WO1990006691A1 - Thermally stable and light stable flame retardant thermoplastic polyolefin and polystyrene compositions - Google Patents

Thermally stable and light stable flame retardant thermoplastic polyolefin and polystyrene compositions Download PDF

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Publication number
WO1990006691A1
WO1990006691A1 PCT/US1989/005627 US8905627W WO9006691A1 WO 1990006691 A1 WO1990006691 A1 WO 1990006691A1 US 8905627 W US8905627 W US 8905627W WO 9006691 A1 WO9006691 A1 WO 9006691A1
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Prior art keywords
flame retardant
compoεition
compound
bicyclic
halogen
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PCT/US1989/005627
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French (fr)
Inventor
Nicolai A. Favstritsky
Enrico J. Termine
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Great Lakes Chemical Corporation
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Priority to KR1019900701817A priority Critical patent/KR910700007A/en
Priority to JP90502089A priority patent/JPH03502820A/en
Publication of WO1990006691A1 publication Critical patent/WO1990006691A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65748—Esters of oxyacids of phosphorus the cyclic phosphorus atom belonging to more than one ring system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • 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
    • C08K5/527—Cyclic esters

Definitions

  • thermoplastic polyolefin and polystyrene compositions relate to thermal and light stable flame retardant thermoplastic polyolefin and polystyrene compositions. More particularly, this invention relates to thermoplastic compositions which are flame retardant and which resist thermal degradation or photochemically-induced degradation. These compositions comprise bicyclic phosphate compound(s); halogen-containing flame retardant( ⁇ ); and polystyrene or polyolefin resin.
  • compositions produced in accordance with this invention have a reduced tendency to develop color, to change melt viscosity, or to lose mechanical strength under conditions that are present during polymer processing or end-use. Description of the Prior Art.
  • polystyrene and polyolefin ⁇ such as homopolymers and copolymers of polypropylene, polyethylene, and polybutylene, may be flame retarded with halogen-containing flame retardant ⁇ .
  • flame retardant additive ⁇ are susceptible to thermal and photochemically-induced degradation during processing of the thermoplastic resin, or during polymer use conditions.
  • thermoplastic composition may develop a darkened appearance during processing, indicating polymer or flame retardant chemical decomposition; or the thermoplastic composition may suffer an increase or decrease in melt viscosity, limiting, for example, the recycle of industrial scrap ("regrind") or environmental plastic waste; or the thermoplastic composition may lose mechanical strength, thus reducing the overall service life of the polymeric material.
  • British Patent No. 889,338 describes the production of bicyclic phosphites, pho ⁇ phonate ⁇ , thiophosphates, and ⁇ elenophosphates. These compo ⁇ ition ⁇ are said to be stabilizer ⁇ for vinyl halide re ⁇ in ⁇ . They are alleged to be useful as heat ⁇ tabilizer ⁇ for vinyl chloride re ⁇ in, and as antioxidant ⁇ for fat ⁇ and oil ⁇ .
  • the British '338 Patent does not show any examples of bicylic phosphates, nor doe ⁇ it specify the u ⁇ e of bicyclic pho ⁇ phate ⁇ , such a ⁇ pentaerythritol-ba ⁇ ed bicyclic pho ⁇ phate ⁇ of the present invention, which can be employed as a stabilizer for polystyrene or polyolefin resin. Furthermore, the British '338 Patent doe ⁇ not disclose that cyclic pho ⁇ phate ⁇ of the pre ⁇ ent invention could be used with halogen-containing flame retardant ⁇ to produce flame retardant thermoplastic compo ⁇ itions which re ⁇ i ⁇ t thermal or photochemically-induced degradation.
  • British Patent No. 999,793 describes a proces ⁇ to produce organic phosphates by subjecting organic phosphites to reaction with peracetic acid.
  • This patent shows a method for producing the most preferred bicyclic phosphate of the present invention, 2,6,7-trioxa-l- pho ⁇ phobicyclo[2.2.2]-octane-4-methanol-l-oxide (vide infra) _ and teaches the use of acetal ring-containing pho ⁇ phate ⁇ a ⁇ pla ⁇ ticizer ⁇ or functional fluid ⁇ .
  • the British '793 Patent does not disclose the compo ⁇ itions of the present invention.
  • U.S. Patent No. 4,341,694 discloses a composition comprising 2,6,7-trioxa-l-phosphobicyclo[2.2.2]octane-
  • a primary object of this invention i ⁇ to provide thermal and light ⁇ table flame retardant thermoplastic polyolefin and poly ⁇ tyrene compo ⁇ itions.
  • a related object is to provide compo ⁇ ition ⁇ of the character de ⁇ cribed which resist thermal degradation or photochemically induced degradation.
  • a further object is to provide polystyrene or polyolefin resin compositions incorporating bicyclic phosphate compounds and halogenated flame retardant ⁇ .
  • thermopla ⁇ tic polyolefin or poly ⁇ tyrene resin compo ⁇ itions incorporating an additive mixture comprising a halogen-containing flame retardant; and a bicyclic phosphate compound of the following Formula (I):
  • X is OH, OR', or OC(0)R'
  • R is H or a saturated or un ⁇ aturated ⁇ traight-chain or branched-chain C--C.- al yl
  • R' i ⁇ a ⁇ aturated or un ⁇ aturated ⁇ traight-chain or branched chain C.-C-- alkyl.
  • thermoplastic polyolefin and polystyrene resin compo ⁇ ition ⁇ which are flame retardant and which re ⁇ ist thermal degradation or photochemically induced degradation and which incorporate an additive mixture compri ⁇ ing one or more bicyclic phosphate compounds and one or more halogen-containing flame retardant ⁇ .
  • Compo ⁇ ition ⁇ produced in accordance with thi ⁇ invention have a reduced tendency to develop color, to change melt vi ⁇ co ⁇ ity, or to lose mechanical strength under conditions pre ⁇ ent during polymer proces ⁇ ing or in u ⁇ e.
  • Preferred bicyclic pho ⁇ phate ⁇ in accordance with this invention are compounds of Formula (I) where X i ⁇ OH or OC(0)R' .
  • the most preferred bicyclic compounds are 2,6,7-trioxa-phosphobicyclo[2.2.2]-octane-4-methanol-l- oxide (Compound BCP, that i ⁇ , Formula [I] when R i ⁇ H and X i ⁇ OH), and 2,6,7-trioxa-l-pho ⁇ phobicyclo[2.2.2]- octane-4-methanol, acetate, 1-oxide (Compound BCP-A, that i ⁇ , when R i ⁇ H and X i ⁇ OC(O)CH-).
  • the halogen-containing flame retardant compound may be any brominated or chlorinated aliphatic or aromatic organic compound that can be used in thermoplastic compo ⁇ ition ⁇ .
  • Preferred halogen-containing compounds are hexabromocyclododecane, tetrabromobi ⁇ phenol A, tetrabromobi ⁇ phenol A bi ⁇ -(dibromopropylether), dibromo(dibromoethyl)cyclohexane, tetrabromocyclooctane, bi ⁇ -(dibromonorbornane dicarboximido)ethane, bi ⁇ -(tetrabromophthalimido)ethane, Diel ⁇ -Alder adduct of chlorinated cyclopentadiene and unsaturated cycloaliphatic compound, bi ⁇ -(tribromophenoxy- ethyl)tetrabromobisphenol A ether, pentabromodiphenyl
  • Re ⁇ ins which may be treated in accordance with the invention include thermopla ⁇ tic ⁇ ⁇ uch a ⁇ poly ⁇ tyrene and copolymers of ⁇ tyrene with butadiene and acrylonitrile ("ABS copolymer ⁇ ") and homopolymer ⁇ and copolymers of polyolefin ⁇ ⁇ uch a ⁇ polypropylene, polyethylene, and polybutylene.
  • ABS copolymer ⁇ thermopla ⁇ tic ⁇ ⁇ uch a ⁇ poly ⁇ tyrene and copolymers of ⁇ tyrene with butadiene and acrylonitrile
  • Polystyrene and polypropylene are preferred thermoplastics in accordance with this invention.
  • the poly ⁇ tyrene may be any thermoplastic poly ⁇ tyrene, especially impact modified grades, as described in Modern Plastics Encyclopedia. Vol. 63, No. 10A, 74 (1986), or grades suitable for making foamed products.
  • the additives of the invention are used with impact grades classified by notched impact values between
  • the polypropylene may be any thermoplastic polypropylene, especially homopolymer type, as described in Modern Pla ⁇ tics Encyclopedia. Vol. 63, No. 10A, 12 (1986), or grade ⁇ suitable for making foamed product ⁇ .
  • the additive ⁇ of thi ⁇ invention are u ⁇ ed with grades cla ⁇ ified by melt flows between 2 and 30 g/10 min. , and most preferably between 4 and 10 g/10 min.
  • Enhancing agent ⁇ u ⁇ eful in accordance with thi ⁇ invention comprise the oxide ⁇ and halide ⁇ of group ⁇ IV-A and V-A of the periodic table; organic or inorganic compound ⁇ of phosphorus, nitrogen, boron or sulfur; and oxide ⁇ and halide ⁇ of, for example, zinc, magnesium and titanium, all a ⁇ di ⁇ clo ⁇ ed in U.S. Patent No. 4,016,139.
  • Preferred enhancing agent ⁇ in accordance with thi ⁇ invention are the oxide ⁇ of antimony, ar ⁇ enic and bismuth, with the oxides of antimony being especially preferred.
  • the compo ⁇ ition ⁇ of thi ⁇ invention may additionally incorporate one or more antioxidant ⁇ , hindered amine light ⁇ tabilizer ⁇ , or acid ⁇ cavenger ⁇ .
  • antioxidant i ⁇ 2,2-bi ⁇ [ [3-[3,5-bi ⁇ (l,l-dimethylethyl)- 4-hydroxypheny1]-1- oxopropoxy]methyl]1,3-propanediy1 3,5,-bi ⁇ (1,l-dimethylethyl)-4-hydroxybenzenepropanoate; especially preferred hindered amine light stabilizer is bis(2,2,6,6-tetramethyl-4-piperidinyl)-sebecate; and especially preferred acid scavenger is magnesium aluminum hydroxy carbonate g 4 5 A1 2 (0H) 13 C0 3 .
  • the scope of the present invention includes the incorporation of other additives in the composition so far as to produce a particular end result.
  • additive ⁇ include, without limitation, blowing agent ⁇ , heat stabilizers, light stabilizers, pla ⁇ ticizer ⁇ , pigments, pre ⁇ ervative ⁇ , ultraviolet light ⁇ tabilizer ⁇ , fillers, antioxidant ⁇ , antistatic agent ⁇ and other materials well known to those skilled in the art, for example, a ⁇ de ⁇ cribed in Modern Plastics Encyclopedia, Vol. 63, No. 10A, McGraw-Hill, Inc. (1986).
  • the bicyclic phosphate ⁇ of the present invention may be used alone or as mixture ⁇ of any ⁇ uch compound ⁇ . When mixture ⁇ of bicyclic pho ⁇ phate ⁇ are employed, substantially any combinations of amounts and proportions of the individual compound ⁇ may be used.
  • the u ⁇ e of Compound BCP and Compound BCP-A i ⁇ especially preferred in accordance with thi ⁇ invention.
  • the halogen-containing flame retardant ⁇ of the pre ⁇ ent invention may be used alone or as mixture ⁇ of any such compound ⁇ .
  • substantially any combinations of amounts and proportions of the individual compound ⁇ may be used.
  • the bicyclic pho ⁇ phate compound and halogen-containing flame retardant are provided a ⁇ a mixture u ⁇ eful as an additive which may be added to poly ⁇ tyrene or polyolefin re ⁇ in compo ⁇ ition ⁇ .
  • the additive mixture utilize ⁇ bicyclic pho ⁇ phate in halogen-containing flame retardant in a weight ratio lying in the range of about 0.001 to 0.200, most preferably, about 0.005 to 0.050.
  • poly ⁇ tyrene refer ⁇ to poly ⁇ tyrene available from Huntsman Chemical Corporation a ⁇ PS 3037; the term polypropylene refer ⁇ to polypropylene available from Hi ont Chemical Company a ⁇ Profax 6301; and the term acrylonitrile- butadiene- ⁇ tyrene refer ⁇ to acrylonitrile-butadiene- ⁇ tyrene available from Borg Warner Corporation a ⁇ Cycolac GSM 1000.
  • thermoplastic compo ⁇ ition ⁇ were compounded in a 3/4" eingle screw extruder (L D 25:1) at 430 °F. The extrudate wa ⁇ pelletized and re-extruded ten times. The melt vi ⁇ co ⁇ ity of the final extrudate wa ⁇ ea ⁇ ured by a melt flow technique.
  • Examples 1-2 are flame retardant polypropylene compositions containing 4.0% hexabromocyclododecane (Flame Retardant HBCD), available under the trademark CD-75P from Great Lakes Chemical Corporation, and, re ⁇ pectively, 0.1% and 0.2% 2,6,7-trioxa-l-pho ⁇ phobicyclo[2.2.2] octane-4-methanol-l-oxide (Compound BCP).
  • Flame Retardant HBCD hexabromocyclododecane
  • CD-75P from Great Lakes Chemical Corporation
  • Comparative Example 1 ⁇ how ⁇ the inherent melt vi ⁇ co ⁇ ity of a non-flame retardant polypropylene compo ⁇ ition which ha ⁇ been subjected to multiple extrusions. Comparative Example 2 shows that Flame
  • Retardant HBCD has a detrimental effect on polymer melt viscosity, as evidenced by an increase in melt flow from 29.3 g/10 min (Comparative Example 1) to 77.1 g/10 min (Comparative Example 2).
  • Compound BCP i ⁇ added to the composition the damaging effects of Flame Retardant HBCD on the melt vi ⁇ co ⁇ ity of polypropylene re ⁇ in are reduced.
  • Example 1 and Example 2 show less change in melt flow than Comparative Example 2.
  • Example ⁇ 3-4 are flame retardant polypropylene compo ⁇ ition ⁇ containing 0.1% hindered phenolic antioxidant (Compound AO), which i ⁇ available from Ciba-Geigy Corporation a ⁇ Irganox 1010, and 0.1% acid ⁇ cavenger (Compound AS), which i ⁇ available from Kyowa Chemical Indu ⁇ try a ⁇ DHT-4A, respectively.
  • Compound AO hindered phenolic antioxidant
  • Compound AS 0.1% acid ⁇ cavenger
  • Example 3 ⁇ how ⁇ the effectivene ⁇ of Compound BCP in the pre ⁇ ence of a hindered phenolic antioxidant
  • Example 4 ⁇ how ⁇ the effectivene ⁇ of Compound BCP in the pre ⁇ ence of an acid ⁇ cavenger.
  • TABLE II contains examples which illustrate the effectiveness of the preferred bicyclic phosphate compound and HBCD in poly ⁇ tyrene re ⁇ in to minimize a change in polymer melt vi ⁇ cosity during proces ⁇ ing.
  • EXAMPLE 5 i ⁇ a flame retardant poly ⁇ tyrene formulation in accordance with thi ⁇ invention containing 0.1% Compound BCP and 2.0% Flame Retardant HBCD.
  • Example 5 illustrates an improvement in melt flow over Comparative Example 5 and Comparative Example 6. Thu ⁇ , Compound BCP is effective in polystyrene when no additional additives are pre ⁇ ent (Comparative Example 5) or when an acid ⁇ cavenger i ⁇ present (Comparative Example 6).
  • the polymer melt was sampled at three minute intervals, and visual in ⁇ pection ⁇ of the appearance of the polymer compo ⁇ ition were made.
  • the color and description of the formulated compo ⁇ ition ⁇ are listed in Table III, and reflect the appearance of the compo ⁇ ition when either the material showed total degradation (that is, developed a black or dark red color or showed signs of decomposition, such a ⁇ off-ga ⁇ ing), or when the 21 minute interval of the te ⁇ t wa ⁇ attained.
  • EXAMPLES 6-10 and COMPARATIVE EXAMPLES 7-12 are flame retardant poly ⁇ tyrene compo ⁇ ition ⁇ containing 0.2% Compound BCP and 4.0%, re ⁇ pectively, Flame Retardant HBCD; dibromo(dibromoethyl) cyclohexane (Flame Retardant TBCH), available from Ethyl Corporation a ⁇ BCL-462; Diele-Alder adduct of hexachlorocyclopentadiene and cyclooctadiene (Flame Retardant CBCO) , available from Occidental Corporation as Dechlorane Plus; and monochloropentabromocyclohexane (Flame Retardant CBCH), available from Dow Chemical Corporation as FR-651.
  • Flame Retardant HBCD flame retardant poly ⁇ tyrene compo ⁇ ition ⁇ containing 0.2% Compound BCP and 4.0%, re ⁇ pectively, Flame Re
  • Example 10 i ⁇ a flame retardant poly ⁇ tyrene compo ⁇ ition containing 0.8% Compound BCP and 16.0% tetrabromobi ⁇ phenol A (Flame Retardant TBBP), available from Great Lake ⁇ Chemical Corporation a ⁇ BA-59P.
  • Example ⁇ 6-10 a ⁇ ⁇ upported by compari ⁇ on ⁇ to Comparative Example ⁇ 8-12 (specified in Table III) illustrate poly ⁇ tyrene compo ⁇ ition ⁇ which re ⁇ i ⁇ t thermal degradation and have le ⁇ tendency to develop color under proce ⁇ ing condition ⁇ .
  • Comparative Example 7 shows the inherent color development of non-flame retardant polystyrene resin which has been subjected to the test procedures.
  • Examples 6-10 illustrate al ⁇ o that Compound BCP is effective in the presence of variou ⁇ halogen-containing flame retardant additives.
  • Example 11 i ⁇ a flame retardant poly ⁇ tyrene compo- ⁇ ition containing 0.2% acetate derivative of Compound BCP (designated Compound BCP-A) and 4.0% Flame Retardant HBCD.
  • Example 11 i ⁇ an illustration of a bicyclic phos ⁇ phate other than Compound BCP which is within the scope of thi ⁇ invention.
  • Example 12 i ⁇ a flame retardant acrylonitrile-butadiene- ⁇ tyrene CABS") compo ⁇ ition containing 0.5% Compound BCP, 4.0% Sb 2 0 3 , and 16.0% Flame Retardant TBBP.
  • Example 12 a ⁇ ⁇ upported by compari ⁇ on to Comparative Example ⁇ 14 ( ⁇ pecified in Table III), i ⁇ an illustration of utility of the pre ⁇ ent invention in ABS re ⁇ in.
  • Comparative Example 13 ⁇ how ⁇ the inherent color develop ⁇ ment of non-flame retardant ABS re ⁇ in which ha ⁇ been ⁇ ubjected to the te ⁇ t procedure ⁇ .
  • Examples 13-14 are flame retardant polypropylene compo ⁇ ition ⁇ containing 0.5% Compound BCP, 1.0% Sb.O.., and, re ⁇ pectively, 3.0% tetrabromobi ⁇ phenol A bis(dibromo- propylether) (Flame Retardant TBPE) and 5.0% Flame Retardant HBCD.
  • Example ⁇ 13-14 a ⁇ supported by comparison to Comparative Example ⁇ 16-17 ( ⁇ pecified in Table III), illustrate the effectivenes ⁇ of the pre ⁇ ent invention to reduce the tendency for diecoloration in flame retardant polypropylene compo ⁇ ition ⁇ .
  • Comparative Example 15 ⁇ how ⁇ the inherent color development of non-flame retardant polypropylene re ⁇ in which ha ⁇ been ⁇ ubjected to the te ⁇ t procedure ⁇ . TABLE III
  • the ends of the te ⁇ t specimens were clamped together, placed in an Xenon Arc Weatherometer (Atlas Model Ci-35), and irradiated according to ASTM D-4459 procedure ⁇ for 3000 hour ⁇ .
  • the te ⁇ t specimen ⁇ were observed periodically for ⁇ ign ⁇ of crack ⁇ or crazing. The time at which failure occured wa ⁇ noted.
  • Example ⁇ 15-16 are flame retardant polypropylene compo ⁇ ition ⁇ containing 0.5% Compound BCP, 10.0% Flame Retardant TBPE, 3.3% Sb-O-, and, re ⁇ pectively, 0.5% hindered amine light stabilizer (Compound HALS), available from Ciba-Geigy Corporation a ⁇ TINUVIN 770, and 0.5% Compound AS.
  • Compound HALS hindered amine light stabilizer
  • Example ⁇ 15-16 a ⁇ supported by comparison to Comparative Example ⁇ 18-19 (specified in Table IV), illustrate the effectiveness of the present invention to reduce the tendency for photochemically-induced mechanical failure in flame retardant polypropylene compo ⁇ ition ⁇ .
  • Thermoplastics compo ⁇ ition ⁇ were compounded, injection molded into 3.0" x 1.0" x 0.125" te ⁇ t specimen ⁇ , and irradiated in a Xenon Arc Weatherometer (Atla ⁇ Model Ci-35), according to ASTM D-4459 procedure ⁇ for 2000 hour ⁇ . Change ⁇ in color were mea ⁇ ured a ⁇ Delta E values, accord ⁇ ing to ASTM-2244 procedure ⁇ .
  • Example ⁇ 17-18 are flame retardant polypropylene compo ⁇ ition ⁇ containing 3.3% Sb ⁇ O-, 10.0% Flame Retardant TBPE, and, re ⁇ pectively, 1.0% BCP Compound and 0.5% Compound BCP.
  • Example ⁇ 19-20 are flame retardant polypropylene composition ⁇ containing 0.5% Compound BCP, 10.0% Flame Retardant TBPE, and, re ⁇ pectively, 0.5% hindered amine light ⁇ tabilizer Compound HALS and 0.5% alkytin-containing ⁇ tabilizer (Compound TLS), available from Witco Chemical Company a ⁇ Mark 1413.
  • Example ⁇ 17-20 a ⁇ supported by comparison to Comparative Example ⁇ 20-22 (specified in Table V), illu ⁇ trate the effectiveness of the present invention to reduce the tendency for photochemically-induced di ⁇ coloration in flame retardant polypropylene compo ⁇ i ⁇ tion ⁇ .

Abstract

Thermally stable and light stable flame retardant polyolefin and polystyrene compositions comprise bicyclic phosphate compound(s), halogen-containing flame retardant(s) and polyolefin or polystyrene resins. These compositions exhibit a reduced tendancy to develop color, to change melt viscosity or to lose mechanical strength under conditions present during polymer processing and end use.

Description

THERMALLY STABLE AND LIGHT STABLE FLAME RETARDANT THERMOPLASTIC POLYOLEFIN AND POLYSTYRENE COMPOSITIONS
BACKGROUND OF THE INVENTION Field of the Invention. This invention relates to thermal and light stable flame retardant thermoplastic polyolefin and polystyrene compositions. More particularly, this invention relates to thermoplastic compositions which are flame retardant and which resist thermal degradation or photochemically-induced degradation. These compositions comprise bicyclic phosphate compound(s); halogen-containing flame retardant(ε); and polystyrene or polyolefin resin.
The compositions produced in accordance with this invention have a reduced tendency to develop color, to change melt viscosity, or to lose mechanical strength under conditions that are present during polymer processing or end-use. Description of the Prior Art.
It is known in the art that polystyrene and polyolefinε, such as homopolymers and copolymers of polypropylene, polyethylene, and polybutylene, may be flame retarded with halogen-containing flame retardantε.
Although efficient in suppressing the rate of combustion in a resin system, most flame retardants tend to affect adverεely one or more key properties of the reεin. For example, many flame retardant additiveε are susceptible to thermal and photochemically-induced degradation during processing of the thermoplastic resin, or during polymer use conditions.
Evidence of degradation may be seen in several ways. For example, the thermoplastic composition may develop a darkened appearance during processing, indicating polymer or flame retardant chemical decomposition; or the thermoplastic composition may suffer an increase or decrease in melt viscosity, limiting, for example, the recycle of industrial scrap ("regrind") or environmental plastic waste; or the thermoplastic composition may lose mechanical strength, thus reducing the overall service life of the polymeric material.
Many prior art references describe the use of stabilizers, such as antioxidantε, hindered phenols, hindered amines, phosphites, and the like, in polystyrene and polyolefins. A general treatise covering this broad topic includes Polymer Stabilization and Degradation. ACS Symposium Series, No. 280. P.P. Klemchuk, ed. , American Chemical Society, Washington, D.C. (1985). However, the selection of a suitable stabilizer for polystyrene and polyolefin resins is not predictable. Stabilizer selection is particularly difficult when flame retardants are employed, exacerbated by the complex interaction between the polymer and the halogen- containing compound.
British Patent No. 889,338 describes the production of bicyclic phosphites, phoεphonateε, thiophosphates, and εelenophosphates. These compoεitionε are said to be stabilizerε for vinyl halide reεinε. They are alleged to be useful as heat εtabilizerε for vinyl chloride reεin, and as antioxidantε for fatε and oilε. The British '338 Patent does not show any examples of bicylic phosphates, nor doeε it specify the uεe of bicyclic phoεphateε, such aε pentaerythritol-baεed bicyclic phoεphateε of the present invention, which can be employed as a stabilizer for polystyrene or polyolefin resin. Furthermore, the British '338 Patent doeε not disclose that cyclic phoεphateε of the preεent invention could be used with halogen-containing flame retardantε to produce flame retardant thermoplastic compoεitions which reεiεt thermal or photochemically-induced degradation.
British Patent No. 999,793 describes a procesε to produce organic phosphates by subjecting organic phosphites to reaction with peracetic acid. This patent shows a method for producing the most preferred bicyclic phosphate of the present invention, 2,6,7-trioxa-l- phoεphobicyclo[2.2.2]-octane-4-methanol-l-oxide (vide infra) _ and teaches the use of acetal ring-containing phoεphateε aε plaεticizerε or functional fluidε. The British '793 Patent, however, does not disclose the compoεitions of the present invention. It doeε not mention bicylic phosphates as being useful for flame retardant thermoplastic resins, nor that the most preferred bicyclic phosphate of the preεent invention can be used with halogen-containing flame retardant additives to yield improved thermoplastic compositions. U.S. Patent No. 3,873,496 describes a flame retardant polyester composition which containε 5 to 25 percent of a hydroxymethyl bicyclic phoεphate compound aε a flame retardant additive. The patentee did not observe the ability of bicyclic phosphateε to act aε heat or melt εtabilizerε for thermoplastic resin compoεitionε which employ halogenated compoundε aε the primary flame retardant additive.
U.S. Patent No. 4,341,694 discloses a composition comprising 2,6,7-trioxa-l-phosphobicyclo[2.2.2]octane-
4-methanol-l-oxide and a nitrogen-containing co-additive, which are intumeεcent and are adaptable to flame retard polyolefinε, polyvinylaromatic reεinε, polycarbonateε, PVC and blends thereof. The patentee did not observe any stabilization of the present invention.
Accordingly, a primary object of this invention iε to provide thermal and light εtable flame retardant thermoplastic polyolefin and polyεtyrene compoεitions. A related object is to provide compoεitionε of the character deεcribed which resist thermal degradation or photochemically induced degradation.
A further object is to provide polystyrene or polyolefin resin compositions incorporating bicyclic phosphate compounds and halogenated flame retardantε.
SUMMARY OF THE INVENTION
The foregoing and other objects, advantages and featureε of the preεent invention may be achievable with thermal and light εtable thermoplaεtic polyolefin or polyεtyrene resin compoεitions incorporating an additive mixture comprising a halogen-containing flame retardant; and a bicyclic phosphate compound of the the following Formula (I):
Figure imgf000007_0001
where X is OH, OR', or OC(0)R'; R is H or a saturated or unεaturated εtraight-chain or branched-chain C--C.- al yl; and R' iε a εaturated or unεaturated εtraight-chain or branched chain C.-C-- alkyl. DESCRIPTION OF THE PREFERRED EMBODIMENTS This invention relates to thermal and light εtable flame retardant theremoplaεtic polyolefin and polyεtyrene compositions. In particular, the invention relates to thermoplastic polyolefin and polystyrene resin compoεitionε which are flame retardant and which reεist thermal degradation or photochemically induced degradation and which incorporate an additive mixture compriεing one or more bicyclic phosphate compounds and one or more halogen-containing flame retardantε. Compoεitionε produced in accordance with thiε invention have a reduced tendency to develop color, to change melt viεcoεity, or to lose mechanical strength under conditions preεent during polymer procesεing or in uεe.
Preferred bicyclic phoεphateε in accordance with this invention are compounds of Formula (I) where X iε OH or OC(0)R' . The most preferred bicyclic compounds are 2,6,7-trioxa-phosphobicyclo[2.2.2]-octane-4-methanol-l- oxide (Compound BCP, that iε, Formula [I] when R iε H and X iε OH), and 2,6,7-trioxa-l-phoεphobicyclo[2.2.2]- octane-4-methanol, acetate, 1-oxide (Compound BCP-A, that iε, when R iε H and X iε OC(O)CH-).
The halogen-containing flame retardant compound may be any brominated or chlorinated aliphatic or aromatic organic compound that can be used in thermoplastic compoεitionε. Preferred halogen-containing compounds are hexabromocyclododecane, tetrabromobiεphenol A, tetrabromobiεphenol A biε-(dibromopropylether), dibromo(dibromoethyl)cyclohexane, tetrabromocyclooctane, biε-(dibromonorbornane dicarboximido)ethane, biε-(tetrabromophthalimido)ethane, Dielε-Alder adduct of chlorinated cyclopentadiene and unsaturated cycloaliphatic compound, biβ-(tribromophenoxy- ethyl)tetrabromobisphenol A ether, pentabromodiphenyl ether, octabromodiphenyl ether, decabro odiphenyl ether, biε-(tribromophenoxy)ethane, bis-(pentabromo- phenoxy)ethane, chloropentabromocyclohexane, (tribromophenoxy)-(dibromononylphenoxy)ethane, pentabromoethylbenzene, pentabromododecylbenzene, carbonate oligomerε of tetrabromobiεphenol A, poly(brominated εtyrene), and brominated polyεtyrene, poly(brominated phenylene) ether, and mixtureε thereof. These halogenated compounds are added to thermoplastic reεinε at levelε such that the reεultant reεin composi- tion may be rendered flame retardant.
Reεins which may be treated in accordance with the invention include thermoplaεticε εuch aε polyεtyrene and copolymers of εtyrene with butadiene and acrylonitrile ("ABS copolymerε") and homopolymerε and copolymers of polyolefinε εuch aε polypropylene, polyethylene, and polybutylene. Polystyrene and polypropylene are preferred thermoplastics in accordance with this invention. The polyεtyrene may be any thermoplastic polyεtyrene, especially impact modified grades, as described in Modern Plastics Encyclopedia. Vol. 63, No. 10A, 74 (1986), or grades suitable for making foamed products. Preferably, the additives of the invention are used with impact grades classified by notched impact values between 0.6 and 3.0 ft-lb/in, and most preferably between 1.0 and 2.5 ft-lb/in.
The polypropylene may be any thermoplastic polypropylene, especially homopolymer type, as described in Modern Plaεtics Encyclopedia. Vol. 63, No. 10A, 12 (1986), or gradeε suitable for making foamed productε. Preferably, the additiveε of thiε invention are uεed with grades claεεified by melt flows between 2 and 30 g/10 min. , and most preferably between 4 and 10 g/10 min.
The compoεitionε of this invention also desirably incorporate one or more enhancing agents. Enhancing agentε uεeful in accordance with thiε invention comprise the oxideε and halideε of groupε IV-A and V-A of the periodic table; organic or inorganic compoundε of phosphorus, nitrogen, boron or sulfur; and oxideε and halideε of, for example, zinc, magnesium and titanium, all aε diεcloεed in U.S. Patent No. 4,016,139. Preferred enhancing agentε in accordance with thiε invention are the oxideε of antimony, arεenic and bismuth, with the oxides of antimony being especially preferred. Antimony trioxide iε the most preferred enchancing agent uεed in the compoεitionε of thiε invention. The compoεitionε of thiε invention may additionally incorporate one or more antioxidantε, hindered amine light εtabilizerε, or acid εcavengerε. Especially preferred antioxidant iε 2,2-biε[ [3-[3,5-biε(l,l-dimethylethyl)- 4-hydroxypheny1]-1- oxopropoxy]methyl]1,3-propanediy1 3,5,-biε(1,l-dimethylethyl)-4-hydroxybenzenepropanoate; especially preferred hindered amine light stabilizer is bis(2,2,6,6-tetramethyl-4-piperidinyl)-sebecate; and especially preferred acid scavenger is magnesium aluminum hydroxy carbonate g4 5A12(0H)13C03. The scope of the present invention includes the incorporation of other additives in the composition so far as to produce a particular end result. Such additiveε include, without limitation, blowing agentε, heat stabilizers, light stabilizers, plaεticizerε, pigments, preεervativeε, ultraviolet light εtabilizerε, fillers, antioxidantε, antistatic agentε and other materials well known to those skilled in the art, for example, aε deεcribed in Modern Plastics Encyclopedia, Vol. 63, No. 10A, McGraw-Hill, Inc. (1986).
The bicyclic phosphateε of the present invention may be used alone or as mixtureε of any εuch compoundε. When mixtureε of bicyclic phoεphateε are employed, substantially any combinations of amounts and proportions of the individual compoundε may be used. The uεe of Compound BCP and Compound BCP-A iε especially preferred in accordance with thiε invention.
The halogen-containing flame retardantε of the preεent invention may be used alone or as mixtureε of any such compoundε. When mixtures of halogen-containing phosphateε are employed, substantially any combinations of amounts and proportions of the individual compoundε may be used. The uεe of hexabromocyclododecane, tetrabromobiεphenol A, chloropentabromocyclohexane, tetrabromobiεphenol A bis-(dibromopropylether), dibromo(dibromoethyl)cyclohexane, tetrabromocyclooctane, biβ-(dibromonorbornane dicarboximido)ethane, and Diels-Alder adduct of hexachlorocyclopentadiene and cyclooctadiene iε eεpecially preferred in accordance with thiε invention.
Desirably, the bicyclic phoεphate compound and halogen-containing flame retardant are provided aε a mixture uεeful as an additive which may be added to polyεtyrene or polyolefin reεin compoεitionε. The additive mixture utilizeε bicyclic phoεphate in halogen-containing flame retardant in a weight ratio lying in the range of about 0.001 to 0.200, most preferably, about 0.005 to 0.050.
The additive mixture iε incorporated into the polymer compoεition at a level εuch that the reεulting reεin compoεition iε rendered flame retardant. In general, the additive mixture iε provided in the flame retardant at a level of about 0.1 - 20.0 percent by weight of the reεin compoεition, preferably about 0.5 - 20.0 percent by weight. Practice of the preεent invention iε illuεtrated by the following exa pleε.
EXAMPLES The following exampleε are given to illustrate the invention and should not be construed aε limiting itε εcope. All percentageε are by weight. The term polyεtyrene referε to polyεtyrene available from Huntsman Chemical Corporation aε PS 3037; the term polypropylene referε to polypropylene available from Hi ont Chemical Company aε Profax 6301; and the term acrylonitrile- butadiene-εtyrene referε to acrylonitrile-butadiene- εtyrene available from Borg Warner Corporation aβ Cycolac GSM 1000. All flame retardant compoεitionε received a V-2 or V-0 rating aε meaεured by the UL-94 teεt. TABLE I containε examples which illustrate the effectivenesε of bicyclic phoεphate compound and halogen-containing flame retardant in polypropylene reεin to minimize a change in polymer melt viεcoεity during proceεεing. The thermoplastic compoεitionε were compounded in a 3/4" eingle screw extruder (L D 25:1) at 430 °F. The extrudate waε pelletized and re-extruded ten times. The melt viεcoεity of the final extrudate waε eaεured by a melt flow technique.
EXAMPLES 1-2 and COMPARATIVE EXAMPLES 1-2
Examples 1-2 are flame retardant polypropylene compositions containing 4.0% hexabromocyclododecane (Flame Retardant HBCD), available under the trademark CD-75P from Great Lakes Chemical Corporation, and, reεpectively, 0.1% and 0.2% 2,6,7-trioxa-l-phoεphobicyclo[2.2.2] octane-4-methanol-l-oxide (Compound BCP).
Comparative Example 1 εhowε the inherent melt viεcoεity of a non-flame retardant polypropylene compoεition which haε been subjected to multiple extrusions. Comparative Example 2 shows that Flame
Retardant HBCD has a detrimental effect on polymer melt viscosity, as evidenced by an increase in melt flow from 29.3 g/10 min (Comparative Example 1) to 77.1 g/10 min (Comparative Example 2). Surprisingly, when Compound BCP iε added to the composition, the damaging effects of Flame Retardant HBCD on the melt viεcoεity of polypropylene reεin are reduced. Example 1 and Example 2 show less change in melt flow than Comparative Example 2.
EXAMPLES 3-4 and COMPARATIVE EXAMPLES 3-4 Exampleε 3-4 are flame retardant polypropylene compoεitionε containing 0.1% hindered phenolic antioxidant (Compound AO), which iε available from Ciba-Geigy Corporation aε Irganox 1010, and 0.1% acid εcavenger (Compound AS), which iε available from Kyowa Chemical Induεtry aε DHT-4A, respectively. Exampleε 3-4 and Comparative Exampleε 3-4 in TABLE I illuεtrate alεo the utility of Compound BCP to inhibit changes in polymer melt viεcoεity when other additiveε are preεent in the thermoplaεtic reεin. Example 3 εhowε the effectiveneεε of Compound BCP in the preεence of a hindered phenolic antioxidant, and Example 4 εhowε the effectiveneεε of Compound BCP in the preεence of an acid εcavenger.
TABLE I
FLAME RETARDANT OTHER ADDITIVE MELT FLOW g/10 Bin TYPE AMOUNT ASTM weight X D-1238
66.6
29.3 77.1
Figure imgf000014_0001
70.7 TABLE I CCONT. ')
Figure imgf000015_0001
Note: Polypropylene resin, 430βF.
TABLE II contains examples which illustrate the effectiveness of the preferred bicyclic phosphate compound and HBCD in polyεtyrene reεin to minimize a change in polymer melt viεcosity during procesεing.
EXAMPLE 5. and COMPARATIVE EXAMPLES 5-6 Example 5 iε a flame retardant polyεtyrene formulation in accordance with thiε invention containing 0.1% Compound BCP and 2.0% Flame Retardant HBCD.
Example 5 illustrates an improvement in melt flow over Comparative Example 5 and Comparative Example 6. Thuε, Compound BCP is effective in polystyrene when no additional additives are preεent (Comparative Example 5) or when an acid εcavenger iε present (Comparative Example 6).
Figure imgf000016_0001
TABLE III εhowε compoεitions of the present invention which have leεε tendency to degrade thermally in variouε polymer εyεtemε.
Thermal degradation waε meaεured by formulating compoεitionε in a Brabender Plaεticorder mixer (Model PL-V300) for 21 minutes, 50-70 rpm, and at the temper¬ atures as specified in TABLE III, Footnote 1. The polymer melt was sampled at three minute intervals, and visual inεpectionε of the appearance of the polymer compoεition were made.
The color and description of the formulated compoεitionε are listed in Table III, and reflect the appearance of the compoεition when either the material showed total degradation (that is, developed a black or dark red color or showed signs of decomposition, such aε off-gaεεing), or when the 21 minute interval of the teεt waε attained. EXAMPLES 6-10 and COMPARATIVE EXAMPLES 7-12 Examples 6-9 are flame retardant polyεtyrene compoεitionε containing 0.2% Compound BCP and 4.0%, reεpectively, Flame Retardant HBCD; dibromo(dibromoethyl) cyclohexane (Flame Retardant TBCH), available from Ethyl Corporation aε BCL-462; Diele-Alder adduct of hexachlorocyclopentadiene and cyclooctadiene (Flame Retardant CBCO) , available from Occidental Corporation as Dechlorane Plus; and monochloropentabromocyclohexane (Flame Retardant CBCH), available from Dow Chemical Corporation as FR-651.
Example 10 iε a flame retardant polyεtyrene compoεition containing 0.8% Compound BCP and 16.0% tetrabromobiεphenol A (Flame Retardant TBBP), available from Great Lakeε Chemical Corporation aε BA-59P.
Exampleε 6-10, aε εupported by compariεonε to Comparative Exampleε 8-12 (specified in Table III) illustrate polyεtyrene compoεitionε which reεiεt thermal degradation and have leεε tendency to develop color under proceεεing conditionε. Comparative Example 7 shows the inherent color development of non-flame retardant polystyrene resin which has been subjected to the test procedures.
Examples 6-10 illustrate alεo that Compound BCP is effective in the presence of variouε halogen-containing flame retardant additives.
EXAMPLE 11 Example 11 iε a flame retardant polyεtyrene compo- εition containing 0.2% acetate derivative of Compound BCP (designated Compound BCP-A) and 4.0% Flame Retardant HBCD. Example 11 iε an illustration of a bicyclic phos¬ phate other than Compound BCP which is within the scope of thiε invention. EXAMPLE 12 and COMPARATIVE EXAMPLES 13-14
Example 12 iε a flame retardant acrylonitrile-butadiene- εtyrene CABS") compoεition containing 0.5% Compound BCP, 4.0% Sb203, and 16.0% Flame Retardant TBBP.
Example 12, aε εupported by compariεon to Comparative Exampleε 14 (εpecified in Table III), iε an illustration of utility of the preεent invention in ABS reεin. Comparative Example 13 εhowε the inherent color develop¬ ment of non-flame retardant ABS reεin which haε been εubjected to the teεt procedureε. EXAMPLES 13-14 and COMPARATIVE EXAMPLES 15-17
Examples 13-14 are flame retardant polypropylene compoεitionε containing 0.5% Compound BCP, 1.0% Sb.O.., and, reεpectively, 3.0% tetrabromobiεphenol A bis(dibromo- propylether) (Flame Retardant TBPE) and 5.0% Flame Retardant HBCD.
Exampleε 13-14, aε supported by comparison to Comparative Exampleε 16-17 (εpecified in Table III), illustrate the effectivenesε of the preεent invention to reduce the tendency for diecoloration in flame retardant polypropylene compoεitionε. Comparative Example 15 εhowε the inherent color development of non-flame retardant polypropylene reεin which haε been εubjected to the teεt procedureε. TABLE III
FLAME RETARDANT
BCP
EXAMPLE ADDITIVE RESIN TYPE AMOUNT , NUMBER weight X TYPE1 weight X COLOR DESCRIPTION
6 0.2 A HBCD 4.0 0 TRANSPARENT
COMP 7 0.0 A 0 TRANSPARENT COMP 8 0.0 A HBCD 4.0 10 OPAQUE
7 0.2 A TBCH 4.0 2 TRANSPARENT COMP 9 0.0 A TBCH 4.0 10 OPAQUE
8 0.2 A CBCO 4.0 0 OPAQUE
COMP 10 0.0 A CBCO 4.0 3 OPAQUE
0.2 A CBCH 4.0 4 OPAQUE 0.0 A CBCH 4.0 10 OPAQUE
0.8 A TBBP 16.0 2 OPAQUE 0.0 A TBBP 16.0 8 OPAQUE 0.2 A HBCD 4.0 2 TRANSPARENT
0.5 B TBBP 16.0 5 OPAQUE 0.0 B 1 OPAQUE 0.0 B TBBP 16.0 8 OPAQUE
0.5 C TBPE 3.0 6 OPAQUE 0.0 C 1 OPAQUE 0.0 C TBPE 3.0 10 OPAQUE
0.5 C HBCD 5.0 1 OPAQUE
Figure imgf000019_0001
0.0 C HBCD 5.0 10 OPAQUE
NOTE 1: A) Polystyrene resin, 450βF; B) Acrylonitrilebutadiene- styrene resin, 4.OX Sb^, 500°F; C) Polypropylene, 1.0X SbjOg, 430°F.
NOTE 2: O=colorless; l=white; 2=light yellow; 3=yellow; 4»dark yellow; 5=light tan; 6=tan; 7=dark tan; 8=brown; 9*dark brown; 10=black, red or decomposed. TABLE IV εhowε polypropylene compoεitionε of the preεent invention which have leεε tendency to loεe mechanical εtrength, when εuch compoεitionε are expoεed to radiation. Thermoplaεtic compoεitionε were compounded and injection molded into teεt specimens, measuring 5.0" x 0.5" x 0.062". The ends of the teεt specimens were clamped together, placed in an Xenon Arc Weatherometer (Atlas Model Ci-35), and irradiated according to ASTM D-4459 procedureε for 3000 hourε. The teεt specimenε were observed periodically for εignε of crackε or crazing. The time at which failure occured waε noted.
EXAMPLES 15-16 and COMPARATIVE EXAMPLES 18-19 Exampleε 15-16 are flame retardant polypropylene compoεitionε containing 0.5% Compound BCP, 10.0% Flame Retardant TBPE, 3.3% Sb-O-, and, reεpectively, 0.5% hindered amine light stabilizer (Compound HALS), available from Ciba-Geigy Corporation aε TINUVIN 770, and 0.5% Compound AS.
Exampleε 15-16, aε supported by comparison to Comparative Exampleε 18-19 (specified in Table IV), illustrate the effectiveness of the present invention to reduce the tendency for photochemically-induced mechanical failure in flame retardant polypropylene compoεitionε.
Figure imgf000021_0001
TABLE V εhowε polypropylene compoεitionε of the preεent invention which have leεε tendency to diεcolor, when εuch compoεitionε are exposed to radiation.
Thermoplastics compoεitionε were compounded, injection molded into 3.0" x 1.0" x 0.125" teεt specimenε, and irradiated in a Xenon Arc Weatherometer (Atlaε Model Ci-35), according to ASTM D-4459 procedureε for 2000 hourε. Changeε in color were meaεured aε Delta E values, accord¬ ing to ASTM-2244 procedureε.
EXAMPLES 17-20 and COMPARATIVE EXAMPLES 20-22
Exampleε 17-18 are flame retardant polypropylene compoεitionε containing 3.3% Sb^O-, 10.0% Flame Retardant TBPE, and, reεpectively, 1.0% BCP Compound and 0.5% Compound BCP.
Exampleε 19-20 are flame retardant polypropylene compositionε containing 0.5% Compound BCP, 10.0% Flame Retardant TBPE, and, reεpectively, 0.5% hindered amine light εtabilizer Compound HALS and 0.5% alkytin-containing εtabilizer (Compound TLS), available from Witco Chemical Company aε Mark 1413.
Exampleε 17-20, aε supported by comparison to Comparative Exampleε 20-22 (specified in Table V), illuεtrate the effectiveness of the present invention to reduce the tendency for photochemically-induced diεcoloration in flame retardant polypropylene compoεi¬ tionε.
TABLE V
Figure imgf000022_0001

Claims

CLAIMS 1. A thermally εtable and light εtable thermo¬ plaεtic reεin compoεition comprising a polyolefin or polyεtyrene reεin and a mixture comprising; at leaεt one halogen-containing flame retardant; and at leaεt one bicyclic phoεphate compound of the formula:
Figure imgf000023_0001
where X iε OH, OR1, or OC(0)R'; R is H or a saturated or unsaturated straight-chain or branched-chain C.-C-- alkyl; and R' is a saturated or unsaturated εtraight-chain or branched chain C--C-- alkyl.
2. A compoεition, aε claimed in claim 1, wherein the halogen-containing flame retardant iε a member selected from the group consisting of hexabromocyclodode¬ cane, tetrabromobisphenol A, chloropentabromocyclohexane, tetrabromobisphenol A bis-(dibromopropylether), dibromo(dibromoethy1)cyclohexane, tetrabromocyclooctane, bis-(dibromonorbomane dicarboximido)ethane, Diels-Alder adductε of hexachlorocyclopentadiene and cyclooctadiene and mixtureε thereof.
3. A compoεition, aε claimed in claim 1, wherein the bicyclic phoεphate compound iε 2,6,7-trioxa-phospho- bicyclo[2.2.2]-octane-4-methanol-l-oxide; or 2,6,7-trioxa- l-phoεphobicylo[2.2.2]-octane-4-methanol, acetate, 1-oxide.
4. A compoεition, aε claimed in claim 1, wherein the reεin iε a member selected from the group conεiεting of polyεtyrene, acrylonitrile-butadiene-εtyrene reεin, and polyethylene, polypropylene and polybutylene homo- and copolymers.
5. A compoεition, aε claimed in claim 4, wherein the member iε polypropylene or polyεtyrene.
6. A compoεition, aε claimed in claim 1, wherein the weight ratio of bicyclic phoεphate compound to halogen-containing flame retardant lieε in the range of about 0.001 to 0.200.
7. A compoεition, aε claimed in claim 1, wherein the mixture of bicyclic phoεphate compound and halogen-containing flame retardant iε provided in the reεin compoεition at a level lying in the range of about 0.1 - 20.0 percent by weight of the overall compoεition.
8. A compoεition, aε claimed in claim 1, and further compriεing at leaεt one member selected from the group conεiεting of antioxidantε, hindered amine light stabilizers, and acid scavengers.
9. A composition, as claimed in claim 8, wherein the antioxidant iε 2,2-biε[t3-[3,5-bis(l,l-dimethylethyl)- 4-hydroxypheny1]-1- oxopropoxy]methyl]1,3-propanediy1 3,5,-biε(1,1-dimethylethy1)-4- hydroxybenzenepropanoate.
10. A composition, aε claimed in claim 8, wherein the hindered amine light εtabilizer iε biε-(2,2,6,6-tetramethyl -4-piperidinyl)-sebecate.
11. A compoεition, aε claimed in claim 8, wherein the acid scavenger is magnesium aluminum hydroxy carbonate
Mg4.5A12(0H)13C03*
12. A flame retardant stabilizing additive mixture for polyolefin or polystyrene resin compositions compris¬ ing: a halogen-containing flame retardant; and a bicyclic phosphate compound of the formula:
Figure imgf000025_0001
where X is OH, OR', or OC(0)R'; R iε H or a saturated or unεaturated εtraight-chain or branched-chain C.-C-- alkyl; and R' iε a εaturated or unsaturated straight-chain or branched chain C--C.- alkyl.
13. A mixture, as claimed in claim 12, wherein the flame retardant is a member selected from the group conεiεting of hexabromocyclododecane, tetrabromobisphenol A, chloropentabromocyclohexane, tetrabromobisphenol A biε- (dibromopropylether), dibromo(dibromoethyl)cyclohexane, tetrabromocyclooctane, bis-(dibromonorbornane dicarboximido)ethane, Diels-Alder adducts of hexachlorocyclopentadiene and cyclooctadiene and mixtureε thereof.
14. A mixture, aε claimed in claim 12, wherein the bicyclic phoεphate compound iε 2,6,7-trioxa-phoεphobicyclo [2.2.2]-octane-4-methanol-l-oxide; or 2,6,7-trioxa-l- phosphobicylo[2.2.2]-octane-4-methanol, acetate, 1-oxide.
15. A mixture, aε claimed in claim 12, wherein the weight ratio of bicyclic phoεphate compound to halogen-containing flame retardant liee in the range of about 0.001 to 0.200.
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991004294A1 (en) * 1989-09-15 1991-04-04 Great Lakes Chemical Corporation Smoke suppressed flame retardant thermoplastic resin compositions
US5627915A (en) * 1995-01-31 1997-05-06 Princeton Video Image, Inc. Pattern recognition system employing unlike templates to detect objects having distinctive features in a video field
WO1997008238A1 (en) * 1995-08-29 1997-03-06 Exxon Chemical Patents Inc. Radiation tolerant polypropylene and its useful articles
US6231936B1 (en) 1995-08-29 2001-05-15 Exxon Chemical Patents, Inc. Radiation tolerant polypropylene and its useful articles
US6800678B2 (en) 1997-06-30 2004-10-05 Ciba Specialty Chemicals Corporation Flame retardant compositions
US6472456B1 (en) 1997-06-30 2002-10-29 Ciba Specialty Chemicals Corp. Flame retardant compositions
US6599963B2 (en) 1997-06-30 2003-07-29 Ciba Specialty Chemicals Corporation Flame retardant compositions
WO2003074603A1 (en) * 2002-03-01 2003-09-12 Dow Global Technologies Inc. Dimensionally-stable propylene polymer foam with improved thermal aging.
WO2004035671A1 (en) * 2002-10-17 2004-04-29 Ciba Specialty Chemicals Holding Inc. Flame retardant compositions
US7109260B2 (en) 2002-10-17 2006-09-19 Ciba Specialty Chemicals Corporation Flame retardant compositions
EP1712586A1 (en) * 2005-04-12 2006-10-18 Dai-Ichi F R Co., Ltd. Flame-retarded foamed plastic compositions and shaped articles
CN102369243A (en) * 2009-03-19 2012-03-07 界面解决方案Ip有限责任公司 Biobased polymer compositions
CN102369243B (en) * 2009-03-19 2014-11-05 界面解决方案Ip有限责任公司 Biobased polymer compositions
EP3492557A4 (en) * 2016-07-29 2020-01-29 Adeka Corporation Flame-retardant composition and flame-retardant synthetic-resin composition

Also Published As

Publication number Publication date
JPH03502820A (en) 1991-06-27
EP0401366A1 (en) 1990-12-12
CA2006134A1 (en) 1990-06-20
KR910700007A (en) 1991-03-13
EP0401366A4 (en) 1991-06-05

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