Use of monomeric pentabromobenzyl monoacrylate as flame retardant

Abstract: Novel flame-retardant composition incorporate as an active ingredient pentabromobenzylester monoacrylate, or a product of its in situ reaction. Articles made of flammable synthetic resins can be rendered flame-­ retarded by the incorporation of the novel flame-retandant compositions.

Description: The present invention relates to the use of a pentabromobenzyl monoacrylate as a flame retardant additive for synthetic resins. It has been known for some time that pentabromobenzylester polyacrylate (PBB-PA) is a valuable flame-retardant material, useful in a number of synthetic resins. PBB-PA is prepared by the polymerization of pentabromobenzyl monoacrylate (PBB-MA), e.g., by the process described in DE-A-25 27 802. The so-obtained PBB-PA polymeric flame-retardant material is then incorporated into the synthetic resin to which it is desired to impart flame-retardant properties, by techniques known to the skilled engineer. It has now been most surprinsingly found, and this is an object of the invention, that the monomer pentabromobenzyl monoacrylate also by himself can be employed as a flame-retardant agent as such, and can be incorporated into the synthetic resin, without first polymerizing it to obtain PBB-PA. It has further been found that synthetic resins which incorporate PBB-MA present substantially shorter total and maximal flaming times in the UL94 test. Various advantages deriving from the use of PBB-MA, as compared to PBB-PA, are self evident, e.g., an entire reaction step - the polymerization of PBB-MA to PBB-PA - can be dispensed with. Thus the present invention is directed to the use of a pentabromobenzyl monoacrylate in blends with a synthetic resin as a flame retardant additive, which does not take part in a homo, co-, or graft polymerization. As will be apparent to those skilled in the art, the said blends may further comprise additional additives, such as conventionally employed flame-retardant synergists, fillers, heat and UV stabilizers, antioxydants, lubricants, plasticizers, etc. It should also be understood that the exact mechanism by means of which PBB-MA imparts flame retardancy to synthetic resins has not been elucidated, but the exact understanding of this phenomena is not critical. However, PBB-MA may at least partly react with other compounds or additives in the polymeric matrix, to give grafts or other types of compounds. However, as long as the result of such a reaction still provides an improvement of the flame retardancy, the goals of the invention are achieved. The method by which PBB-MA is incorporated into a synthetic resin can be any of those commonly employed in the art, e.g., PBB-MA can be blended with the synthetic resin before processing thereof in the plastic processing apparatus, or mixed during processing. The actual incorporation method may affect the precise nature of the resulting dispersion of PBB-MA in the matrix, as hereinbefore detailed, but is not critical to the invention. DETAILED DESCRIPTION The above and other characteristics and advantages of the invention will be better understood from the following examples Example 1 In this and the following examples, contents of active material are given as percent of bromine in the product, to permit a comparison between PBB-MA- and PBB PA-containing specimens. Concentrates of PBB-PA and PBB-MA containing 10% bromine were prepared in the BUSS extruder compounder, according to the following formulations: Component (%) (%) PBB-PA 14.3 - PBB-MA - 14.3 Antimony Trioxide 7.15 7.15 PBT-VALOX 420 (ex General Electric) 78.55 78.55 Bromine 10 10 The processing temperature profile was: CO-kneader: 220°C; pellettizer: 215°C; die: 207°C. The concentrates were "diluted" with pure PBT to the required bromine level, and specimens were prepared for the different tests with an Arburg injection-molding machine, at the following conditions: Processing Temperature Profile : inlet: 210°C; middle zone: 235°C, final zone: 250°C; nozzle: 275°C. Working Pressure : Injection Pressure: 60 Atm.; Holding Pressure: 40 Atm.; Back Pressure: 10 Atm. Timing : Injection Time: 0.1 sec.; Holding Time: 4.0 sec.; Cooling Time: 14.0 sec.; Mould Opening Time: 0.1 sec.; Injection Delay: 0.5 sec.. A 5% Br PBT (polybutyleneterephthalate) specimen (Valox-420) was prepared, using commercially available PBB-PA (FR 1025 - Eurobrom, Holland) and PBB-MA (prepared by IMI, Haifa, Israel). The data and results of tests carried out with these specimens are set forth in Table I below. The virtually zero flaming time of the composition of the invention should be noted. Example 2 Two HIPS (High Impact Polystyrene) specimens (10% Br and a 14% Br) were prepared according to the following procedure, and using the same PBB-MA as in Example 1. The formulation employed was the following: Thickness [mm] Component 1.6 3.2 HIPS/Huels VESTYRON 638 74.4 81.5 ANTIMONY TRIOXIDE (Blue Star - Campine) 5.1 3.6 Mg-Stearate (ex WITCO) 0.5 0.5 TINUVIN P (ex CIBA-GEIGY) 0.5 0.5 PBB-PA/PBB-MA 19.5 13.9 Br/Sb Atomic Ratio 5 5 Bromine 14 10 The formulations were compounded in a Brabender Plastograph at 200°C for 4 minutes at 40 RPM, and subsequently cooled to 130°C at 20 RPM (total processing time: 15-16 mins.). The resulting melt was pressplated 1 min. at 200°C at 1 Atm., and during another minute at 100 Atm., after which it was cooled during 4 mins. to 120°C. Specimens were prepared with a ribbon saw. The results are shown in Table II below. Example 3 Example 2 was repeated, but using ABS (Acrylonitrile-Butadiene-Styrene) as the matrix, to give final 10, 12 and 14% Br contents. The results are detailed in Table III below. Example 4 Flame-retarded Nylon 6 specimens (Capron 8200 MS) were prepared, following the procedures of Example 1, to give a final 9% Br content. The results are set forth in Table IV. 5% Br in PBT (Valox-420) Flame-Retardancy (UL 94 - 3.2 mm) Flame-retardant Additive PBB-PA PBB-MA None Max Flam. (sec) 5 0 >180 Total Flam. (sec) 10 0 >900 Drip no no 5 Rating V0 V0 NR HDT (°C) 198±2 201±0.4 205 Mechanical Properties IZOD Notched (J/m) 87±4 91±6 100 Tensile strength at break (MPa) 104±3 109±1 115 Elongation at break (%) 2.4±0.3 2.4±0.0 3 Tensile Modulus (MPa) 9500±470 9910±530 8000 Flexural Strength (MPa) 175±8 172±2 190 Flexural Modulus (MPa) 6910±380 7560±220 7500 CTI (V) 240-260 250-270 460-520 FR - HIPS Component Formulation No. 1 2 3 4 Bromine (%) 10 10 14 14 HIPS -VESTYRON 638 (ex Huels) 81.5 81.1 74.4 73.9 PBB-PA (ex Eurobrom) -- 14.3 -- 20 PBB-MA ex IMI 13.9 -- 19.5 -- Antimony Trioxide (ex Campine) 3.6 3.6 5.1 5.1 Mg-Stearate (ex WITCO) 0.5 0.5 0.5 0.5 TINUVIN P (ex Ciba-Geigy) 0.5 0.5 0.5 0.5 PROPERTIES: UL-94 1.6 mm thickness -- -- V0 V0 3.2 mm thickness V0 V0 -- -- IZOD NOTCHED IMPACT [J/m] 49 38 -- -- HDT[°C] at 1.82 KPa load 73 79 -- -- FR - ABS Component Formulation No. 1 2 3 4 Bromine (%) 14 12 12 10 ABS (ex Borg-Warner) 75.8 79.3 79.7 83.1 PBB-PA (ex Eurobrom) 20.0 17.1 -- -- PBB-MA ex IMI -- -- 16.7 13.9 Antimony Trioxide (ex Campine) 4.2 3.6 3.6 3.0 PROPERTIES: UL-94 (1.6 mm thickness) V0 V0 V0 V0/V1 IZOD NOTCHED IMPACT [J/m] 85 -- -- -- HDT[°C] at 1.82 KPa load 61 -- -- -- FR - Nylon 6 (CAPRON 8200 HS) Component Formulation No. 1 2 3 Bromine (%) 10 9 9 CAPRON 8200 HS (ex Allied 79.5 81.3 81.3 Chem. Corp) PBB-PA (ex Eurobrom) 14.3 12.9 -- PBB-MA ex IMI -- -- 12.9 Antimony Trioxide (ex Campine) 4.8 4.3 4.3 Mg-Stearate (ex WITCO) 0.5 0.5 0.5 HOSTAFLON TF 9202 (ex Hoechst) 1.0 1.0 1.0 PROPERTIES: UL-94 1.6 mm Max. Flam. [sec] 8 11 5 Total. Flam. [sec] 33 36 14 DRIP no 1 no RATING V0 V0/V1 V0

Claims: Use of a pentabromobenzyl monoacrylate in a blend with a synthetic resin as a flame retardant additive, which does not take part in a homo, co-, or graft polymerisation.

Inventors: FISHLER THEODOR-MOREL, PELED MICHAEL, SCHEINERT YAAKOV, SHORR LEONARD M, FISHLER, THEODOR-MOREL, PELED, MICHAEL, SCHEINERT, YAAKOV, SHORR, LEONARD M.
Applicants: BROMINE COMPOUNDS LTD, BROMINE COMPOUNDS LTD.
Application year: 1989
Main classification: C08K5
IPC codes: C08K5, C09K21, C08L101