CN102675534A - Cationic Fluorocarbon Modified Polyacrylamide Prepared by Ultrasonic Assisted Method - Google Patents

Abstract

The invention discloses a cationic fluorocarbon modified polyacrylamide prepared by an ultrasonic auxiliary method; the method comprises the steps of: firstly, evenly mixing fluorine-containing monomer, cation monomer, acrylamide and water, filling nitrogen for expelling oxygen, adding initiator, carrying out free radical polymerization under the ultrasonic-assistant condition to obtain the cationic fluorocarbon modified polyacrylamide. Due to the efficient dispersive action of ultrasonic wave, hydrophobic monomer can be well dispersed into water solution without adding emulsifying agent or surface active monomer, and copolymerization can be carried out between the hydrophobic monomer and hydrophilic monomer. According to the preparation method, the emulsifying agent or surface active monomer can be avoided being used, so that the aftertreatment of HAPAM is completely omitted, the preparation technology is simplified, and the production efficiency is improved.

Description

Cationic Fluorocarbon Modified Polyacrylamide Prepared by Ultrasonic Assisted Method

technical field

The invention belongs to the field of macromolecule chemistry, in particular to an ultrasonic-assisted method for preparing cationic fluorocarbon-modified polyacrylamide.

Background technique

Polyacrylamide and its derivatives are important polymers with a wide range of applications. Among the many types of polyacrylamide, hydrophobic association polyacrylamide is an important branch. Hydrophobic associative polyacrylamide is made by introducing a small amount of hydrophobic groups into the main chain of polyacrylamide. Due to the hydrophobic interaction between the hydrophobic groups, the molecular chains of polyacrylamide are clustered, which significantly changes the concentration of the solution. Rheological properties, improve the application effect and expand the application field. At present, the hydrophobic groups introduced on the main chain of hydrophobic association polyacrylamide are mainly hydrocarbon hydrophobic monomers. Fluorine-containing monomer is a strong hydrophobic monomer, and its hydrophobic association is stronger than that of hydrocarbon hydrophobic monomers. Therefore, cationic fluorine-containing polyacrylamide copolymerized have a better application effect.

In order to overcome the incompatibility of hydrophobic monomers and hydrophilic monomers and realize the copolymerization of the two, the micellar method is often used in the preparation of hydrophobic associative polyacrylamide, and the surface active monomer method has appeared in recent years. The micellar method is to add a large amount of emulsifier to the polymerization system, emulsify the hydrophobic monomer and then copolymerize with the hydrophilic monomer such as acrylamide, cationic monomer, etc., but the addition of emulsifier will affect the increase of polymer molecular weight, increase There are many problems such as the complexity of the post-processing of the copolymer. Surface-active monomers, also known as polymerizable surfactants, are a class of surfactants containing polymerizable groups, which not only have surface activity, but also can produce homo (co)polymerization reactions under certain trigger conditions, which can completely eliminate Post-processing of HAPAM. At present, the preparation of surface-active monomers suitable for HAPAM is complicated and costly, so the research work on the surface-active monomer method is rarely carried out.

Contents of the invention

The purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art, and to provide an ultrasonic-assisted method for preparing cationic fluorocarbon-modified polyacrylamide without using emulsifiers and surface-active monomers.

In order to achieve the above object, the technical scheme adopted in the present invention is:

1) First, mix the fluorine-containing monomer, cationic monomer, acrylamide and water according to the mass ratio of 1: (1-30): (10-200): (10-10000) to prepare a mixed solution;

2) Next, blow nitrogen into the mixed solution at a rate of 20mL/min-200mL/min for 10-60 minutes;

3) Then, add an initiator of 0.1%-1.0% of the total mass of the monomer and stir evenly;

4) Finally, place it in an ultrasonic generator at 20°C-90°C for ultrasonic polymerization, with an ultrasonic power of 80W-200W, and react for 0.5-5 hours to obtain cationic fluorocarbon-modified polyacrylamide.

The fluorine-containing monomer is trifluoroethyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl acrylate or dodecafluoroheptyl methacrylate ester.

Said cationic monomer is methacryloxyethyltrimethylammonium chloride, dimethylaminoethyl methacrylate or dimethyldiallylammonium chloride.

Said nitrogen is liquid nitrogen or gaseous nitrogen.

Said initiator is ammonium persulfate, potassium persulfate, azobisisobutylamidine hydrochloride, ammonium persulfate-sodium sulfite, potassium persulfate-sodium sulfite, ammonium persulfate-sodium bisulfite, potassium persulfate- Sodium bisulfite, ammonium persulfate-sodium thiosulfate or potassium persulfate-sodium thiosulfate, wherein the mass ratio of oxidizing agent to reducing agent in the oxidation-reduction initiation system is 2:1.

Due to the efficient dispersion of ultrasonic waves, the hydrophobic monomer can be well dispersed in the aqueous solution and copolymerized with the hydrophilic monomer without adding emulsifiers or surface active monomers. The preparation method of the invention can avoid the use of emulsifiers or surface active monomers, so as to completely eliminate the post-treatment of HAPAM, simplify the preparation process and improve production efficiency.

Detailed ways

Example 1, 1) First, the fluorine-containing monomer trifluoroethyl acrylate, the cationic monomer methacryloyloxyethyltrimethylammonium chloride, acrylamide and water are mixed in a mass ratio of 1:1:10:10 than mixing evenly to make a mixed solution;

2) Next, blow nitrogen into the mixed solution at a rate of 20mL/min for 60 minutes;

3) Then, add initiator ammonium persulfate of 1.0% of the total mass of the monomer and stir evenly;

4) Finally, placed in an ultrasonic generator at 20°C for ultrasonic polymerization with an ultrasonic power of 80W, and reacted for 5 hours to obtain cationic fluorocarbon-modified polyacrylamide.

Example 2, 1) First, the fluorine-containing monomer dodecafluoroheptyl methacrylate, the cationic monomer dimethyl diallyl ammonium chloride, acrylamide and water are mixed in a mass ratio of 1:30:200:10000 than mixing evenly to make a mixed solution;

2) Next, blow nitrogen into the mixed solution at a rate of 200mL/min for 10 minutes;

3) Then, add the initiator azobisisobutylamidine hydrochloride with 0.1% of the total mass of the monomer and stir evenly;

4) Finally, placed in an ultrasonic generator at 90°C for ultrasonic polymerization with an ultrasonic power of 200W, and reacted for 0.5 hours to obtain cationic fluorocarbon-modified polyacrylamide.

Example 3, 1) First, mix fluorine-containing monomer trifluoroethyl methacrylate, cationic monomer dimethylaminoethyl methacrylate, acrylamide and water in a mass ratio of 1:10:50:100 Prepare a mixed solution evenly;

2) Next, blow nitrogen into the mixed solution at a rate of 50mL/min for 30 minutes;

3) Then, add the initiator ammonium persulfate-sodium thiosulfate of 0.3% of the total mass of the monomer and stir evenly;

4) Finally, placed in an ultrasonic generator at 50°C for ultrasonic polymerization with an ultrasonic power of 100W, and reacted for 2 hours to obtain cationic fluorocarbon-modified polyacrylamide.

Example 4, 1) First, the fluorine-containing monomer dodecafluoroheptyl acrylate, the cationic monomer methacryloyloxyethyltrimethylammonium chloride, acrylamide and water were mixed at a ratio of 1:20:100:1000 The mass ratio is mixed evenly to prepare a mixed solution;

2) Next, blow nitrogen into the mixed solution at a rate of 100mL/min for 30 minutes;

3) Then, add the initiator azobisisobutylamidine hydrochloride of 0.5% of the total mass of the monomer and stir evenly;

4) Finally, placed in an ultrasonic generator at 60°C for ultrasonic polymerization with an ultrasonic power of 140W, and reacted for 3 hours to obtain cationic fluorocarbon-modified polyacrylamide.

Example 5, 1) First, the fluorine-containing monomer hexafluorobutyl methacrylate, the cationic monomer methacryloyloxyethyltrimethylammonium chloride, acrylamide and water were mixed at a ratio of 1:15:150:5000 The mass ratio is mixed uniformly to prepare a mixed solution;

2) Next, blow nitrogen into the mixed solution at a rate of 100mL/min for 30 minutes;

3) Then, add the initiator azobisisobutylamidine hydrochloride of 0.4% of the total mass of the monomer and stir evenly;

4) Finally, placed in an ultrasonic generator at 50°C for ultrasonic polymerization with an ultrasonic power of 160W, and reacted for 3 hours to obtain cationic fluorocarbon-modified polyacrylamide.

Claims (5)

1. Cationic fluorocarbon modified polyacrylamide prepared by ultrasonic-assisted method, characterized in that: 1) First, mix the fluorine-containing monomer, cationic monomer, acrylamide and water according to the mass ratio of 1: (1-30): (10-200): (10-10000) to prepare a mixed solution; 2) Next, blow nitrogen into the mixed solution at a rate of 20mL/min-200mL/min for 10-60 minutes; 3) Then, add an initiator of 0.1%-1.0% of the total mass of the monomer and stir evenly; 4) Finally, place it in an ultrasonic generator at 20°C-90°C for ultrasonic polymerization, with an ultrasonic power of 80W-200W, and react for 0.5-5 hours to obtain cationic fluorocarbon-modified polyacrylamide. 2. Cationic fluorocarbon-modified polyacrylamide is prepared by ultrasonic-assisted method according to claim 1, characterized in that: said fluorine-containing monomer is trifluoroethyl acrylate, trifluoroethyl methacrylate, hexaacrylate Fluorobutyl, hexafluorobutyl methacrylate, dodecafluoroheptyl acrylate or dodecafluoroheptyl methacrylate. 3. The ultrasonic-assisted method according to claim 1 prepares cationic fluorocarbon modified polyacrylamide, characterized in that: said cationic monomer is methacryloyloxyethyltrimethylammonium chloride, methacrylic acid Dimethylaminoethyl ester or dimethyldiallylammonium chloride. 4. The ultrasonic-assisted method for preparing cationic fluorocarbon-modified polyacrylamide according to claim 1, characterized in that: said nitrogen is liquid nitrogen or gaseous nitrogen. 5. Cationic fluorocarbon modified polyacrylamide is prepared by ultrasonic-assisted method according to claim 1, characterized in that: said initiator is ammonium persulfate, potassium persulfate, azobisisobutylamidine hydrochloride , ammonium persulfate-sodium sulfite, potassium persulfate-sodium sulfite, ammonium persulfate-sodium bisulfite, potassium persulfate-sodium bisulfite, ammonium persulfate-sodium thiosulfate or potassium persulfate-sodium thiosulfate, wherein The mass ratio of oxidizing agent to reducing agent in the oxidation-reduction initiation system is 2:1.