Treatment agent and fiber fabric or coating

Abstract

A treatment agent and a fiber fabric or coating treated by same. The treatment agent comprises an organic silicon polymer, an emulsifier, and an aqueous medium, wherein the organic silicon polymer comprises a structural unit generated by a monomer I, and the monomer I comprises a silicon monomer I-A and an optional silicon monomer I-B. The treatment agent can simultaneously endow a fiber fabric with good oil and water repellent functions and endow a coating with a good anti-fouling or anti-graffiti capability.

Description

Treatment agents and fiber fabrics or coatings

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to the Chinese patent application with application number 202310988989.0 filed on August 7, 2023, and invention name “Treatment agent and fiber fabric or coating”. The entire contents of the above patent application are incorporated into this application as a whole. Technical Field

[0003] The present application relates to a treating agent and fiber fabric or coating after being treated therewith. Technical Background

[0004] In the past, fluoropolymers were used to treat the surface of fiber fabrics for water and oil repellency. Due to their low surface tension, fluoropolymers can change the surface properties of fiber fabrics without affecting their appearance, so they have been widely used.

[0005] However, in recent years, due to the increasing international attention on polyfluoroalkyl substances (PFAS), in March 2023, the European Chemicals Agency (ECHA) launched a public consultation on the proposal submitted by Denmark, Germany, the Netherlands, Norway and Sweden to ECHA to add restrictions on the manufacture, placing on the market and use of PFAS in the REACH restriction chapter (REACH Annex XIVII). The purpose is to give relevant parties the opportunity to express their opinions on the inclusion of PFAS in the REACH restriction chapter for control. After the public consultation, ECHA's Risk Assessment Committee (RAC) and Socio-Economic Analysis Committee (SEAC) will evaluate the proposed restrictions and form opinions based on the consultation opinions. Ultimately, the European Commission will decide whether to include PFAS in the restriction chapter for control.

[0006] In view of the above situation, some new non-fluorine compounds are proposed to replace the existing fluorine-containing finishing agents.

[0007] CN107849187A proposes a method of using a copolymer of acrylate and monomers such as vinyl chloride to form a polymer for finishing textiles, which has a good water-repellent effect.

[0008] CN105765025B proposes a copolymer using long-chain alkyl acrylates. The resulting polymer is used to finish textiles and also has a good water-repellent effect. CN105764980B and CN 105745272B both use similar processes to synthesize treatment agents to achieve water-repellent effects.

[0009] CN114573768B proposes a self-dispersible polymer in water using organic silicon. The formed polymer is used to finish fiber fabrics and has certain water-repellent and oil-repellent effects, but the water-repellent effect is not outstanding.

[0010] Therefore, it is necessary to invent a non-fluorine-based treatment agent that has excellent water-repellent effect and oil-repellent effect, which can effectively resist various water-based and oil-based stains.

[0011] Summary of the Invention

[0012] In a first aspect, the present application provides an organosilicon polymer obtained by emulsion polymerization, which can be used for water- and oil-repellent treatment of fiber fabrics or for anti-fouling or anti-graffiti treatment of coatings.

[0013] Specifically, the organosilicon polymer provided herein includes a structural unit produced by monomer I, wherein monomer I includes silicon monomer IA and optional silicon monomer IB.

[0014] a) The general structural formula of the silicon monomer IA is shown in Formula IA:

[0015] M-Z1 or Z1-M-Z1

[0016] Formula IA

[0017] Wherein, M contains a polymerizable functional group;

[0018] Z1 is selected from the following structures:

[0019] In Z1, R4 is independently C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkaryl, C1-C 20 Alkoxy or R5-O-R6- group, R5 is C1-C 10 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl, R6 is C1-C 20 Alkylene, 1≤a≤200;

[0020] Y1 and Y2 are the same or different and are independently selected from C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Aralkyl, C7-C 12alkylaryl or a structure of formula (1), and also satisfying that 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):

[0021] R7 is independently C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 R8 are each independently C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkaryl, C1-C 20 Alkoxy or R9-OR 10 - group, wherein R9 is C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 The alkylaryl group, R 10 C1-C 20 Alkylene, 0≤b≤200;

[0022] b) The general structural formula of the silicon monomer IB is shown in Formula IB:

[0023] M-Z2 or Z2-M-Z2

[0024] Formula IB

[0025] Wherein, M contains a polymerizable functional group;

[0026] Z2 is selected from the following structures,

[0027] In Z2, R3 is independently C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl, R4 are each independently C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkaryl, C1-C 20 Alkoxy or R5-O-R6- group, R5 is C1-C 10 Alkyl, C6-C 20 Aryl, C7-C12 Arylalkyl or C7-C 12 Alkaryl, R6 is C1-C 20 Alkylene, 1≤a≤200.

[0028] In some embodiments, the polymerizable functional group in M ​​is selected from groups containing carbon-carbon double bonds.

[0029] In some embodiments, in Formula IA and / or Formula IB, M is as shown in Formula I-1:

[0030] CH2=C(R1)-XB-

[0031] I-1

[0032] In formula I-1, R1 is selected from hydrogen atom or C1-C 20 Alkyl; B is selected from C1-C 20 Alkylene, C6-C 20 Aryl and combinations thereof, X is selected from the groups represented by X-1 and X-2,

[0033] -C(O)-O-

[0034] X-1

[0035] -C(O)-N(R2)-

[0036] X-2

[0037] R2 is selected from hydrogen atom or C1-C 20 of alkyl.

[0038] In some embodiments, in Formula I-1, R1 is selected from a hydrogen atom or a C1-C 10 Alkyl, for example, C1-C3 alkyl, C4-C6 alkyl or C8-C 10 In some embodiments, in Formula I-1, B is C1-C 10 Alkylene, for example, C1-C3 alkylene, C4-C6 alkylene or C8-C 10 of alkylene.

[0039] In some embodiments, in Formula I-1, B is C6-C 15 arylene, such as C6-C9 arylene, C 10 -C 12 Arylene or C 13 -C 15 arylene group.

[0040] In some embodiments, in the groups represented by X-1 and X-2, R2 is selected from hydrogen atom or C1-C 10Alkyl, for example, C1-C3 alkyl, C4-C6 alkyl or C8-C 10 of alkyl.

[0041] In some embodiments, in Formula I-1, R1 is selected from a hydrogen atom or a methyl group; B is a C1-C6 alkylene group; and in X, R2 is selected from a hydrogen atom or a methyl group.

[0042] In some embodiments, in Formula IA and / or Formula IB, M is as shown in Formula I-2:

[0043] CH2=C(R1)-WB-

[0044] I-2

[0045] In formula I-2, R1 is selected from hydrogen atom or C1-C 20 alkyl;

[0046] W is selected from the group represented by W-1, W-2, W-3 and W-4,

[0047] -OC(O)-N(R2)- W-2

[0048] -OC(O)-O- W-3

[0049] -OC(O)-ODN(R2)- W-4

[0050] R2 is selected from hydrogen atom or C1-C 20 Alkyl, D is C1-C 20 When W is selected from W-1, B is absent or C1-C 20 When W is selected from W-2, W-3, W-4, B is selected from C1-C 20 Alkylene, C6-C 20 aryl groups and combinations thereof.

[0051] In some embodiments, in Formula I-2, R1 is selected from a hydrogen atom or a C1-C 10 Alkyl, for example, C1-C3 alkyl, C4-C6 alkyl or C8-C 10 In some embodiments, in formula I-2, B is C1-C 10 Alkylene, for example, C1-C3 alkylene, C4-C6 alkylene or C8-C 10 of alkylene.

[0052] In some embodiments, in formula I-2, R2 is selected from hydrogen atom or C1-C 10 Alkyl, for example, C1-C3 alkyl, C4-C6 alkyl or C8-C10 In some embodiments, in formula I-2, D is C1-C 10 Alkylene, for example, C1-C3 alkylene, C4-C6 alkylene or C8-C 10 of alkylene.

[0053] In some embodiments, in Formula I-2, R1 and R2 are selected from hydrogen atoms or methyl groups, and B and D are C1-C6 alkylene groups.

[0054] In some embodiments, when W is selected from W-1, B is absent or is C1-C 10 Alkylene, for example, C1-C3 alkylene, C4-C6 alkylene or C8-C 10 of alkylene.

[0055] In some embodiments, when W is selected from W-2, W-3, and W-4, B is C1-C 10 Alkylene, for example, C1-C3 alkylene, C4-C6 alkylene or C8-C 10 of alkylene.

[0056] In some embodiments, when W is selected from W-2, W-3, and W-4, B is C6-C 15 arylene, such as C6-C9 arylene, C 10 -C 12 Arylene or C 13 -C 15 arylene group.

[0057] In some embodiments, in Formula IA and / or Formula IB, M is as shown in Formula I-3:

[0058] In formula I-3, R1 is selected from hydrogen atom or C1-C 20 Alkyl, B is independently selected from C1-C 20 Alkylene, C6-C 20 aryl groups and combinations thereof.

[0059] In some embodiments, in formula I-3, R1 is selected from hydrogen atom or C1-C 10 Alkyl, for example, C1-C3 alkyl, C4-C6 alkyl or C8-C 10 In some embodiments, in formula I-3, B is C1-C 10 Alkylene, for example, C1-C3 alkylene, C4-C6 alkylene or C8-C 10 of alkylene.

[0060] In some embodiments, in Formula I-3, B is C6-C15 arylene, such as C6-C9 arylene, C 10 -C 12 Arylene or C 13 -C 15 arylene group.

[0061] In some embodiments, in Formula I-3, R1 is selected from a hydrogen atom or a methyl group.

[0062] In some embodiments, in Z1, R4 are each independently C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkaryl, C1-C 10 Alkoxy or R5-O-R6- group, R5 is C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl, R6 is C1-C 10 and / or 1≤a≤100, for example 1≤a≤80; R7 are each independently C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 R8 are each independently C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkaryl, C1-C 10 Alkoxy or R9-OR 10 - group, wherein R9 is C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 The alkylaryl group, R 10 C1-C 10 and / or 0≤b≤100, for example, 0≤b≤80.

[0063] In some embodiments, in Z1, R4 are each independently C1-C6 alkyl, C6-C 10 Aryl, C7-C 10 Aralkyl, C7-C 10 Alkaryl, C1-C6 alkoxy or R5-O-R6- group, R5 is C1-C6 alkyl, C6-C 10Aryl, C7-C 10 Arylalkyl or C7-C 10 R6 is a C1-C6 alkylene group, 1≤a≤30; R7 are each independently a C1-C6 alkyl group, C6-C 10 Aryl, C7-C 10 Arylalkyl or C7-C 10 R8 are each independently C1-C6 alkyl, C6-C 10 Aryl, C7-C 10 Aralkyl, C7-C 10 Alkaryl, C1-C6 alkoxy or R9-OR 10 - group, wherein R9 is C1-C6 alkyl, C6-C 10 Aryl, C7-C 10 Arylalkyl or C7-C 10 The alkylaryl group, R 10 It is a C1-C6 alkylene group, 0≤b≤30.

[0064] In some embodiments, a is an integer from 1-80, an integer from 1-30, an integer from 1-20, or an integer from 1-10.

[0065] In some embodiments, b is 0. 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.

[0066] In particular, R4 and R8 represent C1-C 20 Alkyl, C1-C 20 Alkoxy, C6-C 20 The aryl groups are particularly commonly used, such as C1-C8 alkyl and C1-C4 alkoxy. For example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxy, ethoxy, propoxy and butoxy. Aryl groups include phenyl, tolyl and naphthyl. R4 and R8 can also be of the structure (R5-O-R6)-, where R5 is C1-C 10 Alkyl, R6 is C1-C 10 Alkylene, more common such as CH3O(CH2) x - etc. R6 is a 20 Alkyl groups and C6-C 20 The aryl groups are selected from, for example, alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, hexadecyl, etc., and aromatic groups are phenyl, tolyl and naphthyl, etc.

[0067] In some embodiments, Z1 is selected from one or more of the following structures i-1 to i-4:

[0068] R is independently selected from C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl;

[0069] 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.

[0070] In some embodiments, R is a C1-C3 alkyl group, such as a methyl group.

[0071] In some preferred embodiments, Z1 is selected from the following structures:

[0072] One or more of;

[0073] Me represents a methyl group, 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.

[0074] In some embodiments, in Z2, R3 are each independently C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl, R4 are each independently C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkaryl, C1-C 10 Alkoxy or R5-O-R6- group, R5 is C1-C 10 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl, R6 is C1-C 10 of alkylene.

[0075] In some embodiments, in Z2, 1≤a≤100. In some embodiments, in Z2, 1≤a≤80. According to some embodiments of the present application, in Z2, 1≤a≤30. According to some embodiments of the present application, in Z2, 1≤a≤20. According to some embodiments of the present application, in Z2, 1≤a≤10.

[0076] In some embodiments, in Z2, R3 are each independently C1-C6 alkyl, C6-C 10 Aryl, C7-C 10 Arylalkyl or C7-C 10 Alkaryl, R4 are each independently C1-C6 alkyl, C6-C 10 Aryl, C7-C 10 Aralkyl, C7-C 10 an alkylaryl group, a C1-C6 alkoxy group or an R5-O-R6- group, R5 is a C1-C6 alkyl group, a C6-C 10 Aryl, C7-C 10 Arylalkyl or C7-C 10 Alkaryl, R6 is C1-C 10 Alkylene, 1≤a≤10.

[0077] In some embodiments, Z2 is selected from one or more of the following structures ii-1 to ii-2:

[0078] R is independently selected from C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl;

[0079] 1≤m+1≤60, preferably 1≤m+1≤30; 1≤x≤9, preferably 1≤x≤7.

[0080] In some embodiments, Z2 is selected from the following structures:

[0081] One or more of;

[0082] Me represents a methyl group, ph represents a phenyl group; 1≤m+1≤60, preferably 1≤m+1≤30; 1≤x≤9, preferably 1≤x≤7.

[0083] In some embodiments, m is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9.

[0084] In some embodiments, x is 1, 2, 3, 4, 5, 6, or 7.

[0085] In some embodiments, the silicon monomer IA is selected from

[0086] CH2=C(CH3)C(O)-O-(CH2)3Si(OSi(CH3)3)3;

[0087] CH2=CHC(O)-O-(CH2)3Si(OSi(CH3)3)3;

[0088] CH2=C(CH3)C(O)-O-(CH2)3Si(CH3)(OSi(CH3)3)2;

[0089] CH2=CHC(O)-O-(CH2)3Si(CH3)(OSi(CH3)3)2;

[0090] CH2=C(CH3)C(O)-NH-(CH2)3Si(OSi(CH3)3)3;

[0091] CH2=CHC(O)-NH-(CH2)3Si(OSi(CH3)3)3;

[0092] CH2=C(CH3)C(O)-NH-(CH2)3Si(CH3)(OSi(CH3)3)2;

[0093] CH2=CHC(O)-NH-(CH2)3Si(CH3)(OSi(CH3)3)2;

[0094] CH2=C(CH3)C(O)-O-(CH2)3Si(OSi(CH2CH3)3)3;

[0095] CH2=CHC(O)-O-(CH2)3Si(OSi(CH2CH3)3)3;

[0096] CH2=C(CH3)C(O)-O-CH2-Si(OSi(CH3)3)3;

[0097] CH2=C(CH3)C(O)-O-(CH2)3Si(CH3)[O-[Si(CH3)2O]n-Si(CH3)2C4H9]2,0≤n≤25;

[0098] CH2=CH-ph-Si(OSi(CH3)3)3(ph) );

[0099] CH2=CH-ph-(CH2)2Si(OSi(CH3)3)3(ph) );

[0100] CH2=CH-OC(O)-NH-(CH2)3Si(OSi(CH3)3)3;

[0101] CH2=CH-OC(O)-O-(CH2)3-Si(OSi(CH3)3)3;

[0102] CH2=CH-OC(O)-O-(CH2)2-NH-(CH2)3Si(OSi(CH3)3)3;

[0103] CH2=CH-C(O)-N[-(CH2)3-Si(OSi(CH3)3)3]2;

[0104] CH2=CH-C(O)-N[-(CH2)3-Si(CH3)(OSi(CH3)3)2]2.

[0105] In some embodiments, silicon monomer IB is selected from

[0106] CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl), 1≤n≤25;

[0107] CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C8H 17 , 1≤n≤25;

[0108] CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)3, 1≤n≤25;

[0109] CH2=CH-ph-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9(C4H9 represents butyl, ph represents ), 1≤n≤25;

[0110] CH2=CH-OC(O)-NH-(CH2)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl), 1≤n≤25;

[0111] CH2=CH-OC(O)-O-(CH2)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl), 1≤n≤25;

[0112] CH2=CH-OC(O)-O-(CH2)2-NH-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl), 1≤n≤25;

[0113] CH2=CH-C(O)-N[-(CH2)3-(Si(CH3)2O) n-Si(CH3)2C4H9]2 (C4H9 represents butyl), 1≤n≤25;

[0114] CH2=C(CH3)-C(O)-N[-(CH2)3-(Si(CH3)2O) n -Si(CH3)2C4H9]2 (C4H9 represents butyl group), 1≤n≤25.

[0115] In some embodiments, the organosilicon polymer further comprises a structural unit derived from monomer II,

[0116] CH2=C(R1)-C(O)-O-R3 II

[0117] R1 is a hydrogen atom or a C1-C 20 Alkyl; R3 is C1-C 40 Alkyl, C4-C 30 Cyclic hydrocarbons or C7-C 20 Alkaryl.

[0118] In some embodiments, in Formula II, R1 is a hydrogen atom or a C1-C 10 The alkyl group is preferably a hydrogen atom or a C1-C6 alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group or an n-hexyl group.

[0119] In some embodiments, in Formula II, R3 is selected from C1-C 30 Alkyl or C4-C 20 In some embodiments, in Formula II, R3 is selected from C1-C 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 Alkaryl.

[0120] In some embodiments, monomer II is selected from methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosyl (meth)acrylate, (meth)acrylate) ) benzyl (meth)acrylate, behenyl (meth)acrylate, hexadecyl (meth)acrylate, triacontyl (meth)acrylate, cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tricyclopentyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate or one or more of 2-ethyl-2-adamantyl (meth)acrylate.

[0121] In some embodiments, the organosilicon polymer does not include structural units produced by monomer IV, wherein monomer IV is selected from one or more of dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, N-tert-butylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, dipropylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, diethylaminopropyl (meth)acrylamide or dipropylaminopropyl (meth)acrylamide.

[0122] In some embodiments, the general structural formula of monomer IV is as shown in Formula IV:

[0123] CH2=C(R1)-PBN(R3R4) IV

[0124] In formula IV, P is selected from the groups represented by P-1 and P-2,

[0125] -C(O)-O-

[0126] P-1

[0127] -C(O)-N(R2)-

[0128] P-2

[0129] B is C1-C 20 R1 and R2 are each independently a hydrogen atom or a C1-C 20R3 and R4 are each independently a hydrogen atom, C1-C 18 or R3 and R4 are combined and together with the nitrogen atom form a morpholino group, a piperidino group or a pyrrolidinyl group.

[0130] In some embodiments, the proportion of the structural units generated by silicon monomer IA to the total amount of the structural units generated by silicon monomer IA and the structural units generated by silicon monomer IB, measured by mass percentage, is 1% to 100%, 5% to 100%, 10% to 100%, or 50% to 100%, such as 1%, 5%, 10%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, or a range consisting of any two thereof. The total amount of the structural units generated by silicon monomer IA and the structural units generated by silicon monomer IB is the total amount of the structural units generated by monomer I.

[0131] In some embodiments, the weight content of the structural units generated by monomer I is 30%-100%. In some embodiments, the weight content of the structural units generated by monomer I is 40%-85%. In some embodiments, the weight content of the structural units generated by monomer I is 50%-80%. In some embodiments, the weight content of the structural units generated by monomer I is 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or a range consisting of any two thereof.

[0132] In some embodiments, the weight content of the structural unit generated by monomer II is 5%-70%. In some embodiments, the weight content of the structural unit generated by monomer II is 10%-70%. In some embodiments, the weight content of the structural unit generated by monomer II is 15%-50%. In some embodiments, the weight content of the structural unit generated by monomer II is 20%-45%. In some embodiments, the weight content of the structural unit generated by monomer II is 5%, 7%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or any two thereof.

[0133] In some embodiments, the organosilicon polymer further includes a structural unit produced by a cross-linking monomer III, wherein the cross-linking monomer is a compound having two reactive groups and / or an unsaturated carbon-carbon double bond (preferably (meth)acrylate), or a compound having at least two unsaturated carbon-carbon double bonds (preferably (meth)acrylate), or a compound having at least one unsaturated carbon-carbon double bond and at least one reactive group. Preferred examples of reactive groups include hydroxyl, epoxy, chloromethyl, blocked isocyanate, amino or carboxyl groups.

[0134] In some embodiments, the crosslinking monomer III may be selected from one or more of diacetone (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetylethyl (meth)acrylate, glycidyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, or 2-butanone oxime adduct of ethyl (meth)acrylate-2-isocyanate.

[0135] In some embodiments, the organosilicon polymer does not include a structural unit produced by monomer V, wherein monomer V is selected from one or more of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, or methoxypolyethylene glycol (meth)acrylate.

[0136] In some embodiments, the general structural formula of monomer V is as shown in Formula V: CH2=C(R1)-G-(R2O) q -R3 V

[0137] In Formula V, R1 represents a hydrogen atom or a methyl group, R2 is independently a C1-C6 alkylene group, preferably a C2-C4 alkylene group, q is an integer from 1 to 50, preferably an integer from 1 to 20; R3 represents a hydrogen atom or a C1-C 20 An alkyl group, preferably a hydrogen atom or a C1-C 10 An alkyl group, more preferably a hydrogen atom, a C1-C3 alkyl group;

[0138] Wherein, G is selected from the groups represented by G-1 and G-2,

[0139] -C(O)-OB-

[0140] G-1

[0141] -C(O)-N(R4)-B-

[0142] G-2

[0143] R4 represents a hydrogen atom or a methyl group, B does not exist or is C1-C 20 The alkylene group is preferably absent or C1-C 10 of alkylene.

[0144] In some embodiments, in Formula V, R2 is a C2-C4 alkylene group. In some embodiments, in Formula V, q is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, or 49. In some embodiments, in Formula V, q is an integer from 1 to 20.

[0145] In some embodiments, in Formula V, R3 is a hydrogen atom or a C1-C 10 The alkyl group is, for example, a hydrogen atom, a C1-C3 alkyl group or a C4-C6 alkyl group.

[0146] In some embodiments, in the groups represented by G-1 and G-2, B is absent or is C1-C 10 The alkylene group is, for example, a C1-C3 alkylene group or a C4-C6 alkylene group.

[0147] In some embodiments, the organosilicon polymer does not include a structural unit derived from monomer VI, wherein monomer VI is selected from N-vinyl-2-pyrrolidone, N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-3,3-dimethyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-3-ethylpyrrolidone, N-vinyl-4,5-dimethylpyrrolidone, N-vinyl N-vinyl-5,5-dimethylpyrrolidone, N-vinyl-3,3,5-trimethylpyrrolidone, N-vinyl-5-methyl-5-ethylpyrrolidone, N-vinyl-3,4,5-trimethyl-3-ethylpyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-3-ethylpyrrolidone, N-vinyl-4,5-dimethylpyrrolidone, N-vinyl-5,5-dimethylpyrrolidone, N-vinyl-3,3,5-trimethylpyrrolidone, N-vinyl-5-methyl-5-ethylpyrrolidone Alkanone, N-vinyl-3,4,5-trimethyl-3-ethylpyrrolidone, N-vinyl-2-piperidone, N-vinyl-3-methylpiperidone, N-vinyl-3-methylcaprolactam, N-vinyl-4-methylpiperidone, N-vinyl-4-methylcaprolactam, N-vinyl-4-methylpiperidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-3,5-dimethyl-2-piperidone, N-vinyl-4,4-dimethyl-2-piperidone One or more of ketone, N-vinyl-2-caprolactam, N-vinyl-7-methylcaprolactam, N-vinyl-7-ethylcaprolactam, N-vinyl-3,5-dimethylcaprolactam, N-vinyl-4,6-dimethylcaprolactam, N-vinyl-3,5,7-trimethylcaprolactam, N-vinyl-2-valerolactam, N-vinylhexahydro-2-azacycloheptanone, N-vinyloctahydro-2-azacyclooctanone, N-vinyloctahydro-2-azacyclononanone and N-vinyldecahydro-2-azacyclodecanone.

[0148] In some embodiments, the general structural formula of monomer VI is as shown in Formula VI:

[0149] In Formula VI, n is an integer between 1 and 6, s is an integer between 0 and 16, and each R is the same or different and is independently selected from C1-C 20 The alkyl group is preferably selected from C1-C 10 An alkyl group is more preferably selected from a C1-C6 alkyl group.

[0150] In some embodiments, in Formula VI, n is 1, 2, 3, 4, 5, or 6.

[0151] In some embodiments, in Formula VI, s is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16.

[0152] In some embodiments, in Formula VI, each R is the same or different and is independently selected from a C1-C6 alkyl group, such as a C1-C3 alkyl group or a C4-C6 alkyl group.

[0153] In some embodiments, the organosilicon polymer does not include a structural unit derived from monomer VII, wherein monomer VII is selected from acrylamide, methacrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, N-butylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-isopropylmethacrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-di ... One or more of propyl(meth)acrylamide, N-butylmethacrylamide, N-(meth)acryloylpyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-(meth)acryloylpyrrole, N-(meth)acryloylpiperidone, N-(meth)acryloylmorpholine, N-(meth)acryloylpiperazine, N-(meth)acryloylaziridine, N-(meth)acryloylazetidine, N-(meth)acryloylazepane and N-(meth)acryloylazepane.

[0154] In some embodiments, the general structural formula of monomer VII is as shown in Formula VII:

[0155] CH2=C(R1)-C(O)-N(R2R3) VII

[0156] In formula VII, R1 is selected from hydrogen atom or C1-C 20 The alkyl group, R1 is preferably a hydrogen atom or a methyl group;

[0157] R2 and R3 are each independently selected from hydrogen atom or C1-C 20 R2 and R3 are preferably selected from hydrogen atoms or C1-C 10 An alkyl group, more preferably a hydrogen atom or a C1-C6 alkyl group;

[0158] Alternatively, R2 and R3, together with the nitrogen atom to which they are attached, form a C3-C8 heterocyclic group, preferably a pyrrolidone, piperidinyl, pyrrolidinyl, pyrrolyl, piperidinone, morpholinyl, piperazinyl, aziridine, azetidinyl, azepanyl or azocanyl group.

[0159] In some embodiments, in Formula VII, R1 is selected from a hydrogen atom or a C1-C 10 In some embodiments, in Formula VII, R1 is selected from a hydrogen atom or a C1-C6 alkyl group, such as a C1-C3 alkyl group, a C4-C6 alkyl group. In some embodiments, R1 is preferably selected from a hydrogen atom or a methyl group.

[0160] In some embodiments, in Formula VII, R2 and R3 are each independently selected from a hydrogen atom or a C1-C 10 In some embodiments, in Formula VII, R2 and R3 are each independently selected from a hydrogen atom or a C1-C6 alkyl group, such as a C1-C3 alkyl group, a C4-C6 alkyl group.

[0161] In some embodiments, in Formula VII, R2 and R3, together with the nitrogen atom to which they are attached, form an azacyclic C3-C8 alkyl group.

[0162] In some embodiments, in Formula VII, R2 and R3, together with the nitrogen atom to which they are attached, form pyrrolidone, piperidinyl, pyrrolidinyl, pyrrolyl, piperidonyl, morpholinyl, piperazinyl, aziridinyl, azetidinyl, azepanyl, or azocanyl.

[0163] In some embodiments, the weight average molecular weight of the organosilicon polymer is 1,000-3,000,000, for example, 5,000-2,500,000. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

[0164] In a second aspect, the present application provides a novel silicone polymer emulsion treating agent, which can impart excellent water and oil repellency to the surface of fiber fabrics or impart excellent anti-fouling or anti-graffiti capabilities to coatings, so that fiber fabrics and coatings can effectively resist water-based and oil-based stains.

[0165] In some embodiments, the treatment agent provided herein includes an organosilicon polymer, an emulsifier, and an aqueous medium, wherein the organosilicon polymer is the organosilicon polymer described in the first aspect.

[0166] In other embodiments, the treating agent provided herein comprises an organosilicon polymer, an emulsifier, and an aqueous medium, wherein the organosilicon polymer comprises a structural unit produced by monomer I, monomer I comprises silicon monomer IA and optional silicon monomer IB,

[0167] a) The general structural formula of the silicon monomer IA is shown in Formula IA:

[0168] M-Z1 or Z1-M-Z1

[0169] Formula IA

[0170] Wherein, M contains a polymerizable functional group;

[0171] Z1 is selected from the following structures:

[0172] In Z1, R4 is independently C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkaryl, C1-C 20 Alkoxy or R5-O-R6- group, R5 is C1-C 10 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl, R6 is C1-C 20 Alkylene, 1≤a≤200;

[0173] Y1 and Y2 are the same or different and are independently selected from C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Aralkyl, C7-C 12 alkylaryl or a structure of formula (1), and also satisfying that 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):

[0174] R7 is independently C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 R8 are each independently C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkaryl, C1-C 20 Alkoxy or R9-OR 10 - group, wherein R9 is C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 The alkylaryl group, R 10 C1-C 20 Alkylene, 0≤b≤200;

[0175] b) The general structural formula of the silicon monomer IB is shown in Formula IB:

[0176] M-Z2 or Z2-M-Z2

[0177] Formula IB

[0178] Wherein, M contains a polymerizable functional group;

[0179] Z2 is selected from the following structures,

[0180] In Z2, R3 is independently C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl, R4 are each independently C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkaryl, C1-C 20 Alkoxy or R5-O-R6- group, R5 is C1-C 10 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl, R6 is C1-C 20 Alkylene, 1≤a≤200.

[0181] The inventors of the present application unexpectedly discovered that the polymer emulsion obtained by polymerizing the above-mentioned monomer I and the optional monomer II has an excellent water-repellent effect and an oil-repellent effect, thereby giving the fiber fabric excellent oil and water repellency and the coating anti-fouling and anti-graffiti properties.

[0182] In some embodiments, the polymerizable functional group in M ​​is selected from groups containing carbon-carbon double bonds.

[0183] In some embodiments, in Formula IA and / or Formula IB, M is as shown in Formula I-1:

[0184] CH2=C(R1)-XB-

[0185] I-1

[0186] In formula I-1, R1 is selected from hydrogen atom or C1-C 20 Alkyl; B is selected from C1-C 20 Alkylene, C6-C 20 Aryl and combinations thereof,

[0187] X is selected from the group represented by X-1 and X-2,

[0188] -C(O)-O- X-1

[0189] -C(O)-N(R2)- X-2

[0190] R2 is selected from hydrogen atom or C1-C 20 of alkyl.

[0191] In some embodiments, in Formula I-1, R1 is selected from a hydrogen atom or a C1-C 10 Alkyl, for example, C1-C3 alkyl, C4-C6 alkyl or C8-C 10 In some embodiments, in Formula I-1, B is C1-C 10 Alkylene, for example, C1-C3 alkylene, C4-C6 alkylene or C8-C 10 of alkylene.

[0192] In some embodiments, in Formula I-1, B is C6-C 15 arylene, such as C6-C9 arylene, C 10 -C 12 Arylene or C 13 -C 15 arylene group.

[0193] In some embodiments, in the groups represented by X-1 and X-2, R2 is selected from hydrogen atom or C1-C 10 Alkyl, for example, C1-C3 alkyl, C4-C6 alkyl or C8-C 10 of alkyl.

[0194] In some embodiments, in Formula I-1, R1 is selected from a hydrogen atom or a methyl group; B is a C1-C6 alkylene group; and in X, R2 is selected from a hydrogen atom or a methyl group.

[0195] In some embodiments, in Formula IA and / or Formula IB, M is as shown in Formula I-2:

[0196] CH2=C(R1)-WB- I-2

[0197] In formula I-2, R1 is selected from hydrogen atom or C1-C 20 alkyl;

[0198] W is selected from the group represented by W-1, W-2, W-3 and W-4,

[0199] -OC(O)-N(R2)- W-2

[0200] -OC(O)-O- W-3

[0201] -OC(O)-ODN(R2)- W-4

[0202] R2 is selected from hydrogen atom or C1-C 20 Alkyl, D is C1-C 20 When W is selected from W-1, B is absent or C1-C 20 When W is selected from W-2, W-3, W-4, B is selected from C1-C 20 Alkylene, C6-C 20 arylene groups and combinations thereof.

[0203] In some embodiments, in Formula I-2, R1 is selected from a hydrogen atom or a C1-C 10 Alkyl, for example, C1-C3 alkyl, C4-C6 alkyl or C8-C 10 In some embodiments, in formula I-2, B is C1-C 10 Alkylene, for example, C1-C3 alkylene, C4-C6 alkylene or C8-C 10 of alkylene.

[0204] In some embodiments, in formula I-2, R2 is selected from hydrogen atom or C1-C 10 Alkyl, for example, C1-C3 alkyl, C4-C6 alkyl or C8-C 10 In some embodiments, in formula I-2, D is C1-C 10 Alkylene, for example, C1-C3 alkylene, C4-C6 alkylene or C8-C 10 of alkylene.

[0205] In some embodiments, in Formula I-2, R1 and R2 are selected from hydrogen atoms or methyl groups, and B and D are C1-C6 alkylene groups.

[0206] In some embodiments, when W is selected from W-1, B is absent or is C1-C 10 Alkylene, for example, C1-C3 alkylene, C4-C6 alkylene or C8-C 10 of alkylene.

[0207] In some embodiments, when W is selected from W-2, W-3, and W-4, B is C1-C 10 Alkylene, for example, C1-C3 alkylene, C4-C6 alkylene or C8-C 10 of alkylene.

[0208] In some embodiments, when W is selected from W-2, W-3, and W-4, B is C6-C 15 arylene, such as C6-C9 arylene, C 10 -C 12 Arylene or C 13 -C 15 arylene group.

[0209] In some embodiments, in Formula IA and / or Formula IB, M is as shown in Formula I-3:

[0210] In formula I-3, R1 is selected from hydrogen atom or C1-C 20 Alkyl, B is independently selected from C1-C 20 Alkylene, C6-C 20 aryl groups and combinations thereof.

[0211] In some embodiments, in formula I-3, R1 is selected from hydrogen atom or C1-C 10 Alkyl, for example, C1-C3 alkyl, C4-C6 alkyl or C8-C 10 In some embodiments, in formula I-3, B is C1-C 10 Alkylene, for example, C1-C3 alkylene, C4-C6 alkylene or C8-C 10 of alkylene.

[0212] In some embodiments, in Formula I-3, B is C6-C 15 arylene, such as C6-C9 arylene, C 10 -C 12 Arylene or C 13 -C 15 arylene group.

[0213] In some embodiments, in Formula I-3, R1 is selected from a hydrogen atom or a methyl group.

[0214] In some embodiments, in Z1, R4 are each independently C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkaryl, C1-C 10 Alkoxy or R5-O-R6- group, R5 is C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl, R6 is C1-C 10and / or 1≤a≤100, for example 1≤a≤80; R7 are each independently C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 R8 are each independently C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkaryl, C1-C 10 Alkoxy or R9-OR 10 - group, wherein R9 is C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 The alkylaryl group, R 10 C1-C 10 and / or 0≤b≤100, for example, 0≤b≤80.

[0215] In some embodiments, in Z1, R4 are each independently C1-C6 alkyl, C6-C 10 Aryl, C7-C 10 Aralkyl, C7-C 10 Alkaryl, C1-C6 alkoxy or R5-O-R6- group, R5 is C1-C6 alkyl, C6-C 10 Aryl, C7-C 10 Arylalkyl or C7-C 10 R6 is a C1-C6 alkylene group, 1≤a≤30; R7 are each independently a C1-C6 alkyl group, C6-C 10 Aryl, C7-C 10 Arylalkyl or C7-C 10 R8 are each independently C1-C6 alkyl, C6-C 10 Aryl, C7-C 10 Aralkyl, C7-C 10 Alkaryl, C1-C6 alkoxy or R9-OR 10 - group, wherein R9 is C1-C6 alkyl, C6-C 10 Aryl, C7-C 10 Arylalkyl or C7-C 10 The alkylaryl group, R 10 It is a C1-C6 alkylene group, 0≤b≤30.

[0216] In some embodiments, a is an integer from 1-80, an integer from 1-30, an integer from 1-20, or an integer from 1-10.

[0217] In some embodiments, b is 0. 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.

[0218] In particular, R4 and R8 represent C1-C 20 Alkyl, C1-C 20 Alkoxy, C6-C 20 The aryl groups are particularly commonly used, such as C1-C8 alkyl and C1-C4 alkoxy. For example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxy, ethoxy, propoxy and butoxy. Aryl groups include phenyl, tolyl and naphthyl. R4 and R8 can also be of the structure (R5-O-R6)-, where R5 is C1-C 10 Alkyl, R6 is C1-C 10 Alkylene, more common such as CH3O(CH2) x - etc. R6 is a 20 Alkyl groups and C6-C 20 The aryl groups are selected from, for example, alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, hexadecyl, etc., and aromatic groups are phenyl, tolyl and naphthyl, etc.

[0219] In some embodiments, Z1 is selected from one or more of the following structures i-1 to i-4:

[0220] R is independently selected from C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl;

[0221] 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.

[0222] In some embodiments, R is a C1-C3 alkyl group, such as a methyl group.

[0223] In some preferred embodiments, Z1 is selected from the following structures:

[0224] One or more of;

[0225] Me represents a methyl group, 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.

[0226] In some embodiments, in Z2, R3 are each independently C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl, R4 are each independently C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkaryl, C1-C 10 Alkoxy or R5-O-R6- group, R5 is C1-C 10 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl, R6 is C1-C 10 of alkylene.

[0227] In some embodiments, in Z2, 1≤a≤100. In some embodiments, in Z2, 1≤a≤80. According to some embodiments of the present application, in Z2, 1≤a≤30. According to some embodiments of the present application, in Z2, 1≤a≤20. According to some embodiments of the present application, in Z2, 1≤a≤10.

[0228] In some embodiments, in Z2, R3 are each independently C1-C6 alkyl, C6-C 10 Aryl, C7-C 10 Arylalkyl or C7-C 10 Alkaryl, R4 are each independently C1-C6 alkyl, C6-C 10 Aryl, C7-C 10 Aralkyl, C7-C 10 an alkylaryl group, a C1-C6 alkoxy group or an R5-O-R6- group, R5 is a C1-C6 alkyl group, a C6-C 10 Aryl, C7-C 10 Arylalkyl or C7-C 10 Alkaryl, R6 is C1-C 10 Alkylene, 1≤a≤10.

[0229] In some embodiments, Z2 is selected from one or more of the following structures ii-1 to ii-2:

[0230] R is independently selected from C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl;

[0231] 1≤m+1≤60, preferably 1≤m+1≤30; 1≤x≤9, preferably 1≤x≤7.

[0232] In some embodiments, Z2 is selected from the following structures:

[0233] One or more of;

[0234] Me represents a methyl group, ph represents a phenyl group; 1≤m+1≤60, preferably 1≤m+1≤30; 1≤x≤9, preferably 1≤x≤7.

[0235] In some embodiments, m is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9.

[0236] In some embodiments, x is 1, 2, 3, 4, 5, 6, or 7.

[0237] In some embodiments, the silicon monomer IA is selected from

[0238] CH2=C(CH3)C(O)-O-(CH2)3Si(OSi(CH3)3)3;

[0239] CH2=CHC(O)-O-(CH2)3Si(OSi(CH3)3)3;

[0240] CH2=C(CH3)C(O)-O-(CH2)3Si(CH3)(OSi(CH3)3)2;

[0241] CH2=CHC(O)-O-(CH2)3Si(CH3)(OSi(CH3)3)2;

[0242] CH2=C(CH3)C(O)-NH-(CH2)3Si(OSi(CH3)3)3;

[0243] CH2=CHC(O)-NH-(CH2)3Si(OSi(CH3)3)3;

[0244] CH2=C(CH3)C(O)-NH-(CH2)3Si(CH3)(OSi(CH3)3)2;

[0245] CH2=CHC(O)-NH-(CH2)3Si(CH3)(OSi(CH3)3)2;

[0246] CH2=C(CH3)C(O)-O-(CH2)3Si(OSi(CH2CH3)3)3;

[0247] CH2=CHC(O)-O-(CH2)3Si(OSi(CH2CH3)3)3;

[0248] CH2=C(CH3)C(O)-O-CH2-Si(OSi(CH3)3)3;

[0249] CH2=C(CH3)C(O)-O-(CH2)3Si(CH3)[O-[Si(CH3)2O]n-Si(CH3)2C4H9]2, 0≤n≤25;

[0250] CH2=CH-ph-Si(OSi(CH3)3)3(ph represents );

[0251] CH2=CH-ph-(CH2)2Si(OSi(CH3)3)3(ph represents );

[0252] CH2=CH-OC(O)-NH-(CH2)3Si(OSi(CH3)3)3;

[0253] CH2=CH-OC(O)-O-(CH2)3-Si(OSi(CH3)3)3;

[0254] CH2=CH-OC(O)-O-(CH2)2-NH-(CH2)3Si(OSi(CH3)3)3;

[0255] CH2=CH-C(O)-N[-(CH2)3-Si(OSi(CH3)3)3]2;

[0256] CH2=CH-C(O)-N[-(CH2)3-Si(CH3)(OSi(CH3)3)2]2.

[0257] In some embodiments, silicon monomer IB is selected from

[0258] CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl), 1≤n≤25;

[0259] CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C8H 17 , 1≤n≤25;

[0260] CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)3, 1≤n≤25;

[0261] CH2=CH-ph-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9(C4H9 represents butyl, ph represents ), 1≤n≤25;

[0262] CH2=CH-OC(O)-NH-(CH2)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl), 1≤n≤25;

[0263] CH2=CH-OC(O)-O-(CH2)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl), 1≤n≤25;

[0264] CH2=CH-OC(O)-O-(CH2)2-NH-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl), 1≤n≤25;

[0265] CH2=CH-C(O)-N[-(CH2)3-(Si(CH3)2O) n -Si(CH3)2C4H9]2 (C4H9 represents butyl), 1≤n≤25;

[0266] CH2=C(CH3)-C(O)-N[-(CH2)3-(Si(CH3)2O) n -Si(CH3)2C4H9]2 (C4H9 represents butyl group), 1≤n≤25.

[0267] In some embodiments, the organosilicon polymer further comprises a structural unit derived from monomer II,

[0268] CH2=C(R1)-P-R3 II

[0269] In formula II, P is selected from the groups represented by P-1 and P-2,

[0270] -C(O)-O- P-1

[0271] -C(O)-N(R2)- P-2

[0272] R1 and R2 are each independently a hydrogen atom or a C1-C 20 Alkyl; R3 is C1-C 40 Alkyl, C4-C 30 Cyclic hydrocarbons or C7-C 20 Alkaryl.

[0273] In some embodiments, in Formula II, R1 is a hydrogen atom or a C1-C 10 The alkyl group is preferably a hydrogen atom or a C1-C6 alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group or an n-hexyl group.

[0274] In some embodiments, in Formula II, R2 is a hydrogen atom or a C1-C 10 The alkyl group is preferably a hydrogen atom or a C1-C6 alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group or an n-hexyl group.

[0275] In some embodiments, in Formula II, R3 is selected from C1-C 30 Alkyl or C4-C 20 In some embodiments, in Formula II, R3 is selected from C1-C 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 Alkaryl.

[0276] In some embodiments, monomer II is selected from methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosyl (meth)acrylate, (meth)acrylate) ) benzyl (meth)acrylate, behenyl (meth)acrylate, hexadecyl (meth)acrylate, triacontyl (meth)acrylate, cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tricyclopentyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate or one or more of 2-ethyl-2-adamantyl (meth)acrylate.

[0277] In some embodiments, the organosilicon polymer does not include structural units produced by monomer IV, wherein monomer IV is selected from one or more of dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, N-tert-butylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, dipropylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, diethylaminopropyl (meth)acrylamide or dipropylaminopropyl (meth)acrylamide.

[0278] In some embodiments, the general structural formula of monomer IV is as shown in Formula IV:

[0279] CH2=C(R1)-PBN(R3R4) IV

[0280] In formula IV, P is selected from the groups represented by P-1 and P-2,

[0281] -C(O)-O- P-1

[0282] -C(O)-N(R2)- P-2

[0283] B is C1-C 20 R1 and R2 are each independently a hydrogen atom or a C1-C 20 Alkyl; R3 and R4 are each independently a hydrogen atom, C1-C 18or R3 and R4 are combined and together with the nitrogen atom form a morpholino group, a piperidino group or a pyrrolidinyl group.

[0284] In some embodiments, the proportion of the structural units generated by silicon monomer IA to the total amount of the structural units generated by silicon monomer IA and the structural units generated by silicon monomer IB, measured by mass percentage, is 1% to 100%, 5% to 100%, 10% to 100%, or 50% to 100%, such as 1%, 5%, 10%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, or a range consisting of any two thereof. The total amount of the structural units generated by silicon monomer IA and the structural units generated by silicon monomer IB is the total amount of the structural units generated by monomer I.

[0285] In some embodiments, the weight content of the structural units generated by monomer I is 30%-100%. In some embodiments, the weight content of the structural units generated by monomer I is 40%-85%. In some embodiments, the weight content of the structural units generated by monomer I is 50%-80%. In some embodiments, the weight content of the structural units generated by monomer I is 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or a range consisting of any two thereof.

[0286] In some embodiments, the weight content of the structural unit generated by monomer II is 5%-70%. In some embodiments, the weight content of the structural unit generated by monomer II is 10%-70%. In some embodiments, the weight content of the structural unit generated by monomer II is 15%-50%. In some embodiments, the weight content of the structural unit generated by monomer II is 20%-45%. In some embodiments, the weight content of the structural unit generated by monomer II is 5%, 7%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or any two thereof.

[0287] In some embodiments, the organosilicon polymer further includes a structural unit produced by a cross-linking monomer III, wherein the cross-linking monomer is a compound having two reactive groups and / or an unsaturated carbon-carbon double bond (preferably (meth)acrylate), or a compound having at least two unsaturated carbon-carbon double bonds (preferably (meth)acrylate), or a compound having at least one unsaturated carbon-carbon double bond and at least one reactive group. Preferred examples of reactive groups include hydroxyl, epoxy, chloromethyl, blocked isocyanate, amino or carboxyl groups.

[0288] In some embodiments, the crosslinking monomer III may be selected from one or more of diacetone (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetylethyl (meth)acrylate, glycidyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, or 2-butanone oxime adduct of ethyl (meth)acrylate-2-isocyanate.

[0289] In some embodiments, the weight average molecular weight of the organosilicon polymer is 1,000-3,000,000, for example, 5,000-2,500,000. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

[0290] In some embodiments, the emulsifier is selected from one or more of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant.

[0291] In some embodiments, the nonionic surfactant is selected from one or more of ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides. In some embodiments, the nonionic surfactant is a nonionic surfactant having an oxyalkylene group.

[0292] In some embodiments, the nonionic surfactant can be one or more of linear and / or branched aliphatic oxyalkylene adducts, linear and / or branched fatty acid polyalkylene glycol esters, polyethylene oxide (POE) / polypropylene oxide (POP) copolymers (random copolymers or block copolymers), and oxyalkylene adducts of acetylene glycol.

[0293] In some embodiments, the nonionic surfactant includes addition products of ethylene oxide with hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C12-C16) mercaptan, sorbitan monofatty acid (C7-C9) or (C12-C18) amine, etc.

[0294] In some embodiments, the cationic surfactant is selected from one or more of amine, amine salt, amine salt, imidazoline and imidazolinium salt surfactants.

[0295] In some embodiments, examples of cationic surfactants are R1-N + (R2R3R4)X - , wherein R1, R2, R3 and R4 are independently the same or different hydrogen atoms or hydrocarbon groups with 1 to 50 carbon atoms (e.g. C1-C6 alkyl, C7-C 10 Alkyl, C 11 -C 15 Alkyl or C16 -C 20 alkyl), an aryl group having 6 to 50 carbon atoms, an aralkyl group having 7 to 50 carbon atoms, or an alkaryl group having 7 to 50 carbon atoms, and X is a halogen (e.g., chlorine or bromine), an acid (e.g., an inorganic acid such as hydrochloric acid or an organic acid such as acetic acid (particularly a fatty acid)).

[0296] In some embodiments, the cationic surfactant includes one or more of dodecyltrimethylammonium acetate, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, and trimethyloctadecylammonium chloride.

[0297] In some embodiments, examples of anionic surfactants include 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 zwitterionic surfactants include alanines, imidazolinium betaines, amide betaines, and betaine acetate, and specifically include lauryl betaine, stearyl betaine, laurylcarboxymethylhydroxyethylimidazolinium betaine, lauryl dimethylaminoacetic acid betaine, and fatty amide propyl dimethylaminoacetic acid betaine.

[0298] In some embodiments, the emulsifier is a nonionic surfactant and a cationic surfactant.

[0299] In some embodiments, the mass content of the emulsifier is 0.1%-20%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18% or 19%, based on the mass of the silicone polymer.

[0300] In some embodiments, the aqueous medium is preferably water. In some embodiments, the aqueous medium includes water and an organic solvent. The organic solvent herein is not particularly limited, and any organic solvent that can be mixed with water is applicable to this application. Examples of organic solvents may include acetone, methyl ethyl ketone, ethyl acetate, ethanol, isopropyl alcohol, butyl diglycol, 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.

[0301] In a third aspect, the present application provides a method for preparing the treatment agent according to the second aspect, comprising the following steps:

[0302] (1) mixing water, monomers (monomer I, optional monomer II), an emulsifier, and an optional organic solvent to obtain a pre-emulsion;

[0303] (2) Adding an initiator and an optional molecular weight regulator to the pre-emulsion to carry out a polymerization reaction to obtain a polymer emulsion.

[0304] In some embodiments, the amount of monomer I is 30%-100% of the total monomer amount, preferably 40%-85%, more preferably 50%-80%, for example, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or any two thereof.

[0305] In some embodiments, the amount of monomer II is 5%-70% of the total monomer amount, preferably 10%-70%, more preferably 15%-50%, and further preferably 20%-45%, for example, 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or a range consisting of any two thereof.

[0306] In some embodiments, the amount of silicon monomer IA is 1% to 100%, 5% to 100%, 10% to 100%, 50% to 100%, 50% to 98% by mass in the total amount of silicon monomer IA and silicon monomer IB, for example, 1%, 5%, 10%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98% or a range consisting of any two of them.

[0307] In some embodiments, the initiator is selected from one or more of peroxides, azo compounds and persulfate compounds. In some embodiments, the initiator is selected from water-soluble initiators.

[0308] In some embodiments, the water-soluble initiator is selected from one or more of 2,2'-azobisisobutylamidine dihydrochloride, 2,2'azobis(2-methylpropionamidine) 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.

[0309] 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 above, such as 2,2'-azobisisobutylamidine dihydrochloride.

[0310] In some embodiments, the mass content of the initiator is 0.1%-5%, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% or 4.5%, based on the mass of the monomer.

[0311] In some embodiments, the molecular weight regulator is selected from mercapto compounds, such as 2-mercaptopropionic acid, 2-mercaptoethanol, alkyl mercaptan or mercaptopropionic acid.

[0312] In some embodiments, the mass content of the molecular weight regulator is 0.01%-10%, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%, based on the mass of the monomer.

[0313] In some embodiments, the polymerization reaction temperature is 40° C.-90° C. In some embodiments, the polymerization reaction time is 4 h-20 h.

[0314] In some embodiments, the typical emulsion polymerization process of the present application is as follows:

[0315] Mix water, monomer, emulsifier and organic solvent, first disperse the monomer at high speed for emulsification, introduce nitrogen replacement, add initiator, optional molecular weight regulator and optional organic solvent, heat to the reaction temperature of 40-90℃, and the reaction time varies from 4 to 20 hours.

[0316] In a fourth aspect, the present application provides the use of the organosilicon polymer described in the first aspect, the treating agent described in the second aspect, or the treating agent prepared by the method described in the third aspect in fiber fabrics or coatings.

[0317] In a fifth aspect, the present application provides a water- and oil-repellent fiber fabric, comprising a fiber fabric and the organic silicon polymer described in the first aspect, or the treating agent described in the second aspect, or the treating agent prepared by the method described in the third aspect.

[0318] The present application also provides an antifouling or anti-graffiti coating, which comprises a coating and the organic silicon polymer described in the first aspect or the treating agent described in the second aspect or the treating agent prepared by the method described in the third aspect.

[0319] In some embodiments, the organosilicon polymer described in the first aspect, the treating agent described in the second aspect, or the treating agent prepared by the method described in the third aspect is attached to the surface and / or interior of the fiber fabric or coating.

[0320] In a sixth aspect, the present application provides a method for treating a fiber fabric, comprising contacting the fiber fabric with the organosilicon polymer described in the first aspect, the treating agent described in the second aspect, or the treating agent prepared by the method described in the third aspect.

[0321] The present application also provides a coating treatment method, which comprises contacting the coating with the organosilicon polymer described in the first aspect, the treatment agent described in the second aspect, or the treatment agent prepared by the method described in the third aspect.

[0322] In some embodiments, the contacting is achieved by a surface sizing process, a surface coating process, a wet-end addition process, or an immersion treatment process.

[0323] The treatment agent of the present application can be applied to the treated object using existing known methods. Usually, the treatment agent is dispersed in an organic solvent or water for dilution, and is attached to the surface of the treated object by known methods such as dip coating, spray coating, and foaming cloth, and then dried. In addition, when necessary, it can be applied together with an appropriate cross-linking agent (such as blocked isocyanate) for vulcanization. Insect repellents, softeners, antibacterial agents, flame retardants, antistatic agents, wrinkle-resistant agents, etc. can also be added to the treatment agent of the present application for use together. The concentration of the polymer in the treatment solution in contact with the substrate can be 0.01-10 weight % (especially when dip coating), for example, 0.05-10 weight %.

[0324] In the present application, various examples of fiber fabrics can be cited, including natural fibers of animal or plant origin 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 acetate; inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber; and mixed fiber fabrics thereof.

[0325] Effects of the Invention

[0326] The organosilicon polymer or treating agent of the present application is used for treating fiber fabrics or coatings, and after treatment, it can impart oil-repellent and water-repellent properties to the surface of the fiber fabric and anti-fouling or anti-graffiti properties to the coating. Specific implementation method:

[0327] To make the purpose, technical solutions, and advantages of this application more clearly understood, the present application is further described in detail below with reference to the following examples. These examples are intended only to illustrate this application and are not intended to constitute any limitation to this application. The actual scope of protection of this application is set forth in the claims.

[0328] In this application, unless otherwise specified, the terms used have the general meanings known to those skilled in the art.

[0329] In the present application, the term "alkyl" refers to a straight-chain alkyl or a branched-chain alkyl, non-limiting examples of which 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.

[0330] In the present application, the term "alkylene" refers to a straight chain alkylene or a branched chain alkylene, non-limiting examples of which include: methylene, ethylene, n-propylene, n-butylene, n-pentylene, -CHCH3CH2-, -CHCH3CH2CH2-, CH2CH3CHCH2-, etc.

[0331] In this application, unless otherwise specified, “%” refers to mass percentage.

[0332] 1. Aggregation Method

[0333] The typical emulsion polymerization process of this application is as follows:

[0334] Mix water, monomer, emulsifier and organic solvent, first subject the monomer to high-speed shear emulsification and homogenization, introduce nitrogen replacement, add initiator and optional molecular weight regulator, heat to the reaction temperature of 40-90°C, and the reaction time varies from 4 to 20 hours.

[0335] The manufacturing process of the treatment agent of this application is as follows:

[0336] (1) homogeneously mixing water, monomer, emulsifier and optional organic solvent to obtain a pre-emulsion;

[0337] (2) Adding an initiator and an optional molecular weight regulator to the pre-emulsion to carry out a polymerization reaction to obtain a polymer emulsion.

[0338] 2. Test Method

[0339] Fiber fabric processing

[0340] The fabrics treated in this example were dyed 100% polyester and 100% khaki cotton twill. The treatment method involved impregnating the fabric samples with a certain concentration of the present invention's treatment agent (polymer emulsion) (absorption rate 70%), drying at 110°C for 90 seconds, and baking at 170°C for 60 seconds to obtain fabric samples. The resulting fabric samples were evaluated for their water, water, and oil repellency.

[0341] Evaluation Method

[0342] Test methods for fiber fabrics-Water repellency

[0343] According to Teflon global specifications and quality control testing methods, the sample fabric is tested using liquids containing different volumes of isopropyl alcohol to observe and determine the degree of surface wetting. This test provides a rough index of water stain resistance. The higher the repellency rating, the better the final substrate's resistance to water-based substances. The composition of the standard test liquid is shown in Table 1 below.

[0344] Table 1 Water resistance test grade composition

[0345] Fiber fabric test method - spray water repellency test

[0346] The dynamic water repellency of the treated substrate was measured according to the American Association of Textile Chemical and Tonerists (AATCC) TM-22, referring to published standards. A glass funnel with a volume of at least 250 mL and a nozzle capable of spraying 250 mL of water in 20-30 seconds was used. The test piece frame was a metal frame with a diameter of 15 cm. Three test pieces measuring approximately 20 cm x 20 cm were prepared and secured to the test piece holder frame, ensuring that the sheets were wrinkle-free. With the center of the spray positioned at the center of the sheet, 250 mL of room temperature water was added to the glass funnel and sprayed onto the test piece for 25-30 seconds. The holding frame was removed from the stand. Grasp one end of the frame, with the front surface facing downward, and gently tap the opposite end with a hard object. Rotate the frame 180° and repeat the same procedure, allowing any excess water to drip off. The wet test pieces were rated 0, 50, 70, 80, 90, and 100, starting with poor water repellency and ending with excellent (as shown in Table 2 below). Comparison was made with a wet comparison standard. Results were obtained based on the average of three determinations.

[0347] Table 2 Water repellency rating table

[0348] Test methods for fiber fabrics-Oil resistance

[0349] Oil repellency is evaluated according to the AATCC-TM118 test method. The basic principle is to drop test oils of different surface tensions onto the test cloth. The higher the level, the better the oil repellency. The composition of the standard test liquid is shown in Table 3 below.

[0350] Table 3 Fabric oil resistance test grade composition

[0351] 3. Examples and Comparative Examples

[0352] See Table 4 for chemical abbreviations.

[0353] Table 4 Codes and chemical formulas of various substances

[0354] Example 1

[0355] In a four-necked flask equipped with a reflux condenser, nitrogen inlet tube, thermometer, and stirrer, add 490 g of deionized water, 135 g of Si-B3 monomer, 33 g of dipropylene glycol methyl ether, 6 g of polyoxyethylene isotridecyl ether (EO:18, the number of ethylene oxide units is 18), 1.5 g of polyoxyethylene isotridecyl ether (EO:3, the number of ethylene oxide units is 3), and 60 g of octadecyltrimethylammonium chloride (10% solution). Stir and disperse using ultrasonic emulsification at 60°C for 30 minutes. After nitrogen replacement in the reaction flask, add 2,2 ， A solution of 1.2 g of azobis(2-amidinopropane) dihydrochloride and 20 g of water was heated to 60°C and reacted for 10 hours to obtain a polymer emulsion. The solids content was then adjusted to 20% with deionized water. Comparison of the theoretical solids content with the measured solids content indicated a monomer conversion rate of greater than 98%.

[0356] Examples 2-7

[0357] The same as Example 1, except that Si-B3 is replaced by monomer I with different structures as follows, namely Si-NB3 (Example 2), Si-ph-B3 (Example 3), Si-OCN-B3 (Example 4), Si-OCO-B3 (Example 5), Si-B2 (Example 6), Si-N2-B2 (Example 7).

[0358] The polymer emulsion was tested on fabrics: 100% polyester and 100% cotton fabrics were diluted with tap water to 5%, 3%, and 2% (polymer emulsion content), respectively. The fabrics were then padded, dried at 110°C for 90 seconds, and baked at 170°C for 60 seconds. The resulting fabric samples were evaluated for their water, water, and oil repellency. The results are shown in Table 5.

[0359] Table 5 Performance test table

[0360] Example 8

[0361] In a four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirrer, 490 g of deionized water, 100 g of Si-B3 monomer, 35 g of Si-5 (average molecular weight 500) monomer, 33 g of dipropylene glycol methyl ether, 6 g of polyoxyethylene isotridecyl ether (EO:18, 18 ethylene oxide units), 1.5 g of polyoxyethylene isotridecyl ether (EO:3, 3 ethylene oxide units), and 60 g of octadecyltrimethylammonium chloride (10% solution) were added. The mixture was dispersed by ultrasonic emulsification at 60°C for 30 minutes under stirring. After nitrogen substitution in the reaction flask, 2,2 ，A solution of 1.2 g of azobis(2-amidinopropane) dihydrochloride and 20 g of water was heated to 60°C and reacted for 10 hours to obtain a polymer emulsion. The solids content was then adjusted to 20% with deionized water. Comparison of the theoretical solids content with the measured solids content indicated a monomer conversion rate of greater than 98%.

[0362] Example 9

[0363] In a four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirrer, 490 g of deionized water, 100 g of Si-B3 monomer, 35 g of StA monomer, 33 g of dipropylene glycol methyl ether, 6 g of polyoxyethylene isotridecyl ether (EO:18, the number of ethylene oxide units is 18), 1.5 g of polyoxyethylene isotridecyl ether (EO:3, the number of ethylene oxide units is 3), and 60 g of octadecyltrimethylammonium chloride (10% solution) were added. The mixture was dispersed by ultrasonic emulsification at 60°C for 30 minutes under stirring. After nitrogen substitution in the reaction flask, 2,2 ， A solution of 1.2 g of azobis(2-amidinopropane) dihydrochloride and 20 g of water was heated to 60°C and reacted for 10 hours to obtain a polymer emulsion. The solids content was then adjusted to 20% with deionized water. Comparison of the theoretical solids content with the measured solids content indicated a monomer conversion rate of greater than 98%.

[0364] The performance test was carried out according to the test method of Examples 1-7. The results are shown in Table 6.

[0365] Table 6 Performance test table

[0366] Comparative Example 1

[0367] To a four-necked flask equipped with a reflux condenser, nitrogen inlet, thermometer, and stirrer, add 135 g of Si-B3 monomer, 45 g of DN, 15 g of HEMA, and 195 g of methyl ethyl ketone. Purge with nitrogen for 30 minutes, slowly raise the temperature to 50-60°C, and add 2.5 g of the peroxide initiator, t-butyl peroxypivalate, in portions. The reaction temperature was maintained at 60°C for 20 hours to yield approximately 390 g of a polymer A solution with a solids content of approximately 50%.

[0368] Add 560 g of water and 18 g of glacial acetic acid, keep stirring at 70°C for more than 1 hour, distill off the MEK in the above polymer A solution under reduced pressure, and then adjust the solid content to 25% aqueous solution with deionized water.

[0369] Comparative Example 2

[0370] In a four-necked flask equipped with a reflux condenser, nitrogen inlet tube, thermometer, and stirrer, add 490 g of deionized water, 135 g of StA monomer, 33 g of dipropylene glycol methyl ether, 6 g of polyoxyethylene isotridecyl ether (EO:18, the number of ethylene oxide units is 18), 1.5 g of polyoxyethylene isotridecyl ether (EO:3, the number of ethylene oxide units is 3), and 60 g of octadecyltrimethylammonium chloride (10% solution). Stir and disperse using ultrasonic emulsification at 60°C for 30 minutes. After nitrogen substitution in the reaction flask, add 2,2 ， A solution of 1.2 g of azobis(2-amidinopropane) dihydrochloride and 20 g of water was heated to 60°C and reacted for 10 hours to obtain a polymer emulsion. The solids content was then adjusted to 20% with deionized water. Comparison of the theoretical solids content with the measured solids content indicated a monomer conversion rate of greater than 98%.

[0371] Comparative Example 3

[0372] 135 g of amino silicone oil (ammonia value 0.5 mmol / g, viscosity 1200 cp (25°C)), 9 g of isomeric tridecanol polyoxyethylene ether (EO number: 9), and 9 g of isomeric tridecanol polyoxyethylene ether (EO number: 5) were added to a 1-liter plastic cup and stirred at high speed. Then, 610 g of deionized water was slowly added (addition was completed over 30 minutes). After the addition was completed, the mixture was stirred at high speed for 5 minutes and then at low speed for another 5 minutes to obtain a stable silicone oil emulsion with an effective content of 20%.

[0373] The performance tests were carried out according to the test methods of Examples 1 to 7. The results are shown in Table 7.

[0374] Table 7 Performance test table

[0375] The solid contents of Example 1, Comparative Example 2 and Comparative Example 3 are all 20%, and the solid content of Comparative Example 1 is 25%. However, the contents of silicon monomers or silicon compounds (or long-chain hydrocarbon monomers) in these four examples are basically the same.

[0376] Based on the performance test results in Table 5, Table 6, and Table 7, the polymer emulsions obtained in Examples 1 to 9 of the present application all exhibited good oil-repellent and water-repellent effects when applied to fiber fabrics.

[0377] Comparative Example 1 uses the same silicon monomer I as Example 1, but since solution polymerization is used and the product ultimately needs to be dissolved in water, more water-soluble monomers are introduced into the structure to aid solubility. Ultimately, although the treating agent of this structure has good oil repellency, its water repellency is significantly inferior to that of the present application.

[0378] Comparative Example 2, using a long-chain alkyl monomer as the primary reactant, showed that the treatment agent imparted some water repellency to the fabric, but not oil repellency. Comparative Example 3, using a long-chain silicone oil as the raw material, also showed some water repellency to the fabric, but not oil repellency.

[0379] The technical solution of the present application is not limited to the above-mentioned specific embodiments. Any technical variations made according to the technical solution of the present application fall within the protection scope of the present application.

Claims

1. A treatment agent comprising an organosilicon polymer, an emulsifier and an aqueous medium, wherein: The organosilicon polymer comprises a structural unit produced by monomer I, wherein monomer I comprises silicon monomer IA and optional silicon monomer IB, a) The general structural formula of the silicon monomer IA is shown in Formula IA: M-Z1 or Z1-M-Z1 Formula IA Wherein, M contains a polymerizable functional group; Z1 is selected from the following structures: In Z1, R4 is independently C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkyl, C1-C 20 an alkoxy group or an R5-O-R6- group, R5 is C1-C 10 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl, R6 is C1-C 20 Alkylene, 1≤a≤200; Y1 and Y2 are the same or different and are independently selected from C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Aralkyl, C7-C 12 The alkylaryl group or the structure of formula (1) is an alkylaryl group or the structure of formula (1), and also meets the following requirements: 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): R7 is independently C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 R8 is independently C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkyl, C1-C 20 Alkoxy or R9-OR 10 - group, wherein R9 is C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 The alkylaryl group, R 10 C1-C 20 Alkylene, 0≤b≤200; b) The general structural formula of the silicon monomer IB is shown in Formula IB: M-Z2 or Z2-M-Z2 IB Wherein, M contains a polymerizable functional group; Z2 is selected from the following structures, In Z2, R3 is independently C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 alkylaryl, R4 are each independently C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkyl, C1-C 20 an alkoxy group or an R5-O-R6- group, R5 is C1-C 10 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl, R6 is C1-C 20 Alkylene, 1≤a≤200.

2. The treatment agent according to claim 1, characterized in that M is shown in formula I-1: CH2=C(R1)-XB- I-1 In formula I-1, R1 is selected from a hydrogen atom or a C1-C 20 B is selected from C1-C 20 Alkylene, C6-C 20 arylene groups and combinations thereof; X is selected from the group represented by X-1 and X-2, -C(O)-O- X-1 -C(O)-N(R2)- X-2 R2 is selected from hydrogen atom or C1-C 20 The alkyl group; and / or M is shown in formula I-2: CH2=C(R1)-WB- I-2 In formula I-2, R1 is selected from a hydrogen atom or a C1-C 20 alkyl; W is selected from the group represented by W-1, W-2, W-3 and W-4, -OC(O)-N(R2)- W-2 -OC(O)-O- W-3 -OC(O)-ODN(R2)- W-4 R2 is selected from hydrogen atom or C1-C 20 Alkyl, D is C1-C 20 When W is selected from W-1, B is absent or is C1-C 20 When W is selected from W-2, W-3, W-4, B is selected from C1-C 20 Alkylene, C6-C 20 arylene groups and combinations thereof; and / or M is shown in formula I-3: In formula I-3, R1 is selected from a hydrogen atom or a C1-C 20 Alkyl, B is independently selected from C1-C 20 Alkylene, C6-C 20 arylene groups and combinations thereof.

3. The treatment agent according to claim 1 or 2, characterized in that The organosilicon polymer also includes a structural unit produced by monomer II, CH2=C(R1)-C(O)-O-R3 II R1 is a hydrogen atom or a C1-C 20 Alkyl; R3 is C1-C 40 Alkyl, C4-C 30 Cyclic hydrocarbon or C7-C 20 Alkyl.

4. The treatment agent according to any one of claims 1 to 3, characterized in that The organosilicon polymer does not include a structural unit produced by monomer IV, wherein monomer IV is selected from one or more of dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, N-tert-butylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, dipropylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, diethylaminopropyl (meth)acrylamide or dipropylaminopropyl (meth)acrylamide, Preferably, the general structural formula of monomer IV is as shown in Formula IV: CH2=C(R1)-PBN(R3R4) IV In formula IV, P is selected from the group represented by P-1 and P-2, -C(O)-O- P-1 -C(O)-N(R2)- P-2 B is C1-C 20 R1 and R2 are each independently a hydrogen atom or a C1-C 20 R3 and R4 are each independently a hydrogen atom, a C1-C 18 or R3 and R4 are combined with the nitrogen atom to form a morpholino group, a piperidino group or a pyrrolidinyl group.

5. The treatment agent according to any one of claims 1 to 4, characterized in that 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 optionally an organic solvent.

6. The treatment agent according to any one of claims 1 to 5, characterized in that In terms of mass percentage, the proportion of the structural units generated by silicon monomer IA to the total amount of the structural units generated by silicon monomer IA and the structural units generated by silicon monomer IB is 1% to 100%, 5% to 100%, 10% to 100% or 50% to 100%; and / or The mass content of the structural unit produced by monomer I in the organosilicon polymer is 30%-100%, preferably 40%-85%, more preferably 50-80%; and / or The mass content of the structural unit produced by monomer II in the organosilicon polymer is 5%-70%, preferably 10%-70%, more preferably 15%-50%, and further preferably 20%-45%.

7. The treatment agent according to any one of claims 1 to 6, characterized in that In the silicon monomers IA and IB, R1 is selected from hydrogen or methyl, and B is C1-C 10 alkylene, preferably B is a C1-C6 alkylene; In silicon monomers IA and IB, in X, R2 is selected from a hydrogen atom or a methyl group; In the silicon monomer IA, Z1, and R4 are each independently C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 an alkylaryl group, or an R5-O-R6- group, R5 is C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl, R6 is C1-C 10 alkylene, 1≤a≤80; R7 are each independently C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 R8 is independently C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkyl, or R9-OR 10 - group, wherein R9 is C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 The alkylaryl group, R 10 C1-C 10 Alkylene, 0≤b≤80; In silicon monomer IB, in Z2, R3 are each independently C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 alkylaryl, R4 are each independently C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 an alkylaryl group, or an R5-O-R6- group, R5 is C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl, R6 is C1-C 10 alkylene; 1≤a≤80; and / or In monomer II, R1 is selected from a hydrogen atom or a methyl group; R3 is selected from a C1-C 30 Alkyl, C4-C 20 Cyclic hydrocarbon or C7-C 15 Alkyl.

8. The treatment agent according to any one of claims 1 to 7, characterized in that Z1 is selected from one or more of the following structures i-1 to i-4: Z1 is selected from One or more of; Z2 is selected from one or more of the following structures ii-1 to ii-2: Z2 is preferably selected from: One or more of; R is independently selected from C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl; 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 may be the same or different.

9. The treatment agent according to any one of claims 1 to 8, characterized in that Silicon monomer IA is selected from CH2=C(CH3)C(O)-O-(CH2)3Si(OSi(CH3)3)3; CH2=CHC(O)-O-(CH2)3Si(OSi(CH3)3)3; CH2=C(CH3)C(O)-O-(CH2)3Si(CH3)(OSi(CH3)3)2; CH2=CHC(O)-O-(CH2)3Si(CH3)(OSi(CH3)3)2; CH2=C(CH3)C(O)-NH-(CH2)3Si(OSi(CH3)3)3; CH2=CHC(O)-NH-(CH2)3Si(OSi(CH3)3)3; CH2=C(CH3)C(O)-NH-(CH2)3Si(CH3)(OSi(CH3)3)2; CH2=CHC(O)-NH-(CH2)3Si(CH3)(OSi(CH3)3)2; CH2=C(CH3)C(O)-O-(CH2)3Si(OSi(CH2CH3)3)3; CH2=CHC(O)-O-(CH2)3Si(OSi(CH2CH3)3)3; CH2=C(CH3)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 represents CH2=CH-ph-(CH2)2Si(OSi(CH3)3)3(ph represents )； CH2=CH-OC(O)-NH-(CH2)3Si(OSi(CH3)3)3; CH2=CH-OC(O)-O-(CH2)3-Si(OSi(CH3)3)3; CH2=CH-OC(O)-O-(CH2)2-NH-(CH2)3Si(OSi(CH3)3)3; CH2=CH-C(O)-N[-(CH2)3-Si(OSi(CH3)3)3]2; CH2=CH-C(O)-N[-(CH2)3-Si(CH3)(OSi(CH3)3)2]2; and / or Silicon monomer IB is selected from CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl), 1≤n≤25; <h2 style=";text-align:left;direction:ltr">CH2 = C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C8H<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> 1≤n≤25 CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)3, 1≤n≤25; 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)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl), 1≤n≤25; CH2=CH-OC(O)-O-(CH2)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl), 1≤n≤25; CH2=CH-OC(O)-O-(CH2)2-NH-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl), 1≤n≤25; CH2=CH-C(O)-N[-(CH2)3-(Si(CH3)2O) n -Si(CH3)2C4H9]2 (C4H9 represents butyl), 1≤n≤25; CH2=C(CH3)-C(O)-N[-(CH2)3-(Si(CH3)2O) n -Si(CH3)2C4H9]2 (C4H9 represents butyl), 1≤n≤25; and / or Monomer II is selected from methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosyl (meth)acrylate, dioctyl (meth)acrylate, One or more of dodecyl (meth)acrylate, hexadecyl (meth)acrylate, triacontyl (meth)acrylate, cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tricyclopentyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate or 2-ethyl-2-adamantyl (meth)acrylate.

10. A method for preparing the treating agent according to any one of claims 1 to 9, comprising the following steps: (1) mixing water, monomer, emulsifier and optional organic solvent to obtain a pre-emulsion; (2) Adding an initiator and an optional molecular weight regulator to the pre-emulsion to carry out a polymerization reaction to obtain a polymer emulsion.

11. Use of the treating agent according to any one of claims 1 to 9 or the treating agent prepared by the method according to claim 10 in fiber fabrics or coatings.

12. A water-repellent and oil-repellent fiber fabric, comprising the fiber fabric and the treating agent according to any one of claims 1 to 9 or the treating agent prepared by the method according to claim 10, Preferably, the treating agent according to any one of claims 1 to 9 or the treating agent prepared by the method according to claim 10 is attached to the surface and / or the inside of the fiber fabric.

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

14. An antifouling or anti-graffiti coating, comprising a coating and a treating agent according to any one of claims 1 to 9 or a treating agent prepared by the method of claim 10, Preferably, the treating agent according to any one of claims 1 to 9 or the treating agent prepared by the method according to claim 10 is attached to the surface and / or the inside of the coating.

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