Àug- 21, 1951 A. P. DUNLOP Erm. . 2,564,835 HYDROGENATED FURFURYL 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-jy 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 - 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 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 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„». 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 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 step and since for most purposes a hy drogenated polymer free of tetrahydrofurfuryl Example 5 alcohol is preferable, distillation will be neces A portion of the product of Example 1 was sary eventually. y . distilled under vacuum to give 65 percent distil The plasticizers of the present invention are late and still bottoms of 35 percent. The distil especially effective when used with furan resins, late was then fractionally distilled under a vacu vinyl type resins, etc. The amount of the plas 45 um (4 mm. pressure) giving 26 percent tetrahy ticizer used may vary Widely being generally be drofurfuryl alcohol and the following fractions: tween about 5% or even less to about 50% based upon the Weight of the resin and will be governed by the properties desired to be imparted to the Boiling Yield m resinous compositions. 50 Pgismïl- »am In order to disclose the nature of the present invention still more clearly, the following illus fao-9o ß trative examples Will be given. It is to be under 1 25-150 14 15H8() s stood that the invention is not to be limited to iso-20o 12 the specific conditions or details set forth in these 20H20 s examples except insofar as such limitations are 22o-245 8 specified in the appended claims. Parts given are parts by Weight. y We have found that improved resins may be obtained by condensing an incompletely hydro Example 1 60 genated partially-resinified-furfuryl alcohol with A mixture of 347 parts of a furfuryl alcohol itself or with a thermoplastic resin such as those acid-catalyzed partial polymer, the pH of which derived from the following products: furfuryl had been adjusted to 8 with sodium hydroxide alcohol, furfuryl alcohol-dimethylolurea, fur and having a viscosity of about 2000 centipoises furyl alcohol-phenol-formaldehyde, furfuryl al at 25° C., 52 parts of Raney nickel catalyst and 65 cohol-melamine-aldehyde, furfuryl alcohol-am 152 parts of isopropyl alcohol was hydrogenated monium thiocyanate-aldehyde, alkylfurans, un at 19o-205° C. and a pressure of 1000-1'700 saturated furyl aldehydes, -phenol7 vinyl pounds per square inch. 13.6 parts of hydrogen type compounds, ureaformaldehyde, malamine was taken up in 41/2 hours. Since the starting formaldehyde, etc. This condensation can be material contained 17% water, this represented 70 effected by the use of heat alone, an acidic cat hydrogenation of somewhat less than 85% of the alyst alone or by heat and an acidic catalyst. furanoid unsaturation originally present in the The resultant resins combine strength, toughness, polymer. After removing the catalyst by filtra elasticity, fiexibility, adhesiveness, and high tion and the solvent by vacuum distillation, a chemical resistance with excellent4 insulating liquid was recovered which had a viscosity ap 76 properties which are highly desirable in compo 2,564,835

sitions usedï as insulating enamel's» for coating plication» Serial Number 586,631. filed April electrical» conductors. As an example a wire 4, 12945;. and` a. iurfural-phenol; resinsuch: as pre enamel may be prepared consisting of an in pared.Y according to the. method. described. in completely hydrogenated partially resiniñed U. S. Patent 1,969,890. In theseztests,.a mixture furfuryl alcohol, a fatty acid modiñed alkyd resin consisting. of. 1 part of resin Example; 6, lipari; such as glyceryl phthalate modified with lin turfurylated dimethylolurea resinand 0.02 part seed fatty acids and a suitable solvent such as phosphoric; acid was heated'ior 1- hour at.` 160o acetone, ethyl acetate, benzene, etc. A typical C. Inanothertest, a mixture consisting off 1' formulation is as follows: hydrogenated furfuryl part of; resin Example 6,1 1; part- oi", furfural alcohol polymer> 1 part, modified alkyd resin 1 101 phenol resin and 0.02 part. phosphoric; acid; was> part, and acetone- 2 parts. The nature of this heated for 1 hour at 160° C. In both examples, condensation reaction is rather obscure .but a the resulting', resins possessed good adhesion,` theory of»` explanations is.V as. follows: an incom toughnesaviiexibility and. resistance to; sol-vents; pletely hydrogenatedpartial' polymer will possess The resins of Example 4 and Example 6 were unsaturated bonds and because of those bonds added to the resinous materials listed below to the polymer can condense with itself or copoly determine their compatibility with those resins. merize through cross linkage with other poly In these tests equal quantities of the hydrogenat merizable resins particularly furan resins. ed furfuryl alcohol polymer and the resinous ma Example 6 terial were mixed and gently heated. The fol 20 lowing resinous materials were found to be com A mixture oi” 7’73 parts of a furfuryl alcohol patible with both hydrogenated polymers: cellu acid-catalyzed partial polymer which had been lose acetate-butyrate, cellulose nitrate, ethyl cel neutralized, dehydrated under vacuum, and hav lulose, furfural-phenol resin of Example 8, fur ing a viscosity of about 2000 centipoises at furyl alcohol-ammonium thiocyanate prepared 25° `C., 80 parts of Raney nickel catalyst and 20 25 according to Example 2 of the U. S. Patent parts of isopropyl alcohol was hydrogenated at 2,368,426, furfurylated dimethylolurea of Example 17o-200° C. and a pressure of 1000-1800 pounds 8, methylfuran polymer prepared according to per square inch. 8.6 parts of hydrogen was taken Example 5 of our copending application Serial up in 6 hours which was suñicient to hydrogenate Number 621,592 ñled October 10, 1945, now Pat about 25 percent of the furanoid unsatura 30 ent 2,486,392, granted November 1, 1949, methyl tion originally present in the polymer. methacrylate, phenol-formaldehyde laminating Example 7 varnish, vinyl acetate and vinyl butyral. Resin ous materials such as cellulose acetate, nylon, Since the stroke cure is a measure of the ther styrene, vinyl chloride, vinyl chloride-acetate mo-setting properties of a resin, the following and vinyl-vinylidene chloride exhibited only lim resins were so tested: An acid-catalyzed furfuryl ited compatibility with the hydrogenated poly alcohol partial polymer having a viscosity of mers. Polyethylene is an example of a resinous about 2000 centipoises of 25° C., resin of Example material which is incompatible with the hydro 6 and the resin of> Example 4. The stroke cure genated polymers. has been delined as the time in seconds required Having now described and illustrated our in for a resin to convert from a fusible orliquid con vention, we wish it to be understood that our in dition at a definite temperature while being vention is not to be limited to the speciñc details stroked with a spatula to a conditionat which herein described, except insofar as such limita the spatula either no longer sticks to the resin tions are speciñed in the appended claims. or slides over it with relative ease. In practice We claim: aboutI 2 cc. of the resin is placed on a hot plate, 45 1. A process of producing a composition of mat the temperature of which is adjusted to 145° ter which comprises the hydrogenation` of a par 150° C., and stroked approximately 90-100 strokes tially resiniiied furfuryl alcohol. per minute) with the flat side of a spatula to 2. A process of producing a composition of mat smooth the resin into a square 2 to 3 inches on ter which comprises the hydrogenation of an acid a side. 50 catalyzed partially resinii'led furfuryl alcohol. None of the foregoing resins gave a stroke cure 3. A process of producing a composition of mat in ten minutes in the absence of a catalyst and ter which comprises the hydr-ogenation of a par in addition it was impossible to obtain a stroke tially resiniiied furfuryl alcohol at a tempera cure in ten minutes on the resin of Example 4 ture of 1'70-225" C. and a pressure of 1000-1800 in the presence of a catalyst. The stroke cures 55 pounds per square inch. obtained on the resins in the presence of a cat 4. A process of producing a new thermosetting alyst are summarized below. artiiicial resin which comprises heating an in completely hydrogenated partially resiniñediur Stroke cure in furyl alcohol. seconds 60 5. A process of producing a new thermosetting artiñcial resin which comprises heating an in Catalyst, parts per part of resin Furfuryl ­ alcohol Eëâän’l completely hydrogenated partially resiniñed fur Partial 6 p e furyl alcohol in the presence of an acidic catalyst. polymer 6. A process of producing a new plasticizer 65 which comprises the hydrogenation of a liquid Maleic acid ...... _. 0.05 38 160 Phosphoric acid ...... -_ 0. 001 90 540 partially resinified furfuryl alcohol. Phosphoric acid ...... _. 0. 04 ...... _. 80 7. As a composition oi matter a partially poly merized furfuryl alcohol having a viscosity of Example 8 - 70 10D-80,000 centipoises at 25° C. and wherein at These hydrogenated furfuryl alcohol partial least 25 per cent of the unsaturation of said par polymers are also elîective to impart increased tially polymerized furfurylv alcohol has been vsat flexibility and adherence to other resins, e. g., urated with hydrogen. a furfurylated dimethylolurea resin such as de 8. As a composition of matter a partially poly scribed in @ample 1 of the Dunlop copending ap 75 merized furfuryl alcohol having a viscosity of 2,564,835 7 8 1D0-80,000 centipoises at 25° C. and wherein 25 to 85 per cent of the unsaturation‘of said partially `to 85 per cent of the unsaturation of said par polymerized furfuryl alcohol has been saturated with hydrogen. tially polymerized furfuryl alcohol has been sat ANDREW P. DUNLOP. urated with hydrogen. PAUL R. STOUT. 9. As a composition of matter a partially poly merized furfuryl alcohol having a viscosity of REFERENCES CITED 100G-2000 centipoises at 25° C. and wherein at The following references are of record in the least 25 per cent of the unsaturation of said par tially polymerized furfuryl alcohol has been sat file of this patent: urated with hydrogen. UNITED STATES PATENTS Y l0. As a composition of matter a partially poly merized` furfuryl alcohol having a viscosity of Number Name Date 1,780,652 Lawson ______Nov. 4, 1930 100G-2000 centipoises at 25° C. and wherein 25 2,345,966 Fielder ______Apr. 4, 1944