阅读说明：本技术 一种两性离子型水溶性高分子材料、其制备方法及应用 (Zwitterionic water-soluble polymer material, and preparation method and application thereof ) 是由 王丕新 谭颖 徐昆 迟惠 白云刚 张文德 于 2020-06-01 设计创作，主要内容包括：本发明提供了一种两性离子型水溶性高分材料的制备方法,包括：S1)将N-乙烯基烷基酰胺、丙烯腈与丙烯酸类单体进行聚合反应,得到基础聚合物；S2)将所述基础聚合物进行脒化反应,得到两性离子型水溶性高分子材料。与现有技术相比,本发明得到的脒化反应后的两性离子型水溶性高分子聚合物可有效地用于污泥脱水。(The invention provides a preparation method of a zwitterionic water-soluble high-molecular material, which comprises the following steps: s1) carrying out polymerization reaction on N-vinyl alkyl amide, acrylonitrile and acrylic monomers to obtain a basic polymer; s2) carrying out amidine reaction on the basic polymer to obtain the zwitterionic water-soluble high polymer material. Compared with the prior art, the zwitterionic water-soluble high-molecular polymer obtained after the amidination reaction can be effectively used for sludge dehydration.)

1. A preparation method of a zwitterionic water-soluble polymer material is characterized by comprising the following steps:

s1) carrying out polymerization reaction on N-vinyl alkyl amide, acrylonitrile and acrylic monomers to obtain a basic polymer;

s2) carrying out amidine reaction on the basic polymer to obtain the zwitterionic water-soluble high polymer material.

2. The method according to claim 1, wherein the molar ratio of the N-vinyl alkylamide, the acrylonitrile and the acrylic monomer is (30 to 60): (30-60): (10-40).

3. The method according to claim 1, wherein the number of carbon atoms in the alkyl group of the N-vinyl alkylamide is 1 to 3.

4. The process according to claim 1, wherein the N-vinyl alkylamide is selected from N-vinyl methylamides, N-vinyl ethylamides and N-vinyl propylamides; the acrylic monomer is selected from acrylic acid and/or methacrylic acid.

5. The method according to claim 1, wherein the polymer reaction in step S1) is carried out in the presence of an initiator; the initiator is selected from a redox initiator or an azo initiator; the mass of the initiator is 1 to 3 percent of the total mass of the N-vinyl alkyl amide, the acrylonitrile and the acrylic monomer;

the temperature of the polymerization reaction is 45-65 ℃; the polymerization reaction time is 4-8 h.

6. The preparation method according to claim 1, wherein the step S2) is specifically:

and (2) heating the basic polymer and hydroxylamine hydrochloride in water for reaction, and then adding acid for amidination reaction to obtain the zwitterionic water-soluble high polymer material.

7. The method according to claim 6, wherein the mass of hydroxylamine hydrochloride is 3 to 10% of the mass of the base polymer.

8. The preparation method according to claim 6, wherein the temperature of the heating reaction is 45-60 ℃; the heating reaction time is 0.5-2 h; the temperature of the amidination reaction is 60-95 ℃; the amidine reaction time is 2-8 h.

9. The zwitterionic water-soluble polymer material prepared by the preparation method of any one of claims 1-8 is characterized by being obtained by amidine reaction of a base polymer; the base polymer includes an N-vinyl alkylamide monomer unit, an acrylonitrile monomer unit, and an acrylic monomer unit.

10. The use of the zwitterionic water-soluble polymer material prepared by the preparation method of any one of claims 1 to 8 as a sludge dehydrating agent.

Technical Field

The invention belongs to the technical field of water treatment, and particularly relates to a zwitterionic water-soluble polymer material, and a preparation method and application thereof.

Background

With the rapid development of economic society in China, the discharge amount of industrial wastewater and domestic sewage is increasing day by day, and the sludge yield after sewage treatment is also continuously increased. Untreated sludge enters a natural environment, which not only pollutes the environment, but also causes waste of energy and resources. Therefore, the research and development of a new method for improving the sludge dewatering effect and reducing the sludge water content is a research hotspot in the field of sludge treatment at present.

Cationic polyacrylamide is a sludge dewatering agent widely used at present, and has a good sludge dewatering effect, but the cations of the traditional cationic polyacrylamide cannot fully play the electric neutralization role in the flocculation process due to low charge density and distribution and dispersion in molecular chains, so that the application of the cationic polyacrylamide in sludge dewatering is limited.

Chinese patent publication No. CN101239775A discloses a method for synthesizing a cationic sludge dewatering agent from acrylamide and acryloyloxyethyltrimethyl ammonium chloride, wherein the prepared product has a certain sludge dewatering performance, but the cationic charge density of the selected monomer acryloyloxyethyltrimethyl ammonium chloride is low; chinese patent publication No. CN101239774A discloses a method for preparing amphoteric polymers for sludge dewatering, which selects anionic or nonionic polyacrylamide, formaldehyde, organic amine, sodium bisulfite and other additives, and reacts at a certain temperature to obtain a colloidal aqueous solution, but the product performance is not easily controlled, and the problem of low charge density exists; chinese patent with publication number CN104261651A discloses a polyacrylamide sludge dehydrating agent and a preparation method thereof, which comprises the following components in parts by weight: 40-50 parts of acrylamide, 4-8 parts of vinyl acetate, 3-5 parts of dimethyl diallyl ammonium chloride, 2-4 parts of ethylene oxide, 2-4 parts of maleic anhydride, 4-5 parts of tall oil acid, 2-4 parts of acrylic acid, 4-9 parts of inorganic base, 2-3 parts of an accelerator, 2-3 parts of a chelating agent, 2-4 parts of a surfactant and 60-80 parts of water, but the composition of numerous raw materials is not beneficial to performance regulation and large-scale production.

Therefore, the cationic or zwitterionic polyacrylamide dehydrating agents reported in the prior art still have the problems of low cationic charge density, complex composition, poor performance and the like, so that the demand for novel dehydrating agents is still a research hotspot in the field.

Disclosure of Invention

In view of the above, the technical problem to be solved by the present invention is to provide a zwitterionic water-soluble polymer material containing an amidine structure, a preparation method thereof, and an application thereof, wherein the zwitterionic water-soluble polymer material can be effectively used for sludge dewatering.

The invention provides a preparation method of a zwitterionic water-soluble polymer material, which comprises the following steps:

s1) carrying out polymerization reaction on N-vinyl alkyl amide, acrylonitrile and acrylic monomers to obtain a basic polymer;

s2) carrying out amidine reaction on the basic polymer to obtain the zwitterionic water-soluble high polymer material.

Preferably, the molar ratio of the N-vinyl alkyl amide, the acrylonitrile and the acrylic monomer is (30-60): (30-60): (10-40).

Preferably, the number of carbon atoms in the alkyl group in the N-vinyl alkylamide is 1 to 3.

Preferably, the N-vinyl alkylamide is selected from N-vinyl methylamides, N-vinyl ethylamides and N-vinyl propylamides; the acrylic monomer is selected from acrylic acid and/or methacrylic acid.

Preferably, the polymer reaction in the step S1) is performed in the presence of an initiator; the initiator is selected from a redox initiator or an azo initiator; the mass of the initiator is 1 to 3 percent of the total mass of the N-vinyl alkyl amide, the acrylonitrile and the acrylic monomer;

the temperature of the polymerization reaction is 45-65 ℃; the polymerization reaction time is 4-8 h.

Preferably, the step S2) is specifically:

and (2) heating the basic polymer and hydroxylamine hydrochloride in water for reaction, and then adding acid for amidination reaction to obtain the zwitterionic water-soluble high polymer material.

Preferably, the mass of the hydroxylamine hydrochloride is 3 to 10 percent of the mass of the basic polymer.

Preferably, the temperature of the heating reaction is 45-60 ℃; the heating reaction time is 0.5-2 h; the temperature of the amidination reaction is 60-95 ℃; the amidine reaction time is 2-8 h.

The invention also provides the zwitterionic water-soluble high polymer material prepared by the preparation method, which is characterized in that the zwitterionic water-soluble high polymer material is obtained by amidine reaction of a basic polymer; the base polymer includes an N-vinyl alkylamide monomer unit, an acrylonitrile monomer unit, and an acrylic monomer unit.

The invention also provides an application of the zwitterionic water-soluble polymer material prepared by the preparation method as a sludge dehydrating agent.

The invention provides a preparation method of a zwitterionic water-soluble high-molecular material, which comprises the following steps: s1) carrying out polymerization reaction on N-vinyl alkyl amide, acrylonitrile and acrylic monomers to obtain a basic polymer; s2) carrying out amidine reaction on the basic polymer to obtain the zwitterionic water-soluble high polymer material. Compared with the prior art, the zwitterionic water-soluble high-molecular polymer obtained after the amidination reaction can be effectively used for sludge dehydration.

Drawings

FIG. 1 is an FTIR spectrum of a polymer obtained in example 1 of the present invention;

FIG. 2 is an FTIR spectrum of the product obtained in inventive example 1 after the amidination reaction.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a preparation method of a zwitterionic water-soluble polymer material, which comprises the following steps: s1) carrying out polymerization reaction on N-vinyl alkyl amide, acrylonitrile and acrylic monomers to obtain a basic polymer; s2) carrying out amidine reaction on the basic polymer to obtain the zwitterionic water-soluble high polymer material. The specific reaction process is as follows:

R₁:-H,-CH₃,-CH₂CH₃

R₂:-H,-CH₃

X^-:Cl^-,SO₄ ^-2

in the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.

Carrying out polymerization reaction on N-vinyl alkyl amide, acrylonitrile and acrylic monomers; the carbon atom number of the alkyl in the N-vinyl alkyl amide is preferably 1-5, more preferably 1-4, and still more preferably 1-3; most preferably, the N-vinyl alkylamides are N-vinyl methylamides, N-vinyl ethylamides and N-vinyl propylamides; the acrylic monomer is preferably acrylic acid and/or methacrylic acid; the molar ratio of the N-vinyl alkyl amide, the acrylonitrile and the acrylic monomer is preferably (30-60): (30-60): (10-40), more preferably (33-55): (35-55): (10-30), more preferably (33-50): (40-50): (10-20), most preferably (33-45): 45: 10; in some embodiments provided herein, the molar ratio of N-vinyl alkylamide, acrylonitrile to acrylic monomer is preferably 45: 45: 10; in some embodiments provided herein, the molar ratio of N-vinyl alkylamide, acrylonitrile to acrylic monomer is preferably 33.5: 45: 10; in other embodiments provided herein, the molar ratio of N-vinyl alkylamide, acrylonitrile to acrylic monomer is preferably 26.6: 45: 10; the polymerization reaction in the present invention is preferably a radical copolymerization reaction; the polymerization reaction is preferably carried out in a protective atmosphere; the protective atmosphere is preferably nitrogen; the polymerization reaction is preferably carried out in the presence of an initiator; the initiator is preferably a redox initiator or an azo initiator, more preferably a mixture of ammonium persulfate and sodium bisulfite, VA044 or V50; in the present invention the initiator is preferably added in the form of an aqueous initiator solution; the mass concentration of the initiator aqueous solution is preferably 5-20%, more preferably 8-15%, and still more preferably 10-15%; the mass of the initiator is preferably 1 to 3 percent of the total mass of the N-vinyl alkyl amide, the acrylonitrile and the acrylic monomer, more preferably 1.28 to 2.28 percent, and still more preferably 2 to 2.28 percent; the total mass concentration of the N-vinyl alkyl amide, the acrylonitrile and the acrylic monomer in the polymerization reaction system is preferably 10-20%, more preferably 13-18%, and still more preferably 13.8-16.3%; the polymerization reaction temperature is preferably 45-65 ℃, more preferably 45-60 ℃, further preferably 45-55 ℃ and most preferably 45-50 ℃; the time of the polymerization reaction is preferably 4-8 h, and more preferably 4-6 h; in the present invention, it is preferable that the N-vinyl alkylamide, the acrylonitrile and the acrylic monomer are mixed in water, then the mixture is heated to the reaction temperature by introducing a protective atmosphere, and then the initiator is added to carry out the polymerization reaction.

After the polymerization reaction is finished, the reaction mixture is preferably cooled to room temperature, precipitated by acetone, and dried in vacuum to obtain a base polymer.

Carrying out amidine reaction on the basic polymer to obtain a zwitterionic water-soluble high polymer material; in the present invention, the step is preferably embodied as follows: heating the basic polymer and hydroxylamine hydrochloride in water for reaction, and then adding acid for amidination reaction to obtain a sludge dehydrating agent; the mass of the hydroxylamine hydrochloride is preferably 3 to 10% of the mass of the base polymer, more preferably 4 to 8%, even more preferably 4 to 6%, and most preferably 5%; the mass ratio of the extruded polymer to water is preferably 1: (1-10), more preferably 1: (2-8), preferably 1: (3-6), most preferably 1: (4-5); the temperature of the heating reaction is preferably 45-60 ℃, more preferably 45-55 ℃, and further preferably 50 ℃; the heating reaction time is preferably 0.5-2 h, and more preferably 1-1.5 h; heating for reaction, and adding acid for amidification; the acid is preferably sulfuric acid and/or hydrochloric acid; the mass concentration of the acid is preferably 30-60%, and more preferably 35-50%; the mass ratio of the acid to the base polymer is preferably (1-4): 1, more preferably (1.5 to 3): 1, more preferably (1.8-2.5): 1; the temperature of the amidination reaction is preferably 60-95 ℃, more preferably 70-95 ℃, still more preferably 80-95 ℃, still more preferably 85-95 ℃, most preferably 90-95 ℃; the time of the amidination reaction is preferably 2-8 h, more preferably 4-8 h, and still more preferably 6-8 h.

The zwitterionic water-soluble high-molecular polymer obtained after the amidination reaction can be effectively used for sludge dehydration.

The invention also provides a zwitterionic water-soluble high polymer material prepared by the method, which is obtained by amidine reaction of a basic polymer; the base polymer includes an N-vinyl alkylamide monomer unit, an acrylonitrile monomer unit, and an acrylic monomer unit.

Wherein the N-vinyl alkyl amide, the acrylonitrile and the acrylic monomer are the same as described above, and are not described herein again.

The invention also provides the application of the zwitterionic water-soluble polymer material as a sludge dehydrating agent.

In order to further illustrate the present invention, the following will describe a zwitterionic water-soluble polymer material, its preparation method and application in detail with reference to the following examples.

The reagents used in the following examples are all commercially available.