Document BvVqqd54o511nE04rQaBMLOvo

DISTRIBUTION ON LAST PAGE S. I. DU PONT D5 NEMOURS & COMPANY NEWPORT PLANT PIGMENT COLOR RESEARCH REPORT . TT$Ei. iMPBGVEP CPC^ GREM PRODUCTS ' p e r io d COVERED: August, 1976 - February* 1977 NOTEBOOKS: E-12469, E 12475 PREPARED BY: R. J. Guschl (/% Date.: May 3, 1977 APPROVED BY: 0. W. AndereonDate: May 3, 1977 PREVIOUSLY RELATED REPORTS: None ABSTRACT Experiments directed at CPC green chlorination and breachings have given us several interesting results which could be developed into new or improved green products. A Green G dry toner has been developed which is more transparent than GP-817-D equals Harmons 5018 in transparency and dark flop. The large aggregates in our GT-820-P, which prevent good textile ink dis persibility, are formed during the final stages of ODCB removal. Acceptable and improved GT-820-P has been prepared from both GEU and GGU by several procedures including high turbulence during distillation. A perclene/AS, solvent/surfactant combination can be used to prepare adequate GT-751-D and more transparent greens. DUP050108838 -X- Introduction Although CPC green pigments enjoyed large volume pro duction and sales in 1976, quality was variable and it became obvious that new and improved products are needed to maintain these levels. For sometime, R&D has directed programs at pro ducing strong* yellow and intense green pigments from both plants. Marketing has put its emphasis on expanding green pigment sales through the development of a green presscake for textile ink applications. Although GT-o20-P was developed two years ago to meet this needs it has not been accepted be cause of poor and variable dispersibility in textile ink applications. Only three lots of plant GT-820-P made to date have been acceptable. There has also been a steady demand for a more transparent dry green toner for automotive finishes. Initially, R&D de veloped GP-817-D2 but it was too expensive. Subsequent worko did not improve upon GP-817-D3. Currently, all CPC-II green production uses purchased Japanese LC crude (Dianichiseika (Dian)) for chlorination to GEU. Since we could incrementally save 50^/lb, to use our own LC crude, there is interest in developing a process for making acceptable GT-751-D in CPC-II from our own Luwa dried high purity LC crude (LDHPLC). Objectives o To develop a process for consistently producing GT-820-F with strength in textile inks equal to our standard lot 451. To develop a GT-820-P equal to Sun's green presscake (464-6947) o To develop a dry Green G shade toner equal in strength, hue, intensity and transparency to GP-817-D in automotive products via a practical process. o To develop an improved understanding of green breaching and restore plant GT-751-D quality to strong, yellow and intense. o To develop a GT-805-D with improved strength, intensity and transparency. Summary and Conclusions We have developed a more transparent Green G dry toner for use in automotive finishes. The product is produced from our crudes (LDHPLC) which havebeen GE chlorinated and routinely breached followed by flash distillation to remove the solvent. DU P050108839 1:S W:" : r ^ -2- Summary and Conclusions (Continued) Either ODCB or perclene can be used. The product is more transparent than our earlier GP-817-D and equals Harmon^ 5018. It should be economical to produce. We have identified the critical step in preparing GT--820-P to be the distillation. 3y 0DC3/AS breaching a .good GSTJ or GGU, GT-820-F. equivalent to SL0451 can be prepared by flash distillation, batch distillation with intense agitation or incomplete distillation (50%) followed by solvent washing to remove the residual ODCB. Such presscalces adequately washed with 2-ethoxy ethanol (2EE) and acetone have quality near that of Sun'S 464-6947. The breaching of green crudes has been extensively studied and we have used this information to help obtain strong, yellow and intense GEX from CPC-II, Fundamentally, the variables of reactant concentration, synthesis by-products, reflux time, batch sizie .arid ^chiorinatibn endpoint affect GEX quality. Several new surfactant/solvent systems have been successfully used to generate acceptable GT-75I-D including perclene and Arquad. Substitution of perclene for ODCB in our existing process would give acceptable GT-751-D from both GG and GE crudes. The implications of these studies on GT-805-D are dis cussed. . Patent Situation Much of the work covered in this report is related to current plant processes and is either not patentable or already patented. Our work on a more transparent green or an improved GT-820-P may offer a new twist to an already known process and maybe of interest to Legal if new products result. Program Several contributions to our understanding of green CPC pigments have been made and this work should be pursued to benefit the colors business. Specifically, I feel that the following areas should be developed further: 1. A more transparent green pigment should be developed based on a Luwa-dried high purity LC crude (LDHPLC). This crude should be GE halogenated, breached in either ODCB or perclene and flash distilled. Flash distillation 'is needed to remove the solvent without producing an opaque masstone. DUP050108840 -3- Program (Continued) ; 2. An improved GT-820-P should be pursued following our discovery thb>t; Significant aggregation occurs during the last stages of ODCB removal. Plant samples should be generated from both GE and GG crudes using flash distillation or batch distillation with intense agi tation. Furthermore, the two-solvent breaching concept should be further studied and optimized to develop a GT-82Q-P which equals or exceed Sun's 464-6947. Whether or not sulfonic acid groups are responsible for Sun's improved properties (or could be of value) should be resolved. 3. Serious thought should be given to the use of perclene as the breaching solvent for GT-751-D and the more transparent green product described herein. 4. The differences between our LDHPLC crude and Dian crudes should be resolved and this information should be utilized to make acceptable GT-751-D in CPC-II. Experiments should -- be completed to determine if there are growth inhibitors in EDHPLC-based GE crudes. The author has accepted a transfer to Pigments, Chestnut Run and plans no further work in this area. I wish to thank P.' J. Krape for many hours of discussion and all textile ink evaluations. It took our joint effort to open up the GT-820-P problem. For many long hours in the laboratory, I thank J. T. Johnston and the technicians at Chestnut Run. Thanks also go to W. S. Miller for many dis cussions and access to his experience ?n green pigments. DUP050108841 TABLE OF CONTENTS DISCUSSION A. B. . C. D. E. F. Luwa LC Crude for GE Halogenafcion A Mere Transparent Green Green Breaching Studies Perclene for ODCB in. C-reen Preachings .... An Improved GT-820-P GT-805-D Page No, A 6 12 17 ig m EXPERIMENTAL A. Procedure for GE Chlorination < B. Procedure for GEX Breaching C. Procedure for GGX Breaching D. Procedure for Orchem's Breaching 28 29 30 31 APPENDICES A. W. P. VanVliet letter- to R. J. Guschl Experimental Transparent Green CPC ' B. R. J. Guschl letter on GT-751-D/GT-820-P Quality C. Analytical Method for Determining f ODCB in GT-820-P D. The History of SLOASI, GT-820-P ' E. P, J. Krape letter to J. Jackson (NRD-A-77/ILP-9-77) F. F. J. Krape letter to J. Jackson (G-36-76/ILF-73-76) DUP050108842 -A~ DISCUSSION s A. Lum. LC. Crude for GE Halogenation In CPC-II, all greens are produced by GE halogenation and only Japanese crude LC (Dianichiseika, Dian) is chlorinated. Typically? the use Of our own LC crude (CPC-I synthesized? tray dried) gave a bluer and duller product through this process, although both this crude and the Dian crudes give acceptable GG crudes in CPC-I. The incentive for making an acceptable GT-751-D via GE halogenation from our own crude is a savings of 50d/lb. (incremental cost versus the price of Japanese crude) and we have already demonstrated that the additional pounds of LC crude can be so made in CPC-I without new invest ment1*. The drying capacity for this additional crude is also available in our new Luwa driers. In the laboratory, we chlorinated (GE, Experimental A) several LC crudes without complications. Table I is a.summary of these experiments. Included were a variety of Dxwa-dried LC crude, laboratory synthesized LC, the current Dian crude and several crudes extracted by caustic and acetone before chlorination. Analytical data on the LC crudes appears in Table II. In tinting properties, the Luwa-dried High Purity (> 90$ CPC) LC crudes (LDHPLC) of low kerosene content (<0.6$) made accept- . able GT-751-D after routine breaching. However, there was a noticeable blueness and dullness versus standard. Please note that this type of crude is standard for CPC-I production since mid-19765. The masstones of all laboratory prepared samples were very dark and will be discussed in Part B of this dis cussion. There were no discernible differences between GT -751-D pigments made from LDHPLC synthesized in "LOPS,f kerosene and that synthesized in Deobase kerosene". Using these laboratory results for guidance, X0U-33 was written by W. E. Miller to chlorinate LDHPLC in CPC-II. The XOK called for three sets of experiments on (1) 50$ LDHPLC/50$ Dian (2) 75$ " /25$ " (3) 100$ " /0 " When part 1 was run, the resulting GT-751-D product was very blue and dull7. Since laboratory preachings of these GE crudes also gave very dull products (eg. 103 YA0 LAo)? we concluded that additional work must be done in this area before the plant would be permitted to use only 100$ LDHPLC for GE. Earlier we had observed blueness and dullness, but the effect was not as great as that observed in the plant. DUP050108843 -5- A. Luwa LO crude for QE Balogenatlon (Continued) We strongly suspect fundamental differences between GEU derived from LDHPLC and that produced from Plan crude. Earlier, R. L, Sweet had characterized several such differences between LC crudes synthesized in kerosene and trichlorobenzene (TCB)". He had concluded that kerosene residues and tars are responsible for dull GE breached products and that these impurities can be extracted by acetone (Soxhlet). the darkness of masstone characteristic of GEX made from LDHPLC and the wider x-ray ab sorptions noted in Table I support this position. Note also that Plan crudes are probably TCB synthesized. The experiments necessary to determine if our L$ crudes (LDHPLC) can be used in the GE process were outlined as follows and need to be completed. 1. All the Luwa crude used in XON-33 must be laboratory chlorinated and breached to confirm the plant results. 2. A 50/50 blend of these crudes and Plan crude must be laboratory chlorinated and breached as well. 3. Laboratory chlorinations and breechings should be run on the following crudes as they are and after they have been caustic and acetone extracted. a. Plan crude b. A representative LDHPLC c. Toyo-Japan crude since these crudes have never been acceptable for GE, GG and 3GD use. The extractions for part 3 have already been run and two ehlorinations/breachings have been run side by side. Tested were the extracted Dian crude and one of the LDHPLC crudes used in XOK-33. The extracted Pian crude gave a strong, blue and dull product (94 B^o Dio> E-12475-130A of Table I) and the LDHPLC gave a yellow and intense product (100 Y15 1^5, 130B). It is interesting to note that when the LDHPLC sample was laboratory chlorinated and hydrolyzed in the presence of 2/ Emcol P-10-59, the final GEX was 100 B15 D3.5 (130C). Although these experiments only warrant completion or the above proposed study, it is interesting to postulate that the impurities in normal Dian crude help generate more crystal growth possibly by making the GEU more dispersible in the breaching medium. Re gardless of the mechanism, these results (blue and dull with Dian) are inconsistent with the accepted belief that there are growth inhibitors generated (or already present) in the chlorina tion of LDHPLC. Furthermore, these studies invite further experimentaion and suggest that 100/ LDHPLC could be used in CPC -II to make GT-751-D, If indeed there are identifiable dif ferences between the crudes, a modified breaching procedure would have to be developed* DUP050108844 -6- A. Lima LC Crude for GS Halogenation (Continued) Reference to Table X shows that the depth and trans parency of most of our laboratory chlorinated LDHPLC exceeds the differences demonstrated in Table ill. There is an additional darkness associated with using these crudes over Dian crudes. Since several of the breachings in Table I even exceeded Harmon's 5018 in darkness, we concluded that the quality of Harmon's 5Pl8 masstone can be readily matched using a low kerosene LDHPLC which experiences a short dis tillation time after breaching. Since a plant process which would utilize this information would require 1) use of our LDHPLC and 2) flash distillation of the breached GEX, we proceeded to evaluate these materials as replacements for GP-817-D. Such a process would not be hampered by the unfavorable economics of GP-817-d 3, In related work (see part D of this discussion), we pre- : pared very transparent GE products from LDHPLC by a perclene/AS breaching followed by rapid solvent removal. Since we merely substituted perclene for ODCB, this gave us additional flexi bility for a proposed plant process since we know perclene can be flash distilled readily (BBX). Table IV is a summary of our breaching with perclene and it is again obvious how the use of our LDHPLC (88A) gives darker masstones than those possible with plant chlorinated lots using Dian crude. B. A More Transparent Green The darkness of the mass tones observed in Table I was worthy of further study since we have long sought a more transparent green. All laboratory breachings give dark masstones in comparison to GT-751-L and identical laboratory samples of different distillation times demonstrates how opacity can be varied. Compare JQA of Table III with the normal two hour reflux before distillation tc 313 with a 20-hour reflux before distillation. With longer reflux periods on Dian based crudes, masstone changes from Dkg9 to Dke versus GT-751-L, although both are Ltqq versus Harmon's 5018. For the more transparent green products prepared above, paint evaluations versus GT-751-D, GP-817-D and Harmon's 5018 were obtained. In Ford's TSA (Newark evaluation #78-33(5a ), our experimental green (ODCB, NE'M #1963) is more transparent than GT-751-3 and GP-817-D and equals or exceeds that of Harmon1s 5018. It also has a darker flop in metallies than GT-751-3 and Harmon's 50l8. This evaluation was repeated on another sample (E-12475-61) against standards by W. P. VanVliet of Chestnut Run (see Appendix A) who con cluded "Experimental transparent CPC green E12475-61 Is significantly more transparent compared to Monstral Green G, DUP050108845 SUMMARY OP LABORATORY CHLORINATION'S co g i o o a> a to -rPt s 43 44 K S3 .* S<1J H S3 h a CD .CO e- O S3 +j o o q co S A KJ Sh O td <d in o S3 AI -ou . in 343 CU 03 t-- 03 > I A3O S5 e0h W 43 SH3 h C O1S3 cd PS i 'X o Oh O m UN $ <d IS a ON fes 7in CO P H 0) 4o3 S<D3 rH 43 3 VM Sh fCtD. >h 0 c7 ON oo .<5! Sa3j 0 i t A S' <5 2j 15 rH a! UN S3 CM s5S5 s!a? o <; CM 56; < S H rH .rH in ON in rH ON AA HON Hto rH 43 A f ON HON 4- ON ON 44 A on 43 A ON ACM ON CVI 44 A On rH 4> A + On On A + ON ON 44 A ON 44 A, + ON ON M 4- ON ON 44 A ON 44 a + ON ON 4ON ON 44 A A 43 A ON ON 44 A CM 43 A ON CM 44 A UN 44 A ON ON 44 A ON ON 44 A O cn A 0 cn A co O a cn A cn A 0 O 1--1 . <T> UN HA m rH >H UN A CM 3dON ON ON CM A JA ts1 iH O 3dO ON rH in rH A UN rH >1 in .w UN A UN A UY {x m CO A in CO A o rH A o rH A IN- t- m --. 3dON On O ON ON rH in rH H in >4 o o rH VO O rH in VO CNJ cn .. ON ON OO 3d- UN rH rH O 3dCm' 00 IS" CM ON IN- ' . cn ON' O CO Ov. CM in vsf . rH ON 'ON in cn ON CM&o > CO AH nCd>-- O ro in o o ,c m 04 NO VO vO UN A 0 <d 0 ON O O CVI 00 co rH IS- IS- CO CO rH d A 0 cn cOo S<UD 0X3 r0)3i 1 a rH rH fp >-- rH A A ON 0 0O A CM A VO O0 ,A C0 CO CO O VO 00O ON co vo rH O CM 0AO CD "3 03 A Sh O CO CO vo rH cd g 3 A CO CO <30 CO 1---i vo vo UN vo rH ON ON ON 0. A A 1--I A 0 A S3 cd cd cd cd cd g g g g A rH 3 3 cd AAAA AA CO A O A cd 3 3 A A CP S3 cd 05 cd rH H 3 3 AA A S3 O ,rH 4-> td^ife in CO VO CinO votn$3 is- NO 'S- ON ON ON .IS- CO o H r-=dr S O.OJh UN A I rH VO t CO inO X rH UN rH A I s AA o A vo A o*c On CM CVi 129Fi Luwa 0 .2 6 130C 9 1 *8 O.96 100 D3.5 NA NA H y d ro ly s is w ith 2% Emcol P-1059 DUP050108846 TABLE (C o n tin u e d )I 0.2 -P c CD E*og3*:.- P i a> X r-i cd H=}- 32 P X0 id S3 H Ct Eh :d 0) OJ So3 c -TpO m OQO 0: oi--!' SG5 S03 in' <L> a 3 i -4O> CwO rH 03 btn~ >i ?cstf EH CS P 0H EH CO 0 PSf X. o0o4 -8 in in .b- b~ in lA o o in <3j <<s CM OS rH rH os is rH in4 < 5s SOO rH in IS- CM rH ,, r*--H1 in rH rH D o rH I i 1Ii11 11t111 i + as o rH in on os CO H in rH H HQ QP QH nr os o t- .CO >H CO >H as S3 co JM H >4 in rH X >H p o O o O CO rH o oOoo0P rH H CM H 1--1 rH iH * o oo =c Os 00 . N S3 o o O CM CO O . CO o as in .* CM CM CM Os as CO CO .-=? CO CM CJV Os . as as CVGbI O^fe--in' H b-- X! *r=l- V0 OXiCHM o&3 IH Wi PQ i--! PS H < ffl rH in <! SP VO VO O rH o rH CO CO pp t-- rH o rH P +J m rH CO so OS -=t os rH o p p* l--1 o p Ooooo po 0 oi-0 3Sh O P cS 2 2 z rH a 22 S3 O r-i -P p ctf -fern G D-- H *-=t 3 cn -=4" Os. MO CM .-=h" rH 0S-< Oh OJ o ^ t H- 4-> co CO S3 m so CO r-H4- CO -St ro Lf\ . '* + rH ca I X? o rpH4 O iH 0nV rH 00! S3 tH0o -H rH rH -H 5s1 S3 H s S4 0) d) p 0 rasH. oo a> Xp! bD S3 -r! CQ 3 c3 3 p 0 X! -P P 3, S3 CQ O -P CD s 02 -p <u H ^ H * X? 0Q CO rH n Ctf SO 0J TS ' CM -P IH -p S3 0 ex: w 0 Si 0 S3 O bU 0 Sh rl P O 0 P4 m rH 0 'P-r X! 0 01 o SO !H 0 0 t<5 S3 a) IH H 0 0 rH P XJ ts h in 0 o >--- P 0 0 PI P p| su 5P S3 X rH -P ca Xi CO t>0 -rH * X! 0 CH P <u ir--Hi -r-i O <4 X3 0\ . H s rH 04 CQ O 04 rH S3 Xi 03 0 O 0 mo P o X! S3 -P O 0 ?S o t3 -P H XJ H -P H 0 0 p 0 04 JO 0 t 3 X3 00 IH S3 p pH 4j X? 0 xs 0 02 0 PS P H > 0 O Hi ca 3s &3 S J3 tn DUP050108847 -9- Lot No. 1688 1958 1963 Dian fiian (Ext, 113A) TABLE II LC Crudes % Kero $ wss . 0.l4 2.64 0,20 O.58 1.60 0.46 0 1.06 0 % CPC 84.7 92.3 93.O 91.8 95.6 Lab E10663-11A 0.22 0.58 97.5 2.33 NA m 2.15 - 1.15 DUP050108848 - 10 - TABLE III The Effect of Reflux Time on GEX Breaching Exp, # E-12475) GEU Crude % CPC X-ray Tint Rubout Textile Masstone ~ Ink . (ys.GT-751-I)) Min. Max 3 IB 364 91.5 HA 106 YqjDj Dk5 l60 125 70A 384 90.9 NA 103 y 7 d 7 Dkggig9 (20 hr. Reflux) >200 ISO 70P 4i6 93.3 HA 100 Y8 D3 Dkgg 94b 4x6 93.3 0.70 92 b 7 i x Bkgg+ (No Reflux) I25 95 112.5 100 DUP050108849 PERCLENE FOR ODCB; A MORE TRANSPARENT GREEK w 4-3 P c<D IoM s +3 oso g o AS a X 03 P r4 -P X &04 in o I CM P cinu in t- .P P CO <13 P 0 4O? lT\ to WP 43 s0 icn3O 43 P3 03 03 03 0] -P p 4p3 03 P QAi AS0CV3J p o aCO aP >S4p tH CO o p .0 PS 03 I . Xo - 11 - 0 PO0 0 PX *3 4013 P<0H) Lf3 0 in in CM p p Q p o o rH <iS P< iornH P 04 <00 04 . Is O xsm * cm in X 3 0P4 00 <0444 XJ oi ^o p in c0o3 co 03 o in in pp 03 03 C\J CM 43 43 PP in rH rH 4. 03 ' 03 03 CM43 43 PP jJ P s s $S in C1--M1 in ii--ni co p 03 CM AS p 43 p p) 4P0 in CM p ! CM P ! 03 03 03 03 AS AS pn 03 it-Hf PP + 03 03 03 jf j T j P ppp , in in p pp P in P PP in co CM m p P PQMP O co P VO P in >4 jn >* p T1 in X p !>4 in M CO >4 oo CO VO CO o co CO V0 (H VO oo pp o rH p ooo rH p p .p p p p p * t\ o 3d- . . 03 po o 3d" VO* cO oo CM o o CM 03 in . 03 * 03 CO* op oo sf 03 CO o o p CO 00 ' 00 O o in CM CO CO 3d- . CO in in CO CO <J CM 03 CO P- 3d- 03 03 . 03 03 ' -ON 03 03 & 03 CO 03 03 03 03 X in 04 Xp 5*5 \\ *< XQ X C? 3 H 0c J cm 0 0 0 flX 0 fH 0 0 X!\ 0 O N. p p 0 P 0P p \ 0 P cS > c> o O o to P O 0 P o 5s 0 U *4 <U a :5s *4 O P 0 S 0 0 $-4 p 0 P w o CM |xj PM c m a P P w VO p VO rH -=t it VO VO Pp ll* 3d- VO VO i--1 :rH 3d- w CO wM VO CO < < =4 <d s. 0 S. 0) V 0 0 SLCD O Q> 0 0 0 0 0 0 0 0 03 0 P 0) P P P P P 0 rH O 0 0 o 0P O ?4 P. $4 :0 ?4 CD ?H 0 0 0 0 <D 0) P P P P PP CO < <D CJ CD rH o u CD Ph o 00 P l V0 3t VO OJ 0J CO in i--i 00 p on on P tr il- CO 3S- 4=t -=t 1 P P P W in tr ft3d- fe < X o rH HP CO i P P -=3- CO 00 P in CO <j o rH rH m p <; P o p CO CO 00 00 CO CO P P 03 rH CM rH rH i--1 DUP050108850 * 12 * :b . A More Bransparent Green GT-751-D (standard); slightly more transparent compared to Harmon's Phthalo Green G-5018 and approximately equal in transparency compared to experimental "Ramapo" Green GF-817-D in 'Ford's TSA enamel". A subsequent evaluation of this material (Newark evaluation #77-401) in TPA gave similar results. An evaluation of a perclene prepared sample (E-12475-88a ) in Ford's TSA (Newark evaluation #77-402) showed the same type of high performance. . Outdoor exposures of all these panels are in progress, however at this point it appears that we have generated a long-awaited more transparent green. It is interesting to note how chlorination of LDHPLC gives a desirable, more transparent green, however in part A Of this discussion, we are looking for ways to so modify this crude to give a match to GT-751-D. Fortunately, tint varia tions can be accepted if the .masstone is acceptable for automobile finishes. Although we cannot explain why the masstones are do deep for these materials, the widths at haIf-height of the x-ray absorptions suggest we are pro ducing aggregates of very small crystallites. As an additional incentive to develop a more transparent green product, W. E. Miller has recently demonstrated flash distillation of ODCB from a GEX breached crude in Newport's semi-works9. The only test remaining is the plant chlorina tion of LDHPLC followed by routine breaching and flash dis tillation. ' C> Green-Breaching Studies To meet the objectives of our green program, it was ob vious that we needed to develop an improved understanding of the green breaching process. We hoped that this information would first restore plant GEX quality to yellow and intense and then be useful in developing our new green products. Accordingly, we ran a series of laboratory bTeachings to vary the GEX process. Appropriate controls were included and all evaluations were against N8l04 (GT-751-D) standard. The applications, of these studies to plant production is summarized in Appendix B, a letter written initally to re late plant quality problems to irregularities in the GEX process. A subsequent plant coverage by Quality Control and R&D focused in on those items which were most responsible for poor plant quality1^. 1. Changes in the concentrations of pigment, ODCB and AS in the standard GEX breaching affect quality. DUP050108851 - 13 - Green Breaching, Studies (Continued) TABLE V Effect of Concentration . SxP(E-12475) G__E_U .. Solv./Surf. % CPC Tint Comment l4A 383 ODCB/AS 91.0 103 y 3 i 3 Normal cone l4B 383 ODCB/AS 9-2.2 100-y 3 13 Half cone. l4c 383 ODCB/AS ,91.0 105 b 3 p 5 Double cone Based on the data in Table V, some plant quality problems are probably due to changes in batch size and variability. If all the Ingredients are scaled properly (water and caustic included) there is only a minimal effect on quality as dictated by changes in distillation times. 2. The presence or absence of salts during breaching has no significant effect on quality. Two lots of plant GEU were breached with arid without, 20$ water soluble salts (Table VI). In textile ink applications, all four samples were equally unacceptable as GT-820-P. The only noticeable shift was a slight blue to yellow shift resulting from removing (or preventing) high salt. TABLE VI Water Soluble Salts Exp. (E-12475) GEU 1o CPC X-ray Tint Textile Ink (Min./Max.) % WSS 75A 98 92.2 0.72 99 fn Du 107.5/102.5 21.0 75B 9.9 91.7 0.72 98 BU I15 112.5/102.5 24.9 750 98 91.8 0.76 102 y17 d 17 110/102.5 1 75D 99 92.2 0.92 100 Y13 15 115/102.5 1 3. All variations of GEX breaching used by R&D or Quality Control give comparable products. The variations of pH measurement and additions of surfactants and ODCB do not affect quality. The darkness of masstone is, of course, dependent upon sample size. DUP050108852 - 14 - C. Green Breachiftg Studies (Continued) 4, The amount of reflux time needed for GE breaching appears to significantly affect GT-751-D quality. In the labora tory, quality can be altered by breaching with (100 Y8 Dg) or without (92 By Iy) the usual 2-hour reflux (see Table III) Recent Control Laboratory studies suggest an extended re flux can improve quality (Lot 434, 2-hr., 106 Ypn >20 > 4-hr., 100 Y15 Ix5/Lot 435, 2-hr., 104 Yl5 D13; 4-hr., 99 Yig ly). W. S. Miller is studying this effect on various types of GEU crudes and his work may re-establish the optimum reflux times needed in GE and GG breachings. Apparently the breaching operation must be considered as two discrete processes which occur in sequence. First the agglomerated GEU is broken down into small aggregates or crystallites, then these smaller particles grow to the desired dimensions. Since this growth can go beyond the desired size, extended distillation cycles can lead to very large crystallites and opaque masstones. . On the other hand, extended reflux before solvent re moval probably aids in breaking down the agglomerates and therefore insures a better crystal growth. 5. Although the level of WSS may not affect breached quality, the levels of residual phthalimide (or nonwater soluble salts) can. A lot of plant crude (369) which gave an extremely blue and weak product (,4` 200 B99+ D09+) was washed with caustic and acetone before ... breaching. The extractions improved product quality to 106 Ypq D30 and raised CPC purity. In this same study, several finished GEX>products were extracted by a variety of methods after breaching to remove residual impurities. In this study, we hoped to identify whether residual impurities are responsible for poor tint or pres.sc.ake quality. All these experi ments are summarized In Table VII. It is obvious that when Lot 369 was breached with its impurities (33), it gave an unacceptable product but when the crude was extracted before breaching (86b ), an acceptable (although still dull) product was ob tained. Since this crude was Dian based (hence no residual kerosene), further analysis could shed light on factors which contribute to blueness and dullness. The other experiments summarized in Table VII we re de signed to determine the effects of these impurities on end-use properties. Residual surfactants were also considered in this study. The data show that residual surfactants and impurities are not the cause of poor quality .and poor dispersibility in textile ink systems. Furthermore, since there is little or no change in DUP050108853 - 15 - ' TABLE 711 . Synthesis By-Products on Pigment Quality 1 : Exp. ,{E-12475.V:. GEU % CPC . X-Ray Tint Textile Ink (Min./Max.) 76 , . 78a " 451 91.9 98.0 0.70 100 Y10 I10 107.5/100 Q.60 ' 97 Y5 I5 102.5/97.5 tions` Acetone Ext. 78b 452 98.5 0.56 100 y 30 d 15 112.5/102.5 Acetone Ext. A51-I3 33 86b 451 369 3694 91.3 82.0 92.3 0.80 JFA O.45 99 %o ^20 102.5/102.5 200 Bgg+Dgy-j- 160/125 Compare 106 Y29 D29 107.5/100 ; (1) a h oriCB/AS s tandard breachings (2) Laboratory history to match plant history of SL0451 (3) lot SI0451, but from same loifc distillation crude (A) Purified by acetone and caustic extractions before breaching. DUP050108854 - 16 - C. Green Breaching Studies (Continued) 5. (Continued) properties after washing with solvents or caustic, residual surfactants are not responsible for poor dispersibility as well, hence, there is nothing fundamentally wrong with the surfaetnts we use, (More on textile ink applications in Part R of this discussion,) Basically, these purifications served only to improve the ultimate tinting strength of the pigments by increasing the percent CPC. 6. The chlorination endpoint (whether a batch has been over or underchlorinated) does not affect GT-751-D quality and has only a minor effect on textile ink properties. In 12/76, Quality Control and R&D monitored the plant GE process and published a_list of recommenda tions to guarantee standard quality10. In January (1/77) Six GE batches were halogenated within these guidelines and routinely breached (laboratory). These experiments and other chlorinations are summarized in Table VIII. TABLE VIII The Effect of the Chlorination Endpoint1 Exp. (B-12475) GEU IR % CPC X-Ray Tint Textile Ink (Min./Max.) Comments 70A 334 NA 90.9 NA 103 y 7 d 7 2OO/130 Control 70E 4l6 NA 93.3 . NA 100 Y8 D8 125/95 Control 106a 432 0.14 94.0 0.90 100 Y10D10 117.5/107.5 io 6b 434 0.10 93.9 0,80 103 Yc Dc 115/107.5 106c 435 0.0 94.0 0.88 100 Yft Dp 140/107.5 HOC 110 0.36 93.2 1.00 100 Y5 Ic 112.5/107.5 110D 0.07 94.0 0.78 100 Y3 Iq 125/105 liSc 0.19 9k.2 0.80 120/NA SL-0451 - - - 101 y 17i u 100/95 f1) All ODCB/AS standard breachings (2) Laboratory prepared crude {B-12475-116A) using a GY eutectic salt (No FeCl3) , In summary, all lots, regardless of IR ratio, made acceptable GT-751-E and GT-820-P using our accepted pro cedure. By x-ray, all lots but #110 were properly breached lot 110 showing a broader x-ray pattern indicative of under breaching. Rote also how a crude prepared in a eutectic without BeClg (ll6) gave an acceptable GT-751-D (ll8C) DUP050108855 - 17 C. Green Breaching Studies (Continued) 7. GE crudes finished by the GEX breaching process are near identical in quality when finished by our GGX process (see examples ?QF and 85B of Table IV). 8. Perclene in combination with several surfactant systems can be used to prepare acceptable GT-751-D. See part D of this discussion for more on this subject. 9. The tinting strength of a GEX product can be markedly enhanced by washing the resulting presscake with a solvent such as 2-ethoxy ethanol (2 EE) or acetone. Please note in Table XI how the quality of a routinely breached sample (with only 50$ of its ODCB distilled off) after drying was 117 XpQ D29, but when the same presscake was washed with 2EE or acetone before drying, the tint was 83 Y29 Igo* An enhancement of 34 points in strength *?ith an increase in CPC purity of only 3$. Obviously,, we have re.-oved some cementing agents which make the pigment more dispersible to achieve its ul timate crystallite strength. Although such plant washings would never be practical, we should determine what causes this enhancement and attempt to utilize this information in all GE, GG and GY grades ' 10* GE pigments can be readily breached with Arquad sur factants (Cationic), to give acceptable products. Any extension of this result to optimize this effect could lead to a useful cationic breaching. .Please' note, how ever, that cationic breaching on the acid side (pH=2, 135) did not give an acceptable product. These experiments are summarized in Table IX as are experiments in which 2-5$ CPC-MS (monosulfonic acid) was added to prevent aggregation of the pigment during distillation (see Part E of the discussion). As will be pointed out in this discussion, we have not had success with CPC-MS added. D. Perclene for ODCB In Part B of this discussion, it was pointed out that a more transparent green GT-751-B could be made with either ODCB/AS or perclene/AS on GEU from EDHPLC. The critical step was identified as a quick removal of the breaching solvent*. Table IV also serves as a summary of our other perclene breechings. In the laboratory, we prepared accept able GE pigment (GT-751-D) by breaching in perclene instead of ODCB, Perclene in combination with either the AS sur factant combination (8lB) or Dresinate X (84b ) gave products with acceptable tints, however with Emeol P-10-59 (81a ), a weak product resulted. All these presscakes had poor dis- persibility in textile Ink tests. DUP050108856 TABLE IX Green Cationic Breachings and Breachings Presence of CPC-MS (E-12475) GEU Solv./Surf. 114A 432 ODCB/Arquad 16-50 1143 432 ODCB/Arquad 20 -75 ' 121G 432 ODCB/AS + 5% CPC-MS 123 432 ODCB/Arquad 2C-75 + 5% CPC-MS 13:5. 432 ODCB/Arquad 20-75 1123 432 ODCB/AS +.2% CPC-MS $.CPC X-Ray Tint Tex. Ink (Min./Max 94,9 0.68 106 b 15 d15 150/105 93.8 0.82 100 By d 3 150/100 94,2 0.86 BA 92.3 1.06 111 B50 d50 m 89.4 0,84 115 145/120 93.2 0.80 100 B^ej xl5 130/95 DUP050108857 - 19 D. Perclene for ODCB The list of surfactants which can he successfully used with perclene includes the nonionic Igepal CO-630 (92B). The product was somewhat defensive at 106 Be Dc but accept able. These and the other Preachings in Taole^IV suggest that perclene might readily replace ODCB in both GG and GB Preachings and that a return to the use of Dresinate for GB breachings may be feasible. Further testing, including ' part evaluations would be needed along with a GT-820-P based on perclene to necessitate a plant conversion to perclene. However, if GT-820-P should be the only product which cannot be made with perclene, a partial conversion to perclene may be Justifiable. E. Improved GT-820-P In developing a better understanding of the GEX process to improve GT-751-B quality, we studied many variations of the process. These studies led to the development of a more transparent green and generated a large number of presscake samples. Since a long-term objective of Colors R&D has been to develop an improved GT-820-P for textile ink applications, most of these presscakes were also evaluated for textile ink properties by P. J. Krape of Chestnut Run. The results of these studies have appeared in all the tables of this text and demonstrate that we never generated a presscake even comparable to SL0451 of GT-620-P. ' Even Tn the laboratory under controllable concTi tions", we could make yellow and intense pigments, but none of them had the dispersibility of SL0451 (our in-house standard), It was obvious that we could not hope for acceptable GT-820-P to come from the . plant if we could not even make it in the laboratory. Since only three lots of plant GT-820-P had ever been acceptable (lots 4-51, 762 and 112A), we began to realize that these lots were unique and that our process as is could not re peatedly give acceptable GT-820-P. Yet since three accept able lots had come from the plant, some modification of our plant process was our solution. In Part C of this discussion, we established that there was nothing wrong with ODCB or the AS surfactant since no differences in ink dispersibility were observed with or without residual amounts of these materials present. Re lated work by J. Jackson of Colors R&D, Newark supported this idea and further demonstrated that no major enhance ments were possible by simply changing surfactants. In like manner, the ODCB level of the product did not point to the solution even after these levels were quantitized by an extraction - GO analytical method developed at the Experimental Station (see Appendix C). A careful study of the actual plant history of SL0451 gave us several clues DUP050108858 20 E. Improve4 GT-820-P (Continued) to its uniqueness and each was tested in the laboratory. (The valuable documents which relate the history of SL0451 have been included in Appendix I) to this report.) 1. Lot 451 was chlorinated in a eutectic melt which did not contain FeClv (a GY salt instead of a GE salt). Experiment llSc of Table VIII shows this was not an important variable. 2. Lot 451 was a small batch prepared in CPC-I. In Part C, we established that if batch size is properly scaled, it is not a factor, however variations in the distillation cycles are significant.) 3. Lot 451 was initially incompletely distilled, reslurried in caustic and distilled to dryness. In effect, it received an additional caustic extraction and distillation. In Part C, we established that additional extractions do not make a more dis persible GT-820-P, however, they did improve ultimate strength by improving CPC purity. Com pare, the CPC purity of our products to those of our competitors in Table X. Evaluation in Table VII (76) show that the second distillation did not im prove dispersibility. It only removed the residual ODCB in a more dilute system and increased percent CPC purity. TCith all other leads eliminated and the distillation . suspect, we proceeded to sample a routine green dis tillation and determine if dispersibility is affected by the distillation step. Perhaps the unique dis tillation history of SLQ451 could account for its unique properties. As the data in Table XI shows, it is the distillation which affects dispersibility properties. Specifically, we feel that significant aggregation occurs during the last stages of ODCB removal and it is this aggregation which must be pre vented to make a good GT-O20-P. Although we could simply break up these aggregates after distillation (as suggested by J. Jackson;, it would be better to s:'mply prevent their formation. The experiments summarized in Table XI show how this aggregation was detected and our attempts to date to prevent their formation. Several concepts were tested to prevent this aggregation and from these studies viable processes are possible for routinely producing GT-820-P equivalent to SL0451. DUP050108859 - 21 - E. Improved GT-820-P (Continued) o Three hatches of GE were normally breached and dis tilled to remove varied amounts of ODCB. As reported in the data taken from Table XI3 GE which is not distilled free of ODCB is more acceptable as GT-820-P Exp. # , % ODCB Norn. Actual- Tint Textile Ink Min./Max. 106A 0 0.06 100 Y10 D10 120/92 111B 25 5.62 103 Yll D11 102.5/95 liiA 59 16.10 . 110 y29 d29 97.5/92 Sun 0 0 94 y15 *15 92.5/90 SLQ^51 0 0' 101 y17 *11 100/95 o In experiment 121B, we repeated this incomplete dis tillation and washed off the residual ODCB with large quantities of 2EE and acetone (121B). It is obvious that the ODCB can be washed off without hurting minimum work dispersibility. In fact, the washing so increased , CPC purity to give even a stronger presscake, approaching the strength of Sun's product. It is interesting to note that the tint enhancement was significantly more (see . Part C).'; In experiments 1331 and 133II* this procedure was repeated and the acetone and 2EE washes were, tried separately at lower levels (500 ml/50 g CPC). In both cases, products comparable to SL0451 were obtained but strengths (both tint and textile ink) did not equal 12IB. Apparently fewer impurities were removed and the combined effect of two solvents is somewhat greater than each by itself. The solvent 2ES was selected because Orchem once used a mixed 0DCB/2EE breaching medium (see Experimental D and experiment 132 of Table XI). Although this process gave good GT-751-D, its presscake was difficult to disperse. We had hoped that a 2-solvent system would prevent aggregation during distillation by preventing wetting of the pigment by water frqm ODCB. In experiment 139, we added a large excess of 2EE during distillation (50% point) and obtained a product free of ODCB and slightly stronger than SL0A51. Such a two-solvent approach, although less practical than others, could be the key to a GT-820-P DUP050108860 Improved GT-820-P (Continued) equal to Sun's product since in one process aggregation is prevented and the extraction properties of 2EE are realized during filtration* In the plant, this filtra tion may require additional equipment, however, the twosolvent approach should not be limited to 2EE. Another water soluble solvent might do as well and be acceptable to our plant as is, o Acid extraction before (to remove residual FeClg) and after breaching (to remove cementing agents or other interfering impurities) did not improve GT-820-P properties. o A semi-works flash distillation gave a GEX comparable to S10451 in minimum work dispersions (WEM 1-4 in Table XI). Apparently there is enough turbulence during flash distillation to prevent severe aggregation. o High speed agitation during distillation (137) gives a more dispersible product than normal agitation. In the laboratory, this variable can be used to obtain weak and strong dispersion strength from the same lot of crude GEU. Apparently the troublesome aggregates reduce dispersibility in ink systems but can be easily prevented with proper shear during distillation. Lot SL0451'with its unique history, was made from a good crude which probably experienced an . incomplete distillation with good agitation. o A perclene/AS breaching followed -by an incomplete dis tillation gave a v weak product (121A). The same crude with a 10 hr. reflux (vs. 2 hr. normal) increased minimum work dispersion to 110 (l4l). o Attempts at utilizing Arquad (Cationic) surfactants or adding CPC-MS to give more dispersibility to our presscakes were unsuccessful. o Experiment ll8B shows that both GG and GE crudes can be used to generate acceptable GT-820.-P by incomplete dis tillation to prevent aggregation. In summarizing these experiments, it appears that there are several practical processes for making SL045l-quality GT-820-P, Preferably, we would either use flash distillation or fetch distillation with high agitation. Although the exact experiments have not yet been run, it also appears that GG crudes can be used and that such products (either GE or GG) may also be useful in other end uses, eg. aqueous paint applications. DUP050108861 - 23 - E. Improved GT-820-P (Continued) To exceed SL0451 and approach or exceed the quality of Sun's 464-6947* we may need only to optimize breechings or distillations. We know already that additional strength can be achieved by using a two-solvent breaching as described above (12^/139). The formation of aggregates at the end of distillation is consistent with electrcnmicrographs of our GT-820-P products which show large footbalr-shaped aggregates (see Appendix E). Although Sun's product does not show a full dispersion of discrete crystallites, there are no large clumps of crystal lites. In earlier work on developing a new finishing process for BB gradesll, a process was studied in which TCB was steam distilled from, the pigment and very large aggregates were found at the end of the distillation. In this case, the aggregates did not break up into a filterable presscake and the final product was very lumpy and difficult to wash. At that time. Professor W. Tiller of Stanford University, a con sultant to our department suggested that such aggregation is the result of sudden changes in the solvent medium during the distillation. In effect, the pigment goes from an organic phase of low dielectric constant to a highly aqueous solution of high dielectric and such a shock could cause aggregation. Such aggregation during distillation has been known for years, but it is unfortunate that it was not recognized that it is this aggregation which makes a good pigment into a poorly dispersing presscake for the low work applications . such as textile inks. . The lack of lumps in Sun's product explains why the mas stone of Sun's product is so dark (Dk99+ I0Q4.) versus : our SL0451. Earlier we had made this observation and assumed we wanted a dark masstone green such as our new more trans parent green product (Part 3). Unfortunately these materials did not make good presscakes because the source of their dark mass tones is underbreached small crystallites. It is interesting to note that GEX from which 50$ of the ODCB has been removed, when dried gives a darker mas stone rubout than if allowed to distill to completion. This concept to darkening a masstone (incomplete distillation) must not be forgotten, especially in a system like GT-805-D which is already "underb.re&ehed" versus competition (see Table X and Part F). One final approach which could generate a product which is not highly aggregated could come from a study of our competitors. Sun's product analyzes for 0.2$ sulfur and DUP050108862 E. Improved GT-820-P (Continued) our knowledge of the related Color King process suggests that chlorination in chlorosulfonic acid generates a green with enough sulfonic acid groups present to act as anti-flocculating agents. Our few attempts at using CPC-MS for this purpose (see Table IV) were not successful but should be explored further if our current approaches do not give us a viable process. R. D. Nelson of Newark has yet to resolve the chemical nature of the 0.2$ S found in Sun's 464-6947. P. & : In our program, we had hoped also to develop a GT-805-D with improved strength and transparency. An initial evalua tion of our current product versus strong competition in this area revealed several weaknesses in our product (see Table X). Harmon's G-5400. is the most crystalline product with all competitors (including our GT-805) appearing "underbreached". In CPC purity* most competitors have >95$ CPC whereas GT-805 standard is only 90.6$, hence a strength gain is possible if we could reduce the amount of aluminum benzoate used as extender. Although we have not actually tried to apply our new GEX knowledge to GY products, W. E. Miller will have this opportunity and has already studied the effects of other surfactant systems on the breaching of GYU made from both Japanese LG crudes and EDHPLC<. In future work, a more transparent GY should be possible by either using crudes from IDHPLC or by applying that which we are learning about aggregation during distillation. DUP050108863 TABLE X GT-820-P SX0U51 g t -820-p Sun 464-6947 (C#76298) Competitive Green Products % CPC WSS X-Ray 92.5 95.2 1.47 0,45 0.70 0.54 % BvM Cl ha m GT-805-D . GT-805-D Std. 90.6 BASE 914o 98.8 Harmon's GS^-OO 95.1 Harmon 5018, ' . 92.8 Fastolux Green 264-8137 Chemetron GT-48l8 94,0 94.8 ICI Green GY 95.3 BASF 93-60 ' 97.1 0,27 0.11 2,6 2,6 0.37 0,67 0,45 . 1.3 1.6 1.0 0.54 3.8 0.62 : 3.2' - ' 0.26 3.4 63.O 3.0 40.0 21,0 47.0 16.0 . NA . DUP050108864 ' TABLE X I .. An Improved: GT-820-P - D is t illa t io n S tudies - 26 o' in in Cm * S-r RR H HI >-*N ooo m LC\ in S 0.' n CM > * R ft R o !H dj H H H o . X x C jS wS .* X xa CD -H e-cis P dH_i p CM O Oo |H j H P X in x p in P X vn * X p CM O fen P Q O- rH .rH rH p r-*, . O rH 04 rH O wHM in iH H o X at in .c m rH OJ rH X X XX p r--i m at PO o P H rH in o P o in X rH p in \ X in o 0) p H rH p iH rH CM rH rH R' ft R P rH CM rH rH I--J XX o on p rH o O rH rH H lf\ in .* CM XP PX Xp p .* 04 X Hp Xo j H 04 w Ht X rH X X p o cm R rH rH rH P on P 00 pX P p XX p P \ op X in CM CM . X- in p rH rH 0V 01 rH in O p p p CM RR R pO p m p 04 RX X X rH P rH rH X rH H p CM H P 04 X P CO o CM R O OJ R X P X eg O R CO 1* XI o o o at CO o CO o X VO ' P VO * CO X* 00 oo Oo ooo OJ o o CO X CO. p' X. o oo o o CJ o CC 1--1 o s to * o p p * p 0J . X CO Po o * <M X co * X O'. rH 0J at in .-st at cu p 10 a*. -=t at X p X p. p P P 0\ P p p p P P P p CO 03 X CO X. CD SH < ^Hv+j m W <H a w cu R (H. ra m 03 03 CO OJ R CO C0 fi CO CO OJ CD X * <4 X <s X X X < < CD >--R 'X.' X X rH X X X > m ffl R R R R R R R a R m R ari rH o o O o o o o O O SH O o O 4a O R R Q & R R ,R Q R R CD R R R ro CO o O O <0 Q O o O O PH O o 0= CM CM PP 0J OJ i R rH rH CM OJ CM 10 D R CO 04 ..tt at CM m in p P o St Ht St < 55 p P H ' CJ at at .at o R o rH P P P P rH at at at at X at mPi in at afexat CVJ M P H rH at R rH I 1 3 -- R 3 1--ia ! co cirH Q CM C Q <[* O t 1 rH CO CO R rH CVJ pinx w P R a rH rH rH rH rH rH CM OJ atW'-- at CO co rH rH H rH rH rH /H rH rH DUP050108865 TABLE X I {C o n tin u e d ) ra to in P C to ion o m 1 V-^r oO ft H fftt H -P cU -P wto !H ft 3 CO Ift oin fftt 2? :M X S3 to ft S3 to- CO to o co o in tv- in X 0N ftv pv X X X X \ in ON Gh X rH ov X <n Os X XX c O 04 CM o in O CM CM d o o o in CM H ft ft ft & s rH iH rH ON rH H rH ft iH CO CO c0 in rH VO rH rH vo co ft ft ft H ft ft ft ft i xs <D p in ft to in s CD co CO r--i VO to rH rH rH oCtr*j tM s X S !m iH r-1 S > oO o co O VO to to to CO O o o o o ft ft o ft rH r-i rH r--l rH iH rH ft i--i Sh >toa ft ! CO IS- o CO o CO Xooo o to rH co rH ft oft & o ft " t~ o s >R Os 0- MO . * OS H . Is CO to to CSV ov . cv ON >> P C O XI P 8 co H Li to X CO ft 10 to oft X G 3 ft CCO co CO CO CM H co CO co co P X to! s to X to \ > ft ft ft ft o o o ft ft rH to tXfot .to X ft Xto ft Xto ft u ft ft ft u Oj [--i p HP O CQ ft o ft o ft o ft o ft ft o ft o ft o ft o Pra to XI C co rH to XS b() p 5 P .P. ri P w ri Xf u fot ft P ft CM CM to CM to to- to XI r-I fwt CO to CO to troo cn tCoO tcoo cO to co to CO -=t fat oU O <H co rt Xto lOft id-i Q .? O to S3 W^fi. H -oH ft cvi iOn to C p . m p rH r-i 3 to to -ri to" c? o' o' Hppp rH Sh P ftXS to m ftp '--'O XI 00 00 oO cO VO VO VO VO Oin xass H* xl in to ^fetoCM H ft 1 fH CO H H CO (ft cn CM CO rH CO 1 pg CM CM CO _r CO (M 00 tf CM S-r Si CQ NC__O^ to f,,lHftOI Hto H O ft H H Cil H p4 t I t >: l l I1 fXt ft CO rH <o CO rH rH CO topp ft s rH c m invo t-co DUP050108866 - 28 - EXPERIMENTAL A. Procedure for GE Chlorination - (lei' Equipment: l-liter resin kettle fitted with a chimney vent, overhead stirrer, a Teflon dip tube, thermometer and heating mantle. Also a tank of CI2, rotometer calibrated to about 50 gm/hr. and Gig scrubber with concentrated sulfuric acid. Procedure:' Halogenation: 1. Be sure rotometer is clean and calibrated 2. Mik and add to resin kettle 300 gm AlGl-3 (anhydrous) 51 gm NaCl ' 34 gm FeCl3 3.. Heat to 1750. to melt, cool to 150C. 4. Add 60 gm of LG pigment at a rate so as not to exceed lo5C. Adjust temp, to l65~175C. 5. Add chlorine at $0 gm/hr, below eutectic surface until chlorination is complete as judged by permanganate test or IR test. Hydrolysis: (5-liter or larger battery jar) 1. Dilute 260 ml H^SO^ (cone.) into 3000 ml HgO 2. Add charge from halogenation. 3e careful -- hot from reaction and violent reaction 3 Stir 30 minutes 4. Filter and wash-to 2500 ohms, 5. Save presscake and obtain $ solids, WSS and fo CPC purity on solids. DUP050108867 Procedure for GEX Breaching (10Q g CPC) (E-12469-105) Equipment: 1 liter beaker, 150 ml beaker, magnetic stirrers 2 liter RBF with condenser, mantle and stirrer Procedurei 1, In the 1 liter beaker add in order with moderate stirring, the following: a. 100 g CPC content of green presscake b. . 280 ml water c. 10 ml 50$ caustic d. Agitate 15 minutes e. Check pH, adjust to 12.4-12.6 2. In smaller beaker, add a. 84 ml 0DCB b. 4.4 g aminoethylethanoiamine c. 4.4 g Sulframin 1298 d. Stir 15 minutes on magnetic stirrer e. Add to 2 liter RBF f. Flush out beaker with 80 ml water and add to 2 liter RBF- 2 liter RBF 15 minutes (with ODOB/surfactant) and add contents of 1 liter beaker. Rinse out 1 liter beaker with 120 ml water and add this flush also to the 2 liter RBF ' 4. a. Heat to reflux b. Hold at reflux 2 hours c. Begin distillation. Distill off all 0DCB. Add water if necessary and distill until no more water collects in the Dean-Stark trap 5. Filter and wash to 3000 ohms and if desired, dry presscake at 8-0 C. 6. Obtain from analytical $ solids, $ CPC purity, $ WSS and rubout product against N-8l04 standard. DUP050108868 - 30 - o* Procedure for GGX Breeching (100 g CPC) (-*12469-107) Equipment : 2 liter RBF with mantle* overhead' stirrer and set up for distillation Procedure: 1. Add 260 ml water to 2 liter EBP, agitator on 2. Add 28 ml 50$ caustic 3. Add 3.4 g Dresinate X . 4. Check pH* adjust to over 10 5. Mix until all DresinateX dissolves o. Add 100 g. CPC content of presscake 7. Add dropwise over 15 minutes 82 ml ODCB 8. Adjust volume to 720 ml with water 9. Heat to reflux and distill off ODCB. Distillation complete when no more ODCB comes over to Dean-Stark trap. 10. Filter and wash to 3000 ohms. 11. If desired., dry at 80C. 12. Obtain from analytical % solids* fo CPC purity, fo WSS and rubout product against N-810A standard. DUP050108869 - 31 - D. Procedure for Orchem*s Breaching (E-12475-104 and Ref. #8) Equipment.; 1 liter R3F for reflux and distillation Procedure: , , 1. Weigh out 125 g. CPC content of green presscake 2. Add water (only if presscake is higher than 33$ solids} Amount of water - 380.- (g. presscake) 3.. Add 105 ml 2-e thoxye thano1 4. Add 36 ml 50$ caustic 5. Stir IP minutes 6. Make up a solution of 4.5 g. "Staybelite" with 0DC3 ml ODCB - 65 (g presscake - 125) ( *2 x 125 ') 7. Add "Staybelite"/ODCB solution in 5 minutes to flask 8. Quickly heat to reflux and hold 20 hours 9. Add 80 ml water 10. Adjust pH to over 12 11. .Quickly distill off ODCB 12. Filter and wash to 5000 ohms 13. If desired, dry at 8oC, 14. On dried product, obtain % CPC purity, % WSS and rubout against N-8l04 standard. DUP050108870 APPENDIX A E, I. Du Po n t o e Ne mo u r s 5t Co mp a n y INCOHraiWTCO PIGMENTS DEPARTMENT cc: E.W. Stewart,Pigm.C.R. H.W. Ling,Pigm .C.R. R.H.Zabel,Pigra. C. R. E.E.Jaffe, Pigm. Newport W. S.Struve,Pigm.Newark C.W.Anderson,Pigm.Newport C.F.Rolle.Pigm.Wilm. D.E.Yonker,Pigm.C.R. F.C.Dzielak,Pigm.C.R./File f ir s t & f in a l - a n r d -29-76 Initial Report - S-76227 Chestnut Run December 14, 1976 TO: V R. J. GUSGHL ' PIGMNTS^jMPfllT FROM: W. P. VAN VLIET W*** PIGMENTS-CHESTNUT RUN EXPTL. TRANSPARENT CPC GREEN (INTERMEDIATE SHADE) . E-12476-61 COMPARED TO MONASTRAL GREEN G, GT-751-D IN FORD'S THERMOSETTING ACRYLIC TSA ENAMEL OBJECT: To determine if process modification used in making Experimental Transparent Green, E-12476-61 can significantly improve transparency of CPC greens. INTRODUCTION: E-12476-61 was lab prepared in the shade range of GT-751-D. The experimental was made with Luwa dried high purity LC crude, breached in ODCB and "flash" distilled. R&D feels these process modifications will Improve transparency of CPC greens, without significantly altering tinctorial properties. The chlorinated CPC green was choosen for initial evaluation; however, the technology should be applicable to brominated CPC greens as well. Also included were Harmon's Phthalo Green G-5018 and Experimental "Ramapo" Green GP-817-D for comparative transparency purposes. CONCLUSIONS: Experimental Transparent CPC Green E-12476-61 is significantly more transparent compared to Monastral Green G, GT-751-D (standard); slightly mote transparent compared to Harmon's Phthalo Green G-5018 and approximately equal in transparency compared to Experimental "Ramapo" Green GT-817-D in Ford's TSA enamel. SUMMARY: Tinctorial The tinctorial difference of E-12476-61 compared to GT-751-D (standard) was not a major concern. The experimental, however, is dull and slightly bluer at approximately equal strength compared to the GT-751-D (standard). All samples were steel shot milled because of very limited SETTER THINGS FOR SETTER LIVING . . .THROUGH CHEMISTRY DUP050108871 R> J. GIJSCHL APPENDIX A (Contd.) FIRST & FINAL - ANRD-29-76 Initial Report - S-76227 -2- December 14, 1976 SUMMARY: (cont.) Tinctorial (cont.) quantity and the need for greater recovery than could be obtained by Jiffy sandmill. Earlier work(l)(2) suggests the blueness and possible dullness may be caused by iron reduction. Therefore, future work, with larger quantities, evaluating the tinctorial characteristics of the experimental should be dispersed by sandmill. . The relative order of transparency from best to worst is: .E~12476~21 GT-817-d) Jj* G-*5018 GT-751-D Flocculation All pigments exhibited equally good flocculation resistance. Exposure Durability Exposure series S-76227 will be exposed @ 5S in Florida and recalled every six (6) months for a total of eighteen (18) months. EXPERIMENTAL DETAILS: 1) All paints prepared, according to TF-1040-4 in Ford's TSA enamel by . ballmill (1 pt.), 2) All paints sprayed with automatic spraymation according to TF-8613-1. 3) Paints prepared: . Metallic: 90/10 toner/A1 50/50 toner/Al Tints: 5/95 toner/TiOjj PIGMENTS EVALUATED: Monastral Green G, GT-751-D (PS-89040) Experimental Transparent CPC Green E-12476-61 (sample depleted) Experimental "Ramapo" Green GT-817-D (CS# 121376A) REFERENCES: 1) Monthly Summary, Newark, 10/28/75, A.R.H. 2) Letter to C.F.Rolle from R.C.Horr, 1/16/76 - Color Shift (Blueness) & Dulling Problems with Monastral Green G, GT-751-D in 30J Alkyd LAB WORK BY: C. W. BUEMLER LAB REFERENCE: CWB-76-11-07 WPV:lb DUP050108872 APPENDIX A (Contd.) EXPOSURE SERIES $-76227 5* South Florida Panel # 1 2 3 4 5 6 7 8 . .9 " 10 ", 11 12 . ' Pigment GT-751-D/A1 G-5018/A1 GT-817-D/A1 E-12476-61/A1 GT-751-D/A1 G-5018/A1 GT-817-D/A1 E-12476-61/A1 GT-751-D/Ti02 G~5018/Ti02 GT-817-D/Ti02 E-12476-61/Ti02 Ratio ' Initial : 20 , Gloss, P/B 90/10 tl 11 ft 50/50 It tt II 5/95 II tr ti 78 75 72 70 55 62 41 51 70 61 ' 73 . 74 0.09 0.09 0.09 0.09 0.07 0.07 0.07 0.07 0.5 0.5 0.5 0.5 WFV:mal DUP050108873 APPENDIX B E. I. ou Po n t d e Ne mo u r s S Co mp a n y INCORPORATED Ne w p o r t , De l a w a r e i9804 PIGMENTS DEPARTMENT yT CC; c. F. Roile* - i Irains' E. . Stewart - Chestnu J. B. webster* - r ?, J, Krape* c. G. Hubbard* -- - If *! . S. Struve - Newark R. L. Sweet* J. Jackson* r* G, M, Loughran Newport D, H. Strouss V. J. Lewis* J, Ignace* j. J. Adams - A, F, Lewis - I. A. Berkemeier S. . Severance - . H. Hoffman G. E. vJoodruff S. E. Jaffe* ~ - C. . Anderson* w. E. Miller* ** If f! ir it it ti ir u ft it it September 7, 1976 SUMMARY Gl-751-P/QT-SaO-P MEETING On September .2, i.S76j ft meeting of Newport R&D3 Chestnut Run and Newport Quality Control was held to relate the latest in 820 presscake testing and to discuss current GEX quality. Our goal ' is to develop a coordinated program between members, of these groupsand Newark R&B to develop an adequate 820 product and to consistently get standard quality GEX from the plant. From our meeting3 we concluded that : o .BSD will have full responsibility for developing an improved quality GEX presscake, suitable for both aqueous and oil emulsion ink systems. The product will be comparable to Sun's 454-6947. o Chestnut Run is responsible for developing & non proprietary test for green presscakes which will identify products which will be suitable for all our customers. Until such a test is'developed, Chestnut Run will supply Newport P.&D and Quality Control with the Sherwir.-Williams,.non-ionic aqueous test, which appears adequate for this purpose. BETTER THINGS FOR BETTER LIVING . . . THROUGH QHEKISTfiY DUP050108874 APPENDIX B (C.ontd.) 2- - o The current quality of GEX products is too variable to be acceptable to R&D and Quality Control* Many plant practices must, be corrected and innovations added before GEX will consistently be of ^51 quality (as it should be). R&D will assist Quality Control in developing meaningful procedures. A more detailed summary follows: Current 820-P quality for textile ink. uses o P. J. Krape presented several textile ink test results of our 820-P product versus Sun's product (attached) - In all tests, the aqueous tests are p.ost discriminating; the best being Sherwin-Williams non-ionic aqueous test. - Quality Control's current textile ink test (results attached) is an oil/HaO emulsion test and not good for current screening for aqueous uses, - Initially, it was felt 0451 batch of 820-P equalled Sun; now it appears to be 20$ weak. Chestnut Run will clarify this although we recognize that our 820-P is suitable for oil/HaO systems but not adequate for aqueous. (Please note that 820 was designed for oil/KaO systems) 0 Residual ODCB traces could be making the pigment hydrophobic , ODCB levels need to be defined and correctly " analyzed. , Current GEX finishing o Current process - Halogenation endpoint only by permanganate - Hydrolysis with acid recycle . - Filtration with inadequate washing (KS5 of 2o$ have been observed) .. - Poor sampling of repulp tank to determine batch size for breaching - A breaching procedure which processes from ISOO to ^5-800#/ batch (ODCB.and surfactant levels are adjusted, but not water). - GEX finished .in CPC-II is not much better than that finished in CPC-1 (still needs to improve). DUP050108875 APPENDIX B (Confect.) II. (Continued) -3- o The GEX process oust he changed! (The writer gratefully acknowledges that Julius Jackson and Ron Sweet of Newark , R&D have long noted major shortcomings of our plant pro cedure .) - Halogenation endpoint must he determined by both permanganate and 3E until we are confident of observing the true endpoint* Production must supply . the necessary samples. - Reasonable crude filtration times must be established (5-7 hours) to limit batch overlap in the hydrolysis tank. - The crude filter must include adequate washing of crude. - The acid recycle process must be modified to include checks on both specific gravity and strength. - A recirculating line must be installed in the repulp tank to guarantee a meaningful sample. The alternative is to pack out all slurry in tote bins before charging the breaching tank. Production must wait for testing of this sample before charging the breaching tank. - GEX samples for both CPC-I and CPC-II must be analyzed identically. - The GEX batch size during breaching must be standardized (3000kl00 lbs.). Perhaps the repulp tank will be used to regulate batch size if level probes are updated. III. Blue presscakes (%01 and 502) o Both of our products are weak versus chemetron PK 450% and are finding variable acceptance. - Sdrfactant variations and incompatibility with-customer systems - DC purity i IV. Other items o To coordinate future efforts, copies of 820/751 .related correspondence will be sent to ail people concerned with these problems"{* names on cc). DU P050108876 ^ :; /' V s? APPENDIX B (Contd.) IV. Other items (Continued) o Camples to be exchanged * V. J. Lewis 1. 1 gal. 451 grade 820-P to KJG and PJK 2. 2 (5 gal.) pails 762 to PJK 3. Samples of 109-3, 110-B, 112-A, 762 and 764 (820-P) to RJG and PJK plus two bad batches of 820P to RJG 4. Will rubout 451 (820-P) versus Sun and run both in his oil/HaO test. * P. J. Krape 1. Sample of Sun 464-6947 to RJG and VJL 2. Chemicals for Sherwin Williams nonionic test to RJG and VJL 3. A new non-rproprietary test for screening presscakes to RJG and VJL (when available) 4. Chemetron's PK 4505 to RJG - R. J. Guschl 1. Will Send samples of Sun 464-6947 and Chemetron PK 4504 to Newark for surfactant testing 2. Will develop, better 0DC3 test for 820-P for Quality Control. . R. J. GDSCHL - R&D Research.,Chemist . /tmj* DUP050108877 g APPENDIX B (Contd.) too SST |||| ;. *T l tni-. _5, mi 7J in z a\ o Ui it 5 p 0- Ef S3 s: S '! 11 & si . . %|tr .... NO j<nn <n* ctnQ I?/) Z S?- 0 '* ... tf>% \ 1$ B5? j*x* 0a3In> -i ?gl ... r4\ W 8m 81 <V\{u3~" Q li ai * pL Si*. to i i fes i -- yvr cQ* I] *!a . S/-3 Us? --ifit 14 a fs- SJW ji r* 1 l. liI1 11 1 ! ** 1 if) 00n rCOr i1 in a$ i to u* a r<*r- sg o o 9 og ign 3S iT l i ?5 1 l l in fe o ^ 0* ^ T > cino 5>r S aorfteA SXTfe J * 1 . 1in3 k i!Dp 7$ in In > O03 SQ \ffio^?y> in ift . cr5r H tpr U 8u 37 u) 5 10 icf)r if* \r* ?>'.. in tcri a o g 5 bOo 81 a H o H 0fft gogo" ... u O0 " -- ; .w ' '' j . .. .50 _} 6 u i./ I 3. . tO Slgi Z .5 g Ia -Z 'QL Z 0 1 % ~z a< 6 z OJ dt (P 03 B-t ' g_i _ 3 o 5 g zaz ilsl 2 w <3r Z o %uS g z g T Z 2 -1a 1o . e H z g Zi Cl z az 2 z oy*S, f zg 22 > w to rf c< <Q to O" <r-a S3' CO^ $s in r* r4 +* <T4{ F - S rf* ~ -H l 5c 2 Lu n in <r DUP050108878 / */>VTTVM- 'i to Cl v U-tr 0- in 0^- ~2 2~ ui 'CJ J cc -j r fefiv X lU <n m I" : So iZ U it IF PvwP<O-;r. APPENDIX B (Contd.) Ja). 103 - o 133 o .rco -of? . <5' `3 0- gf l `I 1I Jhpi ISSi <H I $ I is: * -a ' ,4l r- j !i I *3T' ! to jflLf ; <J0*<*iji J I S' 2 0) % 1 'x j ii l|i d| 5jib5* m s<a "It iS 11 ii 1 ?S 111 & Si glUliiUg* ssS M i|I 1| s !jI <3 ...... f8t........ 'a: d : J .....-dl. <ro ll' If 5 O' 2ii-___ ari*r 1. ii 5 *jj yi Q -rt ^11 fa fw -------- .IZ'.,?,_ I-1 g3 < f'S I# oo 8, t> ^3 -. 5dSJ JSials IoiS' o ,,2s1. 5 ! -tar 5? i34 f St jj J ill *S IT aP s $8! af s3m* 3ZST^-lj'. s5 : l 03 !) < ii 0 %5 2* -52 21 2I crurnf3il -- zi?,iaz s 0i O o5 zoz SI .UJ 1 Z0 I1 & o5 z0 azz1 ai Z /* 9 k. 2 > 2 .vr* ... j* --.SP2 . -----------VI 2 <p Ci- DUP050108879 .jDO?rT Sa T IT-WEifE IT TO R. J. GUSCHL : APPENDIX C ~~ 1 AT NEWPORT FROM- L. J. MATISNZ0 > ... . ................................ DATE 11/12/76 X. D c. s 0. E File McKinley Haas"Newport Ringwald DETERMINATION OF RESIDUAL ODCB IN CPC CAKE Please find attached a method for the quantitative determination of ODCB (0-dichlorobenzone) in CPC cake. The procedure is simple, straightforward and existing equipment Newport can be used for the analysis. at The results obtained by this method for the samples you submit ted were: Sample Number % (w/w) ODCB in CPC Cake 762 1,32 764 0,39 451 0 If you have any further questions, do not hesitate and give me a call. QUANTITATIVE.DETERMINATION OF ODCB IN CPC CAKE The analysis is carried out by gas chromatography on hexane solutions used, to extract ODCB from the CPC cake. Sample Preparation Weigh exactly 5.OOg of sample into a 125 ml Erlenmeyer flask. Add 50.00 ml of high purity hexane. Cap the flask with a rubber stopper and shake the mixture at room temperature for ten minutes. Prepare some glass funnels for filtration. Use Whatman IPS paper. Filter the mixtures into clean bottles until the whole volume of the organic phase is collected. Remove'the filtrate, cap and label the solutions. Analys is The analysis is performed with a gas chromatograph under the following conditions: Column: A six foot stainless steel tube with Dexsil-300 Carrier: Helium STOP ACCIDENTS BEFORE THEY STOP YOU DUP050108880 B53 Rev. .8-92 XJOIN'T SAY IT-WRITB :IT vrv w Af V. J. OIIS CHL NEWPORT........ ......... FROM ...L, J. MATIEN20 .... ............. APPENDIX C (Contd.) DATR 11/12/76 Rotameter: 0.5 Inlet Pressure: 50 psig Rate: 20 l/min. Chart Seed: 1 inch/min. Detector: Thermal Conductivity Detector- Temperature: 300 Injection Temperature: 270* Column: 50* - 140* Rate: 15/min. Place a lO.Opl sample in the injection port, run the instrument at the specified heating rate. Use a scale attenuation of 512 for hexane. After three minutes, switch to a scale attenu ation of 2. Integrate and measure the area under both peaks. Calculation The weight percentage of ODCB in CPC cake is given by: % ODCB(w/w) 660 x AODCB + 1.17 x HEX : Where.; AODCB * Peak Area for ODCB Peak A. HEX * Peak Area for Hexane Notes : (1) Whatman 1-PS paper is the only* type of filter paper that can be used to separate the water present in the mixture. (2) The area obtained for ODCB at attenuation X-512 must be divided by 256 to be used op the above given equation. For example, if AHEX 832 (at attenuation X-2) and Ao o c b 151 530 (at attenuation X-512) , the percentage of ODCB in the pigment is: (660)(|jf) %0DCB (HI) + (1.17) (832) LJMrghh STOP ACCIDENTS BEFORE THEY STOP YOU DUP050108881 '* ' V (XJJl . */t ^ Gi y &S.0' $- &<-*+& /... .i-- QsQ-aAJt*. ^ 'A. ..C&e*^ t J^b**""".'. c&c**c ifh . ,. . ~i^ '?* ' *" > sG-v* -gS? L.c__ ../ "7 * /_ (O-tcsss^Ji . &) Y , i (j 3 !3*^o- > ^ ....... .. c}^ ,0JL4dXki\ - ?*-&*- . ''j-i ( t d flu^f /x> ^ . <rn;:*\ Jj^. SUJ&L' Zz l /- --Ce* ... U<j z~_ ____^ _ . ^3^3 V>A^/~ UA^d*-- ' -i * j b~ / ^ - /? >/ c?^i,.. .jSTVu Cufteo^C ; ^^3-2*5*. ^ )nA..^X^t.04-^; >:o >j vj """V^^-v k , &~*3 >^3 / 2$" ^-C* , . ' b. fi^vvn^^.^JCLg, r^x.o r* ' rl #'x- , Q ' >-*+- /* ............. :y.,.* .&>. ^jxz*~> .O-Vc^ ." ' -- " ' """` Mk,' _ -.....:..... ; ' DUP050108882 XKS GPU. :i> * >. ,-. \' V \>' 4` *' . *4r*! ' ^ *> ' . ' ~ :~g t >82o -p : .;; : XOP ;f^3 A &P: *OTpBS'. /. o* - # re--'i ! ijt. HFj-.TTt-i ^ ">igr.|jhw---l. 1 ' r J ' STD. !* KECOB 1, Drain 225 Sfelll ssail decanter to OPC3 stdra.de, g^~ Flwsh- 225: ;v4i^^.^^.dlCTAftaglar....S^t'ea*...- ,/... tr ImluAiag;-- small decanter. . . /- a - : > >,.; . .. y -. V-' B. Pill' 22S Still a gall decanter ... ' ' X^; A - Check .225 Still reflug, lilae-s. oeen ' 5m Plush out 28 Still and li-rrfeff-fro 225 Still via --1 v^c ^ '.-^ gecurculaticn line..- * . Vsgg^^c-^../. of Flush out 22s? Still arid line todnyeW, ' iSfesw-' -Tv.- Blahk ling- ?25lSfrtli to j "v1^-flange near elfrvAtolff^; ?y-,. ;*" -' f^rQ W< A4d 760 x*31 nhg;i rajs**- 17V> - . . | : ,.,,________________ ...,,, . T^T^AdidL full /rot pt...aevi'sfclc '. rqo^l-lc?-%g3.1onS.,,i ,,,.,-- 115%^!, : 5 . Add Grze^GR-Cruds _:(.g^820g>^_ Y * .. ^<7 : - ^i^y :^h q . 28 stiii....... ; ; y?/J V- ^ ,, . .w* z iu..,C3iscft..as..stui., ar^-nttr gr>d f>laan, /z.. c 2',' "r\dd-1^0 gallons of w?-ter. . 5. Turn cn agitator .. ' ^Add -6.^ . lbs,.; Ahin^....FAhyl Ethanol ivrli?~,rajnhf>1 a. **: t5i..- Add, Sr lb?.. . 1P.PH throur^;.wirthQl,f>, \ , 1..^ 71.,,. Agltafca /v TX~dgg pi on T-'-^q ir-r-'qr't*. ;g~i i'wr Tn jl '.^7 1 j>' yii'rwi Pr^jl ?: i ?*r> Tpvn'"t' --.----- --" ,`-v--h*-i -1*--" I ".* f `mdmrnmr- n" f--r *t & r * "7-: *r * J -: .4 j! 2 > [ 'Add' 3- ^,0 ^ I n^n t ;n r* f'l xtr?h r*p:' frf T-^ ;o.c: pf ? 1 7' o.os; et-in jgryv f;gi ig[ Cj y5 ,et ** Sn.r.*roI.^ *r ty^ v.1z\Ti^r irr'ifiyy-- S3.^^.s 'TX^j ,t sH s*0^. irfy^ * ^**1.2 > 0 . If low *A * astr'wH' -uslax 'o^usftlc I! :t : 1-' DUP050108884 0T-830-g, m 439 DUP050108885 DU P050108886 gwSi&'Sif'e?. *- ^^a^f.i^abriSiiai^aakaiM^^^ 7fr.Tiig^ DUP050108887 2. I, 130 PONT DE NEMOURS AND COMPANY Pigments Department t{)a 2. CC: W. S. Struve, Piga., Newark B. H, Perkins, Pigm., Newark tE. E. Jaffe, Pigm., Newport V.. P. Smith, Jr., Piga., Newport A, J. Lewis, Piga,, Newport V. J, Lewis, Eigsa-, Newport C.. F. Belle*. Piga., Wilmington. Newark, New Jersey July 1, 1975 J. R. WEBSTER PIGMENTS CHESTNUT RUN MODIFIED EOTECTIC GREEN PRESSCAKE GT-820-P LOT 451 Ref, 1 JJ - A*P.Smith, Jr. Eutectic Green Presscake GT-820-? 4-30-74 Ref. 2 JJ - W.E.Miller; Eutectic Green Presscake 4-10r75 Ref.. 3 JJ - W.E.Miller CPC Grit `. 6-19-75 As has Been known for some-tine, GT-822-P has not been considered as the ultiaate solution for penetration into textile ink sales versus products such as A.S. 464-6947 since it is inadequate in strength and excessively blue in hue. Eutectic green ex the new plant was supposed to be our basic source of presscake for this type product. . As yet, we have not been given a chance to develop this product in that unit. We have conducted liaitad experiments in the laboratory and recently in the old plant with this type crude. These studies lead to a prototype laboratory product (1991-34C) which was exaained as dry color and in oil in water type textile ink formulations and considered adequate for plant trial (1973) since it gave an excellent dry product and good presscake quantity." Recently two lots of; crude 451, 452 were made available for use in this type operation, which requires a different set of conditions for hydrolysis and breaching than are currently used. The lets were made with Japanese crude and- have * been found to contain large amounts of non-pigaentary impurities (Ref. 3). Laboratory examination showed the products to be defensive in quality (Ref. 2) versus previous eutectic crudes examined by me. /' ' >S We recently were given an opportunity to breach these inadequate crudes in. they < old plant. XQP 439 - Lot 451, 452.' The plant breechings were inadequate* lot ] | 451 being high in 0DC3, and 452 unexpectedly weak (possible because, of process J ^interruption caused by the recent Newport plant explosion). However, laboratory breaching of lot 451 crude gave a presscalc2 which was very close to ODCB free plant press of lot 451. DUP050108888 a sanple of this lab breached material far evaluation. This type of east application was not considered in the prototype studies since the system was not ' in use at that tins. The conclusions of this study tan only be considered tentative, for the above centioced reasons but are considered necessary since .they wifi .provide guidance as to the ;suiability .of the basic system (i.e. surfactant >r crude quality). r JJ/cjS % and S Division 1 <jt- (-S2b-P Lot 451 LB (Lab Breached) X Solids 36 1 qt. to ranove 0DC3) % Solids 36 DUP050108889 fX/r Xsf, (i/*4 papAX a k fo/cf * C&X tec&tf ' a/f/PfX firs iX *&* **. (jtsH. '6-Mtf/t* &6C8 c s aAh / 7csk XA<X 04 U- fi/f s4CU4 #0C$ /f /f0*9i*s/f: /ptd-jbfi&(. ?s Tutfe-i/c Ct~0t<?~fi . . X( 4S4tSl//< ASfCi&x/ y/aX yXk xx T A/ e<$ , // SaiL/ y-.. C&a J a CnA //papAcX . &4 CT-g&a-P. pu./' XtJj ' fifi-CAti. (?**/< " (/ 0 d, <$X/A/fAfrUStf Xf/tya .2&}. Ofr/tr/ pL aT //, X {pic fife,f ,<&*%*. //.J- /2. ?) XX pX Ar - V/rrf /ion. t2 , &XX Z $( /UaP a.</ AA^X&p/i XX pi <x</X l 5if &&U4Xc XX *tJL /2.7 d /r df/ut&s)*. /L.o -n-3 &&-</ /j a /.c A~ /&*/ ady&si Ac X oC^-n.. * @ d/S T/LC4r/S*S " 2,44 1^4. /, / cXt A/?& fi jXeiisd /4#ft bn. a- Soo ft* / . (/$*<4\ A*u. % A/.) ' 7m*a- - S6-tt>pX 0/ $/(/- Jsfrx/I jr\ &di j/ $tXX> DUP050108890 AMx/k fibs Jff $67*- gtrjj/cA** /f Cam/yAn * AJiA gk * f / Jhtm J7l*c</ crgio-0 At r/: <jef ^ /uorr&A fAgt*}. DUP050108891 APPENDIX t K-t3004 E. I. d u Po n t d e Ne mo u r s & Co mp a n y iNcoNiwuVa) PIGMENTS DEPARTMENT cc: W.S.Struve, Pigm., Newark E.E.Daffe, jittgm., Newport C.W.AndersoHzR.J.Guschi, Newport. P.G.Linsen/C.F.Rolie, Pigm., Wilm. E.W.Stewart, Pigm., C.R. H.W.Ling/J.R.Webster, Pigm., C.R. C.G.Hubbard, Pigm., C.R. Chestnut Run February 2, 1977 FIRST REPORT NKD-4-77 ILF-9-77 TO: J. JACKSON Pigments - Newark FROM: P. J. KRAPE \<J Pigments - Chestnut Run (\ NEWARK EXPERIMENTAL GREEN PRESSCARE FOR TEXTILE PRINTING CONCLUSIONS Experimental E-6161-12B had strength equal to Sun's 464-6947 textile grade presscake under low and high shear dispersion in a modified Sherwin-Williams ink. E-6161-12B was -- 2.5% stronger (sensitivity of test is + 2.5%) than GT-820-P, SL-0451 under low shear. The sample was prepared with a homogenization step which apparently disperses agglomerates formed during the present process. Making such a product at Newport would require installing new equipment. EXPERIMENTAL DETAILS o Low Shear - 20 minutes polyethylene "Jiffy" mill with 1/2" Fprox balls. Results on several presscakes have repeatedly correlated with Eppenbach grinds but,since millbase rheology is a significant factor in an Eppenbach dispersion, Chestnut Run considers the "Jiffy" method a screening test and will Eppenbach disperse promising experimental samples if they are large enough. Jiffy test requires <15 g. dry weight, Eppenbach ''-150 g. dry weight. o High shear - 45 minutes polyethylene ''Jiffy'' mill with 1/4" steel shot. The difference in strength between 20 minute and 45 minute grinds is considered a measure of dispersability. Sun's strength increases only ^2.5%; GT-820-P, SL-0451 ^5%; GT-820-P production }10%. b e t t e r t h in g s p o h b e t t e r l iv in g . . . THROUGH c h e mis t r y DUP050108892 J. JACKSON -2- February 2, 1977 p Formula - Sherwin-Williams latest general anionic formula for green, blue, etc. Fresscake is added to a masterbatch mixture of all the ingredients. ELECTRON MICROGRAPHS Sun - clearly visible, separate crystallites of <*.04 um are extensively flocculated throughout the dispersion. Aspect ratio is ~1. Flocculation is continuous - there are no distinct clomps of crystallites. No other material is visible. GT-820-F, SL-0451 - very few'distinct crystallites are . visible-.: They are all clomped into football shaped agglomerates broadly ranging from 0.4 um to 2 um along - - ' the longer axis. Aspect ratio of footballs is v 4/3 crystallites -* '3/1. Background is extensively littered with small translucent needle-like crystals. e Experimental - fewer footballs are visible with many more, :- flocculates and aggregates of crystallites* Sizes and shapes vary over a very broad range. Individual crystal lites appear to be more acicular than Sun's. 45 Minute Steel Shot 20 Minute Porox Balls SHERWIN-WILLIAMS ANIONIC MASTERBATCH . GT-820-? ' Sun . SL-0451 C# 76298 E-6161-12B 95 95 95 ' 100 97.5 97.5 PJK :mal Attachments DUP050108893 APPENDIX F E* I. d u Po n t d e Ne mo u r s St Co mp a n y jNCORROrtATEd FIGMENTS DEPARTMENT .1 , & * l 'Y * cc; P.G.Linsen, Pigm., Wilm. W. S. Struve/J.Jackson, Pigm., Newark . CK.Anderson/R~J. Guschl,/> "Plgnfi / Mewaor t .. ST'.W.Stewart, Pigm, , C.R. H.W.Ling/J.R.Webster, Pigm., C.R. C.G.Hubbard/J.A.Mackiewicz, Pigm., C.R. "> L.A.Schlapfer, Pigm., C.R. . F.C.Dzielak, Pigm., C.R. (File) *" w H.A.Larson, Pigm., C.R. (File) R.I.McLaren/M.D.Wright, Pigm, Chicago i- ' '*> FIRST & FINAL G-36-76 ILF-73-76 TO: C. F. ROLLE Pigments - Wilmington FROM: P. J. KRAPE Pigments - Chestnut Run GREEN PRESSCAKE FOR 3M ROOFING GRANULES CONCLUSIONS: 3M's standard presscake (probably from Sun) is inherantly stronger than GT-820-P. Rubout masstone is very dark, intense, and transparent vs. GT-820-P, suggesting the competitive may have a smaller, more nearly optimal particle size and therefore, higher light absorption with less scattering. In tint, the com petitive was 'w 5% strong and si blue. Earlier work (G-104-72, reported 2/21/73 by V.J.Lewis) showed that GAF's green for roofing granules, 66-3803, could be matched with GT-822-P, BT-436-P, and carbon black. Adding absorption to our green equaled the competitive press cake . The surface of the 3M standard was also much more hydrophobic than GT-820-D and may be more receptive to surfactants thereby yielding a better dispersion and higher strength. Recent work in textile inks support these hypotheses (results to be issued early '77). Surfaces were characterized by shaking presscake in a vial containing half water and half Varsol mineral spirits (see attached photos). Varsol floats above the water. Our presscakes either float in an emulsion layer or fill the water phase. RECOMMENDATIONS: When a new presscake is developed for textile printing, we recommend Sampling 3M, They still refuse to supply a test method for development work. PJKunal Attachments 0 ETTER THI N.GS FOR BETTER LIVING ....T.H&0UGH CHEMISTRY DUP050108894 0 r DUP050108895 REFERENCES 1. J. Jackson, -KN-76-9, "GT-820-F - Presscake Ex Eutectic Green Process" 2. H. Matrick, KN-73-12 3. e . . Gillow, KN-75-3, "High Transparency Ramapo Green Pigments GP-817-D and GP-8l8-Dr' R. J. Guschl, KN 77-3, "Increased CPC Crude Capacity" 5. For more details, see reference 4 and references cited therein 6. E. . Gillow, KN 76-11, "Kerosene Recycle in the Synthesis of Low Chlorine Content Copper Phthalocyanine" 7. . E. Miller, January, 1977 Monthly Summary 8. R. L. Sweet, KN-73-2 9. . E. Miller - To be published 10. This study was summarized in January 1977 by W. E. Miller and published as a letter to Manufacturing 11. R. J. Guschi, KN-77-2, "A New Process for Finishing CPC-BB, the Active Solvent Effect" * DUP050108896 DATE ISSUED: DISTRIBUTION: 1. E. Goniek - Wilmington 2. W. S, Struve * Newark 3. H. B. Clark - Wilmington 4. J. G, Ishikawa - Wilmington 5- E. J. Mead - Experimental Station 6. J. E. Romano - Newport 7* 0. W. Hapka - Wilmington 8. C. F, Rolle - Wilmington 9. E. E. Jaffe/Circ./Pile - Newport 10. E. W, Stexmrt - Chestnut Run 11. B. H. Perkins/J. P. Galvin/A. P. Smith/Newark Library 12. C. W. Anderson * Newport 13. N. J. Kane/Newport Library -Newport l4v P. H. Griswold - Newport 15. W. E, Miller - Newport 16. P. J. Krape - Chestnut Run 17. W. P. VanVliet - Chestnut Run 18. H. Matrick/R. L. Sweet/J. Jackson - Newark 19. R. Z, Portney/J. P. Kane - Newport 20. S. W. Severance/I. A. Berkemeier/W.' G. Hoffman/C. E. Woodruff 21. R. D. Nelson - Newark 22. R. J, Guschi - Chestnut Run 23 & 24 - Central Report Index - Chestnut Run 25. Newark Research Pile - Newark 26. Numerical Pile - Newark 27. C. Hubbard - Chestnut Run 28. " DUP050108897