Document aBVjbqRO9zo3w1o6JYQD3O1mB

S. E. Qebura M. P. Drutnm Date Typed: January 20, 1959 Date Issued: '/3o^j'J Prepared by: S. E. Oebura This report and the information contained herein is the property of the MONSANTO CHEMICAL COMPANY STLCOPCB4095052 STLCOPCB4095053 TABLE OP CONTENTS Page No, VI. VII. INTRODUCTION.................................. ....................................... 1 SUMMARY.................................................................................. CONCLUSIONS.......................................................................................... RECOMMENDATIONS.............................................................. 3 PATENT STATUS...................................................................... REFERENCES............................................................................................. 5 EXPERIMENTAL......................................................................................... 7 A. Apparatus 7 B. Procedure 1. Tetrachlorobispnenol-A (TCBPA) (a) Diglycidyl ether ib) Qlycidyl polyethera 11 (c) Dl- -glycerol roonochlorohydrin 12 2. Hydrolyzed Aroclor 1262 (a) Qlycidyl ether mixture 13 vb) QlyciJyl polyether 16 3. Blahpenol-A (BPA) (a) Liquid Resina (Epon 828 Type} 17 (b) Solid Resina (Epon 1001 Type) 19 VIII. DISCUSSION........................................................... A. Reaction of TCBPA with Excess Epichloro- hydrln........................................... 21 B. Reaction of Hydrolyzed Aroclor 1262 with Excess Epichlorohydrln 23 C. Reaction of BPA with Excess Epichlorohydrln 24 D. Preparation of Polymeric Epoxides 26 E. Preparation of Epoxides from Qlycerol 29 ?. Economic Evaluation of the production of Epon 562, 828 and 1001 Type Resins 30 XI. MATERIAL SPECIFICATIONS AND ANALYTICAL PROCEDURES....................................................... 39 XII. XIII. XIV. TOXICITY AND HAZARDS.................................................................... 41 ACKNOWLEDGMENT................................................................................... 43 APPENDIX............................................................................. A. Patent Survey, Summary 4 Conclusions B. Definitions of terms, Calculations Notebook Pages Physical Properties Jo 47 50 1 4 4 21 43 DSW 621025 STLCOPCB4095054 TABLE OP CONTENTS Cont1 Table XI Reactior of Polyhydrlc Phenols and Epiohlorohydrin Table XII Reactions of TCBPA with Excess Eplchlorohydrln Composition of Hydrolyzed Aroclor 1262 Infra Red Spectra l r f 1*f* STLCOPCB4095055 1- - I. INTRODUCTION: The market for epoxy resins has been prajeoted to substantial quantities1 by I960 (Ref. 1). Monsanto has a basic position in bisphenol-A and other polyhydric phenols wiiicn are used in these products. Considerable capital is Invested in manufacturing facilities for thermosetting resins which may be threatened somewhat by epoxies or which might be advantageously supplemented by a line of epoxy resins. The manufacture of epoxy resins has been considered previously and the opportunity to enter the field as a licensee rejected. As the use of epoxy resins nas grown, the question of their manufacture periodically recurred. Up to the present time no thorough patent search, process study or economic evaluation has been made and these form the only sound basis for defining Mon santo's interest in these products. This report reviews the research contribution to the several projects listed above - a study of the chemistry of epoxy resins with emphasis on the use of Monsanto polyhydroaromatlcs, the development of laboratory processes for commercial epoxies and a search for technological advantage which might result through the use of new chlorinated diphenols (hvdrolyzed Aroclors and tetrachlorobiapheriol-A) (Ref. 2 4 3;. also includea the re sults of economic analyses by Division engineering. This work was supplemented by a thorough patent survey concerning the epoxy resine, made with the cooperation of the Springfield Patent Department. The Initial Intent of this work was to ex plore the ohemlstry of epoxy reslne based on bls-phenol-A (BPA) and other Monsanto dlhydrlcphenols as It pertained to the use of these products in thermosetting reain systems. It developed, however, that these raw materials might be better exploited by entry into the epoxy resin field. It was recognized, that although chlorinated polyhydric phenols might find a place in the epoxy market, entry into the resin field would be determined principally by the economics based on bls-phenol-A. II. SUMMARY: An economic analysis was made of the manufacture of the three basic epoxy resin types in use today: Epon 828* Epon 1001* Epon 562* *3hell Chemical based on bls-phenol-A and eplchlorohydrln; liquid, high epoxy content, used as an Industrial adhesive. based on bls-phenol-A and eplchlorohydrln; solid, low epoxy content, used in surface coatings. %ased on glycerol and eplchlorohydrln; liquid, high epoxy content, uaed as an adhesive and in textile treating. DSW 621027 't STLCOPCB4095056 -2- The studies were based on laboratory procedures developed for the products based on bis-phenol and on a patent procedure for the glycerol based produot. A recommendation to enter the epoxy field as a resin manufacturer can not be made based on the following results of this economic analysis: Return on Investment After Selling Price 50# Tax Marxes BPA Integrated BPA Epon 1001 type *3,000,000 lbs/yr. *5,000,000 lbs/yr. $0.605/lb. 6.0* 6.7* 9.0* 10.7* Epon 828 type *1,000,000 lbs/yr. *3,000,000 lbs/yr. $0.90/lb. 22.0* Epon 562 type *1,000,000 lbs/yr. *3,000,000 lbs/yr." $1.10/lb. 281..S0** Monsanto Sales. The most profitable products and those with the greatest growth potential are tnose which do not allow Monsanto to take full advantage of its raw material position. Epon 828 uses an excess of eplchlorohydrln which contributes most to raw material costs. Epon 562 uses no Monsanto products. Without a basic position in eplchlorohydrln, the eoonoalos are not sufficiently at tractive to encourage capital Investment. Laboratory procedures were developed for the synthesis of liquid and solid epoxy resins based on bls-phenol-A (BPA) in good yields. The dlglyoldylether of tetrachloroblsphenol-A (TCBPA) was prepared in quantitative yields, and a patent application on the process was filed. A series of polymeric epoxleB were synthesized in moderate to high yields by reacting eplchlorohydrln with TCBPA and mixtures of TCBPA and BPA. Tetrachlorobiapheml-A gives epoxy resins of high epoxy content whlon are solid, fast curing and of good color. This raw material should definitely be exploited in the resin field. Hydrolyzed Aroclors (ohlorlnated bl-phenyls) form another series of dlhydrlo aromatics. A laboratory procedure for the prepara tion of the dlglyoldyl ether of hydrolyzed Aroclor 1262 was developed and a patent application filed. The initial samples of hydrolyzed 12o2 were not homogeneous with regard to dlr.ydroxy content) they were as much as 24* mono-hydroxy. This contributed markedly to the poor performance of the resins. It is suggested DSW 621028 ** STLCOPCB4095057 -3- that a new hydrolysis procedure be established which will furnish all dihydroxy components. This raw material should then become attractive as another building block for epoxy resins. A fairly complete patent survey of the epoxy field was made con cerning manufacture, curing and use in other thermosetting systems, including a search in the Washington Patent office. It is concluded that a competitive line of epoxy resins based on BPA can rot be de veloped without infringement. More patent possibilities exist witn systems based on phenolic lump resins, TCBPA and mixtures of BPA and TCBPA. Epoxy resins can be used in combination with many thermo setting systems. Those of principal interest to Monsanto are phenolic-protein adhesives, melamine, urea and phenol formaldehyde reslna, polyurethane, nylona, polyacrylonitriles and sulfonated polystyrene. In the curing of epoxy reains, most of the coverage is specific and covers a broad range of materials. III. CONCLUSIONS: Monsanto's potential sales In the epoxy resir.a field wo(ild be reasonable at the following levels: Epon 828 type Epon 1001 type Epon 362 type 3.000.000 lbs/yr, 5.000.000 1,000,000 At current prices, using market priced raw materials, only Epon 828 ahowa a return on investment sufficiently attractive for capital Investment. As this product is used in greater quantities result ing in lower price, the return quickly becomes marginal. Integra tion of the bls-phenol-A facilities has little effect on these returns due to the relatively low proportion of BPA compared to Epichlorohydrin. Epon 562 does not use BPA and the profitability of Epon 1001 Is not effected markedly by integration of BPA facilities. Epichlorohydrin is common to all of the materials, however, and only through integrated manufacture ot epichlorohydrin can this line of products become interesting economically and tnere is little else to warrant the manufacture of epichlorohydrin. Epoxy resins of the types described can be manufactured in con ventional processing equipment similar to that now employed for the synthesis of solid and heavy viscosity thermosetting products. Monsanto la thoroughly experienced with the techniques involved. Good yields of high quality products have been synthesized in the laboratory from bis-phenol-A, tetrachlorobisphenol-A and hydrolyzed Aroclors. It would be most difficult to enter the epoxy resin field without infringement of patents as reaction products of ble-phenol-A and epichlorohydrin are well covered. Resins based on TCBPA, mixtures of TCBPA with BPA and hydrolyzed Aroclors are relatively free of infringement as are products based on phenol-formaldehyde DSW 621029 I * * 1 f ''I* +* f* STLCOPCB4095058 resins. These products, however, are specialty Items and It Is questionable whether the volume will reach major proportions. The use of epoxy resins as modifiers for Monsanto's line of thermosetting products Is definitely the most promising immediate means of utilizing the properties of epoxies. These modifica tions are essentially patent free and In certain areas viz. phenolic-protein adhesives, offer interesting products. IV. RECOMMENDATIONS: 1. Monsanto should not enter the field of epoxies as a resin produoer. 2. Tetrachloro-bia-phenol-A, hydrolyzed Aroclors and similar dlhydric aromatics are definitely attractive raw materials for epoxies and the program now In effect at Organic and Dayton for developing these products should be encouraged. 3. The use of epoxy resinB and epoxy chemistry In thermosetting systems based on phenol, melamine, etc., is worthy of de tailed study. 4. If manufacture of eplchlorohydrln and its related by-products Is ever considered, the manufacture of epoxy resins will war rant re-examinatlon. V. PATENT STATUS: A patent application is pending on the process for the production of the diglycldyl ether of tetrachlorobisphenol-A and the ether. A patent disclosure claiming the process for the preparation of the glycldyl ether mixture of hydrolyzed Aroclor 1262 has been filed. The results of a fairly complete patent search are summarized below: Manufacture: Monsanto can -- manufacture epoxy reslna based on phenolic lump resins, tetrachloroblsphenol-A, and mixtures of TCBPA with BPA within certain limits. Monsanto can not - develop a competitive line of epoxy resins based on BPA without infringement. Use: Monsanto can - Incorporate epoxy resins in phenolic-protein ad hesive mixtures and probably prepare resins by reaotlng epichlorohydrin with water solutions of the sodium salts of methylol phenols (highly alkaline, liquid phenolic resins). DSW 621030 t* STLCOPCB4095059 -5- Blend epoxy resins with melamine, urea and phenolic resins within certain limits. Ternary blends are mostly free of Infringement. Blend gpoxy resins with polyurethanes, nylons, acrylonitrile, acrylamide, furans, rubber, sulfonated or carboxylated styrenes. Curing: Monsanto can develop specific curing systems and obtain patents, Monsanto can not - cure with well Imown curing agents including carboxylic acids, anhydrides, sulfonic acids (and their chlorides). Isocyanates, Isothiocyanates, poly alcohols, phenolic hydroxyl groups or phosphoric acid. Many specific curing agents are covered which Include amines, polyamides, amides, etc. It may be concluded that the most fruitful area for circumventing existing patents Is the synthesis of epoxy resins based on pheno lic lump resins and from mixtures of BPA and TCBPA. VI. REFERENCES: Approved by: ________________ _ ft.M.Dickey,Patent Dept. (1) S. 0. Oreenlee, Symposium On Epoxy Resins, American ----- Chemical Society Meeting, Atlantic City, September 1956. (2) Memo, J. Dazzl (Dayton) to H. Mohrman (Springfield), 7/19/55 Aroclor Epoxy Resins. (3) Memo, J. A. Herbig (Dayton) to H. C. Qodt (St. Louis) 3/1/56 - Tetrachlorobisphenol-A. (4) Memo, J. Chunga to M. P. Drumm, 1/16/57 (Springfield) Economic Evaluation of Proposed Epoxy Resin Production. (5) Memo, J. Chunga to M. P. Drumm, 1/28/57 (Springfield) Eoonomlc Evaluation of Glycerol Epoxide Resin Production. (6) Memo, S. E. Oebura to M. P. Drumm, 4/6/56 (Springfield Composition of hydrolyzed Aroclor 1262 and its derivatives. (7) Memo, J. A. Herbig (Dayton) to s. E. Gebura (Springfield), 1/10/56 - Epoxy Resins from Hydrolyzed Aroclor 1262. (8) J. Pincke (Santa Clara) oral communication to M. P. Drumm. (9) G. Brown (Seattle) oral communication to S. E. Oebura. (10) Memoranda, S. E. Gebura to (a) R. J. Schatz, 10/30/56, Epoxy Resin Patent Search. (b) R. L. Heider, 11/14/56, Manufacture of Epoxide Resins from Blsphenol-A and Tetrachlorobisphenol-A. (c) R. L. Heider, 1/10/57, Curing of Epoxy Resins. (d) R. L. Heider, 1/17/57, Blends of Epoxies with other Polymer systems. (e) R. L. Heider 1/22/57, Epoxidation of Phenolic resins. DSW 621031 f* ''f' STLCOPCB4095060 Epichlorohydrin, Shell Chemical Corporation Technical Publication, p 7- U. S. 2,324,483, example 2. Memorandum, J. Dazzi to S. E. Oebura, September 15# 1955# Modified Epoxy Resina. U.S. 2% ,4<6I|7/*%,171# example IV. VJ I I f WAJ'ObttOL a U.S. 2,615#007 U.S. 2,640,037# Polyether C. Plastics Division, Seattle (15) R. 0. Neville, Plastics Division, Seattle, Research Report No. SE2265, October 10, 1956, The Synthesis of Aliphatic Epoxy Resins with Particular Reference to those prepared from Ethylene Olycol or Qlycerol. (16) U.S. 2,260,753; 2,327,053; 2,010,726; 2,538,072. ___ (17) U.S. 2,512,996, Complex liquid Polyepoxide A. (18) U.S. 2,581,464. (19) J. L. Jungnlolcel, et al., Organic Analysis, Vol. I, Interscience, New York, 1953# P 136. (20) (21) (22) H. H. Willard, et al.. Elementary Quantitative Analysis, D. Van Nostrand Company, Inc., 1940, p 185. Reference (11), p 35-26. N. I. sax. Handbook of Dangerous Materials, Reinhold Publishing Company, New York, 1951# P 157. (23) Bisphenol-A, Monsanto Chemical Company Technical Data Sheet, April 10, 1956. (24) Reference (22). (25) (26) Shell Chemical Corporation Technical Bulletins SC: 55-69# SC: 55-29, SC:55-26R, SC:55-27, SC:56-l8. Reference (22), p 54, 177-178. (27) Reference (22), p 185. (28) Reference (22), p 157. (29) M. Terptra, St. Louis Data supplied with flash distilled hydrolyzed Aroclcr 1262. STLCOPCB4095061 The syntheses of epoxy resins involve straight forward techni ques of reaction, neutralization, extraction and distillation. Common laboratory equipment designed for these purposes are satisfactory. All of these resins are synthesized according to similar pro cedures: 1. Reaction of epichlorohydrln with a polyhydric compound. This is generally exotharmic and careful control is required. The initial reaction products are chlorohydrin etuers. __ 2. Where an excess of epichlorohydrln 1b used, viz., in high epoxy containing products, the excess is recovered by vacuum distillation. 9 3. The crude product is treated with exoess base and dehydrohalogenated to form the epoxy compounds. 4. Usually, several water washings are required to remove the inorganic salt and unreacted base. 5. The final product is dehydrated undor vacuum to a relatively high end temperature. 6. The products are characterized by analysis for epoxy oxygen, hydrolyzable chloride and ash. The results are translated into percents of diglyoidyl ether and ether chlorohydrins. Detailed experimental procedures are given below for the prepara tion of all products synthesized in this study. A. Apparatus The reactions were carried out in standard laboratory equip ment except as Indicated under separate procedures. This consisted of a 3-necked flask fitted with a stirrer and two U-shaped adapters. The latter were fitted with two Fried richs condensers, a thermometer dipping into the reaction mixture and a stopper. The falsk was heated by a Olas-Col mantle. For the synthesis of the high epoxy containing products, an ice bath was always Included in the experimental t I *** `f ** f1 STLCOPCB4095062 4- z. zS-,U .H I TCBPA The initial condensation of TCBrA with ECH is highly exothermic: it In absolutely neceaaary to have an ice-H20 bath ready when running thia action. TCBPA (1281 g, 7 eq.) and 1298 & ECH (13-8 100* XS) were mixed and heated with atirring to 84. The procedure and obaerva- tiona were aa follows: Time (Min.) Temp, (*C) Remarka 84 The Glas-Col mantle waa removed. 185 cc of NaOH atook aoln (7*7 N) were added at once (1.42 eq). 99-IOO The system refluxed (2 phase reflux) An ice bath was applied intermittently to contain reaction but the temperature waa held above 95** Solid phase appeared (NaCl) Reflux subsided 14 94 Heat waa supplied and the reaction mixture was held at 95-100 for 2.5 hours. The excess ECH was then removed under a continually decreasing pressure and continually increasing temperature to a final pot temperature of 122 at 20-22 mm. 91-7* of the excess ECH waa recovered. DSW 621034 * 1* f* STLCOPCB4095063 To the residue from the distillation (at 110-111*) were added 819 co NaOH at00It soln. (7-7 N, 6.3 eq., 10* overall excess). The mixture cooled to 82*. The mixture was reheated to 112 a.id kept in the range 110-113* for 8.75 hours. The mixture was allowed to cool over approximately 2 hours. During the reaction with NaOH and cooling, samples of the aqueous phase were removed and analyzed for total alkalinity. The results are shown in Graph I. The resin was then washed with H2O. Hot water was added and the mixture heated to 95-102 and kept In this range for 1/2 hour. The mixture was then cooled to about 65-75* end the H2O decanted, The first wash was with 750 ml H2O and the succeeding 4 washes were 1000 ml each. The washes were analyzed for chloride and hydroxyl ions. The results are shown in Table I. TABLE I Wash No. Total eg. Cl Total eg. OH 4.97 I.70 0.22 0.02 0.01 0.35 0.12 0.013 0.002 Neutral to Litmus The product was then dehydrated under vacuum as described below: Time (Min.) Terop.(Pot *C) Pressure (MM) Remarks 0 90 -- Vacuum applied. Varlac at 80V. 5 65 ca-70-8o The mass was too viscous, the vacuum was released and the mass was reheated. 10 80 120-125 Distillation was satisfactory 15 65-70 120-125 Pressure was slowly lowered 25 75 75 -- 35 104 30 Varlac was set at 55V 60 125 25-30 Varlac was set at 45V 75 125 25-30 Distillation was complete The decrease in weight of the original mass was 138g (9# by weight of resin obtained). The yield of produot was lo64g. The product was odorless, sligntly yellow and slightly cloudy and it crystallized slowly on standing at room temperature (m.p. 95-98*). DSW 621035 l* '' t* *- STLCOPCB4095064 EQUIVALENTS NaOH, AQUEOUS PHASE TIKE (Hours). * * ' f * f t. * * f . * ' f `ft * * f * DSW 621036 STLCOPCB4095065 -10- Analysis: Epoxy Oxygen: 6-39- WoVH.w Hydrolyzable Chloride Ash (1600*F): 0.00 The percentage yield was 99.05** The basis for calculating tne yield is given in the Appendix. a nortion of the Droduot was filtered through a medium porosity fritted glass funnel at 130-145* under vacuum to give a perfectly clear, slightly yellow product. The filtration was a very slow process. (b) Isolation of solid dlglycidvl ether of TOBPA A sample of dehydrated tacky product, 458 g, was melted and poured slowly into 1500 cc ice cooled methanol witn vigorous stirring. The mixture was then stirred for 1.75 hours at room temperature. The mixture was filtered. The solid was tritura ted under a small portion of MeOH and filtered. The solid was dried at room temperature overnight. The filtrates were evapora ted to dryness to yield a residue of 25g. (5 *^5*)* After drying overnight, the solid was warmed at 50-60* and dried in a desico&tor under vacuum for several days. The yield of white free flowing powder was 4l8g. [92%). A similar result was obtained using ethanol as a solvent: Melting point range: 93-98*0. Analysis: Epoxy oxygen: 6.525* (97-43* DOE) Hydrolyzable cnloride: 0.165* (1.2?* DOMH) Ash (1600F): 0.0195* The infra red spectrum of this product is shown in Appendix D. (c) Isolation of initial condensation product The same procedure described for the preparation of the diglycidyl ether of TCBA, through the recovery of excess ECH was followed, using 103g TCBPA (1 eq) and l85g (2 eq) ECH. Cooling was not necessary but nevertheless, an lce-H20 bath was kept handy. A one liter flask was used for the experiment. To the residue at about 100* were added 300 cc dioxane (purified by refluxing with solid KOH and distilling). The mixture was filtered and the dioxane filtrate distilled at 30-40 mm to a pot temperature of 120-130. Yield: 269 g. Analysis: Epoxy Oxygen: 1.11, 1.133* Hydrolyzable Chloride: 10.70, 10.495* *t 1 DSW 621037 `f* 'f STLCOPCB4095066 -11- (d) Preparation of the dlglycldyl ether of TCBPA In. dloxane solvent To the product obtained aa above (228g) were added 400 cc dloxane and the product dlaaolved by warning and then finally heated at 97-98*. To the aolutlon were added 104cc NaOH aolutlon (7*5 N, 31.2g NaOH, 10% excess). The temperature dropped to 76. The two phase system was heated to reflux at 92-93 and refluxed for 9.5 hours. During refluxing NaCl precipitated, rue mixture was cooled and filtered. The filtrate waa pourod Into a separatory funnel and the lower aqueous layer withdrawn at room temperature. The upper dloxane layer was transferred to a flask and the dloxane distilled off at 30-40ram to a final pot tempera ture of about 125*C. Yield: 198g (97.5*). Analysis: Epoxy Oxygen: 6.45, 6.4956 Hydrolyzable Chloride: 0.30# Ash: 0.00 (1600*P) (e) Preparation of Qlycldyl Polyethcra This Involves the reaction of ECH with TCBFA in tuc iQOiar ratiO 2 to 1. TCBPA (183 g, l/2m) was mixed with ECH (92.5 6, lm) and warmed to 100*. The mantle was removed and to the solution were added 45 cc of 7.5 N NaOH solution (13.5s, 0.336 eq). The tem perature dropped to 95* and almost immediately rose to reflux at 105-106" (pot temperature). The procedure and observations were as follows: Time (Min) Temp (Pot, *C) Remarks 0 105-106 Refluxing 3 -- Mixture turned cloudy 12 95 Heat supplied to maintain the reaction mass at 95-105 13 95 50.5cc 7.5 N NaOH solution added (15.2g, 0.38 eq). Temperature dropped to 84*. The mass was reneated to 95-105*. 61 97 50.5 co 7.5 N NaOH solution added (IO36 excess). Tempera ture dropped to 87*. The mass was reheated to 95-105*. 136 105-110 The reaction was discontinued. The taffy like product was washed twice with 300 co water at 95-100*, 1/2 hour for each wash. The water washes analyzed 0.974 eq chloride ion. The residue from the wash was dehydrated under vacuum (30-40 mm) to a final pot temperature of 138*C. The resin was a slightly yellow, slightly cloudy soft solid at room temperature. Yield 230 g (96.436) Analysis: Epoxy Oxygen: 5.34, 5.353* ................ Hydrolyzable Chloride: 0.4l, 0.3656 DSW 621038 STLCOPCB4095067 -12- (f) Reaction of ECH With TCBPA In the molar ratio 1^57. to. ! This reaction was carried out In a ateam Jacketed laboratory kettle normally used for preparation of phenol-formaldehyde resins. The speed of the anchor agitator was about 40 RPM. To the kettle were charged 1830 g (5 m) TCBPA and 3880 g of 10* (by weight) NsOH solution. The mixture was stirred and warmed to 45* by circulating 100* HoO in the jacket. At a batch temperature of 45*, 726g (7.86m) ECH were charged rapidly to the kettle. The temperature slowly rose to ^4* when a clear solution was obtained. Within five minutes the mixture turned cloudy and the temperature rrse rapidly to reflux. The reflux stopped at four minutes. Steam was cir culated In the Jacket and the mixture brought to reflux and kept at reflux for about 80 minutes. The aqueous phase was decanted and the resin given 4 one-hour water-washes at 95-100* with 4000 cc HoO. The washed resin was dehydrated under vacuum, first at about 310 mm and finally at about 40 mm to a final pot tempera ture of about 150-l60*c. Yield: 2065g (about 90*). The resin was a yellowish and almost clear brittle solid at room temperature. Analysis: Epoxy Oxygen: 2.41, 2.38* (s) of Resins from Mixtures of TnT~BPA----- ------------------------ TCBPA (9.15g, 0.05 eq), BPA, (108.3, 0.95 eq) and ECH (92-5 g, 1 eq) were mixed and heated to 40*. To the mixture were added 67oc NaOH solution (0.15 g NaOR/cc). The temperature rose rapidly and within five minutes the solution olouded. After 10 minutes stirring, 67 cc NaOH solution wer* added and the mixture heated to reflux (101-102*, Pot Temp). After 25 minutes at reflux, 80 cc NaOH solution (0.3g NaOH/cc) were added and the mixture heated to reflux (108-109*). After 1/2 hour, the mass was cooled to 60* and the aqueous phase was decante '. The resin was washed with H2O at 90-100* until neutral to litmus and practically free of cnloride ion. The resin was dehydrated under vacuum to a final pot tempera ture of 150*C at 34 mm. Yield 159 &* The product was yellowiBh, slightly cloudy and almost solid at room temperature. Analysis: Epoxy Oxygen: 4.87, 4.87* (h) Prepara.tMioaniu.o. f t_heJ---djl-a^.-glycerolmonochlorohydrln This derivative was prepared from a mixture of DGMH and DOE by hydrolysis of the DOE present with aqueous HC1. The material used in the reaction Is described under Run No. 3 Table XII, and is refer red to as "substrate" below. DSW 621039 `tf STLCOPCB4095068 To 250 cc dioxane was added 50cc 6NHC1 (2 excess ever DOE present) and the mixture was warmed to 50. To the mixture was added dropwise 100 g of substrate dissolved in 200 cc dioxane. No vigorous reaction was observed after the addition of about 15 cc. The mixture was heated to 85-92* and the rest of the substrate was added dropwlse over 1.25 hours. After complete addition, the mixture was heated at 92* for 1/2 hour. Dioxane was distilled off to a pot--temperature of 115* at 760 mm during 2.5 hours. The residual cloudy mixture was washed, twice with 400 cc portions of H2O at 70-90" for 0.5 hours each wash. The wash H2O from the second wash was neutral to litmus. After decanting the wash H2O, the residue was dehydrated to a final pot temperature of 136* at about 20 mm. Yield: llOg. Analysis: Calod. for C21H22CI604: Hydrolyzable Chloride: 12.8656 Pound: Hydrolyzable Chloride, 12.4856 The infra-red spectrum of this product is given in Appendix D. The product showed no tendency toward gellatlon on mixing with trlethylenetetramlne and heating at 160*C for 5 minutes. The resin had a dry rubber of 15 seconds at 150"C with triethylenetetramlne. (2) Hydrolyzed Aroclor 1262 (a) Preparation of the Olyoldyl Ether Mixture of Hydrolyzed Aroclor 126<? in Moxane Solution The addition reaction of hydrolyzed Aroclor 1262 and spichlorohydrln (ECH) Is highly exothermic. An ice bath should always be handy when attempting this reaction. To a five liter flask, adapted as already described were charged 1326g (6 eq) hydrolyzed Aroclor 1262 and 1116 g (12 eq, IOO56 excess) ECH. The mixture was wanned to 75* The procedure and observations were as follows: DSW 621040 STLCOPCB4095069 14- Tlme (Min.) 1 3 5 9 9-5 11 11-5 13 21 38 Temp. (Pot, *C) 76 B* 85 90 92 97-98 99-100 100 101 99 ' Remarka Olas-Col mantle removed; 47.6g NaOH was charged (1.19 eq) aa a solution whose normality was about 7-5* The reaction was moderated with the Ice bath in ouch a manner that the reaction mixture was at 95-101. NaCl started precipitating. The reaction was discontinued and the ayeteTM adapted for vacuum distillation for recovery of - excess ECH and H2O. The reaction mixture was subjected to distillation at 30-40 mm to a final pot temperature of 102*. The distillate was a 2-phase system Lower phase: Upper phase: 481 g. 173 g. The temperature of the distillate was 11.5*. At this temperature, the lower phase Is 9&-7% ECH and the upper phase is c.5> ECH (Ref. 11). The distillate therefore contained 486g. ECH and 162 g H2O. The distillation was continued to a pot temperature of 105* at 1-2 xn; 43g of a single phase distillate were obtained. The total ECH recovery was 528.5 g. This was 95Jt of the excess used if the stoichiometric amount reacted to form the product. The residue froa the distillation was dissolved in 2003 g. dloxane (purified by refluxing with KOH pellets and distilling). The mix ture was filtered and the filtrate was returned to the flask and warmed to 90~95*C. To It were sdded 693 co of 7.5 N NaOH solution (5.2 eq, 10 excess). The temperature dropped to 75*. The mixture was reheated to reflux (92) and refluxed for 3.25 hours. During this time NaCl precipitated and the system finally consisted of 2 liquid phases and a solid phase. The mixture was cooled to 51* and filtered, and the filter cake washed with 100 cc dloxane. DSW 621041 f* STLCOPCB4095070 -15- Tt.e filtrate was placed In a separatory funnel and tne layers separated after removing an additional small amount of NaCl which precipitated as the dioxane cooled. The lower dioxane layer was withdrawn, placed In the separatory funnel and allowed to stand overnight. During this time an additional email amount of aqueous phase (upper layer) separated out.' The dioxane layer was separated and the dioxane distilled off at 40-45 mm to a pot temperature of 105* and finally at 2 mm to a pot temperature of 135*C. The yield of pale yellow, slightly cloudy resin was about 1625 g. (101*). Analysis: Epoxy Oxygen: 5*55, 5-54# Hydrolyzable Chloride: 0.15, 0.17* (b) Isolation of the Intermediate Reaction Product in the Reaction of Hydrolyzed Aroclor l2b2 and ~' Excess eH. ~ The same procedure was used as described under (1) through the solution of Che product in dioxane and filtration, using 8 equi valents of hydrolyzed Aroclor 1262 and 1.6 eq NaOH (as a 7-5 N NaOH solution). The dioxane solution was subjected to vacuum distillation to a pot temperature of 100* at 34-37 mm and t.ien to 127*C at 2 nan. Yield: 2296 g. Analysis: Epoxy Oxygen: 1.15*, 1.14* Hydrolyzable Chloride: 9.01, 9-14* Ash (1600*P): 0.00* The theoretical epoxy oxygen for the glycldyl ether of hydrolyzed Aroclor 1262 la 5.76* and the theoretical hydrolyzable chloride content of the -glycerolmonochlorohydrln is 11.3* (Appendix). The above product therefore has a glycldyl ether equivalent per centage of ia4 x l00 m 19.0gt and a chlorohydrln equivalent percentage of 9.07 as the average Cl analyses. X 100 - 80.2*, (c) Preparation of Qlycldyl Ether (OE) Mixtures of Hydrolyzed Aroolor~lgo2 Containing Various Per centages of fens gl -glycerolmonochlorohydrln --J1 ~)erlvativeB. using To prepare ti.ese mixtures, dioxane solutions containing the Initial addition product were reacted with a limited amount of NaOH, cal culated to give the approximate amount of dehydrochlorlnatlon desired. Example: To prepare a mixture composed of about 70* OMH and 30* OE. Dioxane solution (785 g) containing 487 g. adduct (9-29* hydrolyz able chloride - 82.3* QMH) wqs diluted with one liter of dioxane and heated at 85-90* with 7*6 g NaOH.In 15cc H2O for 1/2 hour. y . * >, *4 .-V-. DSW 621042 STLCOPCB4095071 -16- Tht mixture was filtered and the filtrate subjected to vacuum distillation to recover the product as previously described. Yield: 417 g Analysis: Epoxy Oxygen: 1.50, 1.52# Hydrolyzable Chloride: 8.32, 8.19# 1ST By calculations described on pngs Bf. tne product 1 73# OMH and 26# OE. In the above example, the amount of NaOH tt be used was calculated as follows: 487 x 0.113 x -12x 40^ 7>6t; Na0H 35"5 x 0.97 where 487 grams resin, 11.3# * theoretical hydrolyzable chloride for the OMH, 12# - percentage by which the chloride should be re duced, 40 - mol. weight NaOH, 35-5 equivalent weight chloride ion and 97# = purity of NaOH. (d) Preparation of a Qlycldyl Polyether of Hydrolyzed Aroclor 1262 . : To a one liter flask, adapted as already described, were charged 238.S a (1 .nfl <j) hydrolyzed Aroclor 1262 and ICC g (1.08 aq) ECH. The mixture was warmed to 77* and the procedure followed and ob servations made are given below: Time (Min.) Temperature (Pot, *c) Remarks 0 2 4.5 6 12 17 77* 90* 100" 102 105 100 Olas-Col mantle removed, 53 of 7.5 N N80H solution were added. The system waa refluxing The solution turned cloudy Olas-Col mantle was replaced and the mixture heated. To the mixture at 103* were added 53 cc 7.5 N NaOH solution and the mixture was heated at 105-110 for 1/2 hour. At the end of this time 53 cc 7.5 N NaOH solution were charged (10# overall excess) and the mixture was heated at about 110" for one hour. The resin was then washed twice with 300 cc of boiling water for 35 min. each time. The water was removed by decantation. The washed resin was dehydrated to a final pot temperature of 130 at 30-40 mm. The resin was cooled slightly and dissolved in 300 cc methyl ethyl ketone. The mixture was filtered and the filtrate subjected to distillation under vacuum (30-40 mm) to a final pot temperature of about 125-130. The resin waa pale yellow, slightly cloudy and brittle at room temperature. Yield 287 g. Analysis: Epoxy Oxygen: 3.935* Hydrolyzable Chloride: 0.31# DSW 621043 STLCOPCB4095072 -17- () Reaction of a Basic Solution of Hgdroly zed Arocl6f~Ig62~wlt'K"fi<5H~<fteT. I Hydrolyzed Aroclor 1262 (662 g, 3-02 eq) was dissolved with heating in a solution of NaOH 120.8 g, (3-02 eq) dissolved in 885 co H^O (12% by weight) and heated to 65. The ECH was then added dropwlse and the following observations were made: Time (Min.) Temperature, *C ml ECH added Remarks 0 65 0 Heat off. Olaa-Col mantle and flask. ECH addition started 5 65 9 -------11 66 20 18 67 39 Glas-Col mantle removed. 26 67 54 Mixture getting viscous 34 67 -- -- Mixture turned lighter in color___ . 4o 67 75 55 67 100 A whitish viscous mass was obtained. 65 68 125 The mass was more viscous. 80 67-65 150 The mass solidified and could not be stirred. The theoretical amount of ECH required for an equivalent ration was 230 cc. Therefore 65 of the required ECH was added (175.5 g, 1.9 q) The reacting molar ratio BCH/hydrolyzed Aroclor 1262 was 1.9/1' ..887 - l1..c0*2. This ratio was much too low to produce a satisfactory product. A small portion of the product was washed by trituration under H2O and air dried; it contained only 0.9656 epoxy oxygen. (3) Bisphenol-A (BPA) (a) Liquid Resins (Bpon 828 type) BPA 570 g, 2.5m), 929.5 g (10.04m, IOO56 excess) ECH and 15 cc H2O (1J6 by weight of reactants) were charged to a 5 liter flask, adapted as already described. The mixture was warmed to 75. To the solution were added 40 g (0.97 m) NaOH pellets. The procedure and observations were as follows: DSW 621044 STLCOPCB4095073 Remarks 0 12 13 19 20 22 25 26 27 29 31.5 32.5 39 43-5 46 50 ' 75 91 99-10! 95 93 91 66 96 97 93 88-89 97 89 98.5 99 96.5 40g NaOH were added Olas-Col -maotle was removed The mixture refluxed slightly. 40g (0.97 m) NaOH were added. The temperature rose rapidly to 99-100. The mixture was cooled with an ice bath to 91. The NaOH pellets were com pletely diSBolved. 40 g (0.97 m} Nidi TSllCtS were added. The mixture refluxed The mixture refluxed 40g (0.97 tn) NaOH pellets were added The mixture refluxed 50.5 g (1.22 tn) NaOH pellcto were added (2% overall excess) The mixture refluxed. It was cooled to 95 The mixture refluxed The mantle was replaced and the mixture was heated to reflux. The reaction mixture was allowed to reflux for 0.75 hours. The system was then adapted for vacuum distillation. The H2O and excess ECH were distilled off first at about 200 mm to pot tem perature of 97* and then at about 95 mm to a pot temperature of 160*. The two phase distillate, 409.5 g lower laver and 89g upper layer, was calculated to contain 409-3 g ECH and 89.4 g H2O. The ECH consumed in the reaction was 929-5 - 409-3 g " 520.2 g (5-62 m) and the H2O formed was 89.4 - 15 - 74.4 g (4.15m). The apparent reacting molar ratio ECH/fePA was 5-62/2.5 - 2.24. The residue was cooled to 100* and washed as follows. Method of Wash g- No. HoO Temp., Time Removing Wash *C. (hrs.) HoO and temp. gHpO Remarks 1161 1016 1007 995 1022 100-102 1 52-74 1/2 55 1/2 60-75 1/2 95-100 1/2 Syphoned off (100*) Decanted (74*) 1359g 796 Decanted (55*) 907 Decanted (750 990 Separatory Funnel (95*100*) 1066 1013 95-100 1/2 Separatory 12l4g Funnel (95-100*) Clear wash Hg V. cloudy wash H2O V. cloudy wash H2O Cloudy wash H2O Practically clear wash HoO Clear H20 DSW 621045 STLCOPCB4095074 ^ -19- The Mashed resin was dehydrated under vacuum first at about 310 mm to a pot temperature of 115* and then at about 95 mm to a pot temperature of 168. Weight distillate: 195 g. Yield of Resin: 827 g (9256) Analysis: Epoxy Oxygen: 7.24* Hydrolyzable Chloride: 1.13* Epoxide equivalent: 221 __liT~?tn--,sn .-m---m--- -z*v rn .z.x^. Small Scale BPA, (114 g. 0.5 m) was mixed with a solution of NaOH 38.8 g (0.97 m) in 340 cc HpO in a one liter flask, adapted sb already described, and heatea. The procedure and observations were as follows: Time (Min) Temperature (Pot *C) Remarks 25 Variae was set at 50 V. A slur^=. ry was present. Variae was set at 40 V. 72-5 g (0.784 m) ECH were -- charged rapidly. Practically all solids were In solution. The solution was turning cloudy. Resinous material started forming. 59 97 Variae was set at 60 V. A moderately viscous material was present. Variae was set at 40 V. The mixture was heated at 97-100* for an additional 80 minutes. The mixture was cooled to about 70* and the aqueous phase was decanted. Volume 319 cc. The resin was washed with 400 co portions of H2O each at 101-102* for 20 minutes eacn wash. After each wash the mixture was cooled to 70-75* and the aqueous phase was decanted. The reouj.es are as follows: Wash Ho. VjI. Decanted Original Aq phase 1 319 415 390 400 8$ OH .teal 0.025 0.002 0.000 - Cl (meg) 650.76 108.06 8.697 0.6&0 0.134 DSW 621046 1 1 t* t 1{! f STLCOPCB4095075 -20- The total chloride Ion analysis was 0.77 eq. Tni compared with O.78 equivalents of chloride introduced as ECH. The washed resin was dehydrated by distilling off the H2O at 760 mm to a pot temperature of 125" and then to 165 at 40 mm. Yields l49g. The resin was yellowish and slightly cloudy. Analysis: Epoxy Oxygen: 3.10, 3*12$ Average 3*11$ EpWAidc Ev^uiValvut * 515 Kvdrs! n oh.<t mgy The hydrolyzable chloride analysis was based on the fact that only 0.01 eq ECH was not accounted for in the wash HgO. This is 35.5 x 0,01 - 0.355 g of chlorine in 149 g resin or 0.238$. Large Scale For this experiment a 22 liter laboratory scale reactor was used. This consisted of a 22 liter wide neck flask on which was fitted a head through tne center of which passed a stirrer shaft and which__ was adapted for carrying a reflux condenser, a thermocouple well, and a stopper. The flask was heated by a Olas-Col mantle. To the flask were charged 2280 g (10 m) BPA and 776 g (18.82 m) NaOH dissolved in 7756 g H2O. The slurry was heated to 45 and 1450 g (15.69 m) ECH were charged rapidly. The mixture cleared and almost immediately started turning cloudy. Within 20 minutes the temperature rose to 100*. During this time t.-e resin phase formed starting first as globules and gradually coalescing into a continuous mass. The mixture was held at 100-101" for an additional 1.5 hours. The resin phase was allowed to settle (about 4 minutes) and the aqueous phase was decanted. Weight, 8428 g. The resin phase was washed five times with about 8000 g portions of H2O at about 100* for 1/52 hour each wash. The H2O phase was in each case decanted at about 95-100*. The results of the washing are given in Table II. TABLE II Wash No. H2O HgO Charged (g) Decanted (g) Analysis Cl (eq) OH (eq) Net H20 Weight *1 1 8047 2 8206 3 824s 4 8028 5 8256 2 6934 8250 8324 7715 S3. O.832 0.180 0.054 0.018 0.007 14.340 0.180 0.050 0.000 - 3.t-2-2 6878 8238 8321 7714 7905 Z45 Totals 15 430 3 528 46514 Obtained by subtracting from the gross weight of alkaline, aellnt H2O its analyzed equivalent of NaCl and NaOH. *2 Initial H2O phase decanted from the reaction mixture. STLCOPCB4095076 The hyirolyzable chioriae content of the resin was calculated on tne basis that 15.69 - 15.43 0.26 eq chloride was not accounted for. This equaled 35-5 x 0.26 - 9.24 g Cl In 3002 g resin which equals 0.30#. MATERIAL BALANCE Charged Discharged Difference Percent Difference Cl OH H20 Total Hass 15.69 eq 15.43 eq 10.82 eq*l 18.96 eq 48,816 g48,276 g 53,044 g 52,320 g -0.26 eq +0.14 eq -540 g -724 g 1.66# 0.74# 1.1# 1.36# 1 Calculated as 97# minimum NaOH *2 This figure includes 278 g H2O produced In the reaction (15.43 eq). The less of chlorine is probably too high and the figures given are on the assumption that the ECH used was 100# pure. The fcCH used was not analyzed before use because a satisfactory method was not available. Losses taking place during manipulations (by spillage. Incomplete transfers, evaporation losses) were considered the chief reasons for the lack of complete recovery of materials. VIII. DISCUSSION; (A) Reaction of excess ECH with (a) TCBPA, (B) hydrolyzed Aroclor 1262, (C) blsphenol-A, (D) preparation of polymeric epoxides from these pnenols. (E) Additionally, although practically no work was done on the preparation of epoxies from glycerol, a section is included which notes relevant factors of this preparation. (F) Economic evaluation of (C) and (D). (A) Reaction of Excess ECH with TCBPA When a limited- amount of aqueous NaOH was added to a solution of TCBPA in at least 100# excess ECH at temperatures above 55* the following reaction took place exothermically: STLCOPCB4095077 -22- a./' X 4 2 A. -C >; N-voM . (t' +Lj 1. < An v*,l\ rCC ( L ^cu, c t H, Uj ... m. ^/ m Ot /`-I fl This reaction proceeded to completion very rapidly when the equi valent ratio NaOH/TCBPA was between 0.05 - 0.20 and the relative amounts of II and III produced depended on thlB ratio. At the end of this Initial addition reaction, excess ECH and H2O were distilled off and the residue was dehydrochlorinated to give a nigh yield of II, contaminated with traces of III. Table XII (Appendix) lists the results for all the runs made. __ The reactions of TCBPA or hydrolyzed Aroclor 1262 with excess ECH do not follow the same pattern aB the reaction of BPA with excess ECH. The reactions of these diphenol3 with limited amounts of ECH are probably the same however. This will be evident from the data given in the discussion. It is therefore convenient to dis cuss the experimental work as follows: For an optimum yield of II, and an optimum recovery of excess ECH, several variables were recognized: (1) ECH/TCBPA ratio, (2) NaOH/TCBPA (3) temperature and (4) concentration of NaOH. (1) For the preparation of II the equivalent ratio ECH/TCBPA must be 2/1 or greater. At a lower ratio, polymer forma tion would undoubtedly take place. Higher ratios would have no effect on the nature of the produot, but heat dissipation from the exothermic reaction would be much better. (2) Graph II shows the exothermic rise of temperature of the reaction mixture when various amounts of aqueous NaOH were added to a solution of TCBPA in excess ECH at the same initial temperature. It 1b seen that as the ratio NaOH/TCBPA Increased from 0.05 to 0.80, the reaction becomes increasingly uncontrollable because of the rapid rise in temperature, oraph III shows the effect of this increasing ratio on the total analysis of the products obtained. The inflections in the curve are considered to be meaningless; given a more accurate method of analyses, the inflections would probably disappear. This comparison was useful because the departure from 100J6 analysis DSW 621049 STLCOPCB4095078 I IORAPH TIXK (Jljaut) STLCOPCB4095079 STLCOPCB4095080 -23- lndicafced polymer formation. A very adverse effect at high NaOH/TCHPA ratios was the simultaneous destruc tion of *<JH, as Indicated by lowered recoveries of excess ECH. (3) At a constant NaOH/TCBPA ratio of 0.2/1, the temperature at which the NaOH solution was added had very little effect, if any, on the nature of the products obtained Delow i00', duc does effect the ELnotiici-ui. Graph IV illustrates the latter point. For each temperature used in this set of experiments, the product had a very high percentage of II. Above about 100 however, it was noted that the recovery of excess ECH was lower, indicating that ECH was destroyed at the higher temperature. (4) The concentration of NaOH used In the preparation pro cedure is Important in the recovery of excess ECH from the reaction mixture. ECH is recovered by distillation of the two phase system ECH-HgO from the reaction mixture. Since ECH is soluble in HgO to a slight extent, the lower the ccLjcentratiori oi NavH, me ..^guer is the less of ECH to H2O phase for a constant amount of NaOH used. From an economic standpoint, therefore, the concentration of NaOH should be high, if the aqueous phase from the distillation is to be discarded. The second phase of the reaction, the dehydrochlorlnation of the adduct obtained with caustic solution after recovery of excess ECH, has not been extensively studied. The approximate speed of HC1 elimination was shown in Graph I under Experimental Procedures (p 10-11). Considerable improvement In the rate could undoubtedly be obtained by an increase in the percentage of excess NaOH used or by counter-current techniques. The washing of the product obtained was alBo a slow process, and improvements could be introduced; washing by the counter current technique would be much more efficient. The product as obtained by dehydration was always somewhat cloudy. It is thought that this la due to the presence of traces of HoO. Prolonged heating during dehydration would reduce the H2O content of the product but it would appear that drying with a thin film evaporator would be more efficient. The product could, of course, be Isolated with the aid of organic solvento, such as benzene; although this would be a much more rapid process, the necessity for solvent recovery units would be disadvantageous. (B) Reaction of Excess ECH wltn Hydrolyzed Aroclor 1262 The same considerations which were discussed under (a) are ap plicable to the preparation of the glycldyl ether mixture of hy- DSW 621052 STLCOPCB4095081 GRAPH IV (M lnutin) STLCOPCB4095082 -25- VII, by reaction with the excess ECH present and additional i NaOH added, may react again to yield the chlorohydrin derivative. Thus in the case of BPA, it is not possible to perform the Initial addition reaction, recover the excess ECH and then react tne pro duct obtained with caustic (as with TCBPA). An excess of ECH must be present throughout the course of addition of NaOh. If one proceeds with EPA as with TCBPA using ths equivalent iatiu NaOH/fePA ratio 0.3, then the product is not a high epoxy con taining material but one which has an epoxide equivalent of about 400. [The epoxide equivalent of V is 170). The above observations were made in conjunction with experimental work being performed on TCBPA. When a program for obtaining cost estimates for the production of BPA epoxies was initiated, the processes described in the patent literature were followed. In the process for the preparation of Epon 828 type resins (Ref 13), solid caustic is added in portions to a solution of BPA in 150% excess ECH and containing about 1% H2O. Upon completion of -- caustic addition the excess ECH is recovered by distillation and the product is isolated from benzene. Although the process is capaole of reproduction, it was decided that in this study, the benzene system would be eliminated. In the process which was studied during this program, BPA was dissolved in 100% excess ECH and 1% (by weight of reactants) HgO was added. To this solution, starting at 75* NaOH pellets were added in 5 portions in the equivalent ratio NaOH/BPA * 0.194 for four additions, and a final portion of 0.244 (2% overall excess). During the additions, the mixture was cooled with an Ice-HgO bath In order to maintain the reaction mixture at about 95-100. The excess ECH was recovered by distillation, the residue was washed with HpO and the washed resin dehydrated under vacuum. The product obtained by this process was an amber colored fluid resin whose hydrolyzable chloride content was about twice that of the commercial product (1.1% vs. 0.5%). From the analytical data it was shown that by further dehydrochlorinatlon of this product (X to 0.5% Cl), Epon 828 would result. In one experiment, an attempt was made to reduce this content by introducing caustic (5% excess) into the first H2O wash but the attempt was unsuccess ful since a part of the product gelled during the washing cycle. Because of limited time spent on thlB process and because the data obtained were somewhat inconclusive, future work should in corporate the following ideas. (a) It is believed that 100% excess of *-CH Is sufficient for obtaining the proper product but that for better heat control it may be necessary to go as high as 150%. Graph V Illustrates the temperature variations during the reaction cycle using 100% excess ECH. DSW 621054 t* STLCOPCB4095083 -26- (b) The method of caustic addition ia probably satiofactory, but it may be necessary to increase the time between additions in order to effect better dehydrochlorlnation. (c) The recovery of excess ECH by distillation is considered satisfactory. (d) The washing and removal of wash waters should be con ducted at about 9"l00oC. Some additional work may be desirable with respect to addition of caustic to the first wash (a smaller excess than in tne case given above) with the idea of effecting a part of the dehydro chlorination here. (e) Since the products obtained by dehydration were slightly cloudy, i.e. H2O may have been present, it may be nscss* sary to prolong the dehydration or to revert to a thin film evaporator. The aualjraiD should be expand ^ - ~ A ^ 1 , hydroxyl determination and molecular weight determination. The former would especially be useful In obtaining a more precise determination of the ECH requirements of the process. (D) Preparation of Polymeric Epoxides The processes followed for the preparation of polymeric epoxides were those described in the patent literature (Ref 14). In these processes the nature of the product is determined predominently by the molar ratios ECH/^PA and NaOH/ECH, and the manner of addition of the caustic. Qraphs VI and VTI illustrate the varia tion of epoxide equivalents and softening points of resins with the variable ratio ECH/BPA. For the preparation of solid type resins from BPA the synthesis of lipon 1001 was undertaken. For the preparation of this resin the molar ECH/BPA ratio was 1.57 and the NaOH/ECH ratio was about 1.25. The preparation procedure consisted of dispersing BPA in the caustic (10jt), heating to about 45*, and charging the ECH rapidly to BPA-caustic mixture. The tempera ,-e was allowed to rise to about 95-100 (heat supplied) and kept at this range for about 80 minutes. The product was washed with hot water, dehydra ted under vacuum and discharged from the flask while hot. In this procedure, the following variables were recognized: (a) ECH/BPA ratio, and NaOH/ECH ratio, (b) rate of addition of ECH, and rate of stirring, (c) heating period, (d) washing cycle (e) dehydration and (f) yield. Additionally, (g) concentration of caustic must be considered because this factor determines the capacity of the charge. These variables are treated separately below. (a) Molar ratio ECH/BPA and Molar ratio NaOH/ECH The ratio ECH/BPA - 1-57 and the ratio NaOH/ECH - 1.25 was chosen DSW 621056 STLCOPCB4095085 Bpox3.de i-q u lv a x e n t f * f STLCOPCB4095086 --I---- ,__________ ":7"rT t~ Nuabprati llnpil ]alDn oirdinata : _r__p__T_^L__Ln-i.t:o_U_I__* 1. - poinvi of iahti|JtooH_ . ' ;fr ^onpt^nt 1,-Varlabli ~0r-^7 XJ1 /: ----- 1----Ui"_i. ; i i- ii rrr* -/j|_ I -- ----! i ' ( : / :~TMr I T : / ~i....I""' f:f ( ! : K o la r R a tio ECF/fePA i* STLCOPCB4095087 Por the preparation of the r.op*et epoxide equivalent resin, the ECH must be charged rapidly and the stirring should be very efficient- The reactions which are probably "balanced" In the whole process are (a) addition reaction of ECH with BPA and the polymers formed and (b) the addition reaction of BPA with the BPA glycldyl etners formed. It is thought that slow addition of ECH or Inefficient stirring would emphasize reaction (b) and lead to a product whose epoxide equivalent la too high. This is somewhat borne out by the scale up to a laboratory kettle of the BPA charge from 1/2 m to 10 m, to a kettle, where in the last two t.hw Rtirrlng was not aa efficient an In the 1/9 m runs. The- epoxide equivalent for those runs was higher than in the 1/2 m runs, where the correct equivalent was obtained. Table III shows the results from these runs. TABLE III Scale and Equipment 1/2 o Common lab Common lab 22 1 reactor 22 1 reactor gal. lab kettle m. g&l. lab kettle $ Epoxy Oxygen (average) 3-22 3.11 2.87 2.78 2.60 2.48 Epoxide Equivalent 493 515 557 575 615 645 (c) The neatlng period A heating period of 80 minutes was found to be satisfactory for obtaining a product whose hydrolyzable chloride content was very low and comparable to the commercial product. No attempts were made to reduce this (d) Washing cycle The factors considered in the washing cycle were (1) temperature of washing and at decantation and (2) volume of wash water used and (3) time of washing; (2) and (3) were important from the standpoint of capacity. (1) It was found by trial and error that the most efficient pro cess was in washing at a temperature of 95-100 and decanting as DSW 621059 f STLCOPCB4095088 -20- as soon as the resin settled. Very clear wash waters could be decanted using this procedure in contrast to considerable cloudiness when decantation waa carried out at lower temperature. (2) No study was made of the efficiency of washing with reepect to volume of water used per wash. It wsb found however that the volume could be reduced from 8000 cc to 4000 cc on the basis of a 10 m BPA run for a resin yield of about 3000 g. (3) The time factor was not studied either. Washes of one-haif hour each wei-e chosen arbitrarily. This element could easily be determined by removing aliquots of wash at various time in tervals and analyzing for chloride and hydride ions. From these data a time limit for most efficient washing could be chosen. (e) Dehydration The washed resin retained about 50$6 H2O by weight of resin ob tained. It is thought that the dehydration as carried out under reduced pressure (the latter waa determined bv the softening point, of the resin, about 75) represents the limit available with this process. A significant improvement could be introduced however by the use of a tmn film evaporator from the standpoint of continuous operation and perhaps obtainment of a clearer product. (f) Yield This factor is difficult to evaluate properly and no attempts were made in this study to determine the reasons for the ap proximately 9556 yields obtained; it would appear that the yields should be almost quantitative. Some resin was definitely lost to the wash waters (as suspended material, probably not greater than ljj). The best guess would be that the loss in yield is in the BPA, by virtue of its contaminants (e.g. phenol, but only a small percent) and by its Incomplete reaction end removal as the sodium salt in the wash waters. The latter could certainly be quantitatively ascertained by analyeis of the waeh waters for BPA. IfiL. Concentration of Caustic It is easily seen that the use of 10<f> caustic limits the capacity of this process severely. Since this is the concentration used in the patent processes, it waa used in this study. A few "spot" experiments using 30 and 20St caustic were unsuccessful, the re action mass being unatlrr&ble. It appeared from these experiments that about l4-l6j* caustic may be the workable limit with the pre sent process. Although the effect of concentrated caustic on the resin is not known it would appear to be small since in the preparation of Epon 020 type resins, very concentrated caustic is present in the preparation mixture without any drastic loss of epoxy groups. DSW 621060 *1 t '' \' STLCOPCB4095089 In this laboratory no Btudy was made. Include a section in this report on the chemistry of this pre paration since an economic survey was made on this basis. The chemistry in turn was to a good extent deduced from data given in the patent literature (Ref 16). Epoxides from glycerol have reached only the developmental stage; the resin available from Shell is Epon 562. This resin is pre pared by the bulk reaction of ECH and glycerol in the presence of about by weight of reactants of BF3ET2O (Ref 17) followed by dehydrochlorination by salts sucn as NaAl02, NaZnC2, Na2S103 in an organic solvent such as dioxane. The inorganic salts are filtered off and the solvent is distilled to recover the resin. The tr.eoretical reactions are as follows: STLCOPCB4095090 The above reactions are complicated by Interfering reactions, such as polymerization of ECH by BF3, further reaction of I with ECH, hydrolysis of II by H2O, and by products arising from the in complete reaction of glycerol and ECH. lc is intei-eraling to compare the properties of Epon 562 with tne stoichiometry of this preparation. The reaction of equivalent quantities of ECH and glycerol followed by reaction with excess MaAlC-2 should yield approximately equivalent quantities of epoxy oxygen in the product, i.e., the epoxide equivalent of the product should be about 87. The commercial product has an epoxide equivalent of about 145 indicating that undoubtedly the resin contains a large percentage chlorine. This may be due to an in complete reaction of NaAlOg with the chloronydrins or the fact tnat chlorine atoms are present whose functionality is not like that of the chlorohydrin, i.e., they are not as easily removed as HC1 (Ref 18). These views must be taken into consideration if any additional work for the preparation of glycidyl ethers of polyols is undertaken Dy Monsanto. (F) Economic Evaluation of the Production of Epon 562, 828 and TOOl" Type "Resins---------------^------------------------------------- ----- ------------ This section contains a summary of the work performed by J. Chunga of Division Engineering (Ref 4, 5), M. F. Drumm and the writer. It includes; (Si Production of Epons 562, 828 and 1001. (Mr. J. Chunga) Flow diagrams for the production of these resins. iMr. J. Chunga) <0 onographs showing variable returns on investment for variable cost of BIA and ECH and variable selling prices of resins. (Dr. M. F. Drumm and Dr. S. E. Gebura) Production of Epons 562, 828 and 1001. Table IV - Facility A. 1,000,000 lbs/yr Epon 828 and . 3,000,000 lbs/yr Epon 1001. Table V - Facility B. 3,000,000 lbs/yr Epon 828 and 5.000.000 lbs/yr Epon 1001. Table VI - Faoility C and D. 1,000,000 and 3,000,000 lbs/yr Epon 562. Table VII- Facility E, F and G 20,000,000 lbs/yr Epon 828, 20.000.000 lbs/yr Epon 1001 and 20,000,000 lbs/yr Epon 562. STLCOPCB4095091 Epo;. 82^ Production Annual Net Sales Quantity, lbs. Unit price, list.$/lb, Freight charge, $/lb. Net Price, $/lb. Amount ANS ,000,000 0.80 0.01 0.79 790,00 Cost of Goods Sold Manufacturing Raw Materials Direct Conversion Depreciation Indirect Conversion Packaging St Shipping Royalties of 5J< AOS Total Cost Goods Sold 425.60 91.01 17.21 24 .63 20.00 40.00 618.45 Gross Profit Deduct SARE at 10% ANS 171.65 79.00 Net Income Before Taxes Income Taxes at 5036 Net Income Before Taxes 92.55 46.28 Earnings After Taxes 46.27 CAPITAL ESTIMATE SUMMARY FACILITY "A" (in Thousands of Dollars) New Property to be Installed; Building M&E New Fixed Capital 26.4 202.0 22S74- Share Existing Property: at 30% NFC Total Fixed Capital Working Capital Inventory All Others at 1$% ANS Total Working Capital Total Operating Investment Return on Investment 68.5 296.9 66.8 118. 18 apoii 1001 Production 3,000,000 0.605 0.010 0.595 1785.00 1179.90 133.11 26.82 38.10 30.00 90.75 1498.68 286.32 178.50 107.82 53.91 53.91 26.4 122.0 uTBTT 104.6 453-0 173.0 267.8 STLCOPCB4095092 -32- TABLE V ANNUAL PROFIT AND LOSS STATEMENT FACILITY "B" (in Thousands of Dollars) Epon 828 Production 1. Annual Net Sales Quantity, lbs. Unit pric, list Freight Charge, Net price, %/lb. Amount ANS 3,000,000 0.800 0.010 0.790 2370.00 2. Cost of Goods Sold Manufacturing Raw Materials Direct conversion Depreciation Indirect conversion Packaging and Shipping Royalties at 556 AOS Total Cost Goods Sold 1276.80 149.22 2u.4y 4Ct/Vr1\ .4ru\3rv\ 120.00 1667.94 3. Qross Profit 4. Deduct SARE at 10j6 ANS 5. Net Income Before Taxes 6. Income Taxes at 5056 Net Income Before Taxes 7. Earnings after Taxes ........... 702,06 237.00 465.06 232.53 232.53 CAPITAL ESTIMATE SUMMARY FACILITY "B" A. New Property to be Installed: Building M * E^ New Fixed Capital 44.6 44.6 m B. Share Existing Property at 3056 NFC C. Total Fixed Capital D. Working Capital Inventory All others at 1556 ANS Total Working Capital 83.6 362.7 189.2 m E. Total Operating Investment P. Return on Investment 25.656 Epon 1001 Production 3,000,000 0.603 0.010 0.595 2975.00 1966.50 216.15 41.40 e5r9\ .0r\0r\ 151.25 2484.30 490.70 297.50 193.20 96.60 96.60 44.6 44.6 495.0 161.9 701.5 289.2 446.0 "735TS 6.756 ! ' ** DSW 621064 ** STLCOPCB4095093 Case A Case B Case C to.90/lb., list $1.00/lb., list $1.10/lb., list As was anticipated, the price range chosen was sufficient to Indicate the sales conditions for poor and good returns on investment. STLCOPCB4095094 (In Thousands of Dollars) 1. Annual Net Sales Quantity, lbs. Unit price, list $/lb Case A Case B Case C Freight charge, $/lb Net price, $/lb Cas...e A n Case C Amount ANS Case A Case B Case C .2 Cost of Goods Sold Manufacturing Raw materials Direct conversion Depreciation Indirect conversion Packaging Royalties Sc Shipping at 5# AGS Case Case Case A B C "otal Cost Ooods Sold Case A Case B Case C Case A Case B Case C Gross Profit Case A Case B Case C Deduct SAKE at 10# ANS Case A Case B Case C Facility C 1,000,000 0.90 1.00 1.10 0.01 0.89 0 00 i.09 890.00 990.00 1090.00 617.70 109.69 27.05 27.66 27.84 28.02 20.00 45.00 50.00 55.00 847.30 852.48 857.66 42.70 137.52 232,34 89.OO 99.00 109.00 Facility D 3,000,000 0.90 1.00 1.10 0.01 0.89 n on 1 !o9 2670.00 2970.00 3270.00 1853.10 172.38 39.96 52.44 53.01 53.55 60.00 135-00 150.00 165.00 2312.88 2328.45 2343.99 357.12 641.55 926.01 267.00 297.00 327.00 DSW 621066 STLCOPCB4095095 ANNUAL PROFIT AND LOSS STATEMENT (Continued) 5. Net Income Before Taxes Case A Case B Case C 6. Income Taxes at 50% Net Income Before Taxes : Case A Case B Case C 7- Earnings After Taxes Case A Case B Case C Facility C None 38.52 123.34 19.26 61.67 ^--^ 19.26 61.67 Facility D 90.12 344.55 599.01 45.06 172.28 299.51 45.06 172.27 299.50 STLCOPCB4095096 (In Thousands of Dollars) Facility C Hew Froperty to be Installed: Building M&E " New Fixed Capital 60.0 308.5 3EBT5 Share Existing Property: at 30$f NFC 110.6 Tc wG 1 O < y Pori ho) 47Q.1 D. Working Capital Inventory All Others ,at 16% ANS Case A Case B Case C 75. 133-5 148.5 TEjzf Total Working Capital Case A Case B Case C 209.2 22TT2 Case A Case B Case C. 688.3 703.3 718.3 Case A Case B Case C no return 2.7% 8.6% Facility D 97.0 452.0 164.7 713.7 400. W* 1336.8 1381.8 1426.8 STLCOPCB4095097 Epon 828 Production A. Annual Net Sales Quantity, lba. Uni', price, Hat. $/lb. Freight charge, $/lb. Net prloe, $/lb. Amount ANS 2Q,000,000 0.80 0.01 0.79 15,800 B. Coat of Goods Sold Manufacturing Haw Materials Direct Conversion Depreciation Indirect Conversion Packaging and Shipping Royalties at 5* AOS 3,512 A60 64 126 400 800 Total Coat Goods Soli 10,36? C . Oross Profit 5, *38 D. Deduot SARE at 10* ANS 1,580 E. Net Income Before Taxes 3,858 ?. Income Taxes at 50* 1,929 Net Income Before Taxes G. Earninna After Taxes 1,929 Epon 1001 Production Epon 562 Production 20,000,000 0.605 0.010 0.595 11,900 2>j, 000,000 1.00 0.01 0.99 19,800 -- 7,8*6 440 96 120 200 605 9,327 2,573 1,190 1,383 692 98 160 400 1,000 14,592 5,208 1,980 3,228 1,614 691 1,614 DSW 621069 ** STLCOPCB4095098 -33- CAP1TAL ESTIMATE SUMMARY (Tn Fir\ 1 T ar*fl } 20,000,000 pounds per year Epon 828 Epon iOOl Spon 562 Production Production Production A. New Property to be Installed: Building M&E New Fixed Capital 83 n2 815 61 1.140 1,201 302 1,410 1,712 B. Share Exlatlng Property: at 30* NFC 244 360 514 C. Total Fixed Capital: D. Working Capital! 1,059 1,561 2,226 Inventory All Others at 15# ANS 1,241 2^68 Total Working Capital 3,609 E. Total Operating Investment: 4,668 P. Return on Investment: 41* 1.151 1*786 2,945 ^,506 155^ 1,484 2.970 4,454 6,680 24* STLCOPCB4095099 STLCOPCB4095100 STLCOPCB4095101 i' 23 STLCOPCB4095102 Coat o f E p ich lo i*o h yd rin , (i/lb . Cost o f B isphenol-Jt, 4 /lb . iC ost o f E p io h lo ro h y d rin , / l b STLCOPCB4095103 A one-cent drop in selling price reduces return on Investment by 0.6 percentage points. Net Return on Investment After Tax of 50$ 35 T T 30 Coat o f E p lc h lo ro h y d rln In Cents Per Pound Cost o f Q ly c e ro l In Cents Per Pound STLCOPCB4095104 <0(<r XI. MATERIAL SPECIFICATIONS. ANALYTICAL PROCEDURE: Source of Katerlala: Hydrolyzed Aroclor 1262. This material was prepared from Aroclor 1262 which ia a chlorinated biphenyl. Flash distilled hydrolyzed Aroclor 1262 (Monsanto, St. Louis) was used. The ItyIpical material was a glass at room temperature which analyzed .83# chlorine and which had an equivalent weight of 221. Tetrachlorobisphenol-A. Monsanto, St. Louis, Lot No. 22046. Bisphenol-A. Monsanto, St. LouIb. Epichlorohydrin. Shell Development Corporation, 98# min. NaOH. Mallinckrodt, Analytical Reagent, 97# min. r>-- A . opeuri4iluau. trifllD-- i rnitu_ --c JU6 VC*X U|^llcu v rt 1ia_ ip__o__i'_d4-VUl'JI ses fc^ epoxy resins from BPA was directed to producing products with the following specifications. u~vc-o" Liquid resins (Epon 828 type) Solid Resina (Epon 1001 type) ` Liquid Resins from Glycerol (Epon 562 type) Epoxide Equivalent: 190-210 __ Hydrolyzable Chloride: 0.5# Epoxide equivalent: 450-525 Hydrolyzable Chloride: 0.256 Max. Epoxide Equivalent: 140-165 Aromatic Chlorine - The aromatic chlorine content of the products obtained from hydrolyzed Aroclor 1262 was determined at Dayton under the direction of Dr. John Dazzi. Epoxy Oxygen - The procedure followed for epoxy oxygen determina tion was the standard pyridine hydrochloride method (Ref. 19). Apparatus - 100 ml single neck RB flasks, reflux condensers. Reagentb - About 0.2 N pyridine hydrochloride solution prepared by diluting l6cc cored HC1 1 lei to 1000 ml Volume with Fischer certified Reagent pyridine; about 0.1N standard NaOH, phenolphthaleln indicator. Reactions R0CH2CH-CH2 + It, HC1 I II (Excess) Pyridine Reflux / R0CH2CK - CH2 I OH II (Excess) + NaOH NaCl + H20 -7* DSW 621076 STLCOPCB4095105 -40- Prooedure The pyridine hydroohloride was compared with standard NaOH using, phenolphthalein indicator. The volume of NaOH required for 25cc of reagent was recorded. (A) The sample to be analyzed was weighed directly into a flask. To the flaak were added boiling chips and 25 cc reagent. The flask was warmed slowly and swirled occasionally to dissolve the sar;p?.c The solution was refluxed for 1/2 hour. The flask was cooled in an ice - H2O bath. Pour drops of phenolphthalein were added and the solution was titrated with standard NaOH to the pink end point. During the titration the flask was kept in an ice H2O bath. The volume of NaOH used was recorded (B). The percent epoxy oxygen was calculated from the equation St Epoxy Oxygen a(A-B) N X 0.016 x 100 1 U-- a I JV.&. /1 where N is the normality of the NaOH Hydrolyzable Chloride The procedure described here was not applicable to solid resins from BPA because of their insolubility in ethanol. Hydrolyzable chloride was determined by converting the organic chloride into soluble inorganic chloride and analyzing by the Volhard method (Ref 20). Apparatus - The equipment used for epoxy oxygen analysis was also used here. Reagents - Standard AgNOo and KSCN, PeS04, KNO3 (6N), nitrobenzene and approximately 0.5 N ethanolic KOH. Reactions - ROCHoCH - CHo I OH STLCOPCB4095106 -41- heated and swirled occasionally to affect solution. The mixture was then refluxed for one hour. During the reflux the mixture was swirled oooasionally in order to keep the mass well dispersed in the ethanollc solution. The mixture was cooled, diluted with 10-15 cc distilled HgO and acidified with HNO3. The soluble chloride was analyzed by Fhe Volhard method. % Hydrolyzable Chloride (C-D) x 0.03546 x 100 weight sample (is) where C - ml AgNO^ used x its normality and D - ml KSCN used x its normality XII. TOXICITY AND HAZARDS: (1) Epichlorohydrln (ECH) Epichlorohydrln may polymerize violently in the presence of acldi . catalysts. Caution must be observed In order that large volumes of ECH do not come in contact with these catalysts (Ref 21). BlBpnenol-A - Bisphenol-A is moderately irritating to the skin and eyes. It should be removed from the skin with soap and water and flushed from the eyes with clean water, if contact occurs. Oral LD50 to rats is 6.5 g per kilo. The chemical is not considered hazardous to handle, but contact should be avoided or promptly remedied as above (Ref 23). Tetrachloroblsphenol-A and Hydrolyzed Aroclor 1262 The toxicity of tnese new materials is unknown. It may be as sumed that the precautions used for working with phenol Itself can be applied here. For phenol, the liquid or solutions are very corrosive to the akin. Phenol is readily absorbed through the skin and mucous membranes, it can also be absorbed through the lungs as gastrointestinal treact. After absorption the toxic effects are exerted primarily upon the central nervous system but following sufficient exposure, there can be edema of the lungs, kidney, liver, pancreas and spleen. Exposure to toxic amounts usually results in death in a few hours (Ref 24). Blsphenol-A Epoxides Studies to determine acute toxicity have shown that the resins (Epon type) are practically non toxic. The oral administration of more than 6cc liquid resin (Epon 834 type) per kilo of body weight was tolerated by white mice without symptoms. There was no hazard from vapor exposure. The solid resins (Epon 1001 type' present no hazard whatever in ordinary industrial use. DSW 621078 STLCOPCB4095107 &>'* i -42- Cases ol dermatitis among workura haudlin,, liquid resins (Epons 828, 834, 562) have established that the latter will cause ski'i irritation in hypersensitive individuals. In t..e normal indiv-ciual, andling methods which minimize skin contact would ordinarily suf fice as a precautionary measure. The latter includes gloves, i.eavy aprons and full face shields. In case of contact protective creams, such products as Merphenex, Acid Mantle and Kerodex have been found beneficial (Ref 25). Tetrachloroblaphenol-A and Hydrolyzed Aroclor 1262 Epoxides The toxicity of these new materials is unknown. It may be assumed tnat the precautions necessary for handling bisphenol-A epoxide resins are applicable here also. BP3 - Etnerate This material is flammable and can cause explosions. It is easily inhaled because it is volatile. It is toxic. The fluoride con tent of this material renders it an irritant to the skin, eyes and mucous membranes. The material should be used in closed systems, if possible. Personnel exposed to it should wear protective __ clothing, safety goggles and a respirator. The material should be stored in a ooql place out of direct rays of the sun away from areas regarded as acute fire nazards (Ref 26). Olycerol A combustible liquid and a moderate fire hazard. It is considered relatively non toxic. It can cause iritis, slight internal con gestion and Blight necrosis. Personnel who handle large quantities should proteot the eyes with chemical safety goggltB. To fight fires of this aterial, water (fog or spray), oarbon dioxide, carbon tetrachloride and dry chemical may be used (Ref 27) Pioxane A flammable liquid and dangerous fire hazard. The liquid is dangerous to the eyes and can cause lackrymatlon. One of the earliest symptoms of intoxication is misty vision. It also produces irritation of the lungs and prolonged exposure can cause narcosis. It has insidious long range effects and prolonged exposure can produce damage to the liver and kidneys. Toxic amounts may be absorbed througn the skin. It is capable of forming peroxides and it can explode when distilled. Dloxane snould be used in closed systems or with adequate exhaust ventilation. For protection of the eyes personnel should wear chemical safety goggles. If the concentration is over 50 ppm, a respirator should be worn. It should bs stored in a cool, well ventilated place away from acute fire hazard or powerful oxidizing agents. To fight fires of this material carbon dioxide, carbon betrachlorl.de and dry chemical may be used (Ref 28). DSW 621079 STLCOPCB4095108 Dayton: St. Louis: ring) H. Kelly (Patent Dept.), G. Adams and P. Shapras (Infra-Red Spectra). J. Dazzl and J. Herblg M. Terpstra and R. Cass r\ Witnessed by /jw ft. P. iSrumra, Group Leader XIV: APPENDIX: The conclusions drawn from the U.S. patent survey concerning epoxy resins are given below. The report on this survey will be Issued separately. It should be noted that purchase of epoxide resins permits their curing or blending without patent infringement. Manufacture of Resins Monsanto can manufacture, without patent infringement, resins from bisphenol-A (BPA) by reactions where the molar ratio of eplchlorohydrin (ECH) to BPA is 1.6 - 1.9 to 2.1 to 3.9- These ratios give products whose properties are such that they would not provide a competitive line of epoxide resins and result In a narrow range of properties. Patents prevent the manufacture of resins from BPA by reactions where the molar ratio of ECH to BPA is 1.1 - 1.5, 2.0 or 4.0 or greater. A variety of resins from tetrachlorobisphenol-A (TCBP-A) or mixtures of TCBPA and BPA can be manufactured which oould very well be competitive in the epoxide resin field. Patents prevent the manufacture of monomeric glyoidyl ethere from polyhydrlc phenols where the molar ratio of ECH to polyhydrlc phenol is 4.0 or greater. Resins of high molecular weight cannot be pro- STLCOPCB4095109 duced from low molecular weight resins or monomeric glycidyl ethers by further reaotlon with dlhydrlc phenols without patent Infringement. The production of the adduct of glycerol and ECH In the presence of fluorine containing catalysts Is claimed by patents. Monsanto oan produce this adduct however. In the pre sence of other acid aotlng catalysts, eg. FeCl3, H2SO4 etc. Monsanto cannot produoe the epoxide resin derived from this adduct by hydrochlorlnatlng It with sodium aluminate, zlncate or silicate in an organio solvent. It may be possible to prepare this resin by other dehydroohlorinating processes, whether a particular process Infringes the patent literature will be determined by toe nature of the product obtained, i.e. its chloride content and type of chloride. No patents were found whloh claim the processes or products of the epoxidation of phenol aldehyde novolaca. Since this is being done commercially in England, British patents may exist and may be copending In the U. S. Although the epoxidation of the alkali salts of methylol phenols la covered by only a single patent, it is thought that this patent could be troublesome. The claims would tend to include the -- Monsanto West Coast resinB which have a high content of monomeric methylol phenols. The claims do not include the polymerio one stage phenol formaldehyde resins. Curing The patent literature describes a large number of curing reagents. For the moat part theae are specific reagents for which specific advantages are claimed. Monsanto could, therefore, easily enter Into the field of utilization of hardeners by developing new curing systems or specific curing reagents possessing superior properties to those disclosed so far. The functional groups which are not oompletely blocked by the patent literature include amine, carboxy lic add, mercaptan, amide aldehyde, ketone, and various combina tions of these functional groups or their derivatives. Patents prevent the use of hardeners which contain in general one to three of the functional groups carboxylic acid anhydride, sulfuric acids or their chlorides. Isocyanate, isothiocyanate, polyol (containing at least two primary OH), phenolic hydroxyl, phosphoric acids and derivatives. - In addition Monsanto may not use the specific curing reagents which are listed in Table VIII. Blende of Epoxide Resina (a) phenol, melamine or urea aldehyde condensates. The patent situation concerning the blending of epoxide reslne with aldehyde condensates of phenol, melamine or urea is extremely complex. It is not possible to state any definite conclusions with respect to these blends until a thorough examination of the situation by the patent department is made. With this reservation, it is DSW 621081 * STLCOPCB4095110 irww- 5-* - possible to reach the following conclusions: (a) Monsanto can formulate ternary or higher blends which may be Improvements on the binary systems covered In the patents; (b) In a limited number of cases, it may be possible to formulate binary blends which fall outside the patented limits of components; (c) patents prevent the formulation of higher blends of epoxides with these condensates which are listed in Table IX. (b) Other polymeric systems - Monsanto cannot utilise those blends of epoxies with other polymeric systems which are listed in Table X. The blends of polymeric systems with epoxies which have not been uncovered in the patent survey include polyurethane. Nylon type, acrylonitrile, acrylamide, furan, thlokol, rubber, vinylidene cyanide sulfonated or carboxylated styrene, terephthallc and isophthalic acid types and various copolymeric systems which are not listed in the tables. STLCOPCB4095111 STLCOPCB4095112 STLCOPCB4095113 R - a t le a s t 14 C atoms X* group capable re a c tin g w ith epoxide group STLCOPCB4095114 STLCOPCB4095115 j f rU .3 . P a te n t Number o f Type o f ----- Bo,------------ Sate------- C laim s---------- agent--------------------------- Rangeg p o jc ld e _____________ 2,717,885 9/13/55 * BP3 s a lt o f amines N.S. P h e n o lic Iaph i , ^ ^ R alkyl, phenyl - k- OH, alkoxy . 1-2 - n 0.01-3 - * + (b) tsrephthallo or lao phthallo acids or lower alkyl esters (0) glycerin U.S. Patent No. 2., 528, 360 2,5ai,>il 2,521,912 2,687,397 2,730,467 Date Ho. of Claims 10/31/50 21 9/12/50 13 9/12/50 7 8/2vs* 9 1/10/56 3 TABLE Q Type of Epoxide PHP PHP A Blend of Epoxide with Alkylated condensate of aldehyde and amines or amides polyhydrlc phenol Phenol-aldehyde condensate alkaline catalyst . Phenol-aldehyde condensate PHP PHP alkaline catalyst ITrea-CHgO condensate Neutral salt of amine and a sulfonic acid amine; ETgHH, ET3N, 1-Rt^HH, aniline, pyridine, morpholine cetyldlmethylamine -Urea^CHgQ condensate epoxide ^ JCH-CHp R3-{j^-(CB20H)n 2,703,765 If- 2,631,138 2,687,396 2.637,716 2,637,715 : 2,458,796 3/8/55 14 3AO/33 12 8/24/54 2 5{5A3 5/5/53 15 1/11/49 21 BPA BPA PH? PHP Z-(CHa)x n-1-3 Solvent alkyl, aryl Butylated urea-CHgO, me1amineCHgO, or propylated urea - CHpO condensates Sslicylle acid, ^-chloro ealioyllo acid, aoetyl salicylic aold Alkylated-urea -- CHpO ' condensate Hydrocarbon containing 1-3 SO3H or SO{>CL groupn 1. A phenol -CH2O resin reaction product of 2. (a) RTffSiXy0u-(a-j--n) R- alkyl or phenyl X- OH, alkoxy m 1-2, n- 0.01-3 (b) CO2H COgH 0" 0 CO2B COp2HH or lower esters (c) glyoerin Polybaslc carboxyic acid or anhydride; polyamine alkyl ether of CHgO condensate of phenol, urea, melamine or dlcyandlamiae '< Polybaslc acid or anhydride dloyandiaml de alkyl ether of CH^O condensate of phenol, urea, melamine or dioyandlaside Dlcyandlamide; ether of CHpO condensate of urea, phenol, melamine or dicyandiamld* 60-80* N.S. N.3. H.B. - N.S. 5-2016 60-8016 (10-3056 epoxide) 1/B - 6/5 equivalent N.S. 1/0 - 6/5 equivalent 0.06 - 0.6 m. N.S. DSW 621087 STLCOPCB4095116 V4 Fitat Ho. 2,511.913 2.494,295 2,707,177 2,705,223 2,699,413 8,602,785 2,596,737 2,591,539 2,542,664 2,502,145 2,604,464 2,662,870 2,736,717 2,713,565 2,689,834 2,626,223 2,742,448 2,687,398 Pate Ho. of Claims 6/20/50 lk 1/10/50 6 k/z6/55 20 3/29/55 12 1/11/55 T/Sf* 5/lg/52 AA/52 2 2/20/51 8/28/50 8 7/22/52 10 12A 5/53 10 2/28/56 7/lg/55 9/21/5** 2 1/20/53 Ik 4/1J/56 8/24/54 5"JL trp* of Bland of Epoxide with PHP Aldehyde-aromatic amine condensate PHP Aldehyde-an*matlc sulfonamide condensate A Trlally1cyanureta PHP Trlallyloyanurete Plastisol of a vinyl halide resin or vinyl oopolymrti A Poly***ric polyamide PHP containing free amine and carboxyl groups DHP Alkaline condensation product of ClUO and a mono or dlalkyl phenol or mixtures H3P0Jj - Solvent DHP Polyvinyl ester of a . fatty acid Unsat fatty . acid ester of an epox ide of a HP PHP Hor.ohaslc aold modified aliqrd aldehyde-amide or amine condensate 25-7556 10-25S6 5-50% epoxide A Phenol-vegetable oil 20 parts/18 epoxide condensate (2il) containing 166 parts/16 epoxide at least 2 phenolic OH PHP Phenol-vegetable oil'' condensate (2:1) containing at least 2 phenolic OH 50-50 3 parts epoxide to 1 of condensate DOE of BP A Styrene-acryl lc acid o methacrylic acid from at least 50 parts styrene aid at least 5 parts aold Amine or quartenary ammonium compound 1 mole DOE for every two CO^H groups 0.5 by weight of copolymer DHP Cooolymer of (a) styrer.e (50 parts) One epoxide group for each CO2H group (b) acrylic or methacrylic acid (at least 5 parts) (c) vinyl pyridine (0.05-1-0 parts/100 parts (a b) Hat. drying oil aold ester of an epoxide of a DHP halogen subst. styrenes PHP Polyvinylacetal resin 2 aDrenyloxybensene containing 1-3 CHgOU roups N.S N.S 0.2-356 H.S. Epoxy ester (castor oil dehydrated acIds) PHP Polyeater-amide Containing 7-35^ polymerised | styrene Reacted In ratios to give specified softening points BPA Alkyl orthotitanate B-hydroxyaalne or polyuilne H.S. N.S. BPA Reaction product of (a) R^t3jX04-^pn) 70-9056 R- alkyl, phenyl - jc- OH, alkoxy n- 1-2 - n- 0.01-3 + n<4 (b) terephthalic or Iso phthallc acids or lower alkyl esters (c) glycerin DSW 621088 STLCOPCB4095117 O. n- aNa a P0* HC* HK4 J0 < p4i a 3 O H- 1 3 O OO *(1t a HV* a < * a o n 0 <t Ui o 3" a 4 P- 1o * o3 aC t3 oa 9a c j 4 < 4 3 O P* (Vi Pa- 4 4 a Apa av- 4 P ct ^or 4 4 11 ao o OH a ro <4 rOoN *i 4 P- p ct O O p co-op-)- , a cr C rr a P 3 A O *1 P4 a.o c *iP H- a 4 a PP p ct < WOO P P ON3T t? am ct PP ......'0'>s'0` Pfr: O 33 <P P 4 A ON 3 <7 4 ** <7,0 4 tr c HP P O O ct < O O' 4 V * 4P 4 3 ct tf.S. Patent No. 2,695,276 2,709,664 2,528,417 2,731.437 2,555,169 2,559,333 '$*=- 2,564,194 2,590,059 2,595,619 2,609,355 Pate No7~of Cl&lmi 11/23/54 5 5/31/55 23 10/31/50 i/17/56 5/29/51 8 7/3/51 15 8/14/51 10 3/18/52 9 5/6/52 15 9/2/52 12- - Type of Epoxide DHP PHP A PHP DOR of a blsphenol A Mixture of A and PHP PHP A PHP A PHP A TABLE X - oon't Blend of Epoxide with Polymerlo ailafiol Ratal coating let coat - A polyvinyl acetal 2nd coaC - Pigmented epoxide reain 3rd coat - Epoxide reaIn Phenolic pitch (t^a^H-C^S-R 0 R-(C2H40CH20C2Hj<SB)n - C2H4OCU2OC2U4 - Halogen containing organic subatance, M.W.>2000 Halogen confining organic aubatanoe, M.W.^2000 . Organic material containing halogen, H.W.>l62 Organic natter containing 10-75)< halogen, M.W.>2000 Cadid.ua or alkaline earth aalt of a carboxylic acl'l Halogen contlnlng polymer dlaaldea of carbonic acli and derivatives Vinyl chloride oopolymera containing -at least. 70% EVC . ester of unsat alcdhol and a dicarboxyllc a'id containing an oleflnic bon'* Salt of a carbo^llc sell whose Ionization constant la less than that of phthallc add DSW 621089 STLCOPCB4095118 -47- Appendlx B; Deflnitlons Epoxide Equivalent. The epoxide equivalent wolght of an epoxy resin la the weight of resin required to yield l6g (one equivalent) , of oxlrane oxygen. The value oa obtained by dividing 16 by the -- analyzed percent of epoxy oxygen (E.O.) and multiplying by 100. Epoxide Equivalent - ^ Equivalent weight to esterification. The weight of resin required to completely esterify bOg acetic acid or 280g Cl8 fatty acid is the equivalent welgnt to esterification. Calculations ^ The viffid <.A i on l a 11 on e for the dlglycldyl of TCBPA and hydrolyzed Aroclor 1262 and for the polymeric resins are com plex. The fuctors which were not considered in calculating the yields are: i . *- a ~ ~ l.s. pc.Cent of phenol or phenolic derivatives present. b) The purity of the eplchlorohydrin Ic) The H2O content of the reslnc d) The hydroxyl analysis of the products For the dlglycldyl ethers of TCBPA and hydrolyzed Aroclor 1262 it was assumed that the material was 100# pure and that Its conversion in the reaction was oraplete. The extent of the conversion of the material to the dlglycldyl ether and to the corresponding chlorohydrin derivatives was deter mined by analysis for epoxy oxygen and hydrolyzable chloride. The expected yield was then compared with the actual yield. Example Referrinigg to the product obtained by the procedure given on page (1' 0). The epoxy oxygen and hydrolyzable chloride analysis were 6.39# and 0.47# (average) respectively. Assuming that only monomeric products were formed, these values represent 6.^ x m Q g^ conversion to dlglycldyl ether and 0.47 n derivative. 127BE " conversion to the chlorohydrin Since seven equivale .ts TCBPA were used and since the equivalent weights of the dlglycldyl ether and the corresponding chlorohydrin derivatives are 239 and 275*5 respectively, the expected yield for 100# conversion of TCBPA was 7 x 239 x 0.954 - 1596 g weight ether expected 7 x 275.5 x O.0365 70g weight chlorohydrin expected l665g expected ylold DSW 621090 STLCOPCB4095119 -48- The actual was l664g. The percentage yield was 1664 lbbh X 100 ;9.8# For the polymeric solid resins, it w*s assumed that the materials were 100# pure were completely Incorporated into the product and that the molar amount of ECH used represented the molar amount of HC1 split off. Example: Referring to the product, obtained b- the procedure des cribed on page (M. 4escrlbed en -page 20) Expected Yield - 2280g (BPA) + l450g (15.69m) ECH - (36.5 x 15.69) 6 HC1 - 3157g. The actual yield was 3002g. The percentage yield was X 100 - 95-2# For the liquid resins from BPA, it was again assumed that 100# pure reaccants were used and that BPA was completely converted. It was also assumed that the ECH consumed in the reaction was in corporated into the product. Example: Referring to the product obtained by the procedure des cribed on page (17 ex. 3). The amount of ECH incorporated Into the product waB 520.2g (5-62M). Of this amount 827 x .0113 ,, o.264m aPP*ared aa in tne product 35.4 ' (827g) by virtue of its hydrolyzable chloride analysis. The amount of HC1 to be split off was therefore 5-62 - 0.26 5-36m * 190g HC1. The expected yield was therefore 570g BPA + 520g ECH - 190g HC1 900g. The actual yield was 827g- The percentage yield was there- f0rC * 100 - 92#. Calculations for the Recovery of excess ECH. The excess ECH was recovered by distillation from the reaction mixture of the two phase system ECH-H2O. The system was allowed to separate and its temperature was adjusted by warming under the hot water tap. The separate layers were then removed and weighed. The ECH and H2O contents of the phases were calculated on the basis of the table reproduced on following page (Ref 11). f* f DSW 621091 STLCOPCB4095120 Weight $ ECH Temperature (*C) Lower Layer Upper Layer 0.0 10.0 20.0 25.0 30.2 98.91 98.74 9?:S 6.48 6.52 6.58 6.60 Calculations for the composition of Epon 828, 1001 and 1004 in terms of BPA and ECH. By using the epoxide equivalent weight of resin and the equivalent weight to esterification, it was possible to approximate tne ratio ECH/BPA contained in the resin. For these calculations the following constants were used. Epon Resin Epoxide Equivalent Average Ester Equivalent 19c--210 450--525 870--1025 200 85 488 145 947 190 lght of ECH incorporated into the resins (a) Epon 828 Calculate the epoxy equivalence for the esterification equivalent (85g) from the epoxide equivalent of 200: 2$& * oA2 equivalents opoxy oxygen This value is equivalent to 0.84 equivalents of hydroxyl to esteri fication. Therefore in the esterification equivalent 1-0.84 - 0.16' equivalents of hydroxyl is present from ECH Incorporated into the polymeric chain and chlorohydrin portion of the resin. The total equivalents ECH incorporated is therefore 0.42 + 0.16 - O.58 equivalents. Since 56 is the equivalent weight of ECH incorporated into the resin 56 x C.58 - 32.48g ECH equivalent in the resin In 85g of resin, therefore, 85-32.5 - 52.5g (0.23m) BPA is in corporated . The molar ratio ECH/BPA in the resin is therefore O.58 - 2.4 Proceeding in the same manner for Epons 1001 and 1004 the ECH/bPk ratio is found to be I.52 and 1.25 respectively. DSW 621092 !* STLCOPCB4095121 Blaphenol-A (Ref 23). Empericaj. Formula: Molecular Weight: Appearance: Melting Range: C15H16O2 228.28 White flakes 150-155 (Solidification Range) ' !* '* STLCOPCB4095122 STLCOPCB4095123 STLCOPCB4095124 STLCOPCB4095125 ^Sy -52- Appendlx C; Composition of Hydrolyzed Aroclor 1262 and lta Derivatives^ The nydrolysls of Aroclor 1262 at Dayton and St. Louis has ap parently produced a mixture of mono and dlhydroxy derivatives. Analysis for chlorine and equivalent weight has given results which Indicate strongly that the product is a mixture of hydroxy materials. To our knowledge, this has not been considered pre viously . Considering hydrolyzed Aroclor 1262 as a mixture of mono and dlhydroxy products, the percentage composition can be calculated in terms of (a) its chlorine analysis and (b) its equivalent weignt. Prom these data, the theoretical aromatic chlorine content of the derivatives of hydrolyzed Aroclor 1262 can be calculated. It Is also possible to visualize a reaction of hydrolyzed Aroclor 1262 to its glycldyl ether and chlorohydrin derivatives, lr. which structures are ignored and only the equivalent weight is con sidered. By reference to the chlorine analysis of hydrolyzed Aroclor 1262, the aromatic chlorine content of the glycldyl ether and chlorohydrin derivatives can be calculated. From the calculations the following conclusions have been reacned: a. The chlorine analysis and equivalent weight determination are in agreement with each other. b. Hydrolyzed Aroclor 1262 may contain as much as 24# of the monohydroxy derivative, according to calculations Laaed on the equivalent weight. c. Calculations based on the chlorine analysis of hydrolyzed Aroclor 1262 gave a percentage composition from which the correct aromatic chlorine % for the derivatives could not be calculated. It was found, however, that only a small difference in the chlorine analysis of hydrolyzed Aroclor 1262 {about 1#) reflects a large difference in the per centage composition calculations. Analytical data supplied with hydrolyzed Aroclor 1262: # Cl: 48.83 Equivalent weight: 221 Reaction of hydrolyzed Aroclor 1262 to Its glycldyl ether. Substrate #C1, 48.83 E.W'. 92.5 E.W., 221 -glycerolmonochlorohydrln (GMH)-HClv. -------- ' E.W., 313.5 Glycidyi ether (QE) E.W., 277 (1) DSW 621097 ' f* STLCOPCB4095126 -53- Calculatlon of per cent epoxy oxygen (E.O.) for G E and percent aliphatic chlorine in GMH, baaed on the HY 1262 equivalent weight 221 which 1b a determined value. E.O. - 16 X 100 - 5.77 277 ft aliph. Cl - 55.46 X 100 - 11.31 ftrnr The percent aromatic chlorine for GMH and GE was calculated by multiplying the percent chlorine found for hydrolyzed Aroclor 1262 by a factor indicating the increase in the E.W. of GMH and GE. For GMH, * Aromatic Cl - 221 X 48.83 - 34.42 3TJ3 For GE, % Aromatic Cl - 221 X 48.83 38.85 277 Tne percent of GE in any mixture of GMH and GE ia found by divld:'.nfi_ the % E.O. found by *-he maximum value of E.O. possible. 56 GE % E.O. Found 5.77 -- The percent GMH ia similarly found by dividing % aliphatic chlorine found by the maximum value aliphatic chlorine possible. % GMH - $6--AliprhnCrl--F-o-u-n-d' The theoretical aromatic chlorine for any mixture of GMH and GE is the sum of the percent QE and QMH found in the mixture multiplied l the theoretical # Aromatic Cl for each component respectively. For any mixture containing only GMH and GE: % Aromatic Cl j# Aliphatic Chlorine Foundj ^4 42 + EQ Foundft .c Cl " Aliphatic Cl x 3.04 + 56 E.O. x 6 .73 Results: Sample % E.O. % Aliph Cl % Aromatle Cl Calcd. Found* ;fd-3) FD-3A) FD-4) FD-6B) FD-7A) FD-8) 3.38 5.38 3.52 5.37 5.48 1.14 4.98 0.55 4.53 0.53 0.49 9.08 37.89 37.88 37.46 37.69 38.37 35.27 37.18 39.00 36.38 39.09 39.10 35.49 subtracting ^ Aiipn Cl found. -0.71 +1.12 -1.08 +1.40 +0.73 +0.22 DSW 621098 itfitf rsf{u4 soffit STLCOPCB4095127 -54- The fair agreement between the oaloulated and found values for aromatic Cl lndloatea that the analyzed perdent Cl and E.W. of hydrolyzed Aroclor 1262 are In agreement. II. Calculation of the percentage composition of hydrolyzed Aroclor 1262 from the equivalent weight 221 (analytical value); kUoH Y A XL f\ /CCK'f 1 . c n/1 p 7 r / il'vi y a' Iy Assuming that only the species (A) and (B) are present. Let x = % A in the mixture y % B In the mixture 175 (.Olx) Contribution of (A) to the equivalent weight. 368 (.Cly) - Contribution of (b) to the equivalent weight. Thnn x + y 100 1.75* - 3.68y 221 And x - 76.2 y - 23.8 If It is assumed that only 4 components can be present in the reaction mixture resulting from HY 1262 and epichlorohydrin, f C. W, c U - Q - I-/ 7 c m.i n ~c\. CK <, <! < H j f-h eg u") & /o t-0- (..Q 2 a' 'Ji.vT O' h Uj-H2 *4 -Zt'f O -3.-71 yi.rv yH Cs ire**, 3/v? '"/v : i \ then the % aromatic chlorine, % E.O., and % aliphatic chlorine is found by adding the contributions of each component to that per cent. The contributions are in turn found by multiplying the theoretical constants listed under each component by the percent of that com ponent present in the mixture, calculated in the equations (2). For GMH: Aromatic Cl - 31.47 (.762) + 44.27 (^238) - 34.51 Aliphatio Cl - 12.88 (.762) + 7.70 (.238) - 11.64 # For OE: %.. Aromatic Cl - 3---6--.-4--5- (,.-7--6---2- -) +. 4--8--.-0--8-- (.2389 - 39 = 21 *" E" -~- - 6.9"2 (.776'-2-) + 3' .77 (.238) - 6.06 ? 1t* STLCOPCB4095128 -55- Ufllng the same argument discussed previously, for any mixture containing QMH and QE, * Aromatic Cl ' (r*--AllipThT^Crl--P-o-u-n-dj) ih Ci +* r(E".6O^.55F--ound)) 70 01 ResultB - * Aliph Cl (2.96) + * ]E.O. (6.47) Sample EP 1262 (FD-3) EP 1262 (PD-3A) EP 1262 (fd-4) EP 1262 (FD-6B) EP 1262 (FD-7A) EP 1262 (FD-8) * E.O. 3.38 5.38 3.52 5.37 5.46 1.14 * Aliph Cl UJ 4.98 0.55 4.53 0.53 o.4q 9.08 * Aromatic Cl Calcd. Pound* 36.65 36.40 36.18 36.21 36.91 34.26 37.18 39.00 36.38 39.09 39.10 35.49 After subtracting * Aliphatic Chlorine found. +0.53 +2.6C +0 .PC +2 .t+2.:.-- +1.23 Although the spread in calculated and found values for aromatic chlorine is much greater than in the preceeding case, the data nevertheless indicates that hydrolyzed Aroelor 1262 contains a substantial percent of the monohydroxy derivative. Calculation of theoretical chlorine for hydrolyzed Aroelor 1262 baa-, cn the percentage composition found from the analytical equivalent weight 221: 48.1 (.762) + 55.3 (.238) - 49.81* This is O.98* off from the found value of 48.83*. This same method was used to calculate the percentage composition of hydrolyzed Aroolor 1262 Lot No. Z-2201 for which the analyses were 50.0* Cl and E.W. - 219. Based on the E. W. 219, the percentage composition was calculated to be: * A 77.2 (di-hydroxy) * B m 22.8 (mono-hydroxy) ' ' !* ** -* i * STLCOPCB4095129 -56- III. Calculation of percentage composition of nydrolyzed. Aroolor 1262 using the chlorine analysis 48,8jt which was obtained on a sample with an analytical E.W. of 221. The same roecles used under II are considered. Let x - f A; 48.1x Contribution of (A) c. Cl anal. y - f B; 55,3y - Contribution of (B) to Cl anal. Then x + y - 1 48.1 x + 55.3 y - 48.8 (3) 'nd x - 0.903 y - 0.097 By reference to tne components listed on page (5) For OMh, f Aromatic Cl - 31.4? (.903) 4- 44.2' (.037) - 32.72 f Aliphatic cl - 12.88 (.903) + 7.70 (.097) - 12.38 Por 0E, f Aromatic Cl - 36.45 (.903) + 48.08 (.097) - 37.57 f E.O. - 6.92 (.903) + 3.77 (097) - 6.60 Using the argument previously discussed, for any mixture oontainir;. (* tic Cl - ( i Cl Found L op 7p . (? 15H38 r 32,72 0, Found) .60 ) J1*7( cJ;t1 - % Aliph Cl (2.64) + f E.O. (5.69) Results: Sample % E.O. % Aliph Cl. f Aromatic Cl Calcd. Found* EP 1262 EP 1262 EP 1262 EP 1262 EP 1262 EP 1262 (FD-3) ,FD-3A) FD-4) PD-6B) TO-7A) [PD-o) 3.38 5.38 3.52 5-h 5.48 1.14 4.98 0.55 4.53 0.53 0.49 9.08 After subtracting f> Aliph Cl found. 32.38 32.05 31.99 31.96 32.47 30.46 37.18 39.00 36.38 39.09 39.10 35.49 +4.80 +6.95 +4.39 +7.13 +6.63 +5.03 DSW 621101 < * ' * ? !l i STLCOPCB4095130 The wide spread In Che calculated and found values for aromatic chlorine indicated that the percentage composition calculated from % Cl, found for hydrolyzed Aroclor 1262, is not a suitable criter ion for calculating theoretical aromatic Cl for QMH and GE. It should be noted here, however, that a difference of only about In the chlorine analysis of hydrolyzed Aroclor 1262 reflects a large difference in toe percentage composition calculations. Thus, if it is assumed that the theoretical % Cl for nydrolyzed Aroclor 1262, as calculated from the E. W. 221 (pg.55), is correct, then x+y-1 48.1 x + 55.3g - 49.81 x - 76.4 (% A) y - 23.6 {% B) A difference of 0.9836 Cl haa reflected a difference of 90.3 - 70.4 13.9 in percentage (A) in the mixture. Similarly fo'- Lot No. Z-22C1, a difference of O.2656 Cl was found tc reflect Terence of 4.6j6 in the percentage (A) in the mixt IV. Calcula 3 of the equivalent weight of QE using the percent.^ composite _>n determined by (a) E.W. - 221 and (b) % Cl - 48.8: (cf components listed on page 54) (a) 231 (.762) + 424 (.238) - 277 (b) 231 (.903) + 424 (.097) - 250 -'he experimentally determined equivalent weight of OE was 28l. Therefore, the reaction (1) and the percentage composition deter mined from the E.W. 221 equations (2) gave values for the equivalent weight of OE which were in close agreament with the f our c value, while the percentage composition determined by % Cl - 48.8 equations (3) gave a value for the equivalent weight of OE which differed widely from the found value. Appendix D: Infra red Spectra The infra red spectra were obtained on the solid phases of the compounds uBlng a NaCl resin and a Perkin Elmer Model 21 spectro meter . A. Tetraohlorobisphenol-A B. Tetraohlorobiaphenol-A diglycldyl ether. The band at about lluw was taken to be the oxirane band. The spectrum shows only a negligible amount of hydroxyl ab sorption. C. Tetrachlorobisphenol-A di- K-glycerolmonochlorohydrin. In this spectrum the oxirane band is absent and the OH band appeared as expected. The spectra of the epoxides of bisphenol and glycerol have been pub lished previously. In these spectra the band at 10.95 m. was assigned to the oxirane group (Ref 31). DSW 621102 STLCOPCB4095131 STLCOPCB4095132 STLCOPCB4095133 - i4.r-. iw ft-' STLCOPCB4095134 STLCOPCB4095135 STLCOPCB4095136 STLCOPCB4095137 -24drolyzed Aroclor 1262. This phase of the epoxy program was carried out cooperatively with Dr. J. Dazzi and Mr. J. Herbig at Dayton. Because the composition of hydrolyzed Aroclor 12o2 was a mixture whose composition varied, it was desirable to track the course of its addition reaction with ECH by considering the equivalent, weight of the mixture only. (Aromatic chlorine analysis was also considered but was rejected because the oxygen analysis cf the initial mixtures received for eooxidation were Inconsistent with a dihydroxy product). The nature of the products was reasoned from the ECH stoichiometry of the reaction, epoxy oxygen analysis, hydrolyzable chloride amlysis and total chlorine analysis. Prom these data it was possible to obtain some approximate calculations from which it could be shown that hydrolyzed Aroclor 1262 was a mixture of hydroxy materials which contained as much as 24# of monohydroxy derivatives. These calcu lations and their results are shown in Appendix C. (C) Reaction of Blsphenol-A with Excess ECH When a limited amount of aqueous NaOH is addad to a solution of BPA in excess ECH above 45, the predominant exothermic reaction STLCOPCB4095138