Document 8VowjrDD85kp15ndR34EzKw4m

4 4 * ) POSSIBILITIES FOR EXPANSION OF THE BIPHENYL PRODUCT LINE F * ^ Q, E. Thompson diagrammed as follows. benzene products in com be % \ 1* I 1,* >1 i * Minor Products "Major11 Prod. Line isopropyl biphenyl ^lkYlatiqn_blphenyl ^ r>Aroclor 12--ceriesi Hydrogenated terphenyl <-H--p-< -- terphenyls Cl2 ^Aroclor 5^--series (a) HB 40 + (b) MCS 460 higher polyphenyls + Montar 9 Aroclor 12^2 bisphenoxybiphenyl (Therminol 77) In view of a possible decline in Aroclor usage, oppor tunities for expanding the biphenyl line in other direct ions need to be explored. Such other directions may include (a) new uses of biphenyl itself, (b) expand usefulness of various biphenyl derivatives and finally (c) modify the benzene - biphenyl process so that more terphenyls are p r o duced, and expand uses of these products. 1. Modifying Biphenyl-Terphenyl Process Considering the last of the above mentioned avenues first, this approach seems to be the direction of most current promise. Terphenyls and products derived therefrom (HB-40) appear to be increasing in demand or at least have evident potential. An experimental p r o cess study is just getting underway at Anniston. O b jectives include finding better ways of increasing the terphenyl/biphenyl ratio, and new promoters will be examined. Oxygen-containing additives such as methanol, 2-propanol and acetone are currently employed, and a reactor temperature of approximately 750C is required. In thiB connection, recent results reported by Fields and Meyerson (l) indicate that nitrobenzene is a better promoter and it allows the thermal process to be run at 600C. Additional details of this work are given in 03b3 -2- l Appendix I. Since the probable sequence of reactions is that shown below the possibility of using meta-dinitrobenzene and obtaining m-terphenyls directly suggests itself (2). The economic~"benefit of this approach may be open to question, however. 2. Biphenyl Derivatives While chlorinated biphenyls are the only important commercial derivatives, certain other substituted bi phenyls have received some commercial attention, both within and ex-Monsanto. Thus, 4-hydroxyldiphenyl (p-phenylphenol) reacts with formaldehyde to give a resin used in wear-resistant surface coatings. This phenol is produced by the sulfonation of diphenyl followed by sodium hydroxide fusion or, along with 2-hydroxydiphenyl (o-phenylphenol), as a by-product from the hydrolysis of chlorobenzene with aqueous sodium hydroxide. 2-hydroxydlphenyl, particularly as its sodium salt, is used as a preservative, a germicide, or a fungicide. 4,4 -dihydroxydiphenyl may be produced by sulfonation followed by sodium hydroxide fusion. Diphenyl may be nitrated readily and the nitrodlphenyls reduced to produce analogs of aniline. The 4,4-diaminodiphenyl, benzidine (qv) is an important dye intermediate. Diphenyl may also be alkylated and sulfonated to produce wetting agents. Of the alkyl biphenyls, isopropyl biphenyl has the most attractive fluid properties, and when reduced to isopropylbicyclohexyl, serves as a diluent in tractive oils. Presumably isopropylbiphenyl could be utilized in a cumene-phenol type process to afford hydroxybiphenyls. Excellent lists of polyphenyls and alkylpolyphenyls with certain of their physical properties have been compiled by Malcolm McEwen (2). Parts of these are given in Appendix II. O i ^ 33 Nfc* ) 5. Uses of Diphenyl It cel f Currently diphenyl Is used primarily as a heat transfer medium. Its eutectic with diphenyl ether is marketed as Dowtherm A In this country and Dlphyl in Europe. Monsanto has served a limited reactor coolant market with biphenylterphenyl mixtures. More recently diphenyl has found application as a dye-carrier for polyester fibers and some 20M lb/year are said to be consumed in this application. Internally we have experimented with diphenyl-phenylsulfide mixtures as possible competition for Dowtherm A. Unfor tunately only about 10$ biphenyl can be used and at this level provides no significant advantage over phenylsulfide alone. A more promising composition of the Dowtherm A type consists of biphenyl (-^28$), diphenyl ether (28$) and Santowax WR (^-44$), Santowax V/R is a terphenyl-higher polyphenyl mixture obtained from Santowax R by removing a major portion of the benzene-insoluble p , p 1-terphenyl and higher polyphenyl isomers. A summary of various biphenyl eutectic mixtures is included in Appendix II. For those interested in additional details, a reasonably up-to-date review of biphenyl and terphenyl chemical technology is given in by Hubbard and Poffenberger December 29, 1969 References : 1. E. K. Fields and S. Meyerson, Accounts of Chem.Res., 2j 275(1969). 2. George Urry - Monsanto consultant 5. M. McEwen, "Organic Coolant Data Book," Technical Publication A T -1, July 1958. 4. N. Poffenberger and H. L. Hubbard in Klrk-Othmer*s Encyclopedia of Chemical Technology, 2nd Ed. Vol. 7, p. 191-204. NEV 0 3 6 2 3 4  -1 35. K. ITALOS AM) S. M e YEHSON I lienclon of Nitrobenzene with Benzene Tlie CtlU ion or radical is therefore the major primary decomposition product from nitrobenzene both under electron impact am! in thermolysis. This conclusion led ur to investigate reactions of nitrobenzeno with other aromatic compounds at GOO. Benzene alone under these conditions, GOO and 9-sec contact time, was almost all recovered; it gave only 0.01 wt % of bi phenyl. Nitrobenzene with benzene gave the products shown in Table IV. Phenol is a minor product, sug gesting that the decomposition of nitrobenzene to phenyl radical anti nitrogen dioxide is uniinolccular, but that the intro-nitrite rearrangement may be of higher order. The yields of products are considerably different for the reactions at the two different concen tration ratios, ami thus give a clue to the mechanism of biphenyl formation. The increasing proportion of bi phenyl with decreasing concentration of nitrobenzene (yields based on moles of nitrobenzene) implies that most of the biphen}*] arises by reaction with benzene rather than by dimerization of the phenyl radical from nitrobenzene decomposition. At a nitrobenzcne:benzenc mole ratio of 1:5, the yield of biphenyl and tcrphcnyl combined, ns measured by gas chromatography, was Ev5 mole % based on 1 mole of phenyl radical pro duced per mole of nitrobenzene decomposed. At a mole ratio of 1 :25 the yield on the same basis jumped to 170%. Both the phenyl radical and the nitrogen di oxide from the nitrobenzene may have been involved. The probable sequence of reactions is given in Scheme IV. Scheme IV NO, U - 0 + N0> NO, + M ------ HNO, + ( f j 0 +O -* O O +.M . JThc gnscs from the reaction of nitrobenzene with ben zene consisted almost entirely of NO, with small amounts of CO, X30, X,, and II,. The NO, fragment of the nitrobenzene molecule apparently ends up chiefly as nitric oxide, either by direct reduction or viaa series of free-radical hydrogen abstractions and decom positions" Ttblo IV Reaction of Nitrobenzene with Renzono* RelativecoDceolmtba* Produel Phenol Nnphlhalcna Biphenyl Dibenzofuran Phenyl ether, hydroxybiphenyl Tcrphcnyl Phenyldibcnr-ofuran Thcnyl diphenyl ether Qimlcrphrnyl Diphcnyldibcnr.ofuran Biphonylyl ether Quinqucpbcnyl Triphcnyldibcncofuran *1nilrobcoitDcbeaifn* 1:1 1:23 i .a 1 0.3 100.0 11.f. X 3.4 100 1 3 4 4 . 4 23 7.3 1.0 6.2 2 1.8 0.3 0.9 0.3 I* vvv ,lAJitkubbuino y bcc,lol&l pressure1 atm, as werea! pyrolyscs described in this article. 1Relative intensity of the parent peaks of components in the low-voltage (7.5 V, un corrcctcd) moss spectra normalized Vobiphenyl - 100. * Mole ratio. NEV 0 3 6 2 3 5 A pffc'wditf I ORGANIC COOLANT DATABOOK T E C H N I C A L PUBLICATION No. AT-1 JU LY , t95B Compitati by: MALCOLM McEWEN MONSANTO CHEM ICAL COMPANY O rganic Cham lcale Division Development Department Lindbergh and Olive Street Road St. Louis 24, M issouri NEV 036236 I f GENERAL PROPERTIES (CHAIN-TYPE POLYPHENYLS) COMPOUND Biphenyl Formula C iiHn Mofoeufor Weqht Mellinq Point c. 154.2 69.050 (2 ) Boilinq Point C . 254.7 (30) Mrllinq Point ` F. 56 (3) Boih* Poir : F 471 ( Terphenyl, o* Torphenyl, m- Tarphenyl, p- CriHir 230.3 56.25 (10) 332 133 610 |: 87.45 (10) 364 189 68/ (; 212.7 (10) 385 415 725 (: Quater phenyl, o.oQuaterphenyl, m.mQuaterphonyl, o.tnQuaterphonyl, p,p- C iiH n 306.4 116 86 90 318 420 (3) 471 520 (3) 245 (3) 167 (3) 195 (3) 604 (3) 780 830 ( 968 Quaterphonyl, m,pS'-phonyl-iM-tarphenyJ 2'-phanyl-i-torphenyl 166 173.7 (3) 331 13) 45?MT"'"* (3j 345 1057 Quinquepheny), Quinquephenyl, p,p,p* Quinquephenyl, p,m,oQuinquephenyl, p.m.p- Quinquephenyl, p,m,mQuinquephenyl, o.m.oQuinquephonyl, jn.m.oQuinquephenyl, p.p.m2,S'-diphonyl-p-terphnyl 2\ 6'-diphenyl-|i-torpli0nyl 2,3'-diphonyl.p-terphenyl C *H 3B2.5 98 392 653 144.5-145,5 (3] 264-66 (194) 155 (198) 155.5-156.5 113-114 (14) 269-70 (9) 277.78 (9) 190-4 (9) 208 | } 737 (3) 792-794 507-11 311 112-14 (14) 235 37 1201 SI 6-1B 530-32 374 81 c H etaphenyl, o,0,0,0Hoiaphenyl, p,p,p.pHexaphenyt, p,b,o,p* Heiaphenyl, Heiaphenyl, p,p,m,p- C mH m 458.6 185 470 185 (9) 365 (3) 677 (3) 365 2\3\5* lnphenyl/7-torphenyl 251-53 (9) 484-88 HepUphenyl, pHeiaphenyl bemene B^'-biphenyllpJ-p-m-p-quinphenyl C .,H n 634.7 545 449.5 (9) 230-32 (9) 1013 (3) 840-42 400, :-(.m. |9) 446-50 745 Oclnphenyl, ml^ '/.f^^'-haiaplitnYlliiphinyl Nonephenyl, m7`,3*,3'',6',&,,-heiephnyI-p-qua1er phenyl Diciphanyl, mUndeetphonyl, mDuodec phenyl, m* Trodeciphenyl, mQualluordeciphenyl, m* Quindeclphcnyl, mSedocphenyl, m- C,,H m CiiH a Cv.H.t C*.H ,* C ,.H ,, C j.H k C mH m ' CnHl C .K - 6I0.7S 686 767 838 914 990 1066 1147 I7IR 348 (9) 166 (3) 318-19 (9) 184 (3) 202 (3) 227 (3 ) 245 (3) 270 (3) 292 (3) 321 (3) 658 331 604-6 363 396 433 473 510 55fl 610 NEV 036237 GENERAL PROPERTIES (ALKYL FOLYPHENYL5) COM POUNO M o th y l b i p h o n y l , 2* M alh y lb ip h o n y ), 3M ethylbiphonyl, 4E t h y l b i p h e n y l , 2* Ethylbiphonyf, 3Elhylbiphcnyl, 4D m athylbphr.nyl, 2,2D i m e t h y l b i p h c n y l , 2 , 3 'D fn elh y lb p lian y l, 2,4*D im elliylbiphefiyl, 3,2'D i m c l h y l h i p h e f i y l , 3 , 3 `D i n ' c t h y l h i p h a n y l , 3,4"* D im e th y lb ip h c n y l, 4,4*D im elhylbiphenyl, 2,4D im elhylbiphanyl, 2,6D im ethylbiphonyl, 3,4D iniolhylbiphenyl, 3,5P ro p o n y lb ip h c n y l, 2Tiim cthylbiphenyl. 2.4,6P ro p y lb ip h en y l, 2Propylbiphenyl, 3P r e p y l h t p h e n y l , 4* liopropylbphehyl, 2liopropylbphenyl, 3Itopropylbiphenyl, 4lio p ro p y lb ip h e n y l. M ix tu r 3 ft 4 n-Bulylbiphonyl, 2Sec-Butylbiphenyl, 2tert-Butylbiphenyl, 2terl-R utylbipficnyl. 4t e t i a m e t h y l b i p h e n y l , 7 . 2 ' , 5 , 5 't e t i a m e t h y l b i p h e n y l , 2 , 2 ' 16 ,6* D i-ethylbiphenyl, 2,2'D i- e th y lb lp h o n y l, 4.4** liopropylbiphenvl, 2-melhyl-5A rny lb ip h en y l H eiam ethylbiphenyt F orm ulo CiiH , C m H ii Ci,H , C ,.H ,, C ,,H m C iiH i, C iH i* C icH ii C kH u C rH *, C ,.H ,, M olecular W eight 168.2 182.3 182.3 182.3 (94.3 196.3 196.3 196.3 210.3 210.3 224.3 234.3 M elting Point C . o (3) 4 (3) 47 |3 ) -- 6 (3) - 2 7 (3) 34 (31 18 ( 3 ) Liq- 0 ) Liq. (3 ) Boiling Point CC . 255 (3) 272 (3) 767 (3) 266 (3) 284 (31 283 (3) 264 (3) 270 (3) 274 (3) 7 (3) 16 (3 ) 121 m Liq. . 0 ) Liq. (3) 33 (3) 12 (3 ) 285 (3) ?cn (3) 292 (3) 264 (3) 263 (31 282 (3) 274 (31 -- 12 (31 Liq. (3) 40 (31 24 (3) -- 54 (18) - 1 3 (3) 8 (3) 21 13) 53 (3) 67 (3) 1 (3) Liq. (3) 0 (3) 221 (31 277 (31 270 (3) 294 (3) 303 (3) 295 (14] 291 (3 ) 282 (3) 282 (3) 285 (3) 274 (3) 313 (3) 269 | ] | 30S 320 (3) M elting Point F. 32 40 117 21 -- 17 94 64 Liq. Liq. 81 45 60 250 Liq. Liq. 91 II II Liq. 104 76 -- 65 8 46 70 177 152 173 Liq. 32 (751 176 Bo P K A 5 5 5 5 5 5i 5 5: r 5' 5' 5! 51 51 55*. 4] 5] 51 Si 51 Si 55 54 54 SA - 52 53 51 tf tr NEV 03623 GENERAL PROPERTIES (ALKYL POLYPHENYLS) COMPOUND Hexylbiplianyl, 2 1 ? )Hatylbiphonyl, 3 | ? } Dlliopropylhiohonyl (miind Unm>.ri) Di-n-Uutylbiphmyl, 4,4* -- Di-(*c-ButyIblpli*nyl, 4,4'- Di-IrH-Piitylhiphinyl. 4,4 Di>trrt-Amyll>iptionyl, 4,4*Dibarylbiphenyl Tiiluirylfiijifinnyl O-lerpImnyl, V-inftthyl T*ir->lunyl. 4 vinyl* Tuiplixnyl, 3\6'-difnrlfiyl<t-Tt>ffjlipnyl, iiopropyl* ii.Tniphnnyl, 4-hutylm-Tctplioiiyl, S'-inrlhyl* m-1 orphany1, 4-propylm-T*iphnnyl, Iiopropyl* m-Torp honyl. 4,4*\5*-1rimathyl m-Torphan>l, M -Torphony!, m.iyl (? ) nt-Tnrplitnyl, 4-n-oelylni-Terptirnyl, 4.4''-JimBtliyl-5'toIyl p-Tolphanyl, 2-mathylp-Terphonyl, 3-metIiyl/Torphanyl, 4 -mathylff'Torphanyl, 2,5-dimethyl* p-Tarphonyl, 2*,5,-dimaljiylp-Tarphnnyl, 4,,4,,-dimo!hyl* p-Tarphonyl, 2,2,,t5,5"*tatramthyl* p.Ter phenyl, dinlhylp-Torphnnyl, 4 ,`'-dlcyrlohryl- o.o-quafirphenyl, 7,2m*dlmathyl o.o-quilarphenyl, 4t4 ",*dimathyl p,p*qutarph?nvl. 4,4"'-diniolhyl ]'-phinyl fi-lrt|ilienyl, 2-mothyl 2*phanyI-p-torptmnyl, J'^ -d in u lh y l p-haaephanyl, 4 ,4 ',,,-dlm athvl Formula CuHit C*H* CnHw C.Hi, CrHi* CuH,, C :H n C.H,, CnHie Ci:Htt CitHu Ct.HM C H :i C..H CmHm CjtHi* CcHu CH b C mH u C uHb CwHi CpH k Molecular W e lrj tit 238.4 266.4 294.5 322.5 406.7 244.3 256.3 253.3 272.4 284.4 244.3 272.4 300.4 342.5 348.5 244.3 258.3 286.4 394.6 334.4 320.4 334.4 360.4 Malting Point C. -- 38 (3) - 4 0 (3) -3 1 (IB) 50 (3) Llq. (3) . I2D (?) Liq. (3) -- 30 -- 23 10? (3) < I ? J _ 130 (3) 44 (3) -8 1(7 (3) .6 5 (3) 100 l^ -t (?) 92. (3) 16? (3) 207 (3) 15? (3) 183 (3) 24? (31 12 (3 ) 260 (? ) II? (3) M3 ( ? ) 334 .(3) 130 (197) 157 (IM ) 162-63 (?) Boiling Point c. 318 (3 ) 322 (3 ) 330 (18) 384 (3) 363 (3 ) 326 (? ) 360 (3) 375 436 150=" (31 193,5*0.01 ( 3 ) lyflo.iiwM ( 3 | 161,mra (3) 394 (3 ) 406 (3 ) 415 2B0;t,,ni" ( 193) 270:.Bmcu ( 9 ) Malting Point OF. -- 36 -- 40 -- 74 137 Uq. 263 Liq. -- 22 ( 1 | -- ? (3) 228 111 266 112 20 (3 ) 243 14? 217 (35) 330-40 197 337 405 31? 361 431 233 536 236 236 633 266 315 324-25 Soiling Point F. 604 611 676 723 685 M9 630 707 815 (3) 307 *"," a 4 55.5'*" 3S2-.nu: 329imu 741 762 77? [75| 53 E39 (9 ) 036239 UE* .* !* ,i 1 i iI I I i GENERAL PROPERTIES (EUTECTIC MIXTURES) MIXTURE COMPOSITION Piph*rrYl/nopMlialen D^-Kcnyl.'o-lpiphonyl Diphciiyl/iii-lofpSonyl Riphenyl/ji-t "phenyl m . I' lp h i-n y l/fi-l n fp h ifty l ni-lcrplicnyl/^-teipticnyl <-l<r.*pltc:ty!//.trrplifnyl BpKrnyljSflntowAi R nap!-iVilinfl/i>-l5rphonyl B>phnyl/rn-torphenyl/n0p(i|}ialsn CipSanyl/m-lerpticnyl/phananthrcna ripKf nyi.'naphlhrtleno'phininlliron* Bptpnyi;t-litpSeny!/n.iphlliol#n# Blphti)T/o-lrrplitnyl|phon< iri|l)ron B'plrn-|!Vi>lc(phrnyl/ni-loiphanyl B iphenyl'a 1ipli?nyl//>*lcrplionyl ri-tcrptirnyl.'/M-lfiphrr.ylfnapIrihalof) if.yV m -iirp I.e o yl.'p fico an llircn Irrph.-nyl'm-terphcnyl/'Morplicnyl ii.toiph?py!/noplilVilcnr/plen*nllirena fcrf-Sm yt,'n phllu!1r n(\f/i-1ctplionyl Liquid Competition (mol*/*) t il 1 2nd 3rd 57 43 40.5 59.5 4S 55 97.1 2.9 33.7 66.3 95.65 4.35 98.15 1.55 91.7 8.3 33.7 66.3 41.0 42.5 42.6 31.2 31.9 30.9 40.2 51.9 53.2 65.8 53.4 65.8 29.0 30.9 37.0 47.8 48.7 47.5 59.2 24.5 25.2 33.5 24.6 33.5 30.0 26.6 20.4 21.0 19.4 21.6 0 .6 23.6 21.6 0.7 22.0 0.7 Vapor Compaction (mol%) li t 2nd 3rd 36.6 63.4 79.1 20.9 20.9 79.1 87.3 12.7 M.P. C . 39.5 23 42 67.8 29.3 85.5 55.75 69 29.2 8.P. C . 234.S 286.5 345.5 263 M.P. F . 10] 73.4 108 154 85 185-9 132.2 157 85 B.P. *>F. 454 547 654 505 Riferonc* (17) (17) (1) (10) (17) (10) (10) (70) (17) 3B.2 85.4 33.2 37.3 71.8 74.1 79.3 15.2 61.7 79,1 IV ) 13.0 I.B 5.3 64.4 9.3 20.3 21.3 21.0 3.3 14.9 2 0 .6 79.9 8 6 .8 60.0 9.3 2.4 53.4 7.9 4.6 0.08 81.5 23.4 0.3 5.8 0.04 23.4 25.3 25.4 10.9 11.9 10.5 22.7 15.3 16.6 28.9 16.9 28.9 250 288 242.5 262 294 297.5 287 279 344 346 275.5 263 75 78 78 51 53 51 73 59 62 84 62 84 482 550 468 504 561 563 549 514 651 655 528 505 (17) (17) (17) (17) (17) (17) (17) ('7) (17) (17) f 17) (17) 036240