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I-IH inier-office memo TENNECO CHEMICALS, INC. A TO From Subjcct Distribution List AT Dr. R. T. Gottesman AT MONTHLY SUMMARY - AUGUST 1973 Piscataway Date August 31, 1973 Copt to Attached are copies of the Monthly Summary reports for August 1973 covering the activities of the Fiscataway laboratories and associated pilot plants at Piscataway, Flemington and Heading. RTG/ec Attachment Distribution List Mr. M. Freifeld Dr. D. Keyworth Dr. P. A. Lobo Dr. T. E. Maggio Dr. M. Rosen (2) Mr. G. 1. Rozand Mr. C. G. Thompson Mr. M. E. Wagshul Dr. L. A. Wigdor / Mr. T. T. Zuhl Gottesman COLORITE 0X1706 2 MONTHLY SUMMARY - AUGUST 1973 \ August 31, 1973 * B. R-125 Pigment Dispersant (G. Kagan, M. Landau) Three pilot plant lots of R-125 (035-131,136,141) have demonstrated acceptable functional performance vs. Tamol 731 in PVA and acrylic paints. A product data sheet is being prepared and material is available for customer sampling and introduction at the Paint Show in November. The pilot plant process proposal was issued and coopera tive work with Process Engineering to initiate manufacture at Garfield is underway. C. Thickeners (G. A. Trautenberg, G. Tirpak) A series of new cellulosic thickeners (XD-7630) from Dow Chemical reputed to be enzyme resistant have been evaluated and found to be quite enzyme resistant. Compared to the standard cellulosic, Natrosol (HEC), the experimental products were about six to seven times more resistant to microbial degradation. Based on this data, these experimental thickeners would not need biocidal protection, although Dow is recommaiding the use of an antimicrobial. IX. LUBRICANTS * A. Automotive Crankcase Lubricants (M. Knapp, R. Smith) A comprehensive program for the development and testing of a synthetic multigrade (10W-40) crankcase oil has been developed through in-house experience and extensive contacts with the major automobile manufacturers. The initial efforts involve optimization of our current crankcase oil, Anderol 472. * B. Rotary Combustion Engine (RCE) Lubricant (M. Knapp, R. Smith) Walker Manufacturing tested Anderol 472 in an RCE-powered car for 20,000 miles and found that this synthetic lubricant produced slightly less wear and lower emissions, but also resulted in more severe engine deposits. Walker has agreed, at recent meetings with Tenneco R&D personnel, to conduct additional tests in their dynamometer-mounted RCE start ing the first week in September. Initial testing will be carried out on a recently-developed low ash shear stable version of Anderol 456, which was chosen as a starting point because it will meet the viscosity requirements for a Dexron II type fluid (which is the General Motors' requirement for this application), FB/amp 4*0 F. Biuoonno COLORITE 011708 > 194 inter office memo T E N N E .0 Q CHEMICALS, INC. To From Subject Dr. R. T. Gottesman AT Dr. A. J Deinet at MONTHLY SUMMARY - AUGUST 1973 Piscataway Piscataway Date Copy to August 31, 1973 I. CHEMICALS/SPECIALTIES * 1. p-Hydroxybenzoic Acid (M. Reale, R. J. Stanaback) A laboratory fusion carried out in all-glass equipment in which dipotassium salicylate was isomerized to para acid utilizing time-tem perature cycles (2 hrs. at 275C.) as recently carried out at Bethlehem Corporation gave a 91% yield of quality product. Although some 4-hydroxyisophthalie acid is formed as by-product, final acid ification to pH 3 avoids the coprecipitation of this impurity with the para acid. Since the feasibility of good quality and yield has now been demonstrated, confirming runs in the laboratory autoclave are underway to determine if the same can be achieved in steel equip ment prior to a final trial at Bethlehem. A work-up procedure to be compatible with the equipment capabilities at the Garfield salicylic acid plant is being developed. The use of hydrochloric acid for partial neutralization of the reactor liquor prior to decolorization with carbon in the steel column at Garfield is deemed unsuitable because of chloride ion corrosion. While the use of sulfuric acid was found to be unsuitable due to the poor solubility of potassium sulfate, carbon dioxide was shown to be en tirely suitable for the partial neutralization and is already avail able in the plant, Bethlehem reactor liquor so treated, followed by decolorization and final precipitation with hydrochloric acid (rubber lined equipment available for this stage) gave an excellent quality product. 2. Dinitro-p-chlorobenzotrifluoride (E. DiBella, R. J. Stanaback) A revised nitration technique has been developed which minimizes the extensive solvolysis encountered when p-chlorobenzotrifluoride is nitrated in the presence of fuming sulfuric acid. It was found that by initially carrying out a'mononitration by use of strong nitric acid alone followed by the use of mixed acid to achieve the dinitro stage a 74% yield of product assaying 987. was achieved. This technique will be utilized to prepared a ten pound sample for BASF. COLORITE 011709  w 2 II. PLASTICS INDUSTRY \ 1. Flame Retardants (E. DiBella. R. J. StanabackY Samples of our flame-retardant emulsifiable concentrate com position based on T-2,3-P/TOF with Tergitol P-28 and NP-27 emul sifiers have been forwarded to the Masonite Corporation and the J. F. Donoval Corporation for evaluation. The evaluation of hexabromobutene-2 (HBB) is continuing on a high priority basis. An emulsion system in which HBB is dispersed in N-methylpyrolidone/toluene/water with Tween-20 was developed and utilized in padding application to various fabric types. Pre liminary results indicated flarae-retardancy was imparted to acetate and wool. In the plastics area, HBB has been successfully incor porated into both high and low density polyethylene and polypro pylene. Incorporation into ABS and polystyrene is in progress and then flammability tests on the entire set of plastics materials will be carried out for use in support of a patent application. The use of diphenyl isodecyl phosphite in conjunction with T-2,3-P has been evaluated for anti-scorch characteristics in polyurethane foam. Although some reduction (similar to that found when using Weston's DHOP) was achieved the results were not comparable to those with Fyrol-2. The basis for this trial was a recent French Patent (#2,143,488) which claimed the use of such phosphites for imparting better stability to T-2,3-P. Based upon an earlier observation that boric acid imparts some smoke suppression to PVC, a sample of dibutyl-2,6-di-t-butyl-4-methyl phenylborate was evaluated in PVC at 15 PHR as a partial replacement for DOP. Only slight flame-retardancy was imparted (LOI of 23.8 vs. 22.6 for control) with no apparent smoke suppression. III. DYES AND INTERMEDIATES A. Dyes 1. Liquid Paper Dyes (M. Feldman, H. Gosch. L. Port, N. Conzo) *k Based on analytical results on competitive liquid paper dyes which have shown them to be essentially aqueous formulations emphasis has been placed on developing this type of formulation. Aqueous solutions of 35% strength have been achieved for both Blue 3RLP and Red NAS by conversion to the triethanolamine salts. These sales have enhanced water solubility and were readily prepared by heating the corresponding ammonium salts with triethanolamine directly in a water system. Sta bility thus far (2 weeks) is excellent and the systems have a desir ably low viscosity. Dyeing tests on paper are to be carried out and pilot plant verification of these processes will follow. Attempts to isolate these two products as the free acids prior to conversion to the triethanolamine salts were unsuccessful. COLORITE 011710 3 The triethanolamine salt of Bond Yellow G was also prepared, but was S found to have insufficient water solubility to achieve 35% strength. '\ Tenneco Bond Yellow G is a phosgenated product, whereas DuPont's "Pontamine" Bond Yellow G has now been identified by the Analytical Department as being a triethanolamine salt of 2-(p-aminophenyl)-6methylbenzothiazole-7-sulfonic acid which has been diazotized and coupled with a pyrazolone. Synthesis has been initiated, therefore, on related structures based on p-aminophenyl benzothiazoles coupled with other economical components. 2. Yellow 3G (L. Schinasi) Trial laboratory runs have shown the feasibility of a solventless process for the preparation of this material which will enable manu facture in non-explosion proof equipment. The procedure consists of a gradual addition of quinoline carboxylic acid (QCA) to molten phthalic anhydride with a short hold at 210C. for reaction completion, drowning the melt in aqueous caustic soda, treating the solution with activated carbon and finally springing Yellow 3G with sulfuric acid. Using a QCA to phthalic anhydride ratio of 1.0:4.25, an 85% yield of product was obtained which showed acceptable dyeings and strength. A tentative Laboratory Process Proposal will be issued shortly prior to pilot plant verification. AJD/srf COLORITE 0117X1 t* nte^h-office memo TENNECO CHEMICALS, INC. To Dr. R. T. Gottesman at Piscataway From Mr. I. Huppe rt at Piscataway Subject MONTHLY SUMMARY - CHEMICAL DEVELOPMENT AUGUST 1973 Date August 31, 1973 Copy to I. CHEMICALS/SPECIALTIES A. Phosphates I. Dibromopropanol (H, Gould, S. Cinco) Additional work on the continuous "heterogeneous" process for preparing DBP dealt with the use of heptane and mineral spirits (S-434) as the initial reaction solvent in place of hexane. Yields for both runs were 86+7. with G.C. purities of 99.9% for the batch distilled product. Further work on reaction systems is pending until Process Engineering can economically evaluate the continuous reaction system. The soda ash treated crude DBP was'continuously distilled through a wiped film evaporator under the conditions de scribed below: Run No. 1 2 3* Temp. C Pressure (mm_ Hg) 185-210 170-200 175-220 30 15 27-30 Feed Rate (ml/Hour) 100 110 200 Yield (%) 85.6 87.7 80.7 DBP Assay* (%) 97.9 97.6 99.3 Moisture (%) 0.49 0.37 0.73 *0nly one-half the volume of 8% soda ash solution was used in this case as compared to Runs No. 1 and 2 to remove acidity. In all runs, the main cut of DBP did not meet the required maximum moisture specification of 0.05%. Emphasis on con tinuous DBP distillation will be maintained until a suitable system is found. ' A sample of Dow Chemical DBP (1440495) was converted in the laboratory to T-2,3-P via the MgO catalyzed plant process in a yield of 85.7% (on POClj) and 82.9% (on DBP). This source of DBP is recommended for T-2,3-P manufacture provided Dow can continuously meet our moisture specification of 0.05% COLOR!TE 011712 Dr. R. T. Gottesman -2- August 31, 1973 2. T-2,3-P (J. P. Sandstedt, S, Cinco) A demonstration batch of T-2,3-P using predistilled DBP and the AICI3 catalyst was made for Fords Plant personnel in the Piscataway Pilot Plant, Yields were 84.0% on DBP and 86.4% on POCl^. Quality was acceptable. Arrangements are being made to reintroduce this process at Fords sometime in September. Pilot Plant HC1 and water washed crude T-2,3-P was worked up in the laboratory to evaluate the effect of Glucoquest AC as a sequestering agent to remove traces of aluminum. Results indicate that a 5% concentration in the soda ash wash facilitates separation and reduces emulsification ten dencies. The resulting product met all LV specifications. This system will be held in reserve in case it is requir ed in plant operations. Corrosion studies were conducted on Celanese Cellulose Acetate Dope containing Tenneco LV Grade T-2,3-P (Fords No. 73-42) in the presence of "Black" Iron. After 28 days at 58C, the iron was insignificantly affected (corrosion rate * 2.7 mils/year). The Dope formulation was unchanged as determined by color and consistency. Similar studies to aid Marketing are in progress using galvanized iron. B. Catalysts (A. Fischer) A quart sample of R-465, a 6% iron (III) 2-ethylhexanoate was prepared and submitted to United Foam Corporation as a match for competitive Cincinnati Milacron Iron 6%. The properties of R-465 are compared below with those of the competitive pro duct . R-465 C.M. Iron 6% Total Iron, % Iron (II), % Non-Volaties, % Viscosity (Gardner- Holdt) Specific Gravity (77F) 6.0 0.18 49.8 A-3 0.903 6.0 0.6 42.5 A-l 0.897 C. Cal/Ink Vehicles (O. Fuchs) Two processes for the preparation of two Cal/Ink vehicle com positions are presently being evaluated in the Process Develop ment Laboratory. One, General Purpose Dispersion Liquid, has been prepared on the first attempt according to the plant pro cedure supplied by Cal/Ink and meets their specifications for acid number, color, viscosity and hydroxyl number. This mate rial will be sent to Cal Ink for functional evaluation. The other, Uni-Cal Vehicle,was still being worked on due to pro cessing difficulties (which may be related to scale-down to glassware) when using the Cal Ink procedure. COLORITE 011713 Dr. R. T. Gottesman II. PLASTICS INDUSTRY -3- August 31, 1973 A. Additives 1. Stearates (S. Hoch) Two pound samples of Experimental Water Dispersible DLG-20 (R-439) were prepared and sent to each of the following for evaluation: Inmont Corp., Morgantown, N. C. Mobil Chemical, High Point, N.C. Lilly Co., High Point, N. C, Reliance Universal, High Point, N. C. Warlick Paint Co., Statesville, N. C, Two pound samples of Experimental Water Dispersible Stearates: S-1058 (zinc stearate); S-1244 (calcium stearate); and USP magnesium stearate; each containing 5% Aerosol OT-B, have been prepared and are available for customer sampling. This initial approach is the first phase of our overall program to develop a line of water dispersible stearates. 2. Plasticizers (I. H. Cooper) Evaluation of the Artisan falling film evaporator has been hampered by mechanical problems. The latest was determined to be the supply of an improperly designed unit for vacuum steam stripping by Artisan. Results to date show the unit to be overdesigned for continuous alcohol removal from DOP. Work is attempting to establish the maximum throughput through the thirteen stages that can be achieved. Best results to date are 125.0 pounds per hour of DOP and 3.5 pounds per hour of steam yielding DOP with less than 0.05% alcohol (specification value) compared to Artisan's stated maximum of 60 pounds per hour to achieve 0.01% for this unit. Operating conditions are 165C and 5 mm Hg. Emphasis will be changed to evaluating simpler units to accomplish the same job. IV. COLORS A. Intermediates * 1. Oxvlvl Para-Phenylene Diamine (G. F. McClain) An oxalylation batch was run in the Pilot Plant to provide presscake for pilot studies of the reduction step and re cycling of the unreacted iron. The oxalylation batch ran without incident and a wet weight yield (1057 lbs.) was obtained which paralled the lab process (906 lbs.). Three reduction batches have been run. The first had to be clari fied by filtration because of problems encountered in trying to decant. Some product was lost and the yield was only 84% CQLORITE 0117X4 Dr. R. T. Gottesman -4- August 31, 1973 of expected, however 20% of the Initial iron charge was \ recovered and used in the next batch. The second batch returned 101% of expected yield and the procedure was improved. A recovery of 30% of the iron which was used in the third batch was made. The third batch has been run and again the decant was successful, however, yield data is not yet available. It is planned to run three more reduction batches which will consume all of the available OPNA and make it possible to calculate yield back to PNA, This should complete Pilot Plant work. Reading Plant personnel have been invited to watch the Pilot Plant reduction and decantation for their comments on the mechanics of the system. 2. p-Nitroaniline (E, Reinhold) A portion of the PNAA (p-nitroacetanilide) presscake from a Pilot Plant PAA (p-arainoacetanilide) batch was hydrolyzed with liquid caustic by a procedure described in Fierz-David to PNA (p-nitroaniline). The hydrolysis was simple and the yield was 72% of theory. Fierz-David projects 72.4% of theory. The PNA derived was converted in the laboratory to Black 10BR by a standard Reading pro cess and the resultant dyestuff was- slightly red in shade (this is the shade normally produced by this process in the plant). The yield on a lab basis was greater than ex pected by 20%. After economic evaluation of this procedure, it will be verified in the Reading Pilot Plant. B. Dyes 1. Direct Fast Blue 3RLP Paper Liquid (G. F. McClain) Presscake from Pilot Plant ammonium chloride precipitated Plant Blue D Crude slurry was converted into liquid. The conversion was made in an enamel kettle with a horseshoe agitator which closely resembles the kettle in the Reading Plant planned for the manufacture of paper liquids. During the processing a considerable amount of ammonia vapor was evolved so that the plant design will require an adequate scrubber. No problems were encountered in the processing and the resultant liquid Is very fluid at 40% strength ver sus dry powder Code 2323. Previous formulations at 35% of the same code were often quite viscous, 2. Yellow FWL (R. Reinhold) Plant Batches 22, 23 and 24 consumed 2646 pounds of Yellow FWL base which at standard yield should have produced 7938 pounds of color. Actual color yield is 8512 pounds or 107.2% of standard. The shades were trace red, trace red and very slightly green respectively, all other tests were acceptable. This process is now ready to be run in the Reading Plant when installation of the new scrubbing equipment is complete. A Pilot Plant Process Proposal will be written. COLORITE 011715 Dr. R. T. Gottesman -5- August 31, 1973 C. Miscellaneous 1. Dyeing Assistant (S. Cinco, R. Caruso) Two thousand pounds of DUROCAR P-73 were prepared in the Piscataway Pilot Plant from Fords chlorinated o-chlorotoluene and are available for customer sampling. Corrosion studies to determine storage vessels and shipping containers gave the fol lowing results: After 7 days at 60C, carbon steel was corroded on the surface and edges and the DUROCAR 73 was slightly discolored. Heresite was unaffected and did not discolor the DUROCAR 73. At 40C for 7 days polyethylene and phosphatized steel were unaffected as was the DUROCAR 73. The control as well as tested samples of DUROCAR 73 emulsion at both 40 and 60C were unstable re sulting in a two-phase system. Initial sampling will be in polyethylene gallon, 5 gallon and IS gallon containers. IH/sgf COLORITE 011716 I-IS4 ntsh-office memo TENNECO CHEMICALS, INC. To From Subject Dr. R. T. Gottesman AT Mr. H. R. Johnson At MONTHLY SUMMARY - AUGUST 1973 ANALYTICAL SERVICES Piscataway Piscataway Date Copy to August 31, 1973 METHODS DEVELOPMENT 1. Liquid Chromatography (P. Ketterer, N. Conzo) The high speed liquid chromatograph equipment has been assembled and is now in operation. A program is underway to set up procedures for the analysis of raw materials and intermediates used in the development and manufacture of dyes. With this technique, for example, the low assay (60-75%) 1-aminoanthraquinone manufactured via the nitration route is readily distinguishable from the high assay (over 90%) product from the sulfonation process. Preliminary runs show that the 1,5- and 1,8-dihydroxyanthraquinones can be separated, and this will serve as the basis for a specific assay method for anthrarufin. Pure reference materials are being prepared using conventional column chromatography techniques. As detailed analytical data become available from liquid chromatography, it should not be necessary to carry out laborious and time consuming dye syntheses to evaluate raw materials. 2. Nuclear Magnetic Resonance Spectroscopy (N. Conzo) The Varian A-60 NMR spectrometer has been delivered. Installa tion and performance check-out is scheduled for completion by September 14. HRJ/ec COLORITE 011717 1-1*4 inter-office memo TENNECO CHEMICALS, INC. % To F AOM subject Dr. R. T. Gottesman At Mr. R. S. Miller at MONTHLY REPORT - AUGUST 1973 Piscataway Piscataway date August 31, 1973 Copt to PLASTICS INDUSTRY Additives I. PVC Processing Aids (D. Goodman, M. Koral, M. Spaulding. E. Szabo) While clear Supercryl 100 has been repeatedly demonstrated in the laboratory and verified in the Polymer Pilot Plant by substituting low levels (0.75, 0.5, 0.375%) of Avirol F0L-1-N for the 1% Duponol WAQE in the polymerization process, extended production plant trials during August on this system have failed to confirm the laboratory results. A plant program was conducted to vary spray drying conditions on the standard Duponol system and the 0.75 and 0.5 phm Avirol systems to determine whether drying temperatures, an apparently significant factor in earlier work, could be adjusted to yield improved clarity product. In both the Fords plant dryer and a spray drying trial at Nichols Engineering there were no clear trends that would indicate that other drying conditions would lead to improved clarity performance. These results are summarized below: Sample No. Surfactant K-120N K-120ND S-100 lot 20132 S-100 lot 20133 D-021-092-A D-021-092-B D-021-092-C D-021-092-D D-021-09Z-E D-021-092-F D-021-092-G D-021-092-AA D-021-092-CC D-021-092-EE D-021-092-M D-021-092-N D-021-092-RR D-021-092-U D-021-092-V D-021-092-GG D-021-092-LL __-- -- 17. Duponol 17. Duponol 1% Duponol 1% Duponol 1% Duponol 1% Duponol 17. Duponol 1% Duponol 17. Duponol 1% Duponol 1% Duponol 1% Duponol 0.75% Avirol 0.75% Avirol 0.757. Avirol 0.57. Avirol 0.57. Avirol 0.57, Avirol 0.5% Avirol Dried At Sample Point ___ -- Fords Fords Fords Fords Fords Fords Fords Fords Fords Nichols Nichols Nichols Fords Fords Nichols Fords Fords Nichols Nichols -- Bagger Bagger Dryer Dryer Screener Collector Collector Bagger Bagger Chamber Chanfcer Chamber Bagger Bagger Chamber Bagger Bagger Chamber Chamber Dryer Temp, F Inlet Outlet -- ... -- ------ ---- 350 -- 500 -- 350 350 -- 500 -- 350 -- 500 -- 350 175 502 185 645 190 350 -- 500 -- 350 170 350 -- 500 655 190 350 170 7. Haze 3.1 2.7 5.1 5.4 4.8 5.6 4.6 3.4 4.1 5.2 4.9 5,0 3.1 4.4 5.8 4.4 4.8 6.1 5.0 7.9 4.4 COLORXTE 011718 2 Since the Avirol batches made during these trials were not acceptable, a second series of plant runs were made at lower Avirol levels and also with a redox catalyst system both of which had led to haze-free product in the laboratory. Prior to making these runs, the Fords raw materials were sampled and run in the laboratory and a lab batch was prepared with the Fords water supply. Both runs yielded clear products. The subsequent plant runs at Fords again did not show any improvement with these changes. During these runs samples of the latex from the reactor were taken and dried in the laboratory. These latexes did not exhibit the haze-free performance obtained from laboratory polymeri zation of the same raw materials. The results indicate that a discrepancy exists between the lab and the plant in the polymerization process which may be related to possible contamination, deterioration or cleaning procedures. R&D and Process Engineering are investigating possible sources of con tamination in the plant, the influence of latex heels in subsequent batches and improved reactor cleaning procedures, 2. Impact Modifier (J. C. Fisher, D. Goodman, M. Koral, M. K. Rosen) The Polymer Pilot Plant has prepared impact modifier latex for a series of drying tests in late August, in conjunction with Process Engineering at Louisville Dryer and Nichols Engineering to define equipment requirements to successfully dry at conmercial rates to 0.57. moisture content. This low a moisture content has yet to be realized in spray drying and flash drying trials to date. The Lousiville Dryer trials will be on a rotary dryer and a flash/ fluidized dryer which they have reconmended, based on preliminary testing of impact modifier samples which were sent to Louisville. The Nichols test will be the final spray drying test in this series. Coagulated Impact modifier was tested at Sharpies on their 14 inch and 30 inch basket centrifuges to determine dewatering character istics of the cake and whether the plow discharge from this cen trifuge will give free flowing wet product for dryer feed. These tests dewatered the cake to the 607. moisture level and the plow dis charge was only partially successful in breaking the cake. This polymer is being sent to Louisville Dryer for their trials. Louisville indicates that they have a cake breaker that can handle this problem whC6h'will be investigated. Previous trials with pilot plant equipmenland a Wyssmont Rotocage Lumpbreaker during August have not re solved this problem which greatly influences drying. Only a limited amount of laboratory time was spent on this program during August to improve crease whitening properties due to the high priority given the Supercryl project. Rubber latex suppliers were contacted for additional SBR starting latex samples and some runs with compositional changes, increased mercaptan levels and procedural changes have been made but are not yet evaluated. COLORITE 011719 -3 - PVC Resins 1. Copolymer (J. C. Fisher, M. K. Rosen) Samples of mixed A and B gelatin from Hormel were evaluated versus standard Atlantic gelatins in pilot plant polymerizations. Stable slurries were polymerized in the pilot plant with the Hormel gelatin mixture used for both T-315 and T-389 and samples are under evaluation at the Plastics Applications Laboratory. RSM/srf R. S. Miller COLORITE 011720