WO2008088498A1 - Formulations et articles non polymères sans hydrocarbure - Google Patents

Formulations et articles non polymères sans hydrocarbure Download PDF

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Publication number
WO2008088498A1
WO2008088498A1 PCT/US2007/024989 US2007024989W WO2008088498A1 WO 2008088498 A1 WO2008088498 A1 WO 2008088498A1 US 2007024989 W US2007024989 W US 2007024989W WO 2008088498 A1 WO2008088498 A1 WO 2008088498A1
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WIPO (PCT)
Prior art keywords
fatty acid
article
group
flame
composition
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PCT/US2007/024989
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English (en)
Inventor
Thomas E. Breuer
James Foreman
Tarun Cholera
Peter Frenkel
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Chemtura Corporation
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Publication of WO2008088498A1 publication Critical patent/WO2008088498A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C5/00—Candles
    • C11C5/002—Ingredients
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L11/00—Manufacture of firelighters
    • C10L11/04—Manufacture of firelighters consisting of combustible material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/34—Other details of the shaped fuels, e.g. briquettes
    • C10L5/36—Shape
    • C10L5/365—Logs
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/40—Solid fuels essentially based on materials of non-mineral origin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

Definitions

  • the present invention relates to moldable and extrudable compositions that are useful for producing articles, such as candles and artificial firelogs.
  • the compositions which are flammable and combustible, comprise additives, e.g. oils, fats, and their derivatives, for improving processing and burn characteristics.
  • Fatty triglycerides and fatty acids derived from them by hydrolysis and removal of glycerin are known to be employed as fuels in candles, fire starter blocks, fireplace logs, and similar articles. They are mixed with polymeric and /or hydrocarbon (waxy-type) fuels or formulated into composites with various forms of fiber or other solid species, usually flammable materials.
  • U.S. Patent No. 3,297,419 discloses a synthetic fuel log produced from a flame- supporting material that is solid at room temperature.
  • a filler or extender of a combustible type is combined with the flame-supporting material.
  • the flame-supporting material and the extender are combined with a binder to provide an elongate synthetic fuel log that is said to remain intact during burning.
  • U.S. Patent No. 3,843,336 discloses a self supporting log having about seventy percent of its fuel value derived from petroleum derivatives contained therein.
  • the log has an extruded thermoset resin skeleton highly filled with particulate vegetable matter.
  • the woody particles are preferably initially impregnated with one or more petroleum derivatives, and subsequently added to an aqueous solution of a prepolymer resin mix.
  • the mixture is then extruded with preferably a screw extruder having a heated die barrel to concentrate the thermoset resin at the outer surface of the extrusion, forming a continuous casing.
  • U.S. Patent No. 4,040,796 discloses an artificial firelog comprised of a flammable body typically formed of a particulate wood and wax mixture preferably with salts added for flame color.
  • a groove is formed along the outer surface of the body and extends substantially its entire length.
  • the groove is filled with gelled starter fuel.
  • the log is preferably formed with at least one substantially flattened side with the gelled fuel filled groove located just above the flattened side whereby the log can be situated with its flattened side on the fireplace grate or andirons and the gelled fuel filled groove located along the lower preferably front, face of the log thereby facilitating the log's fast lighting characteristics.
  • the log is provided with an over-wrapper having an inner low or medium density polyethylene coating and which over-wrapper is heat sealed about the log.
  • the over-wrapper When lighting, the over-wrapper is initially lit and this also ignites the gelled fuel. The heat and pressure from the hot expanding combustion gases then softens and ruptures the over-wrapper and allows the flame to spread along the gelled fuel in the notch thereby fully enveloping the firelog in flame.
  • U.S. Patent No. 4,049,680 discloses organic amide waxes having at least two amide groups per molecule are prepared by reacting monocarboxylic acids preferably fatty acids with organic di- or poly-isocyanates.
  • U.S. Patent No. 4,326,854 discloses a synthetic firelog made by binding cellulosic particles with a combustible binder produced by the interaction of a liquid combustible byproduct or waste product and a modifier, the resulting material being such as to be carbonizable on combustion to form a porous skeleton which maintains the shape of the log during burning.
  • the by-product may be molasses, various waste oils or pitches, or sulfite lye and the modifier interacts physically or chemically therewith to form a plastic, thixotropic binder material.
  • the cellulosic material may be sawdust, paper, or any of a variety of cellulosic residues from the processing of vegetable materials.
  • U.S. Patent No. 4,333,738 discloses an improved synthetic fire log that contains wood fibers or sawdust, coal liquid, molasses and paraffin wax in appropriate quantities.
  • Green sawdust is first heated to a temperature of from 250 to 300 0 F. to reduce the moisture content thereof and provide relatively dry sawdust.
  • To the dry sawdust is added a quantity of coal liquid while the sawdust is at an elevated temperature of at least 200 0 F.
  • molasses is added to the sawdust, coal liquid combination while the combination is in a temperature range of from 115-150 0 F.
  • paraffin wax in block form is added while the foregoing mixture is at an elevated temperature at least sufficient to melt the paraffin.
  • the resulting mixture is poured into a mold and compressed to form a stable, solid, compacted mass after which the mass is removed from the mold thus forming a synthetic fire log.
  • U.S. Patent No. 4,813,975 discloses a composition of matter, which is suitable for manufacturing candles by pressing/extruding, which is based on stearic/palmitic acid and also comprises: 0.2-10% (w.w) of a crystal modifier and optionally 0.5-15% (w.w) of another, as to carbon chain length adjacent, natural fatty acid and/or such fatty acid derivative.
  • a crystal modifier is a mixture of stearic acid and palmitic acid in the weight range of 20-80:80-20.
  • the crystal modifier is usually of the ester type and is derived from a polyol with 2-4 hydroxyl groups and higher fatty acid and/or dimeric fatty acid.
  • 5,868,804 discloses artificial firelogs that provide a natural visual and audible sensation so that the artificial firelogs have both a soothing flickering flame and a crackling or popping sound normally observed only with natural wood logs.
  • the crackling additive can be mustard seeds, sesame seeds and synthetic hollow spheres.
  • U.S. Patent No. 6,017,373 discloses an artificial firelog that contains 2% to about 6% coriander seed added to create a crackling sound that mimics the sounds produced during the burning of natural logs.
  • the random crackling sound continues for approximately the same time period as observed with the burning of natural wood firelogs and has an amplitude and frequency of crackling sound that mimics burning natural wood logs.
  • U.S. Patent No. 6,086,644 discloses a scented candle that includes a candle manufacturing material, a fragrance provider, and at least one of polypropylene glycol and polypropylene glycol monoalkyl ether of a specified general formula.
  • U.S. Patent No. 6,136,054 discloses a synthetic firelog made by mixing specially processed waxed-cardboard or other wax coated papers of varying proportions with a binder/fuel.
  • the binder/fuel consists of a petroleum wax or a mixture of waxes, the nature and extent of which is suitably modified by in situ admixture with the paraffin wax already present in the waxed-cardboard. Sawdust or other wood fillers may also be added.
  • the resulting mixture is extruded, molded, compressed, or otherwise formed, such that the resulting mass is sufficiently solid to hold its shape at normal room temperature.
  • U.S. Patent No. 6,268,466 discloses a low molecular weight, tertiary amide terminated polyamide that may be blended with a liquid hydrocarbon to form a transparent composition having gel consistency.
  • the tertiary amide terminated polyamide may be prepared by reacting "x" equivalents of dicarboxylic acid wherein at least 50% of those equivalents are from polymerized fatty acid, "y” equivalents of diamine such as ethylene diamine, and "z” equivalents of a mono functional reactant having a secondary amine group as the only reactive functionality.
  • the gel contains about 5-50% tertiary amide terminated polyamide, with the remainder preferably being pure hydrocarbon.
  • the gels are said to be useful in formulating personal care products and other articles wherein some degree of gel-like or self-supporting consistency is desired.
  • U.S. Patent No. 6,503,077 discloses a tertiary amide-terminated dimer acid-based polyamide that may be blended with a solvent to form a gel.
  • the solvent may be flammable, and a wick may be added to the resulting gel so as to form a candle.
  • the candle may be formed into a free-standing pillar, or may be better suited to being placed in a container.
  • the solvent may, for example, be mineral oil or triglyceride.
  • a solid coating may be placed around the candle, for advantages including enhancement of the mechanical stability of the gelled body, and elimination of the tendency of a gel to have an oily feel and to accept noticeable fingerprints.
  • the solvent which, in combination with the tertiary amine-terminated dimer acid-based polymer forms a gel may be or include a fragrance material.
  • the gelled composition may also include fatty acid and/or a compound containing one, two, or more ester groups.
  • the article does not contain a wick, and is intended to function as a fragrance-releasing product.
  • U.S. Patent No. 6,521,002 discloses a clear transparent candle, which can be scented, made of a composition comprising at least one polyamide resin; at least one aliphatic acid alkyl ester having 16 to 40 carbon atoms total in the acid and alcohol moieties thereof; at least one unsaturated alcohol having 11 to 20 carbon atoms; at least one polyether diol ester; at least one drying agent selected from the group consisting of saturated alcohols having 14 to 22 carbon atoms, fatty acid amides, and fatty acid bis-amides in specified ranges of proportions, 0 to 3 parts by weight of at least one emulsifier, 0 to 10 parts by weight of at least one fragrance and 0 to 1 part by weight of at least one preservative.
  • the candle can stand alone or be in a container.
  • U.S. Patent No. 6,544,303 discloses a composite scented candle that has a high load scented shell and a core candle with a similar or lesser fragrance load.
  • the inside candle can be wax, paraffin, gel oil or polyamide-based and can be scented or unscented.
  • the outside shell can be made of paraffin wax and a reinforcement having a melting point of at least 70 0 C. and is scented at a level so that fragrance is continuously released without burning and is further activated by lighting the core candle.
  • U.S. Patent No. 6,602,306 discloses an artificial firelog comprising a mixture of combustible materials and a combustible binder and further containing particulate coke comprising about 1% to about 35% by weight of the firelog, the coke particles having a size less than about 4 mm, to create a realistic crackling sound that mimics the sounds produced during the burning of natural logs.
  • the particulate coke has a preferred moisture content between about 2% and about 20% by weight.
  • the particulate coke may be combined in predetermined ratios with other established crackle additives including natural additives such as coriander seed to extend the time period during which the burning artificial firelog crackles.
  • the particulate coke comprises metallurgical coke.
  • U.S. Patent No. 6,706,942 discloses environmentally degradable molded or extruded articles comprising a polyhydroxyalkanoate C4C6 copolymer composition having short annealing cycle times. Such short annealing cycle times are achieved by compositions having a percentage of C6 units of 2-8%.
  • U.S. Patent No. 6,712,865 discloses a colored flame candle and the manufacture thereof.
  • the colored flame candle comprises a candle body and a candle combustion wick, wherein the candle body comprises a primary combustion agent, a higher fatty acid amide and a higher fatty acid triglyceride as the strength- and flexibility-modifier, a color-forming agent and conventional adjuvant such perfumes and pigments.
  • U.S. Patent No. 6,719,816 discloses an artificial firelog comprising combustible cellulosic material, a combustible wax binder and an amount of sodium bicarbonate effective to reduce emissions of particulate matter (PM) and carbon monoxide (CO).
  • the sodium bicarbonate comprises about 1% to about 10% by weight of the artificial firelog. Besides substantially reducing PM and CO emissions during combustion of the artificial firelog, the undesirable odor associated with combustion of the wax binder is decreased and the f ⁇ relog's total burn time is extended. Moreover, the sodium bicarbonate is said to increase the "poke resistance" of the firelog making the log suitable for outdoor use and a natural appearing white ash develops during the course of combustion.
  • polymeric materials can be used instead of or in addition to waxes primarily for candle manufacturing. They are polyamides (U.S. Patent No. 6,544,303; PCT WO 2001095871 and PCT Int. Application WO 2001095871), ester-terminated polyamides or tertiary-amide terminated polyamides (U.S. Patent Nos. 6,268,466 and 6,503,077), in-situ polymerized vegetable oils and unsaturated carboxylic acids or anhydrides (German Patent 19619396) , polyhydroxy alcoholate copolymers (U.S. Patent No. 6,706,942), polyether diol ester (U.S. Patent No.
  • Fatty acids, amides, including bis-amides, esters, and calcium stearate are also known as lubricants for numerous plastic materials (primarily thermoplastics). Such lubricants are added at up to ten weight percent to the polymeric materials to ease their processing [See Plastics Additives Handbook, 5 th edition by Hans Zweifel, Haser Publishers, Kunststoff, 2000].
  • fatty triglycerides and fatty acids derived from them by hydrolysis and removal of glycerin are known to be employed as fuels in candles, fire starter blocks, fire logs, and similar articles. They are mixed with polymeric and /or hydrocarbon (waxy-type) fuels or formulated into composites with various forms of fiber or other solid species, usually flammable materials.
  • natural fats or oils are typically used as they occur, generally in a liquid or paste form at ambient temperature.
  • Fatty acids derived from triglycerides by hydrolysis and removal of the glycerin can also be used as they occur. Some of the properties of each of these can be improved by modifying the fuel stock used. Hydrogenation can be used either on the triglycerides or on the fatty acids to change their physical characteristics by making them harder and more crystalline in nature.
  • the fats and fatty acids can also be blended either in hardened or unhardened state to achieve the desirable properties.
  • fats and oils of differing carbon chain distributions can also be utilized in these formulations to produce an even wider variety of properties. Such techniques are known in the art; however, none of these techniques, alone, is sufficient to meet all the required and above-described desirable characteristics of the products involved.
  • fire logs are composites that contain cellulosic materials, such as sawdust, and a binder that is produced from certain waxes that may also optionally contain combustible additives that impart processing, combustion characteristics, and flame appearance.
  • Non-polymeric, hydrocarbon-free formulations that are based on triglyceride-fatty acid blends (both soft and hard), serving as fuels.
  • the formulations are suitable for manufacturing moldable and/or extrudable compositions and useful articles, such as candles and cellulosic material-filled artificial fire logs or fire starter blocks. Improved processing and flame/burn characteristics are achieved by combining these blends with fatty acid derivatives, such as metal stearates and ethylene bisamides.
  • the present invention is directed to a moldable and/or extrudable composition that is suitable for manufacturing useful shaped articles and is based on triglyceride-fatty acid blends that also comprise fatty acid derivatives to achieve improved processing and flame- burning characteristics.
  • composition comprising a blend of:
  • the present invention is directed to an article of manufacture comprising a composition comprising a blend of:
  • the present invention is directed to a method for improving the processing and flame-burning characteristics of articles comprising a blend of at least one triglyceride and at least one fatty acid, wherein the method comprises adding to said blend at least one fatty acid derivative.
  • the present invention is directed to, inter alia, a composition comprising a blend of:
  • the fatty acid(s) of the blends of the present invention is (are) preferably of the formula RiCOOH, wherein Ri is an aliphatic hydrocarbon radical of 5 to 25 carbon atoms, including, but are not limited to, such acids as caprylic, oleic, capric, linoleic, lauric, linolenic, myristic, eicosenoic, palmitic, lauroleic, margaric, myristoleic, stearic, palmitoleic, arachidic, gadoleic, behenic, erucic, pelargonic, elaeostearic, isostearic, licanic, neodecanoic, arachidonic, 2-ethyl hexanoic, lignoceric, caproic, pentadecanoic, hydroxystearic, phenylstearic, and the like.
  • the acids employed can, if desired, be hardened by hydrogen
  • the triglyceride(s) of the blends of the present invention is (are) an ester, or esters, of glycerol with one or more fatty acids that are preferably of the formula R 1 COOH, wherein Ri is an aliphatic hydrocarbon radical of 5 to 25 carbon atoms, as described above.
  • the fatty acid derivative(s) of the blends of the present invention are preferably selected from the group consisting of metal salts of fatty acids, fatty acid amides, fatty acid bisamides, and mixtures thereof.
  • the fatty acids from which the derivatives are prepared will, again, be of the formula RiCOOH, wherein Ri is an aliphatic hydrocarbon radical of 5 to 25 carbon atoms, as described above.
  • the metallic moiety of the metal salts of the fatty acids is preferably selected from the group consisting of alkali metals and alkaline earth metals, for example, sodium, potassium, magnesium, calcium, and the like. Sodium and calcium are preferred, calcium most preferred.
  • the fatty acid moiety is preferably of the formula RiCOOH, wherein Ri is an aliphatic hydrocarbon radical of 5 to 25 carbon atoms, as described above.
  • the fatty acid moiety most preferably comprises stearate and/or mixtures of stearate with other naturally occurring and commercially available fatty acids. Again, mixtures of such salts can be employed.
  • the bisamide waxes ethylene bisstearamide and methylene bisphenylstearamide, are known and have a number of uses, for example they are used either alone or in admixture with other materials as lubricants for various applications including the compaction of metal powders; the drawing of wire; the extrusion of plastic pipe; sand shell molding; the processing of polystyrene; and as mould release and detackifying agents for synthetic rubbers.
  • bisamide waxes can be used as additives for a number of materials including paper to improve resistance to water and oil; paraffin waxes and asphalts to increase the melting point thereof; adhesives to reduce viscosity and eliminate cold block and tack.
  • Such bisamide waxes have also been used as anti-static agents for cellophane.
  • These bisamide waxes are commercially available and can be manufactured by a process in which a fatty acid is reacted with a diamine at a temperature above the melting point of the resulting amide wax; the reaction proceeds with the evolution of water.
  • the most widely used bisamide wax is ethylene bisstearamide, which can be made by reacting one mole of ethylenediamine with two moles of stearic acid.
  • methylene bisphenylstearamide can be prepared by the reaction of stearic acid with methyl enedianiline.
  • these products can be made by the reaction of a fatty acid of the formula RiCOOH, wherein Ri is and aliphatic hydrocarbon radical of 5 to 25 carbon atoms, as described above, with an organic isocyanate, as disclosed in U.S. Patent No. 4,049,680.
  • ethylene bisamides are preferred. Most preferred is N,N'-ethylene bis-stearamide (EBS).
  • EBS N,N'-ethylene bis-stearamide
  • fatty acid amides that can be employed in the practice of the present invention can be prepared from such fatty acids and monoamines.
  • the total additive content i.e., the content of the fatty acid derivative(s), (C), preferably is in the range of from about 3 to about 99 percent by weight based on the total weight of (A), (B), and (C); more preferably, from about 5 to about 20 percent by weight; most preferably, from about 10 to about 15 percent by weight.
  • compositions and articles of the present invention are in the range of 60/40 to 40/60 for most applications, although wider ranges, such as 90/10 to 10/90, may apply when specific properties, e.g., burn time and/or flame height, are weighted more heavily than others.
  • specific properties e.g., burn time and/or flame height
  • compositions and articles may, if desired, further comprise additional fillers, extenders, modifiers, binders, flame and article colorants, perfumes, and the like.
  • fillers that are cellulose-containing materials will normally be included.
  • cellulose-containing materials can include, but are not limited to, cellulose fiber, cellulose derivatives, wood chips, wood fibers, wood flour, flax, kenaf, sisal, jute, rice hulls, cotton, hemp, and the like.
  • Suitable cellulose-containing fillers for use in the practice of the present invention may be derived from any of a number of available sources, such as ground wood, sawdust, wood flour, ground newsprint, magazines, books, cardboard, wood pulps (mechanical, stone ground, chemical, mechanical-chemical, refined, bleached or unbleached, virgin or recycled, sludge, waste fines), and various agricultural wastes (rice hulls, wheat, oat, barley and oat chaff, coconut shells, peanut shells, walnut shells, straw, corn husks, corn stalks, jute, hemp, bagasse, bamboo, flax, and kenaf).
  • sources such as ground wood, sawdust, wood flour, ground newsprint, magazines, books, cardboard, wood pulps (mechanical, stone ground, chemical, mechanical-chemical, refined, bleached or unbleached, virgin or recycled, sludge, waste fines), and various agricultural wastes (rice hulls, wheat, oat, barley and oat chaff,
  • Fibrous wood material which is preferred because of its abundance and suitability can be derived from either soft woods or evergreens or from hard woods commonly known as broad leaf deciduous trees. While soft wood is the primary source of fiber for use in the practice of the present invention, additional fiber makeup can be derived from a number of secondary or fiber reclaim sources, including bamboo, rice, sugar cane, flex, kenaf and recycled fibers from newspapers, boxes, computer printouts, and the like. Where fillers are included in the compositions of the present invention, they are preferably present in the range from about 1 to about 60 percent by weight, based on the weight of the total composition.
  • the Ring and Ball Test measures strength as the melting point of the fuel is approached: a VA inch thick disc made up of the sample, e.g., a composite, must support a steel ball % of an inch in diameter and weighing 3.5 to 3.6 grams. This is a variation of other ring and ball softening point tests, such as ASTM D 36, and uses the same equipment.
  • the sample disc is % of an inch in diameter in the bottom 0.1 inch of thickness, and 3 A of an inch in diameter in the top 0.15 inch of thickness, thus resting on a lip in the sample holder.
  • the steel ball sits on top of the sample disc, held roughly centered by a retainer with three prongs that keep the ball from rolling.
  • Two of the sample holders, sample discs, balls, and retainers are mounted in a framework and immersed in water in a 1000 mL beaker, with the samples suspended about midway up the beaker.
  • the water is heated on a heating plate at a rate of about 5°F ( about 2.75 0 C) per minute, with moderate stirring of the water by a 30 mm Teflon coated magnetic stirring bar.
  • the temperature is read from a thermometer with its bulb suspended at about the sample level, between the two samples. The temperature at which each ball falls through the sample disc is recorded, and the average value is used as the softening point of that composition.
  • Samples are prepared by weighing appropriate amounts of the fuel and additives into a 250 mL beaker, then adding a 30 mm magnetic stirring bar.
  • the beaker is then placed on a heater/stirrer, and a thermometer is suspended in the beaker so that its bulb does not touch the bottom.
  • the heater is then turned on to a level to produce a surface temperature in the range of 300 to 350 0 F (149 to 177°C) and the stirrer turned on when enough of the sample is molten to allow mixing.
  • the sample is heated and stirred until it is a clear solution - normally above 220 °F (104 0 C).
  • samples of fuels modified by the additives were mixed with wood chips on a 50/50 basis (by weight) and formed by finger pressure into 1.5 inch diameter by a 3/4 inch high conical piles. These comprised 5 grams of wood chips and 5 grams of a fuel/additive blend, each on a 70 mm aluminum weighing cup, arranged in a matrix on a metal surface. Each was ignited with the use of flame about a 3/4 inch long from a Harbor Freight brand butane microtorch that was applied for one second. Flame characteristics were observed and recorded as shown in Table 3. Burn times were recorded in minutes until the flame went out. Flame heights were recorded in centimeters, measured as average heights during stabilized burn by placing a ruler behind the sample and visually measuring the middle of the flickering height.
  • Burn time and flame height of the candle-type formulations and articles were determined on samples cast into cylindrical discs in ring and ball sample holders with wicks suspended in their centers, with the wicks cut off at a height of 0.5 inch above the porcelain surface. Samples were allowed to harden, removed from the rings, and the wicks were ignited as described above. Flame height was measured from candle top to middle of the flickering range, against a ruler as described above. Burn time was recorded in minutes until the flame went out.
  • Table 1 demonstrate the unique ability of ethylene bisamides, especially N,N'-ethylene bis-stearamide (EBS), to increase substantially the ring and ball softening points of triglyceride fuels.
  • EBS N,N'-ethylene bis-stearamide
  • CaSt calcium stearate
  • tallow fatty acids metal stearates, of which calcium stearate (CaSt) was the most efficient, resulted in a less pronounced effect for tallow, hard tallow, and tallow fatty acids.
  • the EBS provides the only effective treatment and even then the effect is small.
  • CaSt was more efficient than EBS for improving the softening point of hard tallow fatty acids, while sodium stearate showed no increase at all in either triglycerides or fatty acids.
  • Table 2 show an unexpected, synergistic effect of the fuel compositions [hard triglyceride (HT), soft triglyceride (T), hard triglyceride fatty acid (HTFA), or soft triglyceride fatty acid (TFA)] and the presence of EBS and/or CaSt on increasing the softening point of the formulations.
  • EBS additive Proper application of the EBS additive caused rapid crystallization of the candle-type formulation in the mold and provided superior strength and stiffness of the produced article even when it was still warm. As shown in Table 4, CaSt increased the length of time the material burns.
  • Sodium stearate provided a highly visible, bright flame. It is known in the art that the addition of sodium stearate to a fuel contributes to a bright yellow flame.

Abstract

L'invention porte sur des compositions comprenant des mélanges d'au moins un triglycéride, d'au moins un acide gras et d'au moins un dérivé d'acide gras de sorte que lesdites compositions présentent de meilleures caractéristiques de traitement et de flamme/combustion. Les compositions peuvent, facultativement, comprendre en outre des charges, des produits de coupage, des modificateurs, des liants, des colorants de flamme et d'article, et des parfums, et sont utiles dans la fabrication, par exemple, de bûches de cheminée, de blocs allume-feu, de bougies et similaires.
PCT/US2007/024989 2007-01-19 2007-12-06 Formulations et articles non polymères sans hydrocarbure WO2008088498A1 (fr)

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US11/656,318 2007-01-19
US11/656,318 US20080172930A1 (en) 2007-01-19 2007-01-19 Hydrocarbon-free, non-polymeric formulations and articles

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WO2008088498A1 true WO2008088498A1 (fr) 2008-07-24

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EP3476939A4 (fr) 2016-07-08 2019-06-05 Tak-Circulator Co., Ltd. Acide nucléique inhibant l'expression du gène mex3b, inhibiteur d'expression du gène mex3b, procédé inhibant l'expression du gène mex3b, agent de prévention ou de traitement des maladies provoquées par l'expression du gène mex3b
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