CN120441760A - Water-dispersible fluorine-free copolymer and treating agent containing same - Google Patents

Abstract

The present invention relates to a water-dispersible fluorine-free copolymer and a treatment agent containing the copolymer. The 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. The fluorine-free copolymer may also comprise repeating units formed from another monomer (D) with good compatibility. The fluorine-free copolymer is well dispersed in aqueous media. The resulting treatment agent exhibits higher oil temperature resistance and more stable oil resistance. Products produced using the treatment agent exhibit higher hardness. Furthermore, during molding production using the treatment agent, molded products do not stick to the mold.

Description

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

Technical Field

The invention relates to the technical field of treating agents, in particular to a water-dispersible fluorine-free copolymer and a treating agent containing the copolymer.

Background

Polymers are widely used in a variety of products and impart specific functions thereto. The fluoride has been widely used because of its low surface tension and imparts excellent water and oil repellency to a wide variety of products. However, fluorine-containing oil-repellent agents produce perfluoro and polyfluoroalkyl species (PFAS) by-products that are environmentally difficult to degrade, which are highly bioaccumulative, toxic and have long-range environmental mobility, and have a non-negligible impact on the environment or ecology. The wax-containing fluorine-free oil-proofing agent is one of the common fluorine-free oil-proofing agents, but the wax-containing fluorine-free oil-proofing agent has a plurality of limitations in the production process of products, including easy blockage in the production process, easy yellowing of the products, general oil-proofing performance and poor stability, and has certain corrosiveness to equipment due to the weak acidity of the pH of the processing liquid.

Currently, many fields are gradually utilizing novel fluorine-free compounds to replace the use of fluorine-containing oil-repellent agents. CN113123164a proposes a fluorine-free water-proof and oil-proof agent which takes edible paraffin, stearic acid, gelatin, edible sodium carbonate, carboxymethyl cellulose and starch as main raw materials, and endows water-proof and oil-proof performance to food packaging products. CN115058918a proposes a fluorine-free oil-repellent agent using acrylic acid, acrylic ester, epoxy silane coupling agent, etc. as main monomers, thereby imparting oil-repellent properties to pulp molded products. CN115515996a proposes an oil-resistant agent which is obtained by modifying an amide compound having a long-chain hydrocarbon group having 7 to 40 carbon atoms and an amide group on a bio-based material and imparts high-temperature oil resistance to the product. However, these fluorine-free oil-repellent agents are not excellent in oil-repellent performance. The existing fluorine-free oil-proofing agent added with the silicon-containing monomer can improve certain oil-proofing effect, but has the defects of low product hardness, poor oil-proofing performance stability, mold sticking of a mold product in the pulp molding production process and the like. Therefore, development of a novel non-toxic and environment-friendly fluorine-free oil-proofing agent with remarkable oil-proofing effect and stable oil-proofing performance is needed to solve the problems and the defects in the related oil-proofing field.

Disclosure of Invention

The invention aims to provide a treating agent containing a water-dispersible fluorine-free copolymer, which does not contain fluorine and can endow a product with water resistance and oil resistance through an internally or externally added treatment mode. Compared with the prior art, the product prepared by the treating agent has the remarkable advantages of higher oil-resistant temperature ①, better oil-resistant effect, more stable oil-resistant performance, greatly improved hardness of ② products, non-sticking of molded products in the ③ molding production process, and the like.

The invention also provides a water-dispersible fluorine-free copolymer. The water-dispersible fluorine-free copolymer comprises a repeating unit formed by a silicon-containing unsaturated monomer (A), a repeating unit formed by a monomer (B) and a repeating unit formed by a monomer (C) having an ionic donor group, and may further comprise a repeating unit formed by an optional other monomer (D) having a good suitability.

In addition to the water-dispersible fluorine-free copolymer, 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.

Thus, in a first aspect the present invention provides a water-dispersible fluorine-free copolymer, as described in detail below.

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

A repeating unit formed from a silicon-containing unsaturated monomer (a);

Repeating units formed from the monomers (B), and

A repeating unit formed from a monomer (C) having an ionic donor group,

Wherein the monomer (B) is a monomer represented by the formula (4):

Wherein R ₁ is independently-H, non-fluorine halogen or C ₁～C₂₀ alkyl with straight chain or branched chain structure;

X' is a structure shown as-W-, -R ₀－、－W－R₀－、－R₀ -W-or-W-R ₀ -W-,

R ₀ is- (CH ₂)_n -or C ₁～C₁₀ alkylene with branched chain structure, n is an integer of 0-20,

W is selected from the structures shown in W ₁～W₄:

-C(=O)-O- W₁

-C(=O)-N(R₂)－ W₂

-O- W₃

-O-C(=O)- W₄

R ₂ is-H or C ₁～C₂₀ alkyl;

Q is a structure represented by formula (5):

Z ₅ and/or M are each independently-H, -OH, non-fluorine halogen, C ₁～C₁₀ alkyl, C ₁～C₁₀ monohydric alcohol group, C ₂～C₁₀ polyhydric alcohol group or C ₁～C₁₀ non-fluorine halogenated alkyl group, q is an integer of 0 to 10, and

In the monomer (B), at least 2 or more groups of non-fluorine halogen, -OH, monohydric alcohol group of C ₁～C₁₀, polyhydric alcohol group of C ₂～C₁₀ and non-fluorine halogenated alkyl group of C ₁～C₁₀ are contained in the-Q-M structure.

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

Wherein q is an integer of 0 to 10,

R ₇ is each independently-H, C ₁～C₁₀ alkyl or C ₁～C₁₀ chloroalkyl,

Each C _xH_2x+1-y(OH)_y is the same or different, x is an integer of 1 to 10, y is an integer of 1 to 10, and y is less than or equal to x in the same group C _xH_2x+1-y(OH)_y.

[3] Further, in the above-described water-dispersible fluorine-free copolymer, the monomer (a) is a monomer represented by the formula (1):

Wherein R ₁ is independently-H, non-fluorine halogen or C ₁～C₂₀ alkyl with straight chain or branched chain 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 a group represented by-R ₀－C₆H₄－R₀－W－R₀,

-C ₆H₄ -is a phenylene group,

R ₀ is independently- (CH ₂)_n -or C ₁～C₁₀) alkylene with branched chain structure, n is an integer of 0-20,

W is selected from the structures shown in W ₁～W₄:

-C(=O)-O- W₁

-C(=O)-N(R₂)－ W₂

-O- W₃

-O-C(=O)- W₄

r ₂ is-H or C ₁～C₂₀ alkyl,

Y is a structure shown in formula (2):

r ₃ is independently alkyl of C ₁～C₁₀, aryl of C ₆～C₂₀ or aralkyl of C ₇～C₂₀, Z ₁ and Z ₂ are independently alkyl of C ₁～C₁₀, aryl of C ₆～C₂₀, aralkyl of C ₇～C₂₀ or a structure shown in formula (3), m is 1 to 300,

R ₄ is independently alkyl of C ₁～C₁₀, aryl of C ₆～C₂₀ or aralkyl of C ₇～C₂₀, Z ₃ and Z ₄ are independently alkyl of C ₁～C₁₀, aryl of C ₆～C₂₀ or aralkyl of C ₇～C₂₀, and k is 0-300.

[4] Further, in the above-mentioned water-dispersible fluorine-free copolymer, in the monomer (A), R ₁ is independently-H, a non-fluorine halogen or an alkyl group having a straight chain or branched chain structure of C ₁～C₁₀,

X is －R₀－、－W－、－C₆H₄－W－、－R₀－W－、－W－R₀－、－R₀－W－R₀－、－C₆H₄－R₀－W－R₀－ or a group represented by-R ₀－C₆H₄－W－R₀ -, R ₀ is independently- (CH ₂)_n -or C ₁～C₁₀ -alkylene having a branched chain structure), n is an integer of 0 to 10,

In Y, R ₃ and/or R ₄ are each independently C ₁～C₅ alkyl, C ₆～C₁₀ aryl or C ₇～C₁₂ aralkyl, Z ₃ and/or Z ₄ are each independently C ₁～C₅ alkyl, C ₆～C₁₀ aryl or C ₇～C₁₂ aralkyl, m is 1-50, and k is 0-50.

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

R is independently C ₁～C₅ alkyl, C ₆～C₁₀ aryl or C ₇～C₁₂ aralkyl, m is 1-35, k1 and k2 are independently 0-35.

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

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

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

Wherein R ₁ is independently-H, non-fluorine halogen or C ₁～C₂₀ alkyl with straight chain or branched chain structure;

X' is a structure shown as-W-, -R ₀－、－W－R₀－、－R₀ -W-or-W-R ₀ -W-,

R ₀ is- (CH ₂)_n -or C ₁～C₁₀ alkylene with branched chain structure, n is an integer of 0-20,

W is selected from the structures shown in W ₁～W₄:

-C(=O)-O- W₁

-C(=O)-N(R₂)－ W₂

-O- W₃

-O-C(=O)- W₄

R ₂ is-H or C ₁～C₂₀ alkyl;

R ₅ and R ₆ are each independently C ₁～C₁₀ alkyl, C ₆～C₂₀ aryl or C ₇～C₂₅ aralkyl.

[9] Further, in the above-mentioned water-dispersible fluorine-free copolymer, in the monomer (C), R ₅ and R ₆ are each independently benzyl.

[10] Further, in the water-dispersible fluorine-free copolymer as described above,

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

the weight ratio of the repeating unit formed by the monomer (B) to the copolymer is 0.1-25%;

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

[11] Further, in the water-dispersible fluorine-free copolymer as described above,

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

the weight ratio of the repeating unit formed by the monomer (B) to the copolymer is 0.1-22%;

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

[12] Further, in the water-dispersible fluorine-free copolymer as described above,

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

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

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

[13] Further, in the water-dispersible fluorine-free copolymer as described above, the copolymer further comprises a repeating unit formed of the optional monomer (D),

The optional monomer (D) includes:

monomers having a pyrrolidone structure and polymerizable unsaturated groups, and/or

Monomers having blocked isocyanate groups and polymerizable unsaturated groups, and/or

Monomers having alkoxysilyl groups and polymerizable unsaturated groups, and/or

Monomers having a glycidyl group and a polymerizable unsaturated group.

[14] Further, in the water-dispersible fluorine-free copolymer as described above,

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

the weight ratio of the repeating unit formed by the monomer (B) to the copolymer is 0.1-25%;

The weight ratio of the repeating unit formed from the monomer (C) to the copolymer is 5 to 40%, and

The weight ratio of the repeating unit formed by the optional monomer (D) to the copolymer is 0 to 10%.

[15] Further, in the water-dispersible fluorine-free copolymer as described above,

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

the weight ratio of the repeating unit formed by the monomer (B) to the copolymer is 0.1-22%;

the weight ratio of the repeating unit formed from the monomer (C) to the copolymer is 10 to 35%, and

The weight ratio of the repeating unit formed by the optional monomer (D) to the copolymer is 0 to 8%.

[16] Further, in the water-dispersible fluorine-free copolymer as described above,

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)-O-C(＝O)-CH(OH)CH₂Cl

CH₂＝CH-CH(OH)CH₂OH

CH₂＝CH-CH₂CH(OH)CH₂OH

CH₂＝CH-C(＝O)-O-CH₂-C(＝O)-O-CH₂CH(OH)CH(OH)CH(OH)CH(OH)CH₂OH

CH₂＝CHCOO-[C(C_xH_2x+1-y(OH)_y)₂-C(R₇)₂]_q-M

CH₂＝C(CH₃)COO-[C(C_xH_2x+1-y(OH)_y)₂-C(R₇)₂]_q-M

CH₂＝CH-C(＝O)-NH-[C(C_xH_2x+1-y(OH)_y)₂-C(R₇)₂]_q-M

CH₂＝C(CH₃)-C(＝O)-NH-[C(C_xH_2x+1-y(OH)_y)₂-C(R₇)₂]_q-M

CH₂＝CHCOO-[C(R₇)₂-C(C_xH_2x+1-y(OH)_y)₂]_q-M

CH₂＝C(CH₃)COO-[C(R₇)₂-C(C_xH_2x+1-y(OH)_y)₂]_q-M

CH₂＝CH-C(＝O)-NH-[C(R₇)₂-C(C_xH_2x+1-y(OH)_y)₂]_q-M

CH₂＝C(CH₃)-C(＝O)-NH-[C(R₇)₂-C(C_xH_2x+1-y(OH)_y)₂]_q-M

CH₂＝CHCOO-[C(R₇)(C_xH_2x+1-y(OH)_y)-C(R₇)(C_xH_2x+1-y(OH)_y)]_q-M

CH₂＝C(CH₃)COO-[C(R₇)(C_xH_2x+1-y(OH)_y)-C(R₇)(C_xH_2x+1-y(OH)_y)]_q-M

CH₂＝CH-C(＝O)-NH-[C(R₇)(C_xH_2x+1-y(OH)_y)-C(R₇)(C_xH_2x+1-y(OH)_y)]_q-M

CH₂＝C(CH₃)-C(＝O)-NH-[C(R₇)(C_xH_2x+1-y(OH)_y)-C(R₇)(C_xH_2x+1-y(OH)_y)]_q-M

CH₂＝CHCOO-[C(R₇)(C_xH_2x+1-y(OH)_y)-C(C_xH_2x+1-y(OH)_y)₂]_q-M

CH₂＝C(CH₃)COO-[C(R₇)(C_xH_2x+1-y(OH)_y)-C(C_xH_2x+1-y(OH)_y)₂]_q-M

CH₂＝CH-C(＝O)-NH-[C(R₇)(C_xH_2x+1-y(OH)_y)-C(C_xH_2x+1-y(OH)_y)₂]_q-M

CH₂＝C(CH₃)-C(＝O)-NH-[C(R₇)(C_xH_2x+1-y(OH)_y)-C(C_xH_2x+1-y(OH)_y)₂]_q-M

CH₂＝CHCOO-[C(C_xH_2x+1-y(OH)_y)₂-C(R₇)(C_xH_2x+1-y(OH)_y)]_q-M

CH₂＝C(CH₃)COO-[C(C_xH_2x+1-y(OH)_y)₂-C(R₇)(C_xH_2x+1-y(OH)_y)]_q-M

CH₂＝CH-C(＝O)-NH-[C(C_xH_2x+1-y(OH)_y)₂-C(R₇)(C_xH_2x+1-y(OH)_y)]_q-M

CH₂＝C(CH₃)-C(＝O)-NH-[C(C_xH_2x+1-y(OH)_y)₂-C(R₇)(C_xH_2x+1-y(OH)_y)]_q-M

CH₂＝CHCOO-[C(C_xH_2x+1-y(OH)_y)₂-C(C_xH_2x+1-y(OH)_y)₂]_q-M

CH₂＝C(CH₃)COO-[C(C_xH_2x+1-y(OH)_y)₂-C(C_xH_2x+1-y(OH)_y)₂]_q-M

CH₂＝CH-C(＝O)-NH-[C(C_xH_2x+1-y(OH)_y)₂-C(C_xH_2x+1-y(OH)_y)₂]_q-M

CH₂＝C(CH₃)-C(＝O)-NH-[C(C_xH_2x+1-y(OH)_y)₂-C(C_xH_2x+1-y(OH)_y)₂]_q-M

Wherein q is an integer of 0 to 10,

R ₇ is independently from each other-H, C ₁～C₁₀ alkyl, C ₁～C₁₀ chloroalkyl,

Each C _xH_2x+1-y(OH)_y is the same or different, x is an integer of 1 to 10, y is an integer of 1 to 10, and y is less than or equal to x in the same group C _xH_2x+1-y(OH)_y,

M is-H, -Cl, -OH, a monohydric alcohol group of C ₁～C₆ or a polyhydric alcohol group of C ₂～C₆.

[17] Further, in the water-dispersible fluorine-free copolymer as described above,

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)_nSi(R)₂[O(Si(R)₂O)_kSi(R)₃]

CH₂＝CHCOO-(CH₂)_nSi(R)₂[O(Si(R)₂O)_kSi(R)₃]

CH₂＝C(CH₃)COO-(CH₂)_nSi[O(Si(R)₂O)_kSi(R)₃]₂(OSi(R)₃)

CH₂＝CHCOO-(CH₂)_nSi[O(Si(R)₂O)_kSi(R)₃]₂(OSi(R)₃)

CH₂＝C(CH₃)-C(＝O)-NH-(CH₂)_nSi(R)₂[O(Si(R)₂O)_kSi(R)₃]

CH₂＝CH-C(＝O)-NH-(CH₂)_nSi(R)₂[O(Si(R)₂O)_kSi(R)₃]

CH₂＝C(CH₃)-C(＝O)-NH-(CH₂)_nSi[O(Si(R)₂O)_kSi(R)₃]₂(OSi(R)₃)

CH₂＝CH-C(＝O)-NH-(CH₂)_nSi[O(Si(R)₂O)_kSi(R)₃]₂(OSi(R)₃)

wherein n is an integer of 0 to 10 independently,

K is each independently 0 to 35,

R is each independently C ₁～C₁₀ alkyl, C ₆～C₂₀ aryl or C ₇～C₂₀ aralkyl.

[18] Further, in the water-dispersible fluorine-free copolymer as described above,

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

CH ₂＝CHCOO-CH₂CH₂-N(CH₃)₂ and/or a salt thereof,

CH ₂＝CHCOO-CH₂CH₂-N(CH₂CH₃)₂ and/or a salt thereof,

CH ₂＝C(CH₃)COO-CH₂CH₂-N(CH₃)₂ and/or a salt thereof,

CH ₂＝C(CH₃)COO-CH₂CH₂-N(CH₂CH₃)₂ and/or a salt thereof,

CH ₂＝CH-C(＝O)-NH-CH₂CH₂-N(CH₃)₂ and/or a salt thereof,

CH ₂＝CH-C(＝O)-NH-CH₂CH₂-N(CH₂CH₃)₂ and/or a salt thereof,

CH ₂＝C(CH₃)-C(＝O)-NH-CH₂CH₂-N(CH₃)₂ and/or a salt thereof, and

CH ₂＝C(CH₃)-C(＝O)-NH-CH₂CH₂-N(CH₂CH₃)₂ and/or salts thereof.

In a second aspect of the present invention, there is provided a treating agent comprising a water-dispersible fluorine-free copolymer, as described below.

[19] A treating agent comprising the water-dispersible fluorine-free copolymer, which is the water-dispersible fluorine-free copolymer according to any one of the above [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.

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

[20] The method for producing a treating agent comprising a water-dispersible fluorine-free copolymer according to [19], comprising the steps of:

(1) Copolymerizing a monomer, an organic solvent and an initiator in a kettle to obtain a polymer solution;

(2) Adding an acid solution into the polymer solution for dispersion treatment;

(3) Desolventizing the dispersed polymer solution to remove the organic solvent, thereby obtaining an aqueous dispersion;

(4) Converting the amino groups in the aqueous dispersion into oxynitride to obtain the treating agent containing the water-dispersible fluorine-free copolymer.

[21] Further, in the above-mentioned production method, in the step (4), the amino group is converted into the oxynitride by adding a hydrogen peroxide solution to the aqueous dispersion for treatment.

In a fourth aspect the present invention provides the use of a treatment agent comprising a water-dispersible fluorine-free copolymer, as described in detail below.

[22] The method according to item [19], wherein the product is treated with the treating agent containing the water-dispersible fluorine-free copolymer by internal or external addition of the treating agent to impart water-and oil-resistant properties to the product, and the product comprises paper products, plastics, fabrics, fur, leather and/or nonwoven fabrics.

[23] Further, in the applications described above, the paper product is treated and then used as a food packaging material or food container.

Advantageous effects of the invention

The fluorine-free copolymer contained in the treating agent of the invention can be well dispersed in an aqueous medium, so that the treating agent with good copolymer dispersion can be obtained, and the preparation of the treating agent and the processing treatment of products are facilitated.

The obtained treating agent has higher oil-resistant temperature and more stable oil-resistant performance.

The hardness of the product prepared by the treating agent is higher, and the product requirement can be better met.

In the molding production process using the treating agent, the molded product does not stick to the mold.

Detailed Description

In order to better understand the above technical solution, exemplary embodiments of the present invention will be described in more detail below.

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

A repeating unit formed from a silicon-containing unsaturated monomer (a);

Repeating units formed from the monomers (B), and

Repeating units formed from monomer (C).

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

In addition, the fluorine-free copolymer may further contain a repeating unit formed from an optional other monomer (D) having a good suitability.

(A) Silicon-containing unsaturated monomer

The silicon-containing unsaturated monomer (A) is a monomer shown in a formula (1),

Wherein R ₁ is different from or the same as each other and is independently-H, a non-fluorine halogen atom or a monovalent organic group. The monovalent organic group described herein may be, for example, a C ₁～C₂₀ alkyl group having a linear 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-R ₀－C₆H₄－R₀－W－R₀ -a group,

-C ₆H₄ -is phenylene.

X is preferably －R₀－、－W－、－C₆H₄－W－、－R₀－W－、－W－R₀－、－R₀－W－R₀－、－C₆H₄－R₀－W－R₀－ or a group represented by-R ₀－C₆H₄－W－R₀ -,

R ₀ is the same or different and each independently is- (CH ₂)_n -or C ₁～C₁₀ alkylene having a branched chain structure),

N is an integer of 0 to 20, preferably an integer of 0 to 10.

W is selected from the structures shown in W ₁～W₄:

-C(=O)-O- W₁

-C(=O)-N(R₂)－ W₂

-O- W₃

-O-C(=O)- W₄

r ₂ is-H or C ₁～C₂₀ alkyl.

R ₁ is independently-H, non-fluorine halogen or C ₁～C₂₀ alkyl with straight chain or branched chain structure. R ₁ is the same or different and is independently-H, methyl, halogen except fluorine, substituted or unsubstituted benzyl. Examples of R ₁ are hydrogen, methyl, chlorine, bromine, iodine. R ₁ is preferably hydrogen, methyl, chlorine. R ₁ is particularly preferably methyl.

R ₂ can be hydrogen, methyl, substituted or unsubstituted benzyl. R ₂ is preferably hydrogen or methyl. R ₂ is particularly preferably methyl.

Y is selected from the structures shown in formula (2):

R ₃ is independently an alkyl group of C ₁～C₁₀, an aryl group of C ₆～C₂₀ or an aralkyl group of C ₇～C₂₀, preferably an alkyl group of C ₁～C₅, an aryl group of C ₆～C₁₀, an aralkyl group of C ₇～C₁₀. Z ₁ and Z ₂ are each independently C ₁～C₁₀ alkyl, C ₆～C₂₀ aryl, C ₇～C₂₀ aralkyl or the following formula (3):

R ₄ is independently an alkyl group of C ₁～C₁₀, an aryl group of C ₆～C₂₀ or an aralkyl group of C ₇～C₂₀, preferably an alkyl group of C ₁～C₅, an aryl group of C ₆～C₁₀, an aralkyl group of C ₇～C₁₀. Z ₃ and Z ₄ are each independently C ₁～C₁₀ alkyl, C ₆～C₂₀ aryl or C ₇～C₂₀ aralkyl, preferably C ₁～C₅ alkyl, C ₆～C₁₀ aryl, C ₇～C₁₀ aralkyl.

K is 0 to 300, for example 0 to 150, preferably 0 to 50, particularly preferably 0 to 35.

M is 1to 300, for example 1to 150, preferably 1to 50, particularly preferably 1to 35.

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

R is each independently C ₁～C₅ alkyl, C ₆～C₁₀ aryl or C ₇～C₁₂ aralkyl. m is 1 to 150, preferably 1 to 50, particularly preferably 1 to 35.

K1 and k2 are each independently 0 to 50, preferably 0 to 35.

The silicon-containing unsaturated monomer (a) is specifically exemplified below, but is not limited thereto.

CH₂＝C(CH₃)COO-(CH₂)₃Si(OSi(CH₃)₃)₃

CH₂＝CHCOO-(CH₂)₃Si(OSi(CH₃)₃)₃

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

CH₂＝CHCOO-(CH₂)₃Si(CH₃)(OSi(CH₃)₃)₂

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

CH₂＝CHCOO-(CH₂)₃Si(CH₃)₂(OSi(CH₃)₃)

CH₂＝C(CH₃)COO-(CH₂)₃Si(OSi(CH₂CH₃)₃)₃

CH₂＝CHCOO-(CH₂)₃Si(OSi(CH₂CH₃)₃)₃

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

CH₂＝CHCOO-(CH₂)₃Si(CH₂CH₃)(OSi(CH₂CH₃)₃)₂

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

CH₂＝CHCOO-(CH₂)₃Si(CH₂CH₃)₂(OSi(CH₂CH₃)₃)

CH₂＝C(CH₃)COO-(CH₂)₃Si(OSi(CH₂-Ph)₃)₃

CH₂＝CHCOO-(CH₂)₃Si(OSi(CH₂-Ph)₃)₃

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

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

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

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

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

CH₂＝CH-C(＝O)-NH-(CH₂)₃Si(OSi(CH₃)₃)₃

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

CH₂＝C(CH₃)COO-(CH₂)_nSi(R)₂[O(Si(R)₂O)_kSi(R)₃]

CH₂＝CHCOO-(CH₂)_nSi(R)₂[O(Si(R)₂O)_kSi(R)₃]

CH₂＝C(CH₃)COO-(CH₂)_nSi[O(Si(R)₂O)_kSi(R)₃]₂(OSi(R)₃)

CH₂＝CHCOO-(CH₂)_nSi[O(Si(R)₂O)_kSi(R)₃]₂(OSi(R)₃)

CH₂＝C(CH₃)-C(＝O)-NH-(CH₂)_nSi(R)₂[O(Si(R)₂O)_kSi(R)₃]

CH₂＝CH-C(＝O)-NH-(CH₂)_nSi(R)₂[O(Si(R)₂O)_kSi(R)₃]

CH₂＝C(CH₃)-C(＝O)-NH-(CH₂)_nSi[O(Si(R)₂O)_kSi(R)₃]₂(OSi(R)₃)

CH₂＝CH-C(＝O)-NH-(CH₂)_nSi[O(Si(R)₂O)_kSi(R)₃]₂(OSi(R)₃)

Wherein Ph is an abbreviation of phenyl, and n is an integer of 0 to 10.

R is independently an alkyl group of C ₁～C₁₀, an aryl group of C ₆～C₂₀ or an aralkyl group of C ₇～C₂₀, preferably an alkyl group of C ₁～C₅, an aryl group of C ₆～C₁₀, an aralkyl group of C ₇～C₁₀, particularly preferably an alkyl group of C ₁～C₅, an aralkyl group of C ₇～C₁₀.

K is independently 0 to 35, preferably 0 to 15.

As the monomer (A), preference is given to acryloxypropyltris (trimethylsiloxy) silane, methacryloxypropyltris (trimethylsiloxy) silane, acryloxypropyltris (triethylsiloxy) silane, methacryloxypropyltris (triethylsiloxy) silane acrylamide propyl tris (trimethylsiloxy) silane, methacrylamidopropyltris (trimethylsiloxy) silane, acrylamide propyl tris (triethylsiloxy) silane, methacrylamidopropyltris (triethylsiloxy) silane, more preferably acryloxypropyltris (trimethylsiloxy) silane, methacryloxypropyltris (trimethylsiloxy) silane, acrylamidopropyltris (trimethylsiloxy) silane, methacrylamidopropyltris (trimethylsiloxy) silane, or mixtures thereof.

(B) Crosslinking monomers

The monomer (B) is a monomer other than the monomer (A), and is a crosslinking monomer.

The monomer (B) is a monomer represented by the formula (4):

R ₁ are identical or different and are each independently-H, a non-fluorine halogen or a monovalent organic radical. The monovalent organic group described herein may be, for example, a C ₁～C₂₀ alkyl group having a linear or branched structure.

X' is a structure shown as-W-, -R ₀－、－W－R₀－、－R₀ -W-or-W-R ₀ -W-, preferably-W-R ₀ -.

R ₀ is- (CH ₂)_n -or C ₁～C₁₀) alkylene having a branched structure, and n is an integer of 0 to 20, preferably an integer of 0 to 10.

W is selected from the structures shown in W ₁～W₄:

-C(=O)-O- W₁

-C(=O)-N(R₂)－ W₂

-O- W₃

-O-C(=O)- W₄

r ₂ is-H or C ₁～C₂₀ alkyl.

R ₁ can be hydrogen, methyl, halogen other than fluorine, substituted or unsubstituted benzyl. Examples of R ₁ are hydrogen, methyl, chlorine, bromine, iodine. R ₁ is preferably hydrogen, methyl, chlorine. R ₁ is particularly preferably methyl.

R ₂ can be hydrogen, methyl, substituted or unsubstituted benzyl. R ₂ is preferably a hydrogen atom or a methyl group. R ₂ is particularly preferably methyl.

Q is selected from the structures represented by formula (5):

Z ₅ is independently each occurrence-H, non-fluorine halogen, -OH, C ₁～C₁₀ alkyl, C ₁～C₁₀ monohydric alcohol group, C ₂～C₁₀ polyhydric alcohol group, C ₁～C₁₀ non-fluorine halogenated alkyl group, preferably-H, -OH, C ₁～C₆ monohydric alcohol group, C ₂～C₆ polyhydric alcohol group.

M is independently-H, a non-fluorine halogen, -OH, an alkyl group of C ₁～C₁₀, a monohydric alcohol group of C ₁～C₁₀, a polyhydric alcohol group of C ₂～C₁₀, a non-fluorine halogenated alkyl group of C ₁～C₁₀, preferably-H, -Cl, -OH, a polyhydric alcohol group of C ₂～C₆.

Q is an integer of 0 to 20, preferably an integer of 0 to 10.

In the crosslinking monomer (B), at least 2 or more groups of non-fluorine halogen, -OH, monohydric alcohol group of C ₁～C₁₀, polyhydric alcohol group of C ₂～C₁₀ and non-fluorine halogenated alkyl group of C ₁～C₁₀ are contained in the-Q-M structure, and Q is an integer of 0-10.

For the integral structure formed by structures Q and M in crosslinking monomer (B), it is preferably a monohydric alcohol group of C ₁～C₁₀ or a polyhydric alcohol group of C ₂～C₁₀, a sugar alcohol group.

The general formula of the monohydric alcohol group referred to in the present invention is as follows:

-C_xH_2x(OH)(10≥x≥1)

the general formula of the polyol groups referred to in the present invention is as follows:

-C_xH_2x+1-y(OH)_y(10≥x≥y≥2)

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

Sugar alcohol groups in the present invention, which are of the general formula:

-C_xH_x+1(OH)_x(10≥x≥2)

Wherein x may be 3, 4,5, 6, 7, 8, 9 or 10 (which may be referred to as a triose, tetrol, pentitol, hexitol, heptitol, xin Tangchun, nonitol or decitol). Among these sugar alcohols, a large number of stereoisomers may exist corresponding to the number of asymmetric carbon atoms.

In the present invention, a chain sugar alcohol group having 3 to 6 carbon atoms is preferably used. Specific examples of sugar alcohols include sorbitol, mannitol, galactitol, xylitol, erythritol, glycerol, and the like.

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

R ₇ in Q-1 to Q-18 is independently-H, C ₁～C₁₀ alkyl, C ₁～C₁₀ chloroalkyl.

C _xH_2x+1-y(OH)_y in the same Q formula and/or among different Q formulas are the same or different, and x is an integer of 1-10, preferably an integer of 1-5. y is an integer of 1 to 10, preferably an integer of 1 to 5. Meanwhile, the y value in any one of the items C _xH_2x+1-y(OH)_y in Q is smaller than or equal to the x value, namely y is smaller than or equal to x. q is an integer of0 to 10, preferably an integer of0 to 5.

The monomer (B) is specifically exemplified below, but is not limited thereto.

CH₂＝C(CH₃)COO-CH₂CH(OH)CH₂Cl

CH₂＝CHCOO-CH₂CHClCH₂(OH)

CH₂＝C(CH₃)COO-CH₂CHClCH₂(OH)

CH₂＝CHCOO-CH₂CHCl₂

CH₂＝C(CH₃)COO-CH₂CHCl₂

CH₂＝CHCOO-CH₂CHCl-CH₂Cl

CH₂＝C(CH₃)COO-CHCl-CH₂Cl

CH₂＝CHCOO-CH₂CH(OH)-CH₂(OH)

CH₂＝C(CH₃)COO-CH₂CH(OH)-CH₂(OH)

CH₂＝CHCOO-CH₂CH(OH)CHCl-CH₃

CH₂＝C(CH₃)COO-CH₂CH(OH)CHCl-CH₃

CH₂＝CHCOO-CH₂CHClCH(OH)-CH₃

CH₂＝C(CH₃)COO-CH₂CHClCH(OH)-CH₃

CH₂＝CHCOO-CH₂CHCl-CHCl-CH₃

CH₂＝C(CH₃)COO-CH₂CHCl-CHCl-CH₃

CH₂＝CHCOO-CH₂CH(OH)-CH(OH)-CH₃

CH₂＝C(CH₃)COO-CH₂CH(OH)-CH(OH)-CH₃

CH₂＝CHCOO-CH₂CHClCH₂-CH₂OH

CH₂＝C(CH₃)COO-CH₂CHClCH₂-CH₂OH

CH₂＝CHCOO-CH₂CHCl-CH₂OH

CH₂＝C(CH₃)COO-CH₂CHCl-CH₂OH

CH₂＝CHCOO-CH₂CH(OH)CH₂-CH₂OH

CH₂＝C(CH₃)COO-CH₂CH(OH)CH₂-CH₂OH

CH₂＝CHCOO-CH₂CH₂CH(OH)-CH₂OH

CH₂＝C(CH₃)COO-CH₂CH₂CH(OH)-CH₂OH

CH₂＝CHCOO-CH₂CH(OH)CHCl-CH₂OH

CH₂＝C(CH₃)COO-CH₂CH(OH)CHCl-CH₂OH

CH₂＝CHCOO-CH₂CHClCH(OH)-CH₂OH

CH₂＝C(CH₃)COO-CH₂CHClCH(OH)-CH₂OH

CH₂＝CHCOO-CH₂CHCl-CHCl-CH₂OH

CH₂＝C(CH₃)COO-CH₂CHCl-CHCl-CH₂OH

CH₂＝CHCOO-CH₂CH(OH)-CH(OH)-CH₂OH

CH₂＝C(CH₃)COO-CH₂CH(OH)-CH(OH)-CH₂OH

CH₂＝CHCOO-CH₂CHClCH₂-CH₂Cl

CH₂＝C(CH₃)COO-CH₂CHClCH₂-CH₂Cl

CH₂＝CHCOO-CH₂CH₂CHCl-CH₂Cl

CH₂＝C(CH₃)COO-CH₂CH₂CHCl-CH₂Cl

CH₂＝CHCOO-CH₂CH(OH)CH₂-CH₂Cl

CH₂＝C(CH₃)COO-CH₂CH(OH)CH₂-CH₂Cl

CH₂＝CHCOO-CH₂CH₂CH(OH)-CH₂Cl

CH₂＝C(CH₃)COO-CH₂CH₂CH(OH)-CH₂Cl

CH₂＝CHCOO-CH₂CH(OH)CHCl-CH₂Cl

CH₂＝C(CH₃)COO-CH₂CH(OH)CHCl-CH₂Cl

CH₂＝CHCOO-CH₂CHClCH(OH)-CH₂Cl

CH₂＝C(CH₃)COO-CH₂CHClCH(OH)-CH₂Cl

CH₂＝CHCOO-CH₂CHCl-CHCl-CH₂Cl

CH₂＝C(CH₃)COO-CH₂CHCl-CHCl-CH₂Cl

CH₂＝CHCOO-CH₂CH(OH)-CH(OH)-CH₂Cl

CH₂＝C(CH₃)COO-CH₂CH(OH)-CH(OH)-CH₂Cl

CH₂＝CH-C(＝O)-NH-CHClCH₂-CH₂OH

CH₂＝C(CH₃)-C(＝O)-NH-CHClCH₂-CH₂OH

CH₂＝CH-C(＝O)-NH-CH₂CHCl-CH₂OH

CH₂＝C(CH₃)-C(＝O)-NH-CH₂CHCl-CH₂OH

CH₂＝CH-C(＝O)-NH-CH₂CH(OH)CH₂-CH₂OH

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

CH₂＝CH-C(＝O)-NH-CH₂CH₂CH(OH)-CH₂OH

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

CH₂＝CH-C(＝O)-NH-CH₂CH(OH)CHCl-CH₂OH

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

CH₂＝CH-C(＝O)-NH-CH₂CHClCH(OH)-CH₂OH

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

CH₂＝CH-C(＝O)-NH-CH₂CHCl-CHCl-CH₂OH

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

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

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

CH₂＝CH-C(＝O)-NH-CH₂CHClCH₂-CH₂Cl

CH₂＝C(CH₃)-C(＝O)-NH-CH₂CHClCH₂-CH₂Cl

CH₂＝CH-C(＝O)-NH-CH₂CHCl-CH₂Cl

CH₂＝C(CH₃)-C(＝O)-NH-CH₂CHCl-CH₂Cl

CH₂＝CH-C(＝O)-NH-CH₂CH(OH)CH₂-CH₂Cl

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

CH₂＝CH-C(＝O)-NH-CH₂CH₂CH(OH)-CH₂Cl

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

CH₂＝CH-C(＝O)-NH-CH₂CH(OH)CHCl-CH₂Cl

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

CH₂＝CH-C(＝O)-NH-CH₂CHClCH(OH)-CH₂Cl

CH₂＝C(CH₃)-C(＝O)-NH-CHClCH(OH)-CH₂Cl

CH₂＝CH-C(＝O)-NH-CH₂CHCl-CHCl-CH₂Cl

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

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

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

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

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

CH₂＝C(CH₃)-O-C(＝O)-CH(OH)CH₂Cl

CH₂＝CH-CH(OH)CH₂OH

CH₂＝CH-CH₂CH(OH)CH₂OH

CH₂＝CH-C(＝O)-O-CH₂-C(＝O)-O-CH₂CH(OH)CH(OH)CH(OH)CH(OH)CH₂OH

CH₂＝CHCOO-[C(C_XH_2x+1-y(OH)_y)₂-C(R₇)₂]_q-M

CH₂＝C(CH₃)COO-[C(C_XH_2x+1-y(OH)_y)₂-C(R₇)₂]_q-M

CH₂＝CH-C(＝O)-NH-[C(C_XH_2x+1-y(OH)_y)₂-C(R₇)₂]_q-M

CH₂＝C(CH₃)-C(＝O)-NH-[C(C_XH_2x+1-y(OH)_y)₂-C(R₇)₂]_q-M

CH₂＝CHCOO-[C(R₇)₂-C(C_XH_2x+1-y(OH)_y)₂]_q-M

CH₂＝C(CH₃)COO-[C(R₇)₂-C(C_XH_2x+1-y(OH)_y)₂]_q-M

CH₂＝CH-C(＝O)-NH-[C(R₇)₂-C(C_XH_2x+1-y(OH)_y)₂]_q-M

CH₂＝C(CH₃)-C(＝O)-NH-[C(R₇)₂-C(C_XH_2x+1-y(OH)_y)₂]_q-M

CH₂＝CHCOO-[C(R₇)(C_XH_2x+1-y(OH)_y)-C(R₇)(C_XH_2x+1-y(OH)_y)]_q-M

CH₂＝C(CH₃)COO-[C(R₇)(C_XH_2x+1-y(OH)_y)-C(R₇)(C_XH_2x+1-y(OH)_y)]_q-M

CH₂＝CH-C(＝O)-NH-[C(R₇)(C_XH_2x+1-y(OH)_y)-C(R₇)(C_XH_2x+1-y(OH)_y)]_q-M

CH₂＝C(CH₃)-C(＝O)-NH-[C(R₇)(C_XH_2x+1-y(OH)_y)-C(R₇)(C_XH_2x+1-y(OH)_y)]_q-M

CH₂＝CHCOO-[C(R₇)(C_XH_2x+1-y(OH)_y)-C(C_XH_2x+1-y(OH)_y)₂]_q-M

CH₂＝C(CH₃)COO-[C(R₇)(C_XH_2x+1-y(OH)_y)-C(C_XH_2x+1-y(OH)_y)₂]_q-M

CH₂＝CH-C(＝O)-NH-[C(R₇)(C_XH_2x+1-y(OH)_y)-C(C_XH_2x+1-y(OH)_y)₂]_q-M

CH₂＝C(CH₃)-C(＝O)-NH-[C(R₇)(C_XH_2x+1-y(OH)_y)-C(C_XH_2x+1-y(OH)_y)₂]_q-M

CH₂＝CHCOO-[C(C_XH_2x+1-y(OH)_y)₂-C(R₇)(C_XH_2x+1-y(OH)_y)]_q-M

CH₂＝C(CH₃)COO-[C(C_XH_2x+1-y(OH)_y)₂-C(R₇)(C_XH_2x+1-y(OH)_y)]_q-M

CH₂＝CH-C(＝O)-NH-[C(C_XH_2x+1-y(OH)_y)₂-C(R₇)(C_XH_2x+1-y(OH)_y)]_q-M

CH₂＝C(CH₃)-C(＝O)-NH-[C(C_XH_2x+1-y(OH)_y)₂-C(R₇)(C_XH_2x+1-y(OH)_y)]_q-M

CH₂＝CHCOO-[C(C_XH_2x+1-y(OH)_y)₂-C(C_XH_2x+1-y(OH)_y)₂]_q-M

CH₂＝C(CH₃)COO-[C(C_XH_2x+1-y(OH)_y)₂-C(C_XH_2x+1-y(OH)_y)₂]_q-M

CH₂＝CH-C(＝O)-NH-[C(C_XH_2x+1-y(OH)_y)₂-C(C_XH_2x+1-y(OH)_y)₂]_q-M

CH₂＝C(CH₃)-C(＝O)-NH-[C(C_XH_2x+1-y(OH)_y)₂-C(C_XH_2x+1-y(OH)_y)₂]_q-M

R ₇ is independently an alkyl group of-H, C ₁～C₁₀, a chloroalkyl group of C ₁～C₁₀.

C _xH_2x+1-y(OH)_y of the same monomer (B) and/or different monomers (B) are the same or different, x is an integer of 1-10, and y is an integer of 1-10. The value of y in any one of the terms C _xH_2x+1-y(OH)_y is less than or equal to the value of x, i.e., y is less than or equal to x.

Q is an integer of 0 to 10, preferably an integer of 0 to 5.

M is preferably-H, -Cl, -OH, a monohydric alcohol group of C ₁～C₆, a polyhydric alcohol group of C ₂～C₆.

As monomers (B) there are preferred hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyethylacrylamide, hydroxyethylmethacrylamide, 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, 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.

(C) Monomers with ionic donor groups

The monomer (C) is a monomer having an ionic donor group. Wherein the ionic donor groups can be divided into anionic donor groups and cationic donor groups.

Examples of the monomer having an anion donor group include monomers having a carboxyl group and a sulfonic acid group. Specific examples of the monomer having an anion donor group include, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, etc., or salts thereof. Specific examples of the salt of the anion donor group include methyl ammonium salt, ethanol ammonium salt, and triethanol ammonium salt.

The monomer (C) having a cation donor group is preferred in the present invention, and examples of the cation donor group are amino groups, preferably tertiary amino groups and quaternary ammonium groups.

In the tertiary amine groups, the two groups bound to the nitrogen atom are preferably identical or different alkyl groups of C ₁～C₅, aryl groups of C ₆～C₁₀, aralkyl groups of C ₇～C₁₂ (e.g.benzyl C ₆H₅－CH₂ -). In the quaternary ammonium group, the 3 groups bound to the nitrogen atom are preferably identical or different C ₁～C₅ alkyl groups, C ₆～C₁₀ aryl groups, C ₇～C₁₂ aralkyl groups (e.g.benzyl C ₆H₅－CH₂ -). The cation donor group may be in the form of a salt.

The monomer (C) is a monomer shown in the formula (6):

R ₁ is different or the same and is independently-H, non-fluorine halogen or monovalent organic group. The monovalent organic groups described herein may be, for example, C ₁～C₂₀ alkyl groups having a linear or branched structure.

X' is a structure shown as-W-, -R ₀－、－W－R₀－、－R₀ -W-or-W-R ₀ -W-, preferably-W-R ₀ -.

R ₀ is- (CH ₂)_n -or C ₁～C₁₀) alkylene having a branched structure, and n is an integer of 0 to 20, preferably an integer of 0 to 10.

W is selected from the structures shown in W ₁～W₄:

-C(=O)-O- W₁

-C(=O)-N(R₂)－ W₂

-O- W₃

-O-C(=O)- W₄

R ₂ is a hydrogen atom or an alkyl group of C ₁～C₂₀.

R ₅ and R ₆ are identical or different and are each independently C ₁～C₁₀ alkyl, C ₆～C₂₀ aryl, C ₇～C₂₅ aralkyl (in particular benzyl C ₆H₅－CH₂ -).

R ₁ can be hydrogen, methyl, halogen other than fluorine, substituted or unsubstituted benzyl. Examples of R ₁ are hydrogen, methyl, chlorine, bromine, iodine. R ₁ is preferably hydrogen, methyl, chlorine. R ₁ is particularly preferably methyl.

R ₂ can be hydrogen, methyl, substituted or unsubstituted benzyl. R ₂ is preferably hydrogen or methyl. R ₂ is particularly preferably methyl.

R ₅ and R ₆ are identical or different C ₁～C₁₀ alkyl, C ₆～C₂₀ aryl, C ₇～C₂₅ aralkyl (in particular benzyl C ₆H₅－CH₂ -). Preferably C ₁～C₅ alkyl, C ₆～C₁₀ aryl, C ₇～C₁₂ aralkyl (e.g. benzyl C ₆H₅－CH₂ -).

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 a C ₁～C₁₀ carboxylic acid (including acetic acid, propionic acid, butyric acid, etc.).

The monomer (C) is specifically exemplified below, but is not limited thereto.

CH ₂＝CHCOO-CH₂CH₂-N(CH₃)₂ and/or a salt thereof,

CH ₂＝CHCOO-CH₂CH₂-N(CH₂CH₃)₂ and/or a salt thereof,

CH ₂＝C(CH₃)COO-CH₂CH₂-N(CH₃)₂ and/or a salt thereof,

CH ₂＝C(CH₃)COO-CH₂CH₂-N(CH₂CH₃)₂ and/or a salt thereof,

CH ₂＝CH-C(＝O)-NH-CH₂CH₂-N(CH₃)₂ and/or a salt thereof,

CH ₂＝CH-C(＝O)-NH-CH₂CH₂-N(CH₂CH₃)₂ and/or a salt thereof,

CH ₂＝C(CH₃)-C(＝O)-NH-CH₂CH₂-N(CH₃)₂ and/or a salt thereof,

CH ₂＝C(CH₃)-C(＝O)-NH-CH₂CH₂-N(CH₂CH₃)₂ and/or salts thereof.

The monomer (C) is preferably dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylamide, diethylaminoethyl methacrylamide or a salt thereof.

The fluorine-free copolymer of the present invention contains, in addition to the repeating units of the monomer (A), the monomer (B) and the monomer (C), optionally, repeating units of other optional monomers (D) having a good suitability.

As such an optional monomer (D), a monomer having a pyrrolidone structure and a polymerizable unsaturated group, a monomer having a blocked isocyanate group and a polymerizable unsaturated group, a monomer having an alkoxysilyl group and a polymerizable unsaturated group, and/or a monomer having a glycidyl group and a polymerizable unsaturated group are included.

Examples of the other monomer (D) include the following compounds:

As the monomer containing a pyrrolidone structure and a polymerizable unsaturated group, there may be exemplified compounds including N-vinyl-2-pyrrolidone, N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-3, 3-dimethyl-2-pyrrolidone.

As the monomer having a blocked isocyanate and a polymerizable unsaturated group, there may be exemplified compounds including (meth) 2-butanone oxime adduct of ethyl ester of 2-isocyanato, (meth) pyrazole adduct of ethyl ester of 2-isocyanato, (meth) 3, 5-dimethylpyrazole adduct of ethyl ester of 2-isocyanato, (meth) 3-methylpyrazole adduct of ethyl ester of 2-isocyanato, (meth) epsilon-caprolactam adduct of ethyl ester of 2-isocyanato, (meth) 2-butanone oxime adduct of ethyl ester of 3-isocyanato, (meth) pyrazole adduct of ethyl ester of 3-isocyanato, (meth) 3-isocyanato, 3, 5-dimethylpyrazole adduct of ethyl ester of 3-isocyanato, (meth) 3-methylpyrazole adduct of ethyl ester of 3-isocyanato, (meth) epsilon-caprolactam adduct of ethyl ester of 3-isocyanato, (meth) 2-butanone oxime adduct of ethyl ester of 4-isocyanato, (meth) 2-butanone oxime of ethyl ester of 3-isocyanato, (meth) 3-isocyanato-ethyl ester of ethyl (meth) and, 3-methylpyrazole adducts of 4-isocyanatoethyl (meth) acrylate, epsilon-caprolactam adducts of 4-isocyanatoethyl (meth) acrylate.

As the monomer containing an alkoxysilyl group and a polymerizable unsaturated group, there may be exemplified 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl dimethoxy methylsilane, 3-methacryloxypropyl triethoxysilane, 3-methacryloxypropyl diethoxyethyl silane, allyl trimethoxysilane.

Examples of the monomer having a glycidyl group and a polymerizable unsaturated group include glycidyl (meth) acrylate and the like.

The amount of the repeating unit formed from 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.

The amount of the repeating unit formed from 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.

The amount of the repeating unit formed from 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.

The amount of the repeating unit formed by the other optional monomer (D) having a good suitability is 0 to 10% by weight, preferably 0 to 8% by weight, based on the copolymer.

The weight average molecular weight of the water-dispersible fluorine-free copolymer of the present invention may be 5000 to 500000, preferably 8000 to 200000.

In the present specification, "(meth) acrylic" means acrylic acid or methacrylic acid.

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

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 may be used. For example, in general, solution polymerization using an organic solvent may be selected to prepare the treatment liquid. The present invention is preferably prepared by means of solution polymerization.

In the present invention, it is preferable that after polymerization (for example, solution polymerization), water/acid solution is added first, and then the organic solvent is removed, thereby dispersing the polymer in water.

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, alcohols such as ethanol and isopropanol, and the like.

As the polymerization initiator, for example, a peroxide, an azo compound, or a persulfate compound can be used. The polymerization initiator is generally water-soluble and/or oil-soluble.

As specific examples of the oil-soluble polymerization initiator, dimethyl 2,2' -azobisisobutyrate, 2' -azobis (2-methylpropanenitrile), 2' -azobis (2-methylbutanenitrile), 2' -azobis (2, 4-dimethylvaleronitrile), 2' -azobis (2, 4-dimethyl 4-methoxyvaleronitrile), 1' -azobis (ethylene-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 are preferably cited.

In addition, specific examples of the water-soluble polymerization initiator are preferably exemplified by 2,2 '-azobisisobutylaminidine dihydrochloride, 2' -azobis (2-methylpropionamidine) hydrochloride, 2 '-azobis [2- (2-imidazolin-2-yl) propane ] sulfate hydrate, 2' -azobis [2- (5-methyl-2-imidazolin-2-yl) propane ] hydrochloride, potassium persulfate, barium persulfate, ammonium persulfate, hydrogen peroxide, and the like.

Regarding the removal of the organic solvent in the polymer solution, it is possible to conduct the removal by heating the polymer solution under (reduced pressure) heating conditions.

The initiator for the solution polymerization is preferably a peroxide or an even compound having a half-life of 8 hours and a decomposition temperature of 30℃or more, such as t-butyl peroxypivalate, 2' -azobis (2-methylpropanenitrile), etc.

The treatment agent containing the water-dispersible fluorine-free copolymer of the present invention can be favorably added externally to a paper substrate or internally to a pulp raw material.

Examples of the paper substrate of the object to be treated include paper, a container made of paper, a molded body made of paper (for example, pulp molding), and the like.

The paper can be manufactured by a conventionally known papermaking method. For example, an internal treatment method in which an oil-resistant treatment agent is added to a pulp slurry before papermaking or an external treatment method in which an oil-resistant treatment agent is applied to paper after papermaking may be used. The treatment method of the treatment agent in the present invention is preferably an internal addition treatment method.

In the case of external addition, the amount of the fluorine-free copolymer contained in the treating agent is preferably 0.01 to 4.0g/m ², particularly 0.1 to 2.0g/m ². The treatment agent is preferably formed from the treatment agent and starch and/or modified starch. The amount of the effective solid component for paper in the treating agent is preferably 3g/m ² or less.

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 based on 100 parts by weight of the pulp forming the paper, and the treating agent is preferably mixed with the pulp.

In the internal treatment with the treating agent, it is preferable to make paper from a pulp slurry having a pulp concentration of 1 to 5.0 wt%. Additives including sizing agents, coagulants, reinforcing agents, defoamers, and the like, and water-dispersible fluorine-free copolymers are added to the pulp slurry. Generally, since pulp is anionic, it is preferable that at least one of the additive and the fluorine-free copolymer is cationic or amphoteric so that the additive and the fluorine-free copolymer can be well fixed to the paper. Preferably, the additive and the fluorine-free copolymer are used in combination of cation or amphoteric, the additive is anionic, the fluorine-free copolymer is in combination of cation or amphoteric, and the additive is in combination of cation or amphoteric, and the fluorine-free copolymer is in combination of anion.

Examples of additives such as sizing agents, coagulants, reinforcing agents and the like are alkylketene dimers, alkenylsuccinic anhydrides, styrenic polymers, urea-formaldehyde polymers, polyethyleneimines, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethyl ammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichloride and polyalkylene polyamine, dicyanodiamide-formalin condensates, dimethyldiallylammonium chloride polymers, olefin/maleic anhydride polymers.

A typical solution polymerization process for treating agents comprising water-dispersed fluorine-free copolymers is as follows:

In the solution polymerization, an organic solvent is added, then the corresponding monomer is added for dissolution, nitrogen is introduced for replacement, an initiator is added, the temperature is raised to 50-120 ℃ by heating, and the reaction time is 5-30 hours.

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

(1) Copolymerizing a monomer, an organic solvent and an initiator in a kettle to obtain a polymer solution;

(2) Adding an acid solution into the polymer solution for dispersion treatment;

(3) Desolventizing the polymer solution to remove the organic solvent to obtain an aqueous dispersion;

(4) The amino groups in the aqueous dispersion are converted into nitroxide compounds, and finally the treating agent containing the water-dispersible fluorine-free copolymer is obtained.

In a preferred embodiment, the amino group is converted to the oxynitride in step (4) by treatment with a hydrogen peroxide solution added to the aqueous dispersion.

The concentration of the fluorine-free copolymer in the treating agent may be 0.01 to 50% by weight, for example, 0.1 to 40% by weight, preferably 1 to 30% by weight, more preferably 5 to 25% by weight.

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

In the present invention, the object to be treated is treated with a treating agent comprising a water-dispersible fluorine-free copolymer. The term "treatment" means that the above-mentioned treating agent is applied to an object to be treated by dipping, spraying, coating, internal addition, or the like. By the treatment, the fluorine-free copolymer as an active ingredient of the treatment agent permeates into the inside of the object to be treated and/or adheres to the surface of the object to be treated or becomes a part of the object to be treated.

Examples

In the present specification, unless otherwise specified, terms used have a general meaning known to those skilled in the art, "%" means "% by weight", and "parts" means "parts by weight".

The following is a paper product processing and testing method:

Paper product processing

Disposable paper products include tissue, thick paper, cardboard, pulp molded, etc., from cartons up to 500 grams per unit area (m ²), kraft papers up to 100 grams per unit area (m ²), tissue papers up to 150 grams per unit area (m ²), to paper-plastic products up to 300 grams per unit area (m ²). The paper product may be chemically bleached pulp or unbleached pulp, crushed wood pulp, chemimechanical pulp, mechanical pulp, etc.

Specific processing method for paper cutlery box

Directly pulping bleached sugarcane pulp/bleached bamboo pulp (3:7), wherein the buckling degree is 23 DEG SR, the pulp concentration is 0.3%, the synthesized treating agent is added, the addition amount is 8% of the absolute dry pulp weight, and a standard paper meal box with 15g of weight is prepared by a small pulping and forming system.

Oil resistance test (paper cutlery box)

Placing the sample on dry glass or a flat plate lined with filter paper, filling with edible oil (salad oil, peanut oil and rapeseed oil) at a specified temperature, standing for 30 minutes, observing whether the sample is deformed, observing whether exuded oil marks exist on the filter paper, and grading according to the following standard, wherein the higher the grade is, the better the oil resistance is;

* The specified temperature of the edible oil is a heat-resistant oil test (100+/-5 ℃) and a cold-resistant oil test (0-5 ℃);

grade 4, inner wall and back are impermeable

Grade 3, color change of inner wall, impermeable back

Grade 2, back Permeability >5%

1 Grade, the back permeability is less than or equal to 5 percent and less than 20 percent, and the sample has no deformation and the underlying filter paper has no obvious exudation

0 Grade, the back permeability is more than or equal to 20 percent

Water resistance test (paper made cutlery box)

The sample was placed on a dry glass or plate lined with filter paper, filled with 95.+ -. 5 ℃ water, and after standing for 30 minutes, the sample was observed for deformation, and the bottom was observed for the phenomenon of negative permeation or leakage. If the sample does not have deformation, yin permeation or leakage, the sample is judged to pass, and if the deformation, yin permeation or leakage occurs, the sample is judged to not pass.

The phenomenon that the bottom is condensed due to the temperature difference between the inside and the outside of the sample during the test is not considered as yin seepage and seepage.

Evaluation of relative yellowing degree (whiteness) of cutlery box

The synthetic treatment agent-added sample and the sample without any treatment agent-added sample were prepared under the same process conditions, respectively, and the synthetic treatment agent-added sample and the sample without any treatment agent were used as a standard, and the change in relative yellowing (whiteness) was visually evaluated. Ratings were given according to the following criteria.

Grade 0 visual apparent whitening compared to standard

Grade 1 visual whitening compared to standard

Grade 2 visual whiteness substantially similar to that of a standard

Grade 3 visual yellowing as compared to standard

Grade 4 visual apparent yellowing compared to standard

Evaluation of cutlery box hardness

The test pieces with and without any treatment agent were prepared under the same process conditions, and the hardness change was visually evaluated by using the test pieces without any treatment agent as a standard. Ratings were given according to the following criteria.

Grade 0, obvious softer than standard

Grade 1, slightly softer than the standard

Grade 2, hardness substantially similar to the standard

Grade 3, slightly stiffer than standard

Grade 4, obvious hardening compared with standard products

Evaluation of anti-sticking Property

And continuously preparing 20 standard cutlery boxes with the weight of 15 g by using a small pulping and forming system, and observing whether the bottom of the die has the die sticking condition. If 20 standard cutlery boxes with the weight of 15 g are continuously manufactured, the situation that the bottom of the die is free of sticking is marked as passing, and if the situation that the die is stuck is marked as not passing.

The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these descriptions.

In this specification, chemical abbreviations are shown in table 1.

Table 1 chemical abbreviations

Example 1

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of Methyl Ethyl Ketone (MEK) was added as a solvent under stirring, and 55G of Si-MNP3, 15G of JMN-201, 3G of JMC-320, and 27G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 2

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of Methyl Ethyl Ketone (MEK) was added as a solvent under stirring, and 65G of Si-MNP3, 5G of JMN-201, 2G of JMC-430, and 28G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 3

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and then 70G of Si-MNP3, 4G of JMN-320, and 26G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 4

A500 mL reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heater was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 80G of Si-MNP3, 2G of JMC-540, and 18G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 5

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of Methyl Ethyl Ketone (MEK) was added as a solvent under stirring, and 80G of Si-MNP3, 2G of JMC-311, 1G of JMC-650, and 17G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃,1.5 g of initiator dimethyl 2,2' -azobisisobutyrate is slowly added, and the reaction temperature is controlled to be 75 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 6

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 60G of Si-MCP7, 10G of JMN-201, 3G of JMC-320, and 27G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5 g of initiator dimethyl 2,2' -azobisisobutyrate is slowly added, and the reaction temperature is controlled to be 75 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 7

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 60G of Si-MCP7, 10G of JMN-201, 2G of JMC-430, and 28G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃,1.5g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 8

A500 mL reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heater was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent with stirring, and then 70G of Si-MCP7, 4G of JMN-320, and 26G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 9

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of Methyl Ethyl Ketone (MEK) was added as a solvent under stirring, and 75G of Si-MCP7, 3G of JMC-540, and 22G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 0.8 g of initiator 2,2' -azobisisobutyronitrile is slowly added, the reaction temperature is controlled to be 75 ℃ for reaction for 12 hours, and copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 10

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 55G of Si-MCPn, 15G of JMN-201, 3G of JMC-320, and 27G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 0.8 g of initiator 2,2' -azobisisobutyronitrile is slowly added, the reaction temperature is controlled to be 75 ℃ for reaction for 12 hours, and copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 11

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of Methyl Ethyl Ketone (MEK) was added as a solvent under stirring, and 65G of Si-MCPn, 6G of JMN-201, 1G of JMC-650, and 28G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 12

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 65G of Si-MCPn, 7G of JMC-320, and 28G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃,0.8 g of initiator 2,2' -azobisisobutyronitrile is slowly added, the reaction temperature is controlled to be 75 ℃ for reaction for 12 hours, and copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 13

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 65G of Si-MCPn, 6G of JMC-430, and 29G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 14

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and then 70G of Si-MCPn, 6G of JMN-320, and 24G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 15

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 75G of Si-MCPn, 2G of JMC-311, 2G of JMC-540, and 21G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 0.8 g of initiator 2,2' -azobisisobutyronitrile is slowly added, the reaction temperature is controlled to be 75 ℃ for reaction for 12 hours, and copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 16

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of Methyl Ethyl Ketone (MEK) was added as a solvent under stirring, and 80G of Si-MCPn, 2G of JMC-650, and 18G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 17

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 60G of Si-MCP3, 10G of JMN-201, 2G of JMN-320, and 28G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃,1.5g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 18

A500 mL reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heater was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 65G of Si-MCP3, 8G of JMN-320, and 27G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 19

A500 mL reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heater was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and then 70G of Si-MCP3, 5G of JMC-320, and 25G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 20

A500 mL reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heater was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 75G of Si-MCP3, 4G of JMC-430, and 21G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 21

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of Methyl Ethyl Ketone (MEK) was added as a solvent under stirring, and 75G of Si-MCP3, 2G of JMC-540, and 23G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 22

A500 mL reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heater was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 75G of Si-MCP3, 2G of JMC-650, and 23G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃,0.8 g of initiator 2,2' -azobisisobutyronitrile is slowly added, the reaction temperature is controlled to be 75 ℃ for reaction for 12 hours, and copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 23

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 75G of Si-MCP3, 2G of JC-320, and 23G of G-MN were sequentially added. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 24

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 75G of Si-MCP3, 2G JMEO-650, and 23G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃,1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 25

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 75G of Si-MCP3, 2G of JRE-650, and 23G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃,1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 26

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 75G of Si-MCPn, 2G of JMPO-650, and 23G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃,1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 27

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 75G of Si-MCP7, 1G of JMC-540, 2G of JMES-211, and 22G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃,0.8 g of initiator 2,2' -azobisisobutyronitrile is slowly added, the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, and copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Example 28

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 75G of Si-MNP3, 1G of JMC-650, 2G of J-220, and 22G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Comparative example 1

A500 mL reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heater was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and then 70G of Si-MCP3, 7G of HEMA, and 23G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Comparative example 2

A500 mL reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heater was prepared, 200G of Methyl Ethyl Ketone (MEK) was added as a solvent under stirring, and 75G of Si-MCP3, 5G of HBMA, and 20G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Comparative example 3

A500 mL reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heater was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 65G of Si-MCP3, 10G HEMAA, and 25G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Comparative example 4

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 65G of Si-MCPn, 10G HEMAA, and 25G-MC were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Comparative example 5

A500 mL reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heater was prepared, 200G of Methyl Ethyl Ketone (MEK) was added as a solvent under stirring, and 70G of Si-MCPn, 10G of HBA, and 20G of G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Comparative example 6

A500 mL reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heater was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 75G of Si-MCPn, 5G of HBMA, and 20G of G-MC were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Comparative example 7

A500 mL reactor equipped with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heating device was prepared, 200G of Methyl Ethyl Ketone (MEK) was added as a solvent under stirring, and then 70G of Si-MCP3, 6G of HEMA, 1G of MOI-BP, and 23G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃, 1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Comparative example 8

A500 mL reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heater was prepared, 200G of isopropyl alcohol (IPA) was added as a solvent under stirring, and 77G of Si-MCP3 and 23G-MN were added in this order. Nitrogen is introduced for replacement, the temperature is slowly raised to 50 ℃,1.5 g of initiator tert-butyl peroxypivalate is slowly added, and the reaction temperature is controlled to be 70 ℃ for reaction for 12 hours, so that copolymerization is carried out. The resulting copolymer-containing solution had a solid content concentration of about 33.3% by weight.

200G of 4.8% acetic acid solution was added to the polymerization solution and stirred to form a salt, and the internal temperature was maintained at 70℃for 1 hour. The organic solvent was removed under reduced pressure to obtain a copolymer aqueous dispersion. Distilled water was further added to the aqueous dispersion to finally obtain a water-dispersible treating agent having a solid content of 20% by weight.

Several different paper products were tested using the treatment agents synthesized in the examples and comparative examples, as follows:

Paper tableware performance test

Directly pulping bleached sugarcane pulp/bleached bamboo pulp (3:7), wherein the buckling degree is 23 DEG SR, the pulp concentration is 0.3%, the synthesized treating agents are added, the addition amounts are 8% of the absolute dry pulp weight respectively, a standard cutlery box with 15 gram weight is prepared by a small pulping forming system, and the cutlery box is tested for water resistance, oil resistance, hardness, whiteness and anti-sticking performance.

The performance test results are shown in tables 2, 3, 4 and 5.

TABLE 2 Performance test results

TABLE 3 Performance test results

TABLE 4 Performance test results

TABLE 5 Performance test results

As shown in tables 2 to 5, the anti-sticking properties of each example were significantly improved compared to comparative examples 7 to 8. In addition, the heat and cold oil resistance of examples 1-16 are significantly improved as compared to comparative examples 4-6. Examples 17-28 have significantly improved hot oil resistance, cold oil resistance, and paper cutlery box hardness compared to comparative examples 1-3. Overall, it can be seen from the results of examples and comparative examples that the treating 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 product is not stuck to the mold during the production process, and the final produced product has higher hardness.

While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that alterations, modifications, substitutions and variations may be made in the above embodiments by those skilled in the art within the scope of the invention.

The technical scheme of the invention is not limited to the specific embodiment, and all technical modifications made according to the technical scheme of the invention fall within the protection scope of the invention.

Claims (23)

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, R ₁ is independently -H, non-fluorinated halogen, or C ₁ to C ₂₀ alkyl having a linear or branched structure; X' is a structure represented by -W-, -R ₀ -, -W-R ₀ -, -R ₀ -W-, or -W-R ₀ -W-, R ₀ is -(CH ₂ ) _n - or a C ₁ to C ₁₀ branched alkylene group, and n is an integer of 0 to 20. W is selected from the structures represented by W ₁ to W ₄ : －C(＝O)－O－ W ₁ －C(＝O)－N(R ₂ )－ W ₂ -O-W ₃ －O－C(＝O)－ W _{4 R2} is -H or _C1 - _C20 alkyl; Q is the structure shown in formula (5): _Z5 and/or M are independently -H, -OH, non-fluorinated halogen, _C1 - _C10 alkyl, _C1 - _C10 monohydric alcohol, _C2 - _C10 polyhydric alcohol or _C1 - _C10 non-fluorinated halogenated alkyl, q is an integer from 0 to 10, and In the monomer (B), the -Q-M structure contains at least two or more groups selected from the group consisting of non-fluorinated halogen, -OH, C ₁ to C ₁₀ monohydric alcohol group, C ₂ to C ₁₀ polyhydric alcohol group, and C ₁ to C ₁₀ non-fluorinated halogenated alkyl group. 2. The water-dispersible fluorine-free copolymer according to claim 1, wherein 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, R ₇ is independently -H, C ₁ to C ₁₀ alkyl or C ₁ to C ₁₀ chloroalkyl, Each C _x H _2x+1-y (OH) _y is the same or different, x is an integer of 1 to 10, y is an integer of 1 to 10, and in the same group C _x H _2x+1-y (OH) _y , 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, R ₁ is independently -H, non-fluorinated halogen, or C ₁ to C ₂₀ alkyl having a linear or branched structure; _{where ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​} -, -C ₆ H ₄ -W-C ₆ H ₄ -, -R ₀ -W-C ₆ H ₄ -, -C ₆ H ₄ -W-R ₀ -, -W -R ₀ -C ₆ H ₄ -, -W - C ₆ H ₄ -R ₀ -, -C ₆ H ₄ -R ₀ -W -, -R ₀ -C ₆ H ₄ -W -, -R ₀ -C ₆ H ₄ -R ₀ -, -W-R ₀ -C ₆ H ₄ -R ₀ -, -R ₀ -C ₆ H ₄ -R ₀ -W-, -C ₆ H ₄ -R ₀ -W-R ₀ -, -R ₀ -C ₆ H ₄ -W-R ₀ -, -R ₀ -W-R ₀ -C ₆ H ₄ a group represented by -R ₀ - or -R ₀ -C ₆ H ₄ -R ₀ -W-R ₀ -, -C ₆ H ₄ - is a phenylene group, R ₀ is independently -(CH ₂ ) _n - or a C ₁ to C ₁₀ branched alkylene group, and n is an integer of 0 to 20. W is selected from the structures represented by W ₁ to W ₄ : －C(＝O)－O－W ₁ -C(=O)-N(R ₂ )-W ₂ -O-W ₃ －O－C(＝O)－W _{4 R2} is -H or _C1 - _C20 alkyl, Y is a structure shown in formula (2): _R3 is independently a _C1 - _C10 alkyl group, a _C6 - _C20 aryl group or a _C7 - _C20 aralkyl group, _Z1 and _Z2 are independently a _C1 -C10 alkyl group, _{a C6} - _C20 aryl group, a _C7 - _C20 aralkyl group or _a structure represented by formula (3), m is 1-300, _R4 is independently a _C1 - _C10 alkyl group, a _C6 - _C20 aryl group or a _C7 - _C20 aralkyl group, _Z3 and _Z4 are independently a _C1 -C10 alkyl group, _{a C6} - _C20 aryl group or a _C7 - _C20 aralkyl group, and k is 0-300 _. 4. The water-dispersible fluorine-free copolymer according to claim 3, characterized in that In the monomer (A), R ₁ is independently -H, a non-fluorinated halogen, or a C ₁ to C ₁₀ linear or branched alkyl group. 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- ;} each _R0 is independently -( _CH2 ) _n- or _{a C1} - _C10 branched alkylene group; n is an integer of 0 to 10; In Y, R ₃ and/or R ₄ are each independently a C ₁ to C ₅ alkyl group, a C ₆ to C ₁₀ aryl group, or a C ₇ to C ₁₂ aralkyl group; Z ₃ and/or Z ₄ are each independently a C ₁ to C ₅ alkyl group, a C ₆ to C ₁₀ aryl group, or a C ₇ to C ₁₂ aralkyl group; 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 is each independently a C ₁ -C ₅ alkyl group, a C ₆ -C ₁₀ aryl group or a C ₇ -C ₁₂ aralkyl group, m is 1-35, and k1 and k2 are each independently 0-35. 6 . The water-dispersible fluorine-free copolymer according to claim 1 , wherein the ionic donor group in the monomer (C) is a cationic donor group. 7 . The water-dispersible fluorine-free copolymer according to claim 6 , wherein the cation donor group is an amino group. 8. The water-dispersible fluorine-free copolymer according to any one of claims 1 to 7, wherein the monomer (C) is a monomer represented by formula (6): Wherein, R ₁ is independently -H, non-fluorinated halogen, or C ₁ to C ₂₀ alkyl having a linear or branched structure; X' is a structure represented by -W-, -R ₀ -, -W-R ₀ -, -R ₀ -W-, or -W-R ₀ -W-, R ₀ is -(CH ₂ ) _n - or a C ₁ to C ₁₀ branched alkylene group, and n is an integer of 0 to 20. W is selected from the structures represented by W ₁ to W ₄ : －C(＝O)－O－W ₁ -C(=O)-N(R ₂ )-W ₂ -O-W ₃ －O－C(＝O)－W _{4 R2} is -H or _C1 - _C20 alkyl; R ₅ and R ₆ are each independently a C ₁ -C ₁₀ alkyl group, a C ₆ -C ₂₀ aryl group, or a C ₇ -C ₂₅ aralkyl group. 9 . The water-dispersible fluorine-free copolymer according to claim 8 , wherein in the monomer (C), R ₅ and R ₆ 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 a repeating unit formed by an 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) 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%; and 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: CH ₂ =C(CH ₃ )-C(=O)-NH-CH ₂ CH ₂ Cl CH ₂ =C(CH ₃ )-COO-CH ₂ CH(OH)CH ₂ Cl CH ₂ =C(CH ₃ )-COO-CH ₂ CH(OH)CH ₂ OH CH ₂ =C(CH ₃ )-C(=O)-NH-CH ₂ CH(OH)CH ₂ OH CH ₂ =C(CH ₃ )-COO-CH ₂ -CH(OH)CH(OH)CH ₂ OH CH ₂ =C(CH ₃ )-COO-CH ₂ -CH(OH)CH(OH)CH(OH)CH ₂ OH CH ₂ =C(CH ₃ )-COO-CH ₂ -CH(OH)CH(OH)CH(OH)CH(OH)CH ₂ OH CH ₂ =C(CH ₃ )-O-CH ₂ CH(OH)CH(OH)CH(OH)CH(OH)CH ₂ OH CH ₂ =C(CH ₃ )-CH ₂ -O-CH ₂ CH(OH)CH(OH)CH(OH)CH(OH)CH ₂ OH CH ₂ =C(CH ₃ )-OC(=O)-CH(OH)CH ₂ Cl CH ₂ ＝CH-CH(OH)CH ₂ OH CH ₂ ＝CH-CH ₂ CH(OH)CH ₂ OH CH ₂ =CH-C(=O)-O-CH ₂ -C(=O)-O-CH ₂ CH(OH)CH(OH)CH(OH)CH(OH)CH ₂ OH CH ₂ =CHCOO-[C(C _x H _2x+1-y (OH) _y ) ₂ -C(R ₇ ) ₂ ] _q -M CH ₂ =C(CH ₃ )COO-[C(C _x H _2x+1-y (OH) _y ) ₂ -C(R ₇ ) ₂ ] _q -M CH ₂ =CH-C(=O)-NH-[C(C _x H _2x+1-y (OH) _y ) ₂ -C(R ₇ ) ₂ ] _q -M CH ₂ =C(CH ₃ )-C(=O)-NH-[C(C _x H _2x+1-y (OH) _y ) ₂ -C(R ₇ ) ₂ ] _q -M CH ₂ =CHCOO-[C(R ₇ ) ₂ -C(C _x H _2x+1-y (OH) _y ) ₂ ] _q -M CH ₂ =C(CH ₃ )COO-[C(R ₇ ) ₂ -C(C _x H _2x+1-y (OH) _y ) ₂ ] _q -M CH ₂ =CH-C(=O)-NH-[C(R ₇ ) ₂ -C(C _x H _2x+1-y (OH) _y ) ₂ ] _q -M CH ₂ =C(CH ₃ )-C(=O)-NH-[C(R ₇ ) ₂ -C(C _x H _2x+1-y (OH) _y ) ₂ ] _q -M CH ₂ =CHCOO-[C(R ₇ )(C _x H _2x+1-y (OH) _y )-C(R ₇ )(C _x H _2x+1-y (OH) _y )] _q -M CH ₂ =C(CH ₃ )COO-[C(R ₇ )(C _x H _2x+1-y (OH) _y )-C(R ₇ )(C _x H _2x+1-y (OH) _y )] _q -M CH ₂ =CH-C(=O)-NH-[C(R ₇ )(C _x H _2x+1-y (OH) _y )-C(R ₇ )(C _x H _2x+1-y (OH) _y )] _q -M CH ₂ =C(CH ₃ )-C(=O)-NH-[C(R ₇ )(C _x H _2x+1-y (OH) _y )-C(R ₇ )(C _x H _2x+1-y (OH) _y )] _q -M CH ₂ =CHCOO-[C(R ₇ )(C _x H _2x+1-y (OH) _y )-C(C _x H _2x+1-y (OH) _y ) ₂ ] _q -M CH ₂ =C(CH ₃ )COO-[C(R ₇ )(C _x H _2x+1-y (OH) _y )-C(C _x H _2x+1-y (OH) _y ) ₂ ] _q -M CH ₂ =CH-C(=O)-NH-[C(R ₇ )(C _x H _2x+1-y (OH) _y )-C(C _x H _2x+1-y (OH) _y ) ₂ ] _q -M CH ₂ =C(CH ₃ )-C(=O)-NH-[C(R ₇ )(C _x H _2x+1-y (OH) _y )-C(C _x H _2x+1-y (OH) _y ) ₂ ] _q -M CH ₂ =CHCOO-[C(C _x H _2x+1-y (OH) _y ) ₂ -C(R ₇ )(C _x H _2x+1-y (OH) _y )] _q -M CH ₂ =C(CH ₃ )COO-[C(C _x H _2x+1-y (OH) _y ) ₂ -C(R ₇ )(C _x H _2x+1-y (OH) _y )] _q -M CH ₂ =CH-C(=O)-NH-[C(C _x H _2x+1-y (OH) _y ) ₂ -C(R ₇ )(C _x H _2x+1-y (OH) _y )] _q -M CH ₂ =C(CH ₃ )-C(=O)-NH-[C(C _x H _2x+1-y (OH) _y ) ₂ -C(R ₇ )(C _x H _2x+1-y (OH) _y )] _q -M CH ₂ =CHCOO-[C(C _x H _2x+1-y (OH) _y ) ₂ -C(C _x H _2x+1-y (OH) _y ) ₂ ] _q -M CH ₂ =C(CH ₃ )COO-[C(C _x H _2x+1-y (OH) _y ) ₂ -C(C _x H _2x+1-y (OH) _y ) ₂ ] _q -M CH ₂ =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 CH ₂ =C(CH ₃ )-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, R ₇ are each independently -H, C ₁ to C ₁₀ alkyl, or C ₁ to C ₁₀ chloroalkyl. Each C _x H _2x+1-y (OH) _y is the same or different, x is an integer from 1 to 10, y is an integer from 1 to 10, and in the same group C _x H _2x+1-y (OH) _y , y≤x, M is -H, -Cl, -OH, a C ₁ -C ₆ monohydric alcohol group, or a C ₂ -C ₆ 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: CH ₂ =C(CH ₃ )COO-(CH ₂ ) ₃ Si(OSi(CH ₃ ) ₃ ) ₃ CH ₂ =CHCOO-(CH ₂ ) ₃ Si(OSi(CH ₃ ) ₃ ) ₃ CH ₂ =C(CH ₃ )COO-(CH ₂ ) ₃ Si[OSi(OSi(CH ₃ ) ₃ ) ₃ ] ₂ (OSi(CH ₃ ) ₃ ) CH ₂ =CHCOO-(CH ₂ ) ₃ Si[OSi(OSi(CH ₃ ) ₃ ) ₃ ] ₂ (OSi(CH ₃ ) ₃ ) CH ₂ =C(CH ₃ )COO-(CH ₂ ) _n Si(R) ₂ [O(Si(R) ₂ O) _k Si(R) ₃ ] CH ₂ =CHCOO-(CH ₂ ) _n Si(R) ₂ [O(Si(R) ₂ O) _k Si(R) ₃ ] CH ₂ =C(CH ₃ )COO-(CH ₂ ) _n Si[O(Si(R) ₂ O) _k Si(R) ₃ ] ₂ (OSi(R) ₃ ) CH ₂ =CHCOO-(CH ₂ ) _n Si[O(Si(R) ₂ O) _k Si(R) ₃ ] ₂ (OSi(R) ₃ ) CH ₂ =C(CH ₃ )-C(=O)-NH-(CH ₂ ) _n Si(R) ₂ [O(Si(R) ₂ O) _k Si(R) ₃ ] CH ₂ =CH-C(=O)-NH-(CH ₂ ) _n Si(R) ₂ [O(Si(R) ₂ O) _k Si(R) ₃ ] CH ₂ =C(CH ₃ )-C(=O)-NH-(CH ₂ ) _n Si[O(Si(R) ₂ O) _k Si(R) ₃ ] ₂ (OSi(R) ₃ ) CH ₂ =CH-C(=O)-NH-(CH ₂ ) _n Si[O(Si(R) ₂ O) _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 is each independently a C ₁ -C ₁₀ alkyl group, a C ₆ -C ₂₀ aryl group, or a C ₇ -C ₂₀ aralkyl group. 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: CH ₂ ＝CHCOO—CH ₂ CH ₂ —N(CH ₃ ) ₂ and/or its salts, CH ₂ ＝CHCOO—CH ₂ CH ₂ —N(CH ₂ CH ₃ ) ₂ and/or its salts, CH ₂ ═C(CH ₃ )COO—CH ₂ CH ₂ —N(CH ₃ ) ₂ and/or its salts, CH ₂ ═C(CH ₃ )COO—CH ₂ CH ₂ —N(CH ₂ CH ₃ ) ₂ and/or a salt thereof, CH ₂ ═CH—C(═O)—NH—CH ₂ CH ₂ —N(CH ₃ ) ₂ and/or a salt thereof, CH ₂ ═CH—C(═O)—NH—CH ₂ CH ₂ —N(CH ₂ CH ₃ ) ₂ and/or a salt thereof, _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 a salt _thereof . 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, comprising the following steps: (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. The use of the treatment agent comprising a water-dispersible fluorine-free copolymer according to claim 19, wherein the product is treated by internally or externally adding the treatment agent to impart water and oil resistance to the product; The products include paper products, plastics, fiber fabrics, fur, leather and/or non-woven fabrics. 23. The use according to claim 22, wherein the paper product is used as a food packaging material or food container after being processed.