阅读说明：本技术 一种过氧化氢专用表面活性剂及其复合物 (Special surfactant for hydrogen peroxide and compound thereof ) 是由 王洪梅 康刚 张继甫 张艺 张豫红 于 2021-10-15 设计创作，主要内容包括：本发明属于过氧化氢消毒剂领域,公开一种过氧化氢专用表面活性剂及其复合物,所述复合物包括如下重量百分比的原料：80～95％Gemini-季铵盐表面活性剂,1％～5％PH缓冲剂,1％～5％稳定剂。本发明选用Gemini阳离子双季铵盐表面活性剂,具有稳定的结构和表面活性,可以与高浓度过氧化物能热稳定共存,通过与缓冲剂和稳定剂复配,使溶液pH值维持在3-6,过氧化氢含量下降率低于15％,可有效提高过氧化氢含量的稳定性,通过提高过氧化氢的稳定性,可解决过氧化氢包装运输中的胀瓶问题。同时,在提高过氧化氢稳定性的前提可以增强过氧化氢的杀菌效果,对于过氧化氢在消毒剂方面的应用具有重要的意义。(The invention belongs to the field of hydrogen peroxide disinfectants, and discloses a special surface active agent for hydrogen peroxide and a compound thereof, wherein the compound comprises the following raw materials in percentage by weight: 80-95% of Gemini-quaternary ammonium salt surfactant, 1-5% of PH buffering agent and 1-5% of stabilizer. The Gemini cationic diquaternary ammonium salt surfactant has stable structure and surface activity, can stably coexist with high-concentration peroxide under the condition of heat, maintains the pH value of a solution to be 3-6 by compounding with the buffering agent and the stabilizing agent, has the hydrogen peroxide content reduction rate lower than 15 percent, can effectively improve the stability of the hydrogen peroxide content, and can solve the problem of bottle expansion in hydrogen peroxide packaging and transportation by improving the stability of the hydrogen peroxide. Meanwhile, the sterilization effect of the hydrogen peroxide can be enhanced on the premise of improving the stability of the hydrogen peroxide, and the method has important significance for the application of the hydrogen peroxide in the aspect of disinfectants.)

1. A surface active agent special for hydrogen peroxide is characterized in that: the surfactant is a Gemini-quaternary ammonium salt surfactant, and the structural general formula of the surfactant is as follows:

wherein R is₁And R₁' are each an alkyl group having 8 to 14 carbon atoms, R₂、R₃Is an alkyl group having 1 to 4 carbon atoms; x^-Is a halogen anion.

2. The surfactant dedicated to hydrogen peroxide according to claim 1, characterized in that: the R is₁And R₁' may be the same or different.

3. A surfactant complex specific for hydrogen peroxide according to claim 1, characterized in that: the compound comprises the following raw materials in percentage by weight: 80-95% of Gemini-quaternary ammonium salt surfactant, 1-5% of PH buffering agent and 1-5% of stabilizer.

4. The surfactant complex dedicated to hydrogen peroxide according to claim 3, characterized in that: the buffer is citric acid-sodium citrate.

5. The surfactant complex dedicated to hydrogen peroxide according to claim 3, characterized in that: the stabilizer is one or more of glycerol, hydroxyethylidene diphosphonic acid and nitrilotriacetic acid.

6. The surfactant complex dedicated to hydrogen peroxide according to claim 3, characterized in that: the preparation method of the compound comprises the following steps: adding a buffering agent and a stabilizing agent into a Gemini-quaternary ammonium salt surfactant, heating to 40-50 ℃, slowly stirring until the solid is completely dissolved, and naturally cooling to room temperature to obtain colorless and transparent viscous liquid.

Technical Field

The invention belongs to the field of hydrogen peroxide disinfectants, and particularly relates to a special surfactant for hydrogen peroxide and a compound thereof.

Background

Hydrogen peroxide, also known as hydrogen peroxide, is a faintly acid colorless transparent liquid, is an important chemical raw material quaternary product, is used as a bleaching agent, an oxidant, a disinfectant, an extracting agent and the like, and is widely applied to the fields of chemical synthesis, papermaking, metal mineral treatment, environmental protection, electronics, military industry, food and medicine and the like. Hydrogen peroxide is active in nature, causes bacterial death by destroying cellular structures, readily decomposes into oxygen and water, has no harmful residues, is called the cleanest disinfectant, and is commonly used for disinfecting and sterilizing object surfaces, skin wound irrigation, food tools and equipment, and medical instruments. However, high-concentration hydrogen peroxide has strong corrosivity to metals, so that sterilization of medical instruments is limited, and low-concentration hydrogen peroxide disinfectant has poor effect, so that the concentration of hydrogen peroxide is reduced by adding a synergist, side effects are reduced, and the sterilization effect is improved.

Surfactants are used as performance additives in many industrial formulations, such as personal and household care, metal treatment, industrial cleaning, oil recovery, pesticides, disinfectants, and the like. Hydrogen peroxide cannot coexist with many surfactants due to its oxidizing property, and the surfactants commonly used for hydrogen peroxide at present include anionic surfactants such as alkyl sulfonate, alkyl carboxylic acid and salt phosphate, amine oxide cationic surfactants, alkylated polyoxyethylene ether, EO-PO block polyether, and alkyl glycoside with a special structure, but the surfactants still have the following defects: the sulfonate anionic surfactant is alkaline, the hydrogen peroxide is acidic, part of the hydrogen peroxide is lost in the compounding process of the sulfonate anionic surfactant and the hydrogen peroxide, and sulfonate and phosphate ester salts can be hydrolyzed into sulfonic acid and phosphate ester with poor water solubility in an acidic environment and are not suitable for high-content hydrogen peroxide; the alkyl glycoside with a special structure is not oxidized under a thermal environment due to ether bond, is only suitable for low-content hydrogen peroxide and is stored at a lower temperature; although the amine oxide type surfactant has the advantages of acid resistance and oxidation resistance, the amine oxide type surfactant is weak in emulsifying and penetrating force, poor in surface tension reducing capability and weak in hydrogen peroxide synergism. Therefore, it is of great practical significance to develop a specific surfactant suitable for hydrogen peroxide as a synergist thereof.

Disclosure of Invention

The invention aims to solve the technical problems that the traditional surfactant for hydrogen peroxide has the defects of poor oxidation resistance and weak synergistic effect, and provides a surfactant special for hydrogen peroxide and a compound thereof, which have good emulsifying property, foaming and foam stabilizing capability, good water solubility and salt resistance, can effectively reduce surface tension and have a synergistic effect on the sterilization effect of the hydrogen peroxide.

In order to solve the technical problems, the technical scheme of the invention is as follows:

the surfactant special for the hydrogen peroxide is a Gemini-quaternary ammonium salt surfactant, and has the following structural general formula:

wherein R is₁And R₁' are each an alkyl group having 8 to 14 carbon atoms, R₂、R₃Is an alkyl group having 1 to 4 carbon atoms; x^-Is a halogen anion.

Preferably, said R is₁And R₁' may be the same or different.

The invention selects the Gemini-quaternary ammonium salt surfactant as the cationic surfactant, has lower critical micelle concentration, good emulsifying property, foaming and foam stabilizing capability, good water solubility and salt tolerance, can effectively reduce the surface tension and has obvious synergistic effect on the sterilization effect of the hydrogen peroxide compared with the traditional monoalkyl quaternary ammonium salt surfactant.

The invention also aims to provide a special surfactant compound for hydrogen peroxide, which comprises the following raw materials in percentage by weight: 80-95% of Gemini-quaternary ammonium salt surfactant, 1-5% of PH buffering agent and 1-5% of stabilizer.

Preferably, the Gemini-quaternary ammonium salt surfactant is one or a mixture of more than one.

Preferably, the buffer is citric acid-sodium citrate.

Preferably, the stabilizer is one or more of glycerol, hydroxyethylidene diphosphonic acid and nitrilotriacetic acid.

Preferably, the preparation method of the compound comprises the following steps: adding a buffering agent and a stabilizing agent into a Gemini-quaternary ammonium salt surfactant, heating to 40-50 ℃, slowly stirring until the solid is completely dissolved, and naturally cooling to room temperature to obtain colorless and transparent viscous liquid.

Compared with the prior art, the invention has the beneficial effects that:

the Gemini cationic diquaternary ammonium salt surfactant has stable structure and surface activity, can stably coexist with high-concentration peroxide under the condition of heat, maintains the pH value of a solution to be 3-6 by compounding with the buffering agent and the stabilizing agent, has the hydrogen peroxide content reduction rate lower than 15 percent, can effectively improve the stability of the hydrogen peroxide content, and can solve the problem of bottle expansion in hydrogen peroxide packaging and transportation by improving the stability of the hydrogen peroxide. Meanwhile, the sterilization effect of the hydrogen peroxide can be enhanced on the premise of improving the stability of the hydrogen peroxide, and the method has important significance for the application of the hydrogen peroxide in the aspect of disinfectants.

Drawings

Figure 1 is a bottle-bulging phenomenon of 20% hydrogen peroxide with 15% of the proprietary surfactant complex of example 1 added (left side) and 20% hydrogen peroxide without any component added (right side) left for 30 days.

Detailed Description

The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

Example 1

A surfactant compound special for hydrogen peroxide is prepared by the following steps: weighing 2g of hydroxyethylidene diphosphonic acid, putting the weighed material into a 250ml beaker, adding 2g of nitrilotriacetic acid, 6g of sodium citrate and 90g of Gemini-quaternary ammonium salt surfactant, and magnetically stirring the mixture for 30min at the temperature of 40 ℃ to obtain a special surfactant compound; wherein the Gemini-quaternary ammonium salt surfactant is represented by R₁And R₁' is 12 carbon alkyl, R₂、R₃Gemini surfactant of methyl and R₁And R₁' is a 14 carbon alkyl group, R₂、R₃The Gemini surfactant as the methyl is prepared from the following components in a mass ratio of 1: 1.

Example 2

A surfactant compound special for hydrogen peroxide is prepared by the following steps: weighing 2g of hydroxyethylidene diphosphonic acid, putting the weighed material into a 250ml beaker, adding 2g of glycerol, 6g of sodium citrate and 90g of Gemini-quaternary ammonium salt surfactant, and magnetically stirring the mixture for 30min at the temperature of 40 ℃ to obtain a special surfactant compound; wherein the Gemini-quaternary ammonium salt surfactant is represented by R₁And R₁' is a 10 carbon alkyl group, R₂、R₃Gemini surfactant of methyl and R₁And R₁' is 12 carbon alkyl, R₂、R₃The Gemini surfactant as the methyl is prepared from the following components in a mass ratio of 1: 1.

Example 3

A surfactant compound special for hydrogen peroxide is prepared by the following steps: weighing 2g of glycerol, putting the glycerol into a 250ml beaker, adding 2g of nitrilotriacetic acid, 6g of sodium citrate and 90g of Gemini-quaternary ammonium salt surfactant, and magnetically stirring the mixture for 30min at 40 ℃ to obtain a special surfactant compound; wherein the Gemini-quaternary ammonium salt surfactant consists ofR₁And R₁' is an 8-carbon alkyl group, R₂、R₃Gemini surfactant of methyl and R₁、R₁' is a 10 carbon alkyl group, R₂、R₃Gemini surfactant of methyl and R₁And R₁' is 12 carbon alkyl, R₂、R₃The Gemini surfactant as the methyl is prepared from the following components in a mass ratio of 1: 1: 1.

Comparative example 1

A hydrogen peroxide surfactant compound is prepared from sodium citrate 6g and Gemini-quaternary ammonium salt surfactant 94g by magnetically stirring at 40 deg.C for 30min, wherein the Gemini-quaternary ammonium salt surfactant is R₁And R₁' is 12 carbon alkyl, R₂、R₃Gemini surfactant of methyl and R₁And R₁' is a 14 carbon alkyl group, R₂、R₃The Gemini surfactant as the methyl is prepared from the following components in a mass ratio of 1: 1.

Comparative example 2

A hydrogen peroxide surfactant complex prepared by the following method: weighing 2g of hydroxyethylidene diphosphonic acid, putting the weighed materials into a 250ml beaker, adding 2g of nitrilotriacetic acid, 6g of sodium citrate and 90g of sodium dodecyl diphenyl ether disulfonate, and magnetically stirring the materials for 30min at the temperature of 40 ℃ to obtain the surfactant compound.

Comparative example 3

A hydrogen peroxide surfactant complex prepared by the following method: weighing 2g of hydroxyethylidene diphosphonic acid, putting the weighed material into a 250ml beaker, adding 2g of nitrilotriacetic acid, 6g of sodium citrate and 90g of lauryl dimethyl amine oxide, and magnetically stirring the mixture for 30min at the temperature of 40 ℃ to obtain the surfactant compound.

Comparative example 4

A hydrogen peroxide surfactant complex prepared by the following method: weighing 2g of hydroxyethylidene diphosphonic acid, putting the weighed material into a 250ml beaker, adding 2g of nitrilotriacetic acid, 6g of sodium citrate and 640090g of polyoxyethylene-polyoxypropylene segmented copolymer, and magnetically stirring the mixture for 30min at the temperature of 40 ℃ to obtain the surfactant compound.

Analysis of experiments

1. Stability of

1.1 detection sample: the stability of the complex with 20% hydrogen peroxide and 30% hydrogen peroxide added to different surfactants was tested separately.

1.2 detection method:

(1) 20% hydrogen peroxide stability: 40g of 50% hydrogen peroxide was taken, 5g, 10g, 15g, and 20g of the surfactant complexes prepared in examples 1 to 3 and comparative example 1 were added, respectively, and water to make up 100g was added, and the mixture was placed in a thermostat at 54 ℃. Another 40g of 50% hydrogen peroxide was added to make up 100g of water to obtain a blank control. The change of the hydrogen peroxide content in 14 days is tested by referring to GB/T1616-2014 industrial hydrogen peroxide.

(2) 30% hydrogen peroxide stability: 60g of 50% hydrogen peroxide was taken, 5g, 10g, 15g, and 20g of the surfactant complexes prepared in examples 1 to 3 and comparative example 1 were added, respectively, and the mixture was made up to 100g with water and placed in an incubator at 54 ℃. 60g of 50% hydrogen peroxide is taken and water is added to make up 100g to be used as a blank control group. The change of the hydrogen peroxide content in 14 days is tested by referring to GB/T1616-2014 industrial hydrogen peroxide.

1.3, detection result:

the specific results are shown in tables 1 to 8, and it can be seen from the experimental data in tables 1 to 6 that the 14-day decrease rate of the 20% hydrogen peroxide concentration and the 14-day decrease rate of the 30% hydrogen peroxide concentration of the hydrogen peroxide added to the surfactant composites prepared in examples 1 to 3 of the present invention are both less than 10% and 15; the changes of% pH values are less than +/-1.0; in the blank control group without adding the surfactant compound, the 14-day reduction rate of 20% hydrogen peroxide reaches about 45%, and the 14-day reduction rate of 30% hydrogen peroxide reaches about 50%, and as can be seen from the data in table 7, the 14-day reduction rate of the hydrogen peroxide only added with the Gemini-quaternary ammonium salt surfactant is also obviously reduced and is reduced from 50% to 24%, which shows that the Gemini-quaternary ammonium salt surfactant prepared by the invention can also improve the stability of the hydrogen peroxide even if no stabilizer is added. Further, as can be seen from the data in table 8, different surfactants have relatively large differences in the stability effects on hydrogen peroxide, and the concentration of 30% of hydrogen peroxide after 30 days by adding the Gemini-quaternary ammonium salt surfactant prepared by the invention is reduced by 4.5%, while the concentration of 30% of hydrogen peroxide after adding other surfactants is greatly reduced, which further illustrates that the Gemini-quaternary ammonium salt surfactant prepared by the invention is a surfactant special for hydrogen peroxide, and can improve the stability of hydrogen peroxide.

Table 1 stability test data for 20% hydrogen peroxide content with various concentrations of the surfactant complex of example 1

Table 2 stability test data for 30% hydrogen peroxide content with various concentrations of the surfactant complex of example 1

Table 3 stability test data for 20% hydrogen peroxide content with various concentrations of the surfactant complex of example 2

Table 4 stability test data for 30% hydrogen peroxide content with various concentrations of the surfactant complex of example 2

Table 5 stability test number for 20% hydrogen peroxide content with various concentrations of the surfactant complex of example 3

Table 6 stability test data for 30% hydrogen peroxide content with various concentrations of the surfactant complex of example 3

Table 7 stability test data for 30% hydrogen peroxide content with addition of 20% of the surfactant complexes of example 1 and comparative example 1

TABLE 830% stability test data for hydrogen peroxide in various surfactants (20% add-on)

Time	Blank space	Surfactant 1	2A1	OA-12	L64
						Initial	30.42％	29.97％	30.36％	30.21％	30.14％
7 days	29.02％	27.91％	26.37％	25.58％	16.82％
						14 days	14.77％	26.64％	12.23％	21.71％	6.56％
30 days	6.06％	25.46％	2.95％	16.87％	0.04％

2. Sterilizing property

2.1 Experimental sample:

(1) experimental strains: candida albicans, Escherichia coli, and Staphylococcus aureus.

(2) Experimental samples: hydrogen peroxide, surfactant Complex specific for example 1, Gemini-Quaternary ammonium surfactant (from R)₁And R₁' is 12 carbon alkyl, R₂、R₃Gemini surfactant of methyl and R₁And R₁' is a 14 carbon alkyl group, R₂、R₃The Gemini surfactant as the methyl is prepared from the following components in a mass ratio of 1: 1 composition).

(3) Neutralizing agent: 0.03mol/L PBS solution of 0.5% Na2S2O3+ 0.7% lecithin + 2% Tween-80.

2.2 Experimental methods: the detection was carried out according to the disinfection specification (2002 edition) 2.1.1.9.5 fungus killing experiment.

2.3 results of detection

The specific results are shown in Table 9. As can be seen from the table, the Gemini quaternary ammonium salt surfactant has a certain sterilization effect, and after being compounded with hydrogen peroxide, the Gemini quaternary ammonium salt surfactant can greatly improve the sterilization effect of the hydrogen peroxide, shorten the sterilization time and reduce the usage amount of the hydrogen peroxide, and further shows that the stability and the sterilization performance of the Gemini quaternary ammonium salt surfactant and the compound thereof on the hydrogen peroxide are obviously improved.

TABLE 9 results of fungus killing experiments

2.3 storing

Respectively packaging 20% of hydrogen peroxide and 20% of hydrogen peroxide added with 15% of the special surfactant compound for example 1 into packaging plastic bottles with the same material specification, sealing the packaging plastic bottles, standing the packaging plastic bottles at room temperature for 30 days, and observing whether the two plastic bottles have a bottle expansion phenomenon or not, wherein the result is shown in figure 1. As can be seen from figure 1, the plastic bottle with the left side added with the special surfactant compound of the invention has no bottle expansion phenomenon, while the hydrogen peroxide with the right side added with any component has obvious bottle expansion phenomenon.

The foregoing is considered as illustrative of the preferred embodiments of the invention, but is made merely for the purpose of providing an understanding of the principles of the embodiments; meanwhile, for a person skilled in the art, according to the present embodiment, there may be a change in the specific implementation and application scope, and in summary, the present disclosure should not be construed as a limitation to the present invention.