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WO1994011425A1 - Ignifuges - Google Patents

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Publication number
WO1994011425A1
WO1994011425A1 PCT/US1993/010606 US9310606W WO9411425A1 WO 1994011425 A1 WO1994011425 A1 WO 1994011425A1 US 9310606 W US9310606 W US 9310606W WO 9411425 A1 WO9411425 A1 WO 9411425A1
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WIPO (PCT)
Prior art keywords
flame
polymer
poly
phosphorus
acid
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Application number
PCT/US1993/010606
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English (en)
Inventor
Keith P. Parsons
Alan Lindsay
Original Assignee
Minnesota Mining And Manufacturing Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Minnesota Mining And Manufacturing Company filed Critical Minnesota Mining And Manufacturing Company
Priority to EP94900530A priority Critical patent/EP0668887A1/fr
Priority to JP6512203A priority patent/JPH08503505A/ja
Publication of WO1994011425A1 publication Critical patent/WO1994011425A1/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
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts

Definitions

  • FLAME RETARDANTS This invention relates to non-halogen-containing flame-retardant additives suitable for use in a variety of thermoplastic and thermoset polymer materials.
  • halogen- containing flame-retardant additives are known and have been used to reduce the flammability of polymer materials.
  • halogenated flame-retardants are known to cause both high smoke generation and the emission of toxic gases which present a hazard to both workers and fire fighters alike, as well as corrosive gases which may damage adjacent circuitry. In addition, these gases may also have wider reaching deleterious environmental effects.
  • Alternatives to halogenated flame-retardants can be broadly classed into either (a) phosphorus-based materials or (b) non-phosphorus-based materials.
  • non-phosphorus-based materials comprise inert filler materials, such as calcium carbonate, which have little anticombustion effect.
  • inert filler materials such as calcium carbonate
  • Alumina trihydrate, magnesium hydroxide and calcium carbonate have been used as flame-retardant additives for polyolefin polymers.
  • Unfortunately, such materials require high loading by weight of the polymer composition to achieve the desired level of flammability performance. This high loading is found to have a pronounced negative effect on the physical properties of the polymer, e.g., tensile strength and/or elongation. Additionally, materials such as alumina trihydrate have poor thermal stability.
  • phosphorus-based flame-retardants are known, particularly the use of inorganic phosphates to generate intumescent formulations which form a protective foamed char when exposed to heat, thereby preventing further combustion.
  • Such formulations have generally found applications in cellulosic type materials, resins and formulations containing low molecular weight polyols for paints, and other such coating materials.
  • Various phosphorus-containing compounds are disclosed in, for example: Chemical Abstracts 2. 111554 and 9J> 143939; U.S. Patent Nos.
  • U.S. Patent No. 4491644 discloses a flame-retardant additive commercially available under the trade name CHARGARD comprising a salt formed from melamine and bis(pentaerythritol phosphate) phosphoric acid formulated for use principally in poly(propylene) .
  • European Patent No. 0115871 discloses flame- retardant additives comprising a nitrogen-containing oligomer and ammonium polyphosphate, which are commercially available under the trade name SPINFLAM in grades specific to a particular polymer, e.g., polyethylene.
  • n is an integer and has a value from 2 to 25;
  • R 1 represents an alkyl group comprising up to 20 carbon atoms
  • R 2 represents R 3 -NH where R 3 represents an alkyl group comprising up to 20 carbon atoms, an aryl nucleus comprising up to 10 carbon ring atoms, or R 2 represents a heterocyclic ring nucleus comprising from 4 to 8 ring atoms, at least one ring atom being nitrogen and linking the ring nucleus to the triazine ring, optionally in combination with a source of phosphorus.
  • R 1 represents an alkyl group comprising up to 20 carbon atoms, an aryl group comprising up to 10 carbon ring atoms or a group represented by -YR 5 where R 5 is an alkyl or other aliphatic group comprising up to 20 carbon atoms or an aryl group comprising up to 10 carbon ring atoms and Y is O, S or —NR 6 where R 6 is a hydrogen atom, an alkyl group comprising up to 20 carbon atoms, an aryl group comprising up to 10 carbon ring atoms or R 5 and R 6 may together form a heterocyclic ring (including the N atom) wherein the other ring atoms are chosen from C, N, O and S;
  • Each R 3 independently represents a divalent aliphatic linking group comprising up to 20 carbon atoms or a divalent aromatic linking group comprising up to 10 carbon ring atoms;
  • R 2 and R 4 independently represent a hydrogen atom, an alkyl group comprising up to 20 carbon atoms or an aromatic group comprising up to 10 carbon ring atoms or, when R 3 is aliphatic, R 2 and R 4 may complete a heterocyclic ring including -N—R 3 —N-, the remaining ring atoms being selected from C, N, 0 and S, and X 1 represents O, S or NR 2 , where R 2 is as defined previously, and
  • X 2 represents O, S or NR 4 , where R 2 and R 4 are as defined previously.
  • Alternative compounds have now been found which are suitable for use in flame-retardant additives for polymer materials having reduced smoke generation, reduced evolution of corrosive gas and improved flammability properties. The compounds are compatible with a variety of polymers applicable for wire and cable insulation, heat recoverable materials and mouldable parts.
  • a non-halogen containing flame-retardant additive comprising a salt of an inorganic phosphorus- containing acid and a polymeric compound which is a homopolymer or copolymer and comprises a linear backbone formed of at least 10 repeat units and contains a plurality of basic nitrogen functionalities.
  • the additives are suitable for use in polymer materials either alone or in combination with other flame-retardant additives, resulting in an additive having reduced smoke generation, reduced evolution of corrosive gases and improved flame-retarding properties.
  • the flame-retardant additives of the invention are compatible with a variety of thermoplastic and thermoset polymers applicable for wire and cable insulation, heat recoverable items, electrical tape and moulded parts.
  • the additives may also be formulated as a dispersion into coating compositions optionally comprising additional ingredients such as, other flame-retardants, fillers, colourants etc.
  • the additives may be employed in caulks, mastics and sealants.
  • a polymer containing a flame-retardant loading of the additives of the invention and an article formed from such a polymer are particularly suitable for use in polymers, especially, but not exclusively, polyolefin polymers.
  • the polymeric compound forming the salt with the phosphorous-containing acid must possess basic nitrogen functionalities which may be present in the backbone or in groups pendant thereto.
  • the backbone of the polymer is linear and is formed of at least 10 repeat units which need not be identical, i.e., the polymer may be a homopolymer or copolymer.
  • the number of backbone atoms per repeat unit varies with the polymer type as is well known in the art. For example, a vinyl addition polymer has 2 backbone carbon atoms per repeat unit, while a polymer formed by a ring-opening process has x backbone atoms per repeat unit, where x is the number of atoms in the original ring.
  • the number of backbone atoms per repeat unit is taken to be the sum of the number of catenary atoms per molecule of each of the monomers.
  • polymers derived from vinyl addition or ring-opening polymerisation are preferred.
  • the backbone must possess at least 20 atoms exclusive of end-capping groups, and preferably it possesses at least 30 atoms.
  • Carbon and nitrogen are the preferred backbone atoms, but other hetero-atoms such as 0, S, P etc may also be present.
  • at least 10 of the backbone atoms are selected from the group consisting of nitrogen atoms which form part of a basic nitrogen functionality, and carbon atoms which are bonded to a pendant group comprising one or more basic nitrogen functionalities.
  • Basic nitrogen functionalities are nitrogen-containing groups which readily form salts with acids via protonation of the nitrogen.
  • Typical examples include amines (primary, secondary or tertiary) and nitrogen-containing heterocycles such as pyridines, pyrollidines, piperidines, orpholines etc.
  • the term linear backbone is used to denote that the polymer possesses a recognisable backbone and is not in the form of a three-dimensional network such as those formed by urea-formaldehyde and melamine-formaldehyde condensates. Thus, the polymer may possess some branches from the backbone providing the polymer remains soluble prior to salt formation.
  • the use of a linear backbone is advantageous in terms of ease of synthesis of the salt as it enables the use of homogenous solutions.
  • the relatively high molecular weight of the polymers having at least 10 repeat units render the additives non-migrating and moisture insensitive in the host polymers.
  • the salt comprises at least one unit represented by general formula
  • R is a nitrogen-containing repeat unit, of the polymeric compound
  • X y " is the deprotonated or partially deprotonated form of the phosphorus-containing acid, and y is an integer.
  • the salt preferably comprises at least ten such units and more preferably from 10 to 50 units.
  • R preferably represents a structure represented by general formula (II) or (III) :- R 1 R 2
  • R 1 and R 2 independently represent H or an alkyl group of up to 5 carbon atoms
  • R 3 represents a group comprising a basic nitrogen functionality. Examples of groups represented by R 3 include:
  • Repeat units other than those represented by formulae II and III may also be present as a result of copolymerisation with other monomers, but this is not preferred.
  • Examples of polymers comprising repeat units of Formula II include (but are not limited to) : polyethyleneimine.
  • Examples of polymers comprising repeat units of Formula III include (but are not limited to) polymers and copolymers of allylamine, 2-vinyl pyridine, 4-vinyl pyridine, 4-aminostyrene, N,N-dimethylaminoethyl methacrylate and N-vinyl pyrollidone.
  • the basic nitrogen functionality may be present from the outset in the monomer(s) used to prepare the polymer (as is the case in the above examples) , or may be generated by chemical conversion of precursor groups on a preformed polymer, e.g., polyvinylamine and its N-alkyl derivatives.
  • Other useful polymers include the cyclopolymers derived from polymerisation of diallylamine derivatives, which comprise interlinked piperidine rings, as described in "Encyclopaedia of Polymer Science and Engineering", 2nd Ed. Vol.4 p.543.
  • Examples of phosphorus-containing acids include (but are not limited to) : orthophosphoric, hypophosphorous, trimetaphosphoric, polyphosphoric, phosphorous, hypophosphoric and pyrophosphoric acids.
  • alkyl group is intended to include not only pure hydrocarbon alkyl chains, such as methyl, ethyl, octyl, cyclo-hexyl, isooctyl, t-butyl and the like, but also alkyl chains bearing conventional non-halogen-containing substituents known in the art, such as hydroxyl, alkoxy, phenyl, nitro, a ino etc.
  • the term “nucleus” is likewise considered to allow for substitution.
  • pyrimidine nucleus would be understood to include not only an unsubstituted pyrimidine ring, but also pyrimidine rings bearing conventional substituents known in the art.
  • alkyl moiety on the other hand is limited to the inclusion of only pure hydrocarbon alkyl chains such as methyl, ethyl, propyl, cyclohexyl, isooctyl, t-butyl and the like.
  • substituents likely to give rise to toxic fumes on combustion, such as nitrile and sulphur-containing species, are not preferred.
  • the flame-retardant additives may optionally be prepared by blending the P/N salts with an additional phosphorus-based flame retardant.
  • the second phosphorus- based additive may comprise any inorganic or organic phosphorus source known in the art which (in the concentration used) does not deleteriously affect the properties of the polymer to which it is added.
  • Preferred examples of the second phosphorus source comprise ammonium polyphosphate (commercially available under the trade name PHOSCHEK P-40 from Monsanto) , melamine phosphate (commercially available under the trade name AMGARD NH from Albright and Wilson) and red phosphorus.
  • the phosphorus source may optionally be encapsulated, e.g., in a water-insoluble resin.
  • a preferred example is ammonium polyphosphate in melamine formaldehyde (commercially available under the trade name EXOLIT 462 from Hoechst- Celanese) .
  • the percentage (by weight) of the second phosphorus-based additive in the combined additive is dependent on the flammability of the polymer which is to be flame-retarded and the level of flame-retardance which is to be achieved, but preferably it is no greater than 70 percent, more preferably no greater than 50 percent and most preferably no greater than 30 percent.
  • the particle size of the P/N salt and the second phosphorus source is important for both flammability performance and for the physical properties of the flame- retarded material.
  • both additive components are in free flowing form and have an average particle size of less than 80 ⁇ m, more preferably less than 40 ⁇ m.
  • Conventional methods to obtain these particle sizes include using sieves, ball milling and jet milling.
  • precipitation of the final product can be optimised to minimise particle size.
  • Preferred polymers include low density poly(ethylene) (LDPE) , poly(ethylene-ethyl acrylate) (EEA) , poly(ethylene-acrylic acid) (EAA) , poly(ethylene-vinyl acetate) (EVA) , poly(propylene) (PP) , ethylene-propylene-diene monomers (EPDM) and copolymers thereof.
  • LDPE low density poly(ethylene)
  • EAA poly(ethylene-ethyl acrylate)
  • EAA poly(ethylene-acrylic acid)
  • EVA poly(ethylene-vinyl acetate)
  • EVA poly(propylene)
  • PP ethylene-propylene-diene monomers
  • EPDM ethylene-propylene-diene monomers
  • the choice of polymer i.e., flammability, melt index (ASTM) and copolymer content, will affect the quantity of flame-retardant added, as will the level of flame- retardance to be achieved.
  • the total flame- retardant loading by weight is from 10 to 60%, preferably from 20 to 50% of the total composition.
  • the flame- retardant additives of the invention are particularly suitable for use in EVA and EEA formulations.
  • Polymers comprising flame-retardant additives of the invention i.e., the P/N salt(s) and optionally the second phosphorus source (referred to hereinafter as the "polymers of the invention" may be cross-linked, for example, either chemically or by high energy radiation.
  • chemical cross-linking methods include the use of free radical initiators, such as dicumyl peroxide, together with co-curing agents, e.g., triallyl isocyanurate, or silane cross-linking technology, e.g., using products commercially available under the trade names MONSIL and SIOPLAS from Maillerfer and Dow Corning respectively.
  • Cross-linking by high energy radiation can also be used, for example, by irradiating with an electron beam. Radiation doses in the range 2 to 40 Mrads, preferably 10 to 20 Mrads are appropriate.
  • radical promoters such as triallyl isocyanurate, can be used.
  • Surface treatments may be used to increase the coupling between the flame-retardant additive and the polymer host matrix.
  • Materials such as zircoaluminates and titanates can be used or, more commonly, silane coupling agents.
  • additives for example, smoke suppressants, anti-oxidants, heat stabilisers, UV stabilisers etc.
  • smoke suppressants for example, smoke suppressants, anti-oxidants, heat stabilisers, UV stabilisers etc.
  • care must be exercised in the selection of these additives so that they do not interfere with the flame-retardant mechanism of the P/N compound(s) .
  • Basic oxides such as magnesium oxide or zinc oxide, are found to be particularly detrimental in large concentrations.
  • additives which contain water of hydration e.g., alumina trihydrate, can also be inhibiting in large concentrations.
  • Polymers incorporating the flame-retardant additives of the present invention can be processed using conventional methods, e.g., Banbury or two-roll mill, and extruded or moulded, either by compression or injection methods.
  • the polymer compositions of the invention are particularly suitable for use in wire and cable insulation, dimensionally recoverable products, especially heat recoverable products, moulded parts, extruded tubings, pipes and tape type constructions, where high levels of flame-retardency together with evolution of low quantities of smoke and toxic corrosive combustion products are required.
  • Dimensionally recoverable products are ones which by appropriate treatment can alter their dimensions. In the case of heat recoverable products, this treatment would be heat.
  • Polymer compositions of the invention where the polymer is cross-linked EEA/EVA are particularly useful in the preparation of flexible, flame-retardant, heat recoverable tubing.
  • the P/N salts can be prepared by conventional procedures. For example, solutions of the nitrogen- containing polymer and the phosphorus-containing acid may be mixed in suitable proportions, causing precipitation of the desired product. Alternatively, a monomer salt may be prepared, and subjected to polymerisation by conventional methods.
  • the invention will now be described with reference to the accompanying, non-limiting Examples in which polymers and flame-retardant additives were compounded using a variety of methods.
  • Polyolefin based formulations were compounded using either an electrically heated Schwabenthan two roll mill at 140°C for LDPE and 75 to 85°C for EVA and EVA/EPDM blends, or mixed using a Brabender PLASTICORDER Torque rheometer, with 30 or 300cm 3 internal mixing head, for 2 minutes at 100°C (EVA/EPDM) AND 140°C (LDPE) .
  • Formulation into other polymers will be discussed under the individual examples.
  • Test pieces were commonly produced by compression moulding using a Gem hydraulic press. Conditions employed were 110°C for 10 minutes (EVA or EVA/EPDM) AND 150°C for 20 minutes (LDPE) with 12 ton pressure. Formulations containing other polymers will be discussed under the individual examples. "EXOLIT IFR-10" and “EXOLIT IFR-23" (Hoechst-
  • Polymer flammability performance in the Examples was generally evaluated by two procedures, namely: the Underwriters' Laboratory UL94 vertical bar flame test and cone calorimeter performance. The latter procedure was also used to determine the smoke and toxic gas production of the materials in the Examples.
  • Underwriter 7 s Laboratory UL94 vertical bar flame test This is a widely accepted test method and is commonly used by suppliers of flame-retardants and flame- retarded materials. In this test a vertically clamped specimen bar is ignited by a flame from a bunsen burner. According to Part 2 of UL94, three levels of performance are defined, designated V-0, V-l and V-2, of which V-0 is the most stringent. In the test, samples not achieving V- 0 and V-l or V-2 are defined as fail.
  • UL94 defines the specimen size as 12.7cm (5 inches) long and 1.27cm (1/2 inch) wide. The thickness of the sample must be no greater than 3.2mm (1/8 inch). UL94 performance obviously depends on specimen thickness and is generally quoted for 1.6mm (1/16 inch) or 3.2mm (1/8 inch).
  • Determination of the obscuration of a laser beam passing through the combustion product stream enables the smoke produced to be measured, usually expressed as a specific extinction area.
  • a variety of toxic gases can also be continuously monitored, in particular carbon monoxide, carbon dioxide and oxides of nitrogen, the first two by means of infrared spectroscopy and the latter by means of a chemiluminescence detector. Additionally the test specimen is mounted on a load cell throughout the test so that all the measured properties can be related to a rate of mass loss.
  • RHR can be visualised as the intensity of the fire, so the lower the values of RHR the better in terms of flammability performance.
  • SEA is a widely used smoke performance parameter relating the amount of smoke produced to the mass loss rate of the burning specimen.
  • Thermal analysis of the product reveals 1 to 2% of volatiles even after prolonged drying.
  • Thermogravimetric analysis (TGA) in air reveals the compound is stable up to ca. 200°C. Ca. 50% weight of residue is retained up to 740°C.
  • PYROPHOSPHATE This Example illustrates an alternative procedure for the preparation of poly(allylammonium) pyrophosphate. The procedure is as disclosed in European Patent Publication No. 145220.
  • EXAMPLE 3 OPTIMISATION OF POLY(ALLYLAMMONIUM) PYROPHOSPHATE FLAMMABILITY PERFORMANCE - UL94 TESTING
  • Phosphorus/nitrogen-containing flame-retardants conventionally comprise three active components, namely: an acid source; a char former and a spumific or blowing agent. In some cases there may be only two active components, e.g., ammonium polyphosphate (APP) with trishydroxyethyl isocyanurate (THEIC) .
  • APP ammonium polyphosphate
  • TCEIC trishydroxyethyl isocyanurate
  • EXAMPLE 4 COMPARATIVE FLAMMABILITY PERFORMANCE - UL94 TESTING
  • This Example compares the flammability performance of poly(allylammonium) pyrophosphate with known phosphorus/nitrogen-containing flame-retardants:
  • the comparative systems were: EXOLIT IFR-10 (Hoechst Celanese) and ammonium polyphosphate (APP) (PHOSCHEK P-40, Monsanto) .
  • the results obtained are shown in TABLE 2. All data refer to samples in non-crosslinked EVA (ELVAX 470) .
  • poly(ally1ammonium) pyrophosphate is a better performer than either of the known phosphorus/nitrogen-containing flame-retardants, with no flaming time observed in attaining its UL94 V-0 rating.
  • This Example demonstrates the flammability performance of poly(allylammonium) pyrophosphate when compared with known phosphorus/nitrogen-containing flame- retardants.
  • the comparative systems were: EXOLIT IFR-10 and EXOLIT IFR-23 (Hoechst-Celanese) . All data refers to samples in non-crosslinked EVA ELVAX 470) . A standard irradiant flux level of 50kWm "2 was employed. Two runs were undertaken for each sample and the results were averaged. The results obtained are reported in TABLE 3.
  • FIGURE 1 shows dramatically the improvement in RHR realised by utilising poly(allylammonium) pyrophosphate as opposed to both EXOLIT IFR-10 and IFR-23.
  • Poly(allylammonium) pyrophosphate produces a better protective char for unburned fuel than either EXOLIT IFR-10 or EXOLIT IFR-23 as evidenced by the lack of a second period of heat release up to nearly 800 seconds.
  • This Example demonstrates the usefulness of surface treatment of the P/N polymeric salts to improve their dispersibility in polymers and hence the physical properties of the resulting material.
  • a number of surface treatment agents can be used, including titanates, silanes, zirconates and zircoaluminates, but the particular example chosen here is the titanate commercially available from Kenrich Petrochemicals Inc. Under the trade designation KR38S.
  • the flame-retardant in this case poly(allylammonium) pyrophosphate, was ball milled for 16 hours in a 2% w/w solution of KR38S in toluene (concentrations of between 0.5% and 5.0% could be used) , resulting in a fine, easily dispersable powder.
  • the particle size can be reduced further by jet milling if necessary.
  • EXAMPLE 8 USEFULNESS OF PAP TREATED WITH VARIOUS COUPLING AGENTS WITH A SECOND PHOSPHORUS SOURCE
  • This example demonstrates the performance of PAP with a variety of titanate and silane coupling agents, with or without the addition of a second phosphorus source, namely ammonium polyphosphate PHOSCHEK P-40) . All materials were evaluated in EVA EPsyn [4:1] in terms of cone calorimeter performance. Coupling agents used were KR38S titanate (Kenrich Petrochemicals Inc.), 3- aminopropyltrimethoxysilane and amyltriethoxysilane. A sample containing ammonium polyphosphate as the flame- retardant is included for comparison. All cone calorimeter experiments were performed at 50kWm "2 irradiant flux and all PAP samples were reduced to a particle size of less than 53 ⁇ m. The results obtained are shown in TABLE 6.
  • EXAMPLE 10 USE AS A FLAME RETARDANT IN POLYOLEFIN/RUBBER BLENDS
  • the flammability performance of PAP alone is compared below with the state-of-the-art commercial non-halogen flame-retardants EXOLIT IFR-10 and EXOLIT IFR-23 and a typical halogenated flame-retardant based on the following commercially available materials - decabromodiphenyloxide (DB) : antimony oxide (ATO) : alumina trihydrate (ATH) (2:1:1).
  • DB was obtained from Great lakes Chemicals, ATO from Anzon America Inc. (11-0000-2556-6) and ATH is the 932 grade from Solem.
  • EXAMPLE 12 USE AS A FLAME RETARDANT IN LOW DENSITY POLYETHYLENE This Example demonstrates the usefulness of compounds of general formula (1) , with or without a second phosphorus source, as flame retardants for low density polyethylene. Formulations were prepared in the aforementioned fashion and evaluated on a cone calorimeter at an irradiant flux of 50kWm" 2 . Formulation constituents were as shown in TABLE 10 in which the following nomenclature is employed:
  • DBDPO decabromodiphenyl oxide (Great Lakes Chemical
  • ATO antimony trioxide (Anzon America Inc.),
  • PHOSCHEK P40 ammonium polyphosphate (Monsanto) ,
  • PAP poly(allylammonium) pyrophosphate
  • the compounds of this invention whether used alone or in conjunction with a second phosphorus source, confer excellent properties upon LDPE in terms of rate of heat release, smoke generation and toxic gas yield, considerably outperforming a widely used flame retardant additive system such as decabromodiphenyl oxide/antimony trioxide.
  • EXAMPLE 13 USE AS A FLAME RETARDANT IN CROSS-LINKED POLYOLEFINS This Example demonstrates the usefulness of PAP, as a 4:1 blend with ammonium polyphosphate PHOSCHEK P-40, in crosslinked ethylene-vinyl acetate copolymer (ELVAX 470) .
  • Formulations were prepared containing either 45% or 50% total flame retardant plus 3% trimethylolpropyl trimethacrylate electron beam prorad and 1 phr stearic acid. These materials were extruded into tubing of outside diameter 0.64cm (0.25 inches) and wall thickness 25 ⁇ m (25mils) , which was then cross-linked by means of exposure to an electron beam dose of lOMRad.
  • Flammability performance was assessed by means of the Underwriters' Laboratories UL224 test for tubing materials. This involves the application of a Bunsen Flame to the vertically clamped tubing for five 15 second burns, each separated by an interval of either 15 seconds or the observed flaming time of the specimen, whichever is greater.
  • the flaming time in each case must not exceed 60 seconds and the material must emit no flaming drips which ignite a cotton wool pad placed underneath the specimen.
  • Each material is generally tested five times, and if any specimen does not meet the pass criteria it is deemed to be not VW-1 rated.
  • EXAMPLE 16 USE AS A FLAME RETARDANT IN THERMOPLASTIC POLYURETHANE This example demonstrates the usefulness of compounds of general formula (1) as flame retardants for thermoplastic polyurethanes. Formulations were compounded on a Schwabenthan PolymixTM two roll mill at 140-145°C and test pieces were fashioned by compression moulding in a Moore hydraulic press at 170°C for five minutes. Evaluations were performed on a cone calorimeter using an external irradiant flux of 50 kW m "2 . A composition containing a flame retardant in accordance with this invention was compared with SpinflamTM MF82/PU, a commercially available phosphorus/nitrogen flame retardant specifically designed for polyurethanes. Formulation constituents were as shown in Table 16: -3Q - TABLE 16
  • EstaneTM 58315 thermoplastic polyurethane (BF Goodrich) , PAP - poly(allylammonium) pyrophosphate, MF82/PU - SpinflamTM MF82/PU (Himont Italia) .
  • PAP shows considerably better performance than SpinflamTM MF82/PU as a flame retardant for thermoplastic polyurethane, as illustrated by longer time to ignition, lower peak rate of heat release whilst showing similar average rate of heat release, and lower yield of a toxic combustion product such as oxides of nitrogen.
  • PAP shows better overall performance than SpinflamTM MF82/PP as a flame retardant for polystyrene, as illustrated by similar (i.e. within 10%) time to ignition, peak rate of heat release and average rate of heat release, whilst displaying a significantly lower yield of a toxic combustion product such as oxides of nitrogen.
  • ACRYLONITRILE This example demonstates the usefulness of compounds of general formula (1) as flame retardants for copolymers of polystyrene and acrylonitrile.
  • Formulations were compounded on a Schwabenthan PolymixTM two roll mill at 130-135°C and test pieces were fashioned by compression moulding in a Moore hydraulic press at 150°C for five minutes. Evaluations were performed on a cone calorimeter using an external irradiant flux of 50 kW nr 2 .
  • a composition containing a flame retardant in accordance with this invention was compared with SpinflamTM MF82/PU, a commercially available phosphorus/nitrogen flame retardant.
  • Formulation constituents were as shown in Table 20:
  • This example demonstates the usefulness of compounds of general formula (1) as flame retardants for poly(vinyl alcohol) .
  • Formulations were compounded on a Schwabenthan PolymixTM two roll mill at 140-145°C and test pieces were fashioned by compression moulding in a Moore hydraulic press at 170°C for five minutes. Evaluations were performed on a cone calorimeter using an external irradiant flux of 50 kW m "2 .
  • a composition containing a flame retardant in accordance with this invention was compared with SpinflamTM MF82/PE, a commercially available phosphorus/nitrogen flame retardant.
  • Formulation constituents were as shown in Table 22:
  • PAP shows better overall performance than SpinflamTM MF82/PE as a flame retardant for polystyrene-co-acrylonitrile as illustrated by similar (i.e. within 10%) peak rate of heat release and yield of a toxic combustion product such as oxides of nitrogen, but a significantly longer time to ignition, albeit with slightly higher average rate of heat release.

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Abstract

Un additif ignifuge non halogéné comprend un sel d'un acide inorganique contenant du phosphore et un composé polymère qui est un homopolymère ou copolymère et se compose d'une ossature linéaire formée d'au moins 10 unités de répétition et contient une pluralité de fonctionalités d'azote basique. Les additifs sont appropriés pour être utilisés dans des matériaux polymères, soit seuls, soit en combinaison avec d'autres additifs ignifuges, ce qui donne lieu à un additif produisant moins de fumée, émettant moins de gaz corrosifs et ayant des propriétés ignifuges améliorées. Les additifs ignifuges de l'invention sont compatibles avec une variété de polymères thermoplastiques et thermodurcis pouvant être utilisés dans l'isolation de fils et de câbles, être appliqués à des articles aptes à récupérer la chaleur, à du chatterton et à des pièces moulées. Les additifs peuvent également être préparés sous forme d'une dispersion dans des compositions de revêtement comprenant éventuellement des ingrédients supplémentaires tels que d'autres ignifuges, des charges de remplissage, des colorants, etc. Les additifs peuvent être aussi utilisés dans les agents de matage, les mastics et les agents d'étanchéité.
PCT/US1993/010606 1992-11-13 1993-11-05 Ignifuges WO1994011425A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP94900530A EP0668887A1 (fr) 1992-11-13 1993-11-05 Ignifuges
JP6512203A JPH08503505A (ja) 1992-11-13 1993-11-05 難燃剤

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9223792A GB2272444B (en) 1992-11-13 1992-11-13 Flame retardants
GB9223792.4 1992-11-13

Publications (1)

Publication Number Publication Date
WO1994011425A1 true WO1994011425A1 (fr) 1994-05-26

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EP (1) EP0668887A1 (fr)
JP (1) JPH08503505A (fr)
CA (1) CA2146558A1 (fr)
GB (1) GB2272444B (fr)
WO (1) WO1994011425A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0775736A2 (fr) 1995-11-27 1997-05-28 Minnesota Mining And Manufacturing Company Composition adhésive sensible à la pression et rubans
US5851663A (en) * 1994-05-25 1998-12-22 Minnesota Mining And Manufacturing Company Flame retardant pressure-sensitive adhesives and tapes
WO2001094458A3 (fr) * 2000-06-05 2002-04-18 Fuller H B Licensing Financ Composition ignifuge
CN103396450A (zh) * 2013-08-01 2013-11-20 苏州科技学院相城研究院 阻燃剂四(0，0-二丁基磷酰基)甘脲化合物及其制备方法
CN103642114A (zh) * 2013-12-26 2014-03-19 河南省聚友塑料有限公司 150℃高强度高电性耐油辐照交联无卤阻燃环保聚烯烃电缆料及其生产方法
EP3326967A1 (fr) * 2016-11-25 2018-05-30 Leibniz-Institut für Polymerforschung Dresden e.V. Polyphosphate multifonctionnel modifié et procédé pour préparer les polyphosphates multifonctionnels modifiés
WO2025195895A1 (fr) * 2024-03-20 2025-09-25 Sabic Global Technologies B.V. Composite polymère/complexe polyélectrolyte (pec) ignifuge
WO2025195894A1 (fr) * 2024-03-20 2025-09-25 Sabic Global Technologies B.V. Composite polymère-complexe polyélectrolyte (pec) ignifuge

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2289680A (en) * 1994-05-25 1995-11-29 Minnesota Mining & Mfg Flame-retardant pressure sensitive adhesives and tapes
DE19919707A1 (de) 1999-04-30 2000-11-02 Clariant Gmbh Brandschutzbeschichtung für Fasermaterialien
DE10015889B4 (de) * 2000-03-30 2005-09-08 Clariant Gmbh Brandschutzbeschichtung
JP2003082291A (ja) * 2001-06-28 2003-03-19 Nippon Zeon Co Ltd ワニス及びその利用
JP2007507564A (ja) * 2003-10-02 2007-03-29 フラウンホーファーゲゼルシャフト ツール フォルデルング デル アンゲヴァンテン フォルシユング エー．フアー． 材料用防火剤のための組成物および防火方法
CN103396448B (zh) * 2013-08-01 2015-09-09 苏州科技学院相城研究院 阻燃剂四(o-异丙基-苯基次膦酰基)甘脲化合物及其制备方法
CN103396445B (zh) * 2013-08-01 2015-09-09 苏州科技学院相城研究院 阻燃剂四(0,0-二丙基磷酰基)甘脲化合物及其制备方法
CN103396449B (zh) * 2013-08-01 2015-10-21 苏州科技学院相城研究院 阻燃剂四(o-乙基-苯基次膦酰基)甘脲化合物及其制备方法
CN103396447B (zh) * 2013-08-01 2016-06-29 苏州科技学院相城研究院 阻燃剂四(o-丁基-苯基次膦酰基)甘脲化合物及其制备方法
CN103396446B (zh) * 2013-08-01 2016-02-24 苏州科技学院相城研究院 阻燃剂四(o-丙基-苯基次膦酰基)甘脲化合物及其制备方法
CN103396444B (zh) * 2013-08-01 2016-02-24 苏州科技学院相城研究院 阻燃剂四(o，o-二异丙基磷酰基)甘脲化合物及其制备方法
JP7228823B2 (ja) * 2019-01-30 2023-02-27 国立研究開発法人森林研究・整備機構 木質材料難燃化処理用組成物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB793196A (en) * 1955-03-04 1958-04-09 Beck Koller & Co England Process for improving the heat-stability of branched chain polyamide resins
JPS53117042A (en) * 1977-03-24 1978-10-13 Otsuka Chem Co Ltd Flame-retardant
JPS6172581A (ja) * 1984-09-17 1986-04-14 Canon Inc インクジエツト記録方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB657081A (en) * 1948-09-07 1951-09-12 Du Pont Improvements in or relating to polymeric polyamines
CH563418A5 (fr) * 1972-02-24 1975-06-30 Sandoz Ag
GB1475685A (en) * 1974-05-02 1977-06-01 Kodak Ltd Polymeric article having reduced surface resistivity
DE2801523B2 (de) * 1978-01-14 1980-06-04 Metallgesellschaft Ag, 6000 Frankfurt Kathodisch abscheidbares Überzugsmittel
EP0145220B1 (fr) * 1983-11-10 1988-06-01 Nitto Boseki Co., Ltd. Procédé de production de polymères de monoallylamine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB793196A (en) * 1955-03-04 1958-04-09 Beck Koller & Co England Process for improving the heat-stability of branched chain polyamide resins
JPS53117042A (en) * 1977-03-24 1978-10-13 Otsuka Chem Co Ltd Flame-retardant
JPS6172581A (ja) * 1984-09-17 1986-04-14 Canon Inc インクジエツト記録方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 7846, Derwent World Patents Index; AN 78-83079A *
DATABASE WPI Week 8621, Derwent World Patents Index; AN 86-135046 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5851663A (en) * 1994-05-25 1998-12-22 Minnesota Mining And Manufacturing Company Flame retardant pressure-sensitive adhesives and tapes
EP0775736A2 (fr) 1995-11-27 1997-05-28 Minnesota Mining And Manufacturing Company Composition adhésive sensible à la pression et rubans
US6022914A (en) * 1995-11-27 2000-02-08 3M Innovative Properties Company Pressure-sensitive adhesive composition and tapes
WO2001094458A3 (fr) * 2000-06-05 2002-04-18 Fuller H B Licensing Financ Composition ignifuge
US6387993B1 (en) 2000-06-05 2002-05-14 H. B. Fuller Licensing & Financing Inc. Flame retardant composition
CN103396450A (zh) * 2013-08-01 2013-11-20 苏州科技学院相城研究院 阻燃剂四(0，0-二丁基磷酰基)甘脲化合物及其制备方法
CN103396450B (zh) * 2013-08-01 2015-09-16 苏州科技学院相城研究院 阻燃剂四(0,0-二丁基磷酰基)甘脲化合物及其制备方法
CN103642114A (zh) * 2013-12-26 2014-03-19 河南省聚友塑料有限公司 150℃高强度高电性耐油辐照交联无卤阻燃环保聚烯烃电缆料及其生产方法
EP3326967A1 (fr) * 2016-11-25 2018-05-30 Leibniz-Institut für Polymerforschung Dresden e.V. Polyphosphate multifonctionnel modifié et procédé pour préparer les polyphosphates multifonctionnels modifiés
WO2025195895A1 (fr) * 2024-03-20 2025-09-25 Sabic Global Technologies B.V. Composite polymère/complexe polyélectrolyte (pec) ignifuge
WO2025195894A1 (fr) * 2024-03-20 2025-09-25 Sabic Global Technologies B.V. Composite polymère-complexe polyélectrolyte (pec) ignifuge

Also Published As

Publication number Publication date
CA2146558A1 (fr) 1994-05-26
JPH08503505A (ja) 1996-04-16
GB2272444A (en) 1994-05-18
EP0668887A1 (fr) 1995-08-30
GB9223792D0 (en) 1993-01-06
GB2272444B (en) 1997-04-02

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