Fluorosilicone polymer, fluorosilicone treating agent and fiber fabric

Abstract

The invention relates to a fluorosilicone polymer, a fluorosilicone treating agent and a fiber fabric treated by the fluorosilicone treating agent. The fluorosilicone polymer comprises a structural unit generated by a fluorine monomer I, a structural unit generated by a silicon monomer II and an optional structural unit generated by a monomer III, and the monomers are defined in the specification. According to the fluorosilicone treating agent provided by the invention, the use of fluorine is reduced, the treated fiber fabric can keep excellent oil repellency, and the water repellency of the fabric is improved.

Description

A fluorosilicone polymer, a fluorosilicone treatment agent, and a fiber fabric. Technical Field

[0001] This application relates to a fluorosilicone polymer, a fluorosilicone treatment agent, and the treated fiber fabric thereof. Background Technology

[0002] In the past, fluoropolymers were used for surface water and oil repellency treatment of fiber fabrics. Because fluoropolymers have low surface tension, they can change the surface properties of fiber fabrics without changing their appearance, so they have been widely used.

[0003] However, in recent years, due to increasing international concern about polyfluoroalkyl substances (PFAS), in March 2023, the European Chemicals Agency (ECHA) launched a public consultation on proposals submitted by Denmark, Germany, the Netherlands, Norway, and Sweden to add restrictions on the manufacture, placement on the market, and use of PFAS to REACH Annex XIVII. The aim was to provide stakeholders with an opportunity to express their opinions on including PFAS in REACH. Following the public consultation, ECHA's Risk Assessment Committee (RAC) and Socioeconomic Analysis Committee (SEAC) will assess the proposed restrictions based on the consultation feedback and formulate their opinions. Ultimately, the European Commission will decide whether to include PFAS in REACH.

[0004] CN103080267A proposes a fluorinated acrylate polymer for finishing fiber fabrics.

[0005] CN1938391B also proposes a fluorinated acrylate polymer for finishing fiber fabrics.

[0006] US5344903 also proposes a fluorinated acrylate quinone polymer for finishing fiber fabrics.

[0007] However, the fluorinated polymers used in the aforementioned existing technologies all have high fluorine content, which can no longer meet further environmental protection requirements. Therefore, reducing the use of fluorides can reduce both the environmental burden and economic costs. However, reducing fluorides will affect oil and water repellency to some extent, and in most applications, good oil and water repellency are generally required simultaneously. Therefore, reducing the fluorine content while maintaining oil repellency or improving water repellency has significant practical value. Summary of the Invention

[0008] In a first aspect, this application provides a fluorosilicone polymer that can be obtained by emulsion polymerization and can be used for water- and oil-repellent treatment of fibrous fabrics.

[0009] Specifically, the fluorosilicone polymer provided in this application includes structural units generated from fluorine monomer I and structural units generated from silicon monomer II.

[0010] The structure of the fluorine monomer I is shown in Formula I:

[0011]

[0012] In Formula I, R1 is selected from hydrogen atoms or C1-C4 alkyl groups;

[0013] A is selected from alkylene-(CH2)n-, where n is 1-10;

[0014] R f Selected from fluorinated C1-C 21 alkyl;

[0015] The silicon monomer II comprises silicon monomer II-1 and silicon monomer II-2.

[0016] The structure of silicon monomer II-1 is shown in formula II-1:

[0017] MZ II-1

[0018] In Formula II-1, M contains polymerizable functional groups;

[0019] Z is selected from the following structures:

[0020]

[0021] In Z, R3 is independently selected from C1-C1. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 20 The alkoxy group or R4-O-R5- group, where R4 is C1-C 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R5 is C1-C 20 Alkylene, 1≤a≤200;

[0022] Y1 and Y2 may be the same or different, and each is independently selected from C1-C2. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups, C7-C 12 The alkylaryl group or the structure of formula (1) is as follows:

[0023]

[0024] R7 is selected independently from C1-C. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl groups; R8 groups are each independently selected from C1-C1. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 20 Alkoxy or R9-OR 10 - group, where R9 is C1-C 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R 10 For C1-C 20 Alkylene, 0≤b≤200;

[0025] The structure of the silicon monomer II-2 is shown in formula II-2:

[0026]

[0027] In Formula II-2, M is selected from groups containing polymerizable groups, and each R1 may be the same or different, independently selected from C1-C1. 10 Alkyl, C6-C 12 aryl, C7-C 12 Aryl or C7-C 12 The alkylaryl groups, each with the same or different X1, are independently silicon-containing groups represented by the following formula II-3 when i=1:

[0028]

[0029] i represents the number of silicon-containing groups shown in Equation II-3, and is an integer selected from 1 to 10;

[0030] In Equation II-3, R1 is selected from C1-C 10 Alkyl, C6-C 12 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl; R2 is selected from C1-C 10 Alkylene;

[0031] X i+1 Selected from hydrogen, C1-C10 Alkyl, C6-C 12 aryl, C7-C 12 Aryl groups, C7-C 12 The alkylaryl group or the silicon-containing group shown in Formula II-3.

[0032] Currently, fluorinated monomers are generally considered to be the most efficient in terms of oil repellency. The applicant unexpectedly discovered that, compared to polymers obtained by polymerizing fluorinated monomer I, when silicon monomer II is used to replace a portion of the fluorinated monomers in the polymerization process, the oil repellency is comparable to that of polymers obtained by polymerizing entirely with fluorinated monomers, thus achieving the goal of reducing the use of fluorinated monomers. Furthermore, when the proportion of silicon monomer replacing fluorinated monomers is relatively large, it exhibits better water repellency than either perfluorinated or persilicone monomers.

[0033] In some embodiments, R1 in Formula I is selected from hydrogen atoms or methyl groups.

[0034] In some embodiments, in Formula I, A is selected from alkylene-(CH2)n-, and n is 2, 3, 4, 5, 6, 7, 8 or 9.

[0035] In some implementations, in formula I, R f Selected from fluorinated C4-C 16 Alkyl group. In some embodiments, R f Selected from perfluorinated C4-C 10 alkyl.

[0036] In some embodiments, fluorine monomer I is selected from...

[0037] CH2=C(R)C(O)-OCH2CH2(CF2)5CF3

[0038] CH2=C(R)C(O)-OCH2CH2(CF2)7CF3

[0039] CH2=C(R)C(O)-OCH2CH2CH2(CF2)5CF3

[0040] CH2=C(R)C(O)-OCH2CH2CH2(CF2)7CF3

[0041] CH2=C(R)C(O)-OCH2CH2(CF2)3CF3

[0042] CH2=C(R)C(O)-OCH2CH2CH2(CF2)3CF3

[0043] R is selected from hydrogen atoms or methyl groups.

[0044] In some embodiments, the polymerizable functional group in M ​​is selected from groups containing carbon-carbon double bonds.

[0045] In some embodiments, M in silicon monomer II-1 and silicon monomer II-2 is as shown in Formula I-1:

[0046] CH2=C(R1)-YB-I-1

[0047] In formula I-1, R1 is selected from hydrogen atoms or C1-C atoms. 20 Alkyl groups;

[0048] Y is selected from the groups shown in Y-1, Y-2, Y-3, Y-4, Y-5, and Y-6.

[0049] -C(O)-O- Y-1

[0050] -C(O)-N(R2)- Y-2

[0051]

[0052] -OC(O)-N-(R2) n - Y-4

[0053] -OC(O)-O- Y-5

[0054] -OC(O)-ODN(R2)- Y-6

[0055] R2 is selected from hydrogen atom or C1-C. 20 Alkyl group, D is C1-C 20 Alkylene; when Y is selected from Y-1, Y-2, Y-4, Y-5, Y-6, B is C1-C 20 Alkylene, C6-C 20 For the aryl group and its combination, when Y is selected from Y-3, B either does not exist or is C1-C. 20 Alkylene, C6-C 20 The aryl group and its combination.

[0056] In some embodiments, in formula I-1, R1 is selected from hydrogen atoms or C1-C atoms. 10 Alkyl groups, such as C1-C3 alkyl groups, C4-C6 alkyl groups, or C8-C6 alkyl groups. 10 Alkyl groups. In some embodiments, in formula I-1, R1 is selected from hydrogen atoms or C1-C6 alkyl groups, preferably hydrogen atoms or methyl groups.

[0057] In some implementations, in formula I-1, B is C1-C 10 Alkylenes, for example, C1-C3 alkylenes, C4-C6 alkylenes, or C8-C6 alkylenes. 10 Alkylene.

[0058] In some implementations, in formula I-1, B is C6-C 15 arylene, such as C6-C9 arylene, C 10 -C 12 aryl or C 13 -C 15 Alpha-aryl groups.

[0059] In some embodiments, in Y of formula I-1, R2 is selected from hydrogen atoms or C1-C atoms. 10 Alkyl groups, such as C1-C3 alkyl groups, C4-C6 alkyl groups, or C8-C6 alkyl groups. 10 Alkyl groups. In some embodiments, in Y of formula I-1, D is C1-C6. 10 Alkylenes, for example, C1-C3 alkylenes, C4-C6 alkylenes, or C8-C6 alkylenes. 10 Alkylene.

[0060] In some embodiments, formula I-1, R1 and R2 are selected from hydrogen atoms or methyl groups, and B and D are C1-C6 alkylene groups.

[0061] In some implementations, when Y is selected from Y-3, B either does not exist or is C1-C. 10 Alkylenes, for example, C1-C3 alkylenes, C4-C6 alkylenes, or C8-C6 alkylenes. 10 Alkylene.

[0062] In some implementations, when Y is selected from Y-1, Y-2, Y-4, Y-5, Y-6, B is C1-C. 10 Alkylenes, for example, C1-C3 alkylenes, C4-C6 alkylenes, or C8-C6 alkylenes. 10 Alkylene.

[0063] In some implementations, when Y is selected from Y-1, Y-2, Y-4, Y-5, Y-6, B is C6-C. 15 arylene, such as C6-C9 arylene, C 10 -C 12 aryl or C 13 -C 15 Alpha-aryl groups.

[0064] In some implementations, in Z of formula II-1, R3 is independently C1-C 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 10 alkoxy or R4-O-R5- group, where R4 is C1-C 10 Alkyl, C6-C10 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R5 is C1-C 10 Alkylene, 1≤a≤100; R7 are each independently C1-C 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl groups; each of the R8 groups is independently C1-C1. 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 10 Alkoxy or R9-OR 10 - group, where R9 is C1-C 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R 10 For C1-C 10 Alkylene, 0≤b≤100.

[0065] In some embodiments, in Z, R3 is each independently a C1-C6 alkyl group, C6-C6 alkyl group, or C6-C6 alkyl group. 10 aryl, C7-C 10 Aryl groups, C7-C 10 The alkylaryl, C1-C6 alkoxy, or R4-O-R5- group, where R4 is a C1-C6 alkyl, C6-C5 alkyl, or C6-C5 alkyl group. 10 aryl, C7-C 10 Aryl or C7-C 10 The alkylaryl group, R5 is a C1-C6 alkylene group, 1≤a≤30; R7 is each independently a C1-C6 alkyl group, C6-C6 alkylene group, C7 ... 10 aryl, C7-C 10 Aryl or C7-C 10 The alkylaryl group; R8 is each an alkyl group of C1-C6, C6-C 10 aryl, C7-C 10 Aryl groups, C7-C 10 alkylaryl, C1-C6 alkoxy or R9-OR 10 - group, wherein R9 is a C1-C6 alkyl group, C6 ...9-C9 alkyl group, C9 10 aryl, C7-C 10 Aryl or C7-C 10 alkylaryl, R 10 For C1-C 16Alkylene, 0≤b≤30.

[0066] In some implementations, a is an integer from 1 to 80, an integer from 1 to 30, an integer from 1 to 20, or an integer from 1 to 10, such as 1, 5, 10, 15, 20, 25, 30, 40, 50, 60, etc.

[0067] In some implementations, b is 0. In some implementations, b is an integer from 1 to 30, an integer from 1 to 20, an integer from 1 to 10, or an integer from 1 to 5.

[0068] In some implementations, Z is independently selected from one or more of the following structures i-1 to i-6:

[0069]

[0070] R are each independently selected from C1-C 10 Alkyl groups (e.g., methyl, ethyl, isopropyl), C6-C 10 Aryl (e.g., phenyl), C7-C 12 Aryl groups (e.g., benzyl) or C7-C 12 alkylaryl (tolyl);

[0071] 1≤m+1≤60, preferably 1≤m+1≤30 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 10, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30); 0≤p≤60, preferably 0≤p≤30 (e.g., 0, 1, 2, 34, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 10, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30) ; 0≤q≤60 (e.g., 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60), preferably 0≤q≤30 (e.g., 0, 1, 2, 34, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 10, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30); 1≤x≤9 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9), preferably 1≤x≤7 (e.g., 1, 2, 3, 4, 5, 6, 7), each x can be the same or different.

[0072] In some embodiments, R is a C1-C3 alkyl group, such as methyl or ethyl.

[0073] In some implementations, Z is selected from

[0074]

[0075]

[0076] One or more of the following;

[0077] R are each independently selected from C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Aryl or C7-C 12 alkylaryl groups;

[0078] Me represents methyl, ph represents phenyl; 1≤m+1≤60, preferably 1≤m+1≤30; 0≤p≤60, preferably 0≤p≤30; 0≤q≤60, preferably 0≤q≤30; 1≤x≤9, preferably 1≤x≤7, and each x can be the same or different.

[0079] In some implementations, m is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9.

[0080] In some implementations, x is 1, 2, 3, 4, 5, 6, or 7.

[0081] Silicon monomer II-1 is selected from

[0082] CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9(1≤n≤25),

[0083] CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C8H 17 (1≤n≤25),

[0084] CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)3(1≤n≤25),

[0085] CH2=C(R)C(O)-O-(CH2)3Si(OSi(CH3)3)3,

[0086] CH2=C(R)C(O)-O-(CH2)3Si(CH3)(OSi(CH3)3)2,

[0087] CH2=C(R)C(O)-NH-(CH2)3Si(OSi(CH3)3)3,

[0088] CH2=C(R)C(O)-NH-(CH2)3Si(CH3)(OSi(CH3)3)2,

[0089] CH2=C(R)C(O)-O-(CH2)3Si(OSi(CH2CH3)3)3,

[0090] CH2=C(R)C(O)-O-CH2-Si(OSi(CH3)3)3,

[0091] CH2=C(CH3)C(O)-O-(CH2)3Si(CH3)[O-[Si(CH3)2O]n-Si(CH3)2C4H9]2(0≤n≤25),

[0092] CH2=CH-ph-Si(OSi(CH3)3)3 (ph represents...) ),

[0093] CH2=CH-ph-(CH2)2Si(OSi(CH3)3)3(ph represents...) ),

[0094] CH2=CH-ph-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl, ph represents...) (1≤n≤25),

[0095] CH2=CH-OC(O)-NH-(CH2)3Si(OSi(CH3)3)3,

[0096] CH2=CH-OC(O)-NH-(CH2)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl) (1≤n≤25),

[0097] CH2=CH-OC(O)-O-(CH2)3-Si(OSi(CH3)3)3,

[0098] CH2=CH-OC(O)-O-(CH2)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl) (1≤n≤25),

[0099] CH2=CH-OC(O)-O-(CH2)2-NH-(CH2)3Si(OSi(CH3)3)3,

[0100] CH2=CH-OC(O)-O-(CH2)2-NH-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl) (1≤n≤25),

[0101] In the formula, R is a hydrogen atom or a methyl group.

[0102] In some embodiments, silicon monomer II-1 includes silicon monomer II-A and / or silicon monomer II-B;

[0103] The general formula of silicon monomer II-A is the same as that of formula II-1, and also satisfies the following conditions: when a is 1, Y1 and / or Y2 are the structures of formula (1); when a is greater than 1 and ≤200, at least one Y1 is the structure of formula (1) and / or at least one Y2 is the structure of formula (1).

[0104] The general formula of silicon monomer II-B is the same as that of II-1, and it also satisfies the following conditions: Y1 and Y2 are the same or different, and each is independently selected from C1-C. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups and C7-C 12 alkylaryl groups.

[0105] In some embodiments, the general formula of silicon monomer II-A is the same as that of formula II-A:

[0106] M-Z1 type II-A

[0107] M contains polymerizable functional groups;

[0108] Z1 is selected from the following structures.

[0109]

[0110] In Z1, R3 is independently selected from C1-C 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 20 The alkoxy group or R4-O-R5- group, where R4 is C1-C 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R5 is C1-C 20 Alkylene, 1≤a≤200;

[0111] Y1 and Y2 may be the same or different, and each is independently selected from C1-C2.20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups, C7-C 12 The alkylaryl group has the structure of formula (1) and satisfies the following conditions: when a is 1, Y1 and / or Y2 are the structures of formula (1); when a is greater than 1 and ≤ 200, at least one Y1 is the structure of formula (1) and / or at least one Y2 is the structure of formula (1):

[0112]

[0113] R7 is selected independently from C1-C. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl groups; R8 groups are each independently selected from C1-C1. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 20 Alkoxy or R9-OR 10 - group, where R9 is C1-C 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R 10 For C1-C 20 Alkylene, 0≤b≤200.

[0114] In this application, the limitation of M in Formula II-A is the same as the limitation of M in Formula II-1.

[0115] In some implementations, in Z1, R3 is independently C1-C. 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 10 alkoxy or R4-O-R5- group, where R4 is C1-C 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R5 is C1-C 10 Alkylene, 1≤a≤100; R7 are each independently C1-C 10 Alkyl, C6-C 10aryl, C7-C 12 Aryl or C7-C 12 alkylaryl groups; each of the R8 groups is independently C1-C1. 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 10 Alkoxy or R9-OR 10 - group, where R9 is C1-C 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R 10 For C1-C 10 Alkylene, and / or 0≤b≤80.

[0116] According to some embodiments of this application, in Z1, R3 is each independently a C1-C6 alkyl group, C6-C6 alkyl group, or C6-C6 alkyl group. 10 aryl, C7-C 10 Aryl groups, C7-C 10 The alkylaryl, C1-C6 alkoxy, or R4-O-R5- group, where R4 is a C1-C6 alkyl, C6-C5 alkyl, or C6-C5 alkyl group. 10 aryl, C7-C 10 Aryl or C7-C 10 The alkylaryl group, R5 is a C1-C6 alkylene group, 1≤a≤30; R7 is each independently a C1-C6 alkyl group, C6-C6 alkylene group, C7 ... 10 aryl, C7-C 10 Aryl or C7-C 10 The alkylaryl group; R8 is each an alkyl group of C1-C6, C6-C 10 aryl, C7-C 10 Aryl groups, C7-C 10 alkylaryl, C1-C6 alkoxy or R9-OR 10 - group, wherein R9 is a C1-C6 alkyl group, C6 ...9-C9 alkyl group, C9 10 aryl, C7-C 10 Aryl or C7-C 10 alkylaryl, R 10 For C1-C 16 Alkylene, 0≤b≤30.

[0117] In some implementations, in formula II-A, a is an integer from 1 to 80, an integer from 1 to 30, an integer from 1 to 20, or an integer from 1 to 10, such as 1, 5, 10, 15, 20, 25, 30, 40, 50, 60, etc.

[0118] In some embodiments, b is 0 in formula II-A. In some embodiments, b is an integer from 1 to 30, an integer from 1 to 20, an integer from 1 to 10, or an integer from 1 to 5 in formula II-A.

[0119] In some implementations, Z1 is selected from one or more of the following structures i-3 to i-6:

[0120]

[0121] R are each independently selected from C1-C 10 Alkyl groups (e.g., methyl, ethyl, isopropyl), C6-C 10 Aryl (e.g., phenyl), C7-C 12 Aryl groups (e.g., benzyl) or C7-C 12 alkylaryl (tolyl);

[0122] 1≤m+1≤60, preferably 1≤m+1≤30 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 10, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30); 0≤p≤60, preferably 0≤p≤30 (e.g., 0, 1, 2, 34, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 10, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30) ; 0≤q≤60 (e.g., 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60), preferably 0≤q≤30 (e.g., 0, 1, 2, 34, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 10, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30); 1≤x≤9 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9), preferably 1≤x≤7 (e.g., 1, 2, 3, 4, 5, 6, 7), each x can be the same or different.

[0123] In some embodiments, R is a C1-C3 alkyl group, such as methyl or ethyl.

[0124] In some preferred embodiments, Z1 is selected from the following structures:

[0125]

[0126] One or more of the following;

[0127] Me represents methyl, 1≤m+1≤60, preferably 1≤m+1≤30; 0≤p≤60, preferably 0≤p≤30; 0≤q≤60, preferably 0≤q≤30; 1≤x≤9, preferably 1≤x≤7, and each x can be the same or different.

[0128] In some embodiments, silicon monomer II-A is selected from...

[0129] CH2=C(R)C(O)-O-(CH2)3Si(OSi(CH3)3)3,

[0130] CH2=C(R)C(O)-O-(CH2)3Si(CH3)(OSi(CH3)3)2,

[0131] CH2=C(R)C(O)-NH-(CH2)3Si(OSi(CH3)3)3,

[0132] CH2=C(R)C(O)-NH-(CH2)3Si(CH3)(OSi(CH3)3)2,

[0133] CH2=C(R)C(O)-O-(CH2)3Si(OSi(CH2CH3)3)3,

[0134] CH2=C(R)C(O)-O-CH2-Si(OSi(CH3)3)3,

[0135] CH2=C(CH3)C(O)-O-(CH2)3Si(CH3)[O-[Si(CH3)2O]n-Si(CH3)2C4H9]2(0≤n≤25),

[0136] CH2=CH-ph-Si(OSi(CH3)3)3 (ph represents...) ),

[0137] CH2=CH-ph-(CH2)2Si(OSi(CH3)3)3(ph represents...) ),

[0138] CH2=CH-OC(O)-NH-(CH2)3Si(OSi(CH3)3)3,

[0139] CH2=CH-OC(O)-O-(CH2)3-Si(OSi(CH3)3)3,

[0140] CH2=CH-OC(O)-O-(CH2)2-NH-(CH2)3Si(OSi(CH3)3)3,

[0141] In the formula, R is a hydrogen atom or a methyl group.

[0142] In some embodiments, the general formula of silicon monomer II-B is shown in formula II-B:

[0143] M-Z2

[0144] Formula II-B

[0145] M contains polymerizable functional groups;

[0146] Z2 is selected from the following structures.

[0147]

[0148] In Z2, Y1 and Y2 may be the same or different, and each is independently selected from C1-C2. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups and C7-C 12 alkylaryl groups; R3 are each independently selected from C1-C1. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 20 The alkoxy group or R4-O-R5- group, where R4 is C1-C 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R5 is C1-C 20 Alkylene, 1≤a≤200.

[0149] In this application, the limitation of M in Formula II-B is the same as the limitation of M in Formula II-1.

[0150] In some implementations, in Z2, Y1 and Y2 may be the same or different, and each is independently selected from C1-C2. 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl groups and C7-C 12 alkylaryl groups; R3 are each independently selected from C1-C1. 10 Alkyl, C6-C 12 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 10 The alkoxy group or R4-O-R5- group, where R4 is C1-C 10 Alkyl, C6-C 12 aryl, C7-C12 Aryl or C7-C 12 alkylaryl, R5 is C1-C 10 Alkylene.

[0151] According to some embodiments of this application, in Z2, 1 ≤ a ≤ 80. According to some embodiments of this application, in Z2, 1 ≤ a ≤ 30. According to some embodiments of this application, in Z2, 1 ≤ a ≤ 20. According to some embodiments of this application, in Z2, 1 ≤ a ≤ 10.

[0152] In some embodiments, in Z2, Y1 and Y2 may be the same or different, each independently selected from C1-C6 alkyl groups, C6-C6 alkyl groups, and C6-C6 alkyl groups. 10 aryl, C7-C 10 Aryl groups and C7-C 10 The alkylaryl group; R3 is independently selected from C1-C6 alkyl groups, C6-C6 alkyl groups, and C6-C6 alkyl groups. 10 aryl, C7-C 10 Aryl groups, C7-C 10 The alkylaryl group, C1-C6 alkoxy group, or R4-O-R5- group, where R4 is a C1-C6 alkyl group, C6-C5-alkyl group, or C4-O-R5-alkyl group. 10 aryl, C7-C 10 Aryl or C7-C 10 The alkylaryl group, where R5 is a C1-C6 alkylene group.

[0153] In some implementations, Z2 is selected from one or more of the following structures i-1 to i-2:

[0154]

[0155] R are each independently selected from C1-C 10 Alkyl groups (e.g., methyl, ethyl, isopropyl), C6-C 10 Aryl (e.g., phenyl), C7-C 12 Aryl groups (e.g., benzyl) or C7-C 12 alkylaryl (tolyl);

[0156] 1≤m+1≤60, preferably 1≤m+1≤30 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 10, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30); 1≤x≤9 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9), preferably 1≤x≤7.

[0157] Z2 is preferably derived from the following structure:

[0158]

[0159] One or more of the following;

[0160] Me represents methyl, ph represents phenyl; 1≤m+1≤60, preferably 1≤m+1≤30; 1≤x≤9, preferably 1≤x≤7.

[0161] In some embodiments, silicon monomer II-B is selected from...

[0162] CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9(1≤n≤25),

[0163] CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C8H 17 (1≤n≤25),

[0164] CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)3(1≤n≤25),

[0165] CCH2=CH-ph-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl, ph represents...)

[0166] (1≤n≤25),

[0167] CH2=CH-OC(O)-NH-(CH2)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl) (1≤n≤25),

[0168] CH2=CH-OC(O)-O-(CH2)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl) (1≤n≤25),

[0169] CH2=CH-OC(O)-O-(CH2)2-NH-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl) (1≤n≤25),

[0170] In the formula, R is a hydrogen atom or a methyl group.

[0171] In some embodiments, in Formula II-2, R1 is selected from C1-C4 alkyl groups, C5-C8 alkyl groups, or C6-C4 alkyl groups. 10aryl; in formula II-3, R1 is selected from C1-C4 alkyl, C5-C8 alkyl or C6-C 10 The aryl group, R2 is selected from C1-C4 alkylene groups, X i+1 Selected from C1-C4 alkyl groups, C5-C8 alkyl groups, C6-C 10 The aryl group or the silicon-containing group shown in formula II-3, where i is 1, 2, 3, 4 or 5.

[0172] In some embodiments, silicon monomer II-2 is selected from...

[0173]

[0174]

[0175] In some embodiments, the fluorosilicone polymer further includes structural units generated from monomer III.

[0176] CH2=C(R1)-C(O)-O-R3III

[0177] In Formula III, R1 is a hydrogen atom or a C1-C atom. 20 Alkyl group; R3 is C1-C 40 Alkyl, C4-C 30 Cyclic hydrocarbon group or C7-C 20 Alkyl aryl.

[0178] In some embodiments, in Formula III, R1 is a hydrogen atom or a C1-C atom. 10 Alkyl group, preferably hydrogen atom or C1-C6 alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or n-hexyl.

[0179] In some embodiments, in Formula III, R3 is selected from C1-C 30 Alkyl or C4-C 20 Cyclic hydrocarbon group. In some embodiments, in Formula III, R3 is selected from C1-C6. 10 Alkyl, C 11 -C 20 Alkyl, C 20 -C 30 Alkyl, C4-C 10 cycloalkyl, C 11 -C 20 Cycloalkanes, C 31 -C 30 Cycloalkanes, C4-C 10 Cycloalkenyl, C 11 -C 20 Cycloolefins, C 31 -C30 Cycloolefins, C7-C 15 Alkyl aryl.

[0180] In some embodiments, monomer III is selected from methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, tert-butyl methacrylate, isooctyl methacrylate, dodecyl methacrylate, myristyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecanyl methacrylate, octadecyl methacrylate, nonadecanyl methacrylate, eicosyl methacrylate, dodecyl methacrylate, and others. One or more of the following: docosyl acrylate, hexadecyl acrylate, triacontyl acrylate, cyclohexyl acrylate, tert-butylcyclohexyl acrylate, benzyl acrylate, isobornyl acrylate, dicyclopentyl acrylate, dicyclopentenyl acrylate, tricyclopentyl acrylate, adamantyl acrylate, 2-methyl-2-adamantyl acrylate, or 2-ethyl-2-adamantyl acrylate.

[0181] In some embodiments, the structural unit generated by fluorine monomer I has a mass percentage content of 10%-90% in the fluorosilicone polymer, for example, 11%, 13%, 15%, 17%, 19%, 20%, 21%, 23%, 25%, 27%, 29%, 30%, 31%, 33%, 35%, 37%, 39%, 40%, 41%, 43%, 45%, 47%, 49%, 50%, 51%, 53%, 55%, 57%, 59%, 60%, 61%, 63%, 65%, 67%, 69%, 70%, 71%, 73%, 75%, 77%, 79%, 80%, 81%, 83%, 85%, 87%, 89%, or any combination thereof. In some embodiments, the structural units generated by fluorine monomer I constitute 20%-80% of the fluorosilicone polymer by mass. In some embodiments, the structural units generated by fluorine monomer I constitute 30%-75% of the fluorosilicone polymer by mass.

[0182] In some embodiments, the structural units generated by silicon monomer II constitute 1%-80% of the fluorosilicone polymer by mass, for example, a range of 1%, 3%, 5%, 7%, 9%, 10%, 11%, 13%, 15%, 17%, 19%, 20%, 21%, 23%, 25%, 27%, 29%, 30%, 31%, 33%, 35%, 37%, 39%, 40%, 41%, 43%, 45%, 47%, 49%, 50%, 51%, 53%, 55%, 57%, 59%, 60%, 61%, 63%, 65%, 67%, 69%, 70%, 71%, 73%, 75%, 77%, 79%, or any combination thereof. In some embodiments, the structural units generated by silicon monomer II constitute 5%-60% of the fluorosilicone polymer by mass. In some embodiments, the structural unit generated by silicon monomer II has a mass content of 10%-50% in the fluorosilicone polymer.

[0183] In some embodiments, the mass ratio of fluorine monomer I to silicon monomer II is 1:100-100:1, for example, 1:97, 1:95, 1:93, 1:90, 1:87, 1:85, 1:83, 1:80, 1:77, 1:75, 1:73, 1:70, 1:67, 1:65, 1:63, 1:60, 1:57, 1:55, 1:53, 1: 50, 1:47, 1:45, 1:43, 1:40, 1:37, 1:35, 1:33, 1:30, 1:27, 1:25, 1:23, 1:20, 1:17, 1:15, 1:13, 1:10, 1:7, 1:5, 1:3, 1:1, 1:0.7, 1:0.5, 1:0.3, 1:0.1, or a range consisting of any two of them.

[0184] In some embodiments, the total mass percentage of fluorine monomer I and silicon monomer II in the fluorosilicone polymer is 40%-100%, for example, 41%, 43%, 45%, 47%, 49%, 50%, 51%, 53%, 55%, 57%, 59%, 60%, 63%, 65%, 67%, 70%, 73%, 75%, 77%, 80%, 83%, 85%, 87%, 90%, 93%, 95%, 97%, 98%, or any combination thereof. In some embodiments, the total mass percentage of fluorine monomer I and silicon monomer II in the fluorosilicone polymer is 60%-99%.

[0185] In some embodiments, the structural unit generated by monomer III has a mass content of 1%-40% in the fluorosilicone polymer, for example, a range of 1%, 3%, 5%, 7%, 9%, 10%, 11%, 13%, 15%, 17%, 19%, 20%, 21%, 23%, 25%, 27%, 29%, 30%, 31%, 33%, 35%, 37%, 39%, or any combination thereof.

[0186] In some embodiments, the proportion of structural units generated by silicon monomer II-A in the total number of structural units generated by silicon monomer II-A and silicon monomer II-B, by mass percentage, is 1% to 100%, 5% to 100%, 10% to 100%, or 50% to 100%, for example, 1%, 5%, 10%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, or any combination thereof. The total number of structural units generated by silicon monomer II-A and silicon monomer II-B is also the total number of structural units generated by monomer II.

[0187] In a second aspect, this application provides a fluorosilicone treatment agent that, while reducing the use of fluorine, enables the treated fiber fabric to maintain excellent water and oil repellency properties.

[0188] In some embodiments, the fluorosilicone treatment agent provided in this application includes a fluorosilicone polymer, wherein the fluorosilicone polymer is the fluorosilicone polymer described in the first aspect.

[0189] In other embodiments, the fluorosilicone treatment agent provided in this application comprises a fluorosilicone polymer, said fluorosilicone polymer comprising structural units generated from fluorine monomer I and structural units generated from silicon monomer II.

[0190] The structure of the fluorine monomer I is shown in Formula I:

[0191]

[0192] In Formula I, R1 is selected from hydrogen atoms or C1-C4 alkyl groups;

[0193] A is selected from alkylene-(CH2)n-, where n is 1-10;

[0194] R f Selected from fluorinated C1-C 21 alkyl;

[0195] The silicon monomer II comprises silicon monomer II-1 and silicon monomer II-2.

[0196] The structure of silicon monomer II-1 is shown in formula II-1:

[0197] MZ II-1

[0198] In Formula II-1, M contains polymerizable functional groups;

[0199] Z is selected from the following structures:

[0200]

[0201] In Z, R3 is independently selected from C1-C1. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 20 The alkoxy group or R4-O-R5- group, where R4 is C1-C 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R5 is C1-C 20 Alkylene, 1≤a≤200;

[0202] Y1 and Y2 may be the same or different, and each is independently selected from C1-C2. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups, C7-C 12 The alkylaryl group or the structure of formula (1) is as follows:

[0203]

[0204] R7 is selected independently from C1-C. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl groups; R8 groups are each independently selected from C1-C1. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 20 Alkoxy or R9-OR 10 - group, where R9 is C1-C 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl or C7-C 12alkylaryl, R 10 For C1-C 20 Alkylene, 0≤b≤200;

[0205] The structure of the silicon monomer II-2 is shown in formula II-2:

[0206]

[0207] In Formula II-2, M is selected from groups containing polymerizable groups, and each R1 may be the same or different, independently selected from C1-C1. 10 Alkyl, C6-C 12 aryl, C7-C 12 Aryl or C7-C 12 The alkylaryl groups, each with the same or different X1, are independently silicon-containing groups represented by the following formula II-3 when i=1:

[0208]

[0209] i represents the number of silicon-containing groups shown in Equation II-3, and is an integer selected from 1 to 10;

[0210] In Equation II-3, R1 is selected from C1-C 10 Alkyl, C6-C 12 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl; R2 is selected from C1-C 10 Alkylene;

[0211] X i+1 Selected from hydrogen, C1-C 10 Alkyl, C6-C 12 aryl, C7-C 12 Aryl groups, C7-C 12 The alkylaryl group or the silicon-containing group shown in Formula II-3.

[0212] Currently, fluorinated monomers are generally considered to be the most efficient in terms of oil repellency. The applicant unexpectedly discovered that, compared to polymers obtained by polymerization of fluorinated monomer I, when silicone monomer II is used to replace part of the fluorinated monomer in emulsion polymerization, the oil repellency is almost unaffected, thus reducing the use of fluorinated monomers, while also providing better water repellency.

[0213] In some embodiments, R1 in Formula I is selected from hydrogen atoms or methyl groups.

[0214] In some embodiments, in Formula I, A is selected from alkylene-(CH2)n-, and n is 2, 3, 4, 5, 6, 7, 8 or 9.

[0215] In some implementations, in formula I, R f Selected from fluorinated C4-C 16 Alkyl group. In some embodiments, R f Selected from perfluorinated C4-C 10 alkyl.

[0216] In some embodiments, fluorine monomer I is selected from...

[0217] CH2=C(R)C(O)-OCH2CH2(CF2)5CF3

[0218] CH2=C(R)C(O)-OCH2CH2(CF2)7CF3

[0219] CH2=C(R)C(O)-OCH2CH2CH2(CF2)5CF3

[0220] CH2=C(R)C(O)-OCH2CH2CH2(CF2)7CF3

[0221] CH2=C(R)C(O)-OCH2CH2(CF2)3CF3

[0222] CH2=C(R)C(O)-OCH2CH2CH2(CF2)3CF3

[0223] R is selected from hydrogen atoms or methyl groups.

[0224] In some embodiments, the polymerizable functional group in M ​​is selected from groups containing carbon-carbon double bonds.

[0225] In some embodiments, M in silicon monomer II-1 and silicon monomer II-2 is as shown in Formula I-1:

[0226] CH2=C(R1)-YB-I-1

[0227] In formula I-1, R1 is selected from hydrogen atoms or C1-C atoms. 20 Alkyl groups;

[0228] Y is selected from the groups shown in Y-1, Y-2, Y-3, Y-4, Y-5, and Y-6.

[0229] -C(O)-O- Y-1

[0230] -C(O)-N(R2)- Y-2

[0231]

[0232] -OC(O)-N(R2)- Y-4

[0233] -OC(O)-O- Y-5

[0234] -OC(O)-ODN(R2)- Y-6

[0235] R2 is selected from hydrogen atom or C1-C. 20 Alkyl group, D is C1-C 20 Alkylene; when Y is selected from Y-1, Y-2, Y-4, Y-5, Y-6, B is C1-C 20 Alkylene, C6-C 20 For the aryl group and its combination, when Y is selected from Y-3, B either does not exist or is C1-C. 20 Alkylene, C6-C 20 The aryl group and its combination.

[0236] In some embodiments, in formula I-1, R1 is selected from hydrogen atoms or C1-C atoms. 10 Alkyl groups, such as C1-C3 alkyl groups, C4-C6 alkyl groups, or C8-C6 alkyl groups. 10 Alkyl groups. In some embodiments, in formula I-1, R1 is selected from hydrogen atoms or C1-C6 alkyl groups, preferably hydrogen atoms or methyl groups.

[0237] In some implementations, in formula I-1, B is C1-C 10 Alkylenes, for example, C1-C3 alkylenes, C4-C6 alkylenes, or C8-C6 alkylenes. 10 Alkylene.

[0238] In some implementations, in formula I-1, B is C6-C 15 arylene, such as C6-C9 arylene, C 10 -C 12 aryl or C 13 -C 15 Alpha-aryl groups.

[0239] In some embodiments, in Y of formula I-1, R2 is selected from hydrogen atoms or C1-C atoms. 10 Alkyl groups, such as C1-C3 alkyl groups, C4-C6 alkyl groups, or C8-C6 alkyl groups. 10 Alkyl groups. In some embodiments, in Y of formula I-1, D is C1-C6. 10 Alkylenes, for example, C1-C3 alkylenes, C4-C6 alkylenes, or C8-C6 alkylenes. 10 Alkylene.

[0240] In some embodiments, formula I-1, R1 and R2 are selected from hydrogen atoms or methyl groups, and B and D are C1-C6 alkylene groups.

[0241] In some implementations, when Y is selected from Y-3, B either does not exist or is C1-C. 10 Alkylenes, for example, C1-C3 alkylenes, C4-C6 alkylenes, or C8-C6 alkylenes. 10 Alkylene.

[0242] In some implementations, when Y is selected from Y-1, Y-2, Y-4, Y-5, Y-6, B is C1-C. 10 Alkylenes, for example, C1-C3 alkylenes, C4-C6 alkylenes, or C8-C6 alkylenes. 10 Alkylene.

[0243] In some implementations, when Y is selected from Y-1, Y-2, Y-4, Y-5, Y-6, B is C6-C. 15 arylene, such as C6-C9 arylene, C 10 -C 12 aryl or C 13 -C 15 Alpha-aryl groups.

[0244] In some implementations, in Z of formula II-1, R3 is independently C1-C 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 10 alkoxy or R4-O-R5- group, where R4 is C1-C 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R5 is C1-C 10 Alkylene, 1≤a≤100; R7 are each independently C1-C 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl groups; each of the R8 groups is independently C1-C1. 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 10 Alkoxy or R9-OR 10 - group, where R9 is C1-C 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R10 For C1-C 10 Alkylene, 0≤b≤100.

[0245] In some embodiments, in Z, R3 is each independently a C1-C6 alkyl group, C6-C6 alkyl group, or C6-C6 alkyl group. 10 aryl, C7-C 10 Aryl groups, C7-C 10 The alkylaryl, C1-C6 alkoxy, or R4-O-R5- group, where R4 is a C1-C6 alkyl, C6-C5 alkyl, or C6-C5 alkyl group. 10 aryl, C7-C 10 Aryl or C7-C 10 The alkylaryl group, R5 is a C1-C6 alkylene group, 1≤a≤30; R7 is each independently a C1-C6 alkyl group, C6-C6 alkylene group, C7 ... 10 aryl, C7-C 10 Aryl or C7-C 10 The alkylaryl group; R8 is each an alkyl group of C1-C6, C6-C 10 aryl, C7-C 10 Aryl groups, C7-C 10 alkylaryl, C1-C6 alkoxy or R9-OR 10 - group, wherein R9 is a C1-C6 alkyl group, C6 ...9-C9 alkyl group, C9 10 aryl, C7-C 10 Aryl or C7-C 10 alkylaryl, R 10 For C1-C 16 Alkylene, 0≤b≤30.

[0246] In some implementations, a is an integer from 1 to 80, an integer from 1 to 30, an integer from 1 to 20, or an integer from 1 to 10, such as 1, 5, 10, 15, 20, 25, 30, 40, 50, 60, etc.

[0247] In some implementations, b is 0. In some implementations, b is an integer from 1 to 30, an integer from 1 to 20, an integer from 1 to 10, or an integer from 1 to 5.

[0248] In some implementations, Z is independently selected from one or more of the following structures i-1 to i-6:

[0249]

[0250] R are each independently selected from C1-C 10 Alkyl groups (e.g., methyl, ethyl, isopropyl), C6-C 10 Aryl (e.g., phenyl), C7-C 12Aryl groups (e.g., benzyl) or C7-C12 alkylaryl groups (tolyl);

[0251] 1≤m+1≤60, preferably 1≤m+1≤30 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 10, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30); 0≤p≤60, preferably 0≤p≤30 (e.g., 0, 1, 2, 34, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 10, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30); 0≤q≤60 (e.g., 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60), preferably 0≤q≤30 (e.g., 0, 1, 2, 34, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 10, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30); 1≤x≤9 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9), preferably 1≤x≤7 (e.g., 1, 2, 3, 4, 5, 6, 7), and each x can be the same or different.

[0252] In some embodiments, R is a C1-C3 alkyl group, such as methyl or ethyl.

[0253] In some implementations, Z is selected from

[0254]

[0255] One or more of the following;

[0256] R are each independently selected from C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Aryl or C7-C 12 alkylaryl groups;

[0257] Me represents methyl, ph represents phenyl; 1≤m+1≤60, preferably 1≤m+1≤30; 0≤p≤60, preferably 0≤p≤30; 0≤q≤60, preferably 0≤q≤30; 1≤x≤9, preferably 1≤x≤7, and each x can be the same or different.

[0258] In some implementations, m is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9.

[0259] In some implementations, x is 1, 2, 3, 4, 5, 6, or 7.

[0260] Silicon monomer II-1 is selected from

[0261] CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9(1≤n≤25),

[0262] CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C8H 17 (1≤n≤25),

[0263] CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)3(1≤n≤25),

[0264] CH2=C(R)C(O)-O-(CH2)3Si(OSi(CH3)3)3,

[0265] CH2=C(R)C(O)-O-(CH2)3Si(CH3)(OSi(CH3)3)2,

[0266] CH2=C(R)C(O)-NH-(CH2)3Si(OSi(CH3)3)3,

[0267] CH2=C(R)C(O)-NH-(CH2)3Si(CH3)(OSi(CH3)3)2,

[0268] CH2=C(R)C(O)-O-(CH2)3Si(OSi(CH2CH3)3)3,

[0269] CH2=C(R)C(O)-O-CH2-Si(OSi(CH3)3)3,

[0270] CH2=C(CH3)C(O)-O-(CH2)3Si(CH3)[O-[Si(CH3)2O]n-Si(CH3)2C4H9]2(0≤n≤25),

[0271] CH2=CH-ph-Si(OSi(CH3)3)3 (ph represents...) ),

[0272] CH2=CH-ph-(CH2)2Si(OSi(CH3)3)3(ph represents...) ),

[0273] CH2=CH-ph-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl, ph represents...) (1≤n≤25),

[0274] CH2=CH-OC(O)-NH-(CH2)3Si(OSi(CH3)3)3,

[0275] CH2=CH-OC(O)-NH-(CH2)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl) (1≤n≤25),

[0276] CH2=CH-OC(O)-O-(CH2)3-Si(OSi(CH3)3)3,

[0277] CH2=CH-OC(O)-O-(CH2)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl) (1≤n≤25),

[0278] CH2=CH-OC(O)-O-(CH2)2-NH-(CH2)3Si(OSi(CH3)3)3,

[0279] CH2=CH-OC(O)-O-(CH2)2-NH-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl) (1≤n≤25),

[0280] In the formula, R is a hydrogen atom or a methyl group.

[0281] In some embodiments, silicon monomer II-1 includes silicon monomer II-A and / or silicon monomer II-B;

[0282] The general formula of silicon monomer II-A is the same as that of formula II-1, and satisfies the following conditions: when a is 1, Y1 and / or Y2 are the structures of formula (1); when a is greater than 1 and ≤200, at least one Y1 is the structure of formula (1) and / or at least one Y2 is the structure of formula (1).

[0283] The general formula of silicon monomer II-B is the same as that of formula II-1, and satisfies the following conditions: Y1 and Y2 are the same or different, and are each independently selected from C1-C. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups and C7-C 12 alkylaryl groups.

[0284] In some embodiments, the general formula of silicon monomer II-A is the same as that of formula II-A:

[0285] M-Z1 type II-A

[0286] M contains polymerizable functional groups;

[0287] Z1 is selected from the following structures.

[0288]

[0289] In Z1, R3 is independently selected from C1-C 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 20 The alkoxy group or R4-O-R5- group, where R4 is C1-C 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R5 is C1-C 20 Alkylene, 1≤a≤200;

[0290] Y1 and Y2 may be the same or different, and each is independently selected from C1-C2. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups, C7-C 12 The alkylaryl group has the structure of formula (1) and satisfies the following conditions: when a is 1, Y1 and / or Y2 are the structures of formula (1); when a is greater than 1 and ≤ 200, at least one Y1 is the structure of formula (1) and / or at least one Y2 is the structure of formula (1):

[0291]

[0292] R7 is selected independently from C1-C. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl groups; R8 groups are each independently selected from C1-C1. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 20 Alkoxy or R9-OR 10 - group, where R9 is C1-C 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R10 For C1-C 20 Alkylene, 0≤b≤200.

[0293] In this application, the limitation of M in Formula II-A is the same as the limitation of M in Formula II-1.

[0294] In some implementations, in Z1, R3 is independently C1-C. 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 10 alkoxy or R4-O-R5- group, where R4 is C1-C 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R5 is C1-C 10 Alkylene, 1≤a≤100; R7 are each independently C1-C 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl groups; each of the R8 groups is independently C1-C1. 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 10 Alkoxy or R9-OR 10 - group, where R9 is C1-C 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R 10 For C1-C 10 Alkylene, and / or 0≤b≤80.

[0295] According to some embodiments of this application, in Z1, R3 is each independently a C1-C6 alkyl group, C6-C6 alkyl group, or C6-C6 alkyl group. 10 aryl, C7-C 10 Aryl groups, C7-C 10 The alkylaryl, C1-C6 alkoxy, or R4-O-R5- group, where R4 is a C1-C6 alkyl, C6-C5 alkyl, or C6-C5 alkyl group. 10 aryl, C7-C 10 Aryl or C7-C 10The alkylaryl group, R5 is a C1-C6 alkylene group, 1≤a≤30; R7 is each independently a C1-C6 alkyl group, C6-C6 alkylene group, C7 ... 10 aryl, C7-C 10 Aryl or C7-C 10 The alkylaryl group; R8 is each an alkyl group of C1-C6, C6-C 10 aryl, C7-C 10 Aryl groups, C7-C 10 alkylaryl, C1-C6 alkoxy or R9-OR 10 - group, wherein R9 is a C1-C6 alkyl group, C6 ...9-C9 alkyl group, C9 10 aryl, C7-C 10 Aryl or C7-C 10 alkylaryl, R 10 For C1-C 16 Alkylene, 0≤b≤30.

[0296] In some implementations, in formula II-A, a is an integer from 1 to 80, an integer from 1 to 30, an integer from 1 to 20, or an integer from 1 to 10, such as 1, 5, 10, 15, 20, 25, 30, 40, 50, 60, etc.

[0297] In some embodiments, b is 0 in formula II-A. In some embodiments, b is an integer from 1 to 30, an integer from 1 to 20, an integer from 1 to 10, or an integer from 1 to 5 in formula II-A.

[0298] In some implementations, Z1 is selected from one or more of the following structures i-3 to i-6:

[0299]

[0300] R are each independently selected from C1-C 10 Alkyl groups (e.g., methyl, ethyl, isopropyl), C6-C 10 Aryl (e.g., phenyl), C7-C 12 Aryl groups (e.g., benzyl) or C7-C 12 alkyl aryl groups (e.g., benzyl);

[0301] 1≤m+1≤60, preferably 1≤m+1≤30 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 10, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30); 0≤p≤60, preferably 0≤p≤30 (e.g., 0, 1, 2, 34, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 10, 20, 21, 22, 23). 24, 25, 26, 27, 28, 29, 30); 0≤q≤60 (e.g., 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60), preferably 0≤q≤30 (e.g., 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60); 1≤x≤9 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9), preferably 1≤x≤7 (e.g., 1, 2, 3, 4, 5, 6, 7), each x can be the same or different.

[0302] In some embodiments, R is a C1-C3 alkyl group, such as methyl or ethyl.

[0303] In some preferred embodiments, Z1 is selected from the following structures:

[0304]

[0305] One or more of the following;

[0306] Me represents methyl, 1≤m+1≤60, preferably 1≤m+1≤30; 0≤p≤60, preferably 0≤p≤30; 0≤q≤60, preferably 0≤q≤30; 1≤x≤9, preferably 1≤x≤7, and each x can be the same or different.

[0307] In some embodiments, silicon monomer II-A is selected from...

[0308] CH2=C(R)C(O)-O-(CH2)3Si(OSi(CH3)3)3,

[0309] CH2=C(R)C(O)-O-(CH2)3Si(CH3)(OSi(CH3)3)2,

[0310] CH2=C(R)C(O)-NH-(CH2)3Si(OSi(CH3)3)3,

[0311] CH2=C(R)C(O)-NH-(CH2)3Si(CH3)(OSi(CH3)3)2,

[0312] CH2=C(R)C(O)-O-(CH2)3Si(OSi(CH2CH3)3)3,

[0313] CH2=C(R)C(O)-O-CH2-Si(OSi(CH3)3)3,

[0314] CH2=C(CH3)C(O)-O-(CH2)3Si(CH3)[O-[Si(CH3)2O]n-Si(CH3)2C4H9]2(0≤n≤25),

[0315] CH2=CH-ph-Si(OSi(CH3)3)3 (ph represents...) ),

[0316] CH2=CH-ph-(CH2)2Si(OSi(CH3)3)3(ph represents...) ),

[0317] CH2=CH-OC(O)-NH-(CH2)3Si(OSi(CH3)3)3,

[0318] CH2=CH-OC(O)-O-(CH2)3-Si(OSi(CH3)3)3,

[0319] CH2=CH-OC(O)-O-(CH2)2-NH-(CH2)3Si(OSi(CH3)3)3,

[0320] In the formula, R is a hydrogen atom or a methyl group.

[0321] In some embodiments, the general formula of silicon monomer II-B is shown in formula II-B:

[0322] M-Z2

[0323] Formula II-B

[0324] M contains polymerizable functional groups;

[0325] Z2 is selected from the following structures.

[0326]

[0327] In Z2, Y1 and Y2 may be the same or different, and each is independently selected from C1-C2. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups and C7-C 12 alkylaryl groups; R3 are each independently selected from C1-C1. 20 Alkyl, C6-C 20aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 20 The alkoxy group or R4-O-R5- group, where R4 is C1-C 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R5 is C1-C 20 Alkylene, 1≤a≤200.

[0328] In this application, the limitation of M in Formula II-B is the same as the limitation of M in Formula II-1.

[0329] In some implementations, in Z2, Y1 and Y2 may be the same or different, and each is independently selected from C1-C2. 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl groups and C7-C 12 alkylaryl groups; R3 are each independently selected from C1-C1. 10 Alkyl, C6-C 12 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 10 The alkoxy group or R4-O-R5- group, where R4 is C1-C 10 Alkyl, C6-C 12 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R5 is C1-C 10 Alkylene.

[0330] According to some embodiments of this application, in Z2, 1 ≤ a ≤ 80. According to some embodiments of this application, in Z2, 1 ≤ a ≤ 30. According to some embodiments of this application, in Z2, 1 ≤ a ≤ 20. According to some embodiments of this application, in Z2, 1 ≤ a ≤ 10.

[0331] In some embodiments, in Z2, Y1 and Y2 may be the same or different, each independently selected from C1-C6 alkyl groups, C6-C6 alkyl groups, and C6-C6 alkyl groups. 10 aryl, C7-C 10 Aryl groups and C7-C 10 The alkylaryl group; R3 is independently selected from C1-C6 alkyl groups, C6-C6 alkyl groups, and C6-C6 alkyl groups. 10 aryl, C7-C 10 Aryl groups, C7-C 10The alkylaryl group, C1-C6 alkoxy group, or R4-O-R5- group, where R4 is a C1-C6 alkyl group, C6-C5-alkyl group, or C4-O-R5-alkyl group. 10 aryl, C7-C 10 Aryl or C7-C 10 The alkylaryl group, where R5 is a C1-C6 alkylene group.

[0332] In some implementations, Z2 is selected from one or more of the following structures i-1 to i-2:

[0333]

[0334] R are each independently selected from C1-C 10 Alkyl groups (e.g., methyl, ethyl, isopropyl), C6-C 10 Aryl (e.g., phenyl), C7-C 12 Aryl groups (e.g., benzyl) or C7-C 12 alkylaryl (tolyl);

[0335] 1≤m+1≤60, preferably 1≤m+1≤30 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 10, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30); 1≤x≤9 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9), preferably 1≤x≤7.

[0336] Z2 is preferably derived from the following structure:

[0337]

[0338] One or more of the following;

[0339] Me represents methyl, ph represents phenyl; 1≤m+1≤60, preferably 1≤m+1≤30; 1≤x≤9, preferably 1≤x≤7.

[0340] In some embodiments, silicon monomer II-B is selected from...

[0341] CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9(1≤n≤25),

[0342] CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C8H 17 (1≤n≤25),

[0343] CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)3(1≤n≤25),

[0344] CCH2=CH-ph-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl, ph represents...)

[0345] (1≤n≤25),

[0346] CH2=CH-OC(O)-NH-(CH2)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl) (1≤n≤25),

[0347] CH2=CH-OC(O)-O-(CH2)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl) (1≤n≤25),

[0348] CH2=CH-OC(O)-O-(CH2)2-NH-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl) (1≤n≤25),

[0349] In the formula, R is a hydrogen atom or a methyl group.

[0350] In some embodiments, in Formula II-2, R1 is selected from C1-C4 alkyl groups, C5-C8 alkyl groups, or C6-C4 alkyl groups. 10 aryl; in formula II-3, R1 is selected from C1-C4 alkyl, C5-C8 alkyl or C6-C 10 The aryl group, R2 is selected from C1-C4 alkylene groups, X i+1 Selected from C1-C4 alkyl groups, C5-C8 alkyl groups, C6-C 10 The aryl group or the silicon-containing group shown in formula II-3, where i is 1, 2, 3, 4 or 5.

[0351] In some embodiments, silicon monomer II-2 is selected from...

[0352]

[0353]

[0354] In some embodiments, the fluorosilicone polymer further includes structural units generated from monomer III.

[0355] CH2=C(R1)-C(O)-O-R3III

[0356] In Formula III, R1 is a hydrogen atom or a C1-C atom. 20 Alkyl group; R3 is C1-C 40 Alkyl, C4-C 30 Cyclic hydrocarbon group or C7-C 20 Alkyl aryl.

[0357] In some embodiments, in Formula III, R1 is a hydrogen atom or a C1-C atom. 10 Alkyl group, preferably hydrogen atom or C1-C6 alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or n-hexyl.

[0358] In some embodiments, in Formula III, R3 is selected from C1-C 30 Alkyl or C4-C 20 Cyclic hydrocarbon group. In some embodiments, in Formula III, R3 is selected from C1-C6. 10 Alkyl, C 11 -C 20 Alkyl, C 20 -C 30 Alkyl, C4-C 10 cycloalkyl, C 11 -C 20 Cycloalkanes, C 31 -C 30 Cycloalkanes, C4-C 10 Cycloalkenyl, C 11 -C 20 Cycloolefins, C 31 -C 30 Cycloolefins, C7-C 15 Alkyl aryl.

[0359] In some embodiments, monomer III is selected from methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, tert-butyl methacrylate, isooctyl methacrylate, dodecyl methacrylate, myristyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecanyl methacrylate, octadecyl methacrylate, nonadecanyl methacrylate, eicosyl methacrylate, dodecyl methacrylate, and others. One or more of the following: docosyl acrylate, hexadecyl acrylate, triacontyl acrylate, cyclohexyl acrylate, tert-butylcyclohexyl acrylate, benzyl acrylate, isobornyl acrylate, dicyclopentyl acrylate, dicyclopentenyl acrylate, tricyclopentyl acrylate, adamantyl acrylate, 2-methyl-2-adamantyl acrylate, or 2-ethyl-2-adamantyl acrylate.

[0360] In some embodiments, the structural unit generated by fluorine monomer I has a mass percentage content of 10%-90% in the fluorosilicone polymer, for example, 11%, 13%, 15%, 17%, 19%, 20%, 21%, 23%, 25%, 27%, 29%, 30%, 31%, 33%, 35%, 37%, 39%, 40%, 41%, 43%, 45%, 47%, 49%, 50%, 51%, 53%, 55%, 57%, 59%, 60%, 61%, 63%, 65%, 67%, 69%, 70%, 71%, 73%, 75%, 77%, 79%, 80%, 81%, 83%, 85%, 87%, 89%, or any combination thereof. In some embodiments, the structural units generated by fluorine monomer I constitute 20%-80% of the fluorosilicone polymer by mass. In some embodiments, the structural units generated by fluorine monomer I constitute 30%-75% of the fluorosilicone polymer by mass.

[0361] In some embodiments, the structural units generated by silicon monomer II constitute 1%-80% of the fluorosilicone polymer by mass, for example, a range of 1%, 3%, 5%, 7%, 9%, 10%, 11%, 13%, 15%, 17%, 19%, 20%, 21%, 23%, 25%, 27%, 29%, 30%, 31%, 33%, 35%, 37%, 39%, 40%, 41%, 43%, 45%, 47%, 49%, 50%, 51%, 53%, 55%, 57%, 59%, 60%, 61%, 63%, 65%, 67%, 69%, 70%, 71%, 73%, 75%, 77%, 79%, or any combination thereof. In some embodiments, the structural units generated by silicon monomer II constitute 5%-60% of the fluorosilicone polymer by mass. In some embodiments, the structural unit generated by silicon monomer II has a mass content of 10%-50% in the fluorosilicone polymer.

[0362] In some embodiments, the mass ratio of fluorine monomer I to silicon monomer II is 1:100-100:1, for example, 1:97, 1:95, 1:93, 1:90, 1:87, 1:85, 1:83, 1:80, 1:77, 1:75, 1:73, 1:70, 1:67, 1:65, 1:63, 1:60, 1:57, 1:55, 1:53, 1: 50, 1:47, 1:45, 1:43, 1:40, 1:37, 1:35, 1:33, 1:30, 1:27, 1:25, 1:23, 1:20, 1:17, 1:15, 1:13, 1:10, 1:7, 1:5, 1:3, 1:1, 1:0.7, 1:0.5, 1:0.3, 1:0.1, or a range consisting of any two of them.

[0363] In some embodiments, the total mass percentage of fluorine monomer I and silicon monomer II in the fluorosilicone polymer is 40%-100%, for example, 41%, 43%, 45%, 47%, 49%, 50%, 51%, 53%, 55%, 57%, 59%, 60%, 63%, 65%, 67%, 70%, 73%, 75%, 77%, 80%, 83%, 85%, 87%, 90%, 93%, 95%, 97%, 98%, or any combination thereof. In some embodiments, the total mass percentage of fluorine monomer I and silicon monomer II in the fluorosilicone polymer is 60%-99%.

[0364] In some embodiments, the structural unit generated by monomer III has a mass content of 1%-40% in the fluorosilicone polymer, for example, a range of 1%, 3%, 5%, 7%, 9%, 10%, 11%, 13%, 15%, 17%, 19%, 20%, 21%, 23%, 25%, 27%, 29%, 30%, 31%, 33%, 35%, 37%, 39%, or any combination thereof.

[0365] In some embodiments, the proportion of structural units generated by silicon monomer II-A in the total number of structural units generated by silicon monomer II-A and silicon monomer II-B, by mass percentage, is 1% to 100%, 5% to 100%, 10% to 100%, or 50% to 100%, for example, 1%, 5%, 10%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, or any combination thereof. The total number of structural units generated by silicon monomer II-A and silicon monomer II-B is also the total number of structural units generated by monomer II.

[0366] In some embodiments, the fluorosilicone treatment agent further includes an emulsifier and an aqueous medium.

[0367] In some embodiments, the emulsifier is selected from one or more of nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.

[0368] In some embodiments, the nonionic surfactant is selected from one or more of ethers, esters, ester ethers, alkanolamides, polyols, and amine oxide surfactants. In some embodiments, the nonionic surfactant is a nonionic surfactant having an oxoalkylene group.

[0369] In some embodiments, the nonionic surfactant may be one or more of the following: linear and / or branched aliphatic alkylene oxide adducts, linear and / or branched fatty acid polyalkylene glycol esters, polyoxyethylene (POE) / polyoxypropylene (POP) copolymers (random copolymers or block copolymers), and alkylene oxide adducts of alkynyl glycol.

[0370] In some embodiments, the nonionic surfactant includes addition products of ethylene oxide with hexylphenol, isooctylphenol, hexadecyl alcohol, oleic acid, alkyl (C12-C16) thiols, sorbitan monofatty acids (C7-C9) or (C12-C18) amines.

[0371] In some embodiments, the cationic surfactant is selected from one or more of amines, amine salts, amine salts, imidazolines, and imidazoline-onium salts.

[0372] In some embodiments, an example of a cationic surfactant is R1-N. + (R2R3R4)X - R1, R2, R3, and R4 are each independently the same or different hydrogen atoms or hydrocarbon groups with 1-50 carbon atoms (e.g., C1-C6 alkyl, C7-C4 alkyl, etc.). 10 Alkyl, C 11 -C 15 Alkyl or C 16 -C 20 Alkyl group, aryl group with 6-50 carbon atoms, aralkyl group with 7-50 carbon atoms or alkylaryl group with 7-50 carbon atoms, where X is a halogen (e.g., chlorine or bromine) or an acid (e.g., inorganic acids such as hydrochloric acid or organic acids such as acetic acid (especially fatty acids)).

[0373] In some embodiments, the cationic surfactant includes one or more of dodecyltrimethylammonium acetate, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, and trimethyloctadecylammonium chloride.

[0374] In some embodiments, examples of anionic surfactants are fatty alcohol sulfates, such as sodium lauryl sulfate; alkyl sulfonates, such as sodium lauryl sulfonate; alkylbenzene sulfonates, such as sodium dodecylbenzene sulfonate; and fatty acid salts, such as sodium stearate. In some embodiments, examples of amphoteric surfactants include alanine derivatives, imidazoline betaines, amide betaines, and acetate betaines, specifically lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazoline betaine, lauryl dimethylaminoacetic acid betaine, and fatty amide propyl dimethylaminoacetic acid betaine.

[0375] In some embodiments, the emulsifier is a nonionic surfactant or a cationic surfactant.

[0376] In some embodiments, the emulsifier content is 0.1%-20% by mass, based on the mass of the fluorosilicone polymer, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, or 19%.

[0377] In some embodiments, the aqueous medium comprises water and an optional organic solvent. In some embodiments, the aqueous medium is preferably water. In some embodiments, the aqueous medium comprises water and an organic solvent. The organic solvent used herein is not particularly limited; any organic solvent miscible with water is suitable for this application. Examples of organic solvents include acetone, methyl ethyl ketone, ethyl acetate, ethanol, isopropanol, butyl diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, etc. It should be noted that the ratio of water to organic solvent is not particularly limited.

[0378] Thirdly, this application provides a method for preparing the fluorosilicone treatment agent described in the second aspect, which includes the following steps:

[0379] (1) Water, monomers (monomer I, monomer II, optional monomer III), emulsifier and optional organic solvent are mixed to obtain a pre-emulsion;

[0380] (2) Add an initiator and an optional molecular weight regulator to the pre-emulsion to carry out a polymerization reaction to obtain a polymer emulsion.

[0381] In some embodiments, monomer I, by weight, accounts for 10%-90% of the total monomer content, preferably 20%-80%, more preferably 30%-75%, for example, a range of 11%, 13%, 15%, 17%, 19%, 20%, 21%, 23%, 25%, 27%, 29%, 30%, 31%, 33%, 35%, 37%, 39%, 40%, 41%, 43%, 45%, 47%, 49%, 50%, 51%, 53%, 55%, 57%, 59%, 60%, 61%, 63%, 65%, 67%, 69%, 70%, 71%, 73%, 75%, 77%, 79%, 80%, 81%, 83%, 85%, 87%, 89%, or any combination thereof.

[0382] In some embodiments, the amount of monomer II, by weight, accounts for 1%-80% of the total monomer, preferably 5%-60%, more preferably 10%-50%, for example, 1%, 3%, 5%, 7%, 9%, 10%, 11%, 13%, 15%, 17%, 19%, 20%, 21%, 23%, 25%, 27%, 29%, 30%, 31%, 33%, 35%, 37%, 39%, 40%, 41%, 43%, 45%, 47%, 49%, 50%, 51%, 53%, 55%, 57%, 59%, 60%, 61%, 63%, 65%, 67%, 69%, 70%, 71%, 73%, 75%, 77%, 79%, or any combination thereof.

[0383] In some embodiments, the mass ratio of fluorine monomer I to silicon monomer II is 1:100-100:1, for example, 1:97, 1:95, 1:93, 1:90, 1:87, 1:85, 1:83, 1:80, 1:77, 1:75, 1:73, 1:70, 1:67, 1:65, 1:63, 1:60, 1:57, 1:55, 1:53, 1: 50, 1:47, 1:45, 1:43, 1:40, 1:37, 1:35, 1:33, 1:30, 1:27, 1:25, 1:23, 1:20, 1:17, 1:15, 1:13, 1:10, 1:7, 1:5, 1:3, 1:1, 1:0.7, 1:0.5, 1:0.3, 1:0.1, or a range consisting of any two of them.

[0384] In some embodiments, the total mass percentage of fluorine monomer I and silicon monomer II in the total monomers is 40%-100%, for example, 41%, 43%, 45%, 47%, 49%, 50%, 51%, 53%, 55%, 57%, 59%, 60%, 63%, 65%, 67%, 70%, 73%, 75%, 77%, 80%, 83%, 85%, 87%, 90%, 93%, 95%, 97%, 98%, or any combination thereof. In some embodiments, the total mass percentage of fluorine monomer I and silicon monomer II in the total monomers is 60%-99%.

[0385] In some embodiments, the amount of monomer III, by weight, accounts for 1% to 40% of the total monomer, for example, 1%, 3%, 5%, 7%, 9%, 10%, 11%, 13%, 15%, 17%, 19%, 20%, 21%, 23%, 25%, 27%, 29%, 30%, 31%, 33%, 35%, 37%, 39%, or any combination thereof.

[0386] In some embodiments, the amount of silicon monomer II-A, by weight, accounts for 1% to 100%, 5% to 100%, 10% to 100%, 50% to 100%, 50% to 98% of the total amount of silicon monomer II-A and silicon monomer II-B, for example, 1%, 5%, 10%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, or any combination thereof.

[0387] In some embodiments, the initiator is selected from one or more of peroxides, azo compounds, and persulfates. In some embodiments, the initiator is selected from water-soluble initiators.

[0388] In some embodiments, the water-soluble initiator is selected from one or more of 2,2'-azobis(2-methylpropanediamine) hydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] hydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] sulfate hydrate, 2,2'-azobis[2-(5-methyl-imidazolin-2-yl)propane] hydrochloride, potassium persulfate, barium persulfate, ammonium persulfate, hydrogen peroxide, and tert-butyl hydroperoxide.

[0389] In some embodiments, the initiator is preferably a water-soluble azo compound with a half-life of 10 hours and a decomposition temperature of 40°C or higher, such as 2,2'-azobisisobutylamidine dihydrochloride.

[0390] In some embodiments, the initiator content is 0.1%-5% based on the mass of the monomer, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, or 4.5%.

[0391] In some embodiments, the molecular weight regulator is selected from thiol compounds, such as 2-mercaptopropionic acid, 2-mercaptoethanol, alkyl thiols, or mercaptopropionic acid.

[0392] In some embodiments, the mass content of the molecular weight regulator is 0.01%-10% based on the mass of the monomer, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%.

[0393] In some embodiments, the polymerization reaction is carried out at a temperature of 40°C to 90°C. In some embodiments, the polymerization reaction is carried out for a duration of 4 hours to 20 hours.

[0394] In some embodiments, the typical emulsion polymerization process of this application is as follows:

[0395] Water, monomers, emulsifiers, and organic solvents are mixed. The monomers are first emulsified by high-speed dispersion, and nitrogen gas is introduced for purging. An initiator, optional molecular weight regulator, and optional organic solvent are added. The mixture is heated to a reaction temperature of 40-90°C, and the reaction time varies from 4 to 20 hours.

[0396] Fourthly, this application provides the application of the fluorosilicone polymer described in the first aspect, the fluorosilicone treatment agent described in the second aspect, or the fluorosilicone treatment agent prepared by the method described in the third aspect in fibrous fabrics.

[0397] Fifthly, this application provides a water- and oil-repellent fiber fabric, comprising a fiber fabric and the fluorosilicone polymer described in the first aspect, or the fluorosilicone treatment agent described in the second aspect, or the fluorosilicone treatment agent prepared by the method described in the third aspect.

[0398] In some embodiments, the fluorosilicone polymer of the first aspect, or the fluorosilicone treatment agent of the second aspect, or the fluorosilicone treatment agent prepared by the method of the third aspect, is adhered to the surface and / or interior of the fibrous fabric or coating.

[0399] In a sixth aspect, this application provides a method for treating a fiber fabric, which includes contacting the fiber fabric with the fluorosilicone polymer described in the first aspect, the fluorosilicone treatment agent described in the second aspect, or the fluorosilicone treatment agent prepared by the method described in the third aspect.

[0400] In some embodiments, the contact is achieved through a surface sizing process, a surface coating process, a wet-end addition process, or an immersion treatment process.

[0401] The fluorosilicone treatment agent of this application can be applied to the treated object using existing known methods. Typically, the treatment agent is dispersed in an organic solvent or diluted in water, then applied to the surface of the treated article using known methods such as dip coating, spray coating, or foam coating, followed by drying. Additionally, it can be applied with a suitable crosslinking agent (e.g., end-capped isocyanate) for vulcanization when necessary. Insect repellents, softeners, antibacterial agents, flame retardants, antistatic agents, anti-wrinkle agents, etc., can also be added to the fluorosilicone treatment agent of this application for use. The concentration of the polymer in the treatment solution in contact with the substrate can be 0.01-10% by weight (especially in dip coating), for example, 0.05-10% by weight.

[0402] In this application, various examples can be cited as fibrous fabrics. For example, natural animal or plant fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and cellulose acetate; inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber; or blends thereof.

[0403] The effects of the invention

[0404] The fluorosilicone polymer or fluorosilicone treatment agent of this application is applied to the treatment of fiber fabrics, which can reduce the use of fluorine elements and impart oil and water repellency to the surface of the fiber fabrics after treatment. Detailed Implementation

[0405] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided in conjunction with embodiments. These embodiments are for illustrative purposes only and are not intended to limit the scope of this application in any way. The actual scope of protection of this application is set forth in the claims.

[0406] Unless otherwise specified, the terms used in this application have the general meanings known to those skilled in the art.

[0407] In this application, the term "alkyl" refers to a straight-chain alkyl or a branched alkyl, and non-limiting examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, etc.

[0408] In this application, the term "alkylene" refers to a straight-chain alkylene or a branched alkylene, and non-limiting examples include: methylene, ethylene, n-propylene, n-butylene, n-pentylene, -CHCH3CH2-, -CHCH3CH2CH2-, CH2CH3CHCH2-, etc.

[0409] Unless otherwise specified, "%" in this application refers to mass percentage.

[0410] I. Aggregation Methods

[0411] The typical emulsion polymerization process of this application is as follows:

[0412] Water, monomer, emulsifier and organic solvent are mixed. The monomer is first emulsified and homogenized by high-speed shearing, then nitrogen is introduced for purging. An initiator and optional molecular weight regulator are added and heated to the reaction temperature of 40-90℃. The reaction time varies from 4 to 20 hours.

[0413] The manufacturing process of the fluorosilicone treatment agent in this application is as follows:

[0414] (1) The water, monomer, emulsifier and optional organic solvent are homogenized and mixed to obtain a pre-emulsion;

[0415] (2) Add an initiator and an optional molecular weight regulator to the pre-emulsion to carry out a polymerization reaction to obtain a polymer emulsion.

[0416] II. Testing Methods

[0417] Fiber fabric treatment

[0418] In this embodiment, the fabrics treated were dyed 100% polyester fabric and 100% khaki cotton twill fabric. The treatment method was as follows: the fabric sample was immersed in a fluorosilicone treatment agent (polymer emulsion) containing a certain concentration of the present application for impregnation treatment (absorption rate 70%), then dried at 110°C for 90 seconds and baked at 170°C for 60 seconds to obtain the sample fabric. The water repellency, water-repellent properties, and oil repellency of the obtained sample fabric were evaluated.

[0419] Evaluation Methods for Fiber Fabrics—Spray Water Repellency Test

[0420] The dynamic water repellency of treated substrates was determined according to the American Association of Textile and Chemical Operators (AATCC) TM-22 standard, referring to the published criteria. A glass funnel with a volume of at least 250 mL and a nozzle capable of spraying 250 mL of water over 20–30 seconds were used. The test piece frame was a metal frame with a diameter of 15 cm. Three test pieces, approximately 20 cm × 20 cm in size, were prepared and fixed to the test piece frame, ensuring the pieces were wrinkle-free. The center of the spray was positioned at the center of the piece, and 250 mL of room temperature water was added to the glass funnel and sprayed onto the test piece over 25–30 seconds. The frame was removed from the table, and one end of the frame was held so that the front surface was under the surface of the frame. The opposite end was gently tapped with a hard object. The frame was then rotated 180° and the same steps were repeated to allow excess water to drip off. The wet test pieces were rated on a scale of 0, 50, 70, 80, 90, and 100, from poor to excellent water repellency (see Table 1 for details). Compare with a moist standard. Obtain the results based on the average of three measurements.

[0421] Table 1 Water Repellency Rating Table

[0422] Water Repellency No. State 100 No surface wetness or water droplets adhering 90 Surface not wet, but small water droplets adhering 80 Surface wet with small, individual water droplets 70 Half of the surface wet, showing small, individual water droplets State of the permeable fabric 50 Surface entirely wet 0 Surface and back entirely wet surface

[0423] Fiber Fabric Test Methods—Oil Resistance

[0424] Oil resistance is evaluated according to the AATCC-TM118 test method. The basic principle is to drop test oils with different surface tensions onto the test cloth. The higher the grade, the better the oil resistance. The composition of the standard test liquid is shown in Table 2 below.

[0425] Table 2 Composition of Fabric Oil Resistance Test Grades

[0426] Oil repellency rating test solution surface tension (mN / m8): n-Heptane 20.07, n-Octane 21.86, n-Decane 23.55, n-Dodecane 25.04, n-Tetradecane 26.73, n-Hexadecane 27.32, Liquid paraffin 65 parts / n-Hexadecane 35 parts 29.61, Liquid paraffin 31.2 surface

[0427] III. Examples and Comparative Examples

[0428] See Table 3 for chemical abbreviations.

[0429] Table 3. Codes and Chemical Formulas of Each Substance

[0430]

[0431]

[0432] Example 1

[0433] Add 200g of deionized water, 115g of AR-F monomer, 20g of Si-B3 monomer, 33g of acetone, 6g of polyoxyethylene isotridecyl ether (EO:18, 18 ethylidene units), 1.5g of polyoxyethylene isotridecyl ether (EO:3, 3 ethylidene units) and 60g of octadecyltrimethylammonium chloride (10% solution) to a four-necked flask equipped with a reflux condenser, nitrogen inlet tube, thermometer and stirrer to obtain a mixture.

[0434] The above mixture was ultrasonically emulsified and dispersed at 50°C for 30 minutes with stirring. After purging the reaction flask with nitrogen, a solution of 1.05 g of 2,2'-azobis(2-amidinylpropane) dihydrochloride and 9 g of water was added. The temperature was raised to 60°C, and the reaction was carried out for 10 hours to obtain a polymer emulsion. The solids content was then adjusted to 25% with deionized water. The comparison between the theoretical solids content and the measured solids content showed that the monomer conversion rate was greater than 98%.

[0435] Examples 2-7

[0436] The experiment was exactly the same as in Example 1, except that different ratios of AR-F and Si-B3 were used. The specific ratios and performance are shown in Test Table 4.

[0437] Comparative Example 1

[0438] Add 200g of deionized water, 135g of AR-F monomer, 33g of acetone, 6g of polyoxyethylene isotridecyl ether (EO:18, 18 ethylidene units), 1.5g of polyoxyethylene isotridecyl ether (EO:3, 3 ethylidene units) and 60g of octadecyltrimethylammonium chloride (10% solution) to a four-necked flask equipped with a reflux condenser, nitrogen inlet tube, thermometer and stirrer to obtain a mixture.

[0439] The above mixture was ultrasonically emulsified and dispersed at 50°C for 30 minutes with stirring. After purging the reaction flask with nitrogen, 2,2 ， A solution of 1.05 g of azobis(2-amidinylpropane)dihydrochloride and 9 g of water was prepared. The mixture was heated to 60 °C and reacted for 10 hours to obtain a polymer emulsion. The solid content was then adjusted to 25% with deionized water. The comparison between the theoretical solid content and the measured solid content showed that the monomer conversion rate was greater than 98%.

[0440] Comparative Example 2

[0441] Add 200g of deionized water, 135g of Si-B3 monomer, 33g of acetone, 6g of polyoxyethylene isotridecyl ether (EO:18, 18 ethylidene units), 1.5g of polyoxyethylene isotridecyl ether (EO:3, 3 ethylidene units) and 60g of octadecyltrimethylammonium chloride (10% solution) to a four-necked flask equipped with a reflux condenser, nitrogen inlet tube, thermometer and stirrer to obtain a mixture.

[0442] The above mixture was ultrasonically emulsified and dispersed at 50°C for 30 minutes with stirring. After purging the reaction flask with nitrogen, a solution of 1.05 g of 2,2'-azobis(2-amidinylpropane) dihydrochloride and 9 g of water was added. The temperature was raised to 60°C, and the reaction was carried out for 10 hours to obtain a polymer emulsion. The solids content was then adjusted to 25% with deionized water. The comparison between the theoretical solids content and the measured solids content showed that the monomer conversion rate was greater than 98%.

[0443] Polymer emulsions were used to test fiber fabrics: 100% polyester fabric and 100% cotton fabric were selected respectively. The polymer emulsions obtained were diluted with tap water to prepare liquids of 4%, 2%, and 1.5% (polymer emulsion content), and then subjected to padding treatment. After that, the samples were dried at 110℃ for 90 seconds and baked at 170℃ for 60 seconds. The water repellency and oil resistance of the obtained samples were evaluated, and the results are shown in Table 4.

[0444] Table 4 Performance Test Table

[0445]

[0446] Example 8

[0447] Add 200g of deionized water, 105g of AR-F monomer, 30g of Si-B3 monomer, 10g of St-A monomer, 33g of acetone, 6g of polyoxyethylene isotridecyl ether (EO:18, 18 ethylidene units), 1.5g of polyoxyethylene isotridecyl ether (EO:3, 3 ethylidene units) and 60g of octadecyltrimethylammonium chloride (10% solution) to a four-necked flask equipped with a reflux condenser, nitrogen inlet tube, thermometer and stirrer to obtain a mixture.

[0448] The above mixture was ultrasonically emulsified and dispersed at 50°C for 30 minutes with stirring. After purging the reaction flask with nitrogen, a solution of 1.05 g of 2,2'-azobis(2-amidinylpropane) dihydrochloride and 9 g of water was added. The temperature was raised to 60°C, and the reaction was carried out for 10 hours to obtain a polymer emulsion. The solids content was then adjusted to 25% with deionized water. The comparison between the theoretical solids content and the measured solids content showed that the monomer conversion rate was greater than 98%.

[0449] Examples 9-11

[0450] The process was identical to Example 8, except that different silicon monomers were used instead of Si-B3: Si-ph-B3 (Example 9), Si-COO-Z3 (Example 10), Si-ph-Z3 (Example 11), and Si-B5 (average molecular weight 500) (Example 12). Polyester and cotton fabrics were treated according to the described fabric treatment method, and performance tests are shown in Figure 5.

[0451] Table 5 Performance Test Table

[0452]

[0453]

[0454] As can be seen from the performance test results in Tables 4 and 5 and the comparative examples, the treatment agent using all fluorinated monomers achieves better oil resistance, while the oil resistance is relatively weak when using all silicone monomers. In the embodiments of this application, by replacing part of the fluorinated monomers with silicone monomers, the resulting fluorosilicone treatment agent, after treating the fabric, showed no significant loss in oil repellency compared to the comparative example treatment agent using only fluorinated monomers. When the silicone monomer substitution ratio was large, although the oil resistance decreased somewhat, the water repellency was better than that using either perfluorinated or persilicone monomers. The solution of this application achieves the goal of reducing fluorine content and also improves water repellency.

[0455] The technical solutions of this application are not limited to the specific embodiments described above. Any technical modifications made based on the technical solutions of this application shall fall within the protection scope of this application.

Claims

1. A fluorosilicone polymer comprising structural units generated from fluorine monomer I and structural units generated from silicon monomer II, wherein the structure of fluorine monomer I is shown in Formula I: In Formula I, R1 is selected from hydrogen atoms or C1-C4 alkyl groups; A is selected from alkylene-(CH2)n-, where n is 1-10; R f Selected from fluorinated C1-C 21 Alkyl, preferably fluorinated C4-C 16 Alkyl group; the silicon monomer II comprises silicon monomer II-1 and silicon monomer II-2, the structure of silicon monomer II-1 being as shown in formula II-1: MZ II-1 In formula II-1, M contains a polymerizable functional group; Z is selected from the following structures: In Z, R3 is independently selected from C1-C1. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 20 The alkoxy group or R4-O-R5- group, where R4 is C1-C 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R5 is C1-C 20 Alkylene, 1≤a≤200; Y1 and Y2 may be the same or different, each independently selected from C1-C2. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups, C7-C 12 The alkylaryl group or the structure of formula (1) is as follows: R7 is selected independently from C1-C. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl groups; R8 groups are each independently selected from C1-C1. 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups, C7-C 12 alkylaryl, C1-C 20 Alkoxy or R9-OR 10 - group, where R9 is C1-C 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R 10 For C1-C 20 Alkylene, 0 ≤ b ≤ 200; the structure of the silicon monomer II-2 is shown in formula II-2: In Formula II-2, M is selected from groups containing polymerizable groups, and each R1 may be the same or different, independently selected from C1-C1. 10 Alkyl, C6-C 12 aryl, C7-C 12 Aryl or C7-C 12 The alkylaryl groups, each with the same or different X1, are independently silicon-containing groups represented by the following formula II-3 when i=1: i represents the number of silicon-containing groups shown in Formula II-3, and is an integer selected from 1 to 10; in Formula II-3, R1 is selected from C1-C 10 Alkyl, C6-C 12 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl; R2 is selected from C1-C 10 Alkylene; X i+1 Selected from hydrogen, C1-C 10 Alkyl, C6-C 12 aryl, C7-C 12 Aryl groups, C7-C 12 The alkylaryl group or the silicon-containing group shown in Formula II-3.

2. The fluorosilicone polymer according to claim 1, characterized in that, In silicon monomers II-1 and II-2, M is as shown in formula I-1: CH2=C(R1)-YB- I-1 In formula I-1, R1 is selected from hydrogen atoms or C1-C 20 Alkyl group; Y is selected from the groups shown in Y-1, Y-2, Y-3, Y-4, Y-5, Y-6, -C(O)-O-Y_1-C(O)-N(R2)-Y-2 -OC(O)-N(R2)- Y-4-OC(O)-O- Y-5-OC(O)-ODN(R2)- Y-6R2 is selected from hydrogen atoms or C1-C 20 Alkyl group, D is C1-C 20 Alkylene; when Y is selected from Y-1, Y-2, Y-4, Y-5, Y-6, B is C1-C 20 Alkylene, C6-C 20 For the aryl group and its combination, when Y is selected from Y-3, B either does not exist or is C1-C. 20 Alkylene, C6-C 20 The aryl group and its combination.

3. The fluorosilicone polymer according to claim 1 or 2, characterized in that, The fluorosilicone polymer also includes structural units generated from monomer III, CH2=C(R1)-C(O)-O-R3III, where R1 is a hydrogen atom or C1-C 20 Alkyl group; R3 is C1-C 40 Alkyl, C4-C 30 Cyclic hydrocarbon group or C7-C 20 Alkyl aryl.

4. The fluorosilicone polymer according to any one of claims 1-3, characterized in that, The structural units generated by fluorine monomer I in the fluorosilicone polymer have a mass percentage content of 10%-90%, preferably 20%-80%, more preferably 30%-75%; and / or the structural units generated by silicon monomer II have a mass percentage content of 1%-80%, preferably 5%-60%, more preferably 10%-50%; and / or the mass ratio of fluorine monomer I to silicon monomer II is 1:100-100:1; and / or the total mass percentage content of fluorine monomer I and silicon monomer II in the fluorosilicone polymer is 40%-100%, for example 60%-99%. The structural units generated by monomer III and / or monomer III account for 1%-40% of the mass content in the fluorosilicone polymer.

5. The fluorosilicone polymer according to any one of claims 1-4, characterized in that, Silicon monomer II-1 includes silicon monomer II-A and / or silicon monomer II-B; the general formula of silicon monomer II-A is the same as that of formula II-1, and satisfies the following conditions: when a is 1, Y1 and / or Y2 are structures of formula (1); when a is greater than 1 and ≤ 200, at least one Y1 is a structure of formula (1) and / or at least one Y2 is a structure of formula (1); the general formula of silicon monomer II-B is the same as that of formula II-1, and satisfies the following conditions: Y1 and Y2 are the same or different, and are each independently selected from C1-C 20 Alkyl, C6-C 20 aryl, C7-C 12 Aryl groups and C7-C 12 alkylaryl groups.

6. The fluorosilicone polymer according to any one of claims 1-5, characterized in that, In Formula I, R1 is selected from hydrogen atoms or methyl groups; A is selected from alkylene-(CH2)n-, where n is 2, 3, 4, 5, 6, 7, 8, or 9; R f Selected from perfluorinated C4-C 10 Alkyl; and / or in formula I-1, R1 is selected from hydrogen atoms or C1-C6 alkyl groups, preferably hydrogen atoms or methyl groups, and B is C1-C6. 10 alkylene or C6-C 15 The arylene group, preferably B is a C1-C6 alkylene group; in Y of formula I-1, R2 is selected from hydrogen atoms or C1-C6 alkyl groups, preferably hydrogen atoms or; and / or in Z of formula II-1, R4 is independently C1-C6. 10 Alkyl group, C6-C 10 aryl, C7-C 12 Aryl or C7-C 12 The alkylaryl group, or R5-O-R6- group, where R5 is C1-C 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl group, R6 is C1-C 10 Alkylene, 1≤a≤80; R7 are each independently C1-C 10 Alkyl group, C6-C 10 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl groups; each of the R8 groups is independently C1-C1. 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, or R9-OR 10 - group, where R9 is C1-C 10 Alkyl, C6-C 10 aryl, C7-C 12 Aryl or C7-C 12 alkylaryl, R 10 For C1-C 10 Alkylene, 0 ≤ b ≤ 80; and / or in formula II-2, R1 is selected from C1-C4 alkyl, C5-C8 alkyl or C6-C 10 aryl; in formula II-3, R1 is selected from C1-C4 alkyl, C5-C8 alkyl or C6-C 10 The aryl group, R2 is selected from C1-C4 alkylene groups, X i+1 Selected from C1-C4 alkyl groups, C5-C8 alkyl groups, C6-C 10 The aryl group or silicon-containing group shown in formula II-3, i is 1, 2, 3, 4 or 5; and / or in formula III, R1 is selected from hydrogen atom or C1-C6 alkyl, preferably selected from hydrogen atom or methyl; R3 is selected from C1-C6 alkyl. 30 Alkyl, C4-C 20 Cyclic hydrocarbon group or C7-C 15 Alkyl aryl.

7. The fluorosilicone polymer according to any one of claims 1-6, characterized in that, Z is selected from one or more of the following structures i-1 to i-6: Z is preferred from One or more of them; R is independently selected from C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Aryl or C7-C 12 The alkylaryl group; Me represents methyl, ph represents phenyl, 1≤m+1≤60, preferably 1≤m+1≤30; 0≤p≤60, preferably 0≤p≤30; 0≤q≤60, preferably 0≤q≤30; 1≤x≤9, preferably 1≤x≤7, and each x can be the same or different.

8. The fluorosilicone polymer according to any one of claims 1-7, characterized in that, Fluorine monomer I is selected from CH2=C(R)C(O)-OCH2CH2(CF2)5CF3, CH2=C(R)C(O)-OCH2CH2(CF2)7CF3, CH2=C(R)C(O)-OCH2CH2CH2(CF2)5CF3, CH2=C(R)C(O)-OCH2CH2CH2(CF2)7CF3, CH2=C(R)C(O)-OCH2CH2(CF2)3CF3 CH2=C(R)C(O)-OCH2CH2CH2(CF2)3CF3R is selected from hydrogen atoms or methyl groups and / or silicon monomers. II-1 is selected from CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (1≤n≤25), CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C8H 17 , (1≤n≤25), CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)3(1≤n≤25), CH2=C(R)C(O)-O-(CH2)3Si(OSi(CH3)3) 3. CH2=C(R)C(O)-O-(CH2)3Si(CH3)(OSi(CH3)3)2,CH2=C(R)C(O)-NH-(CH2)3Si(OSi(CH3)3)3,CH2=C(R)C(O)-NH-(C H2)3Si(CH3)(OSi(CH3)3)2, CH2=C(R)C(O)-O-(CH2)3Si(OSi(CH2CH3)3)3, CH2=C(R)C(O)-O-CH2-Si(OSi(CH3)3)3, CH2=C(CH3)C(O)-O-(CH2)3Si(CH3)[O-[Si(CH3)2O]n-Si(CH3)2C4H9]2(0≤n≤25), CH2=CH-ph-Si(OSi(CH3)3)3(ph means ), CH2=CH-ph-(CH2)2Si(OSi(CH3)3)3(ph represents ), CH2=CH-ph-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl, ph represents (1≤n≤25), CH2=CH-OC(O)-NH-(CH2)3Si(OSi(CH3)3)3, CH2=CH-OC(O)-NH-(CH2)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl) (1≤n≤25), CH2=CH-OC(O)-O-(CH2)3-Si(OSi(CH3)3)3, CH2=CH-OC(O)-O-(CH2)3-[Si(CH3)2C4H9) [2O]n-Si(CH3)2C4H9 (C4H9 represents butyl) (1≤n≤25), CH2=CH-OC(O)-O-(CH2)2-NH-(CH2)3Si(OSi(CH3)3)3, CH2=CH-OC(O)-O-(CH2)2-NH-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl) (1≤n≤25), where R is a hydrogen atom or a methyl group; and / or silicon monomer II-2 is selected from... And / or monomer III is selected from methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, tert-butyl methacrylate, isooctyl methacrylate, dodecyl methacrylate, myristyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecanyl methacrylate, octadecyl methacrylate, nonadecanyl methacrylate, eicosyl methacrylate, dodecyl methacrylate, methpropylene One or more of the following: docosyl acrylate, hexadecyl acrylate, triacontyl acrylate, cyclohexyl acrylate, tert-butylcyclohexyl acrylate, benzyl acrylate, isobornyl acrylate, dicyclopentyl acrylate, dicyclopentenyl acrylate, tricyclopentyl acrylate, adamantyl acrylate, 2-methyl-2-adamantyl acrylate, or 2-ethyl-2-adamantyl acrylate.

9. A fluorosilicone treatment agent, characterized in that, The fluorosilicone treatment agent comprises the fluorosilicone polymer, emulsifier, and aqueous medium according to any one of claims 1-8, preferably, the emulsifier is selected from one or more of nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants; and / or the aqueous medium comprises water and optional organic solvents.

10. A method for preparing the fluorosilicone treatment agent of claim 9, comprising the following steps: (1) Mix water, monomer, emulsifier and optional organic solvent to obtain a pre-emulsion; (2) Add an initiator and optional molecular weight regulator to the pre-emulsion to carry out a polymerization reaction to obtain a polymer emulsion.

11. The use of the fluorosilicone polymer of any one of claims 1-8, the treatment agent of claim 9, or the fluorosilicone treatment agent prepared by the method of claim 10 in fibrous fabrics.

12. A water- and oil-repellent fiber fabric comprising a fiber fabric and a fluorosilicone polymer according to any one of claims 1-8, or a fluorosilicone treatment agent according to claim 9, or a fluorosilicone treatment agent prepared by the method according to claim 10, preferably, the fluorosilicone polymer according to any one of claims 1-8, or the fluorosilicone treatment agent according to claim 9, or the fluorosilicone treatment agent prepared by the method according to claim 10, is attached to the surface and / or interior of the fiber fabric.

13. A method for treating a fiber fabric, comprising contacting the fiber fabric with a fluorosilicone polymer according to any one of claims 1-8, or a fluorosilicone treatment agent according to claim 9, or a fluorosilicone treatment agent prepared by the method according to claim 10, wherein preferably, the contact is achieved by a surface sizing process, a surface coating process, a wet-end addition process, or an immersion treatment process.

Images