CN110935128A - Fireproof cooling hydrogel and preparation method thereof - Google Patents
Fireproof cooling hydrogel and preparation method thereof Download PDFInfo
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- CN110935128A CN110935128A CN201911229298.2A CN201911229298A CN110935128A CN 110935128 A CN110935128 A CN 110935128A CN 201911229298 A CN201911229298 A CN 201911229298A CN 110935128 A CN110935128 A CN 110935128A
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0064—Gels; Film-forming compositions
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0071—Foams
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/06—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires containing gas-producing, chemically-reactive components
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Abstract
The invention relates to the field of manufacturing and application of heat-resistant, heat-insulating, flame-retardant and high-temperature expansion materials, in particular to a hydrogel with fireproof and cooling functions and a preparation method thereof, wherein the hydrogel comprises the following components in parts by weight: 0.05-20 parts of hydrogel thickener; 5-35 parts of a freezing point depressant; 1-30 parts of an expanded foam; 1-15 parts of an intumescent flame retardant; 0.01-1 part of foaming agent; 1-15 parts of a gas generating agent; 0.01-1 part of bactericide; the innovation of the invention is that when the gel directly acts on the surface of the burning object, the gel can be firstly adhered to the surface of the burning object; secondly, foam can be generated on the surface of the burning object, and the foam contains water, so that the water can be sealed in the foam, and the continuous cooling and fire extinguishing capability is realized; after being dried, the water can generate an expanded flame-retardant layer, thereby providing a continuous heat-insulating flame-retardant function and playing the functions of extinguishing fire, reducing temperature, insulating heat and preventing fire re-ignition.
Description
Technical Field
The invention relates to the field of manufacturing and application of heat-resistant, heat-insulating, flame-retardant and high-temperature expansion materials, in particular to a fireproof and heat-insulating hydrogel with flame-retardant, heat-insulating and cooling functions and a preparation method thereof.
Background
The lithium battery is the civil chemical energy with the most advanced performance level and the most rapid development at present, and becomes a preferred matching power supply for high-end products such as mobile phones, notebook computers, digital equipment and the like. However, lithium batteries are dangerous in use and transportation, and the danger may be fatal and even cause a disaster.
According to the statistics of the Federal Aviation Administration (FAA), 144 accidents related to battery smoking, fire, extreme heat or explosion occurred between 1991 and 2014. Many lithium battery burning accidents also occur in the domestic aviation transportation process.
The danger of lithium battery combustion is mainly manifested by smoking, fire, extreme heat or explosion, and possibly a small amount of toxic gas. The FAA study shows that the temperature generated by thermal runaway of lithium batteries exceeds 590 ℃ and that generated by thermal runaway of lithium metal batteries exceeds 760 ℃. Charging a 6000mAh pure lithium cobaltate polymer battery cell to 4.3V, then performing needling simulation on internal short circuit, and immediately combusting the battery, wherein the generated temperature instantaneously exceeds 700 ℃. The danger level of lithium ion battery burning is related to its capacity and the voltage magnitude of the charge: the possibility of combustion is low when the voltage is low and the internal short circuit is low at a certain time, but smoke and even violent dense smoke can be generated and has violent irritation; the greater the voltage, the greater the possibility of short-circuit combustion and the more violent the combustion, and in the case of steel-can batteries, the explosion may occur.
The FAA research shows that the HALON1301 fire extinguishing agent used on the airplane can inhibit the fire of the electrolyte but has no inhibiting effect on the fire of the lithium metal, and when the HALON fire extinguishing agent is used, whether the lithium metal battery or the lithium ion battery increases the risk of fire and explosion along with the increase of unburned hydrocarbon released by the electrolyte. Tests show that although the Halon fire extinguishing agent can inhibit the fire of lithium ion battery combustion, the danger of repeated re-combustion exists after the flame is extinguished, because the temperature reduction capability of the Halon fire extinguishing agent is limited, once the Halon fire extinguishing agent stops being used, the temperature can rapidly rise, the thermal runaway of the lithium ion battery cannot be inhibited, and the possibility that surrounding substances are ignited again exists.
Aiming at the danger of lithium battery combustion, FAA and International aviation Association (ICAO) propose emergency treatment measures for lithium battery combustion: in case of metal lithium battery, rechargeable lithium ion battery and lithium battery package, once the lithium battery is burnt, passengers are evacuated to a safe place, and then fire is extinguished by using Halon fire extinguishing agent or substitute of Halon fire extinguishing agent and water to prevent flame from spreading to adjacent batteries or materials, and after the flame is extinguished, the lithium battery is immediately cooled by using water or non-alcoholic liquid to prevent the lithium battery from being re-burnt.
The above treatment depends on the number of batteries and the intensity of the fire, which may also be more difficult to control if the number of batteries is large and the flame is also large due to the limited water on board the aircraft.
German patent No. WO2011015411 (CN 102470261) proposes extinguishing combustion of a lithium ion battery by using an aqueous solution of a calcium salt and a gel fire extinguishing agent simultaneously, wherein the calcium salt is a mixture of CaCl2 and ca (oh) 2, and the aqueous solution contains a large amount of Cl —, so that the corrosion to metals is relatively high, and the fire extinguishing process is performed by using both the water solution and the gel fire extinguishing agent simultaneously, which brings difficulty in use. Chinese patents CN200310112793, CN200710020580, CN201010562827 and CN201310067726, are water mist fire extinguishing agents of low viscosity aqueous solution, the main components of which are surfactant, water and a small amount of inorganic salt, organic salt, etc., when extinguishing fire, the water consumption is large and is easy to evaporate.
The Chinese patent with application number 01811547 relates to a heat-sensitive polyacrylamide water-soluble polymer fire extinguishing agent, which comprises polyacrylamide polymer, water, surfactant and fire extinguishing agent (ammonium dihydrogen phosphate, potassium hydrogen carbonate, potassium acetate, etc.), and has viscosity of 20-2000 mPa.s (20-2000 cP). The hydrogel is a low-viscosity aqueous solution at a set temperature and is water-insoluble hydrogel above the set temperature. Chinese patent No. 88103151 relates to an inorganic gel aqueous solution fire extinguishing agent of sodium silicate hydrate, which has the disadvantages that: the inorganic hydrogel substance has low water absorption, the residual inorganic substance after water volatilization at high temperature can not play a role of continuously cooling, the temperature can rise after being reduced, and the fire extinguishing capability is limited due to the low water content, and the like.
The lithium battery is characterized in that: when the heat is accumulated to a certain degree, the heat can be burnt or even exploded; the thermal runaway of the lithium battery is easy to cause the thermal runaway of the surrounding lithium battery so as to generate a chain reaction; when the lithium battery is burnt, the flame is large, the temperature is high, and after-burning can be generated if the temperature is not rapidly reduced even if the flame is extinguished; toxic gas is generated during combustion.
In conclusion, the lithium battery combustion extinguishing agent, the organic hydrogel and the inorganic hydrogel extinguishing agent related to the prior patent have the defects when the lithium battery and the package are burnt.
Disclosure of Invention
In order to solve the problems that the temperature can not be rapidly reduced when a fire extinguishing medium is used for extinguishing fire when lithium batteries and packages in a cargo hold are combusted, the temperature is easy to rebound after cooling, the afterburning is generated, and the like on an airplane, particularly to provide a lithium battery, a package combustion hydrogel or other fire treatment hydrogels which are convenient to use, can effectively extinguish the combustion of the lithium battery, can be rapidly cooled, and is not easy to rebound after cooling, and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a fireproof cooling hydrogel is characterized in that: the adhesive comprises the following components in parts by mass:
0.05-20 parts of hydrogel thickener;
5-35 parts of a freezing point depressant;
1-30 parts of an expanded foam;
1-15 parts of an intumescent flame retardant;
0.01-1 part of foaming agent;
1-15 parts of a gas generating agent;
0.01-1 part of bactericide;
at least 50 parts of water.
Further, the expanded foam material comprises waterborne polyurethane, epoxy modified waterborne polyurethane or waterborne acetic acid-ethylene polymer, and the content of the expanded foam material is 5-20 parts.
Further, the foaming agent is a surfactant, the surfactant comprises sulfate anionic surfactant, coconut oil fatty acid diethanolamide, disodium lauryl sulfosuccinate monoester, potassium monododecyl phosphate, potassium lauryl alcohol ether phosphate, fatty alcohol polyoxyethylene ether ammonium sulfate, cocamidopropyl betaine, lauramidopropyl betaine or lauramidopropyl amine oxide, and the content of the foaming agent is 0.01-0.3.
Further, the gas generating agent is a composition of an acid insoluble or slightly soluble in water and a salt soluble in water; the water insoluble acid includes benzoic acid, stearic acid; the content of the acid is 0.1-6 parts, preferably 0.1-3%; the water soluble salt comprises bicarbonate, carbonate; the content of the salt is 0.1-6 parts, preferably 0.1-3 parts.
Further, the hydrogel thickener is one or more of water-soluble high molecular polymers including polyacrylamide and copolymers thereof, polyacrylate and copolymers thereof, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, xanthan gum, agar powder, guar gum, polyvinyl alcohol and sodium alginate.
Further, the content of the water-soluble high molecular polymer is preferably 0.1 to 10 parts, more preferably 0.1 to 3 parts.
The hydrogel thickener is soluble in water to form an aqueous solution, and contains a water-soluble high molecular polymer powder suspended in the aqueous solution and including agar powder or high-crystallinity polyvinyl alcohol powder, wherein the particle size of the powder is 1-100um, preferably 1-50 um.
The content of the high water-absorbing polymer powder is 0.1-5, preferably 0.5-2 parts;
further, the hydrogel thickener is an inorganic water-absorbing material; the inorganic water-absorbing substance comprises one or more of bentonite, diatomite, fumed silica, magnesium aluminum silicate and magnesium lithium silicate;
further, the content of the inorganic water-absorbing substance is 0 to 15 parts, preferably 1 to 10 parts, more preferably 1 to 5 parts.
Further, the hydrogel thickener is a composition of a water-soluble high molecular polymer and an inorganic water-absorbing substance.
Further, the freezing point depressant is an alcohol composition; the alcohol comprises one or more of xylitol, sorbitol, mannitol, ethylene glycol, propylene glycol and bio-based ethylene glycol and propylene glycol.
Further, the intumescent flame retardant comprises expanded graphite and vermiculite, wherein the content of the expanded graphite is 1-15 parts, preferably 1-10 parts; the content of the expanded vermiculite is 1-15 parts, preferably 1-10 parts.
Further, the bactericide is dodecyl dimethyl benzyl ammonium chloride, polyquaternary ammonium salt, benzisothiazolinone, glutaraldehyde and sodium benzoate.
A process for preparing the fire-proof hydrogel with low temp. includes such steps as dissolving the thickening agent in water at ordinary temp. or under heating to obtain a liquid whose concentration is 0.1-10%, dispersing the water-soluble high-molecular polymer powder in the dissolved liquid, and dispersing the freezing-point depressant, expanded foam, expanded flame-retarding filler, foaming agent and disinfectant in said liquid to obtain uniform liquid.
The fireproof cooling hydrogel can be directly sprayed on the surface of a comburent and also can be filled in a gel storage medium such as a gel strip/bag.
Compared with the prior art, the invention has the following beneficial effects:
1. the innovation of the invention is that when the gel directly acts on the surface of the burning object, the gel can be firstly adhered to the surface of the burning object; secondly, foam can be generated on the surface of the comburent, and the foam contains water, so that the water can be sealed in the foam, and the continuous heat insulation, temperature reduction and fire extinguishing capabilities are achieved; after being dried by water, the flame-retardant layer can be expanded to provide a continuous heat-insulating flame-retardant function; when the gel is canned in a storage medium such as a storage strip/bag, the gel can generate a large amount of gas under the action of high temperature to break the storage medium so as to release the gel, thereby playing the functions of extinguishing fire, reducing temperature, insulating heat and preventing fire from reigniting.
2. As the conventional hydrogel extinguishes and cools through the water in the gel, the hydrogel does not have the function of extinguishing and cooling after the water is volatilized. And in the air transportation of lithium cell goods, all lithium cell in the package just can produce thermal runaway in succession after certain lithium cell thermal runaway in the package, and the high duration of temperature of lithium cell thermal runaway is long, adopts conventional aquogel to carry out emergent or prevention and deals with, thereby water volatilizees very easily and loses the emergent or prevention of thermal runaway and deals with the effect. According to the fireproof heat-insulation hydrogel, the hydrogel can generate a foam expansion heat-insulation layer under the action of high temperature or open fire, so that the flame-retardant time, the heat-insulation time and the heat-resisting time are obviously prolonged; the hydrogel is filled in a gel storage medium such as a gel bag, and the gel bag is broken to release gel under the action of high temperature or open fire, thereby playing the functions of cooling, heat insulation and fire extinguishing.
3. The hydrogel contains foaming polymer, and the substance can foam at high temperature to form a thicker foam layer, so that the hydrogel has an effective heat insulation function;
4. according to the requirements, high water-absorbing polymer powder can be added into the hydrogel and suspended in the gel, the polymer powder is dissolved and absorbs water at high temperature, the sprayed or released gel is attached to the surface when being left on the surface of a low-temperature object, and even can be cooled to form an assembly, and the assembly can not flow when being attached to the surface of the object, so that the utilization efficiency of the gel is effectively improved, and the heat-insulating, cooling and flame-retardant functions are realized;
5. the hydrogel contains an expansion heat-insulation flame-retardant filler. The expanded graphite has high expansion speed, thick expansion layer and low expansion speed of vermiculite, but has good heat-insulating property, and the expanded graphite and the vermiculite are combined for use to obtain a heat-insulating flame-retardant expansion layer with thick expansion layer and good heat-insulating property;
6. the hydrogel disclosed by the invention has the advantages that when the expansion flame-retardant layer formed at high temperature is continuously burnt by flame at 1200 ℃, the surface compactness is good, the cracking is difficult, and the burning layer with certain hardness is formed on the burnt surface, so that the flame-retardant and heat-insulating properties are effectively improved.
7. The gel is water-soluble gel, and has good environmental protection performance.
Detailed Description
The mixing of the components herein is not limited by the ratio, any ratio can achieve the technical effect of the hydrogel, and the addition of each component without limitation of concentration indicates that there is no limitation on the concentration, and different concentrations as is conventional in the art can achieve the technical effect, only the effect is different.
Example 1
The fireproof cooling hydrogel comprises the following components in parts by weight and deionized water:
0.5-25 parts of at least one macromolecular hydrogel thickener and more than 75 parts of water.
Example 2
The second scheme of the invention is as follows: contains 10-40 parts of at least one inorganic hydrogel thickener and more than 60 parts of water.
Example 3
Contains 0.1-15 parts of at least one high molecular hydrogel thickener, 1-25 parts of at least one inorganic hydrogel thickener and more than 50 parts of water.
Example 4:
0.5-25 parts of at least one polymer hydrogel thickener, 5-40 parts of freezing point depressant, 0.1-1 part of bactericide and more than 60 parts of water
Example 5:
10-40 parts of at least one inorganic hydrogel thickener, 5-40 parts of a freezing point depressant, 0.1-1 part of a bactericide and more than 50 parts of water.
Example 6:
0.1-15 parts of at least one polymer hydrogel thickener, 1-25 parts of at least one inorganic hydrogel thickener, 5-40 parts of freezing point depressant, 0.1-1 part of bactericide and more than 50 parts of water.
Example 7:
a preparation method of fireproof cooling hydrogel is characterized by comprising the following steps: the operations are sequentially carried out according to the following sequence: a) adding the hydrogel substance into the stirred deionized water, and continuously stirring for 1-2 hours after the addition is finished; b) adding freezing point depressant and stirring for 0.5-1 hour; c) adding bactericide, and stirring for 0.1-0.5 hr respectively to obtain uniform solution.
Example 8:
the operation was carried out in the following order:
slowly adding a polymer hydrogel thickener xanthan gum into the stirred deionized water, and continuously stirring for 1 hour after the addition is finished; b) adding inorganic hydrogel thickener, stirring to completely disperse and dissolve; e) adding the expanded foam and the bactericide, and stirring for 0.5 hours respectively after adding to be uniform.
Example 9:
the operation was carried out in the following order:
a) slowly adding the high-molecular hydrogel thickener acrylic acid copolymer into the stirred deionized water, and continuously stirring until the hydrogel thickener is completely dispersed and dissolved after the addition is finished; b) adding an inorganic hydrogel thickener, and stirring until the inorganic hydrogel thickener is completely dissolved and dispersed; c) Adding the expanded foam material, and uniformly stirring; e) adding other components and stirring uniformly.
Example 10:
the operation was carried out in the following order:
a) slowly adding xanthan gum into the stirred deionized water, and continuously stirring until the xanthan gum is completely dissolved after the xanthan gum is added; b) adding inorganic hydrogel thickener, and continuously stirring until the inorganic hydrogel thickener is completely dissolved; c) Adding ethylene glycol, and stirring uniformly; e) adding benzoic acid and a bactericide, and uniformly stirring f) dissolving sodium carbonate in a proper amount of water, adding the solution, and uniformly stirring.
Example 11:
the operation was carried out in the following order:
a) slowly adding xanthan gum into the stirred deionized water, and continuously stirring until the xanthan gum is completely dissolved after the xanthan gum is added; b) adding inorganic hydrogel thickener, and continuously stirring until the inorganic hydrogel thickener is completely dissolved; c) Adding ethylene glycol, and stirring uniformly; e) uniformly stirring the bactericide, and f) adding polyvinyl alcohol powder and uniformly stirring.
Overcharging a 6000mAh pure lithium cobaltate polymer single battery cell to 4.3V, then coating about 7g of the gel on the surface of the battery cell, and performing an internal short circuit test by needling; performing needle short circuit on the battery cell without the gel coating; and simultaneously binding the two electric cores together by using thin iron wires, coating 10g of gel on the surfaces of the electric cores, and then carrying out a needling internal short circuit test.
And (4) test conclusion:
1) the pure lithium cobaltate single cell without gel coating burns rapidly;
2) the pure lithium cobaltate cell coated with the gel is not burnt, the bottom of the gel is formed into a film, the upper surface of the gel is still the gel, and the phenomenon of no water boiling occurs.
3) The double cells do not burn, the internal temperature of the cells is 720 ℃, and the surface temperature of the gel is 87 ℃.
Example 12
The operation was carried out in the following order:
a) adding magnesium aluminum silicate into the stirred deionized water, and continuously stirring for 1.5 hours after the magnesium aluminum silicate is added; b) adding sorbitol, corrosion inhibitor and bactericide, and stirring for 0.5 hours to be uniform respectively after adding.
Overcharging a 6000mAh pure lithium cobaltate polymer single battery cell to 4.35V, then coating about 4g of the gel on the surface of the battery cell, and performing an internal short circuit test by needling; performing needle short circuit on the battery cell without the gel coating; coating about 10g of the gel on the surface of a battery cell, and performing an internal short circuit test by using acupuncture;
and (4) test conclusion:
1) the pure lithium cobaltate single cell without gel coating burns rapidly;
2) the cell coated with 4g of gel was burned at the edge portion of the cell without gel;
3) the cell coated with 10g of gel burned at the edge portion of the cell without gel, and the flame was small and quickly extinguished. The temperature of the inside of the battery cell is 825 ℃, the temperature of the surface of the battery cell (the surface of the battery cell, which is contacted with the battery cell) is 220 ℃, and the temperature of the surface of gel is 98 ℃.
Example 13
The fireproof cooling hydrogel comprises the following components in parts by weight:
0.1-10 parts of at least one macromolecular hydrogel thickener;
1-10 parts of at least one inorganic hydrogel thickener;
5-25 parts of at least one alcohol;
1-20 parts of at least one expanded foam;
0.1-1 parts of at least one bactericide;
0.01-1 part of at least one foaming agent
1-15 parts of at least one group of gas generating agents
1-10 parts of intumescent flame retardant
50-85 parts of deionized water.
The polymer hydrogel thickener comprises polyacrylamide, potassium polyacrylate, polyvinyl alcohol, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, acrylic acid copolymer, hydroxypropyl methylcellulose, carboxymethyl hydroxyethyl cellulose, xanthan gum, guar gum and sodium alginate
Inorganic hydrogel thickeners include one or more of bentonite, diatomaceous earth, water glass, silica, magnesium aluminum silicate, magnesium lithium silicate, and the like.
The alcohol comprises one or more of glucitol, xylitol, sorbitol, mannitol, ethylene glycol, propylene glycol, glycerol, and bio-based ethylene glycol and propylene glycol.
The salt is one or more of potassium carbonate, potassium bicarbonate, sodium carbonate, and sodium bicarbonate.
The expansion foam material comprises one of waterborne polyurethane, epoxy modified waterborne polyurethane and waterborne acetic acid-ethylene polymer.
The intumescent flame retardant comprises expanded graphite and vermiculite.
The foaming agent is a surfactant, and the surfactant comprises one or more of sulfate anionic surfactants, coconut oil fatty acid diethanolamide, disodium lauryl sulfosuccinate, potassium monododecyl phosphate, potassium lauryl alcohol ether phosphate, fatty alcohol polyoxyethylene ether ammonium sulfate, cocamidopropyl betaine, lauramidopropyl betaine and lauramidopropyl amine oxide.
The gas generating agent is one of water-insoluble acid, benzoic acid and stearic acid;
the bactericide is one of dodecyl dimethyl benzyl ammonium chloride, polyquaternary ammonium salt, benzisothiazolinone, glutaraldehyde and sodium benzoate.
The hydrogel is used for carrying out preventive treatment on the combustion of lithium batteries and lithium battery packages in a pressure sprayer or multilayer composite membrane mode.
The pressure sprayer comprises a hand-press sprayer, an air compressor sprayer and an electric pressure sprayer, and the hydrogel is directly sprayed on the surface of a burning object to extinguish fire, reduce temperature and isolate the burning object.
One of the obvious differences from the existing fire extinguishing medium for combustion of the lithium ion battery is that the hydrogel is a high-viscosity and easily-spreading viscous liquid, the liquid can foam at high temperature, the foam contains water, and when the water is volatilized, an expansion flame-retardant layer can be formed.
The hydrogel of the present invention contains foaming agent and gas generating agent, and the gel is stored in storage medium, such as storage strip or bag, and the gas generated in the gel breaks the gel film at high temperature to release the gel.
The hydrogel of the present invention is distinguished from the prior patents by the use of both organic and inorganic hydrogel materials.
The hydrogel has the advantages of simultaneously using high molecular polymer, inorganic hydrogel material and foam expansion material. The high molecular polymer has large water absorption capacity, thereby being beneficial to extinguishing fire and reducing temperature; the inorganic hydrogel has the advantages of non-inflammability, no boiling of water in the gel at high temperature and the like, and the foam expansion substance can generate foam at high temperature, and the foam contains water. The invention uses the high polymer with high water absorption, the inorganic hydrogel material and the foam expansion material in a matching way, and fully utilizes the advantages of the three.
The hydrogel has the advantages that the hydrogel can form a compact and non-combustible film on the surface of a high-temperature object and a burning object, the film can isolate air and the burning object, so that the flame retardant effect is achieved, particularly, the hydrogel covering the surface of the burning object or the high-temperature object can not be completely formed into a film, only the bottom of the gel and the surface of the high-temperature object or the burning object form a film, and the upper part of the gel still keeps a hydrogel state, so that the good continuous cooling effect is achieved.
The hydrogel of the present invention advantageously contains an appropriate alcohol, so that the hydrogel has a low freezing point, enabling the hydrogel to be effectively used at low temperatures.
Example 14
The gel of example 13 was used.
The utility model provides a lithium cell is thermal-insulated, is cooled down, fire-retardant and explosion-proof with emergent or prevention processing membrane, the gel membrane is Polyethylene (PE)/Polyamide (PA), or PE/PA multilayer coextrusion membrane, and rectangular cavity width is 2cm, and the heat-seal bond seam is wide to be 2mm, each mutual not intercommunication between rectangular cavity, and the rectangular cavity of each gel membrane respectively uses a non-return type inlet, will put out a fire the gel and pour into the long rectangular cavity of gel membrane into through the non-return type inlet.
Pouring the gel into the gel film, placing the gel film on the surface of corrugated paper, placing the corrugated paper on the surface of the aluminum-foil paper, heating the aluminum-foil paper, and when the upper surface of the paper board is heated to 130-200 ℃, the gel is locally broken and part of the gel is released.
Example 15:
the fireproof cooling hydrogel comprises the following components in parts by weight:
0.1-10 parts of at least one macromolecular hydrogel thickener;
1-20 parts of at least one expanded foam;
0.1-1 parts of at least one bactericide;
0.01-1 part of at least one foaming agent
1-15 parts of at least one group of gas generating agents
1-10 parts of intumescent flame retardant
50-85 parts of deionized water.
The utility model provides a lithium cell is thermal-insulated, is cooled down, fire-retardant and explosion-proof with emergent or prevention processing membrane, the gel membrane is Polyethylene (PE)/Polyamide (PA), or PE/PA multilayer coextrusion membrane, and rectangular cavity width is 2cm, and the heat-seal bond seam is wide to be 2mm, each mutual not intercommunication between rectangular cavity, and the rectangular cavity of each gel membrane respectively uses a non-return type inlet, will put out a fire the gel and pour into the long rectangular cavity of gel membrane into through the non-return type inlet.
Pouring the gel into the gel film, placing the gel film on the surface of corrugated paper, placing the corrugated paper on the surface of the aluminum-foil paper, heating the aluminum-foil paper, and when the upper surface of the paperboard is heated to 130-200 ℃, the gel is locally broken, and most of the gel in the gel strip is released.
Example 16:
| components | Parts by mass |
| High-molecular hydrogel thickener: poly(s) are polymerizedVinyl alcohol | 8 |
| Deionized water | 92 |
Example 17:
| components | Parts by mass |
| High-molecular hydrogel thickener: xanthan gum | 0.2 |
| Expanded foam material of vinyl acetate-ethylene polymer | 20 |
| Water (W) | 80 |
Example 18:
| components | Parts by mass |
| High-molecular hydrogel thickener: poly(s) are polymerizedAcrylic acid | 0.1 |
| Expanded foam material of vinyl acetate-ethylene polymer | 20 |
| Foaming agent Cocamidopropyl betaine | 0.05 |
| Water (W) | 80 |
The hydrogels prepared in examples 16-19 were loaded into the following stock media:
the utility model provides a lithium cell is thermal-insulated, is cooled down, fire-retardant and explosion-proof with emergent or prevention processing membrane, the gel membrane is Polyethylene (PE)/Polyamide (PA), or PE/PA multilayer coextrusion membrane, and rectangular cavity width is 2cm, and the heat-seal bond seam is wide to be 2mm, each mutual not intercommunication between rectangular cavity, and the rectangular cavity of each gel membrane respectively uses a non-return type inlet, will put out a fire the gel and pour into the long rectangular cavity of gel membrane into through the non-return type inlet.
The hydrogels prepared in examples 16-19 were filled into gel stock media and evaluated experimentally as follows: placing a gel film on the surface of corrugated paper, placing the corrugated paper on the surface of the aluminum-foil paper, heating the aluminum-foil paper, and enabling the gel film to release gel as follows:
| examples | Evaluation of the test |
| Example 16 | The corrugated paper is burnt through, the gel film is not broken, and the gel cannot be released |
| Example 17 | The corrugated paper is burnt through, the gel film is not broken, and the gel cannot be released |
| Example 18 | The corrugated paper is not burnt through, when the surface temperature of the corrugated paper between the gel film and the corrugated paper is about 200 ℃, the gel film is broken to release gel, and the area of the gel spread on the surface of the corrugated paper is small |
| Example 19 | The corrugated paper is not burnt through, when the surface temperature of the corrugated paper between the gel film and the corrugated paper is 130-170 ℃, the gel film is broken to release gel, the area of the gel spread on the surface of the corrugated paper is large, and the gel film is broken Complete inflation of gel strip during cracking |
| Example 20 | The corrugated paper is not burnt through, when the surface temperature of the corrugated paper between the gel film and the corrugated paper is 180 ℃ at 150- The gel strip expands only at the heated part |
Example 21
A fireproof cooling hydrogel is characterized in that: the adhesive comprises the following components in parts by mass:
0.05-20 parts of hydrogel thickener;
5-35 parts of a freezing point depressant;
1-30 parts of an expanded foam;
1-15 parts of an intumescent flame retardant;
0.01-1 part of foaming agent;
1-15 parts of a gas generating agent;
0.01-1 part of bactericide;
at least 50 parts of water.
The expanded foam material comprises waterborne polyurethane, epoxy modified waterborne polyurethane or waterborne acetic acid-ethylene polymer, and the content of the expanded foam material is 5-20 parts.
The foaming agent is a surfactant, the surfactant comprises sulfate anionic surfactant, coconut oil fatty acid diethanolamide, disodium lauryl sulfosuccinate, potassium monododecyl phosphate, potassium lauryl alcohol ether phosphate, fatty alcohol polyoxyethylene ether ammonium sulfate, cocamidopropyl betaine, lauramidopropyl betaine or lauramidopropyl amine oxide, and the content of the foaming agent is 0.01-0.3 part.
Further, the gas generating agent is a combination of a water-insoluble acid and a water-soluble salt; the water insoluble acid includes benzoic acid, stearic acid; the content of the acid is 0.1-6, preferably 0.1-3; the water-soluble salt comprises ammonium bicarbonate, sodium bicarbonate and sodium carbonate; the content of the salt is 0.1-6, preferably 0.1-3 parts.
The hydrogel thickener is a high molecular water-absorbing polymer; the high-molecular water-absorbing polymer comprises one or more of polyacrylamide, potassium polyacrylate, polyvinyl alcohol, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, acrylic acid copolymer, xanthan gum, agar powder, guar gum, polyvinyl alcohol and sodium alginate.
The content of the high-molecular hydrogel water-absorbing polymer is preferably 0.1-10 parts, and more preferably 0.1-3 parts.
The hydrogel thickener is dissolved in water to form an aqueous solution, and contains dispersed and suspended high water-absorbing polymer powder, agar powder or high-crystallinity polyvinyl alcohol powder with the particle size of 1-100um, preferably 1-50 um at normal temperature.
The content of the high water-absorbing polymer powder is 0.1-5 parts, preferably 0.5-2 parts;
the hydrogel thickener is an inorganic water-absorbing material; the inorganic water-absorbing substance comprises one or more of bentonite, diatomite, fumed silica, magnesium aluminum silicate and magnesium lithium silicate;
the content of the inorganic water-absorbing substance is 0 to 15 parts, preferably 1 to 10 parts, and more preferably 1 to 5 parts.
The hydrogel thickener is a composition of a high-molecular water-absorbing polymer and an inorganic water-absorbing substance.
The freezing point depressant is an alcohol composition; the alcohol comprises one or more of xylitol, sorbitol, mannitol, ethylene glycol, propylene glycol and bio-based ethylene glycol and propylene glycol.
The intumescent flame retardant comprises 1-15 parts of expandable graphite and vermiculite, and the content of the expandable graphite is preferably 1-10 parts; the content of the expanded vermiculite is 1-15 parts, preferably 1-10 parts.
The bactericide is dodecyl dimethyl benzyl ammonium chloride, polyquaternary ammonium salt, benzisothiazolinone, glutaraldehyde and sodium benzoate.
Example 22
A process for preparing the fire-proof and heat-insulating hydrogel includes such steps as dissolving the thickening agent of hydrogel at ordinary temp or under heating to obtain a liquid whose concentration is 0.1-10%, dispersing the high-hydroscopicity polymer powder in the dissolved liquid, and dispersing the freezing-point depressant, expanded foam, expanded flame-retarding filler, foaming agent and disinfectant in said liquid.
Through the embodiment of the invention, the gel in the gel film can be released when the packing box is not burnt, so that the fire hazard of the packing box is prevented, the temperature is reduced, and the heat is insulated.
Through the embodiment of the invention, a large amount of gel can be released at one time from the gel film, so that the timely and deep fire extinguishing and cooling effects are achieved, after the gel is released, the pressure in the gel strip is reduced, but a small amount of gel still exists in the gel strip, so that the continuous heat insulation and cooling effects are achieved.
Through the embodiment of the invention, the gel in the gel film can release only a small amount of gel, and only the gel is released at the heating position, and the gel strip only expands at the heating position and other parts do not expand or slowly expand, thereby playing a role in lasting heat insulation and temperature reduction.
Example 23
The fireproof cooling hydrogel comprises the following components in parts by weight:
11 parts of a hydrogel thickener;
26 parts of a freezing point depressant;
22 parts of an expanded foam;
7 parts of an intumescent flame retardant;
0.05 part of foaming agent;
7 parts of a gas generating agent;
0.03 part of a bactericide;
100 parts of water.
The expanded foam material comprises waterborne polyurethane, epoxy modified waterborne polyurethane or waterborne vinyl acetate-ethylene polymer.
The foaming agent is a surfactant, and the surfactant comprises sulfate anionic surfactant, coconut oil fatty acid diethanolamide, disodium lauryl sulfosuccinate, potassium monododecyl phosphate, potassium lauryl alcohol ether phosphate, fatty alcohol polyoxyethylene ether ammonium sulfate, cocamidopropyl betaine, lauramidopropyl betaine or lauramidopropyl amine oxide.
Further, the gas generating agent is a combination of a water-insoluble acid and a water-soluble salt; the water insoluble acid includes benzoic acid, stearic acid; the water-soluble salt includes ammonium bicarbonate, sodium bicarbonate, and sodium carbonate.
The hydrogel thickener is a high molecular water-absorbing polymer; the high-molecular water-absorbing polymer comprises one or more of polyacrylamide, potassium polyacrylate, polyvinyl alcohol, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, acrylic acid copolymer, xanthan gum, agar powder, guar gum, polyvinyl alcohol and sodium alginate.
The hydrogel thickener is dissolved in water to form an aqueous solution, and contains dispersed and suspended high water-absorbing polymer powder, agar powder or high-crystallinity polyvinyl alcohol powder with the particle size of 40 um at normal temperature.
The hydrogel thickener is an inorganic water-absorbing material; the inorganic water-absorbing substance comprises one or more of bentonite, diatomite, fumed silica, magnesium aluminum silicate and magnesium lithium silicate;
the hydrogel thickener is a composition of a high-molecular water-absorbing polymer and an inorganic water-absorbing substance.
The freezing point depressant is an alcohol composition; the alcohol comprises one or more of xylitol, sorbitol, mannitol, ethylene glycol, propylene glycol and bio-based ethylene glycol and propylene glycol.
The intumescent flame retardant comprises expanded graphite and vermiculite.
The bactericide is dodecyl dimethyl benzyl ammonium chloride, polyquaternary ammonium salt, benzisothiazolinone, glutaraldehyde and sodium benzoate.
Example 24
A process for preparing the fire-proof hydrogel with low temp. includes such steps as dissolving the thickening agent in water to obtain 5% liquid, dispersing the high-hydroscopicity polymer powder in the liquid, and dispersing the freezing-point depressant, expanded foam, expanded flame-retarding filler, foaming agent and bactericide in said liquid.
Claims (10)
1. A fireproof cooling hydrogel is characterized in that: the adhesive comprises the following components in parts by mass:
0.05-20 parts of hydrogel thickener;
5-35 parts of a freezing point depressant;
1-30 parts of an expanded foam;
1-15 parts of an intumescent flame retardant;
0.01-1 part of foaming agent;
1-15 parts of a gas generating agent;
0.01-1 part of bactericide;
at least 50 parts of water.
2. The fireproof cooling hydrogel according to claim 1, wherein: the expanded foam material is waterborne polyurethane, epoxy modified waterborne polyurethane or waterborne acetic acid-ethylene polymer which can stabilize bubbles after being heated or boiled, and the content of the expanded foam material is 5-20 parts.
3. The fireproof cooling hydrogel according to claim 1, wherein: the foaming agent is a surfactant, the surfactant comprises sulfate anionic surfactant, coconut oil fatty acid diethanolamide, disodium lauryl sulfosuccinate, potassium monododecyl phosphate, potassium lauryl alcohol ether phosphate, fatty alcohol polyoxyethylene ether ammonium sulfate, cocamidopropyl betaine, lauramidopropyl betaine or lauramidopropyl amine oxide, and the content of the foaming agent is 0.01-0.3 part.
4. The fireproof cooling hydrogel according to claim 1, wherein: the gas generating agent is a combination of an acid insoluble or slightly soluble in water and a salt soluble in water; the water-insoluble acid includes benzoic acid or stearic acid; the content of the acid is 0.1-6 parts; the water-soluble salt comprises a bicarbonate or carbonate; the content of the salt is 0.1-6 parts.
5. A fireproof cooling hydrogel according to any one of claims 1 to 4, wherein: the hydrogel thickener is a water-soluble high molecular polymer; the water-soluble high molecular polymer comprises one or more of polyacrylamide and a copolymer thereof, polyacrylate and a copolymer thereof, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, xanthan gum, agar powder, guar gum, polyvinyl alcohol and sodium alginate; the content of the water-soluble high molecular polymer is 0.1-10 parts; the hydrogel thickener is soluble in water and improves the viscosity of the aqueous solution; it contains water-soluble high molecular polymer powder which can be dissolved in water only by heating and is dispersed and suspended in water solution at normal temperature, and the water-soluble high molecular polymer powder comprises agar powder or high-crystallinity polyvinyl alcohol powder, and the particle size of the powder is 1-100 um; the content of the high-molecular water-absorbing polymer powder is 0.1-5 parts.
6. A fireproof cooling hydrogel according to any one of claims 1 to 4, wherein: the hydrogel thickener is an inorganic water-absorbing material; the inorganic water-absorbing substance comprises one or more of bentonite, diatomite, fumed silica, magnesium aluminum silicate and magnesium lithium silicate; the content of the inorganic water-absorbing material is 0-15 parts.
7. A fireproof cooling hydrogel according to any one of claims 1 to 4, wherein: the hydrogel thickener is a composition of a water-soluble high-molecular polymer and an inorganic water-absorbing substance.
8. A fireproof cooling hydrogel according to any one of claims 1 to 4, wherein: the freezing point depressant is an alcohol composition; the alcohol comprises one or more of xylitol, sorbitol, mannitol, ethylene glycol, propylene glycol and bio-based ethylene glycol and propylene glycol; the hydrogel contains a bactericide which is dodecyl dimethyl benzyl ammonium chloride, polyquaternary ammonium salt, benzisothiazolinone, glutaraldehyde and sodium benzoate.
9. A fireproof cooling hydrogel according to any one of claims 1 to 4, wherein: the intumescent flame retardant comprises expanded graphite and vermiculite, and the content of the expanded graphite is 1-15 parts; the content of the expanded vermiculite is 1-15 parts.
10. A preparation method of fireproof heat-insulation hydrogel is characterized by comprising the following steps: the hydrogel thickener is dissolved into liquid with the concentration range of 0.1-10% at normal temperature or under heating, the high water-absorbing polymer powder is dispersed in the dissolved liquid, and the freezing point depressant, the expanded foam, the expanded flame-retardant filler, the foaming agent and the bactericide are dispersed in the solution to form uniform liquid.
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