EP1601743A1 - Iron compounds and use as a fire retardant or sound suppressant - Google Patents

Iron compounds and use as a fire retardant or sound suppressant

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Publication number
EP1601743A1
EP1601743A1 EP04719300A EP04719300A EP1601743A1 EP 1601743 A1 EP1601743 A1 EP 1601743A1 EP 04719300 A EP04719300 A EP 04719300A EP 04719300 A EP04719300 A EP 04719300A EP 1601743 A1 EP1601743 A1 EP 1601743A1
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EP
European Patent Office
Prior art keywords
iron
hydroxide
composition
carbonate
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04719300A
Other languages
German (de)
French (fr)
Inventor
Aaron J. Becker
Changzai Chi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP1601743A1 publication Critical patent/EP1601743A1/en
Withdrawn legal-status Critical Current

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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
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/009—Compounds containing iron, with or without oxygen or hydrogen, and containing two or more other elements
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/32—Thermal properties
    • C01P2006/33—Phase transition temperatures
    • C01P2006/36—Solid to solid transition temperatures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

Definitions

  • the present invention relates to an iron containing composition, its method of manufacture and use as a fire retardant. More particularly, the invention relates to a fire resistant composition comprising a flammable host material and a fire retardant selected from the group consisting of an iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide, iron (III) hydroxide or a combination thereof. More particularly, the invention relates to the use of the composition as a sound suppressant. Still more particularly, the invention relates to a method for making an iron containing composition from a metal chloride stream, especially from a by product stream.
  • Fire retardant materials are commonly incorporated into polymer composites, such as for use in plastics, rubbers, adhesive, wire and cable industries. Fire retardant materials typically are those compositions that have high endothermic decomposition enthalpies that absorb energy during a fire to keep the host cool and result in the formation of a char at the surface of the polymer composite during burning to retard vapor phase fuel release, total heat release and time to peak heat release. In addition, these materials also release water or carbon dioxide during the decomposition that functions to smother the flame.
  • Well-known fire retardant materials include aluminum trihydrate, magnesium hydroxide, antimony oxide, organophosphorous compounds and organic halogen containing compounds.
  • the fire retardant can function as a polymer extender, provided that it does not degrade the properties of the polymer.
  • Each fire retardant has its limits of utility.
  • Aluminum trihydrate decomposes in the range of 200°C and cannot be compounded into materials that require compounding temperatures above this range.
  • Magnesium hydroxide decomposes at a temperature above 300°C, but is expensive.
  • Halides and antimony compounds are not only expensive, but are viewed as environmental hazards in Europe and Japan. It seems clear that alternative fire retardant compositions are needed that provide the functionality without the inherent problems associated with many of the commercial products.
  • the fire resistant composition of the present invention comprises a flammable host material and a fire retardant amount of an iron containing composition selected from the group consisting of iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide, and iron (III) hydroxide alone or in combination as a mixture or solid solution.
  • an iron containing composition selected from the group consisting of iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide, and iron (III) hydroxide alone or in combination as a mixture or solid solution.
  • the iron containing composition of this invention or a mixture or solution made from the iron containing composition can be dried to compositions and morphologies fine tuned to have specific decomposition temperatures, compounding characteristics and fire retardancy features appropriate for use with various polymers for commercial plastic, textile and wood product applications.
  • the composition because of its high density, may also be used as a sound suppressant or to retard the electrical breakdown of a variety of host materials. Used as a sound suppressant, the composition of the present invention may be used to replace calcium carbonate, barium sulfate, magnetite and other known materials used for this purpose.
  • the present invention also relates to a sound suppressant material comprising a polymer and an iron containing composition selected from the group consisting of iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide, iron (III) hydroxide and combination thereof.
  • the present invention further provides a process of making an iron containing composition from a metal chloride containing stream rich in ferrous chloride, the process comprising: (a) adjusting the pH of the metal chloride containing stream to about 6 to about 8 by contacting the metal chloride containing stream with a base to produce a brine and precipitate a mixture comprising an iron containing composition selected from the group consisting of iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide and a combination thereof;
  • the metal chloride-containing stream is first contacted with a base to increase the pH of the stream to from about 3.5 to about 5.5 and to form a precipitate of the cationic impurities having a valence state above 2 present as hydroxides and separating the precipitate from the by-product stream to produce a liquor rich in ferrous chloride having a pH of from about 3.5 to about 5.5; the pH of the liquor is then adjusted to about 6 to about 8 by contacting the liquor with a base to produce a brine and precipitate the mixture comprising an iron containing composition selected from the group consisting of iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide, and a combination thereof.
  • the conditions and manner of drying the wet solid composition may be selected to produce desired compositions and morphologies for specific applications for both making fire retardant compositions and sound suppressant materials.
  • modifiers may be added at any time during the process including without limit prior to, during or after the pH adjusting and/or drying steps.
  • modifiers include without limit any metal (II) compound, especially a compound selected from the group consisting of Mg(ll), Mn(ll), Ca(ll) and a mixture thereof.
  • the iron containing composition of this invention may be produced from an industrial by-product of the chlorination of ores for the recovery of metals such as titanium and zirconium and other processes that produce an iron (II) containing by-product such as from hydrochloric acid leaching of ores and hydrochloric acid pickling of steel products.
  • the iron containing composition may also be produced from a carbonate resulting from other processes or naturally occurring carbonates.
  • the present invention further provides a process of converting a by-product metal chloride-containing stream into an iron containing composition, comprising:
  • the invention relates to use of an iron containing composition selected from the group consisting of iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide, iron (III) hydroxide and a combination thereof, particularly, iron carbonate, as a fire retardant, sound suppressant and electrical insulator.
  • an iron containing composition selected from the group consisting of iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide, iron (III) hydroxide and a combination thereof, particularly, iron carbonate, as a fire retardant, sound suppressant and electrical insulator.
  • any naturally occurring iron containing composition can be used, such as iron (II) carbonate and iron (II) hydroxide carbonate.
  • compositions may be processed by drying or heating to convert them into desired mineral crystal states or they may be mixed (as can the compositions made according to the present invention) with other materials to provide compositions having precisely selected thermal properties, or densities, or cost efficiencies, or electrical properties for a particular application.
  • the source of the iron containing composition is an iron-containing solid or ore, for example, siderite
  • the compound can be rendered suitable for use as a fire retardant by grinding.
  • the iron containing composition of this invention can have a lattice structure containing species other than iron.
  • Iron (II) carbonate, iron (II) carbonate hydroxide, iron (II) hydroxide and iron (III) hydroxide can have other metals substituted for some of the iron in the iron (II) carbonate, iron (II) carbonate hydroxide, and iron (II) hydroxide, and iron (III) hydroxide.
  • the iron atoms of iron (II) carbonate can be substituted by manganese or magnesium.
  • the iron containing composition there can be a metal other than iron by simple addition wherein at least one other metal species, such as calcium, fits within the lattice structure.
  • Such other metal species can change the decomposition temperature of the iron containing composition over a range of 200°C.
  • the composition of the present invention may be added to any flammable host material including without limit polymers and wood products as fire retardants to form a fire resistant composition.
  • fire retardant it is meant a composition having high endothermic decomposition enthalpies that absorb energy during a fire to keep the host cool and result in the formation of a char at the surface of the polymer composite during burning to retard vapor phase fuel release, total heat release and time to peak heat release.
  • these materials can also release water or carbon dioxide during the decomposition that functions to smother the flame.
  • the composition can act as a diluent in the host, typically a polymer, thereby reducing the concentration of fuel for the fire.
  • the composition of this invention may also be used as a sound suppressant.
  • the density of the composition is sufficiently high for application as a high density filler for suppressing sound.
  • the composition of the present invention may be employed at least as a partial replacement for calcium carbonate, barium sulfate, magnetite and other similar materials.
  • the density of iron (II) carbonate is 3.8 g/cc
  • the density of iron (II) hydroxide is 3.4 g/cc
  • the density of siderite is in the range of 3.83 - 3.88 g/cc.
  • the iron containing composition of this invention may be used to retard the electrical breakdown of a variety of host materials.
  • a mixed metal chloride containing stream is an example of a suitable source.
  • the invention relates to methods of making the iron containing compositions described herein.
  • the process comprises a "first neutralization" step of contacting a metal chloride stream with a base to increase the pH of the stream to about 3.5 to about 5.5 and form a first precipitate of the 3+ and 4+ metals present in the stream as hydroxides and/or carbonates, and thereby produce a liquor rich in iron (II).
  • the first precipitate is separated from the liquor using any conventional separation means, such as filtration, centrifugation, decanting, and the like.
  • the liquor is treated again with a base in a "second neutralization" step to produce a brine and a second precipitate containing among other metal compositions, iron (II) carbonate, iron (II) carbonate hydroxide, iron (II) hydroxide and combination thereof and a brine solution.
  • the base is used to adjust the pH to about 6 to about 8.
  • the second precipitate is separated from the brine to provide a wet solid, which is then dried.
  • the wet solid is deagglomerated or ground.
  • the first neutralization step can be omitted.
  • the source of metal chlorides is an aqueous metal chloride solution such as is produced by hydrochloric acid pickling of metals.
  • aqueous metal chloride solution such as is produced by hydrochloric acid pickling of metals.
  • hydrochloric acid pickling of steel to remove oxides from the surface in order to make further treatment such as galvanizing possible.
  • solutions conventionally known as pickle liquor, typically comprise 10-26% iron chloride, mainly as ferrous chloride, with some ferric chloride and 0.5- 10% HCI.
  • Metal chloride sources such as pickle liquor exemplify a highly pure ferrous chloride stream. In processing a pickle liquor in accordance with this invention, because of its purity, the first neutralization step can be omitted.
  • a by- product material generated in the reduction of metal ores by carbochlorination is employed.
  • Ores containing titanium and zirconium values are typically rich in iron.
  • the titanium and zirconium are usually recovered from such ores as metal chlorides via carbochlorination leaving as by-product mixtures of iron and other metal chlorides.
  • the composition of the other metal chlorides typically comprises higher valent metals, that is +3 and higher, typically +3 and +4 metal ions and associated anions. The exact composition of higher valent metals present in a by-product stream will depend on the source and processing history of the stream prior to the processing by the present method.
  • the by-product of the carbochlorination of titanium containing ores may be processed using the first and second neutralization steps described herein.
  • the base employed in the processes of this invention can be any alkaline material, including without limit alkali or alkaline earth carbonate or hydroxide, or combination thereof.
  • suitable bases include sodium carbonate, sodium bicarbonate, sodium hydroxide, calcium carbonate, calcium hydroxide, hydrated lime, limestone, and mixtures thereof.
  • the base is selected from the group consisting of sodium carbonate, sodium bicarbonate and calcium carbonate or combination thereof.
  • the base in the second neutralization step is a combination of sodium carbonate and sodium hydroxide.
  • the second precipitate that is, iron (II) carbonate, iron (II) carbonate hydroxide, iron (II) hydroxide, optional other metals substituted for some of the iron is separated using conventional methods, such as filtration, centrifugation, and the like, from the liquid to produce a wet solid and subsequently dried.
  • the drying process may also be controlled as to drying rate, gas environment and temperature to develop specific properties in the resulting composition.
  • the gas environment may be nitrogen, vacuum, or both.
  • the precipitate may be dried at room temperature or at elevated temperature.
  • the precipitate is dried at elevated temperature, such as at a temperature of about 100°C.
  • the wet solid is deagglomerated or ground.
  • Methods of deagglomerating or grinding include, milling, such as media milling, and fluid energy milling. Modifiers, inorganic or organic, may also be added prior to, during, or after each step of neutralization, drying and deagglomerating or grinding.
  • inorganic modifiers include metal (II) compounds, especially compounds selected from the group consisting of Mg(ll), Mn(ll), Ca(ll) and mixtures thereof.
  • An example of a suitable organic modifier is ascorbic acid.
  • Organic compounds known for their ability to stabilize ferrous may also be useful.
  • Such organic compounds include erythorbic acid compounds, hydroxycarboxylic acid compounds and oxocarboxylic acid compounds which are further described in U.S. Patent No. 4,652,435.
  • Erythorbic acid compounds are known as an antioxidant for foods, etc.
  • Such compounds may include erythorbic acid itself and its salts such as sodium and potassium salts.
  • Hydroxycarboxylic acid compounds that may be useful are hydroxycarboxylic acids containing at least one hydroxyl group and at least one carboxyl group in the molecule, or salts of these acids.
  • Specific examples include aliphatic or aromatic compounds having about 2 to about 8 carbon atoms, such as lactic acid, hydroxyacetic acid, hydroxybutyric acid, malic acid, tartaric acid, glyceric acid, citric acid, alpha-rnethylmalic acid, beta-hydroxy-glutaric acid, desoxalic acid, monoethyl tartrate, monoethyl citrate, gluconic acid, galactaric acid, glucronic acid, ketogluconic acid, salicylic acid, p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, gallic acid and hydroxyphthalic acid, and salts of these acids such as sodium, potassium and ammonium salts.
  • oxocarboxylic acid compounds that may be useful are oxocarboxylic acids containing at least one aldehyde or keto group and at least one carboxyl group in the molecule.
  • Specific examples include compounds having 2 to 8 carbon atoms, such as glyoxylic acid, malonaldehydic acid, succinaldehydic acid, pyruvic acid, 2-ketobutyric acid, 4-acetylbutyric acid, 2-ketoglutaric acid, 4-keto-n-valeric acid, acetoacetic acid, oxomalonic acid, oxaloacetic acid and acetonedicarboxylic acid and their salts such as sodium, potassium and ammonium salts.
  • the modifiers act as iron oxidation suppressants and modify the decomposition temperature of the fire retardant compositions of this invention.
  • a pure FeCO3 decomposes at 250°C whereas a synthetic Fe(Mn),(Mg),CO3 composition prepared in the presence of ascorbic acid decomposes at 400°C. It is believed that isoascorbic acid can stabilize the ferrous species on the particle surface, which can provide a composition having a light color.
  • Different product properties in the fire retardant composition of iron (II) carbonate, iron (II) carbonate hydroxide, iron (II) hydroxide, other metals substituted for some of the iron in the iron (II) carbonate, iron (II) carbonate hydroxide, and iron (II) hydroxide, and combination thereof, can be achieved by varying the ratio of sodium carbonate to sodium hydroxide in the second neutralization step. By adjusting the ratio of sodium carbonate concentration to that of sodium hydroxide a fire retardant composition having specific fire retarding properties can be produced.
  • Particle size may be controlled and/or modified by varying the concentration of reactants, both metal chloride, carbonate or bicarbonate, for example the ratio of sodium carbonate to that of sodium hydroxide used in the second neutralization step. Particle size may also be controlled by the method of contacting the reactants, the temperature of the reaction, temperature and time of aging after the reaction, the kind of base used in the neutralization steps (e.g. carbonate or bicarbonate) and any other metal species that may be present (e.g., magnesium, manganese or calcium).
  • concentration of reactants both metal chloride, carbonate or bicarbonate
  • Particle size may also be controlled by the method of contacting the reactants, the temperature of the reaction, temperature and time of aging after the reaction, the kind of base used in the neutralization steps (e.g. carbonate or bicarbonate) and any other metal species that may be present (e.g., magnesium, manganese or calcium).
  • method of contacting the reactants it is meant whether base is added to the metal chloride or whether metal chloride is added to the base to adjust pH to about 6 to about 8. For example it has been found that if metal chloride is added to base it stabilizes ferrous better than if the base is added to the metal chloride.
  • the order of contacting the reactants can be important for producing iron (II) containing products, and can impact color and oxidizability of the ferrous ion.
  • Desired particle size of the iron containing composition of the present invention typically ranges from about 1 to about 10 microns.
  • the compositions produced by the second neutralization step and drying process may be measured by determining the temperature range of decomposition using Thermogravimetric Analysis (TGA) and the energy absorbed upon decomposition by Differential Scanning Calorimetry (DSC).
  • TGA Thermogravimetric Analysis
  • DSC Differential Scanning Calorimetry
  • fire retardants of this invention may be formulated in specific compositions with specific particle size and specific properties.
  • compositions of the base used in pH adjustment steps include composition of the base used in pH adjustment steps, method of mixing (stirring) reactants, presence or absence of air during reaction.
  • the iron containing composition of this invention exhibits a weight loss upon heating between about 100°C and about 500°C, additionally between about 120 and about 450°C of about 20 to about 50%, additionally about 30 to about 40%. Additionally, the iron containing composition of this invention has an enthalpy of endothermal effect of as high as about 800 J/g, possibly higher, and as low as about 200 J/g, additionally about 620 J/g to as low as about 230 J/g.
  • the iron containing composition of this invention has an endothermal peak of at least about 100°C, and preferably, about 120 to about 450 °C. These properties render the iron containing composition useful as a fire retardant particularly when combined with a flammable host material.
  • the iron containing composition of the present invention may be compounded into a flammable host material such as a polymer to produce a fire resistant product, such as a plastic article, film or masterbatch.
  • a flammable host material such as a polymer
  • the compositions may be added to a polymer before it is spun into a fiber, incorporated into a coating, or molded into an article.
  • the compositions may be applied by methods currently used in the art.
  • the method of compounding the composition into a polymer is not critical to the performance of the composition.
  • Methods known in the arts of fire retarding, sound suppressing and electrical insulation for incorporating fire retardant compositions currently known and used may be used for the compositions of the present invention.
  • Polymers which are suitable for use in the fire resistant product of this invention include, by way of example but not limited thereto, polymers of ethylenically unsaturated monomers including olefins such as polyethylene, polypropylene, polybutylene, and copolymers of ethylene with higher olefins such as alpha olefins containing 4 to 10 carbon atoms or vinyl acetate; vinyls such as polyvinyl chloride, polyvinyl esters such as polyvinyl acetate, polystyrene, acrylic homopolymers and copolymers; phenolics; alkyds; amino resins; epoxy resins, polyamides, polyurethanes; phenoxy resins, polysulfones; polycarbonates; polyesters and unsaturated polyesters; polyethers; acetal resins; polyimides; and polyoxyethylenes. Mixtures of polymers are also contemplated.
  • Polymers suitable for use in the present invention also include various rubbers, such as styrene-butadiene rubber, and/or elastomers, either natural or synthetic polymers based on copolymerization, grafting, or physical blending of various diene monomers with the above-mentioned polymers, all as generally known in the art.
  • rubbers such as styrene-butadiene rubber, and/or elastomers, either natural or synthetic polymers based on copolymerization, grafting, or physical blending of various diene monomers with the above-mentioned polymers, all as generally known in the art.
  • polymers suitable for use in the fire resistant products of this invention include plastic and elastomeric polymers.
  • the polymer is selected from the group consisting of polyolefins, polyvinyl chloride, polyamides and polyesters, and mixtures of these. More preferred are polyolefins. Most preferred are polyolefins selected from the group consisting of polyethylene, polypropylene, and mixtures thereof.
  • compositions of the present invention may be formulated into a sound suppressant by compounding with a variety of polymers in weight ratios of about 40 to about 80 wt % of the compositions sited above.
  • compositions useful as electrical insulation may be formulated by compounding with various polymers in weight ratios of from about 5 to about 80 wt % iron containing composition of the present invention. These compositions are useful in automotive wire harness coatings, and the like. When more than one iron containing composition is employed the compositions can be combined in different proportions for a synergistic effect between the compositions.
  • Products incorporating the fire retardant compositions of this invention include wire and cable.
  • wire applications include building wire, telephone and telegraph wire, electrical cords and cord sets, appliance wire, antennae wire, coaxial and data wire and magnet wire.
  • An example of a cable application includes power cable.
  • An advantage of using the fire retardants of this invention is the ability to tailor the composition to meet the application-specific performance standards.
  • Additional products incorporating the fire retardant composition of this invention include synthetic rubber carpet backing, and adhesives for carpet backing, appliance housing, molded electrical products, glass reinforced unsaturated polyesters, cross-linked polyethylene insulation, cast, cross-linked acrylics for example, as used in sheets and fabricated shapes in bathroom vanities, wall panels, kitchen counters, and wood products including pulp and paper and coatings for wood products.
  • Example 1 Deionized water was purged with nitrogen for at least 30 minutes before used to provide de-oxygenated water.
  • NaHCO ⁇ solution was prepared by dissolving 33.6 g NaHCO3 in 180-ml water in a 500 ml glass flask. This NaHCO3 solution was then bubbled with CO2 and heated to 87°C using a hot plate.
  • metal chloride solution was prepared by dissolving 32 g of FeCI 2 .4H2O, 3.98 g of MnCl2.4H 2 0, 3.84 g of MgCI 2 .6H 2 O, and 0.46 g of isoascorbic acid in 180 ml de- oxygenated water.
  • the metal chloride solution was then pumped into the NaHCOs solution during a period of 25 minutes using a peristaltic pump.
  • the temperature of reaction was kept between 76.6°C to 87°C.
  • the slurry was stirred for 30 minutes, during which period the temperature of solution was raised to 92°C.
  • the slurry was then filtered using a 0.2 micron membrane filter.
  • the filter cake was rinsed with 300 ml of de-oxygenated water twice.
  • the cake was dried in a vacuum oven under nitrogen at 100 °C overnight.
  • the cake broke into a free flowing powder upon drying.
  • the dry powder had a narrow size distribution by light scattering measurement using a Matersizer 2000 available from Malvern Instruments with d50 of 11.3 micron.
  • X-ray powder diffraction (XRD) patterns of this powder were similar to the standard reference for FeCOs.
  • the weight loss of this sample was 38.0% between 150°C and 450°C as determined by Differential Thermogravimetric Analysis (DTGA).
  • the enthalpy of endothermal effect of this sample was 743.7 J/g as determined by Differential Scanning Calorimetry (DSC) analysis.
  • the DSC endothermal peak was at 390.0 °C. This sample was stable at room temperature when exposed to air.
  • the XRD, DTGA and DSC showed very little change after exposed to air for one week.
  • Example 2 Deionized water was purged with nitrogen for at least 30 min before being used.
  • NaHCO ⁇ solution was prepared by dissolving 50.4 g of NaHCO3 in 270 ml of water in a 1 -liter jacketed glass reactor. This NaHCO3 solution was bubbled with CO 2 and heated to 85 °C using a circulating bath.
  • metal chloride solution was prepared by dissolving 48.01 g of FeCI 2 .4H 2 0, 5.97 g of MnCI 2 .4H 2 0 and 5.76 g of MgCI 2 .6H 2 O in 270 ml of de-oxygenated water.
  • the metal chloride solution was then pumped into the NaHC0 3 solution during a period of 10 min using a peristaltic pump.
  • the temperature of reaction was kept at 85 °C.
  • the slurry was stirred for 30 minutes, during which period the temperature of solution was raised to 95°C.
  • the slurry was then filtered using a
  • Example 2 The process of Example 2 was repeated except no C0 2 was bubbled into the NaHCOs solution during the reaction.
  • the weight loss of this sample was 38.16% between 150°C and 450°C as determined by DTGA.
  • the enthalpy of endothermal effect of this sample was 637.5 J/g as determined by DSC analysis.
  • the DSC endothermal peak was at 373.8°C. This sample was stable at room temperature when exposed to air.
  • Example 4 The process of Example 2 was repeated except for the following changes: a. 0.69 g isoascorbic acid was added into metal chloride solution; and b. temperature of reaction was 70°C and temperature was maintained at 70°C for 30 minutes after addition of metal chloride solution was complete.
  • the weight loss of this sample was 37.6 % between 150°C and 450°C as determined by DTGA.
  • the enthalpy of endothermal effect of this sample was 608.2 J/g as determined by DSC analysis.
  • the DSC endothermal peak was at 350.3°C. This sample was less stable when exposed to air at room temperature than the product of Example 2. After 4 weeks, this sample turned black, while products of Examples 2 and 3 remained dark green to brown.
  • Example 5 The process of Example 2 was repeated except for the following changes: a. 0.69 g isoascorbic acid was added into metal chloride solution; and b. 4.19 g of CaCl2.H 2 O was added to the metal chloride solution instead of 5.76 g MgCI 2 .6H 2 O.
  • Example 6 The process of Example 2 was repeated except for the following changes: a. 0.69 g isoascorbic acid was added into metal chloride solution; and b. neither MgCI .6H 2 0 nor MnCI 2 .4H 2 0 were added to the metal chloride
  • the weight loss of this sample was 36.41 % between 150°C and 450°C as determined by DTGA.
  • the enthalpy of endothermal effect of this sample was 519.4 J/g as determined by DSC analysis.
  • the DSC endothermal peak was at 324.5°C, which was much lower than the endothermal peaks for products of Examples 2-5.
  • reactions to prepare stable iron carbonate products are performed at temperatures of 70°C or more.
  • Dopants such as Mn, Mg and Ca can affect the stability of iron carbonate products and can be used to tune their decomposition temperatures.
  • Example 7 Sample strips 5 mm wide and 750 mm long were prepared from low density polyethylene compounded with an iron containing composition of this invention derived from siderite. A sample was placed under a radiant panel inside a sample holder in the device described in ASTM method E 1321 and ignited with a spark ignitor at the end of the sample in the high flux region. The progression of the flame spread was monitored visually and recorded on a digital video camera. The point where the flame extinguished was noted. The incident flux was determined from the flux calibration curve. The flux at the self-extinguishment point was termed the minimum flux for spread, "MFFS.” The National Institute of Standards and Technology has determined that MFFS data correlates with bench scale flammability tests such as ASTM E 84 and UL 94 V. The results of the MFFS test showed that siderite performed at least comparably to magnesium hydroxide and aluminum trihydrate and better than calcium carbonate.

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Abstract

The present invention provides fire resistant compositions comprising an iron containing composition having fire retardant properties selected from the group consisting of iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide, iron (III) hydroxide and a combination thereof and a method to manufacture the iron containing composition from a metal chloride stream. The iron containing composition can also be used as a sound suppressant or an electrical insulator.

Description

TITLE IRON COMPOUNDS AND USE AS A FIRE RETARDANT OR SOUND
SUPPRESSANT CROSS REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Application
No. 60/453,309 filed on March 10, 2003 which is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION The present invention relates to an iron containing composition, its method of manufacture and use as a fire retardant. More particularly, the invention relates to a fire resistant composition comprising a flammable host material and a fire retardant selected from the group consisting of an iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide, iron (III) hydroxide or a combination thereof. More particularly, the invention relates to the use of the composition as a sound suppressant. Still more particularly, the invention relates to a method for making an iron containing composition from a metal chloride stream, especially from a by product stream.
BACKGROUND OF THE INVENTION Fire retardant materials are commonly incorporated into polymer composites, such as for use in plastics, rubbers, adhesive, wire and cable industries. Fire retardant materials typically are those compositions that have high endothermic decomposition enthalpies that absorb energy during a fire to keep the host cool and result in the formation of a char at the surface of the polymer composite during burning to retard vapor phase fuel release, total heat release and time to peak heat release. In addition, these materials also release water or carbon dioxide during the decomposition that functions to smother the flame. Well-known fire retardant materials include aluminum trihydrate, magnesium hydroxide, antimony oxide, organophosphorous compounds and organic halogen containing compounds. In cases where the fire retardant is less expensive than the polymer in which it is compounded, the fire retardant can function as a polymer extender, provided that it does not degrade the properties of the polymer. Each fire retardant has its limits of utility. Aluminum trihydrate decomposes in the range of 200°C and cannot be compounded into materials that require compounding temperatures above this range. Magnesium hydroxide decomposes at a temperature above 300°C, but is expensive. Halides and antimony compounds are not only expensive, but are viewed as environmental hazards in Europe and Japan. It seems clear that alternative fire retardant compositions are needed that provide the functionality without the inherent problems associated with many of the commercial products.
SUMMARY OF INVENTION The fire resistant composition of the present invention comprises a flammable host material and a fire retardant amount of an iron containing composition selected from the group consisting of iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide, and iron (III) hydroxide alone or in combination as a mixture or solid solution.
The iron containing composition of this invention or a mixture or solution made from the iron containing composition can be dried to compositions and morphologies fine tuned to have specific decomposition temperatures, compounding characteristics and fire retardancy features appropriate for use with various polymers for commercial plastic, textile and wood product applications. The composition, because of its high density, may also be used as a sound suppressant or to retard the electrical breakdown of a variety of host materials. Used as a sound suppressant, the composition of the present invention may be used to replace calcium carbonate, barium sulfate, magnetite and other known materials used for this purpose.
Thus, the present invention also relates to a sound suppressant material comprising a polymer and an iron containing composition selected from the group consisting of iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide, iron (III) hydroxide and combination thereof.
The present invention further provides a process of making an iron containing composition from a metal chloride containing stream rich in ferrous chloride, the process comprising: (a) adjusting the pH of the metal chloride containing stream to about 6 to about 8 by contacting the metal chloride containing stream with a base to produce a brine and precipitate a mixture comprising an iron containing composition selected from the group consisting of iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide and a combination thereof;
(b) separating the mixture from the brine to produce a wet solid composition essentially free of the brine; and (c) drying, and preferably, deagglomerating or grinding the wet solid composition to form the iron containing composition.
In a further embodiment of the process of this invention, useful for waste streams containing amounts of cationic impurities having a valence state above 2, the metal chloride-containing stream is first contacted with a base to increase the pH of the stream to from about 3.5 to about 5.5 and to form a precipitate of the cationic impurities having a valence state above 2 present as hydroxides and separating the precipitate from the by-product stream to produce a liquor rich in ferrous chloride having a pH of from about 3.5 to about 5.5; the pH of the liquor is then adjusted to about 6 to about 8 by contacting the liquor with a base to produce a brine and precipitate the mixture comprising an iron containing composition selected from the group consisting of iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide, and a combination thereof. The conditions and manner of drying the wet solid composition may be selected to produce desired compositions and morphologies for specific applications for both making fire retardant compositions and sound suppressant materials.
If desired, one or more modifiers may be added at any time during the process including without limit prior to, during or after the pH adjusting and/or drying steps. Examples of modifiers include without limit any metal (II) compound, especially a compound selected from the group consisting of Mg(ll), Mn(ll), Ca(ll) and a mixture thereof.
The iron containing composition of this invention may be produced from an industrial by-product of the chlorination of ores for the recovery of metals such as titanium and zirconium and other processes that produce an iron (II) containing by-product such as from hydrochloric acid leaching of ores and hydrochloric acid pickling of steel products. The iron containing composition may also be produced from a carbonate resulting from other processes or naturally occurring carbonates.
Thus, the present invention further provides a process of converting a by-product metal chloride-containing stream into an iron containing composition, comprising:
(a) contacting the metal chloride containing by-product with a base to increase the pH of the by-product to from about 3.5 to about 5.5 and to form a precipitate of any cations with a valence state above 2, typically 3+ and 4+ metals which are usually present as hydroxides; (b) separating the precipitate from the by-product to produce a liquor rich in ferrous chloride having a pH of from about 3.5 to about 5.5;
(c) adjusting the pH of the liquor to about 6 to about 8 by contacting the liquor with a base to produce a brine and precipitate a mixture comprising a composition selected from the group consisting of iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide, and a combination thereof;
(d) separating the mixture from the brine to produce a wet solid composition essentially free of the brine; and (e) drying, and preferably, deagglomerating or grinding of the wet solid composition to form the iron containing composition.
DETAILED DESCRIPTION In one embodiment, the invention relates to use of an iron containing composition selected from the group consisting of iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide, iron (III) hydroxide and a combination thereof, particularly, iron carbonate, as a fire retardant, sound suppressant and electrical insulator. Thus, any naturally occurring iron containing composition can be used, such as iron (II) carbonate and iron (II) hydroxide carbonate. These compositions may be processed by drying or heating to convert them into desired mineral crystal states or they may be mixed (as can the compositions made according to the present invention) with other materials to provide compositions having precisely selected thermal properties, or densities, or cost efficiencies, or electrical properties for a particular application. When the source of the iron containing composition is an iron-containing solid or ore, for example, siderite, the compound can be rendered suitable for use as a fire retardant by grinding.
The iron containing composition of this invention can have a lattice structure containing species other than iron. Iron (II) carbonate, iron (II) carbonate hydroxide, iron (II) hydroxide and iron (III) hydroxide can have other metals substituted for some of the iron in the iron (II) carbonate, iron (II) carbonate hydroxide, and iron (II) hydroxide, and iron (III) hydroxide. As an example, the iron atoms of iron (II) carbonate can be substituted by manganese or magnesium. Alternatively, in the iron containing composition there can be a metal other than iron by simple addition wherein at least one other metal species, such as calcium, fits within the lattice structure. Such other metal species can change the decomposition temperature of the iron containing composition over a range of 200°C. The composition of the present invention may be added to any flammable host material including without limit polymers and wood products as fire retardants to form a fire resistant composition. By "fire retardant" it is meant a composition having high endothermic decomposition enthalpies that absorb energy during a fire to keep the host cool and result in the formation of a char at the surface of the polymer composite during burning to retard vapor phase fuel release, total heat release and time to peak heat release. In addition these materials can also release water or carbon dioxide during the decomposition that functions to smother the flame. Also, the composition can act as a diluent in the host, typically a polymer, thereby reducing the concentration of fuel for the fire.
The composition of this invention, because of its high density, may also be used as a sound suppressant. The density of the composition is sufficiently high for application as a high density filler for suppressing sound. The composition of the present invention may be employed at least as a partial replacement for calcium carbonate, barium sulfate, magnetite and other similar materials. The density of iron (II) carbonate is 3.8 g/cc, the density of iron (II) hydroxide is 3.4 g/cc, and the density of siderite is in the range of 3.83 - 3.88 g/cc.
Further because of the high dielectric breakdown voltages and low conductivity, the iron containing composition of this invention may be used to retard the electrical breakdown of a variety of host materials.
There are many sources, industrial or natural, that can provide a metal chloride starting material for the iron containing composition of the invention. A mixed metal chloride containing stream is an example of a suitable source.
Thus, in another embodiment, the invention relates to methods of making the iron containing compositions described herein. In a typical process of making the iron containing composition of this invention, the process comprises a "first neutralization" step of contacting a metal chloride stream with a base to increase the pH of the stream to about 3.5 to about 5.5 and form a first precipitate of the 3+ and 4+ metals present in the stream as hydroxides and/or carbonates, and thereby produce a liquor rich in iron (II). The first precipitate is separated from the liquor using any conventional separation means, such as filtration, centrifugation, decanting, and the like. Then the liquor is treated again with a base in a "second neutralization" step to produce a brine and a second precipitate containing among other metal compositions, iron (II) carbonate, iron (II) carbonate hydroxide, iron (II) hydroxide and combination thereof and a brine solution. In the second neutralization step, the base is used to adjust the pH to about 6 to about 8. The second precipitate is separated from the brine to provide a wet solid, which is then dried. Optionally, the wet solid is deagglomerated or ground.
When the source of the metal chloride starting material is rich in ferrous chloride, typically a highly pure ferrous chloride stream containing a relatively small amount of other compounds especially cations with a valence state above 2, the first neutralization step can be omitted.
In one particular embodiment of the present invention, the source of metal chlorides is an aqueous metal chloride solution such as is produced by hydrochloric acid pickling of metals. A particular example is hydrochloric acid pickling of steel to remove oxides from the surface in order to make further treatment such as galvanizing possible. Such solutions, conventionally known as pickle liquor, typically comprise 10-26% iron chloride, mainly as ferrous chloride, with some ferric chloride and 0.5- 10% HCI. Metal chloride sources such as pickle liquor exemplify a highly pure ferrous chloride stream. In processing a pickle liquor in accordance with this invention, because of its purity, the first neutralization step can be omitted.
In another process of making the iron containing composition a by- product material generated in the reduction of metal ores by carbochlorination is employed. Ores containing titanium and zirconium values are typically rich in iron. The titanium and zirconium are usually recovered from such ores as metal chlorides via carbochlorination leaving as by-product mixtures of iron and other metal chlorides. The composition of the other metal chlorides typically comprises higher valent metals, that is +3 and higher, typically +3 and +4 metal ions and associated anions. The exact composition of higher valent metals present in a by-product stream will depend on the source and processing history of the stream prior to the processing by the present method. The by-product of the carbochlorination of titanium containing ores may be processed using the first and second neutralization steps described herein. The base employed in the processes of this invention can be any alkaline material, including without limit alkali or alkaline earth carbonate or hydroxide, or combination thereof. Examples of suitable bases include sodium carbonate, sodium bicarbonate, sodium hydroxide, calcium carbonate, calcium hydroxide, hydrated lime, limestone, and mixtures thereof. Preferably, the base is selected from the group consisting of sodium carbonate, sodium bicarbonate and calcium carbonate or combination thereof.
Preferably, the base in the second neutralization step is a combination of sodium carbonate and sodium hydroxide.
The second precipitate, that is, iron (II) carbonate, iron (II) carbonate hydroxide, iron (II) hydroxide, optional other metals substituted for some of the iron is separated using conventional methods, such as filtration, centrifugation, and the like, from the liquid to produce a wet solid and subsequently dried. The drying process may also be controlled as to drying rate, gas environment and temperature to develop specific properties in the resulting composition. The gas environment may be nitrogen, vacuum, or both. The precipitate may be dried at room temperature or at elevated temperature. Preferably, the precipitate is dried at elevated temperature, such as at a temperature of about 100°C. Optionally, after separation of the wet solid from the brine, the wet solid is deagglomerated or ground. Methods of deagglomerating or grinding include, milling, such as media milling, and fluid energy milling. Modifiers, inorganic or organic, may also be added prior to, during, or after each step of neutralization, drying and deagglomerating or grinding.
Examples of inorganic modifiers include metal (II) compounds, especially compounds selected from the group consisting of Mg(ll), Mn(ll), Ca(ll) and mixtures thereof. An example of a suitable organic modifier is ascorbic acid. Organic compounds known for their ability to stabilize ferrous may also be useful. Such organic compounds include erythorbic acid compounds, hydroxycarboxylic acid compounds and oxocarboxylic acid compounds which are further described in U.S. Patent No. 4,652,435. Erythorbic acid compounds are known as an antioxidant for foods, etc. Such compounds may include erythorbic acid itself and its salts such as sodium and potassium salts. Hydroxycarboxylic acid compounds that may be useful are hydroxycarboxylic acids containing at least one hydroxyl group and at least one carboxyl group in the molecule, or salts of these acids. Specific examples include aliphatic or aromatic compounds having about 2 to about 8 carbon atoms, such as lactic acid, hydroxyacetic acid, hydroxybutyric acid, malic acid, tartaric acid, glyceric acid, citric acid, alpha-rnethylmalic acid, beta-hydroxy-glutaric acid, desoxalic acid, monoethyl tartrate, monoethyl citrate, gluconic acid, galactaric acid, glucronic acid, ketogluconic acid, salicylic acid, p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, gallic acid and hydroxyphthalic acid, and salts of these acids such as sodium, potassium and ammonium salts. The oxocarboxylic acid compounds that may be useful are oxocarboxylic acids containing at least one aldehyde or keto group and at least one carboxyl group in the molecule. Specific examples include compounds having 2 to 8 carbon atoms, such as glyoxylic acid, malonaldehydic acid, succinaldehydic acid, pyruvic acid, 2-ketobutyric acid, 4-acetylbutyric acid, 2-ketoglutaric acid, 4-keto-n-valeric acid, acetoacetic acid, oxomalonic acid, oxaloacetic acid and acetonedicarboxylic acid and their salts such as sodium, potassium and ammonium salts.
The modifiers act as iron oxidation suppressants and modify the decomposition temperature of the fire retardant compositions of this invention. For example, a pure FeCO3 decomposes at 250°C whereas a synthetic Fe(Mn),(Mg),CO3 composition prepared in the presence of ascorbic acid decomposes at 400°C. It is believed that isoascorbic acid can stabilize the ferrous species on the particle surface, which can provide a composition having a light color.
Different product properties in the fire retardant composition of iron (II) carbonate, iron (II) carbonate hydroxide, iron (II) hydroxide, other metals substituted for some of the iron in the iron (II) carbonate, iron (II) carbonate hydroxide, and iron (II) hydroxide, and combination thereof, can be achieved by varying the ratio of sodium carbonate to sodium hydroxide in the second neutralization step. By adjusting the ratio of sodium carbonate concentration to that of sodium hydroxide a fire retardant composition having specific fire retarding properties can be produced. Particle size may be controlled and/or modified by varying the concentration of reactants, both metal chloride, carbonate or bicarbonate, for example the ratio of sodium carbonate to that of sodium hydroxide used in the second neutralization step. Particle size may also be controlled by the method of contacting the reactants, the temperature of the reaction, temperature and time of aging after the reaction, the kind of base used in the neutralization steps (e.g. carbonate or bicarbonate) and any other metal species that may be present (e.g., magnesium, manganese or calcium).
By "method of contacting the reactants," it is meant whether base is added to the metal chloride or whether metal chloride is added to the base to adjust pH to about 6 to about 8. For example it has been found that if metal chloride is added to base it stabilizes ferrous better than if the base is added to the metal chloride. The order of contacting the reactants can be important for producing iron (II) containing products, and can impact color and oxidizability of the ferrous ion.
Desired particle size of the iron containing composition of the present invention typically ranges from about 1 to about 10 microns. To develop specific properties in the composition of the present invention, the compositions produced by the second neutralization step and drying process may be measured by determining the temperature range of decomposition using Thermogravimetric Analysis (TGA) and the energy absorbed upon decomposition by Differential Scanning Calorimetry (DSC). After characterizing the thermal properties of different products produced by varying conditions including rate of neutralization, composition of the base, operating temperature and digesting (reaction) time, method of contacting the reactants, and other operating conditions, fire retardants of this invention may be formulated in specific compositions with specific particle size and specific properties. Other operating conditions include composition of the base used in pH adjustment steps, method of mixing (stirring) reactants, presence or absence of air during reaction. The iron containing composition of this invention exhibits a weight loss upon heating between about 100°C and about 500°C, additionally between about 120 and about 450°C of about 20 to about 50%, additionally about 30 to about 40%. Additionally, the iron containing composition of this invention has an enthalpy of endothermal effect of as high as about 800 J/g, possibly higher, and as low as about 200 J/g, additionally about 620 J/g to as low as about 230 J/g. As measured by differential Scanning Calorimetry, the iron containing composition of this invention has an endothermal peak of at least about 100°C, and preferably, about 120 to about 450 °C. These properties render the iron containing composition useful as a fire retardant particularly when combined with a flammable host material.
Thus, the iron containing composition of the present invention may be compounded into a flammable host material such as a polymer to produce a fire resistant product, such as a plastic article, film or masterbatch. The compositions may be added to a polymer before it is spun into a fiber, incorporated into a coating, or molded into an article. For topical applications, the compositions may be applied by methods currently used in the art.
In using the compositions of the present invention, the method of compounding the composition into a polymer is not critical to the performance of the composition. Methods known in the arts of fire retarding, sound suppressing and electrical insulation for incorporating fire retardant compositions currently known and used may be used for the compositions of the present invention.
Polymers which are suitable for use in the fire resistant product of this invention include, by way of example but not limited thereto, polymers of ethylenically unsaturated monomers including olefins such as polyethylene, polypropylene, polybutylene, and copolymers of ethylene with higher olefins such as alpha olefins containing 4 to 10 carbon atoms or vinyl acetate; vinyls such as polyvinyl chloride, polyvinyl esters such as polyvinyl acetate, polystyrene, acrylic homopolymers and copolymers; phenolics; alkyds; amino resins; epoxy resins, polyamides, polyurethanes; phenoxy resins, polysulfones; polycarbonates; polyesters and unsaturated polyesters; polyethers; acetal resins; polyimides; and polyoxyethylenes. Mixtures of polymers are also contemplated.
Polymers suitable for use in the present invention also include various rubbers, such as styrene-butadiene rubber, and/or elastomers, either natural or synthetic polymers based on copolymerization, grafting, or physical blending of various diene monomers with the above-mentioned polymers, all as generally known in the art.
Thus, in general, polymers suitable for use in the fire resistant products of this invention include plastic and elastomeric polymers. Preferably, the polymer is selected from the group consisting of polyolefins, polyvinyl chloride, polyamides and polyesters, and mixtures of these. More preferred are polyolefins. Most preferred are polyolefins selected from the group consisting of polyethylene, polypropylene, and mixtures thereof.
The compositions of the present invention may be formulated into a sound suppressant by compounding with a variety of polymers in weight ratios of about 40 to about 80 wt % of the compositions sited above.
Also compositions useful as electrical insulation may be formulated by compounding with various polymers in weight ratios of from about 5 to about 80 wt % iron containing composition of the present invention. These compositions are useful in automotive wire harness coatings, and the like. When more than one iron containing composition is employed the compositions can be combined in different proportions for a synergistic effect between the compositions.
Products incorporating the fire retardant compositions of this invention include wire and cable. Examples of wire applications include building wire, telephone and telegraph wire, electrical cords and cord sets, appliance wire, antennae wire, coaxial and data wire and magnet wire. An example of a cable application includes power cable. An advantage of using the fire retardants of this invention is the ability to tailor the composition to meet the application-specific performance standards. Additional products incorporating the fire retardant composition of this invention include synthetic rubber carpet backing, and adhesives for carpet backing, appliance housing, molded electrical products, glass reinforced unsaturated polyesters, cross-linked polyethylene insulation, cast, cross-linked acrylics for example, as used in sheets and fabricated shapes in bathroom vanities, wall panels, kitchen counters, and wood products including pulp and paper and coatings for wood products.
EXAMPLES Example 1 Deionized water was purged with nitrogen for at least 30 minutes before used to provide de-oxygenated water. NaHCOβ solution was prepared by dissolving 33.6 g NaHCO3 in 180-ml water in a 500 ml glass flask. This NaHCO3 solution was then bubbled with CO2 and heated to 87°C using a hot plate. In a separate container, metal chloride solution was prepared by dissolving 32 g of FeCI2.4H2O, 3.98 g of MnCl2.4H20, 3.84 g of MgCI2.6H2O, and 0.46 g of isoascorbic acid in 180 ml de- oxygenated water. The metal chloride solution was then pumped into the NaHCOs solution during a period of 25 minutes using a peristaltic pump. The temperature of reaction was kept between 76.6°C to 87°C. After finishing pumping the metal chloride solution, the slurry was stirred for 30 minutes, during which period the temperature of solution was raised to 92°C. The slurry was then filtered using a 0.2 micron membrane filter. The filter cake was rinsed with 300 ml of de-oxygenated water twice. The cake was dried in a vacuum oven under nitrogen at 100 °C overnight. The cake broke into a free flowing powder upon drying. The dry powder had a narrow size distribution by light scattering measurement using a Matersizer 2000 available from Malvern Instruments with d50 of 11.3 micron. X-ray powder diffraction (XRD) patterns of this powder were similar to the standard reference for FeCOs. The weight loss of this sample was 38.0% between 150°C and 450°C as determined by Differential Thermogravimetric Analysis (DTGA). The enthalpy of endothermal effect of this sample was 743.7 J/g as determined by Differential Scanning Calorimetry (DSC) analysis. The DSC endothermal peak was at 390.0 °C. This sample was stable at room temperature when exposed to air. The XRD, DTGA and DSC showed very little change after exposed to air for one week.
Example 2 Deionized water was purged with nitrogen for at least 30 min before being used. NaHCOβ solution was prepared by dissolving 50.4 g of NaHCO3 in 270 ml of water in a 1 -liter jacketed glass reactor. This NaHCO3 solution was bubbled with CO2 and heated to 85 °C using a circulating bath. In a separate container, metal chloride solution was prepared by dissolving 48.01 g of FeCI2.4H20, 5.97 g of MnCI2.4H20 and 5.76 g of MgCI2.6H2O in 270 ml of de-oxygenated water. The metal chloride solution was then pumped into the NaHC03 solution during a period of 10 min using a peristaltic pump. The temperature of reaction was kept at 85 °C. After finishing pumping the metal chloride solution, the slurry was stirred for 30 minutes, during which period the temperature of solution was raised to 95°C. The slurry was then filtered using a
0.2 micron membrane filter to produce a filter cake. The cake was rinsed with 300 ml of de-oxygenated water twice. The cake was dried in a vacuum oven under nitrogen at 100°C overnight. The cake broke into free flowing powder upon drying. X-ray powder diffraction patterns of this powder were similar to the standard reference for FeCOs. The weight loss of this sample was 38.16% between 150°C and ~450°C as determined by Differential Thermogravimetric Analysis (DTGA). The enthalpy of endothermal effect of this sample was 670.7 J/g as determined by Differential Scanning Calorimetry (DSC) analysis. The DSC endothermal peak was at 381.3°C. This sample was stable at room temperature when exposed to air.
Examples The process of Example 2 was repeated except no C02 was bubbled into the NaHCOs solution during the reaction. The weight loss of this sample was 38.16% between 150°C and 450°C as determined by DTGA. The enthalpy of endothermal effect of this sample was 637.5 J/g as determined by DSC analysis. The DSC endothermal peak was at 373.8°C. This sample was stable at room temperature when exposed to air.
Example 4 The process of Example 2 was repeated except for the following changes: a. 0.69 g isoascorbic acid was added into metal chloride solution; and b. temperature of reaction was 70°C and temperature was maintained at 70°C for 30 minutes after addition of metal chloride solution was complete.
The weight loss of this sample was 37.6 % between 150°C and 450°C as determined by DTGA. The enthalpy of endothermal effect of this sample was 608.2 J/g as determined by DSC analysis. The DSC endothermal peak was at 350.3°C. This sample was less stable when exposed to air at room temperature than the product of Example 2. After 4 weeks, this sample turned black, while products of Examples 2 and 3 remained dark green to brown.
Example 5 The process of Example 2 was repeated except for the following changes: a. 0.69 g isoascorbic acid was added into metal chloride solution; and b. 4.19 g of CaCl2.H2O was added to the metal chloride solution instead of 5.76 g MgCI2.6H2O.
The weight loss of this sample was 35.9 % between 150°C and 450°C as determined by DTGA. The enthalpy of endothermal effect of this sample was 562.3 J/g as determined by DSC analysis. The DSC endothermal peak was at 363.1 °C. This sample was more stable when exposed to air at room temperature than the product of Example 2. After 4 weeks, the color of this sample was lighter than all other samples. Example 6 The process of Example 2 was repeated except for the following changes: a. 0.69 g isoascorbic acid was added into metal chloride solution; and b. neither MgCI .6H20 nor MnCI2.4H20 were added to the metal chloride
The weight loss of this sample was 36.41 % between 150°C and 450°C as determined by DTGA. The enthalpy of endothermal effect of this sample was 519.4 J/g as determined by DSC analysis. The DSC endothermal peak was at 324.5°C, which was much lower than the endothermal peaks for products of Examples 2-5.
The Table below summarizes the results of Examples 1 to 6.
TABLE
The results from the Examples, as summarized in the Table illustrate the following
1. Preferably, reactions to prepare stable iron carbonate products are performed at temperatures of 70°C or more.
2. Dopants such as Mn, Mg and Ca can affect the stability of iron carbonate products and can be used to tune their decomposition temperatures.
Example 7 Sample strips 5 mm wide and 750 mm long were prepared from low density polyethylene compounded with an iron containing composition of this invention derived from siderite. A sample was placed under a radiant panel inside a sample holder in the device described in ASTM method E 1321 and ignited with a spark ignitor at the end of the sample in the high flux region. The progression of the flame spread was monitored visually and recorded on a digital video camera. The point where the flame extinguished was noted. The incident flux was determined from the flux calibration curve. The flux at the self-extinguishment point was termed the minimum flux for spread, "MFFS." The National Institute of Standards and Technology has determined that MFFS data correlates with bench scale flammability tests such as ASTM E 84 and UL 94 V. The results of the MFFS test showed that siderite performed at least comparably to magnesium hydroxide and aluminum trihydrate and better than calcium carbonate.

Claims

CLAIMS What is claimed is:
1. A fire resistant composition comprising a flammable host material and a fire retardant effective amount of an iron containing composition selected from the group consisting of iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide, iron (III) hydroxide, and combination thereof.
2. The fire resistant composition of Claim 1 further comprising a modifier.
3. The fire resistant composition of Claim 2 wherein the modifier is an inorganic modifier.
4. The fire resistant composition of Claim 3 wherein the inorganic modifier is selected from the group consisting of metal (II) compounds.
5. The fire resistant composition of Claim 4 wherein the metal (II) compound is selected from the group consisting of Mg(ll), Mn(ll), Ca(ll), and mixture thereof.
6. The fire resistant composition of Claim 2 wherein the modifier is an organic modifier.
7. The fire resistant composition of Claim 6 wherein the modifier is ascorbic acid.
8. The fire resistant composition of Claim 6 wherein the organic modifier is selected from the group consisting of erythorbic acid compounds, hydroxycarboxylic acid compounds, oxocarboxylic acid compounds and combination thereof.
9. The fire resistant composition of Claim 1 wherein the iron containing composition has a weight loss upon heating between 150°C and 450°C of about 30 to 50%; an enthalpy of endothermal effect of at least 500 J/g and an endothermal peak of at least 300°C.
10. The fire resistant composition of Claim 1 wherein the iron containing composition is selected from the group consisting of iron carbonate, iron carbonate hydroxide, iron (II) hydroxide, iron (III) hydroxide and a combination thereof having at least one cationic species having a valence state of 2+.
11. The fire resistant composition of Claim 10 wherein the cationic species is magnesium, manganese or calcium or combination thereof.
12. A process of making an iron containing composition from a metal chloride containing stream, comprising: (a) adjusting the pH of the metal chloride containing stream to about 6 to about 8 by contacting the metal chloride containing stream with a base to produce a brine and precipitate a mixture comprising a composition selected from the group consisting of iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide, and combination thereof;
(b) separating the mixture from the brine to produce a wet solid composition essentially free of the brine; and (c) drying the wet solid composition to form the iron containing composition.
13. The process of Claim 12 in which the metal chloride containing stream comprises at least one cationic species having a valence state of above 2+ and further comprising prior to step (a) contacting the metal chloride containing stream with a base to increase the pH of the stream to from about 3.5 to about 5.5 to form a precipitate of the cations having a valence state of above 2+; and separating the precipitate to produce a ferrous chloride-rich metal chloride containing stream having a pH of from about 3.5 to about 5.5.
14. The process of Claim 12 wherein in the following order the metal chloride containing stream is added to the base.
15. A process of converting a by-product stream containing a metal chloride into an iron containing composition selected from the group consisting of iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide, and combination thereof comprising:
(a) contacting the metal chloride containing by-product stream with a base to increase the pH of the by-product stream to from about 3.5 to about 5.5 and to form a precipitate of any cations with a valence state above 2; (b) separating the precipitate from the by-product stream to produce a liquor rich in ferrous chloride having a pH of from about 3.5 to about 5.5;
(c) adjusting the pH of the liquor to about 6 to about 8 by contacting the liquor with a base to produce a brine and precipitate a mixture comprising a composition selected from the group consisting of iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide, and combination thereof; (d) separating the mixture from the brine to produce a wet solid composition essentially free of the brine; and
(e) drying the wet solid composition to form the iron containing composition.
16. The process of Claim 12 or Claim 15 further comprising deagglomerating the wet solid.
17. The process of Claim 12 or Claim 15 further comprising grinding the wet solid.
18. The process of Claim 14 wherein in the step (c) in the following order the liquor is added to the base.
19. An electrical insulator comprising a polymer and a fire retardant effective amount of an iron containing composition selected from the group consisting of iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide, iron (III) hydroxide, and combination thereof.
20. A sound suppressant comprising a polymer and an iron containing fire retardant composition selected from the group consisting of iron (II) carbonate, iron carbonate hydroxide, iron (II) hydroxide, iron (III) hydroxide, and combination thereof in a sound suppressant effective amount which ranges from about 40 to about 80 wt % of the fire retardant composition.
EP04719300A 2003-03-10 2004-03-10 Iron compounds and use as a fire retardant or sound suppressant Withdrawn EP1601743A1 (en)

Applications Claiming Priority (3)

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US45330903P 2003-03-10 2003-03-10
US453309P 2003-03-10
PCT/US2004/007480 WO2004081144A1 (en) 2003-03-10 2004-03-10 Iron compounds and use as a fire retardant or sound suppressant

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PL219632B1 (en) 2010-01-14 2015-06-30 Termo Organika Spółka Z Ograniczoną Odpowiedzialnością Prepared styrene polymers and method for the preparation of styrene polymers

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JPS5787462A (en) * 1980-11-20 1982-05-31 Kyowa Chem Ind Co Ltd Flame-retardant resin composition containing magnesium oxide with its surface treated
US6162375A (en) * 1994-07-21 2000-12-19 Fire-Trol Holdings, L.L.C. Fugitive color fire retardant composition for aerial application
US6156228A (en) * 1994-11-16 2000-12-05 Houghton International, Inc. Trialkoxyalkylphosphate-based fire resistant fluid containing triglyceride
US6277296B1 (en) * 1999-11-30 2001-08-21 Atlantic Research Corporation Fire suppressant compositions

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