HI W N I 'H I W“ "V 'H l' ‘l W n Hi 4"” I!” , _ ”I'W’HFI'» l. ll TH ' POLYMEREZATION OF BUTADIENE MONOXIDE Thesis for the Degree of M. S. MICHKGAN STATE COLLEGE Robert Ray Bloor 1948 1.“ng POLYHEHIZATIUI‘Q {3F iii-TANK}: i‘ifliu'OKTIDE 3y R‘O-‘EEKT RAY SLO‘JR A TEC°i3 suzasrrna In Tue SCADGL 0F JEAGLATE sIJsIE“ 0F unculuaa SYATC COLL QC 3? AafISJLTUQE A43 APPLIED SC CfiCE m 'lfl PAJTIAL FLLFQLLEEST OF Tdfi Riffi37CMERT$ L” ‘-,I- s: «P .- I‘I‘ ULQJCD-Q. Jr . m :r, rs- phi-ring: ritzJTk. \ .Jr \"’-.¢':V'.. DEPAlTfiEIT OF CdEMISTRY Had 3.371.611 Ehe author wisacs to express his fratitudo and ‘J I _v or $43 help and encourafiement givau by ' 1 5"?) Jr- Ralph 9- buila aufi Dr. R. C. Luston durifij the Gears” of this investi*v* a ‘ . -4‘1‘011. T . f". ‘0:- ’EF ~"'-.f'11""".‘>'_!"£"{" 1““ I. 'v‘ .5111“ ‘ Lia J Higtorical - — ~ ~ - - - - - — - - - - - - - ' - - - - - - ' Experiqental - - - - - - - - - - * - - - - * * ' - - ' ' ' ‘ (l) Potasailm hydroxide as a C3??ly$t for £339 Polymerization of Butadiene'fiouoxide - - - - - - — - - _ - - - - - - - - - .(z) Bauzoyl Paroxiue as a Catalyst for L383 Polymorizrtion of Butadiena xouoxide - - - — - - - — — - - - - - - - - - - 3 \ -(gj metallic JCTilm as a Catalyat tor Solution Polymerization of $¢tadiene honoxiie — — — - — - — — - - - - - - - - - - - (é) flodi‘m Fonnalfichyde Eulfoxylate as a Catalyst for bras Polymerization of figtauieue Konoxida — — - - — - - - - _ - - f (5) line tgloride a3 a Catalyst for tue mass Polymer;zation 5' '1? ~...::-‘,V. ‘ -. 01 puta-;euw uoflox1;e — " I 9 " .l" :2 Q 9 :a I ‘-V 2‘. ‘ ‘. '-. 3 I‘. - --. ‘L;) lOT‘t lam}; but 1 ifiTOXl. 3 ’1: a \.'L';"~13.L‘dilt f. r th‘: Jiba C: Folymarization of butaaieue monaxiée - - - - - - - - - - - - ‘\7) Lalfuric sci} a; & Catalyst for the mass Polymerization of Edtajienc kouoxide - - - - - - - - - - - - - - - - - - - '(C) 3330tion of Butajiene nonexide in aqueous Lmulsion with Eota?sium {arsulfate ard Ferrous Zulfsta a3 Co—catalysta — - I ‘ ‘ ‘v a + q. ' s, A ' , r, ' _ \ \.'.1} ..’e l:1)r..1;.‘. Lib 1‘) 1 0L -‘-.)CXJ’ LILJEJIihj - .- .- c- .o c. — - — - - — .- I .. : v . mm \1) .‘B‘St _'._(:,.no L. ‘1’ 3 '_I (4 (_‘v f _"«Dl-“'!f;(!1~ - — c- - — — - .— - - - - u- - - - ' f’ o ‘k 4 . a f.' a : ‘ ‘¢;4) ‘OlaEIHDIhvi _;0:Lf-:I~_11 ~.a 1" LG‘}. .I n - - ¢ - I. - - - - - - - - - A .". K,“ V 4 '\ \J s gd 0n anr?*~ Bald Wn*~"”ifiot‘0u3 - n — - — - - - - - . ‘ . .h ..‘...m . ~ -...4 0-. .. .Lu *4 F A ll 1} la la N‘ q",~~‘. T ‘ ‘ ' - r‘ "c-udu$uL C ‘KVLL ;? tUflffiiiQ LOflt'd. -} -~E‘ ‘ 1 ..' r.".' '3' ‘ uJGhL;? Jgtenn;uat‘oa — - - - - - ”)..-'.-,...‘ .1... -,.... +‘ .‘WNDCHnU;C ”spur“ gdulods - - - - .‘:1!.(:i - .— - _ - - - - - — t1£T£33UCTIJK The structure of butadiene moaoxide sugvests-ita possible use as a monomer since both the epoxide bond and doublo bond readily underro polymerization. This work was uriertaxev as an investigation of the effect of various catalysts and polymerizing techniqueo upon the poly- merizitg prOpe.ties of butadiere monoxide. The structures of the polymers obtained during the course of this work were to be characterized. HISTOEICfiL Part 1 Tue first preparation of butadieno monoxide, (l, a oxy o, 4 " r1 butylene) was reported by Pariselle (1)’\~) in 1310. The prepara- tion was made from epiLrOmohydrin by treatment with potassium hydroxide. Pariselle also made a Study of some of the prOperties of the compound and published the results of his investigation.iu ’ '. r " 1:13 “). In 1955 Zuiolph Pummerer and Wilhelm Ruodel ‘5) an- nouncod that they had syntneaized butaéieno oxide by treating butadiene with perbenzoic acid. Recegflj tne Colwncia Snomical fiivision of the Pittsburgh Plate Jlaso Company has put butafiiono uonoxido on the chemical market. Simultaneously several papers ll)"9) have appeared from their laboratories in which a detailefl procedure for the preparation of butadione monoxide 1. described. The First stop in tnis pro- cedure is the synthooio of l—ohloro-é-buteue-é-ol from a mixture of butadione aoi carbon dioxide treated with a so solution of calcium hypochlorite. The temperature is carefully controlled between 0 - 50 C. The product is extracted with ether and then distilled, being collected between to - 5&0 C. The l-chlorO-J- buten-A—ol.is then treated with a so; solution of soiium hydroxide, and the butadione monoxide is removod continuously as it forms. It is dried over calcium chloride and redistilled being collected between oo - 75° C. Since polymerization of butadione monoxide will involve either the epoxide linkaro, the double bond, or both, a brief review of the methods which have been applied to too polymerization ‘ of epoxidee and olefine follows. The polymerization of the simplest epoxide, ethylene oxide, V was effected and studied by Ytaudihger (Q).in 1350. Various polymers of ethylene oxide were made ran ing from a viscous liquid to a wax 11KB solid. Staudinger proposed a linear structure with ether liuxajes uniting the individual units. Soon after Staudinger's worx, and over a period of five years from 1350 to 1935, the I. G. Farben Company filed a number of patents on methods of polymerizing ethylene oxide.(7)"\15} These patents, without exceptioa,.in- volved the use of potaeaium hydroxide or sodium hydroxide aa catalyets for the polymerizationa. A vapor phase tecnnique was described in which the vapors of ethylene oxide were passed over the catalyst at temperatures ranging from au to aooo C. Some of the patents recommended that the polymerization be carried out in the preaeuce of an inert solvent such as benzene, carbon tetra- cnloride, or acetone. Acii catalysts such as sodium bieulphate, aluminum sulphate, and certain acid phOSphates were found to yield the cyclic ether dioxaie. The olefinic nature of butadieue monoxide can best be likened to l, 3 butaiiehe since by splitting the epoxide ring a pseudo l, b diolefiuic Character would result. outadiene was first polymerizei.in ldlu by the Russian chemist Lobedev. Thile not the first synthetic rubber produced, poly butadiene and.ite derivatives soon proved to be superior to the earlier lSOpPBue rubbers whicd had been synthesized. The impact of World bar 1 wave Hreat impetus to the manufacture of butadieue rubbers in Germany. The first such rubber produced by the Germans I'r '\ \i. u. Farben Company) was called buna and was produced through the use of a sodium catalyst. In the nrme Buaa, toe "Bu" stands for butadieno and the ”na" for sodium. Later other catalysts were employed for the polyrarization of butadiene, and it was polymer- ;ized.in aqueous emulsions. Eutaiiene pclymerizes linearly to elastoweric analois of rubber in which there is some cross linkage due to l, 2 addition. Jae hundred per cent butadiene rubbers never have appeared on 'the American market, but they have been manufactured for over ten years by the Russians as " Q x A" and "3 n B" rubbers. The "i” and "b" decoto the source of the butadiene; "A"-from alcohol or "B" from petroleum. The Poles also developed a butadiene rubber which they called gar. doth Juasians and Poles used the sodium catalytic method. Etc widest application of butadiene in the manufacture of synthetic rubbers ic.itu ueo in copolymerizution to produce the different "Suva" rubbers. the course of toe.investiration of too polymerizability of u a heretofore unpolymerized uonomor, each of the several main methods for effecting A polymerization should he tried. A brief summary of these methods, of which there are four, is incluled. ‘ihcy.may be listed as: (l) macs polymerization, a“) solution polymerization, (3) emulsion polymerization, and (e) vapor phase polymerization. 533 polymerization involves either the monomer alone or the monomer plus a catalvqt. many monocerq will polymerize on standiuv or noon the application of heat. To a vast number of othcre a catalyst muct be addcd. These catalyqts are usually orqanic aub- gtanccs qoluble in the monomer and include such compounds as benzoyl peroxide, tertiary butyl peroxide, sodium formaldehyde sulfoxylatey and other erranic peroxides and persulfates. In addition to these the electroghjlic catalysts such as aluminum chloride, stannic chloride, and boron triflooride may be enployed. It is usually found that the application of heat increases the rats of poly- merization nlea the mars tecLuique is being applied. 'There are seve r31 deter1nininq factor3 irvolved 11 a nwa 3 polvmerization. ‘Tne rate of the polymerization will.iucroaao with aa.increase in catalyst canoeutrgtion up to a ceréuin maximum, and tuon 13113 off increaaed pres3ures increage the rate of polymerization, and the oxygon of the aimoapgera has b13n shown to have a slight ionibitiag effect. 'in solution poljnerizatioz, the zwlaculir uoi3Lts of the polvmers are much lower than tbo.;93 pol ymers formed by the othor methods. This is apparently cue to termi 54103 of the chains by solvent moleoul e‘. lxe solveut must be inert and the ideal solvent is one in wni 0:1 the mononor is 1iOlUb1ti, and 1:13 pol-111.31“ 11* not. The catalysts which may be Pmploved are the some as those listed for maua polymerizaLLOu. Tho tamycretaras employed are ue'all" moierato, and the lipiz get is naturally the reflux temperatures of the solution. Carryigg a polymerization out at reflux tarpor« ature affords a 3001 mi; of fol loxi1j the course of a polymerization Since the temperature will rise as the polymerization proceeis. several factors effect 391111 ion polyr erization. The effect of increasin:i tr e co'w 3ntratio:1 of :0 catalyst is found to be the same as that in maas polymerization. The greater the ratio of monomer to solvent, the faster+ 21a rate; and any increase in temperature will also increase the rate of polymerization. lhe nature of the rolvent itself will determine 1113 rate, and thus a monomer might polymerize ten times faster.in carbon tetrachloride than in toluene. 'Tle emulsion polymerization mazuoi mas certrifi advantaves not posseosci by too solution or m;ss netaafiz. Tue most outstanding advantage.is the caltrol OVex tLe wariouo 3L1,es or the polymeri- zation; otoero include ease of aidition of material during the course of the reaction, no troublosoue or eXpeosive solvents and excellent polymerization ufi low temporatu.oo. The technique of emulsion loLxd€PlZdt on.involve9 SURFELCqu the monomer in an a catalyst and an Cflhlb fyinfi agent. aqueooe Eoiution coatalri r Lama emulsif"ing afiento CL no ml used include sod ium and potassilm oleates ayd 3+9 earazes, laureates, r241: 903p, Duponol fl, Aerosol ,, .,. . a. _~~ . Isa . a ._ ‘ _' .' A ..~ ", 71 s r . ‘ o 1, 321 firetret. lhewe eullzlf or; may be neutral, cationic or 1 fiJ L) $- ¥ a (3 Ho ,‘5 L CD \' ~1re. The catal; ats employefl are not assium persulfate, ammonium Loreulfate, benzovl Doro H H C» .9 d :‘D '1 $9 \ 3 ‘D d' L“ 0 acid, and hydroren peroxide. froqoters or cocatalyots have also boen fouwd to accel- erate emulsion polymerizatioo. These so called cooafalysts are .izwridblvrdu312? ALthS and their uao?ulness seems to depend upon a rcdox system being eat up in the reaction. many factors apparently affect the rate of emulsion poly- m erization. 1hese are (l) atxoapherlc oxyiou, ‘3) catalyst conceu+ ration, {o} tempera; u 3, (1) concentration and type of dispcreiug agent, L J) p w of the reaction, {L} type and concen- tration of promoter, i?) difflSiOh rate of the nonower into the aqueous phase, {a} purfiols 5129, (lo) trargfer a note, \11) rate rt. 0 stirring, and {lo} inruritioa. loo initial concentration of monomer and t .o raz'o of mox.vmr" to watwr goons to have very little "Q‘1_ ertect. The last of the foar methods of poly e “izatioa, toe vapor pnase method,.is not widely used in toe laboratory. It baa already bean mentioned in coanectiou with the diocusaion of the polymeri- zation of ethylene exile. ’1 Potassium Hydroxide as a Catalyst for the mass Polymerization of Butadiene ionoxidc (A) Rearentsi (l) Baker‘s C. P. Potassium hydroxide (a) Butadiene monoxide - Columbia Chemical Division of the Pittsburph Plate Slass Company (8) Exocrimsnt l: (U Ten to fifteen ml. of butacicre monoxide were-introiuced into a pyrex Carius tube by use of a pipette in such a manner as to avoid wetting the sides of tne tube. .A weiched amount of from one to ten grams of potassium hydroxiie was aoflcd, and the Curios tube was then sealed in an oxygen flame. Since butafliene.is hi?h1y.inflammable, the tube was sealed while.immersed.iu an ice bath. :3 tube was heated.in a Carius furnace, and the usual temper- ature employed was 1:30 C, however, during the course of the in- vestigation temperatures between logo C and cooo C were also used. The polymer obtained from various runs showed little difference.in characteristics, the averaoe lenith of time for polymerization being about six hours plus or minus two hours. The polymer was found to have the following solubility characteristics; it was soluble in metuyl alcohol, ethyl alcohol, acetone, and chloroform. it was insoluble.in etner, benzene, carbon tetrachloride, and water. 11 Benzoyl Feroxids as 3 Catalyst for the Polymerization of Butadiane Lonoxide (h) ieaxents: -il) Benzoyl Peroxide - Eastman Kodak COMpany -($) Butadiene Jouoxide — Columbia Chemical Company {3) Exoerimentalz {l} tass polymerization was attemptei. The technique cocaisted .in placing accurately weighed samples of butadiene monoxide in a series of test tubes. Eeuzoyl peroxide was then added in amounts varying from .Uot to 5.0; based on the weight of monomer present. "3 heae samples were then heated.in an oven at a temperature of 39° C. At tne end of fifteen days, there was no visual evidence of polymerization. The samples were then distilled under vacuum, and in edcu case a very small residue {less than one ml) of a br0wnisa viscous liquid remained. (L) } sealed Cariua tube technique similar to tnat described for .1 the potassium hydroxide polymer was attempted. Ten ml of the butadisne monoxide was used, and the benzoyl peroxide was varied from 1.0 to 2.3» based on tue weight of monomer. The temperature of the furnace was uaintaiued at 136° C for eight ”cure; ard, at the enfi of that time, there was.no visual evidence of polymer. The contents of too tube were distilled under vacuum aid.in each case about one ml of a dark brown residue remaine.. .ill tetallic Sodium as a Jatalyst for the Solution Polymerization of fiutadiene -oaoxiie (l) Xylene id} Sodium Baud Catalyst (a) Preoaratiou: Two 81d cue-half grams of metallic sodium were '- .1 placed in a coxe bottle, and fifty ml of xylene were added. The 10 coke bottle and its contents were then placed in an oil bath and heated to loco C at which point the sodium was molten. The bottle was then removed, tightly atopoered, and chance vigorously. Upon cooling, the sodium should remain as very fine grains. The efficiency of the catalyst.ie increased by increased surface area or decreased particle size. To the catalyst allowed to cool to room temperature were added fifty m1 of butaiicne monoxide. The bottle was capped and placed in a water hath desirced for agitation. The bath temper- ature was nainteiied at to to 70° C, eni the bottle and its contents were mechanically shaken for an eight hour period. Later reestioue were carried out for twelve, eichtecn, forty-two and sixty hour periods, and the longer the period of heating the greater the yield of polymer. The contents of the flock were decanted from the sodium, and the xylene removed by distillation ”1 under a vacuum. excess heating near the end of the distillation causes further polymerization of the polymer. This takes place violently. The polymer was found to have the following solubility characteristics; it was soluble in .thyl alcohol, methyl alcohol, acetone, and partly soluble in water. It wee insoluble in benzene, carbon tetrachloride, anfi c her. IV Sodium Formaldehyde flulfoxylate as a catalyst for the Mass Polymerization of Butaliene ionoxide (A) Reacentt (1) Sodium Formaldehyde Sulfoxylate - Eaetman gode: Company (B) Experimentgl: 11 both the Kass uni fiBfilGd tube tecnniques were employsd. The experiment was similar in every respect to that coniucted with bonzoyl peroxide. At the 81d of four days, the test tube samples contained.in an oven at goo 3 showed no signs of polymerization. Upon distillation of too excess monomer, no resiiue was found. The Carlos tube reaction was heated at low - 199° C for ten hours. rv’ It contained one per cent catalyst baoafl on the wei,zt of the monomer, and no polymerization occurred. V Zinc Ctloride a3 a Satnljst for the Mass Folyuorization of Butaiiena floroxiio (A) 1222332121; Tho procefiure wag the sooe as that de3orihcd above excegt that only Carina tube reactions were run. The catalyst was ‘ present as 1.5; of the nonomor, too ml of the butadione monoxide being emoloyod. The tube was heated for eight hours at logo C and at the and of that time no polymorization had occurred. VI Tertiary Butyl Peroxide as a Catalyst for the Vase Polymer- ization of Butadieie.xoooxiio (If) “77?.xf'5JT—it: {1} Tertiary Butyl Peroxide - Shell Oil Company (B) Fxnorirental: use Carina reaction identical to those already d A sealed described was carried out. ibe tube contained ten ml of monomer and the catalyst was present as 1.U£ of the weirht of the monomer. The furnace was heated at 140° - 1to° C for eight hours, and at ‘the end of that time no polymerization had taken place. “pen distillation under a vacuum no re3idua was obtained. VII Sulfuric Acid as a Catalytic Reagent for the Ease Polymerization I} a of Butadiene Aonoxide (A) Experimentali ‘v Thirty ml of 3 u sulfuric acid were added to a three necked liter flask fitted with an efficient stirrer, reflux condenser, and separatory funnel. Adequate means for cooling if necessary were provided. Approximately EU ml of butadiene monoxide were added with stirring over a period of three hours. The butadiene monoxide should not be added in a constant dropwise manner, but in lots of three or four drops spaced at time intervals. The reaction will become very warm; and upon dissipation of tnis heat, another three or four drops may be added. The reaction should not be cooled externally with ice in order to hasten the addition of the butadiene monoxide. Such a procedure introduces a lag during which time unreacted material accumulates. The reaction then proceeds with explosive violen e. Caution is also advised against the addition of acid to the monomer. This leads to an explosive reaction. An efficient stirrer is of the utmost importance. The reaction product was washed with 5; sodium carbonate solution and then distilled through a Vigreaux column of 30 cm. at lo mm. pressure. After removal of excess water a fraction was collected over a range between 30 109° C. The substance, a clear oily liquid, gave the sodium periodate test for 1, a glycols. The diphenyl urethane was prepared ‘31) and melted at 1ee° C. Foe compound is probably erythrol since the diphenyl urethane of erythrol is reported.in the literature to have a melting point of or. 130 b. Viii The Reaction of Butadiene hononide.in Emulsion with Potassium 13 Persulfate as 8 Catalyst and Ferrous Sulfate as Co-catalyst (A) Froceduret (l) A three necxed one liter flask fitted with stirrer and reflux condenser was charged with 20o ml of water containing It Duponol G and .03 h potassium persulfate based on the amount of water present. Seventy-five ml of butadiene monoxide was added and the reaction was stirred for 7.5 hours. At the end of that time, no reaction had occurred. .(2) A flask, equipped as described in preceeding experiment.in (l) was charged with'auo ml of water containing 15 Uuponol G and .02 K potassium persulfate. Five hundreths (o.ou) g of ferrous sulfate was-introduced after 75 ml of butadiene monoxide had been added. .At the end of ten minutes, a temperature rise occurred, and the emulsion became a one phase system. The reaction was stirred for a two hour period. A second experiment was carried out in which the Duponol G was eliminated from the foregoing charge just described. Reaction again occurred, and the stirring was continued for a total of three hours. The oily reaction products from both eXperiments were filtered free of the ferric salt and were then distilled. The major por)ioc of the orfianic material was shown to have a boiling range of 93 - 1oa° C. It was a light yellow liquid having an irritating odor, and was identified by preparation of its L, d dinitroghenylhydrazone tm.p. loo - 108° C). A mixed melting showed no depression when carried out with the known 2, 4 dinitrOphenylhydrazone of crotonaldehyde (m.p. lo? - 154° C, lit. 130° C) and the 2, 4 dinitrophenyl hydrazone prepared from the unknown. IX Analytical 14 (A) Determination of Epoxide Bonds -(1) Jethanolyaie of Polymerized Butadiene Konoxide (14) (a) Base Catalyzed Methanolyeia; To a DUO ml flask were added to ml of absolute methyl alcohol (dried over magnesium methoxide) and O.o E of sodium. The mixture was heated to reflux, and a solution of 34 grams of polymer in 150 of cc of absolute methyl alcohol were added over a period of one hour. 'The refluxing was then continued for an additional five hours. The reaction was allowed to stand over night and 5 cc of acetic acid were added to decompose the sodium metnozide. The excess methyl alcohol was removed under vacuum and a viscous red material remained. {b} Acid Catalyzed ivf“3221;£i*: Thirteen grams of the polymer were dissolved in so cc of absolute methyl alcohol. The solution was aidei to a refluxing mixture containing 30 cc of absolute methyl alcohol and one gram of concentrated sulfuric acid. The addition tooK about one half an hour. [he reaction was then refluxed for an additional £.3 hour period. The excess methanol was removed under vacuum leaving a dark‘viecous residue. (5) xethoxyl Determination \a) Apoaratuet (l) Zeieel metnoxyl apparatus {l} Constant boiling hydriooic acid (a) 335 aqueous solution of soiium acetate (5) lot solution of potassium acetate in acetic acid \i) Phenol (3} Bromine (d) L05 solution of potassium iodide (V) 903 formic acid .(o) 0.05 A sodium thiosulfate solution (c) Procedure; Tne method is basically that of Clark (lJi with a few modifications. fipproximately o0 m5. of polymer were placed.in the bottom of the boiling flask on a boiling rod. Two ml of constant boiling hydriodic acid and one ml of melted phenol were dded. Toe trap was filled with water, and the apparatus was joined by tenaion springs. 'Iue receivers were filled with a total of five ml of the acetic acid solution of potassium acetate con- taining ten drone of bromine. Approximately two thirds of th bromine - potassium acetate regent was used in tea first of the two receivers, and the remainder was placed in the second. Carbon dioxide was swept thru the system, and heat was applied with a micro burner. Jhe rate of heating and the pasaare of the carbon dioxide care so reiulated that the vapors from the boiling liquid passed no more than one half the way up toe column. The time of reflux was set at one and one half hours. The contacts of the receivers were washed into a 330 ml Erlenmeyer flask containing five ml of cog aqueous sodium acetate solution, and the excess bromine was reduced with o - 10 drOpe of woe formic acid. Tue contents of the fleet were then diluted with water and 10 ml of a 10; potassium iodide solution were added. One ml of c0nceutrated sulfuric acid was then introduced. The liberated iodide was titrated with .03 A aodium tniosulfatc solution. One ml of .oc i tniosulfate solution is equivalent to 0.830% mg of methoxyl. (4) Data on Epoxida Bond Determinations 1s The following table gives the percentages of methoxyl . groups in the polymer. TABLE I SisPLE I it! :ill A‘ERASE l. rotassium nydroxioe polymer 6.5 5.3 o.5 o.o 2. Sodium polymer 17.0 6.v 1o.o 1s.u é. Sulfuric acid residue 6.5 3.0 4.1 3.7 4. Emulsion residue 0.1 6.0 5.4 3.3 {C} Double Bond Estermiuatious 0:1: f-k kl) firoaine andit (a) foe method of Uhrig and Levine ‘1”) employing a a} bromine solution in glacial acetic acid was tried on the monomer. Some ( f 33‘ (9 addition took place, out it «as not quantitative nor were {b} A a} solution of bromine in carbon tetrachloride was tried. (h) .erCuric Acetate fliiition to tne Footie 291i {17) (a) lo accurately weighed samples were aiiei i to 3 grams of mercuric acetate. The samples were allowed to stard s to 19 minutes. Ten ml of water were tien added followed by 2d ml of meth"l alcohol and 20 ml of a saturated sodium chloride solution. 'Iae samples were then left to stand for an additional ten minutes. Sweaty ml of carbon tetrachloride were the: added. The acetic acic liberated is on a male for mole basis with double bonds and was titrated with standard base. gs) To; effect of various solvents on the system was;investigated. The following solvents were used; acetone, dioxane, and ethyl acetate. The procedure used was the same as ccscribed except 17 that the polymer samples were initially dissolved with a combination of methyl alcohol and solvent. in each case the amount of solvent used was varied. The results were not reproducible, and the end point was indistinct. {c} Data on Lercuric Acetate Determinations \1) “fine following table represents the amount of unsaturatiou.in percent remaining.in the polymer based upon the number of milli- equivalente of standard base required to titrate th monomer. No solvent for the polymer-mercuric acetate addition product was added. TASLE’tl SAMPLE - I :,| :51] 1- ~ 3 me? lQ£.o 108.3 - - - 2. Benzoyl Peroxide Residue 74.4 b$.3 31.0 3.. iotassium Hydroxide iolymer 63,0 5;,0 - - - 4:. 30d ium Polymer '75. 4. C13. (5 5,3. 3 (a) The following table.is desiqtei to show the effect of addinfi acetone or dioxane 33 a solvent in the mercuric acetate determination of double bonds. inc amount of unsaturation is expressed in percent. TASLEilNI SAMPLE SOLVEfiT N0 SOLVENT 20 ml 30 ml 35 ml 1. monomer acetone 95,0 54,9 61.9 8. Potassium dioxame ---- 11.3 9.3 1i.5 Hydroxide Polymer -($) Ferbenzoid Acid Determination 01 gambit ”5,": 3*“I (a) -Prcperatioe of Ferbenzoic acid (Lil The preparation was carried out as deecribed.in Drgeuic ‘TH ;yitncei3 Collected Vol. 1 pp QSl-éfié. Th benzoyl peroxide used was purchased from Eastman aodak Company. (b) Proc admire; Samples containing approximately 13 m. e. of double bonds were chosen, and this was calculated as approximately 0.3 gram. The sample was then dissolved in fifty ml of chloroform, and 33 ml of tne perhenzoic acid solution were added and the total volume made up.io a 1o° ml volumetric flask with chloroform. All volumes were measured at about -J° C. The unreacted percenzoic acid was deter- mined by pipettinc 1o m1 aliquot portions of the sample.icto a-auo ml Erlenmeyer containing LO ml of a 103 solution of potassium iodide and Lo ml of a 0.1 i acetic acid solution. The liberated iodine was titrated with a 0.1 a thioeulfate solution. The de- composition of the perbenzoic acid solution standing for three weeks at -b° C was found to be negligible. A series of curves were plotted. (Fig. I and II}. is} urOmatfl - Hromifle ”ethod for ?ouhle Loud Determinations l‘U) . 1 N \a) neatents: 4‘ \l) 0.1 3 bromate ~bromide solution (a) 9,3 I mercuric sulfate aolution (c) $lacial acetic acid sulfuric acid a; C ‘5 (a) a a sodium chloride solution to) 20$ solution of potassium.iodide \i) 0.1 J solution of sodium ttiosulfats {b} Elected one: A lo to lo; excess of the 0.1 a bromate-bronide solution was 1 added to a duo ml irlenmeyer flask followed by five ml of e i . . .3. .¥...nll.h~% sulfuric acid. The flask and contents were allowed to stand for three minutes then so ml of 0.2 d mercuric sulfate solution were ;introduced. The polymer, dissolved in 15 ml of chloroform was then ;introduced, and 20 ml of glacial acetic acid were added. The flask was then wrappodzin a cloth and shaken.iutermittently for lb minutes. At the end of this period, 13 ml of the 3 W sodium chloride solution were added, and then 15 m1 of a BC; solution of sotaasium iodide were introduced. The solution was shaken for 1 minute and then titrated with standard sodium thiosulfate solution. (0) Data The followiny table expresses in oorccut the total unsaturation w... . u . ~ 4:- 1..., remcicilz in tso types 01 poly.er. TABLiilV POLYmER 3AM?LE I it ~lll IV ‘20. (J (ft. L; (I I \w 1. Sodium Lo. 9 i.‘ ’ a. Potassium hydroxide cu.é 33.? 01.4 tb.3 his Bo t Double 1391308111 V" H" (5' 1 an; 40 Snfiium.Polyuer Percent internal Unsaturauion Leg;,eud (3- Run I ll— Run II 6 - Run III cu ?Q ca SQ law 110 1:0 190 1&0 'TH uia 70 7O 10 5 Potassium fiydroxide Polymer Percent Internal Unsaturation L '3 t ', *3 n =‘l 0- Run I 0- Run 11 O — Run VIII nded-odcpd onto--0..-” 10 EC GD 4; cc L: ?o co at lut llu lcu loo 1&0 ‘Tl‘ .—H k- _ 5/ bun-J 33 7173'le 0""! Part II?“ ’olimerizution: r The search for compounds which can be used as mouooere.is an unending one. This investigation was undertaken for the purpose of determining the polymerizing properties of butadiene monoxide, a compound whose peeuio-diene characteristics eucgeets.its possible use as a monomer. The work consistei ofginveetigating the effectiveness of a large nuuber of catelyete for inducing polymerization of butadieue monoxide, and an attempt to cuaructerize the structure of the polymer by fieterminatiou of residual double bonds and epoxide lil‘ka‘ies. The.inv stifietion revealed that butaiieaa monoxide is polymerizatle, but that the conditions urder wnicn polymers were obtained were more ringous then the structure of tne monomer wouli.imgly. Beuzoyl peroxide au 8 catalyst for tLe mass polymerization of butedieae monoxide was ineffective. A larre number of experi- ments were made usiig various catalytic strengths and t.mperetures; and in each case, when the excees monomer was removei under vacuum, only a very small amount of brown viscous reeiiue rewained. The temperature at which the runs were maie and the duration of time did not effect the amount of this reeiiual material. The residues were soluble in most organic soIVenie eni insoluble in water. A determination of the amount of uiauturetiou by the mercuric acetate method, while not quantitative, revealed that nuch unsaturation .CI '1' 0;“) remained. Tertiary butyl peroxide, sodium formaldehyde sulfoxylate, and the electrophilic catalyst zinc chloride failed to produce polymerization. The mass technique with these catalysts was employed over a wide temperature range, and various catalytic ceaceutratioau were used. idea the excess monomer was rcaoved under vacuum, no residual material was obtained. when butadiene monoxide was heated in a sealed tube over a potassium hydroxide catalyst, a dark red polymer was obtained. This material varied from a wax like solid to a viscous liquid. Various catalyst concentrations were used and apparently had little effect upon the nature of the polymer. The time required to obtain a polymer from the different runs was found to be a Varying factor not dependent on the temperature employed or the amount of catalyst usei. The average length of time required was six hours, but this was found to vary by as much as plus or minus two hours. The use of a bird shot sodium catalyst resulted in a dark red viscous liquid. ILe yield of polymer was found to be directly dependent upon the length of time the reaction was heated.in the water bath, and the viscosity of the polymer was found to increase as the amount of solvent used was decreased. The partial solu- bility of this polymer in water distinruishes it from the polymer obtained by using a potassium hydroxide catalyst. From the structures to he suvfiested later for these polymers, the partial water solubility of the sodium polymer would be expected due to the hydrolysis of the epoxide bonds which predominate.in this polymer. Dilute sulfuric acid does not behave iu its usual role of an electrOpnilic catalyst for the polgmerization of butadiene monoxide. While rapid addition of an excess of sulfuric acid leads to the formation of polymeric material along with much decomposition, careful addition a? the monomer to a dilute sulfuric acid solution will lead to the formation of erythrol. all samples of erythrol obtained gave a positive Schiff's test indicating small traces of an aldehyde, probably crotonaldehyde. However that aldehyde was not present.ia sufficient quantities to yield a derivative with phenylhydraziue. Upon distillation of the reaction products obtained from the aidition of the butadiene monoxide to dilute sulfuric acid, viol at polymeriZatiou with much decomposition occurred near the end of the process. This may be poetulated to be the result of lenydration of the erythrol in the presence of sulfuric acid to yield a conjugated dieue structure activated by a hydroxy group. iii: ii ii ii Ii. :1 5i (2 — ‘ : .i L' ‘ z - ' f! - . o - C - L - C - u -h;0 b - C - u ~‘CJ 1 r ’ ' {iii (Jii (331 Further polymerization fails to occur.if the sulfuric acid.ia removed from the reaction product before distillation is attempted. The attempt to obtain a polymer through the use of potassium pereulfate as a catalyst ani ferrous sulfate as a cocatalyst.in a water emulsion with butadiene monoxide did not yield a polymer. The product obtained was crotonaldehyde plus some traces of a hydroxyl compound, possibly erythrol, as evidenced by a positive ceric nitrate teat. Ehen the reaction product was distilled, the last fraction remaining.in the flask polymerized with some decom- position. Such a phenomena should be expected since aldehydes have been shown to polymerize to low molecular weight materiel upon heating in the prezence of a base or upon the application of heat alone. In the case of crotonaldehyue we have a conjufiatei system of double bonds which are usually easily polymerized. J. L pg; 1 y L 1 c 41. :mi: 1' [LC’LL 5.1 A number of methods for the determina ion of double bonds were tested. Eromine in acetic acid solution would not add to either tho monomer or polymer, and bromine in carbon tetrachloride would add to both monomer and polymer but not quantitatively. A mercuric acetate method was found to yield cousietant res ts for the monomer although elibhtly high (table.li), but the results obtained with polymer were not reproducible. The chief difficulty encountered in the uae of this method on polymeric samples was too formation of a flocculent yellow or tau precip- itate upon the adéition of the saturatei sodium chloride solution. It is believed that this precipitate was the mercuric acetate addition compOund of the polymer, and it served to effectively .mask the phenolphthalein end point. Various solvents such as acetone, dioxane, ani ethylacetate were added to dissolve the precipitate; and.it was measurably reduced, but the col point was found to vary with the aucunt of solvent added. (table III} The results of the perbenzoic acid method for the determi- nation of internal unsaturation of the sodium and potassium hydroxide polymers are shown by figures I and Il. The curves are seen to become linear after a pariod.in which the perbenzoic acid :is rapidly used up. Little interpretation can be made regarding the total unsaturation present; but since the oxidation of to internal double bonds by percenzoic acid proceeds at a rate roagnly ten times greater then tee oxidation of the external deutle Danae, that portion of Lhfi curve duriag union the perbenzoic acid.ia rapidly used up Can be attributed to the.internal bond reaction witn perbenzoic acid, and the linear portion is due to toe slower oxidation of the external double bonds plus some side chain oxidatior. npplyinv tee fiXiPJLOldLiOH procedure of Heffer and Jouason i*‘} the.interuel double bond concentration can be read from the Sraphs. ine method coAsiste of extreoolatiny the linear section of tne curve until it meets the ordinate, nd the percent of internal unsaturation can be read directly. The extra- polation is represented by the dotted lines of greens I and ii. lhe bromate—bromide method irdi was found to be the only method giving reprofluciole results for toe amount of total unsatu- ration present in the polymers. The results of these determina- tions are given in table ii. Ihe epoxide content of the polymers wee determined by splitting the epoxide ring with subsequent methyletiOu resulting in a polymer containing pendent methoxyl_groupe. foe mettoxyl content wee taeu determined. 'ine results of these determinations are given in table I. In the interpretation of this data, it m at be born in mind that the methyletion reaction itself is not quantitative. The yields obtained by Bartlett and floes ‘1’; for tee methanolyeis of butadiene monoxide were approximately Lon of tneoreticel. This therefore is tne maximum efficiency that can be expected from metnanolyeie of the oolgmer. Therefore any value for methoxyl content must theoretically be multiplied DJ two to approach a quantitative estimate of the epoxide bond content of the polymer. 27 In: metnoxyl contents listed.in table I are given in weight percent. A calculation of the theoretical maximum value for the weignt percent due to metnoxyl groups will show-it to be 36.5%. thus, for example,.if a methoxyl determioutiou yielded a value of lg} this value m‘st fiffit Le multipliud by two and than iivided by 3;.op to yield tho percentage of epoxide bond re- maining as such in the polymer. In this case, the approximate epoxide content 13 120.333. 11; Ttruciurcs o; the lotoo:iuw pyiroiia and Lodiul Polgmers The structure of a polymer of butadiene monoxide could theoretically be postulated in three ways. Ina epoxide bond alons could polymerize, or ouly the double bond could polymerize, or both tne epoxije coma &Jd tno double 00nd could take part in too polymerization. {he possible structures follow. ‘A' a 2:. ‘52] -1 ‘1 I i.‘ ‘1 I; 1; (.1 6L. :1 L: .‘I “u -" Q ‘ 'I '\ ’I a. U c b — ._, - J - J .- V -- -V - V - I" - b — I | I I ‘ n—a,“ 1“-" ‘ n _ ‘ fl I ‘I J—\ .I, .- l 5 a - V. V — VA‘o' ‘ oz; .1, u s a! ‘ I M A 0 O I T T A J. 't 1 v v u - . . I 1'! fl .1 'J 1* 2‘ I! ) H Lv 5-0 OJ C) I ("J I () II 0 I (2 I O I Q I 0 II C.) I ('2 I The problcn of characteriaiv; the JiflCCHDO of the polymer 233 aorroacFoi by corrnlnfilu; unaljficul int; :3 the epoxiie bond wnfl +he unsaturatio: raraizitc 1‘ the pol;nor. Theoratically tho potacfiiun Fg'roriln a»*u153f Should result in the rclymerization o” the oymxil» bond :10 e. Zhis would result 'in a rolymer havifij structur» I at} «A enoxife hor€ content of ‘ o 'qu A gifl '.§p'\ ' E; I‘ . .n zero while the unsaturation would be 100% of theoretical. Actually such is not the case. The average methoxyl content is seen to be 6.6% x 2 or 12.6%. Dividing by 56.5% gives a value of 0%.Cfi for the epoxide bond content. The sum of the total unsaturation present and the epoxide bond content approaches 100% which theoretically would be predicted. Referring to figure II and extrapolating, the.intornal unsaturation is approximately 42%. Thus a statistical picture of the structure of the potassium hydroxide polymer would be a chain 42% of which would have a structure as shown in structure 111, bi.6fi, would be as pictured in structure II, while the remainder would conform to structure I. Theoretically the sodium catalyst should result in the poly- merization of the olefinic linkafes and give a structure as represented in structure II. Such is not actually the case. Calculations from tables I and IV show an approximate epoxide bond content of 90; and a total unsaturation value of 53.33. Reference to fivure i and extrapolation yields an internal beau concentration of about 175. -Althounh the figures for the total unsaturation and the epoxide bond content are not, in this case, as closely complimentary as were the figures for the potassium hydroxide polymer, the low value for the.internal unsaturation is as would be expected due to the tendency of sodium to favor a 1,'2 addition resulting in side chains. The structure postulated for the sodium polymer therefore would be predominantly that of structure II, while the unsaturation existing in the polymerzis divided about fifty-fifty between the.internal double bond structure and the pendent olefinic structure.1. Apparently 1f“ I‘dlll'l. LE” 9... .I . Us“ 1{,. 'vv {Db 4.1!. I .2 t . ‘i a, the results for total unsaturation as given by the bromate- bromide method for the sodium polymer are too high. IV mechanism for the Formation of Crotonaldehyde in the Pegction of Butadiene nonoxide in Aqueous Emulsion with Potassium Persulfate and Ferrous Sulfate as Co—catalysts Bartlett and Ross (14) reported the presence of crotonaldehyde .in the reaction product from the methanolysis of butadiene mon- oxide in the presence of a sulfuric acid catalyst, but made no attempt to account for its presence. The following cationic mechanism involving addition and elimination of protons is postulated for the potassium persulfate emulsion reaction to account for the larfe amount of crotonaldehyde formed. t1 4 a n 'ri‘5 2&3 H 2-32; :13 Ii H H I I n t I I I ! _____.; c u I c c:C-C-C—-—-3CJ=C-C-C lossof CZC-C—C: °. .0. + O > 3 n 'r ,in ‘.' 1- ’ u ‘t I; -'.,. ti r. :1 acid _ III-2 E 5 3i . a” I I I .___.___I. r- I 0 I GIG-3:3 ketolizes C-C=C--330 l n U Since K333 potassium persulfate Cd in aqueous solution will decompose yieldin: sulfuric acid, a source of protons is readily available. V Wechanism for the Formation of E ythrol in the Reaction of stadiene ficnoxide'witn Bilute Sulfuric Acid C2. As previously pointed out Bartlett and Ross obtained only a small amount of crotonaldehyde in the methanolysis of butadiene monoxide. The predominant product was the methyl ether. Such was found to be true in the case of the hydrolysis reaction of the butadiene monoxide. Only a trace of an aldehyde was found "Hi to be present. iue following mechanism is auufested for the fun atiou o? tue erythrol aul accounts for the fact that very little alieh'de i4 Formed-in the case of the hyirolysis reaction. Tale apparently is due to the greater concentration of sulfuric acid is tie case of the arythrul formation, as conpared to the very small traces of sulfuric acid liberated by the decomoosition of potassium persulfate in aqueous solution. 2:. ii a '5; z: -1. :5 at, :i» .1 -1 :1 — 'I d "iw- O - ‘J ‘- c—c-c-.t c—c-t-c—-‘c-C~C-c: .flj. «r , e, ' *1: o 0;: a li.1380" ‘3 u 2-! *0" '5 '5 ' "(J Lu. .;J t I. Aid 1. . 1“}: “f" c:c-c-c ‘—'"" ":c-c-c i. l I l :5 32: 0:1 0:- c 4 In conclusion the author would like to point out that much yet remains to be done on the investigation of butadieae 'monoxide as a fiononer. lacy catalysts not employed by this investigator remain to be examined. A few of these include aluminum chloride, and the acid catalysts reported to be specific for the eflozide bond 1.8. sodium bisulfate, aluminum sulfate, and certain of the acid phosyhates. The possibilities for tn cocolymerizatiou of butadiene monoxide with'various other monomers aupears especially interestin . ern though this .irvestixation has shown that butadiene monoxide will polymerize only upon rather rigorous treatment, many examples of copoly- merizetion.icclude a monomer that homopolymerizes. 'Fhe synthesis of new monomers is assuming a najor importance in the polymer field today. Butadiene monoxide might well serve as a starting point for many synthesis of this type. A further '- stuuy at the various rnrctinne with the ataxifle bond or tfie 036 of buiuiiuue possxole awaiting profiuots fo the Comble t monoxide may well nrove to be cuite ixterastiur 7,:23‘ ?;;:'51'$Y {1) Eutaiiene moroxile was fouod to D9 poly ablr but under covditions much more vi orous than 154 geeudo fiiolefio character- istio3 would ifiplj. {1‘1 . (J) Iotansium hyiroxiie vnq sham; to be a c mlyzt for Ere flasa OlVHVFLLFTlO of bnmaflinLa no 0x113 resultiu7 it a polJmer low in epoxiia boxd coqtant had Cfldtaiflimh a Pointively largo amount of unsaturatioa. {b} a aofiium Sand catalyst drovei to L9 effective for the solution polymerizetiou of buiudiane Kgngfl13_. it 35; “.4 ifi a toly": "i and relatiV%ly low in its awavu t of :3" H- by ;.J 7". l 0 \"1 v 9 24 h“ ; .. ~ P O O r-r ( {1 c: 1' \J 1'.) H O ’\ I '- - u .- U Q ;- _‘ , ‘ W ‘ I 1 ~ ‘_ 9", (%) "nVanl ;:!0 x13@, soilhm formKLJzuyae LJLfoxylate, t- hu‘¢¢ , -. . ; . n .9 :- - . r ,"h. 0 «- oar xide and fith cal rid: were ine?fect1ve as Cdtalfcufi Lor tam "o‘v‘P" ”3,-0" of bu*3lie“e monoxiéo. ..._a.i ~tlot and push dzo\xposx- tiou. Yfiis Profuzfi nrovrfi to ”e u worxahla. .,,\ ~- I ' ' ' 0 -' . ~ y“ I 9" I a .V 1“ (a) oxlute gulfdrlc a01i 13d oatufiiane. :0fi0AL.o rcsulteu 14 tum L..'W i .‘ ' - I -- 'F - 4‘ ' . ' . . --' ' «Vu- Forraulon o: sryturol \ w ' 7 ' 3 ‘ “-v). A ?W ~1ble ”GChd“1““ UR Q; ts forwation is suggested. P" for (7) Butadiene monoxide in aqueous eflulsion with pota