CN103931627B - A kind of organic blowing agent composite synergistic fungicidal preservative - Google Patents

Abstract

The invention relates to a compound synergistic bactericidal preservative for organic foaming agents, which consists of 2-methylisothiazolinone and/or 1,2 benzisothiazolinone (BIT) and/or dichlorovinyl salicyl Amide, sodium pyrithione and/or sodium hydroxymethylglycinate, sodium thiram and/or o-phenylphenol, phenethyl alcohol and/or benzyl alcohol, regulator, solvent and water. The present invention uses a variety of different bactericidal, antiseptic and bactericidal agents that are complementary to each other to compound. It works well in use.

Description

A compound synergistic bactericidal preservative for organic foaming agent

technical field

The invention belongs to the technical field of preparation of chemical antiseptic and antifungal agents, and relates to a compound synergistic bactericidal antiseptic for organic foaming agents and a preparation method thereof.

Background technique

In the process of producing high-performance foam concrete, foaming agent is an essential substance. High-quality foaming agents are required to have the advantages of low cost, easy availability of raw materials, high foaming power and long foam stabilization time, especially the foam stabilization time must meet the actual use requirements.

Animal protein and plant protein foaming agents have entered the field of building foam in large quantities so far. The outstanding advantage they have in common is that the foam is particularly stable and can not be defoamed for a long time (the time for complete defoaming is mostly longer than 24 hours), which is unmatched by other types of foaming agents. Therefore, the current domestic foaming agent basically takes the protein foaming agent as the development direction, such as a kind of composite animal and plant protein foaming agent disclosed in the patent text of Chinese Patent No. Powder, soybean meal, wine tank, sodium fatty alcohol polyoxyethylene ether sulfate, sodium dodecylbenzenesulfonate, tea saponin and other substances. However, for foaming agents based on animal and plant proteins, because they are rich in nutrients (protein and sugar), they are easily contaminated and deteriorated by microorganisms, causing problems such as discoloration, flatulence, odor, and precipitation, and even lose practical value in severe cases. , and the bad smell of foaming agent containing protein is very big, almost can't be used, also brings environmental pollution problem thus. In addition, users sometimes add natural surfactants such as soybean lecithin, tea saponin, papermaking black liquor, and sugar residue to the formula in order to improve the foaming ability, which further increases the difficulty of anti-corrosion of the foaming agent. In addition, since protein-containing raw materials are highly susceptible to bacterial contamination during storage, microorganisms are introduced during the production of foaming agents, which makes the consumption of conventional bactericidal preservatives much higher, and it is very difficult to preserve them.

There are many kinds of known bactericidal preservatives at present, but there is no efficient and safe bactericidal preservative that is specially used for organic foaming agents containing a large amount of protein and carbohydrates on the market, and generally all use common paint bactericidal preservatives instead. The commonly used single type of bactericidal preservative has very limited antiseptic and bactericidal ability and low efficiency for foaming agents containing a large amount of protein and sugar, which can be judged from its minimum bactericidal concentration (MIC) value, and the summer storage period is only ten It will deteriorate and stink in about a day, and a large number of corruption cases have appeared. Obviously, for organic foaming agents with high concentrations of protein and sugar, a single preservative cannot achieve the desired antiseptic effect at all.

Contents of the invention

The object of the present invention is to solve the problems existing in the prior art, and to provide a compound synergistic bactericidal preservative for organic foaming agents with theoretical basis, reasonable formula, high cost performance and good bactericidal and antiseptic effect.

The active ingredient of the compound synergistic bactericidal preservative for organic foaming agent provided for realizing the purpose of the above invention is composed of the following material raw materials in percentage by weight:

The remainder is water;

The antiseptic and bactericide A is selected from one or more of the following substances: 2-methylisothiazolinone, 1,2 benzisothiazolinone (BIT), dichlorovinyl salicylamide, Phenols and their salts; the antiseptic and bactericide B is selected from one or more of the following substances: sodium pyrithione and sodium hydroxymethylglycinate; the antiseptic and bactericide C is selected from the following substances One or more of: Sodium methazine, ortho-phenylphenol; The antiseptic and bactericide D is selected from one or more of the following substances: phenylethyl alcohol, benzyl alcohol; The solvent is the following substances One or more of: 1,2 propylene glycol, polyethylene glycol, dipropylene glycol, ethylene glycol; the regulator is an alkali metal hydroxide.

The preferred weight portion proportioning scope of the material raw material of compound synergistic bactericidal preservative for organic blowing agent of the present invention is:

The balance is water.

The further technical solution of the present invention is that the antiseptic and bactericide A is 1,2 benzisothiazolinone (BIT), the antiseptic and bactericide B is sodium hydroxymethylglycinate, and the antiseptic and bactericide The agent C is o-phenylphenol, and the antiseptic and bactericide D is phenylethyl alcohol; the solvent is polyethylene glycol, dipropylene glycol; the regulator is sodium hydroxide or potassium hydroxide, wherein hydrogen is preferably sodium oxide.

The method for preparing the composite synergistic bactericidal preservative for the organic foaming agent comprises the following processing steps:

1. Stir and heat the solvent to 25°C to 30°C, add antiseptic and fungicide A and stir evenly, then add a regulator accounting for 70% to 75% of the weight of the modifier component to completely dissolve the antiseptic and fungicide A;

2. Add antiseptic and fungicide C and antiseptic and fungicide B to deionized water under stirring, and gradually add the remaining regulator to dissolve completely;

3. Stir and mix the solution prepared in step 1 and step 2, add antiseptic and bactericide D and stir evenly to obtain a compound synergistic antiseptic antiseptic product for organic foaming agent.

The beneficial effects of the present invention are as follows.

1. The present invention adopts the combination of different bactericidal preservatives with complementary bactericidal spectrums to make them exert the best bactericidal and antiseptic effects, and realize complementary advantages according to the antibacterial spectrums of related preservatives. The formation of scientific compatibility can take into account both rapid sterilization and long-term Composite preservative with better adaptability of antibacterial efficacy. In the formulation of the present invention, antiseptic bactericide C (especially o-phenylphenol) is very active, and has broad-spectrum antiseptic, antiseptic and mildew-proof capabilities, and its water solubility and relatively comprehensive antiseptic and antiseptic capabilities are utilized here; antiseptic Bactericide A (benzisothiazolinone, dichlorovinyl salicylamide, phenols and their salts) is mainly used to kill bacteria, and has excellent antiseptic and bactericidal ability under slightly alkaline conditions; (especially sodium hydroxymethylglycinate), as an excellent low-toxic preservative, has been widely used in mildew and sterilization of starch, paint, textile size, etc. The mildew performance and the synergistic effect with other components improve the safety of the product; antiseptic and fungicide D (phenylethyl alcohol or benzyl alcohol, etc.) The scope of protection (space) increases; The solvent (polyethylene glycol or propylene glycol) used in the present invention has a foam-stabilizing effect on the organic foaming agent containing protein, can prolong the duration of the bubbles, and is also a good solvent for preservatives.

2. The use of the compound synergistic bactericidal preservative for the organic foaming agent can reduce the production cost of the foaming agent, and the amount added is far less than that of adding phenol or sodium benzoate bactericidal preservatives alone in the past.

3. The present invention scientifically combines the anti-corrosion inside the foaming agent system in the container with the anti-corrosion in the space above the container to provide all-round anti-corrosion protection for the foaming agent material, effectively preventing microorganisms from developing drug resistance to preservatives, anti-corrosion safety and Comprehensive protection is high, because the growth of microorganisms often starts on the top of the container and on the surface, especially the reproduction and growth of mold starts from the surface.

4. The antiseptic system of the present invention has good compatibility with the foaming agent, especially at high temperatures (such as up to 80-100°C), it can be added directly, because the selected bactericidal preservatives have high temperature resistance, which is in the usual Rarely seen in preservative applications. Direct high-temperature addition is easy to disperse evenly, dissolves faster, and has higher sterilization efficiency. At the same time, it reduces cooling time and saves energy.

5. The pH value (pH value) of the composite synergistic bactericidal preservative for the organic foaming agent of the present invention has a relatively large application range, especially under neutral to alkaline conditions, the effect is the best.

Six, the production method of compound synergistic bactericidal preservative for organic foaming agent of the present invention is simple, and production cost is low, is easy to realize scale production.

detailed description

Example 1

The preparation method of an embodiment of the compound synergistic bactericidal preservative for organic foaming agent of the present invention comprises the following processing steps:

1. Weigh 10.2 kg of BIT (12 kg of 85% BIT), disperse it in 35 kg of polyethylene glycol 400, stir and heat to 30°C, add 4.5 kg of 45% sodium hydroxide to dissolve the BIT, the pH is 9～ 10;

2. Add 4 kg of o-phenylphenol and 16 kg of 50% sodium hydroxymethylglycinate to 10 kg of deionized water under stirring, and gradually add 1.6 kg of 45% aqueous sodium hydroxide solution to completely dissolve it;

3. Stir and mix the solution of step 2 and step 1, add 7 kg of benzyl alcohol, add deionized water to a total of 100 kg and stir evenly (adjust the pH value with very little sodium hydroxide or hydrochloric acid if necessary), to obtain the present invention A compound synergistic bactericidal preservative for an organic foaming agent, the pH value of the compound synergistic bactericidal preservative is 9.2.

According to the compound synergistic bactericidal preservative for organic foaming agent prepared according to the above steps, its formula combination is determined through strict microbial tests, mainly the mutual synergistic test research, and, through laboratory microbial challenge tests and in Guangdong Nearly 100 times of practical application verification in Dongguan and other places, the anti-corrosion effect is very satisfactory, and the purpose of the invention has been achieved.

The synergy experiment between the preservative composition of the present invention with the mixed microorganisms extracted from the production site environment and the deteriorated organic foaming agent can illustrate the problem better. Mixed bacteria were obtained by microbiological separation of deteriorated organic foaming agents. These deteriorated organic foaming agents came from North China, East China and South China, which mainly reflected that the isolated mixed bacteria were widely representative. These microorganisms are mainly Pseudomonas and Bacillus aerogenes, mixed with yeast and mold. Use tryptic soybean broth agar as the nutrient medium and cultivate for 48 hours. The minimum bactericidal concentrations of the three preservatives to the mixed bacteria on the production site are respectively: Q _A =15 (ppm), Q _B =25 (ppm), Q _C =10 (ppm). When the three kinds are used in combination, according to the synergistic coefficient (SI) summarized by FCKU11, when SI>1, the combined use of several preservatives will not only fail to synergize, but also antagonize each other, which means it is counterproductive and increases toxicity. , reducing the effect of preservatives, resulting in waste and damage to the environment; when SI=1, it only has a superimposed effect; only when SI<1, there is a synergistic effect, and the greater the difference with 1, The stronger the synergistic effect, this is also the goal pursued in theory. SI _{= Qa} /QA+ _Qb /QB _{+ Qc} /Qc _. Q _A , Q _B , and Q _C are the minimum inhibitory concentrations of preservative A, preservative B, and preservative C to microorganisms when they are used alone. Screen the appropriate combination to achieve the purpose of inhibiting the mixed microorganisms taken from the production site, then there are the results in Table 1:

Table 1: The synergistic killing effect of the combined use of three preservatives on the mixed bacteria on site

This is part of a synergy experiment. The combination with the best effect in theory is: benzisothiazolinone: sodium hydroxymethylglycinate: o-phenylphenol=6:5:1.5, considering the price, toxicological safety and space protection characteristics (phenylethanol is space Bactericide) obtained the proportional relationship between the preservative composition of the present invention.

The compound synergistic bactericidal preservative that embodiment 1 obtains and use phenol or sodium benzoate alone, or BIT, or chloromethylisothiazolinone and methylisothiazolinone mixture (Kasone) are carried out normal temperature anticorrosion contrast test, track The deterioration of organic foaming agent (Table 2). The test was carried out at a constant temperature of 30°C. When the sample deteriorated, a large amount of gas was generated, causing the package to bulge and deform.

It is found that when the compound synergistic bactericidal preservative of the present invention is added in an amount of 0.2% of the quality of the foaming agent, the shelf life of the foaming agent has exceeded 180 days; when the amount added is 0.3%, it will not deteriorate for more than one year. Under the same conditions, when other preservatives are used, the shelf life of the foaming agent does not exceed 50 days, and the shortest is 10 days. It can be seen that the bactericidal and antiseptic effect of the compound synergistic bactericidal preservative of the present invention is very ideal, far exceeding the bactericidal and antiseptic ability of commonly used preservatives.

Table 2: Comparison of the effectiveness of the synergistic composite preservative of the present invention and other preservatives

Example 2

The preparation method of another embodiment of the composite synergistic bactericidal preservative for the organic foaming agent of the present invention comprises the following process steps:

1. Weigh 12 kg of BIT (14.1 kg of 85% BIT), disperse it in 40 kg of 1,2-propylene glycol, stir and heat to 30°C, add 5.5 kg of 45% sodium hydroxide to dissolve BIT, and the pH is 9 ~10;

2. Add 5 kg of o-phenylphenol and 14 kg of 50% sodium hydroxymethylglycinate to 10 kg of deionized water under stirring, and gradually add 1.9 kg of 45% sodium hydroxide aqueous solution to completely dissolve it;

3. Stir and mix the solution of step 2 and step 1, add 8 kg of benzyl alcohol, add deionized water to a total of 100 kg and stir evenly (adjust the pH value with very little sodium hydroxide or hydrochloric acid if necessary), to obtain the present invention Another compound synergistic bactericidal preservative for organic foaming agents, the pH value of the compound preservative is 9.5.

The composite synergistic bactericidal preservative obtained in Example 2 is used for the SH-126 high-efficiency composite magnesite organic foaming agent product produced in Dongguan, and the bacterial classification added therein is mixed bacteria, including Pseudomonas aeruginosa, Grape aureus Coccus, Escherichia coli, Candida albicans, Aspergillus niger, Penicillium fungus, Trichoderma viride, cultured at a constant temperature of 37°C for 28 days, regularly inspecting the growth and reproduction of bacteria and molds, and giving the challenge test results after 28 days (table 3). Test concentration: preservative added 0.3%. In addition, the practical application also shows that the addition of 0.3% can make the organic foaming agent keep for 4 months without deterioration under the condition of high temperature and high humidity.

Table 3 Composite synergistic bactericidal preservative of the present invention 0.3% is to the challenge test of mixed microorganism

Claims (3)

1. an organic blowing agent composite synergistic fungicidal preservative, it is characterised in that the effective constituent of this composite synergistic fungicidal preservative is made up of the raw material of substance of following weight per-cent:

Described anticorrosion and bactericidal agent A is 1,2 BITs; Described anticorrosion and bactericidal agent B is Sodium hydroxymethyl glycinate; Described anticorrosion and bactericidal agent C is orthoxenol; Described anticorrosion and bactericidal agent D is phenylcarbinol; Described solvent is polyoxyethylene glycol; Described conditioning agent is sodium hydroxide.

2. an organic blowing agent composite synergistic fungicidal preservative, it is characterised in that the effective constituent of this composite synergistic fungicidal preservative is made up of the raw material of substance of following weight per-cent:

Described anticorrosion and bactericidal agent A is 1,2 BITs; Described anticorrosion and bactericidal agent B is Sodium hydroxymethyl glycinate; Described anticorrosion and bactericidal agent C is orthoxenol; Described anticorrosion and bactericidal agent D is phenylcarbinol; Described solvent is 1,2-propylene glycol; Described conditioning agent is sodium hydroxide.

3. one kind for the preparation of the method for organic blowing agent described in claim 1 or 2 with composite synergistic fungicidal preservative, it is characterised in that comprises following processing step:

Step 1: by stirring solvent and be heated to 30 DEG C, add anticorrosion and bactericidal agent A and stir evenly, the conditioning agent adding part value subsequently makes anticorrosion and bactericidal agent A dissolve completely, and the weight being added conditioning agent accounts for the 70%��75% of conditioning agent component weight value;

Step 2: agitating deionized water, adds anticorrosion and bactericidal agent C and anticorrosion and bactericidal agent B wherein, and the conditioning agent adding surplus gradually makes it dissolve completely;

Step 3: by the solution stirring mixing obtained through step 1 and step 2, add anticorrosion and bactericidal agent D and stir evenly, obtain organic blowing agent composite synergistic fungicidal preservative product.