Document MMeL4DZ2EJ5oO3XxZKnLm8Xoa

/-!/ Confidential EXPLORATORY AROCLOR CHEMISTRY. PART I. ETHERS BY ALCOHOLYSIS. HYDROLYZED AROCLOR DERIVATIVES RD-5fi-Int Report Ho. llQl () August 1, 1958 ReE RESEARCH Dayton, Ohio By: J. Dazzi Chemists: J. Dazzi, G. E- Bennett and D. B. Sharp . , Job Nos. a-9261; 4-9310; 9379 1 > l`-tt U Hr- (Ullljlf ... > >i- M i> inn,'i'it' iif V , DISTRIBUTI 0~TT Organic Chemicals Division .t .. a) J. H._Lum !b) M. C. Thro^ahl c ; P. B. Zlenty St^ Louis St. Louis S t. Lou 1s Rcsearch and Engineering, Division d J E. W. Gluesenkamp/F. C. Meyer ie) Milton Kosmln r) H. K. Nason g) D. B. Sharp hj Extra 1) Extra Dayton Dayton St.. Louis Day ton Dayton Day ton j) Extra 'V'l Day ton (k) Research and Development Files St. Louis MONS 021039 t 1 1 1 TAB L E OP CONTENTS 1 1--_________________ I- PURPOSE 1-----------1 . 1 i II. SUMMARY ti _ CONCLUSIONS .IV.. . RECOMMENDATIONS v. DATA AND DISCUSSION 1________ _______________ VL_____ EVALUATION DATA i______ ____________ yji_...,,. - EXPERIMENTAL ..DETAILS i--___________ mi PATENT STATUS i-- IX. REFERENCE x. DESCRIPTION OF RECOMMENDED PROCESS ____ COST ESTIMATES . XII.. _TOXICiTX_Wffil HAZARDS t 1 i i r 1 __________ XUX____ ANALYTICAL PROCEDURES 1 XIV . ACKNOWLEDGMENTS _____xv^_____ ^APPENDIX 1 Pane No. 1 2 k 5 6 10 11 19 2C 21 22 2} 2U 25 26 1 MONS 021040 1 I i. PURPOSE Confidential This report relates initial experiments with Aroclors as chemical intermediates. A specific objective was to convert Aroclors, a low cost Monsanto product, to ethers for test as functional fluids and dielectrics. Also reported is early scouting research on the conden sation of hydrolyzed Aroclors (diphenols) with ethylene chlorohydrin, ethyl chloroacetate, and a diisocyanate. A program covering specific phases of this Aroclor chemistry was submitted in four detailed memos (R-l-J). Later work with hydrolyzed Aroclor 1268, now an Organic Division Development item, is reported elsewhere (R-7)- This report covers part time work carried out between November 1953 and June 1956. ConMcnli*' In!''"'' ' d(.i i.lu h I conlsms c fji.i r of M>>1' . ' ^ owl w'.hIc ni*l 1,1 r, i, ii-.iiv ou1 > ' < *' r 1 1 ' . rut.'lil I'............. ,, r ,!, V ' 1' 1J ; " w ,1 ji ,iii nl 1 >*' * l ' ' i .. / ( .'n;u ,(J nu.l " 'I t I 1. MONS 021041 II. SUMMARY ETHERS Highly chlorinated Aroclors such as 1271, 1276, 1258 and 5460 react smoothly at 1J0-220OC in the presence of caustic with alcohols such as 2- ethylhexanol and butyl cellosolve to form the corres ponding dlethera in high yields. Aroclor 5^60 gives a mixture of di- and triethers. Aroclor 1262 and excess m-cresol gives a mixture of mono-, di-( and tricresyl ethers. To prepare mono-ether, a large excess of Aroclor 125^ was reacted with 2-ethylhexanol and caustic. No reaction took place between Aroclor 1270, excess allyl alcohol, and caustic at reflux temperature. Ethylene glycol falls to form 0-hydroxyethyl ether with Aroclor 1271 and 1268. Instead, conversion to the corresponding hydrolyzed Aroclor occurs. This unexpected observation led to our work c- polychlorodiphenols from ATic'Clors, and eventual transfer to Organic Chemicals Division Development. Glycerol, immiscible with Aroclor 1268, failed to react and only a trace of partly hydrolyzed material was isolated. Glycols possessing isolated hydroxyl groups, such as 1,5- pentanediol, form an ether alcohol, shown first on 1,2,U- trichlorobenzene, a model compound. The single experiment gave 23# conversion and yield of the 5"(2^-dichloro- phenoxy)pentanol.* 2 HYDROLYZED AROCLOR 1270 DERIVATIVES Scouting research demonstrates that ethylene chlorohydrin and alkyl chloro- acetates condense with hydrolyzed Aroclors to yield the corresponding ether alcohol (I) and ether acid (II). 2HONS 0210^2 Further studies are needed in order to secure samples sufficiently pure for evaluation in polymer formation. A new polyurethane was prepared from hydrolyzed Aroclor 1270 and ailsocyanatodiphenylmethane. Eight patent disclosures were submitted on reported Aroclor chemis try. EVALUATION Replacement of two chlorine atoms in Aroclor by alkoxy groups substantially reduces the viscosity of the material. The 2-ethylhexyl ethers derived from Aroclor 1271 and 1260 showed some promising properties as industrial fluids. Because of the high chlorine content, the flash point of these ethers was very high (630F). Mono-2-ethylhexyl ether of Aroclor 12pA represents a new type of dielectric, but pricewise, such chloroethers could never compete with Aroclors. The di-2-ethylhexyl ethers of Aroclor 1271 and 1268 are more symmetrical molecules and consequently have poor dielectric properties. Details are summarized in Table II. 3HONS 0210'*3 III. CONCLUSIONS New ethers derived from highly chlorinated Aroclors are readily prepared in high yield using procedures adapted from those specified for preparation of pentachlorophenyl ethers (R-4). Aroclor 1271 and 1270 give diethers, while Aroclor 5^60 gives a mixture of di- and triethers. Mono ethers of Aroclors may be prepared in low conversion by using excess Aroclor. Ethers can be prepared from Aroclors and phenols and glycols other than 1,2-glycols; ethylene glycol gives hydrolysis only, and glycerol is unreactive. Dihydroxyoctachlorobiphenyl condenses with ethylene chlorohydrin and with chloroacetates to give the corresponding ether alcohols and ether carboxylic acid derivatives. It is questionable whether they can be purified sufficiently to be good polymer intermediates. These ethers derived from Aroclor show some promise as functional fluids and dielectrics but nave no outstanding advantages. a. HONS 021044 IV. RECOMMENDATIONS Continue exploratory work on Aroclor chemistry as suggested in R-2 and Prepare ethers and thioethers derived from Arociors and Cij-CiS alcohols and mereaptana. Evaluate the thioethers as corrosion inhibitors in oil and gasoline. Reinvestigate the preparation of diallyl ether derived from Aroclor 1268 and 1270 using higher reaction temperature or the method with pyridine catalyst (R-6). React mercaplobenzothiazole with Arociors using dimethylformamide or dimetnyl sulfoxide as solvent. Investigate the reaction between equal moles of Aroclor 1270 and sodium salts of bisphenol A or dihydroxyoctachlorobipheny1 using dimethyl sulfoxide a3 solvent. 5MQNS G21045 V. DATA AND DISCUSSION ETHERS Ethers derived from hexachlorobenzene, the first, type of compounds prepared In 19^7 by the author as possible polyvinyl chloride plasticizers, were very Incompatible. In 1953, some scouting experiments were made on preparing ethers from Aroclor 1270 using the excellent procedure given in R-4 for the preparation of pentachlorophenyl ethers. As expected, this procedure worked well for Aroclors giving di-ethers. The process consists of heating Aroclor and solid caustic at J60C with excess (5056) 2-ethylhexanol for 4.5 hr, while the water is distilled off at the rate of formation. Etherification goes rapidly with little coloration. Water extracts the sodium chloride formed and excess NaOH used. No hydrolysis (caustic-soluble material) of Aroclor 1271 takes place at 160C under conditions used in Expt. 1. The reaction mixture was neutralized in later experiments before washing. This eliminates emulsion formation. A sample of crude bis{2-?thj h.exyloxyJoctachloroblphenyl (?00 g) was distilled over 1 5 hr period to give 190 E, bp 256-267C/0.25-05 mm, without indication of decompo sition. The distillate is a rather viscous, yellow, odorless 1lquld. Aroclor 1260, containing less reactive chlorine atoms, gave a mixture of mono- and diether at 160C (expt. 2). A mixture of dl- and trl-butoxyethyl ether is formed on heating Aroclor 5460, caustic, and butyl ccllosolve at l60C for 4.5 hr. (Expt. 3) No process studies were made on the ether!fleations of Aroclor 1271, 1260 and 5460 in Expt. 1-3. Minor process variation should Increase the conversion. (Expt. 3) Allyl alcohol failed to react at 110C with Aroclor 1271, most likely due to too low a reaction temperature (Expt, 6). This experiment should be repeated under pressure allowing a higher reaction temperature, A diallyl ether of Aroclor may be of interest Inside Monsanto, especially as a cross-linking agent for polymers. 6. HONS 021046 I The mono-ether of Aroclor 125^ was obtained by reaction of equal moles of 2-ethylhexanol and caustic with a large excess (AiOOjC) of the Aroclor, Reaction was quite slow, even at 230C and over a long period (26 hr) Expt. ^). The more highly chlorinated fraction in Aroclor 12?^ reacted first, as expected {Expt. ^). Although the mono-ether has a rather low pour point and fair dielectric prererties, the process is expensive and gives low conversion. Preparation of aryl ether of Aroclor 1262 requires much longer reaction times and higher temperatures than for alkyl Aroclor ethers. This was shown in the only experiment tried {No. 5), where Aroclor 1262 reacted with excess m-cresol. The distilled reaction product was a mixture of mono-, di-, and tri-ether. It is conceivable that more than 2 alkyl ether groups can be introduced since in the ca3c of hexachlorobenzene up to J chlorine atoms were replaced by 2-ethylhexyloxy groups {R-9) (288805), No attempts were made to prepare methyl and ethyl ethers of Aroclors. According to R-iJ, hexachlorobenzene falls to form methyl and ethyl ethers. That this is the case for Aroclor 1271 has to be demonstrated by experiment. Rocklin (R-6) has an excellent method for the preparation of pentachlorophenyl methyl ether using hexachlorobenzene, methanol and caustic in pyridine. It is conceivable that this method may work for the preparation of methyl or ethyl ethers of Aroclor 1271, 1270, 1268 and 5^60. Ethers derived from unsaturated alcohols such as allyl and propargyl alcohol should also be prepared from Aroclors and hexachlorobenzene by the Rocklin procedure. Unsaturated ethers are not mentioned in his paper (R-6). No ether alcohol is formed on heating Aroclor 1271 with ethylene glycol and caustic {Expt. 8). Instead, hydrolysis {mono- and dl-) takes place. This hydrolysis initiated o-r studies on hydrolyzed Aroclor, now transferred to the Organic Cnemical Division for development (R-7). The mechanism for the unexpected behavior of ethylene glycol is not known. Glycerol failed to react with Aroclor 1268 at temperatures between 125-170C {Expt. 9). Glycerol is immiscible with Aroclor which may account for this result. No common solvent was found for this mixture. 7. MOMS 0210^7 To evaluate glycols other than 1,2-glycols, 1,5-pentanediol and 1,2,^-trlchlorobenzene were chosen as model compounds. The latter Is readily distilled from the reaction mixture. A single experiment at 210C for 2 hr, gave the desired 5-(2,3-dlchlorophenoxy)pentanol In 32.5% conversion and 8.9 yield (Expt. 10). This new ether alcohol is very low'meltlng (-35C). A part of the 1,2,^-trichlorobenzene (15 7%) hydrolyzed to 2.d-dichlorophenol. It is conceivable that 1,5-per.tanedlol will also react with Aroclor 1270. Pyridine as a catalyst-solvent (R-6) should be investigated for this reaction. Neopentyl alcohol and pentaerythrltol also should be tried with a model compound, 1,2,4-trichlorobenzene, and then with Aroclors. No thloethers derived from Aroclors were prepared. By analogy with hexachlorobenzene, syntheses from mercaptans should go smoothly. DERIVATIVES OF HYDROLYZED AROCLORS The most promising derivatives of hydrolyzed Aroclors are the bls-glycidyl ethers, on which most of our time was spent. This work Is reported separately (R-S). Bls-hydroxyethy1 ether of Aroclor 1271 was prepared by condensation of hydrolyzed Aroclor with ethylene chlorohydrin. Reaction was rapid and quantitative {Expt. 11). This ether alcohol Is very soluble in most organic solvents. The same general method was used to condense hydrolyzed Aroclor 5J46O (mixture of dl- and trihydroxy) with ethylene chlorohydrin. No efforts were made to separate Isomers. Our main object was to demonstrate a method to prepare B-hydroxyethyl ethers derived from various hydrolyzed Aroclors (Expts. 11 and 12). A possible use for an ether alcohol derived from Aroclors is as an intermediate for polyesters and alkyd resins. For certain evaluation studies only dl-functlonal material should be used first; this will require extensive purification studies. Anotner series of Aroclor derivatives are the carboxylic esters obtained In quantitative conversion by condensing hydrolyzed Aroclor 1271 with ethyl chloroacetate. The product is very soluble in common solvents and failed to crystallize from several solvents tried. The same difficulty was observed when trying to recrystallize the free acid, obtained by hydrolysis of the corresponding ester. Nevertheless, puri fication of such acids and alcohols should be studied. Our preliminary solubility studies were limited to test tube size experiments. HONS 8 0210^8 Use of difunctional acids and alcohols derived from Aroclor will probably be limited to applications where high purity is not required, e.g., alkyds. These compound will probably not be pure enough for "fiber-polymer" types. All our Sroclor derivatives are probably mixtures of isomers and their separation is a problem in itself (R-5)* Low-chlorinated, monohydroxy Aroclor condensed with chloroacetic acid gives a product similar to 2,4-D, and should be tested for herblcidal activity. POLYURETHANES Hydrolyzed Aroclor 1270 reacts with d1i3ocy ana todiphe nylme thane to form a polyurethane. Since the starting material used was only partly difunctional, shown later by improved analytical procedures, the urethane formed is low in molecular weight. The value of this new urethane should be determined on a sample derived from dl-hydrolyzed Aroclor 1270 or 1268. NEW SOLVENT POR AROCLOR 1270 Dimethyl sulfoxide is an excellent solvent for Aroclor 1270. It has the advantage over dime thylformamide of being stable to aqueous alkali; therefore, it should be evaluated as a solvent for reactions of Aroclor 1270 with sodium cyanide, sodium isethionate and pentaerythritol, all which are soluble in dimethyl sulfoxide (Expt. 16). 9HONS 021049 L VI. EVALUATION Ethers derived fro*. Aroclors are very heat stable and presumably flame-resistant, which suggests their use as Industrial fluids, especially where fire retarding properties are required. Data reported by St. Louis are given In Table I. Viscosity properties are poor. A longer alkyl group, combined with a lower Aroclor might overcome the vlscority deficiency. The evaluated ethers possess a very high fire point (625F); their flash points are between 510-5o0F. This early lead on Aroclor ethers as functional fluids led later to preparation of ethers possessing superior properties as functional fluids (R-9). Initial work indicates low breakdown on heating at 350OR for 75 hrs . Aroclor ethers were also screened as dielectrics. Data are summarized in Table II. Lot number K-779 and K-780 are rather symmetrical molecules, consequently their dipole moments are low. The mono-2-ethylhexyl ether of Aroclor 125** possesses superior dielectric properties (Lot number 15^615^7). The pour points of these two samples are 10C and 5C, respectively, which is rather high. These few experiments indicate that little chance exists t^ develop an ether from Aroclor possessing dielectric properties good enonsn to stand the substantially higher cost of t^e final product. Ti Is work led to the preparation of o-chlorophenyl 2-butox,yethyl ether possessing a pour point of -70C and a dielectric constant of 7*25 at 25C. Data on this and other ethers derived from chlorobenzenes Is the subject of a special report (r<-9). Monsanto has no purification procedure to eliminate all conducting impurities. General routine biological toxicant evaluation at Creve Coeur of U ,ll ' -bis-(2-ethylhexyloxy )octachlorobiphenyl (undistilled product, Expt. 1) and 2-ethylhexyl ether of Aroclor 1260 (mixture of mono- . ia di-ether, Expt. 2) failed to reveal special activity. These two ethers were screened as CP Numbers 8076 and 8077. respectively. 10 HONS 021050 I VII. E XPERIMENTAL DETAIL S APPARATUS All experiments were conducted in standard taper, Pyrex glass equipment. The flask was heated by means of a heating mantle. Qood stirring was applied to eliminate local overheating. For high vacuum distil lations a separately heated 10-lnch Vlgreux column was used. A Dean and Stark trap was used in the Expts. 1-10 to separate the water at the rate of formation. EXPERIMENTS 4,4I'-Bls(2-ethylhexyloxy)octachloroblphenyl - Expt. 1 (288806-8) This experiment was performed after successful preparation of di-2-ethylhexyl ether of hexachlorobenzene (280805, R-9) A mixture consisting of Aroclor 1271 (1 mole, 499 g), 2-ethylhexanol (6 moles, 780 0), NaOH (3 moles, 120 g as ground pellets), and 55 ml toluene was stirred at l6oC for 4.5 hr. The water was removed at the rate of formation. Etherification wtu .apid with little change in color. The reaction product was treated with water to remove NaCl and excess NaOH. An emulsion appeared, but disappeared on acidification. The dried reaction mixture was heated at 230C/0.3 mm to ''emove 421 g unreacted 2-ethylhexanol, n*5 1.5686. Conversion 75-95^* Anal. : C, 47-82; H, -51J Cl, ill.07, 41.08. A sample (200 g) of this ether was distilled at 256-265C/ 0.25-0.5 mm to collect: (l) 170,,g, bp 255-265, ni5 1.5576; (2) 58 g, bp 260-67C/0.5 nun, n^5 1.5725; and (jf residue, 2.4 g. Duration of dlstlllation^was 1.5 hr with no indication of decomposition. Anal.: Calcd. MW 686; C, 29.00; H, 4.96; Cl, 41.45 Pract. 1. Pound: C, 30.31; H, 5-52; Cl, 38.17, 38.28, 38-47. Some material was lost due to emulsion formation,accounting for lower than expected conversion value. 11. HONS 021051 I I 2-Ethylhexyl ether of Aroclor 1260 -Expt. 2 (288830-1) A mixture consisting of Arcelor 1260 (1.5 moles, 552 g), 2-ethylhexanol (6 moles, 780 g), NaOH (i4 moles, 3? excess), I and 60 ml toluene was stirred at 170C for 6.5 hr while collecting 60 ml of water. The reaction mixture was diluted at 100C with **00 ml of water, neutrallaed with I 1.07 moles HC1 and washed at 80-100C (good layer separation). The excess alcohol was removed by steam distillation giving H30 r n^5 1.11380, (2-ethvlhexanol, ng-1 l.^JOOj,. Residue I was sti rred at 125-1 30C/i mm to give 727 g, n25 1.5500. Conversion was 86.This ether was treated with fine AloO- et 120C, filtered and Its resistivity was measured and found to be 1 x 1012 ohms-cm at 25C. I Anal, found: C, 55-5^; H, 6.59; Cl, 29.85. These values Indicate it Is a mixture of mono and dlether of Arocior 1260. The product Is considerably less viscous thar . oclor 1260 - > Butoxygthyl ether of Aroclor 5^60 - Expt. 5 (528975-77) Aroclor 5^60 (O.96 mole. 5^0 g) was dissolved in butyl cellosolve (8 moles, 9^ g) at 70C, then 4 moles NaOH flak-s wa3 added. A mild exothermic reaction increased - temperature ip to 115C. The pot temperature was giduunlly Increased from 1 dO up to l60C over 1.75 hr , 1 while collecting 72 ml of water. The mixture was stirred for k.jj hr at l6oC, cooled, and diluted with 900 ml of water. Acidification to a pH of 8 required 0.68 mole HC1. The organic layer was shaken with NaOH (105C): nc hydrolyzed Aroclor was extracted. The final product was heated for 0.6 hr at 210c/ 0.5 mm to give 7**0 g residue, 96% convert ion calculated as trieth-'r. Anal . Calcd . (C^6H13.5CI6 .l-^Hij. 5): C, 55-^5; H, **.38: Cl,29-08 "Found: C, 55-65; H, 5.51; H, 5-51; Cl, 28-27, 28.31. The c. H, and Cl values chec*. for the trl-ether. It Is a viscous material and was not further investigated. Mono 2-ethylhexyl ether of Aroclor 125*4 - Expt. **(303286,303297) Monoethers of Aroclors are unsymmetrlcal molecules and therefore should be low melting and might find use as dielectrics and functional fluids. A mixture consisting of Aroclor 125** (5 moles, 16J2.5 g), 2-ethylhexanol (l mole, 130 g), and one mole NaOH was heated at 230C for 26 hr, while the water was collected (13 ml) with 2-ethylhcxanol, which was returned to the reaction mixture. The washed product was fractionally distilled to give 137** g unreacted Aroclor, bp 170-2100C/1 mm, analysing 52 "'"!$> Cl. The reatd* e (2**5 g, n^P I.582O) was distilled at 1.6 mm as tabulated below. 12 HONS 021052 i ! Fr. No. bp, C W.tjg n25 nD 1 200-21 19.2 1.6152 2 225-40 42.4 1.5918 3 241-45 61.0 1.5788 4 245-40 84.3 1.5766 Residue 33- Anal. Calcd. for C20H20C150: Anal. Pound (jf)1 l Cl C H 49,06 46.36 2.78 42.33 38.72 30.53 52.78 3.87 4.63 38.01 53.01 4.70 39.1 52.8 4.42 Analysis values of fraction 3 and 4 check for a monoether. The residue (33 g) is a dark semisolid. Fractions 3 and 4 were screened as dielectrics (Table II). Cresyl ether of Aroclor 1262 - Expt. 5 (343706 gy L. Beck) A mixture consisting of Aroclor 1262 (1.2 moles, 468 g), m-cresol (5 moles, 518 g) , KOH (2.6 moles, 148 g), and 160 ml of toluene was heated under stirring. The water formed was removed at the rate of formation.collectlng 60 ml while the mixture was heated at 170C for 8 hr. Neutralization required 1-2 moles HC1 indicating a rather low conversion, therefore, the mixture was not worked up. The same fresh charge was heated at 200C for 12 hr in the presence of copper powder as catalyst. After reaction, 400 ml of water was added and the mixture was neutralized with 0.25 mole HC1 and washed. Excess cresol wau distilled off (208 g) and the residue was fractionally distilled at 1 mm. Frac t . bp, C wt,K Anal. Found (#): c -------- H cl 1 170-200 85 48.45 2.25 46.95 2 200-240 208 53-32 2.95 40.35 3 24-280 110 57-03 2.97 34.85 4 300-310 61 62.16 4.14 27.80 5 Residue Anal . Calcd . for: mono cre3yl ether MW di n fi ti tri rl H tl 100 458.8 530.3 601.8 70.87 40,65 57.80 65.80 4.13 2.25 3.26 4.05 14.90 44.65 31.92 21 .85 15- HONS 021053 II I \I Analyses show thata mixture containing mono, dl- and trl- 1 I I cresyl ethers was formed. All these compounds are very heat stable. Attempt to prepare the diallyl ether of Aroclor 1271 - grc t 6 { 2<)s3037 A mixture consisting of Aroclor 12?1 (0.5 mole, 250 g). allyl alcohol (*4 moles, 2^40 g), and 1Q00 ml xylene was refluxed under stirring withojt dissolving completely. To this was added 1.1 moles of NaOH and 2 g of Cu powder and reflux continued at 110C while collecting Iwater. Apparently the temperature was too low; practically no reaction took place. Tne planned run In the bomb at higher temperature was never made. | Attempts to react Aroclors with ethylene glycol - Expt. 7 ( 2838344-5) Aroclor 1260 (1-5 moles, 552 g), ethylene glycol (10 moles, 620 g), NaOH (*4 moles), and xylene I (1*50 ml) was heated first at 130C, then up to l8oC for a total of six hr. The reaction mixture was neutralized using 1.03 moles of HC1, washed, and dried to give 500 g product. Anal. Found; C, 39-97: H, 2-32; Cl, 445.66; OH, 8.50. Hydrolysis took place lr.stc_` of ether formation. Aroclor 1271 - Expt, 8 (293301-2) A mixture consisting oi' Aroclor 1271 (0-5 mole, 2'49-6 g), ethylene glycol (5.2 moles, 2hQ g), ethylene glycol diethyl ether as solvent (700 g), and 70 ml toluene was stirred at 150-170C for 10 hr. Reaction product (206 g), mp. 220C. was Identified later as crude hydrolyzed Aroclor 1271 formed in 89.856 conversion. This unsuccessful ether synthesis opened up hydrolysis of Aroclors (R-10). Anal. Calcd. for Ci?:jo02C18: C, 51-20; H, 0.44^; Cl, 6l.6 Pound: C, 32.a5; H, 1-32; Cl. 59-37- Attempted reaction between glycerol and Aroclor 1258 ~~ Expt. Q (2858442-3 ) Aroclor 1260 (1-33 moles, 600 g), glycerol (6 moles, 552 g), NaOH (3.1 moles), and 200 ml xylene were stirred at 125-i?00C over a 5 hr period collecting a total of 7C ml water. Mat' lal v/as washed and neutralized to give 4;5l g unreacted Aroclor 1268. Prom the wash waters was Isolated 20 g of product. Anal. Found (%): C, 32.78; H, 1,55; Cl, 62.12. This was Identified later as partly hydrolyzed Aroclor 1268. No common solvent could ue fouri for glycerol and Aroclor 1268. Glycerol hca'c-d with NaOH (mole ratio 2:1) reacts rapidly at 12(~ i 4iCC to form the sodium salt and water (2388^8). in MONS 021054 Reaction between 1,2,4-trichlorobenzene and 1, 5-pentanediol - Sxpt. 10 f34370tt. 343713 by L. Beck) l,2,V'frich'loro- benzene is lower boiling and easier to fractionate than Aroclors or hexachlorobenzone, hence was used as a model compound to reinvestigate the preparation of ether alcohols. 1,5-Fentanediol was used to find out if the distance between the OH groups changes the rate of reaction (hydrolysis only occurred with 1,2-glycol). A mixture consisting of 1,2 ,4 - trichlorobenzene (0.75 mole, 155-5 g)t KOH (0.75 mole, 42 g), excess 1,5-pentanediol (6 moles, 624 g), and 125 ml toluene was stirred at 120c while collecting the water at the rate of formation. The pot temperature was increased gradually to 210C and kept 2 hr at this temperature. The salt formed waa filtered off (ill g KCl) and the filtrate was neutralized with 0.114 mole HCl and then extracted with ether. The ether solution was treated with caustic to extract 20 g of 2,4-dichlorophenol. The ether solution was distilled to recover 46 g (36# of charge) of 1,2,4-trichlorobenzene and the fractions tabulated below. Frac t. . bP^ C mm 25 Wt. nD Anal, Found(#): C H Cl OH 1 140-150 18 18 1.4645 57.9 10.5 6.9 22.65 2 150-150 0.8 10 1.4782 ** 150-155 0.8 61 1.5255 4 220-250 0.8 0 1.5281 Anal. Calcd. for ether alcohol : 59.9 54.3 55 .4 55.0 9.6 9.00 7-90 6.1 25.8 6.82 6.2 25.9 4.57 5-6 28.5 6.83 Analytical values for fraction 3 indicate that the desired 5-(2,4-dichlorophenoxy )pentanol was obtained in '52.5# conversion and 48-9# yield. Reaction between hydrolyzed Aroclors and pt.hylene chlorohydrln Hydrolyzed Aroclor 1270 - Exot. 11 (328985-4) Hydrolyzed Aroclor 1270 (0.242 mole, ill g of partly dihydrolyzed Aroclor, 6.16# OH, calcd. 7.40) was dissolved in NaOH (0.485 mole 2.5 N and stirred at 75C while ethylene chlorohydrln (0.55 mole, 42.3 g) was added at once. The mixture was heated up to 90-95C; the solution turned neutral to phenolphthalein 15HONS 021055 after 10 minutes. It was kept at 90-95C for 5 hr and then given several hot water washes. No unreacted hydrolyzed Aroclor was found on extraction with caustic. The organic material solidifies on standing and could be ground to a powder (124 g) possessing an mp. of 112C (not sharp. Conversion was 92-9$ Anal. Calcd. MW 547-4: C, 35-90; H, 1.83; Cl, M.6; OH, 6.22 Pound; C, 36-92; H, 2-71; Cl, 50.19; 50-83; OH, 6.64, 6.73. The OH content of starting material was determined 2 yerrs after its preparation when the modified OH method was available. Hydrolyzed Aroclor 5460 - Expt. 12 (328995-6) The ?ame general procedure as in the previous run was used. Hydrolyzed Aroclor 5460 (121.2 g of mixed di- and tri-hydroxy cpd, 328966-7) was dissolved in NaOH (0.75 mole 2.5 N) and the ethylene chlorohydrin (1 mole 80.4 g) was added at once at 85C. After 20 more minutes the pH of the mixture turned to 8. It was heated for a total of 3 hr at 85-95C. and then washed until free of ionic Cl, to give 132 g of a light powder. Conversion was 92.5# calculated as a mixture of di- and trl-ether. Anal. Calcd. tri-ether: C, 4li-95; H, 3-04; Cl, 37-0; OH, 7-98 Cl, 43.6; OH, 5-52 Found: C, 44.21; H, 2.6l; Cl, 42.38, 42.44; OH, 5-45, 5.73 Reaction between ethyl chloroacetate and hydrolyzed Aroclors_ Hydrolyzed Aroclor 1271 - Expt. 13 (334605-8) Caustic (0.8 mole 32 g] was dissolved in 906 ml of absolute ethanol and hydrolyzed Aroclor 1271 (0.4 mole, 184,9 g, 7<6C# OH) was added. Redistilled ethyl chloroacetate (0.88 mole, 108 g) was added at once at 70C and the system was refluxed for 14 hr; salt precipitation started after 0-5 hr and total salt formed was 48.2 g(0.84 mole). The ethanol was distilled off at reduced pressure. The semi-solid residue is very soluble In the low normal and branched alcohols anddioxane, No precipitation occurred from ethanol solution kept at -4ooc over night. Precipitation using solvents such as pentane, ether, water failed to yield a crystalline precipitate; only oils were formed. The crude ester was dissolved In 900 ml cf ethanol and refluxed 10 hr with NaOH (0.9 mole, 9 N). The ethanol-water mixture (750 ml) was distilled off, the residue diluted with 1000 ml of water, and refluxed. The water soluble material was filtered off and the filtrate was acidi fied to yield 162 g of acid. 16 MQNS 021056 Anal. Calcd for ether acid: C, 33*2; H, 1.04; Cl. 49,04; NE, 289.1 Pound: C, 32.72; H, 1-31; Cl, 54.28, 54.55; ME, 311.4,315.8 The reagent used for Cl analysis failed to dissolve the sample completely. No solvent was found to purify the material by /ecrystalllzation to the point where it could be used as an intermediate for polyester type polymers. Hydrolyzed Aroclor 1262 - Expt. 14 (334617) A solution consisting 'of'partially dihydrolyzed Aroclor 1262 (212 g, N 221, calcd. as diphenol 176.5, prepared in St. Louis Pilot Plant) waa dissolved in 900 g ethanol containing 1.2 moles of NaOH and the system was refluxed. Ethyl chloroacetate (3.52 moles, 160 g) was added over a 68-mln period and reflu-; was continued for 16 hr. Material was iso lated as in the revious experiment, theiheated up to 120oc at 1 mm under good stirring to give 303 g product. Anal Pound: 41.55% C, 3-16% H. Product failed t- dissolve in reagent used in the modified H-8-57. The values found i. dicate, as expected, a mixture of mono- and diester. Infrared analysis, run as No. 5285, was inconclusive due to overlapping of bands for suspected functional groups Polyurethane derived from hydrolyzed Aroclor 1270 - Expt. 15 {31o06tf J~ Equal moles of hydrolyzed Aroclor 1270 (0.015 mole, 6.93 g, 316051, partly dihydrolyzed product) and diisocyanatu llphenylmethane were stirred at 100-11GC for 0-5 hr using 20 g xylene as solvent. Indications were of an incomplete reaction, therefore, 1 drop of N-methylmorpholine was added and stirring was continued for one hr at 120-30C. A solid precipitated on cooling, was filtered off and washed with hot xylene to gi.e 9.2 g residue (I). Precipitation of the filtrate gave a white powder, 0.6 g (II). Anal. Calcd- MW (til.7),.: C, 45.52; h, 1.97; Cl, 39.6-.N, 3-92 Found: (I) Z, 47-30; H, 2.48; Cl, d2.92; N, 3-57 (II) C, 43.89; H, 2.37; Cl, 37-18; N, 2.74 Starting material was not completely difunctional (OH found 6.16%, calcd. 7.82*), therefore, only a low molecular weight polymer could be formed. Product is free of phenolic groups. 17. MQNS 021057 Solvent for Aroclor 1270 - Exot. 16 (3104^2) Aroclor 1270 is insoluble in most organic solvents. As soon as dimethyl sulfoxide (DMS) was announced a sample was ordered (January 1955) from Stepan Chemical Company and found to be an excellent solvent for Aroclor- Furthermore, DMS ia stable to caustic and dissolves sodium cyanide, sodium isethionate and penta- erythritol, all compounds slated for reaction wiIk Aroclor 1270 when time allows. 18 . HONS 0210&B VIII. PATENT SITUATION Eight patent disclosures were submitted as a result of this work on Aroclor Chemistry. D-158* D-1686 J. Dazzi - Preparation of ethers of chlorinated biphenyls and their uses as functional fluids, 6-3-5*. J. Dazzi - Ethers derived from chlorinated biphenyls as new dielectrics, 9-7-5*- D-1838 J. Dazzi - Dimethyl sulfoxide as a solvent for Aroclor 1270 and suggested uses, 3-8-55- D-19*l J. Dazzi - New halogenated polyurethane derived from hydrolyzed Aroclor 1270, 7-18-55. D-2051 ,T. Dazzi - New triethers prepared from chlorinated terphenyl (Aroclor 5*60), 12-16-55. D-2266 J. Dazzi - New synthesis of ether alcohols using 1,2,*-trichlorobenzene and 1,5-pentanediol, 9-14-56. D-2699 J. Dazzi - New acids derived from hydrolyzed Aroclors and chloroacetic acid, 5-6- 58. D-2700 J. Dazzi - New ether alcohols derived from hydrolyzed Aroclors and ethylene chlorohydrin, 5-6-58. Disclosure D-1686 was filed in November 1955 as part of four patent applications on chloroethers as n**w dielectrics, see Dayton Cases 1658, 1660, 1662 and 1663. More experimental data are needed in order to widen claims for submitted disclosures. 19HONS 021G&9 k IX. R E FERENCES 1. Dazzi, J. - New epoxy compounds derived from Aroclor, memo to the Idea Review Committee, dated 11-16-54. 2. Dazzi, J. - New organic chlorine (Aroclor) derivatives, memo to the Idea Review Committee, dated 4-26-55 5. Dazzi, J. - The Aroclors and other halogenated aromatics as chemical intermediates, memo to Dr. C. A. Hochwalt, 1-16-56 Part I; Part II, 12-14-56; Part III, 11-7-57 4. P. B. Report No. 588 - I. 0. Farben (Verdingen 1945) Preparation of pentachlorophenyl ethers. 5. P. B- Report No. 589 - I. G. Farben (Verdingen 1943) Hydrolysis of decachlorobiphenyl. 6. Rocklin, A. L. - Substitution reactions of hexachlorobencene. J- Org. Chan, 21_, 1478-80 (1956). 7. Schwendeman, Craver, Dazzi, LeBlanc, and Herbig, Synthesis and Application studies on Hyarolyzed Aroclors and Derivatives, RD-56-Pln. Rep. No. 1115 8. Dazzi, J., Exploratory Aroclor Chemistry. Part III. Glycidylation of Hydrolyzed Aroclors, RD-58-Int. Rep. No. 118?. 9. Dazzi, J., New Chloroaryl Ethers and other Exploratory Investigations During 1955-1957, RD-58-Fln. Rep. No. 1180. 10. Dazzi, J., Exploratory Aroclor Chemistry. Part II. Diphenols by Hydrolysis. RD-58-Int. Rep. No. 1182. 20 . MONS 021060 X. DESCRIPTION OP RECOMMENDED PROCESS Not applicable to this report. 21 . MOWS 0^1061 I XI. COST ESTIM A T E S None were prepared on compounds described in this reporl. HONS 22. 021062 XII. TOXICITY AND HAZARDS No special toxicity tests were made on compounds described in this report. A skin irritation was the consequence of the author's exposure over several years to Aroclors, octachloronaphthalene and their derivatives. 2% HONS 02lOfc3 XIII. ANALYTICAL PROCEDURES Carbon and hydrogen combustions were run at oOOC. Nitrogen was determined by the Dumas method. Chlorine analysis was run by C-35-55 method, which gives low values on compounds high in chlorine, such as the Aroclors 1268, 1270, 5460 and their derivatives. Tie current modified H-8-57 Cl method was developed after the compounds described were prepared. For the OH determination in Expt. 10 the H-3-56 procedure was used. 2t. HONS 021064 XIV. ACKNOWLEDGMENTS We thank Messrs. A. M. Ellenburg, St. Louis, and A. S. Kenyon, Dayton for measuring the dielectric properties on Aroclor ethers and R. E. Hatton, St. Louis, for evaluating Aroclor ethers as functional fluids. The assistance of L- H. Beck in carrying out two experiments is acknowledged. We thank the various groups in Dayton for elemental and infrared analyses. 25. NONs 021065 XV. APPENDIX APPENDIX A - NOTEBOOK REFERENCES 288806 288807 288808 288851 288852 28885'* 288855 2888*42 2888*15 2888*40 298501 298502 598305 303286 303287 310432 316088 328975 328976 328977 328983 328984 328995 328996 334605 334606 334607 334608 334608 3^617 343706 343708 343713 APPENDIX B - DETAILED LIST OF EXPERIMENTS Ethers Expt. No. 2-Ethylhexyl ether of Arocior 1271 (dlether) 1 2-Ethylhexyl ether of Arocior 1260 (mixture of mono- and di-) 2 Butoxyethyl etner of Arocior 5^60 (mixture of diand tri-) 2-Ethylhexyl ether of Arocior 1254 (mono-) m-Cresyl ether of Arocior 1262 (mono-, dl- and tri Attempts to prepare allyl ether of Arocior 1271 26 HONS 021066 Ethers (Cont'd.) Expt. No. Attempts to react Aroclor 1260 with ethylene glycol to form an ether 7 Attempts to react Aroclor 1271 with ethylene glycol to form an ether 8 Attempt to react Aroclor 1268 with glycerol 9 Preparation of 5-(2,^-dichlorophenoxy)pentanol 10 Reaction Between Ethylene Chlorohydrln and Hydrolyzed Aroclors Hydrolyzed Aroclor 1270 11 Hydrolyzed Aroclor 5^60 12 Reaction Between Ethyl Chloroacetate and Hydrolyzed Aroclors Hydrolyzed Aroclor 1271 15 Hydrolyzed Aroclor 1262 14 Polyurethane Derived From Hydrolyzed Aroclors 1270 15 Dimethyl Sulfoxide Solvent for Aroclor 1270 16 APPENDIX C - TABLES Aroclor Ethers as Functional Fluids Dielectric Properties of Aroclor Ethers Table I Table II 27. MQNS 021067 TABLE I AHOCLOR ETHERS AS FUNCTIONAL FLUIDS4 Lot No. Viscosity, cs., 210F 100F Viscosity index Specific gravity 25/25C Flash point F Fire point F Pour point F J-171**1 108.9 19200. --560 630 -- J-1715' 27.?6 1*120 -77 1.191 510 625 + 30 1. J-171*, i4,14'-Bls(2-ethylhexyloxy)octachlorobiphenyl Expt. 1, undlstilled. 2. J-1*415, 2-Ethylhexyloxytetrachlorobiphenyl, mixture as mono- and di-ether, Expt. 2, undistilled. 3. No breakdown of J-1715 at 350F for 75 hours. Evaluated by Dr. R. E. Hatton, St. Louis and sorted by memo to J. D., 5-12-5*1. ' HONS 021068 TABLE II DIELECTRIC PROPERTIES OP AROCLOR ETHERS Temp, QC 100 25 -25 -55 6o cycles DK-----3*41 1.22 5-85 2-5 2.96 4.3 no data 1 kc PK FF 3.43 3-89 2.92 .17 1.02 1.2 10 kc JiL 3*42 3-77 2.91 .06 4.9 1.1 loO kc jsL PF 3.43 3.40 0 10 2.89 0.7 Lot Number K-779 100 4.01 2.3 3-98 0.1 3*99 0.1 3*98 0 25 4.70 0.1 4.65 0.2 4.62 2.3 4.20 14.4 K-780 -25 3.11 11.7 2.80 3-9 2.72 1.5 2.67 1.8 -55 no da ta 100 ll.Jll 3-1 4.42 0.18 4.44 0.1 4.04 0 K-1546 25 5-22 0.6 5-24 0.15 5*24 1.4 5-16 9*8 100 4.84 28.5 4.6 1.8 4.65 0.2 4.61 0 25 5-50 0.6 5-51 1.4 5*51 1.4 5-23 13.0 K-1547 1) Lot No. K-779 4 ,4' -Bls(2-ethylhexyloxy Joctachlorobiphenyl, Expt. 1, undistilled. Lot No. K-780, 2-Ethylhexyloxytetrachlorob1phenyl, mixture of mono- and dl-ether, Expt. 2, undlstllled. Lot No. K-1546, 2-Ethylhexyioxy-X,X,X,X,X-pentachloroblphenyl, Expt. 4, fraction 3Lot No. K-15^7, 2-Ethylhexyloxy-X,X,X,X,X-pentachlorobiphenyl, Expt. 4, fraction 4. MONS 021069