Water-dispersible fluorine-free copolymer and treating agent containing same

Abstract

The present invention relates to a water-dispersed fluorine-free copolymer and a treatment agent comprising the same. The copolymer includes: 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 the fluorine-free copolymer may further comprise a repeating unit formed from another monomer (D) having good adaptability. The fluorine-free copolymer can be well dispersed in an aqueous medium; the oil-resistant temperature of the obtained treating agent is higher, and the oil-resistant performance is more stable; the hardness of the product prepared by the treating agent is higher; and in a molding production process using the treating agent, a molded product is not adhered to a mold.

Description

Technical Field

[0001] The present invention relates to the technical field of treatment agents, and in particular to a water-dispersible fluorine-free copolymer and a treatment agent containing the copolymer. Background Art

[0002] Polymers are widely used in a variety of products and give them specific functions. Fluoride is widely used because of its low surface tension and its ability to give many products excellent water and oil resistance. However, fluorine-containing oil repellents produce perfluorinated and polyfluorinated alkyl substances (PFAS) byproducts that are difficult to degrade in the environment. These substances are highly bioaccumulative, toxic, and have long-range environmental migration, causing significant impacts on the environment or ecology. Wax-containing fluorine-free oil repellents are one of the common fluorine-free oil repellents, but wax-containing fluorine-free oil repellents have many limitations in the production process of products, including easy clogging during the production process, easy yellowing of the products, general oil resistance, poor stability, and because the pH of the processing fluid is weakly acidic, it is also corrosive to the equipment.

[0003] At present, many fields are gradually using new fluorine-free compounds to replace the use of fluorine-containing oil-proofing agents. CN113123164A proposes a fluorine-free water-proof and oil-proofing agent with edible paraffin, stearic acid, gelatin, edible sodium carbonate, carboxymethyl cellulose, and starch as the main raw materials, which gives food packaging products water-proof and oil-proof properties. CN115058918A proposes a fluorine-free oil-proofing agent with acrylic acid, acrylate, epoxy silane coupling agent, etc. as the main monomers, thereby giving pulp molded products oil-proof properties. CN115515996A proposes an amide compound modified with a long-chain hydrocarbon group with 7 to 40 carbon atoms and an amide group on a bio-based material, which gives the product high-temperature oil resistance. However, the oil-proofing properties of these fluorine-free oil-proofing agents are not good. Among them, the existing fluorine-free oil-proofing agents with added silicon-containing monomers can improve the oil-proofing effect to a certain extent, but still have many defects such as low product hardness, poor oil-proofing performance stability, and mold product sticking during pulp molding production. Therefore, it is urgent to develop a new type of fluorine-free oil repellent that is non-toxic, environmentally friendly, and has significant oil repellency and stable oil repellency to solve the problems and shortcomings in the related oil repellency field. Summary of the Invention

[0004] The present invention provides a fluorine-free treatment agent comprising a water-dispersible fluorine-free copolymer. This treatment agent can be used to impart water and oil resistance to products through either internal or external addition. Products produced using this treatment agent offer numerous significant advantages over existing technologies: ① higher oil resistance temperatures, improved oil resistance, and more stable oil resistance; ② significantly improved product hardness; and ③ molded products do not adhere to molds during production.

[0005] The present invention also provides a water-dispersible fluorine-free copolymer. The water-dispersible fluorine-free copolymer comprises repeating units formed from a silicon-containing unsaturated monomer (A), repeating units formed from a monomer (B), and repeating units formed from a monomer (C) having an ionic donor group; and may further comprise repeating units formed from another optional monomer (D) with good compatibility.

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

[0007] Therefore, the first aspect of the present invention provides a water-dispersible fluorine-free copolymer, which is described in detail below.

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

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

[0010] a repeating unit formed from monomer (B); and

[0011] a repeating unit formed from a monomer (C) having an ionic donor group,

[0012] Wherein, the monomer (B) is a monomer represented by formula (4):

[0013]

[0014] Wherein, R1 is independently -H, non-fluorinated halogen or C1~C 20 an alkyl group having a straight-chain or branched structure;

[0015] X' is a structure represented by -W-, -R0-, -W-R0-, -R0-W-, or -W-R0-W-,

[0016] R0 is -(CH2) n - or C1~C 10 A alkylene group having a branched structure, wherein 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 C1~C 20Alkyl;

[0023] Q is the structure shown in formula (5):

[0024]

[0025] Z5 and / or M are independently -H, -OH, non-fluorinated halogen, C1-C 10 Alkyl, C1~C 10 Monohydric alcohol group, C2~C 10 Polyol groups or C1~C 10 A non-fluorinated halogenated alkyl group, q is an integer from 0 to 10, and

[0026] In the monomer (B), the -Q-M structure contains non-fluorinated halogen, -OH, C1-C 10 Monohydric alcohol group, C2~C 10 Polyol groups, C1~C 10 At least two or more non-fluorinated halogenated alkyl groups.

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

[0028]

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

[0030] R7 are each independently -H, C1-C 10 Alkyl or C1~C 10 The chloroalkyl group,

[0031] Each C x H 2x+1-y (OH) y The same 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 Here y≤x.

[0032] [3] Furthermore, in the above-mentioned water-dispersible fluorine-free copolymer, the monomer (A) is a monomer represented by formula (1):

[0033]

[0034] Wherein, R1 is independently -H, non-fluorinated halogen or C1~C 20 an alkyl group 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 -, -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 phenylene,

[0037] R0 are each independently -(CH2) n - or C1~C 10 A alkylene group having a branched structure, wherein 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 C1~C 20 The alkyl group,

[0044] Y is a structure shown in formula (2):

[0045]

[0046] R3 are each independently C1 to C 10 Alkyl, C6~C 20 Aryl or C7~C 20 Aralkyl, Z1 and Z2 are independently C1 to C 10 Alkyl, C6~C 20 Aryl, C7~C 20 or a structure represented by formula (3), wherein m is 1 to 300,

[0047]

[0048] R4 are each independently C1 to C10 Alkyl, C6~C 20 Aryl or C7~C 20 Z3 and Z4 are independently C1 to C 10 Alkyl, C6~C 20 Aryl or C7~C 20 The aralkyl group of alkyl is alkyl, and k is 0 to 300.

[0049] [4] Furthermore, in the above-mentioned water-dispersible fluorine-free copolymer, in the monomer (A), R1 is independently -H, non-fluorine halogen or C1-C 10 Alkyl groups having a linear or branched structure,

[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-, and R0 is independently -(CH2) n - or C1~C 10 A alkylene group having a branched structure, wherein n is an integer from 0 to 10,

[0051] In Y, R3 and / or R4 are each independently a C1-C5 alkyl group, a C6-C 10 Aryl or C7~C 12 Z3 and / or Z4 are independently C1 to C5 alkyl, C6 to C 10 Aryl or C7~C 12 wherein m is 1 to 50 and k is 0 to 50.

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

[0053]

[0054] R are each independently C1 to C5 alkyl, C6 to C 10 Aryl or C7~C 12 wherein m is 1 to 35, and k1 and k2 are each independently 0 to 35.

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

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

[0057] [8] Furthermore, in the above-mentioned water-dispersible fluorine-free copolymer, the monomer (C) is a monomer represented by formula (6):

[0058]

[0059] Wherein, R1 is independently -H, non-fluorinated halogen or C1~C 20 an alkyl group having a straight-chain or branched structure;

[0060] X' is a structure represented by -W-, -R0-, -W-R0-, -R0-W-, or -W-R0-W-,

[0061] R0 is -(CH2) n - or C1~C 10 A alkylene group having a branched structure, wherein 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 C1~C 20 Alkyl;

[0068] R5 and R6 are independently C1 to C 10 Alkyl, C6~C 20 Aryl or C7~C 25 of aralkyl.

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

[0070]

[10] Furthermore, in the above-mentioned water-dispersible fluorine-free copolymer,

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

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

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

[0074]

[11] Furthermore, in the above-mentioned water-dispersible fluorine-free copolymer,

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

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

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

[0078]

[12] Furthermore, in the above-mentioned water-dispersible fluorine-free copolymer,

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

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

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

[0082]

[13] Furthermore, in the above-mentioned water-dispersible fluorine-free copolymer, the copolymer further comprises a repeating unit formed by an optional monomer (D),

[0083] The optional monomers (D) include:

[0084] A monomer having a pyrrolidone structure and a polymerizable unsaturated group; and / or

[0085] a monomer having a blocked isocyanate group and a polymerizable unsaturated group; and / or

[0086] a monomer having an alkoxysilyl group and a polymerizable unsaturated group; and / or

[0087] A monomer having a glycidyl group and a polymerizable unsaturated group.

[0088]

[14] Furthermore, in the above-mentioned water-dispersible fluorine-free copolymer,

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

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

[0091] The weight ratio of the repeating units formed by monomer (C) relative to the copolymer is 5 to 40%; and

[0092] The weight ratio of the repeating units formed by the optional monomer (D) relative to the copolymer is 0 to 10%.

[0093]

[15] Furthermore, in the above-mentioned water-dispersible fluorine-free copolymer,

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

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

[0096] The weight ratio of the repeating units formed by monomer (C) relative to the copolymer is 10 to 35%; and

[0097] The weight ratio of the repeating units formed by the optional monomer (D) relative to the copolymer is 0 to 8%.

[0098]

[16] Furthermore, in the above-mentioned water-dispersible fluorine-free copolymer,

[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] Wherein, q is an integer from 0 to 10,

[0138] R7 are each independently -H, C1-C 10 Alkyl, C1~C 10 The chloroalkyl group,

[0139] Each C x H 2x+1-y (OH) y The same 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) ywhere y≤x,

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

[0141]

[17] Furthermore, in the above-mentioned water-dispersible fluorine-free copolymer,

[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] wherein n is independently an integer from 0 to 10,

[0156] k is independently 0 to 35,

[0157] R are independently C1 to C 10 Alkyl, C6~C 20 Aryl or C7~C 20 of aralkyl.

[0158]

[18] Furthermore, in the above-mentioned water-dispersible fluorine-free copolymer,

[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 salts thereof,

[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] The second aspect of the present invention provides a treating 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 the water-dispersible fluorine-free copolymer according to any one of [1] to

[18] above;

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

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

[0172]

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

[19] comprises the following steps:

[0173] (1) copolymerizing monomers, organic solvents, and initiators in a kettle to obtain a polymer solution;

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

[0175] (3) desolventizing the dispersed polymer solution to remove the organic solvent to obtain an aqueous dispersion;

[0176] (4) converting the amino groups in the aqueous dispersion into nitrogen oxides to obtain the treating agent comprising the aqueous dispersion type fluorine-free copolymer.

[0177]

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

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

[0179]

[22] The use of a treatment agent comprising a water-dispersible fluorine-free copolymer as described in

[19] , wherein the product is treated by internally or externally adding the treatment agent to make the product water-resistant and oil-resistant; the product includes paper products, plastics, fiber fabrics, fur, leather and / or non-woven fabrics.

[0180]

[23] Furthermore, in the application described above, the paper product is processed and used as a food packaging material or food container.

[0181] Advantageous 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 well-dispersed copolymer, which is beneficial to the preparation of the treatment agent and the processing of the product.

[0183] The obtained treating agent has higher oil resistance temperature and more stable oil resistance.

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

[0185] During the molding production process using the treating agent, the molded product does not stick to the mold. DETAILED DESCRIPTION

[0186] In order 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 a silicon-containing unsaturated monomer (A);

[0189] a repeating unit formed from monomer (B); and

[0190] The repeating unit is formed from monomer (C).

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

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

[0193] (A) Silicon-containing unsaturated monomer

[0194] The silicon-containing unsaturated monomer (A) is a monomer represented by formula (1),

[0195]

[0196] Wherein, R1 are different or the same and are independently -H, non-fluorine halogen atoms or monovalent organic groups. The monovalent organic group mentioned here can be, for example, C1 to C 20 An alkyl group having a straight chain or branched chain 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-,

[0198] -C6H4- is a phenylene group.

[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 are the same or different and are independently -(CH2) n - or C1~C 10 A branched alkylene group,

[0201] n is an integer of 0-20, preferably an integer of 0-10.

[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 C1~C 20 of alkyl.

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

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

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

[0211]

[0212] R3 are each independently C1 to C 10 Alkyl, C6~C 20 Aryl or C7~C 20 The aralkyl group is preferably a C1 to C5 alkyl group, a C6 to C 10 Aryl, C7~C 10 Z1 and Z2 are independently C1 to C 10 Alkyl, C6~C 20 Aryl, C7~C 20 or the following formula (3):

[0213]

[0214] R4 are each independently C1 to C 10 Alkyl, C6~C 20 Aryl or C7~C 20 The aralkyl group is preferably a C1 to C5 alkyl group, a C6 to C 10 Aryl, C7~C 10 Z3 and Z4 are independently C1 to C 10 Alkyl, C6~C 20 Aryl or C7~C 20 The aralkyl group is preferably a C1 to C5 alkyl group, a C6 to C 10 Aryl, C7~C 10 of aralkyl.

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

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

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

[0218]

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

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

[0221] Specific examples of the silicon-containing unsaturated monomer (A) are shown below, but the invention is not limited thereto.

[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 the abbreviation of phenyl, and n is an integer of 0 to 10.

[0267] R are independently C1 to C 10 Alkyl, C6~C 20 Aryl or C7~C 20 The aralkyl group is preferably a C1 to C5 alkyl group, a C6 to C 10 Aryl, C7~C 10 Aralkyl, particularly preferably C1 to C5 alkyl, C7 to C 10 of aralkyl.

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

[0269] As monomer (A), preferred are acryloxypropyl tris(trimethylsiloxy)silane, methacryloxypropyl tris(trimethylsiloxy)silane, acryloxypropyl tris(triethylsiloxy)silane, methacryloxypropyl tris(triethylsiloxy)silane, acrylamidopropyl tris(trimethylsiloxy)silane, methacrylamidopropyl tris(trimethylsiloxy)silane, acrylamidopropyl tris(triethylsiloxy)silane, and methacrylamidopropyl tris(triethylsiloxy)silane; more preferred are acryloxypropyl tris(trimethylsiloxy)silane, methacryloxypropyl tris(trimethylsiloxy)silane, acrylamidopropyl tris(trimethylsiloxy)silane, methacrylamidopropyl tris(trimethylsiloxy)silane, or a mixture thereof.

[0270] (B) Cross-linking monomer

[0271] Monomer (B) is a monomer other than monomer (A) and is a crosslinking monomer.

[0272] The monomer (B) contained is a monomer represented by formula (4):

[0273]

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

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

[0276] R0 is -(CH2) n - or C1~C 10 In the alkylene group having a branched structure, n is an integer of 0 to 20, and preferably an integer of 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 C1~C 20 of alkyl.

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

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

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

[0286]

[0287] Z5 are each independently -H, non-fluorinated halogen, -OH, C1-C 10 Alkyl, C1~C 10 Monohydric alcohol group, C2~C 10 Polyol groups, C1~C 10The non-fluorinated halogenated alkyl group is preferably -H, -OH, a C1-C6 monohydric alcohol group, or a C2-C6 polyhydric alcohol group.

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

[0289] q is an integer of 0-20, preferably an integer of 0-10.

[0290] In the crosslinking monomer (B), the -Q-M structure contains non-fluorinated halogen, -OH, C1-C 10 Monohydric alcohol group, C2~C 10 Polyol groups, C1~C 10 At least two or more groups in the non-fluorinated halogenated alkyl group, q is an integer from 0 to 10.

[0291] The overall structure formed by the structures Q and M in the crosslinking monomer (B) is preferably C1 to C 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 the present invention is as follows:

[0293] -C x H 2x (OH)(10≥x≥1)

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

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

[0296] In the present invention, monohydric alcohol refers to an alcohol containing only one hydroxyl group in the molecule, polyol refers to an alcohol containing two or more hydroxyl groups in the molecule, and sugar alcohol refers to a polyol with the same number of carbon atoms and hydroxyl groups (i.e., x=y) obtained by reducing aldose or ketose.

[0297] The sugar alcohol groups in the present invention have the following general formula:

[0298] -C x H x+1 (OH) x (10≥x≥2)

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

[0300] In the present invention, it is preferred to use a chain sugar alcohol group having 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 in Q-1 to Q-18 is independently -H, C1-C 10 Alkyl, C1~C 10 of chloroalkyl groups.

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

[0305] Specific examples of the monomer (B) are shown below, but the monomer is not limited thereto.

[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 are each independently -H, C1-C 10 Alkyl, C1~C 10 of chloroalkyl groups.

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

[0419] q is an integer of 0-10, preferably an integer of 0-5.

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

[0421] Preferred monomers (B) include 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-tetrahydroxy pentyl methacrylate, 2,3,4,5,6-pentahydroxyhexyl methacrylate and / or mixtures thereof, particularly preferably 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-tetrahydroxypentyl methacrylate, 2,3,4,5,6-pentahydroxyhexyl methacrylate and / or mixtures thereof.

[0422] (C) Monomers having an ionic donor group

[0423] Monomer (C) is a monomer having an ionic donor group, wherein the ionic donor group can be divided into anionic donor groups and cationic donor groups.

[0424] Examples of monomers having anion donor groups include monomers having carboxyl groups and sulfonic acid groups. Specific examples of monomers having anion donor groups include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and salts thereof. Specific examples of salts of anion donor groups include methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0425] The present invention prefers monomers (C) having cation donor groups. Examples of cation donor groups are amino groups, preferably tertiary amino groups and quaternary ammonium groups.

[0426] In the tertiary amino group, the two groups bonded to the nitrogen atom are preferably the same or different C1 to C5 alkyl, C6 to C 10 Aryl, C7~C 12 In the quaternary ammonium group, the three groups bonded to the nitrogen atom are preferably the same or different C1 to C5 alkyl, C6 to C 10 Aryl, C7~C 12 The cation donor group may be in the form of a salt.

[0427] Monomer (C) is a monomer represented by formula (6):

[0428]

[0429] R1 are different or the same, and are independently -H, non-fluorine halogen or monovalent organic group. The monovalent organic group mentioned here can be, for example, C1 to C 20 An alkyl group having a straight chain or branched chain structure.

[0430] X' is a structure represented by -W-, -R0-, -W-R0-, -R0-W-, or -W-R0-W-, and is preferably -W-R0-.

[0431] R0 is -(CH2) n - or C1~C 10 In the alkylene group having a branched structure, n is an integer of 0 to 20, and preferably an integer of 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~C 20 of alkyl.

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

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

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

[0441] R5 and R6 are the same or different and are C1~C 10 Alkyl, C6~C 20 Aryl, C7~C 25 Aralkyl (especially benzyl C6H5-CH2-). Preferably C1-C5 alkyl, C6-C 10 Aryl, C7~C 12 Aralkyl (such as benzyl C6H5-CH2-).

[0442] The cation donor group as a salt is a salt with an acid. The acid used in the present invention is preferably an organic acid, such as C1-C 10 of carboxylic acids (including acetic acid, propionic acid, butyric acid, etc.).

[0443] Specific examples of the monomer (C) are shown below, but the monomer is 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 salts thereof,

[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 salts thereof,

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

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

[0453] In addition to the repeating units formed by monomer (A), monomer (B) and monomer (C), the fluorine-free copolymer of the present invention may optionally further comprise repeating units formed by other optional monomer (D) with better adaptability.

[0454] Such optional monomers (D) include monomers having a pyrrolidone structure and a polymerizable unsaturated group, monomers having a blocked 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) include the following compounds:

[0456] As the monomer containing a pyrrolidone structure and a polymerizable unsaturated group, exemplified compounds 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 the monomer having a blocked isocyanate and a polymerizable unsaturated group include: a 2-butanone oxime adduct of 2-isocyanateethyl (meth)acrylate, a pyrazole adduct of 2-isocyanateethyl (meth)acrylate, a 3,5-dimethylpyrazole adduct of 2-isocyanateethyl (meth)acrylate, a 3-methylpyrazole adduct of 2-isocyanateethyl (meth)acrylate, an ε-caprolactam adduct of 2-isocyanateethyl (meth)acrylate, a 2-butanone oxime adduct of 3-isocyanateethyl (meth)acrylate, a pyrazole adduct of 3-isocyanateethyl (meth)acrylate, and a 2-butanone oxime adduct of 2-isocyanateethyl (meth)acrylate. adduct of 3-isocyanatoethyl (meth)acrylate, 3,5-dimethylpyrazole adduct of 3-isocyanatoethyl (meth)acrylate, 3-methylpyrazole adduct of 3-isocyanatoethyl (meth)acrylate, ε-caprolactam adduct of 3-isocyanatoethyl (meth)acrylate, 2-butanone oxime adduct of 4-isocyanatoethyl (meth)acrylate, pyrazole adduct of 4-isocyanatoethyl (meth)acrylate, 3,5-dimethylpyrazole adduct of 4-isocyanatoethyl (meth)acrylate, 3-methylpyrazole adduct of 4-isocyanatoethyl (meth)acrylate, ε-caprolactam adduct of 4-isocyanatoethyl (meth)acrylate.

[0458] Examples of the monomer containing an alkoxysilyl group and a polymerizable unsaturated group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldiethoxyethylsilane, and allyltrimethoxysilane.

[0459] As the monomer containing a glycidyl group and a polymerizable unsaturated group, compounds that can be exemplified include glycidyl (meth)acrylate and the like.

[0460] The amount of the repeating unit composed of the monomer (A) is 40 to 90% by weight, preferably 45 to 85% by weight, more preferably 50 to 85% by weight, based on the fluorine-free copolymer.

[0461] The amount of the repeating unit composed of the monomer (B) is 0.1 to 25% by weight, preferably 0.1 to 22% by weight, more preferably 0.1 to 20% by weight, based on the fluorine-free copolymer.

[0462] The amount of the repeating unit composed of the monomer (C) is 5 to 40% by weight, preferably 10 to 35% by weight, more preferably 15 to 35% by weight, based on the fluorine-free copolymer.

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

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

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

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

[0467] The polymerization method of the copolymer of the present invention is not particularly limited, and conventional polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization, and radiation polymerization can be used. For example, generally, solution polymerization using an organic solvent can be selected to prepare the treatment solution. In the present invention, solution polymerization is preferably used for preparation.

[0468] In the present invention, it is preferred that after polymerization (eg solution polymerization), water / acid solution is first added and then the organic solvent is removed to disperse the polymer in water.

[0469] Examples of the organic solvent include ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and methyl acetate; glycols 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 isopropyl alcohol.

[0470] As the polymerization initiator, for example, peroxides, azo compounds, or persulfate compounds can be used. The polymerization initiator is generally water-soluble and / or oil-soluble.

[0471] Specific examples of the oil-soluble polymerization initiator include preferably dimethyl 2,2'-azobisisobutyrate, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), dimethyl 2,2'-azobis(2-methylpropionate), benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, t-butyl peroxypivalate, and the like.

[0472] Specific examples of water-soluble polymerization initiators preferably include 2,2'-azobisisobutylamidine dihydrochloride, 2,2'-azobis(2-methylpropionamidine) hydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] hydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] sulfate hydrate, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] hydrochloride, potassium persulfate, barium persulfate, ammonium persulfate, and hydrogen peroxide.

[0473] The organic solvent in the polymer solution can be removed by heating the polymer solution (under reduced pressure).

[0474] The initiator for solution polymerization is preferably a peroxide or an azo compound with a half-life of 8 hours and a decomposition temperature of 30° C. or higher, such as tert-butyl peroxypivalate, 2,2′-azobis(2-methylpropionitrile), and the like.

[0475] The treating agent comprising the water-dispersible fluorine-free copolymer of the present invention can be preferably externally added and attached to a paper substrate or internally added to a pulp raw material.

[0476] Examples of the paper substrate as the object to be processed include paper, containers made of paper, and molded articles made of paper (for example, pulp molding).

[0477] Paper can be produced by conventional papermaking methods. For example, an internal addition method, in which an oil-resistant treatment agent is added to the pulp slurry before papermaking, or an external addition method, in which an oil-resistant treatment agent is applied to the paper after papermaking, can be employed. The treatment method of the present invention preferably employs an internal addition method.

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

[0479] In the internal addition, the amount of the treating 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 treating agent is mixed with the pulp.

[0480] In the treatment with internal addition of the treatment agent, papermaking is preferably performed using a pulp slurry having a pulp concentration of 1 to 5.0% by weight. Additives, including sizing agents, coagulants, strengthening agents, defoaming agents, and water-dispersible fluorine-free copolymers, are added to the pulp slurry. Generally, because paper pulp is anionic, it is preferred that at least one of the additive and the fluorine-free copolymer be cationic or amphoteric to ensure good fixation of the additive and the fluorine-free copolymer to the paper. Preferred combinations include a cationic or amphoteric additive and fluorine-free copolymer; a cationic or amphoteric additive and a cationic or amphoteric fluorine-free copolymer; and a cationic or amphoteric additive and an anionic fluorine-free copolymer.

[0481] Examples of additives such as sizing agents, coagulants, and reinforcing agents include alkyl ketene dimers, alkenyl succinic anhydrides, styrene-based polymers, urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide-based polymers, polyamine-based polymers, polydiallyldimethylammonium chloride, alkylamine·epichlorohydrin condensates, condensates of alkylene dichlorides and polyalkylene polyamines, dicyandiamide·formalin condensates, dimethyldiallylammonium 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 first added, and then the corresponding monomer is added for dissolution, nitrogen is introduced for displacement, an initiator is added, and the temperature is heated to a reaction temperature of 50 to 120° C. The reaction time is 5 to 30 hours.

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

[0485] (1) copolymerizing monomers, organic solvents, and initiators in a kettle to obtain a polymer solution;

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

[0487] (3) desolventizing the polymer solution to remove the organic solvent to obtain an aqueous dispersion;

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

[0489] In a preferred embodiment, in step (4), the amino groups are converted into nitrogen oxides by adding a hydrogen peroxide solution to the aqueous dispersion for treatment.

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

[0491] In the preparation of the treating agent, the copolymerization method of the fluorine-free copolymer is preferably solution polymerization.

[0492] In the present invention, the substrate is treated with a treatment agent comprising a water-dispersible fluorine-free copolymer. "Treatment" means applying the treatment agent to the substrate by dipping, spraying, coating, internal addition, or the like. During treatment, the fluorine-free copolymer, an active ingredient in the treatment agent, penetrates the substrate and / or adheres to its surface or becomes part of it.

[0493] Example

[0494] In this specification, unless otherwise specified, the terms used have the general meanings known to those skilled in the art; "%" means "% by weight"; and "part(s)" means "part(s) by weight."

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

[0496] Processing of paper products

[0497] The paper products that can be processed include thin paper, thick paper, cardboard or pulp molding, etc. 2 ) reaches 500g of paper box, or per unit area (m 2 ) reaches 100g of kraft paper, from unit area (m 2 ) up to 150g of thin paper, to unit area (m 2 ) up to 300 grams of paper and plastic products can be processed. The raw materials of paper products can be chemically bleached pulp or unbleached pulp, wood pulp, chemical mechanical pulp, mechanical pulp, etc.

[0498] Specific treatment methods for paper lunch boxes

[0499] Bleached sugarcane pulp / bleached bamboo pulp (3:7) was directly pulped with a Shore beating degree of 23°SR and a pulp concentration of 0.3%. A synthesized treatment agent was added in an amount of 8% by weight of the absolute dry pulp to produce a standard paper lunch box weighing 15 grams using a small pulping and molding system.

[0500] Oil resistance test (paper lunch box)

[0501] Place the sample on a dry glass or flat plate lined with filter paper and fill it with edible oil (salad oil, peanut oil, rapeseed oil) at a specified temperature*. After standing for 30 minutes, observe whether the sample has deformed and whether there is oil stain on the filter paper. Rating is given according to the following standards. The higher the grade, the better the oil resistance.

[0502] *Specified temperature of edible oil: hot oil test (100±5℃), cold oil test (0~5℃);

[0503] Level 4: The inner wall and the back are impermeable

[0504] Level 3: The inner wall is discolored and the back is impermeable

[0505] Level 2: Backside permeability > 5%

[0506] Level 1: 5% ≤ back penetration rate < 20%, and the sample has no deformation, and there is no obvious oil mark on the filter paper underneath

[0507] Level 0: Backside permeability ≥ 20%

[0508] Water resistance test (paper lunch box)

[0509] Place the sample on a dry glass or flat plate lined with filter paper and fill it with water at 95±5℃. After standing for 30 minutes, observe the sample for deformation and for any seepage or leakage from the bottom. If the sample does not show any deformation, seepage or leakage, it is considered "passed". If it does, it is considered "failed".

[0510] During the test, water vapor condenses at the bottom of the sample due to the temperature difference between the inside and outside of the sample. This phenomenon is not considered as negative seepage or leakage.

[0511] Evaluation of relative yellowing degree (whiteness) of lunch boxes

[0512] Under the same process conditions, prepare samples with and without the addition of a pre-synthesized treatment agent. Use the pre-synthesized treatment agent sample as the standard sample. Visually evaluate the relative yellowing (whiteness) change between the pre-synthesized treatment agent sample and the standard sample. Rating is given according to the following criteria.

[0513] Level 0: Compared with the standard product, it is obviously whiter when visually observed.

[0514] Level 1: visibly whitened compared to the standard product

[0515] Level 2: The whiteness is basically similar to the standard product when visually inspected

[0516] Level 3: Yellowing is visible when compared with the standard product

[0517] Level 4: Compared with the standard product, the yellowing is obvious

[0518] Lunch box hardness evaluation

[0519] Under the same process conditions, samples with and without the addition of a pre-treated agent were prepared. The pre-treated sample was used as a standard. The hardness changes of the samples with the pre-treated agent and the standard were visually evaluated. Ratings were given according to the following criteria.

[0520] Level 0: obviously softer than the standard product

[0521] Level 1: slightly softer than the standard product

[0522] Level 2: Similar hardness to the standard product

[0523] Level 3: Slightly harder than standard products

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

[0525] Anti-sticking performance evaluation

[0526] Use a small pulping and molding system to continuously produce 20 standard lunch boxes weighing 15 grams. Observe the mold bottom for any sticking. If no sticking occurs after 20 consecutive productions, the result is marked as "pass." If sticking occurs, the result is marked as "fail."

[0527] The following Examples and Comparative Examples illustrate the present invention in detail, but these descriptions do not limit the present invention.

[0528] In this manual, chemical abbreviations are shown 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 heater was prepared. 200 g of methyl ethyl ketone (MEK) was added as a solvent while stirring. 55 g of Si-MNP3, 15 g of JMN-201, 3 g of JMC-320, and 27 g of G-MN were then added in that order. The reaction mixture was purged with nitrogen and the temperature was slowly raised to 50°C. 1.5 g of t-butyl peroxypivalate (initiator) was slowly added. The reaction temperature was maintained at 70°C for 12 hours to allow copolymerization to proceed. The resulting solution containing the copolymer had a solids concentration of approximately 33.3% by weight.

[0534] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0535] Example 2

[0536] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heater was prepared. 200 g of methyl ethyl ketone (MEK) was added as a solvent while stirring. 65 g of Si-MNP3, 5 g of JMN-201, 2 g of JMC-430, and 28 g of G-MN were then added in that order. Nitrogen was introduced, and the temperature was slowly raised to 50°C. 1.5 g of t-butyl peroxypivalate (initiator) was slowly added. The reaction temperature was maintained at 70°C for 12 hours to allow copolymerization to proceed. The resulting solution containing the copolymer had a solids concentration of approximately 33.3% by weight.

[0537] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0538] Example 3

[0539] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heater was prepared. 200 g of isopropyl alcohol (IPA) was added as a solvent while stirring, followed by 70 g of Si-MNP3, 4 g of JMN-320, and 26 g of G-MN. The mixture was purged with nitrogen, and the temperature was slowly raised to 50°C. 1.5 g of t-butyl peroxypivalate (initiator) was slowly added, and the reaction temperature was maintained at 70°C for 12 hours to allow copolymerization to proceed. The resulting solution containing the copolymer had a solids concentration of approximately 33.3% by weight.

[0540] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0541] Example 4

[0542] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heater was prepared. 200 g of isopropyl alcohol (IPA) was added as a solvent while stirring, followed by 80 g of Si-MNP3, 2 g of JMC-540, and 18 g of G-MN. The reaction mixture was purged with nitrogen, and the temperature was slowly raised to 50°C. 1.5 g of t-butyl peroxypivalate (initiator) was slowly added, and the reaction temperature was maintained at 70°C for 12 hours to allow copolymerization to proceed. The resulting solution containing the copolymer had a solids concentration of approximately 33.3% by weight.

[0543] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0544] Example 5

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

[0546] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0547] Example 6

[0548] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heater was prepared. 200 g of isopropyl alcohol (IPA) was added as a solvent while 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 was introduced, the temperature was slowly raised to 50°C, and 1.5 g of the initiator, 2,2'-dimethyl azobisisobutyrate, was slowly added. The reaction temperature was controlled at 75°C and the reaction was allowed to proceed for 12 hours to effect copolymerization. The resulting solution containing the copolymer had a solids concentration of approximately 33.3% by weight.

[0549] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0550] Example 7

[0551] Preparation possesses the reactor of the volume 500mL of whipping appts, thermometer, reflux cooler, dropping funnel, nitrogen inlet and heater, under agitation add 200 grams of isopropyl alcohol (IPA) as solvent, then add 60 grams of Si-MCP7, 10 grams of JMN-201, 2 grams of JMC-430 and 28 grams of G-MN successively.Burn nitrogen replacement, slowly be warming up to 50 ℃, and slowly add 1.5 grams of initiator tert-butyl peroxypivalate, 70 ℃ of controlled reaction temperature reactions 12 hours, carry out copolymerization.The solid component concentration of the resulting solution that contains multipolymer is about 33.3 weight %.

[0552] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0553] Example 8

[0554] Preparation possesses the reactor of the volume 500mL of agitating appts, thermometer, reflux cooler, dropping funnel, nitrogen inlet and heater, under agitation add 200 grams of isopropyl alcohol (IPA) as solvent, then add 70 grams of Si-MCP7, 4 grams of JMN-320 and 26 grams of G-MN successively.Burn nitrogen replacement, slowly be warming up to 50 ℃, and slowly add 1.5 grams of initiator tert-butyl peroxypivalate, control 70 ℃ of reactions of temperature of reaction 12 hours, carry out copolymerization.The solid component concentration of the resulting solution that contains copolymer is about 33.3 weight %.

[0555] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0556] Example 9

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

[0558] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0559] Example 10

[0560] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heater was prepared. 200 g of isopropyl alcohol (IPA) was added as a solvent while 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 was introduced, the temperature was slowly raised to 50°C, and 0.8 g of the initiator, 2,2'-azobisisobutyronitrile, was slowly added. The reaction temperature was maintained at 75°C for 12 hours to allow copolymerization to proceed. The resulting solution containing the copolymer had a solids concentration of approximately 33.3% by weight.

[0561] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0562] Example 11

[0563] Prepare the reactor with a capacity of 500mL equipped with a stirring device, a thermometer, a reflux cooler, a dropping funnel, a nitrogen inlet and a heater. Under stirring, 200 grams of methyl ethyl ketone (MEK) are added as a solvent, followed by the sequential addition of 65 grams of Si-MCPn, 6 grams of JMN-201, 1 gram of JMC-650 and 28 grams of G-MN. Nitrogen is introduced for replacement, the temperature is slowly raised to 50°C, and 1.5 grams of initiator tert-butyl peroxypivalate are slowly added. The reaction temperature is controlled to be 70°C for 12 hours for copolymerization. The solid content concentration of the resulting solution containing the copolymer is approximately 33.3% by weight.

[0564] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0565] Example 12

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

[0567] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0568] Example 13

[0569] Preparation possesses the reactor of the volume 500mL of agitating appts, thermometer, reflux cooler, dropping funnel, nitrogen inlet and heater, under agitation add 200 grams of isopropyl alcohol (IPA) as solvent, then add 65 grams of Si-MCPn, 6 grams of JMC-430 and 29 grams of G-MN successively.Burn nitrogen replacement, slowly be warming up to 50 ℃, and slowly add 1.5 grams of initiator tert-butyl peroxypivalate, control 70 ℃ of reactions of temperature of reaction 12 hours, carry out copolymerization.The solid component concentration of the resulting solution that contains copolymer is about 33.3 weight %.

[0570] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0571] Example 14

[0572] Preparation possesses the reactor of the volume 500mL of agitating device, thermometer, reflux cooler, dropping funnel, nitrogen inlet and heater, under stirring, add 200 grams of isopropyl alcohol (IPA) as solvent, then add 70 grams of Si-MCPn, 6 grams of JMN-320 and 24 grams of G-MN in sequence.Burn into nitrogen replacement, slowly be warming up to 50 ℃, and slowly add 1.5 grams of initiator tert-butyl peroxypivalate, control reaction temperature 70 ℃ of reactions 12 hours, carry out copolymerization. The solid component concentration of the resulting solution that contains copolymer is about 33.3 weight %.

[0573] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0574] Example 15

[0575] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heater was prepared. 200 g of isopropyl alcohol (IPA) was added as a solvent while 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 was introduced, the temperature was slowly raised to 50°C, and 0.8 g of the initiator, 2,2'-azobisisobutyronitrile, was slowly added. The reaction temperature was maintained at 75°C for 12 hours to allow copolymerization to proceed. The resulting solution containing the copolymer had a solids concentration of approximately 33.3% by weight.

[0576] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0577] Example 16

[0578] Preparation possesses the reactor of the volume 500mL of agitating device, thermometer, reflux cooler, dropping funnel, nitrogen inlet and heater, under stirring, add 200 grams of methyl ethyl ketone (MEK) as solvent, then add 80 grams of Si-MCPn, 2 grams of JMC-650 and 18 grams of G-MN in sequence. Feed nitrogen replacement, slowly be warming up to 50 ℃, and slowly add 1.5 grams of initiator tert-butyl peroxypivalate, control reaction temperature 70 ℃ of reactions 12 hours, carry out copolymerization. The solid component concentration of the resulting solution that contains copolymer is about 33.3 weight %.

[0579] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0580] Example 17

[0581] Preparation possesses the reactor of the volume 500mL of agitating appts, thermometer, reflux cooler, dropping funnel, nitrogen inlet and heater, under agitation add 200 grams of isopropyl alcohol (IPA) as solvent, then add 60 grams of Si-MCP3, 10 grams of JMN-201, 2 grams of JMN-320 and 28 grams of G-MN successively.Burn nitrogen replacement, slowly be warming up to 50 ℃, and slowly add 1.5 grams of initiator tert-butyl peroxypivalate, control 70 ℃ of reactions of temperature of reaction 12 hours, carry out copolymerization.The solid component concentration of the resulting solution that contains copolymer is about 33.3 weight %.

[0582] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0583] Example 18

[0584] Preparation possesses the reactor of the volume 500mL of whipping appts, thermometer, reflux cooler, dropping funnel, nitrogen inlet and heater, under agitation add 200 grams of isopropyl alcohol (IPA) as solvent, then add 65 grams of Si-MCP3, 8 grams of JMN-320 and 27 grams of G-MN successively.Burn nitrogen replacement, slowly be warming up to 50 ℃, and slowly add 1.5 grams of initiator tert-butyl peroxypivalate, control 70 ℃ of reactions of temperature of reaction 12 hours, carry out copolymerization.The solid component concentration of the resulting solution that contains copolymer is about 33.3 weight %.

[0585] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0586] Example 19

[0587] Preparation possesses the reactor of the volume 500mL of whipping appts, thermometer, reflux cooler, dropping funnel, nitrogen inlet and heater, under agitation add 200 gram isopropyl alcohols (IPA) as solvent, then add 70 gram Si-MCP3, 5 gram JMC-320 and 25 gram G-MN successively.Burn nitrogen replacement, slowly be warming up to 50 ℃, and slowly add 1.5 gram initiator tert-butyl peroxypivalate, 70 ℃ of controlled reaction temperature reactions 12 hours, carry out copolymerization.The solid component concentration of the resulting solution that contains multipolymer is about 33.3 % by weight.

[0588] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0589] Example 20

[0590] Preparation possesses the reactor of the volume 500mL of whipping appts, thermometer, reflux cooler, dropping funnel, nitrogen inlet and heater, under agitation add 200 grams of isopropyl alcohol (IPA) as solvent, then add 75 grams of Si-MCP3, 4 grams of JMC-430 and 21 grams of G-MN successively.Burn nitrogen replacement, slowly be warming up to 50 ℃, and slowly add 1.5 grams of initiator tert-butyl peroxypivalate, 70 ℃ of controlled reaction temperature reactions 12 hours, carry out copolymerization.The solid component concentration of the resulting solution that contains multipolymer is about 33.3 weight %.

[0591] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0592] Example 21

[0593] Preparation possesses the reactor of the volume 500mL of whipping appts, thermometer, reflux cooler, dropping funnel, nitrogen inlet and heater, under agitation add 200 grams of methyl ethyl ketone (MEK) as solvent, then add 75 grams of Si-MCP3, 2 grams of JMC-540 and 23 grams of G-MN successively.Burn nitrogen replacement, slowly be warming up to 50 ℃, and slowly add 1.5 grams of initiator tert-butyl peroxypivalate, control 70 ℃ of reactions of temperature of reaction 12 hours, carry out copolymerization.The solid component concentration of the resulting solution that contains copolymer is about 33.3 weight %.

[0594] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0595] Example 22

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

[0597] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0598] Example 23

[0599] Preparation possesses the reactor of the volume 500mL of whipping appts, thermometer, reflux cooler, dropping funnel, nitrogen inlet and heater, under agitation add 200 grams of isopropyl alcohol (IPA) as solvent, then add 75 grams of Si-MCP3, 2 grams of JC-320 and 23 grams of G-MN successively.Burn nitrogen replacement, slowly be warming up to 50 ℃, and slowly add 1.5 grams of initiator tert-butyl peroxypivalate, control 70 ℃ of reactions of temperature of reaction 12 hours, carry out copolymerization.The solid component concentration of the resulting solution that contains multipolymer is about 33.3 weight %.

[0600] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0601] Example 24

[0602] Preparation possesses the reactor of the volume 500mL of whipping appts, thermometer, reflux cooler, dropping funnel, nitrogen inlet and heater, under agitation add 200 grams of isopropyl alcohol (IPA) as solvent, then add 75 grams of Si-MCP3, 2 grams of JMEO-650 and 23 grams of G-MN successively.Burn nitrogen replacement, slowly be warming up to 50 ℃, and slowly add 1.5 grams of initiator tert-butyl peroxypivalate, control 70 ℃ of reactions of temperature of reaction 12 hours, carry out copolymerization.The solid component concentration of the resulting solution that contains copolymer is about 33.3 weight %.

[0603] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0604] Example 25

[0605] Preparation possesses the reactor of the volume 500mL of whipping appts, thermometer, reflux cooler, dropping funnel, nitrogen inlet and heater, under agitation add 200 grams of isopropyl alcohol (IPA) as solvent, then add 75 grams of Si-MCP3, 2 grams of JERE-650 and 23 grams of G-MN successively.Burn nitrogen replacement, slowly be warming up to 50 ℃, and slowly add 1.5 grams of initiator tert-butyl peroxypivalate, control 70 ℃ of reactions of temperature of reaction 12 hours, carry out copolymerization.The solid component concentration of the resulting solution that contains multipolymer is about 33.3 weight %.

[0606] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0607] Example 26

[0608] Preparation possesses the reactor of the volume 500mL of agitating device, thermometer, reflux cooler, dropping funnel, nitrogen inlet and heater, under stirring, add 200 grams of isopropyl alcohol (IPA) as solvent, then add 75 grams of Si-MCPn, 2 grams of JMPO-650 and 23 grams of G-MN in sequence. Feed nitrogen replacement, slowly be warming up to 50 ℃, and slowly add 1.5 grams of initiator tert-butyl peroxypivalate, control reaction temperature 70 ℃ of reactions 12 hours, carry out copolymerization. The solid component concentration of the resulting solution that contains copolymer is about 33.3 weight %.

[0609] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0610] Example 27

[0611] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heater was prepared. 200 g of isopropyl alcohol (IPA) was added as a solvent while 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 was introduced, the temperature was slowly raised to 50°C, and 0.8 g of the initiator 2,2'-azobisisobutyronitrile was slowly added. The reaction temperature was controlled at 70°C and the reaction was allowed to proceed for 12 hours to carry out copolymerization. The resulting solution containing the copolymer had a solids concentration of approximately 33.3% by weight.

[0612] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0613] Example 28

[0614] A 500 mL reactor equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heater was prepared. 200 g of isopropyl alcohol (IPA) was added as a solvent while stirring, followed by 75 g of Si-MNP3, 1 g of JMC-650, 2 g of J-220, and 22 g of G-MN. The reaction mixture was purged with nitrogen, and the temperature was slowly raised to 50°C. 1.5 g of t-butyl peroxypivalate (initiator) was slowly added, and the reaction temperature was maintained at 70°C for 12 hours to allow copolymerization to proceed. The resulting solution containing the copolymer had a solids concentration of approximately 33.3% by weight.

[0615] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0616] Comparative Example 1

[0617] Preparation possesses the reactor of the volume 500mL of whipping appts, thermometer, reflux cooler, dropping funnel, nitrogen inlet and heater, under agitation add 200 grams of isopropyl alcohol (IPA) as solvent, then add 70 grams of Si-MCP3, 7 grams of HEMA and 23 grams of G-MN successively.Burn nitrogen replacement, slowly be warming up to 50 ℃, and slowly add 1.5 grams of initiator tert-butyl peroxypivalate, control 70 ℃ of reactions of temperature of reaction 12 hours, carry out copolymerization.The solid component concentration of the resulting solution that contains multipolymer is about 33.3 weight %.

[0618] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0619] Comparative Example 2

[0620] Preparation possesses the reactor of the volume 500mL of agitating device, thermometer, reflux cooler, dropping funnel, nitrogen inlet and heater, under stirring, add 200 grams of methyl ethyl ketone (MEK) as solvent, then add 75 grams of Si-MCP3, 5 grams of HBMA and 20 grams of G-MN in sequence. Feed nitrogen replacement, slowly be warming up to 50 ℃, and slowly add 1.5 grams of initiator tert-butyl peroxypivalate, control reaction temperature 70 ℃ of reactions 12 hours, carry out copolymerization. The solid component concentration of the resulting solution that contains copolymer is about 33.3 weight %.

[0621] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0622] Comparative Example 3

[0623] Preparation possesses the reactor of the volume 500mL of whipping appts, thermometer, reflux cooler, dropping funnel, nitrogen inlet and heater, under agitation add 200 grams of isopropyl alcohol (IPA) as solvent, then add 65 grams of Si-MCP3, 10 grams of HEMAA and 25 grams of G-MN successively.Burn into nitrogen replacement, slowly be warming up to 50 ℃, and slowly add 1.5 grams of initiator tert-butyl peroxypivalate, control 70 ℃ of reactions of temperature of reaction 12 hours, carry out copolymerization.The solid component concentration of the resulting solution that contains copolymer is about 33.3 weight %.

[0624] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0625] Comparative Example 4

[0626] Preparation possesses the reactor of the volume 500mL of agitating device, thermometer, reflux cooler, dropping funnel, nitrogen inlet and heater, under agitation add 200 grams of isopropyl alcohol (IPA) as solvent, then add 65 grams of Si-MCPn, 10 grams of HEMAA and 25 grams of G-MC successively.Burn into nitrogen replacement, slowly be warming up to 50 ℃, and slowly add 1.5 grams of initiator tert-butyl peroxypivalate, control 70 ℃ of reactions of temperature of reaction 12 hours, carry out copolymerization. The solid component concentration of the resulting solution that contains copolymer is about 33.3 weight %.

[0627] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0628] Comparative Example 5

[0629] Prepare a 500mL reactor equipped with a stirring device, a thermometer, a reflux cooler, a dropping funnel, a nitrogen inlet, and a heater. 200 grams of methyl ethyl ketone (MEK) were added as a solvent under stirring, followed by the addition of 70 grams of Si-MCPn, 10 grams of HBA, and 20 grams of G-MN. Nitrogen was introduced for replacement, the temperature was slowly raised to 50°C, and 1.5 grams of initiator tert-butyl peroxypivalate were slowly added. The reaction temperature was controlled to 70°C for 12 hours to copolymerize. The resulting solution containing the copolymer had a solids content of approximately 33.3% by weight.

[0630] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0631] Comparative Example 6

[0632] Prepare a 500mL reactor equipped with a stirring device, a thermometer, a reflux cooler, a dropping funnel, a nitrogen inlet, and a heater. Under stirring, 200 grams of isopropyl alcohol (IPA) are added as a solvent, followed by the addition of 75 grams of Si-MCPn, 5 grams of HBMA, and 20 grams of G-MC. Nitrogen is introduced for replacement, the temperature is slowly raised to 50°C, and 1.5 grams of initiator tert-butyl peroxypivalate are slowly added. The reaction temperature is controlled to 70°C for 12 hours to copolymerize. The solid content concentration of the resulting solution containing the copolymer is approximately 33.3% by weight.

[0633] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0634] Comparative Example 7

[0635] Preparation possesses the reactor of the volume 500mL of whipping appts, thermometer, reflux cooler, dropping funnel, nitrogen inlet and heater, under agitation add 200 grams of methyl ethyl ketone (MEK) as solvent, then add 70 grams of Si-MCP3, 6 grams of HEMA, 1 gram of MOI-BP and 23 grams of G-MN successively.Burn nitrogen replacement, slowly be warming up to 50 ℃, and slowly add 1.5 grams of initiator tert-butyl peroxypivalate, control 70 ℃ of reactions of temperature of reaction 12 hours, carry out copolymerization.The solid component concentration of the resulting solution that contains copolymer is about 33.3 weight %.

[0636] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0637] Comparative Example 8

[0638] Preparation possesses the reactor of the volume 500mL of agitating appts, thermometer, reflux cooler, dropping funnel, nitrogen inlet and heater, under agitation add 200 grams of isopropyl alcohol (IPA) as solvent, then add 77 grams of Si-MCP3 and 23 grams of G-MN successively.Burn nitrogen replacement, slowly be warming up to 50 ℃, and slowly add 1.5 grams of initiator tert-butyl peroxypivalate, control 70 ℃ of reactions of temperature of reaction 12 hours, carry out copolymerization.The solid component concentration of the resulting solution that contains copolymer is about 33.3 weight %.

[0639] 200 g of 4.8% acetic acid solution was added to the polymerization solution and stirred to form salts. 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 obtain a water-dispersible treatment agent with a solids concentration of 20% by weight.

[0640] The treatment agents synthesized in the examples and comparative examples were used to test 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 beating degree of 23°SR and a pulp concentration of 0.3%. A synthesized treatment agent was added in an amount of 8% of the absolute dry pulp weight. A standard lunch box weighing 15 grams was made using a small pulping and molding system, and the water resistance, oil resistance, hardness, whiteness, and anti-sticking properties of the lunch box were tested.

[0643] The performance test results are shown in Table 2, Table 3, Table 4 and Table 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, compared to Comparative Examples 7-8, the anti-sticking properties of each embodiment are significantly improved. In addition, compared to Comparative Examples 4-6, the hot oil resistance and cold oil resistance of Examples 1-16 are significantly improved. Compared to Comparative Examples 1-3, the hot oil resistance, cold oil resistance and hardness of the paper lunch box of Examples 17-28 are significantly improved. Overall, it can be seen from the results of the Examples and Comparative Examples that the treatment agent comprising the fluorine-free copolymer 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 the production process, and the final product produced has a higher hardness.

[0653] Although the embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. A person skilled in the art may alter, modify, replace and modify the above embodiments within the scope of the present invention.

[0654] The technical solution of the present invention is not limited to the above-mentioned specific embodiments. Any technical variations made according to the technical solution of the present invention fall within the protection scope of the present invention.

Claims

1. A water-dispersible fluorine-free copolymer, characterized in that: The copolymer comprises: Repeating units formed from a silicon-containing unsaturated monomer (A); a repeating unit formed from monomer (B); and a repeating unit formed from a monomer (C) having an ionic donor group, Wherein, the monomer (B) is a monomer represented by formula (4): Wherein, R1 is independently -H, non-fluorinated halogen or C1~C 20 an alkyl group having a straight-chain or branched structure; X' is a structure represented by -W-, -R0-, -W-R0-, -R0-W-, or -W-R0-W-, R0 is -(CH2) n - or C1~C 10 A alkylene group having a branched structure, wherein n is an integer from 0 to 20, W is selected from the structures shown in W1 to W4: -C(=O)-O- W1 -C(=O)-N(R2)- W2 -O- W3 -O-C(=O)- W4 R2 is -H or C1~C 20 Alkyl; Q is the structure shown in formula (5): Z5 and / or M are independently -H, -OH, non-fluorinated halogen, C1-C 10 Alkyl, C1~C 10 Monohydric alcohol group, C2~C 10 Polyol groups or C1~C 10 A non-fluorinated halogenated alkyl group, q is an integer from 0 to 10, and In the monomer (B), the -Q-M structure contains non-fluorinated halogen, -OH, C1-C 10 Monohydric alcohol group, C2~C 10 Polyol groups, C1~C 10 At least two or more non-fluorinated halogenated alkyl groups.

2. The water-dispersible fluorine-free copolymer according to claim 1, characterized in that Q is selected from one or more of the following structures Q-1 to Q-18: Wherein, q is an integer from 0 to 10, R7 are each independently -H, C1-C 10 Alkyl or C1~C 10 The chloroalkyl group, Each C x H 2x+1-y (OH) y The same 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 Here 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~C 20 an alkyl group 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-, -C6H4- is phenylene, R0 are each independently -(CH2) n - or C1~C 10 A alkylene group having a branched structure, wherein n is an integer from 0 to 20, W is selected from the structures shown in W1 to W4: -C(=O)-O-W1 -C(=O)-N(R2)-W2 -O-W3 -O-C(=O)-W4 R2 is -H or C1~C 20 The alkyl group, Y is a structure shown in formula (2): R3 are each independently C1 to C 10 Alkyl, C6~C 20 Aryl or C7~C 20 Aralkyl, Z1 and Z2 are independently C1 to C 10 Alkyl, C6~C 20 Aryl, C7~C 20 or a structure represented by formula (3), wherein m is 1 to 300, R4 are each independently C1 to C 10 Alkyl, C6~C 20 Aryl or C7~C 20 Z3 and Z4 are independently C1 to C 10 Alkyl, C6~C 20 Aryl or C7~C 20 The aralkyl group of alkyl is alkyl, and k is 0 to 300.

4. The water-dispersible fluorine-free copolymer according to claim 3, characterized in that In the monomer (A), R1 is independently -H, non-fluorinated halogen or C1-C 10 Alkyl groups 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 R0 is independently -(CH2) n - or C1~C 10 A alkylene group having a branched structure, wherein n is an integer from 0 to 10, In Y, R3 and / or R4 are each independently a C1-C5 alkyl group, a C6-C 10 Aryl or C7~C 12 Z3 and / or Z4 are independently C1 to C5 alkyl, C6 to C 10 Aryl or C7~C 12 wherein m is 1 to 50 and k is 0 to 50.

5. The water-dispersible fluorine-free copolymer according to claim 3 or 4, characterized in that Y is selected from one or more of the following structures Y-1 to Y-3: R are each independently C1 to C5 alkyl, C6 to C 10 Aryl or C7~C 12 wherein m is 1 to 35, and k1 and k2 are each independently 0 to 35.

6. The water-dispersible fluorine-free copolymer according to any one of claims 1 to 5, characterized in that The ionic donor group contained in the monomer (C) is a cationic donor group.

7. The water-dispersible fluorine-free copolymer according to claim 6, characterized in that The cation donor group is an amino group.

8. The water-dispersible fluorine-free copolymer according to any one of claims 1 to 7, characterized in that The monomer (C) is a monomer represented by formula (6): Wherein, R1 is independently -H, non-fluorinated halogen or C1~C 20 an alkyl group having a straight-chain or branched structure; X' is a structure represented by -W-, -R0-, -W-R0-, -R0-W-, or -W-R0-W-, R0 is -(CH2) n - or C1~C 10 A alkylene group having a branched structure, wherein n is an integer from 0 to 20, W is selected from the structures shown in W1 to W4: -C(=O)-O-W1 -C(=O)-N(R2)-W2 -O-W3 -O-C(=O)-W4 R2 is -H or C1~C 20 Alkyl; R5 and R6 are independently C1 to C 10 Alkyl, C6~C 20 Aryl or C7~C 25 of aralkyl.

9. The water-dispersible fluorine-free copolymer according to claim 8, characterized in that In the monomer (C), R5 and R6 are each independently a benzyl group.

10. The water-dispersible fluorine-free copolymer according to any one of claims 1 to 9, characterized in that The weight ratio of the repeating units formed by monomer (A) relative to the copolymer is 40 to 90%; The weight ratio of the repeating unit formed by monomer (B) to the copolymer is 0.1 to 25%; The weight ratio of the repeating unit formed from the monomer (C) to the copolymer is 5 to 40%.

11. The water-dispersible fluorine-free copolymer according to any one of claims 1 to 9, characterized in that The weight ratio of the repeating units formed by monomer (A) to the copolymer is 45 to 85%; The weight ratio of the repeating unit formed by monomer (B) relative to the copolymer is 0.1 to 22%; The weight ratio of the repeating unit formed from the monomer (C) to the copolymer is 10 to 35%.

12. The water-dispersible fluorine-free copolymer according to any one of claims 1 to 9, characterized in that The weight ratio of the repeating units formed by monomer (A) to the copolymer is 50 to 85%; The weight ratio of the repeating unit formed by monomer (B) relative to the copolymer is 0.1 to 20%; The weight ratio of the repeating unit formed from the monomer (C) to the copolymer is 15 to 35%.

13. The water-dispersible fluorine-free copolymer according to any one of claims 1 to 9, characterized in that The copolymer further comprises repeating units formed from optional monomer (D), The optional monomers (D) include: 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.

14. The water-dispersible fluorine-free copolymer according to claim 13, characterized in that The weight ratio of the repeating units formed by monomer (A) relative to the copolymer is 40 to 90%; The weight ratio of the repeating unit formed by monomer (B) to the copolymer is 0.1 to 25%; The weight ratio of the repeating units formed by monomer (C) relative to the copolymer is 5 to 40%; and The weight ratio of the repeating units formed by the optional monomer (D) relative to the copolymer is 0 to 10%.

15. The water-dispersible fluorine-free copolymer according to claim 13, characterized in that The weight ratio of the repeating units formed by monomer (A) to the copolymer is 45 to 85%; The weight ratio of the repeating unit formed by monomer (B) relative to the copolymer is 0.1 to 22%; The weight ratio of the repeating units formed by monomer (C) relative to the copolymer is 10 to 35%; as well as The weight ratio of the repeating units formed by the optional monomer (D) relative to the copolymer is 0 to 8%.

16. The water-dispersible fluorine-free copolymer according to any one of claims 1 to 9, characterized in that The monomer (B) is selected from one or more of the following: CH2=C(CH3)-C(=O)-NH-CH2CH2Cl 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)-OC(=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(=O)-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(=O)-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(=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=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(=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=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(=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=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(=O)-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 from 0 to 10, R7 are each independently -H, C1-C 10 Alkyl, C1~C 10 The chloroalkyl group, Each C x H 2x+1-y (OH) y The same 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 where y≤x, M is -H, -Cl, -OH, a C1-C6 monohydric alcohol group, or a C2-C6 polyhydric alcohol group.

17. The water-dispersible fluorine-free copolymer according to any one of claims 1 to 9, characterized in that 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(=O)-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(=O)-NH-(CH2) n Si[O(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 is independently an integer from 0 to 10, k is independently 0 to 35, R are independently C1 to C 10 Alkyl, C6~C 20 Aryl or C7~C 20 of aralkyl.

18. The water-dispersible fluorine-free copolymer according to any one of claims 1 to 9, characterized in that The monomer (C) is selected from one or more of the following: CH2=CHCOO—CH2CH2—N(CH3)2 and / or its salts, CH2=CHCOO—CH2CH2—N(CH2CH3)2 and / or its salts, CH2=C(CH3)COO-CH2CH2-N(CH3)2 and / or its salts, CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and / or its salts, CH2=CH-C(=O)-NH-CH2CH2-N(CH3)2 and / or salts thereof, CH2=CH-C(=O)-NH-CH2CH2-N(CH2CH3)2 and / or its salts, CH2=C(CH3)-C(=O)-NH-CH2CH2-N(CH3)2 and / or its salts, and CH2=C(CH3)-C(=O)-NH-CH2CH2-N(CH2CH3)2 and / or its salts.

19. A treatment agent comprising a water-dispersible fluorine-free copolymer, characterized in that: The water-dispersible fluorine-free copolymer is a water-dispersible fluorine-free copolymer according to any one of claims 1 to 18; The treatment agent further comprises a liquid medium of water, an organic solvent or a mixture of water and an organic solvent.

20. The method for preparing a treatment agent comprising a water-dispersible fluorine-free copolymer according to claim 19, wherein: The following steps are involved: (1) copolymerizing monomers, organic solvents, and initiators in a kettle to obtain a polymer solution; (2) adding an acid solution to the polymer solution for dispersion treatment; (3) desolventizing the dispersed polymer solution to remove the organic solvent to obtain an aqueous dispersion; (4) converting the amino groups in the aqueous dispersion into nitrogen oxides to obtain the treating agent comprising the aqueous dispersion type fluorine-free copolymer.

21. The preparation method according to claim 20, characterized in that In step (4), the amino groups are converted into nitrogen oxides by adding a hydrogen peroxide solution to the aqueous dispersion for treatment.

22. Use of the treating agent comprising a water-dispersible fluorine-free copolymer according to claim 19, characterized in that: After the product is treated by internally or externally adding the treatment agent, the product is made water-resistant and oil-resistant; The products include paper products, plastics, fiber fabrics, fur, leather and / or non-woven fabrics.

23. The use according to claim 22, characterized in that After being processed, the paper product can be used as food packaging material or food container.

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