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WO2013007509A1 - Formulation permettant d'obtenir un polyuréthanne - Google Patents

Formulation permettant d'obtenir un polyuréthanne Download PDF

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Publication number
WO2013007509A1
WO2013007509A1 PCT/EP2012/062299 EP2012062299W WO2013007509A1 WO 2013007509 A1 WO2013007509 A1 WO 2013007509A1 EP 2012062299 W EP2012062299 W EP 2012062299W WO 2013007509 A1 WO2013007509 A1 WO 2013007509A1
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Prior art keywords
polyurethane
phosphate
formulation
polyurethane product
product
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PCT/EP2012/062299
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English (en)
Inventor
Rene Alexander Klein
Giacomo GIANNINI
Christopher Ian Lindsay
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Huntsman International Llc
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Publication of WO2013007509A1 publication Critical patent/WO2013007509A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts
    • 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
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/5205—Salts of P-acids with N-bases
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/325—Calcium, strontium or barium phosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • the present invention relates to formulations suitable to provide polyurethane and polyurethanes obtained by reacting said formulations.
  • Formulations suitable to provide polyurethane (PU) and polyurethanes obtained by reacting said formulations are well known in the art.
  • Polyurethane mainly flexible and rigid foams, is used in transportation, refrigeration, home furnishing, building and construction, marine, and business machines. For many of these products, it is necessary to add flame retardants to the polyurethane.
  • flame retardants to the polyurethane.
  • polyurethane since most of the end applications are internal, polyurethane is in a critical situation and directly subjected to increasingly stringent regulations which on one side require high fire safety standards and on the other side limit the use of potentially toxic but extremely effective flame retardants.
  • Halogenated fire retardants are generally very effective, requiring relatively small quantities to be added in the final product in order to obtain outstanding flame retardant properties, but they have been included in the list of priority pollutant as a hazardous priority pollutant, and their use is being limited.
  • flame retardants can actually reduce the product's physical properties, cause processing problems and shorten the useful life of a product if they are not compatible with the material itself or other additives.
  • Some halogenated flame retardants are very effective at concentrations of a few percent whereas many inorganic flame retardants require concentrations of 30% or higher, thus degrading the mechanical value of the plastic part.
  • more environmental- friendly flame retardants are used in the place of halogenated compounds, such as inorganics or melamine, a compromise has to be found between the achieving of acceptable fire properties and the high load required, which is detrimental to the material performance.
  • a formulation suitable to provide polyurethane comprises:
  • phosphate component selected from the group consisting of ammonium polyphosphate (APP), and melamine phosphates and mixtures thereof, and;
  • metal phosphate particle wherein the metal is selected from the group consisting of Ca, Mg, Al and Zn.
  • the present invention also encompasses a polyurethane product, obtained by reacting a formulation according to the first aspect of the invention.
  • the polyurethane products obtained by reacting a formulation according to the first aspect of the present invention surprisingly show improved fire resistance properties.
  • This combination of ingredients produces a reduction of peak heat release rate (PHR ) and total heat released (THR) in cone calorimeter experiments.
  • the invention can be used to achieve extremely high fire performances.
  • phosphate component selected from the group consisting of ammonium polyphosphate (APP) and melamine phosphates and mixtures thereof, preferably the phosphate component comprises or even consists of ammonium polyphosphate and;
  • particles of metal phosphates are selected from the group comprising tricalcium phosphate, hydroxyapatite, dicalcium phosphate, monocalcium phosphate, magnesium phosphate, aluminium phosphate, and zinc phosphate or combination thereof, preferably tricalcium phosphate particles, dicalcium phosphate particles, hydroxyapatite particles, or combination thereof.
  • the formulation according to the invention comprises: (a) at least one polyurethane forming mixture; (b) at least one phosphate component selected from the group consisting of ammonium polyphosphate (APP) and melamine phosphates and mixtures thereof, and; (c) at least one metal phosphate particle, wherein the metal phosphate particle is selected from the group comprising tricalcium phosphate, hydroxyapatite, dicalcium phosphate, monocalcium phosphate, magnesium phosphate, aluminium phosphate, and zinc phosphate or combination thereof; tricalcium phosphate particles, dicalcium phosphate particles, hydroxyapatite particles or a combination thereof.
  • the metal phosphate particles may be micro-, or nano-particles.
  • Particles smaller than 300 ⁇ may be used in order to minimize disruption of the foam cell structure.
  • micro-particles “micron-particles” “micron-sized particles” “micro-sized particles” are to be understood as particles having an average diameter of between 0.1 ⁇ and 300 ⁇ , more preferably 0.1 ⁇ and 150 ⁇ .
  • nano-particles or “nano-sized particles” are to be understood as particles having an average diameter of between 1 nanometer and 100 nanometers.
  • the at least one metal phosphate particle may have a maximum particle size (D99) of less than 300 ⁇ , e.g. less than 200 ⁇ , even less then 170 ⁇ , e.g. less than 150 ⁇ .
  • the at least one metal phosphate particle may have a maximum particle size (D99) of less than 100 ⁇ , such as less than 50 ⁇ , for example of less than 30 ⁇ , for example of less than 20 ⁇ , for example of less than 10 ⁇ , e.g. less than 1 ⁇ .
  • particle average size may be expressed as "Dxx" where the "xx" is the volume percent of that particle having a size equal to or less than the Dxx.
  • the D99 is defined as the particle size for which ninety-nine percent by volume of the particles has a size lower than the D99.
  • the D50 can be measured by sieving, by BET surface measurement, or by laser diffraction analysis.
  • the amount of the metal phosphate particles, preferably of tri-calcium phosphate , dicalcium phosphate, hydroxyapatite or a combination thereof in the formulation can range from 0.2 to 10% by weight based on 100% by weight of the formulation, e.g., from 0.2%> to 8% by weight.
  • the amount of metal phosphate in the formulation is ranging between 0.5 % to 6 % by weight.
  • the ratio of weight % of the at least one metal phosphate particle over the weight % of the phosphate component is in the range of 0.01 to 0.3, preferably 0.01 to 0.2, preferably from 0.02 to 0.14, more preferred in the range of 0.02 to 0.11 yet more preferably from 0.03 to 0.08.
  • the weight % of the phosphate component and the weight % of the metal phosphate particles both refer to the weight of the component, either the metal phosphate particles or the phosphate component, over the total weight of the formulation.
  • the formulation comprises a phosphate component selected from the group consisting of ammonium polyphosphate and melamine phosphates, and mixtures thereof.
  • the phosphate component may comprise at least one melamine phosphate selected from the group consisting of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate.
  • the phosphate component comprises Ammonium polyphosphate.
  • Ammonium polyphosphate is known and described as, for example, a flame retardant.
  • Ammonium polyphosphate is an inorganic salt of polyphosphoric acid and ammonia.
  • the chemical formula of ammonium polyphosphate is [NH 4 P0 3 ] n and corresponds to the general formula (I), wherein n is greater than 100:
  • the chain length (n) of this polymeric compound is both variable and can be branched, and can be greater than 100, preferably greater than 1000.
  • the ammonium polyphosphate has the general formula (II):
  • n greater than 100, preferably greater than 1000.
  • the phosphate component can be a melamine phosphate compound selected from the group consisting of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate, or a mixture thereof.
  • the melamine phosphate compound has general formula (III):
  • the phosphate component may or may not be encapsulated.
  • Suitable non encapsulated phosphate component can be readily available commercially, under the tradename Exolit AP-422 from Clariant, FR Cros 484 from Budenheim, Antiblaze LR3 from Albemarle, APP1001 from Dgtech International and Aflammit PCI 202 from Thor.
  • the phosphate component in particular a polyphosphate, is encapsulated.
  • encapsulated ammonium polyphosphate are described in U.S. Patent Nos. 4,347,334, 4,467,056, 4,514,328, and 4,639,331 hereby incorporated by reference.
  • Such encapsulated ammonium polyphosphates contain a hardened, water insoluble resin enveloping the individual ammonium polyphosphate particles.
  • the resin may be a phenol- formaldehyde resin, an epoxy resin, a surface reacted silane, a surface reacted melamine or a melamine-formaldehyde resin.
  • the encapsulated ammonium polyphosphate flame retardant available under the trademark FR CROS C 60, FR CROS C30, FR CROS C70 from Chemische Fabrik Budenheim, Budenheim am Rhein, Germany, EXOLIT 462 from Hoechst Celanese Corporation, Somerville, N.J.
  • the encapsulated ammonium polyphosphate flame retardant can be a melamine-formaldehyde encapsulated ammonium polyphosphate additive.
  • Suitable encapsulated melamine compounds are described in US 6,015,510 hereby incorporated by reference.
  • Such melamine compounds contain an outer coating.
  • Such coating compounds may comprise organo silanes such as alkyl silanes, amino silanes, mixtures of alkyl silanes and polysiloxanes; esters; polyols; dicarboxylic acids; aromatic or aliphatic dianhydrides; melamine formaldehyde; and mixtures thereof.
  • the phosphate component and preferably ammonium polyphosphate, can be present in the flame retardant composition in an amount ranging from 10% to 50% by weight based on 100% by weight of the formulation, preferably from 12 to 45% by weight, more preferably from 15 to 40% by weight.
  • the formulation comprises at least one polyurethane forming mixture.
  • the at least one polyurethane forming mixture is present in the formulation in an amount ranging from 30 to 90% by weight based on 100% by weight of the formulation, preferably from 50 to 80% by weight, more preferably from 60 to 75% by weight.
  • the polyurethane forming mixture may comprise: at least one isocyanate compound; and at least one isocyanate reactive component.
  • the present invention is useful for its flame retardant effects in polyurethane and polyurea materials and in particular in polyurethane and polyurea foams.
  • Polyurea materials can be made by reacting an isocyanate compound, preferably a polyisocyanate and at least one polyamine and polyurethanes can be made by reacting an isocyanate compound preferably polyisocyanates with one of more polyols.
  • Polyamine may be selected from any suitable type of polyamines, such as polyether polyamines.
  • Isocyanate compounds are preferably polyisocyanate compounds.
  • Suitable polyisocyanates used may be aliphatic, araliphatic and/or aromatic polyisocyanates, typically of the type R- (NCO) x with x being at least 2 and R being an aromatic, aliphatic or combined aromatic/aliphatic group.
  • R are diphenylmethane, toluene, dicyclohexylmethane, hexamethylene, or groups providing a similar polyisocyanate.
  • Non-limiting examples of suitable polyisocyanates are diphenylmethane diisocyanate (MDI) - type isocyanates in the form of its 2,4'-, 2,2'- and 4,4'-isomers and mixtures thereof (also referred to as pure MDI), the mixtures of diphenylmethane diisocyanates (MDI) and oligomers thereof (known in the art as "crude” or polymeric MDI ), and reaction products of polyisocyanates (e.g. polyisocyanates as set out above), with components containing isocyanate-reactive hydrogen atoms forming polymeric polyisocyanates or so-called prepolymers.
  • MDI diphenylmethane diisocyanate
  • oligomers thereof known in the art as "crude” or polymeric MDI
  • reaction products of polyisocyanates e.g. polyisocyanates as set out above
  • components containing isocyanate-reactive hydrogen atoms forming polymeric polyis
  • tolylene diisocyanate also known as toluene diisocyanate, and referred to as TDI
  • TDI tolylene diisocyanate
  • 2,4 TDI and 2,6 TDI in any suitable isomer mixture
  • HMDI or HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • butylene diisocyanate trimethylhexamethylene diisocyanate
  • di(isocyanatocyclohexyl)methane e.g.
  • 4,4'-diisocyanatodicyclohexylmethane (f1 ⁇ 2MDI), isocyanatomethyl-l,8-octane diisocyanate and tetramethylxylene diisocyanate (TMXDI), 1,5-naphtalenediisocyanate (NDI), p-phenylenediisocyanate (PPDI), 1,4- cyclohexanediisocyanate (CDI), tolidine diisocyanate (TODI), any suitable mixture of these polyisocyanates, and any suitable mixture of one or more of these polyisocyanates with MDI-type polyisocyanates.
  • TXDI 4,4'-diisocyanatodicyclohexylmethane
  • NDI 1,5-naphtalenediisocyanate
  • PPDI p-phenylenediisocyanate
  • CDI 1,4- cyclohexanediiso
  • the polyurethane is generally prepared by reacting a polyisocyanate with isocyanate reactive components which are typically components containing isocyanate-reactive hydrogen atoms, such as a hydroxyl terminated polyester (polyester polyols), a hydroxyl terminated polyether (polyether polyols), a hydroxyl terminated polycarbonate or mixture thereof, with one or more chain extenders, all of which are well known to those skilled in the art.
  • isocyanate reactive components which are typically components containing isocyanate-reactive hydrogen atoms, such as a hydroxyl terminated polyester (polyester polyols), a hydroxyl terminated polyether (polyether polyols), a hydroxyl terminated polycarbonate or mixture thereof, with one or more chain extenders, all of which are well known to those skilled in the art.
  • the hydroxyl terminated polyester intermediate (polyester polyols),can be generally a linear polyester having a number average molecular weight (Mn) of from about 500 to about 10000, desirably from about 700 to about 5000, and preferably from about 700 to about 4000, an acid number generally less than 1.3 and preferably less than 0.8.
  • Mn number average molecular weight
  • the molecular weight is determined by assay of the terminal functional groups and is related to the number average molecular weight.
  • the polymers are produced by (1) an esterification reaction of one or more glycols with one or more dicarboxylic acids or anhydrides or (2) by transesterification reaction, i.e. the reaction of one or more glycols with esters of dicarboxylic acids.
  • Suitable polyester intermediates also include various lactones such as polycaprolactone typically made from caprolactone and a bifunctional initiator such as diethylene glycol.
  • the dicarboxylic acids of the desired polyester can be aliphatic, cycloaliphatic, aromatic, or combinations thereof.
  • Suitable dicarboxylic acids which can be used alone or in mixtures generally have a total of from 4 to 15 carbon atoms and include: succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, dodecanedioic, isophthalic, terephthalic, cyclohexane dicarboxylic, and the like.
  • Anhydrides of the above dicarboxylic acids such as phthalic anhydride, tetrahydrophthalic anhydride, or the like, can also be used.
  • Adipic acid is the preferred acid.
  • the glycols which are reacted to form a desirable polyester intermediate can be aliphatic, aromatic, or combinations thereof, and have a total of from 2 to 12 carbon atoms, and include ethylene glycol, 1 ,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2- dimethyl- 1,3-propanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, and the like.
  • 1,4-Butanediol is the preferred glycol.
  • Hydroxyl terminated polyether intermediates are preferably polyether polyols derived from a diol or polyol having a total of from 2 to 15 carbon atoms, preferably an alkyl diol or glycol which is reacted with an ether comprising an alkylene oxide having from 2 to 6 carbon atoms, typically ethylene oxide or propylene oxide or mixtures thereof.
  • hydroxyl functional polyether can be produced by first reacting propylene glycol with propylene oxide followed by subsequent reaction with ethylene oxide. Primary hydroxyl groups resulting from ethylene oxide are more reactive than secondary hydroxyl groups and thus are preferred.
  • Useful commercial polyether polyols include poly(ethylene glycol) comprising ethylene oxide reacted with ethylene glycol, poly(propylene glycol) comprising propylene oxide reacted with propylene glycol, poly(tetramethyl glycol) (PTMG) comprising water reacted with tetrahydrofuran (THF).
  • Polyether polyols further include polyamide adducts of an alkylene oxide and can include, for example, ethylenediamine adduct comprising the reaction product of ethylenediamine and propylene oxide, diethylenetriamine adduct comprising the reaction product of diethylenetriamine with propylene oxide, and similar polyamide type polyether polyols. Copolyethers can also be utilized in the current invention.
  • Typical copolyethers include the reaction product of glycerol and ethylene oxide or glycerol and propylene oxide.
  • the various polyether intermediates generally have a number average molecular weight (Mn), as determined by assay of the terminal functional groups which is an average molecular weight, of from about 500 to about 10000, desirably from about 500 to about 5000, and preferably from about 700 to about 3000.
  • Hydroxyl terminated polycarbonate intermediates can be prepared by reacting a glycol with a carbonate.
  • US 4131731 is hereby incorporated by reference for its disclosure of hydroxyl terminated polycarbonates and their preparation. Such polycarbonates are linear and have terminal hydroxyl groups with essential exclusion of other terminal groups. The essential reactants are glycols and carbonates.
  • Suitable glycols are selected from cycloaliphatic and aliphatic diols containing 4 to 40, and preferably 4 to 12 carbon atoms, and from polyoxyalkylene glycols containing 2 to 20 alkoxy groups per molecule with each alkoxy group containing 2 to 4 carbon atoms.
  • Diols suitable for use in the present invention include aliphatic diols containing 4 to 12 carbon atoms such as butanediol-1,4, pentanediol-1,4, neopentyl glycol, hexanediol-1,6, 2,2,4-trimethylhexanedion-l,6, decanediol-1,10, hydrogenated dilinoleylglycol, hydrogenated diolelylglycol; and cycloaliphatic diols such as cyclohexanediol- 1 ,3, dimethylolcyclohexane-1 ,4, cyclohexanediol- 1 ,4, dimethylolcyclohexane- 1 ,3, 1 ,4-endomethylene-2-hydroxy-5-hydroxymethyl cyclohexane, and polyalkylene glycols.
  • the diols used in the reaction may be a single diol or a
  • Non-limiting examples of suitable carbonates for use herein include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-ethylene carbonate, 1,3-pentylene carbonate, 1,4- pentylene carbonate, 2,3-pentylene carbonate and 2,4-pentylene carbonate.
  • dialkylcarbonates cycloaliphatic carbonates, and diary lcarbonates.
  • the dialkylcarbonates can contain 2 to 5 carbon atoms in each alkyl group and specific examples thereof are diethylcarbonate and diprop
  • Cycloaliphatic carbonates can contain 4 to 7 carbon atoms in each cyclic structure, and there can be one or two of such structures.
  • the other can be either alkyl or aryl.
  • the other can be alkyl or cycloaliphatic.
  • Preferred examples of diarylcarbonates, which can contain 6 to 20 carbon atoms in each aryl group, are diphenylcarbonate, ditolylcarbonate and dinaphthylcarbonate.
  • the reaction is carried out by reacting a glycol with a carbonate, preferably an alkylene carbonate in the molar range of 10: 1 to 1 :10, but preferably 3: 1 to 1 :3 at a temperature of 100°C to 300°C and at a pressure in the range of 0.1 to 300 mm Hg in the presence or absence of an ester interchange catalyst, while removing low boiling glycols by distillation.
  • a carbonate preferably an alkylene carbonate in the molar range of 10: 1 to 1 :10, but preferably 3: 1 to 1 :3 at a temperature of 100°C to 300°C and at a pressure in the range of 0.1 to 300 mm Hg in the presence or absence of an ester interchange catalyst, while removing low boiling glycols by distillation.
  • the hydroxyl terminated polycarbonates can be prepared in two stages.
  • a glycol is reacted with an alkylene carbonate to form a low molecular weight hydroxyl terminated polycarbonate.
  • the lower boiling point glycol is removed by distillation at 100°C to 300°C, preferably at 150°C to 250°C, under a reduced pressure of 10 to 30 mm Hg, preferably 50 to 200 mm Hg.
  • a fractionating column is used to separate the by-product glycol from the reaction mixture.
  • the by-product glycol is taken off the top of the column and the unreacted alkylene carbonate and glycol reactant are returned to the reaction vessel as reflux.
  • a current of inert gas or an inert solvent can be used to facilitate removal of by-product glycol as it is formed.
  • amount of by-product glycol obtained indicates that degree of polymerization of the hydroxyl terminated polycarbonate is in the range of 2 to 10
  • the pressure is gradually reduced to 0.1 to 10 mm Hg and the unreacted glycol and alkylene carbonate are removed. This marks the beginning of the second stage of reaction during which the low molecular weight hydroxyl terminated polycarbonate is condensed by distilling off glycol as it is formed at 100°C to 300°C, preferably 150°C to 250°C and at a pressure of 0.1 to 10 mm Hg until the desired molecular weight of the hydroxyl terminated polycarbonate is attained.
  • Molecular weight (Mn) of the hydroxyl terminated polycarbonates can vary from about 500 to about 10000 but in a preferred embodiment, it will be in the range of 500 to 2500.
  • suitable extender glycols i.e., chain extenders
  • suitable extender glycols are lower aliphatic or short chain glycols having from about 2 to about 10 carbon atoms and include, for instance, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6- hexanediol, 1,3-butanediol, 1,5-pentanediol, 1 ,4-cyclohexanedimethanol, hydroquinone di(hydroxyethyl)ether, neopentylglycol, and the like, with 1,4-butanediol and hydroquinone di(hydroxyethyl)ether being preferred.
  • the polyurethane is generally made from the abovementioned isocyanate reactive component such as a hydroxyl terminated polyester, polyether, or polycarbonate, preferably polyether, which is further reacted with a polyisocyanate, preferably a diisocyanate, along with extender glycol.
  • the formulation can also comprises non-fire-retardant mineral fillers such as certain oxides, carbonates, silicates, borates, stannates, mixed oxide hydroxides, oxide hydroxide carbonates, hydroxide silicates, or hydroxide borates, or a mixture of these substances.
  • calcium oxide aluminum oxide, manganese oxide, tin oxide, boehmite, dihydrotalcite, hydrocalumite, or calcium carbonate.
  • Preferred compounds are silicates and hydroxide silicates. These fillers are usually added in amounts of between 1 to 20 % by weight based on the formulation, preferably between 1 and 10 % by weight.
  • additives apart from the fillers may be used in the formulation of this invention.
  • Additives such as catalysts, stabilizers, lubricants, colorants, antioxidants, antiozonates, light stabilizers, UV stabilizers and the like may be used in amounts of from 0 to 5 wt% of the composition, preferably from 0 to 2 wt%.
  • PU polyurethane
  • TPU thermoplastic PU
  • soft, semi-rigid or rigid PU foams may be provided.
  • Foams can be made by using chemical or inert blowing agents while conducting above reactions or by using a gas in order to create a froth during these reactions.
  • a useful chemical blowing agent is water.
  • the foams may be rigid, semi-rigid, flexible and microcellular elastomeric; they may have an integral skin or not and they may be made in a mould, on a laminator or a slabstock machine. Densities of the foams may vary widely e.g. 10 - 1000 kg/m 3 .
  • Non foam polyurethane and polyurea materials may be made in a similar way, in absence of a blowing agent.
  • the TPU products can be made from the abovementioned intermediates such as a hydroxyl terminated polyester, polyether, or polycarbonate, preferably polyether, which is further reacted with a polyisocyanate, preferably a diisocyanate, along with extender glycol desirably in a so-called one-shot process or simultaneous co-reaction of polyester, polycarbonate or polyether intermediate, diisocyanate, and extender glycol to produce a high molecular weight linear TPU polymer.
  • the preparation of the macroglycol is generally well known in the art and any suitable method may be used.
  • the weight average (Mw) of a TPU polymer can be generally about 50000 to 800000, and preferably from about 90000 to about 450000 Daltons.
  • the equivalent weight amount of diisocyanate to the total equivalent weight amount of hydroxyl containing components can be typically from about 0.95 to about 1.10, desirably from about 0.96 to about 1.02, and preferably from about 0.97 to about 1.01.
  • the present invention also encompasses a polyurethane product, obtained by reacting a formulation according to the invention.
  • the polyurethane product may be a thermoplastic polyurethane product.
  • the polyurethane product may be a polyurethane elastomeric product.
  • the polyurethane product may be a polyurethane foam, such as a polyurethane flexible foam or a polyurethane rigid or semi-rigid foam.
  • the polyurethane product may be a polyurethane coating.
  • the polyurethane product may be used for cable and wire applications.
  • the polyurethane product is a thermoplastic polyurethane product used for cable sheating. In particular it can be utilized as a cable jacket as set forth in further detail below.
  • TPU products can be used as thermal and/or electric insulators for electrical conductors.
  • the TPU products can be used as jacketing for electrical conductors in wire and cable construction applications, such as jacketing for armored cable, industrial robotic equipment, non-metallic sheath cable, deep well pump cables and other multiple conductor assemblies and consumer goods.
  • insulated and “non-conductive” means electrically insulating and electrically non-conductive.
  • electrically non- conductive is synonymous of "electrically insulating” and these terms may be used interchangeably.
  • electrically insulating or “electrically non- conductive” material is a material that resists the flow of electric charge, also called a dielectric, as is well known to the skilled person.
  • the polyurethane products obtained by reacting a formulation according to the first aspect of the present invention surprisingly show improved fire resistance properties.
  • FIGRA flame retardancy
  • FIGRA Peak HRR / time to Peak HRR (kW/m 2 sec). All these parameters can also be determined by using a Mass Loss Calorimeter instead of an Oxygen Consumption Calorimeter.
  • Limiting Oxygen Index (LOI) can be measured using a Stanton Redcroft instrument according to the standard ASTM 2863 (standard test method for measuring the minimum oxygen concentration to support candle like combustion of plastics ASTM D2863/77 Philadelphia PA American Society for Testing and Materials 1977). The data for the Examples have been presented using some of these measurements.
  • the polyurethane products obtained when subjected to cone calorimeter experiment, shows a significant reduction of the peak of heat release (PHRR, expressed in kW/m 2 ), the total heat release (THRR, expressed in kW/m 2 ) and improves the ratio PHRR/Tig, Tig being the time to ignition.
  • PHRR peak of heat release
  • THRR total heat release
  • Tricalcium phosphate particles Ca 3 (P0 4 ) 2 nanoparticles supplied by Nanocerox (U.S.A).BET surface area was 21 m 2 /g, corresponding to average primary particle size of 93 nm.
  • the samples are based on polyurethane elastomeric formulation obtained by polymerizing 48.4 parts of polyol Arcol 1374 (Bayer MaterialScience), 7.4 parts of chain extender Daltoped AO 00009 (1,4 butanediol, Huntsman PU) with 43.8 parts of pre-polymer isocyanate Suprasec 2433 (Huntsman PU) using 0.4 parts of catalyst Dabco S25 (Air Products).
  • Ammonium polyphosphate (APP) (Exolit AP 422, Clariant) was dispersed in both polyol and isocyanate prepolymer by high shear mixing using a Heidolph mixer equipped with a cowel blade at 4000rpm for 40 minutes.
  • the fraction of APP to be added to each stream was calculated in proportion to the polyol/isocyanate weight fraction.
  • the required amount of metal phosphate particles was then added to the polyol (or to the dispersion of APP in polyol) and mixed by high shear mixing using a Heidolph mixer equipped with a cowel blade at 4000rpm for 40 minutes followed by sonication for 20 minutes (2sec active-2sec rest) at 40% amplitude using a Sonic VCX 500.
  • the high shear mixing step was performed under a nitrogen flow in order to avoid the incorporation of moisture contained in the air.
  • the appropriate amount of polyol/APP/particle was weighed in a paper cup, 1,4 butanediol was added and the mixture was mixed at 400 rpm for 10 minutes under vacuum. Then the proper amount of isocyanate/ APP was added to the mixture, which was then stirred under vacuum at 800 rpm for 60 seconds. The catalyst Dabco 25S was added drop by drop and the mixture was again stirred at 800 rpm for 20 seconds. At this step, the blend was quickly poured in an aluminum mould (preventively sprayed with release agent) placed on a hot plate at 85°C. After 1 hour the casting was removed and post cured at 85°C for 24 hours in an oven.
  • LOI limited oxygen index
  • a composition comprising a mixture of hydroxyapatite (Cas(P0 4 ) 3 (OH)), dicalcium phosphate (CaHP0 4 ) and tricalcium phosphate (Ca 3 (P0 4 ) 2 ) particles supplied by Prolabo- VWR (product number 22417.293; Lot#10A120002 31.01.2012).
  • the mixture contained Ca 5 (P0 4 ) 3 (OH) / CaHP0 4 / Ca 3 (P0 4 ) 2 in the following proportions: 60 / 30 / 10 (determined by XRD analysis).
  • the samples are based on polyurethane flexible coating formulation obtained by polymerizing 47.8 parts of polyol Daltocel F526 (Huntsman PU), 10.3 parts of chain extender Daltoped AO 00009 (1,4 butanediol, Huntsman PU) with 41.8 parts of isocyanate Suprasec 2020 (Huntsman PU).
  • Ammonium polyphosphate (APP) (Exolit AP 422, Clariant) was dispersed in both polyol and isocyanate prepolymer by high shear mixing using a Heidolph mixer equipped with a cowel blade at 4000rpm for 30 minutes.
  • the fraction of APP to be added to each stream was calculated in proportion to the polyol/isocyanate weight fraction.
  • the required amount of metal phosphate particles was then added to the polyol (or to the dispersion of APP in polyol) and mixed by high shear mixing using a Heidolph mixer equipped with a cowel blade at 4000rpm for 30 minutes.
  • the high shear mixing step was performed under a nitrogen flow in order to avoid the incorporation of moisture contained in the air.
  • the appropriate amount of polyol/ APP/particle was weighed in a paper cup, 1,4 butanediol was added and the mixture was mixed at 400 rpm for 1 minute under vacuum. The proper amount of isocyanate/ APP was quickly added to the mixture, which was then stirred with a disposable spatula until the blend started to heat up. At this step, the blend was quickly poured in an aluminum mould (preventively sprayed with release agent) placed on a hot plate at 42°C. After 1 hour the casting was removed and post cured at 80°C for 24 hours in an oven.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Cette invention concerne une formulation permettant d'obtenir un polyuréthanne, ladite formulation comprenant (a) au moins un mélange formant un polyuréthanne ; (b) au moins un composant de phosphate choisi dans le groupe constitué par le polyphosphate d'ammonium (APP) et les phosphates de mélamine, et leurs mélanges ; et (c) au moins une particule de phosphate métallique, le métal étant choisi dans le groupe constitué par Ca, Mg, Al et Zn.
PCT/EP2012/062299 2011-07-12 2012-06-26 Formulation permettant d'obtenir un polyuréthanne WO2013007509A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119505519A (zh) * 2025-01-21 2025-02-25 湖南强泰新材料有限公司 一种聚氨酯复合材料及其制备方法和应用

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US4131731A (en) 1976-11-08 1978-12-26 Beatrice Foods Company Process for preparing polycarbonates
US4347334A (en) 1980-02-13 1982-08-31 Hoechst Aktiengesellschaft Particulate agent for impeding the combustibility of combustible substances
US4467056A (en) 1979-12-08 1984-08-21 Hoechst Aktiengesellschaft Particulate agent for impeding the combustibility of combustible materials
US4514328A (en) 1982-05-12 1985-04-30 Hoechst Aktiengesellschaft Particulate material reducing the ignitability of combustible substances
US4639331A (en) 1983-05-07 1987-01-27 Hoechst Aktiengesellschaft Process for making pulverulent ammonium polyphosphates stable to hydrolysis
EP0276726A2 (fr) * 1987-01-27 1988-08-03 Mankiewicz Gebr. & Co. (GmbH & Co. KG) Masse moulée et son utilisation
US6015510A (en) 1996-08-29 2000-01-18 E. I. Du Pont De Nemours And Company Polymer flame retardant
EP1132563A2 (fr) * 2000-03-07 2001-09-12 Intumex Brandschutzprodukte AG Ruban coupe-feu intumescent enrobé sur trois côtés ainsi que joint d'étanchéité combiné pour gaz chauds et froids
EP1705221A1 (fr) * 2005-03-26 2006-09-27 Clariant Produkte (Deutschland) GmbH Utilisation de stabilisateurs pour l'agents d'ignifugation agglomérés thermostabilisés contenant du phosphore
WO2007068599A1 (fr) * 2005-12-14 2007-06-21 Tesa Ag Bande de matiere a enrouler, faite d'un film de polyurethane thermoplastique
WO2009016129A1 (fr) * 2007-07-28 2009-02-05 Chemische Fabrik Budenheim Kg Matériau polymère ignifuge

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4131731A (en) 1976-11-08 1978-12-26 Beatrice Foods Company Process for preparing polycarbonates
US4467056A (en) 1979-12-08 1984-08-21 Hoechst Aktiengesellschaft Particulate agent for impeding the combustibility of combustible materials
US4347334A (en) 1980-02-13 1982-08-31 Hoechst Aktiengesellschaft Particulate agent for impeding the combustibility of combustible substances
US4514328A (en) 1982-05-12 1985-04-30 Hoechst Aktiengesellschaft Particulate material reducing the ignitability of combustible substances
US4639331A (en) 1983-05-07 1987-01-27 Hoechst Aktiengesellschaft Process for making pulverulent ammonium polyphosphates stable to hydrolysis
EP0276726A2 (fr) * 1987-01-27 1988-08-03 Mankiewicz Gebr. & Co. (GmbH & Co. KG) Masse moulée et son utilisation
US6015510A (en) 1996-08-29 2000-01-18 E. I. Du Pont De Nemours And Company Polymer flame retardant
EP1132563A2 (fr) * 2000-03-07 2001-09-12 Intumex Brandschutzprodukte AG Ruban coupe-feu intumescent enrobé sur trois côtés ainsi que joint d'étanchéité combiné pour gaz chauds et froids
EP1705221A1 (fr) * 2005-03-26 2006-09-27 Clariant Produkte (Deutschland) GmbH Utilisation de stabilisateurs pour l'agents d'ignifugation agglomérés thermostabilisés contenant du phosphore
WO2007068599A1 (fr) * 2005-12-14 2007-06-21 Tesa Ag Bande de matiere a enrouler, faite d'un film de polyurethane thermoplastique
WO2009016129A1 (fr) * 2007-07-28 2009-02-05 Chemische Fabrik Budenheim Kg Matériau polymère ignifuge

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A. MORGAN; M. BUNDY, FIRE MATER, vol. 31, 2007, pages 257 - 283

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119505519A (zh) * 2025-01-21 2025-02-25 湖南强泰新材料有限公司 一种聚氨酯复合材料及其制备方法和应用

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