Document R2Bw7Mp8oxkKVM0Vewr8vkqan

NT'* FP,CE eo TENNECO CHEMICALS, INC. s To Distribution List* From Dr. R, T. Gottesman Si'B /ter MONTHLY SUMMARY - JUNE At AT Date June 29, 1973 Copy to Attached are copies of the Monthly Summary reports for June 1973 covering the activities of the Piscataway laboratories and associated pilot plants at Piscataway, Flemington and Reading. RTG/ec Attachments Distribution List* Mr. M. Freifeld Dr. D. Keyworth Dr. P. A. Lobo Dr. T. E. Maggio Dr. M. Rosen (2) Mr. G. I. Rozand Mr. C. G. Thompson Mr. M. E, Wagshul Dr. L. A. Wigdor 3- M milr.nf.1^, Mr. T. T. Zuhl R. T.i Gottesman COLORXTE 011744 1-114 inter.office memo TENNEQO CHEMICALS, INC. To Dr. R. T. Gottesman at Piscataway from y, Buono At Piscataway Subject MONTHLY SUMMARY - JUNE 1973 Date June 29, 1973 Copy to X. COATINGS INDUSTRY A. Microbiocides 1. Biocide and Compatibility Screening (E. DiBella, P. Minieri, H. Sidi, G. Trautenberg, G. Tirpak, G. Kagan, M. Landau) (a) TIP Candidate Compounds Lower level biocide screening was completed on the fourteen compounds (from a group of fifty-eight) which were reported last month to have significant antimicrobial activity at 2%. The candidates which continued to show excellent bio cidal responses without major paint incompatibilities, plus two additional maleimide compounds synthesized and screened this month, are as follows: (1) Tetrahydro-3,5-d imethylaminopropy1-2H, 1,3,5-thiadiazine-2-thione dihydrosulfide (2) Tetramethylol melamine (3) Maleimide, N-(2,6-dimethyl)phenyl (4) Maleimide(2-methyl-6-ethyl)phenyl (5) Maleimide(2,6-diisopropyl)phenyl (6) 1,4 Dimethylolplperazlne (7) Maleimide (2-methyl-6-chloro)phenyl Paint compatibility evaluations have been initiated on compounds (3), (4), (5) and (7). The remaining materials will be evaluated when additional quantities are made. Can preservative evaluations are scheduled for compounds (1), (2) and (3). % Paint stability (4 weeks at 120F) and can preservative evaluations on the eight promising low cost formaldehyde releasing TID compounds are underway. Twenty-five additional TID compounds are currently under going primary biocide screening. COLORXTE 011745 2 MONTHLY SUMMARY - JUNE 1973 June 29, 1973 5 \ (a) TIP Candidate Compounds (continued) * Can preservative evaluations were completed on nine TID compounds. Three materials (shown below) gave biocidal responses comparable to Nuosept 77 and are scheduled for paint compatibility evaluations. (1) 1,2-Dihydroxymethylbenzimidazole (2) Tetrahydro-3,5-dibutyl-2(H)1,3,5-thiadiazine-2-thione (3) Morpholine N-(4,5-dihydro-6~methylpyridaz-3-one-2-yl) methyl * Paint compatibility evaluations have been completed on four TID fungicide candidate compounds. Morpholine, H-(methylbenzimidaz-l-yl)methyl: Ethylene glycol showed acceptable paint performance in both latex paints and has been exposed at Piscataway and Puerto Rico. O-anisaldehyde, N-methylhydrazone was unacceptable in either paint, while the remaining two, ji-dimethylaminopropiophenone hydrochloride and N-hydroxymethyl-5-chlorobenzotriazole, were acceptable in PVA and exposed. * (b) Tenneco Pasadena Laboratory Candidate Compounds Paint compatibility studies have been completed on the four promising Pasadena candidates. All were found unacceptable in both PVA and acrylic due to excessive yellowing and/or objectionable odor. * (c) Chevron Candidate Compounds Results on weathered films containing NU-74-3 and NU-4-5 indicate that NU-4-5 is much superior to NU-74-3 both in terms of zone formation and surface fungal resistance. Superior zone formation, but not surface fungal resistance, is obtained with NU-4-5 when compared to both Fungitrol 11 and 22. Further studies with NU-4-5 are underway. (d) Maybridge Chemical Company Compounds A quarterly report on the biocide screening of forty Maybridge compounds has been issued. Two compounds showed significant activity: (1) N-(2,6-diethyl-phenyl)maleimide (2) 2-amino-4-methylquinoline. The maleimide derivative provided the structural lead for four of the active compounds listed in section (a). Twenty additional Maybridge compounds have been submitted and are undergoing primary biocide screening. COLORITE 01X746 MONTHLY SUMMARY - JUNE 1973 -3 - June 29, 1973 * 2. Fungitrol 11 (G. Trautenberg, G. Kagan, G. Tirpak, M. Landau) Dispersion Studies The dispersion formulation containing 50% Fungitrol 11 in Nuosperse 657 and mineral spirits has been selected for further studies because of the superior shelf stability (at 120F) over dispersions containing 557. and 60% active com pound. Paint prepared with the aged 507. Fungitrol 11 dis persion is currently undergoing fungicidal evaluation. * 3. Fungitrol 22 (G. Trautenberg, G. Tirpak) Zone of inhibition and surface fungal resistance evaluations on weathered and unweathered vinyl films showed no increased biocide efficacy when bis(trichloromethyl)sulfone (the addi tive in Vlnyzene BP-10) or the active ingredient in Nuodex 100VT (dodecyl dimethyl benzyl ammonium naphthenate) were added as adjuvants to the Fungitrol 22 formulation. Details of these studies are in Research Report 3006-3. Our program to screen active TID compounds as vinyl biocides is continuing. Sixteen compounds, including all of the maleimide candidates, have been selected for evaluation. B. Driers * 1. Loss-of-Dry Inhibitor (G. Kagan, M. Landau) Blends of 1.2% Cobalt/2.1% Calcium/3.2% Zinc at 2% and 0.6% Cobalt/ 2.17. Calcium/3.27. Zinc used as loss-of-dry additives at 2% and 3% on vehicle solids still look promising after two months' aging. Corroboration of these results are underway in several paint formu lations and one month data is still being gathered. Hie green trim test enamel which was expected to lose dry has not shown this effect after one month. Examination of this paint for loss-of-dry will continue another month. 2. Water Dispersible Driers (G. Kagan, M. Landau) * In four water thinnable coating systems (three air dry and one baked), the Cyclodex driers (Co, Pb, Zr, Ca) performed as well as Cincinnati Milacron's water-soluble products both initially and after the paints were aged one month at 120F. The tests included viscosity, pH, gloss, hardness and dry times. Aging the driers at 120F for two weeks prior to incorporation in paint had no adverse effect on their paint functionality with the exception of Cyclodex lead which exhibited a longer Initial dry time than the room temperature sample. COLORITE 011747 MONTHLY SUMMARY - JUNE 1973 -4- June 29, 1973 \ * 3. Low Temperature Driers (G. Kagan, M. Landau) The major problem of lead replacement in oil-based house paints with equivalent drying performance at low temperatures (>~'50F) has not yet been resolved by the coatings industry. None of the commercially available auxiliary metals which we have examined, i.e., Ca, Zn, Zr or Ce have shown any promise as replacements for lead under these drying conditions. Recently, in a preliminary evaluation, barium was tried as a replacement for lead in two customer oil-based house paints and, although equivalent drying performance to lead was not demonstrated, barium showed some very promising results. Additional evalua tions of barium are currently underway, in anticipation of toxicity restriction with barium, a preliminary extraction test of a barium-based coating has indicated less than 0.6% barium metal was extracted. This is well within the 1.0% limit currently suggested by EPA. Nevertheless, because of the potential toxicity problem with barium, driers based on the relatively "non-toxic" strontium will also be evaluated for this application. II. LUBRICANTS A. New Base Fluids (M. Knapp) Three neopentyl polyol esters were obtained from Hatco (Hatcol3912, 3914 and 3955) for evaluation as potential base oils for high temper ature lubricants. Preliminary screening for oxidation stability was done utilizing Tenneco Method FL-8 with the following results; Oxidation Stability (24 Hours @190C) Fluid* Hatco1 3955 Hatcol 3912 Hatcol 3914 DTDA Viscosity @100F, cSt Viscosity Change, % Acid Number Change Sludge, mg/gm oil Corrosion Fe Cu A1 Mg Ag 29.3 + 3.9 + 0.08 , 1.21 Tarnish tl 82.5 + 1.8 + 0.09 0.02 Tarnish tt 100.6 + 1.7 + 0.11 0.03 Tarnish II 29.6 + 4.9 + 0.17 0.33 Tarnish II No Change No Change No Change No Change H It II II II II II tt * All fluids compounded with a high temperature anti-oxidant package. COLORITE 011748 5 MONTHLY SUMMARY - JUNE 1973 *> \ June 29, 1973 A. New Base Fluids (continued) Based on these results, Hatcol 3912 and 3914 are preferred. All three fluids were also compounded into greases and subjected to 190C in thin layers. Again, Hatcol 3912 and 3914 were found to be superior. Optimization of the additive package is currently underway with the initial objective being development of a superior replacement for Anderol 761 High Temperature Grease. B. Lubricant Additives (M, Knapp) A sample of a new, reportedly outstanding extreme pressure (EP) additive identified as "ATA" (arsenous tetrathioantimoniate) was obtained from Keystone Lubricants for evaluation. This material is an insoluble fine brown powder with an LD50 of 7.5 grams/kilogram (practically non-toxic). It is recommended for dispersion in both oils and greases. Initial tests at levels lower than Keystone's recommendation (5%) indicate that it is an effective EP agent at levels as low as 0.1%. High temperature oxidation studies are currently underway. * C. Reformulation of Anderol 536/537 (M. Knapp) A reformulation of these products was necessitated by the sudden unavailability of one of the components, Alox 575. Both 536 and 537 are rust preventives with 537 being a concentrate and 536 being a water emulsion of 537. Candidate replacements have been developed based on analytical and laboratory test results. Rust testing in the humidity cabinet at Chestertown is currently under way. D. Competitive Product Evaluation (M. Knapp) Ultrachem recently developed a match for Shell's Tivella A synthetic speed reducer lubricant. A sample of this material was obtained from Boston Gear Company where they are currently using it in one of their gear reducer models. Our evaluation of this product gave the following results: COLORITE 011749 MONTHLY SUMMARY - JUNE 1973 6- - June 29, 1973 \ D. Competitive Product Evaluation (continued) Competitive Lubricant Evaluations Ultra Chem Grease Tivella A Anderol 735 Product Type Semi-fluid grease Base Oil Composition Polyether Worked Penetration 490 NLGI Classification 000 Four-Ball Wear, mm 0.6 Four-Ball Weld, kg 160 Semi-fluid grease Polyether 380 0 0.6 110 Semi-fluid grease Diester 460 000 0.4 160 Anderol 735 is our recommended product for this application. FB/amp F. Buono COLORITE 011750 I IM INTER orncE memo TENNECO CHEMICALS, INC. To \ From Subject R. T. Gottesman At A. J, Deine t At MONTHLY SUMMARY - JUNE 1973 Piscataway Piscataway Date Copy to June 29, 1973 I. CHEMICALS/SPECIALTIES 1. Phosphates (L. Schinasi) * Previous procedures for the preparation of BD-307 were based on charging either all of the required epichlorohydrin or phosphorus oxychloride to the reactor followed by gradual addition of the other reactant. The presence of such large amounts of unreacted materials during the early stages of these procedures was felt to be potentially hazardous on a commercial scale. It has now been demonstrated that BD-307 of excellent yield and quality can be ob tained by a procedure in which separate streams (in their correct stoichiometric ratios) of epichlorohydrin and phosphorus oxy chloride are simultaneously charged to a reactor at 110-120C. con taining a "heel" of BD-307 and magnesium oxide catalyst. The reaction proceeds smoothly, requires no wash step and has shown a 93% yield of product (based on POCI3). As an extension of this technique an approach utilizing a continuous overflow reactor will be evaluated. 2. p-Hydroxybenzoic Acid (M. Reale) * Work is continuing on a process for isomerizing dipotassium sal icylate to dipotassium p-hydroxybenzoate utilizing conditions com patible with the Garfield salicylic acid plant. One of the major problems has been the phase change from a powdered solid to a paste like fluid and back to a hard non-free-flowing solid which presented agitation problems. We have now found that a slower programmed heating rate can completely eliminate the liquid phase, evidently by isomerizing sufficient material at a low temperature* so that the system does not pass through a low melting eutectic point on a final heat-up. The total isomerization time is seven hours with two hours required at the top temperature of 275C. This initial work Indicates a yield of at least 90% with excellent color. No inert solvent is required. Corrosion r^te against carbon steel was found acceptable at 2.6 to 3.6 mils per year. Further confirmatory work will be carried out since this procedure would be entirely compatible with the sal acid plant. Trial runs at Bethlehem will be recommended if our initial data is confirmed by work currently in progress. COLORXTE 011751 2- II. PLASTICS INDUSTRY 1. Flame Retardants (M. Reale, J. Stanaback, E. DiBella) Some additional laboratory work is underway on our prime fire re tardant plasticizer, diphenyl (l,3-dichloropropyl)phosphate, to resolve some minor problems which were indicated as the result of recent pilot plant runs. These include the development of suitable reaction control points and a re-progranming of time/temperature rates to minimize excess entrainment losses through the condenser. Polyurethane foam preparations with two Butler candidates, N-phenyl di(2,3-dibromopropyl)phosphamide and N,N~di(2,3-dibromopropyl phosphoryl)diaminoethane, showed self-extinguishment but some adverse physical properties such as foam shrinkage for the first material and incomplete rise and tight foam for the second. Further tests are warranted since reformulation may correct these deficiencies. Further evaluation of our poly(polychlorobenzyl)phosphonate at Hazleton has indicated some foam shrinkage due to too high a degree of polymerization. Additional material of a lower degree of poly merization is being prepared. A higher ester (e.g., octyl) of a simple unpolymerized dialkyl-ochlorobenzyl phosphonate is also being prepared for screening to gether with three other materials selected from our existing list of candidates as low volatile flame retardant PVC plasticizers for automobile use. The screening of isophthalonitrlle, various levels of manganese carbonate, and other Inorganic manganese compositions indicated all of these materials to be ineffective as smoke suppressants in poly urethane foams. To-date we have found no materials suitable for this purpose including materials related to those patented for this use in rigid foams. As the result of continued screening aimed at preparing an emulsified T-2,3-P for the textile industry we have achieved a system stable at the required 10% T-2,3-P level on dilution with water. This was achieved by diluting T-2,3-P with an equal weight of TOF to lower its density and formulating with Tergitol P-28 and HP 27 emulsifiers. This material will be sampled to the textile industry after additional work to optimize this system is completed. A program aimed at preparing various suitable formulations and ex tending the use areas of Pasadena's hexabromobutene-2 has been under taken. The poor solubility of this material precludes the formation of a true solution, but preliminary results indicate the polyvinyl pyrrolidones may achieve stable dispersions in water. Hexabromobutene itself is too unstable in flexible polyurethane formulations resulting in foam collapse. The use of organic phosphites- and epoxides to nullify dehydrohalogenation is being evaluated. COLOR!TE 011752 -3 - III. DYES AND INTERMEDIATES A. Intermediates * 1. Oxaly1-p-Phenylenediamine (M. Feldman) Laboratory work has been completed on a process for the self-manu facture of oxalyl-p-phenylenediamine (OPPD). This work was under taken since the sole domestic manufacturer (DuPont) notified us of discontinuance of this item. Our process is based on an earlier Reading plant procedure to which we have added the recycle of cer tain process streams as featured in a DuPont process for added yield and lower raw material consumption. In this procedure pnitroaniline is oxalylated with oxalic acid and the resultant oxalylp-nitroaniline reduced with iron to OPPD. Samples of our material were converted to Direct Blue 0 which was found acceptable in all evaluation tests at Reading. Yield of OPPD based on p-nitroaniline is 96%. 2. Leucotetra (M. Feldman) The current process used for the manufacture of Leucotetra at Beaufort involves a multi-step process in which anthrarufin is con verted to Acid Blue 45 and this reduced to Leucotetra. The labor atory has been looking at an alternate approach which represents a shorter synthesis scheme and could represent increased productivity and lower raw material costs. In this approach we have chlorinated anthraquinone to 1,4,5,8-tetrachloroanthraquinone and are now studying its hydrolysis to the 1,4,5,8-tetrahydroxy compound which on reduction with sodium hydrosulfite yields leucotetra. Possible means of hydrolysis for the tetrachloro compound are either caustic fusion or treatment with sulfuric acid/boric acid. The current Beaufort process will also be re-evaluated by R&D since consistent yield and quality are not achieved. 3. Durofix Replacement (H. Sidi) As a result of the favorable evaluations shown by our initial set of candidates in comparison to Durofix NYL and Chromasist 2R, addi tional samples have been prepared and submitted for evaluation. These samples utilized various ratios of naphthalene sulfonic acid to-dihydroxydiphenyl sulfone (DDS) to formaldehyde in the conden sation in order to arrive at optimized cost/performance. Commercial DDS Is offered by Monsanto at 70c/lb. and this material represents the major contributor to the cost of our product. As a possible cheaper substitute, condensation products utilizing partial as well as complete replacement of DDS by trichlorophenol were also pre pared and submitted for evaluation. Attempts to completely or par tially replace DDS with a cheaper phenolic such as bis-phenol A were unsuccessful due to gellation of the product. It*is anticipated that evaluation of the current set of samples will lead to final ization of our product. COLORITE 011753 Yellow 4GLP Liquid (L. Port, H. Gosch) Work has been completed on a liquid formulation for use in the paper trade. A 40% formulation in polyethyleneglycol-water has passed all paper dye tests and found to be acceptable. The formulation itself also showed acceptable stability, viscosity and odor and a Laboratory Process Proposal will be issued. Golden Yellow RP Liquid (L. Port, H. Gosch) A 40% stable formulation based on a triethyleneglycol-water system has been developed for use in the paper trade. This material has passed all paper tests and shown complete accept ability in our evaluations. A Laboratory Process Proposal for its preparation will be Issued. Orange C (M. Feldman) Orange C is one of a line of dyes produced at Reading which utilizes 1-naphthylamine, a material included in a recent gov ernment list of hazardous substances requiring special handling precautions. As an approach to circumvent special handling a modified Orange C based on substitution of 1,6-Cleve's Acid (l-aminonaphthalene-6-sulfonic acid) for 1-naphthylamine was pre pared. Dye tests, however, showed this material to be an un acceptable substitute for Orange C since it yielded considerably redder shades and heavier multifiber staining on cotton, viscose and wool. Poor build-up from light to heavier shades was also indicated. AJD/srf A. J. Deinet COLORXTE 011754 I 194 NTEH-ofFicE memo TENNECO CHEMICALS, INC. to Dr. R. T. Gottesmsn at Piscataway from Mr. I. Huppert at Piscataway Subject MONTHLY SUMMARY - CHEMICAL DEVELOPMENT JUNE 1973 Date June 29, 1973 Copy to I. CHEMICALS/SPECIALTIES A. Phosphates 1. Dlbromopropano1 (S. Cinco, H. Gould) Work was instituted on the development of a continuous solvent process for the preparation of DBP which would not infringe on existing patents. Preliminary data indi cates this to be a feasible approach. Yields of distilled DBP, in limited trials at 10-15 and 30-35C were in the 84-867= region with purities ranging from 98.9 to 99.77= DBP. The most recent work at 35-45C, with residence times of 3 to 4 minutes, gave an 84.67= yield of distilled DBP (assay not available yet). This short residence time is expected to permit commercialization in a small reactor. The procedure entails simultaneous addition of solvent (chlorobenzene), bromine and allyl alcohol to a stirred, jacketed reactor while a continuous take-off of crude pro duct through a bottom stopcock is in progress. This is followed by batch distillation. Continuous distillation of this crude is presently being investigated. The possi bility of using a tube-type reactor is not attractive on a laboratory scale due to poor mixing; low yields of DBP were obtained. This approach should ,however, be accept able on larger scale runs. Future investigations on the above continuous procedure will deal with solvent and concentration effects. 2, T-2,3-P (J. Sandstedt, S. Cinco) A sample of Fords bulk stored DBP was converted to T-2,3-P in the laboratory and Pilot Plant prior to implementation of the AlCl^ proces's at Fords. Results are; on DBP Yield on P0C1'* Bleach Required Laboratory Pilot Plant 73-53 Pilot Plant 73-54 86.8 82 85 88.8 84 87 No Yes Yes Reasons for the yield differences are being investigated. A laboratory work-up of the Pilot Plant crude (73-53) after COLORITE 011755 Dr. R. T. Gottesman -2- June 29, 1973 it had been acid and water washed gave an 84.4% (POCI3) yield. This indicated that the lower yield was due to some process variation prior to the steam strip step. Pilot Plant produced DBP via the TID "heel" process was converted to T-2.3-P in 92% P0C13 and 91% DBP yield and did not require bleaching. This duplicated laboratory experience and verified that equipment and operations were satisfactory. The Fords AICI3 trial has been postponed until the yield and scale-up diffe rences are solved at the pilot level. Attempts are in progress to determine why the MgO cata lyzed process consistently gives lower yields than the AICI3 process. A T-2,3-P (Pilot Plant 72-46) sample was treated with gaseous HC1 for 3.5 hours at 90-95C in the presence of the standard quantity of MgO cata lyst resulting in a 1% w/w absorption of gas. Sub sequent analysis showed substantial degradation of the starting T-2,3-P by the HC1, Untreated T-2,3-P (72-46) After HC1 Treatment Dibromopropanol Tribromopropane Unknowns T-2.3-P 0.08% 0.07 7.22 92.78 The same investigation will be conducted with T-2,3-P and HC1 in the presence of AICI3. Previous corrosion testing, carried out using the Celanese cellulose acetate formulation, passivated bronze and T-2,3-P from Fords Plant (Lot No. 73-42) and Michigan Chemical, show ed these materials to behave in a satisfactory manner. A previous "Tenneco" T-2,3-P from the AlClo process (Pilot Plant Lot No. 72-46) caused severe discoloration and cor rosion when in contact with virgin bronze. This same, now passivated bronze, in contact with T-2,3-P made from Great Lakes DBP in the AICI3 process, showed this T-2,3-P to be equivalent to that from the Fords Plant (MgO process) and Michigan Chemical when used in the Celanese formulation. A Research Report *(No. 1908-11, June 11, 1973) was issued summarizing this work. B. Fuel Oil Additives (J. P. Sandstedt, M. Q. Ceprini, I. H. Cooper A. Fischer) The ammonium soap process for preparing Chromium 8-X was success fully demonstrated in the Elizabeth Plant during the week of June 13-20, 1973. A yield of 17,100 lbs. (95%) of Nuodex Chromium 8-X was obtained for delivery to United Aircraft COLORXTE 011756 Dr. R. T. Gottesman -3- June 29, 1973 who are presently evaluating this additive in land-based turbine engines at power plants throughout the country. The combined sodium and potassium level was 0.002% or less (spec. 0.02% maximum). The viscosity of P+ was an improvement over the laboratory (V) and Pilot Plant (S) values. The Pilot Plant prepared two drums (799 lbs, net) of R-406 in fulfillment of an order from Cosmopolitan Chemicals, This magnesium-iron-manganese system is a replacement for the lead-containing NUODEX D-1759. The laboratory process for NUODEX X-1247 (10% magnesium naphthenate) was verified. Processing difficulties were overcome by increasing the excess magnesium sulfate level from the 77a, recommended by the laboratory to 10%, Mate rial is now available for customer and licensee sampling. A Pilot Plant Process Proposal will issue in July. * C. Benzoic Acid (M. Q. Ceprini, A. Fischer) Hydrolysis of benzoic acid still bottoms (Benzotar), which has an approximate composition of 15% benzoic acid, 48% benzyl benzoate, 24% benzoic anhydride and 13% non-volatiles, was carried out for four hours using 5 to 107, excess equiva lents of sodium. A commercially feasible process is under investigation involving fuel oil extraction of the hydroly sate after adjustment to pH 6 to remove tars, followed by toluene extraction to selectively remove the benzyl alcohol and then toluene solution of the benzoic acid after acidi fication of the aqueous phase. It is anticipated that the fuel oil extract can be burned, that the toluene-benzyl alcohol fraction can be recovered by distillation and that the benzoic acid extract can be fed directly into the dis tilling columns of the Garfield benzoic acid facility. Over 85% of the benzoic acid values present in the "Benzotar" are recovered in the toluene extract. This will be more than one million pounds per year of additional benzoic acid production. In another work-up procedure 897 of the poten tial benzoic acid values present were recovered as an offwhite solid (99.9% GC assay). This was done by adjusting the hydrolysate to pH 5.6, decolorizing with Darco S-51 and filter aid, precipitating the benzoic acid down to pH 1 at 60C and finally, filtering and drying. D. Chlorination Technology 1. 2,4-Dichlorobenzoyl Chloride (J. DeGaetano) Using a FeCl^ catalyzed hydrolysis over a tWb hour period at 110C, 2,4-dichlorobenzotrichloride was converted to 2,4dichlorobenzoyl chloride in 95% yield. The product quality is well within production specifications. COLORITE 011757 Dr. R. T, Gottesman -4- June 29, 1973 Analysis Specifications Assay,% Color, APHA Congealing Point,C 98.7 15 20.8 96.0, Minimum 50, Maximum 16.5, Minimum Trials with zinc chloride (64 hours) or mixed zinc chloridemagnesium oxide (24 hours) catalyst systems were unsuccessful. Addition of the water in the PeCl^ process over an 8 hour period to simulate plant limitations of HC1 handling, caused no difficulty. In this case, a 94% yield of "in-spec" product was obtained. Normal water addition, followed by 20 hours of reflux before distillation showed no yield or quality loss of 2,4-dichlorobenzoyl chloride. However, when only half the required water was added and the reaction held at 120C for 20 hours before completing it, only 77% yield of product was obtained. Based on problems encountered in parachlorobenzoyl chloride produced using a ferric chloride catalyst, work is underway where addition time will be extended to 12 hours and distillation time to 6 hours. II. PLASTICS INDUSTRY A, Additives 1, Tin Stabilizers (E, Szabo, H, Gould, S. Hoch) Samples of laboratory prepared I0TG were converted to NUOSTABE V-1562 and evaluated by the Flemington Applications Laboratory. The IOTG's varied in the source of'oxo" isooctyl alcohol used for esterification with thioglycolic acid. All samples were equal to the laboratory prepared control in press ed plaque clarity and color. However, only one of them was equal to the control in oven heat stability testing, namely, the one made using Ashland Chemical alcohol, without sub sequent distillation for purification of IOTG. Since this represented the most economical approach, repeat prepara tion for verification is in progress. Evaluation of Aceto Chemical's DBT0 showed it to be equal to a laboratory control in pressed plaque clarity and color but slightly poorer in oven heat stability. Since the use of Aceto's DBTO represents a modest cost saving and since the availability of a secondary supplier is desirable, modi fied V-1562's (with 5% "tris") were prepared and determined to be functionally acceptable. NUOSTABE V-1528 (Plant Lot No. 69480) containing precipi tated material (due to overcharge of DBTO) was treated with 0.25 to 1.0% 1-46 after filtration. Only the samples con taining 0.75% and 1.0% 1-46 remained stable and were eval uated along with a sample treated with IOTG (by Elizabeth Plant personnel). The sample treated with added IOTG (in a molar amount equal to the DBTO overcharge) was found to be functionally acceptable by the Plastics Applications Laboratory. COLORXTE 011758 . R, T. Gottesman -5- June 29, 1973 2, Stabilizer Intermediates (S. Hoch) Matches for Ferro's FDA stabilizers containing zinc, calcium and magnesium benzoates and stannous stearate in epoxidized soybean oil were prepared. These samples were made where the respective salts were heated at 150160C in a.) NUOPLAZ 849, b.) a 1:1 mixture of NUOPLAZ 849 and Polyguard (FDA phosphite). Samples were also made in which the benzoates were prepared _in situ in the above two solvent systems. These materials will be func tionally evaluated after metals analyses are successfully completed, Reaction of barium chloride with sodium hydroxide to yield barium hydroxide resulted in the desired formation, but due to solubility in water, losses were experienced. A summary of three runs is listed below: Sample No. E-019:10A E-019:10B E-019:10C Reactant Concentration as Ba(0H)? in Water, 7, 15.3 19.6 24.5 Barium Hydroxide Yield,?, 61.0 72.4 70.5 Chloride,?, 3.3 2.9 11.4 Emphasis on studying this route as a replacement for commer cially unavailable barium hydroxide will be continued. A Pilot Plant Process Proposal for the manufacture of 1-237 Stabilizer Intermediate, using the wet fusion method, was issued. Studies were initiated on the preparation of the material by dry fusion in the Pilot Plant's Abbe paste mixer. Results from the initial runs tabulated below demonstrate the feasibility of the technique; however, additional work is required to "zero in" on operating conditions and time cycles. Analysis Results Specifications Remarks D-028-148 Moisture, ?, Free Fatty Acid,?, Color % 0.84 3.00 Brown 1.00, Max. 3.00, Max. White All materials charged at outset; 1% excess barium; unreacted cadmium. D-028-149 Moisture, % Free Fatty Acid,?, Barium,% 1.3 2.0 8.1 1.0, Max. 3.0, Max. 7.7-8.1 D-028-154 Moisture, % Free Fatty Acid,?, Barium, ?, Cadmium, ?, Color 2.7 4.6 7.9 14.4 Off white # 1.0, Max. 3.0, Max. 7.7-8.1 14.4-15.1 White Stoichiometric meta charged; sequential charging order; no attempt to vacuum d; Stoichiometric meta charged sequentially additional water am acetic acid charged no attempt to vacuui dry. COLORXTE 011759 Dr. R. T. Gottesman -6- June 29, 1973 3. Stearates (J. Sandstedt, S. Hoch) S \ Dry blends of DLG-20, S-1244 and magnesium stearate (USP) and varying amounts of wetting agents were made to produce water dispersible materials. The best results, based on water dispersibility, were obtained with Aerosol OT-B at 5,0% use level. These materials are available for customer eval uation. Two samples of S-1244 (Ca stearate) were prepared, one in tap water and one in deionized water for subsequent evaluation by Amoco, After analyses are completed, the sam ples will be transmitted to the customer. This work was done in an attempt to determine causes of rejection of our S-1244 by Amoco. B. Plasticizers * 1. Alcohol Substitutes (0, Fuchs) Functional evaluations by the Flemington Applications Labor atory of n-hexyl-isodecyl phthalate (NHIDP) in a 40:60 ratio (n-hexyl:isodecyl), indicated this material to be a promising candidate as a substitute for DOP. A total of 4-1/2 gallons of additional plasticizer has been prepared by the laboratory for further testing at Flemington (E-004-91, E-004-101). Two other NHIDP samples containing hexyl:isodecyl ratios of 50:50 and 75: 25 were also prepared for similar testing. Substitutes for di-tridecyl phthalate (DTDP)(E-004-97) and di-tridecyl adipate (DTDA)(E-004-99) were prepared in the laboratory using Neodol 23 alcohol in place of trldecyl alcohol. Neodol 23 is a mix ture of linear and alcohols produced by Shell. These esters will be sent for functional comparison to their tridecyl alcohol counterparts, both as plasticizers and lubricants. 2. Polymeric Plasticizers (R. Caruso) A third batch of POLYESTER IX was run in Chestertown according to the revised Pilot Plant Process Proposal 1502-6 (Revision 2), modified to reduce plant time cycles below 24 hours. Both acid number and viscosity specifications were not achieved; attempts to rework the batch were unsuccessful. The material initially produced had an acid number and viscosity of 3,0 and 140 cs @ 210F, respectively; the reworked material resulted in an acid number of 2.5 and a viscosity of 130 cs @ 210F. Subsequent analysis and laboratory work-up of the prepolymer showed it to be comparable to Pilot Plant material. Plant Pilot Plant Hydroxyl Number Acid Number Viscosity cs (3 210F 64 0.62 168 * 64 0.44 165 Lab Conversion Conversion to PE-IX Ac id Numbe r Viscosity i 174 Pilot Plant 1.96 161 COLORITE 011760 Dr. R. T. Gottesman -7- June 29, 1973 Samples of the plant product were submitted to Flemington for functional evaluation. This work shows the problems to be associated with determining the correct palmitic acid charge for Chestertown operations. Variable amounts of palmitic acid are distilled from the reaction mass under vacuum. 3. Plasticizers (I. H. Cooper) The Artisan falling film evaporator was installed in the Piscataway Pilot Plant. Evaluation of this unit for con tinuous alcohol removal from various plasticizers has begun. III. COATINGS INDUSTRY A. Can Preservative (R. Caruso) The hydroxymethylation step (using a filtration technique process) was run in the Pilot Plant. Approximately 16 pounds of product was recovered in hand; 28 pounds of an expected 30 pounds, based on laboratory experience, has been accountable. Major problems were encountered during the final quenching and crystallization, in that the solids tended to agglomerate. This was possibly a result of the minimal agitation levels used. The evaluation of the hydroxymethylation using a trituration pro cedure is underway. A comparison of the two techniques and a critique of the overall can preservative synthesis in its present form will be made in July so that process development work may be completed. B. Pigment Dispersant (J. Gerrity) Evaluation of the laboratory process for R-125 Pigment Dispersant is completed. Product meeting chemical, physical, and functional requirements has been produced. Determination of optimal filtration requirements for plant operations is required since inordinate quan tities of filter aid and recirculation times were required in the Pilot Plant to achieve product brilliancy. It is planned to use a Sparkler Filter on the pilot scale to solve this problem, IV. COLORS * A. Liquid Dyes (G, F, McClain) 1. Duronvl Fast Black KPD Liquid (Textile) Three mixes were produced during June for a total of 11,322 pounds. A Pilot Plant Process Proposal has* been written and if the plant equipment can be readied in time, the next mix should be made in the Reading Plant under the guidance of Pilot Plant personnel. COLORITE 011761 Dr. R, T, Gottesman -8- 2. Sky Blue M Liquid (Paper)(G, F. McClain) June 29, 1973 Based upon performance in the Pilot Plant a Process Pro posal for this liquid was written, and succeeding manufacture should be in the Reading Plant with the initial production under indirect supervision by Pilot Plant personnel. B. Intermediates 1. p-Aminoacetani1ide (G. F. McClain, E. Reinhold) The delays in getting ice for manufacture of PAA Ba 6 in May resulted in a yield that was only 66% of theory when 80% was expected. Early in June the ice system in the Azo area was repaired and when a good supply of ice was assured BA 7 was started. The four salient changes as set forth in the May report were utilized in producing Ba 7, the processing was done without incident and all cycles were as projected. The yield as deliverable PAA was 78% of theory and an additional 2.7% was recovered in the wash liquors for the succeeding batch, hence the total yield is 80.8%cftheory versus 80% expected. The filtrate contained only 26.8 p<xuxis of real PAA which is 80.5% of the theoretical yield, the product loss in the filtrate was reduced from 63.8 pounds on Ba 5 to 26.8 pounds for Ba 7 and the reduction in loss was achieved by concentrating the batch by evaporation to 50% of the original volume prior to precipitation. Strength of the PAA presscake is 91.3%. Functional evaluation and analytical testing are not complete. A rough cost calculation will be made based upon the above results before proceeding with further Pilot Plant work. 2. Metanilic Acid (J. DeGaetano, L. Schinasi) In preliminary developmental runs, nitrobenzene was sulfonated and then reduced to give metanilic acid (metaminobenzene sul fonic acid) in 727. yield (assay corrected) with an assay value of 96%. Analysis of a sodium salt solution prior to isolation indicated an 847. yield at this stage. Laboratory prepared metanilic acid was then converted to GLN base in 90% yield based on amino content. Conversion of the GLN base to Yellow G via phosgenation followed by dyeing applications testing will determine the acceptability of "in-house" prepared metanilic acid. 3. Tolidine Base Dyes (G, F, McClain, E. Reinhold) The plant Process Laboratory has developed a method to substi tute o-tolidine for benzidine in the synthesis of the benzidine series of dyes. Some promising results were obtained on Black GX in which a dye was produced that could be "shaded" to code with a green component. Based upon those results a pilot batch was run. The performance paralleled the lab work in that the shade was somewhat red, however, the tinctorial strength was only 180%. The minimum strength that will allow for the addition COLORITE 011762 Dr. R , T. Gottesman ' -9- June 29, 1973 \*> of the necessary shading components is 250%. The low strength is apparently due to a high volume which resulted in a need for large quantities of salt for complete precipitation. Four sig nificant points have been found in the process that can be chang ed which will result in a reduction in volume and improvement in the tinctorial strength. The batch was split into two parts and the yield on part A is 105% of that expected, part B is not dry. Based upon the above data, a second trial batch is being schedul ed. 4. Scarlet MG (For Red NAS Liquid)(G. F, McClain) To confirm the ammonium chloride precipitation that was done on Ba 149, two drums were taken from Ba 150 and moved to the Pilot Plant. The batch was precipitated with ammonium chloride using a procedure outlined by Colors Synthesis Group. The precipitation was normal, but filtration and washing were difficult and slow. The presscake will be evaluated as soon as it is discharged from the press. * 5. Benzidine From Hydrozobenzene (E. Reinhold, L. Schinasi) A progress report has been issued which covers the work done in the Reading Pilot Plant lab. Hydrazobenzene is rearranged with HC1 to form benzidine and the benzidine thus formed is tetrazotized in situ and coupled to an amine to form the dye. Preliminary results are encouraging, but work has been halt ed pending an interpretation of OSHA regulations, and TID in terest in maintaining a position in benzidine based colors. C . Dyes 1. Polysoerse Yellow 3G (G. F. McClain) The last pilot batch of Yellow 3G had a strong odor of trichloro benzene, even after washing with isopropyl alcohol and large amounts of water. To remove final traces of TCB a sample was dissolved in the lab in water and caustic and heated to 95C for a few minutes until no odor of TCB remained. The sample was then cooled and re-precipitated with HC1. The resultant crystal was soft, well defined and filtered well with no odor of residual TCB. The batch was then treated similarly in the Pilot Plant and presscake sam ples sent to Paterson for evaluation; the initial dyeinga were green and dull - probably due to contamination. The samples are being redyed and when results are obtained, we will utilize this technique or some modification of it in isolating a portion of the next batch which is to be run in July. The vertical leaf filter, on loan from PisCataway, is also being prepared for a trial filtration on Yellow 3G. COLORXTE 011763 Dr. R. T, Gottesman -10- VI. MISCELLANEOUS (I. H. Cooper) June 29, 1973 The Artisan falling film evaporator was tested by representatives of the Newport Division in their process development work for NUPEL 900 emul sion. Technical support and manpower were provided by the Pilot Plant staff. IH/sgf COLORXTE 011764 1 194 NTER. OFFICE MEMO TENNECO CHEMICALS, INC. TO pr _ R. T. Gottesman At fhom Mr. H. R. Johnson At Siejeci MONTHLY SUMMARY - JUNE 1973 ANALYTICAL SERVICES* Piscataway Piscataway o*te June 28, 1973 Copy to METHODS DEVELOPMENT (N, Conzo, I. Wakeman) 1. 2-Aminonaphthalene-5,7-disulfonic acid (ADS): Detection of Impurities by TLC - Procedure No. M-000.82 2. Triphenylphosphite: Determination of Hydrolysis Products Procedure No, GC-74.0 MISCELLANEOUS 1. Triphenylphosphite (S-256) (I. Wakeman) Four different lots of S-256 from Weston (new samples, not previously opened) showed an average of 0.867. diphenyl phos phite, with a range of 0.5 to 1.137.. This confirms our opinion that commercial triphenylphosphite samples inherently contain acidic esters because of the ease with which the product hy drolyzes. Hydrolysis data on S-256, and the above analyses, are being supplied to Slegle for their use in opposing a German patent on phosphites which claims addition of acidic esters as an improvement. 2. Environmental (N. Eider) Environmental control data were supplied to Maremont Corp., IBM, General Tire and Rubber Co., and Kendall Co. in reply to requests for impurity levels and potential carcinogens In Tenneco products. In view of the recent OSHA emergency temporary standard on carcinogens, we can expect a large number of inquiries pertaining to this standard. Except in the case of certain dyes, analytical work will not be required to answer the customers' requests. HRJ/sgf R// son COLOR!TE 011765 1-1*4 TENNECOnter'oVp.ce memo CHEMICALS, INC. To From Dr. R. T. Gottesman At Mr. R. S. Miller At MONTHLY REPORT - JUNE 1973 Piscataway Piscataway Date June 29, 1973 Copy to PLASTICS INDUSTRY Additives 1. Flow Modifier (D. Goodman, M. Koral, M. C. Spalding, E. Szabo) A haze problem continues to exist with Supercryl 100 as compared to Acryloid K-120N. Utilizing a pressed thick plaque technique as a screening test and light transmission and haze data from the Flemington Applications Lab. it was determined that only a mar ginal improvement in haze was achieved by the substitution of Avirol POL-l-N for the regular surfactant at the Fords plant. A direct comparison of lab dried flow ndifier resin versus plant dried resin was made by sampling latex made at the be ginning of the Avirol experiment which confirmed earlier obser vations that lab dried resin provides less haze than plant dried resin. % Light % Appearance, Transmission Haze Thick Plaque K-120ND (Control) Plant Latex, Plant Dried Plant Latex. Lab Dried 97.6 96.0 96.5 3.0 Clear 5.5 Hazy 4.4 Reduced Haze Based on the possible contribution of the plant drying process to the haze problem, an attempt was made to change spray dryer con ditions during the Avirol campaign. A study of flow modifier lots that were reported to give satisfactory performance in customers' applications was made. The spray drying records of these lots (002, 017, 023, 025, 027) revealed that they were processed at a higher outlet temperature (185F. vs. 170F.) and lower pressure differential (1/2" vs. 1 1/2" vacuum) than current conditions. The functional testing of segments of resin dried at the following conditions gave about equivalent results. 170F. 185F. 185F. 180F. Outlet Temp., Outlet Temp., Outlet Temp., Outlet Temp., 1 1/2" Press. Differential 1 1/2" Press. Differential l/2" Press, Differential 1/2" Press. Differential (Standard) There were no appreciable improvements in haze. COLORXTE 011766 2 In addition, a study of spray drier cleanliness was made by \ collecting wall scrapings after the Avirol run had been com pleted, The wall scrapings gave an unexpectedly good performance in functional tests. "U Light Transmission % Haze Appearance, Thick Plaque E-014-23-A, Plant Control E-014-23-E Wall Scrapings 95.8 97.3 5.0 Hazy 3.9 Reduced Haze These wall scrapings are being analyzed to determine what provided the improved results. We speculate increased surfactant in the scrapings. There is also the possibility that combustion gases from the indirectfired burners are leaking into the drying chamber. Process Engin eering will explore this as well as other spray dryer conditions in order to optimize product quality. In the laboratory the influence of incremental addition of monomer to provide a more uniform comonomer sequence is under study. In respective runs, ethyl acrylate and methyl methacrylate were with held and added to the reaction incrementally. The pressed plaque screening test showed improvement with ethyl acrylate added in crementally. These results were confirmed by the Applications Lab. A slight worsening with added methyl methacrylate was noticed, al though this result needs to be confirmed. Methanol extraction of Acryloid K-120N showed 0.65% ash (as Na SO^) vs. 0.27, in Supercryl. Sodium lauryl sulfate was identified as the surfactant extracted from Acryloid K-120N with superior haze free properties. 2. Impact Modifier (J. C. Fisher, D. Goodman, M. Koral, M. K. Rosen) The Pilot Plant has scaled up the initial laboratory 3 stage graft polymerization process to the 300 gallon stainless steel E reactor and developed methods for monomer addition and proper agitation. This vessel provided a significant quantity of latex which was used to develop engineering data on the various isolation and drying processes being considered for a plant process. The graft impact modifier polymerization was found more succeptable to wall scaling and required a higher level of agitation in the 300 gallon reactor than the Supercryl 100H process which was run in this same reactor. Acceptable, mechanically stable latex was achieved on the third batch. COLORITE 011767 -3 Coagulation studies with Pilot Plant latex which is then dewatered on the Fletcher basket centrifuge indicates that the centrifuge cake will contain 30-50% moisture depending on the coagulation technique employed. Most promising is the use of Mg C^/H Cl which produces the 30% moisture level and was verified on the laboratory and 200 gallon scale. Vacuum filtration was less reproducible and troublesome compared to centrifugation as a dewatering method. The Pilot Plant Mikro-Pulverizer was found unsatisfactory for breaking the centrifuge cake prior to feeding the Strong Scott dryer. A low shear cake breaking device seems more desirable. Direct spray drying of latex at Nichols Engineering and drying of centrifuge wet cake in the Pilot Plant Strong Scott dryer have both shown the impact modifier product to be quite heat sensitive and difficult to dry to the < 0.5% moisture content required. A summary of the drying conditions studied is shown below: Dryer Inlet Temp. F Outlet Temp. F Volatiles % Nichols Spray Dryer Nichols Spray Dryer Nichols Spray Dryer 285 305 405 135 10.2 150 3.1 200 0.7 Strong Scott Strong Scott Strong Scott Strong Scott 200 130 2.0 200 145 3.0 250 160 1.2-2.0 225 175 0.6-0.8 The Nichols dryer showed considerable tendency toward wall build up at temperatures above 300F. Nichols personnel indicate that this can be overcome by proper dryer design and they indicate that a dryer could be designed to operate economically at a 150F.AT for this process. The existing Fords Supercryl dryer only appears good for 400 lb./hr. based on trials to date. Another one day trial at Nichols has been scheduled by Process Engineering to finalize the feasibility and economics of spray drying. Drying tests in the Strong Scott appear more promising and better performance is expected now that the coagulation and centrifuge steps have been improved. This work is continuing. % Freeze coagulation of latex followed by centrifugation produces a 10% moisture content wet cake and a very dense desirable dried product. Sandvik is determining the feasibility of using their continuous belt freezer to coagulate latex. COLORITE 011768 4- - PVC Resins 1, Pasadena PVC Process (D. Goodman, J. C. Fisher, F. Kantzler, M. Koral, D. Kryzwicki, M. K. Rosen, N. Eider) A number of requests for flow sheet review, pollution analysis and design data have been answered in the following areas. a. Raw Material Analysis b. Physical Properties of Raw Materials and Process Solutions c. Physical Properties of Resins for Bulk Handling Equipment d. Effluent Water Composition and Treatment e. Molecular Sieve or Activated Carbon Treatment of Air Emissions 2. Chemical Foam Blending Resins (J. C. Fisher, M. K. Rosen) Burlington BR-501 continues to be acceptable in the foam wicking test although performance has diminished. BR-501 slurry was ob tained from Burlington, treated with sodium bisulfite and its performance is being evaluated to determine if best wicking per formance can be restored without interfering with other resin properties. If successful a plant trial with sodium bisulfite will be requested. RSM/srf R. S. Miller COLOR!TE 011769