Bactericide and preparation method thereof

Abstract

The invention relates to the technical field of oil exploitation, and discloses a bactericide and a preparation method thereof.Sodium dodecyl benzene sulfonate, a quaternary ammonium salt modified cardanol polymer and water are added into a stirrer and stirred, and the bactericide is obtained after stirring is finished. Quaternary ammonium salt, pyridine and morpholine in the quaternary ammonium salt modified cardanol polymer all have good bactericidal effects. Pyridine has a strong bactericidal effect and can interfere with cell wall formation, DNA replication and repair and destroy a membrane structure; the morpholine can inhibit the generation of a cell wall membrane; the cardanol group has a better bactericidal effect, and the cardanol reacts with 2, 2-bis (bromomethyl)-1, 3-propylene glycol, so that the substitution degree of the cardanol is improved, and the bactericidal effect of the cardanol is better.

Description

Technical Field

[0001] The invention relates to the technical field of petroleum extraction, in particular to a bactericide and a preparation method thereof. Background Art

[0002] In oilfield exploitation, gathering and water injection systems, bacteria cause serious biological corrosion to pipelines and equipment, causing huge losses to oil and gas production. Therefore, how to avoid this phenomenon is the key to solving the problem. Existing bactericides have weak bactericidal effects and poor killing effects on sulfate-reducing bacteria and saprophytes. For example, patent CN114931147A discloses an oilfield bactericide and its preparation method. The invention solves the problems of high content of sulfate-reducing bacteria, saprophytes, and iron bacteria in oilfield produced water and reinjection water, corrosion of equipment and pipelines, and unsatisfactory bactericidal effects of polymer injection. However, the composition is relatively complex and the bactericidal effect needs to be improved. Summary of the invention

[0003] 1. Technical issues to be resolved In view of the deficiencies of the prior art, the present invention provides a bactericide and a preparation method thereof, which have good bactericidal effect.

[0004] (II) Technical solution To achieve the above object, the present invention provides the following technical solution: a fungicide comprising the following components by weight: 6-10 parts by weight of sodium dodecylbenzene sulfonate, 5-12 parts by weight of quaternary ammonium salt-modified cardanol polymer, and 10-15 parts by weight of water.

[0005] Preferably, the preparation method of the quaternary ammonium salt modified cardanol polymer is: (1) Add N-methylimidodiacetic acid and vinyl chloride to a reactor containing acetonitrile solvent, react at 70-95°C for 14-18 hours, cool to room temperature, concentrate under reduced pressure, and wash with petroleum ether to obtain intermediate 1; (2) Add intermediate 1 and 3-amino-6-morpholinylpyridine to N,N-dimethylformamide solvent, stir to dissolve, then add pyridine and triphenyl phosphite, reflux at 120-135°C for 12-15h, filter the solvent after the end, wash the product with deionized water and ethanol in turn, and obtain quaternized olefinic ammonium pyridine; (3) Add quaternary alkenyl pyridine, alkenyl cardanol and 1-vinylimidazole to N,N-dimethylformamide solvent, add ammonium persulfate initiator after dissolution, react at 90-110°C for 3-6h, remove the solvent by vacuum distillation after reaction, filter, wash and dry to obtain quaternary ammonium salt modified cardanol polymer.

[0006] Preferably, the mass ratio of N-methyliminodiacetic acid to vinyl chloride in (1) is 0.9-1.2:1.

[0007] Preferably, in the (2), the mass ratio of the intermediate 1, 3-amino-6-morpholinylpyridine, pyridine and triphenyl phosphite is 1:2.2-2.4:0.01-0.03:0.02-0.03.

[0008] Preferably, the mass ratio of quaternized alkenyl pyridine, alkenyl cardanol, 1-vinylimidazole and ammonium persulfate initiator in (3) is 1.2-1.4:1:1.1-1.3:0.01-0.04.

[0009] Preferably, the preparation method of olefinated cardanol in (3) is: S1. Add 2,2-bis(bromomethyl)-1,3-propanediol and cardanol to an acetone solvent, stir evenly, then continue to add 3-5 mol / L sodium hydroxide aqueous solution, react at 60-85° C. for 5-7 hours, and after the reaction is completed, neutralize, concentrate, filter, wash and dry to obtain intermediate 2; S2. Add 5-9 parts by weight of intermediate 2 and 2-3 parts by weight of 1-acrylate-3,5-aminoacetic acid-isotriazine to N,N-dimethylformamide solvent, stir evenly, then add 0.2-0.3 parts by weight of p-toluenesulfonic acid catalyst to carry out esterification reaction to introduce olefinic groups, react at 80-120°C for 10-15h, and then distill under reduced pressure, filter and dry to obtain olefinic cardanol.

[0010] Preferably, the mass ratio of 2,2-bis(bromomethyl)-1,3-propanediol to cardanol in S1 is 1:1.2-1.6.

[0011] Preferably, the preparation method of the fungicide is: adding sodium dodecylbenzene sulfonate, quaternary ammonium salt-modified cardanol polymer, and water into a stirrer, stirring for 10-12 minutes, and then obtaining the fungicide.

[0012] 3. Beneficial technical effects The invention provides a fungicide by adding sodium dodecylbenzene sulfonate, quaternary ammonium salt modified cardanol polymer and water into a stirrer and stirring the mixture to obtain the fungicide.

[0013] The tertiary amine group of N-methyliminodiacetic acid and the chlorine group in vinyl chloride are subjected to quaternization reaction to generate a quaternary ammonium salt group, and a carboxyl group and an alkenyl group are introduced at the same time to obtain an intermediate 1; the carboxyl group in the intermediate 1 and the amino group in 3-amino-6-morpholinylpyridine are subjected to amidation reaction to introduce an alkenyl group, thereby obtaining an alkenyl quaternized pyridine; the alkenyl quaternized pyridine, alkenyl cardanol, and 1-vinylimidazole are subjected to polymerization reaction to obtain a quaternary ammonium salt-modified cardanol polymer.

[0014] The quaternary ammonium salt, pyridine and morpholine in the quaternary ammonium salt modified cardanol polymer all have good bactericidal effects. Quaternary ammonium salts can be adsorbed onto negatively charged bacteria, forming high-concentration ion clusters on the bacterial surface, which directly affect the normal function of bacterial cells and destroy the permeability of cell walls, leading to cell lysis and death; pyridine has a strong bactericidal effect, which can interfere with cell wall formation, DNA replication and repair, and destroy membrane structure; morpholine can inhibit the formation of cell wall membranes; the triazine group can also kill sulfate-reducing bacteria and saprophytes; the cardanol group itself has a good bactericidal effect, and the cardanol reacts with 2,2-bis(bromomethyl)-1,3-propanediol to increase its degree of substitution, making its bactericidal effect better. DETAILED DESCRIPTION

[0015] Preparation of 1-acrylate-3,5-aminoacetoxy-s-triazine: refer to the authorized patent CN116196898A in the prior art. Example 1

[0016] (1) Add N-methyliminodiacetic acid and vinyl chloride into a reactor filled with 15 ml of acetonitrile solvent, wherein the mass ratio of N-methyliminodiacetic acid to vinyl chloride is 0.9:1, react at 70°C for 14 hours, cool to room temperature after reaction, concentrate under reduced pressure, and wash with petroleum ether to obtain intermediate 1; (2) Add intermediate 1 and 3-amino-6-morpholinyl pyridine to 20 ml of N,N-dimethylformamide solvent, stir to dissolve, then add pyridine and triphenyl phosphite, wherein the mass ratio of intermediate 1, 3-amino-6-morpholinyl pyridine, pyridine, and triphenyl phosphite is 1:2.2:0.01:0.02, reflux at 120° C. for 12 h, filter the solvent after the end, wash the product with deionized water and ethanol in turn, and obtain alkenyl quaternized pyridine; (3) Add 2,2-bis(bromomethyl)-1,3-propanediol and cardanol to 18 ml of acetone solvent, wherein the mass ratio of 2,2-bis(bromomethyl)-1,3-propanediol to cardanol is 1:1.2, stir evenly, then continue to add 3 mol / L sodium hydroxide aqueous solution, react at 60°C for 5 h, and after the reaction is completed, neutralize, concentrate, filter, wash and dry to obtain intermediate 2; (4) Add 5 parts by weight of intermediate 2 and 2 parts by weight of 1-acrylate-3,5-aminoacetoxy-s-triazine to 16 ml of N,N-dimethylformamide solvent, stir evenly, then add 0.2 parts by weight of p-toluenesulfonic acid catalyst, react at 80° C. for 10 h, and then distill under reduced pressure, filter and dry to obtain olefinated cardanol; (5) Add alkenyl quaternary ammonium pyridine, alkenyl cardanol, and 1-vinylimidazole to 14 ml of N,N-dimethylformamide solvent, add ammonium persulfate initiator after dissolution, wherein the mass ratio of alkenyl quaternary ammonium pyridine, alkenyl cardanol, 1-vinylimidazole, and ammonium persulfate initiator is 1.2:1:1.1:0.01, react at 90°C for 3 hours, and after the reaction, remove the solvent by distillation under reduced pressure, filter, wash and dry to obtain a quaternary ammonium salt modified cardanol polymer; (6) Add 6 parts by weight of sodium dodecylbenzene sulfonate, 5 parts by weight of quaternary ammonium salt-modified cardanol polymer, and 10 parts by weight of water into a stirrer and stir for 10 minutes to obtain a fungicide. Example 2

[0017] (1) Add N-methyliminodiacetic acid and vinyl chloride into a reactor filled with 25 ml of acetonitrile solvent, wherein the mass ratio of N-methyliminodiacetic acid to vinyl chloride is 1.2:1, react at 95°C for 18 hours, cool to room temperature after reaction, concentrate under reduced pressure, and wash with petroleum ether to obtain intermediate 1; (2) Add intermediate 1 and 3-amino-6-morpholinyl pyridine to 30 ml of N,N-dimethylformamide solvent, stir to dissolve, then add pyridine and triphenyl phosphite, wherein the mass ratio of intermediate 1, 3-amino-6-morpholinyl pyridine, pyridine, and triphenyl phosphite is 1:2.4:0.03:0.03, reflux at 135° C. for 15 h, filter the solvent after the end, wash the product with deionized water and ethanol in turn, and obtain alkenyl quaternized pyridine; (3) Add 2,2-bis(bromomethyl)-1,3-propanediol and cardanol to 32 ml of acetone solvent, wherein the mass ratio of 2,2-bis(bromomethyl)-1,3-propanediol to cardanol is 1:1.6, stir evenly, then continue to add 5 mol / L sodium hydroxide aqueous solution, react at 85°C for 7 h, and after the reaction is completed, neutralize, concentrate, filter, wash and dry to obtain intermediate 2; (4) 9 parts by weight of the intermediate 2 and 3 parts by weight of 1-acrylate-3,5-aminoacetoxy-s-triazine were added to 28 ml of N,N-dimethylformamide solvent and stirred evenly. Then, 0.3 parts by weight of p-toluenesulfonic acid catalyst was added thereto and reacted at 120° C. for 15 h. After the reaction, the mixture was distilled under reduced pressure, filtered and dried to obtain olefinated cardanol. (5) Add alkenyl quaternary ammonium pyridine, alkenyl cardanol, and 1-vinylimidazole to 25 ml of N,N-dimethylformamide solvent, add ammonium persulfate initiator after dissolution, wherein the mass ratio of alkenyl quaternary ammonium pyridine, alkenyl cardanol, 1-vinylimidazole, and ammonium persulfate initiator is 1.4:1:1.3:0.04, react at 110°C for 6 hours, and after the reaction, remove the solvent by distillation under reduced pressure, filter, wash and dry to obtain a quaternary ammonium salt modified cardanol polymer; (6) 10 parts by weight of sodium dodecylbenzene sulfonate, 12 parts by weight of quaternary ammonium salt-modified cardanol polymer, and 15 parts by weight of water are added into a stirrer and stirred for 12 minutes to obtain a fungicide. Example 3

[0018] (1) Add N-methyliminodiacetic acid and vinyl chloride into a reactor filled with 20 ml of acetonitrile solvent, wherein the mass ratio of N-methyliminodiacetic acid to vinyl chloride is 1.1:1, react at 85°C for 16 hours, cool to room temperature after reaction, concentrate under reduced pressure, and wash with petroleum ether to obtain intermediate 1; (2) Add intermediate 1 and 3-amino-6-morpholinyl pyridine to 25 ml of N,N-dimethylformamide solvent, stir to dissolve, then add pyridine and triphenyl phosphite, wherein the mass ratio of intermediate 1, 3-amino-6-morpholinyl pyridine, pyridine, and triphenyl phosphite is 1:2.3:0.02:0.025, reflux at 126°C for 14 hours, filter the solvent after the end, wash the product with deionized water and ethanol in turn, and obtain alkenyl quaternized pyridine; (3) Add 2,2-bis(bromomethyl)-1,3-propanediol and cardanol to 26 ml of acetone solvent, wherein the mass ratio of 2,2-bis(bromomethyl)-1,3-propanediol to cardanol is 1:1.5, stir evenly, then continue to add 4 mol / L sodium hydroxide aqueous solution, react at 74°C for 6 h, and after the reaction is completed, neutralize, concentrate, filter, wash and dry to obtain intermediate 2; (4) 8 parts by weight of the intermediate 2 and 2.5 parts by weight of 1-acrylate-3,5-aminoacetoxy-s-triazine were added to 24 ml of N,N-dimethylformamide solvent and stirred evenly. Then, 0.25 parts by weight of p-toluenesulfonic acid catalyst was added thereto and reacted at 90° C. for 12 h. After the reaction, the mixture was distilled under reduced pressure, filtered and dried to obtain olefinated cardanol. (5) Add alkenyl quaternary ammonium pyridine, alkenyl cardanol, and 1-vinylimidazole to 20 ml of N,N-dimethylformamide solvent, add ammonium persulfate initiator after dissolution, wherein the mass ratio of alkenyl quaternary ammonium pyridine, alkenyl cardanol, 1-vinylimidazole, and ammonium persulfate initiator is 1.3:1:1.2:0.03, react at 100° C. for 5 h, and after the reaction, remove the solvent by reduced pressure distillation, filter, wash and dry to obtain a quaternary ammonium salt modified cardanol polymer; (6) 8 parts by weight of sodium dodecylbenzene sulfonate, 9 parts by weight of quaternary ammonium salt-modified cardanol polymer, and 13 parts by weight of water were added into a stirrer and stirred for 11 minutes to obtain a fungicide. Example 4

[0019] (1) Add N-methyliminodiacetic acid and vinyl chloride into a reactor filled with 15 ml of acetonitrile solvent, wherein the mass ratio of N-methyliminodiacetic acid to vinyl chloride is 0.9:1, react at 70°C for 14 hours, cool to room temperature after reaction, concentrate under reduced pressure, and wash with petroleum ether to obtain intermediate 1; (2) Add intermediate 1 and 3-amino-6-morpholinyl pyridine to 20 ml of N,N-dimethylformamide solvent, stir to dissolve, then add pyridine and triphenyl phosphite, wherein the mass ratio of intermediate 1, 3-amino-6-morpholinyl pyridine, pyridine, and triphenyl phosphite is 1:2.2:0.01:0.02, reflux at 120° C. for 12 h, filter the solvent after the end, wash the product with deionized water and ethanol in turn, and obtain alkenyl quaternized pyridine; (3) Add 2,2-bis(bromomethyl)-1,3-propanediol and cardanol to 32 ml of acetone solvent, wherein the mass ratio of 2,2-bis(bromomethyl)-1,3-propanediol to cardanol is 1:1.6, stir evenly, then continue to add 5 mol / L sodium hydroxide aqueous solution, react at 85°C for 7 h, and after the reaction is completed, neutralize, concentrate, filter, wash and dry to obtain intermediate 2; (4) 9 parts by weight of intermediate 2 and 2 parts by weight of 1-acrylate-3,5-aminoacetoxy-s-triazine were added to 22 ml of N,N-dimethylformamide solvent and stirred evenly. Then, 0.3 parts by weight of p-toluenesulfonic acid catalyst was added thereto and reacted at 120° C. for 15 h. After the reaction, the mixture was distilled under reduced pressure, filtered and dried to obtain olefinated cardanol. (5) Add alkenyl quaternary ammonium pyridine, alkenyl cardanol, and 1-vinylimidazole to 18 ml of N,N-dimethylformamide solvent, add ammonium persulfate initiator after dissolution, wherein the mass ratio of alkenyl quaternary ammonium pyridine, alkenyl cardanol, 1-vinylimidazole, and ammonium persulfate initiator is 1.3:1:1.2:0.03, react at 100° C. for 5 h, and after the reaction, remove the solvent by reduced pressure distillation, filter, wash and dry to obtain a quaternary ammonium salt modified cardanol polymer; (6) 8 parts by weight of sodium dodecylbenzene sulfonate, 9 parts by weight of quaternary ammonium salt-modified cardanol polymer, and 12 parts by weight of water were added into a stirrer and stirred for 11 minutes to obtain a fungicide. Example 5

[0020] (1) Add N-methyliminodiacetic acid and vinyl chloride into a reactor filled with 22 ml of acetonitrile solvent, wherein the mass ratio of N-methyliminodiacetic acid to vinyl chloride is 1.2:1, react at 95°C for 18 hours, cool to room temperature after reaction, concentrate under reduced pressure, and wash with petroleum ether to obtain intermediate 1; (2) Add intermediate 1 and 3-amino-6-morpholinyl pyridine to 24 ml of N,N-dimethylformamide solvent, stir to dissolve, then add pyridine and triphenyl phosphite, wherein the mass ratio of intermediate 1, 3-amino-6-morpholinyl pyridine, pyridine, and triphenyl phosphite is 1:2.4:0.03:0.03, reflux at 135° C. for 15 h, filter the solvent after the end, wash the product with deionized water and ethanol in turn, and obtain alkenyl quaternized pyridine; (3) Add 2,2-bis(bromomethyl)-1,3-propanediol and cardanol to 20 ml of acetone solvent, wherein the mass ratio of 2,2-bis(bromomethyl)-1,3-propanediol to cardanol is 1:1.5, stir evenly, then continue to add 4 mol / L sodium hydroxide aqueous solution, react at 74°C for 6 h, and after the reaction is completed, neutralize, concentrate, filter, wash and dry to obtain intermediate 2; (4) 8 parts by weight of the intermediate 2 and 3 parts by weight of 1-acrylate-3,5-aminoacetoxy-s-triazine were added to 18 ml of N,N-dimethylformamide solvent and stirred evenly. Then, 0.25 parts by weight of p-toluenesulfonic acid catalyst was added thereto and reacted at 90° C. for 12 hours. After the reaction, the mixture was distilled under reduced pressure, filtered and dried to obtain olefinated cardanol. (5) Add alkenyl quaternary ammonium pyridine, alkenyl cardanol, and 1-vinylimidazole to 19 ml of N,N-dimethylformamide solvent, add ammonium persulfate initiator after dissolution, wherein the mass ratio of alkenyl quaternary ammonium pyridine, alkenyl cardanol, 1-vinylimidazole, and ammonium persulfate initiator is 1.2:1:1.1:0.01, react at 90°C for 3 hours, and after the reaction, remove the solvent by distillation under reduced pressure, filter, wash and dry to obtain a quaternary ammonium salt modified cardanol polymer; (6) Add 6 parts by weight of sodium dodecylbenzene sulfonate, 5 parts by weight of quaternary ammonium salt-modified cardanol polymer, and 12 parts by weight of water into a stirrer and stir for 10 minutes to obtain a fungicide.

[0021] Comparative Example 1 6 parts by weight of sodium dodecylbenzene sulfonate, 5 parts by weight of cardanol polymer and 12 parts by weight of water were added into a stirrer and stirred for 10 minutes to obtain a fungicide.

[0022] Comparative Example 2 Commonly used fungicide 1227 in oil fields.

[0023] The present invention uses the fungicides prepared in Examples 1-5 as experimental examples and Comparative Examples 1-2 as control examples, and tests their antibacterial properties respectively, and the test results are shown in Table 1. The injection water of a certain oil field injection station, sulfate-reducing bacteria (SRB) and saprophytic bacteria (TGB) were used as experimental strains after laboratory culture. The bactericidal rate evaluation was tested according to the China National Petroleum Corporation Enterprise Standard Q / SY49-2010 "Technical Requirements for Bactericides for Oil Fields" Table 1: Bactericidal rate test.

[0024] project SRB sterilization rate (%) TGB sterilization rate (%) Example 1 99.3 99.4 Example 2 99.9 99.9 Example 3 99.9 99.7 Example 4 99.7 99.6 Example 5 99.6 99.7 Comparative Example 1 90.3 92.1 Comparative Example 2 80.8 82.4 It can be seen from Table 1 that the fungicide examples 1-5 prepared by the present invention have better fungicidal effects than the comparative examples 1-2.

[0025] 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 fungicide, characterized in that: The invention comprises the following components by weight: 6-10 parts by weight of sodium dodecylbenzene sulfonate, 5-12 parts by weight of quaternary ammonium salt-modified cardanol polymer, and 10-15 parts by weight of water.

2. The bactericide according to claim 1, characterized in that The preparation method of the quaternary ammonium salt modified cardanol polymer is: (1) Add N-methylimidodiacetic acid and vinyl chloride to a reactor containing acetonitrile solvent, react at 70-95°C for 14-18 hours, cool to room temperature, concentrate under reduced pressure, and wash with petroleum ether to obtain intermediate 1; (2) Add intermediate 1 and 3-amino-6-morpholinylpyridine to N,N-dimethylformamide solvent, stir to dissolve, then add pyridine and triphenyl phosphite, reflux at 120-135°C for 12-15h, filter the solvent after the end, wash the product with deionized water and ethanol in turn, and obtain quaternized olefinic ammonium pyridine; (3) Add quaternary alkenyl pyridine, alkenyl cardanol and 1-vinylimidazole to N,N-dimethylformamide solvent, add ammonium persulfate initiator after dissolution, react at 90-110°C for 3-6h, remove the solvent by vacuum distillation after reaction, filter, wash and dry to obtain quaternary ammonium salt modified cardanol polymer.

3. The bactericide according to claim 2, characterized in that The mass ratio of N-methyliminodiacetic acid to vinyl chloride in (1) is 0.9-1.2:

1.

4. The bactericide according to claim 2, characterized in that The mass ratio of the intermediate 1, 3-amino-6-morpholinylpyridine, pyridine and triphenyl phosphite in (2) is 1:2.2-2.4:0.01-0.03:0.02-0.

03.

5. The bactericide according to claim 2, characterized in that The mass ratio of quaternized olefinic ammonium pyridine, olefinic cardanol, 1-vinylimidazole and ammonium persulfate initiator in (3) is 1.2-1.4:1:1.1-1.3:0.01-0.

04.

6. The fungicide according to claim 2, characterized in that The preparation method of olefinated cardanol in (3) is as follows: S1. Add 2,2-bis(bromomethyl)-1,3-propanediol and cardanol to an acetone solvent, stir evenly, then continue to add 3-5 mol / L sodium hydroxide aqueous solution, react at 60-85° C. for 5-7 hours, and after the reaction is completed, neutralize, concentrate, filter, wash and dry to obtain intermediate 2; S2. Add 5-9 parts by weight of intermediate 2 and 2-3 parts by weight of 1-acrylate-3,5-aminoacetoxy-isotriazine to N,N-dimethylformamide solvent, stir evenly, then add 0.2-0.3 parts by weight of p-toluenesulfonic acid catalyst thereto, react at 80-120°C for 10-15h, and then distill under reduced pressure, filter and dry to obtain olefinated cardanol.

7. The fungicide according to claim 6, characterized in that The mass ratio of 2,2-bis(bromomethyl)-1,3-propanediol to cardanol in S1 is 1:1.2-1.

6.

8. A method for preparing the fungicide according to any one of claims 1 to 7, characterized in that: The preparation method of the fungicide is as follows: sodium dodecylbenzene sulfonate, quaternary ammonium salt-modified cardanol polymer and water are added into a stirrer, and stirred for 10-12 minutes to obtain the fungicide.