CN106280165B

CN106280165B - High molecular fire-retardant and fire-extinguishing gel and preparation method thereof

Info

Publication number: CN106280165B
Application number: CN201610789455.5A
Authority: CN
Inventors: 许志峰; 蔡建文; 张念慈; 蔡志勇; 靳松; 邸明伟
Original assignee: HEILONGJIANG PROV FOREST PROTECTION INSTITUTE
Current assignee: HEILONGJIANG PROV FOREST PROTECTION INSTITUTE
Priority date: 2016-08-31
Filing date: 2016-08-31
Publication date: 2021-07-13
Anticipated expiration: 2036-08-31
Also published as: CN106280165A

Abstract

A high molecular fire-retardant and fire-extinguishing gel and a preparation method thereof relate to a fire-retardant and fire-extinguishing gel and a preparation method thereof. The preparation method of the polymer fire-retardant and fire-extinguishing gel comprises the following steps: firstly, preparing a neutralization solution; secondly, adding a cross-linking agent, an initiator and an adhesion promoter; thirdly, polymerization reaction; dispersing the produced super absorbent resin in the vegetable oil; and fifthly, adding a stabilizer into the suspension. The gel prepared by the invention is always kept in a uniformly dispersed liquid state, can be directly siphoned into a water tank when in use, can be directly sprayed without stirring and mixing, does not need to wait, block or agglomerate, has good dispersibility, does not damage spraying equipment, does not delay fighting of fire, and fundamentally solves the defects of the existing powdery solid product; and can be sprayed for use.

Description

High molecular fire-retardant and fire-extinguishing gel and preparation method thereof

Technical Field

The invention relates to a fire-retardant and fire-extinguishing gel and a preparation method thereof.

Background

The Polymer gel is a gel-state substance formed by a Super Absorbent Polymer (SAP) after absorbing water. The super absorbent resin has a special three-dimensional space network structure, and can absorb water which is hundreds times heavier than the super absorbent resin in mass in a three-dimensional space grid, so that high polymer polymeric gel is formed.

The space structure of the polymer gel is similar to the water film-forming foam AFFF or class A foam from the microscopic view, the difference is that the gaps of the three-dimensional space network structure of the polymer gel can be filled with water, and the 'water bubbles' filled with water can greatly improve the heat insulation protection performance compared with the foam filled with air only. If the heat of a fire is to reach the surface of the protected layer, it must evaporate each "blister" and the energy of the fire is absorbed to a large extent, reducing its destructive power. When fire is extinguished, the contained water is evaporated and gasified to absorb a large amount of heat, the volume is also rapidly enlarged, and when the water vapor accounts for 30% of the combustion space or is cooled to a temperature below the flash point and the ignition point of a combustion substance, the combustion can be automatically stopped.

The stacked structure of the polymer gel hydrate can significantly hinder the evaporation of water therein. After the flame-retardant material is covered on the surface of a burning substance, an insulating area can be formed on the surface of a flame and a protected object, and the insulating area plays a role in oxygen insulation and heat insulation, so that the heat transfer of burning is cut off, and finally, the burning is forced to stop. The high molecular polymer gel hydrate can isolate the high temperature of 2000 ℃ and keep for a long time.

The high molecular polymer gel can resist flame and can be sprayed on surrounding inflammable buildings and important facilities (such as compressed natural gas cylinders, railway tank trucks, vehicles, ships, airplanes, trees, even glass, windows and the like), thereby ensuring the safety of the covering to a certain extent. The high-molecular polymer gel can be used for forming a forest fire barrier belt, can absorb water hundreds of times of the weight of the forest fire barrier belt, has small drift evaporation in the fire extinguishing process, can achieve the purpose of fire extinguishing due to water loss heat consumption, can form an insulating area between fire and combustible to form a fire retardant barrier to isolate air, still plays a role in protection at the high temperature of 3500 ℃, and is a technical measure for rapidly, safely and environmentally forming the forest fire barrier belt. The polymer gel is used for extinguishing fire, can extinguish fire including A-class combustible substances, is very effective, and can reduce the probability of reburning besides quickly cooling the combustible substances. The polymer gel has another characteristic that after the gel protective layer at a certain point is damaged by the attack of a violent fire, the gel protective layer on the upper layer of the point can slide down to be covered on the wounded surface again, and the fire in the area is extinguished. Meanwhile, the high-molecular polymer gel is not easy to drift and diffuse, and can be sprayed by an airplane to carry out fire-retarding and fire-extinguishing operations. In areas where water supply is limited, the polymeric gel can help firefighters extinguish as much fire as possible with as little water as possible.

In addition, the macromolecular polymeric gel has the obvious advantages of large water absorption capacity, high water absorption rate, strong water retention capacity, no toxicity, no odor and the like, and is considered to have wide application prospect.

However, the polymer gel prepared at present can be subjected to gel dilution after standing for 48 hours at room temperature, so that the originally viscous gel becomes diluted, and the dilution becomes more and more obvious as the time is prolonged, and finally the gel is in a clear water shape. Therefore, the polymer gel is dried or dehydrated to form solid particles, and the solid particles are mixed with water when used. Because the high molecular polymer gel is a high water absorption substance, the high molecular polymer gel has high drying or dehydration difficulty, is easy to agglomerate and agglomerate during rehydration, and has reduced flame retardant and fire extinguishing performance after rehydration.

Disclosure of Invention

The invention aims to provide a high-molecular polymer gel which can be stored for a long time and is not denatured.

The preparation method of the polymer fire-retardant and fire-extinguishing gel comprises the following steps:

firstly, adding sodium hydroxide or sodium carbonate aqueous solution into acrylic acid under stirring until the neutralization degree is 60-90%, simultaneously controlling the reaction temperature to be 35-50 ℃ and mixing for 15-50 minutes to obtain a neutralized solution;

secondly, sequentially adding a cross-linking agent, an initiator and an adhesion promoter into the obtained neutralized liquid, and continuously stirring for 15-50 min to obtain a polymerization liquid;

thirdly, carrying out polymerization reaction on the obtained polymerization liquid at the temperature of 50-100 ℃ for 1-6 hours to generate super absorbent resin;

dispersing the generated super absorbent resin in the vegetable oil, and uniformly stirring for 2-5 hours to obtain a suspension;

fifthly, adding a stabilizing agent into the suspension to form uniform high-molecular fire-retarding and extinguishing gel;

wherein, the adhesion promoter in the second step is one or more selected from PN-700, PN-701, PN-702, DN-801, DN-630, DN-631, DN-630, DN-9311 and DN-808, and the dosage of the adhesion promoter is 0.001 to 5 percent of the mass of the neutralizing liquid in the first step.

The high-molecular fire-retardant and fire-extinguishing gel disclosed by the invention is sealed at room temperature and is stored for 3-5 years (even longer) without generating denaturation conditions such as layering, dilution, precipitation and the like.

The high molecular fire-retardant and fire-extinguishing gel does not contain any nonylphenol polyoxyethylene ether or petroleum distillate except the effective components, only contains vegetable oil and is completely biodegraded, and has biosafety.

The high molecular fire extinguishing gel additives used in China at present are all solid powder or particles, and before the fire extinguishing gel is used, the fire extinguishing gel must be dissolved in water to absorb water and swell. However, in the process, a certain time is needed for water absorption and swelling, the swelling is not uniform, and the agglomeration and caking are easy to occur; resulting in untimely fire suppression and easy blockage of the spraying apparatus.

The gel prepared by the invention is always kept in a uniformly dispersed liquid state, can be directly siphoned into a water tank when in use, can be directly sprayed without stirring and mixing, does not need to wait (namely mixing and using), does not agglomerate or agglomerate, has good dispersibility, does not damage spraying equipment, does not delay fighting of fire, and fundamentally solves the defects of the existing powdery solid product; and can be sprayed for use.

Drawings

FIG. 1 is a high molecular fire-retardant and extinguishing gel fire-retardant experiment, in which the skin is not damaged after burning by a blast lamp.

Detailed Description

The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.

The first embodiment is as follows: the preparation method of the high-molecular fire-retardant and fire-extinguishing gel comprises the following steps:

The polymer fire-retardant and fire-extinguishing gel prepared by the embodiment is used for unsealing, the cover opening needs to be screwed down, a small amount of layering can occur during reuse, and only up-and-down shaking is needed to be uniform, so that the using effect is not influenced.

The second embodiment is as follows: the present embodiment differs from the first embodiment in that: and the stirring speed of the fourth step is 60 r/min. Other steps and parameters are the same as those in the first embodiment.

The third concrete implementation mode: the present embodiment is different from the first or second embodiment in that: in the second step, the adhesion promoter is DN-630, and the dosage of the adhesion promoter is 0.03 percent of the mass of the neutralizing liquid in the first step. Other steps and parameters are the same as in one or both embodiments.

The fourth concrete implementation mode: the present embodiment is different from the first to third embodiments in that: in the second step, the cross-linking agent is selected from one or more of N, N ' -methylene bisacrylamide, N ' -methylene bismethacrylamide, N ' -ethyl bisacrylamide, ethylene glycol, diethylene glycol, glycerol, polyoxyethylene glycol, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether and polyglycerol diglycidyl ether; the dosage of the cross-linking agent is 0.001-2.5% of the mass of the neutralization solution in the step one. Other steps and parameters are the same as those in one of the first to third embodiments.

The fifth concrete implementation mode: the present embodiment is different from one of the first to fourth embodiments in that: in the second step, the initiator is hydrogen peroxide, potassium persulfate, sodium persulfate or ammonium persulfate, and the dosage of the initiator is 0.001-5% of the mass of the neutralizing liquid in the first step. The other steps and parameters are the same as those in one of the first to fourth embodiments.

The sixth specific implementation mode: the present embodiment is different from one of the first to fifth embodiments in that: the vegetable oil in the fourth step is selected from one or more of vegetable oil, corn oil, olive oil, rapeseed oil, soybean oil and blend oil, and the amount of the vegetable oil is 10-20% of the mass of the neutralization solution in the first step. Other steps and parameters are the same as those in one of the first to fifth embodiments.

The seventh embodiment: the present embodiment differs from one of the first to sixth embodiments in that: and in the fifth step, the stabilizing agent consists of an emulsifying agent and a thickening agent. Other steps and parameters are the same as those in one of the first to sixth embodiments.

The specific implementation mode is eight: the seventh embodiment differs from the seventh embodiment in that: the emulsifier is selected from one or more of glycerol monostearate, diglyceride monostearate, sucrose fatty acid ester, span 80, tween 60 and modified soybean lecithin, and the using amount of the emulsifier is 0.5-1% of the mass of the neutralization solution in the step one. Other steps and parameters are the same as those in the seventh embodiment.

The specific implementation method nine: the seventh embodiment differs from the seventh embodiment in that: the step thickener is selected from one or more of starch, gelatin, sodium alginate, casein, guar gum, chitosan, gum arabic, xanthan gum, soybean protein gum, natural rubber, lanolin and agar, and the amount of the thickener is 0.1-0.5% of the mass of the neutralization solution in the step one. Other steps and parameters are the same as those in the seventh embodiment.

The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: the concentration of the aqueous solution of sodium hydroxide or sodium carbonate was 20 WT%. Other steps and parameters are the same as those in one of the first to ninth embodiments.

The concrete implementation mode eleven: the present embodiment differs from the first to tenth embodiments in that: in the second step, the cross-linking agent is propylene glycol diglycidyl ether, and the dosage of the cross-linking agent is 0.18 percent of the mass of the neutralization solution in the first step. The other steps and parameters are the same as those in one of the first to tenth embodiments.

The specific implementation mode twelve: the present embodiment differs from one of the first to eleventh embodiments in that: in the second step, the initiator is sodium sulfate, and the dosage of the initiator is 0.16 percent of the mass of the neutralization solution in the first step. Other steps and parameters are the same as those in one of the first to eleventh embodiments.

Example 1

firstly, adding acrylic acid into a reaction kettle (F type 1000L reaction kettle, manufactured by Jiangsu Yang chemical equipment manufacturing limited company), then dissolving 20 wt% of sodium carbonate and slowly dripping into the reaction kettle filled with the acrylic acid, opening a jacket for cooling, controlling the temperature to be 35-50 ℃, and stirring for 15-50 min to ensure that the neutralization degree reaches 60-90% to obtain a neutralization solution;

secondly, sequentially adding propylene glycol diglycidyl ether accounting for 0.18 percent of the mass of the neutralization solution, sodium persulfate accounting for 0.16 percent of the mass of the neutralization solution and DN-630 accounting for 0.03 percent of the mass of the neutralization solution into the obtained neutralization solution, and continuously stirring for 15-50 min to obtain polymerization solution;

dispersing the generated super absorbent resin into soybean oil accounting for 15% of the mass of the neutralization solution, and uniformly stirring for 2-5 hours to obtain a suspension;

wherein the stabilizer consists of sucrose fatty acid ester accounting for 0.8 percent of the mass of the neutralization solution and starch accounting for 0.8 percent of the mass of the neutralization solution.

Experiment:

1. simulated combustion wood buttress construction

3 same simulated combustion wood piles are built according to the national standard GB 4066.2-2004, and the building method of the wood piles is as follows: 50 Korean pine wood strips with the specification of 12mm multiplied by 210mm and the water content of 8% -12% are crossly lapped on a prepared iron stand by 5 Korean pine wood strips in each layer and dividing the Korean pine wood strips into 10 layers at 90 degrees. A metal pallet with the specification of 250mm multiplied by 60mm is placed under the wood pile.

2. After the polymer fire-retardant and fire-extinguishing gel is prepared, the polymer fire-retardant and fire-extinguishing gel is stored for 5 years at room temperature in a closed and standing mode, and then observation and experiments are carried out

The macromolecular fire-retardant fire-extinguishing gel stored for 5 years does not generate denaturation conditions such as layering, dilution, precipitation and the like. The polymer fire-retardant and fire-extinguishing gel can be stored for a long time.

Fire extinguishing experiment:

under the experimental conditions that the temperature is 20 ℃ and the wind speed is 1m/s, 3 metal trays are filled with the same amount of No. 93 unleaded gasoline for vehicles, 3 wood stacks are ignited at the same time, and the timing is started while the gasoline is ignited. When the wood crib burns for 3min, the polymer fire-retardant and fire-extinguishing gel of the embodiment is used for extinguishing fire of the wood crib in 3 burning processes. When the high-molecular fire-retardant and fire-extinguishing gel is used, the high-molecular fire-retardant and fire-extinguishing gel is sprayed at a position which is not less than 1.8m away from the wood stack, then is close to the wood stack and is sprayed to the top, the bottom, the side and the like, but cannot be sprayed to the back of the wood stack. When in fire extinguishing, the high molecular fire-retardant and fire-extinguishing gel is siphoned into the water tank and then continuously sprayed, the spraying amount (water and the high molecular fire-retardant and fire-extinguishing gel) is 10L/s, and an operator and any part of the fire extinguisher should not touch the model.

Data was recorded as follows:

(1)1 highest temperature in the centre of the wood crib when each wood crib was burned for 3 min.

(2) And (3) extinguishing the fire by using the polymer fire-retardant and fire-extinguishing gel stored for 5 years, so that the central temperature of the wood stack is reduced to 300 ℃ for a long time.

(3) The time for extinguishing the open fire of the wood crib is used by the macromolecular fire-retardant and fire-extinguishing gel stored for 5 years.

(4) And observing whether the wood stacks extinguished after 20min have the re-burning phenomenon.

Experimental data: A. the highest temperature of the center of the wood pile is 747 ℃; B. the average time required for the center temperature of the wood pile to be reduced from 745 ℃ to 300 ℃ is 45 s; C. the time average time to extinguish an open fire was 54 s; D. no afterburning occurred.

Experimental data prove that the high-molecular fire-retarding and fire-extinguishing gel still has excellent fire-extinguishing effect after being stored for 5 years.

Fire retardant experiment 1:

under the condition that the air temperature is 29 ℃ and the air speed is 3-7 m/s, two stacks with the same specification are manufactured, namely 84 pines with the specification of being about 7 centimeters (+/-0.2 centimeter) in length of 1 meter and the water content of 10-14 percent are divided into 14 layers and placed on an angle iron bracket, and 10 liters of No. 93 motor gasoline is used on an ignition disc respectively. The polymer fire-retardant and fire-extinguishing gel of the embodiment is formed by spraying siphon water on one wood stack, and the thickness of the gel is 5-10 mm; the other stack was sprinkled with 9 liters of tap water. The gasoline sprayed below the wood crib of the polymer fire-retardant and fire-extinguishing gel of the embodiment is extinguished after burning for 6 minutes and 58 seconds, and the wood crib is not burnt and remains intact. The sprinkler wood stack is ignited and the fire is violent.

Experiments show that the high-molecular fire-retardant and fire-extinguishing gel still has excellent fire-retardant effect after standing and storing for 5 years.

Fire retardant experiment 2:

spraying the macromolecular fire-retardant and fire-extinguishing gel with siphon water on the iron door, leaving a letter mark on the iron door without covering the macromolecular fire-retardant and fire-extinguishing gel, and then baking the iron door by using a blast lamp. After the end of the broiling, the letter mark is found to be obviously discolored, and the part covered by the high-molecular fire-retardant and fire-extinguishing gel is safe and innocent.

Selecting 2 cans of iced cola, 1 can of iced cola without protection, spraying another 1 can of polymer fire-retardant and fire-extinguishing gel prepared by the method of the invention with siphon water, and then baking with a spray gun at the same temperature. 2 the tank coke has a distinct change, the coke sprayed with the polymer fire-retardant fire-extinguishing gel is safe and innoxious, and the unprotected coke is already heated and burst. The gel-protected cola was opened and drunk until the taste was cool.

The high molecular fire-retardant and fire-extinguishing gel prepared by the method is smeared on the skin on the back of the hand, and then the high temperature blowtorch is used for burning, so that the skin under the high molecular fire-retardant and fire-extinguishing gel is not damaged at all (as shown in figure 1).

Claims

1. The preparation method of the polymer fire-retardant and fire-extinguishing gel is characterized by comprising the following steps:

firstly, adding acrylic acid into a reaction kettle, then dissolving sodium carbonate with the concentration of 20 wt% and slowly dripping the sodium carbonate into the reaction kettle filled with the acrylic acid, starting a jacket for cooling, controlling the temperature to be 35-50 ℃, and stirring for 15-50 min to ensure that the neutralization degree reaches 60-90% to obtain a neutralization solution;

2. A polymeric fire retarding and extinguishing gel prepared according to the method of preparation of claim 1.