WO2023087579A1

WO2023087579A1 - Synthesis process for macromolecular bactericide-polyolefin carbamidine

Info

Publication number: WO2023087579A1
Application number: PCT/CN2022/080262
Authority: WO
Inventors: 赵晴晴; 韩爱芹
Original assignee: 山东志存科技有限公司
Priority date: 2021-11-18
Filing date: 2022-03-11
Publication date: 2023-05-25
Also published as: CN114369188A

Abstract

The present invention relates to a synthesis process for a macromolecular bactericide-polyolefin carbamidine. The technical solution comprises the following steps: 1) adding hexamethylenediamine and ethyl acrylate into a reaction kettle, heating while stirring, and adding an initiator; 2) continuing heating, adding dicyandiamide and guanidine hydrochloride that are uniformly mixed, and dropping hydrochloric acid as a catalyst at a constant temperature; 3) heating multiple times, and performing a constant temperature reaction; 5) after the reaction is completed, dropping clear water into the reaction kettle, and fully stirring; and 6) adjusting the pH value to 6-9 to obtain a polyolefin carbamidine macromolecular bactericide. The present invention has the following beneficial effects: 1) microorganisms in the environment or on the surface of an object can be quickly killed at a relatively low concentration; 2) the product is safe to use because the product does not contain chlorine or heavy metals, and an organic solvent is not included; 3) no harm to the human body is caused when the product stays on the skin surface; 4) unpolluted and safe production is achieved, and waste gas, waste water and waste residues are not produced; and 5) usage is convenient, and a satisfactory usage result can be achieved without requiring a complex compounding process.

Description

A kind of synthesis technique of macromolecule bactericidal-polyolefin carbazine

technical field

The invention relates to a synthesis process of a bactericide, in particular to a synthesis process of a macromolecule bactericide-polyolefin carbazine.

Background technique

In people's daily life, microorganisms such as bacteria and viruses are ubiquitous. Common bacteria include Escherichia coli, Staphylococcus, Streptococcus, Pseudomonas aeruginosa, Proteus, etc. , nose, and pharynx, and some live in the intestines and urethra. When the bacteria multiply to a certain extent, they will inevitably cause various diseases to the human body. In addition, there are also various pathogenic bacteria in food. Botulinum toxin, Salmonella, Staphylococcus aureus, Vibrio parahaemolyticus, Escherichia coli, etc. can cause food poisoning in varying degrees. Therefore, it is particularly necessary to develop a fungicide that can be used on the skin surface and in food packaging, so that it has long-acting broad-spectrum antibacterial properties and has the advantages of safe use and green production.

The common fungicides with similar functions and safe and non-toxic side effects on the market are mainly products containing guanidine groups such as polyhexamethylene monoguanidine and polyhexamethylene biguanide, which have changed the chlorine content of the original fungicides. Or the disadvantage of containing heavy metal ions, which greatly improves the safety of use. However, due to the limitations of the structure and molecular weight of the two products, the application scenarios and usage methods of these two products are different, resulting in limitations in use and limited popularization and application. Moreover, the synthesis of biguanides needs to be carried out in organic solvents, reducing the production safety.

Contents of the invention

The purpose of the present invention is to address the above-mentioned defects in the prior art, and to provide a synthesis process of macromolecular bactericidal polyolefin carbazine, which combines the monoguanide structure and the biguanide structure in the same macromolecule, and multifunctional block copolymerization form, a new fungicide was synthesized.

The present invention mentions a kind of synthetic technique of macromolecular sterilization-polyolefin carbazine, and its technical scheme is to comprise the following steps, by weight:

1) Add 2 to 9 parts of hexamethylenediamine and 2 to 8 parts of ethyl acrylate into the reactor, heat up while stirring, and when the temperature rises to 50°C, add 0.05 to 0.15 parts of initiator;

2) Continue to raise the temperature. When the temperature rises to 80-100°C, add 2-6 parts of dicyandiamide and 2-7 parts of guanidine hydrochloride that are evenly mixed, and drop 0.25-0.75 parts of hydrochloric acid as a catalyst while maintaining the temperature;

3) Continue to heat up, when the temperature rises to 110-120°C, stop heating, and react at constant temperature for 4-6 hours;

4) Continue to heat up, when the temperature rises to 130-140°C, stop heating, and react at constant temperature for 2-4 hours;

5) After the reaction is completed, add 18-20 parts of clear water dropwise to the reactor, and fully stir;

6) Adjust the pH value to between 6-9 with 0.5-1 part of disodium citrate;

7) The obtained solution is the polyolefin carbacilidine macromolecular fungicide of the present invention.

Preferably, the above-mentioned initiator is azobisisobutyronitrile.

Preferably, the synthesis technique of the macromolecule bactericidal-polyolefin carbazine mentioned in the present invention, the preferred technical scheme is: comprising the following steps, in parts by weight:

1) Add 5.8 parts of hexamethylenediamine and 5 parts of ethyl acrylate into the reaction kettle, raise the temperature while stirring, and when the temperature rises to 50°C, add 0.1 part of azobisisobutyronitrile as an initiator;

2) Continue to heat up. When the temperature rises to 80-100°C, add 4.2 parts of dicyandiamide and 4.78 parts of guanidine hydrochloride that are evenly mixed, and drop 0.5 parts of hydrochloric acid as a catalyst while maintaining the temperature;

5) After the reaction is complete, add 19 parts of clear water dropwise to the reactor and stir fully;

6) Adjust the pH value to between 6-9 with 0.8 part of disodium citrate;

Compared with the prior art, the beneficial effects of the present invention are specifically as follows:

On the one hand, during production, the shortcoming that the synthesis of biguanide needs to be carried out in an organic solvent before is abandoned, which not only improves the safety of production, but also increases the molecular weight of the product, and adopts a one-step synthesis method to synthesize biguanide and monoguanidine groups into The form of block exists in the macromolecule, so that the product has the advantages of both biguanide and monoguanide; on the other hand, due to the introduction of ethyl acrylate, the chain structure of the macromolecule can be extended, increasing the molecular weight of the product, and the greater the molecular weight , the higher the safety of staying on the skin surface, the green safety in the use process is realized; in addition, when the present invention is used, it can quickly kill the microorganisms in the environment or the surface of objects with a lower concentration; moreover, it is safe to use and the product Contains no chlorine, no heavy metals, and no organic solvents.

Description of drawings

Fig. 1 is embodiment of the present invention 1 in the bacteriostatic zone test comparison picture of Escherichia coli;

Fig. 2 is embodiment 2 in the bacteriostatic zone test contrast picture of Escherichia coli;

Fig. 3 is embodiment 3 in the bacteriostatic zone test comparison picture of Escherichia coli;

Fig. 4 is embodiment 1 in the antibacterial zone test contrast picture of Staphylococcus aureus;

Fig. 5 is the comparison picture of embodiment 2 in the antibacterial zone test of staphylococcus aureus;

Figure 6 is a comparison picture of the inhibition zone test of Staphylococcus aureus in Example 3.

Detailed ways

Preferred embodiments of the present invention are described below, and it should be understood that the preferred embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

Embodiment 1: polyolefin carbacilidine macromolecule fungicide, its preparation method is:

1) Add 580kg of hexamethylenediamine and 500kg of ethyl acrylate to the reactor, heat up under stirring, and when the temperature rises to 50°C, add 10kg of azobisisobutyronitrile as an initiator;

2) Continue to heat up. When the temperature rises to 80-100° C., add 420 kg of dicyandiamide and 478 kg of guanidine hydrochloride that are uniformly mixed, and drop 50 kg of hydrochloric acid as a catalyst while maintaining a constant temperature;

5) After the reaction is completed, add 1900kg of clear water dropwise to the reactor and stir fully;

6) adjust the pH value to between 6-9 with 80kg disodium citrate;

Embodiment 2: polyolefin carbazine macromolecule fungicide, its preparation method is:

1) Add 870kg of hexamethylenediamine and 250kg of ethyl acrylate to the reactor, heat up under stirring, and when the temperature rises to 50°C, add 5kg of azobisisobutyronitrile as an initiator;

2) Continue to heat up. When the temperature rises to 80-100° C., add 210 kg of dicyandiamide and 717 kg of guanidine hydrochloride that are uniformly mixed, and drop 25 kg of hydrochloric acid as a catalyst while maintaining a constant temperature;

6) adjust the pH value to between 6-9 with 100kg disodium citrate;

Embodiment 3: polyolefin carbacilidine macromolecule fungicide, its preparation method is:

1) Add 290kg of hexamethylenediamine and 750kg of ethyl acrylate to the reactor, heat up under stirring, and when the temperature rises to 50°C, add 15kg of azobisisobutyronitrile as an initiator;

2) Continue to heat up. When the temperature rises to 80-100° C., add 630 kg of dicyandiamide and 240 kg of guanidine hydrochloride that are uniformly mixed, and drop 75 kg of hydrochloric acid as a catalyst while maintaining a constant temperature;

5) After the reaction is completed, 1800kg of clear water is added dropwise to the reactor and fully stirred;

6) adjust the pH value to between 6-9 with 60kg disodium citrate;

The process of the present invention makes it contain monoguanidine group and biguanide group in the macromolecule at the same time, so as to achieve the following purposes: 1) it can quickly kill microorganisms on the environment or object surface with a lower concentration; 2) it is safe to use, The product does not contain chlorine, heavy metals, or organic solvents; 3) When it stays on the skin surface, it will not harm the human body; 4) The production is green and safe, and does not produce three wastes; 5) It is easy to use and does not require complex compounding process, which can achieve satisfactory results.

The present invention is through internal performance experiment, and process is as follows:

1) Bactericidal performance evaluation: Escherichia coli and Staphylococcus aureus were selected to test the bactericidal performance, and the bactericidal test was divided into two types: the inhibition zone test and the bactericidal rate test.

2) Inhibition zone test:

① Prepare 100 mL of liquid medium: 0.3 g of beef extract, 0.5 g of sodium chloride, 1.0 g of peptone, add water to 100 mL, adjust the pH to about 7.2 with 10% sodium hydroxide, and autoclave at 121 °C for 20 min. Divide 10mL of liquid culture medium into 4 bottles, and fill the remaining 60mL into another bottle.

② Solid medium 400mL: 1.2g beef extract, 2.0g sodium chloride, 6.0g agar powder, 4.0g peptone, adjust the pH to about 7.2 with 10% sodium hydroxide, and autoclave at 121°C for 20min. In the actual experiment, determine the configuration amount of solid medium and the number of petri dishes according to the number of samples to be tested.

③ One-time inoculation: wait for the temperature to drop to about 60°C, take out 2 bottles of liquid culture solution, add 1-2 loops of the strain to be tested, and put it in a 37°C heating shaker for 12-24 hours.

④Secondary inoculation: Pipette 1mL of the cultured bacteria solution into the other two bottles of liquid culture solution, and put them in a heating shaker for 2-4 hours.

⑤ Bacterial culture test inhibition zone: prepare a sterilized petri dish and mark it. Add 50 μL of the bacteria to be tested to each Petri dish. Pour an equivalent amount of solid culture medium into the Petri dish to completely cover it, shake it evenly, add small round paper pieces at each concentration after solidification, and drop 10 μL or 50 μL of fungicides of different concentrations on the paper piece, with sterilized pure medium in the middle. Water makes a blank. Put it in a 28-35°C incubator, turn it over after 2 hours, and incubate for 12-24 hours.

The test results are shown in Figures 1-6.

3) Sterilization rate test:

③ One-time inoculation: Wait for the temperature to drop to about 60°C, take out 2 bottles of liquid culture solution, add 1-2 loops of the strain to be tested, and put it in a heating shaker at 37°C for 12-24 hours.

⑤ Bacterial culture test sterilization rate: Prepare the sterilized petri dish and mark it. Add 50 μL of the bacteria to be tested and 1 mL of fungicides of different concentrations into the petri dish. Pour an appropriate amount of solid medium into the Petri dish to completely cover it, shake it well, put it into an incubator at 28-35°C after solidification, turn it over after 2 hours, and incubate for 12-24 hours.

⑥ Read the number of viable bacteria in the petri dish and calculate the sterilization rate.

The test results are shown in the table below:

The solubility of the samples of the three examples in water is very good, no foam is generated during use, the use is convenient, and the skin feels good. As can be seen from the results of the bacteriostatic zone test and the bactericidal rate test, the bactericidal effects of the three products are equivalent, and the product comprehensive evaluation of Example 1 is slightly better than that of Example 2 and Example 3, but it can be clearly seen that the three products Each product has an excellent bactericidal effect at the use concentration (1‰～1%).

The above descriptions are only some of the preferred embodiments of the present invention, and any person skilled in the art may modify the technical solutions described above or modify them into equivalent technical solutions. Therefore, corresponding simple modifications or equivalent transformations carried out according to the technical solution of the present invention belong to the protection scope of the present invention.

Claims

A kind of synthetic technique of macromolecular sterilization-polyolefin carbazine is characterized in that comprising the following steps, by weight:

1) Add 2 to 9 parts of hexamethylenediamine and 2 to 8 parts of ethyl acrylate into the reactor, heat up while stirring, and when the temperature rises to 50°C, add 0.05 to 0.15 parts of initiator;

2) Continue to raise the temperature. When the temperature rises to 80-100°C, add 2-6 parts of dicyandiamide and 2-7 parts of guanidine hydrochloride that are evenly mixed, and drop 0.25-0.75 parts of hydrochloric acid as a catalyst while maintaining the temperature;

3) Continue to heat up, when the temperature rises to 110-120°C, stop heating, and react at constant temperature for 4-6 hours;

4) Continue to heat up, when the temperature rises to 130-140°C, stop heating, and react at constant temperature for 2-4 hours;

5) After the reaction is completed, add 18-20 parts of clear water dropwise to the reactor, and fully stir;

6) Adjust the pH value to between 6-9 with 0.5-1 part of disodium citrate;

7) The obtained solution is the polyolefin carbacilidine macromolecular fungicide of the present invention.
According to claim 1, the macromolecule bactericidal-polyolefin carbacilidine synthesis process is characterized in that: the initiator is azobisisobutyronitrile.
The synthetic technique of macromolecular sterilization-polyolefin carbazine according to claim 2, is characterized in that: comprise the following steps, by weight:

1) Add 5.8 parts of hexamethylenediamine and 5 parts of ethyl acrylate into the reaction kettle, heat up under stirring, and when the temperature rises to 50°C, add 0.1 part of azobisisobutyronitrile as an initiator;

2) Continue to heat up. When the temperature rises to 80-100°C, add 4.2 parts of dicyandiamide and 4.78 parts of guanidine hydrochloride that are evenly mixed, and drop 0.5 parts of hydrochloric acid as a catalyst while maintaining the temperature;

3) Continue to heat up, when the temperature rises to 110-120°C, stop heating, and react at constant temperature for 4-6 hours;

4) Continue to heat up, when the temperature rises to 130-140°C, stop heating, and react at constant temperature for 2-4 hours;

5) After the reaction is complete, add 19 parts of clear water dropwise to the reactor and stir fully;

6) Adjust the pH value to between 6-9 with 0.8 part of disodium citrate;

7) The obtained solution is the polyolefin carbacilidine macromolecular fungicide of the present invention.