阅读说明：本技术 一种高效水基灭火剂的制备方法 (Preparation method of efficient water-based fire extinguishing agent ) 是由 袁大想 吴健泳 于 2021-09-13 设计创作，主要内容包括：该发明涉及灭火材料技术领域,具体关于一种高效水基灭火剂的制备方法；该发明的一种高效水基灭火剂中有机磷化合物高温下生成的聚磷酸以及磷酸共同在凝聚相中发挥阻燃作用,且阻燃剂无不含卤素,无毒,有利于环保,具有良好的应用前景,而且也为含磷乙烯基阻燃剂增加一个新品种；阻燃性能优异,为推动低碳、环保、绿色、安全的新材料领域的发展具有重要意义。(The invention relates to the technical field of fire extinguishing materials, in particular to a preparation method of a high-efficiency water-based fire extinguishing agent; polyphosphoric acid and phosphoric acid which are generated by organic phosphorus compounds at high temperature in the high-efficiency water-based fire extinguishing agent jointly play a flame retardant role in a condensed phase, and the flame retardant is free from halogen, non-toxic, beneficial to environmental protection, good in application prospect, and a new variety is added for the phosphorus-containing vinyl flame retardant; the flame retardant property is excellent, and the flame retardant has important significance for promoting the development of the field of new materials which are low-carbon, environment-friendly, green and safe.)

1. A preparation method of a high-efficiency water-based fire extinguishing agent comprises the following steps of:

s1: under the protection of nitrogen, 200-250 parts of ionized water are put into a stirring container and heated to raise the temperature;

s2: firstly, stirring 1.0-3.5 parts of dispersing agent, 1.2-4.0 parts of initiator and 4-9 parts of water-based high polymer until the dispersing agent, the initiator and the water-based high polymer are completely dissolved, then adding 17-50 parts of bis-trimethylsilyl vinyl phosphate, 0.5-5 parts of vinyl guanamine and 0.1-2.4 parts of 4-allyl aminobenzoate, uniformly mixing, and finally adding 1.1-3.2 parts of dispersion stabilizer;

s3: controlling the reaction temperature, stirring and reacting for 3-5h, and cooling to room temperature after the reaction is finished to obtain the high-efficiency water-based extinguishing agent.

2. The method for preparing the high-efficiency water-based fire extinguishing agent according to claim 1, wherein the method comprises the following steps: the temperature in the S1 is 50-70 ℃.

3. The method for preparing the high-efficiency water-based fire extinguishing agent according to claim 1, wherein the method comprises the following steps: the dispersing agent in the S2 is one or a combination of several of nonylphenol polyoxyethylene ether, sodium dodecyl sulfate, sodium polynaphthalene formaldehyde sulfonate and sodium lignosulfonate.

4. The method for preparing the high-efficiency water-based fire extinguishing agent according to claim 1, wherein the method comprises the following steps: the mass portion of the dispersing agent in the S2 is optimized to be 1.3-3.2 portions.

5. The method for preparing the high-efficiency water-based fire extinguishing agent according to claim 1, wherein the method comprises the following steps: and the initiator in the S2 is ammonium persulfate or potassium persulfate.

6. The method for preparing the high-efficiency water-based fire extinguishing agent according to claim 1, wherein the method comprises the following steps: the mass portion of the initiator in the S2 is optimized to be 1.5-3.5.

7. The method for preparing the high-efficiency water-based fire extinguishing agent according to claim 1, wherein the method comprises the following steps: the water-based high polymer in the S2 contains a plurality of hydrophilic groups, including polymers of hydroxyl, carboxyl, amine or polyethylene oxide chain segments.

8. The method for preparing the high-efficiency water-based fire extinguishing agent according to claim 7, wherein the method comprises the following steps: the water-based high polymer in the S2 is selected from Polyacrylamide (PAM), Hydrolyzed Polyacrylamide (HPAM) and polyvinylpyrrolidone (PVP).

9. The method for preparing the high-efficiency water-based fire extinguishing agent according to claim 1, wherein the method comprises the following steps: the mass portion of the aqueous high polymer in the S2 is optimized to be 5-8.5.

10. The method for preparing the high-efficiency water-based fire extinguishing agent according to claim 1, wherein the method comprises the following steps: the mass part of the bis-trimethylsilyl vinyl phosphate in the S2 is optimized to be 20-27 parts.

11. The method for preparing the high-efficiency water-based fire extinguishing agent according to claim 1, wherein the method comprises the following steps: the mass portion of the vinyl guanamine in the S2 is optimized to be 1.2-3.5 portions.

12. The method for preparing the high-efficiency water-based fire extinguishing agent according to claim 1, wherein the method comprises the following steps: the mass portion of the 4-allyl aminobenzoate in the S2 is optimized to be 0.2-2.0 portions.

13. The method for preparing the high-efficiency water-based fire extinguishing agent according to claim 1, wherein the method comprises the following steps: the dispersion stabilizer in the S2 is one or a combination of more of fumed silica, organic bentonite, carboxymethyl cellulose and polyvinyl alcohol.

14. The method for preparing the high-efficiency water-based fire extinguishing agent according to claim 1, wherein the method comprises the following steps: the reaction temperature in the S3 is 60-80 ℃.

15. The method for preparing the high-efficiency water-based fire extinguishing agent according to claim 1, wherein the method comprises the following steps: and the stirring speed in the S3 is 60-120 r/min.

16. The preparation method of the high-efficiency water-based fire extinguishing agent according to claims 1-15, wherein the preparation method comprises the following steps: the preparation method of the high-efficiency water-based fire extinguishing agent is applied to various fire extinguisher equipment or devices.

Technical Field

The invention relates to the technical field of fire extinguishing materials, in particular to a preparation method of a high-efficiency water-based fire extinguishing agent.

Background

Conventional water-based flame retardant products are mainly foamed products, which comprise the following three components: 1) a source of acid; 2) a carbon source; 3) and (4) a gas source. The substances as acid sources are mainly: halides, ammonium phosphate, ammonium polyphosphate, urea phosphate, sulfates, boric acid, and the like; the substances used as gas sources mainly comprise urea, ammonium bicarbonate, melamine, dicyandiamide and derivatives thereof; the carbon source mainly includes polyhydric alcohol, starch, etc. The biggest problem with conventional water-based flame retardants is that most materials are not water-soluble. Therefore, a dispersing agent and an anti-settling agent have to be added, so that the surface of the treated product has the problems of opacity, serious precipitated crystal and the like, the surface quality of the product is greatly influenced, and the mechanical property of the product is greatly influenced due to the serious hygroscopicity of some components; in addition, some components are not degradable, which brings harm to ecological environment.

Organophosphorus flame retardants include phosphorus (phosph) ates, phosphites, organophosphates, phosphine oxides, phosphorus-containing polyols, and the like, but most commonly phosphorus (phosph) ates and their oligomers. For example, Fyrol76 is an oligomer formed by the polycondensation of di (2-chloroethyl) vinylphosphonate with methylphosphonate, which can be used alone or in combination with N-methylolallylamine, and potassium persulfate as a catalyst to initiate radical polymerization to graft N-methylol groups onto cellulose, rendering cellulose-containing fabrics, such as cotton or blends thereof, flame retardant. Phosphorus oxide flame retardants are also used in natural fibers, tris (aziridinyl) phosphine oxide (APO) is a flame retardant for cotton fabrics, which not only imparts flame retardancy to cotton fabrics, but also imparts ironing free properties to cotton fabrics, but the safety and hygiene issues of aziridinyl groups limit the industrial application of APO. And some phenylphosphine oxides containing two reactive groups, such as diphenyl-2, 5-bis (hydroxyethoxy) phenylphosphine oxide, methyl bis (3, 5-dibromo-4-hydroxyethoxyphenyl) phosphine oxide, and the like, are used for flame-retarding polyester fibers.

CN201210592631.8 discloses a fire extinguishing agent, which is prepared by uniformly stirring hydrophilic solid powder and water or aqueous solution, adding surfactant, uniformly mixing, then adding hydrophobic solid particles, mixing and dispersing: 1 to 25 parts of hydrophilic solid powder, 0.001 to 2 parts of water-soluble surfactant, 2 to 100 parts of hydrophobic solid particles and 100 parts of water or aqueous solution. The invention provides a preparation method of a fire extinguishing agent. Compared with the existing fire extinguishing agent, the fire extinguishing agent can play the roles of suffocation, cooling, isolation and chemical inhibition at the same time, and has high fire extinguishing efficiency; and the fire extinguishing agent of the invention adds the surfactant in the water phase, thus reducing the dispersion rotating speed in the preparation process, shortening the dispersion time and improving the preparation efficiency.

Disclosure of Invention

The invention provides a preparation method of a high-efficiency water-based fire extinguishing agent, belonging to the technical field of fire extinguishing materials.

A preparation method of a high-efficiency water-based fire extinguishing agent comprises the following steps of:

s1: under the protection of nitrogen, 200-250 parts of ionized water are put into a stirring container and heated to raise the temperature;

s2: firstly, 1.0-3.5 parts of dispersant, 1.2-4.0 parts of initiator and 4-9 parts of water-based high polymer are stirred until completely dissolved, then 17-50 parts of bis-trimethylsilyl vinyl phosphate (CAS 18291-41-3), 0.5-5 parts of vinylguanamine and 0.1-2.4 parts of 4-allyl aminobenzoate are added and uniformly mixed, and finally 1.1-3.2 parts of dispersion stabilizer are added;

s3: controlling the reaction temperature, stirring and reacting for 3-5h, and cooling to room temperature after the reaction is finished to obtain the high-efficiency water-based extinguishing agent.

Further, the temperature in the S1 is 50-70 ℃;

further, the dispersing agent in S2 is one or a combination of several of nonylphenol polyoxyethylene ether, sodium dodecyl sulfate, sodium polynaphthalene formaldehyde sulfonate, and sodium lignosulfonate;

further, the mass part of the dispersing agent in the S2 is optimized to be 1.3-3.2 parts;

further, the initiator in the S2 is ammonium persulfate or potassium persulfate;

further, the mass portion of the initiator in the S2 is optimized to be 1.5-3.5;

further, the water-based high molecular polymer in S2 contains a plurality of hydrophilic groups, including polymers of hydroxyl, carboxyl, amine or polyethylene oxide segments;

further, the water-based high molecular polymer in the S2 is selected from Polyacrylamide (PAM), Hydrolyzed Polyacrylamide (HPAM), polyvinylpyrrolidone (PVP);

further, the mass portion of the aqueous high molecular polymer in the S2 is optimized to be 5-8.5 parts;

further, the mass part of the bis-trimethylsilyl vinyl phosphate in the S2 is optimized to be 20-27 parts;

further, the mass part of the vinyl guanamine in the S2 is optimized to be 1.2-3.5 parts;

further, the mass part of the 4-allyl aminobenzoate in the S2 is optimized to be 0.2-2.0 parts;

further, the dispersion stabilizer in S2 is one or a combination of fumed silica, organic bentonite, carboxymethyl cellulose and polyvinyl alcohol;

further, the reaction temperature in the S3 is 60-80 ℃;

further, the stirring speed in the S3 is 60 r/min;

furthermore, the preparation method of the high-efficiency water-based fire extinguishing agent is applied to various fire extinguisher equipment or devices.

The reaction mechanism is as follows:

the equation for its partial reaction is schematically:

the bis-trimethylsilyl vinyl phosphate is polymerized with vinyl guanamine and allyl 4-aminobenzoate to obtain the novel flame retardant, and the structure of the compound is shown as the following formula:

the introduction of the vinylguanamine into the branched polymer chain can greatly improve the softening point temperature and the glass transition point temperature of the polymer, increase the relative density and the solubility and improve the heat resistance of the polymer.

The technical effects are as follows:

(1) introducing a water-based high molecular polymer as an adhesive base material to form a flame-retardant coating; and silicon, namely nitrogen phosphorus silicon type water-based flame retardant finishing agent, is introduced. Due to the introduction of siloxane, the compatibility of the siloxane and a water-soluble phosphorus-nitrogen composite system is poor, but the system is uniform and stable. The phosphorus-nitrogen-silicon flame-retardant system is adopted, and the silicon-phosphorus synergistic flame-retardant effect is shown in the combustion process, the phosphoric acid substances can promote the generation of a coke layer, and the layered silicon dioxide generated by siloxane degradation prevents the oxidation of a carbonization layer, so that the stability of the carbon layer is further improved, and the synergistic effect of silicon and phosphorus is further enhanced. The addition amount of silanes is small, the flame retardant property is excellent, and a high-temperature resistant, good-toughness and glassy barrier layer is formed on the surface carbon layer when the smoke suppression property is good and the combustion is carried out, so that the barrier effect of the carbon layer is obviously improved.

(2) Polyphosphoric acid generated by the organic phosphorus compound at high temperature and phosphoric acid play a flame retardant role together in a condensed phase. The flame retardant disclosed by the invention is free of halogen, non-toxic, beneficial to environmental protection and good in application prospect, and a new variety is added to the phosphorus-containing vinyl flame retardant; the flame retardant property is excellent, and the flame retardant has important significance for promoting the development of the field of new materials which are low-carbon, environment-friendly, green and safe.

Detailed Description

The water machine fire extinguishing agent is identified according to the standard of GB 17427-1998 national fixed fire extinguishing system and fire-resistant member quality supervision and inspection center, the fire extinguishing performance reaches IA level, and the water machine fire extinguishing agent is particularly suitable for extinguishing various oil (particularly light oil) fires, has strong self-sealing capability, good re-combustion resistance, quick fire extinguishing and difficult decay and deterioration, is suitable for common foam fire extinguishers, is widely suitable for airports, oil depots, ships, warehouses, gas stations, petrochemical enterprises, families and the like, and has higher practical application value and wide market prospect

Example 1

S1: under the protection of nitrogen, 200g of ionized water is put into a stirring container and heated to 50 ℃;

s2: firstly, 1.0g of nonylphenol polyoxyethylene ether, 1.2g of potassium persulfate and 4g of Polyacrylamide (PAM) are stirred until the nonylphenol polyoxyethylene ether, the potassium persulfate and the PAM are completely dissolved, then 17g of bis-trimethylsilyl vinyl phosphate (CAS 18291-41-3), 0.5g of vinylguanamine and 0.1g of 4-allyl aminobenzoate are added and uniformly mixed, and finally 1.1g of fumed silica is added;

s3: controlling the reaction temperature to be 60 ℃, stirring the mixture at the rotating speed of 60r/min, reacting the mixture for 3 hours, and cooling the mixture to room temperature after the reaction is finished to obtain the high-efficiency water-based extinguishing agent.

Example 2

S1: under the protection of nitrogen, 210g of ionized water is put into a stirring container and heated to 50 ℃;

s2: firstly, stirring 1.5g of sodium dodecyl sulfate, 1.8g of potassium persulfate and 5g of Polyacrylamide (PAM) until the sodium dodecyl sulfate, the potassium persulfate and the PAM are completely dissolved, then adding 25g of bis-trimethylsilyl vinyl phosphate (CAS 18291-41-3), 1.5g of vinylguanamine and 0.6g of 4-allyl aminobenzoate, uniformly mixing, and finally adding 1.8g of fumed silica;

s3: controlling the reaction temperature to be 60 ℃, stirring the mixture at a rotating speed of 70r/min, reacting the mixture for 3 hours, and cooling the mixture to room temperature after the reaction is finished to obtain the high-efficiency water-based extinguishing agent.

Example 3

S1: under the protection of nitrogen, 220g of ionized water is put into a stirring container and heated to 60 ℃;

s2: firstly, stirring 2.4g of sodium polynaphthalenesulfonate, 2.4g of potassium persulfate and 6g of Hydrolyzed Polyacrylamide (HPAM) until the sodium polynaphthalenesulfonate, adding 35g of bis-trimethylsilyl vinyl phosphate (CAS 18291-41-3), 3g of vinylguanamine and 1.5g of 4-allyl aminobenzoate, uniformly mixing, and finally adding 2.4g of organobentonite;

s3: controlling the reaction temperature to be 70 ℃, stirring the mixture at the rotating speed of 80r/min, reacting the mixture for 4 hours, and cooling the mixture to room temperature after the reaction is finished to obtain the high-efficiency water-based extinguishing agent.

Example 4

S1: under the protection of nitrogen, 230g of ionized water is put into a stirring container and heated to 60 ℃;

s2: firstly, stirring 3.0g of sodium lignosulfonate, 3.0g of ammonium persulfate and 7g of polyacrylamide (HPAM) until the sodium lignosulfonate, the ammonium persulfate and the polyacrylamide are completely dissolved, then adding 40g of bis-trimethylsilyl vinyl phosphate (CAS 18291-41-3), 4g of vinylguanamine and 2.0g of 4-allyl aminobenzoate, uniformly mixing, and finally adding 2.8g of organic bentonite;

s3: controlling the reaction temperature to be 80 ℃, stirring the mixture at a speed of 90r/min, reacting the mixture for 4 hours, and cooling the mixture to room temperature after the reaction is finished to obtain the high-efficiency water-based extinguishing agent.

Example 5

S1: under the protection of nitrogen, 240g of ionized water is put into a stirring container and heated to 70 ℃;

s2: firstly, stirring 3.2g of sodium dodecyl sulfate, 3.5g of ammonium persulfate and 8g of polyvinylpyrrolidone (PVP) until the sodium dodecyl sulfate, the ammonium persulfate and the polyvinylpyrrolidone are completely dissolved, then adding 45g of bis-trimethylsilyl vinyl phosphate (CAS 18291-41-3), 4.5g of vinylguanamine and 2.2g of 4-allyl aminobenzoate, uniformly mixing, and finally adding 3.0g of carboxymethyl cellulose;

s3: controlling the reaction temperature to be 70 ℃, stirring the mixture at the rotating speed of 100r/min, reacting the mixture for 4 hours, and cooling the mixture to room temperature after the reaction is finished to obtain the high-efficiency water-based extinguishing agent.

Example 6

S1: under the protection of nitrogen, 250g of ionized water is put into a stirring container and heated to 70 ℃;

s2: firstly, 3.5g of nonylphenol polyoxyethylene ether, 4.0g of ammonium persulfate and 9g of polyvinylpyrrolidone (PVP) are stirred until the nonylphenol polyoxyethylene ether, the ammonium persulfate and the polyvinylpyrrolidone are completely dissolved, then 50g of bis (trimethylsilyl) vinyl phosphate (CAS 18291-41-3), 5g of vinylguanamine and 2.4g of 4-allyl aminobenzoate are added and uniformly mixed, and finally 3.2g of polyvinyl alcohol is added;

s3: controlling the reaction temperature to be 80 ℃, stirring the mixture at the rotating speed of 120r/min, reacting the mixture for 4 hours, and cooling the mixture to room temperature after the reaction is finished to obtain the high-efficiency water-based extinguishing agent.

EXAMPLES evaluation