CN100384896C - Preparation method of acrylamide-sodium acrylate polymer nanoparticle microemulsion - Google Patents

Abstract

The preparation method of acrylamide-sodium acrylate polymer nanoparticle microemulsion relates to a new material preparation method for oil recovery, water treatment, papermaking, textile, printing and dyeing, special coatings, adhesives and ink additives. The method is acrylamide It is obtained through inverse microemulsion polymerization with sodium acrylate as comonomer, compound emulsifier, solvent oil and water as dispersion medium and redox initiation system. The product of the invention is widely used in the fields of oil recovery, water treatment, papermaking, weaving, printing and dyeing, special paint, adhesive, ink and sugar production.

Description

Preparation method of acrylamide-sodium acrylate polymer nanoparticle microemulsion

technical field

The present invention relates to a material preparation method, in particular to a preparation method of acrylamide-sodium acrylate polymer nanoparticle microemulsion, which is widely used in oil extraction, water treatment, papermaking, textile, printing and dyeing, special coatings, adhesives, inks and Sugar and other fields.

Background technique

Acrylamide homopolymers and copolymers are widely used water-soluble polymer materials. The main polymerization methods include aqueous solution polymerization, inverse emulsion polymerization and inverse microemulsion polymerization. The products are dry powder, emulsion, microemulsion or latex.

Due to the limitation of process conditions, the solid content in the aqueous solution polymerization product is low, and imidization reaction easily occurs to form gel, and high molecular weight acrylamide homopolymer and copolymer products cannot be obtained.

Acrylamide homopolymers and copolymers of inverse emulsion polymerization are thermodynamically unstable systems in which latex is suspended in the oil phase, and are prone to delamination and flocculation, and there are also problems such as gel and particle distribution are too wide.

Microemulsion polymerization is a new polymerization technology developed in recent years. It is an oil-water bicontinuous phase system with high stability and transparency. The microemulsion of inverse microemulsion polymer nanoparticles has high stability, small and uniform particle size, and fast reaction rate. However, compared with inverse emulsion polymerization products, it has the disadvantages of low molecular weight and high emulsifier content.

CN 1597715A has described a kind of preparation method of polyacrylamide emulsion, and its component is (weight part): acrylamide 5-150, acryloyloxyethyl dimethyl benzyl ammonium chloride 10-110, dispersant 5- 50. Ammonium sulfate 30-200, anhydrous sodium sulfate 10-100, initiator 0.01-0.10, reducing agent 0.01-0.10, acetic acid 1-50, seed emulsion and deionized water 500. At 20-50°C, react for 10-20h to obtain a product with a solid content of 30%, and its storage period is more than half a year (0-25°C).

US 5545688 describes a kind of inverse microemulsion polymerization technology, with Tween and Span as emulsifier, isomerized paraffin oil is oil phase, 40% AM is water phase, sodium bromate/SO redox initiator, temperature control 40 ℃ Next, a transparent polyacrylamide microemulsion with a molecular weight of 7 million was obtained, the solid content was 17%, and the emulsifier was an oil phase (E/M) of 70%.

CN 1508162A describes a method for preparing a low-cost polyacrylamide nano-microemulsion. The temperature of the reaction system is controlled at 20-50°C for 2-4 hours. The emulsifier is a macromolecular surfactant: sorbitol trioleate: nonyl Base phenol polyoxyethylene ether=5～10:40～60:30～55, and the weight ratio (E/M) of emulsifier monomer is 10～18%. Polymerize to obtain a transparent polyacrylamide nano-microemulsion with a molecular weight up to 30 million.

These methods have certain effects, but they cannot effectively solve the problems of emulsion stability, low molecular weight of the product, complicated preparation process, slow dissolution rate of powder, easy formation of fish-eye-shaped insoluble matter and high cost, and are difficult to meet the needs of practical applications.

Contents of the invention

The purpose of the present invention is to overcome above-mentioned deficiency, a kind of preparation method of acrylamide (AM)-sodium acrylate (SA) polymer nanoparticle microemulsion is provided.

The purpose of the present invention is achieved through the following technical solutions:

The invention is obtained by using acrylamide and sodium acrylate as comonomers, using composite emulsifier, solvent oil and water as dispersion medium and redox initiation system, and polymerizing in reverse microemulsion.

For the composite emulsifiers Span80 and Tween60, the concentration of the emulsifier is 10-12% of the total mass of the oil phase, and the HLB value of the composite emulsifier is controlled between 8.0-9.6.

The dosage of the AM-SA comonomer: the monomer concentration is 30-48% of the total mass of the water phase, and the monomer ratio is AM:SA=2-4:1.

Described dispersion medium: solvent oil and water are the dispersion medium, the oil-water ratio is between 1.0:1～1.5:1, and the solvent oil is kerosene, diesel oil, mineral oil, liquid paraffin, preferably kerosene.

The redox initiation system: Ammonium persulfate [(NH4)2S2O8]-sodium bisulfite (NaHSO3) is the redox initiator, the initiator concentration is 0.3～0.9‰ of the total amount of monomers, ammonium persulfate: Sodium bisulfite=1:0.7～0.9.

Advantage and effect of the present invention are:

1. The emulsion has good stability and can be stored at 0-30°C for more than 10 months;

2. The dosage of emulsifier is low, which is 10-12% of the total mass of the oil phase;

3. The production cycle is short, and the reaction time is 1 hour (40°C);

4. High solid content, easy to dilute, 30-40%;

5. The molecular weight of the product is suitable, and the viscosity-average molecular weight is 3.0-7.0×105 Daltons;

6. Good solubility, fully dissolved in 3 minutes, no insoluble matter;

7. The cost is low, the preparation system is simple, the raw materials are cheap, and the preparation process is simple and convenient.

8. The products are widely used in fields such as oil extraction, water treatment, papermaking, textile, printing and dyeing, special coatings, adhesives, inks and sugar production.

Description of drawings

The accompanying drawing is a transmission electron micrograph (×23000) of the direct dilution of the acrylamide-sodium acrylate polymer nanoparticle microemulsion of the present invention.

Detailed ways

Span80-Tween60 is used as compound emulsifier, solvent oil and water are used as dispersion medium, and ammonium persulfate-sodium bisulfite is used as redox initiation system. When the reaction temperature is 30-45°C, the emulsifier concentration is 10-12% of the total mass of the oil phase, the monomer concentration is 30-48% of the total mass of the water phase, and the initiator concentration is 0.3-0.9‰ of the total monomer mass A uniform, stable and transparent microemulsion was obtained. The product obtained by IR, ¹³ C-NMR and GPC analysis is a random copolymer with a viscosity-average molecular weight of 3.0-7.0×105 Daltons, a number-average molecular weight of 1.5-4.9×105 Daltons, and a weight-average molecular weight of 3.0-7.0×105 dalton.

Preparation process route of the present invention:

(1) Preparation of monomer aqueous solution: after acrylic acid (AA) is neutralized into sodium acrylate (SA) with sodium hydroxide, the monomer aqueous solution of required concentration is prepared according to the mass ratio of SA and AM;

(2) Prepare emulsifier solution: dissolve the emulsifier in mineral spirits, and fully emulsify for 30 minutes under slow stirring;

(3) Microemulsion polymerization: Slowly add the aqueous monomer solution dropwise into the emulsifier solution (30-45°C water bath), at a certain stirring speed, blow nitrogen to drive oxygen, and after blowing nitrogen at a constant temperature for 1 hour, add the required amount of initiator Agent (NH)4S2O8 and NaHSO3, under the protection of nitrogen, initiate polymerization at 40°C, and react for about 1 hour to obtain a transparent AM-SA polymer nanoparticle microemulsion;

(4) Preparation of powder: after the reaction, the emulsion was precipitated with absolute ethanol, washed repeatedly with acetone, and dried in vacuum at 50° C. for 24 hours to obtain a white solid powder.

Solvent oil of the present invention can be kerosene, diesel oil, mineral oil, liquid paraffin, preferably kerosene.

Below in conjunction with example the present invention is described in further detail.

Example 1

In the four-necked flask that thermometer, reflux condenser, nitrogen conduit and dropping funnel are equipped with, add 500g kerosene, then add Span80 emulsifier 39.60g, Tween60 emulsifier 20.40g (HLB8.0) and be dissolved in kerosene, in collection Fully emulsify for 30 minutes with slow stirring under a hot magnetic stirrer; add 61.5g AA and dissolve it in 200g of 20% sodium hydroxide deionized aqueous solution, and neutralize it into SA; add 123g of AM to make monomer aqueous solution (AM: SA=2:1); Slowly add the monomer aqueous solution into the emulsifier solution (30-45°C water bath), at a certain stirring speed, blow nitrogen to drive oxygen, and after constant temperature nitrogen blowing for 1h, add the total amount of monomer 0.9‰ initiator (NH)4S2O80.0874g and NaHSO30.0786g (1:0.9), under the protection of nitrogen, initiate polymerization, and the initiation reaction is carried out at 40°C, and the reaction is about 1h, and the transparent AM-SA polymer nano particle microemulsion. The amount of emulsifier is 12% of the total mass of the oil phase, the solid content is 33%, and the viscosity-average molecular weight is 3.466×105 Daltons;

After the reaction, the emulsion was precipitated with absolute ethanol, washed repeatedly with acetone, and dried under vacuum at 50° C. for 24 hours to obtain a white solid powder.

Example 2

The preparation process route is the same as in Example 1, only the components of the reaction system are changed.

Change the consumption of composite emulsifier (the amount of emulsifier is 10% of the total mass of the oil phase) and the HLB value (being 9.6), that is, Span80 emulsifier 25g, Tween60 emulsifier 25g are dissolved in 500g kerosene, under the heat collecting magnetic stirrer Fully emulsified for 30 minutes under slow stirring; 36.9gAA was dissolved in 200g of 12% sodium hydroxide deionized aqueous solution, and neutralized into SA; then added 147.6gAM (AM:SA=4:1) to make monomer aqueous solution; The aqueous solution is added dropwise to the emulsifier solution, and the initiator (NH)4S2O80.0326g and NaHSO30.0228g (1:0.7) of 0.3‰ of the total monomer amount are added, and the initiation reaction is carried out at 40°C, and the reaction is about 1h, that is, Transparent AM-SA polymer nanoparticle microemulsion. The amount of emulsifier is 10% of the total mass of the oil phase, the solid content is 31%, and the viscosity-average molecular weight is 6.264×105 Daltons.

Example 3

The preparation process route is the same as in Example 1, only the components of the reaction system are changed.

The consumption of compound emulsifier (the emulsifier consumption is 12% of the total mass of the oil phase) and the HLB value (for 8.5), namely Span80 emulsifier 36.23g, Tween60 emulsifier 23.77g are dissolved in 500g kerosene, in heat collecting magnetic stirrer Fully emulsified under slow stirring for 30 minutes; 46.1gAA was dissolved in 150g of 20% sodium hydroxide deionized aqueous solution, and neutralized into SA; then added 138.4gAM (AM:SA=3:1) to make monomer aqueous solution; The monomer aqueous solution is added dropwise to the emulsifier solution, and 0.5‰ initiator (NH)4S2O80.051g and NaHSO30.041g (1:0.8) of the total amount of monomers are added, and the initiation reaction is carried out at 40°C for about 1h to obtain Transparent AM-SA polymer nanoparticle microemulsion. The amount of emulsifier is 12% of the total mass of the oil phase, the solid content is 40%, and the viscosity-average molecular weight is 7.004×105 Daltons.

Claims (3)

1. the preparation method of acrylamide-sodium acrylate polymer nanoparticle microemulsion, the method uses acrylamide and sodium acrylate as comonomer, with composite emulsifier, solvent oil and water as dispersion medium and redox initiation system, by reaction It is obtained by phase microemulsion polymerization, and is characterized in that: Span80 and Tween60 composite emulsifiers, the emulsifier concentration is 10-12% of the total mass of the oil phase, the HLB value of the composite emulsifier is controlled between 8.0-9.6, and the monomer concentration It is 30-48% of the total mass of the water phase, the monomer ratio is acrylamide: sodium acrylate = 2-4:1, solvent oil and water are the dispersion medium, the oil-water ratio is between 1.0-1.5:1, and the solvent oil is kerosene , diesel, mineral oil or liquid paraffin. 2. the preparation method of acrylamide-sodium acrylate polymer nanoparticle microemulsion according to claim 1 is characterized in that: the solvent oil used is kerosene. 3. the preparation method of acrylamide-sodium acrylate polymer nanoparticle microemulsion according to claim 1, is characterized in that: described redox initiation system is redox initiator with ammonium persulfate-sodium bisulfite, The initiator concentration is 0.3-0.9‰ of the total monomer mass, ammonium persulfate: sodium bisulfite=1:0.7-0.9.

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