Silicon-containing polymer, treating agent as well as preparation method and application of treating agent

Abstract

The invention relates to a silicon-containing polymer, a treating agent and a preparation method and application of the treating agent. The silicon-containing polymer comprises a repeating unit generated by a silicon-containing monomer I and a repeating unit generated by a monomer II, the silicon-containing monomer I comprises a silicon-containing monomer I-1a and / or a silicon-containing monomer I-1b, and the polymer or the treating agent containing the polymer can be used for treating various articles such as paper products, textile fabrics and stones and endows the articles with oil-repellent and water-repellent functions.

Description

Silicon-containing polymer, treating agent, preparation method and application thereof

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to the Chinese patent application with application number 202211300863.1 filed on October 24, 2022, and invention name “A silicon-containing polymer, treatment agent, preparation method and application thereof”. 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 silicon-containing polymer, a treatment agent containing the polymer, and a preparation method and application thereof, which can be used for surface and internal addition treatment of various articles, such as paper products, natural stone, concrete, fiber fabrics, synthetic leather, non-woven fabrics, asbestos, fur or plastic, and impart oil and water repellency to the surface of the articles. Technical Background

[0004] Polymers have been widely used in surface and internal treatment of paper, textiles, leather, stone, etc. They can give the surface of objects multiple functions, thereby improving the durability of the objects. For example, after paper is treated, it can withstand oil-rich foods; after textile treatment, it can improve its ability to withstand various stains; after stone treatment, it can maintain the original appearance of the stone for a long time.

[0005] CN103975107B proposes a solution using a barrier coating. This patent mainly adopts the method of emulsion polymerization to produce a polymer emulsion by adding starch and emulsifier, and then applies it to paper by coating. Although this method can also block grease, it will bring two problems. First, a large amount of coating is required to have an oil-proof effect. Second, it is only applicable to papermaking machines with coating equipment and cannot be completed directly on general papermaking machines. The process applicability is not strong and the cost is also high. CN100360612C proposes to use polysiloxane and polyvinyl alcohol to cross-link under the action of a catalyst and disperse them through a surfactant. The resulting treatment agent can be used for paper coating treatment, but at the same time, the process applicability is not strong. CN112513370A proposes a method of using a long-chain acrylic ester copolymer to achieve paper treatment, thereby achieving the effect of repelling oil and water, but this method has been found to have a poor barrier effect on hot oils with temperatures above 80°C.

[0006] CN107849187A proposes a method for finishing textiles using a copolymer of acrylic esters and monomers such as vinyl chloride to form a polymer that has excellent water-repellent properties. CN110114435A proposes a method for finishing textiles using a copolymer of acrylic esters, compounded with a wax emulsion, and other materials, that also has excellent water-repellent properties. CN105377935B uses an aqueous polyurethane dispersion to finish textiles, also having excellent water-repellent properties. However, these polymers have poor oil-repellent properties and limited protective properties.

[0007] CN105764980B proposes using long-chain acrylic esters to form an emulsion with a cationic emulsifier for physical treatment of porous materials such as fiber, stone, and leather, achieving a water-repellent and oil-diffusing effect. However, its effectiveness in preventing water-diffusing effects was found to be limited, particularly with regard to grease and oil.

[0008] Summary of the Invention

[0009] The present application aims to provide a silicon-containing polymer and a treatment agent containing the polymer, which can be used to treat a variety of articles, thereby imparting oil and water repellency to the surfaces of the articles. The present application also provides a method for preparing the treatment agent.

[0010] In a first aspect, the present application provides a silicon-containing polymer comprising repeating units generated from a silicon-containing monomer I and repeating units generated from a monomer II, wherein the silicon-containing monomer I comprises a silicon-containing monomer I-1a or / and a silicon-containing monomer I-1b.

[0011] The general structural formula of the silicon-containing monomer I-1a is shown in Formula I-1a: CH2=C(R1)-WBZ I-1a

[0012] In formula I-1a, R1 is selected from hydrogen atom or C1-C 20 alkyl;

[0013] 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

[0014] 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 C1-C 20 alkylene;

[0015] The general structural formula of the silicon-containing monomer I-1b is shown in Formula I-1b:

[0016] In formula I-1b, R1 is selected from hydrogen atom or C1-C 20 Alkyl; B is C1-C 20 alkylene;

[0017] Formula I-1 a In formula I-1b, Z is independently selected from the following structures:

[0018] In the formula, R4 is independently C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkaryl 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 Alkylene, 1≤a≤200;

[0019] Y1 and Y2 are the same or different and are independently selected from C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 The alkylaryl group, and the structure of formula (I):

[0020] 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 or R9-OR 10 - group, wherein R9 is C1-C 10 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 The alkylaryl group, R 10 C1-C 10 Alkylene, 0≤b≤200;

[0021] The general structural formula of monomer II is shown in formula (II): CH2=C(R1)-PBN(R3R4) (II)

[0022] In formula (II), P is selected from the groups represented by P-1 and P-2, -C(O)-O- P-1 -C(O)-N(R2)- P-2

[0023] 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 18 R3 and R4 are combined and together with the nitrogen atom form a morpholino group, a piperidino group or a pyrrolidinyl group.

[0024] According to some embodiments of the present application, Can be

[0025] According to some embodiments of the present application, in Formula I-1a, when W is selected from W-1, B may not exist, that is, Formula I-1a is CH2=C(R1)-WZ.

[0026] According to some embodiments of the present application, the silicon-containing monomer I further includes a silicon-containing monomer I-2,

[0027] The general structural formula of the silicon-containing monomer I-2 is shown in Formula I-2: CH2=C(R1)-XBZ I-2

[0028] In formula I-2, R1 is selected from hydrogen atom or C1-C 20 Alkyl; B is C1-C 20 alkylene;

[0029] X is selected from the group represented by X-1 and X-2, -C(O)-O- X-1 -C(O)-N(R2)- X-2

[0030] R2 is selected from hydrogen atom or C1-C 20 Alkyl;

[0031] Z is selected from the following structures:

[0032] Wherein R4 is independently C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Aralkyl, C7-C 12Alkaryl 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 Alkylene, 1≤a≤200;

[0033] Y1 and Y2 are the same or different and are independently selected from C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 The alkylaryl group, and the structure of formula (I):

[0034] 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 or R9-OR 10 - group, wherein R9 is C1-C 10 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 The alkylaryl group, R 10 C1-C 10 Alkylene, 0≤b≤200.

[0035] According to some embodiments of the present application, in Z of Formula I-1a and / or Formula I-1b and / or Formula I-2,

[0036] When a is 1, Y1 and / or Y2 is a structure of formula (I); when a is greater than 1 and ≤ 200, at least one Y1 is a structure of formula (I) and / or at least one Y2 is a structure of formula (I):

[0037] 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 20Aryl, C7-C 12 Aralkyl, C7-C 12 Alkaryl or R9-OR 10 - group, wherein R9 is C1-C 10 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 The alkylaryl group, R 10 C1-C 10 Alkylene, 0≤b≤200.

[0038] According to some embodiments of the present application, R7 is 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 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 of alkylene.

[0039] According to some embodiments of the present application, 0≤b≤100.

[0040] According to some embodiments of the present application, R7 is independently C1-C6 alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 R8 are each independently C1-C6 alkyl, C6-C 10 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkaryl or R9-OR 10 - group, wherein R9 is C1-C6 alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 The alkylaryl group, R 10 It is a C1-C6 alkylene group.

[0041] According to some embodiments of the present application, the silicon-containing polymer further comprises a repeating unit produced by monomer III, and the general structural formula of monomer III is shown in formula III: CH2=C(R1)-G-(R2O) q -R3 III

[0042] In formula III, 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 or a C1-C3 alkyl group;

[0043] Wherein, G is selected from the groups represented by G-1 and G-2, -C(O)-O-(CH2) n - G-1 -C(O)-N(R4)-(CH2) n - G-2

[0044] R4 represents a hydrogen atom or a methyl group, and n is an integer of 0-10, preferably an integer of 0-5.

[0045] According to some embodiments of the present application, the proportion of the repeating units generated by silicon-containing monomer I-1a and / or silicon-containing monomer I-1b in the repeating units generated by silicon-containing monomer I 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 a range consisting of any two thereof. The total amount of the repeating units generated by silicon-containing monomers I-1a and I-1b and the repeating units generated by silicon-containing monomer I-2 is the total amount of repeating units generated by silicon-containing monomer I.

[0046] According to some embodiments of the present application, in the polymer, the mass content of the repeating units produced by the silicon-containing monomer I is 30%-90%, preferably 40%-85%, more preferably 50%-80%, for example, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or a range consisting of any two of them.

[0047] According to some embodiments of the present application, in the polymer, the mass content of the repeating units produced by monomer II is 5%-65%, preferably 10%-50%, more preferably 15%-45%, for example, 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or a range consisting of any two of them.

[0048] According to some embodiments of the present application, in the polymer, the mass content of the repeating units produced by monomer III is 1%-40%, preferably 5%-30%, more preferably 10%-25%, for example, 1%, 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or a range consisting of any two of them.

[0049] It is easy for those skilled in the art to understand that the silicon-containing polymer of the present application is formed by polymerization of monomers, and the monomers used for polymerization include the silicon-containing monomer I and the monomer II, and the silicon-containing monomer I includes the silicon-containing monomer I-1a and / or the silicon-containing monomer I-1b. Optionally, the monomer may also include the monomer III.

[0050] According to some embodiments of the present application, the proportion of silicon-containing monomer I-1a and / or silicon-containing monomer I-1b in silicon-containing monomer I is 1% to 100%, 5% to 100%, 10% to 100% or 50% to 100% by mass, 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.

[0051] According to some embodiments of the present application, the proportion of silicon-containing monomer I in the total monomer amount is 30%-90% by mass, preferably 40%-85%, more preferably 50%-80%, for example, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or a range consisting of any two thereof.

[0052] According to some embodiments of the present application, the proportion of monomer II in the total monomer amount is 5%-65% by mass, preferably 10%-50%, more preferably 15%-45%, for example, 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or a range consisting of any two thereof.

[0053] According to some embodiments of the present application, the proportion of monomer III in the total monomer amount is 1%-40% by mass, preferably 5%-30%, more preferably 10%-25%, for example, 1%, 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or a range consisting of any two thereof.

[0054] According to some embodiments of the present application, in the silicon-containing monomers I-1a, I-1b and I-2, R1 is selected from a hydrogen atom or a methyl group.

[0055] According to some embodiments of the present application, in silicon-containing monomers I-1a, I-1b and I-2, B is selected from C1-C 10 The alkylene group is preferably a C1-C6 alkylene group.

[0056] According to some embodiments of the present application, in the silicon-containing monomer I-1a, D is selected from C1-C 10 The alkylene group is preferably a C1-C6 alkylene group.

[0057] According to some embodiments of the present application, in the silicon-containing monomers I-1a, I-1b and I-2, R2 is selected from a hydrogen atom or a methyl group.

[0058] According to some embodiments of the present application, in Z, R4 are each independently C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkaryl 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 Alkylene, and / or 1≤a≤80;

[0059] R7 is 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 or R9-OR 10 - group, wherein R9 is C1-C 10 Alkyl, C6-C 10 Aryl, C7-C12 Arylalkyl or C7-C 12 The alkylaryl group, R 10 C1-C 10 alkylene, and / or 0≤b≤80.

[0060] According to some embodiments of the present application, in Z, R4 are each independently C1-C6 alkyl, C6-C 10 Aryl, C7-C 10 Aralkyl, C7-C 10 Alkaryl or R5-O-R6- group, R5 is C1-C6 alkyl, C6-C 10 Aryl, C7-C 10 Arylalkyl or C7-C 10 alkylaryl, R6 is a C1-C6 alkylene group, 1≤a≤30;

[0061] R7 are each independently C1-C6 alkyl, 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 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.

[0062] 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.

[0063] 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.

[0064] In some embodiments, Z is independently selected from one or more of the following structures i-1 to i-6:

[0065] R is independently selected from C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C7-C 12 Alkaryl;

[0066] 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.

[0067] In some embodiments, R is a C1-C3 alkyl group, such as a methyl group.

[0068] In some preferred embodiments, Z is selected from the following structures:

[0069] One or more of;

[0070] Me represents a methyl group, ph represents a phenyl 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.

[0071] In some embodiments, m is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9.

[0072] In some embodiments, x is 1, 2, 3, 4, 5, 6, or 7.

[0073] According to some embodiments of the present application, in the structure of monomer II, R1 and R2 are selected from hydrogen atoms or methyl groups; B is a C1-C6 alkylene group; R3 and R4 are independently C1-C3 alkyl groups, hydroxyethyl groups or benzyl groups, or R3 and R4 are combined and together with the nitrogen atom form a morpholino group, a piperidino group or a pyrrolidinyl group.

[0074] According to some embodiments of the present application, the silicon-containing monomer I-1a is selected from

[0075] CH2=CH-ph-Si(OSi(CH3)3)3(ph represents ),

[0076] CH2=CH-ph-(CH2)2Si(OSi(CH3)3)3(ph represents ),

[0077] CH2=CH-ph-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9(C4H9 represents butyl, ph represents )(1≤n≤25)

[0078] CH2=CH-OC(O)-NH-(CH2)3Si(OSi(CH3)3)3,

[0079] CH2=CH-OC(O)-NH-(CH2)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl) (1≤n≤25),

[0080] CH2=CH-OC(O)-O-(CH2)3-Si(OSi(CH3)3)3,

[0081] CH2=CH-OC(O)-O-(CH2)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl) (1≤n≤25),

[0082] CH2=CH-OC(O)-O-(CH2)2-NH-(CH2)3Si(OSi(CH3)3)3, and

[0083] CH2=CH-OC(O)-O-(CH2)2-NH-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl group) (1≤n≤25).

[0084] According to some embodiments of the present application, the silicon-containing monomer I-1b is selected from

[0085] CH2=CH-C(O)-N[-(CH2)3-Si(OSi(CH3)3)3]2,

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

[0087] CH2=CH-C(O)-N[-(CH2)3-(Si(CH3)2O) n -Si(CH3)2C4H9]2 (C4H9 represents butyl) (1≤n≤25) and

[0088] CH2=C(CH3)-C(O)-N[-(CH2)3-(Si(CH3)2O) n -Si(CH3)2C4H9]2 (C4H9 represents butyl group) (1≤n≤25).

[0089] According to some embodiments of the present application, the silicon-containing monomer I-2 is selected from

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

[0091] CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl) (1≤n≤25),

[0092] CH2=C(CH3)C(O)-NH-(CH2)3Si(OSi(CH3)3)3, and

[0093] CH2=C(CH3)C(O)-NH-(CH2)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl group) (1≤n≤25).

[0094] According to some embodiments of the present application, monomer II 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, and dipropylaminopropyl (meth)acrylamide.

[0095] According to some embodiments of the present application, monomer III is selected from 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, methoxypolyethylene glycol (meth)acrylate, preferably hydroxyethyl methacrylate and 4-hydroxybutyl acrylate.

[0096] According to some embodiments of the present application, the weight average molecular weight of the polymer is 8-2 million, preferably 20-1.5 million. According to some embodiments of the present application, the polymer is in the form of an ammonium salt or a nitrogen oxide.

[0097] The present application further provides a treating agent, comprising the silicon-containing polymer described above and a solvent, wherein the solvent comprises water and / or an organic solvent.

[0098] In some embodiments, the organic solvent is one or more of acetone, methyl ethyl ketone, 4-methyl-2-pentanone, ethyl acetate, butyl acetate, N-methyl-2-pyrrolidone, N,N-dimethylformamide, ethanol, isopropanol, n-propanol, butyl carbitol, and dipropylene glycol methyl ether.

[0099] The present application also relates to a method for producing the above-mentioned treatment agent, which comprises the following steps:

[0100] (1) Monomers (including silicon-containing monomer I, monomer II, and optionally selected monomer III) are polymerized in an organic solvent to obtain a polymer solution.

[0101] According to some embodiments of the present application, the proportion of silicon-containing monomer I-1a and / or I-1b in the silicon-containing monomer I is 1% to 100%, 5% to 100%, 10% to 100%, 50% to 100%, 50% to 98% by mass, 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 thereof.

[0102] According to some embodiments of the present application, the amount of silicon-containing monomer I in the total amount of monomers is 30%-90% by mass, preferably 40%-85%, more preferably 50%-80%, for example, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or a range consisting of any two thereof.

[0103] According to some embodiments of the present application, the amount of monomer II is 5%-65% of the total monomer amount, preferably 10%-50%, more preferably 15%-45%, for example, 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or a range consisting of any two thereof.

[0104] According to some embodiments of the present application, the amount of monomer III in the total monomer amount is 0-40%, preferably 1%-40%, more preferably 5%-30%, and further preferably 10-25%, for example, 1%, 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or a range consisting of any two thereof.

[0105] As required, the manufacturing method may further include any one or more of the following steps (2), (3), and (4):

[0106] (2) adding water for dispersion while removing the organic solvent from the polymer solution, or removing the solvent first and then adding water for dispersion;

[0107] (3) adding an organic acid to convert the amino groups in the polymer into ammonium salts;

[0108] (4) Add an oxidizing agent (such as hydrogen peroxide) to convert the amino groups of the polymer into nitrogen oxides.

[0109] In addition, the present application also provides the use of the above-mentioned silicon-containing polymer or the above-mentioned treatment agent or the treatment agent prepared by the above-mentioned method in fiber fabrics, leather, non-woven fabrics, asbestos, fur, concrete, natural stone, paper products or plastics.

[0110] In addition, the present application also provides a product treated with the above-mentioned silicon-containing polymer or the above-mentioned treatment agent or the treatment agent prepared by the above-mentioned method, and the product can be fiber fabric, leather, non-woven fabric, asbestos, fur, concrete, natural stone, paper products or plastics.

[0111] The present application also provides a method for treating a product, which comprises contacting the product with the above-mentioned silicon-containing polymer or the above-mentioned treating agent or the treating agent prepared by the above-mentioned method, wherein the product is a paper product, natural stone, concrete, fiber fabric, synthetic leather, non-woven fabric, asbestos, fur or plastic.

[0112] Preferably, the contacting is achieved by wet-end addition, surface sizing or coating processes.

[0113] In the present application, examples of paper products include but are not limited to paper, paper carriers such as paper cups, paper bowls, paper plates, etc.

[0114] Effects of the Invention

[0115] The silicon-containing polymers and the resulting treatment agents of this application can be easily dispersed in solvents or water and applied to a variety of items, such as paper products, natural stone, concrete, fiber fabrics, synthetic leather, non-woven fabrics, asbestos, fur, and plastics. Treatment methods include coating, immersion, internal addition, and other methods. The silicon-containing polymers and the resulting treatment agents of this application can impart oil- and water-repellency to the surfaces of these items. Specific implementation method:

[0116] 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.

[0117] In this application, unless otherwise specified, the terms used have the general meanings known to those skilled in the art.

[0118] 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.

[0119] 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.

[0120] In this application, unless otherwise specified, “%” refers to mass percentage.

[0121] 1. Aggregation Method

[0122] The polymerization method of the present polymer is not particularly limited, and conventional free radical polymerization methods such as bulk polymerization, solution polymerization in an organic solvent, and emulsion polymerization in water can all be used.

[0123] In the present application, it is preferred that after polymerization (such as solution polymerization or emulsion polymerization), water and acid are added and then the solvent is removed to obtain an aqueous dispersion; alternatively, the solvent may be removed and then water and acid are added to obtain an aqueous dispersion.

[0124] As the initiator of the polymer, peroxide, azo compound or persulfate compound can be used. The polymerization initiator can be an oil-soluble or water-soluble initiator according to the polymerization system.

[0125] Examples of oil-soluble polymerization initiators preferably include 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), dimethyl-2,2'-azobis(2-methylpropionate), benzoyl peroxide, di-t-butyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like.

[0126] Examples of the water-soluble polymerization initiator include preferably 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, tert-butyl hydroperoxide, and the like.

[0127] The polymerization initiator is preferably a peroxide or an azo compound with a half-life of 10 hours and a decomposition temperature of 40° C. or higher, such as tert-butyl peroxypivalate, 2,2′-azobis(2-methylpropionitrile), and the like.

[0128] The typical solution polymerization process of this application is as follows:

[0129] First add the solvent, then add the corresponding monomer to dissolve, introduce nitrogen to replace the oxygen, add the initiator, heat to the reaction temperature of 40-120°C, and the reaction time varies from 4 to 20 hours.

[0130] The manufacturing process of the treatment agent of this application is as follows:

[0131] (1) placing silicon-containing monomer I, monomer II and optional monomer III in an organic solvent in proportion, and adding an initiator to carry out polymerization;

[0132] (2) After the polymerization is completed, water is added for dispersion to remove the organic solvent as needed;

[0133] (3) Adding acid to convert the amino groups in the polymer into ammonium salts as needed;

[0134] (4) If necessary, add an oxidizing agent to the above dispersion for treatment.

[0135] 2. Test Method

[0136] Paper handling and testing methods

[0137] The paper that can be processed includes thin paper, thick paper, cardboard, or pulp molding, etc. 2 ) reaches 300 grams of paper box, or unit area (m 2 ) reaches 80g of kraft paper, from unit area (m 2 ) up to 100g of thin paper, to unit area (m 2 ) Paper and plastic products weighing up to 200 grams can be processed.

[0138] The raw materials of paper can be chemically bleached pulp or unbleached pulp, wood pulp, chemical mechanical pulp, mechanical pulp, etc. Resin components such as polyamide, polyolefin, polyvinyl alcohol, etc. can also be added to these pulps. The methods of paper processing are as follows:

[0139] (1) Wet end treatment: Paper plastic weight 350 g / m 2

[0140] The sugarcane pulp board is directly subjected to pulping treatment, with a decomposition degree of 600 ml of Canadian freedom and a pulp concentration of 0.3%. Alkyl ketene dimer (AKD) sizing agent is added in sequence, with an addition amount of 2% of the dry paper weight, and then a synthesized treating agent is added, with an addition amount of 1-15% of the dry paper weight.

[0141] The pulp was poured into a 10-inch round mold according to the specified weight, and then the water was removed by vacuum filtration. The round tableware was then baked in the mold at 150°C for 120 seconds to evaluate its oil and water repellency.

[0142] (2) Surface sizing treatment examples:

[0143] Preparation of test paper: Paper weight 50 g / m 2

[0144] Chemical pulp LBKP (bleached kraft pulp from broadleaf trees) and NBKP (bleached kraft pulp from coniferous trees) were used in a ratio of 5:5. The pulp was debonded to a debonding degree of 200 ml (Canada Freedom). Cationic starch MC-2 produced by Guangxi Mingyang Biochemical Company was added during the papermaking process at an amount of 1% by weight of the pulp. The paper was then made using a Fourdrinier machine to a weight of 50 g / m 2 of tissue paper.

[0145] The starch solution used for sizing is non-ionic modified hydroxyethyl starch, Penford Gum 290 produced by Penford, at a concentration of 5%. The starch solution is first heated to above 90°C for gelatinization. After gelatinization is complete, a pre-synthesized treatment agent is added, with the concentration of the treatment agent in the starch solution ranging from 1 to 15% by weight. The starch solution temperature is maintained at no less than 70°C. The paper is surface-sizing treated until the liquid absorption exceeds 70%, and then dried to obtain the treated paper.

[0146] (3) Surface coating example:

[0147] Preparation of test paper: Paper weight 230 g / m 2

[0148] The paper is made of five layers, of which the bottom and top layers are chemical pulp boards LBKP (broadleaf bleached kraft pulp) and NBKP (coniferous bleached kraft pulp), with a ratio of 7:3. The middle three layers are made of chemical mechanical pulp or mechanical pulp board, which are compounded on the paper machine to a weight of 230 g / m 2 of cardboard.

[0149] The coating starch used was cassava coating starch MS-1 produced by Guangxi Mingyang Biochemical Company. The starch concentration was 20%. The starch was added to water and heated to above 90°C for gelatinization. After gelatinization, a prepared paper treatment agent was added. The concentration of the treatment agent in the starch solution was 1-15% (mass concentration). The starch temperature was maintained at no less than 50°C and applied to the top layer of the paperboard using a paper coating machine. The coating amount was 3-8 g / m. 2 .

[0150] Oil and water repellency evaluation

[0151] The following examples and comparative examples illustrate the present invention in detail, but are not intended to limit the present invention. In the following experiments, unless otherwise specified, the addition amounts (%) are all parts by weight.

[0152] The test methods used below are as follows.

[0153] Oil repellency test evaluation

[0154] (1) Hot oil resistance test

[0155] Pour 85°C hot oil (salad oil, peanut oil, rapeseed oil) onto the paper product, observe for 20 minutes to see if there is any penetration, and then rate and score it.

[0156] 5 points: no surface discoloration;

[0157] 4 points: slight discoloration of the surface;

[0158] 3 points: surface discoloration and slight penetration;

[0159] 2 points for severe penetration.

[0160] Water repellency evaluation

[0161] (1) Cobb test

[0162] The test is carried out according to GB / T1540-2002 or ISO 535:1991.

[0163] The principle is to measure the height of the support 10mm water at 100cm 2 The weight of water absorbed by the paper in 1 minute (g), this value is converted into weight per 1 square meter (g / m 2 ).

[0164] The Cobb absorbency tester usually uses a flip cylinder tester. The metal cylinder is cylindrical and its inner cross-sectional area is generally (100±0.2)cm 2 , the corresponding inner diameter is (112.8±0.2) mm. If a small area cylinder is used, the recommended area should be no less than 50cm 2 , the water volume should be reduced accordingly to maintain a water height of 10 mm. The cylinder height is 50 mm. The portion of the cylinder's annular surface that contacts the specimen should be smooth and sufficiently rounded to prevent damage to the specimen from the cylinder's edges. To prevent water leakage, a layer of elastic, non-absorbent rubber pad or washer should be added to the flip cylinder lid and the flat pressing base. The metal pressure roller should have a width of (200 ± 0.5) mm, a mass of (10 ± 0.5) kg, and a smooth surface.

[0165] Cut the treated paper sample into 10 (125±5) mm square or ￠(125±5) mm circular specimens (5 on each side). For instruments with a small test area, the specimen size should be slightly larger than the outer diameter of the cylinder to avoid leakage caused by too small a specimen, and to avoid operation being affected by too large a specimen.

[0166] Before placing the specimen, ensure that the cylindrical ring surface and rubber pad in contact with the specimen are dry. Keep hands away from the test area. Use a graduated cylinder to measure 100mL of water and pour it into the cylinder. Then, place the weighed specimen onto the cylindrical ring surface with the test surface facing downward. Place the gland over the specimen and clamp it securely to the cylinder.

[0167] Turn the cylinder 180° and start a stopwatch to time the absorption. Allow the sample to absorb water for 60 seconds. 10-15 seconds before the end of absorption, turn the cylinder upright, loosen the gland clamp, and remove the sample. Note that the test water should be replaced after every five tests to avoid affecting the test results. At the moment the specified absorption time is reached, place the sample, which has been removed from the cylinder, with the absorbent surface facing down, on a pre-laid absorbent paper. Place another piece of absorbent paper on top of the sample and immediately apply no additional pressure using a metal roller, rolling back and forth once every 4 seconds to remove any remaining water from the sample surface. Quickly remove the sample, fold it in half with the absorbent surface facing inward, then fold it in half again and weigh it to the nearest 0.001g. For thick cardboard, the sample may not fold easily; in this case, weigh it again as soon as possible.

[0168] The Cobb value is expressed by the following formula: C = (g2-g1) / F

[0169] Where: C cobb value;

[0170] g2—weight of the sample after absorbing water;

[0171] g1—weight of sample before water absorption;

[0172] F—100cm 2 Test area.

[0173] (2) Hot water resistance test

[0174] This method directly tests the ability of paper to resist hot water. The test method is relatively simple. Generally, the treated paper is made into a container that can hold liquids. 100°C boiling water is poured into it and observed for 30 minutes to see if there is any leakage. If there is no leakage, it passes. This method is suitable for pulp molded products.

[0175] Stone processing and testing methods:

[0176] The natural stones that can be processed include: marble, granite, sandstone, slate, etc.

[0177] Taking sandstone as an example, soak the sandstone sample in a treatment solution diluted with water at a certain multiple. After removing it, let it air dry for 48 hours at a temperature not lower than 25°C. Then, drip salad oil, mustard sauce, coffee, vinegar, etc. onto the sandstone surface and observe the wetting state. If there is no penetration, it means the impedance is better.

[0178] 5 points: no surface discoloration;

[0179] 4 points: slight discoloration of the surface;

[0180] 3 points: surface discoloration and slight penetration;

[0181] 2 points for severe penetration.

[0182] 2. Examples and Comparative Examples

[0183] See Table 1 for chemical abbreviations:

[0184] Table 1

[0185] Example 1

[0186] A 1000 mL four-necked flask equipped with a reflux condenser, nitrogen inlet, thermometer, and stirrer was charged with 76 g of Si-ph-B3, 25 g of DN, 15 g of HEMA, and 120 g of methyl ethyl ketone (MEK). Nitrogen was introduced for 30 minutes, and the temperature was slowly raised to 50-60°C. Then, 1.5 g of a peroxide initiator, t-butyl peroxypivalate, was added portionwise. The reaction temperature was controlled at 60°C and the reaction was allowed to proceed for 20 hours, yielding approximately 236 g of a polymer A solution with a solids content of approximately 50%. This solution was tested using gas chromatography-mass spectrometry, revealing that the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the resulting polymer was nearly identical to that of the added monomers.

[0187] 340 g of water and 10 g of glacial acetic acid were added, and the mixture was stirred at 70° C. for more than 1 hour. MEK in the polymer A solution was distilled off under reduced pressure to obtain an aqueous dispersion with a solid content of 25%.

[0188] Examples 2-7

[0189] The same procedures as in Example 1 were used, except that Si-ph-B3 was replaced with the following silicon-containing monomers I having different structures: Si-ph-B1 (Example 2), Si-N2-B2 (Example 3), Si-N2-B1 (Example 4), Si-OCN-B3 (Example 5), Si-OCO-B3 (Example 6), and Si-phO-B3 (Example 7). The solutions were tested using gas chromatography-mass spectrometry, and the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the resulting polymer was nearly identical to that of the added monomers.

[0190] Comparative Example 1

[0191] In a 1000 mL four-necked flask equipped with a reflux condenser, nitrogen inlet, thermometer, and stirrer, 76 g of Si-5 (average molecular weight 500), 25 g of DN, 15 g of HEMA, and 120 g of methyl ethyl ketone (MEK) were added. Nitrogen was introduced for 30 minutes, and the temperature was slowly raised to 50-60°C. Then, 1.5 g of t-butyl peroxypivalate (a peroxide initiator) was added portionwise. The reaction temperature was controlled at 60°C and the reaction was allowed to proceed for 20 hours to obtain approximately 236 g of a polymer A solution with a solids content of approximately 50%. This solution was tested using gas chromatography-mass spectrometry, and the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the resulting polymer was nearly identical to that of the added monomers.

[0192] 340 g of water and 10 g of glacial acetic acid were added, and the mixture was stirred at 70° C. for more than 1 hour. MEK in the polymer A solution was distilled off under reduced pressure to obtain an aqueous dispersion with a solid content of 25%.

[0193] Performance Testing

[0194] The aqueous dispersions synthesized in the examples and comparative examples were used as treatment agents to test several articles:

[0195] 1) Paper Tableware Test: Prepare a 1wt% pulp solution, add 2wt% of AKD sizing agent and 10wt%, 6wt%, and 3wt% of treatment agent, respectively, by dry paper weight. Form a 10-inch disc weighing 20g. Test with 85°C salad oil for 20 minutes, and grade based on penetration. Test with 100°C boiling water for 30 minutes, scoring as passing or leaking.

[0196] 2) Paper test: select 50 g / m 2 The thin paper was treated by surface sizing with the concentrations of the treating agent being 5wt%, 4wt% and 3wt% respectively, and the hot oil resistance and Cobb water absorption value were tested.

[0197] 3) Paper test: select 230 g / m 2 The cardboard was treated by coating with the concentrations of the treating agent being 5wt%, 4wt% and 3wt% respectively, and the hot oil resistance and Cobb water absorption value were tested.

[0198] 4) Sandstone Testing: Dilute the treatment agent with water to 3wt%, 2wt%, and 1wt% liquid, respectively. Soak sandstone samples in the liquid and allow them to air dry for 48 hours at a temperature not lower than 25°C. Then, drip salad oil and coffee onto the sandstone surface, observe the wetting state, and grade and score the samples.

[0199] The test performance summary of Examples 1-7 and Comparative Example 1 is shown in Table 2.

[0200] Table 2 Test performance comparison table

[0201] It can be seen from the test performance of the above embodiments and comparative examples that various treatment agents all exhibit relatively good oil and water repellency properties. Among them, the treatment agents prepared using branched silicon monomers Si-ph-B3 and Si-ph0-B3 have better oil repellency than the treatment agents prepared using linear silicon monomers Si-ph-B1 or Si-5 at high dosages. However, when the amount of treatment agent added is reduced, the performance of the former two is significantly better than the latter two, indicating that the former two have better oil repellency and higher efficiency.

[0202] Example 8

[0203] In a 1000 mL four-necked flask equipped with a reflux condenser, a nitrogen inlet, a thermometer, and a stirrer, 48 g of Si-ph-B3, 28 g of Si-5 (average molecular weight 500), 25 g of DN, 15 g of HEMA, and 120 g of methyl ethyl ketone (MEK) were added. Nitrogen was introduced for 30 minutes, and the temperature was slowly raised to 50°C-60°C. Then, 1.5 g of t-butyl peroxypivalate (a peroxide initiator) was added portionwise. The reaction temperature was controlled at 60°C and the reaction was allowed to proceed for 20 hours to obtain approximately 236 g of a polymer A solution with a solids content of approximately 50%. This solution was tested using gas chromatography-mass spectrometry, and the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the resulting polymer was nearly identical to that of the added monomers.

[0204] 340 g of water and 10 g of glacial acetic acid were added, and the mixture was stirred at 70° C. for more than 1 hour. MEK in the polymer A solution was distilled off under reduced pressure to obtain an aqueous dispersion with a solid content of 25%.

[0205] Example 9

[0206] In a 1000 mL four-necked flask equipped with a reflux condenser, nitrogen inlet, thermometer, and stirrer, 76 g of Si-ph-B3, 25 g of DM, 15 g of HEMA, and 120 g of methyl ethyl ketone (MEK) were added. Nitrogen was introduced for 30 minutes, and the temperature was slowly raised to 50-60°C. Then, 1.5 g of the peroxide initiator, t-butyl peroxypivalate, was added portionwise. The reaction temperature was controlled at 60°C and the reaction was allowed to proceed for 20 hours, yielding approximately 236 g of a polymer A solution with a solids content of approximately 50%. This solution was tested using gas chromatography-mass spectrometry, revealing that the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the resulting polymer was nearly identical to that of the added monomers.

[0207] 340 g of water and 10 g of glacial acetic acid were added, and the mixture was stirred at 70° C. for more than 1 hour. MEK in the polymer A solution was distilled off under reduced pressure to obtain an aqueous dispersion with a solid content of 25%.

[0208] Example 10

[0209] A 1000 mL four-necked flask equipped with a reflux condenser, nitrogen inlet, thermometer, and stirrer was charged with 76 g of Si-ph-B3, 25 g of DN, 15 g of 4-HBA, and 120 g of methyl ethyl ketone (MEK). Nitrogen was introduced for 30 minutes, and the temperature was slowly raised to 50-60°C. Then, 1.5 g of the peroxide initiator, t-butyl peroxypivalate, was added portionwise. The reaction temperature was controlled at 60°C and the reaction was allowed to proceed for 20 hours, yielding approximately 236 g of a polymer A solution with a solids content of approximately 50%. This solution was tested using gas chromatography-mass spectrometry, revealing that the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the resulting polymer was nearly identical to that of the added monomers.

[0210] 340 g of water and 10 g of glacial acetic acid were added, and the mixture was stirred at 70° C. for more than 1 hour. MEK in the polymer A solution was distilled off under reduced pressure to obtain an aqueous dispersion with a solid content of 25%.

[0211] The test method is the same as that of Example 1. The test performance summary of Examples 8-10 is shown in Table 3.

[0212] Table 3 Test performance comparison table

[0213] 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 silicon-containing polymer comprising repeating units derived from a silicon-containing monomer I and repeating units derived from a monomer II, wherein the silicon-containing monomer I comprises a silicon-containing monomer I-1a and / or a silicon-containing monomer I-1b, The general structural formula of the silicon-containing monomer I-1a is shown in Formula I-1a: CH2=C(R1)-WBZ I-1a In formula I-1a, R1 is selected from hydrogen atom or 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 C1-C 20 When W is selected from W-2, W-3, W-4, B is C1-C 20 alkylene; The general structural formula of the silicon-containing monomer I-1b is shown in Formula I-1b: In formula I-1b, R1 is selected from hydrogen atom or C1-C 20 Alkyl, B is independently C1-C 20 alkylene; In Formula I-1a and Formula I-1b, Z is independently selected from the following structures: In the formula, R4 is independently C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkaryl 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 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 Arylalkyl or C7-C 12 The alkylaryl group, and the structure of formula (I): 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 or R9-OR 10 - group, wherein R9 is C1-C 10 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 The alkylaryl group, R 10 C1-C 10 Alkylene, 0≤b≤200; The general structural formula of monomer II is shown in formula (II): CH2=C(R1)-PBN(R3R4) (II) In formula (II), P is selected from the groups 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 Alkyl; R3 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.

2. The silicon-containing polymer according to claim 1, wherein Silicon-containing monomer I also includes silicon-containing monomer I-2, The general structural formula of the silicon-containing monomer I-2 is shown in Formula I-2: CH2=C(R1)-XBZ I-2 In formula I-2, R1 is selected from hydrogen atom or C1-C 20 Alkyl; B is C1-C 20 alkylene; 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 Alkyl; Z is selected from the following structures: Wherein R4 is independently C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkaryl 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 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 Arylalkyl or C7-C 12 The alkylaryl group, and the structure of formula (I): 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 or R9-OR 10 - group, wherein R9 is C1-C 10 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 The alkylaryl group, R 10 C1-C 10 Alkylene, 0≤b≤200.

3. The silicon-containing polymer according to claim 1 or 2, wherein In the formula I-1a and / or formula I-1b and / or formula I-2, When a is 1, Y1 and / or Y2 is a structure of formula (I); when a is greater than 1 and ≤ 200, at least one Y1 is a structure of formula (I) and / or at least one Y2 is a structure of formula (I): 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 or R9-OR 10 - group, wherein R9 is C1-C 10 Alkyl, C6-C 20 Aryl, C7-C 12 Arylalkyl or C7-C 12 The alkylaryl group, R 10 C1-C 10 Alkylene, 0≤b≤200; Preferably, R7 is 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 Alkane Aryl 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≤100.

4. The silicon-containing polymer according to any one of claims 1 to 3, wherein Also included are the repeating units produced by monomer III, The general structural formula of monomer III is shown in Formula III: CH2=C(R ) -G-(R2O) q -R3 III In formula III, 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 or a C1-C3 alkyl group; Wherein, G is selected from the groups represented by G-1 and G-2, -C(O)-O-(CH2) n - G-1 -C(O)-N(R4)-(CH2) n - G-2 R4 represents a hydrogen atom or a methyl group, and n is an integer of 0-10, preferably an integer of 0-5.

5. The silicon-containing polymer according to any one of claims 1 to 4, wherein In terms of mass percentage, the proportion of silicon-containing monomer I-1a and / or I-1b in the total amount of silicon-containing monomer I is 1% to 100%, 5% to 100%, 10% to 100%, or 50% to 100%; and / or The mass content of the repeating units produced by the silicon-containing monomer I in the polymer is 30%-90%, preferably 40%-85%, more preferably 50%-80%; and / or The mass content of the repeating units produced by monomer II in the polymer is 5%-65%, preferably 10%-50%, more preferably 15%-45%; and / or The mass content of the repeating units produced by monomer III in the polymer is 1%-40%, preferably 5%-30%, more preferably 10%-25%; and / or In terms of mass percentage, the proportion of silicon-containing monomer I in the total monomer amount is 30%-90%, preferably 40%-85%, more preferably 50%-80%; and / or the proportion of monomer II in the total monomer amount is 5%-65%, preferably 10%-50%, more preferably 15%-45%; and / or the proportion of monomer III in the total monomer amount is 1%-40%, preferably 5%-30%, more preferably 10%-25%.

6. The silicon-containing polymer according to any one of claims 1 to 5, wherein In the silicon-containing monomer I, R1 and R2 are selected from hydrogen atoms or methyl groups, and B and D are C1-C 10 alkylene, preferably B and D are C1-C6 alkylene; in Z, R4 are each independently C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 of Aralkyl, C7-C 12 Alkaryl 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 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 are each independently C1-C 10 Alkyl, C6-C 10 Aryl, C7-C 12 Aralkyl, C7-C 12 Alkaryl 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 monomer II, R1 and R2 are selected from hydrogen atoms or methyl groups; B is C1-C 10 alkylene, preferably B is a C1-C6 alkylene; R3 and R4 are independently a hydrogen atom, a C1-C3 alkyl, a hydroxyethyl or a benzyl group, or R3 and R4 are combined and together with the nitrogen atom form a morpholino group, a piperidino group or a pyrrolidinyl group.

7. The silicon-containing polymer according to any one of claims 1 to 6, wherein Z is independently selected from one or more of the following structures i-1 to i-6: Z 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 a methyl group, ph represents a phenyl 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.

8. The silicon-containing polymer according to any one of claims 1 to 7, wherein Silicon-containing monomer I-1a is selected from CH2=CH-ph-Si(OSi(CH3)3)3(ph represents )， 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)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); and / or Silicon-containing monomer I-1b is selected from 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, 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) Silicon-containing monomer I-2 is selected from CH2=C(CH3)-C(O)-O-(CH2)3Si(OSi(CH3)3)3, CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents butyl) (1≤n≤25), CH2=C(CH3)C(O)-NH-(CH2)3Si(OSi(CH3)3)3, CH2=C(CH3)C(O)-NH-(CH2)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents a butyl group) (1≤n≤25); Monomer II 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, and dipropylaminopropyl (meth)acrylamide; and / or Monomer III 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, and methoxypolyethylene glycol (meth)acrylate, preferably hydroxyethyl methacrylate and 4-hydroxybutyl acrylate.

9. A treating agent comprising the silicon-containing polymer according to any one of claims 1 to 8 and a solvent, wherein the solvent comprises water and / or an organic solvent. Preferably, the organic solvent is one or more of acetone, methyl ethyl ketone, 4-methyl-2-pentanone, ethyl acetate, butyl acetate, N-methyl-2-pyrrolidone, N,N-dimethylformamide, ethanol, isopropanol, n-propanol, butyl carbitol, and dipropylene glycol methyl ether.

10. A method for preparing the treatment agent according to claim 9, comprising the following steps: (1) polymerizing the monomers in an organic solvent to obtain a polymer solution; Optionally, (2) adding water to the polymer solution for dispersion and then removing the organic solvent, or first removing the solvent and then adding water for dispersion; Optionally, (3) adding an acid to the polymer solution to convert the amino groups in the polymer into ammonium salts; Optionally, (4) the polymer solution is treated with aqueous hydrogen peroxide to convert the amino groups into nitroxides.

11. Use of the silicon-containing polymer according to any one of claims 1 to 8, the treating agent according to claim 9, or the treating agent prepared by the method according to claim 10 in paper products, natural stone, concrete, fiber fabrics, synthetic leather, non-woven fabrics, asbestos, fur, or plastics.

12. The product treated with the silicon-containing polymer according to any one of claims 1 to 8, the treating agent according to claim 9, or the treating agent prepared by the method according to claim 10, wherein the product is paper products, natural stone, concrete, fiber fabrics, synthetic leather, non-woven fabrics, asbestos, fur, or plastic.

13. A method for treating a product, comprising contacting the product with the silicon-containing polymer according to any one of claims 1 to 8, the treating agent according to claim 9, or the treating agent prepared by the method according to claim 10, wherein the product is a paper product, natural stone, concrete, fiber fabric, synthetic leather, non-woven fabric, asbestos, fur, or plastic. Preferably, the contacting is achieved by wet-end addition, surface sizing or coating processes.

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