Polyurethane plastic compositions containing bis-aryloxy flame retardants
United States X {,3 Anderson H c 7 6 K 1 POLYURETHANE PLASTIC COMPOSITIONS CONTAINING BIS-ARYLOXY FLAME RETARDANTS Arnold L. Anderson, Alma, Mich.  
 Assignee: Michigan Chemical Corporation, St.  
 Louis, Mich.  
 The portion of the term of this patent subsequent to Mar. 4, 1992, has been disclaimecl.  
 Filed: Feb. 8, 1973 Appl. N0.Z 330,786  
 Related US. Application Data Continuation-impart of Ser. No. 260,240, June 6. 1972, abandoned.  
 Inventor:  
 [ Notice:  
  52 vs. c1.... 260/45 R; 260/37 N; 260/4575 R;  
  266/775 55 161. C1 C08g 51/60 Field Of Search 260/459 R, 45.95 6. 613 B.  
 260/33.2 R. 2.5 A1, DIG. 24; 106/15 FP [56] References Cited UNITED STATES PATENTS 5/1968 Gouinlock 260/4575 R 2/1971 Schwarcz et al. 260/45] R 4/1972 Yzmugi ct ul 161/403 2/1973 Kutner 260/4595 G Primary Examiner-M. J. Welsh Attorney, Agen1,-ur FirmRobert M. Phipps; James I. Mullen; Robert S. Frieman 1 [57] ABSTRACT Plastic compositions containing polyurethanes and his- BEST AVAILA%COPY aryloxy compounds having the formula wherein aryl is from the group zml 18 Claims, No Drawings BEST AVAILABLE COPY 1 POLYURETHANE PLASTIC COMPOSITIONS CONTAINING BIS-ARYLOXY 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: U.S. Pat. Nos. 2,130,990, 2,186,367, 2,329,033; 3,666,692, 3,686,320, 3,658,634; German Pat. Nos. 1,139,639. 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 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 polyurethanes (including, without limitation, rigid foams, semi-rigid foams, flexible foams, rubbers and adhesives). More specifically, the present invention covers plastic compositions containing polyurethanes and certain bis-aryloxy compounds (hereinafter defined) as flame retardants for said plastic compositions.  
  Polyurethanes and utility thereof are known in the art as exemplified by Polyurelhanes, B. A. Dombrow, (Reinhold Plastics Applications Series), Reinhold Publishing Corporation, New York, 1965 and Modern Plastics Encyclopedia 1972-1973, Vol. 49: No. 10A, October, 1972, pages 110, 112, 162, 276, 278, 279, 282 and 283 and which publications are in toto incorporated herein by reference.  
  The need for flame retarding polyurethanes has also been recognized in the art as exemplified by U.S. Pat. No. 3,347,822 and Modern Plastics Encyclopedia, ibid, pages 222, 456-458 and which publications are in toto incorporated herein by reference.  
  The resulting disadvantages in the utilization of various prior art materials as flame retardants for polyurethanes include, without limitation, factors such as thermal migration, heat instability, light instability, nonbiodcgradable, 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 polyurethanes and concurrently will not, by incorporation therein, adversely effect the .chemical and/or physical and/or mechanical properties of the resultant polyurethane plastic composition.  
  The prior art problem of providing a flame retarded polyurethane 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 polyurethane plastic compositions which are flame retarded.  
  Another object of the present invention is to provide a material for polyurethane 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 polyurethane 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 bisaryloxy compounds in polyurethane to subsequently provide flame retarded compositions which exhibit outstanding chemical, physical and mechanical properties.  
  The bis-aryloxy compounds used in the present invention compositions have the formula:  
 Z is bromine or chlorine; m and m are integers each independently having a value of l-7; i and i are integers each independently having a value of 0-2; alkylene is a straight or branched chain alkylene group having from 1 to 6 carbon atoms e.g. CH C 11,, C l-l C,l-l,,, C 11 C 11 and CH CH(CH )CH A is from the group cyano (-CN), nitro (-NO lower alltoxy (e.g. OCl-l OCH lower alkyl e.g. CH C l-l C 11 C 11 fluorine, dialkylamino e.g. -N(CH N(C H phenyl (C l-l halo-phenyl, benzyl (Cl-l C H and halo-benzyl; and y is an integer having a value of l-5.  
  ln Formula I, the sum ofi m or i -lm is not greater than 7 and i y is not greater than 5.  
  It is to be understood that all of the compounds falling within the above Formula I and as heretofore defined are generically described herein as bis-aryloxy&#34; compounds.  
  Illustrative (but without limitation) of some of the present invention bis-aryloxy compounds are shown below:  
 0 (a1ky1ene) -0 (aryl) the exemplary definitions of A, Z, alkylene, aryl, m, m, i, i and y are listed in Table l.  
 BEST AVAILABLE COPY In general, the bis-aryloxy compounds are prepared 50 and glycols), or aqueous solvents (e.g. water, a mixture by reacting a halogenated napthol with a halogenated &#39;alkane or a monohalophenoxy haloalkane (depending upon which bis-aryloxy compound is desired) at elevated temperatures in the presence of a basic material of water and alcohol and a mixture of water and ketone) can be employed. The desired end product, i.e. the bis-aryloxy compound, can be recovered from the reaction mass via various methods such as distillation such as alkali metal hydroxides, carbonates, bicarbon- 55 or crystallization after cooling the reaction mass to tone, and methyl iso-butyl ketone), alcohols (e.g. 60  
 methanol, ethanol, iso-propyl alcohol, butyl alcohol about 10-30 C and adding water thereto. 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-napthoxy compounds are prepared according to the following reactions:  
 0H xtalk lenem a aux (tit) 0 (alkylerte) 0 BEST AVAILABLE COPY o I ,o (I) A A ln the above reaction, X is halogen, preferably chlo- The amount utilized, however, is such amount which rine and alkylene is the same as defined herein. Where l0 achieves the objectives described herein. m and m and i and i are different integers, then equiv- It is to be understood that the term polyurethanes as alent molar portions of the particular halogenated napused herein means polymers containing repeated urethol are used with equivalent portions of dissimilar hathane linkages logenated napthol. H 0 Specifically, the unsymmetrical aryloxy compounds i are prepared, for example, according to the following N C L reactions:  
 Z Z v Q 011 base 021a (e.g.EL&#39;-1OH H0?! 9 A1 I A- I It) (1v) 1 m A1 x(a1k 1ene) -o z 1 I, v i (m m 0 (alkylene) 0- 0 2 1 In the above reaction, X is halogen, preferably chlowhere R is aromatic or aliphatic group. These polymers rine, and alkylene is the same as defined herein. a are generally made by reacting a polyisocyanate with a The above reactions are conducted at temperatures 40 compound having a plurality of active hydrogens (i.e. ranging from the freezing point of the Initial reaction a compound having active hydrogen and which gives a mass to the boiling point thereof. Preferably the tempositive Zerewitinoff test). peratures are from about 40 C to about 200 C and more preferably from about 50 C to about 175 C. lt is to be understood that the reaction can be conducted under sub-atmospheric (e.g. l/l0-8/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 processes can 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 Another facet of the Presem invention relates to the utilized in practicing any of the preferred embodiments use Of Certain metal Compounds with the y y of the invention described in the examples set forth OmPOUndS to promote a cooperative effect therebe- Thus the polyurethanes used in the present invention compositions is any polyurethane herein defined and which one so desires to flame retard. It is to be understood that the polyurethanes 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 polyurethanes can have additives (such as those mentioned and described herein) already conaddition of the bis-aryloxy compounds.  
 herein. tween and thus enhance the flame retardancy ofthe re- The amount of bis-aryloxy compound employed in sultant plastic composition as compared to the flame the present invention compositions is any quantity retardancy of either one component used separately.  
 which will effectively render the polyurethane contain- These enhancing agents&#34; are from the group antiing composition flame retardant. In general, the mony, arsenic, bismuth, tin and zinc-containing comamount used is from about 1 to 25 percent by weight, pounds. Without limitation, examples of said enhancbased on the total weight of the composition. Preferaing agents include Sb O SbCl SbBr;,, Sbl SbOCl, bly, the amount employed is from about 5 to about 20 A5 0 A5 0 ZnBO,, BaB O,.H,O, 2.ZnO.3B,O percent by weight. lt is to be understood that any 3.5H O and stannous oxide hydrate. The preferred enamount can be used as long as it does not substantially hancing agent is antimony trioxide.  
 adversely effect the chemical and/or physical and/or The amount of enhancing agent employed in the tained therein or added concurrently with or after the mechanical properties of the end polymer composition. present invention compositions is any amount which BEST AVAlLABLE COPY when used with said bis-aryloxy compounds will promote a cooperative effect therebetween. In general, the amount employed is from about 1 to about percent, v,-referably from about 2 to about 10 percent. by weight, dased on the total weight of plastic composition. Higher amounts can be used as long as the desired end result is achieved.  
  1t 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; anitoxidants; 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; carbon; 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 earth, novaculite, quartz, sand, tripoli, fumed colloidal silica, silica aerogel, wet process silica); silicates (asbestos, kaolimite, mica, nepheline syenite, talc, wollastonite, alumi num silicate and calcium silicate); and inorganic compounds such as barium ferrite, barium sulfate, molybdenum disulflde 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 (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 to about 75 percent and specifically from about 1 to about 50 percent.  
  The bis-aryloxy compounds can be incorporated in to the polyurethanes 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 polyurethanes per se. Where one so desires, the bis-aryloxy compounds may be rnicronized into finely divided particles prior to incorporation into the polyurethanes.  
 EXAMPLE 1 pound indicated in Table 11 are mixed in a paper cup with mechanical agitation at 1000 rpm for about 10 seconds. Approximately 0.22 (0.19 ml) grams of stannous octoate is added via a syringe to the above resultant mixture in the cup. After 5 seconds of agitation, approximately 50 grams (41 m1) toluene diisocyanate is added via a pipet, the mixture agitated for another 5 seconds and then the overall mixture is discharged into a gallon paper container. The foam is then allowed to rise. After the foam has completely risen, it is allowed to set for about 2 minutes at 20 C and then it is postcured in a forced draft oven at 220 F for about 12 minutes. Prior to any testing, the foam is allowed to set at room temperature (20-25 C) for 1 week.  
  Portions of the samples of each respective formulation (Nos. 1-14 Table 11) prepared according to the above-described procedure are then subjected to two different standard flammability tests, i.e. MVSS No. 302 and ASTM D-2863-70. The Motor Vehicle Safety Standard No. 302 is, in general, the application of a burner to a test specimen (strip) for 15 seconds and the timing of the burning for a specified length of the strip. This procedure is fully set forth in Fire Journal, Vol. 66, No. 4, July 1972 pages 34-37 and 44, published by National Fire Protection Association, Boston. Mass, and which is incorporated herein by reference. ASTM No. D-2863- 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 predicted 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 11 FLAMMABILITY DATA FOR POLYURETHANE PLASTIC COMPOSlTlONS Referring to Table 11, the bis-aryloxy number relates to the structural heretofor set forth in Table 1; a difference of 2 percent in the Oxygen lndex values is considered significant; and the MVSS 302 values are set forth in burning rates expressed as inches per minute.  
  The results shown in Table 11 demonstrates the unique effectiveness of these bis-aryloxy as flame retardants for polyurethanes. Specifically, formulation No. l (the control) had a 0.1. of 17.3 and MVSS 302 value BEST AVAlLABLE COPY of 4.9. ln Nos. 2-14, the use of the particular bisaryloxy results in a significant increase in fire retardancy as measured by 0.1. Furthermore, these formulations also had a reduction in MVSS 302 burning rates and in some cases, the material being tested is found to be self-extinguishing (SE).  
 EXAMPLE ll EXAMPLE lIl Samples of each of formulation Nos. l-l4 prepared according to the above described procedure of Example l are subjected to the following ASTM test in order to ascertain other properties of the resultant plastic compositions:  
 Tensile Strength (at break) ASTM Test No. D4564 Density ASTM Test No. D-l564 Ultimate Elongation 1 ASTM Test No. D-l564 (4) Tear Strength 1 ASTM Test No. D-l564 (5) Compression Deflection ASTM Test No. D-l564 The aforementioned ASTM Test is a standard test in the art and is utilized collectively in order to ascertain the efficacy of a polymeric system as an overall flame retarded composition for commercial application. This ASTM Test is to be considered as incorporated herein by reference.  
  The results of this ASTM test shows that the physical properties of the present invention compositions are basically the same (except O.l. and MVSS 302 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 lV aryloxy compound 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 bis-aryloxy compound are quite compatible with the plastic material. The bis-aryloxy 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 polyurethane having incorporated therein a flame retardant which is a bis-aryloxy compound having the formula:  
 (alkylene) --O- (aryl) rine, dialkylamino, phenyl, halo-phenyl, benzyl or halobenzyl; and alkylene is a straight or branched chain alkylene group having from I to 6 carbon atoms.  
 BEST AVAILABLE COPY 2. The composition as set forth in claim 1 wherein al- 11. The composition as set forth in claim 8 wherein kylene is C l-l Z is bromine.  
  3. The composition as set forth in claim 1 wherein al- 12. The composition as set forth in claim 8 wherein kylene is C H Z is chlorine.  
  4. The composition as set forth in claim 1 wherein al- 13. A plastic composition containing polyurethane kylene is C H having incorporated therein a flame retardant which is 5. The composition as set forth in claim 2 wherein Z a bis-aryloxy compound having the formula:  
  I O (alkylene) 0 1/ is bromine. Z is selected from the group consisting of bromine or 6. The composition as set forth in claim 2 wherein Z chlorine; m and m are integers having a value of 1-7; is chlorine. iand i&#39; are integers having a value of 0-2; A is selected 7. A plastic composition containing polyurethane from the group consisting of cyano. nitro, lower alkoxy, having incorporated therein a flame retardant which is l0 er alkyl flu dialkylamin ph yl. a a bis-aryloxy compound having the formula: phenyl. benzyl or halo-benzyl; and alkylene is a straight I 5 &#39;--l-0-----(alkylene)0 q Z f a k c I 4-! Z is selected from the group consisting of bromine or or branched chain alkylene group having from 1 to 6 chlorine; m is an integer having a value of 1-7; is an 40 carbon atoms. integer having a value of l-5; i and i are integers hav- 14. The composition as set forth in claim 13 wherein ing a value of 0-2; A is selected from the group consistalkylene is C H ing of cyano, nitro, lower alkoxy, lower alkyl. fluorine, 15. The composition as set forth in claim 13 wherein dialkylamino, phenyl, halo-phenyl, benzyl or haloalkylene is C H benzyl; and alkylene is a straight or branched chain 111- 16. The composition as set forth in claim 13 wherein kylene group having from 1 to 6 carbon atoms. alkylene is C H 8. The composition as set forth in claim 7 wherein al- 17. The composition as set forth in claim 14 wherein kylene is C H Z is bromine.  
  9. The composition as set forth in claim 7 wherein al- 18. The composition as set forth in claim 14 wherein kylene is CH Z is chlorine.  
  10. The composition as set forth in claim 7 wherein alkylene iS C Hg.  
 &#39; Pa 1 UNITED STATES PATENT OFFICE ge CERTIFICATE OF CORRECTION PATENT NO. 1 3 0 00 DATED 1 April 29, 1975 INVENTOR( Arnold L. Anderson It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  
 IN THE ABSTRACT: Right hand column, third line, after the word group insert:  
 Z and Z and Column 3, line 1 delete the formula O and substitute therefore:  
 TABLE I Where aryl O Z Page 2 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. I DATED April 29, 1975 |NVENTOR(S) Arnold L. Anderson It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  
 Column 3 on the line before the graphic formula between entries for Compounds No. 25 and 26 insert:  
 where aryl Column 3 on the line before the graphic formula between entries for Compound No. 50 and 51 insert:  
 where aryl Column 5 on the line between the entries for Compound No. 75 and 76 delete the indistinguishable graphic formula and insert:  
 Where aryl G Column 12, lines 35-40 (being Claim 1, line 4) the indistinguishable formula is:  
 O-(alkylene) --O(aryl) Page 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 1 3,880,800  
 DATED 1 April 29, 1975 |NVENTOR(S) 1 Arnold L. Anderson It is Certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  
 Column 12-, line 45, (being Claim 1, line 5) after the word group insert:  
 Z and Column 13, lines 26-37 (being Claim 7, line 4) the indistinguishable formula is:  
 (alkylene) -0 Z Signed and Scaled this seventh Day Of October 1975 [SEAL] Arrest:  
 RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner of Paren rs and Trademarks