WO1992003499A1 - Improved flame retardant resin composition containing styrenic polymers - Google Patents

Improved flame retardant resin composition containing styrenic polymers Download PDF

Info

Publication number
WO1992003499A1
WO1992003499A1 PCT/US1991/005888 US9105888W WO9203499A1 WO 1992003499 A1 WO1992003499 A1 WO 1992003499A1 US 9105888 W US9105888 W US 9105888W WO 9203499 A1 WO9203499 A1 WO 9203499A1
Authority
WO
WIPO (PCT)
Prior art keywords
flame retardant
composition
styrene
set forth
compatibilizing agent
Prior art date
Application number
PCT/US1991/005888
Other languages
French (fr)
Inventor
Deenadayalu Chundury
Neil A. Burditt
Original Assignee
Ferro Corporation
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 Ferro Corporation filed Critical Ferro Corporation
Publication of WO1992003499A1 publication Critical patent/WO1992003499A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • C08L25/08Copolymers of styrene
    • C08L25/10Copolymers of styrene with conjugated dienes

Definitions

  • the present invention generally relates to flame retardant styrene polymer compositions that have improved impact strength.
  • the compositions additionally have flexural modulus and heat deflection properties similar to styrene polymer compositions not containing flame retardants.
  • European Patent Applications 262,615 and 87/05615 to Haaf and Abolins relate to flame retardant polyphenylene ether compositions and more specifically to compositions of a polyphenylene ether resin and a high impact polystyrene in which a post brominated polystyrene oligomer or polymer and antimony oxide are used in combination to impart better flame resistance, impact strength, and mold flow.
  • IPO International Bureau 88/03542 relates to modified polyphenylene ether resins having improved flow properties and, in particular, it relates to modified polyphenylene ether resins incorporating a brominated al enyl aromatic resin, a diester of tetrabromophthalic acid, and a flame retardant enhancer such as antimony trioxide.
  • Flame retardant polystyrenes have various applications in injection molded products such as television cabinets, television racks, business machine housings, table-top and lap-top computers, smoke detec ⁇ tor housings and modular furniture including hospital furniture.
  • compositions of the present invention are also useful especially for making other molded articles such as medical disposal boxes for the receipt, storage, and eventual disposal of contaminated medical products; for electrical boxes and connectors, electrical materi ⁇ als, and the like.
  • flame retardant polystyrene may be acceptable when the flame retardant is decabromodiphenyloxide without the use of a com- patibilizer, in a preferred embodiment of the inven ⁇ tion, the flame retardant excludes this composition and its analogs.
  • These brominated diphenyl oxides may pyrolize to form furans which are potentially hazardous and environmentally toxic.
  • a flame retardant package of the present invention such as brominated polystyrene and to utilize the co - patibilizing agent to improve the impact properties.
  • the impact strength of the flame retardant polymer is further augmented by incorporating therein a compatibilizing agent comprising a block copolymer.
  • the present invention relates to a flame retardant package which comprises a flame retardant, a flame retardant synergist and an compatibilizing agent.
  • the flame retardant is a brominated styrene polymer such as brominated polys ⁇ tyrene.
  • the compatibilizing agent is a styrene butadi ⁇ ene block copolymer.
  • the present invention comprises four com ⁇ ponents: a styrene polymeric resin, a flame retardant synergist, a flame retardant, and a compatibilizing agent or property enhancer.
  • this invention can be en ⁇ visioned as a two component system comprising the styrene polymer and a flame retardant package where the package comprises the flame retardant, the flame retar ⁇ dant synergist and the compatibilizing agent.
  • the blend compositions of the present invention can be blended in a one part or two part process. In the one part process, all of the ingredients are mixed in the same step although they may be etered at various points of the mastication process. In the two part process, two or more ingredients may be premixed such as the flame retardant package.
  • the styrene polymeric resins having utility in this invention comprises high impact polystyrene (HIPS) , polystyrene, poly- ⁇ -methylstyrene, polyvinyl naphtha ⁇ lene, styrene-acrylonitrile copolymer, styrene maleic anhydride copolymer, EPDM modified styrene acrylonitrile copolymer, styrene-acrylic copolymer, acrylonitrile- styrene-acrylic terpolymer, polystyrene-polyphenylene oxide blend, or acrylonitrile-butadiene-styrene graft copolymer.
  • HIPS high impact polystyrene
  • polystyrene poly- ⁇ -methylstyrene
  • polyvinyl naphtha ⁇ lene polyvinyl naphtha ⁇ lene
  • High impact polystyrene is understood in the art as a thermoplastic resin product from styrene monomer along with elastomers such as polybutadiene which are introduced into the polystyrene matrix.
  • Polystyrene homopolymers, polystyrene copoly- mers, or terpolymers or graft copolymers and blends thereof are preferred.
  • the above-noted styrene polymer- ic resins are generally commercially available and have a weight average molecular weight of from about 100,000 to about 1,000,000 and preferably from about 200,000 to about 300,000.
  • the amount of the various flame retardants which are utilized are generally dictated by a desirable UL (Underwriters Laboratories, Inc.) 94 flammability rating.
  • the UL 94 test is a vertical burning test.
  • a material having a V-0 rating allows only minimal burning and no flaming drip of a standard bar of specified thickness.
  • the V-l rating allows longer burn times than the V-0, but not flaming drip.
  • the V-2 rating allows the same burn time as the V-l and also allows flaming drip.
  • the fail rating is given any material not meeting the V-0, V-l, or V-2 criteria.
  • the choice of the variously rated flame-retardant polystyrene resins depends upon the end use.
  • compositions having UL9 ratings from V-0 to V-2 may be useful depending on the application. It may be preferable to achieve the V-0 rating for certain ap ⁇ plications.
  • the styrene polymeric resins of the present invention contain a flame retardant synergist comprising antimony oxide or sodium antimonate. Its main function is to promote the flame retardancy properties of the flame retardant.
  • the synergist is employed in effective amounts to improve the flame retardancy within the styrenic resin.
  • an effective amount of synergist is from about 1 to about 8 parts, preferably from about 3 to about 7 parts and most preferably from about 4 to about 6 parts by weight per 100 parts by weight of the resin components.
  • Suitable flame retardants comprising hal- ⁇ ena- ted organic compounds are utilized in association with the antimony component.
  • suitable halo- genated organic compounds include brominated dipen- taerithritol, tetrabromobisphenol A, ethylene-bistetra- bromophthalimide, ethylenebisdibromonorbornane-dicarbox- imide, tetrabromobisphenol A-bis(2,3-dibromopropyl ether) , octabromodiphenyl oxide, hexabromocyclododec- ane, hexabromodiphenoxy ethane, decabromodiphenoxy ethane, decabromodiphenyloxide, tetradecabromodiphenoxy benzene, brominated polystyrene, tetradecabromodiphenyl- oxide, poly-dibromophenylene oxide, phenoxy terminated
  • Brominated organic compounds which are especially preferred comprise brominated polystyrene, hexabromocyclododecane, ethylene-bistetra- bromophthalimide and ethylene dibromonorbornane-dicar- boximide.
  • the flame retardant excludes brominated diphenyl oxides such as octabromodiphenyl oxide, decabromodiphenyl oxide, tetradecabromodiphenyl oxide, poly-dibro aphenyl- ene oxide and the like.
  • the flame retardant is thus preferably brominated polystyrene such as a high olecu- lar weight and low molecular weight brominated polysty ⁇ rene.
  • the high molecular weight brominated polystyrene is generally understood to have a molecular weight of from about 100,000 to about 400,000, while the low molecular weight brominated polystyrene is generally understood to have a molecular weight of from about 1,000 to about 20,000. At the present time those brominated polystyrenes having a molecular weight between 20,000 and 100,000 could fall into either category and therefore should be understood to be encompassed in the present invention.
  • the compatibilizing agent is preferably a copolymer of styrene and butadiene or isoprene.
  • This copolymer is preferably a block copolymer having a diblock, triblock. multi-block or a star radial composition.
  • the block copolymer is a styrene-butadiene copolymer having generally a butadiene content of from about 20 percent to about 80 percent and a styrene content of from about 80 percent to about 20 percent.
  • the buta ⁇ diene is from 35 to 65 percent, most preferably it is from 40 to 60 percent with the styrene comprising the remainder.
  • the compatibilizers are commercially available having various styrene-butadiene levels. Available from Shell Oil Co. is a material having about 75 percent butadiene and about 25 percent styrene under the name Kraton® D.
  • Other impact modifiers include partially hydrogenated styrene butadiene or isoprene block copoly- mers (for example, Kraton® G) and functionalized block copolymers (for example, raton® GF 1901) .
  • Both Fina and Firestone market a 50 percent butadiene and 50 percent styrene under the name Finaprene® and Stereon®, respectively.
  • the intermediate block copolym ⁇ er employed in this invention has a butadiene-styrene content of about 50:50 and gave unexpected results.
  • the terms diblock, triblock, multiblock or star radial copolymers are understood in the art as is illustrated in the Encyclopedia of Polymer Science and Engineering. Volume 2, 1985, pp. 325-326, published by John Wiley & Sons, New York, incorporated herein by reference.
  • the multiblock copolymers are understood to have an A je -B- a 'A jj -B ⁇ A jj -B, ⁇ type of structure.
  • this product has a desirable ratio of styrene to butadiene in the range of around 40/60 and a desirable weight average molecular weight of from about 50,000 to 100,000, and more par- ticularly 75,000 to 95,000.
  • the amount of compat ⁇ ibilizing agent generally ranges from about 1 to about 18 and preferably from about 4 to about 15 and most preferably from about 6 to about 12 for every 100 parts by weight of the styrene resin.
  • the polymer composition While obtaining a polymer composition meeting UL 94 V-0 criteria, the polymer composition also has an acceptable impact strength.
  • the compatibil ⁇ izing agent imparts a notched Izod impact strength improvement of at least about 10 percent, preferably about 20 percent, and most preferably >30 percent over a comparable flame retardant polymer composition not containing the compatibilizing agent.
  • compositions have improved Gardner and Izod impact values and similar heat deflection and flexural modulus values.
  • the latter are unexpected because normal addition of traditional impact modifiers such as styrene-butadiene rubbers or ethylene-propylene rubbers reduces heat deflection and flexural modulus significantly.
  • those values remain unexpectedly high.
  • the composi ⁇ tions have superior heat deflection properties. All of these improvements are believed to indicate an improved morphological compatibility of the various components of this system, the mechanics of which are not fully understood.
  • composition of this invention can also contain various traditional additives in conventional amounts.
  • various fillers and pigments can be added such as talc, calcium carbonate, bentonite, wollastonite, clay, silica, magnesium carbonate, dolo ⁇ mite, glass fibers, carbon black, titanium dioxide and other pigments, and the like.
  • the amounts of said fillers generally range from about l to about 40 and desirably from about 1 to about 30 for every 100 parts by weight of the styrene resin.
  • antioxidants blowing agents, light stabilizers, lubricants, proces- sing aids, and the like, well known to the art and to the literature, can also be utilized when desired generally in small amounts as up to about 5 parts by weight for every 100 parts by weight of the polystyrene- based polymer.
  • the composition of the present invention is prepared in a processing device, such as an extruder, for example, a twin-screw or a single-screw extruder, an intensive mixer, a continuous mixer, a Buss kneader, or the like.
  • a processing device such as an extruder, for example, a twin-screw or a single-screw extruder, an intensive mixer, a continuous mixer, a Buss kneader, or the like.
  • the composition can be compounded in a one step process or a two step process in which a premix is formed.
  • the processing device should be operated at a temperature sufficient to melt the styrene resin polymer which naturally will vary with molecular weight. On the other hand, the temperature should not exceed the degradation temperature of any of the components.
  • tempera- tures of from about 250°F to about 500°F can be util ⁇ ized, with from about 400°F to about 450°F being pre ⁇ ferred.
  • the torque parameters of the processing device should be fairly sufficient to masticate the styrene resin and generally has from moderate to high torque. Shear rates vary from 300 to 5,000 sec-1, and preferably from 3,000 to 4,500 sec-1.
  • all of the various components forming the flame retardant styrene resin composition of the present invention are added together to the processing device wherein they are mixed and blended to obtain said composition.
  • a master batch of flame retardant and compatibilizing agent and optionally the flame retardant synergist are premixed to give a master batch and a portion of the master batch is then added to the styrene resin (and respectively, if necessary, the flame retardant syner ⁇ gist) to form the composition of this invention.
  • styrene resin for every 100 parts by weight of styrene resin there is employed from about 1 to about 8 parts flame retardant synergist, from about 10 to about 25 parts flame retardant and from about 1 to about 18 parts compatibilizing agent.
  • flame retardant synergist for every 100 parts by weight of styrene resin, there is employed from about 3 to about 7 parts flame retardant synergist, from about 14 to about 22 parts flame retardant and from about 4 to about 15 parts of compatibilizing agent.
  • styrene resin there is employed from about 4 to about 6 parts flame retardant synergist, from about 16 to about 20 parts flame retardant, and from about 6 to about 12 parts of compatibilizing agent.
  • the following tables illustrate the prepara ⁇ tion and evaluation of flame retardant compositions of the present invention.
  • Various HIPS resins are utilized in the following tables.
  • the HIPS resins employed are not only from different manufacturers, but also have different styrene-butadiene content.
  • the flame retar ⁇ dant is a brominated polystyrene of either a high molecular weight (Mw «300,000) identified as Pyro-Chek® 68PB or a low molecular weight (Mw «3000) identified as Pyro-Chek® LM. Both are available from The Ferro Corpo ⁇ ration.
  • the compatibilizing agents are identified in the tables.
  • One such preferred composition is a styrene-butadiene-styrene block copolymer having a weight average molecular weight of «85,000 with the name Stereon® 840A, available from The Firestone Tire & Rubber Company.
  • the compounding of the flame-retardant styrene resin compositions described herein was carried out in a standard counter-rotating twin-screw extruder (34mm American Leistritz) .
  • the starting material was intro ⁇ quizd into the extruder in the indicated amounts through a funnel; compounding was continuous with the screws being operated at 100 rp and the temperature being maintained at or below 460°F.
  • the flame retardant polystyrene resin was extruded through a two-hole die into a water bath, then air-dried and chopped into pellets about 1/8" long and 3/16" in diameter.
  • the compositions were also processed where indicated in a Banbury mixer at a temperature of 250°-320°F and a shear rate of 200 to 5,000.
  • pellets were then processed in a Van Dorn injection older having a 6-ounce shot capacity and a
  • HIPS RESIN 100 81 79.5 76.5 73.5
  • EXAMPLE 1 USE OF STEREON 840A TO IMPROVE IMPACT WHILE SUBSTANTIALLY MAINTAINING HDT AND FLEXURAL MODULUS
  • HIPS RESIN Huntsman 840
  • Pyrocheck LM Fluorescence LM
  • Thermoguard S, M & T 4 4 4 Stereon 840A (Firestone) 3.0 4.5 7.5
  • EXAMPLE 2 USE OF STEREON 840A TO IMPROVE IMPACT WHILE SUBSTANTIALLY MAINTAINING HDT AND FLEXUP MODULUS
  • EXAMPLE 3 USE OF STEREON 840A TO IMPROVE IMPACT WHILE SUBSTANTIALLY MAINTAINING HDT AND FLEXURAL MODULUS
  • EXAMPLE 4 USE OF KRATON D-1101 TO IMPROVE IMPACT OF FILLED SYSTEMS WHILE MAINTAINING HDT
  • HIPS RESIN Hunt ⁇ man 840
  • Talc Cantal 45-90, Cantal
  • Sb,0 (Thermoguard S, M & T) Pyrocheck 68 PB (Ferro) Kraton D-1101 (Shell) Stereon 840A (Firestone) 7.5 K Resin KR-01 (Phillips) 7.5
  • EXAMPLE 5 USE OF THREE TYPES OF BLOCK COPOLYMERS TO IMPROVE IMPACT PROPERTIES WHILE MAINTAINING HDT AND MODULUS PROPERTIES
  • EXAMPLE 6 USE OF INEXPENSIVE FILLER (TALC) WHILE MAINTAINING KEY PHYSICAL PROPERTIES OF FLAME RETARDANT HIPS COMPOSITIONS CONTAINING BLOCK COPOLYMER
  • HIPS RESIN Huntsman 840
  • Pyrocheck 68 PB Ferro
  • Sb_0_ Thermoguard S, M & T
  • Stereon 840A (Fire ⁇ tone)
  • HIPS RESIN Huntsman 840
  • EXAMPLE 8 EFFECT OF BLOCK COPOLYMER IN FLAME RETARDANT HIPS COMPOSITIONS (PYROCHECK 68 PB VS. LM)
  • HIPS RESIN (Huntsman 840) 81.0 76.0 76.0 76.0 76.0 76.0
  • EXAMPLE 9 EFFECT OF MISCELLANEOUS COMPATIBILIZERS IN FLAME RETARDANT HIPS COMPOSITIONS (*Pre-mixed together in a Banbury Mixer).
  • Table I illustrates a significant improvement in elongation and impact values with the addition of the compatibilizing agent while maintaining heat deflection temperatures and flexural modulus and, of course, achieving the desired flame retardancy through the use of a low molecular weight brominated polystyrene.
  • Table II illustrates a similar effect with a different high impact polystyrene resin and also through the use of the low molecular weight brominated poly- styrene.
  • Table III illustrates the effect with the same resin used in Table II, but with the high molecular weight brominated polystyrene flame retardant.
  • Table IV illustrates two additional resins and an additional compatibilizing agent. These samples further illustrate similar performance characteristics even in the presence of filler.
  • Table . shows three separate block copolymers as compatibilizing agents used in comparable resin systems. This data illustrates that Stereon® 840A is a preferred compatibilizing agent to improve impact properties.
  • Stereon 840A is illustrated as improving impact properties and maintain- ing heat deflection, even in the presence of fillers, such as talc.
  • Table VII illustrates the effect of processing equipment on the present invention showing the improve ⁇ ments in impact properties for systems blended in both Banbury mixers and twin screw extruders. It is noted that the data set forth in this Table was collected from four different studies designed to show the significance of processing conditions on the present invention.
  • Table VIII illustrates the use of two differ- ent flame retardants in the same resin system.
  • Table IX illustrates the effect of various compatibilizing agents used in a pre-mix with the flame retardant. It also illustrates the use of a peroxide to further improve impact properties.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A flame retardant styrene composition that has improved impact strength is provided while maintaining heat deflection temperature and flexural modulus. The impact strength is improved through the use of a styrene butadiene block copolymer compatibilizing agent. In a preferred embodiment, the use of a brominated diphenyl oxide as a flame retardant is avoided.

Description

IMPROVED FLAME RETARDANT RESIN COMPOSITION CONTAINING STYRENIC POLYMERS
FIELD OF THE INVENTION
The present invention generally relates to flame retardant styrene polymer compositions that have improved impact strength. The compositions additionally have flexural modulus and heat deflection properties similar to styrene polymer compositions not containing flame retardants.
BACKGROUND
Heretofore, whenever flame retardants were added to various thermoplastic polymers such as styrene resins, various physical properties were affected such as reduced impact strength. This is due to the fact that while imparting flame retardancy, the flame retar- dant causes embrittlement when added to produce the desired flame retardancy.
European Patent Applications 262,615 and 87/05615 to Haaf and Abolins, respectively, relate to flame retardant polyphenylene ether compositions and more specifically to compositions of a polyphenylene ether resin and a high impact polystyrene in which a post brominated polystyrene oligomer or polymer and antimony oxide are used in combination to impart better flame resistance, impact strength, and mold flow. IPO International Bureau 88/03542 relates to modified polyphenylene ether resins having improved flow properties and, in particular, it relates to modified polyphenylene ether resins incorporating a brominated al enyl aromatic resin, a diester of tetrabromophthalic acid, and a flame retardant enhancer such as antimony trioxide. Flame retardant polystyrenes have various applications in injection molded products such as television cabinets, television racks, business machine housings, table-top and lap-top computers, smoke detec¬ tor housings and modular furniture including hospital furniture.
The compositions of the present invention are also useful especially for making other molded articles such as medical disposal boxes for the receipt, storage, and eventual disposal of contaminated medical products; for electrical boxes and connectors, electrical materi¬ als, and the like. While the impact properties of flame retardant polystyrene may be acceptable when the flame retardant is decabromodiphenyloxide without the use of a com- patibilizer, in a preferred embodiment of the inven¬ tion, the flame retardant excludes this composition and its analogs. These brominated diphenyl oxides may pyrolize to form furans which are potentially hazardous and environmentally toxic. Thus, it is preferred to use a flame retardant package of the present invention such as brominated polystyrene and to utilize the co - patibilizing agent to improve the impact properties.
SUMMARY OF THE INVENTION
Generally, when flame retardancy is imparted to styrene polymeric resins, impact strength is reduced due to the fact that the polymeric resins become embrit¬ tled. In the present invention the impact strength of the flame retardant polymer is further augmented by incorporating therein a compatibilizing agent comprising a block copolymer.
Thus, the present invention relates to a flame retardant package which comprises a flame retardant, a flame retardant synergist and an compatibilizing agent. In a preferred embodiment, the flame retardant is a brominated styrene polymer such as brominated polys¬ tyrene. The compatibilizing agent is a styrene butadi¬ ene block copolymer. DETAILED DESCRIPTION OF THE INVENTION
The present invention comprises four com¬ ponents: a styrene polymeric resin, a flame retardant synergist, a flame retardant, and a compatibilizing agent or property enhancer.
Alternatively, this invention can be en¬ visioned as a two component system comprising the styrene polymer and a flame retardant package where the package comprises the flame retardant, the flame retar¬ dant synergist and the compatibilizing agent. Similar¬ ly, the blend compositions of the present invention can be blended in a one part or two part process. In the one part process, all of the ingredients are mixed in the same step although they may be etered at various points of the mastication process. In the two part process, two or more ingredients may be premixed such as the flame retardant package.
The styrene polymeric resins having utility in this invention comprises high impact polystyrene (HIPS) , polystyrene, poly-α-methylstyrene, polyvinyl naphtha¬ lene, styrene-acrylonitrile copolymer, styrene maleic anhydride copolymer, EPDM modified styrene acrylonitrile copolymer, styrene-acrylic copolymer, acrylonitrile- styrene-acrylic terpolymer, polystyrene-polyphenylene oxide blend, or acrylonitrile-butadiene-styrene graft copolymer. Of these, the preferred is high impact polystyrene. High impact polystyrene is understood in the art as a thermoplastic resin product from styrene monomer along with elastomers such as polybutadiene which are introduced into the polystyrene matrix.
Polystyrene homopolymers, polystyrene copoly- mers, or terpolymers or graft copolymers and blends thereof are preferred. The above-noted styrene polymer- ic resins are generally commercially available and have a weight average molecular weight of from about 100,000 to about 1,000,000 and preferably from about 200,000 to about 300,000.
The amount of the various flame retardants which are utilized are generally dictated by a desirable UL (Underwriters Laboratories, Inc.) 94 flammability rating. The UL 94 test is a vertical burning test. A material having a V-0 rating allows only minimal burning and no flaming drip of a standard bar of specified thickness. The V-l rating allows longer burn times than the V-0, but not flaming drip. The V-2 rating allows the same burn time as the V-l and also allows flaming drip. The fail rating is given any material not meeting the V-0, V-l, or V-2 criteria. The choice of the variously rated flame-retardant polystyrene resins depends upon the end use.
Compositions having UL9 ratings from V-0 to V-2 may be useful depending on the application. It may be preferable to achieve the V-0 rating for certain ap¬ plications. The styrene polymeric resins of the present invention contain a flame retardant synergist comprising antimony oxide or sodium antimonate. Its main function is to promote the flame retardancy properties of the flame retardant. The synergist is employed in effective amounts to improve the flame retardancy within the styrenic resin. Generally, an effective amount of synergist is from about 1 to about 8 parts, preferably from about 3 to about 7 parts and most preferably from about 4 to about 6 parts by weight per 100 parts by weight of the resin components.
Various flame retardants comprising hal-^ena- ted organic compounds are utilized in association with the antimony component. Examples of suitable halo- genated organic compounds include brominated dipen- taerithritol, tetrabromobisphenol A, ethylene-bistetra- bromophthalimide, ethylenebisdibromonorbornane-dicarbox- imide, tetrabromobisphenol A-bis(2,3-dibromopropyl ether) , octabromodiphenyl oxide, hexabromocyclododec- ane, hexabromodiphenoxy ethane, decabromodiphenoxy ethane, decabromodiphenyloxide, tetradecabromodiphenoxy benzene, brominated polystyrene, tetradecabromodiphenyl- oxide, poly-dibromophenylene oxide, phenoxy terminated bisphenol A carbonate oligomers containing from about 50 to about 60 percent bromine, brominated epoxy resins containing from about 30 to about 60 percent bromine, and mixtures thereof. Brominated organic compounds which are especially preferred comprise brominated polystyrene, hexabromocyclododecane, ethylene-bistetra- bromophthalimide and ethylene dibromonorbornane-dicar- boximide.
In a preferred embodiment of the invention, the flame retardant excludes brominated diphenyl oxides such as octabromodiphenyl oxide, decabromodiphenyl oxide, tetradecabromodiphenyl oxide, poly-dibro aphenyl- ene oxide and the like. The flame retardant is thus preferably brominated polystyrene such as a high olecu- lar weight and low molecular weight brominated polysty¬ rene. The high molecular weight brominated polystyrene is generally understood to have a molecular weight of from about 100,000 to about 400,000, while the low molecular weight brominated polystyrene is generally understood to have a molecular weight of from about 1,000 to about 20,000. At the present time those brominated polystyrenes having a molecular weight between 20,000 and 100,000 could fall into either category and therefore should be understood to be encompassed in the present invention.
Also incorporated into the styrene resin is a compatibilizing agent which functions to improve the impact properties of the blend. Further, this com¬ patibilizing agent could be termed a property enhancer. The compatibilizing agent is preferably a copolymer of styrene and butadiene or isoprene. This copolymer is preferably a block copolymer having a diblock, triblock. multi-block or a star radial composition. The block copolymer is a styrene-butadiene copolymer having generally a butadiene content of from about 20 percent to about 80 percent and a styrene content of from about 80 percent to about 20 percent. Preferably the buta¬ diene is from 35 to 65 percent, most preferably it is from 40 to 60 percent with the styrene comprising the remainder.
The compatibilizers are commercially available having various styrene-butadiene levels. Available from Shell Oil Co. is a material having about 75 percent butadiene and about 25 percent styrene under the name Kraton® D. Other impact modifiers include partially hydrogenated styrene butadiene or isoprene block copoly- mers (for example, Kraton® G) and functionalized block copolymers (for example, raton® GF 1901) . Both Fina and Firestone market a 50 percent butadiene and 50 percent styrene under the name Finaprene® and Stereon®, respectively. Phillips Petroleum markets a material having about 25 percent butadiene and 75 percent styrene under the name K-resin. The intermediate block copolym¬ er employed in this invention has a butadiene-styrene content of about 50:50 and gave unexpected results. The terms diblock, triblock, multiblock or star radial copolymers are understood in the art as is illustrated in the Encyclopedia of Polymer Science and Engineering. Volume 2, 1985, pp. 325-326, published by John Wiley & Sons, New York, incorporated herein by reference. In particular, the multiblock copolymers are understood to have an Aje-B-a'Ajj-B^Ajj-B,^ type of structure. Stereon is an example of such a product. Further, this product has a desirable ratio of styrene to butadiene in the range of around 40/60 and a desirable weight average molecular weight of from about 50,000 to 100,000, and more par- ticularly 75,000 to 95,000. The amount of compat¬ ibilizing agent generally ranges from about 1 to about 18 and preferably from about 4 to about 15 and most preferably from about 6 to about 12 for every 100 parts by weight of the styrene resin.
While obtaining a polymer composition meeting UL 94 V-0 criteria, the polymer composition also has an acceptable impact strength. Typically, the compatibil¬ izing agent imparts a notched Izod impact strength improvement of at least about 10 percent, preferably about 20 percent, and most preferably >30 percent over a comparable flame retardant polymer composition not containing the compatibilizing agent.
These compositions have improved Gardner and Izod impact values and similar heat deflection and flexural modulus values. The latter are unexpected because normal addition of traditional impact modifiers such as styrene-butadiene rubbers or ethylene-propylene rubbers reduces heat deflection and flexural modulus significantly. In the present invention, those values remain unexpectedly high. In particular, the composi¬ tions have superior heat deflection properties. All of these improvements are believed to indicate an improved morphological compatibility of the various components of this system, the mechanics of which are not fully understood.
The composition of this invention can also contain various traditional additives in conventional amounts. For example, various fillers and pigments can be added such as talc, calcium carbonate, bentonite, wollastonite, clay, silica, magnesium carbonate, dolo¬ mite, glass fibers, carbon black, titanium dioxide and other pigments, and the like. The amounts of said fillers generally range from about l to about 40 and desirably from about 1 to about 30 for every 100 parts by weight of the styrene resin. Various antioxidants, blowing agents, light stabilizers, lubricants, proces- sing aids, and the like, well known to the art and to the literature, can also be utilized when desired generally in small amounts as up to about 5 parts by weight for every 100 parts by weight of the polystyrene- based polymer.
The composition of the present invention is prepared in a processing device, such as an extruder, for example, a twin-screw or a single-screw extruder, an intensive mixer, a continuous mixer, a Buss kneader, or the like. As previously discussed, the composition can be compounded in a one step process or a two step process in which a premix is formed. Customarily, the processing device should be operated at a temperature sufficient to melt the styrene resin polymer which naturally will vary with molecular weight. On the other hand, the temperature should not exceed the degradation temperature of any of the components. Usually, tempera- tures of from about 250°F to about 500°F can be util¬ ized, with from about 400°F to about 450°F being pre¬ ferred. The torque parameters of the processing device should be fairly sufficient to masticate the styrene resin and generally has from moderate to high torque. Shear rates vary from 300 to 5,000 sec-1, and preferably from 3,000 to 4,500 sec-1. Typically, all of the various components forming the flame retardant styrene resin composition of the present invention are added together to the processing device wherein they are mixed and blended to obtain said composition. Alternatively, a master batch of flame retardant and compatibilizing agent and optionally the flame retardant synergist are premixed to give a master batch and a portion of the master batch is then added to the styrene resin (and respectively, if necessary, the flame retardant syner¬ gist) to form the composition of this invention.
Generally, for every 100 parts by weight of styrene resin there is employed from about 1 to about 8 parts flame retardant synergist, from about 10 to about 25 parts flame retardant and from about 1 to about 18 parts compatibilizing agent. Preferably, for every 100 parts by weight of styrene resin, there is employed from about 3 to about 7 parts flame retardant synergist, from about 14 to about 22 parts flame retardant and from about 4 to about 15 parts of compatibilizing agent. Most preferably, for every 100 parts by weight of styrene resin, there is employed from about 4 to about 6 parts flame retardant synergist, from about 16 to about 20 parts flame retardant, and from about 6 to about 12 parts of compatibilizing agent.
EXAMPLES
The following tables illustrate the prepara¬ tion and evaluation of flame retardant compositions of the present invention. Various HIPS resins are utilized in the following tables. The HIPS resins employed are not only from different manufacturers, but also have different styrene-butadiene content. The flame retar¬ dant is a brominated polystyrene of either a high molecular weight (Mw«300,000) identified as Pyro-Chek® 68PB or a low molecular weight (Mw«3000) identified as Pyro-Chek® LM. Both are available from The Ferro Corpo¬ ration. The compatibilizing agents are identified in the tables. One such preferred composition is a styrene-butadiene-styrene block copolymer having a weight average molecular weight of «85,000 with the name Stereon® 840A, available from The Firestone Tire & Rubber Company.
The compounding of the flame-retardant styrene resin compositions described herein was carried out in a standard counter-rotating twin-screw extruder (34mm American Leistritz) . The starting material was intro¬ duced into the extruder in the indicated amounts through a funnel; compounding was continuous with the screws being operated at 100 rp and the temperature being maintained at or below 460°F. The flame retardant polystyrene resin was extruded through a two-hole die into a water bath, then air-dried and chopped into pellets about 1/8" long and 3/16" in diameter. The compositions were also processed where indicated in a Banbury mixer at a temperature of 250°-320°F and a shear rate of 200 to 5,000.
The pellets were then processed in a Van Dorn injection older having a 6-ounce shot capacity and a
110-ton clamping capacity. Various configuration specimens were molded to carry-out the tests described in Tables I through IX.
The physical properties described in the following examples are obtained in accordance with ASTM or UL standard test procedures as identified below: PROPERTY TEST PROCEDURE
Tensile Strength ASTM D-638
Elongation ASTM D-638 Flexural Modulus (tangent) ASTM D-790
Izod Impact (Notched) ASTM D-256
(Method A)
Izod Impact (Unnotched) ASTM D-256
Gardner Impact ASTM D-3029 Heat Deflection Temperature ASTM D-648
Flame Resistance UL 94
TABLE I
COMPOSITION; 1 2 3 4 5
HIPS RESIN (ASAHI V-O) 100 81 79.5 76.5 73.5
Pyrocheck LM (Ferro) 15 15 15 15
Sb-O, (Thermoguard S, M & T) 4 4 4 4
Stereon 840A (Firestone) 1.5 4.5 7.5
PHYSICAL PROPERTIES!
Elongation at Break (%)
Flexural Modulus, Kpsi
Izod Impact, Notched (ft-lb/in)
Izod Impact, Unnotched (ft-lb/in)
Gardner Impact (in-lb)
Heat Deflection Temp, at 264 psi, C
UL-94 1/8"
1/16"
1/32"
Figure imgf000013_0001
EXAMPLE 1: USE OF STEREON 840A TO IMPROVE IMPACT WHILE SUBSTANTIALLY MAINTAINING HDT AND FLEXURAL MODULUS
COMPOSITION;
HIPS RESIN (Huntsman 840) 78 76.5 73.5 Pyrocheck LM (Ferro) 15 15 15 Sb-O, (Thermoguard S, M & T) 4 4 4 Stereon 840A (Firestone)
Figure imgf000014_0001
3.0 4.5 7.5
PHYSICAL PROPERTIES;
Flexural Modulus, Kpsi
Izod Impact, Notched (ft-lb/in)
Izod Impact, Unnotched (ft-lb/in)
Gardner Impact (in-lb)
Heat Deflection Temp, at 264 psi, C
UL-94 1/8"
1/16"
1/32"
Figure imgf000014_0002
EXAMPLE 2: USE OF STEREON 840A TO IMPROVE IMPACT WHILE SUBSTANTIALLY MAINTAINING HDT AND FLEXUP MODULUS
TABLE III
COMPOSITION;
HIPS RESIN (Huntsman 840) 81 77.25 73.5 Pyrocheck 68 PB (Ferro) 15 15 15 Sb_0_ (Thermoguard S, M & T) 4 4 4 Stereon 840A (Firestone) 3.75 7.5
PHYSICAL PROPERTIES;
Flexural Modulus, Kpsi
Izod Impact, Notched (ft-lb/in)
Izod Impact, Unnotched (ft-lb/in)
Gardner Impact (in-lb)
Heat Deflection Temp, at 264 psi, C
UL-94 1/8"
1/16"
1/32"
Figure imgf000015_0001
EXAMPLE 3: USE OF STEREON 840A TO IMPROVE IMPACT WHILE SUBSTANTIALLY MAINTAINING HDT AND FLEXURAL MODULUS
Figure imgf000016_0001
COMPOSITION;
HIPS RESIN (Dow 475U)
Pyrocheck 68 PB (Ferro)
Sb,0, (Ther oguard S, M fi T)
Talc (Jet Fill 100, Steetley)
Kraton D-1101 (Shell)
HIPS Resin (Dow 492U)
Figure imgf000016_0002
PHYSICAL PROPERTIES;
Elongation, Break (%)
Flexural Modulus, Kpsi
Izod T-mpact, Notched (ft-lb/in)
Izod Impact, Unnotched (ft-lb/in)
Gardner Impact (in-lb)
Heat Deflection Temp, at 264 psi, C
Figure imgf000016_0003
EXAMPLE 4: USE OF KRATON D-1101 TO IMPROVE IMPACT OF FILLED SYSTEMS WHILE MAINTAINING HDT
TABLE V
COMPOSITION;
HIPS RESIN (Huntβman 840) Talc (Cantal 45-90, Cantal) Sb,0, (Thermoguard S, M & T) Pyrocheck 68 PB (Ferro) Kraton D-1101 (Shell)
Figure imgf000017_0001
Stereon 840A (Firestone) 7.5 K Resin KR-01 (Phillips) 7.5
PHYSICAL PROPERTIES;
Elongation, Break (%) Flexural Modulus, Kpsi Izod Impact, Notched (ft-lb/in) Izod Impact, Unnotched (ft-lb/in) Gardner Impact (in-lb) Heat Deflection Temp, at 264 psi, UL-94 1/16" 1/32"
Figure imgf000017_0002
EXAMPLE 5: USE OF THREE TYPES OF BLOCK COPOLYMERS TO IMPROVE IMPACT PROPERTIES WHILE MAINTAINING HDT AND MODULUS PROPERTIES
TABLE VI
COMPOSITION;
HIPS RESIN (Huntsman 840)
Pyrocheck LM (Ferro)
Sb2θ, (Thermoguard S, M & T)
Stereon 840A (Firestone)
Talc (Cantal 45-90 Cantal)
Figure imgf000018_0001
Talc (Select-A-Sorb, R.T. Vanderbilt) 10.0
PHYSICAL PROPERTIES;
Elongation, Break (%) 22.0 34.0 28 27
Flexural Modulus, Kpsi 431 295 308 296
Izod Impact, Notched (ft-lb/in) 0.5 1.9 1.4 1.2
Izod Impact, Unnotched (ft-lb/in) 2.2 5.8 4.8 4.5
Gardner Impact (in-lb) 3 16 15 14
Heat Deflection Temp, at 264 psi, C 90 88 87 87
UL-94 1/32" V-O V-0 V-0 V-O
EXAMPLE 6; USE OF INEXPENSIVE FILLER (TALC) WHILE MAINTAINING KEY PHYSICAL PROPERTIES OF FLAME RETARDANT HIPS COMPOSITIONS CONTAINING BLOCK COPOLYMER
TABLE VII
COMPOSITION; B.M. T.S.
HIPS RESIN (Huntsman 840) 81.0 81.0 Pyrocheck 68 PB (Ferro) 15.0 15.0 Sb_0_ (Thermoguard S, M & T) 4.0 4.0 Stereon 840A (Fireβtone)
Figure imgf000019_0002
PHYSICAL PROPERTIES;
Elongation, Break (%)
Flexural Modulus, Kpsi
Izod Impact, Notched (ft-lb/in)
Izod Impact, Unnotched (ft-lb/in)
Gardner Impact (in-lb)
Heat Deflection Temp, at 254 psi, C
Figure imgf000019_0004
UL-94 1/32"
Figure imgf000019_0003
V-O V-0
EXAMPLE 7; EFFECT OF PROCESSING ON IMPACT PROPERTIES OF FLAME RETARDANT
Figure imgf000019_0001
HIPS COMPOSITIONS (T.S. ~- Twin Screw Extruder & B.M. ~~ Banbury Mixer)
Figure imgf000020_0001
TABLE VIII
COMPOSITION; 1 2
HIPS RESIN (Huntsman 840) 81.0 81.0 Sb-O, (Thermoguard S, M & T) 4.0 4.0 Stereon 840A (Firestone) 7.5 7.5 Pyrochek 68 PB (Ferro) 15.0 Pyrocheck LM (Ferro) 15.0
PHYSICAL PROPERTIES;
Tensile Strength
Flexural Moduluβ, Kpsi
Izod Impact, Notched (ft-lb/in)
Izod Impact, Unnotched (ft-lb/in)
Gardner Impact (in-lb)
Figure imgf000020_0003
Figure imgf000020_0002
EXAMPLE 8: EFFECT OF BLOCK COPOLYMER IN FLAME RETARDANT HIPS COMPOSITIONS (PYROCHECK 68 PB VS. LM)
TABLE IX
COMPOSITION;
HIPS RESIN (Huntsman 840) 81.0 76.0 76.0 76.0 76.0 76.0
Pyrocheck 68 PB (Ferro) 15.0 15.2* 15.2* 15.2* 15.2* 15.2*
Sb_0_ (Thermoguard S, M & T) 4.0 4.0 4.0 4.0 4.0 4.0
Kraton G-1651 (Shell) 4.8* 3.6*
Kraton G-1901 F (Shell) 1.2* 4.8*
KR-03 (Phillips) 4.8* 4.8*
CR-10 Peroxide concentrate, Polyvel) 0.05
PHYSICAL PROPERTIES;
Flexural Modulus, Kpsi
Izod Impact, Notched (ft-lb/in)
Izod Impact, Unnotched (ft-lb/in)
Gardner Impact (in-lb)
Heat Deflection Temp, at 264 psi,
UL-94 1/8"
1/16"
1/32"
Figure imgf000021_0001
EXAMPLE 9: EFFECT OF MISCELLANEOUS COMPATIBILIZERS IN FLAME RETARDANT HIPS COMPOSITIONS (*Pre-mixed together in a Banbury Mixer).
Table I illustrates a significant improvement in elongation and impact values with the addition of the compatibilizing agent while maintaining heat deflection temperatures and flexural modulus and, of course, achieving the desired flame retardancy through the use of a low molecular weight brominated polystyrene.
Table II illustrates a similar effect with a different high impact polystyrene resin and also through the use of the low molecular weight brominated poly- styrene.
Table III illustrates the effect with the same resin used in Table II, but with the high molecular weight brominated polystyrene flame retardant.
Table IV illustrates two additional resins and an additional compatibilizing agent. These samples further illustrate similar performance characteristics even in the presence of filler.
Table . shows three separate block copolymers as compatibilizing agents used in comparable resin systems. This data illustrates that Stereon® 840A is a preferred compatibilizing agent to improve impact properties.
In Table VI, the use of Stereon 840A is illustrated as improving impact properties and maintain- ing heat deflection, even in the presence of fillers, such as talc.
Table VII illustrates the effect of processing equipment on the present invention showing the improve¬ ments in impact properties for systems blended in both Banbury mixers and twin screw extruders. It is noted that the data set forth in this Table was collected from four different studies designed to show the significance of processing conditions on the present invention.
Table VIII illustrates the use of two differ- ent flame retardants in the same resin system.
Table IX illustrates the effect of various compatibilizing agents used in a pre-mix with the flame retardant. It also illustrates the use of a peroxide to further improve impact properties.
While in accordance with the Patent Statutes, the best mode and preferred embodiment has been set forth, the scope of the invention is not limited there¬ to, but rather by the scope of the attached claims.

Claims

WHAT IS CLAIMED IS:
1. A flame retardant composition, comprising: a styrene polymer, a flame retardant, a flame retardant synergist; and a compatibilizing agent.
2. A composition as set forth in Claim l, wherein the compatibilizing agent is a copolymer of styrene butadiene.
3. The composition as set forth in Claim 2, wherein the styrene-based resin comprises high impact polystyrene, polystyrene, poly-α-methylstyrene, polyvin- yl naphthalene, styrene-acrylonitrile copolymer styrene maleic anhydride copolymer, EPDM modified styrene acrylonitrile copolymer, acrylic-styrene-acrylic copoly¬ mer, or acrylonitrile-butadiene-styrene copolymer.
4. The composition as set forth in Claim 3, wherein the flame retardant is one or more of brominated polystyrene, ethylene-bistetrabromophthalimide, ethyl- enebisdibromonorbornane-dicarboximide, hexabromocyclodo- decane, and the flame retardant synergist is one or more of antimony oxide or sodium antimonate.
5. The composition as set forth in Claim 4, wherein the styrene is present at 100 parts per weight, the flame retardant is present at from about 10 to about 25 parts per weight, the flame retardant synergist is present at from 1 to about 8 parts by weight, and the compatibilizing agent is present from about 2 to about 18 parts by weight.
6. The composition as set forth in Claim 5, wherein said styrene polymer is a high impact polys¬ tyrene.
7. The composition of Claim 6, wherein said flame retardant is low molecular weight brominated polystyrene.
8. The composition of Claim 7 , wherein said compatibilizing agent has from about 35 to about 65 percent of butadiene and from about 65 to about 35 percent of styrene.
9. The composition as set forth in Claim 8, wherein said compatibilizing agent has from about 40 to about 60 percent butadiene and from about 40 to about 60 percent styrene.
10. The composition of Claim 8, wherein said compatibilizing agent is a multi-block copolymer.
11. A flame retardant composition as set forth in Claim 10, further including a filler.
12. A flame retardant composition as set forth in Claim 10, further comprising a peroxide.
13. A flame retardant composition as set forth in Claim 12, wherein a premix is made comprising said flame retardant and said compatibilizing agent.
14. A flame retardant composition comprising a styrene polymer and a flame retardant package, said flame retardant package comprising a flame retardant, a flame retardant synergist, and a compatibilizing agent, said composition having a UL-94 flammability rating of V-2 or better.
15. A composition as set forth in Claim 14, wherein said flame retardant is brominated polystyrene.
16. A flame retardant composition as set forth in Claim 15, wherein said styrene comprises a high- impact polystyrene.
17. A flame retardant composition as set forth in Claim 16, wherein said compatibilizing agent is a copolymer of styrene and butadiene having from 40 to 60 percent of butadiene and from 40 to 60 percent styrene.
18. A flame retardant composition as set forth in Claim 17, wherein the notched Izod impact strength of the composition is within at least minus 20 percent of the comparable value of a comparable composition without said flame retardant package.
19. A flame retardant package for use in a styrene resin comprising from about 14 to about 22 parts of a brominated polystyrene flame retardant, from about 1 to about 8 parts of antimony oxide, or sodium an- timonate, and from about 1 to about 18 parts of a block copolymer of butadiene styrene having from about 40 to about 60 percent butadiene and from about 40 to about 60 percent styrene.
20. A process for the production of a flame retardant composition comprising blending together a styrene resin with a flame retardant package, said flame retardant package comprising from about 52 to about 88 parts flame retardant, from about 6 to about 17 parts of a flame retardant synergist, and from about 6 to about 31 parts of a compatibilizing agent.
21. A process as set forth in Claim 20, wherein said composition is blended at a shear of from about 2,000 to about 5,000 sec-1, and a temperature of from about 250°F to about 500°F.
22. A process as set forth in Claim 21, wherein a premix comprises at least said flame retard¬ ant and said compatibilizing agent.
PCT/US1991/005888 1990-08-23 1991-08-19 Improved flame retardant resin composition containing styrenic polymers WO1992003499A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US57193890A 1990-08-23 1990-08-23
US571,938 1990-08-23

Publications (1)

Publication Number Publication Date
WO1992003499A1 true WO1992003499A1 (en) 1992-03-05

Family

ID=24285675

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1991/005888 WO1992003499A1 (en) 1990-08-23 1991-08-19 Improved flame retardant resin composition containing styrenic polymers

Country Status (2)

Country Link
AU (1) AU8534591A (en)
WO (1) WO1992003499A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996035357A1 (en) * 1995-05-08 1996-11-14 Shell Oil Company Storage cabinet and assembly

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4098761A (en) * 1974-03-04 1978-07-04 Hooker Chemicals & Plastics Corp. Halogen containing fire retardant additive with improved heat stability
US4136135A (en) * 1977-03-03 1979-01-23 Monsanto Company Styrene/maleic anhydride copolymers
US4154776A (en) * 1975-10-31 1979-05-15 Labofina S.A. High impact polystyrene composition
US4267284A (en) * 1977-01-07 1981-05-12 Phillips Petroleum Company Tough, transparent articles from styrene polymers blended with certain block-random copolymers
US4374220A (en) * 1968-09-18 1983-02-15 Raychem Corporation Imide flame retardants and compositions containing them
US4386188A (en) * 1981-01-16 1983-05-31 Sweetheart Plastics, Inc. Thermoformable polymer blend composition
US4735983A (en) * 1985-02-05 1988-04-05 Mitsui Toatsu Chemicals, Inc. Flame-retardant styrene-base resin composition
US4829118A (en) * 1987-10-09 1989-05-09 Great Lakes Chemical Corporation Flame retardant ABS resin compositions
US4945018A (en) * 1983-08-23 1990-07-31 General Electric Company Crosslinkable flame retardant composition of polyolefin and polyphenylene ether

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4374220A (en) * 1968-09-18 1983-02-15 Raychem Corporation Imide flame retardants and compositions containing them
US4098761A (en) * 1974-03-04 1978-07-04 Hooker Chemicals & Plastics Corp. Halogen containing fire retardant additive with improved heat stability
US4154776A (en) * 1975-10-31 1979-05-15 Labofina S.A. High impact polystyrene composition
US4267284A (en) * 1977-01-07 1981-05-12 Phillips Petroleum Company Tough, transparent articles from styrene polymers blended with certain block-random copolymers
US4136135A (en) * 1977-03-03 1979-01-23 Monsanto Company Styrene/maleic anhydride copolymers
US4386188A (en) * 1981-01-16 1983-05-31 Sweetheart Plastics, Inc. Thermoformable polymer blend composition
US4945018A (en) * 1983-08-23 1990-07-31 General Electric Company Crosslinkable flame retardant composition of polyolefin and polyphenylene ether
US4735983A (en) * 1985-02-05 1988-04-05 Mitsui Toatsu Chemicals, Inc. Flame-retardant styrene-base resin composition
US4829118A (en) * 1987-10-09 1989-05-09 Great Lakes Chemical Corporation Flame retardant ABS resin compositions

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996035357A1 (en) * 1995-05-08 1996-11-14 Shell Oil Company Storage cabinet and assembly

Also Published As

Publication number Publication date
AU8534591A (en) 1992-03-17

Similar Documents

Publication Publication Date Title
US5194482A (en) Flame retardant resin composition containing styrenic polymers
US5112898A (en) High impact polystyrene containing low molecular weight brominated polystyrene
US4172826A (en) Polyphenylene ether resin compositions containing EPDM rubber-modified alkenyl aromatic resins and hydrogenated elastomeric block copolymers
US5112897A (en) High impact polystyrene containing low molecular weight brominated polystyrene
US4196116A (en) Impact resistant polyphenylene ether compositions containing EPDM rubber-modified alkenyl aromatic resins and hydrogenated diblock copolymers
US5112896A (en) High-impact polystyrene containing low molecular weight brominated polystyrene
JP2004521983A (en) Flame retardant syndiotactic polystyrene resin composition
US5382627A (en) Polyphenylene ether resin composition
JPH0570679A (en) Flame retardant polyolefin resin molded body
JP2824067B2 (en) Flame retardant resin composition
WO1992003499A1 (en) Improved flame retardant resin composition containing styrenic polymers
JPH11323064A (en) Flame-retardant styrene-based resin composition
KR100782701B1 (en) Rubber modified styrenic flame retardant resin composition
JP2005145988A (en) Flame-retardant styrenic resin composition
JPS58129030A (en) Coloration-preventive flame retardant comprising stabilized halogenated organic cpd and boron cpd
JPS59126460A (en) Polyphenylene ether resin composition
JPH10120863A (en) Flame-retardant resin composition
JPH04370134A (en) Halogen-free flame-retarding resin composition
JPH0873684A (en) Flame-retardant resin composition
JP2005281327A (en) Method for molding polystyrene resin using flame retardant masterbatch resin composition and molding obtained thereby
KR100373212B1 (en) Fire retardant styrene based resin composition having superior impact resistance
GB2300860A (en) Flame retardant styrene polymer
US4581403A (en) ABS plastic made transparent and flame retardant with Br2 -Br8 diphenyl ethers
US20020004542A1 (en) Ignition resistant monovinylidene aromatic copolymer composition
JPH07228739A (en) Styrene resin composition

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BB BG BR CA FI HU JP KP KR LK MC MG MW NO RO SD SU

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU NL SE

NENP Non-entry into the national phase

Ref country code: CA