阅读说明：本技术 一种低泡型非离子表面活性剂的制备方法和应用 (Preparation method and application of low-foam nonionic surfactant ) 是由 王杰 王伟松 金一丰 陈荧杰 张美军 于 2021-03-25 设计创作，主要内容包括：本发明提供一种新的低泡型非离子表面活性剂的制备方法和应用,该制备方法化学反应式如下：其中,R表示C8-C10的直链烷基,b为5-6范围内的任一数字,m为2-4范围内的任一整数,n表示8-12范围内的任一整数；该制备方法是通过烷基糖苷聚氧丙烯醚与氯甲烷在碱性催化剂作用下反应获得。本发明的低泡型非离子表面活性剂具有优异的高温稳定性,可以应用于高温下燃料泄露处理,有效避免火灾和爆炸危险。(The invention provides a preparation method and application of a novel low-foam nonionic surfactant, wherein the chemical reaction formula of the preparation method is as follows:)

1. A preparation method of a novel low-foam nonionic surfactant is characterized by comprising the following steps: the chemical reaction formula is as follows:

wherein R represents a C8-C10 linear alkyl group, b is any number within the range of 5-6, m is any integer within the range of 2-4, and n represents any integer within the range of 8-12;

the preparation method is obtained by reacting alkyl glycoside polyoxypropylene ether with methyl chloride under the action of an alkaline catalyst.

2. The process for preparing a novel low-foaming nonionic surfactant according to claim 1, wherein: the preparation method specifically comprises the following steps:

(1) mixing alkyl glycoside polyoxypropylene ether with an alkaline catalyst uniformly under an anaerobic condition, and dehydrating at the temperature of 100-120 ℃ and the stirring speed of 500-700 rpm;

(2) and (3) after the dehydration treatment, cooling the mixture to 80-90 ℃, adding chloromethane for methylation reaction, and desalting after the reaction is finished to obtain the catalyst.

3. The process for producing a novel low-foaming nonionic surfactant according to claim 1 or 2, characterized in that: the alkali catalyst is sodium hydroxide, potassium hydroxide and solid sodium methoxide.

4. The process for producing a novel low-foaming nonionic surfactant according to claim 1 or 2, characterized in that: the molar ratio of the glucoside polyoxypropylene ether, the basic catalyst and the chloromethane is 1: (5-6): (5-6).

5. A low-foaming nonionic surfactant, characterized in that: is obtained by the preparation method of any one of claims 1 to 3.

6. Use of a low-foaming nonionic surfactant according to claim 5 for treating fuel leakage at elevated temperatures.

7. A fuel treating agent characterized by: comprising the low-foaming nonionic surfactant of claim 5.

8. A fuel treatment agent according to claim 7, characterized in that: the fuel treating agent also comprises water, and the mass ratio of the water to the low-foam nonionic surfactant is as follows: (5-10): 1.

9. a method of treating leaked fuel, characterized by: the method comprises the following steps:

spraying the fuel treatment agent according to claim 7 or 8 on a fuel leakage area.

Technical Field

The invention relates to the technical field of surfactant preparation, in particular to a preparation method and application of a low-foam nonionic surfactant.

Background

The alkyl glycoside is a green functional surfactant which is internationally recognized at present, has the advantages of low surface tension, strong wetting power, strong detergency, no toxicity, no harm, no stimulation and the like, and is an excellent surfactant with the alkyl glycoside polyoxypropylene ether obtained by the polymerization reaction of Propylene Oxide (PO). The existing method for preparing alkyl glycoside polyoxypropylene ether comprises the following steps: firstly, melting a catalyst and pure alkyl glucoside together, then completely placing the catalyst and the pure alkyl glucoside into a high-pressure reaction kettle, replacing the mixture for 3 times by using high-purity nitrogen, heating the high-pressure reaction kettle to 180 ℃, and controlling the rotating speed of the reaction kettle to be 700r/min so as to prevent overhigh reaction temperature caused by over-severe polymerization reaction; observing the induced reaction of introducing a small amount of PO by controlling the reaction pressure to be 0.3-0.4MPa, controlling the reaction temperature to be unchanged, and continuously introducing the PO amount under the corresponding addition amount into the reaction kettle; after the feeding is finished, the reaction temperature is continuously maintained, and after the pressure in the kettle is not reduced any more, the product is cooled and taken out. By adding different amounts of PO, alkyl glycoside polyoxypropylene ethers with different degrees of polymerization are obtained. The problem with this process is that the resulting product is extremely unstable at high temperatures, is prone to decomposition, and has a significant impact on its use, particularly at high temperatures.

Disclosure of Invention

Aiming at the problems of the prior art for preparing the alkyl glycoside polyoxypropylene ether, the invention aims to provide a preparation method and application of a novel low-foaming nonionic surfactant. The low-foam nonionic surfactant obtained by the preparation method has excellent high-temperature stability, can be applied to fuel leakage treatment at high temperature, and effectively avoids fire and explosion hazards. The technical scheme of the invention is as follows:

in a first aspect, the present invention provides a process for preparing a low-foaming nonionic surfactant, having the chemical formula:

wherein R represents a C8-C10 linear alkyl group, b is any number within the range of 5-6, m is any integer within the range of 2-4, and n represents any integer within the range of 8-12;

the preparation method is obtained by reacting alkyl glycoside polyoxypropylene ether with methyl chloride under the action of an alkaline catalyst.

Further, the preparation method specifically comprises the following steps:

(1) mixing alkyl glycoside polyoxypropylene ether with an alkaline catalyst uniformly under an anaerobic condition, and dehydrating at the temperature of 100-120 ℃ and the stirring speed of 500-700 rpm;

(2) and (3) after the dehydration treatment, cooling the mixture to 80-90 ℃, adding chloromethane for methylation reaction, and desalting after the reaction is finished to obtain the catalyst.

Further, the alkali catalyst is sodium hydroxide, potassium hydroxide or sodium methoxide.

Further, the molar ratio of the glycosyl glycoside polyoxypropylene ether, the basic catalyst and the methyl chloride is 1: (5-6): (5-6).

In a second aspect, the present invention provides a low-foaming nonionic surfactant obtained by the above-mentioned production method.

In a third aspect, the present invention provides the use of a low-foaming nonionic surfactant as described above for treating fuel leakage at high temperatures.

In a fourth aspect, the present invention provides a fuel treating agent comprising the above low-foaming nonionic surfactant.

Further, the fuel treating agent also comprises water, and the mass ratio of the water to the low-foam nonionic surfactant is as follows: (5-10): 1.

in a fifth aspect, the present invention provides a method of treating a leaking fuel, comprising: the fuel treatment agent described above is sprayed on the fuel leakage area.

The invention provides a novel surface treating agent which has excellent high-temperature stability, can be used for emergency treatment of leaked fuel under high-temperature conditions, and effectively avoids fire and explosion risks.

Detailed Description

In the description of the present invention, it is to be noted that those whose specific conditions are not specified in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturers. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.

Example 1

This example provides a method for preparing a low-foaming nonionic surfactant, the chemical reaction formula is as follows:

in the above formula, m is 2 and n is 9.

The preparation method is obtained by reacting alkyl glycoside polyoxypropylene ether with methyl chloride under the action of an alkaline catalyst, and specifically comprises the following steps:

(1) mixing alkyl glycoside polyoxypropylene ether with sodium hydroxide uniformly under an anaerobic condition, and dehydrating at the temperature of 110 ℃ and the stirring speed of 600 rpm;

(2) and (3) after the dehydration treatment, cooling the mixture to 85 ℃, adding chloromethane to perform methylation reaction, and desalting after the reaction is finished to obtain the catalyst.

In the above preparation method, the molar ratio of the polyglycidyl ether, the basic catalyst and the methyl chloride is 1: 5: 6.

example 2

This example provides a method for preparing a low-foaming nonionic surfactant, the chemical reaction formula is as follows:

in the above formula, m is 3 and n is 10.

The preparation method is obtained by reacting alkyl glycoside polyoxypropylene ether with methyl chloride under the action of an alkaline catalyst, and specifically comprises the following steps:

(1) mixing alkyl glycoside polyoxypropylene ether with sodium hydroxide uniformly under an anaerobic condition, and dehydrating at 100 ℃ and a stirring speed of 500 rpm;

(2) and (3) after the dehydration treatment, cooling the mixture to 80 ℃, adding chloromethane to perform methylation reaction, and desalting after the reaction is finished to obtain the catalyst.

In the above preparation method, the molar ratio of the polyglycidyl ether, the basic catalyst and the methyl chloride is 1: 5: 5.

example 3

This example provides a method for preparing a low-foaming nonionic surfactant, the chemical reaction formula is as follows:

in the above formula, m is 3 and n is 11.

The preparation method is obtained by reacting alkyl glycoside polyoxypropylene ether with methyl chloride under the action of an alkaline catalyst, and specifically comprises the following steps:

(1) mixing alkyl glycoside polyoxypropylene ether with sodium hydroxide uniformly under an anaerobic condition, and dehydrating at the temperature of 120 ℃ and the stirring speed of 700 rpm;

(2) and (3) after the dehydration treatment, cooling the mixture to 90 ℃, adding chloromethane to perform methylation reaction, and desalting after the reaction is finished to obtain the catalyst.

In the above preparation method, the molar ratio of the polyglycidyl ether, the basic catalyst and the methyl chloride is 1: 6: 6.

example 4

10g of each of the low-foaming nonionic surfactants of examples 1 to 3 was used for decomposition test, and the decomposition test was carried out by sufficiently calcining the resultant mixture in an experimental microwave sintering furnace HAMiLab-V at a high temperature of 350 ℃ and subjecting the treated exhaust gas to anhydrous copper sulfate to test H in the mixed gas₂O- -testing of CO in a gas mixture with clarified lime water₂Using sodium hydroxide solution to remove CO from the gas mixture₂Removal of water by concentrated sulfuric acid to prevent interference with subsequent experiments copper oxide (CO and H) by burning₂) Testing of water with anhydrous copper sulfate to test for the presence of H₂In the presence of clear lime water to test for CO₂The presence or absence of CO was further examined and the resulting species were detected as shown in Table 1.

TABLE 1 high-temperature roast products of examples 1 to 3

Product name	The product obtained by high-temperature roasting
		Straight chain octaalkyl glycoside polyoxypropylene ether methyl end-capping	CO2、H2O
Straight chain nonaalkyl glycoside polyoxypropylene ether methyl end-capping	CO2、H2O
		Straight chain decaalkylglycoside polyoxypropylene ether methyl end-capping	CO2、H2O

Example 5

10g of each of the low-foaming nonionic surfactants of examples 1 to 3 and 10g of the alkyl glycoside polyoxypropylene ether were subjected to thermogravimetric analysis (i.e., the temperature at which the mass of the substance to be measured changes after being put in was the decomposition temperature) by a thermogravimetric analyzer TG NETZSCH TG209F3 Nevio calorimeter, and the decomposition temperatures at which the capped low-foaming nonionic surfactants were decomposed were 299.7 ℃, 300 ℃ and 299.8 ℃, respectively, and the alkyl glycoside polyoxypropylene ether was completely decomposed at 200 ℃.

Example 6

The products obtained in examples 1 to 3 were formulated into a surfactant solution having a mass concentration of 0.25%, and the foaming properties of the surfactant were measured at 50 ℃ by means of a Roche foam meter with reference to GB/T13173.61991 method.

The specific method comprises the following steps:

(1) the thermostat was turned on and when the thermostat reached a certain temperature, the pipe clamped the temperature of the water bath, stabilizing at 40 ℃. + -. 0.5 ℃.

(2) The inner wall of the graduated tube is flushed with distilled water, and the inner wall of the graduated tube is flushed with a test solution and also flushed completely.

(3) The graduated tube piston was closed and a further dropper was used to inject 50ml of the test solution to the 50ml graduation where the test solution was preheated to 40 ℃.

(4) The dropping tube was filled with 200ml of a test solution, which was previously heated to 40 ℃.

(5) The dropping liquid pipe is arranged on a prepared pipe frame and is vertical to the section of the graduated pipe, so that the solution flows to the center of the graduated pipe, and the outlet of the dropping liquid pipe is arranged on the 900mm graduation line.

(6) The piston of the dropping tube was opened to allow the solution to flow down. When the solution in the dropping tube has run out, a stopwatch is started immediately, the well measures the foam height, and then the height is recorded after 5 minutes, 10 minutes and 15 minutes, and the foam value is expressed as the foam height. The foaming ability and foam stability of the surfactant were evaluated by the height of the generated foam, and the results are shown in table 2, which indicates that the alkyl glycoside polyoxypropylene ether methyl prepared in 3 examples is capped as a low foaming type nonionic surfactant.

TABLE 2 foam Properties of the products obtained in examples 1 to 3

Example 7

Experiment of fire extinguishing

The low-foaming nonionic surfactants of examples 1 to 3 were tested for their ability to treat leakage of fuel

The low-foaming nonionic surfactant obtained in example 1 was prepared as an aqueous solution having a concentration of 15%. Then, a cylinder of 10cm in diameter was prepared, fuel was introduced into the cylinder to simulate a leakage process, a solid water-insoluble aliphatic alcohol fuel was introduced in an amount of about 1kg, then the fuel was ignited, and the surfactant solution of example 1 was sprayed over the fuel from above the cylinder for 30 seconds to extinguish the flame. In the process, the high-heat fuel evaporates water, so that the alkyl glycoside polyoxypropylene ether methyl end-capped product is changed into a solid extinguishing fuel again, and the problem that the fuel is diffused and discharged into a sewer is solved in time due to low foaming property. And because of having excellent high temperature stability, can not cause the problem that the alkyl glycoside polyoxypropylene ether methyl-terminated product of the covering fuel loses efficacy because of decomposing at high temperature, reach more stable safe fire extinguishing effect.

The low-foaming nonionic surfactants of examples 2 and 3 were tested for fuel leakage handling ability according to the above protocol. The flame was extinguished within 30 s.

In conclusion, the products of the high-temperature roasting of the surface treating agent are carbon dioxide and water, the high-temperature stability is excellent, the safety and the reliability are realized, the high-temperature surface treating agent can be used for emergently treating leaked fuel under the high-temperature condition, and the fire and explosion risks are effectively avoided.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.