Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions 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
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/06—Polystyrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/16—Halogen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions 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
  • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen

Definitions

• the present invention relates to the use of l molecular weight brominated polystyrenes in high impa polystyrene, whereby good retention of physical prope ties including impact strength is obtained whi achieving excellent flame retardancy.
• a brominated polystyrene having a degree polymerization of approximately 2,000 when used in hi impact polystyrene provides excellent flame retardan and stability but has a very negative effect on k physical properties such as impact strength. This effe is generally unacceptable.
• U.S. Patent No. 3,075,944 relates to fla retardant compositions containing polyolefins which c be made by substituting a diaro atic or an aromati aliphatic ether containing at least three bromine atoms
• U.S. Patent No. 3,830,766 relates to flam proofing acrylonitrile-butadiene-styrene (ABS)polymers incorporating therein an aromatic bromine compoun antimony trioxide or antimony oxychloride and optional an organo chlorine compound.
• ABS flam proofing acrylonitrile-butadiene-styrene
• U.S. Patent No. 3,897,373 relates thermoplastic molding compositions based on styr polymers and flameproofed with an organic bromine c pound. They contain a synergistic azo compound and be converted to self-extinguishing shaped articles profiles.
• U.S. Patent No. 3,943,195 relates to a thermo plastic molding material based on styrene polymers an olefin polymers which have been flameproofed with a organic bromine compound. Brominated oligomers or poly mers of dialkylbenzenes, trialkylbenzenes or tetraalkyl benzenes serve as flameproofing agents. The moldi material may be processed into self-extinguishing mol ings.
• 3,962,164 relates to flam proofing acrylonitrile-butadiene-styrene (ABS) polymer incorporating therein certain mono- and diphenyl aromat bromine compounds such as octabromodiphenyl, antimo trioxide, or antimony oxychloride and optionally organo chlorine compound.
• ABS flam proofing acrylonitrile-butadiene-styrene
• U.S. Patent No. 4,049,622 relates to therm plastic molding compositions based on styrene polymer preferably formed styrene polymers, which have be flameproofed with an organic bromine compound.
• U.S. Patent No. 4,074,032 relates to a proce for the manufacture of heat-stable, brominated olig styrenes by brominating selectively hydrogenated olig styrenes in halogenated solvents in the presence of Lew acids at from about minus 25°C to 20°C.
• the brominat oligomers are highly heat-stable and can be processed, themselves or as components of mixtures with oth thermoplastics, to give various shaped articles.
• U.S. Patent No. 4,107,231 relates to flam proofed linear polyesters containing, as flameproofi agents, halogenated oligomeric styrenes and ⁇ ynergist compounds.
• U.S. Patent No. 4,137,212 relates to a flam proofed nylon molding composition which can be process by thermoplastic methods and which contains, as t flameproofing agent, from 5 to 30 percent by weight brominated styrene oligomers and a synergistic met oxide.
• the composition may be used for the manufactu of injection moldings for the electrical industry.
• U.S. Patent No. 4,143,221 relates to styre polymers or copolymers containing bromine which a manufactured by cationic polymerization of the monome or of the monomer plus a copolymerizable monomer of t isobutylene or nuclear-alkylated styrene type, in organic solvent in the presence of a Lewis acid catalys Bromine is then added to the solution without fir working up the latter.
• the catalyst used for the bro nation is the same as that used for the polymerizatio If necessary, fresh catalyst may be added before t bro ination.
• reaction solution is extracted with water until it bromide-free, and the solvent, generally a halohyd carbon, is then stripped off. Products containing up about 80 percent by weight of bromine may be obtain They have a pale yellowish color and exhibit no signi cant decomposition up to 340°C. They may be used flameproofing agents for thermoplastics.
• U.S. Patent No. 4,151,223 relates to fibers filaments of linear thermoplastic polyesters, contain halogen-containing flameproofing agents and synergis agents therefor, in which the flameproofing agents chlorinated and/or brominated oligomeric styrenes. fibers and filaments of the invention are used for manufacture of textiles of low flammability.
• U.S. Patent No. 4,200,702 relates to ther plastic molding compositions based on rubber-modif styrene-acrylonitrile copolymers containing a halogena styrene oligomer as the effective flameproofing ag which is sufficiently heat-stable, does not interf with processing on conventional machinery, does corrode or cause coatings on such machinery, and virtually no adverse effect on the impact strength of t polymers.
• the flameproofing agent as a rule has a degr of polymerization of from 3 to 200 and can be incorp rated into the polymer by conventional methods; t polymer may or may not contain additional synergist agents and processing auxiliaries, which are incorporat in the conventional manner and in the convention amounts.
• U.S. Patent No. 4,360,455 relates to a mixtu of brominated oligomeric polystyrenes having a degree polymerization of from 3 to 400, and low molecular weig brominated aromatic compounds of the diphenyl ether ty which are obtained by polymerizing the non-brominat starting materials, in a halohydrocarbon solvent, using Lewis acid catalyst.
• the reaction mixture is then brom nated and extracted with water to remove hydrogen bromi and catalyst, and the solvent and volatile constituen are separated from the product.
• the bromination carried out at from minus 30°C to 130°C.
• the fin mixtures have a low melt viscosity and are therefo particularly suitable for incorporation, as a flam proofing agent, into thermoplastics.
• U.S. Patent No. 4,352,909, to Barda et relates to a process for producing a trihalogenat polystyrene flame retardant for synthetic resins, where high molecular weight polystyrene is reacted with bromi chloride in a chlorinated hydrocarbon solvent, und substantially anhydrous conditions, in the presence of catalytic amount of a Lewis acid.
• German Patentschrift 151,075 relates to sel extinguishing polystyrene compositions containing bro nated oligomers of alpha methyl-styrene as flame ret dants with minimum loss of mechanical properties.
• oligomer contains from 40 to 70 weight percent ring-bo bromine and has a molecular weight of from about 1,000 about 5 , 000.
• the low molecular weight brominated pol styrene of the present invention generally have a degr of polymerization of from about 3 to about 20 and halogenated content, e.g., bromine, of from about percent to about 76 percent by weight.
• High impact polystyrene is commercially ava able and is well known to the literature as well as the art.
• High impact polystyrene (HIPS) is produced f styrene monomers along with elastomers and is genera available in various impact-strength grades.
• HIPS generally produced by introducing elastomers such polybutadiene into the polystyrene matrix for imp modification and is generally produced by either a s pension process or more preferably by a mass continu polymerization process.
• the low molecular weight brominated polys renes of the present invention are oligomers and gen ally have a degree of polymerization, i.e., number repeating units, of from about 3 to about 20, genera from about 5 to about 15, desirably from about 6 to ab 12, and preferably from about 7 to about 9.
• the repe ing units generally have the formula
• the amount of the bromine is generally from about percent to about 76 percent, desirably from about percent to about 71 percent, and preferably from about percent to about 70 percent by weight with regard to t total weight of each repeating unit.
• the molecul weight distribution of the oligomers is generally narr such as at 4.0 or less, and preferably 2.5 or les
• Retention of impact properties when using l molecular weight brominated polystyrenes as flame reta dants is a function of molecular weight and the degree bromination. As the molecular weight increases, impa retention will decline at a constant bromine leve Conversely, as the bromine content incorporated with t polystyrene increases, impact retention will decline at given or constant molecular weight. Therefore, optimiz tion of property retention is generally a balancing such factors.
• the amount of the low molecular weight bro i ated polystyrene oligomer utilized is generally an effe tive amount to achieve good flame retardancy.
• effective amounts of the low molecular weig brominated polymers are utilized to produce good fla retardancy but as an unexpected result, effective superior impact retention is obtained, especially comparison with high molecular weight brominated pol styrene having a degree of polymerization of approx mately 2,000.
• An effective level of flame retardan would be, for example, VO at 1/8 inch thickness UL-9 Physical properties which are notably retained include impact strength such as measured by notched Izod, rever Izod, Gardner impact, elongation, and the like.
• Effective amounts of the brominated polystyre oligomer of the present invention are generally f about 3 percent to about 20 percent by weight, desira from about 10 percent to about 18 percent by weight, preferably from about 14 to about 16 percent by weight the oligomer based upon the total weight of the oligo and the high impact resistant polystyrene.
• the compositions of the present invention be readily mixed and processed on conventional equipm such as extruders, Banburys, two-roll mills, and like, do not cause mold fouling, and are non-bloomi
• Blending takes place at a temperature generally ab the melting point of HIPS such as from about 250°F about 500°F.
• the blends of the present invention can cont various conventional additives in conventional amounts known to the art as well as to the literature.
• the HIPS can contain various conventional ult violet light inhibitors, various lubricant agents such calcium stearate, and the like.
• Additives which generally utilized due to their low cost and effect flame retarding properties are various antimony b synergists, equivalences thereof, derivatives there and the like, with a typical example being antim trioxide.
• the amount of antimony base synergists generally based upon the amount of brominated polystyr and generally ranges from about 1 part for every 2 t parts by weight of the brominated polystyrene.
• various additives and flame retardants such as antim trioxide can either be added directly to the HIPS blended therewith and subsequently this mixture blen with the low molecular weight brominated polystyrenes alternatively, added to and blended with the low mole lar weight brominated polystyrenes and subsequent blended with the HIPS.
• the blends of the present inve tion generally have a flame retardance of VO at 1/8 in UL-94.
• any conventional mixing device can utilized such as an extruder, a Banbury, a two-roll mil or the like.
• the blends of the present invention can utilized wherever flame retardancy HIPS is desired su as for small appliances, television cabinets, comput housings, and the like.
• High Irrpact PS (Huntsman 3037) 100 84 81 81 81
• High I ⁇ act PS (Am. Hoechst 840) 100 84 81 81 81
• Example 2 generally demonstrates that as the degree polymerization of the brominated polystyrene is increa ed, the physical property retentions such as notched Iz decreases.
• Examples 3 through 7 show good proper retention using the low molecular weight brominat polystyrenes of the present invention as compared to high molecular weight brominated polystyrene as well that good property retention is obtained utilizing variety of high impact polystyrenes made by differe manufacturers. While in accordance with the Patent Statute the best mode and preferred embodiment has been s forth, the scope of the invention is not limited theret but rather by the scope of the attached claims.

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• 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)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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Cited By (10)

Citations (7)

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• 1990
  • 1990-06-04 EP EP19900909421 patent/EP0431119A4/en not_active Withdrawn
  • 1990-06-04 JP JP2508852A patent/JPH04500382A/ja active Pending
  • 1990-06-04 AU AU58338/90A patent/AU5833890A/en not_active Abandoned
  • 1990-06-04 WO PCT/US1990/003150 patent/WO1990015095A1/en not_active Application Discontinuation
  • 1990-06-04 CA CA002033332A patent/CA2033332C/en not_active Expired - Lifetime
  • 1990-06-04 KR KR1019910700136A patent/KR0168325B1/ko not_active IP Right Cessation

Patent Citations (7)

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