WO1989003854A1 - Esters de tetrahalophthalate ignifuges destines a certaines resines - Google Patents

Esters de tetrahalophthalate ignifuges destines a certaines resines Download PDF

Info

Publication number
WO1989003854A1
WO1989003854A1 PCT/US1988/003839 US8803839W WO8903854A1 WO 1989003854 A1 WO1989003854 A1 WO 1989003854A1 US 8803839 W US8803839 W US 8803839W WO 8903854 A1 WO8903854 A1 WO 8903854A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
styrene
butadiene
flame retardant
carbons
Prior art date
Application number
PCT/US1988/003839
Other languages
English (en)
Inventor
Joseph Michael Bohen
Ronald Francis Lovenguth
Original Assignee
Pennwalt 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
Priority claimed from US07/115,688 external-priority patent/US4938894A/en
Priority claimed from US07/115,211 external-priority patent/US4762861A/en
Priority claimed from US07/173,344 external-priority patent/US4912158A/en
Priority claimed from US07/173,343 external-priority patent/US4954542A/en
Priority claimed from US07/173,691 external-priority patent/US4923917A/en
Priority to BR888807274A priority Critical patent/BR8807274A/pt
Priority to AU27854/89A priority patent/AU626532B2/en
Application filed by Pennwalt Corporation filed Critical Pennwalt Corporation
Publication of WO1989003854A1 publication Critical patent/WO1989003854A1/fr
Priority to NO89892684A priority patent/NO892684L/no
Priority to DK323589A priority patent/DK323589D0/da
Priority to FI893189A priority patent/FI893189A0/fi
Priority to KR1019890701219A priority patent/KR890701679A/ko

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids

Definitions

  • This invention relates to flame retardant compositions containing at least one tetrahalophthalate ester and a certain resin, which is selected from: (A) Acrylonitrile-Butadiene-Styrene (ABS) Terpolymer Resins;
  • inventive composition may contain one or more brominated and/or chlorinated compounds present in an amount effective to provide additional flame retardancy to the resin.
  • ABS resins are known in the art as a class of thermoplastics which are characterized by excellent properties such as chemical resistance, abuse resistance, stain resistance, etc. A discussion of typical properties of ABS resins are described on pages 1-64, 1-66, and 1-68 of Charles A. Harper's "Handbook of Plastics and Elastomers" which is published by McGraw-Hill Book Company in 1975. These pages are hereby incorporated by reference. ABS resins are terpolymers which are, in general, derived from acrylonitrile, styrene, and butadiene.
  • graft polymers in which acrylonitrile and styrene are grafted onto a polybutadiene or rubber phase which may further be dispersed in a rigid styrene-acrylonitrile (SAN) matrix.
  • SAN styrene-acrylonitrile
  • Other ABS resins are mechanical polyblends of elastomeric and rigid copolymer, e.g. butadiene-acrylo nitrile rubber and SAN. (See G.C. Hawkins, "Condensed Chemical Dictionary", 10th Edition, p. 3, 1981 as well as U.S. Patent Nos. 4,107,232; 4,206,290; 4,487,886; 4,567,218; and 4,579,906 all of which are incorporated herein by reference.
  • ABS resin Any group of tough, rigid thermoplastics deriving their name from the three letters of the monomers which produce them; Acrylonitrile-Butadiene-Styrene. Most contemporary ABS resins are true graft polymers consisting of an elastomeric polybutadiene or rubber phase, grafted with styrene and acrylonitrile monomers for compatibility, dispersed in a rigid styrene-acrylonitrile (SAN) matrix.
  • SAN rigid styrene-acrylonitrile
  • x, y, and z may independently vary from about 10 to about 1,500.
  • x, y, and z may independently vary from about 10 to about 1,500.
  • analogs of each of the monomeric components above may be substituted in whole or in part, and is within the definition of ABS resin.
  • ⁇ -methylstyrene may be substituted for styrene and methacrylonitrile for acrylonitrile.
  • Descriptions of the compositions of various ABS resins and how they are prepared may be found in U.S. Patent Nos.
  • ABS resins are useful in many commercial applications such as automotive, business machines, telephone, etc., where high impact strength is required as well as in the production of molded articles.
  • Polystyrene resins find extensive use in the manufacture of packaging material, refrigerator doors, air conditioner cases; machine housings, electrical equipment, toys, clock, TV, and radio cabinets, thermal insulation, ice buckets, containers, furniture construction, appli ⁇ ances, dinnerware, etc.
  • the preparation and description of polystyrene and expandable polystyrene are well known in the art. They are discussed in G. Hawley, “Condensed Chemical Encyclopedia", 10th Edition, pp 838 and 976 (1981); Kirk-Othmer “Encyclopedia of Chemical Technology", 2nd Edition, Vol. 9, pp 847-884 (1966) and Vol. 19, pp 85-134 (1969); A.E. Platt in "Encyclopedia of Polymer Science and Technology", Vol.
  • Polycarbonate resins are known in the art as a class of thermoplastics that are characterized by excellent properties such as electrical, dimensional stability, high impact strength, toughness, and flexibility. In general, they are prepared by the reaction of a dihydric phenol with a carbonate ester, phosgene, or a bis chloroformate ester.
  • U.S. Patent Nos. 2,999,835; 3,169,121; 3,879,348; 4,477,632; 4,477,637; 4,481,338; 4,490,504; 4,532,282; 4,501,875; 4,594,375; and 4,615,832 describe in detail the preparation of various classes of polycarbonate resins, the teachings of which are incorporated herein by reference.
  • polycarbonate resins are useful in many commercial applications as engineering thermoplastics and in the manufacture of molded articles.
  • PBT resins are known in the art as a class of thermoplastics that are characterized by excellent properties such as thermal stability, good resistance to brittleness, low friction and wear, chemical resistance, etc. In general, they are prepared by the polycondensation of terephthalic acid or a diester of terephthalic acid, such as dimethyl terephthalate (DMT), with 1,4 butanediol.
  • DMT dimethyl terephthalate
  • U.S. patents 2,645,319; 3,047, 539; 3,953,394; and 4,024,102 describe in detail the preparation of PBT, the teachings of which are incorporated herein by reference.
  • Styrene-Maleic Anhydride (SMA) copolymer resins find extensive use in the manufacture of molded articles and foamed products. In general, they are prepared by copolymerizing styrene and maleic anhydride in the proper ratio and under the appropriate conditions. The preparation and description of SMA copolymers are described in U.S. Patent Nos. 2,769,804; 2,971,939; 3,336,267; and 3,966,843, the teachings of which are incorporated herein by reference. SMA polymers burn rapidly and are generally not used in applications which require fire retardant polymers such as radio and television cabinets, tables, chairs, appliance housings and the like. (See U.S. Patent 4,151,218 which is incorporated by reference).
  • U.S. Patent No. 4,098,704 describes the use of these materials as textile finishing agents.
  • U.S. Patent Nos. 4,298,517 and 4,397,977 disclose these compounds as flame retardants for halogenated resins.
  • no teachings have been found which show these compounds as flame retardants or processing aids for ABS resins.
  • ABS Acrylonitrile-Butadiene-Styrene
  • R is selected from the group consisting of hydrogen, an alkyl or substituted alkyl of 1 to 30 carbons, hydroxyalkyl of 2 to 20 carbons, polyhydroxyalkyl of 3 to 10 carbons, and
  • R 8 is an alkyl or substituted alkyl of 1 to 18 carbons, and b is 1 to 50;
  • R 1 is selected from the group consisting of hydrogen, an alkyl or substituted alkyl of 1 to 30 carbons, alkenyl or substituted alkenyl of 2 to 22 carbons, where R 7 is an alkyl of 1 to 18 carbons; a polyhydroxyalkyl of 3 to 12 carbons;
  • R 2 is independently selected from the class consisting of H and CH 3 - ;
  • R 3 , R 4 , R 5 , and R 6 are independently selected from the class consisting of H and an alkyl of 1 to 18 carbons;
  • X is selected from 0 to NH
  • A is selected from Cl or Br.
  • the weight ratio of (I) to (II) is within the range of about 100:1 to about 2:1.
  • (III) Brominated and/or chlorinated flame retardants other than (I) which optionally may be present.
  • composition can also contain other brominated and/or chlorinated flame retardants.
  • Preferred other brominated flame retardants are selected from the group consisting of
  • ABS resin a portion or all of acrylic and styrenic monomers comprising the resin include methacrylonitrile or ⁇ -methylstyrene, or methacrylonitrile and ⁇ -methylstyrene.
  • the preferred ABS resin is comprised of monomeric units of a vinyl aromatic monomer, a vinyl nitrile monomer, and a butadiene monomer and the number of units of each monomer is independently within the range of from about 10 to about 1500.
  • the polystyrene resin is selected from one of the following:
  • n is within the range of greater than 1 to about 3,000;
  • the homopolymer of (B)(a) above is in the form of a polystyrene foam.
  • the foam is preferably prepared by polymerizing the repeatable homopolymer unit in the presence of a liquid or gaseous blowing agent and said agent has a boiling point that is below the softening point of the polystyrene and does not dissolve said polystyrene.
  • the preferred blowing agents are selected from the group consisting of one or more of propane, butane, pentane, hexane, heptane, cyclohexane, methyl chloride, dichlorodifluoroethane, 1,1,2 trifluoroethane, and 1,1,2 trichloroethane.
  • polybutylene terephthalate resins that may be used in the present invention have the following repeated structural units of the formula:
  • n is 0 to 100.
  • the weight ratio of (styrene): (maleic anhydride) may be 1-19:1.
  • Polyolefins and substituted polyolefin resins that are useful include: polyethylene (low density, linear low density, and high density); polypropylene; ethylenepropylene copolymers; ethylenevinylacetate copolymers; polyvinylacetate; polyvinyl alcohol derived from polyvinylacetate; poly-4-methyl pentene-1; polyisobutylene; polyacrylate esters; and polymethacrylate esters.
  • polystyrene; styrene-butadiene copolymers chlorinated polyethylene; chlorinated polypropylene; polyvinylchloride; acrylonitrile-butadiene-styrene; polyethyleneterephthalate; polybutyleneterephthalate; polyphenylene oxide; and/or polyphenylene oxide/high impact polystyrene blends.
  • polystyrene; styrene-butadiene copolymers chlorinated polyethylene; chlorinated polypropylene; polyvinylchloride; acrylonitrile-butadiene-styrene; polyethyleneterephthalate; polybutyleneterephthalate; polyphenylene oxide; and/or polyphenylene oxide/high impact polystyrene blends.
  • polyethylene; polypropylene; polyacrylate; and polymethacrylate either alone or in the foregoing physical blends.
  • R is an alkyl or substituted alkyl of 1 to 10 carbons, A is Br, X is oxygen, p is 0 to 20 (most preferably 0), and q is 1 to 6 (most preferably 1). More preferably R is
  • the invention also comprehends a method for preparing a flame retardant plastic composition having enhanced processability properties which comprises incorporating a flame retarding effective amount of one or more of the above tetrahalophthalate esters of (II) in one or more of the above resins.
  • This invention also comprehends the method of improving the flame retardancy, processability, and physical properties such as impact strength of the specified resins by incorporating in the resins the tetrahalophthalate compounds as described above alone or in combination with other bromine and/or chlorinated flame retardants.
  • the preferred compounds are:
  • brominated and/or chlorinated compounds that may be used in combination with the tetrahalophthalates are any of those that are well known in the art.
  • Preferred halogenated flame retardant examples are
  • the tetrahalophthalate by itself or additionally with (III) other brominated and/or chlorinated flame retardants is added to (I) theresin in any convenient manner, such as blending or extruding in order to get a uniform composition.
  • Flame retardant synergists such as antimony oxide (Sb 2 O 3 ) may also be added if desired.
  • other additives such as thermal stabilizers, ultraviolet stabilizers, reinforcing agents, organic polymers, mold release agents, blowing agents, colorants, and the like may also be optionally included.
  • a further advantage of the tetrahalophthalates alone or in combination with other brominated and/or chlorinated compounds as used in this invention is their improved compatibility with the resins.
  • ABS resins that may be used in this invention are, in general, derived from acrylonitrile, styrene, and butadiene and have the following general structure:
  • x, y, and z may independently vary from about 10 to about 1,500. It is understood that analogs of each of the components above that comprise the ABS resins may be substituted in whole or in part.
  • the ratio of tetrahalophthalate or a mixture of tetrahalophthalate and one or more brominated and/or chlorinated compounds to ABS resins that will impart flame retardancy to the latter may vary from 1:100 to about 1:2 depending on the application.
  • the ratio of tetrahalophthalate to other brominated and/or chlorinated compounds may vary from 100:0 to about 1:99.
  • the styrenic resins that may be used in the present invention are the following: polystyrene homopolymer, both crystalline and non-crystalline forms; expandable polystyrene beads, and rubber-modified polystyrene which include medium impact polystyrene, high impact polystyrene (HIPS), and super high impact polystyrene.
  • the homopolymers of styrene both crystalline and non-crystalline, have the following repeatable unit wherein n is greater than 1 to about 2000-3000.
  • the non-crystalline forms are generally prepared by polymerizing styrene with peroxide catalyst such as those described in U.S. Patent 4,281,067 while the crystalline stereoregular isotactic form uses Ziegler-Natta catalysts [See I. Pasquon in Encyclopedia of Polymer Science and Technology, Vol. 13, pp. 14, 19-20, and 31 (1970)].
  • Expandable polystyrene beads are those that are prepared by incorporating a volatile expanding or blowing agent during the polymerization of styrene.
  • blowing or expanding agents that may be used to cause polystyrene to foam are well known in the art. They may be liquid or gaseous, do not dissolve the styrene polymer, and have boiling points below the softening point of the polymer (See Column 6 in U.S. Patent 4,618,468). Suitable blowing agents are aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclohexane or halogen hydrocarbons such as methyl chloride, dichlorodifluoromethane, 1,1,2 trifluoroethane, 1,1,2 trichloroethane and the like. Mixtures of the above may also be used. Typically, expanding agents are used in amounts of about 2 to 20% by weight.
  • Rubber-modified polystyrenes that are suitable include medium, high, and super high impact polystyrenes. In these compositions, the rubber is dispersed in the polystyrene matrix as discrete particles (See U.S. Patent 4,341,890). Many rubber-modified styrenes are prepared by polymerizing styrene in the presence of a rubber such as polybutadiene or a styrene-butadiene copolymer (SBR). Some grafting of the styrene to the rubber takes place during polymerization, The weight ratio of the rubber to polystyrene may vary from about 2:98 to about 25:75.
  • SBR styrene-butadiene copolymer
  • the moderate impact polystyrene will contain about 2 to about 4% rubber, the high impact polystyrene greater than about 10% to about 25%. [See H. Keskkula in "Encyclopedia of Polymer Science and Technology” Vol. 13, pp. 396 and 400-404 (1970)].
  • the polycarbonate resins that may be employed in the present invention use typical dihydric phenols such as are disclosed in U.S. Patent 3,334,154, which is incorporated herein by reference. They are as follows:
  • Example 2 To the compound of Example 1 were added 348.0 g (6.0 moles) of propylene oxide and 2.0 liters of toluene. The mixture was heated at 60o-100oC. The solvent and residual propylene oxide were removed to give the product in almost quantitative yield.
  • the analytical data were consistent with the assigned structure:
  • Example 18 To 634.0 g(1.0 mole) of the composition of Example 18 is added 116 g (2.0 moles) of propylene oxide in 200 ml of toluene. The reaction mixture is heated from 60o-100oC for 3-5 hours, and then concentrated to give the product in nearly quantitative yield.
  • the analytical data are consistent with the assigned structure:
  • the mixture was cooled to about 100°C and tetrabromophthalie anhydride, 614.5 g (1.35 moles) and sodium acetate, 1.62 g were addei and the mixture was reheated to reflux and held for 25 hours.
  • propylene oxide, (156.4 g, 2.69 moles, 100% excess) was added and the mixture heated to and held at 100°C for 2.5 hours.
  • This compound was prepared by the procedure described in Example 25 except that poly(echylene glycol 200) was used in place of poly(ethylene 300).
  • Product is viscous Liquid. Calcd . % Br , 51.0 . Found % Br, 49.3. Analytical data was consistent with the assigned structure .
  • This compound was prepared by the procedure described in Example 25 except that polyethylene glycol 600) was used in place of poly(ethylene glycol 300).
  • Product is a viscous liquid. Calcd. % Br, 39.5. Found % Br, 39.3. Analytical data is consistent with the assigned structure.
  • Example 21 This compound was prepared by the procedure described in Example 25 except that poly(ethylene glycol 400) was used in place of poly(ethylene glycol 300). Product is a viscous liquid. Calcd. % Br, 44.2. Found % Br, 44.0. Analytical data is consistent with the assigned structure.
  • This compound was prepared by the procedure outlined in Example 29 except that aethoxycarbowax 350 was used in place of methanol and epoxybutane in place of propylene oxide. Product is a viscous liquid. Calcd. % Br, 36.5. Found % Br, 37.2. Analytical data is consistent with the assigned structure.
  • Example 33 This compound was prepared by the procedure outlined Example 29 except that 2-ethylhexanol-1 was used in place methanol. Product is a viscous liquid. Calcd. % Br, 50.0. Found % 52.7. Analytical data is consistent with the assigned structure.
  • This compound was prepared by the procedure outlined in Example 29 except that epichlorohydrin was used in place of propylene oxide . Calcd . % Br , 35 .7. Found % 35 .4. Analytical data is consistent with the assigned structure .
  • methoxycarbowax 350 (300.0 g, 0.89 mole) in dry toluene (184 ml) was added sodium methoxide (48.0 g, 0.90 mole) in methanol. The aethanol was then distilled off atmospherically. Tetrabromophthalic anhydride was then added (442.2 g, 0.89 mole) along with an additional. 50 al of toluene. The reaction mixture was refluxed for 2 hours and after cooling to room temperature, epichlorchycrin (106.94 g, 1.16 moles) was added. The mixture was refluxed for 20 hours. After the solvent and excess epichlorohydrin were distilled, a viscous dark product was obtained. Calcd. % Br, 37.2. Found % Br, 40.4. Analytical data is consistent with assigned structure.
  • Methoxycarbowax 350 and toluene were refluxed for 1 hour in order to distill out a small amount of water.
  • Tetrabromophthalic anhydride (1:1 mole ratio with methoxycarbowax 350) and sodium acetate were added and the mixture refluxed for 17 hours.
  • an excess of diazomethane (prepared from the decomposition of N-methyl-N-nitroso-p-toluene sulfonamide by sodium hydroxide) in ethyl ether was added and the mixture allowed to stand overnight. The excess diazomethane was decomposed by adding acetic acid and the solvent removed by distillation. Product is viscous liquid. Calcd. % Br, 39.2. Found % Br, 37.4. Analytical data is consistent with the assigned structure.
  • Example 39 Di(2-ethylhexyl) tetrabromophthalate was prepared by the procedure described by Spatz et. al (I & EC Product Research and Development, Vol. 8, No. 4, 395 (1969).
  • Poly(ethylene glycol 600) 885.4 g (1.40 moles), tetrabromophthalic anhydride, 1298.4 g (2.80 moles), potassium acetate, 1.35 g, and toluene (1000 g) were charged into a one-gallon glass-lined reactor and heated to 120°C. After 4 hours at this temperature, ethylene oxide, 246.68 g (5.60 moles) was pumped into the reactor in 3/4 hour while maintaining the temperature at 120oC. After one hour Longer of beating, the mixture was cooled to room temperature, the excess ethylene oxide was then vented, and the product collected. After stripping off the toluene, 2250 g of the product was isolated in 99% yield as a viscous liquid. Calcd. % Br, 39.2. Found % Br, 38.8. Analytical data is consistent with the assigned structure.
  • Example 3 To the product of Example 3, 453.8 g (0.27 mole), acetic anhydride, 83.4 g (0.82 mole), potassium acetate, 1.0 g, and toluene, 400 ml, were refluxed for 8 hours. After cooling to room temperature, the reaction mixture was transferred to a separatory funnel and extracted first with 100 ml of a 16% potassium bicarbonate solution and then with 100 al of water. After distilling off the solvent, 335.0 g (64% yield) of product was obtained as a viscous liquid. Calcd. % Br, 36.8. Found % Br, 32.9. Analytical data is consistent with the assigned structure.
  • 2-ethylhexanol, 130.2 g (1.0 mole). and potassium acetate, 0.24 g were heated to and kept at 120oC for 4 hours.
  • the mixture was cooled to 60oC and potassium carbonate, 35.9 g (0.26 mole), was added.
  • Tetrabromophthalic anhydride 231.9 g (0.5 mole), 2-[2-methoxyethoxy]-ethanol, 360.5 g (3.0 moles), stannous oxalate, 2.32 g , and xylene, 200 ml, were refluxed (temp. 160oC) for 18 hours during which time, theory water was collected.
  • the xylene and excess 2-[2-methoxyethoxy]-ethanol were distilled under reduced pressure to give 332 3 of crude product as a wet white solid.
  • This compound was prepared by the procedure outlined in Example 43 except using 2-(2-ethoxyethoxy]-ethanol,
  • Example 45 This compound was prepared by the procedure outlined in Example 1 except that docosyl alcohol (behenyl alcohol) was used in place of poly(ethylene glycol 600) and propylene oxide in place of ethylene oxide. Product is a viscous liquid. Calcd. % Br, 37.7. Found % Br, 36.5. Analytical data is consistent with the assigned structure.
  • This compound was prepared by the procedure outlined in Example 1 except that tricontyl alcohol was used in place of poly(ethylene glycol 600) and propylene oxide in place of ethylene oxide.
  • Product is a viscous liquid.
  • This compound was prepared by the procedure outlined in Example 4 except that methoxycarbowax 550 was used in place of 2-[2-methoxyethoxy]-ethanol.
  • the flame retardancy of the compounds of this invention are demonstrated with respect to ABS resins.
  • the compositions were prepared by mixing together the flame retardants, antimony oxide, and ABS on a roller until the compounds were blended thoroughly.
  • the compounds were pelletized at 230-245°C and then injection molded into test specimens at 230°C.
  • the UL-94 vertical burn test was run and compared to a control consisting of ABS itself.
  • ABS Acrylonitrile-styrene-butadiene terpolymer
  • DTBPE 1,2-bis(2,4,6-tribromophenoxy)-ethane
  • DOTBP Dioctyl tetrabromophthalate (45% Bromine)
  • AO Antimony Oxide
  • the conventional flame retardant, DTBPE greatly reduces the impact strength of ABS compared to those examples where a portion of the DTBPE is replaced by the ABS-containing flame retardant compositions of this invention.
  • HDT Heat Reflection Temperature
  • ABS (a) 100 100 100 DTBPE - 22 11 DOTBP - - 17 AO - 4 4
  • compositions of this invention were prepared by mixing together the flame retardants, antimony oxide, and high impact polystyrene on a roller until the compounds were blended thoroughly.
  • the compounds were pelletized at 200-260°C and then injection molded into test specimens at 230°C.
  • the UL-94 vertical burn test was run and compared to a control consisting of the impact polystyrene itself.
  • DOTBP Dioctyl Tetrabromophthalate (45% Bromine)
  • Examples 58 through 64 are all run at equal bromine levels. Partial or total replacement of the conventional flame retardant (DBDPO) with the esters disclosed in this invention improves the flame retardancy of the polystyrene as can be seen by the UL-94 results for the 0.062" specimens. Examples and clearly demonstrate that the total bromine levels can be reduced when the compositions of this invention are used and still yield comparable or better flame retardancy. Examples 65-70
  • HIPS 100 84 81.5 76.4 73.9 80.8 DBDPO - 12 9 3 - -
  • control (100% polystyrene)
  • comparison no tetrahalophthalate ester
  • the conventional flame retardant, DBDPO greatly reduces the impact strength of the polystyrene (see Example 66).
  • the compositions containing the material of the invention clearly improve the impact strength to a point where it is better than the comparison example.
  • the extrusion rates were measured during pelletization to determine the processing characteristics of the compounds.
  • compositions of this invention are demonstrated with respect to polycarbonate resins.
  • the compositions were prepared by mixing together the flame retardants, antimony oxide, and polycarbonate resin on a roller until the compounds were blended thoroughly.
  • the compounds were pelletized at 160-305°C and then injection molded into test specimens at 271°C.
  • the UL-94 vertical burn test was run and compared to a control consisting of the polycarbonate resin itself. The following tests were performed on the various materials according to the appropriate ASTM method.
  • PC Polycarbonate polymer
  • BPC Brominated Polycarbonate Oligomer (58% Bromine)
  • DOTBP Dioctyl Tetrabromophthalate (45% Bromine) TABLE I (C)
  • BPC conventional flame retardant
  • Examples 76-79 are all run at equal bromine levels. Partial or total replacement of the conventional flame retardant, BPC, with the esters disclosed in this invention results in greatly enhanced flow characteristics as shown by the improved melt flow properties measured according to ASTM D-1238.
  • the polycarbonate resin containing compositions of this invention show improved tensile properties when compared to the control, and comparable to that of the conventional flame retardant, BPC. Furthermore, the polycarbonate resin containing compositions of this invention maintain percent elongation.
  • the flame retardancy of the compounds of this invention are demonstrated.
  • the compositions were prepared by mixing together the flame retardants, antimony oxide, and polybutylene terephthalate (PBT) on a roller until the compounds were blended thoroughly.
  • the compounds were pelletized at 150-216°C and then injection molded into test specimens at 235°C.
  • the UL-94 vertical burn test was run and compared to a control consisting of PBT itself. Melt flow of the various materials were determined according to ASTM D-1238.
  • PBT Polybutylene Terephthalate
  • BPC Brominated Polycarbonate Oligomer (58% Bromine)
  • DOTBP Dioctyl Tetrabromophthalate (45% Bromine)
  • AO Antimony Oxide
  • control (100% polybutylene terephthalate)
  • comparison no tetrahalophthalate ester
  • compositions of this invention have at least equivalent flame retardancy to the BPC conventional flame retardant used in PBT (Example 81).
  • Examples 81-83 are all run at equal bromine levels. Partial or total replacement of the conventional flame retardant (BPC) with the compositions of this invention results in enhanced flow characteristics as shown by the improved melt flow properties measured according to ASTM D-1238.
  • BPC flame retardant
  • control (100% polybutylene terephthalate)
  • polybutylene terephthalate resin compositions containing the flame retardants of this invention greatly improve the impact strength relative to the control (Example 84) and the BPC conventional flame retardant, (Example 85) used in PBT while maintaining both tensile strength and percent elongation properties.
  • the flame retardants of this invention significantly improve the heat distortion temperature (HDT) and flow properties relative to the control.
  • compositions with SMA resins In the following examples, the flame retardancy of the compounds of this invention are demonstrated.
  • the compositions were prepared by mixing together the flame retardants, antimony oxide, and SMA on a roller until the compounds were blended thoroughly.
  • the compounds were pelletized at 95-245°C and then injection molded into test specimens at 190-204°C.
  • the UL-94 vertical burn test was run and compared to a control consisting of SMA itself. Melt flow of the various materials were determined according to ASTM D-1238.
  • compositions of this invention have at least equal flame retardancy to the DBDPO commercial conventional flame retardant used in SMA (Example 87).
  • examples 88-91 are all run at equal bromine levels. Partial replacement of the conventional flame retardant (DBDPO) with the compositions of this invention results in enhanced flow characteristics as shown by the improved melt flow properties measured according to ASTM D-1238.
  • SMA resin compositions containing the flame retardants of this invention greatly improve the impact strength relative to the control (Example 92) and the DBDPO commercial flame retardant with PBT (Example 93), while maintaining both tensile strength and percent elongation properties.
  • thermoelectric temperature (HDT) of the compositions of this invention are comparable to both the control and to DBDPO.

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

Sont décrits des compositions de résine plastique ignifuge aux caractéristiques d'écoulement améliorées, contenant un ester de tétrahalophthalate, l'utilisation de l'ester de tétrahalophthalate comme auxiliaire de traitement ignifuge dans une résine, un procédé conférant des caractéristiques d'ignifugation et d'écoulement amélioré à une résine, ainsi qu'un procédé de fabrication d'une résine ignifuge aux caractéristiques d'écoulement améliorées, dans lequel on choisit la résine parmi (A) l'acrylonitrile-butadiène-styrène, (B) le polystyrène, (C) le polycarbonate, (D) le téréphthalate de polybutylène, et (E) un copolymère d'anhydride styrène-maléique, ainsi que (F) une polyoléfine ou une polyoléfine substituée.
PCT/US1988/003839 1987-10-30 1988-10-28 Esters de tetrahalophthalate ignifuges destines a certaines resines WO1989003854A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BR888807274A BR8807274A (pt) 1987-10-30 1988-10-28 Composicao plastica retardadora de chama,processo para comunicar caracteristicas de retardo de chama e escoamento aperfeicoado a resinas,processo para fabricar resina reticar resina retardante de chama,e produto retardador de chama ardente de chama e produto retardador de chama
AU27854/89A AU626532B2 (en) 1987-10-30 1988-10-28 Tetrahalophthalate esters as flame retardants for certain resins
NO89892684A NO892684L (no) 1987-10-30 1989-06-28 Tetrahaloftalatestere som flammehemmere for visse resiner.
FI893189A FI893189A0 (fi) 1987-10-30 1989-06-29 Tetrahaloftalatestrar som brandskyddsvaetskor foer vissa hartser.
DK323589A DK323589D0 (da) 1987-10-30 1989-06-29 Som ildretarderende midler for visse harpikser tjenende tetrahalogenphthalatestere
KR1019890701219A KR890701679A (ko) 1987-10-30 1989-06-30 특정수지용 난연제로서의 테트라할로프탈레이트 에스테르

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
US115,211 1987-10-30
US07/115,211 US4762861A (en) 1987-10-30 1987-10-30 Tetrahalophthalate esters as flame retardants for polystyrene resins
US115,688 1987-10-30
US07/115,688 US4938894A (en) 1987-10-30 1987-10-30 Tetrahalophthalate esters as flame retardants for ABS (acrylonitrile-butadiene styrene terpolymer) resins
US07/173,691 US4923917A (en) 1988-03-25 1988-03-25 Tetrahalophthalate esters as flame retardants for styrene-maleic anhydride copolymer (SMA) resins
US07/173,343 US4954542A (en) 1988-03-25 1988-03-25 Tetrahalophthalate esters as flame retardants for polybutylene terephthalate resins (PBT)
US173,691 1988-03-25
US07/173,344 US4912158A (en) 1988-03-25 1988-03-25 Tetrahalophthalate esters as flame retardants for polycarbonate resins
US173,343 1988-03-25
US173,344 1988-03-25

Publications (1)

Publication Number Publication Date
WO1989003854A1 true WO1989003854A1 (fr) 1989-05-05

Family

ID=27537405

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1988/003839 WO1989003854A1 (fr) 1987-10-30 1988-10-28 Esters de tetrahalophthalate ignifuges destines a certaines resines

Country Status (10)

Country Link
EP (1) EP0339074A4 (fr)
JP (1) JPH02502026A (fr)
AU (1) AU2126392A (fr)
BR (1) BR8807274A (fr)
CA (1) CA1337310C (fr)
DK (1) DK323589D0 (fr)
ES (1) ES2018098A6 (fr)
FI (1) FI893189A0 (fr)
HU (1) HUT54720A (fr)
WO (1) WO1989003854A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0386406A1 (fr) * 1989-03-10 1990-09-12 Elf Atochem North America, Inc. Esters polyhaloaromatiques ignifuges pour des résines polyoléfiniques
WO1996035754A1 (fr) * 1995-05-09 1996-11-14 E.I. Du Pont De Nemours And Company Composition de resine de polyester resistant aux flammes
US5760161A (en) * 1997-02-10 1998-06-02 Albemarle Corporation Process for making unsaturated, thermosetting, brominated phthalic anhydride/polyol polyester resins
WO2004094517A1 (fr) * 2003-04-21 2004-11-04 Albemarle Corporation Mousses a base de polymere de styrene ignifugees
US7423069B2 (en) 2002-05-06 2008-09-09 Crompton Corporation Blends of tetrahalophthalate esters and phosphorus-containing flame retardants for polyurethane compositions
US7615168B2 (en) 2005-03-21 2009-11-10 Chemtura Corporation Flame retardants and flame retarded polymers
US8129457B2 (en) 2006-03-22 2012-03-06 Chemtura Corporation Flame retardant blends for flexible polyurethane foam
WO2022018036A1 (fr) * 2020-07-23 2022-01-27 Pts Gmbh Composition de revêtement exempte de styrène

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012131764A (ja) * 2010-12-03 2012-07-12 Kawasaki Kasei Chem Ltd エステル組成物及びその製造方法
JP5938899B2 (ja) * 2011-12-27 2016-06-22 川崎化成工業株式会社 ポリウレタンフォーム製造原料用エステル組成物及びポリウレタンフォームの製造方法

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3766249A (en) * 1971-07-21 1973-10-16 Koppers Co Inc Brominated cinnamic acid esters
US3775165A (en) * 1971-07-19 1973-11-27 Deering Milliken Res Corp Polymers of improved flame retardance
US3947421A (en) * 1973-01-19 1976-03-30 Basf Aktiengesellschaft Self-extinguishing polyester molding compositions
US3966676A (en) * 1975-02-18 1976-06-29 Velsicol Chemical Corporation Bis-(halophenyl) 2,3,5,6-tetrachloro-terephthalate and fire retardant compositions prepared therefrom
US4024102A (en) * 1974-02-13 1977-05-17 Celanese Corporation Molding composition suitable for forming improved flame retardant three-dimensional shaped articles
US4032481A (en) * 1976-01-30 1977-06-28 Arco Polymers, Inc. Heat stabilizers for expandable styrene polymers
US4098704A (en) * 1977-02-25 1978-07-04 Pennwalt Corporation Polyoxyalkylene tetrahalophthalate ester as textile finishing agent
US4107231A (en) * 1975-04-09 1978-08-15 Basf Aktiengesellschaft Flame-retardant linear polyesters
JPS53120755A (en) * 1977-03-30 1978-10-21 Sumitomo Chem Co Ltd Flame-retardant composition
US4295886A (en) * 1973-10-09 1981-10-20 Avtex Fibers Inc. Flame-retardant polyester fiber compositions
US4397977A (en) * 1979-08-23 1983-08-09 Pennwalt Corporation Tetrahalophthalates as flame retardant plasticizers for halogenated resins

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3833641A (en) * 1971-08-16 1974-09-03 Union Carbide Corp Halo-aryl amide-ester polyols
US4094850A (en) * 1975-10-06 1978-06-13 Monsanto Company Flame retardant composition
JPS55108435A (en) * 1978-12-22 1980-08-20 Pennwalt Corp Polyoxyalkylenetetrahaloterephthalate as flame retardant plasitizer for halogenated resin
DE3034634C2 (de) * 1980-09-13 1982-11-11 Chemische Fabrik Kalk GmbH, 5000 Köln Tetrabromphthalsäureester, Herstellung und Verwendung als Brandschutzmittel in Kunststoffen
US4361666A (en) * 1982-01-04 1982-11-30 Monsanto Company Styrenic polymer additive
GB8431792D0 (en) * 1984-12-17 1985-01-30 Sandoz Ltd Organic compounds

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3775165A (en) * 1971-07-19 1973-11-27 Deering Milliken Res Corp Polymers of improved flame retardance
US3766249A (en) * 1971-07-21 1973-10-16 Koppers Co Inc Brominated cinnamic acid esters
US3947421A (en) * 1973-01-19 1976-03-30 Basf Aktiengesellschaft Self-extinguishing polyester molding compositions
US4295886A (en) * 1973-10-09 1981-10-20 Avtex Fibers Inc. Flame-retardant polyester fiber compositions
US4024102A (en) * 1974-02-13 1977-05-17 Celanese Corporation Molding composition suitable for forming improved flame retardant three-dimensional shaped articles
US3966676A (en) * 1975-02-18 1976-06-29 Velsicol Chemical Corporation Bis-(halophenyl) 2,3,5,6-tetrachloro-terephthalate and fire retardant compositions prepared therefrom
US4107231A (en) * 1975-04-09 1978-08-15 Basf Aktiengesellschaft Flame-retardant linear polyesters
US4032481A (en) * 1976-01-30 1977-06-28 Arco Polymers, Inc. Heat stabilizers for expandable styrene polymers
US4098704A (en) * 1977-02-25 1978-07-04 Pennwalt Corporation Polyoxyalkylene tetrahalophthalate ester as textile finishing agent
JPS53120755A (en) * 1977-03-30 1978-10-21 Sumitomo Chem Co Ltd Flame-retardant composition
US4397977A (en) * 1979-08-23 1983-08-09 Pennwalt Corporation Tetrahalophthalates as flame retardant plasticizers for halogenated resins

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
See also references of EP0339074A4 *
V.M. BHATNAGER "Fire Retardants: Proceedings of 1974 Intl. Symposium on Flammability and Fire Retardants" May 1-2, 1974 by Technomic Pub. Co. (Westport, Connecticut) see pages 170 to 171, especially figures 5 and 6. *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0386406A1 (fr) * 1989-03-10 1990-09-12 Elf Atochem North America, Inc. Esters polyhaloaromatiques ignifuges pour des résines polyoléfiniques
WO1996035754A1 (fr) * 1995-05-09 1996-11-14 E.I. Du Pont De Nemours And Company Composition de resine de polyester resistant aux flammes
US5990213A (en) * 1995-05-09 1999-11-23 E. I. Du Pont De Nemours And Company Flame resistant polyester resin composition
US5760161A (en) * 1997-02-10 1998-06-02 Albemarle Corporation Process for making unsaturated, thermosetting, brominated phthalic anhydride/polyol polyester resins
US7423069B2 (en) 2002-05-06 2008-09-09 Crompton Corporation Blends of tetrahalophthalate esters and phosphorus-containing flame retardants for polyurethane compositions
WO2004094517A1 (fr) * 2003-04-21 2004-11-04 Albemarle Corporation Mousses a base de polymere de styrene ignifugees
US7615168B2 (en) 2005-03-21 2009-11-10 Chemtura Corporation Flame retardants and flame retarded polymers
US7696256B2 (en) * 2005-03-21 2010-04-13 Crompton Corporation Flame retardants and flame retarded polymers
US8129457B2 (en) 2006-03-22 2012-03-06 Chemtura Corporation Flame retardant blends for flexible polyurethane foam
WO2022018036A1 (fr) * 2020-07-23 2022-01-27 Pts Gmbh Composition de revêtement exempte de styrène

Also Published As

Publication number Publication date
HUT54720A (en) 1991-03-28
FI893189A (fi) 1989-06-29
JPH02502026A (ja) 1990-07-05
HU886711D0 (en) 1991-01-28
EP0339074A4 (en) 1991-07-03
DK323589A (da) 1989-06-29
EP0339074A1 (fr) 1989-11-02
CA1337310C (fr) 1995-10-10
AU2126392A (en) 1992-10-29
ES2018098A6 (es) 1991-03-16
BR8807274A (pt) 1989-10-31
DK323589D0 (da) 1989-06-29
FI893189A0 (fi) 1989-06-29

Similar Documents

Publication Publication Date Title
EP1063252A1 (fr) Resine ininflammable, composition a base de cette resine, et procede de fabrication correspondant
EP0235266B1 (fr) Esters de tetrahalophtalate utilises comme retardateurs de la flamme pour des resines d'ether de polyphenylene
EP0339074A4 (en) Tetrahalophthalate esters as flame retardants for certain resins
US4762861A (en) Tetrahalophthalate esters as flame retardants for polystyrene resins
US5112896A (en) High-impact polystyrene containing low molecular weight brominated polystyrene
WO2004072179A1 (fr) Compositions de resine thermoplastique ininflammable sans halogene
US4197370A (en) Foamable polyphenylene oxide composition with thermally unstable copolymer as foaming agent
JPS61157512A (ja) 成型しうる組成物、成型した製品を製造する方法及びランダム共重合体
US3966677A (en) Self-extinguishing polystyrene resin composition
US4923916A (en) Tetrahalophthalate esters as flame retardants for polystyrene resins
US4743637A (en) Flame retardant compounds and thermoplastic compositions containing the same
CA2054695A1 (fr) Composition de resine ininflammable
DD290203A5 (de) Tetrahalophthalat-ester als flammschutzmittel fuer bestimmte kunststoffe
WO1988003542A1 (fr) Ethers de polyphenylenes modifies a inflammation retardee possedant des caracteristiques d'ecoulement ameliorees
AU2785489A (en) Tetrahalophthalate esters as flame retardants for certain resins
EP0189668B1 (fr) Composition de moulage résistant à la flamme comprenant un copolymère styrène, anhydride maléique, dibromostyrène
US4938894A (en) Tetrahalophthalate esters as flame retardants for ABS (acrylonitrile-butadiene styrene terpolymer) resins
AU580833B2 (en) Thermoplastics containing brominated homopolymer
EP0782588B1 (fr) Copolymeres dibromostyrene et glycidyl (meth)acrylate
US4626573A (en) Flame-retardant molded composition incorporating a poly(N-(bromophenyl)maleimide-co-styrene-co-maleic anhydride) copolymer
US4927873A (en) Halophenyl ester flame retardants for polyphenylene ether resins
US4959481A (en) Flame retardant compounds and thermoplastic compositions containing the same
EP0687696A1 (fr) Compositions de poymère ignifugées comprenant des résines thermiquement stables
JPS62164759A (ja) ポリカ−ボネ−ト樹脂とアルケニル芳香族共重合体との耐燃性ブレンド
PT88909B (pt) Processo de preparacao de resina retardadoras de chama contendo, como agente retardador de chama, esteres de tetra-haloftalato

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

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

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE BJ CF CG CH CM DE FR GA GB IT LU ML MR NL SE SN TD TG

WWE Wipo information: entry into national phase

Ref document number: 1988909875

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 893189

Country of ref document: FI

WWP Wipo information: published in national office

Ref document number: 1988909875

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1988909875

Country of ref document: EP