Passive fire protection device with silicone foam

Abstract

The present invention relates to a passive fire protection device, the device having a density of 0.20 g / cm 3 The passive fire protection device comprises at least one strip comprising less than 1000 ppm silicone foam. The passive fire protection device is particularly useful for protecting equipment critical to the security and safety of a facility, such as cables, cable trays, ventilation and smoke exhaust ducts, feed-throughs, fittings, and cabinets.

Description

[Technical Field]

[0001] The present invention relates to the technical field of silicone foams, more particularly to devices, in particular Cables and cable trays, ventilation ducts and smoke exhaust ducts; Feedthroughs (cable, steel, copper, stainless steel piping, etc.), fire-rated feedthroughs; ·Fire seal; Fire-resistant enclosures to protect certain equipment, especially equipment critical to the safety and security of the facility (pumps, valves, sensors, actuators, etc.) This application relates to the use of silicone foam strips for passive fire protection of buildings.

[0002] Passive fire protection ("PFP") refers to all preventive fire protection measures based on the use of fire compartments or fire-resistant construction elements. A "PFP" device is an item that enables a building or part of a building to withstand fire for a set, defined time. The fire resistance of an installation is verified and certified by tests carried out in accordance with ISO EN 1366 "Tests for the fire resistance of technical installations". [Background technology]

[0003] A cable tray is a device for routing one or more cables (typically electrical, computer, or multimedia cables) or pipes to facilitate the flow of fluids (air, gas, etc.).

[0004] The use of fire-resistant coverings to protect cable trays is a common practice. Passive fire blankets are generally flexible devices that have the properties of a fire barrier and mechanical strength up to 1300°C.

[0005] For example, the following prior art documents can be mentioned: EP 0 612 540 describes a flexible protective device with fire barrier properties, which comprises a composite of fibrous and / or textile elements constructed by bonding; EP 2072087 A1 describes a fire mat comprising at least two fibrous subassemblies based on mineral fibre wool mats separated by a mineral fibre fabric, at least one layer of fire-resistant adhesive bonding the fibrous subassemblies together, and an envelope containing a mineral fibre fabric impregnated with a flame-retardant silicone and surrounding all the fibrous subassemblies; EP 2 694 164 also describes a fire-resistant coating that comprises a plurality of superimposed fiber layers with a fire-resistant adhesive layer disposed between two of the fiber layers.

[0006] In these various documents, the firewall material contains at least one fibrous element. However, if the fibrous product breaks, it can generate residues that tend to clog safety devices in equipment, such as cooling circuits. Therefore, the presence of fibrous elements is undesirable in high-risk facilities such as nuclear power plants.

[0007] A solution to this particular problem is proposed in EP 3799935. This patent application describes a fire blanket comprising a first layer of a heat-resistant material, in particular a woven fabric of glass fiber or meta-aramid fiber, and a second layer of a flame-retardant material. Furthermore, the same document describes a fire protection device using one or more staggered blankets. According to the document, fire blankets have the advantages of being lightweight, flexible, and eliminating the risk of protruding fibers that could clog filters if the cable tray protection is damaged during a steam or other jet of air blast. However, these blankets are difficult to assemble. The blankets must be positioned to ensure an area for the flame-extinguishing material to expand in the event of a fire.

[0008] The object of the present invention is therefore to propose a new passive fire protection device that is flexible, lightweight, easy to handle, has fire barrier properties and good mechanical strength up to 1300°C. This new device is advantageously free of fibrous elements and can protect equipment important for safety and security in high-risk facilities such as nuclear power plants. Furthermore, this new device may be removable, washable and decontaminated. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] European Patent Application Publication No. 0612540 [Patent Document 2] European Patent Application Publication No. 2072087 [Patent Document 3] European Patent Application Publication No. 2694164 [Patent Document 4] European Patent Application Publication No. 3799935 Summary of the Invention [Problem to be solved by the invention]

[0010] More generally, the object of the invention is to propose a novel device for the passive fire protection of equipment, in particular equipment that is important for the safety and security of the installation, such as cables, cable trays, ventilation and smoke exhaust ducts, feedthroughs, seals and enclosures. [Means for solving the problem]

[0011] The subject of the present invention is therefore a passive fire protection device, 3 Another subject of the present invention is a passive fire protection device comprising at least one strip comprising a silicone foam having a density less than 1000 MPa. Another subject of the present invention is a method for manufacturing a passive fire protection device, comprising (A) manufacturing a strip comprising a silicone foam, said manufacturing comprising: Producing a silicone composition capable of forming a foam by releasing a gas; placing the composition into a mold; closing said mold; Crosslinking and / or curing the silicone composition to obtain a strip containing silicone foam. The method includes the steps of:

[0012] The subject of the invention is also the use of said device for the passive fire protection of installations, in particular for the wrapping of installations that are important for the safety and security of the installation, such as cables, cable trays, ventilation and smoke exhaust ducts, feed-throughs, seals and enclosures, particularly preferably cable trays in high-risk installations such as nuclear power plants. [Brief explanation of the drawings]

[0013] [Figure 1] 1 shows an embodiment of a mold according to the present invention. [Figure 2] 2A and 2B show an embodiment of a strip according to the present invention before (2A) and after (2B) demolding. [Figure 3] 1 illustrates an embodiment of a passive fire protection device according to the present invention. [Figure 4] 3 is a photograph of a strip obtained according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0014] Unless otherwise specified, all viscosities of silicone oils referred to in this disclosure correspond to dynamic viscosity values ​​at 25°C known as "Newtons", i.e. dynamic viscosities measured in a manner known per se using a Brookfield viscometer at a shear rate gradient sufficiently low so that the measured viscosity is independent of the rate gradient.

[0015] The subject of the present invention is therefore a passive fire protection device, 3A passive fire protection device comprising at least one strip comprising a silicone foam having a density of less than 1000 psi.

[0016] A strip can be defined as a shape whose thickness is significantly less than its length and width. A strip is typically Length: 50cm~5m; Width: 10cm-50cm; Thickness: 1cm to 5cm It can be said that:

[0017] The term "silicone foam" refers to an organopolysiloxane composition in foam form.

[0018] According to a preferred embodiment, the silicone foam according to the present invention is obtained from a silicone composition that crosslinks by polyaddition and generates hydrogen during the foaming reaction.

[0019] However, without being limited by any theory, the foaming phenomenon can be explained as follows: A polyaddition-crosslinkable composition is used that includes an organopolysiloxane having silicon-bonded vinyl groups, an organopolysiloxane containing silicon-bonded hydrogen atoms, and a pore-forming agent containing hydroxyl groups. The hydroxyl groups of the pore-forming agent react with the organopolysiloxane having hydride functional groups to generate hydrogen gas and silanol. The silanol then reacts with the organopolysiloxane having hydride functional groups through a hydrogen condensation reaction to generate a second hydrogen gas molecule, while another polydiorganosiloxane having silicon-bonded vinyl groups simultaneously reacts with another organopolysiloxane having hydride functional groups through an addition reaction, helping to build a silicone foam network.

[0020] Although the above polyaddition-crosslinkable composition is a preferred embodiment of the silicone foam according to the present invention, other silicone compositions capable of forming foam are entirely conceivable, as long as the composition releases gas that allows the foaming phenomenon. According to one embodiment, the silicone composition comprises a pore-forming agent that expands the material under the action of heat by decomposition with the release of gas, particularly in the case of azo derivatives such as azodicarbonamide, releasing nitrogen, carbon dioxide, and ammonia. According to another embodiment, the silicone composition comprises a pore-forming agent that expands the material under the action of heat by undergoing a phase change, typically from liquid to gas, particularly in the case of low-boiling solvents.

[0021] According to a preferred embodiment, the silicone foam is obtained from a silicone composition comprising: At least two silicon bonds C2-C per molecule 12 at least one organopolysiloxane A containing alkenyl groups, at least one organopolysiloxane B containing at least two SiH units per molecule, a catalytically effective amount of at least one hydrosilylation catalyst C, and at least one pore-forming agent D containing hydroxyl groups;

[0022] At least two silicon bonds C2-C per molecule 12 The organopolysiloxane A containing alkenyl groups may preferably be a linear organopolysiloxane formed from: at least two siloxyl units of the formula: Y a R 1 b SiO (4-a-b) / 2 (Wherein, Y is C2 to C 12 represents an alkenyl group, preferably a vinyl group; R 1represents a monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably selected from alkyl groups having 1 to 8 carbon atoms such as methyl, ethyl, and propyl, cycloalkyl groups having 3 to 8 carbon atoms, and aryl groups having 6 to 12 carbon atoms; a=1 or 2, b=0, 1, or 2, and the sum of a+b=2 or 3; and Optionally, the unit: R 1 c SiO (4-c / 2) (In the formula, R 1 has the same meaning as above, and c=2 or 3.

[0023] In the above formula, multiple R 1 It is understood that when groups are present they may be the same or different from one another.

[0024] In the description of organopolysiloxane A below, the following nomenclature is used to represent the siloxyl units: M: Siloxyl unit R 1 3SiO 1 / 2 , M Vi :YR 1 2SiO 1 / 2 and Y2R 1 SiO 1 / 2 Siloxyl units selected from D: Siloxyl unit R 1 2SiO 2 / 2 , D Vi :Y2SiO 2 / 2 and YR 1 SiO 2 / 2 Siloxyl units selected from T: Siloxyl unit R 1 SiO 3 / 2 , Q: Siloxyl unit SiO 4 / 2 , Y and R 1 is as defined above.

[0025] Terminal units M and M ViExamples of the siloxy group include a trimethylsiloxy group, a dimethylphenylsiloxy group, a dimethylvinylsiloxy group, and a dimethylhexenylsiloxy group.

[0026] D and D Vi Examples of the unit include a dimethylsiloxy group, a methylphenylsiloxy group, a methylvinylsiloxy group, a methylbutenylsiloxy group, a methylhexenylsiloxy group, a methyldecenylsiloxy group, and a methyldecadienylsiloxy group.

[0027] An example of a T unit is a methylsiloxy group.

[0028] At least two silicon bonds C2-C per molecule 12 The organopolysiloxane A containing alkenyl groups preferably contains siloxyl units D and / or D Vi and terminal siloxyl units M and / or M Vi The linear organopolysiloxane may consist essentially of

[0029] Examples of linear organopolysiloxanes that can be organopolysiloxane A according to the present invention are: · Dimethylvinylsilyl terminated poly(dimethylsiloxane); · Dimethylvinylsilyl-terminated poly(dimethylsiloxane-co-methylphenylsiloxane); Dimethylvinylsilyl-terminated poly(dimethylsiloxane-co-methylvinylsiloxane); and · Trimethylsilyl terminated poly(dimethylsiloxane-co-methylvinylsiloxane).

[0030] Preferably, organopolysiloxane A comprises terminal dimethylvinylsilyl units, and more preferably organopolysiloxane A is a dimethylvinylsilyl-terminated poly(dimethylsiloxane).

[0031] Preferably, organopolysiloxane A is an oil having a dynamic viscosity of 100 mPa·s to 100,000 mPa·s, preferably 100 mPa·s to 80,000 mPa·s, more preferably 1000 mPa·s to 50,000 mPa·s.

[0032] Preferably, organopolysiloxane A has a mass content of alkenyl units of 0.001% to 30%, preferably 0.01% to 10%, more preferably 0.02% to 5%.

[0033] The silicone composition preferably comprises 40% to 80% by weight of organopolysiloxane A, more preferably 50% to 70% by weight of organopolysiloxane A. According to one embodiment, the silicone composition comprises C2 to C 12 It does not include any branched organopolysiloxanes or resins containing alkenyl units.

[0034] Organopolysiloxane B is an organopolysiloxane containing at least two SiH units per molecule. It is therefore an organohydrogenpolysiloxane compound. Preferably, compound B contains at least three SiH units.

[0035] The organopolysiloxane B may advantageously be an organopolysiloxane comprising at least two, preferably at least three, siloxyl units of the formula: H d R 2 e SiO (4-d-e) / 2 (In the formula, R 2 represents a monovalent group containing 1 to 12 carbon atoms, d=1 or 2, e=0, 1 or 2, and d+e=1, 2 or 3; and optionally other units of the formula: R 2 f SiO (4-f) / 2 (In the formula, R 2 has the same meaning as above, and f=0, 1, 2 or 3.

[0036] In the above formula, multiple R 2 It is understood that when groups are present they may be the same or different from one another.

[0037] Preferably, R 2 R may represent a monovalent group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an aryl group having 6 to 12 carbon atoms, which may be substituted with at least one halogen atom such as chlorine or fluorine. 2 can advantageously be selected from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, xylyl, tolyl and phenyl. The symbol d is preferentially equal to 1.

[0038] In the description of organopolysiloxane B below, the following nomenclature has been used to represent the siloxyl units: M: Siloxyl unit R 2 3SiO 1 / 2 , M': siloxyl unit R 2 2HSiO 1 / 2 , D: Siloxyl unit R 2 2SiO 2 / 2 , D': Siloxyl unit R 2 HSiO 2 / 2 , T: Siloxyl unit R 2 SiO 3 / 2 , Q: Siloxyl unit SiO 4 / 2 , where R 2 is as defined above.

[0039] Organopolysiloxane B may have a linear, branched, or cyclic structure. The degree of polymerization is preferably 2 or greater. Generally, the degree of polymerization is less than 5,000. The viscosity of organopolysiloxane B is preferably 1 mPa·s to 5,000 mPa·s, more preferably 1 mPa·s to 2,000 mPa·s, and even more preferably 5 mPa·s to 1,000 mPa·s.

[0040] In the case of a linear polymer, it is essentially formed from siloxyl units D and / or D' and terminal siloxyl units M and / or M'. In the case of a cyclic polymer, it is essentially formed from siloxyl units D and / or D'.

[0041] Examples of organohydrogenpolysiloxanes that can be organopolysiloxane B according to the invention are: · Hydrogenodimethylsilyl-terminated poly(dimethylsiloxane); · Trimethylsilyl-terminated poly(dimethylsiloxane-co-methylhydrogensiloxane); · Hydrogenodimethylsilyl-terminated poly(dimethylsiloxane-co-methylhydrogensiloxane); · Trimethylsilyl-terminated poly(methylhydrogensiloxane); and · Cyclic poly(methylhydrogensiloxane).

[0042] When polyorganohydrogensiloxane B has a branched structure, it is preferably selected from the group consisting of silicone resins of the following formula: ·M'Q in which the silicon-bonded hydrogen atom is held by the M group; ·MM'Q, where the silicon-bonded hydrogen atom is held by part of the M unit; · MD'Q in which the silicon-bonded hydrogen atom is held by a D group; · MDD'Q in which the silicon-bonded hydrogen atom is held by part of the D group; ·MM'TQ, where the silicon-bonded hydrogen atom is held by part of the M unit; · Silicon-bonded hydrogen atoms are held by some of the M and D units MM'DD'Q; · and mixtures thereof.

[0043] Preferably, organopolysiloxane B has a mass content of Si—H hydrogenosilyl functional groups of 0.2% to 91%, more preferably 3% to 80%, and even more preferably 15% to 70%.

[0044] Advantageously, the molar ratio of hydrogenosilyl Si—H functional groups of organopolysiloxane B to alkene functional groups of organopolysiloxane A is between 5 and 100, preferably between 10 and 90, preferentially between 15 and 65, and more preferentially between 20 and 55.

[0045] The silicone composition according to the invention preferably comprises from 1% to 20% by weight of organopolysiloxane B, more preferentially from 3% to 15% by weight.

[0046] The hydrosilylation catalyst C can be selected, in particular, from platinum and rhodium compounds, but also from silicon compounds such as those described in WO 2015 / 004396 and WO 2015 / 004397, germanium compounds such as those described in WO 2016 / 075414, or nickel, cobalt, or iron complexes such as those described in WO 2016 / 071651, WO 2016 / 071652, and WO 2016 / 071654. Catalyst C is preferably a compound derived from at least one metal belonging to the platinum group. These catalysts are well known. In particular, the complexes of platinum with organic products described in U.S. Pat. No. 3,159,601, U.S. Pat. No. 3,159,602, U.S. Pat. No. 3,220,972, EP Pat. No. 0,057,459, EP Pat. No. 0,188,978 and EP Pat. No. 0,190,530, as well as the complexes of platinum with vinylorganosiloxanes described in U.S. Pat. No. 3,419,593, U.S. Pat. No. 3,715,334, U.S. Pat. No. 3,377,432 and U.S. Pat. No. 3,814,730 may be used.

[0047] Preferably, catalyst C is a compound derived from platinum. In this case, the amount of catalyst C by weight, calculated as the weight of platinum metal, is generally 2 ppm to 400 ppm, preferably 5 ppm to 200 ppm, based on the total weight of the silicone composition.

[0048] Preferably, catalyst C is Karstedt platinum.

[0049] The hydroxyl-containing pore former D can be selected from the group consisting of water, polyols, monofunctional alcohols, organosilanes containing at least one silanol group, organosiloxanes containing at least one silanol group, and mixtures thereof.

[0050] According to a preferred embodiment, the pore-forming agent D is water. Water can be added directly to the silicone composition. Alternatively, water can be introduced in the form of an aqueous silicone emulsion, such as a direct silicone oil-in-water emulsion or an inverse silicone water-in-oil emulsion, which contains a continuous silicone oil phase, an aqueous phase, and a stabilizer. According to one embodiment, water is introduced via a silicone oil-in-water emulsion with a water content of about 60% by weight. Introducing water into the silicone composition via an emulsion improves the dispersibility of water in the silicone composition and its stability during storage.

[0051] According to another embodiment, the pore-forming agent D is a polyol. Preferably, it is an organic polyol containing 3 to 12 carbon atoms and at least two hydroxyl groups per molecule. The polyol may be linear or branched, and may optionally contain one or more aromatic rings. Examples include saturated polyhydric alcohols containing at least two hydroxyl groups per molecule, as described in U.S. Pat. No. 4,871,781. Examples of polyols that can be used as pore-forming agents according to the present invention are: diols, such as 1,2-ethanediol, 2,3-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol; Triols, such as 1,2,3-propanetriol and 2,2-bis(hydroxymethyl)butanol; tetritols, such as erythritol and pentaerythritol; Pentitols, such as arabitol, xylitol and methylpentitol; hexitols, such as mannitol and sorbitol; and Cycloaliphatic polyols, such as cyclohexanediol, cyclohexanetriol and inositol.

[0052] According to another embodiment, the pore-forming agent D is a monofunctional alcohol. Preferably, it is an organic alcohol containing 1 to 12 carbon atoms and one hydroxyl group per molecule. The alcohol may be linear or branched, and may optionally contain one or more aromatic rings. Examples of monofunctional alcohols that can be used as pore-forming agents according to the present invention are methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, t-butanol, n-octanol, benzyl alcohol, and mixtures thereof.

[0053] According to yet another embodiment, the pore-forming agent D is an organosilane containing one or more silanol groups. These compounds can be represented, for example, by formula (1) or (2): (1)(R 3 )3SiOH (2)(R 3 )2Si(OH)2 (wherein, R 3 may represent a monovalent group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an aryl group having 6 to 12 carbon atoms, each of which may be substituted with at least one halogen atom such as chlorine or fluorine. In the above formula, multiple R 3 It is understood that when groups are present they may be the same or different from one another.

[0054] Examples of organosilanes containing one or more silanol groups that can be used as pore formers in accordance with the present invention are (CH3)3SiOH, (C6H5)SiOH, (CH3)(C6H5)2SiOH, and (C6H5)2Si(OH)2.

[0055] According to yet another embodiment, the pore former D is an organosiloxane containing one or more silanol groups. Preferably, it is an organopolysiloxane compound formed from: at least one siloxyl unit of the formula: R 3 g (OH) h SiO (4-g-h) / 2 (In the formula, R 3 has the same meaning as above; g=0, 1 or 2, h=1 or 2, and the sum of g+h=1, 2 or 3; and Optionally, a unit of the formula: R 3 i SiO (4-i) / 2 (In the formula, R 3 has the same meaning as above, where i=0, 1, 2 or 3.

[0056] The silicone composition may contain any other compounds, in particular at least one inorganic filler, in particular silica or quartz, or a mixture thereof; at least one heat-resistant and / or fire-resistant additive; at least one diorganopolysiloxane gum; diorganopolysiloxane oils in which each end of the chain is blocked with a triorganosiloxy unit in which the organic radicals bonded to the silicon atom are selected from alkyl radicals containing from 1 to 8 carbon atoms; · Cross-linking inhibitors; · Dye-based; Optionally other fillers.

[0057] According to a preferred embodiment, the silicone composition comprises an inorganic filler, preferably a combusted silica or a precipitated silica. The silica-type inorganic filler has a specific surface area of ​​at least 50 m, as measured by the BET method. 2 / g, especially 50m 2 / g~400m 2 / g, preferably 70m 2 / g, an average primary particle size of less than 0.1 μm (micrometer) and a bulk density of less than 200 g / liter. 2 / g~300m 2 / g BET specific surface area.

[0058] The silica-type inorganic filler, which is preferably hydrophilic, can be incorporated directly into the silicone composition, or can be optionally treated with a compatibilizer.In a variant, these silicas can be optionally treated with one or more organosilicon compounds commonly used for this purpose, such as organosilanes or organosilazanes.These compounds include methylpolysiloxanes such as hexamethyldisiloxane and octamethylcyclotetrasiloxane, methylpolysilazanes such as hexamethyldisilazane, hexamethylcyclotrisilazane and tetramethyldivinyldisilazane, chlorosilanes such as dimethyldichlorosilane, trimethylchlorosilane, methylvinyldichlorosilane and dimethylvinylchlorosilane, and alkoxysilanes such as dimethyldimethoxysilane, dimethylvinylethoxysilane and trimethylmethoxysilane. These compounds can be used alone or in mixtures (see French Patents 1,126,884, 1,136,885, 1,236,505, and British Patent 1,024,234). According to a preferred embodiment, the silica is treated in situ when mixed with all or part of the organopolysiloxane A. According to an advantageous embodiment, the silica is treated with one or more hexaorganodisilazanes. Even more preferably, the silica is treated with hexamethyldisilazane, alone or in a mixture with divinyltetramethyldisilazane.

[0059] The silica may optionally be pre-dispersed in silicone oil to obtain a suspension. It is particularly preferred to use a suspension of combustion silica, in particular treated with hexamethyldisilazane, in a polyorganosiloxane oil, in particular a vinyl-treated polyorganosiloxane.

[0060] Alternatively or in addition, the silicone composition of the present invention may contain at least one other inorganic filler, namely, quartz. Preferably, ground natural quartz having an average particle size of less than 10 microns is used. The quartz may optionally be treated to improve its compatibility with the organopolysiloxane.

[0061] According to a preferred embodiment, the silicone composition comprises a mixture of silica and quartz, the mass ratio between quartz and silica being preferably between 0.5 and 4, more preferably between 1 and 3.6, even more preferably between 1.5 and 3.2, and even more advantageously between 1.5 and 2.8.

[0062] Other inorganic fillers are also contemplated, particularly fillers such as diatomaceous earth, calcium carbonate and / or kaolin.

[0063] The silicone composition may optionally contain at least one heat-resistant and / or fire-resistant additive. These heat-resistant and / or fire-resistant additives are well known to those skilled in the art. These may be advantageously selected from the group consisting of salts, oxides, and hydroxides of metals such as iron, titanium, aluminum, nickel, and copper; salts, hydroxides, and oxides of rare earth metals such as cerium and lanthanum; organic phosphorus compounds; platinum derivatives; carbon black; and calcium, aluminum, and / or potassium silicates, such as mica and wollastonite. Hydrated inorganic fillers include oxides or carbonates of calcium, magnesium, or aluminum, such as magnesium hydroxide Mg(OH)2, aluminum hydroxide Al(OH)3, hydromagnesite with the empirical formula Mg5(CO3)4(OH)2·4H2O, and calcium hydroxide. According to another embodiment, hollow glass microspheres can be added to the silicone composition.

[0064] The silicone composition may optionally contain at least one diorganopolysiloxane gum having a viscosity of greater than 1000 Pa·s, preferably greater than 2000 Pa·s, at 25°C, and in which the diorganopolysiloxane chain has the formula RSiO 2 / 2 and consists essentially of units of the formula RSiO 1 / 2 where the R group represents an alkyl group containing 1 to 8 carbon atoms or an alkenyl group containing 2 to 6 carbon atoms. However, there are also RSiO units along the diorganopolysiloxane chain. 2 / 2 Smaller units other than RSiO3 / 2 and / or SiO 4 / 2 The existence of the unit RSiO 2 / 2 A proportion of 2% or less of the number of units is not excluded. Preferably, the diorganopolysiloxane gum contains at least two silicon-bonded C2-C 12 Advantageously, the diorganopolysiloxane gum has a mass content of vinyl units of more than 0.3%, preferably more than 0.5%, more preferably between 0.5% and 6%, even more preferably between 0.5% and 4%, and even more preferably between 1% and 3.5%.

[0065] If the silicone composition contains a crosslinking inhibitor (or addition reaction retarder), this may be selected from the following compounds: organopolysiloxanes (which are advantageously cyclic and substituted by at least one alkenyl, with tetramethylvinyltetrasiloxane being particularly preferred), pyridine, organic phosphines and phosphites, unsaturated amides, alkyl maleates, and acetylenic alcohols such as 1-ethynyl-L-cyclohexanol, 3-methyl-L-dodecin-3-ol, 3,7,11-trimethyl-1-dodecin-3-ol, 1,1-diphenyl-2-propyn-1-ol, 3-ethyl-6-ethyl-1-nonyn-3-ol, and 3-methyl-1-pentadecin-3-ol.

[0066] According to one embodiment, the silicone composition comprises (by weight, based on the total weight of the silicone composition): a. At least two silicon bonds C2 to C per molecule 12 40% to 80% by weight of at least one organopolysiloxane A containing alkenyl groups, b. 1% to 20% by weight of at least one organopolysiloxane B containing at least two SiH units, preferably at least three SiH units per molecule; c. 2 ppm to 400 ppm (calculated by weight of platinum metal) of a hydrosilylation catalyst C selected from platinum compounds; and d. 0.3 wt% to 2.5 wt% of pore-forming agent D; e.100m 2 / g~300m 2 at least 3% by weight of fused silica having a specific surface area of ​​ / g, f. at least 6% by weight of at least one crushed quartz inorganic filler, and g. 0.4% to 5% by weight of at least one heat-resistant additive and / or fire-resistant additive include.

[0067] According to another embodiment, the silicone composition comprises (by weight, based on the total weight of the silicone composition): a. At least two silicon bonds C2 to C per molecule 12 40% to 80% by weight of at least one organopolysiloxane A containing alkenyl groups, b. 1% to 20% by weight of at least one organopolysiloxane B containing at least two SiH units, preferably at least three SiH units per molecule; c. 2 ppm to 400 ppm (calculated by weight of platinum metal) of a hydrosilylation catalyst C selected from platinum compounds; d. 0.3 wt% to 2.5 wt% of pore-forming agent D; e.100m 2 / g~300m 2 3% to 14% by weight of at least one inorganic filler which is a fired silica having a specific surface area of ​​1 / g; f. 6% to 25% by weight of at least one ground quartz inorganic filler; g. 0.4% to 5% by weight of at least one flame retardant additive; h. a cross-linking inhibitor in an amount of 0 to 3000 ppm by mass, and i. At least two silicon bonds C2 to C 12 0 to 4% by weight of diorganopolysiloxane gum containing alkenyl groups include.

[0068] Such silicone compositions that allow the production of silicone foams are described, for example, in WO 2021 / 014058.

[0069] According to one embodiment, the silicone composition of the present invention can be prepared from a two-component (or multi-component) system characterized by two (or more) different parts intended to be mixed together to form the silicone composition. In particular, in the case of the preferred silicone composition described above, the silicone composition can be prepared from a two-component system characterized by one containing catalyst C but not organopolysiloxane B, and the other containing organopolysiloxane B but not catalyst C. Other multi-component systems can also be provided to improve shelf life and / or optimize the viscosity of each component. For example, the silicone composition of the present invention can be prepared from a three-component (or multi-component) system characterized by two (or more) different parts intended to be mixed together to form the silicone composition.

[0070] The mixing of the two-component (or multi-component) parts can typically be carried out in a mixer (such as a pitched-blade mechanical mixer, a low-pressure dynamic mixer, or any other conventional mixing system) at about ambient temperature, i.e., between 10°C and 40°C. An increase in the temperature of the silicone composition may be observed during this mixing, depending on the type of mixer and the applied shear. If crosslinking or curing of the silicone foam is to be accelerated, mixing can be carried out at higher temperatures, advantageously between 40°C and 70°C.

[0071] Good quality mixing is important to obtain a homogeneous silicone foam with good mechanical properties.

[0072] The silicone composition undergoes a crosslinking and / or curing process to yield a silicone foam. This process may last for a variety of periods depending on the silicone composition and the temperature. Generally, a silicone foam with good properties is obtained after a few minutes to a few hours, depending on the temperature and the concentration of catalyst and inhibitor in the silicone composition.

[0073] The silicone foam according to the invention advantageously has a low density, preferably less than 0.20 g / mL, more preferentially less than 0.17 g / mL, and is visually uniform, with a uniform distribution of cell sizes within the foam and no large cells with a diameter of 2 mm or more.

[0074] The silicone foam according to the present invention is advantageous in that it is lightweight, has good mechanical properties, has excellent fire resistance, and does not produce toxic gases when burned.

[0075] These remarkable properties make silicone foam flexible and easy to handle, making it advantageous for use in passive fire protection devices.

[0076] Preferably, the silicone foam according to the present invention is not a smoke-producing material. The term "smoke-producing material" refers to a material that is capable of expanding under the influence of heat above a certain temperature.

[0077] One subject of the present invention is a method for manufacturing a passive fire protection device, comprising: (A) manufacturing a strip comprising silicone foam, said manufacturing comprising: Producing a silicone composition capable of forming a foam by releasing a gas; placing the composition into a mold; closing the mold; and Crosslinking and / or curing the silicone composition to obtain a strip containing silicone foam. The method includes the steps of:

[0078] The closed mold defines a hollow volume corresponding to the shape of the article to be molded. The mold may have a simple geometric shape, such as a parallelepiped, as shown in Figure 1.

[0079] Preferably, the bottom and top walls of the mold define the largest surface of the molded article, and the side walls define the thickness of the molded article.

[0080] According to a first embodiment shown in Figure 1, the mold (1) is composed of side walls (2) (four side walls are shown here), a bottom wall (3), and a top wall or cover (4). The bottom wall (3) can optionally be provided with feet (5) for supporting the mold. As shown in Figure 1, the cover (4) is preferably removable. In producing a strip according to the present invention, a silicone composition can be placed in the mold (1) (Configuration 1A), and then the cover (4) can be attached to the side walls, thereby defining a closed hollow volume (Configuration 1B).

[0081] According to another embodiment (not shown), the mold can be composed of two mold halves that, when assembled, define a closed hollow volume. In carrying out the method according to the invention, the silicone composition can typically be poured into the closed hollow volume defined by the two assembled mold halves.

[0082] The walls of the mould may consist of a material suitable for ensuring its mechanical strength, for example a metal, typically steel or aluminium, a hard plastic, typically PET, polypropylene or polycarbonate, or a composite material.

[0083] According to a preferred embodiment, the mold is provided with a means for venting gases generated during the crosslinking and / or curing reaction of the silicone composition. In one embodiment, at least a portion of the wall of the mold according to the present invention is formed from two adjacent materials, for example, a rigid gas-permeable outer material in the form of a grid or perforated plate, and a gas-permeable, liquid-impermeable inner material. Specifically, since the silicone composition is deposited in the mold in liquid form, a leak-proof inner material must be provided to contain the liquid silicone composition before the crosslinking and / or curing reaction. Preferably, the inner material is a flexible material, typically a fibrous material. The fibrous material may be of natural, artificial, and / or synthetic origin. It may also be a woven, knitted, or nonwoven fibrous material. In the case of a woven or knitted fibrous support, i.e., a woven or knitted fabric, the threads are preferably based on a thermoplastic polymer. Examples of suitable thermoplastic copolymers include polyolefins, polyesters, polyalkylene oxides, polyoxyalkylenes, polyhaloalkylenes, poly(alkylene phthalates or terephthalates), poly(phenyl or phenylene), poly(phenylene oxides or sulfides), polyvinyl acetate, polyvinyl alcohol, polyvinyl halide, polyvinylidene halide, polyvinyl nitrile, polyamides, polyimides, polycarbonates, polysiloxanes, polymers of acrylic or methacrylic acid, polyacrylates or methacrylates, natural polymers such as cellulose and its derivatives, synthetic polymers such as synthetic elastomers, or thermoplastic copolymers containing at least one monomer identical to any of the monomers contained in the above polymers, as well as mixtures and / or alloys of all of these copolymers. If the fibrous material is composed of a thermoplastic polymer, this is preferably a polyester, such as polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), copolymers and mixtures thereof, or a polyamide, such as polyamide 6, polyamide 6.6, polyamide 4, polyamide 1.1, polyamide 1.2, polyamide 4-6, 6-10, 6-12, 6-36, 12-12, copolymers thereof and mixtures thereof.

[0084] Also according to this preferred embodiment, at least the top and bottom walls of the mold are designed to allow escape of gases generated during the crosslinking and / or curing reaction of the silicone composition. Specifically, the bottom and top walls of the mold preferably define the largest surface of the molded strip. The side walls, which preferably define the thickness of the strip, have a smaller surface area.

[0085] After depositing the silicone composition, the mold can be closed, for example, using a lid, as shown in Figure 1B. The hollow volume defined by the closed mold should preferably remain fixed and withstand the pressure generated by the expanding foam. Fixing means are known to those skilled in the art, and include, for example, fasteners between the lid and the sidewall, weights placed on top of the lid, hydraulic systems to keep the lid closed, etc.

[0086] Finally, strip production involves a step consisting of crosslinking and / or curing the silicone composition to obtain a silicone foam. This step may last for a variety of periods depending on the silicone composition and temperature of the deposition step. Generally, a silicone foam with good properties is obtained after a few minutes to a few hours, depending on the temperature and the concentration of catalyst and inhibitor in the silicone composition.

[0087] Advantageously, the entire silicone foam production method is carried out under air or nitrogen flushing to avoid the risks associated with hydrogen generation during the process. Furthermore, the silicone foam production method is preferably carried out at atmospheric pressure and room temperature to also avoid the risks associated with hydrogen generation. Room temperature is generally between 15°C and 40°C, typically about 25°C. In addition to safety considerations, carrying out the method at atmospheric pressure and / or room temperature offers significant advantages in terms of technical simplification and implementation costs.

[0088] The method according to the present invention can optionally include an additional step of annealing the silicone foam. This optional annealing step can consist of a heat treatment at a temperature between 50°C and 200°C, preferably between 100°C and 150°C, lasting from one to several hours, preferably from one to four hours. This can improve the fire resistance and mechanical properties of the silicone foam, if necessary. However, this step is not essential, and the method is preferably characterized by not including an additional annealing step.

[0089] After crosslinking and / or curing and optional annealing, a strip containing the silicone foam is obtained and can be demolded. Advantageously, the material of the inner surface of the mold, i.e., the material that comes into contact with the silicone composition before crosslinking and / or curing and then comes into contact with the silicone foam after crosslinking and / or curing, is selected to facilitate demolding. To this end, the material is selected from those that have little or no adhesion to the silicone foam after crosslinking and / or curing. Preferably, the material of the inner surface of the mold is polyester. Alternatively, the material can be surface-treated, for example with a fluorocarbon coating, to improve its non-stick properties to the silicone foam.

[0090] In addition to the silicone foam, the passive fire protection device according to the present invention can advantageously comprise a textile support. Textile supports that can be used in passive fire protection devices are known to those skilled in the art. Specific examples are described in EP-A-3799935. The textile support is preferably made of a heat-resistant material, such as a glass fabric or a meta-aramid fiber fabric that can withstand temperatures above 500°C. Glass fibers have the advantage of being inexpensive and having high mechanical strength.

[0091] According to a preferred embodiment, the strip comprises a layer of silicone foam and a textile support. In this context, step (A) of preparing the strip comprises a step consisting of placing the textile support in a mold before depositing a silicone composition capable of forming a foam by releasing gas. Step (A) can therefore be described as follows: Producing a silicone composition capable of forming a foam by releasing a gas; · Placing the textile support in the mold; applying the composition to the textile substrate; closing the mold; and Crosslinking and / or curing the silicone composition to obtain a strip containing silicone foam. The method includes the steps of:

[0092] After crosslinking and / or curing, the resulting silicone foam adheres to the textile support. The strip comprising the silicone foam layer and textile support can be demolded. Figure 2 shows the resulting strip before demolding (Configuration 2A) and after demolding (Configuration 2B). The strip (9) comprises a textile support (7) and a layer of silicone foam (8) adhered to the textile support (7). According to the illustrated embodiment, certain inner walls of the mold (1) and lid (4) are coated with a non-stick polyester fibrous material (6). During demolding, the cover (4) is removed and the strip (9) can be easily removed from the mold (1).

[0093] Advantageously, it is possible to avoid the use of an adhesion primer between the silicone foam layer and the textile support, in particular because in the above manufacturing method the crosslinking and / or curing reaction of the silicone foam takes place directly on the textile support, and therefore adhesion is obtained without the need for additional adhesion primers.

[0094] The method of manufacturing a passive fire protection device according to the present invention may also include the step of (B) assembling one or more of said strips comprising silicone foam.

[0095] The assembly can be carried out by those skilled in the art in a manner known in the art. The device may comprise strips of any thickness that are mechanically and / or chemically bonded (bonded). For example, a strip comprising the silicone foam according to the invention can be rolled up on itself. According to another embodiment, several strips according to the invention can be stacked on top of each other. Optionally, intermediate layers can be arranged between each strip. This can optionally contain additives useful for passive fire protection and / or mechanical reinforcement.

[0096] According to a first embodiment, the passive fire protection device of the present invention can include, in addition to the silicone foam strip, one or more layers containing additives useful for passive fire protection. Such additives are well known to those skilled in the art. The term "additives useful for passive fire protection" refers to compounds that prevent or inhibit the spread of fire. These include, in particular, metal hydroxides that decompose under the influence of heat and release water. The most widely used metal hydroxides for their passive fire protection properties include aluminum hydroxide (ATH) and magnesium hydroxide. The use of refractory particles is described, for example, in EP 2072087. Metal metasilicates include, for example, sodium metasilicate hydrate (Na2SiO3·nH2O). The use of such additives can improve the fire resistance of the device and slow the temperature rise of the protected equipment.

[0097] According to another embodiment, the passive fire protection device of the present invention does not contain any additives capable of releasing basic water at high temperatures. In particular, the passive fire protection device of the present invention does not contain any metal metasilicates. However, without wishing to be limited by this theory, the inventors believe that the potential release of alkali metal hydroxides by metal metasilicates may cause degradation of the silicone foam strips at high temperatures.

[0098] FIG. 3 shows an embodiment of a passive fire protection device (10) according to the present invention, including three strip thicknesses arranged around a cable tray (11). The first strip thickness comprises a first layer of silicone foam (12) and a first textile support (13). This first strip thickness is combined with a second strip thickness comprising a second silicone foam layer (14) and a second textile support (15). This second strip thickness is combined with a third strip thickness comprising a third silicone foam layer (16) and a third textile support (17). Between each strip thickness is an intermediate layer (18), which may contain additives useful for passive fire protection and / or mechanical reinforcement. However, according to one embodiment not shown, the passive fire protection device (10) according to the present invention does not include an intermediate layer (18), and the strip thicknesses are directly adjacent to each other.

[0099] The first, second, and third strips, comprising the silicone foam layer and the fabric support layer, may typically have a thickness between 1 cm and 3 cm. The middle layer may typically have a thickness between 0 cm and 2 cm. Thus, the thickness of the entire assembled device may be between 3.2 cm and 13 cm according to this embodiment.

[0100] The subject of the invention is also the use of said device for the passive fire protection of installations, in particular of equipment important for the safety and security of the facility, such as, for example: Cables and cable trays, ventilation ducts and smoke exhaust ducts; Feedthroughs (cable, steel, copper, stainless steel piping, etc.), fire-rated feedthroughs; ·Fire seal; Fire-resistant enclosures to protect certain equipment, especially equipment critical to the safety and security of the facility (pumps, valves, sensors, actuators, etc.).

[0101] In particular, the equipment in question can be selected from those critical to the safety and security of the facility, in particular high-risk installations such as nuclear power plants. According to a particular embodiment, the subject of the invention is the use of said passive fire protection device for wrapping cable trays, preferably in high-risk installations such as nuclear power plants. According to another particular embodiment, the subject of the invention is the use of said passive fire protection device for the manufacture of hopper sleeves, in particular for cables, tubes or hoses.

[0102] The passive fire protection device proposed by this invention does not contain any fiber components, ensuring safety and security even in high-risk facilities. It is also lightweight, flexible, easy to handle, removable, washable, and decontaminated, making it an eco-friendly design. The device can be disassembled and reassembled on-site without the need for a completely new replacement. Therefore, it is possible to reduce the negative impact on the environment throughout the product's life cycle while maintaining its performance.

[0103] Other details or advantages of the present invention will appear more clearly from the following examples, given purely by way of illustration. [Example]

[0104] A foam-forming, polyaddition crosslinkable silicone composition was prepared by mixing the compounds listed in Table 1 below at room temperature.

[0105] [Table 1]

[0106] A mold consisting of a 150 x 35 x 2 cm perforated steel frame was lined with a polyester fabric at the bottom, followed by a commercially available glass fabric approximately 2 mm thick. A cover, also consisting of a perforated steel plate, was covered with the polyester fabric.

[0107] The silicone composition was deposited onto the glass fabric in the mold and spread evenly over the bottom of the mold using a scraper (approximately 3 mm liquid layer), after which the cover was attached to the frame to form a closed mold.

[0108] After 45 minutes at 23°C, the resulting foam was demolded. As can be seen in Figure 4, the resulting strip comprises a layer of glass fabric and silicone foam. The density of the foam is approximately 0.15 g / mL. The silicone foam adheres perfectly to the support glass fabric. The resulting strip is homogeneous, light, and flexible. It can be easily handled and folded.

[0109] The premises protected by the strips obtained above are tested according to European standard EN 1366-3. After passing the fire resistance test, the entire system is classified as EI120, which is a classification for the fire behavior of the construction (E = airtightness - the ability of the partitioning components to withstand the penetration of fire on the non-fire side, I = thermal insulation - the ability to prevent the transfer of heat when exposed to a unilateral fire, unless a surface or material on the non-fire side is ignited) and the fire resistance duration (120 = duration (min) - the time during which both E and I criteria are met).

Claims

1. A passive fire protection device having a resistance of 0.20 g / cm 3 A passive fire protection device comprising at least one strip comprising a silicone foam having a density of less than 1000 psi.

2. 10. The passive fire protection device of claim 1, wherein the silicone foam is obtained from a silicone composition that crosslinks by polyaddition and generates hydrogen by its foaming reaction.

3. The silicone foam is At least two silicon bonds C per molecule 2 ~C 12 at least one organopolysiloxane A containing alkenyl groups, at least one organopolysiloxane B containing at least two SiH units per molecule; a catalytically effective amount of at least one hydrosilylation catalyst C, and at least one pore-forming agent D containing hydroxyl groups 3. A passive fire protection device according to claim 1 or 2, obtained from a silicone composition comprising:

4. The silicone composition comprises, by weight based on the total weight of the silicone composition: a. At least two silicon bonds C per molecule 2 ~C 12 40% to 80% by weight of at least one organopolysiloxane A containing alkenyl groups, b. 1% to 20% by weight of at least one organopolysiloxane B containing at least two SiH units per molecule, preferably at least three SiH units; c. 2 ppm to 400 ppm (calculated by weight of platinum metal) of a hydrosilylation catalyst C selected from platinum compounds; and d. 0.3 wt% to 2.5 wt% of Pore Forming Agent D; e. 100m 2 / g to 300m 2 at least 3% by weight of fused silica having a specific surface area of ​​1.05g / g, f. at least 6% by weight of at least one crushed quartz inorganic filler, and g. 0.4% to 5% by weight of at least one heat-resistant additive and / or fire-resistant additive 4. The passive fire protection device of claim 3, comprising:

5. A passive fire protection device according to any preceding claim, wherein the passive fire protection device comprises a fabric support.

6. 6. A passive fire protection device according to claim 5, wherein said strip does not include an adhesive primer between said layer of silicone foam and said fabric support.

7. 7. A method for manufacturing a passive fire protection device according to any one of claims 1 to 6, comprising the steps of: (A) manufacturing a strip comprising silicone foam, said manufacturing comprising: - Producing a silicone composition capable of forming a foam by releasing a gas; - placing the composition into a mold; - closing the mold; and Crosslinking and / or curing the silicone composition to obtain a strip containing silicone foam. A method comprising the steps of:

8. 8. The method for manufacturing a passive fire protection device according to claim 7, wherein the mold comprises means for allowing the evacuation of gases generated during the crosslinking and / or curing reaction of the silicone composition.

9. 9. The method of claim 7 or 8, further comprising the step of: (B) assembling one or more of said strips comprising silicone foam.

10. 8. The method of claim 7, wherein the passive fire protection device further comprises one or more layers comprising an additive useful in passive fire protection, such as a metal metasilicate.

11. 8. The method of claim 7, wherein the passive fire protection device does not contain any additives capable of releasing basic water at elevated temperatures.

12. 7. Use of a passive fire protection device according to any of claims 1 to 6 for the passive fire protection of installations, in particular equipment important for the safety and security of the installation, such as cables, cable trays, ventilation and smoke exhaust ducts, feed-throughs, seals and enclosures.

13. 13. Use according to claim 12 for wrapping cable trays, preferably in high-risk facilities such as nuclear power plants.

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