Abs plastic compositions containing bis-phenoxy flame retardants
United States Patent [191 Anderson et al.  
 [111 3,876,612 [451 *Apr. 8,1975  
 [ ABS PLASTIC COMPOSITIONS CONTAINING BIS-PHENOXY FLAME RETARDANTS [75] Inventors: Arnold L. Anderson; Robert J.  
 Nulph, both of Alma, Mich.  
 [73] Assignee: Michigan Chemical Corporation,  
 St. Louis, Mich.  
 [* Notice: This portion of the term of this patent subsequent to May 14, 1991 has been disclaimed.  
 [221 Filed: Feb. 8, 1973 [21] Appl. No.: 330,802  
 Related U.S. Application Data [63] Continuation-impart of Ser. No. 260,240. June 6.  
 1972. abandoned.  
 [52] U.S. Cl 260/459 R; 260/42; 260/4222; 260/4575 R; 260/4595 G [51] Int. Cl. C08f 45/60 [58] Field of Search 260/459 R, 45.95 G, 613 13,  
 260/332 R, 2.5 A]. DIG. 24; 106/15 FR [56] References Cited UNITED STATES PATENTS 3.385.819 5/1968 Gouinlock 260/4575 R 3.560.441 2/1971 Schwarcz et a1.  
 3,658.634 4/1972 Yanagi et ul 161/403 5 7 ABSTRACT Plastic compositions containing acrylonitrilebutadiene-styrene and bis-phenoxy compounds having the formula Ai A&#34; wherein Z is bromine or chlorine, m and m are integers having a value of l-5, i and i&#39; are integers having a value of 0-2, R is herein defined and A is cyano, nitro, lower alkoxy, lower alkyl. fluorine, dialkylamino, phenyl, halo-phenyl, benzyl or halobenzyl.  
 14 Claims, No Drawings ABS PLASTIC COMPOSITIONS CONTAINING BIS-PIIENOXY 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; 2,329,033; 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)&#34; 14,500 as cited in Volume 77, Chemical Abstracts, column 153737k (1972); Chemical Abstracts, Volume 13, column 448 Chemical Abstracts, Volume 31, column 7045 and Journal of the Chemical Society, pages 2972-2976 (1963). All of these publications are to be considered as incorporated herein by reference.  
  ABS plastics and utility thereof are known in theart as exemplified by ABS Plastics, C. H. Basdekis&#39;, (Reinhold Plastics Applications Series), Reinhold Publishing Corporation New York, 1964 and Modern Plastics Encyclopedia 1972-1973, Vol. 49: No. 10A, Oct., 1972, pages 10, 14,16, l7, 19, 142 and 143 and which publications are in toto incorporated herein by reference.  
  The need for flame retarding ABS plastics has also been recognized in the art as exemplified by U.S. Pat. No. 3,422,048and U.S. Pat. No. 3,418,263 and Modern Plastics Encyclopedia, ibid, pages 142, 143, 202, 203 and 456-458 and which publications are in toto incorporated herein by reference.  
  The resultant&#39;disadvantages in the utilization of various prior art materials as flame retardants for ABS 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&#39;demand for a material which will function as a flame retardant in ABS and concurrently will not, by incorporation therein, adversely effect the chemical and/or physical and/or mechanical properties .of the resulting ABS plastic composition.  
  The prior art problem of providing a flame retarded ABS composition having desired chemical, physical and mechanical properties has now been substantially solved by the present invention and the abovedescribed disadvantages substantially overcome.  
 Accordingly, one of the main objects of the present are flame retarded.  
  Another object of the present invention is to provide a material for ABS plastic compositions which will not substantially adversely effect the chemical and/or 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&#39;ABS 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 bisphenoxy compounds in ABS to subsequently provide flame retarded compositions which exhibit outstanding chemical, physical and mechanical properties.  
  The bis-phenoxy compounds used in the present invention composition have the formula:  
 and R is from the group (a) CH Cl-l(Ol-l)-Cl-l (b) CH Cl-l (Cl-l 0l-I)--- CH (c) (ct-1 0 (m where w 1-6 I where X=H, 01,31  
 (f) CH ca where S saturated ring In Formula I, i-lm or i m is not greater than 5.  
  It is to be understood that all of the compounds falling within the above Formula l and as heretofore defined are generically described herein as bis-phenoxy compounds.  
 present invention bis-phenoxy compounds are shown below:  
 systems to make the resultant polymer flame retardant. 10 the exemplary definitions of A, Z, R. i, i m and m are listed in Table I.  
 Table 1 Compound No. 2 m m A 1 1&#39; R 1 Br 2 2 o CH2CH(OH)CH2 2 Br 3 3 o 0 cn cmorncu 3 c1 2 2 o o cn cmomcn 4 Br 2 2 -CN 1 1 cu cmorncn 5 Br 2 2 -110 1 1 cu cmomcn 6 Br 2 2 -ocu 1 1 cn cruomcu 7 Br 3 3 -ocn 1 1 .CH2CH(0H)CH2 8 Br 2 2 -cu 1 1 CH2CH(OH)CH2 9 Br 2 2 F 1 1 cn cmomcn 10 Br 2- 2 -N(cu 1 1 CH2CH(OH)CH2 11 r 2 2 0 11 1 y 1 cn cmouicu 12 Br 2 2 C H3Br- 1 1 CH2CH(OH)CH2 13 4 Br 2 2 -cn c u 1 1 cu cruomcn 14 Br 2 2 -CH C H Br 1 1 cn cnmmcu 15 Br 3 3 -c H c1 1 1 cu cummcu 16 c1 3 3 F 1 1 cn cmomcn 17 c1 2 2 -CN 2 2 cn cmomcn 13 Br 4 4 0 0 cn cmomcu 19 c1 3 3 -C5H Br3 1 1 cn cmomcn 20 c1 3 3 410 2 2 cu cruomcu 21 c1 2 2 0ca 1 1 cucmomcn 22 c1 4 4 4B 1 1 cn cnwmcn 23 c1 3 3 F 2 2 CH2CH(0H)CH2 24 Br 1 1 4 11 1 1 CHZCIKOIOCHZ 25 Br 1 1 -oc n 1 1 cn cn(&#39;ou)cn &#39;Ifable I Con&#39;d! Compound No. 2 m m A -1 1&#39; a R 14% c1 3 3 F 2 2 -c11 c(c 11 )n- 1119 Br 1 1 11 1 1 -c11 c(c u )n- B1. 1 1 -oc H 1 1 -c11 c{c 11 )11- 151 Br 1 2 2 -0 o 11 0 :3 1-52 31 3 0 0 11 0 c11 153&#39; c1 2&#39; 2 0 &#39;o 11 0 ca, 154 Br 2 V 2 I -cm 1 1 11 C C3 155 Br 2 2 -uo 1 1 H26 011 156 Br 2 2 -o ;11 1 1 11 C c11 157 13 3 3 -ocu 1 1 11 a 011 15s Br 2 2 -c11 1&#39; 1 11 a 011 159 Br 2 2 F 1 1 11 s ca, 160 Br 2 2 -N(CH3)2 1 1 11 a C 161 B7: 2 2 0 11 I 1 1 11 1: ca 162 a: 2 v 2 -C H Br 1 1 11 s 011 163 13r- 2 2 -ca c 11 1 I 1 11 C 011 164 131: 2 .2 Cl-1 0 8331? 1 1 11 0 (211 165 Br 3 -3 41 11 01 1 1 11 0 cu 166 c1. 3 3 F 1 1 11 s 011 167 I c1 2 2 -CN 2 2 11 a e11, 153 B1 4 4 0 0 11 C ca; 169. c1 &#39;3 3 4 11 13 1 1 112C C52 170 c1 .3 3 -no 2 2 11 C 611 171 c1 2 2 -oc1-1 1 1 11 C CH2 172 c1 4 4 4:11 1 1 11 0 ca, 17-3 01 3&#34;- 3 r &#39;2&#34; 2 11 C s C 174 B1: 1 1 4 11 1 1 11 0 c 1 175 Br 1 1 OC4H9 1 1 11 g (SJ-L c 1 15151113151; the 115155519 bmpsunds a by reacting a halogenated phenol with a halogenated re prepared 0- alkane at elevated temperatures in the presence of af basic material such as alkali-metal hydroxides, carbon ates, bicarbonates, oxides and hydrides. The preferred alkali metals are potassiumand sodium. Where one desires to increase, for example, ease of handling the reaction mass, solvtfi such as ketones (e.g., acetone, methyl ethyl ketone, and methyl iso-butyl ketone), alcohols (e.g., methanol, ethanol, iso-propyl alcohol, butyl alcohol and glycols), oraqueous solvents (e.g water, a mixture of water and alcohol and a mixture of water and ketone) can be employed. The desired end product i.e., the bis-phenoxy 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 bis-phenoxy compounds are prepared according to the following reactions:  
 z-z O- OH XRx (II) (III) 2,, O o R in the above reaction, X is halogen, preferably chlorine and R is the same as defined herein. Where In and m and i and i&#39; are different integers, then equivalent molar portions of the particular halogenated phenol are used with equivalent portions of dissimilar halogenated phenol.  
  The above reaction is 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/lO-8/l0 atmospheres), atmospheric or super-atmospheric (e.g., l.5-l0 atmospheres) pressure. Preferably, the reaction is carried out at atmospheric pressure.  
  The above-described processescan be carried out with conventional, readily available chemical processing equipment. For example, a conventional glass-lined 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 inventiondescribed in the examples set forth herein.  
  The amount of bis-phenoxy compound employed in the present invention compositions is any quantity which will effectively render the acrylonitrilebutadiene-styrene 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 to about percent by 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 ABS as used herein means acrylonitrile-butadiene-styrene copolymers which are thermoplastic polymers produced, for example (but without limitation), by blending a styrene/acrylonitrile copolymer with butadiene-based rubber, ,or by grafting butadiene-based rubber (usually polybutadiene) with styrene/acrylonitrile chains, or by copolymerization of styrene, acrylonitrile and. butadiene monomers.  
  Thus the acrylonitrile-butadiene-styrene used in the present invention compositions is any acrylonitrile butadiene-styrene herein defined and which one so desires to flame retard. It is to be understood that the acrylonitrile-butadiene-styrene used can be a virgin material, i.e., substantially free of additives such as stabilizers, plasticizers, dyes, pigments, fillers, and the like,  
 ZHX  
 or the acrylonitrile-butadiene-styrene can have additives,(such as those mentioned and described herein) already contained therein or added concurrently with or after the addition of the bis-phenoxy compounds.  
  Another facet of the present invention relates to the use of certain metal compounds with the bis-phenoxy 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&#34; are from the group antimony, arsenic, bismuth, tin and zinc-containing compounds. Without limitation, examples of said enhancing agents include Sb O SbCl SbBI&#39;3, SbI SbQCl, AS203, AS205, ZnBO BaB O &#39;H O, 2&#39;ZnO-3B O &#39;3&#39;5- H 0 and stannous oxide hydrate. The preferred enhancing agent is antimony trioxide.  
  The amount of enhancing agent employed in the present invention compositions is any amount which when used with said bis-phenoxy compounds will promote a cooperative effect therebetween. In general, the amount employed is from about 1 to about 15 percent, preferably from about 2 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.  
  It 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 promoters; antioxidants; antistatic agents; antimicrobials; colorants; flame retardants such as those 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 polymersand elastomerplastic blends); silica products (diatomaceous earth, .novacu lite, quartz, sand, tripoli, fumed colloidal silica, silica aerogel, wet process silica); silicates&#39;(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 compositions 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 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 to about 75 percent and specifically from about 1 to about 50 percent.  
  The bis-phenoxy compounds can be incorporated into the acrylonitrile-butadiene-styrene 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 acrylonitrile-butadiene styrene per se. Where one so desires, the bis-phenoxy compounds may be micronized into finely divided particles prior to incorporation into the acrylonitrile-butadiene-styrene.  
 EXAMPLE I An ABS plastic material, (Marbon TP-2098, a product of Marbon Division, Borg-Warner Corporation, Washington, W.Va. and containing antioxidants, lubricants, releasing agents and titanium dioxide pigment) is utilized as the base resin in order to prepare 26 formulations (plastic compositions). With the exception of formulation No. l, the particular bis-phenoxy compound (and the antimony trioxide enhancing agent where indicated) is incorporated into the plastic by adding both to a Brabender mixer (Plastic-Corder,&#34; torque Rheometer, Model PLV-l50, C. W. Brabender lnstruments Inc., South Hackensack, NJ.) The mixer is equipped with a pair of roller type blades positioned within a head provided with heat transfer means.  
  The 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 ll. 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 three inches by 5 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 different 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, and extinguishment. This procedure is fully set forth in Underwriters Laboratories bulletin entitled UL 94, Standard for Safety, First Edition, Sept. 1972 and which is incorporated herein by reference. ASTM No. D-2863- 70 is 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 considered as incorporated (in toto) herein by reference.  
  The results of these flammability tests are shown in Table ll.  
 TABLE II FLAMMABILITY DATA FOR ABS PLASTIC COMPOSlTlONS CONTAlNING BlS-PHENOXY COMPOUNDS FORMULA- BlS-PHENOXY COM- ENHANCING OXYGEN UL 94 TlON POUND AGENT INDEX NO. NO. I! Sb O /1 7r l. 0 0 18.5 SB 2. 2 l5 0 21.5 SB 3. 2 l5 5 32.0 SE0 4. l9 l5 0 205 SB 5. l9 l5 5 29.5 SE-l 6. 33 I5 0 22.0 SB 7. 33 15 5 29.0 SE-l 8. 47 15 O 21.0 SB 9. 47 l5 5 28.0 SE-l ll). 67 l5 0 22.5 SB 1 l. 67 15 5 30.5 SE-l 12. 83 15 0 24.5 SB 13. 83 15 5 40.0 SE-() 14. 92 15 0 23.0 SB 15. 92 15 5 36.0 SE-O 16. I02 15 0 23.0 SB 17. 102 15 5 31.5 SE-O l8. 1 l9 l5 0 22.5 SB l9. 1 l9 l5 5 30.0 SE-l 20. I27 15 O 2L0 SB 2l. 127 15 5 30.5 SE-l 22. M5 15 0 20.5 SB 23. M5 15 5 29.0 SE-l 24. 152 l5 0 22.0 SB 25. I52 l5 5 32.0 SE-O 26. 15 5 32.5 SE-O Referring to Table II, the bis-phenoxy compound number relates to the structural formulae heretofor set forth in Table I; a difference of 2 percent 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 bis-phenoxy compounds as flame retardants for ABS. Specifically, formulation No. l (the control) had a 0.1. of 18.5 and UL 94 value of SB. In Nos. 2, 4, 6. 8, l0, l2, l4, l6, 18, 20,22 and 24, the use of the particular bis-phenoxy compound results in a significant increase (1.5-6.0 percent) in fire retardancy as measured by 0.1. (While these formulations also had a SB rating, UL 94, the individual U.L. rating has a wide range of values and thus the 0.1. number is, in this case, 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 bis-phenoxy compound is fully demonstrated via the results obtained from testing formulation Nos. 3, 5, 7, 9, 11,13, l5,l7,19,2l, 23, 25 and 26. The highest UL 94 ratings and significantly higher 0.1. values (9.5-2] .5 percent increase) are obtained.  
 EXAMPLE I] EXAMPLE III Portions of the solid samples of Formulation Nos. l-26 prepared according to the above described procedure of Example I are subjected to the following ASTM tests in order to ascertain other properties of the resultant plastic composition:  
 Tensile Strength (at break) Flexural Strength Flexural Modulus Notched Izod Impact Heat Distortion Temperature (HDT) ASTM Test No. D638-6IT: ASTM Test. No. D790-63: ASTM Test No. D790-63; ASTM Test No. D256-56; and  
 ASTM Test No. D648-56.  
  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 0.1. 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 I and III are repeated except 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 Strip samples of each of Formulation Nos. 1 through 26 Table II, are subjected to light stability tests via the use of a Weather-Ometer,&#34; model 25/18 W. R., Atlas Electrical Devices Company, Chicago, Illinois. Utilizing an operating temperature of F and a 50 percent relative humidity, each strip is subjected to 200 hours of simulated daylight&#34; via the use of a carbon arc. The results show that after 200 hours, there is no significant discoloration in any strip tested and which demonstrates that the present invention compositions are highly resistant to deterioration by light.  
 EXAMPLE VI Samples of each of Formulation Nos. 1 through 26 Table II, are subjected to temperature (thermal) stability tests via the use of thermal gravimetric analysis (TGA). This test employed the use of a Thermal Balance,&#34; model TGS-l, Perkin-Elmer Corporation, Norwalk, Connecticut and an electrical balance, Cahn 2580 model, Cahn Instrument Company, Paramount, California. The results of these tests show that the bisphenoxy compounds 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 bisphenoxy compounds are quite compatible with the plastic material. The bis-phenoxy compound stability thus aids in providing sufficient flame retardancy at the plastic decomposition temperature. This test also demonstrates that these compounds do not exhibit migration.  
  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 functionality 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 possess 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 to be comprehended as within the scope of this invention.  
 What is claimed is:  
  l. A plastic composition containing acrylonitrilebutadiene-styrene polymer having incorporated therein an effective amount of a flame retardant which is a 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 l-; i and i are integers having a value of 02; A is selected from the group consisting of cyano, nitro, lower alkoxy. lower alkyl, fluorine, dialkylamino, phenyl, halo-phenyl, benzyl and halo-benzyl; and R is selected from the group consisting of (a) CH cams) CH2 (b) CH2 cH(cu&#39; o1i)-&#39; CH2 HQQ- 0 np where w I 1-6 CH2 CH2 where X H, Cl, Br  
 (e) cn c o) cu (f) CH2- CH where S saturated ring 2. The composition as set forth in claim 1 wherein i and i are both 0.  
  3. The composition as set forth in claim 1 wherein i and i are both 1.  
  4. The composition as set forth in claim 1 wherein i and i are both 2.  
  5. The composition as set forth in claim 3 wherein Z is bromine and A is cyanol 6. The composition as set forth in claim 3 wherein Z is bromine and A is nitro.  
  7. The composition as set forth in claim 3 wherein Z is bromine and A is lower alkoxy.  
  8. The composition as set forth in claim 3 wherein Z is bromine and A is lower alkyl.  
  9. The composition as set forth in claim 3 wherein Z is bromine and A is fluorine.  
 10. The composition as set forth in claim 3 wherein Z is bromine and A is halo-benzyl. =l