WO2019218339A1 - 含全氟聚醚基的硅烷化合物、其制备方法、表面处理剂及物品 - Google Patents

含全氟聚醚基的硅烷化合物、其制备方法、表面处理剂及物品 Download PDF

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WO2019218339A1
WO2019218339A1 PCT/CN2018/087473 CN2018087473W WO2019218339A1 WO 2019218339 A1 WO2019218339 A1 WO 2019218339A1 CN 2018087473 W CN2018087473 W CN 2018087473W WO 2019218339 A1 WO2019218339 A1 WO 2019218339A1
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group
independently
integer
formula
perfluoropolyether
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PCT/CN2018/087473
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English (en)
French (fr)
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陈以静
王其观
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广州优尔材料科技有限公司
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Priority to EP18918731.3A priority Critical patent/EP3798281B1/en
Priority to JP2020535120A priority patent/JP7100704B2/ja
Priority to CN202010099614.5A priority patent/CN111138652B/zh
Priority to US17/055,986 priority patent/US20210214495A1/en
Priority to CN201880000606.1A priority patent/CN109071793B/zh
Priority to KR1020207021958A priority patent/KR102268922B1/ko
Publication of WO2019218339A1 publication Critical patent/WO2019218339A1/zh
Priority to US17/019,167 priority patent/US11149042B2/en
Priority to JP2022025923A priority patent/JP2022084615A/ja

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Definitions

  • the present invention relates to the field of surface treatment agents, and more particularly to a silane compound containing a perfluoropolyether group, a process for producing the same, a surface treatment agent containing the perfluoropolyether group-containing silane compound, and an article treated using the surface treatment agent.
  • a film layer capable of forming a hydrophobic, oleophobic, antifouling, low friction coefficient, and durability property on the surface thereof is Due to the low surface energy properties of the perfluoropolyether in the molecule, on the other hand, the siloxane group in the molecule can be combined by dehydration condensation reaction on the surface of the substrate to form a chemical bond.
  • the surface treatment agent containing the composition is uniformly dispersed on the substrate by spraying or vapor deposition, and cured to form a film layer having a protective function. Since the film layer is only a few nanometers and transparent, it does not affect the surface appearance and light transmittance of the substrate.
  • the film layer prepared by the existing perfluoropolyether-based silane compound has high wear resistance, can withstand steel wire reciprocating wear resistance more than 5,000 times, even up to 10,000 times, the surface of the film layer The dynamic friction coefficient can be reduced to about 0.05.
  • the existing perfluoropolyether-containing silane compounds have problems in that the synthesis process is difficult, the number of process steps is long, the process is long, and the original material structure is special and not easy to obtain, which results in high price and high production cost.
  • the present invention provides a novel perfluoropolyether-based silane compound and a process for the preparation thereof.
  • the invention provides a perfluoropolyether-containing silane compound of formula (1):
  • Rf is F-(CF 2 ) m -(OC 4 F 8 ) p -(OC 3 F 6 ) q -(OC 2 F 4 ) r -(OCF 2 ) s -OC(Z)F-( CF 2 ) t -, where p, q, r and s are each independently an integer of 0 or more and 200 or less, and the sum of p, q, r and s is at least 1, with p, q, r and s and enclosed in parentheses
  • the order and number of occurrences of each repeating unit are arbitrary in the formula; m and t are integers of 0 or more and 30 or less, respectively, and Z is F or CF 3 ;
  • the said independently means that the letters may have the same or different values within the range of each occurrence in the chemical formula.
  • the p, q, r, and s are each independently an integer of 0 or more and 200 or less, and each of p, q, r, and s may be referred to as an integer of 0 or more and 200 or less in each of the chemical formulas. . It will be understood that the respective independent meanings below are the same.
  • X 1 is a divalent organic group
  • X 2 is a carbonyl group, a sulfur group or an acid anhydride
  • T is independently independent at each occurrence, and is a hydroxyl group, a hydrolyzable group or a hydrocarbon group;
  • Q is independent at each occurrence, and is -Y-SiR 1 j R 2 3-j ;
  • Y is independent at each occurrence and is a divalent organic group
  • R 1 is independently present at each occurrence and is an alkoxy group, a hydroxyl group or a group hydrolyzable to a hydroxyl group, wherein preferably R 1 is -OR 3 , wherein R 3 is a substituted or unsubstituted C 1-3 alkane a group, preferably R 3 is a methyl group, an ethyl group, a propyl group, an isopropyl group;
  • R 2 is independent of each occurrence, and is C 1-22 alkyl or Q'.
  • Q' has the same meaning as Q, that is, Q' is independent at each occurrence, and is also -Y-SiR 1 j R 2 3-j ; It can be understood that the following Q' and Q have the same meaning.
  • j is independent of each of Q and Q', that is, j in Q' and j in Q may be the same or different numerical values, and are integers selected from 0 to 3, and the sum of j is 1 or more;
  • k is independent of 1 or 2, preferably k is 2.
  • Rf may also be the following formula (a) or (b):
  • m and t are independent, m is an integer of 1-16, t is an integer of 0-2, r and s are independent, respectively, an integer of 1 or more and 200 or less, and the sum of p, q, r and s is 10 Above 200 or less, the order and number of existence of each repeating unit having p, q, r, and s and enclosed in parentheses are arbitrary in the formula.
  • X 1 in the above formula (1) may be a group shown below:
  • R 4 is C 1-6 alkyl or substituted C 1-6 alkyl
  • X 3 is selected from -O-, -S-, ortho, meta or p-phenylene, ortho, meta or para-benzylidene, -C(O)O-, -CONR 5 -, -O-CONR 5 -, -NR 5 -, -Si(R 6 ) 2 -, -(Si(R 6 ) 2 O) f -Si(R 6 a group in 2 - and -(CH 2 ) g -, each independently occurring, R 5 being independently a hydrogen atom, a phenyl group or a C 1-6 alkyl group, and R 6 is a C 1-6 alkyl group or a Substituted C 1-6 alkyl; X 4 is a divalent group; f is independent of each occurrence, is an integer from 1 to 100, and g is independent of each occurrence, and is an integer from 1 to 20;
  • X 4 is a group represented by -(R 7 ) a -(X 5 ) b -R 8 -, wherein:
  • R 7 is -(CH 2 ) c -, ortho, meta or p-phenylene or o-, m- or p-benzylidene; c is an integer from 1 to 20;
  • R 8 is -(CH 2 ) d -, ortho, meta or p-phenylene or o-, m- or p-benzylidene; d is an integer from 1 to 20;
  • X 5 is -(X 6 ) e -, and each of X 6 is independent of each occurrence, and is selected from -O-, -S-, ortho, meta or p-phenylene, o-, m- or p-benzylidene, -C ( O)O-, -CONR 5 -, -O-CONR 5 -, -NR 5 -, -Si(R 6 ) 2 -, -(Si(R 6 ) 2 O) f -Si(R 6 ) 2 - And a group in -(CH 2 ) g -, each independently of R 5 , is a hydrogen atom, a phenyl group or a C 1-6 alkyl group, and each of R 6 is independently independent, and is phenyl or C. 1-6 alkyl, f is independent of each occurrence, is an integer from 1 to 100, g is independent of each occurrence, and is an integer from 1 to 20; and
  • T is independently selected each time, and is selected from the group consisting of a hydroxyl group, -O(R 7 ), a C 1-12 alkyl group, a C 2-12 alkenyl group, a C 2-12 alkynyl group, and a phenyl group.
  • R 7 is a C 1-12 alkyl group, preferably each independently of T, is independently a hydroxyl group, or -O(R 7 ), and R 7 is a C 1-12 alkyl group.
  • the present invention provides a perfluoropolyether group-containing silane compound having the following chemical formula (2),
  • q, r and s are each independently an integer of 0 or more and 200 or less, and the sum of q, r and s is at least 1, and the order of existence of each repeating unit enclosed in parentheses marked with q, r or s is arbitrary in the formula.
  • m is an integer from 1 to 16, t is 0 or 1, and Z is a fluorine atom or a trifluoromethyl group;
  • X is a divalent organic group
  • T being a hydroxyl group, a hydrolyzable group or a hydrocarbon group
  • Y is independent of each occurrence, and is a divalent organic group
  • R 1 is independently present each time, and is an alkoxy group, a hydroxyl group or a group hydrolyzable to a hydroxyl group, wherein an alkoxy group is preferred, and an alkoxy group of C 1-3 is more preferred;
  • R 2 is independent of each occurrence, and is C 1-22 alkyl or Q', and Q' has the same meaning as Q;
  • j is independent of each of Q and Q', is an integer selected from 0 to 3, and the sum of j is 1 or more;
  • k is independent, 1 or 2, preferably k is 2.
  • X is a group represented by -(R 3 ) a -(X 1 ) b -R 4 -, wherein:
  • R 3 is -(CH 2 ) c -, ortho, meta or p-phenylene or o-, m- or p-benzylidene; c is an integer from 1 to 20; a is 0 or 1;
  • R 4 is -(CH 2 ) d -, ortho, meta or p-phenylene or o-, m- or p-benzylidene; d is an integer from 1 to 20;
  • X 1 is -(X 2 ) e -;
  • b is 0 or 1;
  • X 2 is independent of each occurrence, and is selected from -O-, -S-, ortho, meta or p-phenylene, o-, m- or p-benzylidene, -C(O)O-, -CONR 5 -, - a group in O-CONR 5 -, -NR 5 -, -Si(R 6 ) 2 -, -(Si(R 6 ) 2 O) f -Si(R 6 ) 2 - and -(CH 2 ) g -
  • R 5 is independently present at each time, and is a hydrogen atom, a phenyl group or a C 1-6 alkyl group.
  • Each occurrence of R 6 is independently a phenyl group or a C 1-6 alkyl group, and f is present each time. Independently, they are integers from 1 to 100, and g is independent of each occurrence, and is an integer from 1 to 20; e is an integer from 1 to 10.
  • X is a C 1-20 alkylene group, -R 3 -X 3 -R 4 - or -X 4 -R 4 -, wherein X 3 is -O-, -S- , -C(O)O-, -CONR 5 -, -O-CONR 5 -, -Si(R 6 ) 2 -, -(Si(R 6 ) 2 O) f -Si(R 6 ) 2 -, -O-(CH 2 ) h -(Si(R 6 ) 2 O) f -Si(R 6 ) 2 -, -CONR 5 -(CH 2 ) h -(Si(R 6 ) 2 O) f -Si (R 6 ) 2 -, -CONR 5 -(CH 2 ) h -(Si(R 6 ) 2 O) f -Si (R 6 ) 2 -, -CONR 5 -
  • R 3 is -(CH 2 ) c -, and R 4 is -(CH 2 ) d -, wherein c is an integer of from 1 to 20; and d is an integer of from 1 to 20.
  • X is a C 1-20 alkylene group, -(CH 2 ) c -O-(CH 2 ) d , -(CH 2 ) c -(Si(R 6 ) 2 O) f -Si(R 6 ) 2 -(CH 2 ) d -, -(CH 2 ) c -O-(CH 2 ) h -(Si(R 6 ) 2 O) f -Si(R 6 ) 2 -(CH 2 ) d - , c is an integer from 1 to 20; d is an integer from 1 to 20; each occurrence of R 6 is independently phenyl or C 1-6 alkyl; h is an integer from 1 to 20; Independently, they are integers from 1 to 100.
  • X is selected from the group consisting of -CH 2 -, -(CH 2 ) 2 -, -(CH 2 ) 3 -, -(CH 2 ) 4 -, -(CH 2 ) 6 -, -CH 2 C 6 H 4 -, -CH 2 OCH 2 -, -CH 2 O(CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 -, -CH 2 O(CH 2 ) 6 -, -CH 2 C 6 H 4 -OCH 2 -, -CONH-(CH 2 ) 3 -, -CON(CH 3 )-(CH 2 ) 3 -, -CON(Ph)-(CH 2 ) 3 -, Ph is phenyl , -CON(CH 3 )-(CH 2 ) 6 -, -CON(Ph)-(CH 2 ) 6 -, Ph is phenyl, -CON(CH 3 )-(CH 2 ) 6
  • each occurrence of T is independent, each selected from the group consisting of hydroxyl, -O(R 7 ), C 1-12 alkyl, C 2-12 alkenyl, C 2-12 alkynyl and phenyl, R 7 is C 1-12 alkyl.
  • each occurrence of T is independently independent of a hydroxyl group, or -O(R 7 ), and R 7 is a C 1-12 alkyl group.
  • j is 3.
  • the perfluoropolyether group-containing silane compound represented by the formula (2) has a number average molecular weight of from 500 to 10,000, preferably from 1,000 to 8,000, more preferably from 3,000 to 6,000.
  • the present invention provides a perfluoropolyether group-containing silane compound having the following chemical formula (3),
  • Rf is F-(CF 2 ) m -(OC 3 F 6 ) q -(OC 2 F 4 ) r -(OCF 2 ) s -OC(Z)F-(CF 2 ) t -,q,r And s are each independently an integer of 0 or more and 200 or less, and the sum of q, r, and s is at least 1, and the order of existence of each repeating unit surrounded by the parentheses of q, r, or s is arbitrary in the formula, m is An integer from 1 to 16, t is 0 or 1, and Z is a fluorine atom or a trifluoromethyl group;
  • X is a divalent organic group, preferably X is a C 1-6 alkylene group, a -CH 2 C 6 H 4 - or a substituent having a substituent on the benzene ring -CH 2 C 6 H 4 -;
  • Y 1 , Y 2 are each independently a C 1-6 alkylene group
  • Q 1 , Q 2 are each independently an alkoxy group, a hydroxyl group or a group hydrolyzable to a hydroxyl group;
  • R 1 , R 2 are each independently C 1-6 alkyl or phenyl;
  • n is an integer from 1 to 3, preferably n is 3.
  • Rf is CF 3 (OC 2 F 4 ) r (OCF 2 ) s OCF 2 , wherein r and s are each independently an integer of 0 or more and 200 or less, and the sum of r and s is at least 1.
  • the order of existence of each repeating unit enclosed by the brackets r and s is arbitrary in the formula;
  • X is C 1-6 alkylene, -CH 2 C 6 H 4 - -CH have a substituent on the benzene ring or 2 C 6 H 4 -;
  • Y 1 , Y 2 are each independently a C 1-6 alkylene group
  • Q 1 , Q 2 are each independently an alkoxy group, a hydroxyl group or a group hydrolyzable to a hydroxyl group;
  • R 1 and R 2 are each independently a C 1-6 alkyl group or a phenyl group.
  • X is -CH 2 -, -CH(CH 3 )-, -C 2 H 4 -, -C 3 H 6 -.
  • Y 1 and Y 2 in the formula (3) are -(CH 2 ) 3 -, respectively.
  • Q 1 and Q 2 are each independently a C 1-6 alkoxy group, and more preferably, Q 1 and Q 2 are independently -OCH 3 and -OCH(CH 3 ) 2 , respectively. , -OC 2 H 5 or -OC 3 H 7 .
  • the perfluoropolyether silane compound represented by the formula (3) has a number average molecular weight of from 500 to 10,000, preferably from 1,000 to 8,000, more preferably from 3,000 to 6,000.
  • the present invention also provides a method for preparing a perfluoroether-containing silane compound represented by formula (1),
  • Rf is F-(CF 2 ) m -(OC 4 F 8 ) p -(OC 3 F 6 ) q -(OC 2 F 4 ) r -(OCF 2 ) s -OC(Z)F-( CF 2 ) t -, where p, q, r and s are each independently an integer of 0 or more and 200 or less, and the sum of p, q, r and s is at least 1, with p, q, r and s and enclosed in parentheses
  • the order and number of occurrences of each repeating unit are arbitrary in the formula; m and t are integers of 0 or more and 30 or less, respectively, and Z is F or CF 3 ;
  • X 1 is a divalent organic group
  • X 2 is a carbonyl group, a sulfur group or an acid anhydride
  • T is independently independent at each occurrence, and is a hydroxyl group, a hydrolyzable group or a hydrocarbon group;
  • Q is independent at each occurrence, and is -Y-SiR 1 j R 2 3-j .
  • Y is independent at each occurrence and is a divalent organic group
  • R 1 is independently present at each occurrence and is an alkoxy group, a hydroxyl group or a group hydrolyzable to a hydroxyl group;
  • R 2 is independently independent at each occurrence, and is C 1-22 alkyl or Q′, wherein Q′ and Q have the same meaning;
  • j is independent of each of Q and Q', is an integer selected from 0 to 3, and the sum of j is 1 or more;
  • k is independent, 1 or 2.
  • the acid halide reagent is (COCl) 2 , SOCl 2 , POCl 3 , PCl 5 or SOBr 2 .
  • the aminosilane coupling agent is HNQ k T 2-k , and the meanings of Q, T, and k are the same as defined in the above formula (1).
  • the present invention provides a method for preparing a perfluoropolyether group-containing silane compound represented by formula (2),
  • the method includes:
  • R f is:
  • q, r and s are each independently an integer of 0 or more and 200 or less, and the sum of q, r and s is at least 1, and the order of existence of each repeating unit enclosed in parentheses marked with q, r or s is arbitrary in the formula.
  • m is an integer of 1 to 16, t is 0 or 1, and Z is a fluorine atom or a trifluoromethyl group;
  • X is a divalent organic group
  • T being a hydroxyl group, a hydrolyzable group or a hydrocarbon group
  • Each time Q is independent, it is -Y-SiR 1 j R 2 3-j ; Y is independent of each time, and is a divalent organic group; each time R 1 is independent, it is alkoxy, a hydroxyl group or a group hydrolyzable to a hydroxyl group, each of R 2 is independently independent, and is C 1-22 alkyl or Q′, wherein Q′ and Q have the same meaning; j is independently in each of Q and Q′, An integer selected from 0 to 3, and the sum of j is 1 or more;
  • k is independent, 1 or 2.
  • the acid halide reagent is an acid halide, preferably an acid chloride, more preferably oxalyl chloride.
  • the aminosilane coupling agent is HNQ k T 2-k , wherein Q is -Y-SiR 1 j R 2 3-j ; Y is a divalent organic group; R 1 is an alkoxy group, a hydroxyl group or a group hydrolyzable to a hydroxyl group, R 2 is a C 1-22 alkyl group or Q', wherein Q' has the same meaning as Q; j is independently in each of Q and Q', and is an integer selected from 0 to 3, j The sum of the sum is 1 or more; k is independent, and is 1 or 2.
  • the preparation of the starting material Rf-CH 2 -OX-COOH used in the foregoing reaction comprises:
  • Step 1 The compound of the formula Rf-CH 2 OH is first reacted with a base in the presence of a solvent, and then subjected to a nucleophilic substitution reaction with a compound of the formula LXG to obtain a compound of the formula Rf-CH 2 -OXG, wherein the formula LXG Wherein L is a leaving group or atom capable of undergoing a nucleophilic substitution reaction, X is a divalent organic group, and G is a group hydrolyzable to a carboxylic acid,
  • Step 2 The compound of formula Rf-CH 2 -OXG obtained by chemical conversion of the compound Rf-CH 2 -OX-COOH is of formula,
  • the base in step 1 is selected from an inorganic base or an organic base;
  • the inorganic base is preferably selected from the group consisting of LiOH, NaOH, KOH, K 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 , NaH, t-BuOK.
  • the organic base is preferably selected from the group consisting of DIPEA (N,N-diisopropylethylamine), DBU (1,8-diazabicycloundec-7-7), 1,1,3,3 At least one of tetramethyl hydrazine.
  • L is selected from a chlorine atom, a bromine atom, an iodine atom or other leaving group capable of undergoing a nucleophilic substitution reaction; and G is selected from the group consisting of an ester group, a nitrile group, an amide group or Substituting at least one of the amide groups.
  • the base in step 2 is selected from at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide and barium hydroxide.
  • the acid in step 2 is selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid.
  • the present invention provides a method for preparing a perfluoropolyether group-containing silane compound represented by formula (3),
  • the method comprises reacting Rf-CH 2 -OX-COOH with an acid halide reagent and an aminosilane coupling agent
  • Rf is F-(CF 2 ) m -(OC 3 F 6 ) q -(OC 2 F 4 ) r -(OCF 2 ) s -OC(Z)F-(CF 2 ) t -,q,r And s are each independently an integer of 0 or more and 200 or less, and the sum of q, r, and s is at least 1, and the order of existence of each repeating unit surrounded by the parentheses of q, r, or s is arbitrary in the formula, m is An integer from 1 to 16, t is 0 or 1, and Z is a fluorine atom or a trifluoromethyl group;
  • X is a divalent organic group, preferably X is a C 1-6 alkylene group, a -CH 2 C 6 H 4 - or a substituent having a substituent on the benzene ring -CH 2 C 6 H 4 -;
  • Y 1 , Y 2 are each independently a C 1-6 alkylene group
  • Q 1 , Q 2 are each independently an alkoxy group, a hydroxyl group or a group hydrolyzable to a hydroxyl group;
  • R 1 , R 2 are each independently C 1-6 alkyl or phenyl;
  • n is an integer from 1 to 3, preferably n is 3.
  • the acid halide reagent is (COCl) 2 , SOCl 2 , POCl 3 , PCl 5 or SOBr 2 .
  • the preparation of the starting material Rf-CH 2 -OX-COOH used in the foregoing reaction comprises:
  • Step 1 reacting a compound of the formula Rf-CH 2 OH with a base in the presence of a solvent, and then performing a nucleophilic substitution reaction with a compound of the formula LXG, wherein L is a leaving group capable of undergoing a nucleophilic substitution reaction Or an atom; G is a group hydrolyzable to a carboxylic acid; X is a divalent organic group, preferably X is a C 1-6 alkylene group, a -CH 2 C 6 H 4 - or a substituent on the phenyl ring -CH 2 C 6 H 4 -; obtaining an ester-based perfluoropolyether compound of the formula Rf-CH 2 -OXG,
  • Step 2 hydrolysis of the compound of formula is of formula Rf-CH 2 -OXG a carboxyl group Rf-CH 2 -OX-COOH perfluoropolyether compound,
  • Rf and X have the same meanings as defined in the above formula (3).
  • the base described in the step 1 is selected from an inorganic base or an organic base; the inorganic base is preferably at least one selected from the group consisting of LiOH, NaOH, KOH, K 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 , NaH, and t-BuOK.
  • the organic base is preferably selected from at least one of DIPEA, DBU or 1,1,3,3-tetramethylguanidine.
  • L is a chlorine atom, a bromine atom or an iodine atom
  • G is an ester group, a nitrile group, an amide group or a substituted amide group.
  • the solvent is a fluorine-containing solvent, preferably a hydrofluoroether or a fluorohydrocarbon.
  • the base in step 2 is selected from at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, and barium hydroxide.
  • the acid in step 2 is selected from the group consisting of inorganic acids, more preferably at least one selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid.
  • the aminosilane coupling agent is a bis(alkoxysilanealkyl)amine.
  • Rf is CF 3 (OC 2 F 4 ) r (OCF 2 ) s OCF 2 , wherein r and s are each independently an integer of 0 or more and 200 or less, and the sum of r and s is at least 1.
  • the order of existence of each repeating unit enclosed by the brackets r, s is arbitrary in the formula; preferably, the sum of r and s is 20-100, and more preferably, the sum of r and s is 30-60.
  • X is C 1-6 alkylene, -CH 2 C 6 H 4 - -CH have a substituent on the benzene ring or 2 C 6 H 4 -;
  • Y 1 , Y 2 are each independently a C 1-6 alkylene group
  • Q 1 , Q 2 are each independently an alkoxy group, a hydroxyl group or a group hydrolyzable to a hydroxyl group;
  • R 1 and R 2 are each independently a C 1-6 alkyl group or a phenyl group.
  • the present invention also provides a surface treatment agent comprising the perfluoropolyether silane compound represented by the above formula (1), formula (2) or formula (3), wherein the surface treatment agent further contains a fluorine solvent, preferably The fluorine solvent is a hydrofluoroether.
  • the surface treatment agent contains 0.01 to 30% by weight, preferably 0.05 to 20% by weight or 10 to 20% by weight of the above perfluoropolyether silane compound.
  • the present invention also relates to an article having a coating formed of the above surface treating agent, and having a coating surface having a water contact angle of at least 110 degrees and a dynamic friction coefficient of not more than 0.05.
  • the item may be, but is not limited to, an optical element, a display screen of a smartphone, tablet or computer.
  • the perfluoropolyether group-containing silane compound of the present invention has good hydrophobicity, oleophobicity, slipperiness, steel wool abrasion resistance and eraser abrasion resistance.
  • the preparation process of the perfluoropolyether group-containing silane compound of the present invention reduces the difficulty of synthesis, the step flow is simplified, and the production cost is greatly reduced. Mainly manifested in: the materials used are all commercially available conventional products, easy to obtain; the reaction of perfluoropolyether modification to obtain new intermediates, new intermediates and silane coupling agents are some common chemical reactions, mild conditions Easy to control; fewer steps are required for product synthesis, the separation and purification steps are simpler, and production costs are more advantageous.
  • the surface treatment agent prepared from the perfluoropolyether compound of the present invention can be used for the surface of a substrate such as glass, so that a substrate such as glass treated therewith has excellent stain resistance, fingerprint resistance, scratch resistance and abrasion resistance.
  • Fig. 1 is a nuclear magnetic resonance spectrum of the ester-based perfluoropolyether compound (M1) in Synthesis Example 1.
  • Fig. 3 is a nuclear magnetic resonance spectrum of a perfluoropolyether group-containing silane compound (A1) in Synthesis Example 1.
  • Fig. 5 is a nuclear magnetic resonance spectrum of a carboxyl perfluoropolyether compound (M4) in Synthesis Example 2.
  • Fig. 6 is a nuclear magnetic resonance spectrum of a perfluoropolyether group-containing silane compound (A2) in Synthesis Example 2.
  • Fig. 7 is a nuclear magnetic resonance spectrum of a carboxyl perfluoropolyether compound (M6) in Synthesis Example 3.
  • Fig. 8 is a nuclear magnetic resonance spectrum of a perfluoropolyether-based silane compound (A3) in Synthesis Example 3.
  • Fig. 9 is an infrared spectrum of a carboxyl perfluoropolyether compound (M2) in Synthesis Example 4.
  • the synthetic technology of existing commercial products is relatively difficult, with many steps, long process, or special material structure, which is difficult to obtain, resulting in high production cost of the products.
  • the present application obtains products with different structures through a new synthetic path, and while maintaining the comprehensive performance to meet the requirements, the synthesis difficulty is reduced, the step flow is simplified, and the production cost is relatively reduced.
  • the materials used are all commercially available conventional products, easy to obtain; (2) the reaction of perfluoropolyether modification to obtain new intermediates, new intermediates and silane coupling agents are some conventional chemical reactions The conditions are mild and easy to control; (3) fewer steps are required for product synthesis, and the separation and purification steps are simpler, so the production cost is more advantageous.
  • the present invention provides a perfluoropolyether group-containing silane compound of the formula (1):
  • Rf can also be of the following formula (a) or (b):
  • the sum of r and s is an integer of 10 or more and 200 or less;
  • m and t are independent, m is an integer of 1-16, t is an integer of 0-2, and r and s are independent, respectively, an integer of 1 or more and 200 or less, and a sum of p, q, r, and s is 10 or more.
  • p, q, r, and s are integers of 1 or more and 200 or less.
  • X 1 is a divalent organic group; preferably, X 1 is a group shown below: -R 4 -X 3 -X 4 -; wherein R 4 is a C 1-6 alkane Or substituted C 1-6 alkyl; X 3 is selected from -O-, -S-, ortho, meta or p-phenylene, ortho, meta or para-benzylidene, -C(O)O-, -CONR 5 -, -O-CONR 5 -, -NR 5 -, -Si(R 6 ) 2 -, -(Si(R 6 ) 2 O) f -Si(R 6 ) 2 - and -(CH 2 ) g a group in which R 5 is independently present at each occurrence, and is a hydrogen atom, a phenyl group or a C 1-6 alkyl group, and R 6 is a C 1-6 alkyl group or a substituted C 1-6 alky
  • X 2 is a carbonyl group (-CO-), a sulfuryl group (-SO-) or an acid anhydride.
  • T is independently a hydroxyl group, a hydrolyzable group or a hydrocarbon group at each occurrence; preferably, each T is independently selected from a hydroxyl group, -O(R 7 ), C 1-12 alkyl, C 2-12 alkenyl, C 2-12 alkynyl and phenyl, and R 7 is C 1-12 alkyl. More preferably, each occurrence of T, independently, is hydroxy, or -O(R 7 ), and R 7 is C 1-12 alkyl.
  • Q is independent at each occurrence, and is -Y-SiR 1 j R 2 3-j , wherein Y is independently independent at each occurrence, and is a divalent organic group;
  • R 1 is in each When present, each independently is an alkoxy group, a hydroxyl group or a group hydrolyzable to a hydroxyl group; preferably, R 1 is -OR 3 , wherein R 3 is a substituted or unsubstituted C 1-3 alkyl group, preferably , R 3 is a methyl group; wherein R 2 is independently independent at each occurrence, and is C 1-22 alkyl or Q′; wherein Q′ and Q have the same meaning; j is independently in each of Q and Q′, An integer selected from 0 to 3, the sum of j is 1 or more; k is independently, and is 1 or 2, and preferably k is 2.
  • the aforementioned X 4 is a group represented by -(R 7 ) a -(X 5 ) b -R 8 -; wherein R 7 is -(CH 2 ) c -, ortho, meta or pair a phenylene group or an o-, m- or p-benzylidene group; R 8 is -(CH 2 ) d -, ortho, meta or p-phenylene or o-, m- or p-benzylidene; X 5 is -(X 6 ) e -; Wherein each of X 6 is independently selected from the group consisting of -O-, -S-, ortho, meta- or p-phenylene, o-, m- or p-benzylidene, -C(O)O-, -CONR 5 -, -O-CONR 5 -, -NR 5 -, -Si(R 6 ) 2 -,
  • the perfluoropolyether group-containing silane compound represented by the above formula (1) has a number average molecular weight of from 500 to 10,000, preferably from 1,000 to 8,000, more preferably from 3,000 to 6,000.
  • the present invention also provides a process for producing a perfluoropolyether group-containing silane compound represented by the above formula (1), which comprises reacting Rf-X 1 -X 2 -OH with an acid halide reagent and an aminosilane coupling agent Generate Rf-X 1 -X 2 -NQ k T 2-k ;
  • the acid halide reagent is an acid halide, a thionyl halide or a phosphoryl halide, preferably an acid chloride, a sulfuryl chloride, a phosphoryl chloride, more preferably an acid chloride, most preferably an oxalyl chloride.
  • the aminosilane coupling agent is HNQ k T 2-k , wherein Q is -Y-SiR 1 j R 2 3-j , wherein Y is a divalent organic group; R 1 is an alkoxy group a group, a hydroxyl group or a group hydrolyzable to a hydroxyl group; preferably, R 1 is -OR 3 , wherein R 3 is a substituted or unsubstituted C 1-3 alkyl group, preferably, R 3 is a methyl group, an ethyl group , propyl or isopropyl; wherein R 2 is C 1-22 alkyl or Q'; wherein Q' has the same meaning as Q; j is independently in each of Q and Q', and is an integer selected from 0 to 3 , the sum of j is 1 or more; k is independently 1, 1 or 2, preferably k is 2; T is a hydroxyl group, a hydrolyzable group or a hydrocarbon
  • the present invention provides a perfluoropolyether group-containing silane compound represented by the following formula (2),
  • q, r and s are each independently an integer of 0 or more and 200 or less, and the sum of q, r and s is at least 1, and the order of existence of each repeating unit enclosed in parentheses marked with q, r or s is arbitrary in the formula.
  • m is an integer of 1 to 16, t is 0 or 1, and Z is a fluorine atom or a trifluoromethyl group;
  • X is a divalent organic group
  • T being a hydroxyl group, a hydrolyzable group or a hydrocarbon group
  • Y is independent of each occurrence, and is a divalent organic group
  • Each of R 1 is independently present, and is an alkoxy group, a hydroxyl group or a group hydrolyzable to a hydroxyl group;
  • R 2 is independent of each occurrence, and is C 1-22 alkyl or Q', and Q' has the same meaning as Q;
  • j is independent of each of Q and Q', is an integer selected from 0 to 3, and the sum of j is 1 or more;
  • k is independent, 1 or 2.
  • k in the above formula (2) is 2.
  • X in the above formula (2) is a group represented by -(R 3 ) a -(X 1 ) b -R 4 -, wherein R 3 is -(CH 2 ) c -, O-, m- or p-phenylene or o-, m- or p-benzylidene; R 4 is -(CH 2 ) d -, ortho, meta or p-phenylene or o-, m- or p-benzylidene; X 1 is -(X 2 e -, wherein each occurrence of X 2 is independently selected from -O-, -S-, ortho, meta or p-phenylene, ortho, meta or para-benzylidene, -C(O)O-, - CONR 5 -, -O-CONR 5 -, -NR 5 -, -Si(R 6 ) 2 -, -(Si(R 6 ) 2 O
  • X in the above formula (2) is C 1-20 alkylene, -R 3 -X 3 -R 4 - or -X 4 -R 4 -, wherein X 3 is -O- , -S-, -C(O)O-, -CONR 5 -, -O-CONR 5 -, -Si(R 6 ) 2 -, -(Si(R 6 ) 2 O) f -Si(R 6 2 -, -O-(CH 2 ) h -(Si(R 6 ) 2 O) f -Si(R 6 ) 2 -, -CONR 5 -(CH 2 ) h -(Si(R 6 ) 2 O f -Si(R 6 ) 2 -, -CONR 5 -(CH 2 ) h -(Si(R 6 ) 2 O f -Si(R 6 ) 2 -, -CONR 5 -(CH
  • R 3 is -(CH 2 ) c -, and R 4 is -(CH 2 ) d -, wherein c is an integer of 1 to 20; d is 1 to An integer of 20.
  • X is C 1-20 alkylene, -(CH 2 ) c -O-(CH 2 ) d , -(CH 2 ) c -(Si(R) 6 ) 2 O) f -Si(R 6 ) 2 -(CH 2 ) d -, -(CH 2 ) c -O-(CH 2 ) h -(Si(R 6 ) 2 O) f -Si(R 6 ) 2 -(CH 2 ) d - wherein R 6 is phenyl or C 1-6 alkyl; c is an integer from 1 to 20; d is an integer from 1 to 20; and f is an integer from 1 to 100; h is an integer of 1-20.
  • X is selected from the group consisting of -CH 2 -, -(CH 2 ) 2 -, -(CH 2 ) 3 -, -(CH 2 ) 4 -, -(CH 2 ) 6 -, -CH 2 C 6 H 4 -, -CH 2 OCH 2 -, -CH 2 O(CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 -, -CH 2 O (CH 2 ) 6 -, -CH 2 C 6 H 4 -OCH 2 -, -CONH-(CH 2 ) 3 -, -CON(CH 3 )-(CH 2 ) 3 -, -CON(Ph)-( CH 2 ) 3 -,Ph is phenyl, -CON(CH 3 )-(CH 2 ) 6 -, -CON(Ph)-(CH 2 ) 6 -, Ph is phenyl, -CON(CH 3 )-(CH 2 ) 6
  • T is independently selected each time, and is selected from a hydroxyl group, -O(R 7 ), C 1-12 alkyl group, C 2-12 alkenyl group, C 2-12.
  • R 7 is C 1-12 alkyl; more preferably, each occurrence of T, independently, is hydroxy, or -O(R 7 ), and R 7 is C 1-12 alkyl.
  • the perfluoropolyether group-containing silane compound represented by the formula (2) has a number average molecular weight of from 500 to 10,000, preferably from 1,000 to 8,000, more preferably from 3,000 to 6,000.
  • the present invention also provides a method for preparing a perfluoropolyether group-containing silane compound represented by the above formula (2), the method comprising:
  • R f is:
  • q, r and s are each independently an integer of 0 or more and 200 or less, and the sum of q, r and s is at least 1, and the order of existence of each repeating unit enclosed in parentheses marked with q, r or s is arbitrary in the formula.
  • m is an integer of 1 to 6
  • t is 0 or 1
  • Z is a fluorine atom or a trifluoromethyl group.
  • X is a divalent organic group
  • T is independent, it is a hydroxyl group, a hydrolyzable group or a hydrocarbon group.
  • Y is independent of each occurrence, and is a divalent organic group.
  • R 1 is independent of each occurrence, and is an alkoxy group, a hydroxyl group or a group capable of hydrolyzing a hydroxyl group.
  • R 2 is independent of each occurrence, and is C 1-22 alkyl or Q',
  • Q has the same meaning as Q
  • j is independent of each of Q and Q', and is an integer selected from 0 to 3, and the sum of j is 1 or more.
  • k is independent, 1 or 2.
  • the acid halide reagent is an acid halide, preferably an acid chloride, more preferably oxalyl chloride.
  • the silane coupling agent is HNQ k T 2-k , wherein Q, T, k have the same meanings as defined in the above formula (2).
  • the preparation of Rf-CH 2 -OX-COOH comprises:
  • Step 1 The compound of the formula Rf-CH 2 OH is first reacted with a base in the presence of a solvent, and then subjected to a nucleophilic substitution reaction with a compound of the formula LXG to obtain a compound of the formula Rf-CH 2 -OXG, wherein the formula LXG Wherein L is a leaving group capable of undergoing a nucleophilic substitution reaction, X is a divalent organic group, and G is a group hydrolyzable to a carboxylic acid,
  • Step 2 The compound of the formula Rf-CH 2 -OXG is chemically converted to obtain the formula
  • the base described in the foregoing step 1 is selected from an inorganic base or an organic base;
  • the inorganic base is preferably selected from the group consisting of LiOH, NaOH, KOH, K 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 At least one of NaH and t-BuOK;
  • the organic base is preferably at least one selected from the group consisting of DIPEA, DBU, and 1,1,3,3-tetramethylguanidine. More preferably, the base is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, and cesium carbonate.
  • L is selected from a chlorine atom, a bromine atom, an iodine atom or other group which can undergo a nucleophilic substitution reaction.
  • G is selected from the group consisting of an ester group, a nitrile group, an amide group or a substituted amide group.
  • the base in step 2 is selected from at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide and barium hydroxide.
  • the acid in step 2 is selected from the group consisting of inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid.
  • the present invention provides a perfluoropolyether group-containing silane compound represented by formula (3),
  • Rf is F-(CF 2 ) m -(OC 3 F 6 ) q -(OC 2 F 4 ) r -(OCF 2 ) s -OC(Z)F-(CF 2 ) t -,q , r, and s are each independently an integer of 0 or more and 200 or less, and the sum of q, r, and s is at least 1, and the order of existence of each repeating unit surrounded by the brackets of q, r, or s is arbitrary in the formula, m is an integer from 1 to 16, t is 0 or 1, and Z is a fluorine atom or a trifluoromethyl group;
  • X is a divalent organic group, preferably X is a C 1-6 alkylene group, a -CH 2 C 6 H 4 - or a substituent having a substituent on the benzene ring -CH 2 C 6 H 4 -;
  • Y 1 , Y 2 are each independently a C 1-6 alkylene group
  • Q 1 , Q 2 are each independently an alkoxy group, a hydroxyl group or a group hydrolyzable to a hydroxyl group;
  • R 1 , R 2 are each independently C 1-6 alkyl or phenyl;
  • n is an integer from 1 to 3, preferably n is 3.
  • Rf is CF 3 (OCF 2 CF 2 ) r (OCF 2 ) s OCF 2 , wherein r and s are each independently an integer of 0 or more and 200 or less, r, s And the order of existence of each repeating unit enclosed by at least 1, the brackets r and s are arbitrary in the formula; preferably, the sum of r and s is at least 10, more preferably 10 to 100, further preferably 20-80, most preferably 30-60;
  • X is C 1-6 alkylene, -CH 2 C 6 H 4 - -CH have a substituent on the benzene ring or 2 C 6 H 4 -;
  • Y 1 , Y 2 are each independently a C 1-6 alkylene group
  • Q 1 , Q 2 are each independently an alkoxy group, a hydroxyl group or a group hydrolyzable to a hydroxyl group;
  • R 1 and R 2 are each independently a C 1-6 alkyl group or a phenyl group.
  • the aforementioned r and s are each independently an integer of 0 or more and 100 or an integer of 10 to 50, and the sum of r and s is at least 10, or at least 20.
  • X in the above formula (3) is -CH 2 - or -CH(CH 3 )-.
  • Y 1 and Y 2 in the above formula (3) are -(CH 2 ) 3 -, respectively.
  • Q 1 and Q 2 are each independently a C 1-6 alkoxy group.
  • Q 1 and Q 2 in the above formula (3) are -OCH 3 , OC 2 H 5 , OC 3 H 7 , OC(CH 3 ) 2 , respectively .
  • n in the above formula (3) is 3.
  • the perfluoropolyether group-containing silane compound represented by the above formula (3) has a number average molecular weight of from 500 to 10,000, preferably from 1,000 to 8,000, more preferably from 3,000 to 6,000.
  • the present invention provides a method for preparing a perfluoropolyether group-containing silane compound represented by the above formula (3),
  • the method comprises reacting Rf-CH 2 -OX-COOH with an acid halide reagent and an aminosilane coupling agent
  • Rf is F-(CF 2 ) m -(OC 3 F 6 ) q -(OC 2 F 4 ) r -(OCF 2 ) s -OC(Z)F-(CF 2 ) t -,q,r And s are each independently an integer of 0 or more and 200 or less, and the sum of q, r, and s is at least 1, and the order of existence of each repeating unit surrounded by the parentheses of q, r, or s is arbitrary in the formula, m is An integer from 1 to 16, t is 0 or 1, Z is a fluorine atom or a trifluoromethyl group; or Rf is CF 3 (OCF 2 CF 2 ) r (OCF 2 ) s OCF 2 , wherein r and s are each independently An integer of 0 or more and 200 or less, the sum of r and s is at least 1, and the order of existence of each repeating unit surrounded by the brackets r and
  • X is a divalent organic group, preferably X is a C 1-6 alkylene group, a -CH 2 C 6 H 4 - or a substituent having a substituent on the benzene ring -CH 2 C 6 H 4 -;
  • Y 1 , Y 2 are each independently a C 1-6 alkylene group
  • Q 1 , Q 2 are each independently an alkoxy group, a hydroxyl group or a group hydrolyzable to a hydroxyl group;
  • R 1 , R 2 are each independently C 1-6 alkyl or phenyl;
  • n is an integer from 1 to 3, preferably n is 3.
  • the acid halide reagent to be used according to some preferred embodiments is not particularly limited, and for the above reaction, an acid halide, particularly an acid chloride, especially oxalyl chloride, can be preferably used.
  • Rf-CH 2 -OX-COOH preparation process comprises:
  • Step 1 reacting a compound of the formula Rf-CH 2 OH with a base in the presence of a solvent, and then performing a nucleophilic substitution reaction with a compound of the formula LXG, wherein L is a leaving group capable of undergoing a nucleophilic substitution reaction , G is a group hydrolyzable to a carboxyl group, X is a divalent organic group; and an ester-based perfluoropolyether compound of the formula Rf-CH 2 -OXG is obtained,
  • Step 2 hydrolysis of the compound of formula is of formula Rf-CH 2 -OXG a carboxyl group Rf-CH 2 -OX-COOH perfluoropolyether compound,
  • Rf, X, and G have the same meanings as in the above formula (3).
  • the base described in step 1 is selected from an inorganic base or an organic base;
  • the inorganic base is preferably selected from the group consisting of LiOH, NaOH, KOH, K 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 , NaH At least one of t-BuOK;
  • the organic base is preferably at least one selected from the group consisting of DIPEA, DBU, and 1,1,3,3-tetramethylguanidine. More preferably, the base is selected from at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate and cesium carbonate.
  • L is a chlorine atom, a bromine atom or an iodine atom.
  • X is a C 1-20 alkylene group, more preferably a C 1-6 alkylene group, a -CH 2 C 6 H 4 - or a substituent on the benzene ring. -CH 2 C 6 H 4 -.
  • G is an ester group, a nitrile group, an amide group or a substituted amide group.
  • the ester may be a methyl ester, an ethyl ester, a propyl ester, an isopropyl ester, a phenyl ester, a benzyl ester or the like.
  • the amides may be N-substituted amides or N,N-disubstituted amides.
  • examples of compounds of L-X-G include, but are not limited to:
  • the base in the aforementioned step 2 is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, and barium hydroxide.
  • the acid in the aforementioned step 2 is selected from the group consisting of inorganic acids, and examples of the inorganic acid may include hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid.
  • the acylating agent is an acid halide, preferably an acid chloride, more preferably oxalyl chloride.
  • the aminosilane coupling agent is preferably a di(alkoxysilanealkyl)amine, more preferably a di(alkoxysilanealkyl)amine.
  • the method for preparing a perfluoropolyether group-containing silane compound comprises the following steps:
  • Step 1 The compound of the formula Rf-CH 2 OH is first reacted with potassium hydroxide at room temperature, and then subjected to nucleophilic substitution with a compound of the formula BrCH 2 COOC 4 H 9 at normal temperature or under heating (preferably 25-75 ° C). to give the ester Rf-CH 2 -OCH 2 COOC 4 H 9 group of the perfluoropolyether compound of formula,
  • Rf is CF 3 (OCF 2 CF 2 ) r (OCF 2 ) s OCF 2 -, r + s is 35-85, and its number average molecular weight is 3000-8000;
  • Step 2 The ester-based perfluoropolyether compound of the formula Rf-CH 2 -OCH 2 COOC 4 H 9 is reacted with a base to be hydrolyzed, and hydrochloric acid is added to adjust the acid separation to obtain a carboxyl group of the formula Rf-CH 2 -O-CH 2 COOH.
  • Perfluoropolyether compound
  • Step 3 The carboxyperfluoropolyether compound of the formula Rf-CH 2 -O-CH 2 COOH is reacted with oxalyl chloride at a temperature of 25-50 ° C, and then at room temperature with bis(trimethylsilyl) The propyl)amine reaction is converted to give a perfluoropolyether silane compound of the formula Rf-CH 2 -O-CH 2 CON[CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] 2 .
  • the solvent to be used is not particularly limited as long as it can dissolve a solvent such as a perfluoropolyether alcohol, an ester-based perfluoropolyether compound or a carboxyl perfluoropolyether compound at normal temperature or under heating.
  • a fluorine-containing solvent such as hydrofluoroether, fluorohydrocarbon or the like is preferable, and nonafluorobutylether, nonafluorobutylmethylether, perfluorohexane, m-trifluorotoluene or the like is more preferable.
  • the preparation process of the present invention can be carried out under normal temperature or under heating.
  • the nucleophilic substitution reaction of the perfluoropolyether alcohol in step 1 can be carried out at 25-75 ° C, and preferably the acid halide reaction of step 3 can be carried out at 25-50 ° C.
  • the present invention is by reacting a compound of formula Rf-CH 2 OH with a compound of the formula LXG nucleophilic substitution reaction, where, L is a leaving group in a nucleophilic substitution reaction occurs, G is hydrolysable to carboxyl group, X is a divalent organic group; to give the formula Rf-CH 2 -OXG perfluoropolyether ester compound, and then by hydrolysis to give an intermediate of formula for the new carboxy Rf-CH 2 -OX-COOH is Perfluoropolyether compound.
  • perfluoropolyether group is bonded to the carboxyl group through the spacer X, subsequent further reaction of the carboxyl group can be easily achieved, such as obtaining the perfluoropolyether group-containing aminosilane compound of the present invention with an aminosilane coupling agent.
  • An intermediate of the formula Rf-CH 2 -OX-COOH can be used as a starting material to easily carry out further subsequent reaction of the carboxyl group, thereby obtaining various derivative compounds containing a perfluoropolyether group and a carbonyl group.
  • a carboxyl group can be reacted with an acid halide reagent to form an acylhalide
  • a carboxylic acid can be condensed with Venus to form an anhydride
  • an alcohol can be condensed to form an ester
  • an amine can be reacted to form an amide.
  • the primary amide can also be produced into a nitrile by dehydration.
  • the perfluoropolyether group-containing silane compound obtained by the present invention is a specific perfluoropolyether group-containing aminosiloxane compound, it is suitably used for a surface treatment agent.
  • the surface treatment agent may comprise a mixture of one or more of the above perfluoropolyether-based silane compounds of the present invention and a liquid medium such as an organic solvent.
  • the organic solvent may be various solvents, and the compound can be dissolved under the conditions that the solvent does not react with the compound of the present invention.
  • the organic solvent examples include a fluorine-containing solvent such as a fluorine-containing alkane, a fluorine-containing halogen alkane, a fluorine-containing aromatic hydrocarbon, and, for example, a hydrofluoroether or the like, or a combination of different solvents.
  • concentration of the perfluoropolyether-based silane compound of the present invention in the surface treating agent can be adjusted as needed, and it can be usually 0.01 to 30% by weight, preferably 0.05 to 20% by weight, more preferably 10 to 20% by weight.
  • concentrations are chosen, such as high concentration for dry coating and lower concentration for wet coating. It can also be prepared to a high concentration, and then diluted at the time of use according to the needs of the coating method.
  • a surface having a water contact angle of 110 degrees or more, preferably 115 degrees or more and a dynamic friction coefficient of less than 0.05 can be formed, as follows. Shown in the embodiment.
  • the substrate to be treated for the surface treatment agent of the present invention to form the surface treatment layer is not particularly limited. Examples thereof may include optical elements, mobile phones, tablet computers, and the like, including inorganic substrates such as glass plates, glass plates containing inorganic layers, ceramics, and the like; organic substrates such as transparent plastic substrates and transparent plastic substrates containing inorganic layers, and the like .
  • the method of forming the treatment layer is not particularly limited, and for example, a wet coating method and a dry coating method can be used.
  • a wet coating method include dip coating, spin coating, flow coating, spray coating, roll coating, and gravure coating.
  • the dry coating method include vacuum evaporation, sputtering, and CVD.
  • Specific examples of the vacuum evaporation method include resistance heating, electron beam, high frequency heating, and ion beam.
  • Examples of the CVD method include plasma CVD, optical CVD, and thermal CVD.
  • the treatment layer is formed on the substrate by a dry or wet coating method, heating, humidification, light irradiation, electron beam irradiation, or the like may be performed if necessary.
  • the thickness of the treatment layer formed by using the surface treatment agent containing the perfluoropolyether silane compound of the present invention is not particularly limited. It is preferably from 1 to 30 nm, more preferably from 3 to 20 nm, further preferably from 5 to 10 nm, depending on the dust resistance, rub resistance and optical properties of the optical element and the screen of the mobile phone or tablet computer.
  • the above substrate containing the present invention is used on a substrate such as various optical elements (antireflection film, optical filter, optical lens, spectacle lens, spectroscopic lens, spectroscope, prism, mirror, etc.) and a screen of a mobile phone, a tablet computer or the like
  • a substrate such as various optical elements (antireflection film, optical filter, optical lens, spectacle lens, spectroscopic lens, spectroscope, prism, mirror, etc.) and a screen of a mobile phone, a tablet computer or the like
  • the surface treatment agent containing the perfluoropolyether silane compound forms the treatment layer
  • adhesion of dirt such as fingerprints, skin oil, sweat, cosmetics, or moisture
  • Adhesively adhering to dirt and moisture can also be easily wiped off, and is scratch-resistant, etc., thereby providing the treatment layer with excellent durability, and can satisfy the anti-fouling and anti-fingerprint of optical components, mobile phones, tablet computers, and the like. Scratch resistance,
  • step 1
  • 0.3mL oxalyl chloride, 0.2mL DMF dissolved in 5mL 1,3-bis(trifluoromethyl)benzene was slowly added dropwise from the dropping funnel, then heated to 50 ° C and stirred for 4 hours, slowly dropped to room temperature and then added dropwise 250-mL three-neck round bottom flask containing 5 1,3-bis(trifluoromethyl)benzene, 4.2 mL diisopropylethylamine, 4 mL bis(3-trimethoxysilylpropyl)amine Stir at room temperature for 5 hours.
  • step 1
  • step 1
  • the obtained colorless liquid (M5) was placed in a 100-mL three-neck round bottom flask equipped with a thermometer and a stirrer, and 9 mL of a 20 wt% potassium hydroxide solution was added, and stirred at 115 ° C for 5 hours. After cooling to room temperature, it was made acidic with 2N hydrochloric acid, and then extracted with distilled water and tetrahydrofuran. Distillation under reduced pressure gave 2.63 g of a colorless transparent product, which is a carboxy perfluoropolyether compound (M6): CF 3 (OCF 2 CF 2 ) r (OCF 2 ) s OCF 2 CH 2 OCH 2 C 6 H 4 COOH
  • the obtained M2 can be further reacted as described in Step 3 of Synthesis Example 1 to obtain A1:CF 3 (OCF 2 CF 2 ) r (OCF 2 ) s OCF 2 CH 2 OCH 2 CON[(CH 2 CH 2 CH 2 Si(OCH 3 ) ) 3 ] 2 .
  • the synthesized compounds A1, A2 and A3 were prepared with hydrofluoroether (3M Company, Novec HFE7200) to a concentration of 20% by mass as surface treatment agent (1), surface treatment agent (2) and surface treatment agent (3);
  • the above surface treatment agent was vapor-deposited onto the chemically strengthened glass by vacuum deposition.
  • the silica was deposited on the chemically strengthened glass by a thickness of 10 nm by electron beam deposition to form a silicon dioxide film, which was deposited on each of the chemically strengthened glass by vacuum deposition.
  • Compound (D) having a thickness of about 8 to 10 nm.
  • the chemically strengthened glass with the deposited film was placed in a 60% humidity and 70 ° C environment for 2 hours to be cured to form a surface treatment layer.
  • a surface treatment layer was formed in the same manner as in Example 1 except that the surface treatment agents (1-3) prepared by substituting the commercially available surface treatment agents 1 to 3 for the compounds A1, A2 and A3 were used.
  • Control surface treatment agent 1 Optool UD 509 (produced by Daikin Industries, Ltd.)
  • Control surface treatment agent 2 Optool DSX-E (produced by Daikin Industries, Ltd.)
  • Control surface treatment agent 3 X-71-195 (Shin-Etsu Chemical Co., Ltd.)
  • the surface treatment agent was prepared in the same manner as in Example 1 except that the following compound 1 was substituted with the compound (A1), and a surface treatment layer was formed.
  • the surface treatment agent (1-3) was dissolved in hydrofluoroether (3M Company, Novec HFE7200) at a concentration of 0.4% by mass to prepare a surface treatment agent (4-6); the surface treatment was carried out using a commercially available spray coating device.
  • the agent (4-6) was uniformly spray-coated on the chemically strengthened glass at a flow rate of 50 mg/sec and a conveying linear velocity of 13 mm/sec.
  • the chemically strengthened glass surface is subjected to plasma treatment prior to coating. Then, the chemically strengthened glass with the spray treatment film was placed in a 60% humidity and 70 ° C environment for 2 hours to be cured to form a surface treatment layer.
  • the surface treatment layer formed on the surface of the substrate was evaluated by the following method, and the results are shown in Tables 1 to 3.
  • the contact angle of the surface treatment layer with respect to water and the contact angle of n-hexadecane were measured by a contact angle measuring device (Beijing Hako Company, HARKE-DWA).
  • the water contact angle of the surface treated layer after rubbing under the following conditions was evaluated using a friction tester (Taber Co., Ltd., 5900). The water contact angle was measured every 1000 times of the round trip (the evaluation was terminated when the water contact angle was less than 100 degrees or 20,000 times of friction or steel wool damage).
  • the surface treatment agent prepared by using the perfluoropolyether compound of the present invention has excellent anti-fouling, anti-fingerprint, scratch-resistance and abrasion resistance resistance to the glass substrate treated thereby, and the overall performance thereof is Better than commercially available products.
  • the preparation method of the compound of the present invention is simple in process, easy to handle and realize.

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Abstract

一种式(1)所示的含全氟聚醚基的硅烷化合物：Rf-X 1-X 2-NQ kT 2-k (1)；式中，Rf为F-(CF 2) m-(OC 4F 8) p-(OC 3F 6) q-(OC 2F 4) r-(OCF 2) s-OC(Z)F-(CF 2) t-，p、q、r和s分别为0以上200以下的整数，p、q、r和s的和至少为1，带有p、q、r和s并用括号括起的各个重复单元在顺序和数量上在式中是任意的；m和t分别为0以上、30以下的整数，Z为F或CF 3；X 1为二价有机基团；X 2为羰基、硫酰基或者酸酐；T在每次出现时分别独立，为羟基、可水解的基团或者烃基；Q在每次出现时分别独立，为-Y-SiR 1 jR 2 3-j；Y在每次出现时分别独立，为二价有机基团；R 1在每次出现时分别独立，为烷氧基、羟基或可水解为羟基的基团；R 2在每次出现时分别独立，为C 1-22烷基或Q'；Q'与Q含义相同；j在各Q和Q'中分别独立，为选自0～3的整数，j的总和为1以上；k分别独立，为1或2。还公开了一种式（2）所示的含全氟聚醚基的硅烷化合物和一种式（3）所示的含全氟聚醚基的硅烷化合物，以及三者的制备方法，含有全氟聚醚基的硅烷化合物的表面处理剂和一种具有表面处理剂形成的涂层的物品。

Description

含全氟聚醚基的硅烷化合物、其制备方法、表面处理剂及物品 技术领域
本发明涉及表面处理剂领域，特别是涉及含全氟聚醚基的硅烷化合物及其制备方法，含有该含全氟聚醚基的硅烷化合物的表面处理剂以及使用该表面处理剂处理的物品。
背景技术
在现有技术中已知含全氟聚醚基的硅烷化合物处理基材时，能够在其表面形成疏水、疏油、防污、低摩擦系数且具有耐久性等性能的膜层，一方面是由于分子中全氟聚醚的低表面能特性，另一方面分子中的硅氧烷基团能在基材表面进行脱水缩合反应形成化学键而结合。将含有该组合物的表面处理剂用喷涂或气相沉积的方式均匀分散到基材上，经加热固化就可以形成具有防护功能的膜层。由于该膜层仅数纳米且透明，不会影响基材表面外观和透光性。
虽然，现有的含全氟聚醚基的硅烷化合物制备的膜层具有较高的耐磨性，可经受钢丝绒往复耐磨5000次以上，甚至可达上万次，所述膜层的表面动摩擦系数可降低到0.05左右。但是，现有的含全氟聚醚基的硅烷化合物存在合成工艺难度大，制程步骤多，流程长，原始物料结构特殊而不易取得等 问题，从而导致其价格昂贵，生产成本高。
发明内容
针对现有技术中的技术问题，本发明提供一种新型全氟聚醚基的硅烷化合物及其制备方法。
一方面，本发明提供式(1)所示的含全氟聚醚基的硅烷化合物：
Rf-X 1-X 2-NQ kT 2-k(1)；
式中，Rf为F-(CF 2) m-(OC 4F 8) p-(OC 3F 6) q-(OC 2F 4) r-(OCF 2) s-OC(Z)F-(CF 2) t-，这里，p、q、r和s分别独立为0以上200以下的整数，p、q、r和s的和至少为1，带有p、q、r和s并用括号括起的各个重复单元的存在顺序和数量上在式中是任意的；m和t分别为0以上、30以下的整数，Z为F或CF 3；
其中，所述分别独立指所述字母在化学式中每次出现均可为其范围内相同或不同的数值。例如所述p、q、r和s分别独立为0以上200以下的整数，指p、q、r和s在化学式中每次出现均可指代为相同或不同的任意的0以上200以下的整数。可以理解的，下文中的分别独立的含义与此相同。
X 1为二价有机基团；
X 2为羰基、硫酰基或者酸酐；
T在每次出现时分别独立，为羟基、可水解的基团或者烃基；
Q在每次出现时分别独立，为-Y-SiR 1 jR 2 3-j；
Y在每次出现时分别独立，为二价有机基团；
R 1在每次出现时分别独立，为烷氧基、羟基或可水解为羟基的基团，其中优选R 1为-OR 3，式中，R 3为取代或非取代的C 1-3烷基，优选地R 3为甲基、乙基、丙基、异丙基；
R 2在每次出现时分别独立，为C 1-22烷基或Q’，Q’与Q含义相同，也即Q’在每次出现时分别独立，也为-Y-SiR 1 jR 2 3-j；可以理解的，下文中的Q’与Q 含义相同均类同。
j在各Q和Q’中分别独立，也即Q’中的j与Q中的j可为相同或不同的数值，为选自0～3的整数，j的总和为1以上；
k分别独立，为1或2，优选地，k为2。
上述式(1)中，Rf还可以为下述式(a)或(b)：
(a)：CF 3-(OC 2F 4) r-(OCF 2) s-OCF 2-
式中，r与s的和为10以上200以下的整数；
(b)：F-(CF 2) m-(OC 4F 8) p-(OC 3F 6) q-(OC 2F 4) r-(OCF 2) s-OC(Z)F-(CF 2) t-
式中，m和t分别独立，m为1-16的整数，t为0-2的整数，r和s分别独立，为1以上200以下的整数，p、q、r和s的和为10以上200以下，带有p、q、r和s并用括号括起的各个重复单元的存在顺序和数量上在式中是任意的。
上述式(1)中X 1可以为如下所示的基团：
-R 4-X 3-X 4-；
其中，R 4为C 1-6烷基或经取代的C 1-6烷基；X 3选自-O-，-S-，邻、间或对亚苯基、邻、间或对亚苄基、-C(O)O-、-CONR 5-、-O-CONR 5-、-NR 5-、-Si(R 6) 2-、-(Si(R 6) 2O) f-Si(R 6) 2-和-(CH 2) g-中的基团，R 5每次出现时分别独立，为氢原子、苯基或C 1-6烷基，R 6为C 1-6烷基或经取代的C 1-6烷基；X 4为二价基团；f每次出现时分别独立，为1～100的整数，g每次出现时分别独立，为1～20的整数；
优选地，X 4为-(R 7) a-(X 5) b-R 8-所示的基团，其中：
R 7为-(CH 2) c-、邻、间或对亚苯基或邻、间或对亚苄基；c为1～20的整数；
a为0或1；b为0或1；
R 8为-(CH 2) d-、邻、间或对亚苯基或邻、间或对亚苄基；d为1～20的整数；
X 5为-(X 6) e-，X 6每次出现时分别独立，为选自-O-、-S-、邻、间或对亚 苯基、邻、间或对亚苄基、-C(O)O-、-CONR 5-、-O-CONR 5-、-NR 5-、-Si(R 6) 2-、-(Si(R 6) 2O) f-Si(R 6) 2-和-(CH 2) g-中的基团，R 5每次出现时分别独立，为氢原子、苯基或C 1-6烷基，R 6每次出现时分别独立，为苯基或C 1-6烷基，f每次出现时分别独立，为1～100的整数，g每次出现时分别独立，为1～20的整数；e为1～10的整数。
上述式(1)中，T每次出现时分别独立，选自羟基、-O(R 7)、C 1-12烷基、C 2-12烯基、C 2-12炔基和苯基，R 7为C 1-12烷基，优选地T每次出现时分别独立，为羟基、或-O(R 7)，R 7为C 1-12烷基。
另一方面，本发明提供具有以下化学通式(2)的含全氟聚醚基的硅烷化合物，
Figure PCTCN2018087473-appb-000001
其中，Rf为
Figure PCTCN2018087473-appb-000002
q、r和s分别独立为0以上200以下的整数，q、r和s之和至少为1，标注q、r或s的括号括起来的各重复单元的存在顺序在式中是任意的，m为1-16的整数，t为0或1，Z为氟原子或三氟甲基；
X为二价有机基团；
T每次出现时分别独立，为羟基、可水解的基团或烃基；
Q每次出现时分别独立，为-Y-SiR 1 jR 2 3-j；
Y每次出现时分别独立，为二价有机基团；
R 1每次出现时分别独立，为烷氧基、羟基或可水解为羟基的基团，其中 优选为烷氧基，更优选为C 1-3的烷氧基；
R 2每次出现时分别独立，为C 1-22烷基或Q’，Q’与Q含义相同；
j在各Q和Q’中分别独立，为选自0～3的整数，j的总和为1以上；
k分别独立，为1或2，优选k为2。
上述式(2)中，优选地X为-(R 3) a-(X 1) b-R 4-所示的基团，其中：
R 3为-(CH 2) c-、邻、间或对亚苯基或邻、间或对亚苄基；c为1～20的整数；a为0或1；
R 4为-(CH 2) d-、邻、间或对亚苯基或邻、间或对亚苄基；d为1～20的整数；
X 1为-(X 2) e-；
b为0或1；
X 2每次出现时分别独立，为选自-O-、-S-、邻、间或对亚苯基、邻、间或对亚苄基、-C(O)O-、-CONR 5-、-O-CONR 5-、-NR 5-、-Si(R 6) 2-、-(Si(R 6) 2O) f-Si(R 6) 2-和-(CH 2) g-中的基团，R 5每次出现时分别独立，为氢原子、苯基或C 1-6烷基，R 6每次出现时分别独立，为苯基或C 1-6烷基，f每次出现时分别独立，为1～100的整数，g每次出现时分别独立，为1～20的整数；e为1～10的整数。
上述式(2)中，优选地X为C 1-20亚烷基、-R 3-X 3-R 4-或-X 4-R 4-，其中，X 3为-O-、-S-、-C(O)O-、-CONR 5-、-O-CONR 5-、-Si(R 6) 2-、-(Si(R 6) 2O) f-Si(R 6) 2-、-O-(CH 2) h-(Si(R 6) 2O) f-Si(R 6) 2-、-CONR 5-(CH 2) h-(Si(R 6) 2O) f-Si(R 6) 2-、-CONR 5-(CH 2) h-N(R 5)-或-CONR 5-(邻、间或对亚苯基)-Si(R 6) 2-；X 4为-S-、 -C(O)O-、-CONR 5-、-O-CONR 5-(CH 2) h-(Si(R 6) 2O) f-Si(R 6) 2-、-CONR 5-(CH 2) h-N(R 5)-或-CONR 5-(邻、间或对亚苯基)-Si(R 6) 2-；R 3为-(CH 2) c-、邻、间或对亚苯基或邻、间或对亚苄基；R 4为-(CH 2) d-、邻、间或对亚苯基或邻、间或对亚苄基；R 5每次出现时分别独立，为氢原子、苯基或C 1-6烷基，R 6每次出现时分别独立，为苯基或C 1-6烷基；h为1～20的整数；f每次出现时分别独立，为1～100的整数。
更优选地，R 3为-(CH 2) c-，R 4为-(CH 2) d-，其中，c为1～20的整数；d为1～20的整数。
进一步优选地，X为C 1-20亚烷基、-(CH 2) c-O-(CH 2) d、-(CH 2) c-(Si(R 6) 2O) f-Si(R 6) 2-(CH 2) d-、-(CH 2) c-O-(CH 2) h-(Si(R 6) 2O) f-Si(R 6) 2-(CH 2) d-，c为1～20的整数；d为1～20的整数；R 6每次出现时分别独立，为苯基或C 1-6烷基；h为1～20的整数；f每次出现时分别独立，为1～100的整数。
进一步优选地，X选自以下基团：-CH 2-、-(CH 2) 2-、-(CH 2) 3-、-(CH 2) 4-、-(CH 2) 6-、-CH 2C 6H 4-、-CH 2OCH 2-、-CH 2O(CH 2) 2-、-CH 2O(CH 2) 3-、-CH 2O(CH 2) 6-、-CH 2C 6H 4-OCH 2-、-CONH-(CH 2) 3-、-CON(CH 3)-(CH 2) 3-、-CON(Ph)-(CH 2) 3-，Ph为苯基、-CON(CH 3)-(CH 2) 6-、-CON(Ph)-(CH 2) 6-，Ph为苯基、-CONH-(CH 2) 2NH(CH 2) 3-、-CONH-(CH 2) 6NH(CH 2) 3-、-CH 2O-CONH-(CH 2) 3-、-CH 2O-CONH-(CH 2) 6-、-C(O)O-(CH 2) 3-、-C(O)O-(CH 2) 6-、-S-(CH 2) 3-、-(CH 2) 2S(CH 2) 3-、-CH 2O-(CH 2) 3Si(CH 3) 2OSi(CH 3) 2(CH 2) 2-、 -CH 2O-(CH 2) 3Si(CH 3) 2OSi(CH 3) 2OSi(CH 3) 2(CH 2) 2-、-CH 2O-(CH 2) 3Si(CH 3) 2O(Si(CH 3) 2O) 2Si(CH 3) 2(CH 2) 2-。
优选地，T每次出现时分别独立，选自羟基、-O(R 7)、C 1-12烷基、C 2-12烯基、C 2-12炔基和苯基，R 7为C 1-12烷基。
进一步优选地，T每次出现时分别独立，为羟基、或-O(R 7)，R 7为C 1-12烷基。
优选地，式(2)中的Q中，j为3。
优选地，式(2)所示的含全氟聚醚基的硅烷化合物，具有500～10,000的数均分子量，优选1000-8000，更优选为3000-6000。
又一方面，本发明提供具有以下化学通式(3)的含全氟聚醚基的硅烷化合物，
Figure PCTCN2018087473-appb-000003
其中，Rf为F-(CF 2) m-(OC 3F 6) q-(OC 2F 4) r-(OCF 2) s-OC(Z)F-(CF 2) t-，q、r、和s分别独立为0以上200以下的整数，q、r和s之和至少为1，标注q、r或s的括号括起来的各重复单元的存在顺序在式中是任意的，m为1-16的整数，t为0或1，Z为氟原子或三氟甲基；
X为二价有机基团，优选地X为C 1-6亚烷基、-CH 2C 6H 4-或苯环上有取代基的-CH 2C 6H 4-；
Y 1，Y 2分别独立地为C 1-6亚烷基；
Q 1，Q 2分别独立地为烷氧基、羟基或可水解为羟基的基团；
R 1，R 2分别独立地为C 1-6烷基或苯基；
n为1至3的整数，优选地，n为3。
优选地，式(3)中，Rf为CF 3(OC 2F 4) r(OCF 2) sOCF 2，其中，r、s分别独立为0以上200以下的整数，r、s的和至少为1，标注r、s的括号括起来的各重复单元的存在顺序在式中是任意的；
X为C 1-6亚烷基、-CH 2C 6H 4-或苯环上有取代基的-CH 2C 6H 4-；
Y 1，Y 2分别独立地为C 1-6亚烷基；
Q 1，Q 2分别独立地为烷氧基、羟基或可水解为羟基的基团；
R 1，R 2分别独立地为C 1-6烷基或苯基。
优选地，式(3)中，X为-CH 2-、-CH(CH 3)-、-C 2H 4-、-C 3H 6-。
优选地，式(3)中Y 1和Y 2分别为-(CH 2) 3-。
优选地，式(3)中，Q 1，Q 2分别独立地为C 1-6烷氧基，更优选地，Q 1，Q 2分别独立地为-OCH 3、-OCH(CH 3) 2、-OC 2H 5或-OC 3H 7。
优选地，式(3)所示的全氟聚醚基硅烷化合物的数均分子量为500～10,000，优选为1000-8000，更优选为3000-6000。
一方面，本发明还提供式(1)所示的含全氟醚基硅烷化合物的制备方法，
Rf-X 1-X 2-NQ kT 2-k(1)；
其包括：
Rf-X 1-X 2-OH+酰卤化试剂+氨基硅烷偶联剂→Rf-X 1-X 2-NQ kT 2-k
式中，Rf为F-(CF 2) m-(OC 4F 8) p-(OC 3F 6) q-(OC 2F 4) r-(OCF 2) s-OC(Z)F-(CF 2) t-，这里，p、q、r和s分别独立为0以上200以下的整数，p、q、r和s的和至 少为1，带有p、q、r和s并用括号括起的各个重复单元的存在顺序和数量上在式中是任意的；m和t分别为0以上、30以下的整数，Z为F或CF 3；
X 1为二价有机基团；
X 2为羰基、硫酰基或者酸酐；
T在每次出现时分别独立，为羟基、可水解的基团或者烃基；
Q在每次出现时分别独立，为-Y-SiR 1 jR 2 3-j，
Y在每次出现时分别独立，为二价有机基团；
R 1在每次出现时分别独立，为烷氧基、羟基或可水解为羟基的基团；
R 2在每次出现时分别独立，为C 1-22烷基或Q’，其中Q’与Q含义相同；
j在各Q和Q’中分别独立，为选自0～3的整数，j的总和为1以上；
k分别独立，为1或2。
优选地，酰卤化试剂为(COCl) 2、SOCl 2、POCl 3、PCl 5或SOBr 2。
优选地，氨基硅烷偶联剂为HNQ kT 2-k，Q、T、k的含义与上述式(1)中限定的含义相同。
另一方面，本发明还提供式(2)所示的含全氟聚醚基的硅烷化合物的制备方法，
Figure PCTCN2018087473-appb-000004
所述方法包括：
将式为Rf-CH 2-O-X-COOH的化合物与酰卤化试剂以及氨基硅烷偶联剂通过反应转化得到式(2)的含全氟聚醚基的硅烷化合物，
Figure PCTCN2018087473-appb-000005
其中，R f为：
Figure PCTCN2018087473-appb-000006
q、r和s分别独立为0以上200以下的整数，q、r和s之和至少为1，标注q、r或s的括号括起来的各重复单元的存在顺序在式中是任意的，m为1～16的整数，t为0或1，Z为氟原子或三氟甲基；
X为二价有机基团；
T每次出现时分别独立，为羟基、可水解的基团或烃基；
Q每次出现时分别独立，为-Y-SiR 1 jR 2 3-j；Y每次出现时分别独立，为二价有机基团；R 1每次出现时分别独立，为烷氧基、羟基或可水解为羟基的基团，R 2每次出现时分别独立，为C 1-22烷基或Q’，其中Q’与Q含义相同；j在各Q和Q’中分别独立，为选自0～3的整数，j的总和为1以上；
k分别独立，为1或2。
优选地，所述酰卤化试剂为酰卤，优选为酰氯，更优选为草酰氯。
优选地，所述氨基硅烷偶联剂为HNQ kT 2-k，其中Q为-Y-SiR 1 jR 2 3-j；Y为二价有机基团；R 1为烷氧基、羟基或可水解为羟基的基团，R 2为C 1-22烷基或Q’，其中Q’与Q含义相同；j在各Q和Q’中分别独立，为选自0～3的整数，j的总和为1以上；k分别独立，为1或2。
优选地，前述反应中所用起始原料Rf-CH 2-O-X-COOH的制备包括：
步骤1：在溶剂存在下使式为Rf-CH 2OH的化合物先和碱反应，再与式为L-X-G的化合物进行亲核取代反应，得到式为Rf-CH 2-O-X-G的化合物，其中式L-X-G中，L为可发生亲核取代反应的离去基团或原子，X为二价有机基团，G为可水解为羧酸的基团，
Figure PCTCN2018087473-appb-000007
步骤2：将式为Rf-CH 2-O-X-G的化合物通过化学转化得到式为Rf-CH 2-O-X-COOH的化合物，
Figure PCTCN2018087473-appb-000008
优选地，步骤1中所述碱选自无机碱或有机碱；无机碱优选选自LiOH、NaOH、KOH、K 2CO 3、Na 2CO 3、Cs 2CO 3、NaH、t-BuOK中的至少一种；有机碱优选选自DIPEA(N,N-二异丙基乙胺)、DBU(1,8-二氮杂二环十一碳-7-稀)、1,1,3,3-四甲基胍中的至少一种。
优选地，步骤1的式L-X-G化合物中，L选自：氯原子、溴原子、碘原子或其他可发生亲核取代反应的离去基团；G选自：酯基、腈基、酰胺基或取代酰胺基中的至少一种基团。
优选地，步骤2中所述碱选自氢氧化钠、氢氧化钾、氢氧化锂和氢氧化铯中的至少一种。
优选地，步骤2中所述酸选自：盐酸、硫酸、磷酸或硝酸。
又一个方面，本发明还提供式(3)所示含全氟聚醚基的硅烷化合物的制备方法，
Figure PCTCN2018087473-appb-000009
所述方法包括：使Rf-CH 2-O-X-COOH与酰卤化试剂以及氨基硅烷偶联剂反应
Figure PCTCN2018087473-appb-000010
其中，Rf为F-(CF 2) m-(OC 3F 6) q-(OC 2F 4) r-(OCF 2) s-OC(Z)F-(CF 2) t-，q、r、和s分别独立为0以上200以下的整数，q、r和s之和至少为1，标注q、r或s的括号括起来的各重复单元的存在顺序在式中是任意的，m为1-16的整数，t为0或1，Z为氟原子或三氟甲基；
X为二价有机基团，优选地X为C 1-6亚烷基、-CH 2C 6H 4-或苯环上有取代基的-CH 2C 6H 4-；
Y 1，Y 2分别独立地为C 1-6亚烷基；
Q 1，Q 2分别独立地为烷氧基、羟基或可水解为羟基的基团；
R 1，R 2分别独立地为C 1-6烷基或苯基；
n为1至3的整数，优选地，n为3。
优选地，所述酰卤化试剂为(COCl) 2、SOCl 2、POCl 3、PCl 5或SOBr 2。
优选地，前述反应中所用起始原料Rf-CH 2-O-X-COOH的制备包括：
步骤1：在溶剂存在下使式为Rf-CH 2OH的化合物先和碱反应，再与式为L-X-G的化合物进行亲核取代反应，其中，L为可发生亲核取代反应的离去基团或原子；G为可水解为羧酸的基团；X为二价有机基团，优选地X为C 1-6亚烷基、-CH 2C 6H 4-或苯环上有取代基的-CH 2C 6H 4-；得到式为Rf-CH 2-O-X-G的酯基全氟聚醚化合物，
Figure PCTCN2018087473-appb-000011
步骤2：将式为Rf-CH 2-O-X-G的化合物水解得到式为Rf-CH 2-O-X-COOH 的羧基全氟聚醚化合物，
Figure PCTCN2018087473-appb-000012
其中，Rf与X与前述式(3)中限定的含义相同。
步骤1中所述的碱选自无机碱或有机碱；无机碱优选选自LiOH、NaOH、KOH、K 2CO 3、Na 2CO 3、Cs 2CO 3、NaH、t-BuOK中的至少一种；有机碱优选选自DIPEA、DBU或1,1,3,3-四甲基胍中的至少一种。
优选地，所述式L-X-G的化合物中，L为氯原子、溴原子或碘原子；G为酯基、腈基、酰胺基或取代酰胺基团。
所述溶剂为含氟溶剂，优选为氢氟醚或氟代烃。
优选地，步骤2中的碱选自氢氧化钠、氢氧化钾、氢氧化锂、氢氧化铯中的至少一种。
优选地，步骤2中的酸选自无机酸，更优选选自盐酸、硫酸、磷酸或硝酸中的至少一种。
优选地，所述氨基硅烷偶联剂为二(烷氧基硅烷烷基)胺。
优选地，式(3)中，Rf为CF 3(OC 2F 4) r(OCF 2) sOCF 2，其中，r、s分别独立为0以上200以下的整数，r、s的和至少为1，标注r、s的括号括起来的各重复单元的存在顺序在式中是任意的；优选地r、s的和为20-100，更优选地，r、s的和为30-60。
X为C 1-6亚烷基、-CH 2C 6H 4-或苯环上有取代基的-CH 2C 6H 4-；
Y 1，Y 2分别独立地为C 1-6亚烷基；
Q 1，Q 2分别独立地为烷氧基、羟基或可水解为羟基的基团；
R 1，R 2分别独立地为C 1-6烷基或苯基。
本发明还提供一种表面处理剂，其含有上述的式(1),式(2)或式(3)所示的全氟聚醚基硅烷化合物，所述表面处理剂还含有氟溶剂，优选地，所述氟溶剂为氢氟醚。
优选地所述表面处理剂含有0.01-30wt％，优选0.05-20wt％或10-20wt％的上述全氟聚醚基硅烷化合物。
本发明还涉及具有由上述表面处理剂形成的涂层的物品，且其涂层表面水接触角至少为110度，动摩擦系数不超过0.05。
所述物品可以但不限于光学元件，智能手机、平板或电脑的显示器屏幕。
本发明的含全氟聚醚基的硅烷化合物具有良好的疏水性、疏油性、爽滑性、耐钢丝绒磨损性及耐橡皮擦磨损性。此外，本发明的含全氟聚醚基的硅烷化合物制备过程降低合成难度，步骤流程得到简化，极大的降低了生产成本。主要表现在：所使用的物料都是市售的常规产品，容易取得；全氟聚醚改性得到新中间体、新中间体与硅烷偶联剂结合的反应都是一些常规化学反应，条件温和易控制；产品合成所需步骤少，分离提纯步骤较简单，生产成本更具优势。
由本发明的全氟聚醚化合物制备的表面处理剂可以用于玻璃等基材表面，使得经其处理的玻璃等基材具有优异的抗污、抗指纹、耐刮擦以及耐磨损性能。
附图说明
图1是合成例1中酯基全氟聚醚化合物(M1)核磁共振波谱图。
图2是合成例1中羧基全氟聚醚化合物(M2)核磁共振波谱图。
图3是合成例1中全氟聚醚基的硅烷化合物(A1)核磁共振波谱图。
图4是合成例2中酯基全氟聚醚化合物(M3)核磁共振波谱图。
图5是合成例2中羧基全氟聚醚化合物(M4)核磁共振波谱图。
图6是合成例2中全氟聚醚基的硅烷化合物(A2)核磁共振波谱图。
图7是合成例3中羧基全氟聚醚化合物(M6)核磁共振波谱图。
图8是合成例3中全氟聚醚基的硅烷化合物(A3)核磁共振波谱图。
图9是合成例4中羧基全氟聚醚化合物(M2)红外光谱图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整的描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本申请的各个特定实施例在以下进行了足够详细的描述，使得具备本领域相关知识和技术的普通技术人员可实施本申请的技术方案。应当理解，还可以利用其它实施例，或者对本申请的实施例进行改进或改变。
从目前的市场和行业要求来看，现有市售产品的合成技术难度都比较高，步骤多、流程长，或者物料结构特殊，不易取得，所以导致其产品的生产成本高。针对这些问题，本申请通过新的合成路径，得到结构不同的产品，在保持综合性能满足要求的同时，降低合成难度，步骤流程得到简化，所以生产成本相对降低。主要表现在：(1)所用物料都是市售常规产品，容易取得；(2)全氟聚醚改性得到新中间体、新中间体与硅烷偶联剂结合的反应都是一些常规化学反应，条件温和易控制；(3)产品合成所需步骤少，分离提纯步骤较简单，所以生产成本更具优势。
为此，本发明提供一种式(1)所示的含全氟聚醚基的硅烷化合物：
Rf-X 1-X 2-NQ kT 2-k(1)；
上式中，Rf为
F-(CF 2) m-(OC 4F 8) p-(OC 3F 6) q-(OC 2F 4) r-(OCF 2) s-OC(Z)F(CF 2) t-，这里，p、q、r和s分别独立为0以上200以下的整数，p、q、r和s的和至少为1，带有p、q、r和s并用括号括起的各个重复单元的存在顺序和数量上在式中是任意的；m和t分别为0以上、30以下的整数，Z为F或CF 3；
Rf还可以为下述式(a)或(b)：
(a)：CF 3-(OC 2F 4) r-(OCF 2) s-OCF 2-
其中，r与s的和为10以上200以下的整数；
(b)：F-(CF 2) m-(OC 4F 8) p-(OC 3F 6) q-(OC 2F 4) r-(OCF 2) s-OC(Z)F(CF 2) t-；
其中，m和t分别独立，m为1-16的整数，t为0-2的整数，r和s分别独立，为1以上200以下的整数，p、q、r和s的和为10以上200以下，带有p、q、r和s并用括号括起的各个重复单元的存在顺序和数量上在式中是任意的。
前述式(1)中，X 1为二价有机基团；优选地，X 1为如下所示的基团：-R 4-X 3-X 4-；其中，R 4为C 1-6烷基或经取代的C 1-6烷基；X 3选自-O-，-S-，邻、 间或对亚苯基、邻、间或对亚苄基、-C(O)O-、-CONR 5-、-O-CONR 5-、-NR 5-、-Si(R 6) 2-、-(Si(R 6) 2O) f-Si(R 6) 2-和-(CH 2) g-中的基团，R 5每次出现时分别独立，为氢原子、苯基或C 1-6烷基，R 6为C 1-6烷基或经取代的C 1-6烷基；X 4为二价基团；f每次出现时分别独立，为1～100的整数，g每次出现时分别独立，为1～20的整数。
前述式(1)中，X 2为羰基(-CO-)、硫酰基(-SO-)或者酸酐。
前述式(1)中，T在每次出现时分别独立，为羟基、可水解的基团或者烃基；优选地，T在每次出现时分别独立地选自羟基、-O(R 7)、C 1-12烷基、C 2-12烯基、C 2-12炔基和苯基，R 7为C 1-12烷基。更优选地，T每次出现时分别独立，为羟基、或-O(R 7)，R 7为C 1-12烷基。
前述式(1)中，Q在每次出现时分别独立，为-Y-SiR 1 jR 2 3-j，其中Y在每次出现时分别独立，为二价有机基团；R 1在每次出现时分别独立，为烷氧基、羟基或可水解为羟基的基团；优选地，R 1为-OR 3，其中，R 3为取代或非取代的C 1-3烷基，优选地，R 3为甲基；其中，R 2在每次出现时分别独立，为C 1-22烷基或Q’；其中Q’与Q含义相同；j在各Q和Q’中分别独立，为选自0～3的整数，j的总和为1以上；k分别独立，为1或2，优选地k为2。
根据一些优选的实施方式，前述X 4为-(R 7) a-(X 5) b-R 8-所示的基团；其中，R 7为-(CH 2) c-、邻、间或对亚苯基或邻、间或对亚苄基；R 8为-(CH 2) d-、邻、间或对亚苯基或邻、间或对亚苄基；X 5为-(X 6) e-；其中X 6每次出现时分别独立，为选自-O-、-S-、邻、间或对亚苯基、邻、间或对亚苄基、-C(O)O-、-CONR 5-、-O-CONR 5-、-NR 5-、-Si(R 6) 2-、-(Si(R 6) 2O) f-Si(R 6) 2-和-(CH 2) g-中的基团；R 5每次出现时分别独立，为氢原子、苯基或C 1-6烷基；R 6每次出现时分别独立，为苯基或C 1-6烷基；f每次出现时分别独立，为1～100的整数；g每次出现时分别独立，为1～20的整数；c为1～20的整数；d为1～20的整数；e为1～10的整数；a为0或1；b为0或1。
根据一些优选实施方式，前述式(1)所示的含全氟聚醚基的硅烷化合物具有500～10,000的数均分子量，优选1000-8000，更优选3000-6000的数均分子量。
本发明还提供前述式(1)所示的含全氟聚醚基的硅烷化合物的制备方法，所述方法包括将Rf-X 1-X 2-OH与酰卤化试剂以及氨基硅烷偶联剂反应生成Rf-X 1-X 2-NQ kT 2-k；
Rf-X 1-X 2-OH+酰卤化试剂+氨基硅烷偶联剂→Rf-X 1-X 2-NQ kT 2-k
根据一些优选实施方式，所述酰卤化试剂为酰卤、亚硫酰卤或磷酰卤，优选为酰氯、硫酰氯、磷酰氯，更优选为酰氯，最优选为草酰氯。
根据一些优选实施方式，所述氨基硅烷偶联剂为HNQ kT 2-k，其中Q为-Y-SiR 1 jR 2 3-j，其中Y为二价有机基团；R 1为烷氧基、羟基或可水解为羟基的基团；优选地，R 1为-OR 3，其中，R 3为取代或非取代的C 1-3烷基，优选地，R 3为甲基、乙基、丙基或异丙基；其中，R 2为C 1-22烷基或Q’；其中Q’与Q含义相同；j在各Q和Q’中分别独立，为选自0～3的整数，j的总和为1以上；k分别独立，为1或2，优选地k为2；T为羟基、可水解的基团或者烃基；优选地，T选自羟基、-O(R 7)、C 1-12烷基、C 2-12烯基、C 2-12炔基和苯基，R 7为C 1-12烷基；更优选地，T为羟基或-O(R 7)，R 7为C 1-12烷基。
根据一些优选实施方式，本发明提供如下式(2)所示的含全氟聚醚基的硅烷化合物，
Figure PCTCN2018087473-appb-000013
其中，Rf为
Figure PCTCN2018087473-appb-000014
q、r和s分别独立为0以上200以下的整数，q、r和s之和至少为1，标注q、r或s的括号括起来的各重复单元的存在顺序在式中是任意的，m为1～16的整数，t为0或1，Z为氟原子或三氟甲基；
X为二价有机基团；
T每次出现时分别独立，为羟基、可水解的基团或烃基；
Q每次出现时分别独立，为-Y-SiR 1 jR 2 3-j；
Y每次出现时分别独立，为二价有机基团；
R 1每次出现时分别独立，为烷氧基、羟基或可水解为羟基的基团；
R 2每次出现时分别独立，为C 1-22烷基或Q’，Q’与Q含义相同；
j在各Q和Q’中分别独立，为选自0～3的整数，j的总和为1以上；
k分别独立，为1或2。
根据更优选的实施方式，前述式(2)中k为2。
根据一些优选的实施方式，前述式(2)中X为-(R 3) a-(X 1) b-R 4-所示的基团，其中，R 3为-(CH 2) c-、邻、间或对亚苯基或邻、间或对亚苄基；R 4为-(CH 2) d-、邻、间或对亚苯基或邻、间或对亚苄基；X 1为-(X 2) e-，其中X 2每次出现时分别独立，为选自-O-、-S-、邻、间或对亚苯基、邻、间或对亚苄基、-C(O)O-、-CONR 5-、-O-CONR 5-、-NR 5-、-Si(R 6) 2-、-(Si(R 6) 2O) f-Si(R 6) 2-和-(CH 2) g-中的基团，其中R 5每次出现时分别独立，为氢原子、苯基或C 1-6烷基；R 6每次出现时分别独立，为苯基或C 1-6烷基；f每次出现时分别独立，为1～100的整数；g每次出现时分别独立，为1～20的整数；c为1～20的整数；d为1～20的整数；e为1～10的整数；a为0或1；b为0或1。
根据一些优选的实施方式，前述式(2)中X为C 1-20亚烷基、-R 3-X 3-R 4-或-X 4-R 4-，其中，X 3为-O-、-S-、-C(O)O-、-CONR 5-、-O-CONR 5-、-Si(R 6) 2-、 -(Si(R 6) 2O) f-Si(R 6) 2-、-O-(CH 2) h-(Si(R 6) 2O) f-Si(R 6) 2-、-CONR 5-(CH 2) h-(Si(R 6) 2O) f-Si(R 6) 2-、-CONR 5-(CH 2) h-N(R 5)-或-CONR 5-(邻、间或对亚苯基)-Si(R 6) 2-；X 4为-S-、-C(O)O-、-CONR 5-、-O-CONR 5-(CH 2) h-(Si(R 6) 2O) f-Si(R 6) 2-、-CONR 5-(CH 2) h-N(R 5)-或-CONR 5-(邻、间或对亚苯基)-Si(R 6) 2-；其中R 3为-(CH 2) c-、邻、间或对亚苯基或邻、间或对亚苄基；R 4为-(CH 2) d-、邻、间或对亚苯基或邻、间或对亚苄基；R 5为氢原子、苯基或C 1-6烷基；R 6为苯基或C 1-6烷基；c为1～20的整数；d为1～20的整数；f为1～100的整数；h为1～20的整数。
根据一些优选的实施方式，前述式(2)中，R 3为-(CH 2) c-，R 4为-(CH 2) d-，其中，c为1～20的整数；d为1～20的整数。
根据一些优选的实施方式，前述式(2)中，X为C 1-20亚烷基、-(CH 2) c-O-(CH 2) d、-(CH 2) c-(Si(R 6) 2O) f-Si(R 6) 2-(CH 2) d-、-(CH 2) c-O-(CH 2) h-(Si(R 6) 2O) f-Si(R 6) 2-(CH 2) d-，其中，R 6为苯基或C 1-6烷基；c为1～20的整数；d为1～20的整数；f为1～100的整数；h为1～20的整数。
根据一些优选的实施方式，前述式(2)中，X选自以下基团：-CH 2-、-(CH 2) 2-、-(CH 2) 3-、-(CH 2) 4-、-(CH 2) 6-、-CH 2C 6H 4-、-CH 2OCH 2-、-CH 2O(CH 2) 2-、-CH 2O(CH 2) 3-、-CH 2O(CH 2) 6-、-CH 2C 6H 4-OCH 2-、-CONH-(CH 2) 3-、-CON(CH 3)-(CH 2) 3-、-CON(Ph)-(CH 2) 3-，Ph为苯基、-CON(CH 3)-(CH 2) 6-、-CON(Ph)-(CH 2) 6-，Ph为苯基、-CONH-(CH 2) 2NH(CH 2) 3-、-CONH-(CH 2) 6NH(CH 2) 3-、-CH 2O-CONH-(CH 2) 3-、-CH 2O-CONH-(CH 2) 6-、 -C(O)O-(CH 2) 3-、-C(O)O-(CH 2) 6-、-S-(CH 2) 3-、-(CH 2) 2S(CH 2) 3-、-CH 2O-(CH 2) 3Si(CH 3) 2OSi(CH 3) 2(CH 2) 2-、-CH 2O-(CH 2) 3Si(CH 3) 2OSi(CH 3) 2OSi(CH 3) 2(CH 2) 2-、-CH 2O-(CH 2) 3Si(CH 3) 2O(Si(CH 3) 2O) 2Si(CH 3) 2(CH 2) 2-。
根据一些优选实施方式，前述式(2)中，T每次出现时分别独立，选自羟基、-O(R 7)、C 1-12烷基、C 2-12烯基、C 2-12炔基和苯基，R 7为C 1-12烷基；更优选地，T每次出现时分别独立，为羟基、或-O(R 7)，R 7为C 1-12烷基。
根据一些优选实施方式，Q所为的-Y-SiR 1 jR 2 3-j中，j为3。
根据一些优选实施方式，式(2)所示的含全氟聚醚基的硅烷化合物具有500～10,000的数均分子量，优选1000-8000，更优选3000-6000的数均分子量。
本发明还提供前述式(2)所示的含全氟聚醚基的硅烷化合物的制备方法，所述方法包括：
将式为Rf-CH 2-O-X-COOH的化合物与酰卤化试剂以及氨基硅烷偶联剂通过反应转化得到式(2)的含全氟聚醚基的硅烷化合物，
Figure PCTCN2018087473-appb-000015
其中，R f为：
Figure PCTCN2018087473-appb-000016
q、r和s分别独立为0以上200以下的整数，q、r和s之和至少为1，标注q、r或s的括号括起来的各重复单元的存在顺序在式中是任意的，m为1～6的整数，t为0或1，Z为氟原子或三氟甲基，
X为二价有机基团，
T每次出现时分别独立，为羟基、可水解的基团或烃基，
Q每次出现时分别独立，为-Y-SiR 1 jR 2 3-j，
Y每次出现时分别独立，为二价有机基团，
R 1每次出现时分别独立，为烷氧基、羟基或可水解羟基的基团，
R 2每次出现时分别独立，为C 1-22烷基或Q’，
Q’与Q含义相同，
j在各Q和Q’中分别独立，为选自0～3的整数，j的总和为1以上，
k分别独立，为1或2。
根据一些优选的实施方式，所述酰卤化试剂为酰卤，优选为酰氯，更优选为草酰氯。
根据一些优选的实施方式，所述硅烷偶联剂为HNQ kT 2-k，其中Q、T、k的含义与前述式(2)中限定的含义相同。
根据一些优选的实施方式，Rf-CH 2-O-X-COOH的制备过程包括：
步骤1：在溶剂存在下使式为Rf-CH 2OH的化合物先和碱反应，再与式为L-X-G的化合物进行亲核取代反应，得到式为Rf-CH 2-O-X-G的化合物，其中式L-X-G中，L为可发生亲核取代反应的离去基团，X为二价有机基团，G为可水解为羧酸的基团，
Figure PCTCN2018087473-appb-000017
步骤2：将式为Rf-CH 2-O-X-G的化合物通过化学转化得到式为
Rf-CH 2-O-X-COOH的化合物，
Figure PCTCN2018087473-appb-000018
根据一些优选的实施方式，前述步骤1中所述的所述碱选自无机碱或有机碱；无机碱优选选自LiOH、NaOH、KOH、K 2CO 3、Na 2CO 3、Cs 2CO 3、NaH、t-BuOK中的至少一种；有机碱优选选自DIPEA、DBU、1,1,3,3-四甲基胍中的至少一种。更优选地碱选自氢氧化钠、氢氧化钾、氢氧化锂、氢氧化铯、碳酸钠、碳酸钾和碳酸铯中的至少一种。
根据一些优选的实施方式，前述步骤1的式L-X-G的化合物中，L选自：氯原子、溴原子、碘原子或其他可发生亲核取代反应的基团。
根据一些优选实施方式，前述步骤1的式L-X-G的化合物中，G选自：酯基、腈基、酰胺基或取代酰胺的基团。
根据一些优选的实施方式，步骤2中所述碱选自氢氧化钠、氢氧化钾、氢氧化锂和氢氧化铯中的至少一种。
根据一些优选的实施方式，步骤2中所述酸选自：盐酸、硫酸、磷酸、硝酸等无机酸。
根据一些优选实施方式，本发明提供式(3)所示的含全氟聚醚基的硅烷化合物，
Figure PCTCN2018087473-appb-000019
其中，其中，Rf为F-(CF 2) m-(OC 3F 6) q-(OC 2F 4) r-(OCF 2) s-OC(Z)F-(CF 2) t-，q、r、和s分别独立为0以上200以下的整数，q、r和s之和至少为1，标注q、r或s的括号括起来的各重复单元的存在顺序在式中是任意的，m为1-16的整 数，t为0或1，Z为氟原子或三氟甲基；
X为二价有机基团，优选地X为C 1-6亚烷基、-CH 2C 6H 4-或苯环上有取代基的-CH 2C 6H 4-；
Y 1，Y 2分别独立地为C 1-6亚烷基；
Q 1，Q 2分别独立地为烷氧基、羟基或可水解为羟基的基团；
R 1，R 2分别独立地为C 1-6烷基或苯基；
n为1至3的整数，优选地，n为3。
根据更优选的实施方式，式(3)中，Rf为CF 3(OCF 2CF 2) r(OCF 2) sOCF 2，其中，r、s分别独立为0以上200以下的整数，r、s的和至少为1，标注r、s的括号括起来的各重复单元的存在顺序在式中是任意的；优选的是r、s的和至少为10，更优选为10-100，进一步优选为20-80，最优选为30-60；
X为C 1-6亚烷基、-CH 2C 6H 4-或苯环上有取代基的-CH 2C 6H 4-；
Y 1，Y 2分别独立地为C 1-6亚烷基；
Q 1，Q 2分别独立地为烷氧基、羟基或可水解为羟基的基团；
R 1，R 2分别独立地为C 1-6烷基或苯基。
根据一些优选实施方式，前述r、s分别独立为0以上100以下的整数或10-50的整数，r、s的和至少为10，或至少为20。
根据一些优选实施方式，前述式(3)中X为-CH 2-或-CH(CH 3)-。
根据一些优选实施方式，前述式(3)中Y 1和Y 2分别为-(CH 2) 3-。
根据一些优选实施方式，前述式(3)中Q 1，Q 2分别独立地为C 1-6烷氧 基。
根据一些优选实施方式，前述式(3)中Q 1，Q 2分别为-OCH 3、OC 2H 5、OC 3H 7、OC(CH 3) 2。
根据一些优选实施方式，前述式(3)中n为3。
根据一些优选实施方式，前述式(3)所示含全氟聚醚基的硅烷化合物的数均分子量为500～10,000，优选为1000-8000，更优选为3000-6000。
根据一些优选实施方式，本发明提供前述式(3)所示含全氟聚醚基的硅烷化合物的制备方法，
Figure PCTCN2018087473-appb-000020
所述方法包括：使Rf-CH 2-O-X-COOH与酰卤化试剂以及氨基硅烷偶联剂反应
Figure PCTCN2018087473-appb-000021
其中，Rf为F-(CF 2) m-(OC 3F 6) q-(OC 2F 4) r-(OCF 2) s-OC(Z)F-(CF 2) t-，q、r、和s分别独立为0以上200以下的整数，q、r和s之和至少为1，标注q、r或s的括号括起来的各重复单元的存在顺序在式中是任意的，m为1-16的整数，t为0或1，Z为氟原子或三氟甲基；或者Rf为CF 3(OCF 2CF 2) r(OCF 2) sOCF 2，其中，r、s分别独立为0以上200以下的整数，r、s的和至少为1，标注r、s的括号括起来的各重复单元的存在顺序在式中是任意的；优选的是r、s的和至少为10，更优选为10-100，进一步优选为20-80，最优选为30-60；
X为二价有机基团，优选地X为C 1-6亚烷基、-CH 2C 6H 4-或苯环上有取代 基的-CH 2C 6H 4-；
Y 1，Y 2分别独立地为C 1-6亚烷基；
Q 1，Q 2分别独立地为烷氧基、羟基或可水解为羟基的基团；
R 1，R 2分别独立地为C 1-6烷基或苯基；
n为1至3的整数，优选地，n为3。
根据一些优选的实施方式所使用的酰卤化试剂没有特别限定，对于上述反应，可以优选使用酰卤，特别是酰氯，尤其是草酰氯。
根据一些实施方式，Rf-CH 2-O-X-COOH的制备过程包括：
步骤1：在溶剂存在下使式为Rf-CH 2OH的化合物先和碱反应，再与式为L-X-G的化合物进行亲核取代反应，其中，L为可发生亲核取代反应的离去基团，G为可水解为羧基的基团，X为二价有机基团；得到式为Rf-CH 2-O-X-G的酯基全氟聚醚化合物，
Figure PCTCN2018087473-appb-000022
步骤2：将式为Rf-CH 2-O-X-G的化合物水解得到式为Rf-CH 2-O-X-COOH的羧基全氟聚醚化合物，
Figure PCTCN2018087473-appb-000023
其中，Rf、X、G与前述式(3)中的含义相同。
根据一些优选实施方式，步骤1中所述的所述碱选自无机碱或有机碱；无机碱优选选自LiOH、NaOH、KOH、K 2CO 3、Na 2CO 3、Cs 2CO 3、NaH、t-BuOK中的至少一种；有机碱优选选自DIPEA、DBU、1,1,3,3-四甲基胍中的至少一 种。更优选碱选自：氢氧化钠、氢氧化钾、氢氧化锂、氢氧化铯、碳酸钠、碳酸钾和碳酸铯中的至少一种。
根据一些优选实施方式，前述式L-X-G的化合物中，L为氯原子、溴原子或碘原子。
根据一些优选实施方式，前述式L-X-G的化合物中，X为C 1-20亚烷基，更优选为C 1-6亚烷基，-CH 2C 6H 4-或苯环上有取代基的-CH 2C 6H 4-。
根据一些优选实施方式，所述式L-X-G的化合物中，G为酯基、腈基、酰胺基或取代酰胺基团。进一步地，所述酯的例子可以是甲酯、乙酯、丙酯、异丙酯、苯酯、苄酯等。酰胺类的例子可以是N-取代酰胺或N,N-二取代酰胺。
根据一些优选实施方式，L-X-G的化合物的例子包括但不限于：
Figure PCTCN2018087473-appb-000024
根据一些优选方式，前述步骤2中的碱选自氢氧化钠、氢氧化钾、氢氧化锂、氢氧化铯中的至少一种。
根据一些优选实施方式，前述步骤2中的酸选自无机酸，无机酸的例子可以包括盐酸、硫酸、磷酸或硝酸。
根据一些优选实施方式，所述酰化试剂是酰卤，优选为酰氯，更优选为草酰氯。
根据一些优选实施方式，所述氨基硅烷偶联剂，优选为二(烷氧基硅烷烷基)胺，更优选为二(烷氧基硅烷烷基)胺。
根据本发明的一个比较优选的实施方式，制备含全氟聚醚基的硅烷化合物的制备方法包括以下步骤：
步骤1：使式为Rf-CH 2OH的化合物先和氢氧化钾在室温反应，再与式为BrCH 2COOC 4H 9的化合物在常温或加热下(优选25-75℃)进行亲核取代反应，得到式为Rf-CH 2-OCH 2COOC 4H 9的酯基全氟聚醚化合物，
Figure PCTCN2018087473-appb-000025
Rf为CF 3(OCF 2CF 2) r(OCF 2) sOCF 2-，r+s为35-85，其数均分子量为3000-8000；
步骤2：将式为Rf-CH 2-OCH 2COOC 4H 9的酯基全氟聚醚化合物与碱反应水解，加盐酸调节酸性分离后得到式为Rf-CH 2-O-CH 2COOH羧基全氟聚醚化合物，
Figure PCTCN2018087473-appb-000026
步骤3：将所述式为Rf-CH 2-O-CH 2COOH的羧基全氟聚醚化合物与草酰氯在25-50℃温度下反应，然后在室温下与二(三甲基甲硅烷基丙基)胺反应转化得到式为Rf-CH 2-O-CH 2CON[CH 2CH 2CH 2Si(OCH 3) 3] 2的全氟聚醚硅烷化合物。
Figure PCTCN2018087473-appb-000027
本发明的制备过程中，所使用的溶剂没有特别限制，只要能够在常温或加热条件下溶解全氟聚醚醇、酯基全氟聚醚化合物、羧基全氟聚醚化合物等的溶剂即可，优选为含氟溶剂，如氢氟醚，氟代烃等，更优选为九氟丁基乙醚、九氟丁基甲醚、全氟己烷、间三氟甲苯等。
本发明的制备过程可以在常温或加热条件下进行。优选在步骤1的全氟聚醚醇的亲核取代反应可以在25-75℃进行，优选步骤3的酰卤化反应可以在25-50℃下进行。
如上所述，本发明通过使式为Rf-CH 2OH的化合物与式为L-X-G的化合物进行亲核取代反应，其中，L为可发生亲核取代反应的离去基团，G为可水解为羧基的基团，X为二价有机基团；得到式为Rf-CH 2-O-X-G的酯基全氟聚醚化合物，再通过水解得到式为Rf-CH 2-O-X-COOH的全新中间体羧基全氟聚醚化合物。由于全氟聚醚基通过间隔基X与羧基相连，因此，使得羧基的后续进一步反应变得容易实现，如与氨基硅烷偶联剂得到本发明的含全氟聚醚基的氨基硅烷化合物。式为Rf-CH 2-O-X-COOH的中间体可以作为起始原料容易地进行羧基的进一步后续反应，从而得到各种含全氟聚醚基和羰基的衍生化合物。例如羧基可与酰卤试剂反应生成酰卤(acylhalide),与羧酸跟金星缩合反应生成酐，与醇类缩合生成酯，与胺类反应生成酰胺，一级酰胺还可通过脱水制备成腈。
由于本发明得到的含全氟聚醚基的硅烷化合物是特定的含全氟聚醚基的 氨基硅氧烷化合物，因此适合用于表面处理剂。表面处理剂可以包含本发明的上述全氟聚醚基的硅烷化合物的一种或多种的混合物和诸如有机溶剂等液体介质。有机溶剂可以是各种溶剂，在所述溶剂不与本发明的化合物发生反应的条件下，能够溶解所述化合物。所述有机溶剂的例子包括含氟溶剂，如含氟烷烃、含氟卤烷烃、含氟芳香烃和，例如氢氟醚等，也可以是不同溶剂的组合。本发明的含全氟聚醚基硅烷化合物在表面处理剂中的浓度可以根据需要调节，通常可以是0.01-30wt％，较好是0.05-20wt％，更优选是10-20wt％。根据所采用的涂布方式不同，选择不同的浓度，如高浓度适合干式涂布，较低浓度适合湿式涂布。也可以制备成高浓度，再根据涂布方式的需要在使用时进行稀释。
当用本发明的表面处理剂处理表面时，即使所得的层仅有几个纳米的厚度，也可形成水接触角为110度以上，优选为115度以上，动摩擦系数小于0.05的表面，如随后的实施例中所示。
用于本发明的表面处理剂进行处理以形成表面处理层的基材没有特别限制。其例子可以包括光学元件、手机、平板计算机等，包括无机基材，如玻璃板、含有无机层的玻璃板和陶瓷等；有机基材如透明塑料基材和含有无机层的透明塑料基材等。
所述形成处理层的方法没有特别限制，例如可以使用湿式涂布法和干式涂布法。湿式涂布法的例子包括浸渍涂布、旋涂、流涂、喷涂、辊涂和照相凹版式涂布等方法。干式涂布法的例子包括真空蒸发、溅射和CVD等方法。 真空蒸发法的具体例子包括电阻加热、电子束、高频加热和离子束等方法。CVD法的例子包括等离子体CVD、光学CVD和热CVD等方法。
通过干式或湿式涂布法在所述基材上形成处理层之后，如果需要，可以进行加热、增湿、光辐射、电子束辐射等。
通过使用含有本发明的全氟聚醚基硅烷化合物的表面处理剂形成的处理层的厚度没有特别限制。根据光学元件以及手机、平板计算机的屏幕的防尘、耐擦性和光学性能，优选为1-30nm，更优选为3-20nm，进一步地为5-10nm。
当在基材例如各种光学元件(抗反射膜、光学滤镜、光学透镜、眼镜镜片、分光镜片、分光镜、棱镜、镜子等)以及手机、平板计算机等的屏幕上使用含有本发明的上述含全氟聚醚基硅烷化合物的表面处理剂形成处理层时，可以防止诸如指纹、皮肤油、汗、化妆品等污垢或湿气的粘附而不劣化所述光学元件及屏幕的光学特性，即使粘附上污垢和湿气，也能容易地擦掉，而且耐刮擦等，由此使所述处理层具有优异的耐用性，能够满足光学元件以及手机、平板计算机等对抗污、抗指纹、耐刮擦、高爽滑度和耐磨持久性的要求。
实施例
合成例1
依据以下步骤合成含有全氟聚醚基的硅烷化合物A1
步骤1：
在备有搅拌器的100-mL三口圆底烧瓶中加入10g平均组成为 CF 3(OCF 2CF 2) r(OCF 2) sOCF 2CH 2OH(r、s之和为35-42)的全氟聚醚改性醇(数均分子量为3500～4000)、15mL 1,3-二(三氟甲基)苯和5mL乙二醇二甲醚、2.6g 50wt％的氢氧化钾溶液，室温下搅拌3小时。然后向反应瓶依序加入3.8mL溴乙酸叔丁酯、0.42g四丁基溴化铵，在50℃下搅拌5小时。经水萃取和减压蒸馏得到无色透明产物9.6g，即为酯基全氟聚醚化合物(M1)：CF 3(OCF 2CF 2) r(OCF 2) sOCF 2CH 2OCH 2COOC 4H 9
以核磁共振波谱仪鉴定，其新增结构的特征 1H化学位移如下表所示
Figure PCTCN2018087473-appb-000028
步骤2：
在装有温度计和搅拌器的100-mL三口圆底烧瓶中加入9.6g步骤1得到的酯基全氟聚醚化合物(M1)、17g 10wt％的氢氧化钾溶液，在100℃搅拌3小时。降至室温，加入10mL四氢呋喃，并用2N盐酸调整至酸性后加入30mL氢氟醚HFE-7200(3M公司生产)，搅拌。移除非氟相(即上层溶液)，氟相以2N盐酸洗涤2遍，最后减压蒸馏得到无色透明产物9.0g，即为羧基全氟聚醚化合物(M2)：CF 3(OCF 2CF 2) r(OCF 2) sOCF 2CH 2OCH 2COOH
以核磁共振波谱仪鉴定，其新增结构的特征 1H化学位移如下表所示
Figure PCTCN2018087473-appb-000029
步骤3
在装有滴液漏斗、温度计和搅拌器的100mL四口圆底烧瓶中加入9.0g步骤2得到的羧基全氟聚醚化合物(M2)、15mL 1,3-二(三氟甲基)苯溶解、0.3mL草酰氯，0.2mL DMF溶于5mL 1,3-二(三氟甲基)苯由滴液漏斗缓慢滴加进去，然后升温到50℃搅拌4小时，降至室温后缓慢滴加到装有5 1,3-二(三氟甲基)苯、4.2mL二异丙基乙基胺、4mL二(3-三甲氧基甲硅烷基丙基)胺的250-mL三口圆底烧瓶中，室温搅拌5小时。加入40mL全氟己烷，用18mL甲醇萃取三次，氟相在减压下蒸馏除去挥发成分，得到无色至淡黄色产物，即为末端具有三甲氧基硅烷的下述全氟聚醚基的硅烷化合物(A1)：CF 3(OCF 2CF 2) r(OCF 2) sOCF 2CH 2OCH 2CON[(CH 2CH 2CH 2Si(OCH 3) 3] 2
以核磁共振波谱仪鉴定，其新增结构的特征 1H化学位移如下表所示
Figure PCTCN2018087473-appb-000030
合成例2
依据以下步骤合成含有全氟聚醚基的硅烷化合物A2
步骤1：
在备有搅拌器的100-mL三口圆底烧瓶中加入10g平均组成为CF 3(OCF 2CF 2) r(OCF 2) sOCF 2CH 2OH(r+s范围为47～52)的全氟聚醚改性醇(数均分子量为4500～5000)、15mL 1,3-二(三氟甲基)苯和5mL乙二醇二甲醚、2.0g 50wt％的氢氧化钾溶液，室温下搅拌3小时。然后向反应瓶依序加入3.2mL溴乙酸叔丁酯、0.32g四丁基溴化铵，在50℃下搅拌5小时。经水萃取和 减压蒸馏得到无色透明产物9.6g，即为酯基全氟聚醚化合物(M3)：CF 3(OCF 2CF 2) r(OCF 2) sOCF 2CH 2OCH 2COOC 4H 9
以核磁共振波谱仪鉴定，其特征 1H化学位移如下表所示
Figure PCTCN2018087473-appb-000031
步骤2：
在装有温度计和搅拌器的100-mL三口圆底烧瓶中加入9.6g步骤1得到的酯基全氟聚醚化合物(M3)、17g 10wt％的氢氧化钾溶液，在100℃搅拌10小时。降至室温，加入10mL四氢呋喃，并用15％盐酸调整至酸性后加入30mL氢氟醚HFE-7200(3M公司生产)，搅拌。移除非氟相(即上层溶液)，氟相以2N盐酸洗涤2遍，最后减压蒸馏得到无色透明产物9.0g，即为羧基全氟聚醚化合物(M4)：CF 3(OCF 2CF 2) r(OCF 2) sOCF 2CH 2OCH 2COOH
以核磁共振波谱仪鉴定，其特征 1H化学位移如下表所示
Figure PCTCN2018087473-appb-000032
步骤3
在装有滴液漏斗、温度计和搅拌器的100-mL四口圆底烧瓶中加入9.0g步骤2得到的羧基全氟聚醚化合物(M4)、18mL 1,3-二(三氟甲基)苯溶解、0.23mL草酰氯，0.15mL DMF溶于5mL 1,3-二(三氟甲基)苯由滴液漏斗缓慢滴加进去，然后升温到50℃搅拌4小时，降至室温后缓慢滴加到装有9mL1,3-二(三氟甲基)苯、1.6mL二异丙基乙基胺、2.9mL二(3-三甲氧基甲硅烷基丙基)胺的250-mL三口圆底烧瓶中，室温搅拌5小时。加入72mL全氟 己烷，用43mL甲醇萃取三次，氟相在减压下蒸馏除去挥发成分，得到无色至淡黄色产物即为末端具有三甲氧基硅烷的下述全氟聚醚基的硅烷化合物(A2)：
CF 3(OCF 2CF 2) r(OCF 2) sOCF 2CH 2OCH 2CON[(CH 2) 3Si(OCH 3) 3] 2
以核磁共振波谱仪鉴定，其特征 1H化学位移如下表所示
Figure PCTCN2018087473-appb-000033
合成例3
依据以下步骤合成含有全氟聚醚基的硅烷化合物A3
步骤1：
在备有搅拌器的100-mL三口圆底烧瓶中加入3g平均组成为CF 3(OCF 2CF 2) r(OCF 2) sOCF 2CH 2OH(r+s範圍為35～42)的全氟聚醚改性醇(均数分子量为3500～4000)、9mL 7200和3mL t-BuOH溶解，接着加入0.45g t-BuOK，室温下搅拌1.5小时。然后向反应瓶依序加入1.5g BrCH 2C 6H 4COOC 4H 9、0.12g四丁基溴化铵，在50℃下搅拌1.5小时。经水萃取后减压蒸馏得到无色透液体(M5)：CF 3(OCF 2CF 2) r(OCF 2) sOCF 2CH 2OCH 2C 6H 4COOC 4H 9。
将所得之无色透液体(M5)加入装有温度计和搅拌器的100-mL三口圆底烧瓶中，并且加入9mL 20wt％的氢氧化钾溶液，在115℃搅拌5小时。降至室温，用2N盐酸调整至酸性后加入蒸馏水和四氢呋喃萃取。减压蒸馏得到无色透明产物2.63g，即为羧基全氟聚醚化合物(M6)： CF 3(OCF 2CF 2) r(OCF 2) sOCF 2CH 2OCH 2C 6H 4COOH
以核磁共振波谱仪鉴定，其特征 1H化学位移如下表所示
Figure PCTCN2018087473-appb-000034
步骤2：
在装有滴液漏斗、温度计和搅拌器的100-mL四口圆底烧瓶中，加入2.0g羧基全氟聚醚化合物(M6)、6mL 1,3-二(三氟甲基)苯溶解、70ul草酰氯和40ul DMF，然后升温到50℃搅拌5小时，降至室温后缓慢滴加到装有2mL1,3-二(三氟甲基)苯、0.72mL三乙胺、0.85mL二(3-三甲氧基甲硅烷基丙基)胺的25mL三口圆底烧瓶室温搅拌5小时。加入10mL全氟己烷，用4mL甲醇萃取五次，经过滤膜过滤，减压下蒸馏除去挥发成分，得到无色透明产物1.2g，即为末端具有三甲氧基硅烷的下述全氟聚醚基的硅烷化合物(A3)：CF 3(OCF 2CF 2) r(OCF 2) sOCF 2CH 2OCH 2C 6H 4CON[(CH 2) 3Si(OCH 3) 3] 2
以核磁共振波谱仪鉴定，其特征 1H化学位移如下表所示
Figure PCTCN2018087473-appb-000035
合成例4
依据以下步骤合成含有全氟聚醚基的羧基化合物M2
在备有搅拌器的100-mL三口圆底烧瓶中加入1g平均组成为CF 3(OCF 2CF 2) r(OCF 2) sOCF 2CH 2OH(r+s范围为35～42)的全氟聚醚改性醇(均数分子量为3500～4000)、1.5mL 1,3-二(三氟甲基)苯和0.5mL乙二醇二甲醚,室温搅拌，接着加入0.09g氢化钠，观察到气泡产生。然后向反应瓶依序加入0.199g ClCH 2CN、0.044g四丁基溴化铵，在50℃下搅拌3小时。加入5mL氢氟醚HFE7200，经滤膜过滤得亮黄色透明溶液，经水萃取，减压蒸馏得到黄棕色产物(M7)：CF 3(OCF 2CF 2) r(OCF 2) sOCF 2CH 2OCH 2CN。接着加入3g 20％氢氧化钾溶液，在115℃下回流水解。酸化提纯，得0.74g产物，即为羧基全氟聚醚化合物(M2)：CF 3(OCF 2CF 2) r(OCF 2) sOCF 2CH 2OCH 2COOH
以核磁共振波谱仪鉴定，其特征 1H化学位移如下表所示
Figure PCTCN2018087473-appb-000036
以傅里叶变换红外光谱仪鉴定，其结构特征吸收峰如下表所示
Figure PCTCN2018087473-appb-000037
所得M2可以如合成例1中步骤3所述进一步反应得到A1：CF 3(OCF 2CF 2) r(OCF 2) sOCF 2CH 2OCH 2CON[(CH 2CH 2CH 2Si(OCH 3) 3] 2。
实施例1-3
将合成所得的化合物A1、A2和A3与氢氟醚(3M公司，Novec HFE7200)调制成20％质量浓度，作为表面处理剂(1)、表面处理剂(2)和表面处理剂(3)；将上述表面处理剂以真空沉积法蒸镀到化学强化玻璃上。在真空压力小于4×10 -3Pa下，先利用电子束沉积方法将二氧化硅以10nm厚度沉积到化学强化玻璃上形成二氧化硅膜，再以真空沉积方式在每一片化学强化玻璃上沉积約8～10nm厚度的化合物(D)。然后，将附有沉积膜的化学强化玻璃置于60％湿度及70℃环境下2小时进行固化，使其形成表面处理层。
比较例1至3
除了使用下述市售表面处理剂1至3取代化合物A1、A2和A3调制成的表面处理剂(1-3)之外，按照与实施例1所述相同方法形成表面处理层。
对照表面处理剂1：Optool UD 509(produced by Daikin Industries,Ltd.)
对照表面处理剂2：Optool DSX-E(produced by Daikin Industries,Ltd.)
对照表面处理剂3：X-71-195(Shin-Etsu Chemical Co.,Ltd.)
比较例4
除了使用下述对照化合物1取代化合物(A1)之外，按照实施例1所述的相同方法调制表面处理剂，並形成表面处理层。
对照化合物1：
CF 3(OCF 2CF 2) r(OCF 2) sOCF 2CH 2OCH 2CH 2CH 2Si(OCH 3) 3
实施例4-6
将表面处理剂(1-3)以0.4％质量浓度溶解在氢氟醚(3M公司，Novec HFE7200)中，制成表面处理剂(4-6)；使用市售喷涂涂布装置，将表面处理剂(4-6)以流速50mg/sec，输送线速度13mm/sec均匀喷涂涂布在化学强化玻璃上。在涂布之前，化学强化玻璃表面需经过电浆处理。然后，将附有喷涂处 理膜的化学强化玻璃置于60％湿度及70℃环境2小时进行固化，使其形成表面处理层。
通过下述方法来评价形成于基材表面的表面处理层，将結果示于表1至表3。
1.疏水疏油性的评价
利用接触角测定装置(北京哈科公司，HARKE-DWA)测定表面处理层对于水的接触角及正十六烷的接触角。
2.爽滑性的测定
使用摩擦系数仪(济南三泉中石公司，MXS-05A)，以下述条件测试相对公事物纸(达伯埃)的动摩擦系数。
接触面积：63mm×63mm；
负荷：200g
线速度：100mm/min
行程：30mm
3.耐磨损性评价
使用磨擦试验机(Taber公司，5900)，以下述条件磨擦后的表面处理层的水接触角进行评价。每经过来回次数1000次，测定水接触角度(当水接触角度低于100度或20000次摩擦或钢丝绒损毁时终止评鉴)。
(1).耐钢丝绒磨损性
钢丝绒：BONSTAR#0000
负荷：1kg/cm 2
移动行程：40mm
移动速度：60rpm
(2).耐橡皮擦磨损性
橡皮擦：Minoan MB006004，6.0mm
荷重：1kg
移动行程：40mm
移动速度：40rpm
表1疏水疏油性及爽滑性
Figure PCTCN2018087473-appb-000038
表2耐钢丝绒磨损性
Figure PCTCN2018087473-appb-000039
Figure PCTCN2018087473-appb-000040
表3、耐橡皮擦磨损性
Figure PCTCN2018087473-appb-000041
从以上实施例可见，采用本发明的全氟聚醚化合物制备的表面处理剂使得经其处理的玻璃基材具有优异的抗污、抗指纹、耐刮擦以及耐磨损性能，其综合性能均优于市售产品。而且本发明化合物的制备方法过程简单，易于操作和实现。
上述实施例仅供说明本发明之用，而并非是对本发明的限制，有关技术领域的普通技术人员，在不脱离本发明范围的情况下，还可以做出各种变化和变型，因此，所有等同的技术方案也应属于本发明公开的范畴。

Claims (58)

  1. 一种式(1)所示的含全氟聚醚基的硅烷化合物：
    Rf-X 1-X 2-NQ kT 2-k  (1)；
    式中，Rf为F-(CF 2) m-(OC 4F 8) p-(OC 3F 6) q-(OC 2F 4) r-(OCF 2) s-OC(Z)F-(CF 2) t-，这里，p、q、r和s分别为0以上200以下的整数，p、q、r和s的和至少为1，带有p、q、r和s并用括号括起的各个重复单元在顺序和数量上在式中是任意的；m和t分别为0以上、30以下的整数，Z为F或CF 3；
    X 1为二价有机基团；
    X 2为羰基、硫酰基或者酸酐；
    T在每次出现时分别独立，为羟基、可水解的基团或者烃基；
    Q在每次出现时分别独立，为-Y-SiR 1 jR 2 3-j；
    Y在每次出现时分别独立，为二价有机基团；
    R 1在每次出现时分别独立，为烷氧基、羟基或可水解为羟基的基团；
    R 2在每次出现时分别独立，为C 1-22烷基或Q’；
    Q’与Q含义相同；
    j在各Q和Q’中分别独立，为选自0～3的整数，j的总和为1以上；
    k分别独立，为1或2。
  2. 根据权利要求1所述的含全氟聚醚基的硅烷化合物，其中k为2。
  3. 根据权利要求1或2所述的含全氟聚醚基的硅烷化合物，其中R 1为-OR 3，式中，R 3为取代或非取代的C 1-3烷基。
  4. 根据权利要求3所述的含全氟聚醚基的硅烷化合物，其中R 3为甲基。
  5. 根据权利要求1-4中任一所述的含全氟聚醚基的硅烷化合物，其中Rf为下述式(a)或(b)：
    (a)：CF 3-(OC 2F 4) r-(OCF 2) s-OCF 2-
    式(a)中，r与s的和为10以上200以下的整数；
    (b)：F-(CF 2) m-(OC 4F 8) p-(OC 3F 6) q-(OC 2F 4) r-(OCF 2) s-OC(Z)F-(CF 2) t-
    式(b)中，m为1-16的整数，t为0-2的整数，r和s分别独立，为1以上200以下的整数，p、q、r和s的和为10以上200以下，带有p、q、r和s并用括号括起的各个重复单元的存在顺序和数量上在式中是任意的。
  6. 根据权利要求1-5中任一所述的含全氟聚醚基的硅烷化合物，其中X 1为如下所示的基团：
    -R 4-X 3-X 4-；
    式中，R 4为C 1-6烷基或经取代的C 1-6烷基；X 3选自-O-，-S-，邻、间或对亚苯基、邻、间或对亚苄基、-C(O)O-、-CONR 5-、-O-CONR 5-、-NR 5-、-Si(R 6) 2-、-(Si(R 6) 2O) f-Si(R 6) 2-和-(CH 2) g-中的基团，R 5每次出现时分别独立，为氢原子、苯基或C 1-6烷基，R 6为C 1-6烷基或经取代的C 1-6烷基；X 4为二价基团；f每次出现时分别独立，为1～100的整数，g每次出现时分别独立，为1～20的整数。
  7. 如权利要求6所述的含全氟聚醚基的硅烷化合物，其特征在于：
    X 4为-(R 7) a-(X 5) b-R 8-所示的基团，
    式中：
    R 7为-(CH 2) c-、邻、间或对亚苯基或邻、间或对亚苄基；
    R 8为-(CH 2) d-、邻、间或对亚苯基或邻、间或对亚苄基；
    X 5为-(X 6) e-；
    X 6每次出现时分别独立，为选自-O-、-S-、邻、间或对亚苯基、邻、间或对亚苄基、-C(O)O-、-CONR 5-、-O-CONR 5-、-NR 5-、-Si(R 6) 2-、-(Si(R 6) 2O) f-Si(R 6) 2-和-(CH 2) g-中的基团；
    R 5每次出现时分别独立，为氢原子、苯基或C 1-6烷基；
    R 6每次出现时分别独立，为苯基或C 1-6烷基；
    f每次出现时分别独立，为1～100的整数；
    g每次出现时分别独立，为1～20的整数；
    c为1～20的整数；
    d为1～20的整数；
    e为1～10的整数；
    a为0或1；
    b为0或1。
  8. 根据权利要求1-7任一所述的含全氟聚醚基的硅烷化合物，其特征在于，T每次出现时分别独立，选为羟基、-O(R 7)、C 1-12烷基、C 2-12烯基、C 2-12炔基或苯基，R 7为C 1-12烷基。
  9. 根据权利要求1-8任一所述的含全氟聚醚基的硅烷化合物，其特征在于：T每次出现时分别独立，为羟基、或-O(R 7)，R 7为C 1-12烷基。
  10. 一种式(2)所示的含全氟聚醚基的硅烷化合物，
    Figure PCTCN2018087473-appb-100001
    其中，Rf为
    Figure PCTCN2018087473-appb-100002
    q、r和s分别独立为0以上200以下的整数，q、r和s之和至少为1，标注q、r或s的括号括起来的各重复单元的存在顺序在式中是任意的，m为1-16的整数，t为0或1，Z为表示氟原子或三氟甲基；
    X为二价有机基团；
    T每次出现时分别独立，为羟基、可水解的基团或烃基；
    Q每次出现时分别独立，为-Y-SiR 1 jR 2 3-j；
    Y每次出现时分别独立，为二价有机基团；
    R 1每次出现时分别独立，为烷氧基、羟基或可水解为羟基的基团；
    R 2每次出现时分别独立，为C 1-22烷基或Q’；
    Q’与Q含义相同；
    j在各Q和Q’中分别独立，为选自0～3的整数，j的总和为1以上；
    k分别独立，为1或2。
  11. 根据权利要求10所述的含全氟聚醚基的硅烷化合物，其特征在于：k为2。
  12. 根据权利要求10或11所述的含全氟聚醚基的硅烷化合物，其特征在于：X为-(R 3) a-(X 1) b-R 4-所示的基团，
    式中：
    R 3为-(CH 2) c-、邻、间或对亚苯基或邻、间或对亚苄基；
    R 4为-(CH 2) d-、邻、间或对亚苯基或邻、间或对亚苄基；
    X 1为-(X 2) e-；
    X 2每次出现时分别独立，为选自-O-、-S-、邻、间或对亚苯基、邻、间或对亚苄基、-C(O)O-、-CONR 5-、-O-CONR 5-、-NR 5-、-Si(R 6) 2-、-(Si(R 6) 2O) f-Si(R 6) 2-和-(CH 2) g-中的基团，R 5每次出现时分别独立，为氢原子、苯基或C 1-6 烷基；
    R 6每次出现时分别独立，为苯基或C 1-6烷基；
    f每次出现时分别独立，为1～100的整数；
    g每次出现时分别独立，为1～20的整数；
    c为1～20的整；
    d为1～20的整数；
    e为1～10的整数；
    a为0或1；
    b为0或1。
  13. 根据权利要求10-12任一所述的含全氟聚醚基的硅烷化合物，其特征在于：X为C 1-20亚烷基、-R 3-X 3-R 4-或-X 4-R 4-，式中，X 3为-O-、-S-、-C(O)O-、-CONR 5-、-O-CONR 5-、-Si(R 6) 2-、-(Si(R 6) 2O) f-Si(R 6) 2-、-O-(CH 2) h-(Si(R 6) 2O) f-Si(R 6) 2-、-CONR 5-(CH 2) h-(Si(R 6) 2O) f-Si(R 6) 2-、-CONR 5-(CH 2) h-N(R 5)-或-CONR 5-(邻、间或对亚苯基)-Si(R 6) 2-，
    X 4为-S-、-C(O)O-、-CONR 5-、-O-CONR 5-(CH 2) h-(Si(R 6) 2O) f-Si(R 6) 2-、-CONR 5-(CH 2) h-N(R 5)-或-CONR 5-(邻、间或对亚苯基)-Si(R 6) 2-，
    h为1～20的整数，
    R 3为-(CH 2) c-、邻、间或对亚苯基或邻、间或对亚苄基；
    R 4为-(CH 2) d-、邻、间或对亚苯基或邻、间或对亚苄基；
    R 5每次出现时分别独立，为氢原子、苯基或C 1-6烷基
    R 6每次出现时分别独立，为苯基或C 1-6烷基；
    f每次出现时分别独立，为1～100的整数；。
  14. 根据权利要求13所述的含全氟聚醚基的硅烷化合物，其特征在于：
    R 3为-(CH 2) c-，R 4为-(CH 2) d-，式中，c为1～20的整；d为1～20的整数。
  15. 根据权利要求10-14任一所述的含全氟聚醚基的硅烷化合物，其特征在于：X为C 1-20亚烷基、-(CH 2) c-O-(CH 2) d、-(CH 2) c-(Si(R 6) 2O) f-Si(R 6) 2-(CH 2) d-或-(CH 2) c-O-(CH 2) h-(Si(R 6) 2O) f-Si(R 6) 2-(CH 2) d-，
    式中，R 6每次出现时分别独立，为苯基或C 1-6烷基；
    c为1～20的整；
    d为1～20的整数；
    f为1～100的整数；
    h为1～20的整数。
  16. 根据权利要求10-15任一所述的含全氟聚醚基的硅烷化合物，其特征在于：X选自以下基团：-CH 2-、-(CH 2) 2-、-(CH 2) 3-、-(CH 2) 4-、-(CH 2) 6-、-CH 2C 6H 4-、-CH 2OCH 2-、-CH 2O(CH 2) 2-、-CH 2O(CH 2) 3-、-CH 2O(CH 2) 6-、-CH 2C 6H 4-OCH 2-、-CONH-(CH 2) 3-、-CON(CH 3)-(CH 2) 3-、-CON(Ph)-(CH 2) 3-，Ph为苯基、-CON(CH 3)-(CH 2) 6-、-CON(Ph)-(CH 2) 6-，Ph为苯基、-CONH-(CH 2) 2NH(CH 2) 3-、-CONH-(CH 2) 6NH(CH 2) 3-、-CH 2O-CONH-(CH 2) 3-、-CH 2O-CONH-(CH 2) 6-、-C(O)O-(CH 2) 3-、-C(O)O-(CH 2) 6-、-S-(CH 2) 3-、-(CH 2) 2S(CH 2) 3-、-CH 2O-(CH 2) 3Si(CH 3) 2OSi(CH 3) 2(CH 2) 2-、 -CH 2O-(CH 2) 3Si(CH 3) 2OSi(CH 3) 2OSi(CH 3) 2(CH 2) 2-、-CH 2O-(CH 2) 3Si(CH 3) 2O(Si(CH 3) 2O) 2Si(CH 3) 2(CH 2) 2-。
  17. 根据权利要求10-16任一所述的含全氟聚醚基的硅烷化合物，其特征在于：T每次出现时分别独立，选自羟基、-O(R 7)、C 1-12烷基、C 2-12烯基、C 2-12炔基和苯基，R 7为C 1-12烷基。
  18. 根据权利要求10-17任一所述的含全氟聚醚基的硅烷化合物，其特征在于：T每次出现时分别独立，为羟基或-O(R 7)，R 7为C 1-12烷基。
  19. 根据权利要求10-18任一所述的含全氟聚醚基的硅烷化合物，其特征在于：Q中，j为3。
  20. 根据权利要求10-19任一所述的含全氟聚醚基的硅烷化合物，其特征在于：其具有500～10,000的数均分子量。
  21. 一种式(3)所示的含全氟聚醚基的硅烷化合物，
    Figure PCTCN2018087473-appb-100003
    式中，Rf为F-(CF 2) m-(OC 3F 6) q-(OC 2F 4) r-(OCF 2) s-OC(Z)F-(CF 2) t-，q、r和s分别独立为0以上200以下的整数，q、r和s之和至少为1，标注q、r或s的括号括起来的各重复单元的顺序在式中是任意的，m为1-16的整数，t为0或1，Z为氟原子或三氟甲基；
    X为二价有机基团，优选地X为C 1-6亚烷基、-CH 2C 6H 4-或苯环上有取代基的-CH 2C 6H 4-；
    Y 1，Y 2分别独立，为C 1-6亚烷基；
    Q 1，Q 2分别独立，为烷氧基、羟基或可水解为羟基的基团；
    R 1，R 2分别独立，为C 1-6烷基或苯基；
    n为1至3的整数；
    或者，Rf为CF 3(OC 2F 4) r(OCF 2) sOCF 2，其中，r、s分别为0以上200以下的整数，r、s的和至少为1，标注r、s的括号括起来的各重复单元的顺序在式中是任意的；优选地，r、s的和为20-100；
    式中，X为C 1-6亚烷基、-CH 2C 6H 4-或苯环上有取代基的-CH 2C 6H 4-；
    Y 1，Y 2分别独立，为C 1-6亚烷基；
    Q 1，Q 2分别独立，为烷氧基、羟基或可水解为羟基的基团；
    R 1，R 2分别独立，为C 1-6烷基或苯基。
  22. 根据权利要求21所述的含全氟聚醚基的硅烷化合物，其特征在于，n为3。
  23. 根据权利要求21或22所述的含全氟聚醚基的硅烷化合物，其特征在于X为-CH 2-、-CH(CH 3)-、-CH 2C 6H 4-。
  24. 根据权利要求21-23任一所述的含全氟聚醚基的硅烷化合物，其特征在于Y 1和Y 2分别为-(CH 2) 3-。
  25. 根据权利要求21-24任一所述的含全氟聚醚基的硅烷化合物，其特征在于Q 1，Q 2分别独立地为C 1-6烷氧基。
  26. 根据权利要求25所述的含全氟聚醚基的硅烷化合物，其特征在于Q 1，Q 2分别独立地为-OCH 3、-OCH(CH 3) 2、-OC 2H 5或-OC 3H 7。
  27. 根据权利要求21-26任一所述的含全氟聚醚基的硅烷化合物，其特征在于n为3。
  28. 根据权利要求21-27任一所述的含全氟聚醚基的硅烷化合物，其特征在于：所述硅烷化合物的数均分子量为500～10,000。
  29. 一种式(1)所示的含全氟醚基硅烷化合物的制备方法，
    Rf-X 1-X 2-NQ kT 2-k(1)；
    包括：
    Rf-X 1-X 2-OH+酰卤化试剂+氨基硅烷偶联剂→Rf-X 1-X 2-NQ kT 2-k
    式中，Rf为F-(CF 2) m-(OC 4F 8) p-(OC 3F 6) q-(OC 2F 4) r-(OCF 2) s-OCZF(CF 2) t-，这里，p、q、r和s分别独立为0以上200以下的整数，p、q、r和s的和至少为1，带有p、q、r和s并用括号括起的各个重复单元在顺序和数量上在式中是任意的；m和t分别为0以上、30以下的整数，Z为F或CF 3；
    X 1为二价有机基团；
    X 2为羰基、硫酰基或者酸酐；
    T在每次出现时分别独立，为羟基、可水解的基团或者烃基；
    Q在每次出现时分别独立，为-Y-SiR 1 jR 2 3-j；
    Y在每次出现时分别独立，为二价有机基团；
    R 1在每次出现时分别独立，为烷氧基、羟基或可水解为羟基的基团；
    R 2在每次出现时分别独立，为C 1-22烷基或Q’，其中Q’与Q含义相同；
    j在各Q和Q’中分别独立，为选自0～3的整数，j的总和为1以上；
    k分别独立，为1或2。
  30. 根据权利要求29所述的方法，其特征在于，酰卤化试剂为(COCl) 2、SOCl 2、POCl 3、PCl 5或SOBr 2。
  31. 根据权利要求29或30所述的方法，其特征在于，氨基硅烷偶联剂为HNQ kT 2-k，Q为-Y-SiR 1 jR 2 3-j；
    T在每次出现时分别独立，为羟基、可水解的基团或者烃基；
    k为1或2。
  32. 一种式(2)所示的含全氟聚醚基的硅烷化合物的制备方法，
    Figure PCTCN2018087473-appb-100004
    所述方法包括：
    将式为Rf-CH 2-O-X-COOH的化合物与酰卤化试剂以及氨基硅烷偶联剂通过反应转化得到式(2)的含全氟聚醚基的硅烷化合物，
    Figure PCTCN2018087473-appb-100005
    其中，R f为：
    Figure PCTCN2018087473-appb-100006
    p、q和r分别独立为0以上200以下的整数，q、r和s之和至少为1，标注q、r或s的括号括起来的各重复单元的顺序在式中是任意的，m为1～16的整数，t为0或1，Z为氟原子或三氟甲基；
    X为二价有机基团；
    T每次出现时分别独立，为羟基、可水解的基团或烃基；
    Q每次出现时分别独立，为-Y-SiR 1 jR 2 3-j；
    Y每次出现时分别独立，为二价有机基团；
    R 1每次出现时分别独立，为烷氧基、羟基或可水解为羟基的基团；
    R 2每次出现时分别独立，为C 1-22烷基或Q’，其中Q’与Q含义相同；
    j在各Q和Q’中分别独立，为选自0～3的整数，j的总和为1以上；
    k分别独立，为1或2。
  33. 根据权利要求32所述的方法，其特征在于，所述酰卤化试剂为酰卤，优选为酰氯，更优选为草酰氯。
  34. 根据权利要求32或33所述的方法，其特征在于，所述氨基硅烷偶联剂为HNQ kT 2-k，其中Q为-Y-SiR 1 jR 2 3-j；
    T每次出现时分别独立，为羟基、可水解的基团或烃基；
    k为1或2。
  35. 根据权利要求32-34任一所述的方法，其特征在于，还包括：
    步骤1：在溶剂存在下使式为Rf-CH 2OH的化合物先和碱反应，再与式为L-X-G的化合物进行亲核取代反应，得到式为Rf-CH 2-O-X-G的化合物，其中式L-X-G中，L为可发生亲核取代反应的离去基团或原子，X为二价有机基团，G为可水解为羧酸的基团
    Figure PCTCN2018087473-appb-100007
    步骤2：将式为Rf-CH 2-O-X-G的化合物通过化学转化得到式为Rf-CH 2-O-X-COOH的化合物
    Figure PCTCN2018087473-appb-100008
  36. 根据权利要求35所述的方法，其特征在于，步骤1中所述碱选自无机碱或有机碱；所述无机碱优选选自LiOH、NaOH、KOH、K 2CO 3、Na 2CO 3、Cs 2CO 3、NaH、t-BuOK中的至少一种；所述有机碱优选选自DIPEA、DBU、1,1,3,3-四甲基胍中的至少一种。
  37. 根据权利要求35或36所述的方法，其特征在于，步骤1的式L-X-G 化合物中，L选自：氯原子、溴原子、碘原子或其他可发生亲核取代反应的离去基团。
  38. 根据权利要求35-37任一所述的方法，其特征在于，步骤1的式L-X-G化合物中，G选自：酯基、腈基、酰胺基或取代酰胺基中的至少一种基团。
  39. 根据权利要求35-38任一所述的方法，其特征在于，步骤2中所述碱选自氢氧化钠、氢氧化钾、氢氧化锂和氢氧化铯中的至少一种。
  40. 根据权利要求35-39任一所述的方法，其特征在于，步骤2中所述酸选自：盐酸、硫酸、磷酸或硝酸。
  41. 一种式(3)所示含全氟聚醚基的硅烷化合物的制备方法，
    Figure PCTCN2018087473-appb-100009
    包括：使Rf-CH 2-O-X-COOH与酰卤化试剂以及氨基硅烷偶联剂反应
    Figure PCTCN2018087473-appb-100010
    其中，Rf为F-(CF 2) m-(OC 3F 6) q-(OC 2F 4) r-(OCF 2) s-OC(Z)F-(CF 2) t-，q、r、和s分别独立为0以上200以下的整数，q、r和s之和至少为1，标注q、r或s的括号括起来的各重复单元的顺序在式中是任意的，m为1-16的整数，t为0或1，Z为氟原子或三氟甲基；
    X为二价有机基团，优选地X表示C 1-6亚烷基、-CH 2C 6H 4-或苯环上有取代基的-CH 2C 6H 4-；
    Y 1，Y 2分别独立地为C 1-6亚烷基；
    Q 1，Q 2分别独立地为烷氧基、羟基或可水解为羟基的基团；
    R 1，R 2分别独立地为C 1-6烷基或苯基；
    n为1至3的整数，优选地，n为3。
  42. 根据权利要求41所述的含全氟聚醚基的硅烷化合物的制备方法，其特征在于，式(3)中，Rf为CF 3(OC 2F 4) r(OCF 2) sOCF 2，其中，r、s分别独立为0以上200以下的整数，r、s的和至少为1，标注r、s的括号括起来的各重复单元的顺序在式中是任意的；
    X为C 1-6亚烷基、-CH 2C 6H 4-或苯环上有取代基的-CH 2C 6H 4-；
    Y 1，Y 2分别独立地表示C 1-6亚烷基；
    Q 1，Q 2分别独立地表示烷氧基、羟基或可水解为羟基的基团；
    R 1，R 2分别独立地表示C 1-6烷基或苯基。
  43. 根据权利要求41或42所述的制备方法，其特征在于，所述酰卤化试剂为(COCl) 2、SOCl 2、POCl 3、PCl 5或SOBr 2。
  44. 根据权利要求41-43任一所述的方法，其特征在于，还包括：
    步骤1：在溶剂存在下使式为Rf-CH 2OH的化合物先和碱反应，再与式为L-X-G的化合物进行亲核取代反应，其中，L为可发生亲核取代反应的离去基团或原子，G为可水解为羧酸的基团，X为二价有机基团，优选为C 1-6亚烷基、-CH 2C 6H 4-或苯环上有取代基的-CH 2C 6H 4-；得到式为Rf-CH 2-O-X-G的酯基全氟聚醚化合物，
    Figure PCTCN2018087473-appb-100011
    步骤2：将式为Rf-CH 2-O-X-G的化合物水解得到式为Rf-CH 2-O-X-COOH的羧基全氟聚醚化合物，
    Figure PCTCN2018087473-appb-100012
    其中，Rf为F-(CF 2) m-(OC 3F 6) q-(OC 2F 4) r-(OCF 2) s-OC(Z)F-(CF 2) t-，q、r、和s分别独立为0以上200以下的整数，q、r和s之和至少为1，标注q、r或s的括号括起来的各重复单元的顺序在式中是任意的，m为1-16的整数，t为0或1，Z为氟原子或三氟甲基。
  45. 根据权利要求44所述的方法，其特征在于，步骤1中所述的碱选自无机碱或有机碱；所述无机碱优选选自LiOH、NaOH、KOH、K 2CO 3、Na 2CO 3、Cs 2CO 3、NaH、t-BuOK中的至少一种；所述有机碱优选选自DIPEA、DBU或1,1,3,3-四甲基胍中的至少一种。
  46. 根据权利要求44-45任一所述的方法，其特征在于，所述式L-X-G的化合物中，L为氯原子、溴原子或碘原子。
  47. 根据权利要求44-46任一所述的方法，其特征在于，所述式L-X-G的化合物中，G为酯基、腈基、酰胺基或取代酰胺基团。
  48. 根据权利要求44-47任一所述的方法，其特征在于，所述溶剂为含氟溶剂，优选为氢氟醚或氟代烃。
  49. 根据权利要求44-48任一所述的方法，其特征在于，步骤2中的碱选自氢氧化钠、氢氧化钾、氢氧化锂、氢氧化铯中的至少一种。
  50. 根据权利要求44-49任一所述的方法，其特征在于，步骤2中的酸选 自无机酸。
  51. 根据权利要求44-50任一所述的方法，其特征在于，步骤2中的酸选自盐酸、硫酸或硝酸中的至少一种。
  52. 根据权利要求41-51任一所述的方法，其特征在于，所述氨基硅烷偶联剂为二(烷氧基硅烷烷基)胺。
  53. 一种表面处理剂，含有权利要求1-28所述的全氟聚醚基的硅烷化合物。
  54. 根据权利要求53所述的表面处理剂，其特征在于，所述表面处理剂含有氟溶剂。
  55. 根据权利要求53所述的表面处理剂，其特征在于，所述氟溶剂为氢氟醚。
  56. 根据权利要求53-55所述的表面处理剂，其特征在于，所述表面处理剂含有0.01-30wt％的全氟聚醚基的硅烷化合物，优选0.05-20wt％或10-20wt％的全氟聚醚基的硅烷化合物。
  57. 一种物品，其特征在于具有由权利要求53-56任一所述的表面处理剂形成的涂层，且其表面水接触角至少为110度，动摩擦系数不超过0.05。
  58. 根据权利要求57所述的物品，其特征在于：所述物品为光学元件，智能手机、平板或电脑的显示器屏幕。
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