Method for preparing fluorocarbon-modified polyacrylamide by using soap-free emulsion method

Abstract

The invention discloses a method for preparing fluorocarbon-modified cationic polyacrylamide by a soap-free emulsion polymerization method and belongs to the technical field of water-soluble polymer synthesis. The method comprises the following steps of: adopting a free radical polymerization method, taking pure water as a solvent, and taking potassium persulphate (KPS) as an initiator; dispersing a novel fluorocarbon / hydrocarbon mixed cationic surface active monomer with surface activity in the system in the form of a micelle; copolymerizing the novel fluorocarbon / hydrocarbon mixed cationic surface active monomer with acrylamide (AM) in the absence of an emulsifier and in the presence of a single solvent, namely pure water, thus successfully synthesising a perfluorocarbon-modified amphoteric hydrophobic associated polymer with temperature-resistant, viscosity-increasing and anti-shearing performances; and carrying out simple treatments to obtain the powder product. The prepared fluorocarbon-modified hydrophobic associated polymer can be widely applied to the fields of oilfield development, coating, fire-fighting, printing, electroplating, daily-use chemical industry, medicine, and the like.

Description

technical field

[0001] The invention relates to a method for preparing fluorocarbon-modified polyacrylamide, in particular to a method for preparing fluorocarbon-modified cationic polyacrylamide through a soap-free emulsion polymerization method, and belongs to the technical field of water-soluble polymer synthesis. Background technique

[0002] Fluorocarbon-modified polyacrylamide refers to a class of water-soluble polymers that introduce perfluorohydrophobic groups into polyacrylamide macromolecular chains. Compared with hydrocarbon hydrophobic groups, fluorocarbon hydrophobic groups have more excellent hydrophobic association properties, because the cohesive energy density and surface energy between fluorocarbon atoms are small, and it is easy to form a complex network structure, thus Enhance the viscosity and shear resistance of polymers. At the same time, the extremely strong thermal and chemical stability of the fluorocarbon alkyl chain also endows the fluorocarbon mo...

Examples

Embodiment 1

[0059] Embodiment 1. Preparation of fluorocarbon / hydrocarbon mixed type cationic surface-active monomer

[0060] (1) Preparation of compound I

[0061] Weigh 0.88g (10mmol) of N, N-dimethylethylenediamine and dissolve it in 15ml of DMF, transfer to a condenser tube (connected with CaCl 2 Drying tube), nitrogen tube, and constant pressure dropping funnel in a 50ml three-neck round bottom flask, then put it into a constant temperature water bath at 25°C, add the rotor, start stirring, and pass through nitrogen to remove oxygen for 30min. Weigh 2.62g (12mmol) of Boc anhydride and dissolve in 10ml of DMF, then transfer to a 25ml constant pressure dropping funnel. Open the cock, drop the Boc anhydride dissolved in DMF into the three-neck flask drop by drop, after 0.5h, remove the constant pressure dropping funnel. After the mixture was reacted for 1 h, 2.45 g (15 mmol) of 6-bromo-1-hexene was dissolved in 5 ml of DMF and transferred to a 10 ml constant pressure dropping funnel. ...

Embodiment 2

[0068] Embodiment 2. Preparation of fluorocarbon modified polyacrylamide

[0069] (1) Transfer 80ml of deionized water into a 250ml four-necked round-bottom flask equipped with a mechanical stirring rod, a spherical condenser, a nitrogen vent tube, and a thermometer, and weigh 7.0582g (99.3mmol) of acrylamide into the four-necked flask , into N 2 , stirred at room temperature for 1h.

[0070] (2) Weigh 0.4391g (0.7mmol) of fluorocarbon / hydrocarbon mixed cationic surfactant monomer, dissolve it in 10ml of deionized water, and after fully dissolving, it becomes a yellow clear and transparent solution, and transfer it to a four-necked bottle after standing for 10min In the process, rinse the remaining liquid and foam repeatedly with 10ml of deionized water and transfer them into the reaction system together. The temperature of the reaction system was raised to 65°C, and the stirring was continued, and the N 2 Protection, keep 30min.

[0071] (3) Weigh 0.0541g (2mmol / L) of potas...

Embodiment 3

[0074] Embodiment 3. Preparation of fluorocarbon modified polyacrylamide

[0075] As described in Example 2, the difference is that the monomer feed ratio is changed to 0.2509 g of fluorocarbon / hydrocarbon mixed cationic surface active monomer and 7.0795 g of acrylamide to obtain 7.0880 g of light yellow powder of fluorocarbon modified polyacrylamide , the yield was 96.7%.

technical field

[0001] The invention relates to a method for preparing fluorocarbon-modified polyacrylamide, in particular to a method for preparing fluorocarbon-modified cationic polyacrylamide through a soap-free emulsion polymerization method, and belongs to the technical field of water-soluble polymer synthesis. Background technique

[0002] Fluorocarbon-modified polyacrylamide refers to a class of water-soluble polymers that introduce perfluorohydrophobic groups into polyacrylamide macromolecular chains. Compared with hydrocarbon hydrophobic groups, fluorocarbon hydrophobic groups have more excellent hydrophobic association properties, because the cohesive energy density and surface energy between fluorocarbon atoms are small, and it is easy to form a complex network structure, thus Enhance the viscosity and shear resistance of polymers. At the same time, the extremely strong thermal and chemical stability of the fluorocarbon alkyl chain also endows the fluorocarbon mo...

Examples

Embodiment 1

[0059] Embodiment 1. Preparation of fluorocarbon / hydrocarbon mixed type cationic surface-active monomer

[0060] (1) Preparation of compound I

[0061] Weigh 0.88g (10mmol) of N, N-dimethylethylenediamine and dissolve it in 15ml of DMF, transfer to a condenser tube (connected with CaCl 2 Drying tube), nitrogen tube, and constant pressure dropping funnel in a 50ml three-neck round bottom flask, then put it into a constant temperature water bath at 25°C, add the rotor, start stirring, and pass through nitrogen to remove oxygen for 30min. Weigh 2.62g (12mmol) of Boc anhydride and dissolve in 10ml of DMF, then transfer to a 25ml constant pressure dropping funnel. Open the cock, drop the Boc anhydride dissolved in DMF into the three-neck flask drop by drop, after 0.5h, remove the constant pressure dropping funnel. After the mixture was reacted for 1 h, 2.45 g (15 mmol) of 6-bromo-1-hexene was dissolved in 5 ml of DMF and transferred to a 10 ml constant pressure dropping funnel. ...

Embodiment 2

[0068] Embodiment 2. Preparation of fluorocarbon modified polyacrylamide

[0069] (1) Transfer 80ml of deionized water into a 250ml four-necked round-bottom flask equipped with a mechanical stirring rod, a spherical condenser, a nitrogen vent tube, and a thermometer, and weigh 7.0582g (99.3mmol) of acrylamide into the four-necked flask , into N 2 , stirred at room temperature for 1h.

[0070] (2) Weigh 0.4391g (0.7mmol) of fluorocarbon / hydrocarbon mixed cationic surfactant monomer, dissolve it in 10ml of deionized water, and after fully dissolving, it becomes a yellow clear and transparent solution, and transfer it to a four-necked bottle after standing for 10min In the process, rinse the remaining liquid and foam repeatedly with 10ml of deionized water and transfer them into the reaction system together. The temperature of the reaction system was raised to 65°C, and the stirring was continued, and the N 2 Protection, keep 30min.

[0071] (3) Weigh 0.0541g (2mmol / L) of potas...

Embodiment 3

[0074] Embodiment 3. Preparation of fluorocarbon modified polyacrylamide

[0075] As described in Example 2, the difference is that the monomer feed ratio is changed to 0.2509 g of fluorocarbon / hydrocarbon mixed cationic surface active monomer and 7.0795 g of acrylamide to obtain 7.0880 g of light yellow powder of fluorocarbon modified polyacrylamide , the yield was 96.7%.

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