Polyolefin plastic compositions containing halogenated aryl compounds as flame retardants
United States Patent 1191 Anderson 1*Apr. 29, 1975 POLYOLEFIN PLASTIC COMPOSITIONS [56] References Cited CONTAINING HALOGENATED ARYL U ITED STATES PATENTS COMPOUNDS AS FLAME RETARDANTS 3,385,819 5/1968 Gouinlock 260/45.75 R 75 Inventor; A Anderson, Alma, i 3,560,441 2/l97l Schwarcz et al. 260/45.7 R 3,658,634 4/1972 Yanagi et al....... l6l/403 ASSIgHeeI Michigan Chemical Corporation, 3,717,609 2/1973 Kutner 260/45.95 0  
 Louis, Mich.  
  Primary E.\&#39;aminerM. J. Welsh 1 Nonce The Porno of h term of Attorney, Agent, or FirmRobert M. Phipps; James .I.  
 patent subsequent to July 16, 1991, Mullen. Robert S Frieman has been disclaimed.  
  [57] ABSTRACT [22] Flled&#39; 1973 Plastic compositions containing polyolefins and halo- [21] Appl. No.: 330,824 genated aryl compounds having the formula Ai I 1 2 M R M&#39; Q z I Related U.S. Application Data wherein Z is bromine or chlorine, m and m are inte- [63] Continuation-impart 6f Ser. N6. 260,240, June 6, g s a i g a value of i and i ar nt g rs ha ing 1972, abandoned. a value of 0-2, R is herein defined, M and M are each independent and are from the group oxygen, nitrogen [52] U.S. Cl 260/45.9 R; 260/42; 260/42.22; or sulfur with the proviso that M and M cannot con- 260/45.75 R currently be oxygen in both cases, and A is chlorine, [51] Int. Cl. C08f 45/60 cyano, nitro, lower alkoxy, lower alkyl, fluorine, dial- [58] Field of Search. 260/45.95 G, 2.5 A], 45.95 C. kylamino, phenyl, halo-phenyl, benzyl, or haloben- 260/613 B, 33.2 R, 45.9 R, DIG. 24; 106/15 FP zyl.  
 29 Claims, No Drawings POLYOLEFIN PLASTIC COMPOSITIONS CONTAINING HALOGENATED ARYL COMPOUNDS AS FLAME RETARDANTS This application is a continuation-in-part of copending application Ser. No. 260,240, filed June 6, 1972 and now abandoned. The entire specification of this case; Ser. No. 260,240, is to be considered as incorporated herein by reference.  
  The prior art considered in conjunction with the preparation of this application is as follows: US. Pat. Nos. 2,130,990; 2,186,367; 2.329033; 3,666,692: 3,686,320; 3,658,634; German Pat. No. 1,139,636; German Pat. No. 2,054,522; Japanese Pat. No. (72) 14,500 as cited in Volume 77. Chemical Abstracts, column l53737k (1972); Chemical Abstracts. Volume 13, column 448 Chemical Abstracts. Volume 31, column 7045&#34;: and Journal of the Chemical Society, pages 2972-2976 (1963). All of these publications are to be considered as incorporated herein by reference.  
  The present invention relates to plastic compositions containing polyolefins (including, without limitation, polyethylene and polypropylene). More specifically, the present invention covers plastic compositions containing polyolefins and certain halogenated aryl compounds (hereinafter defined) as flame retardants for said plastic compositions.  
  Polyolefins and utility thereof are known in the art as exemplified by Polyolefin Plastics, T.O..l. Kresser,  
 (Van Nostrand Reinhold Plastics Applications Series). Van Nostrand Reinhold Company, New York, 1969 and Modern Plastics Encyclopedia 1972-1973, Vol. 49: No. 10A. October, 1972, pages 78. 83, 85, 86. 89-92, 97 and 158-160 and which publications are in toto incorporated herein by reference.  
  The need for flameretarding polyolefins has also been recognized in the art as exemplified by US. Pat. No. 3,133,038, 3,347,822 and 3.422.048 and which publications are in toto incorporated herein by reference.  
  The resultant disadvantages in the utilization of various prior art materials as flame retardants for polyolefins include, without limitation, factors such as thermal migration, heat instability, light instability, nonbiodegradable, toxicity, discoloration and the large amounts employed in order to be effective. Thus, there is always a demand for a material which will function as a flame retardant in polyolefins and concurrently will not, by incorporation therein, adversely effect the chemical and/or physical and/or mechanical properties of the resultant polyolefin plastic composition.  
  The prior art problem a flame retarded polyolefin composition having desired chemical, physical and mechanical properties has now been substantially solved by the present invention and the above-described disadvantages substantially overcome.  
  Accordingly, one of the main objects of the present invention is to provide polyolefin plastic compositions which are flame retarded.  
  Another object of the present invention is to provide a material for polyolefin plastic compositions which will not substantially adversely effect the chemical and- /0r physical and/or mechanical properties of said compositions.  
  A further object of the present invention is to provide a flame retardant which is economic and easy to incorporate into polyolefin plastics without being degraded or decomposed as a result of blending or processing operations.  
  It has been found that the foregoing objects can be obtained by the incorporation of a new class of halogenated aryl compounds in olyolefins to subsequently provide flame retarded compositions which exhibit outstanding chemical, physical and mechanical properties.  
  The halogenated aryl compounds used in the present invention compositions have the formula:  
  ln Formula 1 above, Z is bromine or chlorine, in and m are integers each independently having a value of l-S; i and i are integers each independently having a value of 0-2: M and M are each independent and are from the group oxygen. nitrogen and sulfur with the proviso that M and M cannot concurrently be oxygen in both cases and where M and/or M is nitrogen, the formula is A is from the group chlorine, cyano (-CN), nitro (-NO lower alkoxy (e.g. -OCH OC HS). lower alkyl (e.g. CH C H C H C,H,,), fluorine, dialkylamino e.g. N(CH;,) N(C H,-,) phenyl (C,;H halophenyl, benzyl (CH- C,,H and halo-benzyl&#39;, and R is from the group alkylene: branched or straight or halo-branched chain group having from one to six carbon atoms (e.g. CH2, c a C3116, c 11 -C(CH3)H-, -(ca )c(ca where w 1-6 where X H, Cl, Br  
 where S saturated ring  polymeric systems to make the resultant polymer flame It is to be understood that all of the compounds fall- 25 retardantlllustrative (but without limitation) of some of the present invention halogenated aryl compounds are shown below:  
  3 CH CH(0A) CH (c) CH CH(CH H0) d) (cn 0 H CH CH f) CH -C(O) CH (8) CH on @D H C CH ln Formula L i m or i m is not greater than 5.  
 ing within the above Formula I and as heretofore defined are genetically described herein as halogenated aryl? compounds.  
  Com- -pound Nn.  
  The halogenated aryl compounds are found to be compatible with and effective additives for various ONNN ON NSSSNNO O NNON NON NON NNNSSSO Table I-Continued cowipeu d No, Z m m&#39; A i i R M M&#39; 9.02 Br 2 2 0 0 s s 203 01 2 0 0 N s 20.1 Br 2 2 -CN 1 1 I :11 s 0 205 Br 2 2 --1:0 1 1 2 2 0 N Br 2 2 0c:1 1 1 2 2 1-1 11 207 Dr 3 3 -0ca 1&#39; CH2 0 11 20s Br 2 2 411 1 1 H C- e11 3 s 209 B1: 2 2 F 1 1 CH 0 s 2111 Br 2 2 -N(ca 1 1 H2 H N N 7311. Z. 635 ,H2 2 5 S 212 Br 2 2 -C H B1.2 l l 2 2 N Q? 213 Br 2 2 411 0 11 1 v 1 N- s 21 1 Br 2 2 41152 11 315 1 1 Z Z N 215 Br 3 3 -c ,H c1 1 1 s s 215 c1 3 3 F 1 1 2 N N 217 c1 2 2&#39; -01: 2 2 :1 0  
 2111 Br 4 o p o Hzc 11 s 219 c1 3 3 -C H Br 1 1 H29 o 220 C1 3 3 -N0 2, 2 S 5 2:21 c1 2 2 -0ca 1 1 H c-{S}- 011 s 11 &#39;22 c1. 5 4 411 1 1 HZC 7 N 1* 2: 53 c1 3&#39; F 2 &#39;2&#34; 112C 0 a 2 1 Br 1 l C4H9 1 l HZC $611., N O 225 Br 1 1 -oc 11 1 1 2C s%- :1 1-1 lngeneral, .thehalogenated compounds are pre- 60 as ketones (e.g. acetone, methyl ethyl ketone, and metpared by reacting a halogenated phenol thiophenol or hyl iso-butyl ketone), alcohols (e.g. methanol, ethanol, aryl amine with a halogenated alkan at elevated temiso-propyl alcohol, butyl alcohol and glycols), aqueous peratures in the presence of a basic material such as alsolvent (e.g. water, a mixture of water and alcohol and kali metal hydroxides, carbonates,bicarbonates, oxides a mixture of water and ketone), and polar aprotic soland hydrides. The preferred alkali metals are potassium and sodium. Where one desires to increase, for example, ease of handling the reaction mass, solvents such vents such as dimethylformamide (DMF), dimethyl sulfoxide DMSO) and ethers such as tetrahydrofuran (Tl-IF), can be employed. The desired end product i.e.  
 the halogenated aryl compound, can be recovered from the reaction mass via various methods such as distillation or crystallization. Where the end product requires recovery via crystallization, various aromatic solvents such as benzene, toluene, xylene, dichlorobenzene and the like can be used.  
  Specifically, the symmetrical halogenated aryl compounds are prepared, for example, according to the following reactions:  
  The above-described processes can be carried out with conventional, readily available chemical processing equipment. For example, a conventional glasslinked vessel provided with heat transfer means, a reflux condenser and a mechanical stirrer can be advantageously utilized in practicing any of the preferred embodiments of the invention described in the examples set forth herein. The above described processes and resultant products, i.e., the halogenated aryl compounds,  
  base sa x-R-x (111) I A1 A1 z O s R. s Z v In the above reaction, X is halogen, preferably chlorine and R is the same as defined herein. Where m and m and i and i are different integers, then equivalent molar portions of the particular halogenated phenol, thiophenol or aryl amine are used with equivalent portions of dissimilar halogenated phenol, thiophenol or aryl amine.  
  The unsymmetrical halogenated aryl compounds are prepared, for example, according to the following reactions:  
  Inthe above reaction, X and R are the same as mentioned above. The above reactions are conducted at temperatures ranging from the freezing point of the initial reaction mass to the boiling point thereof. Preferably the temperatures are from about 40 C to about 200 C and more preferably from about 50 C to about 175 C. It is to be understood that the reaction can be conducted under sub atmospheric (e.g. l/l-8/l0 atmospheres), atmospheric or super-atmospheric (e.g. 1.5- atmospheres) pressure. Preferably, the reaction is carried out at atmospheric pressure.  
 are more fully described in the present applicants copending patent application Ser. No. 330,838 filed Feb. 8, 1973, and which is incorporated herein by reference.  
  The amount of halogenated aryl compound in the present invention compositions is any quantity which will effectively render the polyolefin containing composition flame retardant. In general, the amount used is from about 1 to 25 percent by weight, based on the total weight of the composition. Preferably, the amount employed is from about 5 to about 20 percent by ORX weight. It is to be understood that any amount can be used as long as it does not substantially adversely effect the chemical and/or physical and/or mechanical properties of the end polymer composition. The amount utilized, however, is such amount which achieves the objectives described herein.  
 It is to be understood that the term polyolefins as used herein means butylene polymers, ethylene polymers (such as low and high density polyethylene), olefin polymers, and propylene polymers (such as polypropylene), including crosslinked, filled and/or reinforced versions of the same.  
  Butylene polymers include, without limitation, those derived from the monomers l -butene (H C=CHCH CH 2-butene (CH CH=CH iso butylene (Cl-l C=Cl-l 3-methyl-l-butene (H C=CHCH(CH and cyclobutene (HC=CHCH CH Ethylene polymers include, without limitation, polymers of the formula (CH CH with various degrees of wide branches and including polyethylene (high and low density), crosslinked polyethylene, wax blends, ethylene-vinyl acetate copolymers and blends, ethylene-alkyl acrylate copolymers and blends, carboxylcontaining ethylene copolymers, ionomers, and other derivatives of polyethylene.  
  Olefin polymers are those polymers derived from higher olefins such as C C,  
  Propylene polymers include, without limitation, the crystalline homopolymers of propylene including oxidized, chemically modified, and graft modified propylene polymers and polypropylene.  
  Thus the polyolefins used in the present invention composition is any polyolefin herein defined and which one so desired to flame retard. It is to be understood that the polyolefins used can be a virgin&#34; material, i.e. substantially free of additives such as stabilizers, plasticizers, dyes, pigments, fillers, and the like, or the polyolefins can have additives (such as those mentioned and described herein) already contained therein or added concurrently with or after the addition of the halogenated aryl compounds.  
  Another facet of the present invention relates to the use of certain metal compounds with the halogenated aryl compounds to promote a cooperative effect therebetween and thus enhance the flame retardancy of the resultant plastic composition as compared to the flame retardancy of either one component used separately. These enhancing agents are from the group antimony, arsenic, bismuth, tin and zinc-containing compounds. Without limitation, examples of said enhancing agents include Sb O SbCl SbBr Sbl SbOCl, As O AS ZnBO BaB O .l-l O, 2.ZnO.3B O .3.5- H 0 and stannous oxide hydrate. The preferred enhancing agent is antimony trioxide.  
  the amount of enchancing agent employed in the present invention compositions is any amount which when used with said halogenated aryl compounds will promote a cooperative effect therebetween. In general, the amount employed is from about 1 percent to about percent preferably from about 2 percent to about 10 percent, by weight, based on the total weight of plastic composition. Higher amounts can be used as long as the desired end result is achieved.  
  lt is also within the scope of the present invention to employ other materials in the present invention compositions where one so desires to achieve a particular end result. Such materials include, without limitation, adhesion promotors; antioxidants; antistatic agents; antimicrobials; colorants; flame retardants such as those listed on pages 456-458, Modern Plastics Encyclopedia, ibid, (in addition to the new class of flame retardants described herein); heat stabilizers; light stabilizers; pigments; plasticizers; preservatives; ultraviolet stabilizers and fillers.  
  In this latter category, i.e. fillers, there can be mentioned without limitation, materials such as glass; carb0l&#39;l; cellulosic fillers (wood flour, cork and shell flour);  
 calcium carbonate (chalk, limestone, and precipitated calcium carbonate); metal flakes; metallic oxides (aluminum,-beryllium oxide and magnesia); metallic powders (aluminum, bronze, lead, stainless steel and zinc); polymers (comminuted polymers and elastomer-plastic blends); silica products (diatomaceous eanh, novaculite, quartz, sand, tripoli, fumed colloidal silica, silica aerogel, wet process silica); silicates (asbestos. kaolimite, mica, nepheline syenite, talc, wollastonite, aluminum silicate and calcium silicate); and inorganic compounds such as barium ferrite, barium sulfate, molybdenum disulfide and silicon carbide.  
  The above mentioned materials, including fillers, are more fully described in Modern Plastics Encyclopedia, ibid, and which publication is incorporated herein (in toto) by reference.  
  The amount of the above described materials employed in the present invention composition can be any quantity which will not substantially adversely effect the desired results derived from the present invention compositions. Thus, the amount used can be zero (0) percent, based on the total weight of the composition, up to that percent at which the composition can still be classified as a plastic. In general, such amount will be from about 0 percent to about percent and specifically about 1 percent to about 50 percent.  
  The halogenated aryl compounds can be incorporated in to the polyolefins at any processing stage in order to prepare the present invention compositions. In general, this is undertaken prior to fabrication either by physical blending or during the process of forming polyolefins per se. Where one so desires, the halogenated aryl compounds may be micronized into finely divided particles prior to incorporation into the polyolefins.  
 EXAMPLE l T he resultant mixture is heated to about 245 C.; at  
 this temperature, it is in a molten state. The percentages by weight of each component utilized in the respective formulations are listed in Table II. Each formulation is discharged from the mixer and upon cooling solidifies and is ground into chips. The chips are subjected to compression molding in a Wabash press by placing said chips between two platens, the bottom of which contains four equal size depressions 3 inches by five inches by one-eighth inch deep. The top platen is then placed over the bottom platen and heat transfer means supplied thereto in order to melt said chips and thus provide solid samples (after cooling) for testing.  
  Portions of the solid samples of each respective formulation (Nos. 1-26) prepared according to the above described procedure are then subjected to two differ- .ent standard flammability tests, i.e. UL 94 and ASTM D-2863-70. The UL 94 is, in general, the application of a burner to a test specimen (strip) for a certain period of time and observation of combustion, burning, extinguishment. This procedure is fully set forth in Underwriters Laboratories bulletin entitled UL 94, Standard for Safety, First Edition, September 1972 and which is incorporated herein by reference. ASTM No. D-2863- 70 is &#39;a flammability test which correlates the flammability of a plastic specimen to the available oxygen in its immediate environment; this correlation is stated as an Oxygen Index, 0.1., level predicated upon the percent oxygen in the gaseous medium which is required to just provide a steady state of continuous burning of the plastic specimen. This ASTM method is fully described in 1971 Annual Book of ASTM Standards Part 27, published by the American Society For Testing and Materials, 1916 Race Street, Philadelphia, Pa.; this publication is to be consider as incorporated (in toto) herein by reference.  
  The results of these flammability tests are shown in Table 11.  
 TABLE II FLAMMABILITY DATA FOR POLYPROPYLENE PLASTIC COMPOSITIONS CONTAINING HALOGENATED ARYL COMPOUNDS Formula- Halogenated Enhancing Oxygen tion Aryl Compound Agent Index UL 94 No. No. fr Sb O: 71 7:  
  l. 0 18.0 Burns 2. l 20 0 20.5 SB 3. 1 20 25.0 SB 4. 2 0 19.5 SB 5. 2 20 10 23.0 SB 6. 3 20 0 19.0 SB 7. 3 20 10 24.0 SB 8. 4 20 0 19.5 SB 9. 4 20 10 25.0 SB 10. 32 20 0 21.0 SB 11. 32 20 10 27.5 SE-2 12. 37 20 0 19.0 SB 13. 37 20 10 23.5 SB 14. 65 20 0 19.5 SB 15. 65 20 10 23.0 SB 16. 79 20 0 195 SB 17. 79 20 10 24.0 SB 18. 122 20 0 19.5 SB 19. 122 20 10 23.0 SB 20. 143 20 0 21.0 SB 21. 22. 159 20 0 19.5 SB 23. 159 20 10 24.0 $8 24. I81 20 0 19.0 SB 25. 181 20 10 23.0 SB 26. 205 20 10 26.5 SB  
  Referring to Table II, the halogenated aryl compound number relates to the structural formulae heretofor set forth in Table l; a difference of 2% in the Oxygen Index values is considered significant; and the UL 94 values are on a graduated scale wherein the highest degree to lowest degree of flame retardancy is respectively SE-O, SE-l, SE-2, SB and Burns.  
  The results shown in Table II demonstrate the unique effectiveness of these halogenated aryl compounds as flame retardants for polypropylene. Specifically, formulation No. 1 (the control) had a 0.1. of 18.0 and UL 94 value of Burns. In Nos. 2, 4, 6, 8, 10, 12, l4, l6, 18, 20, 22 and 24, the use of the particular halogenated aryl compound results in a significant increase (1.03.0 percent increase) in fire retardancy as measured by 0.]. (While these formulations had a SB rating, UL 94, the individual U.L. rating has a wide range-of values and thus the 0.1. number in this case,&#39;more indicative of increased flame retardancy).  
  The use of an enhancing agent such as Sb O to promote a cooperative effect between such agent and the halogenated aryl compound is fully demonstrated via the results obtained from testing formulation Nos. 3, 5, 7, 9,11,13,l5,l7,19, 21, 23, 25 and 26. The highest UL 94 ratings and significantly higher 0.1. values (50-105 percent increase) are obtained.  
 EXAMPLE II Example I is repeated twoce; once using a 10 percent halogenated aryl compound level and 3 percent Sb O level and secondly, 15 percent and 5 percent levels respectively. At both levels, the 0.]. values and UL 94 ratings are slightly lower than the 20/10 percent levels of Example I.  
 EXAMPLE III Portions of the solid samples of Formulation Nos. 1-26 prepared according to the above described procedure of Example 1 are subjected to the following ASTM tests in order to ascertain other properties of the resultant plastic composition:  
 ( l Tensile Strength (at break) ASTM Test No. D63861T; (2) Flexural Strength ASTM Test No. D790-63; (3) Flexural Modulus ASTM Test No. D790-63; (4) Notched Izod Impact ASTM Test No. D256-56: and (5) Heat Distortion Temperature (HDT) ASTM Test No. D64856.  
  Each of the aforementioned ASTM tests are standard tests in the art and are utilized collectively in order to ascertain the efficacy of a polymeric system as an overall flame retarded composition for commercial application. All of these ASTM Tests are to be considered as incorporated herein by reference.  
  The results of these ASTM tests show that the physical properties of the present invention compositions are basically the same (except 0.]. and UL 94 values) as the plastic material without the flame retardant (i.e. formulation No. 1). Thus, there is no substantial adverse effect on the physical properties of the plastic material when the novel compounds are incorporated therein.  
 EXAMPLE IV The procedure of Examples 1 and III are repeated ex-&#39; cept that the enhancing agent used is zinc borate instead of Sb- O Substantially the same results are obtained using zinc borate as those obtained using Sb O EXAMPLE V discoloration in any strip tested and which demon strates that the present invention compositions are highly resistant to deterioration by light.  
  EXAMPLEVI 7 Samples of each of Formulation l. .(c o&#39;ntrol) through 26 Table &#34;are subjected to temperature thermal) stability tests via the&#34; use of thermal gravimetric analysis (T GA). This test employed the useof a Thermal Balance, model TGS-l, PerkinElmer Corporation, Norwalk, Conn. and an electrical balance, Cahn 2580 model, Cahn InstrumentC ompany, Paramount, California. The results of these tests show &#34;that the halogenated aryl containing Formulations had more than adequate stability for melt processing and subsequent heat aging (i.e. high temperature applications) and thus demonstrating that the particular halogenated aryls are quite compatible with the polypropylene material. The halogenated aryl stability thus aids in providing sufficient flame retardancy at the polypropylene decomposition temperature. This test also demonstrates that the halogenated aryls do not exhibit migrations EXAMPLE VII Examples I VI are repeated again utilizing a low 18 ality of any particular material in any polymer system until it is actively undergone incorporation therein and the resultant plastic composition tested according to various ASTM Standards. Furthermore, it is necessary, in order to have commercial utility. that the resultant flame retarded plastic composition posess characteristics such as being non-toxic. Use of these compounds in the plastic material has accomplished all of these objectives.  
  The above examples have been described in the foregoing specification for the purpose of illustration and not limitation. Many other modifications and ramifications will naturally suggest themselves to those skilled in the art based on this disclosure. These are intended density polyethylene plastic material as the base resin instead of the polypropylene material. The results obtained from the repeat of these examples show that the halogenated aryls are effective in providing flame retarded polyethylene composition which has commercial application.  
 EXAMPLE VIII Examples I VI are repeated again utilizing a high density polyethylene plastic material as the base resin instead of the polypropylene material. The results obtained from the repeat of these examples show that the halogenated aryls are effective in providing flame retarded polyethylene composition which has commercial application.  
  In view of the foregoing Examples and remarks, it is seen that the plastic compositions. which incorporate these compounds. possess characteristics which have been unobtainable in the prior art. Thus. the use of these compounds in the above described plastic material as flame retardants therefor is quite unique since it is not possible to predict the effectiveness and functionto be comprehended as within the scope of this invention.  
 What is claimed is:  
 l. A plastic composition containing polyolefm having incorporated therein a flame retardant which is a halogenated aryl compound having the formula:  
 wherein Z is selected from the group consisting of bromine or chlorine; m and m are integers having a value of 1-5; 1&#39; and i are integers having a value of 0-2; M and M are each independent and are selected from the group consisting of oxygen, nitrogen or sulfur with the proviso that M and M cannot concurrently be oxygen in both cases and where M and/or M is nitrogen. the formula is A is selected from the group consisting of chlorine,  
 cyanno, nitro, lower alkozy, lower alkyl, fluorine, dialkylamino, phenyl, halo-phenyl, benzyl, or halobenzyl; and R is selected from the group consisting of (a) alkylene group having from one to six carbon atoms (b) ca ca(0a) c11 (c) CH CIKCH OII) .CH  
 (cl) (CH 0 (CH where w 1-6 X where X ll, Cl, Br  
 0 CH2 Q (f) 011 c(o) cu (g) CH CII where S saturated ring  19 20 2. The composition as set forth in claim 1 wherein i 6. The composition as set forth in claim 5 wherein i and i are both 0. and i are both 0.  
  3. The composition as set forth in claim 1 wherein i 7. The composition as set forth in claim 5 wherein i and i are both 1. and i are both 1.  
  4. The composition as set forth in claim 1 wherein i s 8. The composition as set forth in claim 5 wherein i and i are both 2. and i are both 2.  
  5. A plastic composition containing polyolefin having 9. The composition as set forth in claim 6 wherein R incorporated therein a flame retardant which is a halois an alkylene group having from I to 6 carbon atoms. genated aryl compound having the formula; 10. A plastic composition containing polyolefin hav- A A1 I Z S R S Z i wherein Z is selected from the group consisting of bro- 2O ing incorporated therein a flame retardant which is a mine or chlorine; m and m are integers having a value halogenated aryl compound having the formula:  
 . H a H r Z N R N I of 1-5; i and i are integers having a value of 0-2; A is wherein Z is selected from the group consisting of broselected from the group consisting of chlorine. cyano. mine or chlorine; m and m are integers having a value nitro. lower alkoxy lower alkyl fluorine. dialkylamino. of 1-5; 1&#39; and i are integers having a value of 0-2; A is phenyl. halo-phenyl, benzyl, or halobenzyl; and R is selected from the group consisting of chlorine, cyano, selected form the group consisting of nitro. lower alkoxy. lower alkyl. fluorine, dialkylamino (a) alkylene group having from one to six carbon atoms (b) CH CH(0H) CH 0 W where w 1-6 &#39;where X H, Cl, Br n a 4 (f) CH- C(0)&#39; -CH (g) 011 CH where S saturated phenyl halo-phenyl. benzyl or halobenzyl; and R is sewherein z&#39;is bromine jor, chlorine, m and m are integers lected from the group consisting of having a value of l -5, i and i&#39;are integers having a (a) alkylene group having from one to six carbon atoms (c) cu Cli(CH OH) c11 v i n where X a H, Cl, Br  
  n 4 CH 9}- CH2 (f) cH2 (0)- (:2  
 (g) 011 cu where S saturatedii c c11 ring ll. The composition as set forth in claim 10 wherein value of 0-2; A is chlorine, cyano, nitro, lower alkoxy,  
 i and i are both 0. lower alkyl, fluorine, dialkylamino, phenyl, halo- 12. The composition as set forth in claim 10 wherein phenyl, benzyl, or halobenzyl; and R is selected from i and i are both 1. the group consisting of (a) alkylene group having from one to six carbon atoms (b) Cli Cl-I(0l-l) CH e r ware:  
 (d) (CH 0 (CH where w 1-6 (e) 4 x where x a, Cl, Br  
 CH 0 CH (f) ca c(o) c11 (3) CH gr) CH where S saturated 2 2 ring 13. The composition as set forth in claim 10 wherein 16. The composition as set forth in claim 15 wherein iandi are both 2. i and are both 0.  
  17. The composition as set forth in claim 15 wherein i and i are both 1.  
  18. The composition as set forth in claim 15 wherein i and i are both 2. 1  
  15. A plastic composition containing polyolefin hav- 19. The composition as set forth in claim 16 wherein ing incorporated therein a flame retardant which is a R is an alkylene group having from 1 to 6 carbon halogenated aryl compound having the formula: atoms.  
  14. The composition as set forth in claim 11 wherein R is an alkylene group having from 1 to 6 carbon atoms.  
 A1 A l wherein Z is bromine or chlorine. m and m are integers having a value of 1-5; i and i are integers having a value of 0-2; A is chlorine, cyano, nitro. lower alkoxy. 15  
 lower alkyl. fluorine; dialkylamino. phenyl. halophenyl, benzyl, or halobenzyl; and R is selected from the group consisting of 23. The composition as set forth in claim 20 wherein iand i are both 2.  
  24. The composition as set forth in claim 21 wherein R is an alkylene group having from 1 to 6 carbon atoms.  
 25. A plastic composition containing polyolefm having incorporated therein a flame retardant which is a halogenated aryl compound having the formula:  
 A A l S-R-0 Zr wherein Z is bromine or chlorine, m and m are integers having a value of 1-5; i and i are integers having a (a) alkylene group having from one to six carbon atoms cn CH2 (f) cn 0(0) CH2 2]. The composition as set forth in claim 20 wherein [and i are both 0.  
  22. The composition as set forth in claim 20 wherein [and i are both l.  
 where w B 1-6 where X H, Cl, Br  
 where S saturated ring value of 0-2; A is chlorine, cyano, nitro, lower alkoxy,  
 4 lower alkyl, fluorine, dialkylamino, phenyl, halophenyl, benzyl, or halobenzyl; and R is selected from the group consisting of (a) alkylene group having from one to six carbon atoms (b) CH --CH(OH) CH (c) 0:1 CH(CH20H) 011 where w 1-6 where X H, Cl, Br  
  (g) cH on where S saturated ring 26. The composition as set forth in claim 25 wherein i and i areboth 2. i and i are both 0. 29. The composition as set forth in claim 26 wherein 27. The composition as set forth in claim 25 wherein R is an alkyiene group having from 1 to 6 carbon i and i&#39; are both i. atoms.  
 28. The composition as set forth in claim 25 wherein t a