Document e0O8b0RVmXBKnJyjQoDmdyYG

E. I. DU PONT DE NEMOURS & COMPANY KREBS PIGMENTS DEPARTMENT 256 VANDERPOOL STREET NEWARK, NEW JERSEY Serial No. KN-52-10 Copy No, 3 \ I NEWARK PLANT A PIGMENT COLOR RESEARCH REPORT i PIGMENTS FROM "PONSOtt* BED EL k Period Covered December 1949 to Jane 1951 va ro rl ^ NJ S797 FILE, 223.63 DATE- 5/22/52 DUP050069036 con tot #1 * Um&piml File 2 Beaearch Office (223*63) 3 - Library File (2^.63) A * Or* . S* Struve, Jackson Lab* 5 - By. J. *. Tully/fir. A* Siegel 6 Jackson Laboratory 7~&sfera 8~ 9 n Serial Ho, IQH&40 Copsr Ho* 3 mm bl mt PXQMWt COLOH RESEARCH REPOST Final Report TITLE; FXGNOniS FROM *mSOL BED HI Period Covered2 December 1949 to June 1951 Charge; A-II-C-183 SUBMITTED B3fs P. H. GRISWOLD APPROVED HI ; J, H. COOPER ' DATE SUBMITTED; April 21, 1952 DATE ISSUED; 5/22/52 DUP050069037 asmmm The object of this Investigation was to deteirain the best method of finishing "Fpasol" fed Hi. for use m & rad pigment, awl to prepare material for Sales Service evaluation. "Ponsol^ fed HL (formerly referred to as Wat fed 33w) was discovered in Jackson laboratory during 1947 and investigated as a vat dye, where its excell ent lightfaatnsss made it especially interesting (1). This property of lightf&stness as well as chemical inertness stimulated interest in it as a pigment. The stability of the molecule is apparently associated with the high degree of hydrogen bonding possible between the amino hydrogens and their electron deficient neighboring atoms, as well as the lack of reactive groups. Preliminary tests of HPonsolw fed EL. as a pigment were made by W. S. Struve at Jackson laboratory and B J. Godfrey at Hew&rk. The first samples HSX6l and K&4&2 were acetone-shot milled and acid pasted respectively. These products were found to have good lightfastness and bleed resistance, the acid pasted material was more interesting because of its bright transparent masstone (2). This acid pasted product and a later sample KS~206 showed serious reactivity in alkyd and lacquer grinds (3) as well as darkening on baking in alkyd, These effects were lessened by autoclaving the acid-pasted pigment and using an aliphatic solvent (VH and P) in place of the more aromatic type (Amseo B) in the paint . grinds (4). Sscamination of materials before and after autoclaving indicated a decrease in average particle size and a decrease in the degree of crystallinity (5) To minimize these undesirable effects of pigments finished by acid pasting, all subsequent samples, so finished, were autoclaved at Jackson laboratory by W S* Struve. The results of these preliminary teats were of sufficient interest to warrant a more complete examination and comparison with other possible finishing methods. Tinctorialiy the best finishing method is acid-pasting and autoclaving because of the strong, intense, yellow hue and dark, intense masstone of the pro duct . Judging by physical behavior the best product is that obtained by acetone shot milling. However, this material is very blue and dull tinctorialiy with a very milky, brown masstone. The acid-pasted autoclaved product shows considerable reactivity in alkyd systems and tends to bleed in both baking alkyd and vinyl. The acetone milled product has none of these disadvantages. Dispersion milling yields a product which lies between the two extremes in physical properties found above and is very near the acid lasted material tinctorialiy, being slightly bluer and duller. DUP050069038 The salt xailled product is generally poor* being 'weak tinctorial# and exhibiting excessive reactivity and bleed. Products made by - acetone milling are essentially the same as acetone shot milled material in all respects. Acid(psOTutoid) swelling yields a very weak and* therefore* uninteresting product. Ho great effort has been made to change the fundamental bleed or reactivity behavior of the acid-pasted autoclaved product* nor has the acetone Hilled product been altered toward the more desirable yellow hue* AccompHshaeat of either one of these ends would lead to a more desirable pigment. the acid-pasted autoclaved product was chosen as the most desirable pigment (6) and an order was placed with Orehem (00-5131) for 100# of this material.. This was converted into 10 lbs. of the RaJaapott MP-64X-D, lot 1372* 20.8 lbs. (solids basis) of the RsasapoK pulp AEP~643~D, lot 3370, and 327 lbs. of &HL650"D* s.w. 2645 (a 10$ lake of Red RX. prepared by extending ARP-642HP with blanc fixe), the products were submitted to Sales Service for evaluation and formulation for sales proaotion (7). Since the production of ttPonaolB Ssd HI is not standardised* this lot was bluer and duller than the lot previously purchased on which all the initial tests had been made. DISCTSSIQM MPonsoln Red HI Crude w&s finished by the following methods: X) Acid-pasting and autoclaving 2) Acetone-ball milling 3 ) Dispersion milling 4) Salt milling 5) HF-aceton milling 6) Acid {persButoid) swelling the products were converted to barium resinate lakes for evaluation. A preliminary comparison of the mode of l&kiug the acid-pasted, autoclaved material through use of ammonium or sodium resinate showed the former to have a slight advantage in texture as indicated by rate of strength development of inks (N.B. 3340-2 and 234CMS). AH subsequent KEesaposw were made from the ammonium resinate emulsion and contain 76.1$ dye and 23.9$ barium resinate. The accompanying charts show the comparisons of these finishing methods in rubout* alkyd and vinyl evaluations. DUP050069039 V iftrl Evaluation DUP050069041 The rates of strength development in acetone shot milling, dispersion milling and salt milling indicated that ell reached maximum strength after 96 hrs. milling time* "tempos" were made from pigment which had been milled for this length of time, in each case, for the evaluation comparisons* "HF*acetone milling was carried ot for two hours* An additional hour of this type of : milling showed a negligible strength increase* Attemptsto oxidize the bluer shade product obtained by acetone milling to a yellower hue were made with chromic acid, hypochlorite and hydrogen peroxide. Chromate gave a very slight advantage in yielding yellower hue, but the other two oxidizing agents produced products even bluer than the control (1340-21). Acetone milling crude "Ponsol" find Hi. in the presence of chromate or chromate with trisodium phosphate did not improve the resulting shade toward a yellower hue. (2340-24). Grinding crude dye with slkyd vehicle gave excessively blue, dull products of no interest (2340*29) Solvents other than acetone were examined for shot milling finishing. Methanol, ethanol, isopropanol, methyl acetate, "Celsnese Solvent 601", "Cellosolve1*, dimethyl formamlde, dioxane, nitrobenzene, psrchloroethylene, and a 3% solution of "Blancol" in water were employed. The organic solvents gave products equivalent to that with acetone except in the eases of nitrobenzene and perehloroethylene which were very weak. The product from the "Blancol" water grind was very dull, but considerably yellower than acetone milled material (134G-26). Ball milling of crude "Fonsol" Hod HL was carried out in water with agents determined to be good wetting and dispersing agents such as "Triton 2-100", "Aaaaoujqc AO", Sp-717", "Sfchomsen C/25", "Ethoaeen C/60", "Areskleen 400", "Igepon T", "Quponol G" and "Victowet 12". The products where the "Ethoseens", "Igepon f" or "Duponol G" were used gave rather strong pigments for water grinds and yellower hue compared to the aoetone milled product, but were not sufficiently good to warrant further investigation* (1340-30). Dispersion adUMeg with small amounts of dispersing agent other than "Span 80" such as capric acid, "Duponol G", triethanolandne-Cig ester or silicone polymer gave no improvements in strength or hue of the product, nor any benefit in the reactivity behavior in alhyd system (1340-31)* The second lot of "Ponsol" Bed EL manufactured by Orchem was finished by acid-pasting and autoclaving, acetone milling, and dispersion milling. In all cases the same relative tinctorial comparisons of these methods held true. All products were bluer and duller than the similar products made from the previous lot . This dye is not made by a standardized plant procedure and evidently the method of manufacture affects the final tinctorial properties. (1340-34, 30, 39, 40). DUP050069042 to. attempt, b s Bade to produce a high strength lake frost crude dye by reducing & slurry of the crude in the presence of barium sulfate with sodium hydrosulfite, followed by air oxidation* The product was very weak compered to a lake made by simple mixing of acid-pasted and autoclaved pigment paste with blsnc flags* (1340-24). Linoleum lakes of BL-28Q-D and 8X-237-D types were made from a paste of acid-pasted, autoclaved Bed RL. The very weak, dull tinctorial, properties of the products showed them to be of no interest in the linoleum field. (1340-3 & 4)* A BL-282-D type lake of acetone-milled material was made in the hope of reducing the flocculation tendency observed on use of the "Eamapo" of this type of finished product in alkyd. A very definite improvement in flocculation resistance was obtained when this lake was used. (1340-28B). A BT-2B4-D type product was made from acetone milled "Ponsol" Bed RL ami found to have better texture than the untreated pigment, although weaker. The "Bam&po" ms better in texture than either as judged by rate of strength development on the 3~roll ink mill. (1340-28C). A lake consisting of 15$ "Ponsol" Red HL (finished by acid-pasting and autoolaving) and 85$ barium sulfate was made by both slurry mixing the components or precipitating the barium sulfate in the Bed RL slurry* Ho noticeable differences were found in the strength or texture of the products prepared by these methods. The finally accepted method for making such a highly extended lake was to slurry the past of the resinated acid-pasted autoclaved "FUnaol" Rsd EL with "blane fixe" to form a product containing 10$ toner (ABL-650-D). EIPBRIEBHTM,; H.Ba 1325 Jackson laboratory} 2560 gam* of 96$ sulfuric acid charged to kettle and cooled to 5*6. 256 gms. Ponsol Red RL crude added slowly keeping temperature below 10*6. Stirred until dissolved (2-4 hours). Added over an hour period to 56(H) gm. ice and 20,000 gms. water agitated* Stirred an additional hour, pressed and washed acid free to Congo Red paper. h *b . 1325 Done by W S. Struve at Jackson Laboratory; 1706 gms. of acid-pasted Ponsol Red RL paste 256 gem. solids basis) charged to autoclave. 854 gms* water added and stirred to a smooth paste. Neutralized with 5 gm ammonia. Auto clave closed and heated to 150"C. for one-half hour under autogenous pressure. Cooled to 75*0. pressed and washed once. "Raasapp" Fpraralation ABP-641-B (N.B. 1340-34) 1176.5 gms. of acid-pasted, autoclaved "Ponsol" Red RL paste (solids basis 200 gm.) weighed into 20 liter jar and volume made up to 2500 ml. The following ammonium resinate emulsion prepared and added with good agitation: To 366 ml. water in 4 liter beaker were added 62*7 gas. of freshly pulverized "K Wood, resin". 40 ml* of cone, ammonium hydroxide added and heated to dissolve and disperse the resin. Heated to boil and held until pH DUP050069043 ms 9*2 and the emulsion ms stable. This emulsion ms added to the pigment slurry through a 60 mesh screen over a 5 minute period. A solution of 31.34 gn* barium chloride dihydrate in 167 ml. water mas added dropwise in a 5 minute period. Agitation continued for 5 min. then heated to the boiland heli30 minutes. Flood! to 15 liters, filtered and washed free of chloride. Dried at 140*F. field 2630 gms. Composition: "Ponsol" Red 76,1$, Barium resinate 23.9$. s.w. 2645 ..5 lbs. of abMU-D dry basis) made up to 50 gallons. 76 lbs. Blanc Fixe added over 30 minutes through recirculating draft tube. Draft tube allowed to recirculate for 60-minutes. Pressed with agitation, dried at 140F. for 48 hrs* Pulverised at regular speed, field 82 lbs. Composition: Ponsol Bed HL 10$, Barium resinate 3.12$, Blanc Fixe 86.83$. DUP050069044 SEFEREHCES 1. "Hsw Vat Reds of the Qsdiaaole Type** Progress Report - F.B. Stilmar <HB~53-S No. 89, Serial No. 20070 wVat Reds Containing the CkdiazoXe and Triazole Ring" t, B. Stilmar, JLB-53-H.8. No. 8. Serial No* 17278 wVat Bed 33 Final Sample; Gxdiazole Fat Colors II" Problem Report ** F. B. Stilsaar JLR~53~190, No. 1. Serial No. 20021 2. Research Laboratory Moisorandm 48-44 12/31/48. 3. Research laboratory Kesaorandua 49-2? 3/29/49* " 49-27 5/3/49* 4. Research laboratory Heaorandum 50-25 8/21/50, letters W. S, Struve to 0. B, Killian - 12/22/49. 5. letter; A. R, Hanks to W. S. Struve - 11/30/49. 6. letter* 0. B. Killian to J. . Tolly 4/6/51. 7. Sales Service Reports 52-6 7/26/51 52-8 10/27/51 52-9 12/14/51 8. Research Notebooks 1288, 1325 and 1340.