WO2013045965A1 - Composition ignifuge de polyesters exempte d'halogène - Google Patents

Composition ignifuge de polyesters exempte d'halogène Download PDF

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Publication number
WO2013045965A1
WO2013045965A1 PCT/IB2011/002262 IB2011002262W WO2013045965A1 WO 2013045965 A1 WO2013045965 A1 WO 2013045965A1 IB 2011002262 W IB2011002262 W IB 2011002262W WO 2013045965 A1 WO2013045965 A1 WO 2013045965A1
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flame retardant
composition according
weight
thermoplastic composition
polyester
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PCT/IB2011/002262
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English (en)
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Ugo Zucchelli
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Italmatch Chemicals S.P.A.
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Priority to PCT/IB2011/002262 priority Critical patent/WO2013045965A1/fr
Publication of WO2013045965A1 publication Critical patent/WO2013045965A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • 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
    • 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
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive

Definitions

  • halogen free flame retardant agents/additives represent, generally speaking, more expensive solutions compared to traditional brominated FR
  • some preference has been given to halogen free flame retardant additives because of environmental as well as safety reasons.
  • halogen free flame retardant agents (FR) are of increasing interest in the thermoplastic polymers market. Basic requirements for these products are: good processing performances in compounding and moulding conditions, good mechanical and electrical properties in the solid state, no blooming or discoloration, good flame retardant properties in both reinforced and unreinforced polymers.
  • Organic phosphinates are a new family of halogen free flame retardant agents, particularly efficient when used in the case of polyesters, especially when used in conjunction with a melamine containing compound, the resulting mixture being more effective than organic phosphinates alone.
  • These products with particular regard to zinc and especially aluminium diethyl phosphinate, are currently commercially available under the "Exolit OP" brand.
  • a polyamide or a polyester polymer or their mixtures is flame retarded by a melamine condensation product and an organic compound containing at least 14% phosphorus.
  • trimethylpropanol ester of methylphosphoric acid and a Zn salt of dimethylphosphonic acid are used as suitable flame retardant phosphorus containing compounds.
  • Trimethylpropanol ester of methylphosphoric acid is an highly viscous liquid difficult to dose. Special dosing pumps are required, usually heated up to decrease the viscosity of the compound, or even organic volatile solvents as acetone are used in mixtures to decrease viscosity of the phosphorous flame retardant agent.
  • thermoplastic polyester is made flame retardant by the addition of an oligomeric organic phosphate ester, a phenolic polymer (novolac), and a melamine base flame retardant compound selected from melamine pyrophosphate, phosphate, polyphosphate and cyanurate.
  • a melamine base flame retardant compound selected from melamine pyrophosphate, phosphate, polyphosphate and cyanurate.
  • novolac compounds are yellow or orange coloured as such.
  • the few existing uncoloured novolacs turn on deeply dark after processing in polyesters. This is an undesired drawback, when it is necessary to produce light colour pigmented items.
  • experimental examples according to WO 2005/026258 were replicated, and a good flame retardant performance was observed only at high loadings (30%).
  • thermoplastic polyester mixed with a vinyl resin is flame retarded by the addition of a phosphoric acid ester, a triazine based on cyanuric acid or isocyanuric acid and an alkaline earth metal compound as hydrolysis stabilizer. Described compositions show good performances in flame retardant activity, hydrolysis capability, tracking resistance and metal pollution resistance. Reported Examples always indicate a 30% total load in order to achieve a UL-94 V0 rating at 0,8mm. Experimental examples according to US 7135509 were replicated, and indeed a good performance was only observed at high loadings of 30% or more, but no results at lower loading were observed.
  • Intumescent fire retardant materials are widely diffused as efficient halogen free flame retardant agents, providing a carbonaceous char on the surface of the polymer and protecting the underlying material from the action of the incident heat flux while reducing the heat transfer to the substrate.
  • Intumescent formulations include three major components: a phosphoric acid source deriving from a polyphosphate, a so called “carbonific agent” or “char forming agent”, deriving from a polyol and a blowing agent such as melamine or melamine cyanurate.
  • a phosphoric acid source deriving from a polyphosphate
  • a blowing agent such as melamine or melamine cyanurate.
  • Intumescent systems are industrially utilized in coatings and in relatively low melting point polymers like, for instance, polyethylene and polypropylene, but are not used in linear thermoplastic polyesters.
  • Hypophosphites have the following chemical formula:
  • n is an integer number ranging from 1 to 4 in dependence of the valence of the metal Me.
  • the metal Me is any atom belonging to the groups I, II, III and IV of the periodic table of the elements.
  • Sodium and calcium Hypophosphites are widely commercially available and are normally produced by reacting the corresponding metal hydroxide on yellow phosphorus, for instance according to the following reaction scheme:
  • Hypophosphite of metals other than Calcium and Sodium are normally produced through the hypophosphorus acid reaction on the metal hydroxide or by exchange reaction with the corresponding soluble metal salts (see for instance "Hypophosphorus Acid and its salts", Russian Chemical Review, 44 (12), 1975). Hypophosphites are simpler molecules compared to organic phosphinates and are also easier to be prepared. Hypophosphites may be even used as starting raw material for subsequent organic phosphinates production.
  • Thermoplastic polyester moulding materials containing Hypophosphites were described in the art, see for instance WO 2010/080491 , US 2009/0088512, WO 09/010812, WO 08/119693, WO 08/06549, WO 07/084664, WO 05/121232, US 20050137297, WO 03/014212 (equivalent to US 71692812 ), WO 99/57187 (equivalent to US 6,503,969), WO 98/17720.
  • WO 2010/080491 describes a polyester flame retardant composition containing at least a phosphinate salt, at least a phosphonate oligomer (polymer or copolymer), and at least a melamine derivative.
  • Hypophosphite is cited in the experimental Examples reported in WO 2010/080491, Hypophosphites are claimed as being included in the general formula of Phosphinates (case in which Rl and Rl are Hydrogen).
  • No UL-94 thickness condition details are reported in the examples of WO 2010/080491 , so from the information given by this document it is not possible to get any information about the flame retardant efficiency of the described system.
  • Phosphonate oligomers are however based on expensive ingredients, so the formulation as described in WO 2010/080491 results to be very expensive and with no industrial applicability.
  • US 2009/0088512 describes a polyester flame retardant composition containing from 40 to 64.9% by weight of a thermoplastic polyester, from 5 to 10% by weight of polycarbonate, from 10 to 15% of a phosphinic acid salt of given formula, from 5 to 10% by weight of melamine polyphosphate, from 15 to 30% by weight of reinforcing materials and from 0.1 to 2% by weight of further additives.
  • a thermoplastic polyester from 5 to 10% by weight of polycarbonate, from 10 to 15% of a phosphinic acid salt of given formula, from 5 to 10% by weight of melamine polyphosphate, from 15 to 30% by weight of reinforcing materials and from 0.1 to 2% by weight of further additives.
  • Such composition gives stable and reliable UL-94 V0 classification at 0,8mm, and GWIT 775°C, and elongation at break higher than around 2%.
  • Hypophosphites are included, as a particular case, in the given general formula (case in which Rl and Rl are Hydrogen).
  • polyester compositions comprising Hypophosphites where shown not possible to be extruded, together with Melamine polyphosphate or any other polyphosphate, because they result in decomposition reactions.
  • polymers based on polycondensates like polyesters, polyamides and polycarbonates are flame retarded by a mixture of hypophosphite (preferred is aluminium) and dihydro-oxa-phospho-phenantrene derivatives of given formula.
  • a flame retardant polyester contains hypophosphites, especially Calcium and Aluminium, a phosphine suppression package, and a charring polymer to boost flame retardant action.
  • Charring polymers comprise polyetherimide, polyphenyleneoxide, polyethersulfone, polyphenylene sulfone, polyphenylene sulphide, phenol-formaldehyde resins and combinations thereof.
  • a disadvantage of the use of charring polymers is their high price, their limited compatibility and dispersion limits, and also their tendency to cause discoloration phenomena.
  • thermoplastic vulcanized polyester is made flame retardant by the addition of an organic phosphinate or an hypophosphite.
  • a polyester is flame retarded by the addition of aluminium hypophosphite and conventional additives.
  • a flame retardant polyester composition comprises a nitrogen containing flame retardant agent, an organic phosphinate or an hypophosphite and a charring polymer to booster flame retardant characteristics.
  • Charring polymers comprise polyetherimide, polyphenyleneoxide, polyethersulfone, polyphenylene sulfone, polyphenylene sulphide, phenol-formaldehyde resins and combinations thereof.
  • a disadvantage of charring polymers is represented by the high price, their limited compatibility and dispersion limits, and also their tendency to cause discoloration phenomena.
  • a polyester comprising a mixture of an hypophosphite having a preferred particle size distribution and a nitrogen flame retardant, preferably mixed in advance and then feed to the melt, confers a particularly desired set of advantageous properties to the moulded composition.
  • a polyester comprising a mixture of an hypophosphite and a nitrogen containing flame retardant, excluding melamine cyanurate, shows good flame retardant properties.
  • a polyester comprising a mixture of an hypophosphite, melamine cyanurate, and an ester or amide of saturated or unsaturated aliphatic carboxylic acids, shows good flame retardant properties.
  • polyesters thermoplastic flame retardant formulations based on Hypophosphites are either based on expensive synergic combinations (in case of WO 2010/080491) or are simply impracticable (in case of US2009/0088512) or results in lower flammability performances compared to organic phosphinates (in case of all the others documents here mentioned).
  • Object of the present invention is to provide halogen-free highly flame retardant linear polyesters, unreinforced or reinforced, based on Hypophosphites.
  • highly flame retardant means V0 classification on thin items according to international standard UL-94.
  • Thin items means thickness of the sample specimens preferably lower than about lmm, and more preferably equal to 0,8 mm or even lower.
  • Another object of the present invention is to provide halogen free flame retardant linear polyester with high Glow Wire resistance, particularly passing the GWIT test at 775°C, according to IEC 61335-1.
  • Another object of the present invention is to provide halogen free flame retardant linear polyester with high comparative tracking index, particularly of about 600V measured according to IEC 1 12 with standard solution A.
  • Another object of the present invention is to provide halogen free flame retardant moulding composition and articles based on linear polyesters with good electrical properties, mechanicals and weathering resistance.
  • a polymer composition comprising:
  • thermoplastic polyester polymer a) at least a thermoplastic polyester polymer
  • Hypophosphorus acid metal salt also called inorganic Phosphinate or Hypophosphite, where phosphorus valence state is equal to +1, as a first flame retardant (FR) component
  • composition may additionally include:
  • a preferred embodiment according to the present invention is a composition consisting of components a) to e) where the total percentage of components a) to e) must be 100%.
  • Another preferred embodiment is a composition consisting of components a) to f) where the total percentage of components a) to f) must be 100%.
  • said other conventional additives are selected as processing aids, heat and process stabilizers, UV stabilizers, antidripping agents as PTFE (polytetrafluorethylene), pigments, dispersing agents, mould release additives, nucleating agents, partially crosslinked elastic polymers, and their mixtures.
  • PTFE polytetrafluorethylene
  • said other conventional additives are selected as processing aids, heat and process stabilizers, UV stabilizers, antidripping agents as PTFE (polytetrafluorethylene), pigments, dispersing agents, mould release additives, nucleating agents, partially crosslinked elastic polymers, and their mixtures.
  • said at least an Hypophosphorus acid metal salt also called inorganic Phosphinate or Hypophosphite where phosphorus valence state is equal to +1
  • first flame retardant (FR) component is Aluminium Hypophosphite.
  • said nitrogen based flame retardant agent as a second flame retardant (FR) component is Melamine cyanurate
  • said organic polyhydric additive as a third flame retardant (FR) component is Pentaerythritol, Dipentaerythritol, Polypentaerythritol or their mixtures.
  • thermoplastic polyester polymer is linear polyester.
  • the flame retardant (FR) components total content is preferably lower than 35% by weight on the total weight of the composition, and more preferably lower than 30% by weight on the total weight of the composition, so that mechanicals and electrical properties are satisfactory with respect to most of the desired applications.
  • thermoplastic polyester resin is any polyalkene terephtalate, based on at least an aromatic dicarboxylic acid and at least an aliphatic or aromatic dihydroxy compound.
  • Particular preferred polyesters are derived from polybutylene terephthalate (normally abbreviated “PBT”) and polyethylene terephtalate (normally abbreviated “PET”).
  • PBT polybutylene terephthalate
  • PET polyethylene terephtalate
  • thermoplastic polyester includes also thermoplastic vulcanized elastomers, i.e.
  • thermoplastic copolyester elastomers like copolyether ester (normally abbreviated "COPES”, or "TPE-E”).
  • Product of this type are, at the filing date of the present application, commercially available, for example as Hytrel ®(Du Pont) and are also describe in the state of the art (for instance in US 3651014).
  • Hypophosphites also called Hypophosphorus acid metal salt also called inorganic Phosphinate
  • hypophosphite The selection of the most appropriate Hypophosphite is subjected to a number of critical factors. Particularly, suitable hypophosphites must have sufficient thermal stability to overcome melt processing at temperature higher than around 200°C. If they do form hydrates, then they must be used in the corresponding anhydrous form and they must not be hygroscopic when they are subsequently exposed to ambient humidity.
  • Hypophosphites are Aluminum hypophosphite (CAS 7784-22-7), Calcium hypophosphite (CAS 7789-79-9), Manganese hypophosphite (10043-84-2), Magnesium hypophosphite (CAS 10377-57-8), Zinc hypophosphite (CAS 15060-64-7), Barium hypophosphite (CAS 171258-64-3). Most preferred in the purpose of present invention are Aluminum and Calcium hypophosphites.
  • Aluminum hypophosphite corresponding to chemical formula ⁇ 1(3 ⁇ 4 ⁇ 0 2 )3, is currently produced by Italmatch Chemicals Spa (under commercial name "Phoslite IP-A") in a white powder form with a low humidity level, high purity and different PSD suitable for thermoplastic processing.
  • Phoslite IP-A Italmatch Chemicals Spa
  • Calcium hypophosphite corresponding to chemical formula Ca(H 2 P0 2 ) 2 , is also currently produced by Italmatch Chemicals Spa (under commercial name "Phoslite IP-C"). This compound shows lower flame retardant performances in polyester when compared to Aluminum hypophosphite. However, it can be advantageously used in those applications where thermal resistance of Aluminum hypophosphite would be critical.
  • Aluminum and Calcium hypophosphites being flammable powders as most of anhydrous hypophosphites, are often commercialized as a dry blend powder with other solid flame retardants or even in masterbatch form, for easier transport and manipulation.
  • Nitrogen base flame retardant agents are also subjected to a number of critical factors. Particularly, suitable Nitrogen based flame retardant agents must have sufficient thermal stability to overcome melt processing at temperature higher than around 200°C, and must also be characterized by a high Nitrogen content, for example higher than 40%, (indicated by nitrogen atom percentage with respect to 100% of the nitrogen containing compound).
  • the Nitrogen content is about 49% on 100% of melamine cyanurate.
  • Molecular mass is the mass of one molecule of a substance and is expressed in the unified atomic mass units (u). (1 u is equal to 1/12 the mass of one atom of carbon- 12), while Molar mass (molar weight) is the mass of one mole of a substance and is expressed in g/mol.
  • a commonly used nitrogen based flame retardant agent is Ammonium Polyphosphate (NH 4 P0 3 ) n .
  • Ammonium Polyphosphate is sufficient thermally stable as such, it gives undesired reaction and decomposition when put in contact with Hypophosphites (see Comparative Example C. 15).
  • Ammonium Polyphosphate as a source of Nitrogen is out of the scope of present invention, being not compatible with Hypophosphites.
  • Preferred Nitrogen based flame retardant agents according to the present invention comprise triazine derivatives, complexes and condensation products, with high Nitrogen content.
  • Triazine is the chemical species of six-membered heterocyclic ring compound with three Nitrogen atoms replacing carbon-hydrogen units in the benzene ring structure.
  • Preferred triazine derivatives within the scope of the invention are derivatives of symmetric triazines.
  • a review on derivative of symmetric triazine is given in "Recent applications of 2,4,6-trichloro-l,3,5-triazine and its derivatives in organic synthesis, Tetraedron 62 /2006 9597 9522".
  • Nitrogen based flame retardant agent is Melamine Cyanurate.
  • Melamine cyanurate chemical formula 3 ⁇ 4 ⁇ 9 ⁇ 9 ⁇ 3, is a complex of Melamine and Cyanuric acid that is characterized by a high Nitrogen content about 49%.
  • Condensation products of Melamine are Melam (CAS 3576-88- 3), Melem (CAS 1502-47-2), Melon (CAS 3251S-77-7).
  • Melam, Melem, Melon, pure or in mixtures, are also preferred options.
  • Melam Nitrogen content is about 65%.
  • Melamine salts or adduct like Melamine Phosphate, Pyrophosphate or Polyphosphate are out of the scope of the present invention.
  • Melamine phosphate and pyrophosphate are not thermally stable to be processed into thermoplastic polyesters, evolving water at low temperatures around 200°C.
  • Polyphosphate gives undesired reaction and decomposition when in contact with Hypophosphites (see Comparative Example C 14).
  • any Nitrogen salt having even a low residual acidity or anyway able to develop acidity during melt blending gives rise to violent reaction with the Hypophosphite component, while more neutral or mildly basic Nitrogen components are beneficial to the thermal stability of the flame retardant system.
  • Organic polyhydric additive may be defined as an organic molecule containing many hydroxyl (-OH) radicals, not linked to aromatic or coniugated unsatured bonds.
  • Mg(OH) 2 does not belong to organic polyhydric additives definition, despite the fact that hydroxyl groups are present, because it is an inorganic compound.
  • phenol-formaldehyde resins do not belong to organic polyhydric additives definition, because in this case, hydroxyl group is linked to benzene.
  • a polyalcohol (or polyol) like glycerol, C 3 H 5 (OH)3 is an example of organic polyhydric additive.
  • Sugar alcohol are also a class of polyalcohol, and they also are an example of organic polyhydric additive according to the present invention.
  • Organic polyhydric additives may be also selected among polyhydric polymers (also called polymeric polyalcohol or polymeric polyol).
  • Polyhydric polymers may be produced starting from by monomeric polyols such pentaerythritol (in this latter case, obtaining Polypentaerythritol), ethylene glycol and glycerin (in this latter case, obtaining Polyglycerol).
  • Polypentaerythritol as currently commercially available is often a mixture of di-, tri-, terra-, pentaerythritol and may contain also small percentage of other polyols.
  • a preferred polyhydric polymer currently commercially available is Charmor® PP100 (Perstorp).
  • Organic polyhydric additives may be selected also among starch or other carbohydrates.
  • Another organic polyhydric additive within the scope of present invention is Trishydroxyethylisocianurate, chemical formula C 9 Hi5N 3 0 6 .
  • Polyhydric additives suitable to be used according to the present invention are those obtained by reaction between Trishydroxyethylisocianurate with aromatic diacids as terephtalic acid, are described in US5326805. They show lower volatility and lower water solubility compare to pure Trishydroxyethylisocianurate.
  • organic polyhydric additives The selection of most appropriate organic polyhydric additives is subjected to a number of critical factors. Particularly, suitable organic polyhydric additives must have sufficient thermal stability to overcome melt processing at temperature higher than around 200°C.
  • organic polyhydric additives according the invention can react at least partially with the polyester during melt processing, and the result of this reaction is that part of the polyester can be converted into branched polymers, increasing the viscosity of the melt. This reaction, if occurs, depends on temperatures, reaction time, shear, nature and concentration of the organic polyhydric additive used.
  • organic polyhydric additives concentrates made of various polymers previously mixed and/or at least partially reacted with the organic polyhydric additive.
  • Examples of preferred reinforcing fibers according to the present invention are carbon fibers, aramid fibers and preferably glass fibers to be used in the commercially available form of chopped glass.
  • the reinforcing fibers may have been surface treated with a silane compound.
  • Reinforcing fibers are used in the range from 10% to 50%, preferably from 20% to 35% by weight on the weight of the resin: if the amount is lower, no advantage is observed in the mechanical properties and if the amount is higher than 50% by weight, viscosity of the melt is too high.
  • Example of fillers according to the invention are glass beads, hollow glass spheres, amorphous silica, chalk, mica, calcinated kaolin, wollastonite, talc, magnesium carbonate, barium sulphate or similar products and they may have been surface treated with fatty acids or the like or may have been milled in presence of fatty acids or the like.
  • Any particulate substance currently available in the market as a filler for thermoplastic resins may be used in the compositions according to the present invention, provided that the average particle size of the powder, measured by laser instrument, is in the range of about 2 microns to 20 microns.
  • Novel thermoplastic compositions according to the invention may also contain one or more of the following compounds: processing aids, heat and process stabilizers, UV stabilizers, antidripping agents as PTFE (polytetrafluorethylene), pigments, dispersing agents, mould release additives, nucleating agents, partially crosslinked elastic polymers used as impact modifiers, and their mixtures.
  • processing aids heat and process stabilizers
  • UV stabilizers UV stabilizers
  • antidripping agents as PTFE (polytetrafluorethylene)
  • pigments pigments
  • dispersing agents dispersing agents
  • mould release additives nucleating agents
  • nucleating agents partially crosslinked elastic polymers used as impact modifiers, and their mixtures.
  • hyperbranched polymers also known as dentritic polymers
  • hyperbranched polymers are particularly useful to improve processability.
  • Hyperbranched polymers are three dimensional highly branched molecules that have a treelike structure and which comprise one or more branching comonomer units.
  • Hyperbranched polymers are condensate of ethoxylated pentaerythritol , dimethyl propionic acid and are currently commercially available froni t Perstorp AB as Boltorn® and they are also described in US6225404, US6497959, US6663966, WO 2003/004546, EPO Pat. App. No. 1424360 and WO 2004/1 1 1 126.
  • PFS Pentaerythritolmonostearate
  • Hindered phenol heat stabilizer (Irganox 1010, by BASF), hereafter “Irg. 1010”
  • Phosphite process stabiliser (Irgaphos 168, by BASF), hereafter “Irg. 168"
  • IP-A Aluminium hypophosphite
  • Trihydroxyethyl isocianurate Trihydroxyethyl isocianurate, by Sigma Aldrich, hereafter "THEIC"
  • Di pentaerytritol (Charmor DP40, Perstorp), hereafter "DI-PERT"
  • MPP Melamine polyphosphate
  • Phenol formaldehyde resin (by Fenolit), hereafter "PF"
  • counter examples C. 1 1 ,12,13,14,15,16 containing combinations of Hypophosphite and Nitrogen only, show lower flammability performances with respect to the compositions according to the present invention, even at higher loading.
  • Counter Examples C. 11,12,13,14,15,16 are according to the previous art.
  • Counter Examples C. 10,19, 20 show how the presence of all the 3 flame retardant components according to the present invention (first, second and third FR components) is necessary to reach classification UL-94 V0 at 0,8mm. Even at a 30% by weight total loading, Aluminium hypophosphite alone (see comparative example C. 10) do not reach UL-94 V0 at 0,8mm . Also the combination of Aluminium hypophosphite and the organic polyhydric compounds at 30% loading (see comparative examples C. 19, C. 20) do not reach UL-94 V0 at 0,8mm.
  • Examples 6,7,8 according to the present invention show how combinations according to present inventions of Aluminium hypophosphite, melamine cyanurate and organic polyhydric compounds do impart UL-94 V0 classification at 0,8mm on
  • PBT glass fibre reinforced at a total flame retardant loading level of 21% by weight PBT glass fibre reinforced at a total flame retardant loading level of 21% by weight.
  • Example 6 show some increase in torque during compounding due to the chain extension of PBT by Dipentaerythritol (organic polyhydric additive) and consequent increase in viscosity.
  • compositions according to comparative examples C. 17 and C. 18 were very difficult to extrude, giving broken strands, smoke and decompositions. Compositions according to C. 17 and C.18 were not possible to inject mould, giving violent decomposition with flames and fire.
  • C.17 shows how Melamine polyphosphate or melamine - poly (zinc phosphate) or melamine - poly (aluminium phosphate) cannot be used in combination with Hypophosphite in polyester extrusion and injection molding.
  • C.18 shows how ammonium polyphosphate cannot be used in combination with Hypophosphite, in polyester extrusion and injection molding.
  • compositions according to C. 25,26,27,28 gave strong yellowing and discolouration.
  • compositions according to comparative examples C. 29 and C. 30 show how a combination of Melamine condensation product and an organic phosphorous containing compound as trimethylpropanol ester of methylphosphoric acid at 30% by weight of flame retardant loading, show lower flammability performances with respect to preferred compositions according to the present invention.
  • C. 32 show how a combination of an oligomeric phosphate ester, a novolac and melamine polyphosphate at 30% by weight of flame retardant total loading is classified UL-94 VO at 0,8mm, while C. 31 show that at 28% by weight of total flame retardant loading, classification is only UL-94 V2 at 0,8mm.
  • composition according to comparative example C. 33 shows how a combination of a phosphoric acid ester and melamine cyanurate at a total flame retardant content of 30% by weight is able to achieve classification UL-94 V0 at 0,8mm but comparative example C. 34 shows that at a total flame retardant content of 25%, classification is only UL-94 V2 at 0,8mm.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne des compositions ignifuges exemptes d'halogène, comprenant essentiellement des polymères de polyesters linéaires, au moins un sel métallique d'acide hypophosphoreux (de préférence l'hypophosphite d'aluminium), au moins un agent ignifuge à base d'azote (de préférence le cyanurate de mélamine), au moins un composé polyhydrique organique et éventuellement d'autres composants habituels. De telles compositions sont hautement ignifuges.
PCT/IB2011/002262 2011-09-28 2011-09-28 Composition ignifuge de polyesters exempte d'halogène WO2013045965A1 (fr)

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PCT/IB2011/002262 WO2013045965A1 (fr) 2011-09-28 2011-09-28 Composition ignifuge de polyesters exempte d'halogène

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PCT/IB2011/002262 WO2013045965A1 (fr) 2011-09-28 2011-09-28 Composition ignifuge de polyesters exempte d'halogène

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WO2013045965A1 true WO2013045965A1 (fr) 2013-04-04

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Cited By (8)

* Cited by examiner, † Cited by third party
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CN104130558A (zh) * 2014-08-14 2014-11-05 苏州科技学院相城研究院 四(0，0-二甲基磷酰基)甘脲阻燃剂组合物及其应用方法
CN104130557A (zh) * 2014-08-14 2014-11-05 苏州科技学院相城研究院 四(0,0-二丙基磷酰基)甘脲阻燃剂组合物及其应用方法
CN104130555A (zh) * 2014-08-14 2014-11-05 苏州科技学院相城研究院 四(0，0-二苯基磷酰基)甘脲阻燃剂组合物及其应用方法
WO2015141708A1 (fr) * 2014-03-19 2015-09-24 東洋紡株式会社 Composition de résine polyester ignifuge
CN112480616A (zh) * 2020-11-17 2021-03-12 广州科莱瑞迪医疗器材股份有限公司 一种三聚氰胺盐增强低温热塑材料及其制备方法
CN113150383A (zh) * 2021-04-02 2021-07-23 奇瑞新能源汽车股份有限公司 多聚氰胺聚磷酸盐及其制备方法
CN113278203A (zh) * 2021-06-16 2021-08-20 山东泰星新材料股份有限公司 一种聚丙烯用高效无卤阻燃剂的制备方法及应用
CN114989105A (zh) * 2022-07-15 2022-09-02 什邡市太丰新型阻燃剂有限责任公司 无污染合成超细三聚氰胺次磷酸盐的方法及其阻燃方法

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WO2015141708A1 (fr) * 2014-03-19 2015-09-24 東洋紡株式会社 Composition de résine polyester ignifuge
CN104130558A (zh) * 2014-08-14 2014-11-05 苏州科技学院相城研究院 四(0，0-二甲基磷酰基)甘脲阻燃剂组合物及其应用方法
CN104130557A (zh) * 2014-08-14 2014-11-05 苏州科技学院相城研究院 四(0,0-二丙基磷酰基)甘脲阻燃剂组合物及其应用方法
CN104130555A (zh) * 2014-08-14 2014-11-05 苏州科技学院相城研究院 四(0，0-二苯基磷酰基)甘脲阻燃剂组合物及其应用方法
CN112480616A (zh) * 2020-11-17 2021-03-12 广州科莱瑞迪医疗器材股份有限公司 一种三聚氰胺盐增强低温热塑材料及其制备方法
CN113150383A (zh) * 2021-04-02 2021-07-23 奇瑞新能源汽车股份有限公司 多聚氰胺聚磷酸盐及其制备方法
CN113278203A (zh) * 2021-06-16 2021-08-20 山东泰星新材料股份有限公司 一种聚丙烯用高效无卤阻燃剂的制备方法及应用
CN114989105A (zh) * 2022-07-15 2022-09-02 什邡市太丰新型阻燃剂有限责任公司 无污染合成超细三聚氰胺次磷酸盐的方法及其阻燃方法
CN114989105B (zh) * 2022-07-15 2024-01-12 什邡市太丰新型阻燃剂有限责任公司 无污染合成超细三聚氰胺次磷酸盐的方法及其阻燃方法

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