Document Dvay49paJw2b2Yg11O9Y6y7NQ

-XK-70-5 SUBSHTOTB) QUINACRIDONES By: L. R. Lerner 6/68 4/69 R. & 0. Fite Room ,1 -" t ' ' Deft Jackson Laboratory R j. D t1 e P k n TO: __............. Return to CDP Dept Jackson Laboratory R &D. FiteRocm MBPPPjM Return to- :cp Dost Jackson Laboratory R,& D. File Room Return to CDP Dept Jackson Lebcratory R & D. Fite Room Return to iyiu ran (Rev 3 ci CDP Dept. .acksort Laboratory DUPO 50081940 E. I. DU PONT DE NEMOURS & COMPANY 256 YANDERPOOL STREET NEWARK, NEW JERSEY Serial No. KN-70-5 Copy No. 13 RETURN TO JACKSON LABORATOR F1U ROOM NEWARK PLANT PIGMENT COLOR RESEARCH REPORT SUBSTITUTED QUINACRIDONES Period Covered June, 1968 to April, 1969 FILE: DATE: 223.91 1/30/70 NJ 14071 DUP050081941 KN-70-5 1. Numerical File 2. Research Office File, Newark 223.91 3. Newark Library File 223,91 4. M.Hunt/E.Gonick, Pigments Wilmington 5. W.S.Struve S. F.F. Ehrich/E. F. Klenke/B.H. Perkins/Newark Library 7. P.J.Monahan, Newark (Vital Records) 8. N.G.Fisher, Central Research Dept., Wilmington 9. R .H .Wetzel/J. F. Maur er/J. W. Minnich/W .A. Wes t 10. J, Jackson 11. Extra 12. Extra 13. Extra 14. Extra NEWARK PLANT PIGMENT COLORS RESEARCH REPORT SUBJECT s SUBSTITUTED QUINACRIDONES PERIOD COVERED: June, 1968 to April, 1969 SUBMITTED BY: L. R. LERNSR DATE SUBMITTED: 12/15/69 APPROVED BY: F. F. EHRICH f j.s+S` V"'".:? DATE RELEASED: 1/30/70 ABSTRACT A series of new substituted, quinacridones (2,3,9,10-tetrachloro-, 2,9-diacetyl-, 2,9-diaeetamido-, and 2,9-dimethylsulfonyl-QA) were prepared for evaluation as pigmentary materials, and for the determination of the effect of these 2,9-substituents on viscosity behavior in paint systems. All of these substituted quinacridones showed poor lightfastness both in acrylic enamel and acrylic lacquer. They all showed relatively low viscosity in both systems, but a blend of RT-849-D and 2,9~diacetylQA showed a decrease of viscosity that would be expected by a simple additive effect. r et ur n t o JACKSON LABORATORY FILE ROOM DUP050081942 TABLE OF CONTENTS I, INTRODUCTION II. RESULTS AND DISCUSSION Preparation Solubility Viscosity III. EXPERIMENTAL APPENDIX I - Reflectance Spectra APPENDIX IX- X-Ray Diffraction r-MN M Pace I 7 DUP050081943 I. INTRODUCTION Certain quinacridones (QA's) being need in automotive finishes show rather high viscosities in certain paint vehicles. High vis cosity presents a problem in spraying and in reflow# so that it would be desirable to modify the quinacridone in order to improve its rheological properties with respect to this application. A select series of 2,9-substituted QA's were prepared# therefor# which had large differences in Hammett Op functions acetyl (+0.516)# acetamide (-0.015)# metnylsulfonyl (+0.728). In addition# the 2 # 3 # 9,10-tetrachloroQA was also prepared and evaluated. II. RESULTS AND DISCUSSION Preparation The substituted QA's were prepared as follows from the respective amine. In the case of 2# 3# 9#10-tetrachloroQA (ic)# there are three possible products (la#b#and c) when starting with 3#4-dichloroaniline. DUP050081944 -2 It has been shown by others that substitution in the 1 or 4 (8 or 11) positions cause greater solubility than substitution in the 2 or 3 (9 or 10)position. Assuming this greater solubility, the crude tetra-substituted QA was repeatedly acid crystallised and the least soluble product used in this study. (The acid crystallization was repeated until there was no change in the infra-* red spectrum - see below.) Solubility It seemed desirable to determine what effect these sub stituents would have on solubility. This is of particular interest in plastics applications (e.g., quinacridone is partially soluble in nylon, therefore restricting its application in this plastic). Using a procedure developed by H. Matrick (see Experimental), it was determined that all the new disubstituted QA's had a solubility of < 0.014 g/1 in boiling 1-chloronaphthalene (unsubstituted QA has a solubility of 0.084 g/1). In an attempt to find a more sensitive solubility measure, the refluxing 1-chloronaphthalene slurries were checked for fluores cence with a long wavelength ultraviolet lamp, (Ultraviolet Products, Inc. UVL-21 lamp.) The results show that the 2,9-diacetamido and the 2,9-dimethylsulfonyl QA do not fluoresce, While 2,9-diacetyl does show some green emission. These results would indicate a slightly higher solubility for the latter. This assump tion was confirmed by the faster crystallite growth rate of 2,9diacetyl QA in refluxing DMF (electron micrograph) As was antici pated from the low solubilities found, none of the samples showed any color change when extruded in polystyrene at 400 and 60QF. respectively. Due to poor lightfastness, this was not pursued further. Viscosity It was expected that by placing electron-donating or withdrawing groups on quinacridone, the viscosity might he decreased. Table I shows that these substituted QA's do show decreased vis cosity, but a blend of RT-849-D and 2,9-diacetylQA does not show as marked a decrease as would he desired. DUP050081945 3 Table I Quinacridone Swindle # Brookfield Viscosity Measurement Acrylic "Lucite" 11/4/69 6. RPM 12. 30, 60 2,3,9,10-tetracl 2 6.5 11.5 24,5 47.5 diacetamido (large particle) 2 3.0 5,5+ 13.5+ 27.0 " (HP-milled) 2 3.0 6.0 14.5+ 29.0 diacetyl (large particle) 2 4.5 8.0 17.0+ 32.5+ " (HF-milled) 2 19.0+ 33.0+ 63,0 99.5+ dimethylsulfonyl (a 2 phase, large particle) 3.0 5.0 12.0+ 24,0+ RT-792-D, 86979 2 59.0 3 16,5 +73.0 20.5+ Off scale 29.5 40.5 RT-849-D, 90158 2 26.0+ 35,0+ 50.5 83,5 RT-742-D, 00117 2 19.0 29.5 41.0 67.0 Quinacridone TAB 1/20/69 #2 Soindle _6 12 RPM 30 SS. 2,9-diacetyl (large particle) 1.0 1.5 3.0 6.0 " (HP-milled) 0,5 1.0 2.5 5.5 Tetrachloro (HP-milled) 1.5 2.3 5.0 9.0 2,9-diacetamido (large particle) 0.5 1.2 2.8 5.5 " (HP-milled) 0.7 1.2 2.8 6.0 2,9-dimethylsulfonyl (HFmilled - p-phase) 1.5 2.8 6.2 12.0 RT-792-D, SL-86979 7.0 10.0 16,0 23.0 RT-849-D, PS-90158 50.0 56.5 68.0 82.5 RT-742-D, PS-00117 7.0 9.5 13.0 20,5 RT-795-D, 97189 4.5 6.5 10.5 16.0 DUP050081946 Cninacridone - 4. 4/3/69 12 #3 Spindle 20. 60. Ford Cup 2/9-diacetyl (disp.milled) (1897/61A) 1,0 1.5 3.5 6.2 27" RT-792-D 1.7 3,2 7.0 12.5 41" RT-849-D 2.7 30.5 37.5 46.2 100" 4/18/69 #3 Spindle 1897/61A 10%, RT-849-D 90% 1.7 20,0 25.3 32.3 RT-849-D, PS-90158 24.0 28.0 35,2 44.0 Color and Liohtfastness For each of the 2,9-disubstituted QA's, two phases were found (though there may he more). The least stable (a) phase of each/except 2,9-dimethylsulfonyl, was obtained by acid crystalliza tion and the more stable (0) from DMF refluxing or dispersion mill ing, The a-phase of the methylsuIfonyl derivative was obtained directly from its synthesis/ but both acid crystallization and DMF reflux gave 0-phase. Table TE shows the X-ray data for each ccanpound (also see appendix)* Table li X-Ray Diffraction Data a-phase from acid crystallization* 0-phase from DMF reflux w = weak m = medium s as strong Quinacridone Phase 2.9-diacetamidc a "0 2.9-diacetyl " a 0 2 # 9-diraethylsulfonyl 0 a X-Ray PeaTts 7.6(w), 9.0(w)/ 14.1 (s)/ 17.0(s)/ 25.2 (vs) 25.9(s)/ 28.4(m) 4.6(e)* 17.4(w) , 19*0(w), 20.6 (w), 25.9 (vs) 28.2 (m) . 4.4(s), 8,8 (w), 14.0(w), 27.0(vs). 4.8(a)* 9.8(w), 13.8(m), 15.9 (w), 18.9 (w) 19.7 (w), 25.6 (w), 26.7(vs)/ 28.6(w). 7.0(w)* 13.6(m)* 16,8(vs)/ 19,0(w), 20.6(m), 22.0(m), 23.4(s)/ 24.7 (w)/ 26,4(w), 27.2 (m)# 28.0(m) / 28.9 (vs) . 5.0 (w) * 9.9 (w) / 13.0 (m)* 14,9 (w) * 17.4(w), 16.9(w), 19.9(s), 20.9(w)/ 24.2(m)/ 25,4(vs), 28.0 (m). except 2,9-dimethylsulfonyl; crude product from synthesis is a* 0 from both DMF reflux and acid crystallization. DUP050081947 5 The color differences between each of the phases is quite marked, particularly in the case of the 2,9-diacetylQA (see appendix for reflection spectra), Table III shows longest wavelength absopritions of each QA. Table III Longest Wavelength Absorption of Some puinacridones Compound Phase 2,9-diacetylQA If a P 2,9-diacetamidoQA II II a P P 2,9-dimethylsulfonylQA II II a P P 2,3,9,10-tetrachloro Vehicle Zinc oxide drawdown TAE-3 or acrylic "Lucite" Zinc oxide drawdown II if II TAE-3 or acrylic "Lucite" AII crylic "Lll ucite" TAE-3 Acrylic "Lucite" or TAE-3 max(nm) 602 558 576 614 614 546 550 550 556 All 8-phase (and a of 2,9-dimethylsulfonylQA) were exposed in Florida. The results in TAE-3 and acrylic ,,Lucite"are shown in Table IV. In each case, there is a marked "break" in all the panels after three months, thus indicating poor lightfastness. TABLE IV OUTDOOR DURABILITY S-68468 Panel Pigment Initial Gloss 20 Metallies 10/90 Al/Toner P/B 15/100 1 1897--13B-1 46 2 38 45 3 38-1 49 4 39 69 5 39-1 49 6 40C 71 7 RT-792-D, SW-86979 45 8 RT-849-D, 90158 46 9 RT-742-D, 00117 45 Tints 5/95 Toner/White 10 1897-13B-1 63 11 38 68 12 38-1 73 13 39 63 14 39-1 62 15 40C 70 16 RT-792-D 78 17 RT-849-D 74 18 RT-742-D 76 6 Mos. 7f 6f 6f 6f 6f 3f 7f 9f 9,$f 3f 4f At 3 3f 0 4f 5f 4f DUP050081948 Panel Plament 1 1897-61A 2 RT-792-D# 86979 3 RT-849-D,90158 5/95 Toner/White 4 1897-61A 5 RT-792-D,86979 6 RT-849-P,90158 -6 S--69431 A1/Toner Initial 10/90 II (1 Gloss 63 68 60 20 61 60 61 S-69406 Panel 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 Piqment 1897-55B 54C 45B-2 45C 52 G RT-792--D RT-849-D RT-742-D RT-795-D 1897-558 54C 45B-2 45C 526 RT-792-D RT-849-D RT-742-D RT-795-D Al/Toner " 10/90 II II II If ll II ll It 50/50 II 11 II II <1 1 II M P/B init .Gloss 20 0.i'5 72 73 64 62 71 77 49 71 64 0.97 65 66 63 60 63 64 60 67 63 Tints 19 20 21 22 23 24 25 26 27 5/95 Toner/tohite 1897-55.B 54C 45B-2 45C 526 RT-792-D RT-849-B RT-742-D RT-795-D 70 72 69 66 70 72 71 73 69 3 Mos. 7f 10 10 5f 10 10 3 Mos. 7f 5 6 6f 3 9.5f 10 10 10 8f 6 8f 7 3 9.5f 1010 10 9.5 6 8f 6f 3f 10 10 9f 9f DUP050081949 7 The poor lightfastness of these compounds relative to quinacridone could be due to poor packing in the crystal due to the substi tution, This could cause a decrease in the ability of the excited molecule to dissipate its energy by non-reactive pathways. It is also quite possible that the substituents themselves (e.g., acetyl or acetamide) are photoreactive, whatever the reason, these sub stituents are detrimental to lightfastness. EXPERIMENTAL All infrared spectra were recorded on a Perkin-Elmer Model 21 or Model 137. The preparation of 2,9-diacetylQA was typical. Diethyl-2,5-di(4 *-acetvlani1ino)-3.6-dihvdroterephthalate To a 3 liter flask equipped with agitator, thermometer and fife inlet, was added 51.2 g (0.2 mole) of diethyl succinylsuccinate and 1 liter of 2B alcohol. The flask, under nitrogen, was heated until solution Occurred. Then 91 g (0.6 mole) of p-aminoacetophenone and 6 ml (0.070 mole) of concentrated HCl were added. The solution was re fluxed for 3 hrs., cooled to 50c. and filtered. The product was reslurried in 2B alcohol and stirred with a solution of 7.2 g Na2C<>3 in 25 ml H20 for 10 minutes. The product was filtered, washed el" free and dried. Yields 88 g (90%, mp 222-224). Using p-aminoacetanilide, 90 g (0.6 mole) instead of p-aminoacetophenone and CFgCOgH, 5.2 ml (0.070 mole) instead of HCl, a yield of 103.7 g (theoretical 104 g) was obtained (mp 294-296C) . Using 3,4-dichloroaniline (97.2 g, 0.6 mole) as the amine and CF3CO2H, the yield of the corresponding dichloroanilinoterephthalate was 107 g (theoretical 109 g, mp 208-210c.). In order to obtain good yields using p-aminophenylmethylsulfone, n-butanol and CF3CO2H were used instead of 2b alcohol and HCl, This reaction was run 10 hrs. on half scale using 50 g (0.30 mole) of p-aminophenylmethylsulfone. Yield 52.0 g (92%, mp 167-180). 2,9-Diacetvldihvdroquinacridone In a 5 liter flask equipped with an agitator and DeanStark tube, 2 liters of distilled "Dowtherm" was heated to reflux, under a nitrogen atmosphere, 88 g of diethyl-2,5-di(4'acetylaniline) 3,6-dihydroterephthalate was added portionwise. The ethanol genera ted was allowed to come off during and after addition. After all the ethanol was removed, the solution was refluxed for an additional 2 hrs. The solution was cooled to 50-60, filtered and washed with methanol. The product was slurried in methanol, filtered, and dried. The yield was 69 g (96%, mp > 360). The corresponding diacetamidodihydroquinacridone was obtained in quantitative yield (mp 360) by this procedure. The yields of di methylsul fonyl and tetrachlorodihydroquinacridone was 91% and 88% respectively (both mp^> 360C.). DUP050081950 -8 2i9-Diacetylouinacridone In a 2 liter flask equipped with an agitator and condenser was placed 280 ml water# 75 g sodium hydroxide and 48 g (0.12 mole) 2t9~diacetyldihydroguinacridone and 375 ml of methanol. After the solution was stirred for 1.5 hrs.# a solution of 28.2 g (0.13 mole) of sitol in 115 ml of water was added. After refluxing for 2 hrs.# the slurry was flooded to 10 liters with water# filtered# washed alkali~free(brilliant yellow paper) and dried. The yield was 45.3 g (95%# mp 360C. ). The yields jf 2,9-diacetamido-# 2, 9-dimethylsulfonyl-# and 2,3# 9#10-tetrachloroquinacridone were 87# 75# and 88'% respectively. These samples were purified by sulfuric acid crystallizations and hot BMP extractions. In the case of the tetrachloroguinacridone# four acid crystallizations were carried out in order to obtain a product which did not change by ir. Solubility Determinations Pigment solubilities were determined by heating a known weight of pigment (typically 10 to 100 mg) in a flat bottom flask (500 ml) with various amounts (100 ml and up) of solvent (typically 1-chloronaphthalene). The flask was equipped with a reflux conden ser and thermometer placed through the condenser. Stirring was done magnetically and the extent of solution observed by shining an intense beam of light through the flask. See the discussion sections for the results. dc DUP050081951 APPENDIX I REFLECTANCE SPECTRA DUP050081952 DUP050081953 WAVELENGTH IN Ml! I iMironwc 40 60 80 7( 80 500 20 40 60 RECORDING SPECTROPHOTOMETER INSTRUMENT NO. 2646334 E. 1. DU PONT PE NEMOURS & CO. PIGMENTS DEPARTMENT NTEST PATE DUP050081954 400 20 40 60 80 500 20 40 60 80 600 20 40 60 80 700 WAVELENGTH IN MlLUMIGRDMfi T DUP050081955 DUP050081956 00 90 80 70 60 50 40 30 20 10 0 DUPO 50081957 WAVELENGTH IN MILLIMICRONS 80 700 DUP050081958 400 20 80 500 20 40 60 80 600 20 WAVELENGTH IN MILLIMICRONS DUP050081959 appen d ix x i X-RAY DIFFRACTION DUP050081960 DUP050081962 "I* -JHL DUP050081964 t1?f V 111 i I -i H 0! ! i Au | 1 6 S N<OS jrX> V JE S 9 'S' *r v> V !V V or '0 ! 3r i x DUP050081965 a U jf s -a ! o C/5 2 | O^ * jfi J- i * ^ C/^ < n !* s s 5 8n 2. s - J-l .= tt- o 0> <r DUP050081967