Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
  • C09K21/02—Inorganic materials
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
  • C09K21/02—Inorganic materials
  • C09K21/04—Inorganic materials containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/92—Fire or heat protection feature
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
  • Y10T428/249955—Void-containing component partially impregnated with adjacent component
  • Y10T428/249956—Void-containing component is inorganic
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
  • Y10T428/249987—With nonvoid component of specified composition
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249994—Composite having a component wherein a constituent is liquid or is contained within preformed walls [e.g., impregnant-filled, previously void containing component, etc.]
  • Y10T428/249995—Constituent is in liquid form
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated
  • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]

Definitions

• the present invention relates to a new flame retardant composition based on a flame retardant agent impregnated on a porous support such as a mineral oxide of high porosity, its preparation process and its use for flame retardant materials and in particular polymers.
• the flame retardancy of polymers is usually carried out with flame retardants in solid form because their incorporation into the polymer is easy to implement.
• the use of a liquid flame retardant requires the use of pumps. This difficulty of implementation is further increased if the flame retardant to be used is in the form of a viscous liquid. In this case, it is then necessary to provide a system for heating the container containing the flame retardant, supply and outlet pipes and the pump used.
• the addition of flame retardant additives to the polymers is carried out either directly by adding the generally solid flame retardant to the molten polymer or by the use of masterbatches or concentrated mixtures. These mixtures are obtained by premixing a large quantity of the flame retardant in a matrix which may be identical to the polymer to be flame retarded or a polymer enabling better dispersion of the flame retardant.
• the masterbatch is formed, for example in the form of extruded granules or pellets.
• red phosphorus a compound used to flame retard polyamides, is carried out via masterbatches sold under the trade name.
• liquid flame retardants based on phosphorus such as phosphonic acids, their esters and salts, phosphoric esters or phosphinic acids, their esters and salts.
• activation temperature is meant the temperature at which the flame retardant property of the additive occurs either, for example, by decomposition or by reaction with the matrix or another compound of the composition.
• activation temperature is meant the temperature at which the flame retardant property of the additive occurs either, for example, by decomposition or by reaction with the matrix or another compound of the composition.
• a new flame-retardant composition comprising a flame-retardant agent impregnated on a porous solid support, characterized in that the surface of the porous support has a hydrophilic character or hydrophobic, the organophosphorus compound having a hydrophilic or hydrophobic character equivalent to said surface of the porous compound.
• the liquid flame retardant agent or compound is advantageously different from orthophosphoric acid or polyphosphoric acid.
• impregnation is meant that the flame retardant compound is bound at least temporarily to the solid substrate by any type of bond such as absorption in the porous structure of the particle if it exists, wetting or adsorption of the flame retardant compound on the surface of the particles. by at least one layer of the flame retardant compound, or attachment or grafting of the flame retardant compound to the surface of the particles by chemical or physico-chemical bonds.
• adsorption or fixation is facilitated by the choice of a solid substrate having surface properties compatible with the properties of the flame retardant compound.
• a substrate with a hydrophilic surface property is advantageously combined with a flame-retardant compound with a hydrophilic character and vice versa for compounds with a hydrophobic character.
• the solid substrate particle can advantageously comprise elements, radicals which promote the adsorption of the flame retardant compound on the surface of said particle.
• Such a dispersion can be obtained by mixing particles already having such size characteristics in the polymeric material or more advantageously by using granules or agglomerates of substrates formed by the agglomeration of particles or aggregates of which at least 80% by number have a diameter or size less than 1 ⁇ m.
• These granules or agglomerates after addition to the polymeric material and under the action of the shearing forces applied to achieve the dispersion, disintegrate into aggregates or elementary particles, thus making it possible to obtain a very good dispersion of the flame retardant in the polymer or polymeric material.
• the preferred substrates are those whose granules have a total pore volume at least equal to 0.5 ml / g, preferably at least equal to 2ml / g. this pore volume is measured by the mercury porosimetry method with a MICROMERITICS Autopore III 9420 porosimeter, according to the following procedure:
• the pore diameters or sizes are calculated by the relation of WASHBURN with a teta contact angle equal to 140 ° C and a gamma surface tension equal to 485 Dynes / cm.
• mineral substrates or porous support having a pore volume of at least 0.50 ml / g for pores whose diameter or size is equal to or less than 1 ⁇ m are preferred.
• Silicas having a specific surface area measured according to the CTAB method, greater than 50 m 2 / g are preferred.
• silicas used as solid mineral substrate are described only for information and as preferred embodiments. We can also use other silicas obtained by other processes having properties of porosity and dispersibility suitable for carrying out the invention.
• the flame retardant additive comprises a flame retardant compound adsorbed on the particles of mineral substrate.
• this adsorption is obtained by impregnating the granules or agglomerates.
• This impregnation is carried out by any conventional means and, for example, by mixing the substrate with the flame retardant compound in the liquid state or in the form dispersed or dissolved in a solvent. In the latter case, the solvent will be removed, after impregnation of the substrate, by evaporation.
• Amorphous silica can be silica with low water uptake.
• low water uptake is meant a water uptake of less than 6% and preferably less than 3%.
• They may be precipitated silicas described in patent application FR 01 16881 filed on December 26, 2001 by the company Rhodia, pyrogenic silicas or partially dehydroxylated silicas by calcination or by surface treatment.
• these compounds can be impregnated directly on the substrate such as silica for example, or dissolved in a solvent such as, for example, water, organic solvents such as ketones, alcohols, ethers, hydrocarbons, halogenated solvents, for example.
• a solvent such as, for example, water, organic solvents such as ketones, alcohols, ethers, hydrocarbons, halogenated solvents, for example.
• the impregnation is carried out dry, that is to say that the flame retardant compound is gradually added to the solid substrate to allow total impregnation or adsorption.
• the flame retardant compound or the solution of the flame retardant compound has sufficient fluidity.
• this impregnation or adsorption can be carried out at temperatures higher than ambient temperature, and lying in a range between 20 ° C and 200 ° C, preferably less than 100 ° C.
• the porous support or solid substrate can also be dried before impregnation either by drying or by calcination to remove the water present. This makes it possible to adapt the hydrophilic or hydrophobic character of the surface of the porous support as a function of the flame-retardant agentu product to be impregnated.
• Drying can be carried out by any conventional technique known to those skilled in the art.
• the impregnation can be done in a single step or in several successive steps.
• the mineral oxide can also be preheated in the same temperature range to facilitate impregnation.
• a concentrated liquid flame retardant is used.
• the mineral oxide is then impregnated with the solution obtained. In this case, it is possible to remove the solvent from the impregnated mineral oxide by drying.
• the impregnation can be done in a single step or in several successive impregnation steps.
• thermoplastic polymers including thermoplastic elastomers
• the flame-retardant composition of the invention is added to thermoplastic polymers (including thermoplastic elastomers), it is incorporated by mixing, preferably in a single-screw or twin screw extruder.
• the mixture is extruded in the form of articles such as profiles or more advantageously in the form of rods which will be cut into granules.
• the granules are used in the processes for producing articles as a raw material and will be melted to supply the flame retardant composition in the forming processes such as injection molding, extrusion, blow molding or similar processes.
• the total amount of flame-retardant composition according to the invention used varies between 1 to 50% relative to the total weight of the mixture obtained.
• the total amount of flame retardant composition is between 10 to 40% relative to the total weight of the mixture obtained. Even more preferably the total amount of flame retardant composition is between 15 to 30% relative to the total weight of the mixture obtained.
• the mineral oxide impregnated with liquid flame retardant When the mineral oxide impregnated with liquid flame retardant is incorporated into thermosetting polymers, the mineral oxide impregnated with liquid flame retardant and the other additives are incorporated into one of the monomers or oligomers before the polymerization or crosslinking reaction .
• the amounts of mineral oxide impregnated with liquid flame retardant used are in the same proportions as those described for thermoplastic polymers.
• the high porosity silica used is a silica called TIXOSIL 38A from the company RHODIA having a total pore volume of 4.2 ml / g and a useful volume of 2.2 ml / g.
• the amount of concentrated ANTIBLAZE used for the impregnation corresponds to the maximum amount that it is possible to impregnate on the silica, that is to say the volume for which the saturation of the silica is obtained.
• Impregnation is done dry.
• the ANTIBLAZE 1045 is added beforehand heated to 80 ° C in order to make it more fluid with a burette in doses of 25 ml drop by drop.
• the final product is therefore composed of 71.6% by weight of ANTIBLAZE 1045 and 28.4% of silica.
• Diameter (D50) of the particle size distribution is 250 ⁇ m.
• D50 in the field of powder particle size is the diameter or size of particles for which 50% by weight of the particles have a smaller diameter and 50% by weight have a larger diameter.
• the phosphorus content of this powder is 15%.
• the high porosity silica used is a silica called TIXOSIL 38X from the company RHODIA having a total pore volume of 3.6 ml / g and a useful pore volume of 2.0 ml / g. It is a Silica called Microperle which has an excellent flowability and which does not dust.
• silica 3.5 kg are weighed and introduced into a 20 liter LODIGE double jacket mixer.
• the silica is heated to 95 ° C (set temperature of the thermostatic bath equal to 135 ° C).
• the ANTIBLAZE 1045 was previously placed in an oven at 80 ° C overnight. It is then pumped into a jacketed jacketing thermostatically controlled at 99 ° C and introduced into the LODIGE without spraying (introduction rates: 45 min at 4.1 l / h and 1 H30 min at 1.9 l / h).
• the coulter speed in the log is 70 rpm.
• the total amount of ANTIBLAZE 1045 introduced into the silica is 6.696 kg (i.e.
• the final product is then sieved through a 1.25 mm sieve.
• the final product is therefore composed of 65.6% by weight of ANTIBLAZE 1045 and 34.4% of silica.
• the high porosity silica used is a silica called TIXOSIL 38A from the company RHODIA having a pore volume of 4.2 ml / g and a useful pore volume of 2.2 ml / g.
• the amount of concentrated FYROLFLEX BDP used for the impregnation corresponds to the maximum amount that it is possible to impregnate on the silica, ie the volume for which the saturation of the silica is obtained. Impregnation is done dry. FYROLFLEX BDP is added at room temperature with a burette in 25 ml doses dropwise. Weigh 25 grams of silica. The maximum volume reached impregnated is 50m! of FYROLFLEX RDP, i.e. 65 g.
• the final product is therefore composed of 72.2% by weight of FYROLFLEX BDP and 27.8% of silica.
• the phosphorus content of this powder is 7.6%.
• the high porosity silica used is a silica called TIXOSIL 38X from the company RHODIA having a total pore volume of 3.6 ml / g and a useful pore volume of 2.0 ml / g. It is a Silica called Microperle which has an excellent flowability and which does not dust.
• silica 3.5 kg are weighed and introduced into a 20 liter LODIGE double jacket mixer. The silica is heated to 95 ° C (set temperature of the thermostatic bath equal to 135 ° C).
• the ANTIBLAZE CU was previously placed in an oven at 80 ° C overnight. It is then pumped into a jacketed jacketed thermostatically controlled at 99 ° C and introduced into the l sansdige without spraying (introduction rates: 45 min at 4.1 l / h and 1 H 30 min at 1.9 l / h). The coulter speed in the log is 70 rpm.
• the total amount of ANTIBLAZE CU introduced into the silica is 6.696 kg (i.e.
• the final product is then sieved through a 1.25 mm sieve.
• the final product is therefore composed of 65.6% by weight of ANTIBLAZE CU and 34.4% of silica.
• the flame retardants obtained in Example 1 and in Example 2 are incorporated into a polymer matrix of polyamide 6 and polyamide 66 in a molten medium using a single or twin screw extruder.
• the mixture is generally extruded in the form of rods which are cut to obtain granules.
• These granules are used as a raw material for feeding the methods of manufacturing fireproof molded articles by injection, molding, extrusion blow molding or by any other method of shaping articles.
• the properties of these compositions are measured from test pieces obtained by injection of a polyamide composition additivated with the powder of Example 2 according to the procedure described below:
• a polyamide 6 composition comprising 20% glass fibers is extruded in a LEISTRITZ twin-screw extruder with a flow rate of between 6 and 7 kg / hour, by imposing a temperature profile of 250 ° C. on average, and a pressure in the area of degassing of approximately 400 mbar. The material pressure measured at the die is close to 8 bar.
• the product obtained at the end of the preparation described in Example 2 is added using a gravimetric powder metering device at a determined flow rate so as to obtain a rate of product in the polymer of 20% by weight per compared to the final composition.
• the rods obtained are cut into granules.
• the good flowability of the powder makes it possible to use standard dosing systems without any difficulty and especially without dusting. -Preparation of test pieces
• test specimens are obtained by injection under standard conditions, of the granules obtained above, on a 85 ton Billon press, with a cycle time of 40 seconds, a mold temperature of 80 ° C. and a temperature profile imposed on the 250 ° C sheath.
• a polyamide 66 composition comprising 20% glass fibers is extruded in a LEISTRITZ twin screw extruder with a flow rate of between 6 and 7 kg / hour, by imposing a temperature profile in the screw of 280 ° C. on average , and a pressure in the degassing zone of approximately 400 mbar. The material pressure measured at the die is close to 8 bar.
• the product of Example 2 is added in a first test and in a second test the product of Example 4, using a gravimetric powder metering device at a determined flow rate so as to obtain a product content in the polymer by 20% by mass relative to the final composition.
• the good flowability of the powder means that standard dosing systems can be used without any difficulty and above all without dusting.
• the rod obtained is cut into granules in the usual way.
• a polyamide 66 composition comprising 20% glass fibers is extruded in a LEISTRITZ twin screw extruder with a flow rate of between 6 and 7 kg / hour, by imposing a temperature profile in the screw of 280 ° C. on average , and a pressure in the degassing zone of approximately 400 mbar. The material pressure measured at the die is close to 8 bar.
• the product of Example 3 is added using a gravimetric powder metering device at a determined flow rate so as to obtain a product content in the polymer of 20% by mass relative to the final composition.
• the good flowability of the powder means that standard dosing systems can be used without any difficulty and above all without dusting.
• the rod obtained is cut into granules in the usual way.
• the fire behavior of the samples obtained above is determined according to the UL-94 test published by the “Underwriters Laboratories” described in standard ISO 1210: 1992 (F). This test is carried out with specimens of thickness 1.6 and 0.8 mm.
• test specimens obtained above are collated in Table I below.
• test specimens are conditioned by keeping for 48 hours at 23 ° C in an atmosphere with a relative humidity of 50%.
• Example 2 shows that the product obtained at the end of the preparation described in Example 2 gives the polyamide satisfactory flame retardant properties.
• a V0 classification is indeed obtained for a thickness of 1.6 mm for polyamide 66, and flame retardant performance significantly improved for polyamide 6 if it is compared to the same polyamide 6 tested without this additive.
• the flame retardant compositions with the powder of Example 3 could not be tested because it was impossible to produce correct test pieces.
• the polypropylene alone is kneaded for 3 minutes at 200 rpm at 155 ° C.
• the polypropylene alone is kneaded for 3 minutes at 200 rpm at 155 ° C. 20% by weight of the powder corresponding to Example 1 relative to the total weight of the mixture is then introduced into the mixer and the mixing is continued for 3 minutes.
• Pentaerythritol and Melamine in addition to the product corresponding to Example 1 in Polypropylene (Formula 1) gives a classification which remains correct (V2 against NC for Polypropylene alone) but at a higher total additive rate.
• Example 1 There is therefore an interest in the product corresponding to Example 1 as a flame retardant which significantly improves the fire retardancy performance of Polypropylene.

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• 2003
  • 2003-06-27 FR FR0307813A patent/FR2843121B3/fr not_active Expired - Lifetime
  • 2003-08-01 EP EP03758193A patent/EP1525269A2/fr not_active Withdrawn
  • 2003-08-01 CN CNB038214466A patent/CN1320067C/zh not_active Expired - Fee Related
  • 2003-08-01 WO PCT/FR2003/002444 patent/WO2004015016A2/fr active Application Filing
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  • 2003-08-01 BR BR0313365-6A patent/BR0313365A/pt active Search and Examination
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