A method for preparing hydrophobically associated polyacrylamide

Abstract

The invention relates to the technical field of hydrophobically associating polyacrylamide, and discloses a preparation method of hydrophobically associating polyacrylamide. The invention obtains hydrophobically associating polyacrylamide by stirring olefinic quaternary ammonium salt, acrylamide, acrylic acid and methyl acrylate, and then adding ammonium persulfate and sorbitan monooleate emulsifier for continuous reaction. The quaternary ammonium salt group in the hydrophobically associating polyacrylamide improves the temperature resistance, shear resistance and hydrophobicity of the product; the adamantane and benzene ring structure therein improve the stability of the hydrophobically associating polyacrylamide; the olefinic quaternary ammonium salt is introduced into the structure of polyacrylamide to form a relatively long double chain and a gemini quaternary ammonium salt, thereby improving the degree of substitution of the quaternary ammonium salt, and at the same time, the chain will form a spatial physical crosslinking to form a network interpenetration, thereby improving the heat resistance of the polyacrylamide and not being easy to degrade.

Description

Technical Field

[0001] The invention relates to the technical field of hydrophobically associating polyacrylamide, in particular to a preparation method of hydrophobically associating polyacrylamide. Background Art

[0002] Hydrophobically associating polyacrylamide, referred to as HAPAM, is a linear polymer obtained by copolymerizing acrylamide monomers and hydrophobic monomers. In oil production, hydrophobically associating polyacrylamide plays an important role as an oil displacement agent in improving crude oil production efficiency, reducing production costs, and protecting the environment and saving energy. With the development of oil production technology, the requirements for high temperature resistance and shear resistance of polymer oil displacement agents are becoming higher and higher. General polymers cannot meet their production needs. Therefore, how to avoid this phenomenon is the key to solving the problem. For example, patent CN102796222A discloses a method for synthesizing hydrophobically associating polyacrylamide, which only solves the problems of complex synthesis process and high production cost of hydrophobically associating polyacrylamide, but its own high temperature resistance and shear resistance need to be improved. Summary of the invention

[0003] 1. Technical issues to be resolved

[0004] In view of the deficiencies of the prior art, the present invention provides a method for preparing a hydrophobically associated polyacrylamide, which has good high temperature resistance and shear resistance.

[0005] (II) Technical solution

[0006] To achieve the above object, the present invention provides the following technical solution: a method for preparing hydrophobically associating polyacrylamide, wherein the method for preparing hydrophobically associating polyacrylamide is:

[0007] (1) Add 1,3-adamantanediol and propyl caprolactone to N,N-dimethylformamide solvent, mix well, add sodium hydroxide catalyst, react at 65-70°C for 6.5-10h, and after the reaction is completed, distill under reduced pressure, wash, and dry to obtain intermediate 1;

[0008] (2) Add intermediate 1 and 2-methylene succinic anhydride to the reactor, stir evenly, continue to add 4-dimethylaminopyridine catalyst, control the temperature between 50-80°C, react for 1.5-4h, filter after reaction, wash and dry to obtain intermediate 2;

[0009] (3) Add intermediate 2 to toluene solvent, stir and disperse, then add 4-dimethylaminophenol and p-toluenesulfonic acid catalyst, raise the temperature to 105-115°C, react for 7-10 hours, and after the reaction is completed, perform vacuum distillation to obtain intermediate 3;

[0010] (4) Adding intermediate 3 and 1-chloro-2-butene to N,N-dimethylformamide solvent, stirring to dissolve, and reflux heating at 85-92°C for 4.5-6h. After the reaction is completed, cooling, washing and drying to obtain an olefinic quaternary ammonium salt;

[0011] (5) Add quaternary ammonium salt, acrylamide, acrylic acid and methyl acrylate to deionized water and stir at 40-65°C for 1-1.2 hours. Then add ammonium persulfate and sorbitan monooleate emulsifier and continue to react at 30-45°C for 4.5-6 hours. After the reaction is completed, filter, wash and dry to obtain hydrophobically associated polyacrylamide.

[0012] Preferably, the mass ratio of 1,3-adamantanediol, propyl caprolactone and sodium hydroxide in (1) is 1:1.8-2.2:0.05-0.054.

[0013] Preferably, the mass ratio of the intermediate 1, 2-methylenesuccinic anhydride and 4-dimethylaminopyridine in (2) is 1:0.9-1.2:0.025-0.03.

[0014] Preferably, the mass ratio of the intermediate 2,4-dimethylaminophenol to p-toluenesulfonic acid in (3) is 1:1.35-1.5:0.04-0.06.

[0015] Preferably, the mass ratio of the intermediate 3 to 1-chloro-2-butene in (4) is 1:1.12-1.2.

[0016] Preferably, the mass ratio of olefinic quaternary ammonium salt, acrylamide, acrylic acid, methyl acrylate, ammonium persulfate and sorbitan monooleate in (5) is 1:2.4-2.48:1.6-1.65:0.7-1.0:0.05-0.06:0.08-0.1.

[0017] 3. Beneficial technical effects

[0018] The invention prepares hydrophobic associating polyacrylamide by stirring olefinic quaternary ammonium salt, acrylamide, acrylic acid and methyl acrylate, and then adding ammonium persulfate and sorbitan monooleate emulsifier for continuous reaction.

[0019] 1,3-adamantanediol and propyl caprolactone are reacted to obtain intermediate 1; intermediate 1 is then reacted with 2-methylene succinic anhydride to generate ester group, carboxyl group and olefin group to obtain intermediate 2; the carboxyl group in intermediate 2 reacts with the hydroxyl group in 4-dimethylaminophenol to introduce tertiary amino group to obtain intermediate 3, and then the tertiary amino group in intermediate 3 reacts with chlorine in 1-chloro-2-butene to obtain olefinated quaternary ammonium salt. The quaternary ammonium salt group in hydrophobically associated polyacrylamide improves the temperature resistance, shear resistance and hydrophobicity of the product; the adamantane and benzene ring structure improves the stability of hydrophobically associated polyacrylamide; the olefinated quaternary ammonium salt is introduced into the structure of polyacrylamide to form a longer double chain and gemini quaternary ammonium salt, which increases the degree of substitution of the quaternary ammonium salt. At the same time, the chain will form a spatial physical crosslinking to form a network interpenetration, which improves the heat resistance of polyacrylamide and is not easy to degrade. DETAILED DESCRIPTION Example 1

[0020] (1) Add 1,3-adamantanediol and propyl hexanolactone to N,N-dimethylformamide solvent, mix well, add sodium hydroxide catalyst, wherein the mass ratio of 1,3-adamantanediol, propyl hexanolactone and sodium hydroxide is 1:1.8:0.05, react at 65°C for 6.5h, and after the reaction is completed, distill under reduced pressure, wash and dry to obtain intermediate 1;

[0021] (2) Add intermediate 1 and 2-methylene succinic anhydride to the reactor, wherein the mass ratio of intermediate 1, 2-methylene succinic anhydride to 4-dimethylaminopyridine is 1:0.9:0.025, stir evenly, continue to add 4-dimethylaminopyridine catalyst, control the temperature at 50°C, react for 1.5 hours, filter after reaction, wash and dry to obtain intermediate 2;

[0022] (3) Add intermediate 2 to toluene solvent, stir and disperse, then add 4-dimethylaminophenol and p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate 2, 4-dimethylaminophenol and p-toluenesulfonic acid is 1:1.35:0.04, heat to 105°C, react for 7 hours, and after the reaction is completed, perform vacuum distillation to obtain intermediate 3;

[0023] (4) adding intermediate 3 and 1-chloro-2-butene to N,N-dimethylformamide solvent, wherein the mass ratio of intermediate 3 to 1-chloro-2-butene is 1:1.12, stirring and dissolving, and reflux heating at 85°C for 4.5 hours. After the reaction is completed, cooling, washing and drying are performed to obtain an olefinic quaternary ammonium salt;

[0024] (5) Add olefinic quaternary ammonium salt, acrylamide, acrylic acid, and methyl acrylate to deionized water and stir at 40°C for 1 hour. Then add ammonium persulfate and sorbitan monooleate emulsifier and continue to react at 30°C for 4.5 hours. The mass ratio of olefinic quaternary ammonium salt, acrylamide, acrylic acid, methyl acrylate, ammonium persulfate and sorbitan monooleate is 1:2.4:1.6:0.7:0.05:0.08. After the reaction is completed, filter, wash, and dry to obtain hydrophobically associated polyacrylamide. Example 2

[0025] (1) Add 1,3-adamantanediol and propyl hexanolactone to N,N-dimethylformamide solvent, mix well, add sodium hydroxide catalyst, wherein the mass ratio of 1,3-adamantanediol, propyl hexanolactone and sodium hydroxide is 1:2.2:0.054, react at 70°C for 10 hours, and after the reaction is completed, distill under reduced pressure, wash and dry to obtain intermediate 1;

[0026] (2) Add intermediate 1 and 2-methylene succinic anhydride to the reactor, stir evenly, and continue to add 4-dimethylaminopyridine catalyst, wherein the mass ratio of intermediate 1, 2-methylene succinic anhydride and 4-dimethylaminopyridine is 1:1.2:0.03, control the temperature between 80°C, react for 4 hours, filter after completion, wash and dry to obtain intermediate 2;

[0027] (3) Add intermediate 2 to toluene solvent, stir and disperse, then add 4-dimethylaminophenol and p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate 2, 4-dimethylaminophenol and p-toluenesulfonic acid is 1:1.5:0.06, heat to 115°C, react for 10 hours, and after the reaction is completed, perform vacuum distillation to obtain intermediate 3;

[0028] (4) adding intermediate 3 and 1-chloro-2-butene to N,N-dimethylformamide solvent, wherein the mass ratio of intermediate 3 to 1-chloro-2-butene is 1:1.2, stirring and dissolving, and reflux heating at 92°C for 6 hours. After the reaction is completed, cooling, washing and drying are performed to obtain an olefinic quaternary ammonium salt;

[0029] (5) Add olefinic quaternary ammonium salt, acrylamide, acrylic acid, and methyl acrylate to deionized water and stir at 65°C for 1.2 hours. Then add ammonium persulfate and sorbitan monooleate emulsifier and continue to react at 45°C for 6 hours. The mass ratio of olefinic quaternary ammonium salt, acrylamide, acrylic acid, methyl acrylate, ammonium persulfate and sorbitan monooleate is 1:2.48:1.65:1.0:0.06:0.1. After the reaction is completed, filter, wash, and dry to obtain hydrophobically associated polyacrylamide. Example 3

[0030] (1) Add 1,3-adamantanediol and propyl hexanolactone to N,N-dimethylformamide solvent, mix well, add sodium hydroxide catalyst, wherein the mass ratio of 1,3-adamantanediol, propyl hexanolactone and sodium hydroxide is 1:2.0:0.052, react at 67°C for 8.2h, and after the reaction is completed, distill under reduced pressure, wash and dry to obtain intermediate 1;

[0031] (2) Add intermediate 1 and 2-methylene succinic anhydride to the reactor, stir evenly, and continue to add 4-dimethylaminopyridine catalyst, wherein the mass ratio of intermediate 1, 2-methylene succinic anhydride and 4-dimethylaminopyridine is 1:1.1:0.027, control the temperature between 65°C, react for 2.75h, filter after completion, wash and dry to obtain intermediate 2;

[0032] (3) Add intermediate 2 to toluene solvent, stir and disperse, then add 4-dimethylaminophenol and p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate 2, 4-dimethylaminophenol and p-toluenesulfonic acid is 1:1.42:0.05, heat to 110°C, react for 8.5 hours, and after the reaction is completed, perform vacuum distillation to obtain intermediate 3;

[0033] (4) adding intermediate 3 and 1-chloro-2-butene to N,N-dimethylformamide solvent, wherein the mass ratio of intermediate 3 to 1-chloro-2-butene is 1:1.16, stirring and dissolving, and reflux heating at 88°C for 5.2h. After the reaction is completed, cooling, washing and drying are performed to obtain an olefinic quaternary ammonium salt;

[0034] (5) Add olefinic quaternary ammonium salt, acrylamide, acrylic acid, and methyl acrylate to deionized water and stir at 52°C for 1.1 h. Then add ammonium persulfate and sorbitan monooleate emulsifier and continue to react at 37°C for 5.2 h. The mass ratio of olefinic quaternary ammonium salt, acrylamide, acrylic acid, methyl acrylate, ammonium persulfate and sorbitan monooleate is 1:2.44:1.62:0.85:0.055:0.09. After the reaction is completed, filter, wash, and dry to obtain hydrophobically associated polyacrylamide. Example 4

[0035] (1) Add 1,3-adamantanediol and propyl hexanolactone to N,N-dimethylformamide solvent, mix well, add sodium hydroxide catalyst, wherein the mass ratio of 1,3-adamantanediol, propyl hexanolactone and sodium hydroxide is 1:1.8:0.05, react at 65°C for 6.5h, and after the reaction is completed, distill under reduced pressure, wash and dry to obtain intermediate 1;

[0036] (2) Add intermediate 1 and 2-methylene succinic anhydride to the reactor, wherein the mass ratio of intermediate 1, 2-methylene succinic anhydride to 4-dimethylaminopyridine is 1:0.9:0.025, stir evenly, continue to add 4-dimethylaminopyridine catalyst, control the temperature at 50°C, react for 1.5 hours, filter after reaction, wash and dry to obtain intermediate 2;

[0037] (3) Add intermediate 2 to toluene solvent, stir and disperse, then add 4-dimethylaminophenol and p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate 2, 4-dimethylaminophenol and p-toluenesulfonic acid is 1:1.5:0.06, heat to 115°C, react for 10 hours, and after the reaction is completed, perform vacuum distillation to obtain intermediate 3;

[0038] (4) adding intermediate 3 and 1-chloro-2-butene to N,N-dimethylformamide solvent, wherein the mass ratio of intermediate 3 to 1-chloro-2-butene is 1:1.2, stirring and dissolving, and reflux heating at 92°C for 6 hours. After the reaction is completed, cooling, washing and drying are performed to obtain an olefinic quaternary ammonium salt;

[0039] (5) Add olefinic quaternary ammonium salt, acrylamide, acrylic acid, and methyl acrylate to deionized water and stir at 52°C for 1.1 h. Then add ammonium persulfate and sorbitan monooleate emulsifier and continue to react at 37°C for 5.2 h. The mass ratio of olefinic quaternary ammonium salt, acrylamide, acrylic acid, methyl acrylate, ammonium persulfate and sorbitan monooleate is 1:2.44:1.62:0.85:0.055:0.09. After the reaction is completed, filter, wash, and dry to obtain hydrophobically associated polyacrylamide. Example 5

[0040] (1) Add 1,3-adamantanediol and propyl hexanolactone to N,N-dimethylformamide solvent, mix well, add sodium hydroxide catalyst, wherein the mass ratio of 1,3-adamantanediol, propyl hexanolactone and sodium hydroxide is 1:2.2:0.054, react at 70°C for 10 hours, and after the reaction is completed, distill under reduced pressure, wash and dry to obtain intermediate 1;

[0041] (2) Add intermediate 1 and 2-methylene succinic anhydride to the reactor, stir evenly, and continue to add 4-dimethylaminopyridine catalyst, wherein the mass ratio of intermediate 1, 2-methylene succinic anhydride and 4-dimethylaminopyridine is 1:1.2:0.03, control the temperature between 80°C, react for 4 hours, filter after completion, wash and dry to obtain intermediate 2;

[0042] (3) Add intermediate 2 to toluene solvent, stir and disperse, then add 4-dimethylaminophenol and p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate 2, 4-dimethylaminophenol and p-toluenesulfonic acid is 1:1.42:0.05, heat to 110°C, react for 8.5 hours, and after the reaction is completed, perform vacuum distillation to obtain intermediate 3;

[0043] (4) adding intermediate 3 and 1-chloro-2-butene to N,N-dimethylformamide solvent, wherein the mass ratio of intermediate 3 to 1-chloro-2-butene is 1:1.16, stirring and dissolving, and reflux heating at 88°C for 5.2h. After the reaction is completed, cooling, washing and drying are performed to obtain an olefinic quaternary ammonium salt;

[0044] (5) Add olefinic quaternary ammonium salt, acrylamide, acrylic acid, and methyl acrylate to deionized water and stir at 40°C for 1 hour. Then add ammonium persulfate and sorbitan monooleate emulsifier and continue to react at 30°C for 4.5 hours. The mass ratio of olefinic quaternary ammonium salt, acrylamide, acrylic acid, methyl acrylate, ammonium persulfate and sorbitan monooleate is 1:2.4:1.6:0.7:0.05:0.08. After the reaction is completed, filter, wash, and dry to obtain hydrophobically associated polyacrylamide.

[0045] Comparative Example 1

[0046] Compared with Example 5, this comparative example differs in that no alkylene quaternary ammonium salt is added.

[0047] Comparative Example 2

[0048] Compared with Example 5, this comparative example is different in that acrylic acid and methyl acrylate are not added.

[0049] The hydrophobically associating polyacrylamide thickener was dissolved in water and stirred to form a solution with a concentration of 2.5 g / L. The apparent viscosity of the solution was measured using a rotational viscometer at different temperatures. The test results are shown in Table 1.

[0050] Table 1: Apparent viscosity test.

[0051]

[0052] It can be seen from Table 1 that Examples 1-5 of the present invention have better high temperature resistance than Comparative Examples 1-2, and still have higher apparent viscosity at high temperatures.

[0053] The polyacrylamide thickener solution with a concentration of 2.5 g / L was sheared at a high speed of 420 r / min at 25°C and at different shear times to test the apparent viscosity of the solution. The test results are shown in Table 2.

[0054] Table 2: Apparent viscosity test.

[0055]

[0056] It can be seen from Table 2 that Examples 1-5 of the present invention have better shear resistance than Comparative Examples 1-2, and still have higher apparent viscosity under long-term shearing.

[0057] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for preparing a hydrophobically associating polyacrylamide, characterized in that: The preparation method of the hydrophobically associating polyacrylamide is: (1) Add 1,3-adamantanediol and propyl caprolactone to N,N-dimethylformamide solvent, mix well, add sodium hydroxide catalyst, react at 65-70°C for 6.5-10h, and after the reaction is completed, distill under reduced pressure, wash, and dry to obtain intermediate 1; (2) Add intermediate 1 and 2-methylene succinic anhydride to the reactor, stir evenly, continue to add 4-dimethylaminopyridine catalyst, control the temperature between 50-80°C, react for 1.5-4h, filter after reaction, wash and dry to obtain intermediate 2; (3) Add intermediate 2 to toluene solvent, stir and disperse, then add 4-dimethylaminophenol and p-toluenesulfonic acid catalyst, raise the temperature to 105-115°C, react for 7-10 hours, and after the reaction is completed, perform vacuum distillation to obtain intermediate 3; (4) Adding intermediate 3 and 1-chloro-2-butene to N,N-dimethylformamide solvent, stirring to dissolve, and reflux heating at 85-92°C for 4.5-6h. After the reaction is completed, cooling, washing and drying to obtain an olefinic quaternary ammonium salt; (5) Add quaternary ammonium salt, acrylamide, acrylic acid and methyl acrylate to deionized water and stir at 40-65°C for 1-1.2 hours, then add ammonium persulfate and sorbitan monooleate emulsifier and continue to react at 30-45°C for 4.5-6 hours. After the reaction is completed, filter, wash and dry to obtain hydrophobically associated polyacrylamide; The mass ratio of 1,3-adamantanediol, propyl caprolactone and sodium hydroxide in (1) is 1:1.8-2.2:0.05-0.054; The mass ratio of the intermediate 1,2-methylenesuccinic anhydride to 4-dimethylaminopyridine in (2) is 1:0.9-1.2:0.025-0.03; The mass ratio of the intermediate 2,4-dimethylaminophenol to p-toluenesulfonic acid in (3) is 1:1.35-1.5:0.04-0.06; The mass ratio of intermediate 3 and 1-chloro-2-butene in (4) is: 1:1.12-1.2; The mass ratio of olefinic quaternary ammonium salt, acrylamide, acrylic acid, methyl acrylate, ammonium persulfate and sorbitan monooleate in (5) is 1:2.4-2.48:1.6-1.65:0.7-1.0:0.05-0.06:0.08-0.1.

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