Extinguishing polymer composite material

 

(57) Abstract:

The present invention relates to fire fighting facilities. Ozone-extinguishing polymeric composite material contains a polymer binder of cold hardening and microencapsulated fire-extinguishing agent. As a fire extinguishing agent use of the substance class halogen-substituted hydrocarbon having the formula C3F7I eithernF2n+2where n = 5 to 7, or (C2F5)2N(CmF2m+1), where m = 1 - 2. Components included in the composition in a ratio, wt.%: microencapsulated fire-extinguishing agent 40 at 51.4, the polymeric binder is rest. The polymeric binder of cold hardening is chosen from the class of polyepoxides based Dianova or aliphatic epoxy resins, or mixtures Dianov and aliphatic epoxy resins, or class of polyurethanes. The material is a thermosetting polymer composition containing dispersed filler, which is used as microencapsulated fire-extinguishing agent. Fire-extinguishing agent is made in the form of microcapsules, each of which represents microspheres with a diameter of 100 to 400 μm, consisting of spherical polymeric about what emperatur 130 - 149°C and 166 to 190°C. depending on the moulds material can be produced in sheets for lining, fittings desired configuration or mastic cold hardening. The result of the invention is the creation of ozone-safe material to extinguish the fire. 5 C.p. f-crystals, 2 Il.

The present invention relates to fire fighting facilities and is a thermosetting polymer composition containing a fire-extinguishing agent volume steps. The material provides automatic suppression of incipient fires and can be used effectively in the aviation industry to protect the most vulnerable components and assemblies of aircraft; in the energy sector for local automatic protection for the most vulnerable components and assemblies power plants (including nuclear); in the electronics industry to protect against accidental ignition of electronic devices and electrical machines as well as for protection of fire-hazardous and valuable goods during their storage and transportation.

Art

Known application of intumescent fire-retardant materials [1, 2, 3] to prevent the spread of flame, in General consisting of a polymeric binder and fire create a fireproof heat insulating barrier to the spread of fire. The disadvantage of these materials is the lack of active suppression of combustion and, as a consequence, temporary protective actions.

Know the use of liquid, gaseous and aerosol extinguishing agents used in automatic fire extinguishing systems[4, 5, 6, 7, 8, 9, 10, 11, 12, 13]. As these fire extinguishing agents use water (including additives - wetting, anti-freeze, etc ), foam (air-mechanical, chemical), inert gas diluents (carbon dioxide, nitrogen, argon, flue gases, water vapor), halogen-substituted hydrocarbons. For the filing of such substances in the fire requires special fire fighting systems, which, in General, include the charge of the fire-extinguishing substance supply system fire extinguishing substances, sensors fire, secondary electronic devices and actuators. Such devices are widely available for protection of various objects in the construction, aviation, shipbuilding. A significant drawback of such systems that use liquid, gaseous and aerosol extinguishing agents are the high cost, technical complexity, creating the possibility of failures or false sebatian it is known [5] the application of halogenosilanes with a boiling point above 0oC as fire extinguishing substances that do not Deplete the ozone layer of the Earth. It should be noted that these products are used in the form of liquids stored until use in special tanks (containers), and therefore all known systems using these substances have all the disadvantages described above.

Known extinguishing polymeric coatings and composite materials comprising a polymeric binder and microencapsulated fire extinguishing agent volume steps are automatically released from the material when heated [14, 15, 16]. These materials are reliable and effective means of suppressing the surface and in the volume of flammable structures, devices, electric vehicles and other objects. A disadvantage of the known extinguishing materials of this group is used in their composition as extinguishing agents environmentally harmful substances, namely fluorine,Poslednij hydrocarbons that Deplete the ozone layer of the Earth's atmosphere. In particular, in the material [16] in which the extinguishing agent used Halocarbon 114 B2 (Tetra fluorine dibromine ethane), which is the strongest ozone depleting substance with a potential osnago kind of prohibited substances, but use is limited.

Replacement described fluorine-,Poslednij hydrocarbons to other fluorine-containing fire extinguishing agents cannot be made "automatically", as it cannot be predicted in advance and ensure the desired effect of suppressing fire. This effect is determined by both the properties of microencapsulated agent fire extinguishing systems, such as boiling point, heat of vaporization, the size of the microcapsules, the thickness and strength of the shell, the temperature of its explosive opening, and properties of a polymeric matrix: first of all its thermomechanical properties. Only when the synchronization process is explosive destruction of the microcapsules, accompanied by intense emission of vapours fire-extinguishing agent, and its adequacy for the destruction of the polymer matrix at higher temperature due to fire exposure (directly or remotely) can be achieved with a powerful release of fire extinguishing agent in the environment and accordingly suppress the arising of the combustion process. If, under conditions of fire exposure on OGGPCM, the polymer matrix melts (for example, in the case of polyethylene, polypropylene and other thermoplastic polymers), you will lose the effect of "adults who tenderly leads to loss of efficiency of quenching. If the matrix is too resistant, despite developing a high temperature when exposed to fire, it (the matrix) for a long time will be preventing the release of fire extinguishing agent and fire will have time enough to develop that the total amount of extinguishing agent is insufficient for effective suppression.

Disclosure of the invention

Thus, the task which sent the invention is the creation of new extinguishing polymeric material based on polymer matrices filled with microcapsules containing ozone-safe fire extinguishing substances that were not known in microencapsulated form, by

identify parameters of microcapsules (the boiling point of the liquid core, the diameter of the microcapsules, the strength of its shell) to provide explosive destruction when heated in the temperature range 130-190oC;

surveys polymer matrix capable of explosive fracture of the composite at a temperature effect for a massive release of extinguishing substances into the environment.

According to the invention proposes a new ozone-safe extinguishing of polymermetal based Dianova or aliphatic epoxy resins, or mixture Dianov and aliphatic epoxy resins, or class of polyurethanes and fire extinguishing agent, which is used as substances of class halogenorganics compounds having the formula

C3F7I or CnF2n+2or (C2F5)2N(CmF2m+1)

where n = 5 to 7, m = 1 and 2

in the form of microcapsules, opened at a temperature that is included in the range 130-190oC by simultaneous microreserve matrix and shell microcapsules with explosive emission of vapours fire-extinguishing agent into the zone of fire, leading to the suppression of fire, and represents the microspheres with a diameter of 100 to 400 μm, consisting of a polymer shell and a prisoner inside her liquid fire extinguishing agent.

The components included in the composition in the following ratio, wt.%:

Microencapsulated fire-extinguishing agent - 40 - 60

Polymer binder - Rest

According to the invention extinguishing polymeric composite material (hereinafter GPKM) is a thermosetting composition with dispersed filler, which is microencapsulated fire-extinguishing agent. Microcapsules are microspheres with a diameter of 100 to 400 μm, status is neigh fire extinguishing agent in the capsule 90 - 94 wt.%.

According to the invention it is the use of the composition as a fire extinguishing agent substances of class halogen-substituted hydrocarbons having the above formula in the form of microcapsules, as a dispersed filler thermosetting resin composition achieves the effect, namely, that the liquidation of fires do not damage the ozone layer.

The effect of the material is based on intensive gaseous extinguishing agent upon reaching a predetermined temperature (in the range of 130 - 190oC, depending on the composition of the composite). With increasing temperature there is a destruction of the polymer matrix and sharp emission in the environment vapours fire-extinguishing substance. When the vapor concentration of fire extinguishing agent reaches the threshold extinguishing concentration, the resulting foci combustion eliminated.

In the research we identified that to be effective, OGGPCM matrix must meet very specific criteria:

the matrix material should be dimensionally cross-stitched, ensuring no transfer into a plastic state is lower than the temperature of teratur 130-190oC (which, as a rule, are signs of fire or opportunities) should not prevent active allocation of fire extinguishing agent, the matrix will mechanically break down at a temperature of 130-190oC under the influence of steam pressure fire-extinguishing substance (Fig. 1).

Based on experimental data, these values are destructive tension of the polymer matrix under tension should be in the range of 0.2 - 0.6 MPa at a temperature of 130-190oC.

The proposed ozone-safe fire extinguishing substances were not known in microencapsulated form. For microencapsulation method of phase separation (koatservatsii) solutions of gelatin. By changing these parameters in the process of microencapsulation, as the concentration of the components, the temperature and time regimes, the regime of emulsification and others, managed to get a series of microencapsulated fire extinguishing substances, different size capsules and shell thickness. Using these microencapsulated components as filler in polymer matrices have established their optimum performance, providing better efficiency of fire.

Under critical conditions, when enthalpy the output capsules. Due to the fact that the strength of the shell depends on the diameter of the microcapsules, it was found that the optimum diameter of the microcapsules is in the range of 100 to 400 μm. Smaller capsules "late" with the explosion and can rapidly destroy the polymer matrix. Larger capsules do not provide the necessary uniformity of GPKM and therefore acceptable from a practical point of view, the mechanical characteristics of the material (Fig. 2).

When this boiling point fire extinguishing agents in a free state was limited by the range of 40 - 70oC. as part of GPKM when exposed to elevated temperature until the "explosion" of the microcapsules, the liquid is in the overheated state.

Only under these conditions a new ozone-extinguishing material capable of performing the function of the fire-extinguishing system without special sensors and complex control systems that respond to temperature increase as a result of the fire, resulting in his immediate suppression and prevention of the development of the "big" fire.

The manufacturing process claimed extinguishing material can be implemented on standard chemical equipment INIA in an aqueous solution of the polymer shell. The process parameters within the specified method is essentially determined such physical-chemical characteristics of the fire-extinguishing agent, as the boiling point, surface tension, etc.

2. Dosing of ingredients, namely, resin, hardener and microencapsulated fire extinguishing agent in a heated reactor equipped with a mixer.

3. Mixing of the composition.

4. Filling the mold with the liquid composition.

5. Curing of the material.

According to the invention depending on the molds, the material can be produced in sheets for lining or fittings required configuration, mastic cold hardening. If the material comes in the form of mastic cold hardening, stages 3 and 4 are absent, as in stage 1 in the composition is not introduced hardener. All components of this material are ozone-safe, their production and use is not restricted by the Montreal agreement and subsequent similar documents.

Industrial applicability

Example 1. To 29,12 g chlorinated epoxy resin I of the following structure:

< / BR>
where R is the residue of glycerol, n =is laplapan with epichlorohydrin, the mixture is stirred. Then the portions enter 60 g of microencapsulated 2-iodopropane (III), previously obtained by the method of liquid-phase separation in an aqueous gelatin solution, and with stirring, add 3.6 g of polyethylenepolyamine (PEPA). The mass ratio of the polymer binder, which includes I, II and probes, and microencapsulated fire extinguishing agent (III) is 40:60. After thorough mixing, the composition is poured into molds and utverjdayut within 48 hours at a temperature of 20 - 25oC. Physical and mechanical properties of the specified composition: ultimate tensile stress tensile 4.1 and 4.5 MPa, an elongation at break of 25 - 35%.

Fire extinguishing ability of the material was evaluated by the following method. Extinguishing composition in the form of a plate thickness of 5 mm was fixed on the entire inner surface and the lid of a metal box dimensions HH mm In the centre of the box at the bottom was placed a portion of gasoline and set on fire. The moment of quenching was determined visually through a special slit between the walls of the box, which served also to provide access of air to the fire that was even stricter test conditions. The extinguishing of the fire from ignition to extinction of the flame, predel% of the original. In the absence of GPKM on the inner surface of the box (control experiment) gasoline burns out completely.

Example 2. To 43,68 g resin I added 10.92 g of resin II. The mixture was stirred and added to 5.4 g of probes. After stirring portions have introduced 40 g of microencapsulated 2-iodopropane (mass ratio of the polymer binder and microencapsulated fire extinguishing agent was 60:40). After thorough mixing, the composition was poured into the forms and utverjdali within 48 hours at a temperature of 20 - 25oC. characteristics of the material: ultimate tensile stress at elongation of 9.4 and 9.7 MPa, elongation at break 35 - 45%, extinguishing fire 7 seconds.

Example 3. To of 36.4 g of resin (I) was added 3.6 g of probes. After stirring portions have introduced 60 g of microencapsulated 2-iodopropane. Next, the composition was prepared as in example 1. Material characteristics: ultimate tensile stress tensile 0.7 to 1.1 MPa, elongation at break 35 - 60%, extinguishing a fire in 15 seconds.

Example 4. To of 36.4 g of resin II was added 3.6 g of probes. After stirring portions have introduced 60 g of microencapsulated 2-iodopropane. Next, the composition was prepared as in example 1. Eyve - less than 5%, extinguishing a fire in 15 seconds.

Example 5. The composition of example 1, characterized in that the mass ratio of the resins I and II is 1:1. Material characteristics: ultimate tensile stress at elongation of 12.3 to 14.1 MPa, extinguishing fire 7 seconds.

Example 6. The composition of example 1, characterized in that the mass ratio of the resins I and II is 1:4. Material characteristics: ultimate tensile stress tensile 18,8 is 20.1 MPa, elongation at break 20 - 35%, extinguishing a fire in less than 5 seconds.

Example 7. The composition of example 1, characterized in that instead of microencapsulated 2-iodopropane used microencapsulated 1-itemcapturedate. Material characteristics: ultimate tensile stress tensile 4.1 and 4.5 MPa, an elongation at break of 25 - 35%, extinguishing a fire in 5 seconds.

Example 8. The composition of example 1, characterized in that instead of microencapsulated 2-iodopropane the composition is administered microencapsulated performante. Material characteristics: ultimate tensile stress tensile 4.0 to 4.5 MPa, an elongation at break of 25 - 35%, extinguishing a fire in 10 seconds.

Example 9. The composition of example 1, a consistent perforated. Material characteristics: ultimate tensile stress at elongation of 4.2 - 4.5 MPa, an elongation at break of 25 - 35%, extinguishing a fire in 15 seconds.

Example 10. The composition of example 1, characterized in that instead of microencapsulated 2-iodopropane the composition is administered microencapsulated perpertrating. Material characteristics: ultimate tensile stress tensile 4,1 - 4,3 MPa, an elongation at break of 25 - 35%, extinguishing a fire in 15 seconds.

Example 11. The composition of example 1, characterized in that instead of microencapsulated 2-iodopropane the composition is administered microencapsulated performatively. Material characteristics: ultimate tensile stress at elongation of 4.2 and 4.4 MPa, elongation at break 20 - 35%, extinguishing a fire in 10 seconds.

Example 12. To 80 g of linear polyoxypropyleneglycol with a molecular weight of 1000 added 20 g of branched polyoxypropyleneglycol with a molecular weight of 1500, then after stirring enter 17.9 g of diisocyanate and 0.01 g of dibutyltindilaurate tin. After thorough mixing portions impose 177 g microencapsulated 2-iodopropane. The mixture is poured into molds and Oteri is within 1.0 to 1.5 MPa, an elongation at break of 30 to 40%, extinguishing the fire for 12 seconds.

Example 13.

A composition similar to example 10, characterized in that the composition is administered to 78.7 g of microencapsulated 2-iodopropane. Material characteristics: ultimate tensile stress tensile 1.3 to 1.7 MPa, an elongation at break of 40 - 45%, extinguishing a fire in 15 seconds.

Example 14. To 80 g of a complex of the polyester based on adipic acid and diethylene glycol added 0.56 g of glycerin, all mixed and injected 8.7 g of diisocyanate and 0.008 g of dibutyltindilaurate tin. After stirring injected portions 134,6 g microencapsulated 1-iodopropane. After mixing, the composition is placed in a mold and utverjdayut 48 hours at a temperature of 20 - 25oC. characteristics of the material: ultimate tensile stress tensile 2.0 to 2.5 MPa, an elongation at break of 30 to 40%, extinguishing the fire for 12 seconds.

Example 15. A composition similar to example 12, characterized in that the microencapsulated 1-itemcapturedate introduced into the composition in an amount 59,8, the material properties: ultimate tensile stress tensile 2.4 to 2.8 MPa, an elongation at break of 45 - 55%, why is the composition, prigotovleniya as follows. To 29,12 g chlorinated epoxy resin (I) of the following structure:

< / BR>
where R is the residue of glycerol, n = 5 to 6, m = 2 and 3

add 7,28 Dianov g epoxy resin (II), which is a product of condensation of diphenylolpropane with epichlorohydrin, the mixture is stirred. Then the portions enter 60 g of microencapsulated 2-iodopropane (III) and with stirring, add 3.6 g of polyethylenepolyamine (PEPA). The mass ratio of the polymer binder, which includes I, II and probes, and microencapsulated fire extinguishing agent (III) is 40:60. After thorough mixing, the composition is poured into molds and utverjdayut within 48 hours at a temperature of 20 - 25oC.

Sources of information:

1. RF patent N 2028348, MKI C 09 D 163/00, 1996.

2. RF patent N 2043378, MKI C 09 K 5/18-163/00, 175/00, C 09 D 163/00, 1996.

3. "Insulation". - 1992, June, p.23.

4. A. S. USSR N 1699476, MKI A 62 C 35/00, 1991.

5. UK application N 2265309, MKI A 62 D 1/00, 1993.

6. U.S. patent N 5119878, MKI A 62 D 1/00, 1992.

7. U.S. patent N 5117917, MKI A 62 D 1/00, 1992.

8. A. S. USSR N 1804867, MKI A 62 C 35/00, 1993.

9. U.S. patent N 5141654, MKI A 62D 1/00, 1992.

10. Application WO N 9526218, MKI A 62 D 1/08, 1995.

11. The patent With the x2">

14. Japan's bid N 57 - 195128, MKI C 09 J 9/00, A 62 D 1/00, 1982.

15. Japan's bid N 58 - 132056, MKI C 09 D 5/18, 1983.

16. A. S. USSR N 1696446, MKI C 09 D 163/00, C 09 K 21/08, 1991.

1. Extinguishing polymeric composite material consisting of a polymeric binder cold-cured and fire-extinguishing agent, characterized in that as a fire extinguishing agent use of the substance class halogenorganics compounds having the formula: C3F7I, or CnF2n+2or (C2F5)2N(CmF2m+1), where n = 5 to 7, m = 1 - 2, in the form of microcapsules, opened at a temperature that is included in the interval 130 - 149 and 166 - 190oC by simultaneous microreserve matrix and shell microcapsules with explosive emission of vapours fire-extinguishing agent into the zone of fire, leading to the suppression of fire, and represents the microspheres with a diameter of 100 to 400 μm, consisting of a polymer shell and a prisoner inside her liquid fire extinguishing agent, the mixing ratio of the material is, wt.%:

Microencapsulated fire-extinguishing agent - 40 - 51,4

Polymer binder - Rest

2. The material under item 1, characterized in that it is a thermosetting polymer comp is 3. The material under item 1, characterized in that the polymeric binder of cold hardening is chosen from the class of polyepoxides based Dianov, or aliphatic, including chlorine, epoxy resins, or mixtures Dianov and aliphatic epoxy resins, or class of polyurethanes.

4. The material on PP. 1 to 3, characterized in that a represents a plate for lining surfaces.

5. The material on PP.1 to 3, characterized in that it is a mastic cold hardening.

6. The material on PP.1 to 3, characterized in that it is a fitting configuration.

 

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