WO2017184023A1

WO2017184023A1 - Autonomous fire-extinguishing means

Info

Publication number: WO2017184023A1
Application number: PCT/RU2016/050058
Authority: WO
Inventors: Максим Валерьевич КОЛЕСНИКОВ
Original assignee: К5 Лтд
Priority date: 2016-04-22
Filing date: 2016-10-27
Publication date: 2017-10-26
Also published as: RU2616943C1

Abstract

The present invention relates to firefighting technology, and specifically to an autonomous fire-extinguishing means. The use thereof allows for achieving a technical result in the form of broadening an arsenal of fire-extinguishing means via the creation of an autonomous fire-extinguishing means, microcapsules of which have a short activation time. An autonomous fire-extinguishing means according to the present invention contains a polymer binder and a microencapsulated fire-extinguishing agent, each microcapsule of which includes a polymer shell and a core, containing the following components: 2H-heptafluoropropane (Chladone 227ea) or another carrier gas having a boiling point of between -155 and +10°C, a flame retardant and a combustion inhibitor, with the following mass ratio: carrier gas 5-50%, flame retardant 30-70%, combustion inhibitor 1-25%, and the mass ratio of the microcapsules and the polymer binder comprising between 10:1 and 1:4.

Description

AUTONOMOUS FIRE EXTINGUISHING MEANS

FIELD OF THE INVENTION This invention relates to fire fighting equipment, and in particular to an autonomous fire extinguishing agent.

State of the art

Autonomous fire extinguishing means are used to suppress local fire sources in power automation systems, control panels, electrical cabinets at the time of their occurrence, i.e. for in the early stages of fire development.

From the RF patent N ° 2161520 (publ. 10.01.2001), an autonomous fire extinguishing agent is known made of a material with extinguishing properties based on microcapsules of an extinguishing composition distributed in a polymer binder. Microcapsules are microspheres of spherical gelatin shells and a liquid fire extinguishing agent enclosed within each shell, using organohalogen compounds, for example C ₃ FI, which are automatically released by heating.

The disadvantage of this tool is that the manufacture of gelatin shells of microcapsules used in it for microencapsulation of a fire extinguishing composition is a technologically complex and expensive process, which significantly increases the cost of products made using this material.

From the patent of the Russian Federation for utility model N ° 90994 (published on January 27, 2010), another self-contained fire extinguishing agent made of a material with extinguishing properties containing microcapsules with with an extinguishing agent, which is a halocarbon enclosed in a polymer shell of polyurea and / or polyurethane, and a binder, which is used as a polymer resin. The material with extinguishing properties is deposited on a solid-phase carrier, for example, on a metal substrate. This tool provides the operation of microcapsules in the temperature range 110-165 ° C. However, this tool has several disadvantages. So, for example, over time and (or) when the temperature and humidity of the environment fluctuate, the extinguishing layer may crack and crumble from the surface of the substrate. Thus, the fire extinguishing properties of the product deteriorate, and in case of fire it may not work.

The RF patent for utility model N ° 109668 (published October 27, 2011) describes an autonomous fire extinguishing agent made in the form of a multilayer plate made of a sheet of composite material having fire-extinguishing properties by cutting it. The composite material is based on extinguishing microcapsules, which are halocarbon-1, 1,2,2-tetrafluorodibromoethane and (or) 1,1,2-trifluorotrichloroethane and (or) 2-iodine-1,1, 1,2 , 3,3,3 - heptafluoropropane and (or) their mixture with other halocarbons enclosed in a polymer shell of polyurea and (or) polyurethane based on a polyisocyanate prepolymer. Microcapsules are distributed in a binder that includes polymer and mineral constituents. On the formed composite material, on the one hand, for its fastening to the surface of the protected object, an adhesive layer is applied, covered with a protective film.

However, this autonomous fire extinguishing agent does not have sufficiently high strength properties, high resistance cracking, weathering, moisture and water resistance, which reduces its service life as a stand-alone fire extinguishing agent.

The analogue closest in technical essence and technical result achieved is described in the RF patent for utility model N ° 152765 (published on 06/20/2015). In this agent, a fire-extinguishing composite material is applied to the substrate, containing a polymeric binder from a hardened plasticized dibutyl phthalate polyvinyl acetate resin and a mixture of microcapsules including halogen-containing aliphatic saturated hydrocarbons from the class of chladones (freons) as a fire extinguishing agent.

The main disadvantage of this fire extinguishing agent is such negative mechanical and strength properties as brittleness and peeling of the extinguishing material when the agent bends during its installation, strong shrinkage and high crack formation during the formation of thick products (2-5 mm), as well as a long response time .

SUMMARY OF THE INVENTION An object of the present invention is to overcome the disadvantages of the prior art and to achieve a technical result in the form of expanding the arsenal of technical means by creating an autonomous fire extinguishing means having a short response time, high mechanical and strength properties, reliability under normal conditions and when extinguishing a fire.

To solve this problem and achieve the specified technical result, the present invention provides an autonomous fire extinguishing agent containing a polymer binder and microencapsulation a fire extinguishing agent comprising a polymer shell in each microcapsule and a core containing carrier gas as components, having a boiling point of -155 to + 10 ° С, a combustion phlegmatizer and a combustion inhibitor in a mass ratio: carrier gas 5-50 %, combustion phlegmatizer 30-70%, combustion inhibitor 1-25%, and the mass ratio of microcapsules and polymer binder is from 10: 1 to 1: 4.

A feature of the agent of the present invention is that the weight ratio of the polymer shell to the core in the capsule can be from 2:98 to 10:90.

Another feature of the agent of the present invention is that the polymer shell of each microcapsule can be made from one of the polymers selected from the group consisting of polystyrene, polyurethane, polyurea, polyepoxide, polynitrile, polyacrylate, polyamide, or mixtures thereof or products of their copolymerization.

Another feature of the agent of the present invention is that the extinguishing agent may be an azeotropic mixture.

Another feature of the agent of the present invention is that a partially or fully fluorinated hydrocarbon with a carbon-length can be used as a carrier gas.

In this case, the carrier gas can be used: 1-H-heptafluoropropane or 2-H-heptafluoropropane or pentafluoroethane or 1,1,1,3,3,3-hexafluoropropane or mixtures thereof.

Another feature of the means of the present invention is that as a phlegamizer of combustion can be used a substance was used from the group consisting of iodotrifluoromethane, 1 - iodoheptafluoropropane, 2-iodoheptafluoropropane, iodopentafluoroethane, 2,2-diiod-1, 1,1,3,3,3-hexafluoropropane, 1, 2-dibromethane, dibromomethane or mixtures thereof.

Another feature of the agent of the present invention is that, as a combustion inhibitor, a compound of a variable valency metal from the group comprising iron, chromium, manganese, vanadium, molybdenum can be used.

Moreover, as a combustion inhibitor, a compound from the group consisting of diethyl dicyclopentidienyl iron, cyclopentadienyl-tricarbonyl manganese, methylcyclopentadienyltricarbonyl manganese, dibenzenechrome, or their homologs can be used.

Another feature of the agent of the present invention is that a colloidal solution or a stabilized dispersion with a particle size of 0.01-0.1 μm can be used as a combustion inhibitor.

Another feature of the agent of the present invention is that the core may further comprise at least one high molecular weight stabilizer selected from tetrafluoroethylene or hexafluoropropylene oligomers with an average molecular weight of 3000-100000.

Another feature of the agent of the present invention is that the core may further comprise an antioxidant.

Another feature of the agent of the present invention is that the core may further comprise at least one acceptor of halogens and / or hydrogen halides. Another feature of the agent of the present invention is that the shell may have a temperature at which fracture starts and the contents exit in the range of 60 to 260 ° C.

Another feature of the agent of the present invention is that the microcapsules can have a temperature range from the start of the destruction of the shell to the complete release of the contents from 10 to 30 ° C.

Another feature of the agent of the present invention is that it can additionally contain a mineral filler, which can be used from one of the group including corundum powder, chalk, marble, talc, titanium dioxide, carbon black, aerosil.

Another feature of the agent of the present invention is that an aqueous dispersion of polyvinyl acetate or polyacrylate or polystyrene or polyester can be used as the polymer binder.

Another feature of the agent of the present invention is that it may further comprise a fibrous material selected from the group consisting of fiberglass, basalt, silica, polypropylene, polyester.

Another feature of the agent of the present invention is that it may further comprise a dispersed or water-soluble dye.

Finally, another feature of the tool of the present invention is that it may further comprise a carrier layer (substrate) made of nonwoven material 0.05-2 mm thick selected from the group consisting of fiberglass, polypropylene fiber, silica. The implementation of the invention

The proposed autonomous fire extinguishing means is intended for the production of fire extinguishing coatings, fire extinguishing powders and thermally activated fire extinguishing agents (THERMO-OTV technology).

The main difference between the autonomous fire extinguishing means of the present invention is the complex composition of the contents in the core of each microcapsule, the combination of which forms a microencapsulated fire extinguishing agent. The components of this composition are, in addition to a liquefied carrier gas having a boiling point from -155 to + 10 ° С, a combustion phlegmatizer and a combustion inhibitor, and the mass ratio of the components is: carrier gas 5-50%, phlegmatizer of combustion of 30-70%, a combustion inhibitor of 1 25%.

The carrier gas in this microencapsulated extinguishing agent mainly performs a transport function — the delivery of gaseous OTV to the combustion area and regulates the temperatures at which the extinguishing agent starts and ends at the exit of the microcapsules. As a carrier gas, it is effective to use lower partially or completely fluorinated hydrocarbons (carbon chain length C ₁ -C3) having a boiling point in the range from -155 ° C for trifluoromethane (R23 refrigerant) to -16 ° C for heptafluoropropane (refrigerant 227еа). By choosing a carrier gas or a mixture thereof, it is possible to create a microencapsulated extinguishing agent with an internal pressure of 0.3 to 4 Barr inside the microcapsule, which allows a very narrow response range (10-20 ° C) while maintaining the required temperature ry of the onset of operation (60-260 ° C), which gives a high intensity of the OT output and, accordingly, an effective fire extinguishing.

Combustion phlegmatizer in the proposed agent performs the function of the main extinguishing agent. The most effective iodine and bromine-containing fluorocarbons can be used as a burning phlegmatizer: iodotrifluoromethane, or 1-iodoheptafluoropropane, or 2-iodoheptafluoropropane, or iodopentafluoroethane, or 2,2-diiodo-1,1,1,3,3 , 3,3-hexafluoropropane, or 1,2-dibromoethane, or dibromomethane, or mixtures thereof. Since the operational characteristics of the extinguishing agent are determined mainly by the carrier gas used, the parameters and the aggregate state of the phlegmatizer are not of particular importance: phlegmatizers can be used in gaseous, liquid, and solid form.

The combustion inhibitor in the inventive fire extinguishing composition enhances the fire extinguishing effect of the phlegmatizer by actively interrupting the radical combustion chain. As a combustion inhibitor, the use of metal compounds of variable valency, for example, a compound of iron, or chromium, or manganese, or vanadium, or molybdenum, is effective. It is convenient to use complex metallocene compounds (dicyclopentadienyl iron, cyclopentadienyl-tricarbonyl manganese (CTM), methylcyclopentadienyl tricarbonyl manganese, cyclopentadienyl cycloheptatrienyl-vanadium dibenzenechrome and their derivatives), which are very soluble. The introduction of insufficiently soluble combustion inhibitors is possible in the form of a colloidal solution or an ultrathin (0.01-0.1 μm) dispersion stabilized by high molecular weight substances, for example, tetrafluoroethylene oligomers or hexafluoropropylene or tetrafluoroethylene oxide with a rather large average molecular weight (3000-100000). The fluorinated polymer dissolves in the extinguishing core, effectively thickens it and thereby reduces the internal pressure in the capsule and prevents the precipitation and aggregation of the dispersed phase.

The weight ratio of the polymer shell to the core in each capsule of the fire extinguishing agent that forms the basis of the autonomous fire extinguishing agent of the present invention is preferably from 2:98 to 10:90. Moreover, the polymer shell of each microcapsule can be made of one of the polymers selected from the group consisting of polyurethane, polyurea, polyepoxide, polynitrile, polyacrylate, polyamide, or mixtures thereof or products of their copolymerization. At a lower percentage of the material of the shell, its strength is insufficient for reliable storage of the extinguishing agent; at a higher content, the destruction temperature of microcapsules increases significantly (more than 260 ° C).

Preferably, the extinguishing agent is an azeotropic mixture of components, so that when the extinguishing agent is evaporated, it enters the gas phase as a whole without changing the component composition.

The core may also optionally contain any antioxidant, as well as at least one halogen and / or hydrogen halide acceptor. Corrosion activity and toxicity of gas compositions based on polyhalogenated hydrocarbons is largely determined by the presence in them of traces of free halogens (fluorine, iodine) and hydrogen halides (hydrogen fluoride, hydrogen iodide), which are formed when exposed to moisture, oxygen, air, light , as well as under the influence of high temperature in the area of flame combustion during carcass Research Center of ignition. To improve the toxicological characteristics in the proposed fire extinguishing composition, halogen and hydrogen halide acceptors can be used: non-nucleophilic aliphatic and aromatic amines, for example, 2,6-lutidine, triisopropylamine, ditretbutylamine, monomethylaniline, added in an amount of 0.2-0 5% of the mass.

The polymer binder in the stand-alone fire extinguishing agent of the present invention can be, for example, polyvinyl acetate, polyacrylate, polystyrene, polyester used in the form of an aqueous dispersion. The mass ratio of microcapsules to the polymer binder can be from 10: 1 to 1: 4. When the ratio of the microencapsulated extinguishing agent and the polymer binder is more than 10: 1, the resulting material does not have sufficient strength, and when the ratio is less than 1: 4, the material does not have sufficient extinguishing properties.

The self-contained fire extinguishing agent of the present invention may further comprise a mineral filler. As such, it is possible to use, for example, corundum powder, chalk, marble, talc, titanium dioxide, carbon black, aerosil.

The self-contained fire extinguishing agent of the present invention may further comprise fibrous material. Such a material can be, for example, fiberglass, basalt, silica, polypropylene, polyester.

The self-contained extinguishing agent of the present invention may further comprise a particulate or water-soluble dye.

The percentage of mineral filler, fibrous material and dye in a stand-alone fire extinguishing agent in the present invention is selected in a particular case in such a way that the desired mechanical and decorative properties are achieved while maintaining the fire-extinguishing properties of the agent.

For additional mechanical hardening, as well as to increase the manufacturability of production, the stand-alone fire extinguishing means of the present invention may additionally contain a carrier layer on which this means is applied. Such a layer can be a layer with a thickness of 0.05–2 mm from a nonwoven material such as fiberglass, polypropylene fiber, and silica.

A typical manufacturing process of the claimed autonomous means consists of the following sequence of technological operations:

1. Production of a polymer composition for the production of an autonomous fire extinguishing agent:

1.1 Preparation of a working solution of a polymer binder.

1.2 Addition of dry bulk components, homogenization of the mixture.

1.3 Adding a tinting composition.

1.4. Addition of a microencapsulated agent.

1.5. Addition of thickeners, preservatives, aniseptics, rheological and other technological additives.

1.6. Evacuation with stirring at 0.01 MPa.

2.1. Production of fire extinguishing composite material:

2.2. Forming a fire extinguishing composite material using casting molds for manual manufacturing or forming a tape using a slotted extruder in automatic production.

2.3. Primary curing of the composite material. 2.4. The formation of the surface of the material using rolling rollers.

2.5. Final curing (drying) of the material.

2.6. Connection to the carrier layer, application of the adhesive layer (depending on the type of execution).

2.6. Cutting to individual products, labeling and packaging.

The manufacturing process of the extinguishing agent of the present invention can be carried out on typical chemical equipment: liquid mixing reactors, slotted extruders, continuous casting conveyor, casting molds, die cutting machines and laminators.

The choice of a specific set of equipment depends on the type of implementation of the extinguishing agent, the required characteristics, the raw materials used and the required performance.

Fire tests of the obtained samples of an autonomous fire extinguishing agent are carried out as follows.

A metal box of the required volume and degree of leakage, equipped with a door with a sight glass, is used as a model protected volume. A model ignition center and an extinguishing agent sample are installed in the box. A fire center is installed in the center of the box, and the extinguishing agent in its upper part. The center is set on fire, the drawer door is closed. With the help of a stopwatch, the extinguishing time and re-ignition are recorded.

The temperature of the onset of activation (release of OTV) and the end of the allocation of OTV is determined using a thermal balance (derivatograph). For this, a sample of the extinguishing agent material is placed in a thermobalance and the dependence of the mass loss of the sample on its temperature during linear heating is determined at a rate of 3-5 ° C / min. Temperature the response of the agent is defined as the onset of intense loss of mass of the sample, the temperature range of the response is defined as the difference between the end temperature and the onset of intense loss of mass of the sample.

Examples of the implementation of the proposed extinguishing agent and the characteristics obtained are shown in the Table.

As can be seen from the Table, autonomous extinguishing agent samples made according to this application have better fire extinguishing efficiency (lower response temperature, lower response temperature range and shorter extinguishing time) and better flexibility in the absence of cracking.

Thus, the present invention provides a technical result in the form of an autonomous fire extinguishing means having a short response time, high mechanical and strength properties, reliability during normal operation and when extinguishing a fire.

Table. Examples of the implementation of the autonomous extinguishing means according to the invention

radius

bending cm

Time I V- volume 15 l

plate 50 sec 25 sec 35 sec 19 sec size

100x50x5

mm

Table 1 (continued). Examples of the implementation of the world encapsulated extinguishing agent according to the invention

Claims

Claim

1. A stand-alone fire extinguishing agent containing a polymeric binder and a microencapsulated fire extinguishing agent, including in each microcapsule a polymer shell and a core containing carrier gas as components, having a boiling point of -155 to + 10 ° С , combustion phlegmatizer and combustion inhibitor in a mass ratio: carrier gas 5-50%, combustion phlegmatizer 30-70%, combustion inhibitor 1-25%, and the mass ratio of microcapsules and polymer binder is from 10: 1 to 1: 4 .

2. The tool according to claim 1, in which the mass ratio of the polymer shell and the core in said capsule is from 2:98 to 10:90.

3. The agent according to claim 1, wherein the polymer shell of each microcapsule is made from one of the polymers selected from the group consisting of polystyrene, polyurethane, polyurea, polyepoxide, polynitrile, polyacrylate, polyamide, or from mixtures thereof or products of their copolymerization.

4. The tool according to claim 1, in which the fire extinguishing agent is an azeotropic mixture.

5. The tool according to claim 1, wherein the carrier gas is partially or fully fluorinated hydrocarbon with a carbon chain length of Ci-Cz.

6. The tool according to claim 5, in which the carrier gas used is: 1-H-heptafluoropropane or 2-H-heptafluoropropane or pentafluoroethane or 1,1,1, 3,3, 3-hexafluoropropane or their mixtures.

7. The tool according to claim 1, in which a substance from the group consisting of iodotrifluoromethane, 1-iodoheptafluoropropane, 2-iodoheptafluoropropane, iodopentafluoroethane, 2,2-

17

SUBSTITUTE SHEET (RULE 26) diiod-1,1,1, 3,3,3-hexafluoropropane, 1, 2-dibromoethane, dibromomethane or mixtures thereof.

8. The tool according to claim 1, wherein a compound of any metal of variable valency from the group comprising iron, chromium, manganese, vanadium, molybdenum is used as a combustion inhibitor.

9. The agent according to claim 8, wherein a compound of the group consisting of dicyclopentidienyl iron, cyclopentadienyl-tricarbonyl manganese, methylcyclopentadienyltricarbonyl manganese, dibenzenechrom or their homologs is used as a combustion inhibitor.

10. The tool according to claim 1, in which a colloidal solution or a stabilized dispersion with a particle size of 0.01-0.1 μm is used as a combustion inhibitor.

11. The tool according to claim 1, wherein said core further comprises at least one high molecular weight stabilizer selected from oligomers of tetrafluoroethylene or hexafluoropropylene or tetrafluoroethylene oxide with an average molecular weight of 3,000-100,000.

12. The tool according to claim 1, wherein said core further comprises an antioxidant.

13. The tool according to claim 1, wherein said core further comprises at least one halogen and / or halogen hydrogen acceptor.

14. The tool according to claim 1, wherein said shell has a temperature at which fracture starts and the contents exit in the range of 60 to 260 ° C.

15. The tool according to claim 1, wherein said microcapsules are characterized by a temperature interval from the beginning of the destruction of the shell to the complete release of the contents from 10 to 20 ° C.

eighteen

SUBSTITUTE SHEET (RULE 26)

16. The agent according to claim 1, further comprising a mineral filler, one of which is a group of corundum powder, chalk, marble, talc, titanium dioxide, carbon black, aerosil.

17. The agent according to claim 1, wherein polyvinyl acetate or polyacrylate or polystyrene or polyester or their copolymers or mixtures thereof is used as the polymeric binder.

18. The tool according to claim 1, further containing a fibrous material selected from the group comprising fiberglass, basalt, silica, polypropylene, polyester.

19. The tool according to claim 1, additionally containing a dispersed or water-soluble dye.

20. The tool according to p. 1, additionally containing a carrier layer made of non-woven material with a thickness of 0.05-2 mm, selected from the group including fiberglass, polypropylene fiber, silica.

19

SUBSTITUTE SHEET (RULE 26)