml of methanol, remove the volatile matter under reduced pressure distillation of the lower fluorine solution, and obtain 17 g of light yellow product, which is a perfluoropolyether siloxane compound (M41)CF3(OCF2CF2) with four trimethoxysilanes at the end. r (OCF2) s OCF2CH2OCH2CH2CH2CH2CH{CON[(CH2CH2CH2Si(OCH3)3]2}2.

[0106] Synthesis example 2

[0107] Only 15 g of 1,4-dibromobutane in step (1) was replaced by 13 g of 1,2-dibromoethane, and the rest was the same as in Example 1, and finally a perfluoropolyether siloxane compound (M42) CF3 (OCF2CF2) with four trimethoxysilanes at the end was obtained. r (OCF2) s OCF2CH2OCH2CH2CH{CON[(CH2CH2CH2Si(OCH3)3]2}2.

[0108] Synthesis example 3

[0109] Only the 20g in step (1) is averaged to form CF3(OCF2CF2) r (OCF2) s 20g of perfluoropolyether modified alcohol of OCF2CH2OH (r+s is 35-50, number average molecular weight is 4000-5000) has an average composition of CF3(OCF2CF2) r (OCF2) s OCF2CH2OH is replaced by a perfluoropolyether-modified alcohol (r+s is 55-65, and the number average molecular weight is 5500-6500), and finally a perfluoropolyether-based siloxane compound (M43)CF3(OCF2CF2) with four trimethoxysilanes at the end is obtained. r (OCF2) sOCF2CH2OCH2CH2CH2CH2CH{CON[(CH2CH2CH2Si(OCH3)3]2}2.

[0110] Synthesis example 4

[0111] Except that the di(3-trimethoxysilylpropyl)amine in step (4) is replaced by trimethoxy[3-(methylamino)propyl]silane, the rest is the same as in Synthesis Example 1. Finally, a perfluoropolyether siloxane compound (M44)CF3(OCF2CF2) with two trimethoxysilanes at the end is obtained. r (OCF2) s OCF2CH2OCH2CH2CH2CH2CH[CON(CH3)(CH2CH2CH2Si(OCH3)3]2.

[0112] Synthesis example 5

[0113] Except that the di(3-trimethoxysilylpropyl)amine in step (4) is replaced by trimethoxy[3-(methylamino)propyl]silane, the rest is the same as in Synthesis Example 3. Finally, a perfluoropolyether siloxane compound (M45)CF3(OCF2CF2) with two trimethoxysilanes at the end is obtained. r (OCF2) s OCF2CH2OCH2CH2CH2CH2CH[CON(CH3)(CH2CH2CH2Si(OCH3)3]2.

[0114] Synthesis example 6

[0115] The average composition is CF3(OCF2CF2) r (OCF2) s Perfluoropolyether-modified alcohol of OCF2CH2OH (r+s is 35-50, number average molecular weight is 4000-5000), synthesize perfluoropolyether-based siloxane compound (M6)CF3(OCF2CF2) according to the method of Synthesis Example 1 in Patent CN113121813A r (OCF2) s OCF2CH2OCO CH2CH2CON[(CH2CH2CH2Si(OCH3)3]2.

[0116] Synthesis Example 7

[0117] The average composition is CF3(OCF2CF2) r (OCF2) sPerfluoropolyether-modified alcohol of OCF2CH2OH (r+s is 55-65, number average molecular weight is 5500-6500), synthesize perfluoropolyether-based siloxane compound (M7) CF3 (OCF2CF2) according to the method of Synthesis Example 1 in Patent CN113121813A r (OCF2) s OCF2CH2OCO CH2CH2CON[(CH2CH2CH2Si(OCH3)3]2.

[0118] Examples 1-3

[0119] Compounds M41, M42 and M43 obtained in Synthesis Examples 1-3 were mixed with hydrofluoroether (3M Company, Novec HFE7200) to a mass concentration of 20% to serve as surface treatment agents (1), (2) and (3); the surface treatment agents were deposited onto 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 above-mentioned surface treatment agent compound is deposited on each piece of chemically strengthened glass with a thickness of about 8 to 10nm by vacuum deposition. Then, the chemically strengthened glass with the deposited film is placed in an environment of 60% humidity and 120°C for 30 minutes for curing to form a surface treatment layer.

[0120] Embodiments 4 to 6

[0121] Compounds M41, M42 and M43 obtained in Synthesis Examples 1-3 were prepared with hydrofluoroether (3M Company, Novec HFE7200) to a mass concentration of 0.4% as surface treatment agent (1′), surface treatment agent (2′) and surface treatment agent (3′); using a commercially available spray coating device, surface treatment agents (1′), (2′) and (3′) were uniformly sprayed on the chemically strengthened glass at a flow rate of 50 mg / sec and a conveying 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 in an environment of 60% humidity and 120°C for 30 minutes for curing to form a surface treatment layer.

[0122] Comparative Examples 1 to 4

[0123] Compounds M44, M45, M6 and M7 obtained in Synthesis Examples 4-7 were modulated with hydrofluoroether (3M Company, Novec HFE7200) to a mass concentration of 20% as surface treatment agent (4), surface treatment agent (5), surface treatment agent (6) and surface treatment agent (7); and then a surface treatment layer was formed using the same method as in Example 1.

[0124] Comparative Examples 5 to 8

[0125] Compounds M44, M45, M6 and M7 obtained in Synthesis Examples 4-7 were modulated with hydrofluoroether (3M Company, Novec HFE7200) to a mass concentration of 0.4% as surface treatment agent (4′), surface treatment agent (5′), surface treatment agent (6′) and surface treatment agent (7′); then a surface treatment layer was formed using the same method as in Example 4.

[0126] Performance evaluation method

[0127] 1. Evaluation of hydrophobicity and oleophobicity

[0128] The contact angle of the surface treatment layer to water and the contact angle of n-hexadecane were measured using a contact angle measuring device (Contact Angle Meter CA200 produced by Kunshan Beidou Precision Instrument Co., Ltd.). The results are shown in Table 1.

[0129] 2. Determination of Slipperiness

[0130] The dynamic friction coefficient of the relative paper (Daboai) was tested using a friction coefficient meter (Dynamic and Static Friction Tester, MXD-02, produced by Jinan Languang Electromechanical Technology Co., Ltd.) under the following conditions. The results are shown in Table 1.

[0131] Contact area: 63mm×63mm;

[0132] Load: 200g

[0133] Line speed: 100mm / min

[0134] Stroke: 30mm

[0135] 3. Wear resistance evaluation

[0136] The water contact angle of the surface treated layer after rubbing was evaluated using a friction tester (Taber, 5900) under the following conditions.

[0137] (1) Steel wool wear resistance

[0138] After every 4000 back and forth strokes, the water contact angle was measured (the evaluation was terminated when the water contact angle was less than 100 degrees or the steel wool was rubbed 20,000 times or was damaged). The results are shown in Table 2.

[0139] Steel wool: BONSTAR#0000

[0140] Load: 1kg / cm 2

[0141] Travel distance: 40mm

[0142] Moving speed: 60rpm

[0143] (2) Eraser wear resistance

[0144] After every 1000 back and forth times, the water contact angle was measured (the evaluation was terminated when the water contact angle was less than 100 degrees). The results are shown in Table 3.

[0145] Eraser: Minoan MB006004, 6.0mm

[0146] Load: 1kg

[0147] Travel distance: 40mm

[0148] Moving speed: 40rpm

[0149] Table 1 Hydrophobicity, oleophobicity and slipperiness

[0150]

[0151] Table 2 Abrasion resistance of steel wool (water contact angle / °)

[0152]

[0153]

[0154] Table 3 Eraser wear resistance (water contact angle / °)

[0155]

[0156] The above are only specific embodiments of the present invention, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent replacements or modifications made based on the present invention to achieve basically the same technical effects are all included in the protection scope of the present invention.

[0157] The technical features of the above-described embodiments can be combined arbitrarily. In order to make the description concise, all possible combinations of the technical features in the above-described embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification. The above-described embodiments only express several implementation methods of the present invention, and their descriptions are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present invention, several variations and improvements can be made, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be based on the attached claims.

Claims

1. A perfluoropolyether siloxane compound represented by formula (1): R-PFPE-Z1-[X-NQ k T 2-k ]2(1) Where R is R f or Z1-[Y-NQ k T 2-k ]2 represents a group, R f Represents C 1～16 PFPE represents a divalent perfluoropolyether group; Z1 represents a trivalent organic group; X represents a carbonyl group, a sulfonyl group or an acid anhydride; T is independently a hydroxyl group, a hydrolyzable group or a hydrocarbon group at each occurrence; Q is independent at each occurrence, which is -Y-SiR 1 j R 2 3-j ; Y is independently present at each occurrence and is a divalent organic group; R 1 is, independently at each occurrence, an alkoxy group, a hydroxy group, or a group that can be hydrolyzed to a hydroxy group; R 2 Each occurrence is independently a hydrocarbon group or Q′; Q′ has the same meaning as Q; j in each Q and Q' is independently an integer selected from 0 to 3, and the sum of j is at least 1; k is independently 1 or 2.

2. A perfluoropolyether siloxane compound represented by formula (2): R-PFPE-CH2-OZ′-[CO-NQ k T 2-k ]2(2) Where R is R f or CH2-OZ′-[CO-NQ k T 2-k ]2 represents a group, R f Represents C 1～16 PFPE represents a divalent perfluoropolyether group; Z′ represents a trivalent organic group; T, independently at each occurrence, is a hydroxyl group, a hydrolyzable group, or a hydrocarbon group; Q is independent at each occurrence, which is -Y-SiR 1 j R 2 3-j ; Y is independently present at each occurrence and is a divalent organic group; R 1 is, independently at each occurrence, an alkoxy group, a hydroxy group, or a group that can be hydrolyzed to a hydroxy group; R 2 Each occurrence is independently a hydrocarbon group or Q′; Q′ has the same meaning as Q; j in each Q and Q' is independently an integer selected from 0 to 3, and the sum of j is at least 1; k is independently 1 or 2.

3. A perfluoropolyether-based silane compound represented by formula (3): R f -PFPE-CH2-O-Z′-[CO-N-(Y-SiR 1 j R 2 3-j )2]2(3) In the formula, R f Represents C 1～16 PFPE stands for divalent perfluoropolyether group (OC4F8) p -(OC3F6) q -(OC2F4) r -(OCF2) s -OC(Z)F-(CF2) t -, wherein p, q, r and s are integers of 0 to 200 respectively, the sum of p, q, r and s is at least 1, the order and number of the repeating units with p, q, r and s enclosed in parentheses are arbitrary in the formula, t is an integer of 0 to 30, Z is F or CF3; Z' represents a trivalent organic group, preferably Z' is CH2(CH2) a CH, a is an integer of 1 to 9; Y represents a divalent organic group, preferably Y is (CH2) b , b is an integer from 1 to 6; R 1 is an alkoxy group, a hydroxy group or a group that can be hydrolyzed to a hydroxy group; R 2 C 1～6 An alkyl group or a phenyl group; j is an integer from 1 to 3.

4. The perfluoropolyether-based silane compound according to claim 3, characterized in that: j is 3.

5. The perfluoropolyether-based silane compound according to claim 3, characterized in that: Z' is CH2CH2CH or CH2(CH2)3CH.

6. The perfluoropolyether-based silane compound according to claim 3, characterized in that: Y is (CH2)3.

7. The perfluoropolyether-based silane compound according to claim 3, characterized in that: R f CF3; PFPE is (OC2F4) r (OCF2) s OCF2, wherein r and s are integers of 0 to 200 respectively, the sum of r and s is at least 1, and the order of the repeating units enclosed in brackets marked with r and s in the formula is arbitrary; preferably, the sum of r and s is 20-100.

8. A method for preparing a perfluoropolyether-based silane compound of formula (3), R f -PFPE-CH2-O-Z′-[CO-N-(Y-SiR 1 j R 2 3-j )2]2(3) include: Step (1): R f -PFPE-CH2-OH reacts with excess X1CH2(CH2) in the presence of solvent 1,3-di(trifluoromethyl)benzene and strong base potassium hydroxide a-1 The etherification reaction of CH2X2 generates R f -PFPE-CH2-OCH2(CH2) a-1 CH2X2; Step (2): R f -PFPE-CH2-OCH2(CH2) a-1 CH2X2 reacts with di-tert-butyl malonate CH2[COOC(CH3)3]2 in the presence of anhydrous tetrahydrofuran and a superbase sodium hydride to generate R f -PFPE-CH2-OCH2(CH2) a CH[COOC(CH3)3]2; Step (3): R f -PFPE-CH2-OCH2(CH2) a The hydrolysis and acidification reaction of CH[COOC(CH3)3]2 generates dicarboxylic acid compound R f -PFPE-CH2-OCH2(CH2) a CH(COOH)2; Step (4): Dicarboxylic acid compound R f -PFPE-CH2-OCH2(CH2) a CH(COOH)2 reacts with acyl chloride reagent and aminosilane coupling agent NH-(Y-SiR 1 j R 2 3-j )2 to generate a perfluoropolyether-based silane compound of formula (3); Among them, R f Represents C 1～16 PFPE stands for divalent perfluoropolyether group (OC4F8) p -(OC3F6) q -(OC2F4)r-(OCF2)s-OC(Z)F-(CF2) t -, wherein p, q, r and s are integers of 0 to 200 respectively, the sum of p, q, r and s is at least 1, the order and number of the repeating units with p, q, r and s enclosed in parentheses are arbitrary in the formula, t is an integer of 0 to 30, Z is F or CF3; Z' represents a trivalent organic group, preferably Z' is CH2(CH2) a CH, a is an integer of 1 to 9; Y represents a divalent organic group, preferably Y is (CH2) b , b is an integer from 1 to 6; R 1 is an alkoxy group, a hydroxy group or a group that can be hydrolyzed to a hydroxy group; R 2 C 1～6 alkyl or phenyl; j is an integer from 1 to 3; in step (1), X1 and X2 are independently Br or Cl.

9. The method for preparing a perfluoropolyether-based silane compound according to claim 8, characterized in that: In formula (3), R f CF3; PFPE is (OC2F4) r (OCF2) s OCF2, wherein r and s are integers greater than 0 and less than 200 respectively, the sum of r and s is at least 1, and the order of the repeating units enclosed in brackets marked with r and s in the formula is arbitrary; preferably, the sum of r and s is 20-100; j is 3; Z′ is CH2CH2CH or CH2(CH2)3CH; Y is (CH2)3; in step (1), X1 and X2 are both Br.

10. The method for preparing a perfluoropolyether-based silane compound according to claim 8, characterized in that: The acyl halide reagent in step (4) is oxalyl chloride, and the aminosilane coupling agent NH-(Y-SiR 1 j R 2 3-j )2 is bis(3-trimethoxysilylpropyl)amine.

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