Document gvKj2yvgO5ae1Vv6pRojNJjJ

F -Urn t. C H Dnpt Jackson Laboratoiy R &D FileRbCii TO: Return to: CDP Dept. j cUn Laboratory R. & 0. File Room DMPANY Serial No. KN-67-18 Copy No. 21 TO: Return to: COP Dept Jackson Laboratory R. & D. File Room TO:. Return to; COP Dept. Jackson Laboratory R. & D. File Room TO: Return to: COP Dept Jackson Laboratory R. <4 D. File Room TO:. Return to: mu -1700 mv. 3/78) CD3 Dept Jackson Laboratory R. /!, o, Fite Room NEWARK PLANT PIGMENT COLOR RESEARCH REPORT 2,9-; CHARACTERIZATION SOLID SOLUTIONS: Period Covered July, 1967 - September, 1967 223.91 DATE: 10/9/67 N33714 NJ 9346 DUP050027644 KN-67.-1S Copy No. 1. Research Numerical Pile 223.91 2. Research Office Pile 223.91 3. Library 4. M. Bint/E. Gonick, Pigts., Wilm. 5. W. S. Struve/A.A.Brizzolara 6. B.H. Perkins/H. R. Linton/P. F. Ehrich/Newark Library 7. P. J. Monahan (X Pile) 8. N G. Pisher, Cen. Res. , Wilmington 9. R. H. Wetzel/EL H. Gyorgy, Newport 10. C. W. Manger 11. Extra 12. Extra 13. Extra 14. Extra 15. Extra NEWARK PLANT PIGMENT COLORS RESEARCH REPORT SUBJECT: 2,9-DIMETHyLQUINACRLDONE/QUINACRIDONE SOLID SOLUTIONS: CHARACTERIZATION Period Covered:: July, 1967 to September, 1967 Submitted by: C. W. Manee^ vb> " 1! ^ Approved by: B. H. PERKINS .. Date Submitted: 9/22/67 Date Released: 10/9/67 ABSTRACT: A studywas made to determine the differences between solid solu tions of QA/2,9-dimethylQA and 2,9-dimethy1QA, alone and in mix tures with QA. DUP050027645 TABLE OF CONTENTS I. INTRODUCTION II. SUMMARY AND CONCLUSIONS III. PATENT SITUATION IV. SUGGESTIONS FOR FURTHER WORK V, EXPERIMENTAL DETAILS A. Samples Used 1, Available from Others 2. Samples Prepared for This Study a. Dry Mixes (1868-13) b. Refluxed Dry Mixes (1868-13) 0. HT-Drowned Ladder Series (1868-15) B. Results 1. Infrared Spectra 2. X-Ray Diffraction 3. Hue of Solid Solutions C. Procedure for Preparing Mulls for Infrared Spectrophotometry Page 1 1 1 1 2 2 2 2 2 2 2 3 3 3 4 4 DUP050027646 I. INTRODUCTION Because of a patent; situation with 2,9-dime thylquinacridone (2,9-dimethylQA), a brief study was made to determine the differences between solid solutions of 2,9-dimethylQA/QA and dry mix counterparts at low percentages of QA. The study was then expanded to include the complete range of composition from 0 to 100# 2,9-dimethylQA in QA. II. SUMMARY AMD CONCLUSIONS 1. Infrared spectra of solid solutions of QA in 2,9-dimethyl QA are subtly but distinctly different from those of dry mix counterparts in the range below ca. 20# QA. 2. The infrared band of QA in the 13 to 14 micron region varies in wavelength with the crystallographic phase (a, p, and y ) and with composition in solid solutions with 2,9-dimethylQA. A distinct difference in this band is evident between dry mixes and solid solutions (made by HT drowning or dimethylformamide reflux). 3. As little as 1# QA can be readily detected by infrared in mixtures with 2,9-dime thylQA as solid solutions or dry mixes (at ca, 13.35 microns). 4. It has not been possible to distinguish by x-ray diffrac tion between 100# s-2,9-dimethylQA and samples containing up to ca. 10-15# QA as a dry mix or solid solution. 5. In HT-drowned solid solutions, there is a definite change in x-ray diffraction peak positions with composition. Peaks due to the two largest Interplanar spacings are essentially constant over the range 0 to 30# QA. 6. Plushout tints of solid solutions containing 10 and 20# QA are essentially equal to that of 2,9-dimethylQA. A definite cost advantage as well as patent coverage are suggested by this observation, since QA is less costly than 2,9-dimethylQA and solid solutions are covered by our existing patents. III. PATENT SITUATION This studs'- was initiated because of the somewhat confusing patent situation involving 2,9-dimethylQA. It appears that it would be desirable if we would explore the possibilities of making and selling a tinctorially desirable product as a solid solution with low percentages of QA, e, g., 1 to 20#. This type of product would be covered by our solid solution patents. IV. SUGGESTIONS FOR FURTHER WORK In other present or future patent situations which concern substituted QA's, it may be possible to prepare solid solutions of the substituted QA*a with low percentages of QA to give tinctorial properties essentially equal to those of the substi tuted QA Itself. DUP050027647 -2- V. EXPERIMENTAL DETAILS NB-1868-13,15 A. Samples Psed 1. Available from Others A considerable number of samples made by O.J.C. Klein by HT drowning was used In this study. These included the following: Sample Description 1794-17A 1794-17D 1864-8A 1864-8B 1864-80 1864-lA 1864-8D 1846-44A 1846-9A 1846-320 d-QA a-QA (developed) p-2,9-dimethylQA 3#/97# QA/2,9-dimethylQA 7.5#/92.5# " " 12#/$8# ^A/2,9-dimethylQA 31552&//8655## 65#/35# If t| Samples available from the plant or others included: 1868-13A (CWM) HT-drowned p-QA toner (dried RT-887-D,lot 46303) 1713-7 (EEJ) Acid-crystallized a-QA RT-796-D, PS-82148, Dispersion-milled y-QA (10# Ni carbonate) RT-849-r>, TS-84232, Dispersion-milled Maroon B (40# dimethyl QA/60# QA + 10# A1 hydrate) 2. Samples Prepared for this Study a. Dry Mixes (1868-13) The following dry mixes were made for a study of infrared spectra: 1868-13 # QA Phase QA QA Used 2,9-dimethylQA B 10 a 1794-17A 1864-8A 0 10 P 1868-13A 8A 2 10 y' RT-796-D 8A E 1 y RT-796-D 8A b. Refluxed Dry Mixes (1868-13) The above mixes were refluxed in dimethy1formamlde for 4 hours to form solid solutions. c. HT-Drowned Ladder Series (1868-15) A 2,9-dimethylQA/QA ladder series from 0 to 100# 2,9-dime thylQA in 10# steps was made by HT drowning the appropriate mixtures of 98# sulfuric acid solutions according to DUP050027648 3 OJCK*s currently preferred procedure for making "Maroon B" (35# 2,9-dimethy1QA/65# QA) (1864-33A). This procedure used p-toluene sulfonic acid in the acid solution, lhe acid solution was drowned into water flowing at 16 liters/minute at 70 C. giving a4T of ca. 30 C. The slurry was boiled 90 minutes, treated with Smcol/Perclene emulsion, and then boiled to remove the Perclene,. The samples were saved as press cakes (ca. 50 g. dry weight) except for a small quantity which was dried for analysis. B. Results 1. Infrared Spectra Mulls of the above samples in hexachlorobutadiene (HCB) show interesting differences in their Infrared spectra in the region of 13 to 14 microns. (The ordinarily used Nujol has a weak band in this region). Fortunately, 2,9-dimethylQA has no absorption band in this region where QA absorbs very strongly. The position of the QA band(s) varies among the three phases of QA as shown in. Figure 1. The band wavelength also varies with the composition of solid solutions of QA/2,9-dimethylQA made by HT drowning as shown in Figure 2. Figure 3 shows the definite change in the QA band when dry mixes of 10# QA, as the a, p, or 7 phase, with 90# p-2,9-dimethyl QA are refluxed in dimethy1formamide to form the solid solutions. Mixes from all three QA phases give the same solid solution on refluxing in DMF or on HT drowning. Figure 3 also shows that as little as 1# QA can be readily detected by infrared. Potential analytical infrared wavelengths and their approxi mate limits of detectability for QA and 2,9-dimethylQA in solid solutions of the two are as follows s m Microns 9. 74 10.40 13.35 10 10 1 2.9-Dime thylQA Microns 8.32 10.92 10 10 2. X-Ray Diffraction Although the x-ray diffraction records of QA and 2,9-dimethylQA are quite different from each other, as shown in Figure 4, it has not been possible to distinguish by x-ray diffraction between 100# p-2,9-dimethylQA and samples containing up to ca. 10-15# QA as a dry mix or solid solution. DUP050027649 Figure 1 f 2,9 DimethylQA a QA ^ QA 7 QA 13.0 13,5 Wavelength (Microns) DUP05 0027650 Wavelength (M icrons) % 2,9-Dimethy1QA DUP050027651 DUP050027652 :! R e la tive in te n s ity Degrees 29 DUP050027653 -4- Figures 5 and 6 show interesting changes in diffraction peak positions {degrees 29) with # 2,9-dimethylQA in solid solu tion with QA. It should be kept in mind that the peaks at ca, 11,0 to 12,4* are second order to those at ca. 5,4 to 6,2 and would vary proportionately. The peaks at 13.5 to 13.9* are not related to the above and may actually be unresolved multiple peaks. 3. Hue of Solid Solutions Flushout tints of the QA/2,9-dimethylQA HT-drowned ladder series at the low # QA end show that the tint hue is surprisingly close among the samples 0, 10, and 20# QA. There is an abrupt change to a yellower hue at 30# versus 20# QA and 40# QA is definitely yellower vs, 30# QA. As expected, mixes of 10 and 20# p-QA with 2,9-dimethylQA are progressively bluer in tint than the 2,9-dimethy1QA. The tint of the 20# p-QA mix is considerably bluer vs. the solid solution counterpart. Mixes of 10# and 20# *yQA with 2,9-dime thylQA, as expected, are progressively yellower in tint than 2,9-dimethylQA. The 20# *VQA is considerably yellower vs, the solid solution counterpart, C. Procedure for Preparing Mulls for infrared Spectro photometry The procedure used in this study for preparing mulls is as follows: Weigh into stainless steel Wig-L-Bug capsule on rubout balance 0.600 g. Nujol, Hexachlorobutadlene (HOB), etc. Add 0.200 g* sample by weighing into capsule or by weighing separately. Add 6 - 1/8" steel shot. Place cap on capsule and apply black electrical tape to avoid any leakage. Place in Spex Mixer Mill holder using any or all of the six outer holes. Place in Mixer Mill, clamping tightly. Mill 20 minutes, using automatic timer. Place portion of mull between rock salt plates. Adjust amount of sang>le at desired wavelength and run spectrum. DUP050027654 Degrees 29 DUP050027655 agrees 29 DUP050027656