CN111621010B - Preparation method of polyhexamethylene guanidine hydrochloride - Google Patents
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Abstract
A preparation method of polyhexamethylene guanidine hydrochloride comprises the following steps: putting hexamethylenediamine and guanidine hydrochloride into a reactor, stirring and heating until the hexamethylenediamine and the guanidine hydrochloride are dissolved and fully mixed; raising the temperature to 155-165 ℃, and keeping the temperature for 0.5-1.5 hours; the temperature is raised to 165 to 175 ℃, and after the temperature is kept for 1.5 to 2.5 hours, a certain amount of deionized water is added into the reactor every 0.3 to 0.7 hour for 2 to 6 times in total; raising the temperature to 175-180 ℃, and preserving the temperature for 0-1 hour; stopping heating, and adding deionized water into the reactor to reduce the temperature in the reactor to 55-65 ℃; transferring the material to a dilution and decoloration kettle for decoloration and filtration; slowly adding dilute hydrochloric acid to adjust the pH value to 7-8, and observing the color of the solution; if the obtained solution is clear and colorless or light yellow, the obtained solution is the finished product of the polyhexamethylene guanidine hydrochloride; if the obtained solution is yellow or suspended matters exist in the solution, adding activated carbon for decoloring and filtering, and obtaining filtrate which is the finished product of the polyhexamethylene guanidine hydrochloride. The preparation method has the advantages of low cost and low energy consumption.
Description
Technical Field
The invention relates to the technical field of high molecular polymer preparation, and particularly relates to a preparation method of polyhexamethylene guanidine hydrochloride.
Background
The rapid development of modern industry has led to the continuous subdivision and expansion of the application field of industrial bactericides from the traditional industries of textile, daily chemical, paper making, petroleum products, coating and the like to the aspects of human life and living, such as food, medicine, fruits and vegetables, aquatic products, daily chemical detergents, household care products, swimming pools, water treatment and the like. Statistical data show that the market consumption of the global bactericide reaches 131 ten thousand tons in 2013, and is increased by 12.9% compared with 116 ten thousand tons in 2010. China is the market with the fastest growing demand of global bactericides, china has grown into the second largest market of global bactericides in 2013, the consumption reaches about 34 ten thousand tons, the demand of the bactericides in China in 2014-2018 is increased at the rate of 5.6% every year, and the market scale reaches 44.6 ten thousand tons in 2018.
The european union ban in 2014 led the european market to withdraw about three-quarters of 1000 bactericidal actives from the market. With the quit of the traditional bactericide triclosan (Tcs) and the like, a safer and more environment-friendly bactericide polyhexamethylene guanidine hydrochloride (PHMG) is gaining favor and popularizing by professionals and is widely applied to sterilization and mildew prevention of medicines, plant protection, industrial products and daily necessities. Many researchers at home and abroad have studied the disinfection and sterilization performance and toxicology of polyhexamethylene guanidine hydrochloride (PHMG), and a few researchers have reported the synthesis process, but the method has the defects of complex process, harsh conditions, difficult raw material source, difficult separation, purification, central control and detection, large production equipment investment, high production cost, unfavorable batch production and the like. For example:
patent WO99/54291 discloses a method for synthesizing polyhexamethylene guanidine hydrochloride, which comprises the steps of synthesizing a product in two steps, firstly synthesizing guanidine hydrochloride by using guanidine carbonate and ammonium chloride, secondly adding hexamethylenediamine and polyethylene glycol serving as a solvent in the reaction, heating and reacting in two stages, reacting for 3 hours at 150 ℃ in the first stage, reacting for 1 hour at 180 ℃, cooling the reaction solution after the reaction is finished, and after the reaction is finished, forming a solvent layer as an upper layer and forming a product as a lower layer. The unreacted raw materials and oligomers have higher solubility in the polyethylene glycol and are basically insoluble in the product, so a certain purification effect is achieved on the product. But the process still has defects in several aspects, namely, the cost is increased by using the solvent, and partial solvent is remained in the product by adopting a natural layering mode after cooling; secondly, the lower-layer product is condensed into hard solid after cooling, and the material is difficult to be discharged, stirred and dissolved.
Patent CN 1012459141A discloses a preparation method of polyhexamethylene guanidine hydrochloride solid, which is characterized in that guanidine hydrochloride and triethylene diamine are added into an initiator to be polymerized at high temperature, an ion separation exchange membrane separator is adopted after an initial polymer is made into an aqueous solution, polyhexamethylene guanidine hydrochloride is separated from the solution, the separated concentrated solution is dried into solid, and the solid is crushed to obtain the product. In the method, the preparation of the polyhexamethylene guanidine hydrochloride needs two raw materials of guanidine hydrochloride and triethylene diamine, and an initiator (choline chloride or azodiisoheptanonitrile) is also added, so that the cost is increased. In addition, the reaction temperature required in the whole process is required to reach 250 ℃ at most, and the energy consumption is large.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of polyhexamethylene guanidine hydrochloride, which does not need to add extra solvent or initiator and has lower reaction temperature, and compared with the prior art, the preparation method has the advantages of low cost and low energy consumption.
In order to solve the technical problem, the invention provides a preparation method of polyhexamethylene guanidine hydrochloride, which comprises the following steps:
step 1, putting hexamethylenediamine and guanidine hydrochloride into a reactor according to a certain proportion, stirring and heating until the hexamethylenediamine and the guanidine hydrochloride are completely dissolved and fully mixed;
step 2, raising the temperature in the reactor to 155-165 ℃, and preserving the heat for 0.5-1.5 hours;
step 3, heating the temperature in the reactor to 165-175 ℃, keeping the temperature for 1.5-2.5 hours, and adding a certain amount of deionized water into the reactor every 0.3-0.7 hour for 2-6 times in total;
step 4, raising the temperature in the reactor to 175-180 ℃, and preserving the temperature for 0-1 hour;
step 5, stopping heating the reactor, and adding a certain amount of deionized water into the reactor to reduce the temperature in the reactor to 55-65 ℃;
step 6, transferring the materials in the reactor to a dilution decoloring kettle for decoloring and filtering;
step 7, slowly adding dilute hydrochloric acid to adjust the pH value to 7-8, and observing the color of the solution; if the obtained solution is clear and colorless or light yellow, the obtained solution is the finished product of the polyhexamethylene guanidine hydrochloride; if the obtained solution is yellow or suspended matters exist in the solution, adding activated carbon for decoloring and filtering, and obtaining filtrate which is the finished product of the polyhexamethylene guanidine hydrochloride.
In the preparation method of polyhexamethylene guanidine hydrochloride provided by the invention, the molar ratio of the hexamethylene diamine to the guanidine hydrochloride in the step 1 is 1.05.
In the preparation method of the polyhexamethylene guanidine hydrochloride, the temperature in the reactor in the step 2 is increased to 160 ℃, and the temperature is kept for 1 hour.
In the preparation method of polyhexamethylene guanidine hydrochloride provided by the invention, the temperature in the reactor in the step 3 is raised to 170 ℃, deionized water with the mass being 1.2% of the total mass of the hexamethylene diamine and the guanidine hydrochloride added in the step 1 is added into the reactor every 0.5 hour after heat preservation is carried out for 2 hours, and the addition is carried out for 4 times in total.
In the preparation method of the polyhexamethylene guanidine hydrochloride, the temperature in the reactor in the step 4 is increased to 180 ℃, and the temperature is kept for 0.5 hour.
In the preparation method of polyhexamethylene guanidine hydrochloride provided by the invention, in the step 5, the reactor stops heating, and a certain amount of deionized water is added into the reactor, so that the temperature in the reactor is reduced to 60 ℃.
In the preparation method of polyhexamethylene guanidine hydrochloride provided by the invention, the mass of the deionized water added in the step 5 is equal to the total mass of the hexamethylene diamine and the guanidine hydrochloride added in the step 1.
In the method for preparing polyhexamethylene guanidine hydrochloride provided by the invention, the dilute hydrochloric acid used in the step 7 is hydrochloric acid with the mass concentration of 2%.
In the method for preparing polyhexamethylene guanidine hydrochloride provided by the invention, in the step 1, after the hexamethylenediamine and the guanidine hydrochloride are put into the reactor and completely dissolved, nitrogen is introduced into the reactor.
In the preparation method of the polyhexamethylene guanidine hydrochloride provided by the invention, the reactor is connected with a tail gas absorption device.
Compared with the prior art, the preparation method of the polyhexamethylene guanidine hydrochloride has the following beneficial effects:
1. the raw materials and auxiliary materials required by the preparation method are hexamethylenediamine, guanidine hydrochloride, deionized water and dilute hydrochloric acid, and compared with the prior art, the preparation method has the advantages of easiness in obtaining the raw materials and auxiliary materials and lower cost of the raw materials and auxiliary materials.
2. The preparation method has the advantages that the highest temperature in the reactor in the whole process is 180 ℃, which is far lower than the reaction temperature required in the prior art, the energy consumed in the preparation process is greatly saved, and the volatilization of the diamine and the coking and denaturation of materials in the reactor can be avoided.
In a word, the preparation method overcomes the defects that the conventional polyhexamethylene guanidine hydrochloride synthesis process is complex, the flammable and explosive safety production is difficult to guarantee, the equipment is more and expensive, the raw materials and auxiliary materials are more, rare and expensive, the equipment is expensive and the detection is time-consuming in the production process quality, and the like, so that the polyhexamethylene guanidine hydrochloride synthesis process is simple and easy to implement, the safety is guaranteed, the yield is high, the product quality is stable and reliable, the time consumption is short, the raw materials and auxiliary materials are few, the production cost is greatly reduced, and the method has good economic benefit and social benefit.
Detailed Description
The invention provides a preparation method of polyhexamethylene guanidine hydrochloride, which comprises the following steps:
step 1, putting hexamethylenediamine and guanidine hydrochloride into a reactor according to a certain proportion, stirring and heating until the hexamethylenediamine and the guanidine hydrochloride are completely dissolved and fully mixed;
step 2, raising the temperature in the reactor to 155-165 ℃, and preserving the heat for 0.5-1.5 hours;
step 3, raising the temperature in the reactor to 165-175 ℃, keeping the temperature for 1.5-2.5 hours, adding a certain amount of deionized water into the reactor at intervals of 0.3-0.7 hour after keeping the temperature for 2 hours, and adding the deionized water into the reactor at intervals of 0.5 hour after keeping the temperature for 2 hours, wherein the temperature is raised to 170 ℃ for 2-6 times;
step 4, raising the temperature in the reactor to 175-180 ℃, and preserving the temperature for 0-1 hour;
step 5, stopping heating the reactor, and adding a certain amount of deionized water into the reactor to reduce the temperature in the reactor to 55-65 ℃;
6, transferring the materials in the reactor to a dilution and decoloration kettle for decoloration and filtration;
step 7, slowly adding dilute hydrochloric acid to adjust the pH value to 7-8, and observing the color of the solution; if the obtained solution is clear and colorless or light yellow, the obtained solution is the finished product of the polyhexamethylene guanidine hydrochloride; if the obtained solution is yellow or suspended matters exist in the solution, adding activated carbon for decoloring and filtering, and obtaining filtrate which is the finished product of the polyhexamethylene guanidine hydrochloride.
The molar ratio of hexamethylenediamine to guanidine hydrochloride in step 1 is 1.05.
In the step 1, nitrogen is introduced into the reactor after the hexamethylene diamine and the guanidine hydrochloride enter the reactor and are completely dissolved.
And in the step 2, the temperature in the reactor is increased to 160 ℃, and the temperature is kept for 1 hour.
And (3) raising the temperature in the reactor to 170 ℃ in the step 3, keeping the temperature for 2 hours, and adding deionized water with the mass being 1.2% of the total mass of the hexamethylene diamine and the guanidine hydrochloride added in the step 1 into the reactor every 0.5 hour for 4 times.
And in the step 4, the temperature in the reactor is increased to 180 ℃, and the temperature is kept for 0.5 hour.
And in the step 5, stopping heating the reactor, and adding a certain amount of deionized water into the reactor to reduce the temperature in the reactor to 60 ℃.
The mass of the deionized water added in the step 5 is equal to the total mass of the hexamethylene diamine and the guanidine hydrochloride added in the step 1.
The dilute hydrochloric acid used in the step 7 is hydrochloric acid with a mass concentration of 2%.
The reactor is connected with a tail gas absorption device, and the reactor can be an electric heating reaction kettle with a reflux condenser.
The whole preparation process can be divided into two blocks. The first block is a copolymerization process comprising steps 1 through 5. The second block is a neutralization purification process, comprising steps 6 to 7.
In the copolymerization reaction process, the process of synthesizing polyhexamethylene guanidine hydrochloride by one step from hexamethylene diamine and guanidine hydrochloride is completed by controlling the feeding proportion, the temperature and the time and adding a proper amount of deionized water at a proper time. Wherein the reaction process of the hexamethylene diamine and the guanidine hydrochloride is as follows:
the ammonia gas produced in the process can be collected by a tail gas absorption device communicated with the reactor, so that the environmental pollution can not be caused. Because the reactor is filled with nitrogen for atmosphere protection, the reaction process of the hexamethylene diamine and the guanidine hydrochloride is stable, and basically no potential safety hazard exists. In the whole reaction process, the stirring is continued, so that the time of copolymerization reaction is greatly shortened. The whole copolymerization reaction is completely and thoroughly carried out under the condition of fully stirring, and the yield can reach 90 percent.
The neutralization purification process is to neutralize the small amount of NH remaining in the copolymerization reaction product 3 . In the process, hydrochloric acid with the mass concentration of 2% is fully stirred and slowly added, then the color of the solution is observed, if the obtained solution is yellow or suspended substances exist in the solution, activated carbon needs to be added for decoloring and filtering, and finally a pure polyhexamethylene guanidine hydrochloride finished product is obtained.
The specific implementation mode is as follows:
the invention is further illustrated by the following examples, but the scope of the invention as claimed is not limited to the examples.
Example 1
Putting hexamethylenediamine and guanidine hydrochloride into a reactor according to the molar ratio of 1.05; heating the reactor to raise the temperature in the reactor to 155 ℃, and keeping the temperature for 1.5 hours; heating the reactor continuously to raise the temperature in the reactor to 165 ℃, keeping the temperature for 2.5 hours, and adding a certain amount of deionized water into the reactor every 0.7 hour for 6 times in total; continuously heating the reactor to raise the temperature in the reactor to 175 ℃, and keeping the temperature for 1 hour; stopping heating the reactor, and adding deionized water with the mass equivalent to the total mass of the hexamethylene diamine and the guanidine hydrochloride into the reactor to reduce the temperature in the reactor to 65 ℃; transferring the materials in the reactor to a dilution and decoloration kettle for decoloration and filtration; slowly adding dilute hydrochloric acid to adjust the pH value to 7-8, and observing the color of the solution; if the obtained solution is clear and colorless or light yellow, the obtained solution is polyhexamethylene guanidine hydrochloride finished product 1#; and if the obtained solution is yellow or suspended matters exist in the solution, adding activated carbon for decolorization and filtration to obtain a filtrate which is the finished product of polyhexamethylene guanidine hydrochloride No. 1.
Example 2
Putting hexamethylenediamine and guanidine hydrochloride into a reactor according to the molar ratio of 1.05; heating the reactor to raise the temperature in the reactor to 160 deg.c and maintaining for 1 hr; heating the reactor continuously to ensure that the temperature in the reactor rises to 170 ℃, and adding deionized water with the mass being 1.2 percent of the total mass of the hexamethylene diamine and the guanidine hydrochloride added in the step 1 into the reactor every 0.5 hour after keeping the temperature for 2 hours for 4 times in total; continuously heating the reactor to raise the temperature in the reactor to 180 ℃, and keeping the temperature for 0.5 hour; stopping heating the reactor, and adding deionized water with the mass equivalent to the total mass of the hexamethylene diamine and the guanidine hydrochloride into the reactor to reduce the temperature in the reactor to 60 ℃; transferring the materials in the reactor to a dilution and decoloration kettle for decoloration and filtration; slowly adding dilute hydrochloric acid to adjust the pH value to 7-8, and observing the color of the solution; if the obtained solution is clear and colorless or light yellow, the obtained solution is the finished product No. 2 of the polyhexamethylene guanidine hydrochloride; and if the obtained solution is yellow or suspended matters exist in the solution, adding activated carbon for decolorization and filtration, wherein the obtained filtrate is the finished product No. 2 of the polyhexamethylene guanidine hydrochloride.
Example 3
Putting hexamethylenediamine and guanidine hydrochloride into a reactor according to the molar ratio of 1.05; heating the reactor to raise the temperature in the reactor to 165 ℃ and keeping the temperature for 0.5 hour; heating the reactor continuously to raise the temperature in the reactor to 175 ℃, keeping the temperature for 1.5 hours, and adding a certain amount of deionized water into the reactor every 0.3 hour for 2 times; continuously heating the reactor to ensure that the temperature in the reactor is increased to 180 ℃, and preserving the heat for 0.5 hour; stopping heating the reactor, and adding deionized water with the mass equivalent to the total mass of the hexamethylene diamine and the guanidine hydrochloride into the reactor to reduce the temperature in the reactor to 55 ℃; transferring the materials in the reactor to a dilution and decoloration kettle for decoloration and filtration; slowly adding dilute hydrochloric acid to adjust the pH value to 7-8, and observing the color of the solution; if the obtained solution is clear and colorless or light yellow, the obtained solution is polyhexamethylene guanidine hydrochloride finished product No. 3; and if the obtained solution is yellow or suspended matters exist in the solution, adding activated carbon for decolorization and filtration to obtain a filtrate which is the finished product No. 3 of the polyhexamethylene guanidine hydrochloride.
Performance detection
Finished products 1#, 2#, and 3# of polyhexamethylene guanidine hydrochloride prepared in examples 1, 2, and 3, respectively, were diluted into polyhexamethylene guanidine hydrochloride samples with a mass concentration of 0.2%, and then sent to the disinfection detection center of military medical academy of liberty military science and the prevention and control center of Guangdong province disease, respectively, for detection.
The detection result of the disinfection detection center of the military medical science institute of the people's liberation army in China is as follows: (1) the content is stable; (2) the average killing log value of staphylococcus aureus is more than 3.00, the average killing log value of pseudomonas aeruginosa is more than 3.00, and the average killing log value of candida albicans is more than 3.00; (3) the average killing logarithm value of natural bacteria on the surface of the skin is more than 1.00; (4) the eye irritation test is non-irritant, and the irritation reaction intensity of the vagina mucosa irritation test is extremely light.
The detection results of the centers for disease prevention and control in Guangdong province are as follows: (1) the acute oral toxicity test is of actual non-toxic grade; (2) one complete skin irritation test is non-irritating; (3) the one-time damaged skin irritation test is non-irritant; (4) the micronucleus test of mouse marrow addicting to multiple staining red blood cells does not find that the test sample has mutagenesis effect on somatic cells.
This indicates that the polyhexamethylene guanidine hydrochloride with qualified indexes can be prepared by the preparation method provided by the invention.
While embodiments of the present invention have been described, the present invention is not limited to the above embodiments, which are illustrative, rather than restrictive, and many modifications may be made by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. The preparation method of polyhexamethylene guanidine hydrochloride is characterized by comprising the following steps:
step 1, putting hexamethylenediamine and guanidine hydrochloride into a reactor according to a certain proportion, stirring and heating until the hexamethylenediamine and the guanidine hydrochloride are completely dissolved and fully mixed, wherein the reactor is an electric heating reaction kettle with a reflux condenser;
step 2, raising the temperature in the reactor to 155-165 ℃, and preserving the heat for 0.5-1.5 hours;
step 3, heating the temperature in the reactor to 165-175 ℃, keeping the temperature for 1.5-2.5 hours, and adding a certain amount of deionized water into the reactor every 0.3-0.7 hour for 2-6 times; the mass of the deionized water added in each step 3 is equal to 1.2% of the total mass of the hexamethylene diamine and the guanidine hydrochloride added in the step 1;
step 4, raising the temperature in the reactor to 175-180 ℃, and preserving the temperature for 0-1 hour;
step 5, stopping heating the reactor, and adding a certain amount of deionized water into the reactor to reduce the temperature in the reactor to 55-65 ℃; the mass of the deionized water added in the step 5 is equal to the total mass of the hexamethylene diamine and the guanidine hydrochloride added in the step 1;
6, transferring the materials in the reactor to a dilution and decoloration kettle for decoloration and filtration;
step 7, slowly adding dilute hydrochloric acid to adjust the pH value to 7-8, and observing the color of the solution; if the obtained solution is clear and colorless or light yellow, the obtained solution is the finished product of the polyhexamethylene guanidine hydrochloride; if the obtained solution is yellow or suspended matters exist in the solution, adding activated carbon for decoloring and filtering, and obtaining filtrate which is the finished product of the polyhexamethylene guanidine hydrochloride.
2. The method for preparing polyhexamethylene guanidine hydrochloride according to claim 1, wherein the molar ratio of hexamethylenediamine to guanidine hydrochloride in step 1 is 1.05.
3. The method for preparing polyhexamethylene guanidine hydrochloride according to claim 1, wherein the temperature in the reactor in the step 2 is raised to 160 ℃ and maintained for 1 hour.
4. The method for preparing polyhexamethylene guanidine hydrochloride according to claim 1, wherein the temperature in the reactor in the step 3 is raised to 170 ℃, and deionized water is added to the reactor for 4 times every 0.5 hour after 2 hours of heat preservation.
5. The method for preparing polyhexamethylene guanidine hydrochloride according to claim 1, wherein the temperature in the reactor in the step 4 is increased to 180 ℃ and the temperature is maintained for 0.5 hour.
6. The method of claim 1, wherein the heating of the reactor is stopped in the step 5, and an amount of deionized water is added to the reactor so that the temperature in the reactor is reduced to 60 ℃.
7. The method for preparing polyhexamethylene guanidine hydrochloride according to claim 1, wherein the dilute hydrochloric acid used in the step 7 is 2% by mass hydrochloric acid.
8. The method of claim 1, wherein in step 1, after the hexamethylenediamine and the guanidine hydrochloride are fed into the reactor and completely dissolved, nitrogen gas is introduced into the reactor.
9. The method of claim 1, wherein the reactor is connected to a tail gas absorption unit.
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