A water-dispersible copolymer, its preparation method and application

Abstract

The present invention relates to the field of polymer compounds, and relates to a water-dispersible copolymer, a preparation method thereof and an application. The water-dispersible copolymer provided by the present invention comprises repeating units generated from monomer I, repeating units generated from monomer II, and repeating units generated from monomer III. Monomer I is a carbosiloxane dendritic monomer, monomer II is a cationic monomer with a tertiary amine group, and monomer III is a hydrophilic monomer. The copolymer or a composition containing the polymer can be used for surface treatment of paper and endows the paper surface with strong water and oil repellency.

Description

Technical Field

[0001] The present invention relates to the field of high molecular compounds, and more specifically, to a water-dispersible copolymer, a preparation method thereof, and an application thereof. Background Art

[0002] Among numerous surface treatment agents, the most widely used one is the surface treatment agent containing fluoropolymer. Such surface treatment agents have excellent properties such as good waterproof and oil-proof properties, good heat resistance, good film-forming properties, and high chemical stability, and are widely used in fields such as paper, fabric, packaging materials, and water-based coatings. Fluoropolymers are used as paper treatment agents to endow them with oil-proof properties because of their extremely low surface energy. However, due to the fact that long-chain fluoropolymers are not easily degraded in the natural environment, have high bioaccumulation, and are toxic, etc., they will pose certain hazards to the human body and the environment. The patent CN102575435B published by Daikin Industries, Ltd. of Japan includes an oil-proof agent containing a fluorine copolymer for providing excellent waterproof and oil-proof properties to paper, and is obtained by copolymerizing a fluorine-containing (meth)acrylate monomer having 1-6 carbon atoms, a hydrophilic monomer, and a monomer having an anion supply group. Chinese patent CN111040072A discloses an ethylene-based fluorine-containing copolymer applied to paper-based products, which is obtained by free radical copolymerization of a short-chain fluorine-containing monomer, a quaternary amine acrylate monomer, and an acrylic monomer, and its prepared waterproof and oil-proof composition is applied to paper-based products. Although existing research shows that short-chain fluoropolymers have good biodegradability, do not have obvious bioaccumulation, and will not pose potential hazards to human health and the environment, their waterproof and oil-proof properties are poor, which is not conducive to further popularization and use.

[0003] In view of the above situation, some new non-fluoropolymers have been proposed to replace the existing fluorine-containing surface treatment agents. Among them, silicone-based polymers are widely used due to their many advantages such as environmental friendliness, excellent performance, and low cost. The patent documents with publication numbers CN112805434A and CN114573768B disclose a silicone polymer, which can be directly dispersed in water, treat fiber products, and has excellent waterproof performance, but the oil-proof effect is not very good. Summary of the Invention

[0004] The primary object of the present invention is to overcome the problem that the existing non-fluorine treatment agents cannot simultaneously have excellent water and oil repellency, and provide a water-dispersible copolymer.

[0005] Another object of the present invention is to provide a preparation method of a composition containing the above water-dispersible copolymer.

[0006] Another object of the present invention is to provide a composition prepared by the preparation method of the above composition.

[0007] Another object of the present invention is to provide a paper treatment agent containing the above water-dispersible copolymer and composition.

[0008] Another object of the present invention is to provide a paper and / or paper product prepared from the above water-dispersible copolymer, composition or paper treatment agent.

[0009] The above object of the present invention is achieved by the following technical solutions:

[0010] A water-dispersible copolymer, comprising repeating units derived from monomer I, repeating units derived from monomer II and repeating units derived from monomer III:

[0011] The general structural formula of monomer I is as follows:

[0012]

[0013] Wherein, X is a group with a carbon-carbon double bond;

[0014] R 1 and R 2 are each independently a C1-C 10 alkyl group, a C1-C 10 aryl group or a C1-C 10 aralkyl group, and a is any one of 0, 1, 2;

[0015] L is an H atom, a C1-C 10 alkyl group, a C1-C 10 aryl group, a C1-C 10 aralkyl group or a silyl group, or has the following structure:

[0016]

[0017] Wherein, Y is an alkylene group, and p is an integer from 1 to 10;

[0018] R 3 and R 4 are each independently a C1-C 10 alkyl group, a C1-C 10 aryl group or a C1-C 10 aralkyl group, and b is any one of 0, 1, 2;

[0019] M is an H atom, a C1-C 10 alkyl group, a C1-C 10 aryl group, a C1-C 10 aralkyl group or a silyl group;

[0020] The general structural formula of monomer II is as follows:

[0021]

[0022] Among them, R 5 is H or C1-C 10 alkyl;

[0023] Z is N or O;

[0024] Q is an organic group with a tertiary amine;

[0025] The monomer III is selected from one or more of acrylate monomers, acrylamide monomers, polymerizable unsaturated monomers with an anion supply group, polymerizable unsaturated siloxane coupling agents, and polymerizable unsaturated monomers containing polyfunctional groups. The anion supply group is a carboxyl group or a sulfonic acid group, and the polyfunctional groups include one or more of a hydroxyl group, an isocyanurate group, an ester group, and an ether group.

[0026] The copolymer and its composition obtained in the present invention improve the waterproof and oil-proof effects by introducing the monomer I with a dendrimer structure and simultaneously carrying out cationization by using a quaternization reaction. In the monomer I of the present invention, the silicon atoms in the carbon-siloxane unit are radially arranged in a molecular structure, so that the carbon-siloxane unit extends in the form of a dendrimer, endowing the copolymer with stronger water and oil repellency, which is beneficial to further improving the water resistance and oil resistance of the paper surface. When liquids such as water and oil come into contact with the surface of the copolymer, due to the extremely low surface energy of the copolymer, the wetting of the liquids such as water and oil on the surface is prevented, and a protective film is formed on the paper surface, achieving the effects of waterproofing and oil-proofing. Therefore, compared with other linear and simple branched polysiloxanes, it has more excellent waterproof and oil-proof properties.

[0027] Preferably, the mass ratios of the repeating units generated by the monomer I, the repeating units generated by the monomer II, and the repeating units generated by the monomer III are 20-85 wt%: 10-40 wt%: 0-40 wt%.

[0028] Preferably, in the monomer I, R 1 and R 2 are each independently methyl; and / or;

[0029] In L, M is selected from methyl or ethyl; and / or;

[0030] In the monomer II, R 5 is selected from H or methyl; and / or

[0031] X is selected from at least one of an organic group containing an acryloyl group or a methacryloyl group, an organic group containing an alkenyl group and an aryl group, and an organic group composed of an alkenyl group having 2-10 carbon atoms.

[0032] More preferably, X is at least one of vinyl, allyl, acryloyloxy, methacryloyloxy, acrylamido, or methacrylamido.

[0033] Preferably, the monomer I is selected from

[0034]

[0035] at least one of.

[0036] Preferably, the monomer II is selected from one or more of dimethylaminoethyl dimethacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylamide, diethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, and diethylaminopropyl methacrylamide.

[0037] Preferably, the acrylamide monomer of monomer III is methylacrylamide-2-hydroxy methyl ester or acrylamide-2-hydroxy ethyl ester;

[0038] The polymerizable unsaturated monomer having an anion supply group is selected from one or more of methacrylic acid, crotonic acid, maleic acid, itaconic acid, vinyl sulfonic acid, styrene sulfonic acid, vinyl benzene sulfonic acid, acrylamide-tert-butyl sulfonic acid, and salts prepared from the above acids;

[0039] The acrylate monomer is an oxyalkylene-methacrylate monomer having a structure of CH2=CX1C(=O)-O-(RO) n -X2 or CH2=CX1C(=O)-O-(RO) n -O-(O=)CX1C=CH2;

[0040] wherein, X1 is selected from an H atom or a methyl group; X2 is selected from an H atom, a saturated or unsaturated C1~C 10 hydrocarbon group; R is selected from an alkylene group of C2~C3; n is selected from any integer of 1~20; more preferably, n is selected from any integer of 2~10;

[0041] The polymerizable unsaturated siloxane coupling agent is selected from one or more of γ-(methacryloyloxy)propyltrimethoxysilane, γ-(methacryloyloxy)propyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane;

[0042] The polyfunctional and polymerizable unsaturated monomer is selected from one or more of trimethylolpropane triacrylate, pentaerythritol triacrylate, tetraethylene glycol diacrylate, tris(2-hydroxyethyl)isocyanurate diacrylate, tris(2-hydroxyethyl)isocyanurate dimethacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, and tris(2-hydroxyethyl)isocyanurate trimethacrylate.

[0043] The present invention also provides a composition, comprising the copolymer as described above in the present invention and a solvent, wherein the solvent comprises water and / or an organic solvent.

[0044] Specifically, the organic solvent is an aliphatic hydrocarbon, an aromatic hydrocarbon, an ether, an ester, an alcohol or an organosiloxane oligomer.

[0045] Preferably, the aliphatic hydrocarbon is hexane, octane, decane or cyclohexane.

[0046] Preferably, the aromatic hydrocarbon is benzene, toluene or xylene.

[0047] Preferably, the ether is diethyl ether or dibutyl ether.

[0048] Preferably, the ester is methyl acetate, ethyl acetate, butyl acetate or isobutyl acetate.

[0049] Preferably, the alcohol is methanol, ethanol, isopropanol or butanol.

[0050] Preferably, the organosiloxane oligomer is octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane or octamethyltrisiloxane.

[0051] The present invention also relates to a method for preparing the composition as described above, specifically comprising the following steps:

[0052] S1. Polymerize monomers in an organic solvent by free radical polymerization and ionic polymerization methods to obtain a copolymer solution;

[0053] S2. Add an alkylating agent to the copolymer solution to convert the tertiary amine in the copolymer into a quaternary ammonium salt through a quaternization reaction to obtain a quaternized copolymer solution;

[0054] S3. Add a cosolvent to the quaternized copolymer solution, and then add water for dispersion to obtain the composition as described above.

[0055] Preferably, the free radical polymerization reaction is carried out in the presence of a free radical initiator, and the free radical initiator is one or more than two of azo-based or organic peroxide-based initiators.

[0056] Preferably, the azo-based initiator is selected from one or more than two of 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylpentanenitrile) and dimethyl-2,2'-azobis(2-methylpropionate).

[0057] Preferably, the organic peroxide initiator is selected from one or more than two of benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate.

[0058] Preferably, the amount of the radical initiator is 0.1 to 5 wt% of the total weight of all monomers.

[0059] Specifically, the alkylating agent is selected from one or more of haloalkanes, haloalkylbenzene halides, dialkyl sulfates, epoxyalkanes, and sulfonate alkylating agents.

[0060] Preferably, the haloalkane is selected from one or more of chloromethane, chloroethane, chloropropane, chlorobutane, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, bromomethane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromoheptane, bromooctane, bromononane, and bromodecane.

[0061] Preferably, the dialkyl sulfate is dimethyl sulfate.

[0062] Preferably, the epoxyalkane is ethylene oxide.

[0063] Preferably, the sulfonate is methyl p-toluenesulfonate.

[0064] Preferably, the quaternization reaction is carried out under catalyst conditions. Specifically, the catalyst is selected from one or more of Lewis bases, soda ash, caustic soda, and iodide anions.

[0065] Preferably, the co-solvent is selected from one or more of acetic acid, formic acid, acetic acid, propionic acid, and benzoic acid.

[0066] Specifically, when adding the co-solvent to the quaternized copolymer solution in step 3, at least one of a surfactant, a dispersant, a polymer coagulant, a retention aid, a film-forming aid, an antioxidant, an antifoaming agent, an antifreeze, a flame retardant, and a reinforcing agent can also be added to improve the stability of the aqueous dispersion and the wettability to fiber products.

[0067] Preferably, the surfactant is selected from one or more of nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0068] More preferably, the surfactant is at least one of a nonionic surfactant and a cationic surfactant.

[0069] Preferably, the dispersant is a polymer dispersant; more preferably, the polymer dispersant is selected from one or more of styrene-maleic anhydride copolymers, polystyrene sulfonates, polyacrylic acid, polyacrylates, polyacrylamide, acrylamide-acrylic acid copolymers, polyvinyl alcohol, and carboxymethyl cellulose.

[0070] The present invention also protects a paper treating agent containing the above-mentioned water-dispersible copolymer, composition or composition prepared by the above-mentioned preparation method.

[0071] The present invention also protects a paper and / or paper product prepared from the above-mentioned copolymer, the above-mentioned composition, the composition prepared by the above-mentioned preparation method, or the paper treating agent, which comprises paper fibers and the above-mentioned water-dispersible copolymer, composition, composition prepared by the above-mentioned preparation method or paper treating agent.

[0072] Preferably, the paper fibers are bagasse fibers, bamboo pulp fibers or wood pulp fibers.

[0073] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0074] 1. The carbosiloxane dendritic monomer used in the present invention has a molecular structure in which silicon atoms are radially arranged, and the carbosiloxane units extend in the form of dendritic macromolecules. Due to this dendritic macromolecule structure, the copolymers and their compositions obtained therefrom have stronger water and oil repellent properties compared to other linear and simple branched polysiloxanes.

[0075] 2. The copolymers and their compositions obtained by quaternization are applicable to a wider pH value environment and exhibit cationic characteristics in the range from acidic to alkaline, making the copolymers easier to bind to negatively charged fibers.

[0076] 3. The copolymer quaternary salts obtained by quaternization have better water and oil repellent properties compared to the copolymers directly cationized with acids. Detailed Embodiments

[0077] In order to more clearly and completely describe the technical solutions of the present invention, the following further details the present invention through specific examples. It should be understood that the specific examples described herein are only used to explain the present invention and are not used to limit the present invention, and various changes can be made within the scope defined by the claims of the present invention. Description of the Drawings

[0078] Figure 1 and Figure 2 is a water and oil repellency test chart of a paper dinner plate prepared from the water-dispersible copolymer and its composition prepared in the examples and comparative examples of the present invention

[0079] Example 1

[0080] This example provides a preparation method of a water-dispersible copolymer and its composition, including the following steps:

[0081] S1. Place 50.0 g of isopropanol, 18.7 g of carbosiloxane dendritic monomer I1-8, and 4.74 g of ω-hydroxy-polyoxyethylene methacrylate with the molecular formula CH2=C(CH3)-C(=O)-O-(CH2CH2O)5H into a 250 ml four-necked flask (equipped with a stirrer, a thermometer, and two 100 mL dropping funnels), and bubble with nitrogen for sufficient degassing, then heat to 65 °C; dissolve 0.3 g of AIBN initiator in 20 g of isopropanol and place it in a 10 mL dropping funnel; under a nitrogen atmosphere, within 3 h, add the initiator solution dropwise from the dropping funnel to the flask maintained at 65 °C; at the same time, mix 0.8 g of N-methylolacrylamide and 5.76 g of dimethylaminoethyl methacrylate evenly, place them in another dropping funnel, and drop them into the flask from the dropping funnel within 3 h; after the dropping is completed, keep the temperature at 67 °C under a nitrogen atmosphere and stir the mixture, and continue the reaction for 6 h;

[0082] S2. Drop 3.96 g of chlorobutane from the dropping funnel into the mixture over a half-hour period, then stir and react overnight at 65 °C;

[0083] S3. Add 1.0 g of acetic acid to the above solution, then add 50 g of water, stir evenly to obtain a transparent aqueous dispersion solution; obtain the aqueous dispersion copolymer with a solid content of 19.78%.

[0084] Example 2

[0085] A method for preparing an aqueous dispersion copolymer and its composition, which is different from Example 1 in that:

[0086] The monomer I used in S1 is I1-7.

[0087] Example 3

[0088] A method for preparing an aqueous dispersion copolymer and its composition, which is different from Example 1 in that:

[0089] The carbosiloxane dendritic monomer used in S1 is I1-9.

[0090] Example 4

[0091] A method for preparing an aqueous dispersion copolymer and its composition, which is different from Example 1 in that:

[0092] The monomer I used in S1 is I1-1, the mass of monomer I1-1 is 16.5 g, and the mass of ω-hydroxy-polyoxyethylene methacrylate with the molecular formula CH2=C(CH3)-C(=O)-O-(CH2CH2O)5H is 6.94 g, and the solid content of the obtained aqueous dispersion copolymer is 19.28%.

[0093] Example 5

[0094] A preparation method of a water-dispersible copolymer and its composition, which is different from Example 4 in that:

[0095] The monomer I used in S1 is I1-2.

[0096] Example 6

[0097] A preparation method of a water-dispersible copolymer and its composition, which is different from Example 4 in that:

[0098] The monomer I used in S1 is I1-3.

[0099] Comparative Example 1

[0100] A preparation method of a water-dispersible copolymer and its composition, which is different from Example 1 in that:

[0101] The monomer I used in S1 is Si-1000, the molecular weight of Si-1000 is 1000-1200 g / mol, the viscosity is 8-12 cst, and its structural formula is as follows:

[0102]

[0103] Comparative Example 2

[0104] A preparation method of a water-dispersible copolymer and its composition, which is different from Example 1 in that:

[0105] There is no step S2, 3.07 g of acetic acid is directly added for cationization, and then water is added to obtain a water dispersion.

[0106] Comparative Example 3

[0107] A preparation method of a water-dispersible copolymer and its composition, which is different from Example 1 in that:

[0108] The monomer I used in S1 is Si-400, and its structural formula is as follows:

[0109]

[0110] Performance Test

[0111] 1. Preparation of paper lunch boxes

[0112] Grind the natural color sugarcane pulp with a beating degree of 27 SR using a beating machine at a pulp consistency of about 3%; weigh the thick pulp corresponding to 15 g of oven-dry pulp, dilute it with clear water to a pulp consistency of 0.6%, add the prepared copolymer aqueous dispersion, with the addition amount being 2.5% based on the oven-dry pulp, and stir for 2 min; after standing slightly, pour it into a mold and make a wet blank under vacuum suction, then transfer the wet blank to a drying mold for baking; the drying conditions are vacuum suction, upper mold temperature of 185 °C, lower mold temperature of 170 °C, and baking time of 45 s; press it into an 8.86-inch round dinner plate under vacuum, and the thickness of the dinner plate is 0.5 mm.

[0113] 2. Oil-proof performance test

[0114] 2-1. KIT test (oil resistance)

[0115] Lay the paper lunch box flat, do not touch the test surface by hand, with the test surface facing up, drop a drop of the Kit Test standard reagent equipped with castor oil, toluene, and heptane at a height of 25 mm on the paper lunch box, wipe off the remaining Kit Test standard reagent with a clean toilet paper after 15 s, and immediately observe whether the back of the oil drop is penetrated and discolored. If there is no leakage, it passes, and then conduct higher-level tests until the Kit series test liquid is not penetrated and discolored. The oil-proof degree of this paper is the value of the Kit level. The higher the Kit No. level, the better the oil-proof performance. The Kit Test standard reagent is prepared according to the formula in Table 1.

[0116] Table 1 Recipe table of Kit Test standard reagent

[0117]

[0118] 2-2. Evaluation of the oil-proof level based on the leakage situation of the dinner plate

[0119] Pour hot oil at a specified temperature into the round dinner plate, test for 30 min, and then pour out the hot oil. Observe the inner and outer surfaces of the bottom of the lunch box, and evaluate the oil-proof level according to the leakage situation.

[0120] Level 5 means no discoloration on the inner surface;

[0121] Level 4 means a small amount of discoloration on the inner surface and no leakage on the outer surface;

[0122] Level 3 means a small amount of leakage on the outer surface;

[0123] Level 2 means the leakage area on the outer surface is less than 50%;

[0124] Level 1 means the leakage area on the outer surface is greater than 50%;

[0125] Level 0 means immediate leakage on the outer surface.

[0126] 3. Test the waterproof performance

[0127] Pour 95°C hot water close to boiling into the dinner plate, test for 30 minutes, and then pour out the hot water. Observe whether there is leakage at the bottom of the lunch box.

[0128] The performance test data are shown in Table 2, Figure 1 and Figure 2 as shown.

[0129] Table 2 Comparison of test performance results of Examples 1-6 and Comparative Examples 1-3

[0130]

[0131]

[0132] When the copolymers synthesized from carbosiloxane dendritic monomers in Examples 1-6 are used as paper treatment agents, they have good waterproof and oil-proof properties. At 95°C, there is no water leakage; when the oil temperature is between 20°C and 100°C, only a small amount of discoloration occurs on the inner surface, and there is no leakage on the outer surface. The oil-proof grade is above Level 4. In particular, the oil-proof grades of Examples 1 and 5 are both Level 5; the oil-proof grades of Examples 3, 4, and 6 are only Level 4 at an oil temperature of 100°C and Level 5 when the oil temperature is not higher than 50°C; the water-dispersible polymers of Examples 1-6 of the present invention exhibit excellent oil and water resistance.

[0133] From the results of Comparative Example 1 and Comparative Example 3, when the monomer I is the branched silicon monomers Si-1000 and Si-400, the copolymers synthesized therefrom have poor oil-proof performance when used as paper treatment agents.

[0134] From the results of Comparative Example 2, when a copolymer obtained by direct cationization with an organic acid without quaternization reaction is used as a paper treatment agent, the oil-proof performance is also poor.

[0135] Obviously, the above-mentioned embodiments of the present invention are merely examples for clearly explaining the present invention, and are not intended to limit the embodiments of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to enumerate all the embodiments here. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention shall be included in the protection scope of the claims of the present invention.

Claims

1. A water-dispersible copolymer, characterized in that: It includes a repeating unit produced by monomer I, a repeating unit produced by monomer II, and a repeating unit produced by monomer III; The general structural formula of the monomer I is as follows: Wherein, X is a group with a carbon-carbon double bond; R 1 and R 2 Each is independent of C1~C 10 Alkyl, C1~C 10 Aryl or C1~C 10 Aralkyl, a is any one of 0, 1, and 2; L is a H atom, C1~C 10 Alkyl, C1~C 10 Aryl, C1~C 10 Arylalkyl or silyl, or the following structure: Wherein, Y is an alkylene group, and p is an integer from 1 to 10; R 3 and R 4 Each is independent of C1~C 10 Alkyl, C1~C 10 Aryl or C1~C 10 Aralkyl, b is any one of 0, 1, and 2; M is a hydrogen atom, C1~C 10 Alkyl, C1~C 10 Aryl, C1~C 10 Aralkyl or silyl; The general structural formula of the monomer II is as follows: Among them, R 5 H or C1~C 10 alkyl; Z is N or O; Q is an organic group with a tertiary amine; The monomer III is selected from one or more of acrylate monomers, acrylamide monomers, polymerizable unsaturated monomers having anion supplying groups, polymerizable unsaturated siloxane coupling agents, and polymerizable unsaturated monomers containing multifunctional groups, wherein the anion supplying groups are carboxyl groups or sulfonic acid groups, and the multifunctional groups are selected from one or more of hydroxyl groups, isocyanurate groups, ester groups, and ether groups; The mass proportion of the repeating unit produced by monomer I, the repeating unit produced by monomer II, and the repeating unit produced by monomer III is 20-85wt%: 10-40wt%: 0-40wt%.

2. The copolymer according to claim 1, characterized in that In monomer I, R 1 and R 2 are each independently methyl; and / or; X is at least one selected from an organic group containing an acryloyl group or a methacryloyl group, an organic group containing an alkenyl group and an aryl group, and an organic group consisting of an alkenyl group having 2 to 10 carbon atoms; and / or; In L, M is methyl or ethyl; and / or; In monomer II, R 5 It is H or methyl.

3. The copolymer according to any one of claims 1 or 2, characterized in that The monomer I is selected from At least one of .

4. The copolymer according to any one of claims 1 or 2, characterized in that The monomer II is selected from one or more of dimethylaminoethyl dimethacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylamide, diethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide and diethylaminopropyl methacrylamide.

5. The copolymer according to any one of claims 1 or 2, characterized in that In the monomer III, the acrylamide monomer is selected from methacrylamide-2-hydroxymethyl ester or acrylamide-2-hydroxy-ethyl ester; The polymerizable unsaturated monomer having an anion supplying group is selected from one or more of methacrylic acid, crotonic acid, maleic acid, itaconic acid, vinyl sulfonic acid, styrene sulfonic acid, vinylbenzene sulfonic acid and acrylamide-tert-butyl sulfonic acid, and salts thereof; The acrylic acid ester monomer is selected from oxyalkylene-methacrylate monomers, and the structure is CH2=CX1C(=O)-O-(RO) n -X2 or CH2=CX1C(=O)-O-(RO) n -O-(O=)CX1C=CH2; Wherein, X1 is a H atom or a methyl group; X2 is a H atom, a saturated or unsaturated C1-C 10 R is a C2-C3 alkylene group; n is an integer from 1 to 20; n is preferably 2 to 10; The polymerizable unsaturated siloxane coupling agent is selected from one or more of γ-(methacryloyloxy)propyltrimethoxysilane, γ-(methacryloyloxy)propyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and allyltriethoxysilane; The multifunctional and polymerizable unsaturated monomer is selected from one or more of trimethylolpropane triacrylate, pentaerythritol triacrylate, tetraethylene glycol diacrylate, tris(2-hydroxyethyl)isocyanurate diacrylate, tris(2-hydroxyethyl)isocyanurate dimethacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate and tris(2-hydroxyethyl)isocyanurate trimethacrylate.

6. A composition comprising the copolymer according to any one of claims 1 to 5 and a solvent, wherein the solvent comprises water and / or an organic solvent.

7. A method for preparing the composition according to claim 6, comprising the following steps: S1. In an organic solvent, the monomer is polymerized by free radical polymerization and ionic polymerization under the action of an initiator to obtain a copolymer solution; S2. Adding an alkylating agent to the copolymer solution converts the tertiary amine in the copolymer into a quaternary ammonium salt by quaternization reaction to obtain a quaternized copolymer solution; S3. Add a cosolvent to the quaternized copolymer solution, and then add water for dispersion to obtain the composition.

8. A paper treating agent comprising the copolymer according to any one of claims 1 to 5, the composition according to claim 6, or the composition prepared by the preparation method according to claim 7.

9. Paper and / or paper products prepared by the copolymer according to any one of claims 1 to 5, the composition according to claim 6, the composition prepared by the preparation method according to claim 7, or the paper treating agent according to claim 8.

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