Copolymers, compositions, and their applications

Abstract

This application relates to copolymers, compositions containing the copolymer, and products after treatment thereof. The copolymer comprises repeating units derived from monomer I, repeating units derived from monomer II, and repeating units derived from monomer III. The copolymer or compositions containing the copolymer can treat multiple types of articles in a wider range of pH values ​​(acidic, neutral, and alkaline), particularly alkaline, and in coating or immersion environments, thereby imparting oil-repellent and water-repellent properties to the articles.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims priority rights to the following three Chinese patent applications: A Chinese patent application filed on June 2, 2023, with application number 202310652456.5 and the title of the invention being "Copolymer, Composition and Application thereof," A Chinese patent application filed on June 6, 2023, with application number 202310666493.1 and the title of the invention being "Copolymer, Composition and Application thereof," and, A Chinese patent application filed on June 9, 2023, with application number 202310686746.1, and the title of the invention is "Copolymer, Treatment Agent and Water-Repellent and Oil-Repellent Products". All the contents of the three patent applications mentioned above are incorporated into this application.

[0002] This application relates to copolymers used for surface treatment of various articles, such as textiles, leather, nonwovens, furs, concrete, natural stone, paper products, or plastics, compositions containing said copolymers, and applications thereof. [Background technology]

[0003] By processing articles to impart certain functions, such as making their surfaces water-repellent and oil-repellent, it is possible to give articles new functions or extend their service life. There are generally several methods for processing agents that alter the surface properties of articles. A common method involves applying a single layer of film-forming resin to the surface, creating a coating layer with resin properties. However, this method often alters the properties of the article itself. For example, a film-forming coating layer is unacceptable for the surface treatment of porous materials because it alters the article's breathability, appearance, and other properties. For porous materials such as textiles, natural stone, leather, and paper, it is often desirable to impart new functions to the surface without altering its appearance or basic properties.

[0004] Organosilicon copolymers are widely used compounds due to their excellent performance, high inertness, and superior safety. Patent CN100300612 describes an organosiloxane copolymer used in paper processing that provides water and oil repellency to paper. However, such copolymers are based on coating methods, and these coating layers need to be formed, making the process complex.

[0005] CN114573768B describes organosilicon copolymers used in the processing of articles, and such copolymers are cationic copolymers, which have certain limitations in terms of application, and may be invalidated in particular in alkaline environments.

[0006] In modern industrial applications, alkaline environments, especially those with high pH, ​​are more common. For example, in the Hyundai Paper Industry, alkaline papermaking is a mainstream process. Similarly, alkaline environments are more common in the leather mixing process. Furthermore, in stone processing, marble, whose main component is calcium carbonate, reacts with acids, making it particularly important to ensure that chemicals maintain their functionality even in alkaline conditions. Therefore, the development of treatment agents suitable for a wider pH range is required. [Overview of the Initiative]

[0007] This application aims to provide a copolymer and a composition containing the copolymer that can be used in a wider range of pH environments and can impart oil-repellent and water-repellent properties to the surface of porous articles by treating them.

[0008] In the first embodiment, the present application provides a copolymer comprising repeating units derived from monomer I, repeating units derived from monomer II, and repeating units derived from monomer III. a) The general structural formula of monomer I is represented by formula I, [ka] Here, M contains polymerizable functional groups, Z is selected from the structures shown below, [Chemical Formula] In Z, R3 is independently selected from a C1-C 20 alkyl group, a C6-C 20 aryl group, a C7-C 12 aralkyl group, a C7-C 12 alkylaryl group, a C1-C 20 alkoxy group or an R4-O-R5- group, where R4 is a C1-C 20 alkyl group, a C6-C 20 aryl group, a C7-C 12 aralkyl group or a C7-C 12 alkylaryl group, and R5 is a C1-C 20 alkylene group, 1 ≦ a ≦ 200, Y1 and Y2 are the same or different and are each independently selected from a C1-C 20 alkyl group, a C6-C 20 aryl group, a C7-C 12 aralkyl group, a C7-C 12 alkylaryl group or a structure of the following formula (1), [Chemical Formula] R7 is independently selected from a C1-C 20 alkyl group, a C6-C 20 aryl group, a C7-C 12 aralkyl group or a C7-C 12 alkylaryl group, R8 is independently selected from a C1-C 20 alkyl group, a C6-C 20 aryl group, a C7-C 12 aralkyl group, a C7-C 12 alkylaryl group, a C1-C 20 alkoxy group or an R9-O-R 10 - group, where R9 is a C1-C 20 alkyl group, a C6-C 20 aryl group, a C7-C 12 aralkyl group or a C7-C12 It is an alkylaryl group, R 10 C1-C 20 It is an alkylene group, and 0 ≤ b ≤ 200, b) The general structural formula of monomer II is represented by formula II-1, formula II-2, or formula II-3, [ka] In formula II-1, R1 represents a hydrogen atom or a methyl group, R2 is independently a C1-C6 alkylene group, q is an integer from 1 to 50, and R3 is a hydrogen atom or a C1-C 20 Represents the alkyl group, Here, G is selected from the groups represented by G-1 and G-2, [ka] R4 represents a hydrogen atom or a methyl group, and B is either absent or C1-C 20 It is an alkylene group, [ka] In equation II-2, n is an integer from 1 to 6, s is an integer from 0 to 16, and each R is either the same or different, and each is independently C1-C 20 Selected from alkyl groups, preferably C1-C 10 Selected from alkyl groups, more preferably selected from C1-C6 alkyl groups, [ka] In formula II-3, R1 is a hydrogen atom or C1-C 20 Selected from alkyl groups, R2 and R3 are each independently a hydrogen atom or C1-C 20 Selected from alkyl groups, or R2 and R3 together with the nitrogen atom to which they are linked to form a C3-C8 heterocyclic group. c) Monomer III is a monomer having an anion-supplying group and a polymerizable unsaturated group, wherein the anion-supplying group is a carboxyl group or a sulfonic acid group.

[0009] The inventors of this application have unexpectedly discovered that copolymers obtained by polymerizing monomers I, II, and III can be added to a wider range of pH values ​​(acidic, neutral, and alkaline), particularly alkaline, and can be used to treat various articles, such as paper products, by coating and adding them to slurries, thereby imparting excellent oil-repellent and water-repellent properties without altering the basic properties of the articles.

[0010] In some embodiments, in formula II-1, R2 is a C2-C4 alkylene group. In some embodiments, in formula II-1, q is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, or 49. In some embodiments, in formula II-1, q is an integer from 1 to 20.

[0011] In some embodiments, in formula II-1, R3 is a hydrogen atom or C1-C 10 It is an alkyl group, for example, a hydrogen atom, a C1-C3 alkyl group, or a C4-C6 alkyl group.

[0012] In some embodiments, in the groups indicated by G-1 and G-2, B is absent or C1-C 10 It is an alkylene group, for example, a C1-C3 alkylene group or a C4-C6 alkylene group.

[0013] In some embodiments, monomer II is one or more 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, or methoxypolyethylene glycol (meth)acrylate.

[0014] In some embodiments, in formula II-2, n is 1, 2, 3, 4, 5, or 6.

[0015] In some embodiments, in formula II-2, s is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16.

[0016] In some embodiments, in formula II-2, each R is independently selected from C1-C6 alkyl groups, either identical or different, for example, a C1-C3 alkyl group or a C4-C6 alkyl group.

[0017] In some embodiments, the general structural formula of monomer II is represented by formula II-2-1, [ka] In formula II-2-1, R1 to R6 are each independently a hydrogen atom or C1-C 20 Selected from alkyl groups, preferably a hydrogen atom or C1-C 10 The alkyl group is selected from a hydrogen atom or a C1-C6 alkyl group, for example, a C1-C3 alkyl group or a C4-C6 alkyl group.

[0018] In some embodiments, in formula II-2-1, one, two, or three of R1 to R6 are independently selected from hydrogen atoms or C1-C6 alkyl groups, for example, C1-C3 alkyl groups, C4-C6 alkyl groups, and the rest are all hydrogen.

[0019] In some embodiments, the general structural formula of monomer II is represented by formula II-2-2, [ka] In formula II-2-2, R1 to R8 are each independently a hydrogen atom or C1-C 20 Selected from alkyl groups, preferably a hydrogen atom or C1-C10 The alkyl group is selected from a hydrogen atom or a C1-C6 alkyl group, for example, a C1-C3 alkyl group or a C4-C6 alkyl group.

[0020] In some embodiments, in formula II-2-2, one, two, or three of R1 to R8 are each independently selected from hydrogen atoms or C1-C6 alkyl groups, for example, C1-C3 alkyl groups, C4-C6 alkyl groups, and the rest are all hydrogen.

[0021] In some embodiments, the general structural formula of monomer II is represented by formula II-2-3, [ka] In equation II-2-3, R1 to R 10 Each of these is independently a hydrogen atom or C1-C 20 Selected from alkyl groups, preferably a hydrogen atom or C1-C 10 The alkyl group is selected from a hydrogen atom or a C1-C6 alkyl group, for example, a C1-C3 alkyl group or a C4-C6 alkyl group.

[0022] In some embodiments, in formula II-2-3, R1 to R 10 One, two, or three of these atoms are independently selected from hydrogen atoms or C1-C6 alkyl groups, for example, a C1-C3 alkyl group, a C4-C6 alkyl group, and the rest are all hydrogen atoms.

[0023] In some embodiments, the general structural formula of monomer II is represented by formula II-2-4, [ka] In equation II-2-4, R1 to R 12 Each of these is independently a hydrogen atom or C1-C 20 Selected from alkyl groups, preferably a hydrogen atom or C1-C 10The alkyl group is selected from a hydrogen atom or a C1-C6 alkyl group, for example, a C1-C3 alkyl group or a C4-C6 alkyl group.

[0024] In some embodiments, in formula II-2-4, R1 to R 12 One, two, or three of these atoms are independently selected from hydrogen atoms or C1-C6 alkyl groups, for example, a C1-C3 alkyl group, a C4-C6 alkyl group, and the rest are all hydrogen atoms.

[0025] In some embodiments, the general structural formula of monomer II is represented by formula II-2-5. [ka] In equation II-2-5, R1 to R 14 Each of these is independently a hydrogen atom or C1-C 20 Selected from alkyl groups, preferably a hydrogen atom or C1-C 10 The alkyl group is selected from a hydrogen atom or a C1-C6 alkyl group, for example, a C1-C3 alkyl group or a C4-C6 alkyl group.

[0026] In some embodiments, in formula II-2-5, R1 to R 14 One, two, or three of these atoms are independently selected from hydrogen atoms or C1-C6 alkyl groups, for example, a C1-C3 alkyl group, a C4-C6 alkyl group, and the rest are all hydrogen atoms.

[0027] In some embodiments, the general structural formula of monomer II is represented by formula II-2-6. [ka] In equation II-2-6, R1 to R 16 Each of these is independently a hydrogen atom or C1-C 20 Selected from alkyl groups, preferably a hydrogen atom or C1-C 10The alkyl group is selected from a hydrogen atom or a C1-C6 alkyl group, for example, a C1-C3 alkyl group or a C4-C6 alkyl group.

[0028] In some embodiments, in formula II-2-6, R1 to R 16 One, two, or three of these atoms are independently selected from hydrogen atoms or C1-C6 alkyl groups, for example, a C1-C3 alkyl group, a C4-C6 alkyl group, and the rest are all hydrogen atoms.

[0029] In some embodiments, monomer II is N-vinyl-2-pyrrolidone, N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-3,3-dimethyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-3-ethylpyrrolidone, N-vinyl-4,5-dimethylpyrrolidone, N-vinyl-5,5-dimethylpyrrolidone, N-vinyl-3,3,5-trimethylpyrrolidone N-vinyl-5-methyl-5-ethylpyrrolidone, N-vinyl-3,4,5-trimethyl-3-ethylpyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-3-ethylpyrrolidone, N-vinyl-4,5-dimethylpyrrolidone, N-vinyl-5,5-dimethylpyrrolidone, N-vinyl-3,3,5-trimethylpyrrolidone, N-vinyl-5-methyl-5-ethylpyrrolidone, N-vinyl-3,4,5-trimethyl-3-ethylpyrrolidone, N-vinyl-2-pipe Lydone, N-vinyl-3-methylpiperidone, N-vinyl-3-methylcaprolactam, N-vinyl-4-methylpiperidone, N-vinyl-4-methylcaprolactam, N-vinyl-4-methylpiperidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-3,5-dimethyl-2-piperidone, N-vinyl-4,4-dimethyl-2-piperidone, N-vinyl-2-caprolactam, N-vinyl-7-methylcaprolactam, N- It is one or more selected from vinyl-7-ethyl caprolactam, N-vinyl-3,5-dimethyl caprolactam, N-vinyl-4,6-dimethyl caprolactam, N-vinyl-3,5,7-trimethyl caprolactam, N-vinyl-2-valerolactam, N-vinylhexahydro-2-azacycloheptanone, N-vinyloctahydro-2-azacyclooctanone, N-vinyloctahydro-2-azacyclononanone, and N-vinyldecahydro-2-azacyclodecanone.

[0030] In some embodiments, in formula II-3, R1 is a hydrogen atom or C1-C 10It is selected from alkyl groups. In some embodiments, in formula II-3, R1 is selected from a hydrogen atom or a C1-C6 alkyl group, for example, a C1-C3 alkyl group or a C4-C6 alkyl group. In some embodiments, R1 is preferably selected from a hydrogen atom or a methyl group.

[0031] In some embodiments, in formula II-3, R2 and R3 are independently a hydrogen atom or C1-C 10 They are selected from alkyl groups. In some embodiments, in formula II-3, R2 and R3 are each independently selected from hydrogen atoms or C1-C6 alkyl groups, for example, a C1-C3 alkyl group and a C4-C6 alkyl group.

[0032] In some embodiments, in formula II-3, R2 and R3, together with the nitrogen atom to which they are linked, form a nitrogen heterocyclic C3-C8 alkyl group.

[0033] In some embodiments, in formula II-3, R2 and R3, together with the nitrogen atom to which they are linked, form a pyrrolidone, piperidinyl group, pyrrolidinyl group, pyrrolyl group, piperidone group, morpholinyl group, piperazinyl group, azilidinyl group, azetidinyl group, azepanyl group, or azocanyl group.

[0034] In some embodiments, monomer II is acrylamide, methacrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, N-butylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-isopropylmethacrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide It is one or more selected from N-butylmethacrylamide, N-(meth)acryloylpyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-(meth)acryloylpyrrole, N-(meth)acryloylpiperidone, N-(meth)acryloylmorpholine, N-(meth)acryloylpiperazine, N-(meth)acryloylaziridine, N-(meth)acryloylazetidine, N-(meth)acryloylazepane, and N-(meth)acryloylazocane.

[0035] In some embodiments, the polymerizable unsaturated group in monomer III is selected from carbon-carbon double bond-containing groups.

[0036] In some embodiments, monomer III is selected from (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, vinylbenzenesulfonic acid, acrylamide tert-butylsulfonic acid, or salts thereof.

[0037] In some embodiments, polymerizable functional groups in M ​​are selected from carbon-carbon double bond-containing groups.

[0038] In some embodiments, in formula I, M is represented by formula I-1, [ka] In formula I-1, R1 is a hydrogen atom or C1-C20 Selected from alkyl groups, B is C1-C 20 It is an alkylene group, X is selected from the groups represented by X-1 and X-2, [ka] R2 is a hydrogen atom or C1-C 20 Selected from alkyl groups, In some embodiments, in formula I-1, R1 is a hydrogen atom or C1-C 10 Selected from alkyl groups, for example, C1-C3 alkyl groups, C4-C6 alkyl groups or C8-C 10 It is an alkyl group. In some embodiments, in formula I-1, B is C1-C 10 These are alkylene groups, for example, C1-C3 alkylene groups, C4-C6 alkylene groups, or C8-C 10 It is an alkylene group.

[0039] In some embodiments, in the groups represented by X-1 and X-2, R2 is a hydrogen atom or C1-C 10 Selected from alkyl groups, for example, C1-C3 alkyl groups, C4-C6 alkyl groups or C8-C 10 It is an alkyl group.

[0040] In some embodiments, in formula I-1, R1 is selected from a hydrogen atom or a methyl group, B is a C1-C6 alkylene group, and in X, R2 is selected from a hydrogen atom or a methyl group.

[0041] In some embodiments, in formula I, M is represented by formula I-2, [ka] In formula I-2, R1 is a hydrogen atom or C1-C 20 Selected from alkyl groups, W is selected from the groups represented by W-1, W-2, W-3 and W-4. [ka] R2 is either a hydrogen atom or C1-C 20 Selected from alkyl groups, D is C1-C 20 The alkylene group is such that if W is selected from W-1, then B is either absent or C1-C 20 The alkylene group is such that if W is selected from W-2, W-3, and W4, then B is C1-C 20 It is an alkylene group.

[0042] In some embodiments, in formula I-2, R1 is a hydrogen atom or C1-C 10 Selected from alkyl groups, for example, C1-C3 alkyl groups, C4-C6 alkyl groups or C8-C 10 It is an alkyl group. In some embodiments, in formula I-2, B is C1-C 10 These are alkylene groups, for example, C1-C3 alkylene groups, C4-C6 alkylene groups, or C8-C 10 It is an alkylene group.

[0043] In some embodiments, in formula I-2, R2 is a hydrogen atom or C1-C 10 Selected from alkyl groups, for example, C1-C3 alkyl groups, C4-C6 alkyl groups or C8-C 10 It is an alkyl group. In some embodiments, in formula I-2, D is C1-C 10 These are alkylene groups, for example, C1-C3 alkylene groups, C4-C6 alkylene groups, or C8-C 10 It is an alkylene group.

[0044] In some embodiments, in formula I-2, R1 and R2 are selected from hydrogen atoms or methyl groups, and B and D are C1-C6 alkylene groups.

[0045] In some embodiments, if W is selected from W-1, then B is absent or C1-C 10 These are alkylene groups, for example, C1-C3 alkylene groups, C4-C6 alkylene groups, or C8-C 10 It is an alkylene group.

[0046] In some embodiments, when W is selected from W-2, W-3, W-4, B is a C1-C 10 alkylene group, for example, a C1-C3 alkylene group, a C4-C6 alkylene group or a C8-C 10 alkylene group.

[0047] In some embodiments, in Formula I, M is represented by Formula I-3,

Chemical formula

[0048] In some embodiments, in Formula I-3, R1 is selected from a hydrogen atom or a C1-C 10 alkyl group, for example, a C1-C3 alkyl group, a C4-C6 alkyl group or a C8-C 10 alkyl group. In some embodiments, in Formula I-3, B is a C1-C 10 alkylene group, for example, a C1-C3 alkylene group, a C4-C6 alkylene group or a C8-C 10 alkylene group.

[0049] In some embodiments, in Formula I-3, R1 is selected from a hydrogen atom or a methyl group.

[0050] In some embodiments, in Z, R3 are each independently a C1-C 10 alkyl group, a C6-C 10 aryl group, a C7-C 12 aralkyl group, a C7-C 12 alkylaryl group, a C1-C 10 alkoxy group or an R4-O-R5- group, where R4 is a C1-C 10 alkyl group, a C6-C 10 aryl group, a C7-C12 aralkyl group or C7-C 12 It is an alkylaryl group, and R5 is C1-C 10 These are alkylene groups, 1 ≤ a ≤ 100, and R7 is independently C1-C 10 alkyl group, C6-C 10 The aryl group, C7-C 12 The aralkyl group, or C7-C 12 The alkylaryl group is such that R8 is independently C1-C 10 alkyl group, C6-C 10 The aryl group, C7-C 12 aralkyl group, C7-C 12 alkylaryl group, C1-C 10 The alkoxy group or R9-OR 10 - is a base, where R9 is C1-C 10 alkyl group, C6-C 10 The aryl group, C7-C 12 aralkyl group or C7-C 12 It is an alkylaryl group, R 10 C1-C 10 It is an alkylene group, and 0 ≤ b ≤ 100.

[0051] In some embodiments, in Z, R3 is independently a C1-C6 alkyl group, a C6-C 10 The aryl group, C7-C 10 aralkyl group, C7-C 10 The R4 group is an alkylaryl group, a C1-C6 alkoxy group, or an R4-O-R5- group, where R4 is a C1-C6 alkyl group or a C6-C 10 The aryl group, C7-C 10 aralkyl group or C7-C 10 The alkylaryl group is such that R5 is a C1-C6 alkylene group, 1 ≤ a ≤ 30, and R7 is independently a C1-C6 alkyl group and a C6-C 10 The aryl group, C7-C 10 The aralkyl group, or C7-C 10 The alkylaryl group is such that R8 is independently a C1-C6 alkyl group and a C6-C 10The aryl group, C7-C 10 aralkyl group, C7-C 10 Alkylaryl group, C1-C6 alkoxy group or R9-OR 10 - is a group, where R9 is a C1-C6 alkyl group, C6-C 10 The aryl group, C7-C 10 aralkyl group or C7-C 10 It is an alkylaryl group, R 10 C1-C 16 It is an alkylene group, and 0 ≤ b ≤ 30.

[0052] In some embodiments, a is an integer between 1 and 80, an integer between 1 and 30, an integer between 1 and 20, or an integer between 1 and 10.

[0053] In some embodiments, b is 0. In some embodiments, b is an integer between 1 and 30, an integer between 1 and 20, an integer between 1 and 10, or an integer between 1 and 5.

[0054] In some embodiments, Z is independently one or more selected from the following structures i-1 to i-6: [ka] R is independently C1-C 10 alkyl group, C6-C 10 The aryl group, C7-C 12 Selected from an aralkyl group or a C7-C12 alkylaryl 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, where each x may be the same or different.

[0055] In some embodiments, R is a C1-C3 alkyl group, such as a methyl group.

[0056] In some embodiments, Z is [ka] One or more types selected from, R is independently C1-C 10 alkyl group, C6-C 10 The aryl group, C7-C 12 aralkyl group or C7-C 12 Selected from alkylaryl groups, 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, where each x may be the same or different.

[0057] In some embodiments, m is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9.

[0058] In some embodiments, x is 1, 2, 3, 4, 5, 6, or 7.

[0059] In some embodiments, monomer I is selected from the following: CH2=C(CH3)C(O)-O-(CH2)3Si(OSi(CH3)3)3, CH2=CHC(O)-O-(CH2)3Si(OSi(CH3)3)3, CH2=C(CH3)C(O)-O-(CH2)3Si(CH3)(OSi(CH3)3)2, CH2=CHC(O)-O-(CH2)3Si(CH3)(OSi(CH3)3)2, CH2=C(CH3)C(O)-NH-(CH2)3Si(OSi(CH3)3)3, CH2=CHC(O)-NH-(CH2)3Si(OSi(CH3)3)3, CH2=C(CH3)C(O)-NH-(CH2)3Si(CH3)(OSi(CH3)3)2, CH2=CHC(O)-NH-(CH2)3Si(CH3)(OSi(CH3)3)2, CH2=C(CH3)C(O)-O-(CH2)3Si(OSi(CH2CH3)3)3、 CH2=CHC(O)-O-(CH2)3Si(OSi(CH2CH3)3)3、 CH2=C(CH3)C(O)-O-CH2-Si(OSi(CH3)3)3、 CH2=C(CH3)C(O)-O-(CH2)3Si(CH3)[O-[Si(CH3)2O]n-Si(CH3)2C4H9]2、0≦n≦25、 CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9、1≦n≦25、 CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C8H 17 、1≦n≦25、 CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)3、1≦n≦25、 CH2=CH-ph-Si(OSi(CH3)3)3(ph represents

Chem.

Chem.

Chem.

[0060] In some embodiments, monomer I comprises silicon monomer IA and / or silicon monomer IB. The general formula for silicon monomer IA is the same as formula I, and when a is 1, Y1 and / or Y2 have the structure of formula (1), and when a is greater than 1 and ≤200, at least one Y1 has the structure of formula (1) and / or at least one Y2 has the structure of formula (1). The general formula for silicon monomer IB is the same as formula I, and Y1 and Y2 are either the same or different, and each is independently C1-C 20 alkyl group, C6-C 20 The aryl group, C7-C 12 The aralkyl group and C7-C 12 It satisfies the requirement of being selected from alkylaryl groups.

[0061] In some embodiments, the general formula for silicon monomer IA is represented by formula IA, [ka] Here, M contains polymerizable functional groups, Z1 is selected from the following structures: [ka] In the Z1, R3 is independently C1-C 20 alkyl group, C6-C 20 The aryl group, C7-C 12 aralkyl group, C7-C 12 alkylaryl group, C1-C 20 Selected from an alkoxy group or an R4-O-R5- group, where R4 is C1-C 20 alkyl group, C6-C 20 The aryl group, C7-C 12 aralkyl group or C7-C 12 It is an alkylaryl group, and R5 is C1-C 20 It is an alkylene group, and 1 ≤ a ≤ 200, Y1 and Y2 are the same or different, and each is independently C1-C 20 alkyl group, C6-C 20 The aryl group, C7-C 12 aralkyl group, C7-C 12 The alkylaryl group and the structure of formula (1) below are selected, and the conditions are that when a is 1, Y1 and / or Y2 have the structure of formula (1), and when a is greater than 1 and ≤200, at least one Y1 has the structure of formula (1) and / or at least one Y2 has the structure of formula (1), [ka] R7 is independently C1-C 20 alkyl group, C6-C 20 The aryl group, C7-C 12 aralkyl group or C7-C 12Selected from the alkylaryl groups, R8 is independently C1-C 20 alkyl group, C6-C 20 The aryl group, C7-C 12 aralkyl group, C7-C 12 alkylaryl group, C1-C 20 The alkoxy group or R9-OR 10 - is a base, where R9 is C1-C 20 alkyl group, C6-C 20 The aryl group, C7-C 12 aralkyl group or C7-C 12 It is an alkylaryl group, R 10 C1-C 20 It is an alkylene group, and 0 ≤ b ≤ 200.

[0062] In this application, the limitation of M in formula IA is the same as the limitation of M in formula I.

[0063] In some embodiments, at Z1, R3 is independently C1-C 10 alkyl group, C6-C 10 The aryl group, C7-C 12 aralkyl group, C7-C 12 alkylaryl group, C1-C 10 It is an alkoxy group or an R4-O-R5- group, where R4 is C1-C 10 alkyl group, C6-C 10 The aryl group, C7-C 12 aralkyl group or C7-C 12 It is an alkylaryl group, and R5 is C1-C 10 These are alkylene groups, 1 ≤ a ≤ 100, and R7 is independently C1-C 10 alkyl group, C6-C 10 The aryl group, C7-C 12 The aralkyl group, or C7-C 12 The alkylaryl group is such that R8 is independently C1-C 10 alkyl group, C6-C 10 The aryl group, C7-C 12 aralkyl group, C7-C12 alkylaryl group, C1-C 10 The alkoxy group or R9-OR 10 - is a base, where R9 is C1-C 10 alkyl group, C6-C 10 The aryl group, C7-C 12 The aralkyl group, or C7-C 12 It is an alkylaryl group, R 10 is C1-C 10 It is an alkylene group, and / or 0 ≤ b ≤ 80.

[0064] According to some embodiments of the present invention, in Z1, R3 is independently C1-C 10 alkyl group, C6-C 10 The aryl group, C7-C 10 aralkyl group, C7-C 10 The R4 group is an alkylaryl group, a C1-C6 alkoxy group, or an R4-O-R5- group, where R4 is a C1-C6 alkyl group, or a C6-C 10 The aryl group, C7-C 10 aralkyl group or C7-C 10 The alkylaryl group is such that R5 is a C1-C6 alkylene group, 1 ≤ a ≤ 30, and R7 is independently a C1-C6 alkyl group and a C6-C 10 The aryl group, C7-C 10 The aralkyl group, or C7-C 10 The alkylaryl group is such that R8 is independently a C1-C6 alkyl group and a C6-C 10 The aryl group, C7-C 10 aralkyl group, C7-C 10 Alkylaryl group, C1-C6 alkoxy group or R9-OR 10 - is a group, where R9 is a C1-C6 alkyl group, C6-C 10 The aryl group, C7-C 10 The aralkyl group, or C7-C 10 It is an alkylaryl group, R 10 is C1-C 16 It is an alkylene group, and 0 ≤ b ≤ 30.

[0065] In some embodiments, in formula IA, a is an integer between 1 and 80, an integer between 1 and 30, an integer between 1 and 20, or an integer between 1 and 10.

[0066] In some embodiments, b is 0 in formula IA. In some embodiments, b is an integer between 1 and 30, an integer between 1 and 20, an integer between 1 and 10, or an integer between 1 and 5.

[0067] In some embodiments, Z1 is one or more selected from the following structures i-3 to i-6, [ka] R is independently C1-C 10 alkyl group, C6-C 10 The aryl group, C7-C 12 aralkyl group or C7-C 12 Selected from 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; 1 ≤ x ≤ 9, preferably 1 ≤ x ≤ 7, where each x may be the same or different.

[0068] In some embodiments, R is a C1-C3 alkyl group, such as a methyl group.

[0069] In some preferred embodiments, Z1 is one or more selected from the following structures: [ka] Me represents a methyl group, where 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.

[0070] In some embodiments, the silicon monomer I-A is selected from the following. CH2=C(CH3)C(O)-O-(CH2)3Si(OSi(CH3)3)3, CH2=CHC(O)-O-(CH2)3Si(OSi(CH3)3)3, CH2=C(CH3)C(O)-O-(CH2)3Si(CH3)(OSi(CH3)3)2, CH2=CHC(O)-O-(CH2)3Si(CH3)(OSi(CH3)3)2, CH2=C(CH3)C(O)-NH-(CH2)3Si(OSi(CH3)3)3, CH2=CHC(O)-NH-(CH2)3Si(OSi(CH3)3)3, CH2=C(CH3)C(O)-NH-(CH2)3Si(CH3)(OSi(CH3)3)2, CH2=CHC(O)-NH-(CH2)3Si(CH3)(OSi(CH3)3)2, CH2=C(CH3)C(O)-O-(CH2)3Si(OSi(CH2CH3)3)3, CH2=CHC(O)-O-(CH2)3Si(OSi(CH2CH3)3)3, CH2=C(CH3)C(O)-O-CH2-Si(OSi(CH3)3)3, CH2=C(CH3)C(O)-O-(CH2)3Si(CH3)[O-[Si(CH3)2O]n-Si(CH3)2C4H9]2, 0 ≦ n ≦ 25, CH2=CH-ph-Si(OSi(CH3)3)3 (ph represents

Chem.

Chem.

[0071] In some embodiments, the general formula for silicon monomer IB is represented by formula IB, [ka] Here, M contains polymerizable functional groups, Z2 is selected from the following structures: [ka] In Z2, Y1 and Y2 are the same or different, and each is independently C1-C 20 alkyl group, C6-C 20 The aryl group, C7-C 12 The aralkyl group and C7-C 12 Selected from alkylaryl groups, R3 is independently C1-C 20 alkyl group, C6-C 20 The aryl group, C7-C 12 aralkyl group, C7-C 12 alkylaryl group, C1-C 20 The alkoxy group or R4-O-R5- group is selected, where R4 is C1-C 20 alkyl group, C6-C 20The aryl group, C7-C 12 aralkyl group or C7-C 12 It is an alkylaryl group, and R5 is C1-C 20 It is an alkylene group, and 1 ≤ a ≤ 200.

[0072] In this application, the limitation of M in formula IB is the same as the limitation of M in formula I.

[0073] In some embodiments, in Z2, Y1 and Y2 are the same or different, and each is independently C1-C 10 alkyl group, C6-C 10 The aryl group, C7-C 12 The aralkyl group and C7-C 12 Selected from alkylaryl groups, R3 is independently C1-C 10 alkyl group, C6-C 12 The aryl group, C7-C 12 aralkyl group, C7-C 12 alkylaryl group, C1-C 10 The alkoxy group or R4-O-R5- group is selected, where R4 is C1-C 10 alkyl group, C6-C 12 The aryl group, C7-C 12 aralkyl group or C7-C 12 It is an alkylaryl group, and R5 is C1-C 10 It is an alkylene group.

[0074] According to some embodiments of the present invention, in Z2, 1 ≤ a ≤ 80. According to some embodiments of the present invention, in Z2, 1 ≤ a ≤ 30. According to some embodiments of the present invention, in Z2, 1 ≤ a ≤ 20. According to some embodiments of the present invention, in Z2, 1 ≤ a ≤ 10.

[0075] In some embodiments, in Z2, Y1 and Y2 are the same or different, and each is independently a C1-C6 alkyl group and a C6-C 10 The aryl group, C7-C 10 The aralkyl group and C7-C 10Selected from alkylaryl groups, R3 is independently a C1-C6 alkyl group, C6-C 10 The aryl group, C7-C 10 aralkyl group, C7-C 10 Selected from an alkylaryl group, a C1-C6 alkoxy group, or an R4-O-R5- group, where R4 is a C1-C6 alkyl group, C6-C 10 The aryl group, C7-C 10 aralkyl group or C7-C 10 It is an alkylaryl group, and R5 is a C1-C6 alkylene group.

[0076] In some embodiments, Z2 is one or more selected from the following structures i-1 to i-2. [ka] R is independently C1-C 10 alkyl group, C6-C 10 The aryl group, C7-C 12 aralkyl group or C7-C 12 Selected from alkylaryl groups, 1 ≤ m + 1 ≤ 60, preferably 1 ≤ m + 1 ≤ 30, and 1 ≤ x ≤ 9, preferably 1 ≤ x ≤ 7. Z2 is preferably one or more selected from the following structures: [ka] 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.

[0077] In some embodiments, silicon monomer IB is selected from the following: CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (where C4H9 represents a butyl group), 1≦n≦25, CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)2C8H 17, 1≦n≦25, CH2=C(CH3)C(O)-O-(CH2)3[Si(CH3)2O]n-Si(CH3)3, 1≦n≦25, CH2=CH-ph-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9(C4H9 represents a butyl group, and ph is [ka] (represents), 1≦n≦25, CH2=CH-OC(O)-NH-(CH2)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (where C4H9 represents a butyl group), 1≦n≦25, CH2=CH-OC(O)-O-(CH2)3-[Si(CH3)2O]n-Si(CH3)2C4H9 (C4H9 represents a butyl group), 1≦n≦25, CH2=CH-OC(O)-O-(CH2)2-NH-(CH2)3[Si(CH3)2O]n-Si(CH3)2C4H9 (where C4H9 represents a butyl group), 1≦n≦25.

[0078] In some embodiments, the mass content of repeating units derived from monomer I is 30-90%. In some embodiments, the mass content of repeating units derived from monomer I is 40-85%. In some embodiments, the mass content of repeating units derived from monomer I is 45-75%. In some embodiments, the mass content of repeating units derived from monomer I is in the range of 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or any two of these.

[0079] In some embodiments, the mass content of repeating units derived from monomer II is 5-65%. In some embodiments, the mass content of repeating units derived from monomer II is 10-50%. In some embodiments, the mass content of repeating units derived from monomer II is 15-45%. In some embodiments, the mass content of repeating units derived from monomer II is in the range of 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or any two of these.

[0080] In some embodiments, the mass content of repeating units derived from monomer III in the copolymer is 0.5–30%. In some embodiments, the mass content of repeating units derived from monomer III in the copolymer is 3–15%. In some embodiments, it is more preferable that the mass content of repeating units derived from monomer III in the copolymer is 5–10%. In some embodiments, the mass content of repeating units derived from monomer III in the copolymer is in the range of 1%, 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, or any two of these.

[0081] In some embodiments, the ratio of repeating units derived from silicon monomer IA to the total amount of repeating units derived from silicon monomer IA and silicon monomer IB is 1%-100%, 5%-100%, 10%-100%, or 50%-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 any two of these. The total amount of repeating units derived from silicon monomer IA and silicon monomer IB is, i.e., the total amount of repeating units derived from monomer I.

[0082] In some embodiments, the copolymer of this application may or may not include repeating units derived from monomer IV, wherein monomer IV is one or more selected from dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, N-tert-butylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, dipropylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, diethylaminopropyl (meth)acrylamide, or dipropylaminopropyl (meth)acrylamide. Preferably, the general structural formula of monomer IV is represented by formula IV, [ka] In formula IV, P is selected from the groups represented by P-1 and P-2. [ka] B is C1-C 20 The alkylene group is such that R1 and R2 are each independently a hydrogen atom or C1-C 20 It is an alkyl group, and R3 and R4 are each independently a hydrogen atom, C1-C 18 The alkyl group is either a hydroxyethyl group or a benzyl group, or R3 and R4 are bonded together with the nitrogen atom to form a morpholino group, a piperidino group, or a pyrrolidino group.

[0083] In some embodiments, the copolymers of this application do not contain repeating units derived from monomer IV, wherein monomer IV is one or more selected from dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, N-tert-butylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, dipropylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, diethylaminopropyl (meth)acrylamide, or dipropylaminopropyl (meth)acrylamide.

[0084] In some embodiments, the general structural formula of monomer IV is represented by formula IV, [ka] In formula IV, P is selected from the groups represented by P-1 and P-2. [ka] B is C1-C 20 The alkylene group is such that R1 and R2 are each independently a hydrogen atom or C1-C 20 It is an alkyl group, and R3 and R4 are each independently a hydrogen atom, C1-C 18 The alkyl group is either a hydroxyethyl group or a benzyl group, or R3 and R4 are bonded together with the nitrogen atom to form a morpholino group, a piperidino group, or a pyrrolidino group.

[0085] In some embodiments, monomer II is II-3, and the copolymer further comprises repeating units derived from monomer IV. In some embodiments, monomer II is II-3, and the copolymer does not contain repeating units derived from monomer IV.

[0086] In some embodiments, the weight-average molecular weight of the copolymer is 10 to 2 million, for example, 50 to 1.5 million.

[0087] According to a second aspect, the present application provides a composition comprising the copolymer and solvent described in the first aspect, wherein the solvent comprises water and / or an organic solvent. In some embodiments, the organic solvent is one or more of the following: 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.

[0088] In a third aspect, the present application provides a treatment agent comprising the copolymer and solvent described in the first aspect, wherein the solvent comprises water and / or an organic solvent. In some embodiments, the organic solvent is one or more of the following: 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.

[0089] In a fourth aspect, the present application provides a method for preparing the composition described in the second aspect or the treatment agent described in the third aspect, comprising the following steps: (1) Polymerize monomers (including monomer I, monomer II, and monomer III) in an organic solvent to obtain a copolymer solution. In some embodiments, the proportion of monomer I used to the total amount of monomers is 30-90% by mass, preferably 40-85%, more preferably 50-80%, and ranges such as 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or any two of these. In some embodiments, the proportion of monomer II used to the total amount of monomer is 5-65% by mass, preferably 10-50%, more preferably 15-45%, and is in the range of, for example, 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or any two of these. In some embodiments, the proportion of monomer III used to the total amount of monomers is 0.5-30% by mass, preferably 3-15%, more preferably 5-10%, and ranges from, for example, 1%, 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, or any two of these. In some embodiments, the proportion of silicon monomer IA used to the total amount of silicon monomer IA and silicon monomer IB is 1%-100%, 5%-100%, 10%-100%, 50%-100%, 50%-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 any two of these. If necessary, the preparation method may further include one or more of the following steps (2) and (3). (2) After dispersing the copolymer solution with water, remove the organic solvent, or remove the organic solvent first and then add water to disperse it. (3) Add a base to the copolymer solution to convert the carboxyl groups or sulfonic acid groups in the copolymer into carboxylate salts or sulfonates.

[0090] In a fifth aspect, the present application provides the application of the copolymer described in the first aspect, the composition described in the second aspect, the treatment agent described in the third aspect, or a composition or treatment agent prepared by the method described in the fourth aspect, to textiles, leather, nonwoven fabrics, asbestos, fur, concrete, natural stone, paper products, or plastics.

[0091] In a sixth aspect, the present application provides a water- and oil-repellent product comprising a product which is a textile fabric, leather, nonwoven fabric, asbestos, fur, concrete, natural stone, paper product, or plastic, and a copolymer as described in the first aspect, or a composition or treatment agent prepared by the composition as described in the second aspect, or by the method as described in the third aspect.

[0092] In some embodiments, the copolymer described in the first embodiment, the composition described in the second embodiment, the treatment agent described in the third embodiment, or the composition or treatment agent prepared by the method described in the fourth embodiment is applied to the surface and / or interior of the product.

[0093] In a seventh aspect, the present application provides a method for treating a product, which is a textile fabric, leather, nonwoven fabric, asbestos, fur, concrete, natural stone, paper product, or plastic, and which comprises contacting the product with the copolymer described in the first aspect, the composition described in the second aspect, the treatment agent described in the third aspect, or a composition or treatment agent prepared by the method described in the fourth aspect.

[0094] In some embodiments, the contact is achieved by a surface sizing process, a surface coating process, a wet end process, or an immersion process.

[0095] In this application, examples of paper products include, but are not limited to, paper, paper cups, paper bowls, paper trays and other paper-based containers. In some embodiments, paper products include products such as paper, paper boxes, or pulp molds. [Effects of the Invention]

[0096] The copolymers and resulting compositions or treatment agents provided in this application can be easily dispersed in water or a solvent and can be applied to the treatment of various articles such as textiles, leather, nonwoven fabrics, asbestos, furs, concrete, natural stone, paper, and plastics in acidic, alkaline, and neutral environments. Treatment methods include coating, immersion, or internal addition, and can impart oil-repellent and water-repellent properties to the surface of the articles after treatment.

Mode for Carrying Out the Invention

[0097] To make the purpose, technical solution and advantages of the present application clearer, the present application will be described in more detail below by combining examples. These examples are only for explaining the present application and do not limit the present application. The actual protection scope of the present application is described in the claims.

[0098] In the present application, unless otherwise specified, the terms used have the general meanings well-known to those skilled in the art.

[0099] In the present application, the term "alkyl group" refers to a linear alkyl group or a branched alkyl group, and non-limiting examples thereof 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.

[0100] In the present application, the term "alkylene group" refers to a linear alkylene group or a branched alkylene group, and non-limiting examples thereof include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, -CHCH3CH2-, -CHCH3CH2CH2-, CH2CH3CHCH2-, etc.

[0101] In the present application, unless otherwise specified, all "%" refer to mass percentages.

[0102] I. Polymerization Method The polymerization method of the present copolymer 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 adopted.

[0103] In this application, preferably, after polymerization (for example, solution polymerization or emulsion polymerization), water and a base may be added and then the solvent removed to obtain an aqueous dispersion, or the solvent may be removed first and then water and a base may be added to obtain an aqueous dispersion.

[0104] Peroxides, azo compounds, or persulfate compounds can be used as polymer initiators, and depending on the polymerization system, oil-soluble or water-soluble initiators can be used.

[0105] Preferred oil-soluble polymerization initiators 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(cycloethane-1-carbonitride), dimethyl-2,2'-azobis(2-methylpropionate), benzoyl peroxide, di-t-butyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate.

[0106] Preferred water-soluble polymerization initiators 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-methylimidazolin-2-yl)propane] hydrochloride, potassium persulfate, barium persulfate, ammonium persulfate, hydrogen peroxide, and t-butyl hydroperoxide.

[0107] The polymerization initiator is preferably a peroxide or azo compound with a half-life of 10 hours and a decomposition temperature of 40°C or higher, such as t-butyl peroxypivalate or 2,2'-azobis(2-methylpropionitrile).

[0108] A typical solution polymerization process described in this application is as follows: First, the solvent is added, then the corresponding monomer is added and dissolved. After introducing nitrogen gas to replace the oxygen in the solution, the initiator is added, and the mixture is heated to a reaction temperature of 40-120°C for a reaction time of 4-20 hours.

[0109] The preparation steps for the composition or treatment agent of this application are as follows: (1) Monomer I, monomer II, and monomer III are added to an organic solvent in predetermined proportions, and polymerization is carried out by adding an initiator. (2) If necessary, after polymerization is complete, add water to disperse and remove the organic solvent, or remove the organic solvent and then add water to disperse. (3) This is a process in which a base is added as needed to convert the carboxyl groups or sulfonic acid groups in the copolymer into salts.

[0110] 2. Test Method Paper product processing and testing methods Processable paper products include thin paper, thick paper, cardboard, or pulp molds, etc., per unit area (m²) 2 A paper box that weighs 300 grams, with a unit area (rice 2 Kraft paper with a weight of 80 grams, per unit area ( ) 2 ) Thin paper with a weight of 30 grams, unit area ( ) 2 It can process paper and plastic products weighing up to 200 grams.

[0111] The raw materials for paper products may include chemically bleached pulp or unbleached pulp, wood pulp, chemically processed pulp, or mechanical pulp. Resin components such as polyamide, polyolefin, or polyvinyl alcohol may be added to these pulp sheets. The processing method for paper products is as follows: (1) Wet treatment: Paper and plastic weight 350 grams / meter 2 The reed pulp sheet was directly disintegrated, with a beating degree of 600 ml (Canadian standard filtration rate), a pulp concentration of 0.3%, and a pH of approximately 8.7. Alkyl ketene dimer (AKD) sizing agent was added sequentially at an amount of 2% of the dry paper weight, followed by the addition of the fixing agent Alcofix® 159 at an amount of 0.1-0.2%, and finally the synthesized composition was added at an amount of 1-15% of the dry paper weight. Pulp was placed in a 10-inch disc mold filter at a predetermined weight, and moisture was removed by vacuum suction. The mold was baked at 150°C for 120 seconds, and the oil-repellent and water-repellent properties of the disc-shaped tableware were evaluated. (2) Examples of surface sizing treatment: Preparation of test strips: Paper product weight 50 grams / meter 2 A 5:5 ratio of NBKP (bleached softwood kraft pulp) was added to a chemical pulp sheet LBKP (bleached hardwood kraft pulp), and the pulp sheet was beaten to a Canadian standard filtration water content of approximately 200 ml. During the papermaking process, MC-2 type cationic starch manufactured by Guangxi Mingyangyang Biochemical Co., Ltd. was added at a rate of 1% by weight of the pulp sheet, and the paper was made on a wirewheel paper machine, resulting in a paper weight of 50 grams / meter. 2 I obtained some tissue paper. For sizing, Y+L corn oxidized starch manufactured by Jiangxi Hongda Chemical Co., Ltd. was used at a concentration of 5%. First, the starch solution was heated to over 90°C to induce gelatinization. After gelatinization was complete, the pH value of the sizing solution was measured to be 8.5-8.9. The synthesized composition or treatment agent was then added, and the concentration of the composition or treatment agent in the starch solution was 1-15% by weight. The temperature of the starch solution was controlled to over 70°C, and the paper product was first subjected to surface sizing treatment until the liquid absorption exceeded 70%. Next, a drying treatment was performed to obtain the treated paper product. (3) Examples of surface coating: Preparation of test strip products: Paper product weight 230 grams / meter 2 This paper product consists of five layers. The bottom and top layers are made of chemical pulp sheets LBKP (bleached hardwood kraft pulp) and NBKP (bleached softwood kraft pulp) in a ratio of 7:3. The three intermediate layers are made of chemical mechanical pulp or mechanical pulp sheets, and the paper is produced at a weight of 230 grams / m² on the papermaking machine. 2 It was composited onto cardboard. As the coating starch, AS-28 coating starch manufactured by Guangxi Mingyang Biochemical Co., Ltd. was used. The starch concentration was 20%, and gelatinization was performed by adding water to the starch and heating it to over 90°C. After gelatinization was complete, the pH value of the coating solution was measured to be 8.4-8.7. The synthesized composition or treatment agent was added, and the concentration of the composition or treatment agent in the starch solution was 1-15% (mass concentration). The starch temperature was controlled to over 50°C, and it was applied to the top layer of cardboard using a paper product coating machine, with a coating amount of 3-8 grams / meter. 2 That was the case.

[0112] Oil and water repellency evaluation Oil repellency test evaluation Heat oil resistance test Processed paper products were used as containers capable of holding liquids. Hot oil (salad oil, peanut oil, or rapeseed oil) at 85°C was placed in the paper containers, and they were observed for 20 minutes. The presence or absence of penetration was evaluated, and the products were then classified and scored. 5 points. No surface discoloration. 4 points: The surface has slightly discolored. 3. The surface discolored and slightly penetrated. Two points were deeply infiltrated.

[0113] Water repellency evaluation (1) Cobb test This test is conducted in accordance with GB / T1540-2002 or ISO 535:1991. The principle is that a height of 100cm is required to support 10mm of water. 2 The weight (g) of water absorbed per minute by the paper is measured, and this value is calculated as the weight per square meter (g / m²). 2 It was converted to ). Cob absorption testers typically use inverted cylindrical testers. The metal cylinder is a cylindrical body with an internal cross-sectional area of ​​approximately (100 ± 0.2) cm².2 and the corresponding inner diameter was (112.8 ± 0.2) mm. When using a small-area cylinder, the recommended area is 50 cm 2 or more. In this case, in order to ensure a water liquid height of 10 mm, it is necessary to correspondingly reduce the volume of water. The cylinder height is 50 mm, the part of the cylinder annular surface contacting the sample is smooth, and it has sufficient roundness to prevent damage to the sample by the cylinder edge. In order to prevent water leakage, an elastic but water-absorbing rubber pad or gasket should be added in one layer to the inverted cylinder lid and the flat-pressure pedestal. The roller width of the metal pressure roller should be (200 ± 0.5) mm, the mass should be (10 ± 0.5) kg, and the surface should be smooth. The processed paper product sample was cut into 10 samples (5 on each side) with a size of (125 ± 5) mm square or ¢(125 ± 5) mm circular. For equipment with a small test area, the size of the sample should be slightly larger than the outer diameter of the cylinder to avoid water leakage due to the sample being too small and also avoid the influence on the operation due to the sample being too large.

[0114] Before placing the sample, it should be ensured that the cylinder annular surface and the rubber pad contacting the sample are dry, and hands should not contact the test area. After taking 100 mL of water with a graduated cylinder and putting it into the cylinder, the weighed sample was placed on the annular surface of the cylinder with the test surface facing down. The pressing lid was covered on the sample and clamped to fix it with the cylinder.

[0115] The cylinder was rotated 180°, the stopwatch was turned on, and the sample was allowed to absorb water for 60 seconds. Between 10 and 15 seconds before the water absorption was complete, the cylinder was turned over, the clamping device on the retaining lid was loosened, and the sample was removed. Note that the test water should be changed every 5 tests to avoid affecting the test results. The moment the predetermined water absorption time was reached, the sample removed from the cylinder was placed on the pre-laid absorbent paper with the absorbent side down. After placing another sheet of absorbent paper on top of the sample, it was immediately roll-pressed once back and forth within 4 seconds using a metal press roll without applying any other pressure to absorb and dry any remaining water on the sample surface. The sample was quickly removed, the absorbent side was folded inwards, then folded inwards again, and weighed with an accuracy of 0.001 g. With thick cardboard, the sample may be difficult to fold; in this case, the second weighing should be done earlier.

[0116] The Cobb value is expressed by the following formula. C=(g2-g1) / F In the formula, C-Cobb value, g2 - Sample weight after water absorption, g1 - Sample weight before water absorption, F-100cm 2 Test area. (2) Hot water resistance test This method directly tests the heat water resistance of paper products. The test procedure is relatively simple: generally, the treated paper product is placed in a container capable of holding liquid, 100°C boiling water is placed in it, and it is observed for 30 minutes to check for leaks. If there are no leaks, it is considered a pass. This method is applicable to pulp molded products.

[0117] Stone treatment and testing methods: The natural stone materials that can be processed include marble, granite, sandstone, and slate. Taking natural marble as an example, the pH of the treatment solution was uniformly adjusted to 8.3 to prevent corrosion of the marble by acidic liquids. Natural marble samples were immersed in a treatment solution diluted with water to a certain ratio, removed, and allowed to air dry for 48 hours at a temperature of 25°C or higher. After that, salad oil, mustard sauce, coffee, and vinegar were dropped onto the surface of the natural marble, and the wet state was observed. If the liquid did not penetrate, it indicated good resistance. 5 points. No surface discoloration. After 4 minutes, the surface had slightly discolored. 3. The surface discolored and slightly penetrated. Two points were deeply infiltrated.

[0118] III. Examples and Comparative Examples Refer to Table 1 for abbreviations of chemical products. [Table 1]

[0119] Example 1 In a 1000 ml four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, thermometer, and stirrer, 75 g of Si-B3, 50 g of PEG-A, 10 g of MAA, and 135 g of methyl ethyl ketone (hereinafter referred to as MEK) were added. Nitrogen gas was flowed through for 30 minutes, and the temperature was gradually raised to 60°C. 1.4 g of t-butyl peroxypivalate, a peroxide-based initiator, was added, and the reaction was carried out at a controlled temperature of 60°C for 20 hours, yielding approximately 270 g of polymer solution with a solid content of approximately 50%. When the obtained polymer solution was measured using a gas chromatograph-mass spectrometer, the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the obtained polymer was in close agreement with the monomer composition of the added monomers. 538 g of water and 2.5 g of sodium hydroxide were added, and the mixture was stirred at 60°C for more than 1 hour. MEK was then removed from the solution under reduced pressure to obtain an aqueous dispersion with a solid content of 20%.

[0120] Example 2-8 Example 1 was identical to Example 1, except that Si-B3 was replaced with monomer I of the following different structures: Si-NB3 (Example 2), Si-ph-B3 (Example 3), Si-OCN-B3 (Example 4), Si-OCO-B3 (Example 5), Si-B2 (Example 6), Si-N2-B2 (Example 7), and Si-5 (average molecular weight 500) (Example 8). When the resulting polymer solution was measured using a gas chromatograph-mass spectrometer, the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the resulting polymer was in close agreement with the composition of the added monomers.

[0121] Example 9 In a 1000 ml four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, thermometer, and stirrer, 75 g of Si-B3, 50 g of HEMA, 10 g of MAA, and 135 g of methyl ethyl ketone (hereinafter referred to as MEK) were added. Nitrogen gas was passed through for 30 minutes, and the temperature was gradually raised to 60°C. 1.4 g of t-butyl peroxypivalate, a peroxide-based initiator, was added, and the reaction was carried out at a controlled temperature of 60°C for 20 hours, yielding approximately 270 g of polymer solution with a solid content of approximately 50%. When the obtained polymer solution was measured using a gas chromatograph-mass spectrometer, the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the obtained polymer was in close agreement with the monomer composition of the added monomers. 538 g of water and 2.5 g of sodium hydroxide were added, and the mixture was stirred at 60°C for more than 1 hour. MEK was then removed from the solution under reduced pressure to obtain an aqueous dispersion with a solid content of 20%.

[0122] Performance testing Several articles were tested using the compositions synthesized in the examples and comparative examples as treatment agents. 1) Paper tableware test: Using disintegrated reed pulp sheets, a 1 wt% pulp solution was prepared, and the pH value was measured to be 8.6. 2 wt% AKD-type sizing agent by dry paper weight, 0.12% Alcofix® 159 yield improver, and 10 wt%, 6 wt%, and 3 wt% treatment agents by dry paper weight were added, and a 10-inch disc was prepared with a weight of 20 g. It was tested in salad oil at 85°C for 20 minutes, and graded according to the penetration status. It was then tested in boiling water at 100°C for 30 minutes, and a pass or leakage was recorded. 2) Testing of paper products: 50g / m² 2 Thin paper was selected and treated with surface sizing. Y+L corn oxidized starch from Jiangxi Hongda Chemical Co., Ltd. was used as the sizing starch, and the pH of the sizing solution was measured to be 8.7. The concentrations of the treatment agents were 5 wt%, 4 wt%, and 3 wt%, respectively, and the heat oil resistance and cob water absorption values ​​were tested. 3) Testing of paper products: 230 g / m² 2 Cardboard was selected and treated by coating. AS-28 coating starch manufactured by Guangxi Mingyang Biochemical Co., Ltd. was used as the coating starch, and the pH value of the coating solution was measured to be 8.5. The concentrations of the treatment agent were 5 wt%, 4 wt%, and 3 wt%, respectively, and the heat oil resistance and cob water absorption values ​​were tested. 4) Testing of natural marble: The treatment agent was diluted with water to 3 wt%, 2 wt%, and 1 wt%, respectively. To prevent corrosion of the marble by the acidic liquid, the pH value of the treatment agent was uniformly adjusted to 8.3. Marble samples were taken, immersed in the liquid, removed, and air-dried for 48 hours at a temperature of 25°C or higher. Then, salad oil and coffee were dropped onto the surface of the natural marble, and the wet state was observed and graded.

[0123] [Table 2]

[0124] As can be seen from Table 2, under alkaline conditions, the compositions obtained in Examples 1-9, depending on the surface size, coating, or wet-end process (pulp size), all exhibited good oil-repellent and water-repellent properties after treating paper products or marble.

[0125] Comparative Example 1 In a 1000 ml four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, thermometer, and stirrer, 75 g of Si-B3, 40 g of DN, 20 g of PEG-A, and 135 g of methyl ethyl ketone (hereinafter referred to as MEK) were added. Nitrogen gas was passed through for 30 minutes, and the temperature was gradually raised to 60°C. 1.4 g of t-butyl peroxypivalate, a peroxide-based initiator, was added, and the reaction was carried out at a controlled temperature of 60°C for 20 hours, yielding approximately 270 g of polymer solution with a solid content of approximately 50%. When the obtained polymer solution was measured using a gas chromatograph-mass spectrometer, the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the obtained polymer was in close agreement with the monomer composition of the added monomers. 525 g of water and 15 g of glacial acetic acid were added, and the mixture was stirred at 60°C for at least 1 hour. MEK was then removed from the solution under reduced pressure to obtain an aqueous dispersion with a solid content of 20%.

[0126] Comparative Example 2-8 The procedure was exactly the same as Comparative Example 1, except that Si-B3 was replaced with monomer I of the following different structures: Si-NB3 (Comparative Example 2), Si-ph-B3 (Comparative Example 3), Si-OCN-B3 (Comparative Example 4), Si-OCO-B3 (Comparative Example 5), Si-B2 (Comparative Example 6), Si-N2-B2 (Comparative Example 7), and Si-5 (average molecular weight 500) (Comparative Example 8). When the resulting polymer solution was measured using a gas chromatograph-mass spectrometer, the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the resulting polymer was in close agreement with the monomer composition of the added monomers.

[0127] Comparative Example 9 In a 1000 ml four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, thermometer, and stirrer, 75 g of Si-B3, 40 g of DN, 20 g of HEMA, and 135 g of methyl ethyl ketone (hereinafter referred to as MEK) were added. Nitrogen gas was flowed through for 30 minutes, and the temperature was gradually raised to 60°C. 1.4 g of t-butyl peroxypivalate, a peroxide-based initiator, was added, and the reaction was carried out at a controlled temperature of 60°C for 20 hours, yielding approximately 270 g of polymer solution with a solid content of approximately 50%. When the obtained polymer solution was measured using a gas chromatograph-mass spectrometer, the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the obtained polymer was in close agreement with the monomer composition of the added monomers. 525 g of water and 15 g of glacial acetic acid were added, and the mixture was stirred at 60°C for at least 1 hour. MEK was then removed from the solution under reduced pressure to obtain an aqueous dispersion with a solid content of 20%.

[0128] Performance tests were conducted on Comparative Examples 1-9 according to the test method of the Examples. The results are shown in Table 3.

[0129] [Table 3]

[0130] As can be seen from Table 3, under alkaline conditions, the compositions obtained in Comparative Examples 1-9 failed to impart good oil- and water-repellent properties to paper products and marble, depending on the surface size, coating, or wet-end process (pulp size).

[0131] Referring to Tables 2 and 3, it can be seen that the copolymer of this application and the compositions obtained therefrom can impart good oil-repellent and water-repellent properties to articles such as paper in an alkaline environment.

[0132] Example 10 In a 1000 ml four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, thermometer, and stirrer, 75 g of Si-B3, 50 g of NVP, 10 g of MAA, and 135 g of methyl ethyl ketone (hereinafter referred to as MEK) were added. Nitrogen gas was flowed through for 30 minutes, and the temperature was gradually raised to 60°C. 1.4 g of t-butyl peroxypivalate, a peroxide-based initiator, was added, and the reaction was carried out for 20 hours at a controlled temperature of 60°C, yielding approximately 270 g of polymer solution with a solid content of approximately 50%. When the obtained polymer solution was measured using a gas chromatograph-mass spectrometer, the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the obtained polymer was in close agreement with the monomer composition of the added monomers. 538 g of water and 2.5 g of sodium hydroxide were added, and the mixture was stirred at 60°C for more than 1 hour. MEK was then removed from the solution under reduced pressure to obtain an aqueous dispersion with a solid content of 20%.

[0133] Examples 11-17 Example 10 was identical to Example 10, except that Si-B3 was replaced with monomer I of the following different structures: Si-NB3 (Example 11), Si-ph-B3 (Example 12), Si-OCN-B3 (Example 13), Si-OCO-B3 (Example 14), Si-B2 (Example 15), Si-N2-B2 (Example 16), and Si-5 (average molecular weight 500) (Example 17). When the resulting polymer solution was measured using a gas chromatograph-mass spectrometer, the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the resulting polymer was in close agreement with the composition of the added monomers.

[0134] Example 18 In a 1000 ml four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, thermometer, and stirrer, 75 g of Si-B3, 50 g of N-vinyl-2-piperidone, 10 g of MAA, and 135 g of methyl ethyl ketone (hereinafter referred to as MEK) were added. Nitrogen gas was flowed through for 30 minutes, and the temperature was gradually raised to 60°C. 1.4 g of t-butyl peroxypivalate, a peroxide-based initiator, was added, and the reaction was carried out at a controlled temperature of 60°C for 20 hours, yielding approximately 270 g of polymer solution with a solid content of approximately 50%. When the obtained polymer solution was measured using a gas chromatograph-mass spectrometer, the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the obtained polymer was in close agreement with the monomer composition of the added monomers. 538 g of water and 2.5 g of sodium hydroxide were added, and the mixture was stirred at 60°C for more than 1 hour. MEK was then removed from the solution under reduced pressure to obtain an aqueous dispersion with a solid content of 20%.

[0135] Performance testing Several articles were tested using the compositions synthesized in the examples as treatment agents. 1) Paper tableware test: Using disintegrated reed pulp sheets, a 1 wt% pulp solution was prepared, and the pH value was measured to be 8.6. 2 wt% AKD-type sizing agent by dry paper weight, 0.12% Alcofix® 159 yield improver, and 10 wt%, 6 wt%, and 3 wt% treatment agents by dry paper weight were added, and a 10-inch disc was prepared with a weight of 20 g. It was tested in salad oil at 85°C for 20 minutes, and graded according to the penetration status. It was then tested in boiling water at 100°C for 30 minutes, and a pass or leakage was recorded. 2) Testing of paper products: 50g / m² 2 Thin paper was selected and treated with surface sizing. Y+L corn oxidized starch from Jiangxi Hongda Chemical Co., Ltd. was used as the sizing starch, and the pH of the sizing solution was measured to be 8.7. The concentrations of the treatment agents were 5 wt%, 4 wt%, and 3 wt%, respectively, and the heat oil resistance and cob water absorption values ​​were tested. 3) Testing of paper products: 230 g / m² 2Cardboard was selected and treated by coating. AS-28 coating starch manufactured by Guangxi Mingyang Biochemical Co., Ltd. was used as the coating starch, and the pH value of the coating solution was measured to be 8.5. The concentrations of the treatment agent were 5 wt%, 4 wt%, and 3 wt%, respectively, and the heat oil resistance and cob water absorption values ​​were tested. 4) Testing of natural marble: The treatment agent was diluted with water to 3 wt%, 2 wt%, and 1 wt%, respectively. To prevent corrosion of the marble by the acidic liquid, the pH value of the treatment agent was uniformly adjusted to 8.3. Marble samples were taken, immersed in the liquid, removed, and air-dried for 48 hours at a temperature of 25°C or higher. Then, salad oil and coffee were dropped onto the surface of the natural marble, and the wet state was observed and graded.

[0136] [Table 4]

[0137] As can be seen from Table 4, under alkaline conditions, depending on the surface size, coating, or wet-end process (intrapulp size), the compositions obtained in Examples 10-18 all exhibited good oil-repellent and water-repellent properties after treating paper products or marble.

[0138] Comparative Example 10 In a 1000 ml four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, thermometer, and stirrer, 75 g of Si-B3, 40 g of DN, 20 g of NVP, and 135 g of methyl ethyl ketone (hereinafter referred to as MEK) were added. Nitrogen gas was flowed through for 30 minutes, and the temperature was gradually raised to 60°C. 1.4 g of t-butyl peroxypivalate, a peroxide-based initiator, was added, and the reaction was carried out at a controlled temperature of 60°C for 20 hours, yielding approximately 270 g of polymer solution with a solid content of approximately 50%. When the obtained polymer solution was measured using a gas chromatograph-mass spectrometer, the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the obtained polymer was in close agreement with the monomer composition of the added monomers. 525 g of water and 15 g of glacial acetic acid were added, and the mixture was stirred at 60°C for at least 1 hour. MEK was then removed from the solution under reduced pressure to obtain an aqueous dispersion with a solid content of 20%.

[0139] Comparative Example 11-17 The results were exactly the same as Comparative Example 10, except that Si-B3 was replaced with monomer I of the following different structures: Si-NB3 (Comparative Example 11), Si-ph-B3 (Comparative Example 12), Si-OCN-B3 (Comparative Example 13), Si-OCO-B3 (Comparative Example 14), Si-B2 (Comparative Example 15), Si-N2-B2 (Comparative Example 16), and Si-5 (average molecular weight 500) (Comparative Example 17). When the resulting polymer solution was measured using a gas chromatograph-mass spectrometer, the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the resulting polymer was in close agreement with the composition of the added monomers.

[0140] Comparative Example 18 In a 1000 ml four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, thermometer, and stirrer, 75 g of Si-B3, 40 g of DN, 20 g of N-vinyl-2-piperidone, and 135 g of methyl ethyl ketone (hereinafter referred to as MEK) were added. Nitrogen gas was flowed through for 30 minutes, and the temperature was gradually raised to 60°C. 1.4 g of t-butyl peroxypivalate, a peroxide-based initiator, was added, and the reaction was carried out at a controlled temperature of 60°C for 20 hours, yielding approximately 270 g of polymer solution with a solid content of approximately 50%. When the obtained polymer solution was measured using a gas chromatograph-mass spectrometer, the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the obtained polymer was in close agreement with the monomer composition of the added monomers. 525 g of water and 15 g of glacial acetic acid were added, and the mixture was stirred at 60°C for at least 1 hour. MEK was then removed from the solution under reduced pressure to obtain an aqueous dispersion with a solid content of 20%.

[0141] Performance tests were conducted on Comparative Examples 10-18 according to the test method of the Examples. The results are shown in Table 5.

[0142] [Table 5]

[0143] As can be seen from Table 5, under alkaline conditions, depending on the surface size, coating, or wet-end process (pulp size), the compositions obtained in Comparative Examples 10-18 failed to impart good oil-repellent and water-repellent properties to paper products and marble.

[0144] Referring to Tables 4 and 5, it can be seen that the copolymer of this application and the compositions obtained therefrom can impart good oil-repellent and waterproof properties to articles such as paper and marble in an alkaline environment.

[0145] Example 19 In a 1000 ml four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, thermometer, and stirrer, 75 g of Si-B3, 50 g of AM50, 10 g of MAA, and 135 g of methyl ethyl ketone (hereinafter referred to as MEK) were added. Nitrogen gas was flowed through for 30 minutes, and the temperature was gradually raised to 60°C. 1.4 g of t-butyl peroxypivalate, a peroxide-based initiator, was added, and the reaction was carried out at a controlled temperature of 60°C for 20 hours, yielding approximately 270 g of polymer solution with a solid content of approximately 50%. When the obtained polymer solution was measured using a gas chromatograph-mass spectrometer, the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the obtained polymer was in close agreement with the monomer composition of the added monomers. 538 g of water and 2.5 g of sodium hydroxide were added, and the mixture was stirred at 60°C for more than 1 hour. MEK was then removed from the solution under reduced pressure to obtain an aqueous dispersion with a solid content of 20%.

[0146] Examples 20-26 Example 19 was identical to Example 29, except that Si-B3 was replaced with monomer I of the following different structures: Si-NB3 (Example 20), Si-ph-B3 (Example 21), Si-OCN-B3 (Example 22), Si-OCO-B3 (Example 23), Si-B2 (Example 24), Si-N2-B2 (Example 25), and Si-5 (average molecular weight 500) (Example 26). When the resulting polymer solution was measured using a gas chromatograph-mass spectrometer, the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the resulting polymer was in close agreement with the composition of the added monomers.

[0147] Example 27 In a 1000 ml four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, thermometer, and stirrer, 375 g of Si-B, 50 g of N-acryloylpyrrolidine, 10 g of MAA, and 135 g of methyl ethyl ketone (hereinafter referred to as MEK) were added. Nitrogen gas was flowed through for 30 minutes, and the temperature was gradually raised to 60°C. 1.4 g of t-butyl peroxypivalate, a peroxide-based initiator, was added, and the reaction was carried out at a controlled temperature of 60°C for 20 hours, yielding approximately 270 g of polymer solution with a solid content of approximately 50%. When the obtained polymer solution was measured using a gas chromatograph-mass spectrometer, the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the obtained polymer was in close agreement with the monomer composition of the added monomers. 538 g of water and 2.5 g of sodium hydroxide were added, and the mixture was stirred at 60°C for more than 1 hour. MEK was then removed from the solution under reduced pressure to obtain an aqueous dispersion with a solid content of 20%.

[0148] Performance testing Several articles were tested using the aqueous dispersion synthesized in the examples as a treatment agent. 1) Paper tableware test: Using disintegrated reed pulp sheets, a 1 wt% pulp solution was prepared, and the pH value was measured to be 8.6. 2 wt% AKD-type sizing agent by dry paper weight, 0.12% Alcofix® 159 yield improver, and 10 wt%, 6 wt%, and 3 wt% treatment agents by dry paper weight were added, and a 10-inch disc was prepared with a weight of 20 g. It was tested in salad oil at 85°C for 20 minutes, and graded according to the penetration status. It was then tested in boiling water at 100°C for 30 minutes, and a pass or leakage was recorded. 2) Testing of paper products: 50g / m² 2 Thin paper was selected and treated with surface sizing. Y+L corn oxidized starch from Jiangxi Hongda Chemical Co., Ltd. was used as the sizing starch, and the pH of the sizing solution was measured to be 8.7. The concentrations of the treatment agents were 5 wt%, 4 wt%, and 3 wt%, respectively, and the heat oil resistance and cob water absorption values ​​were tested. 3) Testing of paper products: 230 g / m² 2Cardboard was selected and treated by coating. AS-28 coating starch manufactured by Guangxi Mingyang Biochemical Co., Ltd. was used as the coating starch, and the pH value of the coating solution was measured to be 8.5. The concentrations of the treatment agent were 5 wt%, 4 wt%, and 3 wt%, respectively, and the heat oil resistance and cob water absorption values ​​were tested. 4) Testing of natural marble: The treatment agent was diluted with water to 3 wt%, 2 wt%, and 1 wt%, respectively. To prevent corrosion of the marble by the acidic liquid, the pH value of the treatment agent was uniformly adjusted to 8.3. Marble samples were taken, immersed in the liquid, removed, and air-dried for 48 hours at a temperature of 25°C or higher. Then, salad oil and coffee were dropped onto the surface of the natural marble, and the wet state was observed and graded.

[0149] [Table 6]

[0150] As can be seen from Table 6, under alkaline conditions, the treatment agents obtained in Examples 19-27 showed good oil-repellent and water-repellent properties after treating paper products or marble, depending on the surface size, application, or wet-end process (intrapulp size).

[0151] Comparative Example 19 In a 1000 ml four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, thermometer, and stirrer, 75 g of Si-B3, 40 g of DN, 20 g of AM, and 135 g of methyl ethyl ketone (hereinafter referred to as MEK) were added. Nitrogen gas was flowed through for 30 minutes, and the temperature was gradually raised to 60°C. 1.4 g of t-butyl peroxypivalate, a peroxide-based initiator, was added, and the reaction was carried out at a controlled temperature of 60°C for 20 hours, yielding approximately 270 g of polymer solution with a solid content of approximately 50%. When the obtained polymer solution was measured using a gas chromatograph-mass spectrometer, the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the obtained polymer was in close agreement with the monomer composition of the added monomers. 525 g of water and 15 g of glacial acetic acid were added, and the mixture was stirred at 60°C for at least 1 hour. MEK was then removed from the solution under reduced pressure to obtain an aqueous dispersion with a solid content of 20%.

[0152] Comparative Example 20-26 The procedure was exactly the same as Comparative Example 19, except that Si-B3 was replaced with monomer I of the following different structures: Si-NB3 (Comparative Example 20), Si-ph-B3 (Comparative Example 21), Si-OCN-B3 (Comparative Example 22), Si-OCO-B3 (Comparative Example 23), Si-B2 (Comparative Example 24), Si-N2-B2 (Comparative Example 25), and Si-5 (average molecular weight 500) (Comparative Example 26). When the resulting polymer solution was measured using a gas chromatograph-mass spectrometer, the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the resulting polymer was in close agreement with the monomer composition of the added monomers.

[0153] Comparative Example 27 In a 1000 ml four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, thermometer, and stirrer, 75 g of Si-B3, 40 g of DN, 20 g of N-acryloylpyrrolidine, and 135 g of methyl ethyl ketone (hereinafter referred to as MEK) were added. Nitrogen gas was flowed through for 30 minutes, and the temperature was gradually raised to 60°C. 1.4 g of t-butyl peroxypivalate, a peroxide-based initiator, was added, and the reaction was carried out for 20 hours at a controlled temperature of 60°C, yielding approximately 270 g of polymer solution with a solid content of approximately 50%. When the obtained polymer solution was measured using a gas chromatograph-mass spectrometer, the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the obtained polymer was in close agreement with the monomer composition of the added monomers.

[0154] 525 g of water and 15 g of glacial acetic acid were added, and the mixture was stirred at 60°C for at least 1 hour. MEK was then removed from the solution under reduced pressure to obtain an aqueous dispersion with a solid content of 20%.

[0155] Performance tests were conducted on Comparative Examples 19-27 according to the test method of the Examples. The results are shown in Table 7.

[0156] [Table 7]

[0157] As can be seen from Table 7, under alkaline conditions, the treatment agents obtained in Comparative Examples 19-27 could not impart good oil- and water-repellent properties to paper products and marble, depending on the surface size, coating, immersion, or wet-end process (pulp size).

[0158] Referring to Tables 6 and 7, it can be seen that the copolymer of this application and the compositions obtained therefrom can impart good oil-repellent and water-repellent properties to articles such as paper in an alkaline environment.

[0159] While several exemplary embodiments of the present invention have been described, the present invention is not limited to these embodiments. Conversely, those skilled in the art will recognize that several modifications and changes can be made to the embodiments described without departing from the spirit and scope of the invention as set forth in the appended claims.

Claims

1. A copolymer comprising repeating units derived from monomer I, repeating units derived from monomer II, and repeating units derived from monomer III, a) The general structural formula of monomer I is given by formula I, 【Chemistry 40】 Here, M contains polymerizable functional groups, Z is selected from the following structures: 【Chemistry 41】 In Z, R ３ is, independently of each other, C １ -C ２０ alkyl group, C ６ -C ２０ aryl group, C ７ -C １２ aralkyl group, C ７ -C １２ alkylaryl group, C １ -C ２０ alkoxy group or R ４ -O-R ５ - group, and R ４ is C １ -C ２０ alkyl group, C ６ -C ２０ aryl group, C ７ -C １２ aralkyl group or C ７ -C １２ alkylaryl group, and R ５ is C １ -C ２０ alkylene group, 1 ≤ a ≤ 200, Y １ and Y ２ They are identical or different, and each is independent of C １ -C ２０ alkyl group, C ６ -C ２０ The aryl group, C ７ -C １２ The aralkyl group, C ７ -C １２ Selected from the alkylaryl group or the structure of the following formula (1), 【Chemistry 42】 R ７ Each of them independently, C １ -C ２０ alkyl group, C ６ -C ２０ The aryl group, C ７ -C １２ aralkyl group or C ７ -C １２ Selected from alkylaryl groups, R ８ Each of them independently, C １ -C ２０ alkyl group, C ６ -C ２０ The aryl group, C ７ -C １２ The aralkyl group, C ７ -C １２ The alkylaryl group, C １ -C ２０ Alkoxy group or R ９ -O-R １０ - Selected from the base, here, R ９ C １ -C ２０ alkyl group, C ６ -C ２０ The aryl group, C ７ -C １２ aralkyl group or C ７ -C １２ It is an alkylaryl group, R １０ C １ -C ２０ It is an alkylene group, and 0 ≤ b ≤ 200, b) The general structural formula of monomer II is represented by formula II-1, formula II-2, or formula II-3. 【Chemistry 43】 In Equation II-1, R １ R represents a hydrogen atom or a methyl group. ２ Each is independently C １ -C ６ It is an alkylene group, preferably C ２ -C ４ The alkylene group is such that q is an integer from 1 to 50, preferably an integer from 1 to 20, and R ３ is a hydrogen atom or C １ -C ２０ Represents an alkyl group, preferably a hydrogen atom or C １ -C １０ It is an alkyl group, more preferably a hydrogen atom, C １ -C ３ It is an alkyl group, Here, G is selected from the groups represented by G-1 and G-2. 【Chemistry 44】 R ４ represents a hydrogen atom or a methyl group, and B is either absent or C １ -C ２０ The alkylene group is preferably absent or C １ -C １０ It is an alkylene group, 【Chemistry 45】 In formula II-2, n is an integer from 1 to 6, s is an integer from 0 to 16, and each R is the same or different and is independently selected from C １ -C ２０ alkyl groups, preferably selected from C １ -C １０ alkyl groups, more preferably selected from C １ -C ６ alkyl groups, 【Chemistry 46】 In formula II-3, R １ is selected from a hydrogen atom or a C １ -C ２０ alkyl group, and R １ is preferably selected from a hydrogen atom or a methyl group. R ２ and R ３ Each of these is independently a hydrogen atom or C １ -C ２０ Selected from alkyl groups, R ２ and R ３ Preferably a hydrogen atom or C １ -C １０ Selected from alkyl groups, more preferably a hydrogen atom or C １ -C ６ Selected from alkyl groups, or R ２ and R ３ along with the nitrogen atom to which they are linked, C ３ -C ８ A heterocyclic group is formed, preferably a pyrrolidone, piperidinyl group, pyrrolidinyl group, pyrrolyl group, piperidone group, morpholinyl group, piperazinyl group, azilidinyl group, azetidinyl group, azepanyl group or azocanyl group. c) A copolymer in which monomer III is a monomer having an anionic group and a polymerizable unsaturated group, the anionic group being a carboxyl group or a sulfonic acid group.

2. M is expressed by equation I-1, 【Chemistry 47】 In equation I-1, R １ is a hydrogen atom or C １ -C ２０ Selected from alkyl groups, B is C １ -C ２０ It is an alkylene group, X is selected from the groups represented by X-1 and X-2, 【Chemistry 48】 R ２ is a hydrogen atom or C １ -C ２０ Selected from alkyl groups, and / or, M is expressed by equation I-2, 【Chemistry 49】 In Equation I-2, R １ is a hydrogen atom or C １ -C ２０ Selected from alkyl groups, W is selected from the groups represented by W-1, W-2, W-3 and W-4. [Transformation 50] R ２ is a hydrogen atom or C １ -C ２０ Selected from alkyl groups, D is C １ -C ２０ The alkylene group is such that if W is selected from W-1, then B is either absent or C １ -C ２０ The alkylene group is such that when W is selected from W-2, W-3, and W4, B is C １ -C ２０ It is an alkylene group, and / or, M is expressed by equation I-3, 【Chemistry 51】 In formula I-3, R １ is a hydrogen atom or C １ -C ２０ Selected from alkyl groups, B is independently C １ -C ２０ The copolymer according to claim 1, characterized in that it is an alkylene group.

3. The monomer IV may or may not contain repeating units derived from monomer IV, where monomer IV is one or more selected from dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, N-tert-butylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, dipropylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, diethylaminopropyl (meth)acrylamide, or dipropylaminopropyl (meth)acrylamide. Preferably, the general structural formula of monomer IV is represented by formula IV, 【Chemistry 52】 In formula IV, P is selected from the groups represented by P-1 and P-2. 【Chemistry 53】 B is C １ -C ２０ It is an alkylene group, R １ and R ２ Each of these is independently a hydrogen atom, or C １ -C ２０ It is an alkyl group, R ３ and R ４ Each is independently a hydrogen atom, C １ -C １８ The alkyl group, hydroxyethyl group or benzyl group, or R ３ and R ４ The copolymer according to claim 1 or 2, characterized in that it is bonded to a nitrogen atom to form a morpholino group, a piperidino group, or a pyrrolidino group.

4. The mass content of repeating units derived from monomer I in the copolymer is 30-90%, preferably 40-80%, more preferably 45-70%, and / or The mass content of repeating units derived from monomer II in the copolymer is 5-65%, preferably 10-50%, more preferably 15-45%, and / or The copolymer according to any one of claims 1 to 3, characterized in that the mass content of repeating units derived from monomer III in the copolymer is 0.5-30%, preferably 3-15%, and more preferably 5-10%.

5. Monomer I comprises silicon monomer I-A and / or silicon monomer I-B. The general formula for silicon monomer I-A is the same as formula I, and when a is 1, Y １ and / or Y ２ If the structure is as in equation (1), and a is greater than 1 and ≤ 200, then at least one Y １ The structure of formula (1) and / or at least one Y ２ The structure of equation (1) is satisfied, The general formula for silicon monomer I-B is the same as formula I, Y １ and Y ２ They are the same or different, and each is independently C １ -C ２０ alkyl group, C ６ -C ２０ The aryl group, C ７ -C １２ The aralkyl group and C ７ -C １２ The copolymer according to any one of claims 1 to 4, characterized in that it is selected from alkylaryl groups.

6. In equation I-1, R １ is a hydrogen atom or C １ -C １０ Selected from alkyl groups, preferably R １ B is selected from a hydrogen atom or a methyl group, and C １ -C １０ The alkylene group is preferably C １ -C ６ It is an alkylene group, and in X, R ２ is a hydrogen atom or C １ -C １０ Selected from alkyl groups, preferably R ２ is selected from a hydrogen atom or a methyl group. In Equation I-2, R １ is a hydrogen atom or C １ -C １０ Selected from alkyl groups, preferably R １ and R ２ is selected from a hydrogen atom or a methyl group, and B and D are C １ -C １０ The alkylene group is preferably B and D is C １ -C ６ It is an alkylene group, In formula I-3, R １ is a hydrogen atom or C １ -C １０ Selected from alkyl groups, preferably R １ B is selected from a hydrogen atom or a methyl group, and C １ -C １０ It is an alkylene group, In Z, R ３ Each of them independently, C １ -C １０ alkyl group, C ６ -C １０ The aryl group, C ７ -C １２ The aralkyl group, C ７ -C １２ The alkylaryl group, C １ -C １０ The alkoxy group or R ４ -O-R ５ - It is a group, R ４ C １ -C １０ alkyl group, C ６ -C １０ The aryl group, C ７ -C １２ aralkyl group or C ７ -C １２ It is an alkylaryl group, R ５ C １ -C １０ It is an alkylene group, 1 ≤ a ≤ 100, R ７ Each of them independently, C １ -C １０ alkyl group, C ６ -C １０ The aryl group, C ７ -C １２ The aralkyl group of, or C ７ -C １２ It is an alkylaryl group, R ８ Each of them independently, C １ -C １０ alkyl group, C ６ -C １０ The aryl group, C ７ -C １２ The aralkyl group, C ７ -C １２ The alkylaryl group, C １ -C １０ The alkoxy group or R ９ -O-R １０ - It is a base, and here, R ９ C １ -C １０ alkyl group, C ６ -C １０ The aryl group, C ７ -C １２ aralkyl group or C ７ -C １２ It is an alkylaryl group, R １０ C １ -C １０ The copolymer according to any one of claims 1 to 5, characterized in that it is an alkylene group and 0 ≤ b ≤ 100.

7. Z is selected from the following structures: Each Z is independently selected from the following structures i-1 to i-6, one or more types: 【Chemistry 54】 Z is preferably, 【Transformation 55】 It is one or more types selected from, Each R is independently C １ -C １０ alkyl group, C ６ -C １０ The aryl group, C ７ -C １２ aralkyl group or C ７ -C １２ Selected from alkylaryl groups, The copolymer according to any one of claims 1 to 6, 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, and each x may be the same or different.

8. Monomer I 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 )(OSii(CH ３ ) ３ ) ２ 、 CH ２ =CHC(O)-O-(CH ２ ) ３ Si(CH) ３ )(OSii(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 )(OSii(CH ３ ) ３ ) ２ 、 CH ２ =CHC(O)-NH-(CH ２ ) ３ Si(CH) ３ )(OSii(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、 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≦25、 CH ２ =C(CH ３ )C(O)-O-(CH ２ ) ３ [Si(CH] ３ ) ２ O]n-Si(CH ３ ) ３ 、1≦n≦25、 CH ２ =CH-ph-Si(OSi(CH) ３ ) ３ ) ３ (phは 【Transformation 56】 (represents) CH ２ =CH-ph-(CH ２ ) ２ Si(OSi(CH ３ ) ３ ) ３ (phは 【Chemistry 57】 (represents) CH ２ =CH-ph-(CH ２ ) ３ [Si(CH ３ ) ２ O]n-Si(CH ３ ) ２ C ４ H ９ (C ４ H ９ represents a butyl group, and pH is 【Chemistry 58】 (representing), 1 ≤ n ≤ 25, CH ２ =CH-O-C(O)-NH-(CH ２ ) ３ Si(OSi(CH) ３ ) ３ ) ３ 、 CH ２ =CH-OC(O)-NH-(CH ２ ) ３ -[Si(CH ３ ) ２ O]n-Si(CH ３ ) ２ C ４ H ９ (C ４ H ９ (where represents a butyl group), 1 ≤ n ≤ 25, CH ２ =CH-O-C(O)-O-(CH ２ ) ３ -Si(OSi(CH ３ ) ３ ) ３ 、 CH ２ =CH-O-C(O)-O-(CH ２ ) ３ -[Si(CH ３ ) ２ O]n-Si(CH ３ ) ２ C ４ H ９ (C ４ H ９ (where represents a butyl group), 1 ≤ n ≤ 25, CH ２ =CH-O-C(O)-O-(CH ２ ) ２ -NHH-(CH ２ ) ３ Si(OSi(CH) ３ ) ３ ) ３ 、 CH ２ =CH-O-C(O)-O-(CH ２ ) ２ -NH-(CH ２ ) ３ [Si(CH ３ ) ２ O]n-Si(CH ３ ) ２ C ４ H ９ (C ４ H ９ (where represents a butyl group), 1 ≤ n ≤ 25, CH ２ =CH-C(O)-N[-(CH ２ ) ３ -Si(OSi(CH ３ ) ３ ) ３ ] ２ 、 CH ２ =CH-C(O)-N[-(CH ２ ) ３ -Si(CH) ３ )(OSii(CH ３ ) ３ ) ２ ] ２ 、 CH ２ =CH-C(O)-N[-(CH ２ ) ３ - (Si(CH ３ ) ２ O) ｎ -Si(CH ３ ) ２ C ４ H ９ ] ２ (C ４ H ９ (where represents a butyl group), 1 ≤ n ≤ 25, CH ２ = C(CH ３ )-C(O)-N[-(CH ２ ) ３ - (Si(CH ３ ) ２ O) ｎ -Si(CH ３ ) ２ C ４ H ９ ] ２ (C ４ H ９ The copolymer according to any one of claims 1 to 7, characterized in that (where represents a butyl group), and 1 ≤ n ≤ 25 is selected from.

9. Monomer II is one or more 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, or methoxypolyethylene glycol (meth)acrylate, and / or Monomer II includes N-vinyl-2-pyrrolidone, N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-3,3-dimethyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-3-ethylpyrrolidone, N-vinyl-4,5-dimethylpyrrolidone, N-vinyl-5,5-dimethylpyrrolidone, N-vinyl-3,3,5-trimethylpyrrolidone, and N-vinyl-5-methylpyrrolidone. N-Vinyl-5-ethylpyrrolidone, N-vinyl-3,4,5-trimethyl-3-ethylpyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-3-ethylpyrrolidone, N-vinyl-4,5-dimethylpyrrolidone, N-vinyl-5,5-dimethylpyrrolidone, N-vinyl-3,3,5-trimethylpyrrolidone, N-vinyl-5-methyl-5-ethylpyrrolidone, N-vinyl-3,4,5-trimethyl-3-ethylpyrrolidone, N-vinyl-2-piperidone, N-vinyl -3-methylpiperidone, N-vinyl-3-methylcaprolactam, N-vinyl-4-methylpiperidone, N-vinyl-4-methylcaprolactam, N-vinyl-4-methylpiperidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-3,5-dimethyl-2-piperidone, N-vinyl-4,4-dimethyl-2-piperidone, N-vinyl-2-caprolactam, N-vinyl-7-methylcaprolactam, N-vinyl-7-ethyl One or more selected from tylcaprolactam, N-vinyl-3,5-dimethylcaprolactam, N-vinyl-4,6-dimethylcaprolactam, N-vinyl-3,5,7-trimethylcaprolactam, N-vinyl-2-valerolactam, N-vinylhexahydro-2-azacycloheptanone, N-vinyloctahydro-2-azacyclooctanone, N-vinyloctahydro-2-azacyclononanone and N-vinyldecahydro-2-azacyclodecanone, and / or Monomer II includes acrylamide, methacrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, N-butylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-isopropylmethacrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, and N-butylmethacrylamide. One or more selected from crylamide, N-(meth)acryloylpyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-(meth)acryloylpyrrole, N-(meth)acryloylpiperidone, N-(meth)acryloylmorpholine, N-(meth)acryloylpiperazine, N-(meth)acryloylaziridine, N-(meth)acryloylazetidine, N-(meth)acryloylazepane, and N-(meth)acryloylazocan, and / or The copolymer according to any one of claims 1 to 8, characterized in that monomer III is selected from (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, vinylbenzenesulfonic acid, acrylamide tert-butylsulfonic acid, or salts thereof.

10. The copolymer and solvent according to any one of claims 1 to 9, wherein the solvent includes water and / or an organic solvent. Preferably, the organic solvent is one or more of the following: 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, in the composition or treatment agent.

11. (1) A step of polymerizing monomers in an organic solvent to obtain a copolymer solution, (2) Optionally, the step of adding water to the copolymer solution to disperse it and then removing the organic solvent, or removing the organic solvent and then adding water to disperse it, (3) A method for preparing the composition or treatment agent according to claim 10, comprising the step of optionally adding a base to the copolymer solution to convert the carboxyl groups or sulfonic acid groups in the copolymer into carboxylate salts or sulfonate salts.

12. Application of a copolymer according to any one of claims 1 to 9, or the composition or treatment agent according to claim 10, or a composition or treatment agent prepared by the method according to claim 11, to textiles, leather, nonwoven fabrics, asbestos, fur, concrete, natural stone, paper products, or plastics.

13. A product which is a textile fabric, leather, nonwoven fabric, asbestos, fur, concrete, natural stone, paper product, or plastic, and a copolymer according to any one of claims 1 to 9, or the composition or treatment agent according to claim 10, or a composition or treatment agent prepared by the method according to claim 11, Preferably, a copolymer according to any one of claims 1 to 9, or the composition or treatment agent according to claim 10, or a composition or treatment agent prepared by the method according to claim 11, is a water-repellent and oil-repellent product that is applied to the surface and / or interior of the product.

14. The method involves contacting a product that is a textile fabric, leather, nonwoven fabric, asbestos, fur, concrete, natural stone, paper product, or plastic with the copolymer described in any one of claims 1 to 9, or the composition described in claim 10 or the treatment agent described in claim 10, or a composition or treatment agent prepared by the method described in claim 11. Preferably, the contact is achieved by a surface sizing process, a surface coating process, a wet end process, or a dipping process, in a method for processing a product.

Images