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WO2009007715A1 - Mousses de polyuréthane retardatrices de flamme - Google Patents

Mousses de polyuréthane retardatrices de flamme Download PDF

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Publication number
WO2009007715A1
WO2009007715A1 PCT/GB2008/002347 GB2008002347W WO2009007715A1 WO 2009007715 A1 WO2009007715 A1 WO 2009007715A1 GB 2008002347 W GB2008002347 W GB 2008002347W WO 2009007715 A1 WO2009007715 A1 WO 2009007715A1
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WIPO (PCT)
Prior art keywords
mixture according
foam
polyurethane
mixture
clay
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Ceased
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PCT/GB2008/002347
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English (en)
Inventor
John H Daly
John Jamieson Liggat
Lindsay James Mcculloch
Richard Arthur Pethrick
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University of Strathclyde
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University of Strathclyde
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Publication of WO2009007715A1 publication Critical patent/WO2009007715A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates generally to polyurethane foam compositions that incorporate inorganic halide material.
  • the invention also relates to the foams formed from the compositions, the preparation of the foams and uses thereof.
  • Polymeric foam materials are known for a variety of uses. For example, polymer foams are used for insulation in building, in cushioning in automotive seating and in sound-damping and related applications.
  • polyurethane foam material An important factor in determining the use of a polymer foam material is the degree of fire retardancy of the foam. Materials such as unmodified polyurethane foams burn easily to release toxic fumes. It is therefore desirable to have polyurethane foams that resist combustion when ignited and/or which release lower amounts of toxic and/or environmentally undesirable fumes .
  • flame retarding agents have been used as additives to foam compositions to minimise combustion.
  • flame retardants can compromise the desirable physical properties of the final foam material.
  • Clay materials have also been used as additives in flexible polyurethane foams to impart flame retardant properties/char promoting properties (International Patent Application published as WO 2006/003421) .
  • An important property for flexible foams for use in seating is the comfort characteristic to the user. It is desirable for this characteristic to be maintained in fire retardant foams used for seating applications .
  • a mixture for use in forming a foamed polyurethane comprising components necessary for forming a polyurethane foamed material and an inorganic halide.
  • the components necessary for forming a foamed polyurethane generally comprise at least one polyol and/or an amine together with an isocyanate, a catalyst, a surfactant and a blowing agent.
  • the blowing agent may be selected from those known to the person skilled in the art and includes for example water, carbon dioxide and gases such as fluoro/halo carbons methylene chloride.
  • water is understood in the art to act as a blowing agent since the reaction of one water molecule with two isocyanate groups leads to a urea linkage and one molecule of carbon dioxide. Whilst the carbon dioxide functions as the blowing agent, therefore, resultant foams are nevertheless often referred to as "water-blown" foams.
  • a blowing agent is understood by those skilled in the art as either the species that actually foams the polyurethane, or a precursor for such a species.
  • a foam material comprising a polyurethane which comprises an inorganic halide.
  • the inorganic halide should be capable of imparting a fire retarding or fire suppressing effect to the polyurethane material in which it is incorporated.
  • the inorganic halide will typically be considered as a halide salt.
  • the inorganic halide will generally comprise a metal halide or ammonium halide.
  • the metal may be a transition metal or alkali (group I) or alkaline earth
  • transition metal group II metal according to the periodic table of the elements .
  • exemplary transition metals include iron (as ferrous or ferric ions) , manganese, chromium, cobalt, nickel, copper, zinc and the like.
  • Examplary group (I) metals include lithium, sodium, potassium, rubidium and caesium.
  • Examplary group (II) metals include magnesium, calcium, strontium and barium.
  • ammonium halide (NH 4 + halide ⁇ ) is another example of an inorganic halide.
  • Substituted ammonium ions in which one or more of the hydrogen atoms are substituted by another moiety such as an alkyl group R chosen from methyl, ethyl, propyl, butyl and the like are also encompassed.
  • halide/halogen includes fluoro, chloro, bromo and iodo .
  • Iodo, bromo and chloro are included in certain embodiments .
  • halo is iodo. In other particular embodiments, halo is chloro.
  • Preferred inorganic halides include ammonium halide and group (I) metal halides, such as potassium or sodium halide.
  • sodium iodide Most preferred is sodium iodide, potassium iodide and/or ammonium iodide. Also preferred is ammonium chloride.
  • the inorganic halide may be provided in any convenient physical form suitable for processing into a polyurethane foam composition.
  • the inorganic halide is provided as a divided solid such as crystalline, amorphous, conglomerate or granular form or the like, including particulate material and powdered material .
  • the polyurethane foam formulation includes a water component (e.g. as the blowing agent), and the inorganic halide is water-soluble, the aim is to avoid as much as possible dissolution in the water component, otherwise the successful formation of a foam can be compromised.
  • the inorganic halide should be incorporated into the foam mixture so that the final foam is formed successfully, and beneficially includes the inorganic component as a flame retarding agent. Avoidance of dissolution in the water component may be achieved by providing the inorganic halide with a relatively small surface area to reduce the amount of surface contact with the water component. This may be achieved by using relatively course granular material as opposed to finely divided material.
  • the size of the particulate will influence the efficacy of the material and its compatibility with a particular type of foam formulation.
  • approximate particle sizes useful for this purpose range from 10 microns to 10 mm more particularly 10 microns to 0.1 mm.
  • inorganic halides are readily available commercially.
  • a sparingly water-soluble inorganic halide may be used to advantage.
  • the influence of the solid inorganic halide particulate material on the formulation may be reduced by coating the particles with a passivation layer using methods known to those skilled in the art.
  • the inorganic halide particles may be provided with a water-protective coating such as a wax to reduce, inhibit or prevent dissolution through contact with the water component of the polyurethane foam.
  • a water-protective coating such as a wax to reduce, inhibit or prevent dissolution through contact with the water component of the polyurethane foam.
  • the use of an inorganic halide component in polyurethane foams offers an advantage over the organic halides in that the same problems are not encountered at least to the same extent.
  • the mixture according to the first aspect, or foam material according to the second aspect further comprises a further fire retardant.
  • One or more fire retardants may be present.
  • Suitable fire retardants include char promoting agents, such as including melamine, ammonium polyphosphate, trichloropropyl phosphate (TCPP) , triethyl phosphate (TEP) , diethyl ethyl phosphate
  • char promoting agents such as including melamine, ammonium polyphosphate, trichloropropyl phosphate (TCPP) , triethyl phosphate (TEP) , diethyl ethyl phosphate
  • the mixture or foam material according to the invention comprise melamine.
  • mixture or foam material according to the invention comprise APP. In other embodiments the mixture or foam material according to the invention comprise APP and melamine.
  • suitable fire retardants also include flame retardants, such as flame chemistry modifying agents and/or energy absorbers, such as brominated phthalic anhydride based ester, dibromoneopentyl glycol, brominated polyether polyol and aluminium oxide trihydrate or similar alternatives.
  • flame retardants such as flame chemistry modifying agents and/or energy absorbers, such as brominated phthalic anhydride based ester, dibromoneopentyl glycol, brominated polyether polyol and aluminium oxide trihydrate or similar alternatives.
  • melamine may be considered as an energy absorber in that energy is required for it to sublime, thereby acting primarily to stop the foam heating.
  • An alternative energy remover is aluminium trihydrate (ATH) which becomes converted into aluminium oxide by loss of water which requires energy, which otherwise would contribute to melting and degradation of the polymer.
  • ATH aluminium trihydrate
  • clay may be included as a fire retardant, which, without wishing to be bound by theory, is believed to reduce the flow of molten polymer during heating/combustion to inhibit progression of the combustion/polymer burning process, i.e. the clay acts as a rheology modifier. At higher clay levels, it is believed that clay may additionally act as a barrier to the evolution of gaseous decomposition products. During creation of the foam walls, it is believed that exfoliated clay platelets may in certain formulations be formed into structures which are advantageous in reducing gaseous emissions of degradation products .
  • the foam materials may generally require no or less other fire retarding agents if clay particles are dispersed therein to form a polyurethane composite material.
  • polyurethane composite material is defined herein as a polyurethane material having dispersed therein clay particles.
  • the clay particles may be partially or fully exfoliated. It is to be understood that the term exfoliated clay particles relates to clay particles which have been disrupted by suitable energy, which will be described in more detail hereinafter, to overcome the interactions between clay platelets.
  • the exfoliated clay particles includes particles which have been partially disrupted i.e. not all interactions between particles have been overcome and/or fully exfoliated clay particles in which all interactions between clay particles have been overcome.
  • foam material comprising a polyurethane composite material is generally defined to mean that a foam material is formed of a polyurethane composite material .
  • 'foam' and the foam materials described herein includes both so-called 'flexible' and 'rigid' foams.
  • the terms flexible and rigid to describe polyurethane foams are very well understood by those skilled in the art, and are regarded as terms of the art, referred to in, for example in the Kirk-Othmer Encyclopaedia of Chemical Technology.
  • flexible foams may be regarded as having open-cell structure, the cavities within the cell provide flexibility and compressibility characteristic of flexible foam, with so-called rigid foams having a more generally closed-cell structure.
  • open-cells is not a qualification synonymous with flexible nor closed-cell synonymous with rigid as a qualifier for polyurethane foam; rather flexible foams have a generally higher proportion of open cells than rigid foams and vice versa.
  • the rigidity of rigid foam may be achieved, for example, by incorporating a greater degree of cross-linking which leads to the greater concentration of closed-cell structures that lessen flexibility and compressibility.
  • flexible foam as a consequence of its more open-cell structure is generally understood to be a low density material, the most widely used examples of which are referred to as "water-blown" slabstock and moulded foams . Whilst resilience of the foam depends on factors such as cell size and degree of open cells, the quantity of open cells can vary widely.
  • Conventional flexible slabstock foams vary widely in density (from about 12 to about 120 kg irf 3 ) and hardness (from about 30 to about 500 N) .
  • the principal components that provide the polyurethane in flexible foams are typically toluene diisocyanate (typically in commercially produced foam about 80:20 of the 2,4: 2,6 regioisomeric ratio) and random propylene oxide- ethylene oxide polyether polyols of molecular of about 3000 to 4000
  • flexible and rigid foams are reflected in the applications in which they are typically used: flexible foams are often used as cushioning in seating, mattresses, pillows and sometimes cushioned soles in shoes; rigid foams are typically used as insulation for buildings, refrigerators and freezers .
  • a char-promoting agent such as melamine and/or another flame/fire retardant agent, as described above .
  • an amount of melamine may be added in reduced quantity to that conventionally used in the art, e.g. equal to or less than about 20% by weight of the total composition weight, preferably up to 15 wt% .
  • a particular amount of melamine is about 3 wt% .
  • solid melamine can resist effective incorporation into the polyurethane-forming mixture, and also is found to be abrasive, a lower quantity is preferred for these reasons also.
  • an amount of a phosphorus-containing fire-retardant is added in addition to the melamine (which contains nitrogen) to provide an effective fire retardation effect.
  • a nitrogen-phosphorus synergism allows reduced amounts of melamine to be used when a phosphorus-containing fire retardant is additionally used, compared to using melamine alone.
  • a preferred phosphorus-containing fire retardant is ammonium polyphosphate, which is preferably incorporated in solid particulate form.
  • d50 and d90 represent the median or the 50th percentile and the 90th percentile of the particle diameter size distribution. That is, the d50 (d90) is a value on the distribution such that 50% (90%) of the particles have a diameter of this value or less.
  • Nanoclays are clay materials in which the individual platelets are exfoliated or partially exfoliated as described hereinafter, and dispersed within the dispersing medium rather than existing as aggregated stacks of tactoids.
  • the nanoclay materials comprise platelet particles (tactoids) .
  • Effective exfoliation of clay particles improve the gas barrier properties of the foam and enhances char formation under combustion conditions .
  • Dripping of melted foam material is also substantially prevented or at least reduced. Dripping of melted material, particularly in situations where the melt drips into burning foam, can significantly fuel and aid the burning of the foam, and thus accelerate the combustion process.
  • the exfoliated clay appears to increase the viscosity of the foam during melting and therefore dripping is reduced or prevented.
  • the exfoliated clay particles may also reduce oxygen ingress into the foam matrix and reduce volatile product egress from the foam. However, increased clay content can prevent foam collapse during burning to leave open cavities which allow ingress of air/oxygen into the foam material to fuel the burning process.
  • the beneficial rheological (viscosity) properties which the clay brings to the foam to prevent dripping should be balanced against the detrimental foam stiffening properties of the clay during burning to allow oxygen to access the interior regions of the foam which maintains burning. This requires some foam stiffening, but not too much, so that foam collapse does occur to exclude oxygen. Incorporation of exfoliated clay particles can also present difficulties during foam formation, and result in a high viscosity of the composition when forming the foam, particularly the low shear viscosity, resulting in compromised rapid mixing of the composition.
  • Rapid and even mixing of a foam composition prior to foam formation can be important to ensure a homogeneous mixture of reactants is achieved before substantial foaming starts; this ensures as much as possible that a homogeneous foam material is formed with an even cellular distribution and a uniform dispersion of the exfoliated clay platelets.
  • coupling agents are molecules that attach, or couple, to dispersed or exfoliated clay particles serving to reduce the viscosity of dispersions of clay.
  • the inventors of the present invention have also found advantageous use of coupling agents with the clay materials, in particular where the viscosity of the mixture makes mixing difficult or the addition of the clay may inhibit foaming.
  • a coupling agent can advantageously provide a polyurethane foam composition having a viscosity desirable for manipulating the composition prior to foam formation, while maintaining at least some dispersed clay particles therein.
  • a coupling agent can advantageously provide a polyurethane foam composition having a viscosity desirable for manipulating the composition prior to foam formation, while maintaining at least some dispersed clay particles therein.
  • Coupling agents are known and are described in S.J.Monte and G. Sugerman, Kenrich Petrochemicals Inc and A. Damusis and P. Patel Polymer Institute University of Detroit, "Application of Titanate Coupling Agents in Mineral and Glass Fibre Filled RIM Urethane Systems," SPI Urethane Div, 26 th Annual Conference (Nov. 1981). Polyurethanes with inorganic fillers, Nippon Soda Co Ltd, Jpn Kokai Tokkyo Koho JP 60, 71625 28 Sep 1983. all of which are incorporated herein by reference.
  • the coupling agents are described as reducing the viscosity of various polymer compositions . Without wishing to be bound by any particular theory, it is proposed that the coupling agent is able to add to positive sites on the edges of the clay particles which results in blocking the formation of viscosity enhancing 'house of cards' platelet structures.
  • Advantageous coupling agents for use in the present invention comprise neoalkoxy titanate or neoalkoxy zirconate agents.
  • neoalkoxy titanate agent neopentyl (diallyl) oxy tri(dioctyl) phosphato titanate which has the formula (I) indicated below, and is known by the tradename LICA® 12.
  • the coupling agent may be incorporated into a foamed polyurethane composite material at an amount of above 0 to about 10% by weight of the total foam composition weight.
  • An amount of coupling agent of from about 0.001% to about 6% preferably 0.005 to 2% of the weight of the clay in the total foam composition may be used.
  • too much clay material can increase the viscosity of the foam material too much during melting whilst burning, keeping the foam structure open which aids oxygen availability to the foam and maintains burning.
  • a reduction in clay amount to allow at least some foam collapse during burning, but prevent excessive dripping is desirable.
  • Clay materials are natural or artificial minerals comprising particles in the form of platelets, and include smectite, bentonite, vermiculite and halloysite clays.
  • the smectite type can be further categorised into montmorillonite, saponite, beidellite, nontrite, and hectorite.
  • An artifical clay material is for example laponite.
  • a preferred clay material for use in the present invention is bentonite.
  • Another preferred clay material for use in the present invention is vermiculite.
  • An alternative clay material for use in the present invention is a montmorillonite clay which is an aluminosilicate clay of formula: M + y (Al 2 - y Mg y ) (Si 4 )Oi 0 (OH) 2 nH 2 O
  • Suitable montmorillonite clays for use in the present invention may be obtained commercially under the trade name Cloisite® e.g. Cloisite® 6A, Cloisite® 15A, Cloisite® 2OA, Cloisite® 1OA, Cloisite® 25A, Cloisite® 3OB and Cloisite® Na * . These are termed organically modified clay materials but may or may not incorporate an organic modifier.
  • the amount of clay incorporated into the foam composition is generally from zero to about 20% by weight of the total foam composition weight.
  • the amount of clay may be from zero to about 15% by weight of the total foam composition weight.
  • the amount of incorporated clay is from about zero to about 10% by weight of the total foam composition weight, most preferably zero to 5% by weight, e.g. 3%-5% by weight of the total foam composition weight, such as 3% by weight.
  • the exfoliated nanoclay platelets have a thickness of around 1 run and a size in the planar direction of around 0.01 ⁇ m to 100 ⁇ m.
  • d90 30-45 micron
  • d50 10-32 micron.
  • Each individual platelet particle may have a length/thickness ratio of around 200-1000.
  • clay particles having a smaller length to thickness ratio are preferred, such as vermiculite clays, which exfoliate more readily.
  • the clay such as vermiculite
  • the clay is provided as a fine micronized dispersion.
  • a preferred dispersion would be completely exfoliated clay platelets but enhancement over existing foams may be achieved with partially exfoliated clay particles.
  • the platelets generally aggregate together with the planar surfaces adjacent, into stack structures. The space between the platelets in these stacks is generally known as a gallery. The separation of the platelets across the gallery is generally of the order of 3-5 A. In organically modified clay particles the gallery separation has been increased to a value of the order of 18 A.
  • the clay minerals have undergone a cation exchange with at least one cationic organic species.
  • sodium ions on the surface of the clay particles may be exchanged with the cationic organic species .
  • the cationic organic species may comprise for example a quarternary ammonium ion species or an onium species .
  • alkyl ammonium ions e.g. dimethyl dihydrogenatedtallow ammonium, which has the following formula:
  • dimethyl benzylhydrogenatedtallow ammonium which has the following formula:
  • the inventors believe that the cationic organic species modify the surface of the clay particles.
  • the inventors believe that the organic modifier changes the hydrophobicity of the platelet surface thereby enabling better dispersibility of the platelet particles within a hydrophobic polymer material.
  • a cationic organic species may enhance the compatibility of the clay particles with the polymer material.
  • the gallery space separation of clay platelets may be increased through treatment with a cationic organic species to allow the polymer material to enter the gallery space. This may advantageously result in an increased dispersibility of the platelets within the polymer material.
  • polyurethane foams may be made through the use of external addition of a gas or in situ on generation of the polyurethane or a combination of these two mechanisms.
  • the foam-forming gas or a gas precursor material is generally known as a blowing agent.
  • Preferred foam compositions are those in which the gas for forming the foam is generated in situ.
  • the gas may be generated through chemical reaction of a constituent of the foam forming composition.
  • Preferred polyurethane formulations of this type are polyurethanes that generate carbon dioxide gas on mixing the starting materials required for forming the polymer.
  • polyurethane foam typically refers to an open-celled flexible product obtained by reacting a polyisocyanate with isocyanate-reactive hydrogen containing compounds and a foaming agent .
  • the foaming agent or the blowing agent generally used for a polyurethane foam is carbon dioxide, which is generated by the reaction of water with isocyanate groups to give urea linkages and a polyurea-urethane foam.
  • the isocyanate-reactive hydrogen containing compounds may be chosen from polyols, aminoalcohols and/or polyamines .
  • polyols examples include reaction products of alkylene oxide, for example ethylene oxide and propylene oxide; polyesters obtained by the condensation of glycols and higher functionality polyols with polycarboxylic acids; hydroxyl terminated polythioethers; polyamides; polyesteramides ; polycarbonates; polyacetals; and polysiloxanes .
  • isocyanate-reactive compounds include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butane diol, glycerol, trimethylolpropane, ethylene diamine, ethanolamine, diethanolamine, triethanolamine, pentaerythritol, sorbitol, sucrose, polyamines such as ethylene diamine, tolylene diamine, diaminodiphenylmethane and polymethylene polyphenylene polyamines, and aminoalcohols such as ethanolamine and diethanolamine and mixtures thereof .
  • flexible foams are made from random propylene oxide-ethylene oxide polyether polyols of molecular of about 3000 to 4000. Typically the ethylene oxide content in such polyols is about 15% or less. Where very soft foams are desired, the amount of ethylene oxide in the polyol may be increased.
  • polyester polyols rather than polyether polyols, are used. These are typically based on glycol adipates having molecular weights of about 1500 to about 3000. The majority of moulded foams (for example for automotive seating) are based on high molecular weight ethylene oxide-tipped polyols having molecular weights of 5000 to 6000 molecular weight.
  • a flexible polyurethane foam may be prepared by reacting a polyisocyanate with a relatively high molecular weight isocyanate-reactive polymer, e.g. a polyester or polyether polyol, in the presence of a blowing agent and typically including additives such as catalysts, surfactants, fire retardants, stabilisers and/or antioxidants .
  • Suitable surfactants would include polyoxyalkylene polysiloxane copolymers or related materials. It shall be understood that the skilled person will readily determine the amounts of additives required to form a polyurethane foam having certain desired characteristics, such as successful, stable foam formation of intended density. Specific amounts of the components from which a polyurethane foamed material may be formed may be thus determined using the normal skill of the person skilled in the art. As is typical in the art, the quantities of components are typically are expressed in parts by weight of (pbw) or parts per weight (ppw) the mixture from which polyurethane foam is formed. Typically this is with reference to the polyol from which the polyurethanes are formed.
  • the quantity of polyol present in a mixture is 100 pbw or ppw and the other components' quantities defined relative to this.
  • the quantities of polyol present in a mixture are 100 pbw or ppw and the other components' quantities defined relative to this.
  • a typical amount of the phosphorus-containing material is in the range of up to about 30 wt% . This means that 30 parts (by weight) of phosphorus-containing material is added to the composition, with respect to 100 parts (by weight) of polyol .
  • Typical amounts of materials used to make foams according to this invention, and thus present in the mixture from which the foam polyurethanes are formed are: polyol and/or amine (100 pbw) ; diisocyanate (about 40 to about 50 pbw) ; inorganic halide (about 1 to about 10 pbw e.g. about 2 to about 5 pbw) ; blowing agent (e.g. water) (about 1 to about 5 pbw) ; phosphorus-containing material (if present) (about
  • char-promoting agent e.g. melamine
  • nanoclay if present
  • a typical formulation of the present invention comprises the following components:
  • the flexible foam may be prepared according to the one-shot process where the urethane and urea reactions occur simultaneously or using the quasi or semi prepolymer or prepolymer processes .
  • the polyol is first reacted with an excess of isocyanate and the resulting isocyanate prepolymer reacted in a second step with water and the other additives.
  • Flexible foams prepared by the reactive mixing of an isocyanate with a polyol and/or amine may be used to produce moulded foams or generate slabstock foams for use for example as cushioning material in furniture and automotive seating, in mattresses, as carpet backing, foam in diapers, packaging foam, or sound insulation foam.
  • Polyisocyanates for use in the present invention include any of those known in the art for preparing polyurethanes . For example, aliphatic, cycloaliphatic, aryl-aliphatic and aromatic polyisocyanates. Examples of aromatic polyisocyanates include toluene diisocyanate (TDI) e.g.
  • diphenylmethane diisocyanate e.g. the 2,4'-, 2,2'- and 4 , 4 ' -isomers , polymeric isocyanates and isocyanurates, thereof and mixtures thereof, including oligomers thereof.
  • the diisocyanate used to make polyurethane foam is either TDI or MDI and typically each of these are used as mixtures of regioisomers .
  • the diisocyanate typically used to make polyurethane foams comprises a mixture of 80 parts of the 2, 4 '-isomer to 20 parts of the
  • TDI 80:20 This mixture of TDI is commonly referred to as TDI 80:20 in the art.
  • Other regioisomeric mixtures may also be used, for example TDI 65:35.
  • the diisocyanate is MDI. In other embodiments of the invention the diisocyanate is TDI .
  • Diphenylmethane diisocyanate is preferred in certain embodiments of the invention.
  • the mixtures comprise TDI, or mixtures thereof.
  • the diisocyanate is typically TDI or mixtures thereof.
  • rigid foams typically comprise MDI, including regioisomeric mixtures thereof.
  • the present invention in a third aspect provides a method of making a foam material comprising: providing a mixture comprising components required for forming a foamed polyurethane and an inorganic halide for dispersion within said foamed polyurethane, and forming the mixture into a foam material .
  • the foamed material formed by this method may be a flexible or rigid foam material .
  • the mixture comprising components required for forming a foamed polyurethane is previously defined and may further comprise additional preferred components as described hereinbefore, such as clay.
  • the mixture may be provided according to any suitable technique.
  • the inventors have found that the fire retardant properties of the foam composite material benefit from incorporation of clay material which has been subjected to high shear mixing with at least one of the components required for forming the foamed polyurethane e.g. the polyol .
  • High shear mixing may be achieved with a mechanical mixer such as an Ultraturrax mixer.
  • a mechanical mixer such as an Ultraturrax mixer.
  • mechanical mixing alone may not optimise the dispersion of the clay particles into an exfoliated state for certain clays in certain formulations .
  • the use of ultrasound in the presence or absence of mechanical stirring provides an effective means for dispersion of the clay particles within the foam composition into an exfoliated state.
  • the ultrasound is applied as high frequency ultrasound.
  • the frequency range will typically be in the range 1 kHz to 10 MHz but will preferably be in the kilo hertz frequency range.
  • the ultrasound may be applied simultaneously with mechanical mixing .
  • the ultrasound may be applied for a period of time sufficient to achieve desired exfoliation. Depending on the type of process being adopted this could be between for example 0.1 seconds to 2 hours.
  • the ultrasound is applied for a period of time of from 10 seconds to 30 minutes.
  • the ultrasound is applied for a period of time of from 30 seconds to 20 minutes, e.g. 15 minutes .
  • microwaves, infrared radiation or other electromagnetic radiation may be applied to the nanocomposite formulation to achieve dispersion and exfoliation of the clay particles.
  • the effective dispersion of the clay particles in the composition is believed to be associated with the ability to couple energy selectively into molecular species which are capable of supplying the necessary energy to overcome the interactions between the clay platelets.
  • the frequency chosen is preferably that which is associated with binding of water molecules to inorganic species and the hypothesis is that these molecules are selectively excited by the ultrasound which results in exfoliation of the clay particles. Similar mechanisms for the provision of energy to the galleries may be used with other selective forms of irradiation.
  • the Applicant has observed that the use of a coupling agent for modifying the rheological properties of the mixture may be dispensed with when using vermiculite clays in particular.
  • a process for preparing a polyurethane foam comprising the steps of: providing a polyol, inorganic halide, polyisocyanate, water, optionally a clay material, and optionally at least one coupling agent; suitably mixing the components to provide a dispersed mixture; and allowing the dispersed mixture to form a final foamed polyurethane composition.
  • the foam is allowed to cure to form a final polyurethane foam material, such as a nanocomposite foam material.
  • the water may be added before, at the same time, or after the introduction of the polyisocyanate.
  • a typical process comprises the steps of: a) providing one or more clay materials, such as vermiculite, together with other optional solid components: b) providing a polyol, and mixing the components of step a) with the polyol to form a homogenous mixture; c) providing desirable, but optional, components selected from catalysts, amines and surfactants, and introducing and stirring said components together with the mixture obtained from step b) to form a homogeneous mixture; d) providing a solid inorganic halide compound and introducing and dispersing the compound into the mixture obtained from step c); e) providing water and an isocyanate and introducing and dispersing same into the mixture obtained from step d) ; and f) allowing the resultant mixture obtained from step e) to form a foamed polyurethane composition.
  • the mixture obtained from step e) may be transferred to a mould prior to step f) .
  • step f) the composition is allowed to cure.
  • the resultant combination of components may be mechanically mixed prior to foam formation.
  • the solid components may be dispersed using high shear mixing, the dispersal taking place in one or more of the liquid components.
  • the composition Prior to forming the foam nanocomposite material, the composition is usually introduced into a mould to contain the composition during foam formation, or allowed to form a free foaming slab. At least one of the above mixing steps may be carried out simultaneously with the introduction of the composition into the mould or into a free foaming slab form.
  • the composition is introduced into the mould or slab forming structure by means of a reaction injection moulding device.
  • a coupling agent as defined hereinbefore may be introduced during the preparation process .
  • the coupling agent may be provided in the polyol containing mixture.
  • composition may additionally contain other additives, such as clay, catalysts, surfactants, additional fire or flame retarding agents, char promoting agents, stabilisers, colourants and antioxidants .
  • additives such as clay, catalysts, surfactants, additional fire or flame retarding agents, char promoting agents, stabilisers, colourants and antioxidants .
  • these other additives are provided in the polyol containing mixture. If ultrasound is applied, the mixture is preferably stirred and cooled during the application of the ultrasound.
  • the clay particles may comprise any of the clay materials described herein above. Vermiculite and/or cloisite clay particles are preferred, most preferably vermiculite.
  • the polyisocyanate is based on methylenediphenyl diisocyanate or toluene diisocyanate.
  • methylenediphenyl diisocyanate Most preferred is methylenediphenyl diisocyanate.
  • the mixing of the components to achieve the mixture prior to polymerization should be carried out so as to reflect the ability to disperse the components in a satisfactory manner.
  • the mixing protocol to achieve the desired dispersion of the components would reflect the manufacturing process and be appropriate to the manufacturing process and adjusted in the normal fashion known to those skilled in the art.
  • a polyurethane foam material obtainable by the process according to the fourth aspect.
  • an inorganic halide material as a fire retardant in a polyurethane foam material preferably a polyurethane nanoclay foam composite or foam nanocomposite material.
  • Burn testing was performed on the following fire retardant flexible foam formulation using the test method specified in BS 5852 (Section 4 1990) Part II, Methods of test for assessment of the ignitability of upholstered seating by smouldering and flaming ignition sources, which is incorporated herein in its entirety by reference:
  • a test rig is constructed in order to simulate a chair with the fabric to be tested. This rig is subjected to different ignition sources to examine the burning behaviour of a test material.
  • ignition sources There are 8 types of ignition sources, each with different heat intensity. They are classified from 1 to 8, the intensity doubling compared to the preceding source. The most frequently used are ignition source 0, 1 and 5.
  • smouldering cigarette A cigarette is put along the crevice of the test rig and allowed to burn over its entire length. If no flaming or progressive smouldering is observed on both cover and interior material, the test is recorded as no ignition and the material passes the test.
  • -Source 1 simulated match A burner is lighted, held along the crevice of the test rig for 20s and then removed. If no flaming or progressive smouldering is observed on both cover and interior material, the test is recorded as no ignition and the material passes the test.
  • -Source 5 wooden crib 5.
  • a crib is composed of wooden planks, glued together. Lint is attached to the bottom. After adding propane-diol the crib is placed on the test rig and ignited with a match. If no flaming or progressive smouldering is observed on both cover and interior material, the test is recorded as no ignition and the material passes the test. Result
  • test material passes or fails this test (shown as “Y” if tested and “F” if failed and M P" if passed in Table 1 below (column headed “Crib V”).
  • a small scale crib test was used to evaluate the materials. Two pieces of foam approximately 15 cm x 15 cm x 2 cm were placed in the form of 'crib' . One piece being placed vertical and the other piece being horizontal. A piece of cotton loaded with 1 ml of propan-2-ol was placed at the base of the vertical slab and ignited. The loss designed is the difference between the original and the final weights of the foam slabs used in the test. The test was recorded using a video camera. The results are shown in Tables 1 and 2 below.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention porte d'une manière générale sur des compositions de mousse de polyuréthane qui incorporent une matière de type halogénure inorganique. L'invention porte également sur les mousses formées à partir des compositions, sur la préparation des mousses et sur leur utilisation.
PCT/GB2008/002347 2007-07-11 2008-07-10 Mousses de polyuréthane retardatrices de flamme Ceased WO2009007715A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0713394A GB0713394D0 (en) 2007-07-11 2007-07-11 Fire retarded polyurethane foams
GB0713394.5 2007-07-11

Publications (1)

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WO2009007715A1 true WO2009007715A1 (fr) 2009-01-15

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GB (1) GB0713394D0 (fr)
WO (1) WO2009007715A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104017018A (zh) * 2014-06-13 2014-09-03 四川大学 磷酸多元醇酯多价金属盐的制备方法
WO2017043984A1 (fr) * 2015-09-07 2017-03-16 Politechnika Rzeszowska im. Ignacego Łukasiewicza Mousse de polyuréthane souple présentant une inflammabilité réduite et son procédé de production
WO2018202417A1 (fr) * 2017-05-05 2018-11-08 Arcelik Anonim Sirketi Refroidisseur
CN114174366A (zh) * 2019-07-12 2022-03-11 陶氏环球技术有限责任公司 具有改进的燃烧性能的聚氨酯泡沫
CN115024189A (zh) * 2022-05-07 2022-09-09 大连地拓环境科技有限公司 一种多功能立体绿化海绵基质及其制备方法
WO2023129067A1 (fr) * 2021-12-28 2023-07-06 Sabanci Üniversitesi Matériau polymère pour préserver la fraîcheur de produits alimentaires

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US3574148A (en) * 1968-03-07 1971-04-06 Bayer Ag Cellular polyurethane plastics
US4080345A (en) * 1973-08-21 1978-03-21 Metzeler Schaum Gmbh Catalyst mixture for use in trimerizing and/or polymerizing isocyanates and/or for the polyaddition of active hydrogen atom containing polyethers and polyisocyanates
US4575518A (en) * 1983-12-30 1986-03-11 Bayer Aktiengesellschaft Homogeneous storage stable salt-containing mixture
US4686240A (en) * 1985-10-25 1987-08-11 Union Carbide Corporation Process for producing polyurethane foams using foam modifiers
US4743624A (en) * 1987-06-11 1988-05-10 Blount David H Process for the production of flame-retardant polyurethane products
US5106884A (en) * 1988-10-28 1992-04-21 The Dow Chemical Company Flexible polyurea foams having controlled load bearing qualities
WO2002068489A1 (fr) * 2001-02-23 2002-09-06 Cellular Technology International, Inc. Additifs antistatiques comprenant des composes ioniques tetrahalogenes destines la preparation de compositions polymeres d'emballage

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Publication number Priority date Publication date Assignee Title
US3162609A (en) * 1960-05-31 1964-12-22 Dow Chemical Co Self-extinguishing urethane polymer compositions
US3574148A (en) * 1968-03-07 1971-04-06 Bayer Ag Cellular polyurethane plastics
US4080345A (en) * 1973-08-21 1978-03-21 Metzeler Schaum Gmbh Catalyst mixture for use in trimerizing and/or polymerizing isocyanates and/or for the polyaddition of active hydrogen atom containing polyethers and polyisocyanates
US4575518A (en) * 1983-12-30 1986-03-11 Bayer Aktiengesellschaft Homogeneous storage stable salt-containing mixture
US4686240A (en) * 1985-10-25 1987-08-11 Union Carbide Corporation Process for producing polyurethane foams using foam modifiers
US4743624A (en) * 1987-06-11 1988-05-10 Blount David H Process for the production of flame-retardant polyurethane products
US5106884A (en) * 1988-10-28 1992-04-21 The Dow Chemical Company Flexible polyurea foams having controlled load bearing qualities
WO2002068489A1 (fr) * 2001-02-23 2002-09-06 Cellular Technology International, Inc. Additifs antistatiques comprenant des composes ioniques tetrahalogenes destines la preparation de compositions polymeres d'emballage

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104017018A (zh) * 2014-06-13 2014-09-03 四川大学 磷酸多元醇酯多价金属盐的制备方法
WO2017043984A1 (fr) * 2015-09-07 2017-03-16 Politechnika Rzeszowska im. Ignacego Łukasiewicza Mousse de polyuréthane souple présentant une inflammabilité réduite et son procédé de production
WO2018202417A1 (fr) * 2017-05-05 2018-11-08 Arcelik Anonim Sirketi Refroidisseur
CN114174366A (zh) * 2019-07-12 2022-03-11 陶氏环球技术有限责任公司 具有改进的燃烧性能的聚氨酯泡沫
WO2023129067A1 (fr) * 2021-12-28 2023-07-06 Sabanci Üniversitesi Matériau polymère pour préserver la fraîcheur de produits alimentaires
CN115024189A (zh) * 2022-05-07 2022-09-09 大连地拓环境科技有限公司 一种多功能立体绿化海绵基质及其制备方法

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