Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
  • C09K21/06—Organic materials
  • C09K21/12—Organic materials containing phosphorus
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • 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
  • C08K3/30—Sulfur-, selenium- or tellurium-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
  • C08K5/005—Stabilisers against oxidation, heat, light, ozone

Definitions

• the present patent application relates to the preparation of flame-retarded compounds based on high impact polystyrene free of organohalo- genated additives but containing ammonium phos- phate/pentaerythritol, and ammonium bromide and/or iodide and selected metal oxides. All the operative conditions mentioned in the text of the present description should be considered as preferred conditions, even if not expressly declared.
• the external part of a household appliance such as a personal computer or a TV set, heats up and can slowly release the additive into the atmosphere, which can be inhaled by the occupants of the room. Furthermore, in the case of fire, the fumes which develop can contain degradation products of the same additives. For this reason, it is important for the additive not to be dangerous for health.
• Organo-halogenated flame- retardants are the most efficient from the point of view of performances and in many cases they are the only ones capable of permitting the flame-retardant class VO-UL94.
• the products commonly used are: decabromodiphenyloxide, hexabromocyclododecane, tetrabromodiphenol-A and relative derivatives, decabromodiphenylethane and ethylene-bis- tetrabromophthalimide . These derivatives are known as PBDE (PolyBrominated Diphenyl Ethers) .
• formulations based on vinyl aromatic polymers such as high impact polystyrene, containing additives which are not organo- brominated.
• formulations have been found comprising ammonium phosphate, ammonium bromide and metal oxides which have allowed valid results to be obtained in terms of flame-retardancy without impairing the physical- mechanical characteristics of the products to which they have been added.
• the object of the present invention therefore relates to flame-retarded polymeric compositions compris- ing: a. a vinyl aromatic (co) polymer; b. 10-25 phr, preferably 12-18 phr, of a blend of ammonium phosphate (APP) /pentaerythritol (PER) having an APP/PER weight ratio ranging from 2 to 4; c. 3-8 phr, preferably 3.5-7 phr, of an ammonium halide selected from bromide and iodide, preferably ammonium bromide; d.
• APP ammonium phosphate
• PER pentaerythritol
• 0.1-1 phr preferably 0.1-0.5 phr, calculated with respect to the metal, of an oxide selected from MnO 2 , MnO, TiO 2 , ZrO 2 , CuO, Sb 2 O 3 ; and wherein the sum of (b) + (c) ranges from 13 to 30 phr, preferably from 15 to 22 phr.
• vinyl aromatic (co) polymer refers to a (co) polymer obtained from the (co) polymerization of at least one monomer having the following general formula (I) : wherein R is a hydrogen or methyl group, n is zero or an integer ranging from 1 to 5 and Y is preferably an alkyl or alkoxyl radical having from 1 to 4 carbon atoms, possibly in the presence of a reinforcing elastomeric phase.
• vinyl aromatic monomers having the above general formula are: styrene, ⁇ -methylstyrene, methyl- styrene, ethylstyrene, butylstyrene, dimethylstyrene, methoxy-styrene, acetoxy-styrene, etc..
• Preferred vinyl aromatic monomers are styrene and/or ⁇ -methylstyrene.
• (I) can be used alone or in a blend of up to 50% by weight with other copolymerizable monomers.
• these monomers are (meth) acrylic acid, Ci-C 4 alkyl esters of (meth) acrylic acid such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopro- pyl acrylate, butyl acrylate, amides and nitriles of (meth) acrylic acid such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, butadiene, ethylene, divinyl benzene, maleic anhydride, etc.
• Preferred mono- mers which can be present in the copolymer are acrylonitrile and methyl methacrylate.
• the above monomers can be reacted in the presence of any elastomeric compound which can be used as reinforcing product in a vinyl aromatic (co) polymer.
• the preferred elastomeric product is butadiene homopolymer with a number average molecular weight (Mn) ranging from 50,000 to 350,000 and a weight average molecular weight (Mw) ranging from 100,000 to 500,000.
• elastomeric products which can be used instead of polybutadiene or in a mixture with the same, can be selected from homopolymers and copolymers of 1,3- alkadienes containing 40-100% by weight of 1, 3-alkadiene monomer, for example butadiene, isoprene or pentadiene, and 0-60% by weight of one or more monoethylenically unsaturated monomers, selected from styrene, acrylonitrile, ⁇ -methylstyrene, methylmethacrylate and ethylacrylate .
• 1, 3-alkadiene copolymers are styrene- butadiene block copolymers, such as diblock linear elastomers of the S-B type and/or SBS triblock, wherein S represents a polystyrene block having an average molecu- lar weight Mw ranging from 5,000 to 80,000, whereas B represents a polybutadiene block having an average molecular weight Mw ranging from 2,000 to 250,000.
• the quantity of block S in these elastomers ranges from 10 to 50% by weight with respect to the total of the S-B rub- ber.
• Other examples of elastomers which can be used in the process object of the present invention are those listed in European patent 606,931.
• High Impact Polystyrene is the preferred vi- nyl aromatic polymer, consisting of a continuous polystyrene matrix in which polybutadiene homopolymer particles are distributed.
• a rate of 60 rpm was adopted and a mixing time of 8 minutes, of which about 1-2 are necessary for the complete melting/plasticization of the polymeric mass.
• the discharge of the mixing chamber is effected in the short- est possible time, with the help of a compressed air gun to facilitate the cooling and detachment of the melted mass from the metal parts.
• the collected Material was ground in a Colortronic M102L blade mill equipped with a 6 mm grid and cooled with dry ice. Before being introduced into the mill together with the CO 2 , the sample was put in equilibrium with the temperature of the dry ice in a suitable heat-insulated container. After eliminating most of the condensation water (12 hrs under a hood) , the material thus ground was dried for 8 hours under vacuum at 70 0 C.
• the sheets were manually cut with the help of a template and steel cutter, obtaining test-samples having a width of 12.7 mm.
• the small bars thus obtained were finished with sheets of emery paper (N180 and subsequently N400) fixed to a flat base.
• test sample positioned in a suitable clamp in a vertical position, is put in contact with a flame for 10 seconds (tl); after said triggering, the proceeding of the combustion is monitored. If the test sample is extin- guished before being consumed, it is exposed again to the flame for 10 additional seconds (t2) .
• Tg evaluated by means of Differential Scanning CaIo- rimetry (DSC) with a DSC/ Perkin Elmer instrument at a scanning rate of 10°C/min.
• DSC Differential Scanning CaIo- rimetry
• the formulate of this example has a Tg of 92 0 C and can therefore be considered as having adequate thermo- mechanic resistance, completely similar to that of original high impact polystyrene (Tg of 91°C) .
• the formulate has a Tg value of 91.7 0 C and does not pass the flame-retardant test UL94-V. Comparative example 2
• the formulate has a Tg value of 92 0 C and does not pass the flame-retardant test UL94-V.
• Comparative example 4 The procedure of example 1 was repeated, using high impact polystyrene 241.7 g
• the formulate has a Tg value of 89.7 0 C and does not pass the flame-retardant test UL94-V.
• Comparative example 5 The procedure of example 1 was repeated, using high impact polystyrene 262.8 g
• the formulate has a Tg value of 92.5 0 C and does not pass the flame-retardant test UL94-V.
• Example 2
• the formulate has a Tg value of 92.5 0 C and a flame- retardant behaviour which includes the formulate in the UL94-V2 group.
• Example 3
• the formulate has a Tg value of 92.0 0 C and a flame- retardant behaviour which includes the formulate in the UL94-V2 group.
• Example 4
• the formulate has a Tg value of 92.2 0 C and a flame- retardant behaviour which includes the formulate in the UL94-V2 group.
• Example 5
• the formulate has a Tg value of 92.0 0 C and a flame- retardant behaviour which includes the formulate in the UL94-V2 group.
• Comparative example 7 The procedure of example 1 was repeated, using high impact polystyrene 230.1 g
• the formulate has a flame-retardant behaviour which allows it to be included in the UL94-V2 group, but it has a Tg of 52.0 0 C and this value jeopardizes the thermo- mechanical resistance.
• the formulate has a Tg value of 92.4 0 C and does not pass the flame-retardant test UL94-V.
• Comparative example 10 The procedure of example 1 was repeated, using high impact polystyrene 230.1 g
• the formulate has a Tg value of 91.9 0 C and does not pass the flame-retardant test UL94-V. Comparative example 11
• the formulate has a Tg value of 92.4 0 C and does not pass the flame-retardant test UL94-V. Comparative example 12
• the formulate has a Tg value of 91.7 0 C and does not pass the flame-retardant test UL94-V.
• Comparative example 13 The procedure of example 1 was repeated, using high impact polystyrene 244.3 g
• the formulate has a Tg value of 92.3°C and does not pass the flame-retardant test UL94-V. Comparative example 15
• the formulate has a Tg value of 92.2 0 C and does not pass the flame-retardant test UL94-V.

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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)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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Citations (3)

• 2006
  • 2006-10-10 IT IT001938A patent/ITMI20061938A1/it unknown
• 2007
  • 2007-10-01 WO PCT/EP2007/008520 patent/WO2008043448A1/en active Application Filing

Patent Citations (3)

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