Document QkDG34p8DOmmBxznw6kMj0Lo5

*?- > 'St. Louis Research Report No. 2514 PINAL REPORT ON MINOR EXPLORATORY INVESTIGATIONS 1956-57 Job No. 2-02-750.01-5168 July 6, 1959. Written by: W. E. Koerner Work done by: W. E. Koerner STLCOPCB4095840 MONSANTO CHEMICAL COMPANY ORGANIC CHEMICALS DIVISION ST. LOUIS RESEARCH DEPARTMENT St. Louis Research Report No. 2314 PINAL REPORT ON MINOR EXPLORATORY INVESTIGATIONS 1936-57 Job No. 2-02-750.01-3168 July 6j 1959. Written by: W. E. Koerner Work done by: W. E. Koerner 0. B. Cecil W. D. Williams R. E. Keller C. H. Brackbill J. Livasy DSW 621810 I STLCOPCB4095841 DISTRIBUTION 1. Pile 2. W. E. Koerner 3. J. H. Lum - P. B. ZIenty - File 4. Duplicate Pile 5. Central Technical Plies - Creve Coeur 6. 0. B. Cecil 7* A. M. Ellenburg 8. J. H. VanNess 9. Extra 10. Extra This report contains confidential information which is the property of the Monsanto Chemical Company and which shall be disclosed only to duly authorized persons. The recipient is held accountable for the filing and safe custody of the report, which must be returned on demand. DSW 621811 STLCOPCB4095842 TABLE OP CONTENTS Page No. INTRODUCTION......................................................................................................................1 LOW TEMPERATURE DIELECTRICS .................................................................... . 1 ZONE REFINING.................................................................................................................H SURFACE AREA OF CYCLIZATION CATALYSTS................................................ 4 SANTOCEL SURFACE AREAS............................................................................................. k CARBOXYLATION OF BENZOIC ACID TO PHTHALIC ACID............................. 6 SPECIFIC HEAT OF DI(2-BUTOXYETHYL)ADIPATE ....................................... 6 OIL ADDITIVE THERMAL STABILITY..........................................................................6 ELECTRICAL RESISTANCE OF MERSIZE 70R............................................ . 6 PHOSPHOROUS AMIDE REACTION MECHANISM. . . ....................................... 7 DSW 621812 STLCOPCB4095843 1. INTRODUCTION This report covers a variety of projects ranging from physical measurements made at the request of other divisions to original projects originating within our group. Because of this diversity, each section of this report will cover a separate project and will include all pertinent commentary. LOW TEMPERATURE DIELECTRICS The principle criteria for low temperature dielectric fluids are1: 1. The "cracking" (shattering due to strains in the cooled fluid) temperature must be -JOiC. or below. 2. The dielectric constant at -55C. must be no more than 28$ below the +25C. value for 60 f\J and 1 kc. 3. The D. C. Resistivity at 100C. must be greater than 500 X 10 ohm-cm. Aroclor'1242 fails.:t;o meet criterion.#! v. Various.additives^ parr tieularly .TCB, have been mixed with Aroclor 1242 to give fluids which meet' all requirements. Since these low viscosity mixes are "sensitive" to contamination, there was reason to believe that the addition of polymers would raise the viscosity and thereby'"stabilize" the fluid. Cracking temperature, viscosity, dielectric constant, power factor and D.C. resistivity measurements were made at various temperatures on mixtures of Aroclor 1242 with 5$, 10$, 15$ and 30$ of a mix containing 29$ (Poly 85$ 2-ethylhexyl 4- 15$ ethylacrylate) in TCB. Similar measurements were made on a mixture of 90$ Aroclor 1242 and 10$ of the above polymer (without TCB). D.C. resistivity measurements were made on mixtures of Aroclor 1242, TCB and alkylated polystyrene. Since these values did not meet the criteria, no further measurements were made. Data for these measurements are shown in Table I and Graphs 1-4. All samples were cleaned with Attapulgus earth preceding electrical measurements. Paratong Nwai incompatible with Aroclor 1242. ' .. . 1, Of the above mixes, only the 70$ Aroclor 1242-30$ mix of 29$ (Poly. 85$ 2-ethylhexyl + 15$ ethylacrylate) in TCB fulfilled all criteria for low temperature dielectrics, but its D.C. resistivity was not as good as those of less viscous fluids already marketed. Tests designed.to illustrate the sensitivity of this mix to added contamination yielded the data in Table II. Consideration of the conductivities, which would be additive, show the mix to be as sensitive to contamination as pure Aroclor 1242. In general, the following observations may be made about fulfilling the criteria for low temperature dielectrics by the addition of polymers to Aroclor 1242: i Report 2912, Interim Report on Low Temperature Dielectrics, 12/2/53, R. J. Good. ........... DSW 621813 STLCOPCB4095844 2 o co fH in H CT\ O o ov co H co -=J- CM co o m fA fO rH K\ -=f LA -u 0X 1--I 0 0 K o o Xo! > CM o o o o O C"- VO o m H st in <T\ CT\ o 1*0 H o o ocr\ in =t =i* H rH H 0J H- I--PoI Ho fot < pq < ft E-i o 03 o H -p P 0) ft O fPt 00 03 o TJ > >s C O oin o VO cin 0J OJ H in ctr-v i--i ov t1----1 (A -P O H 0 03 CO O O -P *0r3i rOH > Si o >5 0 >in 00 CUO\ o\ ~ i--1 fA t- CM tft vo O co CM VO 0 P U) 3 C 43--> H 0 O P0 0O 0 ftv ft s O 0. E4 oQ o V0O1 c--oI ot-I o mfr-I oo 0o0IIfo- NX o 0o0I ^ * rA >ft in 'eft 'eft o--i i--ini Ift O rA $ H 'eft in CM 'eft m CM +++++++ CM CM CM -=4" -=*" J=t* CM =*" CM -=t" CM =* CM CM CM CM CM CM CM CM rH rH rH rH rH rH rH CM P" pp p CM O O O pp OO pp OO rH iH r--l rH (H rH 0 p CJ O O O O 0 0 0-0 0 C3 O O O P 3 i--oi <P <P; P< <P <P P < P < -P o X o >')TQv t>3JvD. Cs >3v -'Twnv >R >ft H s p c CinJl o ifnfl No Ool iten- roH- pq o Eh a 0 43 0 >ft> 0 O 43 0 rH i--0I s>:> ft 43 O 00 >ft > in x: 43 +0 'eft in 0+ X! CM >i 'ienft S403I co i CM ! roH 'ienft ft co >ft o\ CM >> rH o ft II 0 c 0 p > 43 0 o ft o 0 43 0 rH ! X i--I 0 I *** m DSVV 621814 STLCOPCB4095845 TABLE II Sensitivity of Mixes to Contamination 3. D.C. Resistivity Specific Conductance . (ohm-cm X i?s) (ohm-1 cm'-1 x:.lO-12) 0>0 Sample 231 100" 25" Aroclor 1242 7070 1600 .1415 625 Aroclor 1242 + 10$ of saturated solution of tetrabutylammonium picrate in 1242 1740 360 575 2.78 70$ Aroclor 1242 + 30$ (1)* 945 304 1.059 3.29 90$ above blend + 10$ of saturated solution of tetrabutylammonium picrate in 1242 290 137 3.45 7.30 Aroclor 1242 6080 Aroclor 1242 + 10$ of saturated solution of HC1 in 1242 58.1 70$ Aroclor 1242 + 30$ (l)f 642 90$ above blend + 10$ of saturated solution of HC1 in 1242 21.4 922 .1645 1.085 6.65. 299 17.2 1.56 1150 3.35 1.68 46.7 595 (l)* - 29$ (jtoly 85$ 2-ethylhexyl + 15$ ethylacrylate) In TCB. TABLE III Zone Refining of Impure Phenol Fraction UV Assay Orthophenylphenol Purest (Sample A) 102.6$ (wt./vol.) 0.04$ (wt./wt.) Most Impure (Sample D) ca. 97-99* 3.83 Original Material not run 0.98 * Unreliable assay due to Interference of orthophenylphenol. These results indicated that the.purest sample was better than the ultraviolet standard. It should also be mentioned that the analysis for orthophenylphenol (OPP) was considered accurate only to 0.05$ OPP. Each sample represented roughly 1/8 of the total tube contents. DSW 621815 STLCOPCB4095846 2l 1. Cracking Temperature Although not completely proved. It seems likely that the lowering of the cracking temperature is relatively independent of the additive. 2. Dielectric Constant Lowering The dielectric constant is much more selective. It is doubtful that this criteria could be met by a mix of only Aroclor and polymer. 3. D. C. Resistivity Although the polymers increase the viscosity of the fluid, they apparently introduce electrical contamination. ZONE REPINING The successful use of zone refining in the preparation of extremely pure samples of semi-conductors led to an interest in applying this technique to the purification of organic solids and the concentration of impurities. A limited amount of work in the literature presented encouraging results in the purification of organic compounds. An automatic "pulling" apparatus was constructed to enable a narrow heated zone to traverse a 12 inch length of organic material which was in a tube. The rate of pulling could be made either 0.8 inch/hr. or 1.7 inches/hr. The initial run, in which the organic material was impure phenol, was made in order to gain some experience with the apparatus and to determine whether or not the technique was suitable for very "impure" samples. Twenty-eight passes were made at a rate of 0.8 inch/hr. The results are shown below in TabLe III. The results of further work on this project including a critical comparison of this technique with static crystallization will be presented in a forthcoming final report on Job No. 3531. SURFACE AREA OF CYCLIZATION CATALYSTS We were requested by Dr. Walter Knox of the Lion Oil Company Division to measure surface areas of three samples of an alumina based catalyst which had different past histories. The areas were determined by the method of Brunauer, Emmett and Teller. Calculations were made from nitrogen adsorption isotherms (-195C.). The results are shown in Table IV. The difference between the area of sample 366-162-1 and the other two is significant. SANTOCEL SURFACE AREAS DSW 621816 We were requested by Dr.Harry Teicher of the Inorganic Division to measure the surface area of two samples of silica gel as an aid In the development of a new Santocel. We determined the surface areas using the method of Brunauer, Emmett and Teller calculating the areas from nitrogen adsorption Isotherms. The results are summarized in Table V. STLCOPCB4095847 Sample 366-162-1 366-162-2 366-162-3 TABLE IV 5. Catalyst Surface Areas History Surface Area (sq.m./gm.) Used for 65 cycles 66 Fresh Catalyst 74 Used for 3 cycles 72 TABLE V Santocel Surface Areas Sample Surface Area (sq. meters/gm.) Santocel C, Batch 051020 134 Santocel FR, Pilot Run 231 Santocel JR, Batch 136924 . 370 Santocel FR, Batch 136925 345 Santocel JR, Batch 136926 351 Synton 200, Pilot Plant Lot 4 164 Synton 200, Interim. Production 173 DSW 621817 STLCOPCB4095848 6. CARBOXYLATION OF BENZOIC ACID TO PHTHALIC ACID , A few exploratory experiments were made attempting to carboxylate benzoic acid to phthalic acid using the old Dept. 18 catalyst (phthalic acid decarboxylation) to see if the equilibrium concentration of phthalic acid was high enough to make this an attractive route to phthalic acid. No phthalic acid was recovered from these experiments. The effective ness of the catalyst was proved by decarboxylating phthalic acid to benzqic acid. Estimations by Dr. Kern Sears predicted a very unfavorable equili brium constant for the reaction: benzoic acid($);) + COa(g) ^ phthalic acid($) Subsequent discussion with Prof. G. B. Kistiakowsky brought out the observation that the carboxylation of benzoic acid to phthalic acid should not be greatly different than the carboxylation of benzene to benzoic acid. Highly prebise thermochemical data are available for these compounds and they predict a very unfavorable equilibrium from the point of View of benzoic formation. In considering these conclusions it must be borne in mind that an unfavorable equilibrium for carboxylation with CO2 to- yield the free acid does not rule out the possibility of discovering economically attractive coupled carboxylations in which the carboxylating agent might be a carbonate salt and the final product might be a salt of phthalic acid. ` ' SPECIFIC HEAT OF DI(2-BUTOXYETHYL)ADIPATE The specific heat of dl(2-butoxyethyl)adipate was estimated, using the method of Johnson and Huang (Can. J. Tech. 33,421(1.9^5 ),to be 0.44 at 20C. From a brief survey of similar orgalc"liquids a temperature coefficient of + 0.001/C. was estimated. THERMAL STABILITY OF POLYMERIC OIL ADDITIVES ' A sample of ethylene maleic anhydride copolymer octadecyl imide (40$ In oil) supplied by Dr. Fred Lippmann (Dayton NBP 368521) and a sample of ethylene maleic anhydride copolymer-AIdol l4 esterdimethylaminopropyl imide (66/34) from the Organic Division Engine Laboratory were subjected to differential thermal analysis to see if deterioration of these products could be identified with an observable exothermic or endothermic reaction. No endothermic or exothermic reaction was observed where the samples were heated to 300C. ELECTRICAL RESISTANCE OF MERSIZE 70R Dr. E. Reaville requested a value for the value of the dielectric constant of Mersize 70R to answer a request from an Instrument company Attempts to measure the dielectric constant were unsuccessful and the resistance measurements shown in Table VI suggest that Mersize 70R should be considered a poor conductor rather than a dielectric. DSW 621818 STLCOPCB4095849 TABLE VI Specific Resistivity of Mersize 70R (December 1956 Production)______ _ 7. Tenperature 25C. 95C. Specific Resistivity (ohm-cm) 3 X 10s 0.3 X loo PHOSPHOROUS AMIDE REACTION MECHANISM Dr. T. Reetz has found that the following reaction will take place at 80C. P</N(CH3)a73 + 3R0H --> P(0R)3 + 3(CH3)2NH He has postulated that the reaction will proceed through the following intermediate: _ (ROP/NCCHaJgTV)" H+ This leads to the prediction that mixtures of an alcohol and P/NXCH^g/; should show electrical resistivities lower than either of the component* due to the presence of the ionic reaction intermediate. Such measure ments were made using ethanol (absolute with 0.5$ benzene as denaturant) and are summarized In Table VII. TABLE VII Specific Resistivities at 25C. Sample Specific Resistivity (ohm-cm.) P/N(CH3)a73 Ethanol Equimolar Mixture of alcohol and amide 2 minutes 8n 40 11 7> 98 t! n 192 it after If If If n n mixing n IT ft n 11 3-4 X 10a 9-8 X 10s 5.0 X 10 4.5 X 10 5.0 X 10 5.5 X 10 5.9 X 10 6.4 X 10 DSW 621819 STLCOPCB4095850 8. Qualitatively the data support Dr. Reetz's postulate, but the possibility of trace ionlzable impurities being present in the amide and ionizing to & greater extent in ethanol solution is not ruled out of consideration by these data. NOTEBOOK PAGE NUMBERS Low Temperature Dielectrics A 83255-70 Zone Refining A 107428 Catalyst Surface Areas A 87542-4 Santocel Surface Areas A 77583-6, A 87505-7, A 87509, A 87511-2 Carboxylation of benzoic acid to phthalic acid A 87503-4, A 87508, A 87510, A 87519-20 Specific Heat of Di(2-butoxyethyl)adipate A 96169 Oil Additive Thermal Stability A 41709 Electrical Resistance of Mersize 70R A 94032-3 Phosphorous Amide Reaction Mechanism A 105111-2 WEK:sk 7/17/59 W. E. Koerner DSW 621820 STLCOPCB4095851 3S *T -M O K fcU F H LL a eS S R CO, 10 to the Vfc in ch . 6th /n v e iit` STLCOPCB4095852 339T - n< DSW 621823 STLCOPCB4095854 T D iJe ctr \ G <ra. p w -4- <* -- i". a * Aroc 1 tr |x4l M JL-O- /S rb a *- i -<. It o \ V. 7 'G> / DSW 621824 STLCOPCB4095855 STLCOPCB4095856