Organosilicon polymers and their applications

Abstract

This application relates to an organosilicon polymer and its applications. The organosilicon polymer contains repeating units derived from silicon-containing monomer I-1 and optional silicon-containing monomer I-2, as well as repeating units derived from monomer II. The polymer or a treatment agent containing the polymer can be used to treat various articles, such as textiles, paper products, and stone, to impart oil and water repellency to the articles.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority from a Chinese patent application filed on October 4, 2022, bearing application number 202211217513.9 and titled "Organosilicon Polymer and Its Application," the entire contents of which are incorporated herein by reference.

[0002] (Technical field) This application relates to organosilicon polymers, treatment agents containing said organosilicon polymers, and their preparation and application. [Background technology]

[0003] In recent years, the international community has become increasingly concerned about polyfluoroalkyl substances (PFAS). PFAS are considered to be highly stable and resistant to degradation. The U.S. Environmental Protection Agency (EPA) has published a related report, "Preliminary Risk Assessment of the Development Toxicity Associated with Exposure to Perfluorooctanoic Acid and Its Salts" (http: / / www.epa.gov / opptintr / pfoa / pfoara.pdf), raising concerns about the environmental impact of PFAS. At the same time, the EPA has announced the possibility of PFAS being produced by the decomposition or metabolism of telomers, and has published this information in the Federal Register (FR Vol. 68, No. 73 / April 16, 2003 [FRL-2303-8], http: / / www.epa.gov / opptintr / pfoa / pfoar.pdf). EPA Environmental News For Release: Monday, April 14, 2003. EPA intensifies scientific investigation of a chemical processing AIDS (http: / / www.epa.gov / opptintr / pfoa / pfoafacts.pdf) and related telomer products are widely used in textile finishing, paper, leather, fire protection foam and care products, etc. However, fluorine-containing treatments are thought to be one of the sources of PFAS.

[0004] In light of the above, several new non-fluorinated compounds have been proposed to replace existing fluorine-containing finishing agents. CN107849187A proposes copolymerizing acrylic esters with monomers such as vinyl chloride, and finishing textiles with the resulting polymer to achieve excellent water repellency. CN110114435A proposes using a propylene ester copolymer, further compounding it with a wax emulsion, to achieve excellent water repellency. CN105377935B proposes using an aqueous polyurethane dispersion to achieve excellent water repellency. However, these polymers do not provide desirable oil repellency.

[0005] CN103975107B proposes a solution using a barrier coating. The patent primarily employs emulsion polymerization, adding an emulsifier to starch to produce a polymer emulsion, which is then coated onto the paper. While this method can block oil and grease, it presents two problems: first, the oil-repellent effect is only achieved with a large coating amount; and second, it can only be applied to papermaking machines equipped with coating equipment, meaning it cannot be directly completed on standard papermaking machines, resulting in poor process adaptability and high costs. CN112513370 proposes treating paper with a long-chain acrylic ester copolymer to achieve oil and water repellency, but it was discovered that this method had poor barrier properties against hot oil above 80°C. Therefore, there is a need in this field to develop a treatment agent with improved oil repellency. Summary of the Invention

[0006] An object of the present invention is to provide an organosilicon polymer that can be used to treat a variety of articles to impart oil and water repellency to the surface of the articles, and a treating agent containing said polymer.

[0007] In a first aspect, the present application provides a polymerizable composition comprising a repeat unit derived from Monomer I and a repeat unit derived from Monomer II, where Monomer I comprises silicon Monomer I-1 and silicon Monomer I-2, which are optional monomers; a) The general structural formula of the silicon monomer I-1 is represented by formula I-1: [ka] In formula I-1, R1 is a hydrogen atom or a C1-C 20 and B is selected from the group consisting of C1-C 20 is an alkylene group of the formula X is selected from groups represented by X-1 and X-2; [ka] R2 is a hydrogen atom or a C1-C 20 and selected from the alkyl groups Z1 is selected from the structures shown below: [ka] In Z1, R4 is independently C1-C 20 Alkyl groups, C6-C 20 Aryl groups, C7-C 12 Aralkyl groups, C7-C 12 or an R5-O-R6- group, where R5 is a C1-C 10 Alkyl groups, C6-C 20 Aryl groups, C7-C 12 or an aralkyl group of C7-C 12 and R6 is an alkylaryl group of C1-C 10 and 1≦a≦200; Y1 and Y2 are the same or different and each independently represent C1-C 20 Alkyl groups, C6-C 20 Aryl groups, C7-C 12 or an aralkyl group of C7-C 12 and a structure of formula (I), wherein when a is 1, Y1 and / or Y2 are structures of formula (I), and 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); [ka] R7 is independently C1-C 20 Alkyl groups, C6-C 20 Aryl groups, C7-C 12 or an aralkyl group of C7-C 12 and each R8 is independently a C1-C 20 Alkyl groups, C6-C 20 Aryl groups, C7-C 12 Aralkyl groups, C7-C 12 or an alkylaryl group of R9-OR 10 - group, where R9 is C1-C 10 Alkyl groups, C6-C 20 Aryl groups, C7-C 12 or an aralkyl group of C7-C 12 is an alkylaryl group of the formula R 10 is C1-C 10 and b is an alkylene group represented by the formula: The general structural formula of the silicon monomer I-2 is represented by formula I-2: [ka] In formula I-2, R1 is a hydrogen atom or a C1-C 20 and B is selected from the group consisting of C1-C 20 is an alkylene group of the formula X is selected from groups represented by X-1 and X-2; [ka] R2 is a hydrogen atom or a C1-C 20 and selected from the alkyl groups Z2 is selected from the structures shown below: [ka] In Z2, R3 is independently C1-C 20 Alkyl groups, C6-C 20 Aryl groups, C7-C 12 or an aralkyl group of C7-C 12and each R4 is independently a C1-C 20 Alkyl groups, C6-C 20 Aryl groups, C7-C 12 Aralkyl groups, C7-C 12 or an R5-O-R6- group, where R5 is a C1-C 10 Alkyl groups, C6-C 20 Aryl groups, C7-C 12 or an aralkyl group of C7-C 12 and R6 is an alkylaryl group of C1-C 10 and 1≦a≦200; b) The structural general formula of Monomer II is represented by Formula II: [ka] where R1 and R2 are each independently a hydrogen atom or a C1-C 20 alkyl groups, and B is selected from C1-C 20 R3 and R4 are each independently a hydrogen atom, a C1-C 18 or R3 and R4 combine with the nitrogen atom to form a morpholino, piperidino or pyrrolidino group, providing an organosilicon polymer.

[0008] The inventors unexpectedly discovered that polymerization using the silicon monomer I-1 significantly improves oil repellency and significantly increases oil repellency efficiency, i.e., good oil repellency can be achieved even with a small amount of addition. When the combination of the silicon monomers I-1 and I-2 is used, the resulting polymer can achieve a comprehensive balance of properties, such as a balance between oil repellency and water repellency.

[0009] According to some embodiments of the present application, the organosilicon polymer further comprises repeat units derived from monomer III, c) The structural general formula of Monomer III is represented by Formula III: [ka] In formula III, R1 represents a hydrogen atom or a methyl group; each R2 is independently a C1-C6 alkylene group, preferably a C2-C4 alkylene group; q is an integer of 1-50, preferably an integer of 1-20; R3 is a hydrogen atom or a C1-C 20 is preferably a hydrogen atom or a C1-C 10 is an alkyl group of the formula (I), more preferably a hydrogen atom or a C1-C3 alkyl group; wherein G is selected from groups represented by G-1 and G-2; [ka] R4 represents a hydrogen atom or a methyl group, and n is an integer of 0-10, preferably an integer of 0-5.

[0010] According to some embodiments of the present application, the proportion of repeating units derived from silicon monomer I-1 in the total amount of repeating units derived from silicon monomer I-1 and repeating units derived from silicon monomer I-2, in mass percentage, is 1%-100%, 5%-100%, 10%-100%, or 50%-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 of these. The total amount of repeating units derived from silicon monomer I-1 and repeating units derived from silicon monomer I-2 is also the total amount of repeating units derived from monomer I.

[0011] According to some embodiments of the present application, the mass content of repeat units derived from Monomer I is 30%-90%, preferably 40%-85%, more preferably 50%-80%, such as 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or a range consisting of any two of these.

[0012] According to some embodiments of the present application, the mass content of repeat units derived from monomer II is 5%-65%, preferably 10%-50%, more preferably 15%-45%, such as 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or a range consisting of any two of these.

[0013] According to some embodiments of the present application, the mass content of repeat units derived from monomer III is 1%-30%, preferably 3%-15%, more preferably 5%-10%, such as 1%, 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, or a range consisting of any two of these.

[0014] According to some embodiments of the present application, in the silicon monomers I-1 and I-2, R1 is selected from a hydrogen atom or a methyl group.

[0015] According to some embodiments of the present application, in silicon monomers I-1 and I-2, B is C1-C 10 Preferably, the alkylene group is selected from C1-C6 alkylene groups.

[0016] According to some embodiments of the present application, in X, R2 is selected from a hydrogen atom or a methyl group.

[0017] According to some embodiments of the present application, in Z, R is independently selected from C-C 10 Alkyl groups, C6-C 10 Aryl groups, C7-C 12 Aralkyl groups, C7-C 12 or an R5-O-R6- group, where R5 is a C1-C 10 Alkyl groups, C6-C 10 Aryl groups, C7-C 12 or an aralkyl group of C7-C 12 and R6 is an alkylaryl group of C1-C 10 and / or 1≦a≦80, R7 is independently C1-C 10 Alkyl groups, C6-C 10 Aryl groups, C7-C 12 or an aralkyl group of C7-C 12 and each R8 is independently a C1-C 10 Alkyl groups, C6-C 10 Aryl groups, C7-C 12 Aralkyl groups, C7-C 12 The alkylaryl group R9-OR 10 - group, where R9 is C1-C 10 Alkyl groups, C6-C 10 Aryl groups, C7-C 12 or an aralkyl group of C7-C 12 is an alkylaryl group of the formula R 10 is C1-C 10 and / or 0≦b≦80.

[0018] According to some embodiments of the present application, in Z1, R4 is independently a C1-C6 alkyl group, a C6-C 10 Aryl groups, C7-C 10 Aralkyl groups, C7-C 10 or an R5-O-R6- group, where R5 is a C1-C6 alkyl group, a C6-C 10 Aryl groups, C7-C 10 or an aralkyl group of C7-C 10 R6 is a C1-C6 alkylene group, and 1≦a≦30; R7 is independently a C1-C6 alkyl group, a C6-C 10 Aryl groups, C7-C 10 or an aralkyl group of C7-C 10 R8 is independently a C1-C6 alkyl group, a C6-C 10 Aryl groups, C7-C 10 Aralkyl groups, C7-C 10 or an alkylaryl group of R9-OR 10- group, where R9 is a C1-C6 alkyl group, C6-C 10 Aryl groups, C7-C 10 or an aralkyl group of C7-C 10 is an alkylaryl group of the formula R 10 is a C1-C6 alkylene group, and 0≦b≦30.

[0019] 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.

[0020] 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.

[0021] In some embodiments, Z1 is one or more selected from the following structures i-1 to i-4: [ka] R is independently C1-C 10 Alkyl groups, C6-C 10 Aryl groups, C7-C 12 or an aralkyl group of C7-C 12 and selected from the alkylaryl groups 1≦m+1≦60, preferably 1≦m+1≦30; 0≦p≦60, preferably 0≦p≦30; 0≦q≦60, preferably 0≦q≦30; and 1≦x≦9, preferably 1≦x≦7, where each x may be the same or different.

[0022] In some embodiments, R is a C1-C3 alkyl group, such as a methyl group.

[0023] In some preferred embodiments, Z1 is selected from the following structures: [ka] One or more of the following: Me represents a methyl group, and 1≦m+1≦60, preferably 1≦m+1≦30, 0≦p≦60, preferably 0≦p≦30, 0≦q≦60, preferably 0≦q≦30, and 1≦x≦9, preferably 1≦x≦7, where each x may be the same or different.

[0024] According to some embodiments of the present application, in Z2, R3 is independently C1-C 10 Alkyl groups, C6-C 10 Aryl groups, C7-C 12 or an aralkyl group of C7-C 12 and each R4 is independently a C1-C 10 Alkyl groups, C6-C 10 Aryl groups, C7-C 12 or an aralkyl group of C7-C 12 or an R5-O-R6- group, where R5 is a C1-C 10 Alkyl groups, C6-C 20 Aryl groups, C7-C 12 or an aralkyl group of C7-C 12 and R6 is an alkylaryl group of C1-C 10 is an alkylene group of the formula:

[0025] According to some embodiments of the present application, 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.

[0026] According to some embodiments of the present application, in Z2, R3 is independently a C1-C6 alkyl group, a C6-C 10 Aryl groups, C7-C 10 or an aralkyl group of C7-C 10 R4 is independently a C1-C6 alkyl group, a C6-C 10 Aryl groups, C7-C 10 or an aralkyl group of C7-C10 or an R5-O-R6- group, where R5 is a C1-C6 alkyl group, a C6-C 10 Aryl groups, C7-C 10 or an aralkyl group of C7-C 10 and R6 is an alkylaryl group of C1-C 10 and 1≦a≦10.

[0027] According to some embodiments of the present invention, Z2 is one or more selected from the following structures ii-1 to ii-2: [ka] R is independently C1-C 10 Alkyl groups, C6-C 10 Aryl groups, C7-C 12 or an aralkyl group of C7-C 12 and selected from the alkylaryl groups 1≦m+1≦60, preferably 1≦m+1≦30, and 1≦x≦9, preferably 1≦x≦7; Z2 is suitably selected from the following structures: [ka] One or more of the following: Me represents a methyl group, ph represents a phenyl group, 1≦m+1≦60, preferably 1≦m+1≦30, and 1≦x≦9, preferably 1≦x≦7.

[0028] In some embodiments, m is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9.

[0029] In some embodiments, x is 1, 2, 3, 4, 5, 6, or 7.

[0030] According to some embodiments of the present invention, in the above structure of Monomer II, R1 and R2 are selected from a hydrogen atom or a methyl group; B is a C1-C6 alkylene group; R3 and R4 are each independently a C1-C3 alkyl group, a hydroxyethyl group, or a benzyl group; or R3 and R4 are combined with the nitrogen atom to form a morpholino group, a piperidino group, or a pyrrolidino group.

[0031] According to some embodiments of the present application, the silicon monomer I-1 is 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, Selected from CH2=C(CH3)C(O)-O-(CH2)3Si(CH3)[O-[Si(CH3)2O]n-Si(CH3)2C4H9]2 (0≦n≦25).

[0032] According to some embodiments of the present application, silicon monomer I-2 is CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9(1≦n≦25), CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C8H 17 (1≦n≦25), CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)3 (1≦n≦25).

[0033] According to some embodiments of the present application, monomer II is one or more selected from dimethylaminoethyl(meth)acrylamide, diethylaminoethyl(meth)acrylamide, dipropylaminoethyl(meth)acrylamide, dimethylaminopropyl(meth)acrylamide, diethylaminopropyl(meth)acrylamide, and dipropylaminopropyl(meth)acrylamide.

[0034] According to some embodiments of the present application, the 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, and preferably hydroxyethyl methacrylate, 4-hydroxybutyl acrylate.

[0035] According to some embodiments of the present application, the weight average molecular weight of the polymer is 1,000 to 2,000,000, preferably 5,000 to 1,500,000. According to some embodiments of the present application, the polymer is in the form of an ammonium salt or a nitrogen oxide.

[0036] The present application further provides a treatment agent comprising the organosilicon polymer described above and a solvent comprising water and / or an organic solvent.

[0037] 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, dipropylene glycol methyl ether.

[0038] The present application also relates to a method for producing the treatment agent, (1) The method comprises the step of polymerizing a monomer (including monomer I, monomer II, and optionally monomer III) in an organic solvent to obtain a polymer solution.

[0039] According to some embodiments of the present application, the proportion of the amount of silicon monomer I-1 used to the total amount of silicon monomer I-1 and silicon monomer I-2, by mass, is 1%-100%, 5%-100%, 10%-100%, 50%-100%, 50%-98%, 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 these.

[0040] According to some embodiments of the present application, the proportion of the amount of Monomer I used relative to the total amount of monomers, by mass, 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 these.

[0041] According to some embodiments of the present application, the proportion of the amount of monomer II used relative to the total amount of monomers is 5%-65%, preferably 10%-50%, more preferably 15%-45%, such as 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or a range consisting of any two of these.

[0042] According to some embodiments of the present application, the proportion of the amount of monomer III used relative to the total amount of monomers is 0-30%, preferably 1%-30%, more preferably 3%-15%, and even more preferably 5%-10%, for example, 1%, 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, or a range consisting of any two of these.

[0043] If necessary, the manufacturing method may further include one or more of the following steps (2), (3), and (4). (2) adding water to disperse the polymer solution and simultaneously removing the organic solvent from the polymer solution, or removing the solvent and then adding water to disperse the polymer solution; (3) adding an organic acid to convert the amino groups in the polymer into ammonium salts; (4) A step of adding an oxidizing agent (e.g., hydrogen peroxide) to convert the amino groups of the polymer into nitrogen oxides.

[0044] The present application also provides applications of the organosilicon polymer, the treating agent, or the treating agent prepared by the method described above in textile fabrics, leather, nonwoven fabrics, asbestos, fur, concrete, natural stone, paper products, or plastics.

[0045] The present application further provides a product treated with the organosilicon polymer, the treating agent, or the treating agent prepared by the method, and the product may be textile fabric, leather, nonwoven fabric, asbestos, fur, concrete, natural stone, paper products, or plastic.

[0046] The present application further provides a method for treating an article, comprising contacting the article, which is a textile fabric, leather, nonwoven fabric, asbestos, fur, concrete, natural stone, paper product, or plastic, with the organosilicon polymer, or the treating agent, or the treating agent prepared by the method.

[0047] Preferably, said contacting is achieved by a wet end addition, surface size or application process.

[0048] In this application, examples of paper products include, but are not limited to, paper, paper containers such as paper cups, paper bowls, paper trays, and the like.

[0049] Effect of the invention The organosilicon polymers and resulting treatment agents of the present application are easily dispersed in water and are suitable for the surface treatment of a variety of articles, including textiles, leather, nonwoven fabrics, asbestos, fur, concrete, natural stone, paper, and plastics. Treatment methods include painting, immersion, and other methods such as internal addition. The organosilicon polymers and resulting treatment agents can impart oil and water repellency to the article surface after treatment. DETAILED DESCRIPTION OF THE INVENTION

[0050] In order to make the objectives, technical solutions and advantages of this application clearer, the present application will be further described in detail below in combination with examples. These examples are only for illustrating this application and are not intended to limit the present invention. The actual scope of protection of this application is set forth in the claims.

[0051] In this application, unless otherwise explained, the terms used have their ordinary meanings well known to those skilled in the art.

[0052] In this application, the term "alkyl group" refers to a straight-chain or branched-chain alkyl group, 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, and the like.

[0053] In this application, the term "alkylene group" refers to a straight-chain alkylene group or a branched-chain alkylene group, non-limiting examples of which include methylene, ethylene, n-propylene, n-butylene, n-pentylene, -CHCH3CH2-, -CHCH3CH2CH2-, CH2CH3CHCH2-, and the like.

[0054] In this application, all "%" refers to mass percentage unless otherwise specified.

[0055] 1. Polymerization method The polymerization method for the present polymer is not particularly limited, and any of the conventional radical polymerization methods, such as bulk polymerization, solution polymerization in an organic solvent, and emulsion polymerization in water, can be employed.

[0056] In the present application, preferably, after polymerization (for example, solution polymerization or emulsion polymerization), water and an acid may be added and then the solvent may be removed to obtain an aqueous dispersion, or the solvent may be removed and then water and an acid may be added to obtain an aqueous dispersion.

[0057] As the polymerization initiator, peroxides, azo compounds, or persulfate compounds can be used. The polymerization initiator can be selected to be oil-soluble or water-soluble depending on the polymerization system.

[0058] Preferred examples of the oil-soluble polymerization initiator 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, and diisopropyl peroxydicarbonate.

[0059] Preferred examples of the water-soluble polymerization initiator include 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 t-butyl hydroperoxide.

[0060] As the polymerization initiator, peroxides or azo compounds having a half-life of 10 hours and a decomposition temperature of 40° C. or higher, such as t-butyl peroxypivalate and 2,2′-azobis(2-methylpropionitrile), are preferred.

[0061] A typical solution polymerization process for this application is as follows. First, the solvent was added, then the corresponding monomer was added and dissolved, nitrogen gas was introduced to replace the oxygen therein, and then the initiator was added and the mixture was heated to a reaction temperature of 40°C, and the reaction time was 4-20 hours.

[0062] The manufacturing process of the treatment agent of the present application is as follows. (1) adding monomers I, II and optional monomer III to an organic solvent in a predetermined ratio, and adding an initiator to carry out polymerization; (2) If necessary, after the polymerization is completed, water is added to disperse the mixture and the organic solvent is removed. (3) a step of converting amino groups in the polymer into ammonium salts by adding an acid as needed; (4) optionally treating the dispersion with an oxidizing agent; In the above step (1), the ratio of the amount of silicon monomer I-1 used to monomer I (the total amount of silicon monomer I-1 and silicon monomer I-2) may be 1%-100%, 5%-100%, 10%-100%, or 50%-100% by mass.

[0063] II. Test Method Paper Processing and Testing Methods The types of paper that can be processed include thin paper, thick paper, paperboard, and pulp mold. 2 ) is 300 grams, the unit area (r 2 ) is 80 grams, the unit area (m 2 ) is 100 grams, the unit area (rice 2 ) can also be processed.

[0064] The raw material for paper may be chemically bleached or unbleached pulp, groundwood pulp, chemi-mechanical pulp, mechanical pulp, etc., and resin components such as polyamide, polyolefin, polyvinyl alcohol, etc. may be added to these pulp plates. The paper processing method is as follows. (1) Wet processing: Paper plastic weight 350g / meter 2 Sugarcane pulp plates were directly crushed to a Canadian standard freeness of 600 ml and a pulp concentration of 0.3%. An alkyl ketene dimer (AKD) sizing agent was added to the mixture in an amount of 2% of the dry paper weight, and a synthetic treatment agent was then added in an amount of 1-15% of the dry paper weight. The pulp was placed in a 10-inch dish mold filter at a predetermined weight, and the water content was removed by vacuum suction. The mold was baked at 150°C for 120 seconds, and the oil and water repellency of the dishware was evaluated. (2) Surface size processing example: Preparation of test paper: Paper weight 50 g / meter 2 Chemical pulp plate LBKP (broadleaf bleached kraft pulp) and NBKP (softleaf bleached kraft pulp) were added in a ratio of 5:5, and the pulp plate was beaten to a Canadian standard freeness of 200 ml. During the papermaking process, cationic starch MC-2 type starch manufactured by Guangxi Mingyang Biochemical Co., Ltd. was added in an amount of 1% by weight of the pulp plate, and the weight was beaten on a fourdrinier paper machine until it reached 50 g / m. 2 It was made into tissue paper. The starch solution for sizing uses nonionic modified starch, hydroxyethyl starch, manufactured by Penford Gum 290 starch, with a concentration of 5%. First, the starch solution is heated to above 90°C to gelatinize it. After gelatinization is complete, a synthesized treatment agent is added, with a concentration of the treatment agent in the starch solution of 1-15% by weight. The temperature of the starch solution is controlled to above 70°C, and the paper is first surface-sized until the liquid absorption exceeds 70%, after which it is dried to obtain the treated paper. (3) Surface application example: Preparation of test paper: Paper weight 230 g / meter 2 The paper is made of five layers, of which the bottom and top layers are made of chemical pulp plates LBKP (hardwood bleached kraft pulp) and NBKP (softwood bleached kraft pulp) in a ratio of 7:3, and the middle three layers are made of chemical-mechanical pulp or mechanical pulp plates, with a paper weight of 230g / m on the paper machine. 2 It is compounded with paperboard. The coating starch used was tapioca coating starch MS-1 manufactured by Guangxi Mingyang Biochemical Co., Ltd. The starch concentration was 20%. Water was added to the starch and the mixture was heated to over 90°C to gelatinize it. After gelatinization was complete, a synthesized paper treatment agent was added, with the concentration of the treatment agent in the starch solution being 1-15% (mass concentration). The starch temperature was controlled to over 50°C, and the top layer of the paperboard was coated using a paper coater at a coating weight of 3-8 grams per meter. 2 is.

[0065] Oil and water repellency evaluation The present application will be specifically explained with reference to the following examples and comparative examples, but these explanations are not intended to limit the present application. In the following experiments, unless otherwise specified, all addition amounts (%) are in parts by weight.

[0066] The test methods used below are as follows: Oil repellency test evaluation (1) Hot oil resistance test Hot oil (salad oil, peanut oil, rapeseed oil) at 85°C was poured onto the paper products and observed for 20 minutes, and the presence or absence of penetration was observed and scored. 5 points show no surface discoloration. At 4 minutes, the surface was slightly discolored. Three of the spots had surface discoloration and slight penetration. Two points were heavily penetrated.

[0067] Water repellency evaluation (1) Cobb test The test is carried out in accordance with GB / T1540-2002 or ISO 535:1991. The principle is that a 100cm high tube supporting 10mm of water 2 The weight (g) of water absorbed by the paper in one minute was measured, and this value was calculated as the weight per square meter (g / m 2 ) is converted into The Cobb absorbency tester is usually an inverted cylinder tester. The metal cylinder is cylindrical and its internal cross-sectional area is usually (100±0.2) cm 2 and the corresponding inner diameter is (112.8±0.2) mm. If a small area cylinder is used, the recommended area is 50 cm 2 In this case, the volume of water must be reduced accordingly to ensure a water liquid height of 10 mm. The cylinder height is 50 mm, and the surface of the cylinder that comes into contact with the sample must be smooth and have sufficient roundness to prevent damage to the sample by the cylinder edge. To prevent water leakage, a layer of elastic but non-absorbent rubber pad or gasket should be added to the inverted cylinder lid and flat pressure base. The metal pressure roller should have a roller width of (200±0.5) mm, a mass of (10±0.5) kg, and a smooth surface.

[0068] After the treatment, the paper sample was cut into 10 pieces (5 pieces on each side) of 125±5mm square or 125±5mm circular specimens. For equipment with a small test area, the specimen size should be slightly larger than the outer diameter of the cylinder to avoid water leakage due to the specimen being too small, and also to avoid the influence on the operation due to the specimen being too large.

[0069] Before placing the sample, ensure that the cylinder ring surface and rubber pad that come into contact with the sample are dry, and do not touch the test area with your hands. After taking 100 mL of water from a measuring cylinder and putting it into the cylinder, place the weighed sample on the cylinder ring surface with the test surface facing downwards. Place the clamp lid on the sample and clamp it to fix it to the cylinder.

[0070] The cylinder was then inverted 180°, the stopwatch was started, and the sample was allowed to absorb for 60 seconds. 10–15 seconds before the absorption was complete, the cylinder was turned over, the clamping device for the lid was loosened, and the sample was removed. The test water should be changed every five tests to avoid affecting the test results. At the moment the specified absorption time was reached, the sample was removed from the cylinder and placed, absorbent side down, on top of the absorbent paper already laid out. Another sheet of absorbent paper was then placed on top of the sample, and immediately roll pressed with a metal press roll once back and forth within 4 seconds without applying any other pressure to absorb any remaining water on the sample surface. The sample was quickly removed, folded in half with the absorbent side facing inward, and then folded in half again before being weighed to an accuracy of 0.001 g. Cardboard samples may be difficult to fold; in this case, the second weighing should be performed sooner.

[0071] The Cobb value is expressed as C=(g2-g1) / F. Wherein, C cobb value g2 - weight of sample after water absorption g1 - weight of sample before water absorption F-100cm 2 Test Area

[0072] (2) Hot water resistance test This method directly tests the hot water resistance of paper, and the test method is relatively simple. Generally, the treated paper is placed in a container that can hold liquid, and water at 100°C is poured into it. The paper is then observed for 30 minutes to see if there are any leaks. If there are no leaks, the product is deemed to have passed the test. This method is applicable to pulp molded products.

[0073] Stone Treatment and Testing Methods: Natural stone that can be treated includes marble, granite, sandstone, slate, and the like. Taking sandstone as an example, a sandstone sample was immersed in a treatment solution diluted with water to a certain ratio, and then removed and allowed to air dry for 48 hours at a temperature of 25°C or higher. After that, salad oil, mustard, coffee, vinegar, etc. were dropped onto the sandstone surface and the wet state was observed. If there was no penetration, it indicated good resistance. 5 points: No surface discoloration. At 4 minutes, the surface was slightly discolored. Three of the samples showed surface discoloration and slight penetration. Two points were heavily penetrated.

[0074] II. Examples and Comparative Examples See Table 1 for chemical abbreviations.

[0075] [Table 1] JPEG2025533637000016.jpg201160

[0076] Example 1 A 500 mL four-neck flask equipped with a reflux condenser, nitrogen inlet, thermometer, and stirrer was charged with 76 g of Si-B3, 25 g of DN, 8 g of HEMA, and 110 g of methyl ethyl ketone (MEK). Nitrogen gas was passed through the flask for 30 minutes, and the mixture was gradually heated to 50-60°C. 1.4 g of the peroxide initiator tert-butyl peroxypivalate was added in portions, and the reaction temperature was controlled at 60°C for 20 hours. Approximately 220 g of polymer A solution was obtained, with a solids content of approximately 50%. Measurement of the solution using a gas chromatograph mass spectrometer revealed that the residual mass concentrations of each monomer were all less than 0.1%, indicating that the monomer composition of the resulting polymer closely matched the composition of the added monomers. 315 g of water and 10 g of glacial acetic acid were added, and the mixture was stirred while keeping the temperature at 70° C. for 1 hour or more, and MEK in the polymer A solution was distilled off under reduced pressure to obtain an aqueous dispersion with a solid content of 25%.

[0077] Example 2 A 500 mL four-neck flask equipped with a reflux condenser, nitrogen inlet, thermometer, and stirrer was charged with 48 g of Si-B3, 28 g of Si-5 (average molecular weight 500), 25 g of DN, 8 g of HEMA, and 110 g of methyl ethyl ketone (MEK). Nitrogen was purged for 30 minutes, and the mixture was gradually heated to 50-60°C. 1.4 g of the peroxide initiator tert-butyl peroxypivalate was added in portions, and the reaction temperature was controlled at 60°C for 20 hours. Approximately 220 g of polymer A solution was obtained, with a solids content of approximately 50%. Measurement of the solution using a gas chromatograph mass spectrometer revealed that the residual mass concentrations of each monomer were less than 0.1%, indicating that the monomer composition of the resulting polymer was nearly identical to that of the added monomers. 315 g of water and 10 g of glacial acetic acid were added, and the mixture was stirred while keeping the temperature at 70° C. for 1 hour or more, and MEK in the polymer A solution was distilled off under reduced pressure to obtain an aqueous dispersion with a solid content of 25%.

[0078] Example 3 A 500 mL four-neck flask equipped with a reflux condenser, nitrogen inlet, thermometer, and stirrer was charged with 76 g of Si-B3, 25 g of DN, 8 g of 4-HBA, and 110 g of methyl ethyl ketone (MEK). Nitrogen gas was passed through the flask for 30 minutes, and the temperature was gradually raised to 50-60°C. 1.4 g of the peroxide initiator tert-butyl peroxypivalate was added in portions, and the reaction temperature was controlled at 60°C for 20 hours to obtain approximately 220 g of polymer A solution, with a solids content of approximately 50%. Measurement of the solution using a gas chromatograph mass spectrometer revealed that the residual mass concentrations of each monomer were all less than 0.1%, indicating that the monomer composition of the resulting polymer was nearly identical to the composition of the added monomers. 315 g of water and 10 g of glacial acetic acid were added, and the mixture was stirred while keeping the temperature at 70° C. for 1 hour or more, and MEK in the polymer A solution was distilled off under reduced pressure to obtain an aqueous dispersion with a solid content of 25%.

[0079] Comparative Example 1 A 500 mL four-neck flask equipped with a reflux condenser, nitrogen inlet, thermometer, and stirrer was charged with 76 g of Si-5 (average molecular weight 500), 25 g of DN, 8 g of HEMA, and 110 g of methyl ethyl ketone (MEK). Nitrogen gas was introduced for 30 minutes, and the mixture was gradually heated to 50-60°C. 1.4 g of the peroxide initiator tert-butyl peroxypivalate was added in portions, and the reaction temperature was controlled at 60°C for 20 hours to obtain approximately 220 g of polymer A solution, with a solids content of approximately 50%. Measurement of the solution using a gas chromatograph mass spectrometer revealed that the residual mass concentrations of each monomer were all less than 0.1%, indicating that the monomer composition of the resulting polymer was nearly identical to the composition of the added monomers. 315 g of water and 10 g of glacial acetic acid were added, and the mixture was stirred while keeping the temperature at 70° C. for 1 hour or more, and MEK in the polymer A solution was distilled off under reduced pressure to obtain an aqueous dispersion with a solid content of 25%.

[0080] Comparative Example 2 A 500 mL four-neck flask equipped with a reflux condenser, nitrogen inlet, thermometer, and stirrer was charged with 76 g of Si-B3, 25 g of DM, 8 g of HEMA, and 110 g of methyl ethyl ketone (MEK). Nitrogen was purged for 30 minutes, and the mixture was gradually heated to 50-60°C. 1.4 g of the peroxide initiator tert-butyl peroxypivalate was added in portions, and the reaction temperature was controlled at 60°C for 20 hours to yield approximately 220 g of polymer A solution, with a solids content of approximately 50%. Gas chromatograph mass spectrometry analysis of the solution revealed that the residual mass concentrations of each monomer were all less than 0.1%, indicating that the monomer composition of the resulting polymer closely matched the composition of the added monomers. 315 g of water and 10 g of glacial acetic acid were added, and the mixture was stirred while keeping the temperature at 70° C. for 1 hour or more, and MEK in the polymer A solution was distilled off under reduced pressure to obtain an aqueous dispersion with a solid content of 25%.

[0081] Performance Test The aqueous dispersions synthesized in the examples and comparative examples were used as treatment agents to measure several articles. 1) Paper tableware test: A pulp solution with a concentration of 1 wt% was prepared, and 2 wt% of the dry paper weight of an AKD-type sizing agent and 10 wt%, 6 wt%, and 3 wt% of the dry paper weight of a treatment agent were added to make 10-inch plates weighing 20 g. The plates were tested in 85°C salad oil for 20 minutes and graded according to the penetration rate. They were then tested in 100°C water for 30 minutes and recorded as pass or leak. 2) Paper test: 50g / m 2 The thin papers were selected and treated with surface size method, and the concentrations of the treatment agent were 5wt%, 4wt%, and 3wt%, respectively, and the hot oil resistance and Cobb water absorption were measured. 3) Paper test: 230g / m 2 The cardboards were treated by coating with the treatment agent at concentrations of 5wt%, 4wt%, and 3wt%, respectively, and the hot oil resistance and Cobb water absorption were measured. 4) Sandstone test: The treatment agent was diluted with water to 3 wt%, 2 wt%, and 1 wt% liquids, and sandstone samples were taken and immersed in the liquid. After being removed, they were allowed to dry naturally at a temperature of 25°C or higher for 48 hours, and then salad oil and coffee were dropped onto the surface of the sandstone, respectively, and the wet state was observed, classified, and scored. Table 2 summarizes the test performance of Examples 1 to 3 and Comparative Examples 1 and 2.

[0082] [Table 2]

[0083] As can be seen from the performance test results of Example 1 and Comparative Example 1, the treatment prepared using silicon monomer I-1 alone exhibited better oil repellency than the treatment prepared using silicon monomer I-2 alone at high usage amounts. However, as the amount of treatment added decreased, the performance of the former was clearly superior to that of the latter, indicating that the former had better oil repellency and higher efficiency.

[0084] As can be seen from the performance test results of Example 1 and Comparative Example 2, the treatment prepared using Monomer II DN showed better oil repellency than the treatment prepared using DM at high usage amounts. However, as the amount of treatment added decreased, the performance of the former was clearly superior to the latter, indicating that the former had better oil repellency and higher efficiency.

[0085] Examples 4-10 Instead of Si-B3, Si-B3H (Example 4), Si-B2 (Example 5), Si-NB3 (Example 6), Si-NB3H (Example 7), Si-NB2 (Example 8), Si-B4 (average molecular weight 500) (Example 9), and Si-B5 (average molecular weight 500) (Example 10) were used, respectively. The procedure was the same as in Example 1, except that silicon-containing monomers I-1 with different structures were used. When the resulting polymer solution was measured using a gas chromatograph mass spectrometer, the remaining mass concentrations of each monomer were all less than 0.1%, indicating that the monomer composition of the resulting polymer was almost identical to the composition of the added monomer. The test method was the same as in Example 1, and the test results for Examples 4-10 are shown in Table 3.

[0086] [Table 3] JPEG2025533637000019.jpg29150

[0087] As can be seen from the examples and comparative examples, the organosilicon polymers of the present application and treatment agents containing said polymers have excellent oil repellency, significantly improved oil repellency efficiency, and excellent water repellency.

[0088] While exemplary embodiments of the present invention have been described above, the present invention is not limited to the disclosed embodiments. On the contrary, those skilled in the art will recognize that several modifications and variations can be made to the described embodiments without departing from the spirit and scope of the present invention as set forth in the appended claims.

Claims

1. It comprises repeating units derived from Monomer I and repeating units derived from Monomer II, where Monomer I comprises silicon Monomer I-1 and silicon Monomer I-2, which are optional monomers; a) The general structural formula of the silicon monomer I-1 is represented by formula I-1: 【Chemical 1】 In formula I-1, R 1 is a hydrogen atom or C 1 -C 20 and B is selected from the alkyl groups of C 1 -C 20 is an alkylene group of the formula X is selected from groups represented by X-1 and X-2; 【Chemistry 2】 R 2 is a hydrogen atom or C 1 -C 20 and selected from the alkyl groups Z 1 is selected from the structures shown below, 【Chemistry 3】 Z 1 In this case, R 4 are each independently C 1 -C 20 alkyl group of C 6 -C 20 an aryl group of C 7 -C 12 an aralkyl group of C 7 -C 12 or an alkylaryl group of R 5 -O-R 6 - group, and R 5 is C 1 -C 10 alkyl group of C 6 -C 20 an aryl group of C 7 -C 12 or an aralkyl group of C 7 -C 12 is an alkylaryl group of the formula R 6 is C 1 -C 10 wherein 1≦a≦200; Y 1 and Y 2 are the same or different and each independently represent C 1 -C 20 alkyl group of C 6 -C 20 an aryl group of C 7 -C 12 or an aralkyl group of C 7 -C 12 and the structure of formula (I), wherein when a is 1, Y 1 and / or Y 2 is a structure of formula (I), and when a is greater than 1 and ≦200, at least one Y 1 is a structure of formula (I) and / or at least one Y 2 is a structure of formula (I), 【Chemistry 4】 R 7 are each independently C 1 -C 20 alkyl group of C 6 -C 20 an aryl group of C 7 -C 12 or an aralkyl group of C 7 -C 12 is an alkylaryl group of the formula R 8 are each independently C 1 -C 20 alkyl group of C 6 -C 20 an aryl group of C 7 -C 12 an aralkyl group of C 7 -C 12 or an alkylaryl group of R 9 -O-R 10 - group, where R 9 is C 1 -C 10 alkyl group of C 6 -C 20 an aryl group of C 7 -C 12 or an aralkyl group of C 7 -C 12 is an alkylaryl group of the formula R 10 is C 1 -C 10 and 0≦b≦200. The general structural formula of the silicon monomer I-2 is represented by Formula I-2: 【Chemistry 5】 In formula I-2, R 1 is a hydrogen atom or C 1 -C 20 and B is selected from alkyl groups of the formula C 1 -C 20 is an alkylene group of the formula X is selected from groups represented by X-1 and X-2; 【Chemistry 6】 R 2 is a hydrogen atom or C 1 -C 20 and selected from the alkyl groups Z 2 is selected from the structures shown below, 【Chemistry 7】 Z 2 In this case, R 3 are each independently C 1 -C 20 alkyl group of C 6 -C 20 an aryl group of C 7 -C 12 or an aralkyl group of C 7 -C 12 is an alkylaryl group of the formula R 4 are each independently C 1 -C 20 alkyl group of C 6 -C 20 an aryl group of C 7 -C 12 an aralkyl group of C 7 -C 12 or an alkylaryl group of R 5 -O-R 6 - group, and R 5 is C 1 -C 10 alkyl group of C 6 -C 20 an aryl group of C 7 -C 12 or an aralkyl group of C 7 -C 12 is an alkylaryl group of the formula R 6 is C 1 -C 10 wherein 1≦a≦200; b) The structural general formula of Monomer II is represented by Formula II: 【Chemistry 8】 Here, R 1 and R 2 are each independently a hydrogen atom or C 1 -C 20 alkyl groups, and B is selected from C 1 -C 20 is an alkylene group of the formula R 3 and R 4 are each independently a hydrogen atom, C 1 -C 18 an alkyl group, a hydroxyethyl group, or a benzyl group, or R 3 and R 4 is an organosilicon polymer which is bonded to a nitrogen atom to form a morpholino, piperidino or pyrrolidino group.

2. further comprising a repeat unit derived from Monomer III, The general structural formula of Monomer III is represented by Formula III: 【Chemistry 9】 In Formula III, R 1 represents a hydrogen atom or a methyl group, R 2 are each independently C 1 -C 6 is an alkylene group of the formula C 2 -C 4 where q is an integer of 1 to 50, preferably an integer of 1 to 20, and R 3 is a hydrogen atom or C 1 -C 20 is preferably a hydrogen atom or a C 1 -C 10 is preferably a hydrogen atom or a C 1 -C 3 is an alkyl group of the formula wherein G is selected from groups represented by G-1 and G-2; 【Chemistry 10】 R 4 The organosilicon polymer of claim 1, wherein represents a hydrogen atom or a methyl group, and n is an integer from 0 to 10, preferably an integer from 0 to 5.

3. The organosilicon polymer of claim 1 or 2, wherein the proportion of repeating units derived from silicon monomer I-1 to the total amount of repeating units derived from silicon monomer I-1 and repeating units derived from silicon monomer I-2 is 1%-100%, 5%-100%, 10%-100%, or 50%-100% by mass.

4. The organosilicon polymer of any one of claims 1 to 3, wherein the mass content of repeating units derived from silicon monomer I-1 and silicon monomer I-2 in the polymer is 30%-90%, preferably 40%-85%, more preferably 50%-80%, and / or the mass content of repeating units derived from monomer II in the polymer is 5%-65%, preferably 10%-50%, more preferably 15%-45%, and / or the mass content of repeating units derived from monomer III in the polymer is 1%-30%, preferably 3%-15%, more preferably 5%-10%.

5. In silicon monomers I-1 and I-2, R 1 is selected from a hydrogen atom or a methyl group, and B is C 1 -C 10 Preferably, B is an alkylene group of the formula C 1 -C 6 is an alkylene group of the formula In silicon monomers I-1 and I-2, X is R 2 is selected from a hydrogen atom or a methyl group, In the silicon monomer I-1, Z 1 In this case, R 4 are each independently C 1 -C 10 alkyl group of C 6 -C 10 an aryl group of C 7 -C 12 an aralkyl group of C 7 -C 12 or an alkylaryl group of R 5 -O-R 6 - group, and R 5 is C 1 -C 10 alkyl group of C 6 -C 10 an aryl group of C 7 -C 12 or an aralkyl group of C 7 -C 12 is an alkylaryl group of the formula R 6 is C 1 -C 10 where 1≦a≦80, and R 7 are each independently C 1 -C 10 alkyl group of C 6 -C 10 an aryl group of C 7 -C 12 or an aralkyl group of C 7 -C 12 is an alkylaryl group of the formula R 8 are each independently C 1 -C 10 alkyl group of C 6 -C 10 an aryl group of C 7 -C 12 an aralkyl group of C 7 -C 12 or an alkylaryl group of R 9 -O-R 10 - group, where R 9 is C 1 -C 10 alkyl group of C 6 -C 10 an aryl group of C 7 -C 12 or an aralkyl group of C 7 -C 12 is an alkylaryl group of the formula R 10 is C 1 -C 10 and 0≦b≦80. In the silicon monomer I-2, Z 2 In this case, R 3 are each independently C 1 -C 10 alkyl group of C 6 -C 10 an aryl group of C 7 -C 12 or an aralkyl group of C 7 -C 12 is an alkylaryl group of the formula R 4 are each independently C 1 -C 10 alkyl group of C 6 -C 10 an aryl group of C 7 -C 12 an aralkyl group of C 7 -C 12 or an alkylaryl group of R 5 -O-R 6 - group, and R 5 is C 1 -C 10 alkyl group of C 6 -C 20 an aryl group of C 7 -C 12 or an aralkyl group of C 7 -C 12 is an alkylaryl group of the formula R 6 is C 1 -C 10 and 0≦a≦80. In Monomer II, R 1 and R 2 is selected from a hydrogen atom or a methyl group, and B is C 1 -C 10 Preferably, B is an alkylene group of the formula C 1 -C 6 is an alkylene group of the formula R 3 and R 4 are each independently a hydrogen atom, C 1 -C 3 an alkyl group, a hydroxyethyl group, or a benzyl group, or R 3 and R 4 The organosilicon polymer according to any one of claims 1 to 4, wherein: is bonded to the nitrogen atom to form a morpholino group, a piperidino group, or a pyrrolidino group.

6. Z 1 is one or more selected from the following structures i-1 to i-4, 【Chemistry 11】 Z 1 is preferably 【Chemistry 12】 One or more selected from Z 2 is one or more selected from the following structures ii-1 and ii-2, 【Chemistry 13】 Z 2 is preferably 【Chemistry 14】 One or more selected from Each R is independently C 1 -C 10 alkyl group of C 6 -C 10 an aryl group of C 7 -C 12 or an aralkyl group of C 7 -C 12 and selected from the alkylaryl groups The organosilicon polymer of any one of claims 1 to 5, wherein 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, and 1≦x≦9, preferably 1≦x≦7, where each x may be the same or different.

7. Silicon monomer I-1 is CH 2 =C(CH 3 )C(O)-O-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 、 CH 2 =CHC(O)-O-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 、 CH 2 =C(CH 3 )C(O)-O-(CH 2 ) 3 Si(CH 3 )(OSi(CH 3 ) 3 ) 2、 CH 2 =CHC(O)-O-(CH 2 ) 3 Si(CH 3 )(OSi(CH 3 ) 3 ) 2 、 CH 2 =C(CH 3 )C(O)-NH-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 、 CH 2 =CHC(O)-NH-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 、 CH 2 =C(CH 3 )C(O)-NH-(CH 2 ) 3 Si(CH 3 )(OSi(CH 3 ) 3 ) 2 、 CH 2 =CHC(O)-NH-(CH 2 ) 3 Si(CH 3 )(OSi(CH 3 ) 3 ) 2 、 CH 2 =C(CH 3 )C(O)-O-(CH 2 ) 3 Si(OSi(CH 2 CH 3 ) 3 ) 3 、 CH 2 =CHC(O)-O-(CH 2 ) 3 Si(OSi(CH 2 CH 3 ) 3 ) 3、 CH 2 =C(CH 3 )C(O)-O-CH 2 -Si(OSi(CH 3 ) 3 ) 3 、 CH 2 =C(CH 3 )C(O)-O-(CH 2 ) 3 Si(CH 3 )[O-[Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 ] 2 (0≦n≦25) and / or Silicon monomer I-2 is CH 2 =C(CH 3 )C(O)-O-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (1≦n≦25)、 CH 2 =C(CH 3 )C(O)-O-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 8 H 17 、(1≦n≦255) CH 2 =C(CH 3 )C(O)-O-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 3 (1≦n≦25) and / or Monomer II is one or more selected from dimethylaminoethyl(meth)acrylamide, diethylaminoethyl(meth)acrylamide, dipropylaminoethyl(meth)acrylamide, dimethylaminopropyl(meth)acrylamide, diethylaminopropyl(meth)acrylamide, dipropylaminopropyl(meth)acrylamide, and / or The organosilicon polymer according to any one of claims 1 to 6, wherein Monomer III is one or more selected from the group consisting 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, with hydroxyethyl methacrylate and 4-hydroxybutyl acrylate being preferred.

8. A method for producing a coating composition comprising the organosilicon polymer according to any one of claims 1 to 7 and a solvent comprising 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.

9. (1) polymerizing a monomer in an organic solvent to obtain a polymer solution; Optionally, (2) adding water to the polymer solution to disperse it, followed by removing the organic solvent, or removing the solvent and then adding water to disperse it; Optionally, (3) adding an acid to the polymer solution to convert the amino groups in the polymer into ammonium salts; 9. The method for producing the treating agent according to claim 8, optionally comprising the step of (4) treating the polymer solution with an aqueous hydrogen peroxide solution to convert the amino groups to nitrogen oxides.

10. 10. Application of the organosilicon polymer according to any one of claims 1 to 7, or the treating agent according to claim 8, or the treating agent prepared by the method according to claim 9, to textile fabrics, leather, nonwoven fabrics, asbestos, fur, concrete, natural stone, paper products, or plastics.

11. A product which is a textile fabric, leather, nonwoven fabric, asbestos, fur, concrete, natural stone, paper product, or plastic, and which has been treated with the organosilicon polymer according to any one of claims 1 to 7, or the treating agent according to claim 8, or the treating agent prepared by the method according to claim 9.

12. The method comprises contacting a product, which is a textile, leather, nonwoven fabric, asbestos, fur, concrete, natural stone, paper product, or plastic, with the organosilicon polymer of any one of claims 1 to 7, or the treating agent of claim 8, or the treating agent prepared by the method of claim 9; Preferably, the contacting is achieved by a wet end addition, surface sizing or application process.

Images