WO2010075087A1 - Compositions ignifugeantes sous forme de poudres fluentes, leur préparation et leurs utilisations - Google Patents

Compositions ignifugeantes sous forme de poudres fluentes, leur préparation et leurs utilisations Download PDF

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Publication number
WO2010075087A1
WO2010075087A1 PCT/US2009/068069 US2009068069W WO2010075087A1 WO 2010075087 A1 WO2010075087 A1 WO 2010075087A1 US 2009068069 W US2009068069 W US 2009068069W WO 2010075087 A1 WO2010075087 A1 WO 2010075087A1
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flame retardant
boehmite
flame
composition
liquid
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PCT/US2009/068069
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English (en)
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Thomas Dittmar
Rene G. E. Herbiet
Monika Giesselbach
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Albemarle Corporation
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    • 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
    • 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
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus

Definitions

  • BACKGROUND For many flame retardant applications use of a particulate phosphorus flame retardant is desired. For example, while such liquid flame retardants might be of interest in production of flame retarded wire and cable products, such liquid products are difficult to handle and dose due to high volatility leading to evaporation or due to high viscosity causing problems with flow. Indeed, many polymer producers are equipped for, and accustomed to, using flame retardants in particulate form such as powders and granules.
  • This invention provides an effective way of providing normally liquid phosphorus flame retardants in a less volatile, non-sticky dry form, without exposing the flame retardant to an extra heating step at high polymer melting temperature.
  • the particulate forms of the invention are in the form of powders which have excellent flowability properties and are thus readily handled in various types of commercially- available loading and blending equipment. Moreover, these desirable achievements can be accomplished in an economically-attractive manner.
  • This invention thus provides, among other things, a flame retardant composition
  • a flame retardant composition comprising at least one phosphorus-containing flame retardant that has been absorbed when in the liquid state by (i) a transition alumina, (ii) a boehmite, (iii) a pseudo boehmite, or (iv) a combination of any two or all three of (i), (ii), and (iii), which composition is in the form of a free-flowing powder.
  • compositions if not all such compositions, have a greater flowability in the Vibrating Funnel Test (described hereinafter) than a separate untreated portion of the same transition alumina, boehmite, and/or pseudo boehmite used in forming the flame retardant in the form of a free-flowing powder.
  • particulate flame retardant compositions comprising a mixture of (A) a flame retardant composition in the form of a free-flowing powder as described above and (B) a particulate inorganic flame retardant selected from (a) aluminum trihydrate, (b) magnesium hydroxide, or (c) both of (a) and (b).
  • Still further compositions of this invention are each of those described hereinabove which further comprise high bulk density, high flow particulate silica comprised of finely-divided spherical particles. These compositions have been shown to still further improve flowability characteristics of at least some of the particulate flame retardant compositions of this invention.
  • Methods of preparing a particulate flame retardant composition from at least one liquid phosphorus flame retardant are also provided by this invention.
  • One such method comprises adding at least one phosphorus flame retardant in the liquid state portionwise to a finely-divided (i) transition alumina, (ii) boehmite, (iii) pseudo boehmite, or (iv) any two or all three of (i), (ii), and (iii).
  • liquid phosphorus flame retardant(s) and the finely-divided (i) transition alumina, (ii) boehmite, (iii) pseudo boehmite, or (iv) any two or all three of (i), (ii), and (iii) can be separately and concurrently introduced into the mixing vessel.
  • a flame retarded composition which comprises at least one thermoplastic polymer, thermoset polymer, or elastomer (i.e., natural or synthetic rubber) with which has been blended a flame retardant composition of this invention in the form of a free-flowing powder.
  • the amount of the flame retardant of this invention used in forming such flame retarded compositions is an amount at least sufficient to flame retard the at least one polymer or elastomer with which the free-flowing flame retardant composition of this invention is blended. Such amounts may range from about 5 to about 95 wt%, depending upon the type of composition being formed (e.g., finished polymer or masterbatch blend).
  • the term "powder” means that the specified substance is in the form of separate particles which can be in the form of a powder or small grains of a size up to about the size of smelter grade alumina that has a median particle size of about 100 ⁇ m.
  • the exact size and spatial configuration of the particles is not critical, as long as the particles are freely flowable if subjected to the Vibrating Funnel Test (described hereinafter).
  • the "powder” is a powder or small grains with a median particle size of about 100 ⁇ m which is in a flowable form in the Vibrating Funnel Test.
  • the term "phosphorus-containing flame retardant” refers to organic phosphorus compounds that are in the liquid state at room temperature or that are in the solids state at room temperature but which can be converted into liquid form at an elevated temperature of up to about HO 0 C.
  • the term “carrier” refers to (i) a transition alumina, (ii) a boehmite, (iii) a pseudo boehmite, or (iv) a combination of any two or all three of (i), (ii), and (iii) in the form of a powder and having the ability to absorb at least one phosphorus flame retardant when the latter is in the liquid state.
  • the term "absorbed" means that the liquid phosphorus flame retardant is taken up into the body of the carrier and thus forms an apparently dry blend, i.e., a powder which appears and behaves as if it is dry.
  • the free- flowing flame retardant powdery blends of this invention as formed may involve any of a number of different mechanisms such as absorption within spatial openings or pores within the boehmite, and/or surface absorption, infusion, permeation or other types of interactions between the liquid phosphorus flame retardant and the particles of the carrier. This invention is not intended to be limited to any particular mechanism by which the liquid phosphorus flame retardant becomes taken up by the carrier.
  • the powdery carriers used in the practice of this invention will typically have a suitable volume of pores in their powdery particles.
  • the specific pore volume of the carriers is at least about 500 mm 3 /g, and preferably at least about 700 mm 3 /g, as measured by mercury intrusion porosimetry. Details of such a procedure are set forth hereinafter under the heading "Test Methods”.
  • One preferred type of carrier used in forming the powdery blends of this invention is a transition alumina. Transition aluminas are dehydroxylation products formed when, for example, aluminum hydroxide or boehmite is thermally treated below 1000 0 C. The structure depends on the starting material as well as on the temperature of the treatment.
  • Transition aluminas (chi, eta, rho, gamma, kappa, delta and theta alumina) will be converted into alpha alumina once heated to or calcined at a temperature of at least about HOO 0 C.
  • Methods for the preparation of transition aluminas are known and reported in the literature. See in this connection, Materials Research, 2000, Vol.3, No.4, 104-114, the full disclosure of which is incorporated herein by reference, which gives a good overview of transition aluminas and their preparation.
  • Transition aluminas are available as articles of commerce. Non-limiting examples include: MARTOXID AN/I and MARTOXID AN/I-406 (gamma alumina) from Martinswerk GmbH.
  • transition alumina to be used is essentially devoid of water
  • Boehmite Another type of carrier used in forming the powdery blends of this invention is boehmite.
  • Boehmite in general has the chemical structure AlO(OH) and can be seen as an aluminium hydroxide with less water (about 17%) compared to aluminum trihydroxide Al(OH) 3 (about 34.5%), which is often designated as ATH.
  • Boehmite has a thermal stability higher than that of ATH and can be produced by a hydrothermal process.
  • a precursor to make boehmite via the hydrothermal process can be Al(OH) 3 .
  • One commercially-available boehmite is Condea ® P-200 (Condea Chemie GmbH). Boehmite can also exist in the form of quasi-crystalline boehmites.
  • Nanoboehmite is another material worthy of discussion as another type of carrier for use in the practice of this invention.
  • Nanoboehmite can be considered as a subcategory of boehmites because the crystal size of nanoboehmite is in the nano meter range and its thermal stability and its X-ray diffraction (XRD) pattern have sharp peaks which clearly distinguish it from pseudoboehmite. Therefore, unless expressly indicated to the contrary, the term "boehmite” as used herein, including the claims, is to be understood to include nanoboehmite as a type of boehmite.
  • boehmite substrate which can be used in forming the particulate phosphorus flame retardants of this invention is a particulate nanoboehmite.
  • Such boehmite particles are generally characterized by (i) having a BET specific surface area, as determined by DIN-66132, in the range of from about 20 to about 300 m 2 /g; (ii) exhibiting a maximum loss on ignition (LOI) of about 20% at a temperature of 1200 0 C; (iii) exhibiting a 2% weight loss at a temperature equal or higher than about 25O 0 C and a 5% weight loss at a temperature equal or higher than about 33O 0 C; (iv) being at least partly peptizable; (v) having a crystallite size between 10 and 25 nm; (vi) having an aspect ratio of less than about 2:1; or (vii) any combination of two or more of (i)-(vi), and preferably all of (i)-(vi).
  • LOI maximum loss on ignition
  • pseudoboehmite Another type of carrier used in forming the powdery blends of this invention is a pseudoboehmite. Like boehmite, pseudoboehmite also has the formal structure AlO(OH) but contains more water than boehmite AlO(OH). Boehmite contains 17% bound water but pseudoboehmite can contain more that this. The thermal stability of pseudoboehmite is less as compared to boehmite. Boehmites are synthesized by processes at temperature close to 100 0 C and ambient atmospheric pressures. Usually, pseudoboehmites have very high surface areas, large pores and pore volume and smaller crystal sizes than boehmites.
  • pseudoboehmite The X-Ray diffraction pattern of pseudoboehmites show quite broad peaks and their half- widths are indicative of the crystal size as well as the degree of crystal perfection.
  • the thermal stability of pseudoboehmite is less as compared to boehmite. Pseudoboehmite starts to release water below 200 0 C while boehmite is stable up to at least 300 0 C. While boehmite can be natural and synthetic, pseudoboehmite is not found in nature. Methods for the preparation of pseudoboehmites are known and reported in the literature. A discussion relating to the general topic of pseudoboehmites is provided in U.S. Pat. No.
  • Pseudoboehmites are not usually generally available as articles of commerce. They are mainly used as intermediates, for instance for the production of catalyst carriers.
  • One such material is G45, manufactured by Albemarle Catalysts. It is an intermediate product that is not currently sold on the open market.
  • G45 manufactured by Albemarle Catalysts. It is an intermediate product that is not currently sold on the open market.
  • carriers there are a number of carriers that can be used in the practice of this invention. These are in powder form. What constitutes a powder is a matter of common experience and common sense. The precise particle size of the powder is not critical to the practice of this invention.
  • the specified carriers be in finely-divided powdery form as distinguished from irregular granular form and that the powder have sufficient porosity to absorb the liquid phosphorus-containing flame retardant.
  • the carrier should have a minimum porosity of at least about 700 mm3/g.
  • at least 90 wt% of the powder will have a particle size of no more than about 100 microns, and preferably no more than about 75 microns.
  • Phosphorus Flame Retardants [0026]
  • any phosphorus flame retardant that is in the form of a liquid at room temperature or that can be converted into a liquid state at a temperature of up to about HO 0 C and that can be absorbed by one of the above carriers, can be used pursuant to this invention.
  • many different phosphorus flame retardants are available for use in the practice of this invention.
  • they can be one or more liquid polyphosphate esters that respond to the formula:
  • the number or total number of carbon atoms in the alkyl portion(s) of the alkyl-substituted aryl group(s) can be any number of carbon atoms that results in the compound remaining as a liquid under the conditions specified in the present specification.
  • Preferred liquid polyphosphate esters are those in which R in the above formula is phenyl or alkyl-substituted phenyl, such as tolyl, xylyl, ethylphenyl, isopropylphenyl, and mesityl.
  • the R groups may be the same or different, but preferably are at least isomers of the same group (e.g., various tolyl isomers or various xylyl isomers, etc.) if not all the same isomer. Most preferably R is a phenyl group.
  • 1,3-phenylene, 1,4-phenylene, 4,4'-biphenylene i.e., -C 6 H 4 -CeH 4 -
  • a preferred polyphosphate ester is bisphenol-A bis(diphenylphosphate).
  • Another preferred polyphosphate ester is resorcinolbis(diphenyl phosphate).
  • These products can be the monomeric form of the specified polyphosphate ester (i.e., n in the above formula is 1), or (b) an oligomeric form of the specified polyphosphate ester which may or may not contain the monomeric form of the specified polyphosphate ester and which may be a single oligomer (i.e., n of the above formula is the same for each molecule in the product), but which more often is a mixture of oligomers (i.e., n of the above formula is not the same number for each molecule of the product).
  • n is an average value for the overall product and is greater than 1 but less than about 8.
  • these products contain a small amount of triphenylphosphate which can be regarded as an impurity in which n of the above formula is, of course, zero.
  • Such products are regarded in the art as being closely related compositions which have sufficient similarities to be identified by the same chemical name.
  • Akzo Nobel N. V. offers several polyphosphate ester products under the trademark Fyrolflex.
  • Fyrolflex RDP with a stated phosphorus content of 10.9-11.0 wt%
  • Fyrolflex RDP-B with a stated phosphorus content of 10.6 wt%.
  • liquid phosphorus flame retardants are chlorinated and/or brominated organic esters of an acid of phosphorus such as chlorinated and/or brominated phosphate and polyphosphate esters, chlorinated and/or brominated phosphonate or polyphosphonate esters, chlorinated and/or brominated phosphite esters, and the sulfur analogs of the foregoing such as chlorinated and/r brominated thiophosphates, thiophosphonates, and thiophosphites. Of these materials, liquid phosphorus flame retardants in which the molecule contains only carbon, hydrogen, oxygen, and at least one phosphorus atom are preferred. A number of suitable liquid phosphorus flame retardants are available as articles of commerce
  • the flame retardant In cases where the phosphorus flame retardant is of sufficiently highly viscosity at room temperature to be taken up by the carrier, often the flame retardant can be, and preferably is, heated to a suitable modest temperature, e.g., from about 5O 0 C to about 11O 0 C to reduce its viscosity and thereby facilitate its take up by the carrier.
  • a suitable modest temperature e.g., from about 5O 0 C to about 11O 0 C
  • the highly viscous phosphorus flame retardant in the form of a solution to facilitate take up by the carrier.
  • the phosphorus flame retardant should be sufficiently soluble in a suitable organic solvent to provide a solution of high enough concentration (and low enough viscosity) to yield a powdery blend having a sufficient content of phosphorus to provide adequate flame retardancy.
  • the phosphorus content (calculated as phosphorus) of the powdery blends of this invention should be about 0.05 wt% or more, and preferably about 3 wt% or more, based on the total weight of the powdery blend of this invention.
  • highly preferred commercially- available liquid phosphorus flame retardants for us in the practice of this invention are ANTIB LAZE ® V490 flame retardant, ANTIBLAZE ® V6 Flame Retardant, ANTIBLAZE ® V66 Flame Retardant, ANTIBLAZE ® TL-10-ST Flame Retardant, ANTIBLAZE ® WR-30-LV Flame Retardant, and NCENDX ® P30 flame retardant.
  • the ANTIB LAZE ® flame retardants are hydrocarbyl phosphonates and phosphates or partly chlorinated hydrocarbyl phosphonates and phosphates. All such flame retardants are available from Albemarle Corporation. Typical properties of these products are given below.
  • a flame retardant composition comprising at least one liquid phosphorus flame retardant absorbed by a carrier selected from (i) a transition alumina, (ii) a boehmite, (iii) a pseudoboehmite, or (iv) a combination of any two or all three of (i), (ii), and (iii), which composition is in the form of a free-flowing powder.
  • a flame retardant composition as in A) further characterized in that the flame retardant composition has a greater flowability in the Vibrating Funnel Test (described hereinafter) than a separate untreated portion of the same carrier used in forming that flame retardant composition.
  • a flame retardant composition comprising a mixture of (i) a flame retardant composition as in A) or B) and (ii) a particulate inorganic flame retardant selected from (a) aluminum trihydrate, (b) magnesium hydroxide, (c) boehmite or (d) any two or all three of (a), (b), and (c).
  • the flame retardant compositions described in A) and B) above are effective flame retardants that require no additional flame retardant component.
  • Aluminum trihydrate and magnesium hydroxide in powdery form or in the form of finely divided granules are themselves useful flame retardants and thus either or both of them can be effectively utilized in combination with the particulate flame retardant compositions of this invention.
  • the resultant mixed flame retardant compositions constitute additional compositions of this invention.
  • the proportions of (i) a particulate flame retardant composition of this invention and (ii) aluminum trihydrate and/or magnesium hydroxide flame retardant(s) can be varied.
  • the weight ratio of (i):(ii) is typically in the range of 1:100 to 100:1, and preferably in the range of 1:10 to 10:1. Blending of these components to form these flame retardant mixtures can be accomplished using any conventional powder blending equipment.
  • the phosphorus content (calculated as phosphorus) of the powdery blends of this invention should be at least about 0.05 wt% based on the total weight of the powdery blend. From a cost effectiveness standpoint, the amount of the liquid phosphorus flame retardant(s) present in the resultant powdery blend of this invention should be such that the powdery blend has a phosphorus content of at least about 0.05 wt%, and more preferably at least about 3 wt%.
  • the particulate flame retardant compositions of this invention are free flowing compositions that can be readily handled in hoppers and other material transfer equipment. Nevertheless, in some instances the flowability characteristics of the particulate flame retardant compositions can be further enhanced by including therewith a particulate inorganic flame retardant selected from (a) aluminum trihydrate, (b) magnesium hydroxide, and (c) mixtures of (a) and (b). Flame Retarded Polymer Compositions
  • This invention further includes the provision of flame retarded polymer compositions, in which the polymer can be a thermoplastic polymer, a thermoset polymer, or an elastomer (e.g., natural and synthetic rubbers and blends thereof).
  • the polymer can be a thermoplastic polymer, a thermoset polymer, or an elastomer (e.g., natural and synthetic rubbers and blends thereof).
  • suitable synthetic resins include natural or synthetic rubbers such as EPDM, butyl rubber, isoprene rubber, SBR, NIR, urethane rubber, polybutadiene rubber, acrylic rubber, silicone rubber, fluoro-elastomer, NBR and chloro- sulfonated polyethylene are also included. Further included are polymeric suspensions (latices). [0039] Preferred uses of the flame retardants of this invention are as components of polyethylene and its copolymers or polypropylene and its copolymers for wire and cable applications or resins such as epoxy resins for printed circuit boards and unsaturated polyesters.
  • the various flame retardant additive compositions of this invention are blended with the appropriate substrate polymer(s) or elastomer(s) in an amount that is at least sufficient to provide flame retardancy to the resultant composition.
  • the amount of any given flame retardant in the form of a flame retardant additive composition of this invention will typically fall in the range of about 10 to about 90 wt%, and preferably in the range of about 50 to about 85 wt%, based on the total weight of the resultant flame retarded polymer or elastomer composition.
  • the flame retardant additive compositions of this invention i.e., the flame retardant additive composition comprising at least one liquid phosphorus flame retardant absorbed by (i) a transition alumina, (ii) a boehmite, (iii) a pseudo boehmite, or (iv) a combination of any two or all three of (i), (ii), and (iii), which composition is in the form of a free-flowing powder) can be formed by any conventional blending procedure.
  • any of a wide variety of other common polymer additives can be used either as (1) components of flame retardant additive powders of this invention comprised of a powdery blend and at least one flame retardant additive powder physically admixed or blended therewith or (2) components that are separately blended as a powdery blend and at least one other flame retardant additive powder into the polymer being molded along with a flame retardant additive composition of this invention.
  • Non-limiting examples of the types of additives that can be utilized in this manner include extrusion aids, fatty acids; coupling agents such as amino-, vinyl- or alkyl silanes or maleic acid grafted polymers; sodium stearate or calcium stearate; organoperoxides; dyes; pigments; fillers; blowing agents; thermal stabilizers; antioxidants; antistatic agents; reinforcing agents; metal scavengers or deactivators; impact modifiers; processing aids; mold release aids, lubricants; anti-blocking agents; flame retardant synergists; other flame retardants, including, for example, other mineral flame retardants; UV stabilizers; plasticizers; flow aids; and the like.
  • Suitable flame retardant synergists include antimony trioxide, antimony pentoxide, sodium antimonate, zinc borate, mixed oxides of boron and zinc, alkaline earth borate (preferably calcium borate), mixtures of alkaline earth metal oxide (preferably calcium oxide) and an oxide of boron and/or zinc borate, barium sulfate, zinc sulfide, and the like, or any other suitable flame retardant synergist, provided the synergist does not materially interfere with the performance of the additive system employed.
  • a powdery blend of this invention can be blended with such other components, including the dry polymer resin, and thereafter the blend can be molded by extrusion, compression, or injection molding.
  • the components can be mixed together in a B anbury mixer, a Brabender mixer, a roll mill, a kneader, or other similar mixing device, and then formed into the desired form or configuration such as by extrusion followed by comminution into granules or pellets, or by other known methods.
  • the powdery blends of this invention can be separately dry mixed with the polymer apart from any other additive(s) and thereafter the final dry blend, including other additive(s) if used, can be molded or extruded.
  • the powdery blends of this invention can be separately introduced into and mixed with the polymer in its molten condition, before and/or after the inclusion in the polymer of any other additive(s).
  • the powdery blends of this invention can be utilized in the formation of useful articles of the type normally fabricated by molding or extrusion of conventional flame retarded polymers.
  • foamed or expanded shapes and objects from the compositions of this invention. Molding and extrusion conditions such as temperatures and pressures are within conventional recommended limits. Conditions normally used for producing foamed or expanded shapes and objects from flame retarded polymers can be used with the compositions of this invention, with little or no modification.
  • the Vibrating Funnel Test for measuring flowability of solids involves use of the following test procedure: A 100 gram sample of the material to be tested is weighed into a plastic cup with an accuracy of 0.1 g. To measure flowability, this 100 gram test sample is put into a steel funnel with an upper diameter of 150 mm, an opening diameter of 16 mm, and an angle of 31.5°. This funnel is mounted on a sieving machine, AS 200 Control, from Retsch GmbH. Before putting the sample into the funnel the outlet should be closed with a finger. Once the sample is in the funnel the sieving machine can be switched on and the finger can be removed once the selected vibration amplitude (0.5 or 1.5 mm) is reached.
  • the time necessary to fully discharge the funnel is to be measured with a stop watch.
  • the discharged sample can be collected in the previously used plastic cup.
  • the Vibrating Funnel Test can be used for measuring the flowability of either the powdery blends of this invention or of the silica used for further increasing the flowability of the powdery blends.
  • a description of the method for determining viscosity by use of a Brookfield viscometer is as follows: To measure the viscosity the sample needs to be homogeneously mixed with the resin that is usually Palapreg P17-02 from DSM. The mixing step is conducted by use of a high shear mixer, for instance a high shear mixer from VMA Getzmann GmbH.
  • a 100 g portion of the resin is poured into a plastic beaker and stirred with a dissolver disc of ca. 5 cm diameter at 2.0 rpm.
  • the sample should be added to the resin stepwise, and once the addition is completed the stirrer speed is increased to 4.000 rpm for 3 min.
  • the mix should be maintained in a water bath for 3-4 hours at 23 0 C to reach standard conditions and to release air bubbles. Viscosity measurement is conducted with a Brookfield viscometer DVII+. Depending on the viscosity level of the sample being tested, a spindle of suitable dimensional stability is selected for use.
  • the zero point of the viscosimeter Prior to the viscosity measurement, the zero point of the viscosimeter (a.k.a. viscometer) needs to be adjusted, using the manufacturer's instructions. Once adjusted and equipped with a suitable spindle, the sample-resin-mix is measured in a 180 mL plastic beaker. A value for each oscillating speed of the rotating spindle can be read on the screen of the viscometer. To calculate the final viscosity value the measured value should be corrected. The correcting factor is determined on every resin lot supplied so that the appropriate correction can be applied to the measured values obtained using that resin. To determine the correcting factor, the viscosity of the neat resin is measured.
  • the conditions used both in determining the correcting factor and in determining viscosities of samples using this test procedure are temperature: 23 0 C; vessel used: plastic beaker with 180 mL volume; and spindle operation: rotated at 2 and at 50 rpm.
  • the UL 94 flammability test uses specimens with a size of 127 mm x 12.7 mm x thickness. The thickness can vary depending on final requirements and is usually 1.6 mm or 3.2 mm. Prior to the fire test the specimens are stored at 23 0 C and at 50% relative humidity for 16 hours. To conduct the fire test the specimen is fixed on the upper end to be vertically mounted. The distance from the lower end of the sample to the table is 305 mm. A cotton wood sample (50 x 50 x 6.5 mm) is placed under the specimen. A natural gas fired laboratory scale burner is adjusted having a 19 mm high non-luminous flame; with this adjustment the sample is treated twice for 10 seconds each (the second treatment starts if/when the sample stops burning from first flame treatment). The burning time as well as the glowing time of each flaming is measured with a stop watch. Also, formation of burning droplets igniting the cotton wool needs to be observed and recorded. Classification is as follows: For a V-O rating:
  • the mercury intrusion porosimetry test procedure for measuring specific pore volume involves use of the Porosimeter Pascal 140/440 instrument.
  • the Pascal 140 instrument is able to measure pore radii down to ca. 2 ⁇ m(400 kPa); the Pascal 440 instrument can determine pore radii down to ca. 2 nm (400 MPa).
  • the measuring of the porosity involves sample preparation, filling with mercury, measurement, analysis and calibration. Sample preparation includes cleaning and drying of the porosimeter followed by filling with 1.5 to 2 mL of mercury.
  • the predried sample of ATH, boehmite or other filler is weighted into the sample holder (dilatometer). After that the dilatometer is tightly connected to the porosimeter. The dilatometer is than evacuated for 15 minutes so that the final pressure is ca. 0.01 kPa. Afterwards the dilatometer should be checked again to be tightly connected to the porosimeter. Then the dilatometer is pressurized with atmospheric pressure and filled with mercury. To analyze the data the Pascal 140/440 software has to be started. To calibrate the porosimeter a measurement has to be conducted only with mercury.
  • the funnel is fixed in such a way that between its lower opening and the top rim of the cylinder there is a distance of 27 mm.
  • nanoboehmite ETE 08211 from Martinswerk GmbH were blended with 50 parts of Antiblaze V490 flame retardant in the Henschel mixer at 3000 rpm for about 10 minutes without steam heating.
  • the nanoboehmite was introduced into the Henschel mixer first and the liquid was dosed slowly within a period of time of 20 seconds once the mixer had reached 3000 rpm.
  • Example 1 The bulk density of this blend was determined as described in Example 3 resulting in a value of 778 kg/m 3 .
  • the flowabilities of MAGNIFIN H 10 and of G45 are provided in Example 1.
  • EXAMPLE 5 In order to obtain a flame retardant for unsaturated polyester resins 10 parts of pseudo boehmite G45 was blended with 20 parts of Antiblaze V490 flame retardant in the Henschel mixer at 3000 rpm for about 10 minutes without steam heating. The pseudo boehmite was introduced into the Henschel mixer first and the liquid was dosed slowly within a time of 20 seconds once the mixer has reached 3000 rpm. The resulting powder was blended with additional 70 parts of MARTIN AL ® OL- 104 LEO (Martins werk GmbH) also at 3000 rpm without heating for about 10 minutes to finally obtain a powder blend. The flowability of this powder blend was determined as described in Example 1. The flow times were as follows:
  • EXAMPLE 6 - (COMPARATIVE) [0060]
  • 100 parts of MARTINAL OL- 104 LEO were dispersed in 100 g polyester resin P 17-02 using high shear mixing equipment. The viscosity was measured under the same conditions as in Example 5 and was of about 12.9 pascal- seconds (Pa*s).
  • 100 parts by weight of OL- 104 LEO were dispersed in 100 parts by weight of unsaturated polyester resin P 17-02 to which 2.5 parts by weight of peroxide (Butanox M-50) and 0.5 parts of Byk A 555 had been added. After curing this formulation in metal frames, pieces for the UL 94 test were cut with a band saw.
  • the invention may comprise, consist or consist essentially of the materials and/or procedures recited herein. [0068] This invention is susceptible to considerable variation in its practice. Therefore the foregoing description is not intended to limit, and should not be construed as limiting, the invention to the particular exemplifications presented hereinabove.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)

Abstract

Les compositions ignifugeantes ci-décrites se présentent sous la forme de poudres fluentes et comprennent au moins un ignifugeant contenant du phosphore absorbé par (i) une alumine de transition, (ii) une boehmite, (iii) une pseudoboehmite, ou (iv) une combinaison de deux oxydes quelconques parmi (i), (ii) et (iii) ou des trois oxydes. Un certain nombre de ces compositions présentent, dans un essai en trémie vibrante, une fluidité supérieure à celle d'une partie non traitée distincte de l'alumine de transition, la boehmite et/ou la pseudoboehmite non traitées. C'est le cas même quand l'ignifugeant non traité est un solide à température ambiante et doit ainsi être chauffé à environ 1000 °C pour être transformé en liquide utilisé pour la formation d'une composition ignifugeante absorbée de cette invention. Ces compositions peuvent être utilisées en combinaison avec d'autres ignifugeants inorganiques particulaires. L'invention concerne également la préparation et l'utilisation de ces ignifugeants.
PCT/US2009/068069 2008-12-22 2009-12-15 Compositions ignifugeantes sous forme de poudres fluentes, leur préparation et leurs utilisations WO2010075087A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
DE102014001222A1 (de) 2014-01-29 2015-07-30 Clariant lnternational Ltd Halogenfreie feste Flammschutzmittelmischung und ihre Verwendung
US10640624B2 (en) 2016-12-22 2020-05-05 Lotte Advanced Materials Co., Ltd. Thermoplastic resin composition and article using the same

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Publication number Priority date Publication date Assignee Title
WO2001012553A1 (fr) 1999-08-11 2001-02-22 Akzo Nobel N.V. Procede de preparation de boehmites quasi cristallines a partir de precurseurs economique
EP1153971A1 (fr) * 1998-08-26 2001-11-14 Otsuka Chemical Company, Ltd. Ignifuge poudreux
US7416780B2 (en) * 2002-08-02 2008-08-26 Rhodia Chimie Flame-retardant composition comprising organophosphorus compound impregnated on a porous support, preparation method and use thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1153971A1 (fr) * 1998-08-26 2001-11-14 Otsuka Chemical Company, Ltd. Ignifuge poudreux
WO2001012553A1 (fr) 1999-08-11 2001-02-22 Akzo Nobel N.V. Procede de preparation de boehmites quasi cristallines a partir de precurseurs economique
US6689333B1 (en) 1999-08-11 2004-02-10 Akzo Nobel N.V. Process for the preparation of quasi-crystalline boehmites from inexpensive precursors
US7416780B2 (en) * 2002-08-02 2008-08-26 Rhodia Chimie Flame-retardant composition comprising organophosphorus compound impregnated on a porous support, preparation method and use thereof

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Title
MATERIALS RESEARCH, vol. 3, no. 4, 2000, pages 104 - 114

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014001222A1 (de) 2014-01-29 2015-07-30 Clariant lnternational Ltd Halogenfreie feste Flammschutzmittelmischung und ihre Verwendung
EP3505596A1 (fr) 2014-01-29 2019-07-03 Clariant International Ltd Mélange d'agent ignifuge solide sans halogène et son utilisation
EP3505598A1 (fr) 2014-01-29 2019-07-03 Clariant International Ltd Mélange d'agent ignifuge solide sans halogène et son utilisation
EP3505599A1 (fr) 2014-01-29 2019-07-03 Clariant International Ltd Mélange d'agent ignifuge solide sans halogène et son utilisation
EP3505597A1 (fr) 2014-01-29 2019-07-03 Clariant International Ltd Mélange d'agent ignifuge solide sans halogène et son utilisation
EP3521402A1 (fr) 2014-01-29 2019-08-07 Clariant International Ltd Mélange d'agent ignifuge solide sans halogène et son utilisation
US10640624B2 (en) 2016-12-22 2020-05-05 Lotte Advanced Materials Co., Ltd. Thermoplastic resin composition and article using the same

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