Document aDrkke6ywgzjqo2gK2G7vGZmy

Patent Book Dayton Case 1662 United States Patent Office P, 7;, 2-f0,l*9c^ PeUnted Jan. 20, 1959t^7 12 the liberated acid. Usually from one to two moles of the 1,171,It* alkali meial hydroxide per mole of the furfuryl or tetri* ' hydrofurfuryl alcohol h used An excess of sodium hy ETHERS OF THE FUltAN lull) droxide a not detrimental to the reaction, whereat a molar * quantity which it substantially lets than that of the al Drri, Dio ton, OUo, irtpir to Mottxaare cohol u conducive to lower yield* of ether product. Chemical Company, Si, Uniit, Mo, o eerpererioa ef Delaware The reaction lime and temperature appears to have little, if any, effect on the nature of ihc ether product, No Drawing. Application November M, IMS StrUt No. 55PJ5* i Although a primarily formed mono-ether will react wuh ' another mole ol furfuryl or tctrahytimfurfuryl alcohol ro 4 Oilmt. (a*--M7J) yield e di-elhcr, higher temperature* or continued heal ing do not aulBce in effecting substantia) conversion to (lie di-elhcr. An execs* of amt of said alcohol* over that required for iwpfecamaat of aim chlorine atom should This invention relate! to ethers. and more particularly 14 he present in order to obtain any substantial formanon provide! new ond valuable ethen of chiorophenoli end of tb die-ether. Whether the reactant quantities present iScoho'j of llie furan senes, method* of prepsrrei tha arc thorn which favor rnono-*ubiiiutKM (excess ot tn- tunc, ond dielectric composition* oomprinog the now. chlorobenzene) or whether the properties ere tucli a* to According to (he invention there ere provided ethen M favor di-*ubMittmon (nee** of one of usd alcohols), of it* formula ether formation occurs after healing at temperature of from 100* C. to 2J0* C.. end preferably of from 125* C. to 200* C. for a time of, say, several hours to a day. The progress of the reaction can be generally followed u by noting the alkalinity or the quantity of water being formed. While provision for removal of water during in r `.id) R n (elected from tho dut consoling of the the reaction is not required, better yields of ether product furfuryl end the teirahydrofurfuryl rodicol* end X a e- .and a ready means of determining reaction rate era Irntd from (he cleM comlitinf of chlonn* ond lh redl- afforded by operating it a reaction vernal which a ,il --0--R gg equipped with some water-removing facility, e. g,, a water I hive found (hit compounds hsviaj (he above tor- trap or take-off head. nulla ire readily prepared by heetuii inehlorobeueno Although, as above stated, reaction or the tnchloro- u)i lurfuryl or teirahydrofurfuryl alephof in (he pres- heniene and the furfuryl or tetrahydrefurfuryi alcohol cnee ol on alkali mtUl hydroxide, i, c,, sodium, potoxtium can be so directed as to result in a preponderance of either or Inhinm hydroxide. gg mono- or di-ether formation, generally the product con One clou of compound! of (he above formula include! tains a mixture of the two to varying proportion). These Hit 2-(dichlorophenoxymcihyl)rurani or the l-(dichlompluttosymh>l>tetrahydra(ur*nt, e- |, g-aJ-diehtoro- can he readily separated from each other aod from any unreacted Inula! material and/or from any diluent by pfu.no*yme(hyl 1 furan, 2- (2,6- dichioropheiKUyincthyl )- fractional distillation. White the present condensation liinn. 2 (3.4 - dichtorophenoiymrlhyl jlctrahydrufurea, 40 reaction Hies place iu tire absence of any extraneous sol 2-(2.<-dieftlorophenoxymethyl Hetrshydrofureo, etc vent or diluent, reaction may be facilitated by operating Another dais oC compound* having the above formula in the presence of an men liquid *a solvent or diluent, -nj prepared according to the invention by (Tie con- e. g.. toluene, xylene, ate. iirnianon of a trichlocobeniene with furfury1 or tetrehy- The present ethers are stable, rather high-bnling eom- Jrefurfuryl alcohol include! the M*(furfuryfoxy)chlore. 41 pounds whmh arc useful for a variety of industrial and h-nienci and [he bo(ietrehydroforfiirylo*y)chlocobeo- agncullura) purposes, e. g.. as solvents for polymeric ma 'cart. a. g. 2.2-hh(tctrahydrofurfuryfoxy)chlorohenttnc, terials and as biological toxicants. They are particularly 1 S-hisllurfuryloxy iehlorobewene, M bt*(tetrahydro- valuable aa liquid dielectric*, and are very advantageously (atfnryloxyl-chlorbbenmw, 2J - bu(ietrahydrafurfury[- employed as liquid intpregnants in capacitor aad cable y IcMwobtnrene, 2-Mw*( toriurykuy )cbtorobe*oe, 2, ** manufacture, aa truatarmer coolants, and in the fibrtca- M'tsflurfnrylooylditorobeMene, etc. ioa Of twitch pear. FomottM of the ptnaeni ethen occur* by replacement Charuetaristia of tha present chloro-tthcn are such as af cue r too of the chlorine atoms of the tnehloroben- to render them particularly valuable aa unpregnant* lor rvet by oat or two furfuryloxy radicals. The replace- cellutaric iasulaiing materials. It is known m the art incat rtoetton lakes ptace readily by heating the tnehloro- that impregnation of cellulouc materials, e g, wood pulp tuanoa with furfuryl or ictrehydrofurfiiryi alcohol in paper, cotton, cotton fabric, cellulose acetate fibers and he presence of ait a) Lilt metal hydroxide. Sine* tha textile*, by certain liquid dielectrics provides an insulat rt.iciion may reeull in the replacement of more titan one ing material having a dielectric conitint which n much chlorine atom, when desiring preponderance of tha higher (hen that of eiiher (he celluloaic material before Hihuiiuiion of only one chlorine atom by lb* furfuryloxy M impregnation or of (he liquid dielectric. Some of the first icirahydrofurfuryioxy radical, it a federally advisable liquids used for this purpose were mineral oils, (he di to uve a large exeesi of the tncblorobaoxen*. On ilia electric strength of oil impregnated paper having been utber hand, when the mufor product to be obtained t* tha reported by Bailey (Radio Engineering, 17, ]7. 35 dcil cr, an excess of the furfuryl or tetrehydrofurfuryl (1*17)) to be IS limes as high as tliai of (he oil alone. echo) ii cdvuninyeously used. The quantity of alkali metal However, because mineral oils are readily oxidised, their li-itevide employed n alto somewhat controlltn| in the usefulness ai insulating media and as impregnating agents >ipc of product obtained. Hydrofcn chloride a Itber- for cefiutosic materials hat bean limited in that exposure tied m tt\t replacement of the nuclear chlorine by the to air, sunlight or moisture often tends to gas foimitioa. furiuryicxy or tetrahydtofutfuryloxy moiety of the el- gaseous ionization and fornterioa of wax. These changes <ohol sod io order to obtain good yield* of either the T affect power factor stability. uoco-eihcr or the di-ether, there should be present in Although wood pulp paper, alone, tut good tniulat- the reaction mixture enough of tha elknii to aeutfalire - iaf properties, it it alio affected by exposure to air. ?ix- MQNS 201742 I 9,870,160 34 clI'-'v .1: higher icmperaiurcs While the rate of me distilled tetrahydrofurfuryl alcohol, B, P. 75' C-80* . ,r . ,1 iklnoMlioii is reduced by impregnating the in- C / 20-25 mm, 3 moles (120 g ) of sodium hydroxide .'] *nli oil tins was of hide ndvinl.igc hs nniu.1 md 250 g of toli'cm The mixture was bejted to 152* >*1 uinpiy, ike ill reported to other impr-un il P will,m .iboiit 2 0 hours ,ind at fium Hi' C to l|(j' 1 ,n,v 1111 til.irly the highly chlorinated aromatic & C for 5 hours During the heating period 3ft tc of imir \ Jlu-c iiuk'n.ik hove dielectric vtreiipihv w.iler anil 140 g of toluene was col let ml After si . . n.' iiijjicr than ihove of tiic mineral oils In addi- lowing ihe revuliing reaction mixtuie to cool, it wjt neu a tiiej nc non (l.imm.iolc and more vi ihle to iliv m- lrilized to phenolpijtthjlcin hy treatment with 18 ml of fmt of ,iir, montn.c atul liglu Howe'ir, thi'ii gen- 11'men!ruled livdrochionc acid (equal In 0 22 mole of c 1 iirtuy hit b-cn sunuwh d hampered in 1I1.U under 10 HCIf ,`nd iliJtiicil with 5u0 ml of water, whereupon , - 'pri ,`ine leni|ierin ict and voliagct dieoinpotition nivvi 01 the piecipttntcd sodium chloride went into snju i. t ud big),it .hiotmiied hydrocarbons is m.uufcvicd non The whole was then diluted w uh about 700 ml 1. (';n;eti el.lort. e it evolved, and ibis attacks not only of ether, and filtered. After allowing the filtrate to strin 'c p.ip.r ttl.nh li.ij hcea impregnated but nko llte nsci.il fv Hie organic laver which formed was separated and po; ions ol llie ea[i.icuor Id ihe .uiueouv layer was washed with ether. The ether ti f*1 c prctcti.il nrrn ided cihcrt ere high-boning m .hrnls uact ihue obtained was combined with the Art! organic .(''ich poMcw liiyh rettttinuet and low power factors later, and the combined product was washed with about T i. - Viihimy 10 hign lensperalinct is evidenced by little lot) ml of water and 150 ml. of brine. Distillation of r.o change in potver factor readings after heating for .be washed, orange liquid Ibuv obtained gave (i) 549.4 f-, loin 11 1 nc * C Thor stability is further illustrated to of the sumtantially pure 2-(dichlorophenoaymcthyt). 1 c ,1111 . f f .1 - It r.vivm niiv, whith indicates ficcdom tetrahydrofuran, B. P. I30*-I30* C/0 4-1.0 tpm and 1 rn.it combining urns which would be prevent if dccontjv-11,1' 1 of he Cl? 1. s hid octtirieu The prevent ethers (II) 41 | g of the diether, huftelrahydro.'urfuryloxy). chlorobenzene. 11. P. 192-204' C/0 8-1 0 mm. A mr- rent no bqi.id at low temperatures, whereby there 11 row cut of (f) B. P. 134-140* C./0.6-0 8 mm., analyzed nvni.irit ,1 (here,nr in dielectric constant due to freezing *6 as follows: of [1 c (lipokv 11 c .iltovc cli.ir.ieicri'tics Ihtiv speak for eminent vuilahi'uj of these ciliciv av impregnating agents for eellnloMC | Fw.iut | r,,[ca i", I < t',,iti.i't,ii, piiirmlv md .in embodiment of the prevent invention iv ihe provision of unproved celltilosie tnvulanng agents M )vr<v,|l C................................................. JVrrwnl II ........................................ comm tunc poroiiv ntalcnalv derived from cellulose, e g, Pffwnt Cl ........................... ... . SI 11 1 < us A!, -J tn I :,a pulps iinuv, textiles or papers derived front wood, eot- inn nr linen, whtth porous products have been imprepn icd with viui rihcrs A noteworthy feature of the The diether fraction, 1 e., (II) analysed as follows prevent nvention is the provision of a capacitor compris ing a p ir of electrodes and an insulating agent associated I Fw.ni I S-xk-cl (or CtdluUO. with each of ilic electrodes and isolating them from caeh n.licr v.mi instil,mn agent comprising a eelluiosic materu! mtprcgnaied wuh the present ethers In mder (0 more particularly describe this feature of IVivfiJ ' .......... t'i H ............................. ! >VTcrrt Cl ................................................ ! 01 <*r H 114 t.i H I| I] 4 the invention, details of the construction of n paper capncuor .ire set foitlt here by way of illustration Three sheets of tissue piper (preferably Kraft capacitor iKvi.ci are stacked upon each other, and n thin aluminum foil (about 0 0003" in thickness) is laid on tlic top sheet ' of 1 issuer The foil is then covered with three more sheets of the tissue and another sheet of the foil is placed there on so that the two sheets of metal foil are separated from each other hv the tissues On the second metal sheet Based on the charged 1.2,4-tnchiorobenzcne there was obtained 89 4 percent conversion 10 mono-ether and 5 0 percent to di-ethcr. The 2-(dichlorophcnoxymethylltetrahydrofuran thus obtained was found to have a vol ume resistivity of 55X10* ohm-cm, at 25* C. a pour point of minus 35* C.. and the following dielectnc con stant and power factor values at ihe frequencies and temperature noted below: there arc stacked three more sheets of said tissue and the vi.iek of alternating layers of metal foil and tissues thus -------------------------------------i------------------------- ;---------------------- DkMrk Coaaunc [ boner rmw Tew Fnomaor I I________ olii.uned it wound into a cylindrical roll. This is placed m .1 container, and at this potnl electrical connecting j **C. HWC Z1*C I |CU* c me mv, r g.. wire or bar conductors, depending upon the u PrrcrW ! Pimar rtrroraf I fVrtnf me of ihe assembly, may be connected to the metal foils Mkc . .................... HO I 1) lit1 1; in known manner After drying, prcferthly in n heated iiae.............................. 11 eel to vacuum oven one or more of the present ethers is added 10 111 c container in a quantity sufficient to impregnate The tow power factor values at both test frequencies and morpngh!) the paper content thereof. They container 11 at both tot temperatures show very good siabibi) of the then seated 0 2-(dichiorpplienoxymethyl)lctrahydrofuran Power ca Alirrn mvcly, ami particularly in the manufacture of pacitors in which the present ether tv employed for im vm.ill resistors which for the sake of economy are housed pregnating the paper are particular usetul in thsi ihi't in paner lubes rather lhan in leak-proof containers, the may be used without freezing of the dipoles at tempera tissue paper is impregnated with the present ethers previ tares which approximate the low pour potnl of this ether ous to interleaving with the mctul fotl in the manner de * Testing ot (II). 1 e, ihe btsfteirahydrofurfurytoxyl- scribed above " chlorobenzene, also gave good results, the dielectric eon- The invention is further illustrated but not limned hy smnt and power factor value! of (11) being found to be the following examples 10 5 and I.l$ respectively at 100 kc. and 25* C. Be Exam pie l cause (11) has a solidifying point which is approximately 79 that of (j), a mixture of (I) and (ii) may be employed 1 cirjhydrnfurfuryi alcohol w reacted with tnchloro- as the impregnating agent tn the preparation of paper benzene as follows, capacitors at tranaformer coolants. Tn n 2 liter 3-ncck fl.ivk ept ipperi with stirrer, column and Dean-Mark trap there was charged 2.5 moles (454 Example 2 i) of 1,2,4-inchloroberuene, 3.75 moles (383 g.) of re- 76 Thu example describe* the reaction of 1,2,4-inchloro- 1 1 I, 1 l l I MONS 201743 2,670,106 5C . Hi. icii jl-vdioftirfuryl alcohol mine greater The 2-(diehloroplienoxymclhyl) furan is also advan y in oi ihan those employed in Example tageously employed as impregnating agent in the manu i, iiniiii. .onusiing of 6 75 moles (1,220 g ) of facture of paper capaeitorx ,i oN.ii, ,,ni. K) 15 niolo (1.055 ) of said alco- Although the present ethers are particularly valuable , t, ',l\ ('51. ) of milium hydroxide and 200 ml, C as impregnating agents for cellulosic materials adapted t nit In ill'll ,i 1 ,i icmpcrjlure Of MO-172* C for use as dielectrics, because of their very good elec , 7 '.mini no,,e colliding 154 ml Of water of trical properties, their thermal stability and their ability [, ,.,,or n ! ' it tonned The re.ienon mixture waj lu remain liquid al tow temperatures they arc of gen - 5 ,ncd with I liter of water and neutralized wuh eral utility as liquid dielectrics They are likewise very i nto'L of nydrogen chloride The organic layer If) useful os functional fluids, e. g,, as heat-transfer media v1 .pparaird w.is washed with water and brine and and as hydraulic fluids - i ..iK.i'-ne to j'lienolphtli.ilcin in order to remove any . c-,s wli ill might shil he present. After subsequent Another significant property of the present ethers com prises their sotvem characteristics. The mono-ether Of rCi, jiizmp, filtering and healing of the filtrate at 150' Examples 1 and 2. for example, u 1 powerful solvent C ` y nun in order to remove water and other low ir. for polyvinyl chloride, polystyrene, the polyethylene sul 'o,n' mt.ci.ils tlic residue was fractionated to get fides and various nitrogen-containing polymeric materi ,;_t p pf (I) tlic snhtrantially pt.re 2-(diclilorophcnoxy als Since tlic piescnt ethers are very stable maicnati, - ii j,)icir linilroluran, It P 135-142* C/0 6-0 7 mm they arc paruculaily useful in processes which involve r wing Si 3H% O, 4 96% H. and 28 07% Cl, and extrusion of a polymer solution into a non-solvent, e g , i- ; of (Hi his(ieir.divdiofurfuryloxy)chlorobenrcne, 20 in the manufacture of synthetic fibers , p no-2Oil* C /f) K mm. analyzing 61 00% C. 6 73% What 1 claim tv- II and II 44% Cl Dated on Hie charged 1,2.4-iri- < An ether selected from the class consisting of 2- c .lurobcn/ene, there was obtained 89 5 percent convey (dichlorophcnoxymcthyl I(11 ran, 2 - fdichloraphcrtoxy- , an io the mono-ctltcr and 3 7 percent to the dl-elher. mcthyl hetrahydrofuran, and bis(tctrahydrofurfuryloxy)- Exampl,e J, 'a cltloroben7cne 2. 2-(dichtorophcnoxymcthy|)/uran , ,-nuiurc consumip of 9 motc.x (882 g ) of furfuryl 3 2-(dichIorophenosymethyl)lclra!iydrofuran . co'iol 6 moles I 1086 ) of 1 2,4-inchlorobcnscne, 9 3 4 Bis(lctrahydrofurfuryioxy)cblorobenzcne r,,!is (f-t ) of potassium hydroxide and E50 ml of 11, ure was charged io a 5-liicr, 4-necl. flask equipped go References Cited m the file of this patent i ,u ,i surrer, Ihermomclcr and column bearing a head UNI I ED STATES PATENTS ci rpmnv.d of condensed vapors The mixture was ' , ct! svi:11 snmng, for about I! 5 hours at a pot tern* 2.041.594 Clark............ ........ 1916 p , ,,arc of fiom I'0* C io 159* C During the first 2,072.797 Clark *............ ... 1937 - m hours of heating ihere was collected 191 cc. of water, jj 2,165,813 Prutlon ....___ _ 1919 u,m hcjnng w,is discontinued, about 2 liters of water 2.170,782 Clark .................... 1939 ' s,.i' udded to die reaction mixture, and the whole was 2,277.359 Schirm__________ 1942 1 .led After allowing the filtrate to stratify, the or- 2.418,820 Coggins_________ 1947 yr>i layer whicli formed was separated and washed with 2.456,181 Clark ...________ 1948 v.;?' Water was removed from jhc washed material 40 2,475,801 Novolny________ _________ July 12, 1949 b healing lo 60* C 31 J pressure of JO-35 mm of mer- 2,535,690 Miller___________ 1950 iary Subsequent distillation of the heated material gave 2,666,065 Swadcsh________ 1954 i`9 f of the substantially pure 2-(dichlorophenoxy- 2,711,498 Robinson_______ 1955 rciti)i|furan, D P 80* C.-II5* C/O.I-OJ mm., and ir-iiins at follows: g r*un4 CCittUkd'CltioOr OTHER REFERENCES Beilslem, vol, 6, page 4J2 (1923). 1 l C................................................ U4.xM1* aanid ia HONS 201744