Àug- 21, 1951 A. P. DUNLOP Erm. 2,564,835 HYDROGENATED FURFURYL ALCOHOL PARTIAL POLYMERS v Filed May 4, 1949 Y Furfuryl Alcohol l ì ~ " ­ Polymerization I , _ l Disiil'laiion l r-I-i 1 _ Furfurylu .o Polymers *___* Alcohol Hydrogenotìon „ l | Dislìl'lo'ríon î'L-j y Use os vvis Telrahydro- Polymers furfuryl ‘ Alcohol Polymer Fractions - Inventors: Andrew P.' Dunlop and Poul R.„Stoul nBy. Aghenl Patented Aug. 21, 1951 2,564,835 UNITED STATES QF HYDRQGENATEII ALCOHOL' PARTI‘AE POIìYME-RS* Andrew.v P.: DunlopiRiversidaandf PauLR. Stout,v Chicagmz IlLkv assignors to~The Quaker Oats Company, Chicago, Ill.„»a..corporation of NewA Jersey AppIicatiorrMay; 4„ 1949,` S'erîa'líNo.~ 91,316Á llll. GlafimSi (Cl. MWF-8.8.5). 2. This- invention relates to`v hydrogenated. fur-v` cìum~ chloride,~. ferrie chloride, boron> fluoride.-k f-uryl- alcohol partial» polymers and Ito' the methods»y iodine,> etc.. During; ‘ resiniñcation the . furfuryl of preparing the same. These hydrogenated; alcohol undergoes chemical and physicalfchan_ges` polymers are especially/‘adapted for usefinf-thef to.H yield­ az mixture.-y of fusible.. condensation preparation of- nevvV synthetic» resinousrcomposi‘ -. products.. tions and they` arealso-usefu'l as plasti'cizers .par-1 Partialfresiniñcationof furfuryl alcohol. as de.-` ticularly as plasticizerspfonfuran and vinyl type scribedzabovezis carried out. until the resulting` resinsv with which they are compatible. As used resinous; product .has the. desired viscosity. For herein the term furanresins appliessto: resins exam-ple;l a. suitable,­` partially. resinifìed, _furfuryl derivedfrom furan- compounds and' >isnot‘to be 10 alcohol; resinA formed-¿by heat alone isobtained limitedA to Y resins derivedffromiu-ran itself'. byy kre?luxling,` furfuryl alcohol- to». al :viscous Íresin Certain­ resins or polymers preparedy from having, for. example, a; viscosityV of. ab<:>.ui'„.100r furans and from vinyl compoundsV possess cent‘rpoisesat 25?’ G.` Afsuitable partially-resina? manyv desirable propertiesincluding rImechanicall lied furfuryl- alcoholf-resin.. formed; by the. aid.. strength’ and'chemical resistance; however; ‘with ofi a». catalystfis l obtainedi- by 'heating -furfuryl age they tend to become brittle.v To overcome` alcohol-¿ini an. open . vessel in the., presencen ofÀ` this latter deficiency certainconstituents calledl phosphoric; acid to a .viscous resin having,` for. plasticizersare added.` Many7V of Vthese p_lasticizers4 exam-ple;v a viscosity. of l about .'2-,00‘0--centipoisesr are> costly, are diû'icultto incorporateinto'the al'f;.25,"­V Q. A: suitable partially» resiniñed-.fur composition by milling-because of incompatibility 20 furyl; alcohol> resin may» be formed by- the. with the resin. and in addition, some require a use fof; aacatalyst „alone i by` adding»ç boron;l fluoride,> more or lessy extended'aging period forrtheV de: dissolved in methanol to furfuryl. alcol'iolvthen` velopmentof maximum plasticity. Others; even; allowingfthe; resulting; mixture tof stand;V at about though they are sufficiently compatible initially; 20d-1G.. untila viscousfresin. having-„for example, with the resin givingwrise; tof,improvedcelasticity; 25 a:_vis.cosity>of :about 1,000­ centipoiseszat» 25.?` C.. is. are not suitable since the_^improvement­ obtained' obtained;A When a resin ofthe-desired viscosity-.isg is lost‘when the resin is converted'into‘its‘ñnal' obtained- fthe;` catalystî is l neutralized-.with e sodiumA` state. This causesthev components of the mix hydroxide-.vn y ture to separate With consequent impairment of Weîhave'ßfound ¿thats these-«resins ­ when; hydrav elastic properties... 3,05 genated produce plasticizersfWhíChcpOSsess; many It is an object of the present' invention to pro desirable; C_Lrialìties` including;y »compatibility'~ with vide a new class of plasticizers for furan resins iuran resìns.z..vinylftimeqresinsä.andiotheizgresinss and vinyl type resins whichplasticizers are effec andîlthey-.have ai 10W/_melting point., General-ly;v tive while at the same timer-they avoid the prin- . theyaregliquid or sof-t at lovntemperatures render:-VY cipal objections to the plasticizers previously ingfgthenrgcapable fof being; worked Viii-to 'rr-resins fat; available. ordinarystemperaturesßwith conventionabapnarae: These and other? objects »are obtained by pre tusxandtthey pßßsessa lovv.-Y vapor lpressure.:` paring plasticizers comprising­ hydrogenating, In carrying out the presenilzfínvention .pantiallyg either completely or incompletely, a partially polymerized furfuryl alcoholvprepared according polymerizedfurfuryl. alcohol. The partially. D015@ 40; to the method describedlinhour co-pending ap merized furfuryl alcohol` used inthepresent` inf'v p1ieation~,_.or=..by any. other. suitable. meansiís vention. isa partially resiniñed'furfluryl alcohol> hydrogenatedlin the.. presence of la.. catalyst., of any desired viscosity-short ofthegelstagesand Ria-neynickebplatinum, or. palladium, are .suit` may be prepared by` any of) the known»methods;„l able.. Iiî..desire_d thehydrogenation may; bacon-Í however., we. preferA the methods describeldlinour 45; ducted inthe presenceot a~suitable„»solvent. Fol», co,­pending application, Serial' No. v758,503."íîleltl` lowingç.- hydrogenatiom, the product.ì and catalyst July 2, 1947. mayzbeà separated îbyevilltratiorn.,centrifugation or. Partial resiniflcation ofV furfuryl-alcohoh asis well known, may be. effected by heatlalone, _cata- evaporation`dopant;ationL or-and».A distillation; anyK ' solvent used.» removed.' lysts alone, or by heat and catalysts.` Suitable. When; `furfuryl alcohol .isf-partially. polymerized catalysts which may be usedI are mineral acids,Iv a. complex :mixture consistingëoff: unchangedfiuw organic carboxylic acids and sulfonic acids,A acidic! furyL alcoholì. dimer; trimer:V andiv highec- polyf‘ salts, or ñnely divided metals. vSpecific examples. merio, forms-»off furfuryl `alcohol is~~,obtained­.y »v It of suitable catalysts are: phosphoric acid, sulfuric. a. product-«ot` a more or lesssdeiìnite-fmolecu-lan acid, oxalic acid,> paratoluenesulfonic. acid,l cal.-Í sìzeis desired thefmixtureof polymersobtainedfin 2,564,835 3 proximately equal to that of the starting mate accordance with the method herein described can be separated into appropriate fractions by frac rial and possessed a green-red dichroism. tional distillation, preferably under reduced pres Example 2 sure. Since molecular size and compatibility are A mixture of 303 parts of a furfuryl alcohol related to a certain extent, fractionation makes 6 acid-catalyzed polymer having a pH of 6.3, mois it possible to select a fraction which has the de ture 6% and a viscosity of about 1300 centipoises sired compatibility with the resin used. A plas at 25° C., 30 parts of Raney nickel catalyst and ticizer consisting of large molecular size poly 280 parts of isopropyl alcohol was hydrogenated mers possesses a 10W vapor pressure, consequent at 190°-225° C. and a pressure of 1400-1600 pounds ly for some uses such a fraction is particularly 10 per square inch. ' 5.8 parts of hydrogen was taken desirable. As one example, such a plasticizer is_ up Aintwo hours which represented hydrogenation preferred when used in thin films thus avoiding of somewhat less than 49 percent of the furanoid execessive losses therefrom through evaporation. unsaturation originally present in the polymer. In addition to separating the mixture into frac tions according to molecular size we have found 15 I Example 3 it possible to prepare a colorless or nearly color In this example various mixtures which had less plasticizer by a process involving fractionalv been prepared containing l'l-'lO percent of the distillation. For best results the mixture should hydrogenated product of Example 1 and the re be distilled under vacuum. The distillate soI mainder being the starting material of Example obtained is hydrogenated and then redistilled un 20 1 were cured at1180° C. in the absence of any der vacuum. If a small amount of color can added catalyst. The flexibility of the cured be tolerated the first distillation step may be product varied directly with the amount of hy eliminated. f drogenated product added. All cured samples The figure is a flow sheet of the polymeriza were insoluble in cold aqueous sodium hydroxide, tion-hydrogenation process. An inspection of 25 ethyl ether and carbon tetrachloride. this diagram discloses that the process may be varied in that the polymerized product may be VEzzcample 4 hydrogenated immediately after polymerization A mixture of 840 parts of a furfuryl alcohol and then distilled or the distillation may precede acid-catalyzed partial polymer, the pH of which the hydrogenation step. For practical reasons, 30 had been adjusted to 6.5 with triethanolamine, the latter method is preferred because the re moisture of 10 percent, and having a viscosity of moval of unchanged furfuryl alcohol from the about 2000 centipoises at 25° C., and 114 parts of mixture permits the hydrogenation of a greater Raney nickel catalyst was hydrogenated at quantity of partial polymer per charge and the 205°-215° C. and a pressure of 1200-1500 pounds recovered furfuryl alcohol can be returned to the per square inch. 34 parts of hydrogen was taken polymerization step. Furthermore, if this fur up in about 'l hours which was sufficient to hy furyl-alcohol is not removed it will be reduced drogenate substantially completely the furanoid to tetrahydrofurfuryl alcohol during the hydro unsaturation originally present in the polymer. genation