A water-dispersible fluorine-free copolymer and a treating agent containing the same

Abstract

The present invention relates to a water-dispersible fluorine-free copolymer and a treating agent containing the same. The copolymer contains: a repeating unit formed from a silicon-containing unsaturated monomer (A); a repeating unit formed from a monomer (B); and a repeating unit formed from a monomer (C) having an ionic donor group, and further, the fluorine-free copolymer can contain a repeating unit formed from another monomer (D) having a good adaptability. The fluorine-free copolymer is well dispersed in an aqueous medium; the obtained treating agent has a higher oil resistance temperature and a more stable oil resistance performance; a product produced by the treating agent has a higher hardness; and a molded product does not stick to a mold during a molding production process using the treating agent.

Description

Technical Field

[0001] This invention relates to the field of treatment agents, and more particularly to a water-dispersible fluorine-free copolymer and a treatment agent containing the copolymer. Background Technology

[0002] Polymers are widely used in various products, giving them specific functions. Fluorides, due to their low surface tension, are widely used to impart excellent water and oil repellency to many products. However, fluorinated oil repellents produce perfluorinated and polyfluoroalkyl substances (PFAS) byproducts that are difficult to degrade in the environment. These substances are highly bioaccumulative, toxic, and have long-distance environmental migration capabilities, causing significant impacts on the environment and ecosystem. Wax-based fluorine-free oil repellents are one of the most common types, but they have many limitations in the manufacturing process, including easy clogging during production, easy yellowing of products, generally poor oil repellency, poor stability, and the fact that the processing fluid is weakly acidic, thus also causing some corrosion to equipment.

[0003] Currently, many fields are gradually utilizing novel fluorine-free compounds to replace fluorinated oil-repellent agents. CN113123164A proposes a fluorine-free water and oil repellent agent using edible paraffin wax, stearic acid, gelatin, edible sodium carbonate, carboxymethyl cellulose, and starch as main raw materials, imparting water and oil repellency to food packaging products. CN115058918A proposes a fluorine-free oil repellent agent using acrylic acid, acrylates, and epoxy silane coupling agents as main monomers, thereby imparting oil repellency to pulp molded products. CN115515996A proposes an amide compound modified with long-chain hydrocarbon groups (7-40 carbon atoms) and amide groups on bio-based materials, imparting high-temperature oil resistance to the product. However, the oil repellency performance of these fluorine-free oil repellent agents is not ideal. While existing fluorine-free oil repellent agents with added silicon monomers can improve the oil repellency to some extent, they still suffer from numerous defects such as low product hardness, poor stability of oil repellency, and product sticking to the mold during pulp molding production. Therefore, there is an urgent need to develop new, non-toxic, and environmentally friendly fluorine-free oil repellents that have significant oil-repellent effects and stable oil-repellent performance in order to solve the problems and shortcomings in related oil-repellent fields. Summary of the Invention

[0004] This invention aims to provide a treatment agent comprising a water-dispersible fluorine-free copolymer. This treatment agent is fluorine-free and can impart water and oil resistance to products through internal or external addition. Products made with this treatment agent have numerous significant advantages over existing technologies: ① higher oil resistance temperature, better oil resistance, and more stable oil resistance; ② significantly improved product hardness; ③ non-stick properties during molding processes, etc.

[0005] The present invention also provides a water-dispersible fluorine-free copolymer. The water-dispersible fluorine-free copolymer comprises: repeating units formed by silicon-containing unsaturated monomers (A), repeating units formed by monomers (B), and repeating units formed by monomers (C) having ionic donor groups; it may also comprise repeating units formed by optional other monomers (D) with good compatibility.

[0006] In addition to the water-dispersible fluorine-free copolymer, the treatment agent also contains water and / or an organic solvent, preferably water or a mixture of water and an organic solvent (aqueous medium) as a liquid medium.

[0007] Therefore, the first aspect of the present invention provides a water-dispersible fluorine-free copolymer, as specifically described below.

[0008] [1] A water-dispersible, fluorine-free copolymer, the copolymer comprising:

[0009] Repeating units formed from silicon-containing unsaturated monomers (A);

[0010] Repeating units formed by monomers (B); and

[0011] Repeating units formed by monomers (C) with ionic donor groups,

[0012] Wherein, the monomer (B) is the monomer shown in formula (4):

[0013]

[0014] Wherein, R1 is independently -H, non-fluorinated halogen, or C1~C1. 20 Alkyl groups having a straight-chain or branched structure;

[0015] X' can be a structure represented by -W-, -R0-, -W-R0-, -R0-W-, or -W-R0-W-.

[0016] R0 is -(CH2) n - or C1~C 10 A branched hydrocarbon group, where n is an integer from 0 to 20.

[0017] W is selected from the structures shown in W1 to W4:

[0018] -C(=O)-O- W1

[0019] -C(=O)-N(R2)-W2

[0020] -O- W3

[0021] -O-C(=O)- W4

[0022] R2 is -H or Cl~C 20Alkyl groups;

[0023] Q represents the structure shown in equation (5):

[0024]

[0025] Z5 and / or M are independently -H, -OH, non-fluorinated halogen, C1 to C2, respectively. 10 Alkyl groups, C1-C 10 Monohydric alcohol group, C2-C 10 polyol groups or C1-C 10 The non-fluorinated haloalkyl group, q is an integer from 0 to 10, and

[0026] In the monomer (B), the -Q-M structure contains a non-fluorinated halogen, -OH, C1~C1, and C2. 10 Monohydric alcohol group, C2-C 10 polyol groups, C1-C 10 It has at least two or more groups in the non-fluorinated haloalkyl group.

[0027] [2] Further, in the water-dispersible fluorine-free copolymer as described above, in the monomer (B), Q is selected from one or more of the following structures Q-1 to Q-18:

[0028]

[0029] Where q is an integer from 0 to 10,

[0030] R7 is independently -H, C1 to C1, respectively. 10 Alkyl or C1-C 10 chloroalkyl groups,

[0031] Each C x H 2x+1-y (OH) y Whether they are the same or different, x is an integer from 1 to 10, y is an integer from 1 to 10, and they belong to the same group C. x H 2x+1-y (OH) y In the case of y ≤ x.

[0032] [3] Furthermore, in the water-dispersible fluorine-free copolymer described above, the monomer (A) is the monomer shown in formula (1):

[0033]

[0034] Wherein, R1 is independently -H, non-fluorinated halogen, or C1~C1. 20 Alkyl groups having a straight-chain or branched structure;

[0035] X is -C6H4-, -R0-, -W-, -W-C6H4-, -R0-C6H4-, -C6H4-R0-, -C6H4-W-, -W-R0-, -R0-W-, -R0-W-R0-, -C6H4-W-C6H4-, -R0-W-C6H4-, -C6H4-W-R0-, -W-R0-C6H4-, -W-C6H4-R0 The groups shown are: -C6H4-R0-W-, -R0-C6H4-W-, -R0-C6H4-R0-, -W-R0-C6H4-R0-, -R0-C6H4-R0-W-, -C6H4-R0-W-R0-, -R0-C6H4-W-R0-, -R0-W-R0-C6H4-R0-, or -R0-C6H4-R0-W-R0-.

[0036] -C6H4- is a phenylene group.

[0037] R0 is independently -(CH2). n - or C1~C 10 A branched hydrocarbon group, where n is an integer from 0 to 20.

[0038] W is selected from the structures shown in W1 to W4:

[0039] -C(=O)-O- W1

[0040] -C(=O)-N(R2)-W2

[0041] -O- W3

[0042] -O-C(=O)- W4

[0043] R2 is -H or Cl~C 20 alkyl groups,

[0044] Y represents the structure shown in equation (2):

[0045]

[0046] R3 is independently C1 to C1. 10 Alkyl groups, C6-C 20 aryl or C7~C 20 The aralkyl group, Z1 and Z2 are independently C1 to C2. 10 Alkyl groups, C6-C 20 aryl, C7~C 20 Aryl groups or structures as shown in formula (3), where m is 1 to 300.

[0047]

[0048] R4 is independently C1 to C1.10 Alkyl groups, C6-C 20 aryl or C7~C 20 The aralkyl group, Z3 and Z4 are independently C1 to C4. 10 Alkyl groups, C6-C 20 aryl or C7~C 20 Aryl groups, k is 0 to 300.

[0049] [4] Furthermore, in the water-dispersible non-fluorinated copolymers described above, in the monomer (A), R1 is independently -H, non-fluorinated halogen, or C1~C1. 10 Alkyl groups having straight-chain or branched structures

[0050] X is a group represented by -R0-, -W-, -C6H4-W-, -R0-W-, -W-R0-, -R0-W-R0-, -C6H4-R0-W-R0-, or -R0-C6H4-W-R0-, where R0 is independently -(CH2). n - or C1~C 10 A branched hydrocarbon group, where n is an integer from 0 to 10.

[0051] In Y, R3 and / or R4 are independently C1–C5 alkyl groups, C6–C4 alkyl groups, respectively. 10 aryl or C7~C 12 Aryl group; Z3 and / or Z4 are independently C1-C5 alkyl groups, C6-C4 alkyl groups, respectively. 10 aryl or C7~C 12 Aryl groups, m is 1 to 50, k is 0 to 50.

[0052] [5] Further, in the water-dispersible fluorine-free copolymer as described above, in the monomer (A), Y is selected from one or more of the following structures Y-1 to Y-3:

[0053]

[0054] R is independently a C1–C5 alkyl group, a C6–C5 alkyl group, or a C6–C5 alkyl group. 10 aryl or C7~C 12 The aralkyl group has m ranging from 1 to 35, and k1 and k2 are independently ranging from 0 to 35.

[0055] [6] Furthermore, in the water-dispersible fluorine-free copolymer described above, the ionic donor group in the monomer (C) is a cationic donor group.

[0056] [7] Furthermore, in the water-dispersible fluorine-free copolymer as described above, the cationic donor group in the monomer (C) is an amino group.

[0057] [8] Furthermore, in the water-dispersible fluorine-free copolymer described above, the monomer (C) is the monomer shown in formula (6):

[0058]

[0059] Wherein, R1 is independently -H, non-fluorinated halogen, or C1~C1. 20 Alkyl groups having a straight-chain or branched structure;

[0060] X' can be a structure represented by -W-, -R0-, -W-R0-, -R0-W-, or -W-R0-W-.

[0061] R0 is -(CH2) n - or C1~C 10 A branched hydrocarbon group, where n is an integer from 0 to 20.

[0062] W is selected from the structures shown in W1 to W4:

[0063] -C(=O)-O- W1

[0064] -C(=O)-N(R2)-W2

[0065] -O- W3

[0066] -O-C(=O)- W4

[0067] R2 is -H or Cl~C 20 Alkyl groups;

[0068] R5 and R6 are independently C1 to C1 respectively. 10 Alkyl groups, C6-C 20 aryl or C7~C 25 Aryl groups.

[0069] [9] Furthermore, in the water-dispersible fluorine-free copolymer as described above, R5 and R6 in the monomer (C) are each independently benzyl.

[0070]

[10] Furthermore, in the water-dispersible non-fluorinated copolymers described above,

[0071] The weight ratio of repeating units formed by monomer (A) to the copolymer is 40-90%;

[0072] The weight ratio of repeating units formed by monomer (B) to the copolymer is 0.1 to 25%;

[0073] The weight ratio of repeating units formed by monomer (C) to the copolymer is 5-40%.

[0074]

[11] Furthermore, in the water-dispersible non-fluorinated copolymers described above,

[0075] The weight ratio of repeating units formed by monomer (A) to the copolymer is 45-85%;

[0076] The weight ratio of repeating units formed by monomer (B) to the copolymer is 0.1% to 22%;

[0077] The weight ratio of repeating units formed by monomer (C) to the copolymer is 10-35%.

[0078]

[12] Furthermore, in the water-dispersible fluorine-free copolymers described above,

[0079] The weight ratio of repeating units formed by monomer (A) to the copolymer is 50-85%;

[0080] The weight ratio of repeating units formed by monomer (B) to the copolymer is 0.1 to 20%;

[0081] The weight ratio of repeating units formed by monomer (C) to the copolymer is 15-35%.

[0082]

[13] Furthermore, in the water-dispersible fluorine-free copolymers described above, the copolymer further comprises repeating units formed from optional monomers (D).

[0083] The optional monomer (D) includes:

[0084] Monomers having a pyrrolidone structure and polymerizable unsaturated groups; and / or

[0085] Monomers having terminal isocyanate groups and polymerizable unsaturated groups; and / or

[0086] Monomers having alkoxysilyl groups and polymerizable unsaturated groups; and / or

[0087] Monomers containing glycidyl groups and polymerizable unsaturated groups.

[0088]

[14] Furthermore, in the water-dispersible non-fluorinated copolymers described above,

[0089] The weight ratio of repeating units formed by monomer (A) to the copolymer is 40-90%;

[0090] The weight ratio of repeating units formed by monomer (B) to the copolymer is 0.1 to 25%;

[0091] The repeating units formed by monomer (C) account for 5-40% by weight of the copolymer; and

[0092] The repeating units formed from an optional monomer (D) are 0 to 10% by weight relative to the copolymer.

[0093]

[15] Furthermore, in the water-dispersible non-fluorinated copolymers described above,

[0094] The weight ratio of repeating units formed by monomer (A) to the copolymer is 45-85%;

[0095] The weight ratio of repeating units formed by monomer (B) to the copolymer is 0.1% to 22%;

[0096] The repeating units formed by monomer (C) account for 10-35% by weight of the copolymer; and

[0097] The repeating units formed from an optional monomer (D) are in a weight ratio of 0 to 8% relative to the copolymer.

[0098]

[16] Furthermore, in the water-dispersible non-fluorinated copolymers described above,

[0099] The monomer (B) is selected from one or more of the following:

[0100] CH2=C(CH3)-C(=O)-NH-CH2CH2Cl

[0101] CH2=C(CH3)-COO-CH2CH(OH)CH2Cl

[0102] CH2=C(CH3)-COO-CH2CH(OH)CH2OH

[0103] CH2=C(CH3)-C(=O)-NH-CH2CH(OH)CH2OH

[0104] CH2=C(CH3)-COO-CH2-CH(OH)CH(OH)CH2OH

[0105] CH2=C(CH3)-COO-CH2-CH(OH)CH(OH)CH(OH)CH2OH

[0106] CH2=C(CH3)-COO-CH2-CH(OH)CH(OH)CH(OH)CH(OH)CH2OH

[0107] CH2=C(CH3)-O-CH2CH(OH)CH(OH)CH(OH)CH(OH)CH2OH

[0108] CH2=C(CH3)-CH2-O-CH2CH(OH)CH(OH)CH(OH)CH(OH)CH2OH

[0109] CH2=C(CH3)-O-C(=O)-CH(OH)CH2Cl

[0110] CH2=CH-CH(OH)CH2OH

[0111] CH2=CH-CH2CH(OH)CH2OH

[0112] CH2=CH-C(=O)-O-CH2-C(=O)-O-CH2CH(OH)CH(OH)CH(OH)CH(OH)CH2OH

[0113] CH2=CHCOO-[C(C x H 2x+1-y (OH) y )2-C(R7)2] q -M

[0114] CH2=C(CH3)COO-[C(C x H 2x+1-y (OH) y )2-C(R7)2] q -M

[0115] CH2=CH-C(=O)-NH-[C(C x H 2x+1-y (OH) y )2-C(R7)2] q -M

[0116] CH2=C(CH3)-C(=O)-NH-[C(C x H 2x+1-y (OH) y )2-C(R7)2] q -M

[0117] CH2=CHCOO-[C(R7)2-C(C x H 2x+1-y (OH) y )2] q -M

[0118] CH2=C(CH3)COO-[C(R7)2-C(C x H 2x+1-y (OH) y )2] q -M

[0119] CH2=CH-C(=O)-NH-[C(R7)2-C(C x H 2x+1-y (OH)y )2] q -M

[0120] CH2=C(CH3)-C(=O)-NH-[C(R7)2-C(C x H 2x+1-y (OH) y )2] q -M

[0121] CH2=CHCOO-[C(R7)(C x H 2x+1-y (OH) y )-C(R7)(C x H 2x+1-y (OH) y )] q -M

[0122] CH2=C(CH3)COO-[C(R7)(C x H 2x+1-y (OH) y )-C(R7)(C x H 2x+1-y (OH) y )] q -M

[0123] CH2=CH-C(=O)-NH-[C(R7)(C x H 2x+1-y (OH) y )-C(R7)(C x H 2x+1-y (OH) y )] q -M

[0124] CH2=C(CH3)-C(=O)-NH-[C(R7)(C x H 2x+1-y (OH) y )-C(R7)(C x H 2x+1-y (OH) y )] q -M

[0125] CH2=CHCOO-[C(R7)(C x H 2x+1-y (OH) y )-C(C x H 2x+1-y (OH) y )2] q -M

[0126] CH2=C(CH3)COO-[C(R7)(C x H 2x+1-y (OH) y )-C(C x H 2x+1-y (OH) y )2] q -M

[0127] CH2=CH-C(=O)-NH-[C(R7)(C x H 2x+1-y (OH) y )-C(C x H 2x+1-y (OH) y )2] q -M

[0128] CH2=C(CH3)-C(=O)-NH-[C(R7)(C x H 2x+1-y (OH) y )-C(C x H 2x+1-y (OH) y )2] q -M

[0129] CH2=CHCOO-[C(C x H 2x+1-y (OH) y )2-C(R7)(C x H 2x+1-y (OH) y )] q -M

[0130] CH2=C(CH3)COO-[C(C x H 2x+1-y (OH) y )2-C(R7)(C x H 2x+1-y (OH) y )] q -M

[0131] CH2=CH-C(=O)-NH-[C(C x H 2x+1-y (OH) y )2-C(R7)(C x H 2x+1-y (OH) y )] q -M

[0132] CH2=C(CH3)-C(=O)-NH-[C(C x H2x+1-y (OH) y )2-C(R7)(C x H 2x+1-y (OH) y )] q -M

[0133] CH2=CHCOO-[C(C x H 2x+1-y (OH) y )2-C(C x H 2x+1-y (OH) y )2] q -M

[0134] CH2=C(CH3)COO-[C(C x H 2x+1-y (OH) y )2-C(C x H 2x+1-y (OH) y )2] q -M

[0135] CH2=CH-C(=O)-NH-[C(C x H 2x+1-y (OH) y )2-C(C x H 2x+1-y (OH) y )2] q -M

[0136] CH2=C(CH3)-C(=O)-NH-[C(C x H 2x+1-y (OH) y )2-C(C x H 2x+1-y (OH) y )2] q -M

[0137] Where q is an integer from 0 to 10,

[0138] R7 is independently -H, C1 to C1, respectively. 10 Alkyl groups, C1-C 10 chloroalkyl groups,

[0139] Each C x H 2x+1-y (OH) y Whether they are the same or different, x is an integer from 1 to 10, y is an integer from 1 to 10, and they belong to the same group C. x H 2x+1-y (OH) yIn the case of y≤x,

[0140] M is a -H, -Cl, -OH, a C1-C6 monohydric alcohol group or a C2-C6 polyhydric alcohol group.

[0141]

[17] Furthermore, in the water-dispersible non-fluorinated copolymers described above,

[0142] The monomer (A) is selected from one or more of the following:

[0143] CH2=C(CH3)COO-(CH2)3Si(OSi(CH3)3)3

[0144] CH2=CHCOO-(CH2)3Si(OSi(CH3)3)3

[0145] CH2=C(CH3)COO-(CH2)3Si[OSi(OSi(CH3)3)3]2(OSi(CH3)3)

[0146] CH2=CHCOO-(CH2)3Si[OSi(OSi(CH3)3)3]2(OSi(CH3)3)

[0147] CH2=C(CH3)COO-(CH2) n Si(R)2[O(Si(R)2O) k Si(R)3]

[0148] CH2=CHCOO-(CH2) n Si(R)2[O(Si(R)2O) k Si(R)3]

[0149] CH2=C(CH3)COO-(CH2) n Si[O(Si(R)2O) k Si(R)3]2(OSi(R)3)

[0150] CH2=CHCOO-(CH2) n Si[O(Si(R)2O) k Si(R)3]2(OSi(R)3)

[0151] CH2=C(CH3)-C(=O)-NH-(CH2) n Si(R)2[O(Si(R)2O) k Si(R)3]

[0152] CH2=CH-C(=O)-NH-(CH2) n Si(R)2[O(Si(R)2O)k Si(R)3]

[0153] CH2=C(CH3)-C(=O)-NH-(CH2) n Si[O(Si(R)2O) k Si(R)3]2(OSi(R)3)

[0154] CH2=CH-C(=O)-NH-(CH2) n Si[O(Si(R)2O) k Si(R)3]2(OSi(R)3)

[0155] Where n are independent integers from 0 to 10.

[0156] k can be independently set to 0–35.

[0157] R is independently C1 to C1. 10 Alkyl groups, C6-C 20 aryl or C7~C 20 Aryl groups.

[0158]

[18] Furthermore, in the water-dispersible non-fluorinated copolymers described above,

[0159] The monomer (C) is selected from one or more of the following:

[0160] CH2=CHCOO-CH2CH2-N(CH3)2 and / or its salts,

[0161] CH2=CHCOO-CH2CH2-N(CH2CH3)2 and / or its salts,

[0162] CH2=C(CH3)COO-CH2CH2-N(CH3)2 and / or its salts,

[0163] CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and / or its salts,

[0164] CH2=CH-C(=O)-NH-CH2CH2-N(CH3)2 and / or its salts,

[0165] CH2=CH-C(=O)-NH-CH2CH2-N(CH2CH3)2 and / or its salts,

[0166] CH2=C(CH3)-C(=O)-NH-CH2CH2-N(CH3)2 and / or its salts, and

[0167] CH2=C(CH3)-C(=O)-NH-CH2CH2-N(CH2CH3)2 and / or its salts.

[0168] A second aspect of the present invention provides a treatment agent comprising a water-dispersible fluorine-free copolymer, as described below.

[0169]

[19] A treatment agent comprising a water-dispersible fluorine-free copolymer, wherein the water-dispersible fluorine-free copolymer is a water-dispersible fluorine-free copolymer according to any one of [1]-

[18] above;

[0170] The treatment agent also comprises a liquid medium of water, an organic solvent, or a mixture of water and an organic solvent.

[0171] A third aspect of the present invention provides a method for preparing a treatment agent comprising a water-dispersible fluorine-free copolymer, as detailed below.

[0172]

[20] The method for preparing the treatment agent comprising the water-dispersible fluorine-free copolymer as described in

[19] includes the following steps:

[0173] (1) The monomer, organic solvent and initiator are copolymerized in a reactor to obtain a polymer solution;

[0174] (2) Add an acid solution to the polymer solution for dispersion treatment;

[0175] (3) The organic solvent is removed from the polymer solution after dispersion treatment to obtain an aqueous dispersion.

[0176] (4) The amino group in the aqueous dispersion is converted into a nitrogen oxide compound to obtain the treatment agent containing the water-dispersible fluorine-free copolymer.

[0177]

[21] Furthermore, in the preparation method described above, in step (4), the amino group is converted into a nitrogen oxide compound by adding hydrogen peroxide solution to the aqueous dispersion.

[0178] A fourth aspect of the present invention provides the use of a treatment agent comprising a water-dispersible fluorine-free copolymer, as detailed below.

[0179]

[22] The application of the treatment agent containing the water-dispersible fluorine-free copolymer as described in

[19] , wherein the product is treated by internal or external addition of the treatment agent to give the product water and oil resistance; the product includes paper products, plastics, fiber fabrics, fur, leather and / or non-woven fabrics.

[0180]

[23] Furthermore, in the applications described above, the paper products are processed and used as food packaging materials or food containers.

[0181] Beneficial effects of the invention

[0182] The fluorine-free copolymer contained in the treatment agent of the present invention can be well dispersed in an aqueous medium, thereby obtaining a treatment agent with good copolymer dispersion, which is beneficial to the preparation of the treatment agent and the processing of products.

[0183] The resulting treatment agent has a higher oil resistance temperature and more stable oil resistance.

[0184] The product obtained by the treatment agent has higher hardness and can better meet product requirements.

[0185] During the molding process using the aforementioned treatment agent, the molded product does not stick to the mold. Detailed Implementation

[0186] To better understand the above technical solutions, exemplary embodiments of the present invention will be described in more detail below.

[0187] The water-dispersible fluorine-free copolymer of the present invention comprises:

[0188] Repeating units formed from silicon-containing unsaturated monomers (A);

[0189] Repeating units formed by monomers (B); and

[0190] Repeating units formed by monomers (C).

[0191] In one embodiment, the monomer (C) has an ionic donor group.

[0192] In addition, the fluorine-free copolymer may also contain repeating units formed from other monomers (D) with good compatibility.

[0193] (A) Silicon-containing unsaturated monomers

[0194] The silicon-containing unsaturated monomer (A) is the monomer shown in formula (1).

[0195]

[0196] In this context, R1 may be different or the same, and can be independently a -H, a non-fluorinated halogen atom, or a monovalent organic group. The monovalent organic group mentioned here can be, for example, C1 to C1. 20 Alkyl groups having a straight-chain or branched structure.

[0197] X is -C6H4-, -R0-, -W-, -W-C6H4-, -R0-C6H4-, -C6H4-R0-, -C6H4-W-, -W-R0-, -R0-W-, -R0-W-R0-, -C6H4-W-C6H4-, -R0-W-C6H4-, -C6H4-W-R0-, -W-R0-C6H4-, -W-C6H4-R0 -, -C6H4-R0-W-, -R0-C6H4-W-, -R0-C6H4-R0-, -W-R0-C6H4-R0-, -R0-C6H4-R0-W-, -C6H4-R0-W-R0-, -R0-C6H4-W-R0-, -R0-W-R0-C6H4-R0- or -R0-C6H4-R0-W-R0- are the groups shown.

[0198] -C6H4- is a phenylene oxide.

[0199] X is preferably a group represented by -R0-, -W-, -C6H4-W-, -R0-W-, -W-R0-, -R0-W-R0-, -C6H4-R0-W-R0-, or -R0-C6H4-W-R0-.

[0200] R0 may be the same or different, and each is independently -(CH2). n - or C1~C 10 Hydroxyl groups with branched structures

[0201] n is an integer from 0 to 20, preferably an integer from 0 to 10.

[0202] W is selected from the structures shown in W1 to W4:

[0203] -C(=O)-O- W1

[0204] -C(=O)-N(R2)-W2

[0205] -O- W3

[0206] -O-C(=O)- W4

[0207] R2 is -H or Cl~C 20 Alkyl groups.

[0208] R1 can be independently -H, non-fluorinated halogen, or C1~C1. 20 An alkyl group having a straight-chain or branched structure. R1 may be the same or different, and may be -H, methyl, halogen other than fluorine, substituted or unsubstituted benzyl. Examples of R1 are hydrogen, methyl, chlorine, bromine, and iodine. R1 is preferably hydrogen, methyl, or chlorine. R1 is particularly preferably methyl.

[0209] R2 can be hydrogen, methyl, substituted or unsubstituted benzyl. R2 is preferably hydrogen or methyl. R2 is particularly preferably methyl.

[0210] Y is selected from the structure shown in equation (2):

[0211]

[0212] R3 is independently C1 to C1. 10 Alkyl groups, C6-C 20 aryl or C7~C 20 Aryl groups, preferably C1-C5 alkyl groups, C6-C5 alkyl groups. 10 aryl, C7~C 10 Aryl groups. Z1 and Z2 are independently C1 to C2. 10 Alkyl groups, C6-C 20 aryl, C7~C 20 Aryl groups or the following formula (3):

[0213]

[0214] R4 is independently C1 to C1. 10 Alkyl groups, C6-C 20 aryl or C7~C 20 Aryl groups, preferably C1-C5 alkyl groups, C6-C5 alkyl groups. 10 aryl, C7~C 10 Aryl groups. Z3 and Z4 are independently C1 to C4. 10 Alkyl groups, C6-C 20 aryl or C7~C 20 Aryl groups, preferably C1-C5 alkyl groups, C6-C5 alkyl groups. 10 aryl, C7~C 10 Aryl groups.

[0215] k is 0 to 300, for example 0 to 150, preferably 0 to 50, and particularly preferably 0 to 35.

[0216] m is 1 to 300, for example 1 to 150, preferably 1 to 50, and particularly preferably 1 to 35.

[0217] The specific structure of Y is selected from one or more of Y-1 to Y-3:

[0218]

[0219] R is independently a C1–C5 alkyl group, a C6–C5 alkyl group, or a C6–C5 alkyl group. 10 aryl or C7~C 12 Aryl alkyl group. m is 1 to 150, preferably 1 to 50, and particularly preferably 1 to 35.

[0220] k1 and k2 are each independently 0 to 50, preferably 0 to 35.

[0221] Specific examples of silicon-containing unsaturated monomers (A) are listed below, but are not limited to these.

[0222] CH2=C(CH3)COO-(CH2)3Si(OSi(CH3)3)3

[0223] CH2=CHCOO-(CH2)3Si(OSi(CH3)3)3

[0224] CH2=C(CH3)COO-(CH2)3Si(CH3)(OSi(CH3)3)2

[0225] CH2=CHCOO-(CH2)3Si(CH3)(OSi(CH3)3)2

[0226] CH2=C(CH3)COO-(CH2)3Si(CH3)2(OSi(CH3)3)

[0227] CH2=CHCOO-(CH2)3Si(CH3)2(OSi(CH3)3)

[0228] CH2=C(CH3)COO-(CH2)3Si(OSi(CH2CH3)3)3

[0229] CH2=CHCOO-(CH2)3Si(OSi(CH2CH3)3)3

[0230] CH2=C(CH3)COO-(CH2)3Si(CH2CH3)(OSi(CH2CH3)3)2

[0231] CH2=CHCOO-(CH2)3Si(CH2CH3)(OSi(CH2CH3)3)2

[0232] CH2=C(CH3)COO-(CH2)3Si(CH2CH3)2(OSi(CH2CH3)3)

[0233] CH2=CHCOO-(CH2)3Si(CH2CH3)2(OSi(CH2CH3)3)

[0234] CH2=C(CH3)COO-(CH2)3Si(OSi(CH2-Ph)3)3

[0235] CH2=CHCOO-(CH2)3Si(OSi(CH2-Ph)3)3

[0236] CH2=C(CH3)COO-(CH2)3Si(CH3)(OSi(CH2-Ph)3)2

[0237] CH2=CHCOO-(CH2)3Si(CH3)(OSi(CH2-Ph)3)2

[0238] CH2=C(CH3)COO-(CH2)3Si(CH3)2(OSi(CH2-Ph)3)

[0239] CH2=CHCOO-(CH2)3Si(CH3)2(OSi(CH2-Ph)3)

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

[0241] CH2=CH-C(=O)-NH-(CH2)3Si(OSi(CH3)3)3

[0242] CH2=C(CH3)-C(=O)-NH-(CH2)3Si(CH3)(OSi(CH3)3)2

[0243] CH2=CH-C(=O)-NH-(CH2)3Si(CH3)(OSi(CH3)3)2

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

[0245] CH2=CH-C(=O)-NH-(CH2)3Si(CH3)2(OSi(CH3)3)

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

[0247] CH2=CH-C(=O)-NH-(CH2)3Si(OSi(CH2CH3)3)3

[0248] CH2=C(CH3)-C(=O)-NH-(CH2)3Si(CH2CH3)(OSi(CH2CH3)3)2

[0249] CH2=CH-C(=O)-NH-(CH2)3Si(CH2CH3)(OSi(CH2CH3)3)2

[0250] CH2=C(CH3)-C(=O)-NH-(CH2)3Si(CH2CH3)2(OSi(CH2CH3)3)

[0251] CH2=CH-C(=O)-NH-(CH2)3Si(CH2CH3)2(OSi(CH2CH3)3)

[0252] CH2=C(CH3)-C(=O)-NH-(CH2)3Si(OSi(CH2-Ph)3)3

[0253] CH2=CH-C(=O)-NH-(CH2)3Si(OSi(CH2-Ph)3)3

[0254] CH2=C(CH3)-C(=O)-NH-(CH2)3Si(CH3)(OSi(CH2-Ph)3)2

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

[0256] CH2=C(CH3)-C(=O)-NH-(CH2)3Si(CH3)2(OSi(CH2-Ph)3)

[0257] CH2=CH-C(=O)-NH-(CH2)3Si(CH3)2(OSi(CH2-Ph)3)

[0258] CH2=C(CH3)COO-(CH2) n Si(R)2[O(Si(R)2O) k Si(R)3]

[0259] CH2=CHCOO-(CH2) n Si(R)2[O(Si(R)2O) k Si(R)3]

[0260] CH2=C(CH3)COO-(CH2) n Si[O(Si(R)2O) k Si(R)3]2(OSi(R)3)

[0261] CH2=CHCOO-(CH2) n Si[O(Si(R)2O) k Si(R)3]2(OSi(R)3)

[0262] CH2=C(CH3)-C(=O)-NH-(CH2) nSi(R)2[O(Si(R)2O) k Si(R)3]

[0263] CH2=CH-C(=O)-NH-(CH2) n Si(R)2[O(Si(R)2O) k Si(R)3]

[0264] CH2=C(CH3)-C(=O)-NH-(CH2) n Si[O(Si(R)2O) k Si(R)3]2(OSi(R)3)

[0265] CH2=CH-C(=O)-NH-(CH2) n Si[O(Si(R)2O) k Si(R)3]2(OSi(R)3)

[0266] In the formula, Ph is an abbreviation for phenyl, and n is an integer from 0 to 10.

[0267] R is independently C1 to C1. 10 Alkyl groups, C6-C 20 aryl or C7~C 20 Aryl groups, preferably C1-C5 alkyl groups, C6-C5 alkyl groups. 10 aryl, C7~C 10 Aryl groups, particularly preferably C1-C5 alkyl groups, C7-C6 alkyl groups. 10 Aryl groups.

[0268] k is independently 0 to 35, preferably 0 to 15.

[0269] As monomer (A), acryloyloxypropyltris(trimethylsiloxane), methacryloxypropyltris(trimethylsiloxane), acryloyloxypropyltris(triethylsiloxane), methacryloxypropyltris(triethylsiloxane), acrylamidopropyltris(trimethylsiloxane), methacrylamidopropyltris(trimethylsiloxane), acrylamidopropyltris(triethylsiloxane), methacrylamidopropyltris(triethylsiloxane), methacrylamidopropyltris(triethylsiloxane), and methacrylamidopropyltris(triethylsiloxane) are preferred, and mixtures thereof are also preferred.

[0270] (B) Crosslinking monomers

[0271] Monomer (B) is a monomer other than monomer (A) and is a cross-linking monomer.

[0272] The monomer (B) contained herein is the monomer shown in formula (4):

[0273]

[0274] R1 may be the same or different, and can be independently -H, non-fluorinated halogen, or monovalent organic groups. The monovalent organic groups mentioned here can be, for example, C1 to C1. 20 Alkyl groups having a straight-chain or branched structure.

[0275] X' can be a structure represented by -W-, -R0-, -W-R0-, -R0-W-, or -W-R0-W-, preferably -W-R0-.

[0276] R0 is -(CH2) n - or C1~C 10 The subhydrocarbon group has a branched structure, where n is an integer from 0 to 20, preferably an integer from 0 to 10.

[0277] W is selected from the structures shown in W1 to W4:

[0278] -C(=O)-O- W1

[0279] -C(=O)-N(R2)-W2

[0280] -O- W3

[0281] -O-C(=O)- W4

[0282] R2 is -H or Cl~C 20 Alkyl groups.

[0283] R1 can be hydrogen, methyl, halogen other than fluorine, substituted or unsubstituted benzyl. Examples of R1 are hydrogen, methyl, chlorine, bromine, and iodine. R1 is preferably hydrogen, methyl, or chlorine. R1 is particularly preferably methyl.

[0284] R2 can be hydrogen, methyl, substituted or unsubstituted benzyl. R2 is preferably a hydrogen atom or a methyl group. R2 is particularly preferably methyl.

[0285] Q is selected from the structure shown in equation (5):

[0286]

[0287] Z5 can be independently -H, non-fluorinated halogen, -OH, or Cl~C. 10 Alkyl groups, C1-C 10 Monohydric alcohol group, C2-C 10 polyol groups, C1-C 10The non-fluorinated haloalkyl group is preferably -H, -OH, a monohydric alcohol group of C1 to C6, or a polyhydric alcohol group of C2 to C6.

[0288] M can be independently -H, non-fluorinated halogen, -OH, or Cl~C 10 Alkyl groups, C1-C 10 Monohydric alcohol group, C2-C 10 polyol groups, C1-C 10 The non-fluorinated haloalkyl group is preferably a -H, -Cl, -OH, or a C2 to C6 polyol group.

[0289] q is an integer from 0 to 20, preferably an integer from 0 to 10.

[0290] In the crosslinking monomer (B), the -Q-M structure contains a non-fluorinated halogen, -OH, C1~C1, and C2. 10 Monohydric alcohol group, C2-C 10 polyol groups, C1-C 10 It has at least two or more groups in the non-fluorinated haloalkyl group, where q is an integer from 0 to 10.

[0291] For the overall structure formed by structure Q and M in the crosslinking monomer (B), C1 to C1 are preferred. 10 Monohydric alcohol group or C2-C 10 Polyol groups and sugar alcohol groups.

[0292] The general formula of the monohydric alcohol group referred to in this invention is as follows:

[0293] -C x H 2x (OH)(10≥x≥1)

[0294] The general formula of the polyol group referred to in this invention is as follows:

[0295] -C x H 2x+1-y (OH) y (10≥x≥y≥2)

[0296] In this invention, a monohydric alcohol refers to an alcohol containing only one hydroxyl group in its molecule, a polyhydric alcohol refers to an alcohol containing two or more hydroxyl groups in its molecule, and a sugar alcohol refers to a polyhydric alcohol obtained by reducing aldoses or ketoses to have the same number of carbon atoms and hydroxyl groups (i.e., x = y).

[0297] The sugar alcohol groups in this invention have the following general formulas:

[0298] -C x H x+1 (OH) x (10≥x≥2)

[0299] In the formula, x can be 3, 4, 5, 6, 7, 8, 9, or 10 (which can be called triitol, butylitol, pentitol, hexitol, heptitol, octitol, nonitol, or decitol). Among these sugar alcohols, there may be a large number of stereoisomers corresponding to the number of asymmetric carbon atoms.

[0300] In this invention, it is preferred to use a chain sugar alcohol group with 3 to 6 carbon atoms. Specific examples of sugar alcohols include sorbitol, mannitol, galactitol, xylitol, erythritol, and glycerol.

[0301] Q is selected from one or more of the following structures Q-1 to Q-18:

[0302]

[0303] R7 is independently -H, C1 to C1 in Q-1 to Q-18, respectively. 10 Alkyl groups, C1-C 10 Chloroalkyl groups.

[0304] C in the same Q formula and / or between different Q formulas x H 2x+1-y (OH) y Whether they are the same or different, x is an integer from 1 to 10, preferably an integer from 1 to 5. y is an integer from 1 to 10, preferably an integer from 1 to 5. Meanwhile, any one of C in Q... x H 2x+1-y (OH) y The y-value in the expression is less than or equal to the x-value, i.e., y ≤ x. q is an integer from 0 to 10, preferably an integer from 0 to 5.

[0305] Specific examples of monomer (B) are listed below, but are not limited to these.

[0306] CH2=C(CH3)COO-CH2CH(OH)CH2Cl

[0307] CH2=CHCOO-CH2CHClCH2(OH)

[0308] CH2=C(CH3)COO-CH2CHClCH2(OH)

[0309] CH2=CHCOO-CH2CHCl2

[0310] CH2=C(CH3)COO-CH2CHCl2

[0311] CH2=CHCOO-CH2CHCl-CH2Cl

[0312] CH2=C(CH3)COO-CHCl-CH2Cl

[0313] CH2=CHCOO-CH2CH(OH)-CH2(OH)

[0314] CH2=C(CH3)COO-CH2CH(OH)-CH2(OH)

[0315] CH2=CHCOO-CH2CH(OH)CHCl-CH3

[0316] CH2=C(CH3)COO-CH2CH(OH)CHCl-CH3

[0317] CH2=CHCOO-CH2CHClCH(OH)-CH3

[0318] CH2=C(CH3)COO-CH2CHClCH(OH)-CH3

[0319] CH2=CHCOO-CH2CHCl-CHCl-CH3

[0320] CH2=C(CH3)COO-CH2CHCl-CHCl-CH3

[0321] CH2=CHCOO-CH2CH(OH)-CH(OH)-CH3

[0322] CH2=C(CH3)COO-CH2CH(OH)-CH(OH)-CH3

[0323] CH2=CHCOO-CH2CHClCH2-CH2OH

[0324] CH2=C(CH3)COO-CH2CHClCH2-CH2OH

[0325] CH2=CHCOO-CH2CHCl-CH2OH

[0326] CH2=C(CH3)COO-CH2CHCl-CH2OH

[0327] CH2=CHCOO-CH2CH(OH)CH2-CH2OH

[0328] CH2=C(CH3)COO-CH2CH(OH)CH2-CH2OH

[0329] CH2=CHCOO-CH2CH2CH(OH)-CH2OH

[0330] CH2=C(CH3)COO-CH2CH2CH(OH)-CH2OH

[0331] CH2=CHCOO-CH2CH(OH)CHCl-CH2OH

[0332] CH2=C(CH3)COO-CH2CH(OH)CHCl-CH2OH

[0333] CH2=CHCOO-CH2CHClCH(OH)-CH2OH

[0334] CH2=C(CH3)COO-CH2CHClCH(OH)-CH2OH

[0335] CH2=CHCOO-CH2CHCl-CHCl-CH2OH

[0336] CH2=C(CH3)COO-CH2CHCl-CHCl-CH2OH

[0337] CH2=CHCOO-CH2CH(OH)-CH(OH)-CH2OH

[0338] CH2=C(CH3)COO-CH2CH(OH)-CH(OH)-CH2OH

[0339] CH2=CHCOO-CH2CHClCH2-CH2Cl

[0340] CH2=C(CH3)COO-CH2CHClCH2-CH2Cl

[0341] CH2=CHCOO-CH2CH2CHCl-CH2Cl

[0342] CH2=C(CH3)COO-CH2CH2CHCl-CH2Cl

[0343] CH2=CHCOO-CH2CH(OH)CH2-CH2Cl

[0344] CH2=C(CH3)COO-CH2CH(OH)CH2-CH2Cl

[0345] CH2=CHCOO-CH2CH2CH(OH)-CH2Cl

[0346] CH2=C(CH3)COO-CH2CH2CH(OH)-CH2Cl

[0347] CH2=CHCOO-CH2CH(OH)CHCl-CH2Cl

[0348] CH2=C(CH3)COO-CH2CH(OH)CHCl-CH2Cl

[0349] CH2=CHCOO-CH2CHClCH(OH)-CH2Cl

[0350] CH2=C(CH3)COO-CH2CHClCH(OH)-CH2Cl

[0351] CH2=CHCOO-CH2CHCl-CHCl-CH2Cl

[0352] CH2=C(CH3)COO-CH2CHCl-CHCl-CH2Cl

[0353] CH2=CHCOO-CH2CH(OH)-CH(OH)-CH2Cl

[0354] CH2=C(CH3)COO-CH2CH(OH)-CH(OH)-CH2Cl

[0355] CH2=CH-C(=O)-NH-CHClCH2-CH2OH

[0356] CH2=C(CH3)-C(=O)-NH-CHClCH2-CH2OH

[0357] CH2=CH-C(=O)-NH-CH2CHCl-CH2OH

[0358] CH2=C(CH3)-C(=O)-NH-CH2CHCl-CH2OH

[0359] CH2=CH-C(=O)-NH-CH2CH(OH)CH2-CH2OH

[0360] CH2=C(CH3)-C(=O)-NH-CH2CH(OH)CH2-CH2OH

[0361] CH2=CH-C(=O)-NH-CH2CH2CH(OH)-CH2OH

[0362] CH2=C(CH3)-C(=O)-NH-CH2CH2CH(OH)-CH2OH

[0363] CH2=CH-C(=O)-NH-CH2CH(OH)CHCl-CH2OH

[0364] CH2=C(CH3)-C(=O)-NH-CH2CH(OH)CHCl-CH2OH

[0365] CH2=CH-C(=O)-NH-CH2CHClCH(OH)-CH2OH

[0366] CH2=C(CH3)-C(=O)-NH-CH2CHClCH(OH)-CH2OH

[0367] CH2=CH-C(=O)-NH-CH2CHCl-CHCl-CH2OH

[0368] CH2=C(CH3)-C(=O)-NH-CH2CHCl-CHCl-CH2OH

[0369] CH2=CH-C(=O)-NH-CH2CH(OH)-CH(OH)-CH2OH

[0370] CH2=C(CH3)-C(=O)-NH-CH2CH(OH)-CH(OH)-CH2OH

[0371] CH2=CH-C(=O)-NH-CH2CHClCH2-CH2Cl

[0372] CH2=C(CH3)-C(=O)-NH-CH2CHClCH2-CH2Cl

[0373] CH2=CH-C(=O)-NH-CH2CHCl-CH2Cl

[0374] CH2=C(CH3)-C(=O)-NH-CH2CHCl-CH2Cl

[0375] CH2=CH-C(=O)-NH-CH2CH(OH)CH2-CH2Cl

[0376] CH2=C(CH3)-C(=O)-NH-CH2CH(OH)CH2-CH2Cl

[0377] CH2=CH-C(=O)-NH-CH2CH2CH(OH)-CH2Cl

[0378] CH2=C(CH3)-C(=O)-NH-CH2CH2CH(OH)-CH2Cl

[0379] CH2=CH-C(=O)-NH-CH2CH(OH)CHCl-CH2Cl

[0380] CH2=C(CH3)-C(=O)-NH-CH2CH(OH)CHCl-CH2Cl

[0381] CH2=CH-C(=O)-NH-CH2CHClCH(OH)-CH2Cl

[0382] CH2=C(CH3)-C(=O)-NH-CHClCH(OH)-CH2Cl

[0383] CH2=CH-C(=O)-NH-CH2CHCl-CHCl-CH2Cl

[0384] CH2=C(CH3)-C(=O)-NH-CH2CHCl-CHCl-CH2Cl

[0385] CH2=CH-C(=O)-NH-CH2CH(OH)-CH(OH)-CH2Cl

[0386] CH2=C(CH3)-C(=O)-NH-CH2CH(OH)-CH(OH)-CH2Cl

[0387] CH2=C(CH3)-O-CH2CH(OH)CH(OH)CH(OH)CH(OH)CH2OH

[0388] CH2=C(CH3)-CH2-O-CH2CH(OH)CH(OH)CH(OH)CH(OH)CH2OH

[0389] CH2=C(CH3)-O-C(=O)-CH(OH)CH2Cl

[0390] CH2=CH-CH(OH)CH2OH

[0391] CH2=CH-CH2CH(OH)CH2OH

[0392] CH2=CH-C(=O)-O-CH2-C(=O)-O-CH2CH(OH)CH(OH)CH(OH)CH(OH)CH2OH

[0393] CH2=CHCOO-[C(C X H 2x+1-y (OH) y )2-C(R7)2] q -M

[0394] CH2=C(CH3)COO-[C(C X H 2x+1-y (OH) y )2-C(R7)2] q -M

[0395] CH2=CH-C(=O)-NH-[C(CX H 2x+1-y (OH) y )2-C(R7)2] q -M

[0396] CH2=C(CH3)-C(=O)-NH-[C(C X H 2x+1-y (OH) y )2-C(R7)2] q -M

[0397] CH2=CHCOO-[C(R7)2-C(C X H 2x+1-y (OH) y )2] q -M

[0398] CH2=C(CH3)COO-[C(R7)2-C(C X H 2x+1-y (OH) y )2] q -M

[0399] CH2=CH-C(=O)-NH-[C(R7)2-C(C X H 2x+1-y (OH) y )2] q -M

[0400] CH2=C(CH3)-C(=O)-NH-[C(R7)2-C(C X H 2x+1-y (OH) y )2] q -M

[0401] CH2=CHCOO-[C(R7)(C X H 2x+1-y (OH) y )-C(R7)(C X H 2x+1-y (OH) y )] q -M

[0402] CH2=C(CH3)COO-[C(R7)(C X H 2x+1-y (OH) y )-C(R7)(C X H 2x+1-y (OH) y )] q -M

[0403] CH2=CH-C(=O)-NH-[C(R7)(C X H 2x+1-y (OH) y )-C(R7)(C X H 2x+1-y (OH) y )] q -M

[0404] CH2=C(CH3)-C(=O)-NH-[C(R7)(C X H 2x+1-y (OH) y )-C(R7)(C X H 2x+1-y (OH) y )] q -M

[0405] CH2=CHCOO-[C(R7)(C X H 2x+1-y (OH) y )-C(C X H 2x+1-y (OH) y )2] q -M

[0406] CH2=C(CH3)COO-[C(R7)(C X H 2x+1-y (OH) y )-C(C X H 2x+1-y (OH) y )2] q -M

[0407] CH2=CH-C(=O)-NH-[C(R7)(C X H 2x+1-y (OH) y )-C(C X H 2x+1-y (OH) y )2] q -M

[0408] CH2=C(CH3)-C(=O)-NH-[C(R7)(C X H 2x+1-y (OH) y )-C(C X H 2x+1-y (OH) y )2] q -M

[0409] CH2=CHCOO-[C(C X H2x+1-y (OH) y )2-C(R7)(C X H 2x+1-y (OH) y )] q -M

[0410] CH2=C(CH3)COO-[C(C X H 2x+1-y (OH) y )2-C(R7)(C X H 2x+1-y (OH) y )] q -M

[0411] CH2=CH-C(=O)-NH-[C(C X H 2x+1-y (OH) y )2-C(R7)(C X H 2x+1-y (OH) y )] q -M

[0412] CH2=C(CH3)-C(=O)-NH-[C(C X H 2x+1-y (OH) y )2-C(R7)(C X H 2x+1-y (OH) y )] q -M

[0413] CH2=CHCOO-[C(C X H 2x+1-y (OH) y )2-C(C X H 2x+1-y (OH) y )2] q -M

[0414] CH2=C(CH3)COO-[C(C X H 2x+1-y (OH) y )2-C(C X H 2x+1-y (OH) y )2] q -M

[0415] CH2=CH-C(=O)-NH-[C(C X H 2x+1-y (OH) y )2-C(C XH 2x+1-y (OH) y )2] q -M

[0416] CH2=C(CH3)-C(=O)-NH-[C(C X H 2x+1-y (OH) y )2-C(C X H 2x+1-y (OH) y )2] q -M

[0417] R7 is independently -H, C1 to C1, respectively. 10 Alkyl groups, C1-C 10 Chloroalkyl groups.

[0418] C between the same monomer (B) and / or different monomers (B) x H 2x+1-y (OH) y Whether they are the same or different, x is an integer from 1 to 10, and y is an integer from 1 to 10. Any term C x H 2x+1-y (OH) y The y-value in the expression is less than or equal to the x-value, i.e., y ≤ x.

[0419] q is an integer from 0 to 10, preferably an integer from 0 to 5.

[0420] M is preferably a -H, -Cl, -OH, a monohydric alcohol group of C1 to C6, or a polyhydric alcohol group of C2 to C6.

[0421] As monomer (B), preferably hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyethyl acrylamide, hydroxyethyl methacrylamide, 3-chloro-2-hydroxypropyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylamide, 2,3,4-trihydroxybutyl methacrylate, 2,3,4,5-tetrahydroxypropyl methacrylate, etc. Amyl methacrylate, 2,3,4,5,6-pentahydroxyhexyl methacrylate and / or mixtures thereof, particularly preferred are 3-chloro-2-hydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylamide, 2,3,4-trihydroxybutyl methacrylate, 2,3,4,5-tetrahydroxypentyl methacrylate, 2,3,4,5,6-pentahydroxyhexyl methacrylate and / or mixtures thereof.

[0422] (C) Monomers with ionic donor groups

[0423] The monomer (C) is a monomer with an ionic donor group. Among them, the ionic donor group can be divided into anionic donor groups and cationic donor groups.

[0424] Monomers possessing anion donor groups can be exemplified by monomers containing carboxyl or sulfonic acid groups. Specific examples of monomers possessing anion donor groups include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, etc., or their salts. Specific examples of salts that serve as anion donor groups include methyl ammonium salts, ethanol ammonium salts, triethanolammonium salts, etc.

[0425] The present invention preferably uses monomers (C) having cationic donor groups, examples of which are amino groups, preferably tertiary amine groups and quaternary ammonium groups.

[0426] In the tertiary amine group, the two groups bonded to the nitrogen atom are preferably the same or different C1-C5 alkyl groups and C6-C6 alkyl groups. 10 aryl, C7~C 12 Aryl groups (e.g., benzyl C6H5-CH2-). In the quaternary ammonium group, the three groups bonded to the nitrogen atom are preferably the same or different C1-C5 alkyl groups, C6-C6 alkyl groups, and C7-C8 alkyl groups. 10 aryl, C7~C 12 Aryl groups (e.g., benzyl C6H5-CH2-). The cation donor group can be in the form of a salt.

[0427] The monomer (C) is the monomer shown in formula (6):

[0428]

[0429] R1 may be different or the same, and may be independently -H, non-fluorinated halogen, or monovalent organic groups. The monovalent organic groups mentioned here may be, for example, C1 to C12. 20 Alkyl groups having a straight-chain or branched structure.

[0430] X' can be a structure represented by -W-, -R0-, -W-R0-, -R0-W-, or -W-R0-W-, with -W-R0- being the preferred option.

[0431] R0 is -(CH2) n - or C1~C 10 The subhydrocarbon group has a branched structure, where n is an integer from 0 to 20, preferably an integer from 0 to 10.

[0432] W is selected from the structures shown in W1 to W4:

[0433] -C(=O)-O- W1

[0434] -C(=O)-N(R2)-W2

[0435] -O- W3

[0436] -O-C(=O)- W4

[0437] R2 is a hydrogen atom or a C1-C1 atom. 20 Alkyl groups.

[0438] R5 and R6 may be the same or different, and are independently C1 to C6 respectively. 10 Alkyl groups, C6-C 20 aryl, C7~C 25 Aryl groups (especially benzyl C6H5-CH2-).

[0439] R1 can be hydrogen, methyl, halogen other than fluorine, substituted or unsubstituted benzyl. Examples of R1 are hydrogen, methyl, chlorine, bromine, and iodine. R1 is preferably hydrogen, methyl, or chlorine. R1 is particularly preferably methyl.

[0440] R2 can be hydrogen, methyl, substituted or unsubstituted benzyl. R2 is preferably hydrogen or methyl. R2 is particularly preferably methyl.

[0441] R5 and R6 are either the same or different from C1 to C2. 10 Alkyl groups, C6-C 20 aryl, C7~C 25 Aryl groups (especially benzyl C6H5-CH2-). Preferably C1-C5 alkyl groups, C6-C6 alkyl groups. 10 aryl, C7~C 12 Aryl groups (e.g., benzyl C6H5-CH2-).

[0442] The cation donor group serving as the salt is a salt of an acid. The acid used in this invention is preferably an organic acid, such as C1 to C2. 10 Carboxylic acids (including acetic acid, propionic acid, butyric acid, etc.).

[0443] Specific examples of monomers (C) are listed below, but are not limited to these.

[0444] CH2=CHCOO-CH2CH2-N(CH3)2 and / or its salts,

[0445] CH2=CHCOO-CH2CH2-N(CH2CH3)2 and / or its salts,

[0446] CH2=C(CH3)COO-CH2CH2-N(CH3)2 and / or its salts,

[0447] CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and / or its salts,

[0448] CH2=CH-C(=O)-NH-CH2CH2-N(CH3)2 and / or its salts,

[0449] CH2=CH-C(=O)-NH-CH2CH2-N(CH2CH3)2 and / or its salts,

[0450] CH2=C(CH3)-C(=O)-NH-CH2CH2-N(CH3)2 and / or its salts,

[0451] CH2=C(CH3)-C(=O)-NH-CH2CH2-N(CH2CH3)2 and / or its salts.

[0452] As monomer (C), dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylamide, diethylaminoethyl methacrylamide, and their salts are preferred.

[0453] In addition to the repeating units formed by monomers (A), (B), and (C), the fluorine-free copolymer of the present invention may optionally also include repeating units formed by other optional monomers (D) with good compatibility.

[0454] As such optional monomers (D), there are monomers having a pyrrolidone structure and a polymerizable unsaturated group, monomers having a capped isocyanate group and a polymerizable unsaturated group, monomers having an alkoxysilyl group and a polymerizable unsaturated group, and / or monomers having a glycidyl group and a polymerizable unsaturated group.

[0455] Other monomers (D) can be listed in the following compounds:

[0456] Examples of monomers containing a pyrrolidone structure and a polymerizable unsaturated group include: N-vinyl-2-pyrrolidone, N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, and N-vinyl-3,3-dimethyl-2-pyrrolidone.

[0457] Examples of monomers having end-capped isocyanates and polymerizable unsaturated groups include: 2-butanone oxime adducts of ethyl esters of (meth)acrylate-2-isocyanate, pyrazole adducts of ethyl esters of (meth)acrylate-2-isocyanate, 3,5-dimethylpyrazole adducts of ethyl esters of (meth)acrylate-2-isocyanate, 3-methylpyrazole adducts of ethyl esters of (meth)acrylate-2-isocyanate, ε-caprolactam adducts of ethyl esters of (meth)acrylate-2-isocyanate, 2-butanone oxime adducts of ethyl esters of (meth)acrylate-3-isocyanate, and pyrazole adducts of ethyl esters of (meth)acrylate-3-isocyanate. Compounds, 3,5-dimethylpyrazole adduct of ethyl 3-isocyanate of (meth)acrylate, 3-methylpyrazole adduct of ethyl 3-isocyanate of (meth)acrylate, ε-caprolactam adduct of ethyl 3-isocyanate of (meth)acrylate, 2-butanone oxime adduct of ethyl 4-isocyanate of (meth)acrylate, pyrazole adduct of ethyl 4-isocyanate of (meth)acrylate, 3,5-dimethylpyrazole adduct of ethyl 4-isocyanate of (meth)acrylate, 3-methylpyrazole adduct of ethyl 4-isocyanate of (meth)acrylate, ε-caprolactam adduct of ethyl 4-isocyanate of (meth)acrylate.

[0458] Examples of monomers containing alkoxysilyl groups and polymerizable unsaturated groups include: 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyldimethoxymethylsilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyldiethoxyethylsilane, and allyltrimethoxysilane.

[0459] Examples of monomers containing glycidyl groups and polymerizable unsaturated groups include glycidyl (meth)acrylate.

[0460] The amount of repeating units formed by monomer (A) relative to the fluorine-free copolymer is 40 to 90% by weight, preferably 45 to 85% by weight, and more preferably 50 to 85% by weight.

[0461] The amount of repeating units formed by monomer (B) relative to the fluorine-free copolymer is 0.1 to 25% by weight, preferably 0.1 to 22% by weight, and more preferably 0.1 to 20% by weight.

[0462] The amount of repeating units formed by monomer (C) relative to the fluorine-free copolymer is 5 to 40% by weight, preferably 10 to 35% by weight, and more preferably 15 to 35% by weight.

[0463] The amount of repeating units formed from other alternative monomers (D) with good compatibility is 0 to 10% by weight relative to the copolymer, preferably 0 to 8% by weight.

[0464] The weight-average molecular weight of the water-dispersible fluorine-free copolymer of the present invention can be 5,000 to 500,000, preferably 8,000 to 200,000.

[0465] In this specification, "(meth)acrylic acid" refers to acrylic acid or methacrylic acid.

[0466] The specific polymerization method of the water-dispersible fluorine-free copolymer of the present invention is described below.

[0467] The polymerization method of the copolymers in this invention is not particularly limited; conventional polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization, and radiation polymerization can all be used. For example, solution polymerization using organic solvents can generally be chosen to prepare the treatment liquid. This invention preferably uses solution polymerization for preparation.

[0468] In this invention, it is preferable to add a water / acid solution first after polymerization (e.g., solution polymerization), and then remove the organic solvent, thereby dispersing the polymer in water.

[0469] Examples of organic solvents include ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and methyl acetate; diols such as propylene glycol, dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone (NMP), dipropylene glycol, tripropylene glycol, and low molecular weight polyethylene glycol; and alcohols such as ethanol and isopropanol.

[0470] As polymerization initiators, peroxides, azo compounds, or persulfate compounds can be used, for example. Polymerization initiators are generally water-soluble and / or oil-soluble.

[0471] Specific examples of oil-soluble polymerization initiators include dimethyl 2,2'-azobisisobutyrate, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), 2,2'-azobis(2,4-dimethyl4-methoxypentanonitrile), 1,1'-azobis(cyclohexane-1-carboxynitrile), dimethyl 2,2'-azobis(2-methylpropionate), benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxyneoplastate, diisopropyl peroxydicarbonate, and tert-butyl peroxyneoplastate.

[0472] In addition, specific examples of water-soluble polymerization initiators include 2,2'-azobisisobutylamidine dihydrochloride, 2,2'-azobis(2-methylpropanediidine) hydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] hydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] sulfate hydrate, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] hydrochloride, potassium persulfate, barium persulfate, ammonium persulfate, hydrogen peroxide, etc.

[0473] The removal of organic solvents from polymer solutions can be achieved by heating the polymer solution under reduced pressure.

[0474] The preferred initiator for solution polymerization is a peroxide or azo compound with a half-life of 8 hours and a decomposition temperature of 30°C or higher, such as tert-butyl peroxypentanoate, 2,2'-azobis(2-methylpropionitrile), etc.

[0475] The treatment agent of the present invention, which contains a water-dispersible fluorine-free copolymer, can be well added externally to paper substrates or internally to pulp raw materials.

[0476] Paper substrates that are processed can include paper, containers made of paper, and molded objects made of paper (such as pulp molding).

[0477] Paper can be manufactured using existing, well-known papermaking methods. For example, an internal treatment method can be used, in which an oil-resistant treatment agent is added to the pulp before papermaking, or an external treatment method can be used, in which an oil-resistant treatment agent is applied to the paper after papermaking. The treatment method of the treatment agent in this invention is preferably an internal treatment method.

[0478] In the addition, the amount of fluorine-free copolymer contained in the treatment agent is preferably 0.01–4.0 g / m³. 2 Especially 0.1–2.0 g / m 2 The treatment agent is preferably formed from a treatment agent and starch and / or modified starch. The effective solid content for paper use in the treatment agent is preferably 3 g / m². 2 the following.

[0479] In the addition, the amount of the treatment agent is preferably 0.01 to 50 parts by weight or 0.01 to 35 parts by weight relative to 100 parts by weight of the pulp forming the paper, and the treatment agent is mixed with the pulp.

[0480] In the internal treatment of the processing agent, it is preferable to use pulp with a pulp concentration of 1 to 5.0% by weight for papermaking. Additives, including sizing agents, coagulants, reinforcing agents, defoamers, and water-dispersible non-fluorinated copolymers, are added to the pulp. Generally, the pulp is anionic, so it is preferable that at least one of the additives and the non-fluorinated copolymer is cationic or amphoteric, so that the additives and the non-fluorinated copolymer can be well fixed to the paper. It is preferable to use a combination of cationic or amphoteric additives and non-fluorinated copolymers; a combination of anionic additives and cationic or amphoteric non-fluorinated copolymers; or a combination of cationic or amphoteric additives and anionic non-fluorinated copolymers.

[0481] Examples of additives such as sizing agents, coagulants, and reinforcing agents include alkyl vinyl ketone dimers, alkenyl succinic anhydride, styrene polymers, urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamide-epimyl chloride polymers, polyacrylamide polymers, polyamine polymers, polydiallyl dimethyl ammonium chloride, alkylamine-epimyl chloride condensates, alkylene dichlorides and polyalkylene polyamine condensates, dicyanidamide-formaldehyde condensates, dimethyldiallyl ammonium chloride polymers, and olefin / maleic anhydride polymers.

[0482] A typical solution polymerization process for a treatment agent containing a water-dispersible fluorine-free copolymer is as follows:

[0483] In solution polymerization, an organic solvent is added first, followed by the addition of the corresponding monomer for dissolution. Nitrogen gas is then introduced for displacement, an initiator is added, and the temperature is raised to the reaction temperature of 50–120°C. The reaction time is 5–30 hours.

[0484] Specifically, the preparation method (process) of the treatment agent containing the water-dispersible fluorine-free copolymer can be divided into the following steps:

[0485] (1) The monomer, organic solvent and initiator are copolymerized in a reactor to obtain a polymer solution;

[0486] (2) Add an acid solution to the polymer solution for dispersion treatment;

[0487] (3) The polymer solution is desolventized to remove the organic solvent and obtain an aqueous dispersion;

[0488] (4) The amino groups in the aqueous dispersion are converted into nitrogen oxides to obtain a treatment agent containing a water-dispersible fluorine-free copolymer.

[0489] In a preferred embodiment, step (4) involves treating the aqueous dispersion with an aqueous hydrogen peroxide solution to convert the amino group into a nitrogen oxide compound.

[0490] In the treatment agent, the concentration of the fluorine-free copolymer can be 0.01 to 50% by weight, for example 0.1 to 40% by weight, preferably 1 to 30% by weight, more preferably 5 to 25% by weight.

[0491] In the preparation of the treatment agent, the preferred copolymerization method for the fluorine-free copolymer is solution polymerization.

[0492] In this invention, the workpiece is treated with a treatment agent comprising a water-dispersible fluorine-free copolymer. "Treatment" means applying the treatment agent to the workpiece through impregnation, spraying, coating, or internal addition. Through treatment, the fluorine-free copolymer, as the active ingredient of the treatment agent, penetrates into the interior of the workpiece and / or adheres to the surface of the workpiece or becomes part of the workpiece.

[0493] Example

[0494] Unless otherwise specified, the terms used in this specification have the general meanings known to those skilled in the art; “%” means “weight %”; “parts” means “parts by weight”.

[0495] The following are the processing and testing methods for paper products:

[0496] Paper product processing

[0497] Processable paper products include thin paper, thick paper, linerboard, or molded pulp, etc., from a unit area (m²) 2 A paper box weighing 500 grams, or per unit area (m²) 2 Kraft paper weighing 100 grams, from a unit area (m²) 2 ) reaching 150 grams of thin paper, to a unit area (m²) 2 Paper-plastic products weighing up to 300 grams can be processed. The raw materials for paper products can be chemically bleached pulp or unbleached pulp, wood pulp, chemimechanical pulp, mechanical pulp, etc.

[0498] Specific methods for handling paper lunch boxes

[0499] The pulping process was carried out directly with bleached sugarcane pulp / bleached bamboo pulp (3:7), with a Shore freeness of 23°SR and a pulp concentration of 0.3%. A pre-synthesized treatment agent was added at a rate of 8% by weight of the oven-dry pulp. A standard paper lunch box weighing 15 grams was produced using a small-scale pulping and forming system.

[0500] Oil resistance test (paper lunch box)

[0501] Place the sample on a dry glass or plate lined with filter paper, fill it with edible oil (salad oil, peanut oil, rapeseed oil) at the specified temperature*, let it stand for 30 minutes, observe whether the sample is deformed, and observe whether there are oil stains on the filter paper. Give it a rating according to the following standards. The higher the rating, the better the oil resistance.

[0502] *Specified temperatures for edible oils: heat resistance oil test (100±5℃), cold resistance oil test (0~5℃);

[0503] Level 4: Impermeable on both the inner wall and the back.

[0504] Level 3: Discoloration of the inner wall, no penetration on the back.

[0505] Level 2: Backside penetration rate > 5%

[0506] Grade 1: 5% ≤ back permeability < 20%, and the sample is not deformed and the filter paper underneath has no obvious oil stains.

[0507] Grade 0: Backside permeability ≥ 20%

[0508] Water resistance test (paper lunch box)

[0509] Place the sample on a dry glass or plate lined with filter paper, fill it with water at 95±5℃, and let it stand for 30 minutes. Observe the sample for any deformation, seepage, or leakage at the bottom. If the sample does not show any deformation, seepage, or leakage, it is considered to have "passed"; if deformation, seepage, or leakage occurs, it is considered to have "failed".

[0510] During the test, water vapor condensation at the bottom of the sample caused by the temperature difference between the inside and outside of the sample is not considered as seepage or leakage.

[0511] Relative yellowing (whiteness) rating of lunch boxes

[0512] Samples with and without the pre-synthesized treatment agent were prepared under the same process conditions. The sample without the pre-synthesized treatment agent was used as a standard. The relative yellowing (whiteness) change of the sample with the pre-synthesized treatment agent and the standard were visually evaluated. The samples were rated according to the following criteria.

[0513] Grade 0: Visually noticeably whiter compared to the standard product.

[0514] Level 1: Visually visibly whiter compared to the standard product.

[0515] Level 2: Visually, the whiteness is basically similar to that of the standard product.

[0516] Level 3: Visibly yellowed compared to the standard product.

[0517] Level 4: Visually noticeably yellowed compared to the standard product.

[0518] Food container hardness evaluation

[0519] Samples with and without the pre-synthesized treatment agent were prepared under the same process conditions. The sample without the treatment agent was used as a standard. The hardness changes of the sample with the pre-synthesized treatment agent and the standard were visually evaluated. Ratings were assigned according to the following standards.

[0520] Grade 0: Significantly softer than standard products

[0521] Grade 1: Slightly softer than standard products

[0522] Grade 2: Hardness is basically similar to the standard product.

[0523] Grade 3: Slightly harder than the standard product

[0524] Level 4: Significantly harder than the standard product

[0525] Evaluation of anti-sticking performance

[0526] Twenty standard lunch boxes weighing 15 grams each were produced continuously using a small-scale pulping and molding system. The bottom of the mold was observed for any sticking. If no sticking occurred after producing 20 standard lunch boxes weighing 15 grams each, the result was marked as "passed". If sticking occurred, the result was marked as "failed".

[0527] The following embodiments and comparative examples illustrate the present invention in detail, but these descriptions are not limited to the present invention.

[0528] In this instruction manual, chemical abbreviations are listed in Table 1.

[0529] Table 1 Chemical Abbreviations

[0530]

[0531]

[0532] Example 1

[0533] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of methyl ethyl ketone (MEK) was added as a solvent under stirring, followed by 55 g of Si-MNP3, 15 g of JMN-201, 3 g of JMC-320, and 27 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0534] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0535] Example 2

[0536] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of methyl ethyl ketone (MEK) was added as a solvent under stirring, followed by 65 g of Si-MNP3, 5 g of JMN-201, 2 g of JMC-430, and 28 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids concentration of approximately 33.3% by weight.

[0537] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0538] Example 3

[0539] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 70 g of Si-MNP3, 4 g of JMN-320, and 26 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was maintained at 70 °C for 12 hours to proceed with copolymerization. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0540] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0541] Example 4

[0542] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 80 g of Si-MNP3, 2 g of JMC-540, and 18 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids concentration of approximately 33.3% by weight.

[0543] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0544] Example 5

[0545] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of methyl ethyl ketone (MEK) was added as a solvent under stirring, followed by 80 g of Si-MNP3, 2 g of JMC-311, 1 g of JMC-650, and 17 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of initiator, dimethyl 2,2'-azobisisobutyrate, was slowly added. The reaction temperature was controlled at 75 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids concentration of approximately 33.3% by weight.

[0546] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0547] Example 6

[0548] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 60 g of Si-MCP7, 10 g of JMN-201, 3 g of JMC-320, and 27 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of initiator, dimethyl 2,2'-azobisisobutyrate, was slowly added. The reaction temperature was controlled at 75 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids concentration of approximately 33.3% by weight.

[0549] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0550] Example 7

[0551] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 60 g of Si-MCP7, 10 g of JMN-201, 2 g of JMC-430, and 28 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0552] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0553] Example 8

[0554] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 70 g of Si-MCP7, 4 g of JMN-320, and 26 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was maintained at 70 °C for 12 hours to induce copolymerization. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0555] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0556] Example 9

[0557] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of methyl ethyl ketone (MEK) was added as a solvent under stirring, followed by 75 g of Si-MCP7, 3 g of JMC-540, and 22 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 0.8 g of initiator 2,2'-azobisisobutyronitrile was then slowly added. The reaction temperature was controlled at 75 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids concentration of approximately 33.3% by weight.

[0558] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0559] Example 10

[0560] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 55 g of Si-MCPn, 15 g of JMN-201, 3 g of JMC-320, and 27 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 0.8 g of initiator 2,2'-azobisisobutyronitrile was then slowly added. The reaction temperature was controlled at 75 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0561] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0562] Example 11

[0563] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of methyl ethyl ketone (MEK) was added as a solvent under stirring, followed by 65 g of Si-MCPn, 6 g of JMN-201, 1 g of JMC-650, and 28 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0564] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0565] Example 12

[0566] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 65 g of Si-MCPn, 7 g of JMC-320, and 28 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 0.8 g of initiator 2,2'-azobisisobutyronitrile was then slowly added. The reaction temperature was controlled at 75 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids concentration of approximately 33.3% by weight.

[0567] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0568] Example 13

[0569] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 65 g of Si-MCPn, 6 g of JMC-430, and 29 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids concentration of approximately 33.3% by weight.

[0570] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0571] Example 14

[0572] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 70 g of Si-MCPn, 6 g of JMN-320, and 24 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to proceed with copolymerization. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0573] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0574] Example 15

[0575] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 75 g of Si-MCPn, 2 g of JMC-311, 2 g of JMC-540, and 21 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 0.8 g of initiator 2,2'-azobisisobutyronitrile was then slowly added. The reaction temperature was controlled at 75 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids concentration of approximately 33.3% by weight.

[0576] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0577] Example 16

[0578] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of methyl ethyl ketone (MEK) was added as a solvent under stirring, followed by 80 g of Si-MCPn, 2 g of JMC-650, and 18 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids concentration of approximately 33.3% by weight.

[0579] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0580] Example 17

[0581] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 60 g of Si-MCP3, 10 g of JMN-201, 2 g of JMN-320, and 28 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0582] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0583] Example 18

[0584] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 65 g of Si-MCP3, 8 g of JMN-320, and 27 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0585] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0586] Example 19

[0587] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 70 g of Si-MCP3, 5 g of JMC-320, and 25 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was maintained at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0588] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0589] Example 20

[0590] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 75 g of Si-MCP3, 4 g of JMC-430, and 21 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0591] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0592] Example 21

[0593] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of methyl ethyl ketone (MEK) was added as a solvent under stirring, followed by 75 g of Si-MCP3, 2 g of JMC-540, and 23 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids concentration of approximately 33.3% by weight.

[0594] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0595] Example 22

[0596] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 75 g of Si-MCP3, 2 g of JMC-650, and 23 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 0.8 g of initiator 2,2'-azobisisobutyronitrile was then slowly added. The reaction temperature was controlled at 75 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids concentration of approximately 33.3% by weight.

[0597] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0598] Example 23

[0599] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 75 g of Si-MCP3, 2 g of JC-320, and 23 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0600] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0601] Example 24

[0602] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 75 g of Si-MCP3, 2 g of JMEO-650, and 23 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids concentration of approximately 33.3% by weight.

[0603] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0604] Example 25

[0605] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 75 g of Si-MCP3, 2 g of JERE-650, and 23 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids concentration of approximately 33.3% by weight.

[0606] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0607] Example 26

[0608] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 75 g of Si-MCPn, 2 g of JMPO-650, and 23 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids concentration of approximately 33.3% by weight.

[0609] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0610] Example 27

[0611] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 75 g of Si-MCP7, 1 g of JMC-540, 2 g of JMES-211, and 22 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 0.8 g of initiator 2,2'-azobisisobutyronitrile was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0612] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0613] Example 28

[0614] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 75 g of Si-MNP3, 1 g of JMC-650, 2 g of J-220, and 22 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0615] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0616] Comparative Example 1

[0617] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 70 g of Si-MCP3, 7 g of HEMA, and 23 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction was carried out at 70 °C for 12 hours to copolymerize. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0618] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0619] Comparative Example 2

[0620] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of methyl ethyl ketone (MEK) was added as a solvent under stirring, followed by 75 g of Si-MCP3, 5 g of HBMA, and 20 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0621] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0622] Comparative Example 3

[0623] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 65 g of Si-MCP3, 10 g of HEMAA, and 25 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to proceed with copolymerization. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0624] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0625] Comparative Example 4

[0626] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 65 g of Si-MCPn, 10 g of HEMAA, and 25 g of G-MC. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0627] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0628] Comparative Example 5

[0629] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of methyl ethyl ketone (MEK) was added as a solvent under stirring, followed by 70 g of Si-MCPn, 10 g of HBA, and 20 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was maintained at 70 °C for 12 hours to proceed with copolymerization. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0630] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0631] Comparative Example 6

[0632] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 75 g of Si-MCPn, 5 g of HBMA, and 20 g of G-MC. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0633] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0634] Comparative Example 7

[0635] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of methyl ethyl ketone (MEK) was added as a solvent under stirring, followed by 70 g of Si-MCP3, 6 g of HEMA, 1 g of MOI-BP, and 23 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction was carried out at 70 °C for 12 hours to copolymerize. The resulting copolymer-containing solution had a solids concentration of approximately 33.3% by weight.

[0636] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0637] Comparative Example 8

[0638] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heating device was prepared. 200 g of isopropanol (IPA) was added as a solvent under stirring, followed by 77 g of Si-MCP3 and 23 g of G-MN. Nitrogen gas was introduced for purging, and the temperature was slowly raised to 50 °C. 1.5 g of tert-butyl peroxypentanoate initiator was then slowly added. The reaction temperature was controlled at 70 °C for 12 hours to carry out copolymerization. The resulting copolymer-containing solution had a solids content of approximately 33.3% by weight.

[0639] 200g of a 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt. The internal temperature was maintained at 70°C for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to this aqueous dispersion to finally obtain an aqueous dispersible treatment agent with a solid content of 20% by weight.

[0640] The treatment agents synthesized using the examples and comparative examples were tested on several different paper products, as follows:

[0641] Paper tableware performance test

[0642] Bleached sugarcane pulp / bleached bamboo pulp (3:7) was directly pulped, with a Shore freeness of 23°SR and a pulp concentration of 0.3%. A pre-synthesized treatment agent was added at 8% of the oven-dry pulp weight. A standard 15-gram lunch box was produced using a small-scale pulping and forming system. The lunch box was tested for water resistance, oil resistance, hardness, whiteness, and anti-sticking properties.

[0643] The performance test results are shown in Tables 2, 3, 4 and 5.

[0644] Table 2 Performance Test Results

[0645]

[0646] Table 3 Performance Test Results

[0647]

[0648] Table 4 Performance Test Results

[0649]

[0650] Table 5 Performance Test Results

[0651]

[0652] As shown in Tables 2-5, the anti-sticking properties of all embodiments are significantly improved compared to Comparative Examples 7-8. Furthermore, Examples 1-16 show significantly improved heat and cold oil resistance compared to Comparative Examples 4-6. Examples 17-28 show significantly improved heat and cold oil resistance, as well as the hardness of the paper lunch boxes, compared to Comparative Examples 1-3. Overall, the results from the embodiments and comparative examples show that the treatment agent containing fluorine-free copolymers of the present invention can impart excellent and stable water and oil resistance to pulp molded products. In addition, the molded products do not stick to the mold during production, and the final products have high hardness.

[0653] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make modifications, alterations, substitutions and variations to the above embodiments within the scope of the present invention.

[0654] The technical solutions of the present invention are not limited to the specific embodiments described above. Any technical modifications made in accordance with the technical solutions of the present invention fall within the protection scope of the present invention.

Claims

1. A water-dispersible fluorine-free copolymer, characterized by, The copolymer comprises: a repeating unit formed from a silicon-containing unsaturated monomer (A); a repeating unit formed from a monomer (B); and a repeating unit formed from a monomer (C) having an ionic donor group; wherein the repeating unit formed from the monomer (A) is 50-85% by weight of the copolymer, the repeating unit formed from the monomer (B) is 1-22% by weight of the copolymer, and the repeating unit formed from the monomer (C) is 10-35% by weight of the copolymer; wherein the monomer (B) is a monomer represented by formula (4): Wherein, R1 is independently -H, non-fluorinated halogen, or C1~C1. 20 Alkyl groups having a straight-chain or branched structure; X' is a structure represented by -W-, -R0-, -W-R0-, -R0-W-, or -W-R0-W-, R0is -(CH2) n - or C1-C 10 a branched hydrocarbylene group, n is an integer from 0 to 20, W is selected from structures represented by W1 to W4: -C(=O)-O-W1 -C(=O)-N(R2)-W2 -O-W3 -O-C(=O)-W4 R2 is -H or Cl~C 20 Alkyl groups; Q is a structure represented by formula (5): Z5 and / or M are independently -H, -OH, non-fluorinated halogen, C1 to C2, respectively. 10 Alkyl groups, C1-C 10 Monohydric alcohol group, C2-C 10 polyol groups or C1-C 10 The non-fluorinated haloalkyl group, q is an integer from 0 to 10, and In the monomer (B), the sum of the number of non-fluorine halogen groups and the number of -OH in the structure of -Q-M is ≥ 2, and the number of hydroxyl groups is ≥ 1; the monomer (C) is a monomer represented by formula (6): Wherein, R1 is independently -H, non-fluorinated halogen, or C1~C1. 20 Alkyl groups having a straight-chain or branched structure; X' is a structure represented by -W-, -R0-, -W-R0-, -R0-W-, or -W-R0-W-, R0is -(CH2) n - or C1-C 10 a branched hydrocarbylene group, n is an integer from 0 to 20, W is selected from structures represented by W1 to W4: -C(=O)-O-W1 -C(=O)-N(R2)-W2 -O-W3 -O-C(=O)-W4 R2 is -H or Cl~C 20 Alkyl groups; R5 and R6 are independently C1 to C1 respectively. 10 Alkyl groups, C6-C 20 aryl or C7~C 25 Aryl groups.

2. The water-dispersible fluorine-free copolymer according to claim 1, characterized by Q is selected from one or more of the following structures Q-1 to Q-18: wherein q is an integer of 0 to 10, R7is independently -H, a C1-C4alkyl group or a C1-C4chloroalkyl group, 10 R7is independently -H, a C1-C4alkyl group or a C1-C4chloroalkyl group, 10 R7is independently -H, a C1-C4alkyl group or a C1-C4chloroalk each C x H 2x+1-y (OH) y identical or different, x is an integer from 1 to 10, y is an integer from 1 to 10, and the same group C x H 2x+1-y (OH) y with y < x.

3. The water-dispersible fluorine-free copolymer according to claim 1 or 2, characterized in that, the monomer (A) is a monomer represented by formula (1): Wherein, R1 is independently -H, non-fluorinated halogen, or C1~C1. 20 Alkyl groups having a straight-chain or branched structure; X is -C6H4-, -R0-, -W-, -W-C6H4-, -R0-C6H4-, -C6H4-R0-, -C6H4-W-, -W-R0-, -R0-W-, -R0-W-R0-, -C6H4-W-C6H4-, -R0-W-C6H4-, -C6H4-W-R0-, -W-R0 -C6H4-, -W-C6H4-R0-, -C6H4-R0-W-, -R0-C6H4-W-, -R0-C6H4-R0-, -W-R0-C6H4-R0-, -R0-C6H4-R0-W-, -C6H4-R0-W-R0-, -R0-C6H4-W-R0-, -R0-W-R0-C6H4-R0 -or -R0-C6H4-R0-W-R0-, is represented by a group, -C6H4- is a phenylene group, R0are independently - (CH2) n - or C1~C 10 n is an integer from 0 to 20, W is selected from structures represented by W1 to W4: -C(=O)-O-W1 -C(=O)-N(R2)-W2 -O-W3 -O-C(=O)-W4 R2is -H or C1to C4alkyl, 20 alkyl, Y is a structure represented by formula (2): R3 is independently C1 to C1. 10 Alkyl groups, C6-C 20 aryl or C7~C 20 The aralkyl group, Z1 and Z2 are independently C1 to C2. 10 Alkyl groups, C6-C 20 aryl, C7~C 20 Aryl groups or structures as shown in formula (3), where m is 1 to 300. R4 is independently C1 to C1. 10 Alkyl groups, C6-C 20 aryl or C7~C 20 The aralkyl group, Z3 and Z4 are independently C1 to C4. 10 Alkyl groups, C6-C 20 aryl or C7~C 20 Aryl groups, k is 0 to 300.

4. The water-dispersible fluorine-free copolymer according to claim 3, characterized in that, In the monomer (A), R1is independently for each occurrence -H, a non-fluorine halogen, or a C1to C 10 alkyl having a linear or branched structure, X is a group represented by -R0-, -W-, -C6H4-W-, -R0-W-, -W-R0-, -R0-W-R0-, -C6H4-R0-W-R0-, or -R0-C6H4-W-R0-, and R0is independently - (CH2) n - or C1-C 10 a branched hydrocarbylene group, and n is an integer of 0 to 10, In Y, R3 and / or R4 are independently C1–C5 alkyl groups, C6–C4 alkyl groups, respectively. 10 aryl or C7~C 12 Aryl group; Z3 and / or Z4 are independently C1-C5 alkyl groups, C6-C4 alkyl groups, respectively. 10 aryl or C7~C 12 Aryl groups, m is 1 to 50, k is 0 to 50.

5. The water-dispersible fluorine-free copolymer according to claim 3, characterized by Y is selected from one or more of the following structures Y-1 to Y-3: R is independently a C1-C5 alkyl, C6-C10 aryl or C7-C15 aralkyl group, k1 and k2 are independently 0-35; and m is 1-35 in the Y-1 structure, and m is 1 in the Y-2 or Y-3 structure. 10 R is independently a C1-C5 alkyl, C6-C10 aryl or C7-C15 aralkyl group, k1 and k2 are independently 0-35; and m is 1-35 in the Y-1 structure, and m is 1 in the Y-2 or Y-3 structure. 12 R is independently a C1-C5 alkyl, C6-C10 aryl or C7-C15 6. The water-dispersible fluorine-free copolymer according to claim 1, characterized by In the monomer (C), R5 and R6 are each independently a benzyl group.

7. The water-dispersible fluorine-free copolymer according to claim 1, characterized by the copolymer further comprises a repeating unit formed from an optional monomer (D), The optional monomer (D) includes: a monomer having a pyrrolidone structure and a polymerizable unsaturated group; and / or a monomer having a blocked isocyanate group and a polymerizable unsaturated group; and / or a monomer having an alkoxysilyl group and a polymerizable unsaturated group; and / or a monomer having a glycidyl group and a polymerizable unsaturated group.

8. The water-dispersible fluorine-free copolymer according to claim 7, wherein the repeating unit formed by the monomer (D) is present in a weight ratio of 0 to 8% relative to the copolymer.

9. The water-dispersible fluorine-free copolymer according to claim 1 or 6 or 7 or 8, characterized in that, The monomer (B) is selected from one or more of the following: CH2=C(CH3)-COO-CH2CH(OH)CH2Cl; CH2=C(CH3)-COO-CH2CH(OH)CH2OH; CH2=C(CH3)-C(=O)-NH-CH2CH(OH)CH2OH; CH2=C(CH3)-COO-CH2-CH(OH)CH(OH)CH2OH; CH2=C(CH3)-COO-CH2-CH(OH)CH(OH)CH(OH)CH2OH; CH2=C(CH3)-COO-CH2-CH(OH)CH(OH)CH(OH)CH(OH)CH2OH; CH2=C(CH3)-O-CH2CH(OH)CH(OH)CH(OH)CH(OH)CH2OH; CH2=C(CH3)-CH2-O-CH2CH(OH)CH(OH)CH(OH)CH(OH)CH2OH; CH2=C(CH3)-O-C(=O)-CH(OH)CH2Cl; CH2=CH-CH(OH)CH2OH; CH2=CH-CH2CH(OH)CH2OH; CH2=CH-C(=O)-O-CH2-C(=O)-O-CH2CH(OH)CH(OH)CH(OH)CH(OH)CH2OH; CH2=CHCOO-[C(C x H 2x+1-y (OH) y )2-C(R7)2] q -M; CH2=C(CH3)COO-[C(C x H 2x+1-y (OH) y )2-C(R7)2] q -M; CH2=CH-C(=O)-NH-[C(C x H 2x+1-y (OH) y )2-C(R7)2] q -M; CH2=C(CH3)-C(=0)-NH-[C(C x H 2x+1-y (OH) y )2-C(R7)2] q -M; CH2=CHCOO-[C(R7)2-C(C x H 2x+1-y (OH) y )2] q -M; CH2=C(CH3)COO-[C(R7)2-C(C x H 2x+1-y (OH) y )2] q -M; CH2=CH-C(=O)-NH-[C(R7)2-C(C x H 2x+1-y (OH) y )2] q -M; CH2=C(CH3)-C(=0)-NH-[C(R7)2-C(C x H 2x+1-y (OH) y )2] q -M; CH2=CHCOO-[C(R7)(C x H 2x+1-y (OH) y )-C(R7)(C x H 2x+1-y (OH) y )] q -M; CH2=C(CH3)COO-[C(R7)(C x H 2x+1-y (OH) y )-C(R7)(C x H 2x+1-y (OH) y )] q -M; CH2=CH-C(=O)-NH-[C(R7)(C x H 2x+1-y (OH) y )-C(R7)(C x H 2x+1-y (OH) y )] q -M; CH2=C(CH3)-C(=0)-NH-[C(R7)(C x H 2x+1-y (OH) y )-C(R7)(C x H 2x+1-y (OH) y )] q -M; CH2=CHCOO-[C(R7)(C x H 2x+1-y (OH) y )-C(C x H 2x+1-y (OH) y )2] q -M; CH2=C(CH3)COO-[C(R7)(C x H 2x+1-y (OH) y )-C(C x H 2x+1-y (OH) y )2] q -M; CH2=CH-C(=O)-NH-[C(R7)(C x H 2x+1-y (OH) y )-C(C x H 2x+1-y (OH) y )2] q -M; CH2=C(CH3)-C(=0)-NH-[C(R7)(C x H 2x+1-y (OH) y )-C(C x H 2x+1-y (OH) y )2] q -M; CH2=CHCOO-[C(C x H 2x+1-y (OH) y )2-C(R7)(C x H 2x+1-y (OH) y )] q -M; CH2=C(CH3)COO-[C(C x H 2x+1-y (OH) y )2-C(R7)(C x H 2x+1-y (OH) y )] q -M; CH2=CH-C(=O)-NH-[C(C x H 2x+1-y (OH) y )2-C(R7)(C x H 2x+1-y (OH) y )] q -M; CH2=C(CH3)-C(=0)-NH-[C(C x H 2x+1-y (OH) y )2-C(R7)(C x H 2x+1-y (OH) y )] q -M; CH2=CHCOO-[C(C x H 2x+1-y (OH) y )2-C(C x H 2x+1-y (OH) y )2] q -M; CH2=C(CH3)COO-[C(C x H 2x+1-y (OH) y )2-C(C x H 2x+1-y (OH) y )2] q -M; CH2=CH-C(=O)-NH-[C(C x H 2x+1-y (OH) y )2-C(C x H 2x+1-y (OH) y )2] q -M; CH2=C(CH3)-C(=0)-NH-[C(C x H 2x+1-y (OH) y )2-C(C x H 2x+1-y (OH) y )2] q -M; wherein q is an integer of 0 to 10, R7is independently -H, a C1-C6alkyl group, a C1-C6haloalkyl group, 10 10 a C1-C6haloalkyl group,​ each C x H 2x+1-y (OH) y identical or different, x is an integer from 1 to 10, y is an integer from 1 to 10, and the same group C x H 2x+1-y (OH) y with y < x. M is -H, -Cl, -OH, a C1 to C6 monohydric alcohol group, or a C2 to C6 polyhydric alcohol group.

10. The water-dispersible fluorine-free copolymer according to claim 1, wherein The monomer (A) is selected from one or more of the following: CH2=C(CH3)COO-(CH2)3Si(OSi(CH3)3)3 CH2=CHCOO-(CH2)3Si(OSi(CH3)3)3 CH2=C(CH3)COO-(CH2)3Si[OSi(OSi(CH3)3)3]2(OSi(CH3)3) CH2=CHCOO-(CH2)3Si[OSi(OSi(CH3)3)3]2(OSi(CH3)3) CH2=C(CH3)COO-(CH2) n Si(R)2[O(Si(R)2O) k Si(R)3] CH2=CHCOO-(CH2) n Si(R)2[O(Si(R)2O) k Si(R)3] CH2=C(CH3)COO-(CH2) n Si[O(Si(R)2O) k Si(R)3]2(OSi(R)3) CH2=CHCOO-(CH2) n Si[O(Si(R)2O) k Si(R)3]2(OSi(R)3) CH2=C(CH3)-C(=0)-NH-(CH2) n Si(R)2[O(Si(R)2O) k Si(R)3] CH2=CH-C(=O)-NH-(CH2) n Si(R)2[O(Si(R)2O) k Si(R)3] CH2=C(CH3)-C(=0)-NH-(CH2) n Si[0(Si(R)2O) k Si(R)3]2(OSi(R)3) CH2=CH-C(=O)-NH-(CH2) n Si[O(Si(R)2O) k Si(R)3]2(OSi(R)3) wherein n are each independently an integer of 0 to 10, k are each independently 0 to 35, R is independently C1-C6alkyl, C6-C10aryl or C7-C13aralkyl. 10 R is independently C1-C6alkyl, C6-C10aryl or C7-C13aralkyl. 20 R is independently C1-C6alkyl, C6-C10aryl or C7-C13aralkyl. 20 R is independently C1-C6alkyl, C6-C10aryl 11. The water-dispersible fluorine-free copolymer according to claim 1, wherein The monomer (C) is selected from one or more of the following: CH2=CHCOO-CH2CH2-N(CH3)2and / or a salt thereof, CH2=CHCOO-CH2CH2-N(CH2CH3)2and / or a salt thereof, CH2=C(CH3)COO-CH2CH2-N(CH3)2and / or a salt thereof, CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2and / or a salt thereof, CH2=CH-C(=O)-NH-CH2CH2-N(CH3)2and / or a salt thereof, CH2=CH-C(=O)-NH-CH2CH2-N(CH2CH3)2and / or a salt thereof, CH2=C(CH3)-C(=O)-NH-CH2CH2-N(CH3)2and / or a salt thereof, and CH2=C(CH3)-C(=O)-NH-CH2CH2-N(CH2CH3)2and / or a salt thereof.

12. A treating agent comprising a water-dispersible fluorine-free copolymer, characterized in that, the water-dispersible fluorine-free copolymer is the water-dispersible fluorine-free copolymer according to any one of claims 1-11; the treating agent further comprises a liquid medium of water, an organic solvent, or a mixture of water and an organic solvent.

13. The method for producing a treatment agent comprising a water-dispersible fluorine-free copolymer according to claim 12, characterized by, comprising the following steps: (1) copolymerizing monomers, an organic solvent, and an initiator in a kettle to obtain a polymer solution; (2) adding an acid solution to the polymer solution for dispersion treatment; (3) removing the organic solvent from the polymer solution after dispersion treatment to obtain a water dispersion, i.e., a treating agent.

14. The use of the treatment agent comprising the water-dispersible fluorine-free copolymer according to claim 12, wherein The product is treated by adding the treating agent internally or externally, so that the product has water and oil resistance; the product includes paper products, plastics, fiber fabrics, furs, leathers, and / or non-woven fabrics.

15. The use according to claim 14, wherein the compound is ###0002### The paper product is treated and used as food packaging material or food container. The paper product is treated and used as food packaging material or food container.

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