Document gbQnM3OBqwR7Z1oqXX9KJ4q4G

KN-67-20 . con soj DISTRIBUTION: Research Numerical File Research Office Pile M. Hunt/S, Gonick N R* levins W, S4 Struve/A A. Briazolara J. Hi Cooper/F. F. Perkins/I-LR, Litton 7 W. O'. McOiure/RiA,, Hagemn/H Amoul/Q.C* File 8 P, Ok Monahan {Vital Records) 9 E. Li Rodowskas/W A * Jenkins 10 G* M. Loughran 11 R,, M,, Salerkl/P. N. Odell/Q.C, File 12 R. Wetael 13 H, h 6 Gyorgy 14 Ok W. Minnich 15 Ok F. Maurer 16 R L. Sweet 17 W> E Miller 18 Research File - Colors ~ Newport 19 Extra 20 Extra 21 Extra 22 Extra 23 Extra 24 Extra 25 Extra NEWPORT HAST vtomm c o l o r s r e s e a r c h r e p o r t SUBJECT: HIGHLY BR0MIMTEI5 COMLOGEMTED CPC GREEKS Am "mMSTB&L* GREEK T PERIOD COVERED: JULY, 1962 - JULY, 1965 ~ R. L. SWEET JULY, 196.5 - OCTOBER, 1966 - W, B. MILLER SUBMITTED BY APPROVED BY: S, Li SWEET, I, E MILLER J, W. DATE SUBMITTED DATE RELEASED: 6/8/6? 2/6/68 DATA BOOKS TSC-78, 86, 97, 106 - RESEARCH: 1800 " R. L. SWEET TSC-3182, 3183, 3197, 3201, 3209 - W. E. MILLER DUP050027954 t abl e o f c o r t er t s i . IWfROBUCTIOW 1 XI. s u mma r y 1-3 Ill PREVIOUS WORK IK THIS LABORATORY nr. ESTABLISHMENT OF TARGET 3 3-4 v. PRESENT WORK A. Review of Literature and Methods for Preparation of Brominated CPC 4-7 B. Theoretical Discussion of Eutectic 0ohalogenation 7-10 0. Experimental er& on Eutectic C chalogenat1on 1. Initial Laboratory Development 2. 1x5$ Bromine Excess Process 3. Spectra Test for End-Point Determination on Gohalogenat1on 11-20 20-21 21-23 13. Details on Plant 0ch&logenation s 1. Runs 1 and 2 2. Runs 3 and 4 3. Runs5s 6 and 7 4 Runs S, 9i 10 and 11 5. Standardisation Runs 12, 13, 14 and 15 23-24 24-41 42-46 46-47 47 E, Finishing - Particle Rise Reduction and Adaptation to End Use (Lab) 1. Initial Worh on He'wport-Tyne Solvent Breaching (MTSB) 46 2. Changes in the Eutectic Kelt a. 4 Effect of Temperature before Hydrolysis 48 b Reheating of a Eutectic Melt Before Hydrolysis 48 3. Changes- in Hydrolysis a. Temperature of Hydrolysis Water and Method of Filtration 49 b. Changes in the Hydrolysis Medium 49 e Use of Various Media (Water, water t OBCB, Water -f Methanol, etc.) for Hydrolysis of Eutectic Melt Containing Green Y 49-50 DUP050027955 (TABLE OF C ORTSM'S-C ONT! D ) V. PRESENT WORK-(ConfcM) E. Finishing (Cont:d) 4. Changes in Newport-Type Solvent Breaching (NTSB) a. Surfactants other than Staybelite 50 b. Solvents other than ODCB 50-51 c. Optimisation of Staybelite and ODCB Levels in NT-SB 51"52 5. Treatments After Newport-type Solvent Breaching a. Oxidizing Treatment with N&CIO 52 b - H2SO4 - Arquacl 16 Treatment 52 c. Antifiocc ulating Agents for Very Yellow Shade (TiS) Breens 52-54 6. Alternate Methods of Particle Size Reduction 54 7. Bromination of a purified CPC Blue 54 8. The Use of Orehem * s Solvent Breaching (OSB) a, Initial Results 55 b. Peroxides from 2-Ethoxyethanol 55 9. Treatments Subsequent to OSB for Paint and Plasties a. Flocculation Problem in Paint 56-57 b. Treatments for Plastics (Vinyl) 57-58 P, Relationship of Composition to Quality of Green Y 59 Go Plant Solvent Breaching by 0S3 of Green Y Crude 1. Lot 3 2, Lots 4, 5i 6 & 7 3- Lots 8;1 9? 1-0* & IX 4. Lots 12; 13; 14; & 15 "-Standardi zation Run H. Newark Finishing of Green Y 1. Lot 3 (Semi-Works) 2,, Lots 4; 6 & 7 3 , LOtS 8; 9; & 10 4. Lots 11; 12 & 13 ~ Standardisation Run 59-63 59 60 62 63 63-75 63 70 71 71 DUP050027956 {TABLE OF C OM'ENTS -C ONT*D ) Page V. PRESENT WORK (Cont ;d) I, Comparison of Physical Properties of Green Y with the Competitive Suco GA--48l8 X. Elemental Composition 2 Optical Density 3. Surface Area 4. Electron Micrographs 5,, Speetrophotometric Absorption in B2SQ4 Soltuioii of CPC Greens of Various Bromine Content 6, Reflectance Curves for Very Yellow Shade Greens 7. X-Ray Diffraction Spectra 75-76 76 76-77 77-78 78 78 J,, Preparation of Hexadecabromo-CPC 78-80 VI COSTING 81 VII. PATENT SITUATION 82 Till, FUTURE WORK 83 IX. APPENDICES A, Literature Abstracts on Brominated CPC's 84-96 B. Letter WEM to JWM Outlining Manufacturing Processes and Recommended Equipment Changes 97-99 C, Sulfuric Acid Completion Test 100 D. Letter WEM to ?- Dowd "Monasiral Fast Green 4Y Crude ~ Speetrophotometric Absorbticn in Sulfuric Acid Solu tion" 12/27/65 101-113 E, Letter WEM to G.M. Laughran/ F,, K. Odell "Letter of Transmittal - Very Yellow Shade Green (lf-949)i! 10/10/66. 114-127 INTRODUCTION Cohalogenated products have been on the market since 1959 when Heliogen Yiridine Y (later called Yiridine Toner 66-6001) was introduced by General Aniline, This product contains about 4 Br atoms, the rest being 01 atoms^ it is distinctly yellower than our Green G, G-T-751, It sells for the same orice ($350/lb.) but is some 22$ weaker than GT-T51. Since the introduction of Heliogen Yiridine Y, there have appeared a number of cohalogenated products on the market (Table I), and as time went on, the amount of Bromine content `and corresponding yellowness have increased closer and closer to-the maximum of 15 Br atoms. It was still a question whether a CFG containing 15 Br could be made by a practical method, or even 'whether such a product would be desirable. It would be very yellow but also very weak. Such a product is reported in the literature, (B. Klaxber, Thesis, Tech. Hochschule, Stuttgart, 1959)* prepared in low yield from CFG via AlBr-, and Perrum Redue turn and Br2, and contains 67.8$ Br (15 Br atoms) but no copper analysis is mentioned. It is important to check for demetallization (and subsequent possible degradation of light fastness) since demetallisation was shown to occur on broraln&tlon of CFG with elemental Bromine up to a Bromine content of 13 atoms (Linstead and Dent, U.S. 2,214,469), It is seen in Table I, that standard Ultra,Marine's product GA.-4818 contains 12.0 atoms of Br. This may not be the maximum Br content to be seen eventually in a commercial sample since a higher Br content can be obtained. In this lab, a product CPG Brj.3.1 CI3..2 had already been made in 1959 l'TSC~31~47A\ and designated as a npolypromCBC". To date, trade acceptance of the yellower greens has been slow because of inferior money value vs, conventional phthalocyanine greens. However, since they offer the only practical method of obtaining a yellower CPC green than our GT-751 without losing intensity, there are definite indications of further growth, SUMMARY Bab processes were developed for the cohalogenation of CPC in'eutectic melt to yield a product of goal compo sition containing at least 12 Bromine atoms, the rest Chlorine. These processes were designed to afford the optimum degree of"Bromine utilization, hold time and economy. Plant runs at Chambers Works of Grehem were made and gave products of suitable Bromine and Chlorine contents. SUMMARY OF VERY YELLOW SHADS COMPETITIVE CPC GREENS 37 ^Recalculated from O r ig in a l V alues B r = 2 3 .Oj G i - 2 8 /0 * Cu = 3*9$ t o ta ke account o f Blanc F ixe* found la te r . -jw-Posslbly has Blanc F ixe . 2- - H * tr- VO OD VO O IA H rA on OJ OJ LA 0 0-4* co HH =f cvi .H O on CA CM CA on P -0- CO *>1* st- 04 Ol VO VO VO SJ- CD' H H H r-i r-i <--i H rA r-i H O sO pHCd|l jo j VOA o| -=i- e-u r~l L's-- co CO mH Hi r-} IN* =3H P CA --5 m CA* OO 0 a '-ik 00 =J- 0- H r-i H H in H M3 VO HH r-} r-1 -0P 0 01 u SQ ~SP CM CU* rAm 04.* CA* CVOO 0 H cu * aH- e VO-* CinOa ee'r4) II FQ o r~:| CM <p o H O CO CA CO H (N VO VO A- CM CM O n SOr3i -P .>- CO VO CA CA CO --4 A VO.* co cuA CM CMa in. 0 0 0 0 0oPS< CM OO CO *l* in IN- CO CO co CU CU r-( r-i r*$ r-f r"! a 0 in in m 03 ssi VO o! "S' r-i CA 1 on 0 1 CO * CA on ro i CO j. i .f-01 CO si 1^ Hf VO o| CO in VO 0 00 in .tw CM CM CU CA O tN CA CO CO in .=}CM iH H r-i ofl CO r-i sn*o br--i MC'3-- in lO CA CO o 04 :t Ofr-|PrQlt ii VO CO =5` *> vo 'O CO .. N CA* e*- m vo in * .ft VO in CA CM -m VO on CA CA 0 H CU CM CM on N* Sj- 5S- -1- in m vo Of j}s cup 00 { 1 * VO (N mil VO vo H(H 00 CO 00 0 ft it CO in in vo to CO 00 r-5 vo >1 i in A-- 00 CU H 0 O'! on vo & in m -4; CO NCO S 00 S3 0 O CO 54 O 0 --1 O i% n S-t t O :-;Wl t ~! 0 VO (N O ft H0 0 s* d 0 d r-4 s r-l 01 'O CA in ~i' --o' CA -=4' VO VO vo T\ ifi O -p -p ^3" H CA 0 0 P sfe 0 VO % CO 0 0 in P> 0 0 S3 0 r-i 0 Oi 0 H t--( CO r-! O' r> '0 to 5 to in r--i fei d fe -P H 0 0O VD rf X 0 O J rM A~ r-i *rl LC\ O crj i~4 ccS S3 co a H 0 O C/2 pcs ca f-l S< <") s O in J> 1 i CO in S3 -P O -P 1--i CO CO -H* 5 u =4- j 0 MVO IQ VO ~,1* co 0 C IB rri 0 C5 0 b SN 0 !N t P CM rr---* 0 >53 43 < u S3 CA, S3 CA / :m -=S' i;-0 0 ri O O c 0 O 0 m 0 0VO O 0 0} cd b & s d & r-i 40 OJ 43 H CO 0 ss> 0 fl S3 < H <4 O b O0 3 CO vNcMM! 0 ,H, O VM.3 5 0 00 0w S5 0 CO M DUP050027959 3~ II, SUMMARY (Coni?d) Methods were developed to solvent breach successfully the Green. Y crude, and to finish the solvent breached Green Y in order to make it suitable for use in paint and plastics, in comparison with the competitive pigment, Suco GA-4818". A hexadecabromo CPC with elemental analysis close to that for CPC Bri6 was prepared in a AlBrs-NABr eutectic melt. This product appears to be yellower and duller than the products with about 12 Br atoms, III, PREVIOUS WORK IN THIS LABORATORY The work on very yellow shade greens done about 1959 has been summarized (PTC-60-7). During our work in 1959* the cohalogenated Heliogen Viridine Y (IWY) appeared. This work led to a process yielding a counterpart for STY, containing from 25-30$ each of Bromine and Chlorine, which was equal in yellowness and strength to the competi tive. The process was designed to use the regular equip ment at Newport for chlorination. Plant runs were not carried out, however, because of several reasons. First, the cost estimate for the finished toner was slightly higher than that of GT-751 for a product selling at the same pricey second, an operating difficulty was present in the large amount of heat generated from the complexing of AlCls with SCI2S and third, at this time there appeared to be a very limited impact of the cohalogenated, very yellow shade greens on the market. The work was therefore IV. ESTABLISHMENT OF TARGET The inadequacy of Heliogen Viridine Y (Viridine Toner 66-6001) as a target was demonstrated by the successive appearance of other very yellow shade CPC greens, which contained more Bromine and which were yellower, during I9601962, The target product would have to be at least as yellow as Suco GA-4018 and also suitable in other properties, e.g,, strength, dispersibility, etc. In addition, the product should be capable of blending with Green G (GT-751) to form suitable counterparts to the competitive products in the intermediate shade range from that of GT-751 to Suco GA~48l8, viz,, Ans. Siegle 64~T-27, Viridine Toner 66-6001, Harmon G-5400 and others. In order to find out if such blends would be suitable, an old sample of "polybrom-CPC" was used. This product (TSC-31-47A) had the composition CPCBri o iCX1.2 and had been made by the action of sulfur chloride, alBrs^and Bra on CPC, The process was not suitable for large-scale production of the npolybrom''-CPC because of the evolution of heat during the SCla-AlBrs complexing and the high costs for AlBrs and Br2. This product had been dispersion milled. DUP050027960 4- XY* ESTABLISHMENT OF TARGET Contd) Blends of this !>polybrom"-CPC with GT-751 were made with the indicated compositions: TABLE II Blends of " Folybrom-C PC" With GT-'i n > Bolybrom-CPC " 96 GT-751 Rubout Reading vs. Competitive AS 64-T-27 Heliogen Yiridine Y Harmon's G-5^00 11.1- 5^.3 73*7 88.9 ^5.7 26.3 103, v,Int,Equal Shade 97 , Equal Int. 83 Shade 1005 Equal Int. & Shade All masstones were light vs. the competitive. The close matches in tint* strength, shade and intensity, however, were encouraging to the idea of using !fPolybrom'!- CPC with GT-751 in hiends to match competltives. Y, PRESS' WORK A. REVIEW OF LITERATURE AMO METHODS FOR FREPARATION OF Several of the known methods for the cohalogenation of CPC are given in (PTC-60-?). For the sake of compari son, however, these methods along with alternate methods are included in Table III. TABLE III Routes to Broalnatefl CPC A - Linstead - Bra Heat under Pressure B - AICI3 - SClg - Bra - Pressure Reaction C - Aids - SOCI2 - Bra - Pressure Reaction D - Aids Had - Brg - Eutectic at Atmospheric Pressure E - AlBrs - SCla - Bra (as in TSC-31-47A) F - Synthesis of " Polybroirr'-CPC via Tetrabromophthalic Anhydride Method A is described in B.P. t6l,268 and in J. Chem.. Soe, 1820, [1939J (Linstead). Briefly, CPC was heated with elemental Bra in sealed tubes up to 300C. The product contained high amounts of Bra (to 13 atoms) but almost no copper, demetalliza tion 'taking place. It is possible that the use of a copper source would provide, by this method, a poiyhrominated CPC, However, the fairly high pressures achieved in sealed glass tubes would appear to he difficult to attain and control in large scale use. DUP050027961  57, PRESENT WORK (Coat'd) a . {Coat'd)- ,, Method B was the process developed, for the Heliogen Viridine Y counterpart in p t c -60-7- The process in volved the use of plant equipment used for Green G with ingredients of AICI3, SCla, and Bra- A much higher ratio of AICI3 to SCla was needed, however, in this process along with a lower temperature. This led to an operating difficulty because of the large amount of heat generated in the complexing of the AICI3 and SCI2. In addition, the removal of the final sulfur chloride from the reaction mass, when done at the temperature ordinarily used in the Green G process, gave halogen exchange (Cl for Br) with consequent blueing off. For these reasons, no plant trial was made. To contemplate making a polybrom-GPC by this process would mean increasing the AICI3/SCX2 ratio even more, with an even greater problem due to the heat of complexing. Method C has been shown (PTC-60-7} to be quite operable, and has given CPCs containing up to 8 atoms of Br with a complement of Cl, The method is identical to Method B except that SOClg is substituted for SCla, This process is covered in a patent to General Aniline, Randall and Taras (U.S, 2,873,279). The patent claims a product with 13 Br atoms, 2 Cl atoms, but the analysis indicated only 11 Br atoms, 0,9 Cl atoms- Method C could be run in present equipment, but a separate re covery system for 8OCI2 might be necessary. The heat of complexing of SOCI3 and AlCls is noticeably less than that of SCla AlCls. The explanation for the ability of SOCI2 to allow greater incorporation of Brg into the CPC molecule apparently lies in its lesser tendency to break up to yield free Chlorine- SOCI2 must be heated above 154C before free chlorine is released; 4SOCXs --> 23 Da -f S3CI3 + 4C1.2 Method D has considerable precedence. The old Dupont patent {Fox, tl,S, 2,247,752) (1941) listed procedures (Ex. 8 and 9) for eutectic eohalogenation of CPC by using a eutectic media of AlCls, NaCl, CuCls with Bra and CPC. The Bromine was passed into the melt via a stream of nitrogen. Two products are described, C'PCBrQ, 2CI1.1 and another with 11 Br and 3 Cl. In the first example the copper analysis is shown, but is significantly omitted in the second. Thus the question is raised - is there some dematallization when the eutectic cohalogenation is carried out to 11 Br atoms (where Binstead found demetalliza tion) even when a source of copper is used? In addi tion to this possible problem. Fox used a fairly high (and expensive) ratio of AlCls to CPC. Neither was there any statement regarding Bromine Utilization Efficiency (BUE) or yields. DUP050027962 ~6~ P>iBSffiT WORK {Cont sd) A, (ContM) A eutectic process is also described by Niemann* et al, in U.S. 2*276*860 to General Aniline (1942), The process is like that of Pox except that no CuClj? is used, A composition CPCBr^Olg is obtained. Since I960, a number of other patents have issued* also concerned with eutectic cohalogenation of CPC. Two of these* viz.* BoP. 850* 237 Bel, 601*218 I960 1961* repeat Pox or Niemann, and it is difficult to see why they issued. Both describe eohalogenated products containing only small amounts of Bromine, The ratio of AICI3 to CPC used is about 4. Two other patents* viz,* F.P. 1*263,272 FoP. 1*273*802 1961 1961* are quite different from Fox or Niemann, In F.P, 1*263*272* NaBr is used as the sole source of Bromine* and a composition CPCBrg k CIi i 3 is claimed. In P,P. 1*273*802* elementary Chlorine is not used* instead chlorosulfonlc acid and other compounds furnish the chlorine - by completing such as? ClSOsH + AlCla ^^ l AlClsSOsH 4- C3 A product with a high Br content is described {C'BC?B.rio.9Cl3.0)-. Another patent* U.S, 3,041*192 {1962) describes eutectic cohalogenation in connection with a claim for a method of conditioning using phthalate esters. A product* CPCBrg, cjCln ,, 4 is described. Prom the above discussion of eutectic cohalogen ation* we concluded that this method for making & polyhrom-CPC had possibilities if it could be made to satisfy certain requirements* viz.* (1) Demetallization of CPC must be avoided, (2) High Bromine Utiliziat5,on Efficiency must be obtained, (3) "fields must be high. (4) Suitable equipment must be obtained for running the eutectic cohalogenation. Note: Most of the patents concerning the use of eutectic melts date from 19SI on. There appeared to be a lapse of interest in this method from the time of Fox5s patent in 1941 up to 1961* and gtraetically all of these later patents have become available only Since our work 'on the eutectic route started in 1962. DUP050027963 7 V. PRESENT WORK (Cont5d) A, (Cont{d) Method E used large amount of Aluminum Bromide in proportion to CPC. along with SCla end fairly large amount of Bra* This method appears obviously impractical because of the high cost of AlBrs and Bra, In addition, the heat of complexing between SCla and AlBrs is even greater than that between SCI2 and Aids, This process, however, in TSC-31-47 ,> has given a composition CPCBri3,iCli,2 with the greatest Bromine content ever attained in these laboratories. The copper analysis is somewhat lower than expected, along with the reported' presence of some aiuminum, which appears to indicate some demetallization of CPC and subsequent replacement by Al. No copper source was used in this experi ment, To summarize, this method gives a "polybrom1' CPC but is impractical as it stands. Since demetalli zation was not extensive, however, it appeared that this may not be cause for too much concern if a copper source is used in the cohalogenation, Method F - Synthesis of brominated CPC starting from brominated phthalic anhydride (tetrabromo) was carried out by Moser (U.S. 2,549,842 to Standard Ultra Marine in 1951). Barge amounts of urea along with ancillary agents were used to make a "polybromo"CPC. but the quality of the product was not described. This method has been previously tried in this labora tory, (MB-1624-23,24,27), A discussion of the method was given in {FIC-oO-7) listing disadvantages to the method which include low yield, a difficult synthesis which required TCB as solvent, dullness and hardness of the finished product, and the fact that the identity of the material as a Polybrom-CPC was not clearly established. At this time, the cost of TBPA was |l.25/Ib. in 100-9999 lb, lots. In late 1962, the price of TBPA was reduced to 75 cents/lb. This might make the economics of this process attractive enough to warrant further work, although the lack of equip ment to handle TCB as a solvent Is serious. In summary, these routes to a ''Polybrom"-CPC, the factors of economy, poor operability or patent problems, appeared to rule out all but Method i>. Mo plant equipment is available at Newport or Newark for eutectic halogenation. However, the cost of installing new equipment or modifying old equipment appeared to be modest. In addition, Orchem uses the eutectic melt method for producing polychlor-CPC and it was considered possible that this equipment might be available. Note: The pertinent literature on bromination of CPC is abstracted and given in the Appendix. DUP050027964 PRESEHT WORK (Cont'd) B. THEORETICAL DISCUSSION OF EUTECTIC- C OHALOG-EHATSOM Ho explanation of the mechanism of halogenation of aromatic compounds by halogens in an aluminum chloride - sodium chloride melt appears to he avail-* able. In other media, e.g., water, aqueous dioxane and acetic acid, a number of positively charged regents have been considered as intermediates, e.g., CZ+ Chloronium Ion Br* Bromonium Ion ClOHa* BrOHa-f (Be LaMore and Ridd, Aromatic Substitution - Nitration and Halogenation, Academic Press, Inc,, B,YS, 1959) Of these intermediates, the chloronium and bromonium ions appear to be of primary consideration, the other intermediates being formed from them by addition of solvent molecules. In the ionic media of the eutectic melt, the existence of the Cl* and Br* ions, either free, or as ion pairs, seems a reasonable assumption. The halogenation of the aromatic compound (CPC) may then proceed through an ordinary 'Whel&nd Transi tion State, Wheland Transition State The ex'1' and Br* ions would be produced by the initial complex formations; AlCls + Cl2 --5 [AlCl^ + Cl AlCld + Br2 ~0aeisB^ + Ba Here we are assuming that aluminum chloride exists as the monomer AICX3 in the eutectic melt, and not as the dimer AlaCXgs which is known to be the case in the solid. These equations show that only one half of the halogen can be used for halogenation. However, it has been shown that Bromine can be released from the [AXCl3Br>> complex by elemental Chlorine by exchange, a. g., ,--. jAlCl3Brl0 -f~ Cls v^fAlClJ^ + BrCi BrCl + C10^e Ola + Bx T -9- V. PRSSENT WORK (ContM) B. (Contad) The bonding energies of the Al~Ealogen bond are of the order of 78,0 heal,/mole for the Al~Br bond and 90,5 kcal./mole for the Al-Cl bond. The initial coraplexing of AlOla with Bromine or Chlorine to form a. new Al-Br or Al-Cl bond would then be energetically of this order of magnitude. The exchange reactions mentioned above are driven by the greater bonding energy of the Al-Cl bond over that of the Al-Br bond. This difference being about 12 kcal. That this type of exchange takes place has been demonstrated by the utilization of Bromine in greater than 50$ level., even approaching complete utilization of Bromine. (F.P. 1,263,272, Bel, 601,218) The initial eomplexing of elemental halogen with AlCla is a reaction which develops considerable heat, and which would be energetically favored over the exchange reactions, although these are probably also exothermic. The exchange reactions are driven by the greater bonding energy of the Al-Cl bond (90.5 kcal./mole) than the Al-Br bond (78.0 kcal./ mole) but formation of the aluminum-halogen bond in the initial complex would be expected to release a larger amount of energy. In any process, therefore, where elemental halogen, (Cla or Brs or a mixture) is introduced into a AlCl3-NaCl eutectic melt, eomplexing Is expected to occur first, to the exclusion of exchange reactions. After all the Aids is eomplexed by the stoichiometric molar equivalent of halogen or mixed halogen, then exchange reactions would be expected to occur if more Chlorine is added. A summary of the reactions involved would be; 0 H m [2] Aids + Cla --[a ICJ ^ + Cl ^ (m moles) (m Molds) g) DUP050027966 -10- PRESEi'jT WORK (Cant'd) B-. (Cont;d) fAlClaBrl + Cl* = glOlJ + BrCl (n molesy (n moles) (n moles) BrCl + Cl ~----- * CXs + Br [Aid'll + Hrz Aids + HCX [AlClsBrj W AICI3 + HBr . Reaction [4j does not consume Cls because reaction fja} recycles da back. The equilibrium of [5j| probably lies far to the right since the positively polarized halogen entity Bi has a higher stability than Cl 09. (G. Olahj ct al, 3 J. Org, Chem. 2? 3441 (1962) Equilibrium [4j also likely lies to the right because of the greater stability of Al-Cl bonds compared to Al-Br bonds. The release of hydrogen halide apparently takes place in the major extent by reaction and not jYj since the exchange reactions [4]and |5j consume [AlClsBrj 09 It will be apparent in the following section that an excess of chlorine is to be avoided. Too much chlorine will give replacement of Bromine atoms on the CPC molecule by chlorine atoms. Too little chlorine gives incomplete Bromine utilization since reactions j~4l and |~5jj will not start until enough dg is used in equation f3] to complex the AICI3 which was not initially complexed by Bromine, The desired stoichiometry appears therefore to be expressed by the relationship; Moles Bra + Moles Cla - Moles Aids [s] In addition to the required relationship jj3]. enough Bromine and Chlorine must be used to attain goal compo sition. Por instance,, to attain CPC Bria minimum of 8 moles of Broroine and 8 moles of Chlorine are needed per mole of CPC. DUP050027967 V. PRESENT WORK (Cont'd) C, Experimental Uork on Eutectic Ooh&lcgenation 1, Initial Laboratory Development Our Initial work on cohalogenation of CPC in eutectic melt used arbitrary ratios of CPC> Aids* Bra and Cla. The operations were conducted like Orchem5 s procedure for chlorination of CPC 3 * the AICI3 and IfeCl were charged to a reactor and melted, the CPC added, the melt brought to temperature. Bromine was added on the surface, and then Chlorine was added under the surface. The first experiments (TSC-78-27) used the following ratios at a temperature of 185~190C . with the indicated products: TSC--78-27A TSC-78-27B Aids Had CPC, CP/SF Bra Cla 197 6 41.3 g 4? g 10 g 107 g (In 10 Hr.) 197 41.3 4? 1X1 5? (In 10 hr.) Product: SUE* s CPCBri,70111,2 100 CPCBr^, 0C12 . 2 64 These experiments showed that it was possible to get efficient use of Bromine, and that high Bromine contents could be obtained. *BtBS -- Bromine Utilization Efficiency. Calculated .from: # Br x Yield B:c input From this promising beginning, a time study was made with the following ratio: TSC~7S27I> AlCls laCl CPC, CF./EF Br2 Cl2 197 g 41.3 g 47 g 120 c 148 g (Over 13 hr.) The curve of composition vs. time Is shown in Figure 1. It clearly shows the remarkable replace ment of Bromine atoms attached to the CPC ring by Chlorine atoms. The maximum Bromine content never exceeds much more than 8 atoms per molecule DUP050027968 -12- V. PRESENT H0R1C (Coat5 d) Ch I. Initial Laboratory Development (Cont 5d) of CPC even though more than enough Bromine was used to saturate the CPC ring;, the ratio of Atoms Br/Moles CPC being 2.6*8* The total number of atoms of halogen {Sr 01) continues to rise throughout the run. The implications from this graph are that less Chlorine would have allowed the Bromine content to rise uninter ruptedly* and that a longer hold time would allow a higher degree of completeness of balogsnation to be attained* This and other experiments clearly demonstrated the stoichiometry expressed in Eq* (8.5, For example, a run in which a ratio of A moles Bromine 1*0 mole CPC was used at l4oC* .* and in which essentially no Chlorine was used gave a maximum attainable compo sition of about CPC BrQ Clx* This graph is shown in Figure 2* A similar graph was obtained under these conditions at 225C* However., when Chlorine is added to a run at I40C, with the same ratio of then a higher Bromine content and a greater degree of halogenation is obtained as shown in Figure .3, A similar graph is obtained at 190C, (Figure 4) except that the Bromine curve is lower than at 140C* and the Chlorine curve is higher than at 140WC. In addition* the bromine content drops off at the end* indicating -sms replacement of Bromine atoms by Chlorine* i.e.* slightly too much Chlorine was used* Coal composition was obtained for the first time (Figure 5> 30 Hr*) by using* first of all* a larger Bromine excess {Ratio of 10*8 moles Bromine) * l.O'laole Cm' ~ ' ) second; approximately the amount of Chlorine calcu lated by Sa. (3), This was at 140C, A similar run at 190O'* (Figure 6) again, gave lower Bromine content and greater Chlorine content. Additional runs made at 140*0. with the calculated amount of Chlorine showed that the laboratory procedure was reproduci ble as seen in Table j l T* DUP050027969 -13- 5<$ Jk isV* o o~ <30 rS'/VO.IK DUP050027970 1CX10TOTHEC .M 353-14 C&L__ 1mt -14wm . cctoo **r. so oo X *o--*2 DUP050027971 Ho u r s *4 Cs? Q th DUP050027972 Ft "JJ iO X 10 TO THE CM. KtoFFEi, 4tssrft to. 35S -t4 *t:t t<* 1 10 X iO TO THE CM. 3 5 9 - ! 4 : KEUFFCL ESSKRCO. A DUP050027973 OUu -Mouths 3 to X TO T d T H E C M , 3 5 9 -1 4 K F U F F E L f t ESSEfj CO. *41?r * :' * A. 4i - ScrQ&r-v&'Ut'^fc''*'^ S/^OUV DUP050027974 JCi a t o T O T ^ fJ C M , K f U^fCU u CO DUP050027975 --3-9' V. PRESENT WORK (Cont^d) C, 1. Initial laboratory Development (Cont'd) TABLE IV REPRODUCXBILXTY OF EUTECTIC C OHALOGENATIOXi PROCESS label Bromine . Excess* Product Calc'd. Composition M.W. Rubout Quality TSC-S6-7A~30 Hr, 31$ TSC-86-11A-30 Hr. 31$ TSC-86-12A-28 Hr. 22$ TSC-86-I5A-28 Hr. 22$ (Suco-GA-48l8) CPC Bri2,2 Clp.p, 1634 CPC r12.9 Cil.,6 1659 CPC Bf129 cll,4 1652 c p c Bri2,9 Cl^g 1613 CPC Br12,0 cl2.6 1612 -- 125, Y30, B40 106, YX2, B30 -- 1Q0 | 1/ ^Excess over that needed to make CPC Brrg, Even higher Bromine contents than these could he prepared hy using larger Bromine excesses. When Bromine was added in greater than 100$ excess in a yon at l4oC, products were made with over .14 atoms of Bromine (GPC BrX4,,3 Clo,8) which were coneiderably Yellower than Suco GA-4ol8. At l30C v, lower Bromine contents were attained. The necessity for a source of copper was demon strated in eutectic cohalcgenation, Significant aluminum content resulted when no copper source was used: $ Cu $ Cu $ Found Theory A1 TSC-78-27B (No Cu Source) TSC-86-7A-30 Hr.(CuCla)* 33 3.4 4.2 0.4 3.89 <0.05 '''CuCls as Cu source s- 18$ weight of starting CFO Calculations show that this 0.4$ AX could account for 20$ of the metal in the phthalocyanine complex. This laboratory work was the basis' for the plant c chalogenations Runs 2. 3 and 4 at Chambers Works of Orehem. In runs 1 and 2, it was found that the lab process as described above could not be literally transcribed to the plant since considerably greater loss of elemental Bromine and Chlorine from the eutectic occurred than in the lab. (The plant equip ment has no condenser for condensation of Bromine as does the lab). For this reason., considerably larger amounts of elemental Bromine and Chlorine were used in Runs No. 3 and 4, resulting in goal composition. DUP050027976 V, f ,,i -20- BRESEHT WORK (Coat'd) c. i. Initial Laboratory Development (ContVd) Bold time on Runs Ho. 3 and 4 were., however, longer than desired, "being 44 and 40 hours, respectively. The laboratory process above was designed to be economical of Bromine, since it is an expensive ingredient (about 28 cents/lb.}. 2,. 115# Bromine Excess Process Additional laboratory work had indicated that if a greater excess of Bromine was used in the process, however, then the hold time could be substantially reduced, It was then a matter of obtaining the right balance between Bromine Excess and Reduced Bold Time to make the process most economical. At this time, the eutectic melt was changed slightly in composition in order to reduce vis cosity and to lower the melting point of the melt, A lower melting point was desired to help avoid plugging in the drowning leg from kettle to hydrolysis vat. This new melt contained the follow ing proportions; Aids, anh. mci KCl CuGl, anh. FeCl, antu CPC Crude 2,300 396 180 45 9 550 Pattrts n .if !? If Another change made was the use of HC1 in the hydrolysis water - which gave a little more intensity in the final solvent breached product. The laboratory cohalogenations using the larger excess of Bromine gave goal composition, and showed .reproducibility with Hold Time ranging from 21 to 32^hr, total, as shown in Table V. The ratio of Bromine/CPC in these experiments was about 4.8/1 by weight, which is a .115# excess of Bromine over the amount of Bromine needed when used up completely. This type of process is referred to as the 115# Bromine Excess Process, and is described, in Part B in the Appendix, DUP050027977 V. PRESENT WORK (Cont'd) C, 2, 115$ Bromine Excess Process (Cont'd) TABES COMPARISON OP OR}?,EM Y FROM 115$ BROMINE EXCESS - PROCESS Type $ Br Moles Cl?. c Eut. Excess mwiTm TSC-97-13-D -22-A -25"A TSC-106-1A -IB 150 140 l4o 140 165 A A B B B IIS 1.61 128 1.56 108 1.4 110 1.6 110 1.8 Time Hr.s, Atoms Br Cl Tot . Br si Total 18 3 21 13.82 0.54 2.3 2 25 13.2 0,7 25 4 29 13,6 0.6 25 5 30 13.7 0.8 25 7 32 13.7 1.4 1-4.4 13.9 14,2 14,5 15.1 A * Aida~KaC1-OuCl B i AICI3-RaCl-KCl-FeCl3 - C uCX The table shows that there is little difference resulting from the different types of eutectic melts. The higher temperatures can be used,, apparently, to obtain high degress of complete ness of halogenation without a correlative reduction in Broraine content. For this reason., the plant Runs 5, 6 and 7 were stipulated to be run at 150 5C, (vs. 140C for Runs 1,2,3 and 4), O Spectro Test for End-Point Determination on C ohalogenation -- -------.... ..... ... The determination of endpoint used for Plant cohalogenations Mo, 3 and 4 was primarily by visual comparison of shade of a hydrolyzed crude Breen Y slurry with the shade of a laboratory-made slurry containing a CPC Green of goal composition, Neither this method, nor the completeness test with. 90$ H2SO4 was very satisfactory. The visual comparisons were very difficult to make after enough halogenation had occurred to make the Change from blue to green, and the completeness test gave variable results. The latter does not, of course, relate Bromine and Chlorine content, but only total halogen. An alternative test v>as developed for Plant Runs Mo, 5, 6, and 7 which was called the "Spectro Test". This consisted in hydrolysing a sample of the eutectic into water,isolating the dry Green crude, dissolving it in eone:d, H2SO4 and determining the position of the absorption bands. When the maximum absorption band is shifted to that of a sample with the desired goal composition, then the eutectic melt is ready for lij.rclro3.ysis. DUP050027978 22V. PRESET WORK (Cont !4) C. 3. Spectro Test for End-Point Determination on If the spectrophotometer is of adequate resolution-> a doublet can be resolved. The position of the two peaks is related to Bromine content as is shown in the following table: TABLE VI Relationship of Position of Absorption BH3T'of^!aloi^rrWm"e^rn HsBG-i soluoxon with. Bromine vontent Label Time at Which Sample Taken - Hr, Eun#3s Sample #9 Run$2 s Sample #11 Run#3i Final . Presscake 37 42 44 Atoms Br O'2. 11.5 0-9 12.7 1,6 mT.n.'oiM.'tMa'Aa*l'- 12.4 14.3 y\ Min, A-Max 8l8 S57 831 876 12,9 1,6 14,5 334 879 Suco GA-4818. C//59461 12.0 2,5 14.5 833 880 This table shows that the A-min, and A max, rose continuously during the last part of Plant Bun Ho, 3. Operating directions for this"Spectro Test" were written up by J, R* McCarthy of Ponsol Control Lab, Chambers Works, The directions are given: "MOmSTRAL" GRBEH t t BP.OMZmTXOW OF CPC SPBCTRO TEST Hazards Ho unusual hazards. The plant will hydrolyze the sample (brominated CPC In AlCls-HaCl eutectic) and bring in an acidic slurry. The mixed slurry is acidic. Procedure 1, Set up a sintered glass funnel of "P" porosity on a suction flask. Use a coarse or medium porosity. 2, Filter about 10-15 ml. of slurry. 3, Wash the cake'with four 10-ml. portions of distilled water. 4, Wash the cake with a special .mixed solvent until the washings are practically colorless. {Directions: To make the mixed' solvent5 mix about 200 cc of 2 B alcohol with bout 200 cc of benzene. ,,. label: "Green Y Mixed Solvent; Plaamaole' ) DUP050027979 -23- f. PRESENT WORK (Cont'd) c. "Monastral1' green Y -- Brontination of CPC - Spect.ro Test -"Procedure' 1 Cont * 5, Mash once with about 10 ml acetone. 6, Suck dry, 7, Grind cake in a mortar, 8, Weigh accurately 16 milligrams (between 0.0155 and O.OI65 B-) into a 150 ml beaker, 9, Add about 75 ml cone. H3SO4. (reagent grade). Dissolve, 10. Transfer to a 100 ml Yol. flask and dilute to mark with cone, HsS0 - mix well. 11. Pipette exactly 5 ml of the above solution into another 100 ml Yol, flask and again dilute to the mark with cone. feSO*, 12. Label: "Monasiral Green Y in cone. HaSO* for Spectro, 13. Transport the sample promptly to the Infra-Red Boom in the New Elastomers Laboratory, Leave sample at the DY-2A instrument for Spectro Test by the Elastomers Laboratory personnel, 14. The Elastomers Laboratory personnel will provide a chart showing Absorbance. They will use gears to provide a scan covering 10 .millimicrons wavelength per cm. of paper. They will use tungsten light and lead sulfide detector. They will use 1 cm cells and scan the sample against a blank of cone. I-I2SO4, They will scan from 950 down to 750. They will save the scan for "Monastral" operating supervision. The most important observation is the wavelength at which there is a maximum peak. They will charge this work to IBM Code 4500 (Control Cost Code 2801). Attached to the Elastomer's Lab copy of this procedure is a sample scan made by"George O'Conner on June 15; 1965* The comparisons of absorption spectra of Green Y with Polyehlor-CPC and CPC Greens with intermediate Bromine contents are given in Section V - H (Compari son of Physical Properties of Green Y with the competitive Suco GA~4Sl8}. B. Details on Plant Cohalogsnatlons 1. Runs 1 and 2 wwwrowi mir i o.iry^wevr^o After laboratory cohalogenations had been shown to yield goal quality, two plant runs were made in February, I963J* at Chambers Works of the Organic .Chemicals Dpt. The equipment used was a 30O gal, glass-lined reactor with water Jet draft to elimi nate halogen fumes from the .area, a high stack with DUP050027980  24 V, PRESENT WORK (Cont*d) D. 1, Runs 1 aad 2 (Cont sd) steam injector, and a sampling port. These two runs were designed to reproduce the laboratory process (Table XV) using a 22$ Bromine excess . and an amount of Chlorine calculated by Eq. |Bj . More Bromine was used in Run 1 than in Run 2 because of an unintentional initial fast running into the kettle, in Run 1, of 200 lb. Bromine, a good deal of which was presumably not absorbed, and was swept out by the draft and lost. The details of these runs are given in Table VXi. The product compositions were not of goal quality. About one half of the Bromine used was recovered in the product, Bo Bromine could be detected in the eutectic melt at the end of the run. The rest of the Bromine which was used could only have been lost via the water Jet draft. The product from Run 2, when given a Hewport type solvent breaching was about as yellow in shade as Harmon's 0-5400 (CPC Br8.3 016.4); the product from Run 1 was considerably bluer. Cuprous chloride, in the ratio of 13$ of the weight of CPC, was used as the copper source in these plant runs, and proved effective in preventing replacement of copper by aluminum. The product on Run 2 analysed for 4.24$ Cu^ theory for CPC Brxo Oil.7 with mol. wt. 1493 is 4.25$ Cu. 2, Runs 3 and 4 These runs used more Bromine and/or Chlorine to compensate for some of the halogen loss during Runs 1 and 2, In addition, some changes were made in the equipment to reduce draft on the kettle and subsequent halogen loss. These runs were closely monitored by `'Completion1' tests and by visual com parison of hydrolyzed crude slurry color with similar laboratory slurries of goal composition crudes. The ''Completion" test, described in Appendix 0, depends on the depth of shade of a 90$ Ha-SQ*. solution of the eohalogen&ted green. A very faint shade of yellotr indicates the CPC molecule is com pletely halogenated,, This test is used to check completeness of chlorination in Orchem's regular eutectic CPC polyehlorin&tions. Goal composition (12 or more Bromine atoms and at least 14,5 total halogen atoms) was obtained in both runs 3 and 4, The Composition - Time curves and the Halogen Use Curves are given in Figures 7, 8 and 12, 13* Completion tests indicated complete DUP050027981 2-- 'b - V. PRESENT WORK (ContT d} D. 2. Runs 3 and 4 (Cont'd) halogenation was obtained before the desired shade was obtained. Run 3 save a test for complete halogenation at 40 hr., 20 min. and Bun 4 at 32 hr.* 23 min. Since the shade became progressively yellower and the Bromine content increased after the initial positive completion tests, some exchange of ring-attached Chlorine 'ey Bromine must have occurred, although the analyses are not sufficiently precise to measure this change. Analyses indicating sample composition are undoubtedly low compared to the actual formula. This is because of two reasons: 1) the analy tical procedure inherently entails some loss, and, 2} some impurities remain in the sample supplied for analysis, even after mixed-solvent washing. A prior: It is felt that when comple tion tests' are positive, then the halogen content must be 14.5 atoms of halogen or more. Large excesses of Bromine were used in Runs 3 and 4, viz., 137# and 180# excess over that calculated to be necessary for a polybrom-CPC. Since completion, tests were positive for some time, before the ends of the runs, ana the Bromine contents were greater than .12 Bromine atoms,it is seen, in retrospect, then somewhat less Bromine could have been used in each run to obtain goal composition { h 12 Br and 2.4.5 total halogen atoms). Thus in Run 3, a satisfactory product appears to have been made at least by 40 hours running time, which corresponds to a Bromine usage of 3.,830 lbs. and a Bromine excess of 88# over that needed for a polybrom-CPC. In Run 4, such a product appears to have been made by 325 hours, corresponding to a Bromine usage of 2,330 lbs. and a Bromine excess of l4l#. The percent excesses of total Halogen over theory (99# and 83# respectively""for Runs 3 and 4) do not appear too large for this type of operation. Hormal CPC chlorlnations at Chambers Works use 10 to 19 times the calculated amounts of Chlorine. As indicated elsewhere (Fart V - E) the quality of Runs 3 and 4, after 08B, was equal to 3# strong in strength, noticeably yellow, and, in the case of Lot Ho. 3 also slightly intense, when worked up in the lab. DUP050027983 -27- DUP050027984 HOURS ^ 4 -H A u c , m U S e u g .v i R________ u m Po u y g ^p ^- DUP050027985 Ho o k s HO US DUP050027986 Houp?s DUP050027987 DUP050027988 DUP050027989 DUP050027990 DUP050027991 KEUFFEU a E5 SCR C o DUP050027992 DUP050027993 f DUP050027994 KEUFTCLa f* 359*11 in c h <v5l * i i i jI LI Th *U 0H ** tAI ! i DUP050027995 / V/! DUP050027996 DUP050027997 cupteL &eCRco DUP050027998 PRESENT WORK (ConVd) D. 3., Runs 5j 6 and. 7 These runs were made in June, 1965, for the purposes of checking in the plant our 115$ Bromine Excess - Lab Process {see below) with reduced hold time and to make additional material for standardization. Runs No, 5 and 6 experienced difficulty with absorption of Bromine and Chlorine, This was because of malfunctioning of the tempera ture regulator* giving a considerably lower temp erature - 14 to 27C lower than called for (150C), One of the reasons for the mal-functioning was congealing of the oil in the thermocouple well. As a result of the lower temperature the viscosity of the melt was high* and because of this the efficiency of halogen absorption was reduced. The Halogen Use Curves for these Runs (Figures 9> 10., 11) show that very large Bromine excesses were used. Even with the large amount used in Run 5* the final material did not reach the desired /\max (Table TUI). The shape of the absorption curve itself at this time had become distorted from the usual (doublet) shape, showing a flattening. Since the.hold time had already been excessive by this time and the absorption curve was distorted, it was decided to hydrolyze, even though the A max. was not up to that desired (about 879 mu). This product, after lab-OSB (Orchem Type Solvent Breaching) was predictably quite blue vs, Suco GA-4318 (1800-33), Run 6 also had difficulties with temperature control and used excessive amounts of Bromine but the A.max, was finally brought up (at 51 hr. running time) to 879 mu and hydrolyzed, (Table IX). The lab-OSB material was 5$ strong but still somewhat blue and distinctly dull vs. Suco GA-4818 (l800~33). Apparently this lot was contaminated to some extent with Lot 5. In Run 7s the temperature controller worked nearly normal, although the temperature dropped off 10 toward the end of the run. The regulator was then set 10 high to account for this. The level of eutectic melt was also maintained higher in this Run 7 at a level 27" dry dip) to help ensure low viscosity and halogen absorption. The level was maintained by addition of Aids as needed as the run progressed. This Run 7 absorped both Bromine and Chlorine without difficulty as indi cated by the Halogen Use Curve (Figure 11) and the rapid rise of A max. to that desired - see Table X, The final lab-OSB material was about equal in strength to Suco GA~48i8, vs Yellow, vs. Intense. The masstone of this product was, however, light and similar to Suco, in contrast '43- PROCESS I - 115?* BROMIMS EXCESS Kettle clean and empty. Charge the following ingredients: Aluminum Chloride, anhydrous KaCl KC1 CuCl FeCls, anhydrous CPC Crude 2,300 lb. 396 lb. 180 lb. 45 lb. 9 lb. 550 lb. Heat to 170C,, hold 1/2 hr, or as long as necessary to fluidize the melt. Cool to 150C. + 5C. , hold and stir. Add Bromine------------- --------------*--^--2,680 lb. Through leg in 22 hr. Add Chlorine*---------- --134 lb. .,T>j Through leg in 3 hr, prepare hydrolysis tank with 1000 gal. water + 300 lb. concentrated hydrochloric acid. Drown charge into tank in one stage, stir 1 hr., filter, wash acid-free to Congo Red. Blow press dry and dump to Periaaplex containers. Approx. Yield - 1,500 lb. DUP050028000 -44~ TABLE VIII HUE HCL 5 - PROGRESSION OP ABSORPIIOH PEAKS WITH HALOGEN USE nple number 1 2 3 4 5 6 7 8 9 10 11 12 13 l4 esscake-- Lb.Bra 1450 2000. 2300 2617 2617 2987 .2987 3085 3213 3213 "3423 3483 3508 3508 M.m y <w Lb.Cla 0 0 0 0 130 130 ISO ISO 25O 290 290 290 353 427 ~mu - - *817 817 820 817 813 813 - 810 815 824 825 -826 >uoax." mu - 857 857 858 853 849 849 * 850 850 863 864 864 DUP050028001 -45- TABLE XX RUB NO. 6 - PROGRESSION OP ABSORPTION PEAKS WITH HALOGEN USE Sample Number 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 .16 17 Presscake--------- Lb.Bra 2100 2100 2100 2100 2100 2240 2400 2755 2910 3045 3045 3045 3245 3440 3440 3440 3440 Lb.Cla 0 100 240 330 420 420 420 420 420 420 540 600 600 600 600 720 840* 7\min.~mu 807 - 808 - 809 * 812' 814 819 820 822 824 823 829 833 ------ 835 Xmax.-1TM 844 846 - 846 - 846 848 858 860 863 865 866 873 879 879 TABLE X RUB BO. 7 - PROGRESSION OF ABSORPTION PEAKS WITH HALOGEN USE Sample Humber 1 2 3 4 5 6 7 Presscake------- Lb.Bra 1560 2000 2000 2000 2300 2300 2300 Lb.Cla 0 0 110 175 175 210 270 812 823 828 - 835 - ------ 836 7\fflax.~mu 852 864 869 - 883 ~ 883 DUP050028002 -46- V. PRESENT WORK (Cant'd) D. 3- Runs gj 6 and 7 (Coni'd) to those of Runs 5 and 6, 3 and 4, which were all very dark and transparent vs, Suco GA-4818. The hydrolyses of Run 5, 6 and 7 all took place in a minimum of time (about 20 min.-30 min.) with no plugging or other operating difficulties. A quantity of hydrochloric acid (cone.) equal to 1/2 of the weight of starting CPC crude \?as added to the hydrolysis water in order to improve intensity of the final products. The temperature rise was from 25-55C. during the hydrolysis for all three runs. The use of the Spectro Test for determining the end of the reaction appeared to be satisfactory for identifying the endpoint. An unavoidable time lag of 1.5-3 hours did occur between taking the sample and the appearance of the absorption curve, however, due to the time used for transporting the sample, making up the H2SO4 solution, etc. If a satisfactory endpoint was anticipated on a sample, then the flow of Bromine was cut down to a low level pending confirmation by the absorp tion curve. 4. Runs 8, 9> 10 and 11 These runs were cohalogenated in September, 1965. The 115/5 Bromine Excess process was used. In Run 8 difficulty was experienced with pluggage of the Bromine line resulting in erratic flows to the reactor. In two instances, after partial Bromine line plugs broke loose, excessive Bromine flows caused the eutectic melt-pigment mixtures to erupt, ''bump", out of the kettle. This was corrected by installing a catch pot in the Bromine line to collect extraneous matter. Runs 9 and 10 proceeded with no unusual diffi culties and could be considered typical of what could be done operation-wise without further process or equipment modification. During Run 11, the Dowtherm heater shut down and while repairs were in progress, the reactor temperature dropped. On reheating the charge ''bumped" . DUP050028003 -47- V. PRBSEKT WORK (Cant'd) D. 4. Rims 8, 9, 10 and 11 (Cont'd) The halogen use curves for Runs 8, 9, 10, and 11 are shorn in P'igures 14, 15, 16 and 17. All of the lots finished to the desired spectrophotometric endpoint at Chambers Works. 5* Runs 123 13, 14 and 15 - Standardization Run Runs 12, 13i 14 and 15 were cohalogenated at Chambers Works in January, 1966, according to Process I in the letter; W. E. Miller to J. W. Minnich, "Very Yellow Green CPC - Manu facture at Chambers Works", 4/15/64, (Appendix B) and as modified by the letter: W. E. Miller to P Dowd, "Monastral Past Green 4Y Crude - Spectrophotometric Absorption in Sulfuric Acid Solution", 12/27/65 (Appendix C). Runs 12, 13 and 15 were normal cohalogenatlons and finished at the desired spectrophotometric absorption peaks when the pigment was dissolved in sulfuric acid. The endpoint is a Amax. value between 878 and 882 m/- . At this Amax. value, the A min. should be between 835 and Q4o m /*-. On Run 14, however, Orchem could not go beyond a Amax. of 872 m^/- . All of the known ways to increase Bromine absorption were tried; i.e., adding aluminum chloride and heating to a higher temperature to obtain a thinner melt; adding chlorine and Bromine intermittently over an extended period of time. The 872 Amax. value could not be moved. The Amax. - Amin, va.ues, $ Bromine, $ Chlorine and rubout quality of the laboratory breached products are shown in Table I-WEM. TABLE I - WEM QUALITY - ORCHEM C OHALOGENATIONS Solv. Breached in Lab. Run Amax. / Amin. * % Rubout vs. GT-805-D Lot 00062 Ho. m M- Bromine Chlorine MT Str. Tint 12 880/835 13 880/834 14 872/830 15 880/835 64.02 63.74 62.99 63.74 2.18 2.15 2.86 2.15 V Dk25 V Dk40 V Dk50 V Dk30 95:100 95:100 93:100 97:100 Y14H0 Y10I15 B12I15 y 10sI7 DUP050028004 VO- V. PRESENT WORK (Cont:d) E Finishing - Particle Size Rerlu.ct on, and Adaptation it o ~e w t j s Ti w :t -------------------------- " 1. Initial Work on Newport-Type Solvent Breaching (NTSB) Laboratory Solvent Breechings (SB) of either lab or plant synthesised very yellow shade greens gave results in t'ne beginning very similar by rub out. This procedure for SB v/as the same as that which is used on Green G. vis... about a 1:1 ratio of ODGB to pigment and 3.5# Staybelite. On lab synthesized greens, this NTSB procedure gave products 10-40# weak vs. Suco GA-4Bi8; on the plant materials from Runs 3 and 4. the solvent breached products were 10-15# weak by rubout, and dull. In 30J alkyd these products were also 15-20# weak. 2. Changes in the Eutectic Melt a. Effect of Temperature Before Hydrolysis A eutectic melt of Aids, NaCl, KG1 and FeCl3 from a lab bnomination of CPC, containing a VYS Green of composition CPC Brig.6 Clp.6 was separated into three parts at different tempera tures, viz., 100, 150, 2G0C. Each part v/as hyd.ro3.yzed into water -I- HC1 -J- ice and then given a NTSB with ODGB. By rubout, the products became slightly stronger but also noticeably duller as temperature increased. (TSC-97-25) b. Reheating of a Eutectic Melt Before Hydrolysis The solid melt from the No. 4 Plant Run was reheated - first to 150C and second, to 300G. and then hydrolyzed into water, solvent breached (NTSB) and the products from the two temperatures compared. The 300C product was distinct stronger and bluer than the 150C product, indicating con siderable halogen exchange, which was confirmed by analysis: CPC Brig.5 CI0.9 ----CPC Brio.5 CI4.5 This product v/as not, however, more intense. The 150C product v/as also compared to that obtained by NTSB of the initial No. iJ Plant Presscake. This showed that considerable blueing off occurred ,just by letting the melt stand at room temperature and then heating to 150C. This was confirmed by analysis. (TSC-97-29) DUP050028005 -49- V. PRESET WORK (Cont'd) E. 3 Changes in Hydrolysis a. Temperature of Hydrolysis Water and Method of..Filtration Laboratory experiments changing the tempera ture of the hydrolysis water were made before Plant Runs Nos. 3 and 4. Three different condi tions were used: 1) Cold water (10C) with continuous hydrolysis. 2) Cold water (10C) with batch hydrolysis. 3) Hot water (70C) with batch hydrolysis. The continuous hydrolysis gave after KTSB, distinct dullness and a lightening of masstone; the use of hot water gave even more dullness. All hydrolyses from this point on were then made into cold x;ater with batch hydrolysis. (TSC-86-16, 17) b. Changes in the Hydrolysis Medium Another change in hydrolysis involved the use of HC1 in the hydrolysis water. The HC1 was added in order to ensure that no aluminum hydroxide precipitates upon hydrolysis of Aluminum Chloride. Wo particular strength difference was noted after NTSB betvreen hydrolysis with or without HC1 but the hydrolysis with HC1 gave aproduct which appeared slightly more intense. (TSC-97-13) A mixture of HQA.C and water (50/50) for hydrolysis showed no change after solvent breaching. An equal mixture of Methanol and water gave a product 6$ weak, and very dull. A mixture of Methanol, water and Arquad 16-29 gave an extremely weak product. (TSC-97-29) c. Use of Various Media (Water, water + ODCB, Water -f Methanol'etc. ) "for Hydrolysis of Sutectic Melt Containing fereen Y Changes in the hydrolysis medium from x^rater to mixtures of water and other solvents were made to see if quality improvements could be obtained. DUP050028006 -50- V. PRESENT WORK (Cont'd) E, 3. C. (Contd) The crudes were then isolated and used in NTSB, Table XI gives the changes and quality results when about 75^ of Green Y in eutectic melt is hydrolyzed: TABLE XI Effect of Changes in hydrolysis Tied'ia "on ^uS7^yr'of~^^iirx Label Hydrolysis Media R.0,, Quality TSC-97-29A TSC-97-29B TSC-97-29C TSC-97-29D TSC-97-29E 1 1. HsO + 65c c OJDCB -f- 20Cc HC1 600cc HaO + 600cc CH3OH + 20cc HC1 600cc HaO + 600cc HOAc + 20cc HC1 llOOcc HaO + lOOcc CH3OH + Arquad 16 4- 20c c HC1 1200CC Ha0 +. 20cc HC1 98, vs Dull 106, v s Dull 104, 200, dull 100(Control) This shows no particular advantage to any of the media and solvents used for hydrolysis of eutectic melt containing Green Y. (TSC-97-29) 4. Changes In Newport-Type Solvent Breaching a. Surfactants Other Than Staybelite The NTSB procedure currently used for Green 0 (N-764) stipulates about a one to one ratio of ODCB to green pitment and Staybelite in the amount 3.5% of pigment weight. Extensive testing of an anionic surfactant, G-3300, in place of all or part of the Staybelite Indicated there was no significant advantage over the use of Staybelite. (TSC-97-5) b. Solvents Other Than ODCB CCI4 in the amount of 87$ and 172^ of the 'weight of green pigment was used in place of the ODCB in NTSB, giving products extremely weak vs. the Control with ODCB. Benzene, in the amount of 70$ of pigment weight, also gave relative weak ness, although not as weak as with CCI4. (TSC-86-22, 28) DUP050028007 -51- V, PRESENT WORK (Coat'd) E. 4. b, (Cont'd) Use of nitrobenzene in place of ODCB gave a product slightly weaker and bluer, (TSC-97-25D) c * Optimization of Staybelite and ODCB Levels in UTSS..~ . " ~ Staybelite levels from 2$ to 12$ of pigment were used in. the WTSB of Run $4 Crude with the following resulting strengths; TABLE XII Optimum Staybelite_Le;vel in Newport Soft $ Rub- Alkyd Vinyl 30J Alkyd $ Sx Out 30J-Tints (15 Guts) Metallies CPC* 3A-1 2 110 110 3B-1 4 110 112 3C-1 6 111 117 3D-1 12 112 115 Suco GA- 4813 0-59411 100 100 170 l60 165 168 160 98 io4 100 104 100 93.6 94.0 93.8 92.0 95 *By mixed-solvent extraction. It appears, from the standpoint of strength alone, that, for 30J alkyd, minimum amounts of Sx (Staybelite) are preferred (2-3$). For soft vinyl, however, the maximum strengths appear to be reached at about.4$, ODCB levels from 65 to 172$ of pigment weight were used in Solvent-Breaching of a lab synthesized VYS Green crude at a level of 10$ Staybelite TABLE XIII Optimum ODCB Levels in.Solvent Breaching Label ODCB - $ of Pigment Weight Relative Strength TSC-86-22A-14 TSC-86-22A-.15 TSC-86-22A-16 TSC-86-22A-17 65 86 129 172 97 94 99 96 DUP050028008 -52 V* PBESEKET WORK (Cont'd) E. 4. c. (Cont *d) Shade remains unchanged hut the masstone depth becomes progressively lighter as more ODCB is used. The optimum ODCB level may be at about 86-100$ by weight of pigment. The rubout strength., however,, was still about 15$ less than Suco GA-4818. 5 Treatments After Hewport-Type Solvent Breaching a. Oxidizing Treatment with NaClOs Oxidizing treatments of CPC greens have been previously used to improve intensity. (PTC-oO-7). On solvent breached VYS Greens from lab and plant synthesis* a treatment with NaClOa and H2SO4 was found to improve intensity but gave weakness and a lighter masstone by rubout. In 30J alkyd, no particular effect on strength in tint was noted and the product was more intense, but the metallic was dis tinctly lighter. (TSC-86-12, 19) b. HgS.04 - Arquad 16 Treatment Hot acid extraction of the solvent breached VYS Greens {H2SO4 + Arquad 16 - about 2$ of pigment) was found to give 5-10$ increase in strength in 30J alkyd and more intensity in both tint and metallic* By rubout, however, the acid extracted products were slightly weaker. (TSC-97-5) An increase, to 5$ Arquad 16 later gave improvement in quality, as did also the use of 3$ Armac T, (TSC-97-28). Quality was still deficient vs. competitive Suco GA-4818. c. Antiflocculating Agents for Very Yellow Shade IWsTGriehs---- -t*-*-*-*^---------^-------------- --------- The impetus for the use of these agents arose from the observation that flocculation or a strength difference arose between the sprayed and poured sections of 30J alkyd paint panels when the solvent breached VYS Greens were DUP050028009 -53- V. PRESENT WORK (Cont'd) E. 5. e. (Cont'a) used. Since flocculation in CPC blues is ameliorated by use of CPC-AF or CPC-monosulfonate, similar types of green agents were investigated. The first agent investigated was a water-soluble dye from Orchem ~ Chambers Works called Pontamine Past Green PG (PPG). This is a Chlorinated CPC - tetrasulfonic acid, admixed with Sodium Pyrophosphate diluent, and is prepared by chlorination of CPC - tetrasulfonic acid in a AlCl3-KG:l-NaCl eutectic melt. PPG was wet blended with solvent breached VYS Greens from Plant Runs #3 and #4 at levels of 5 to 10$. The agent was precipitated on the VYS Green by the addition of Calcium ion in neutral solution. On both of the VYS Greens, PFG gave noticeable improvement in strength (4-10$) of flocculation resistance and slightly more intensity in alkyd tint compared to controls without PPG. The metallies become slightly duller. No overstripe bleed could be seen with 10$ PPG. in comparison with Suco GA-4818 these products were, however, still some 3-10$ weak. There is no doubt about the improvement in flocculation resistance brought about by PPG. Since it itself is a VYS Green - much yellower than regular Green G - it does not materially detract from the shade of the hrominated VYS CPC Greens. Light fastness results on the PPG treated products is not yet available. A serious obstacle to its use is its price, quoted by Orchem at $50/lb. It appears to be an experi mental product, and is made by Orchem for only one customer, Procter & Gamble. (TSC-97-14, 16) Other Anti-Flocculating Agents No other suitable agents are available commercially. It was therefore necessary to synthesize such agents ourselves. As starting materials, there are available from Orchem (A) CPC ~ monosulfonate (CPC-MS); (B) Pontamine Past Turquoise 8 GL, which is CPC(S03H)2.535 and (C) CPC ~ tetrasulfonic acid. The correspond ing halogenated agents should be available by halogenation in eutectic melt. The halogenation of (A), (B) and (C) could be done in a manner similar to that used for PFG to give a product of suitable shade, and then the halogenated DUP050028010 V (' \i -54- PRESENT WORK (Cont'd) E. 5. c* Other Anti-FIpeculating Agents (Cont*d) agent could be blended with VYS Green. Alternately, a mixture of CPC crude 4either (A), (B) or (C) could be itself halogenated to a VYS Green. 6. Alternate Methods of Particle Size Reduction Various methods for particle size reduction of Green Y crudes were used in the lab, e.g., dispersion milling, acetone milling and acid swelling. Dispersion milling and acetone milling of Green Y Crude, Lot Wo. 3 gave products which were weaker in tint in 30J Alkyd, and also duller than the corresponding WTSB products. Flocculation resistance of both dispersion milled and acetone milled products were equally as poor as the NTSB products. By rubout, the acetone milled products were a little stronger than the NTSB products but were dull. (TSC-97-7) Acid swelling of pulverized Green Y crudes was done with mixtures of conesd. H3SO4 and Oleum, the ratio of cone *d. HaSO* to Oleum depending upon the particular Green Y crude used* The acid swelled products were much yellower and much duller than the corresponding NTSB products. The particles of acid swelled Green Y showed long transparent crystals, which, in a paint grind, break up, giving bluer shades, Strength of the acid swelled products varied from equality with the NTSB products to very weak. (TSG-97-1, 3> 4) 7, Brominatlon of a Purified CPC Blue In order to see if the dullness of the Green Y was due to impurities in the starting CPC crude, our Newport LC crude was extensively purified by solvent washing and acid and alkaline extraction before brominatlon. After brominatlon to goal composition (CPC Br^ 2 C11 34) and & NTSB, the quality was compared io a similar product from unpurified CPC crude. The comparison showed that the purified crude did not give a more intense Green Y but, on the contrary, gave a distinctly duller and weaker product. An explanation of these results may be that the impurities act in the eutectic melt to keep pigmentary particles (TSC-105-4) DUP050028011 V, PRESENT w o r k (Cont'd) E. 8. The Use of Orchem's Solvent Breaching (QSB) a. Initial Results The solvent breaching done at Chambers Works differs from that done at Newport i-n a number of respects, including the use of 2-ethoxyethanol, the use of stearic acid In place of "Staybelite", the use of an ODCB reflux period and the fact that particular attention is paid to obtain minimum water content in the slurry. This process, applied to Green Y crudes, gave for the first time, products stronger than Suco GA-481S competi tive in strength. In 30J Alkyd this product was, however, still weak vs. Suco GA-48l8, apparently as a result of poorer flocculation resistance. b. Peroxides From 2-Sthoxyethanol A question has been raised on the nature of hazard to be expected in the possible formation of peroxides from 2-ethoxyethanol during the Orchem Type solvent breaching. Even though Orchem at Chambers Works has had long experi ence with 2-ethoxyethanol in solvent breaching, it was still considered desirable to check for the presence of peroxides formed during solvent breaching. For this purpose,, a number of solvent breachings using 2-ethoxyethanol were mad:and the filtered liquid media tested. Analytical methods were tried titrating with permanganate the usual method for determining peroxide. Howeven, it was found that the 2-ethoxyethanol itself consumed permanganate also. Vapor-phase Chroma tography (VFC) was then used. In this test, 2-ethoxyethanol was heated with caustic and HaOa in solution. When this solution was checked by VPG, peaks were identified for air, water and 2-ethoxyethanol but no foreign peaks were present, indicating the absence of any peroxide of 2-ethoxyethanol. The temperature of the column (LAC-247) used for VPG was 150C, which might cause breakdown of the peroxide of 2-ethoxyethanol, but since there -were no foreign peaks at all (corresponding to breakdown products of the peroxide of 2-ethoxyethanol) and no peak for oxygen was present, it is concluded that formation of the peroxide of 2-ethoxyethanol in the system of water, caustic and 2-ethoxyethanol used for the Orchem-Type solvent breaching is extremely improbable. (1800-32) DUP050028012 -56- V. PRESBHT WORK (Cant'd) . 9* Treatments Subsequent to OSB for Paint and Plastics a. Flocculation Problem in Paint Various treatments of the Green Y obtained by OSB were tried to improve flocculation resistance in 30J Alkyd. These included pre cipitation of the calcium salt of Pontamine Fast Green~PG, precipitation of 3$ Aluminum Blancolate or from 5-10$ Aluminum Benzoate (AlBz). The optimum treatment for 30J Alkyd was found to be precipitation of 5$ Aluminum Benzoate, giving a product 10$ strong, better in flocculation resistance, slightly yellow and equal in intensity vs. Suco GA-4818, This product was also the one which gave the best performance in the Universal Vehicle (Bennett Co.). At this time, however, it was noted that new vehicles urere being used in automotive use, e.g., 32J Acrylic and High Gloss Lucite (HGL). In these vehicles the 5$ AlBz product showed poorer behaviour relative to Suco GA-4818 than in 30J Alkyd, Pontamine Fast Green PG and Aluminum Blancolate were also ineffective in 32J and HGL. For these vehicles, additional changes were made necessary. Use of Derivatives of Benzoic Acid Instead of AlBz, various metal salts of benzoic acid derivatives were used, e.g.. Aluminum and Barium salts of the following derivatives: TABLE XIV Benzoic Acid Derivatives Used For Flocculation Resistance in 32J and HGL A p-tert'rbutyl benzoic acid B p-toluene-sulfonic acid C Trimellitic Acid D Xylene-sulfonic acid E o-phthalic acid F Salicylic acid G p-amino benzoic acid H Tere-phthalic acid DUP050028013 -57- V. PRESENT WORK (Cont'd) E 9* a, Use of Derivatives of Benzoic Acid (Cont'd) The Barium salts were used in those cases where the Aluminum salts were too soluble., e.g., B, G, D, E, F, G. Of these salts, the Ba salt of Trimellitie Acid (BaTM) and Xylene Sulfonic Acid gave the most significant improvement in flocculation resistance at levels of about 3$ of the pigment. It was later found, in treatment of the Plant-Breached slurry of Green Y for paint use, that Aluminum Benzoate at a low level - about 2$ - gave products comparable in flocculation resistance to those made with the Aluminum or Barium salts of benzoic acid derivatives listed above. Changes in OSB to Improve Performance in 32J and HGL Flocculation resistance and/or strength was also improved by changing the Orchem Type of Solvent Breaching. Staybelite was substituted for Stearic acid and the amount of 2-ethoxyethanol solvent was increased to one and one-half times the usual amount. These changes made the solvent-breached slurry slow to filter, however, and for this reason an acid treatment was added onto the solvent breaching after the distillation, and before filtration. At this time the surfactant Emcol P-10-59 was also used in a heat development along with the acid (HaSO^) treatment. This slurry filtered satisfactorily. b. Treatments for Plastics (Vinyl) The dispersibility in soft vinyl was checked by the 5 cut vs. 15 cut dispersibility test. The first lab products made by the OSB and finishing on the alkaline side were slightly better than Suco GA-4818 in dispersibility and strength, A simple switching from alkaline to strongly acid (with H2SO4) before filtration gave poor dispersi bility, but if surfactants such as N-Methyl-2Pyrroiidone or Emcol P-10-59 are also used along with the acid in a heat treatment, then dispersi bility is markedly improved. Striking of Calcium Staybelite or Aluminum Benzoate bn the OSB-Aeidtreated slurry also gave products of much better dispersibility than Suco GA-4818, (106-21, 42, 43) laboratory striking of the OSB-acid treated slurry (Plant run - XOP-295) showed that good dispersi bility was obtained. DUP050028014 -58- V. PRESENT WORK (Gont'd) E, 9* b, Treatments for Plastics (Vinyl') (Cont'd) TABLE XV Products for Vinyl Made from Green Y Slurry Precipitant 2% AlBz 4# CaSx (Suco GA-4818) (XOP-295) Relative Strengths 5 Cut 15 Cut Predispersed 100 75 100 105 85 102 300 100 100 As will be described later* the method of pulverization of the final* dry* pigment has a great effect on dispersibility in vinyl* e.g. * high speed pulverization gives.a more dispersi ble product than low speed pulverization. (180Q-1* 19) F. Relationship of Composition to Quality of Green Y Bromine atoms are considerably larger than chlorine atoms and steric considerations are more important when Bromine is attached to CFG than when Chlorine is. Mole cular models of polybrom-CPC cannot be easily constructed. Substitution of bromine atoms in adjacent positions on the CPC tend to distort the bromine atoms from the plane of the CPC ring with consequent interruption of resonance interactions. The greatest amount of distortion would take place when the last bromine atom is placed on the CPC ring to make polybrom-CPC. The suggestion has thus been made that the fully halogenated CPC molecule may accommodate 12 bromine atoms without undue steric hind rance if the rest of the positions are taken up with chlorine atoms. Substitution with more than 12 bromine atoms was suggested to lead to greatly increased dullness and a disproportionate loss of strength in comparison with molecular weight, In order to test this idea, it was necessary to pre pare products of lower bromine contents in a way similar to that in which the plant eohalogenations. Lot No. 3 and Lot No, 4 were made. This was done by reintroducing Lot No. 3 crude Green V into a A1C13-NaCl-CuCl eutectic melt and passing in a calculated amount of chlorine. This gave products of composition close to that of the competitive Suco GA-4818. These crude slurries were then given an QSB (with 2-ethoxyethanol) with final quality as shown in the following Table. DUP050028015 -39V. PHESEM1 WORK (Cont3d) P, Relationship of Composition to Quality of Green Y (Cont'd) TABLE XVI Relationship off Composition to Quality of Green Y Label Sueo GA 48l8 TSC-106-14-2 TSC-106-14-1 Lot No. 3, Green Y Lot. No, 4, Green Y Composition CPC Br12.0 C12.6 GW Bri2.o CI2.6 CPC Bi'12.5 els,4 CPC Bri2,9 CI1.6 CPC Br13^ CI0.9 Str. Shade Int. Mol. Wt 100 Control Control 100 Y6 101 Y4 Bio % IS!! 1611 1655 102 - D5 1659 102 Y6 % 1690 These results show only a very slight trend in strength, which is apparently directly proportional to change in molecular weight. Another comparison was made of compositions slightly lower in bromine content by acid pasting from warm fuming sulfuric acid solutions of the Greens. An apparent strength difference of 19$ was found between CPC Brxi.6 CI3,3 (Strength 91) and CPC Bri2.9 CI1.6 (Strength 112), However, this last product was 12$ weak vs, Sueo GA 48l8 whereas by OSB it was equal in strength, so that the method of finishing has an influence. Also it was later found l^aat Green Y decomposes in heated sulfuric acid solutions, so that this later com parison does not appear to hold. It may be concluded that, at least within the indicated range of bromine content - from 12 to 13,6 that composition has little effect on strength, shade or intensity, G. Plant Solvent Breaching by O.S,,B. of Green Y Crude wrmn------ The modified type of Orchem3s Solvent Breaching developed in the lab to optimize performance in end use systems such as 321 and high gloss Lucite was used in the Newport Plant on Green Y, Lot No, 3, under X0P-295. Some equipment changes were made to the still to permit relaxing. A sulfuric acid extraction was used preceding the breaching in order to bring intensity up to the maximum. Quantities used in the breaching were as follows? Green Y (dry) Water (from presscake) 2-Ethoxyethanol Caustic (N-7) 1,000 lb. 2,110 lb. 525 lb. 15 Gal. Staybelite solution? 35 lb. Staybelite in 62.4 gal. ODCB DUP050028016 60PRESENT WORK (Cont'd) G. Plant Solvent Breaching by OSB of Green Y Crudey (Contfd) The extraction with sulfuric acid subsequent to breaching used: 565 lb. 93$ H2SO4 48 lb. Emcol P-10-59 1,230 gal, Water Only minor operating difficulties were present during the breaching. Some contamination with Green B occurred during the transfer from still to extraction tan!? - probably as a result of contamination in the lines. This caused the product to be considerably bluer and duller than the corresponding lab product. Rubout strengths however, was equivalent to the lab product, and was 3-4$ strong vs. Suco GA--4S18, G# 64-706. Solvent Breaching - Lots 4, 5, 6, & 7 Rubout quality after solvent breaching Lots 4 (crude stock on hand from previous campaign), 5, 6, and 7 in the laboratory and in the plant is shown in Table WEM--1 and Table WEM-2, respectively. TABLE - WEM-1 Laboratory Solvent Breachlngs Rubout vs. Suco GA~4Sl8 C# 64706 Lot 4 Dk2o Lot 5 Bk80 Lot 6 vDk50 Lot 7 Lt^Q 97:100 Y3 X3 75:100 vB .101:100 v B2Qv D20 105:100 YiovsD^ Rubout vs GT-S05-I), Lot 00062 Lot 4 vLt25 Lot 5 vDkjo Lot 6 vDkgo Lot 7 vLt50 102:100 85:100 104:100 102:100 Yi4Il2 VB50 sBy vsltj vY22vli8 TABLE - WEM-2 Plant Solvent Breachings Rubout vs. Suco GA-4818 C# 64706 Lot 4 Lot 5 Lot 6 Lot 7 Dk99Dcic) DkuDu DligcjlLs 170:100 150:100 99:100 109:100 D99 D29 YixD^ DUP050028017 -61- V. BRESEHE WORK (Cont'd) G, Solvent Breaching - Lots 4, 5S 6, & ? (Cont'd) The cause of the poor plant solvent breached quality was not Known although it appeared to be a texture problem: 1. e,, the rubout strength of the weak lots could be improved by increasing the number of mulls on the Hoover Muller. By re-extracting the weak lots in the laboratory the quality could be brought into line (Table - HEM-3). TABLE - HEM-3 Lab Re-extraction of Plant Solvent Breachlngs Rubout ys, Suco <JA-48l8 C# 64706 Lot 4 Dried "As Is" Lot 4 Filtered and Washed Lot 4 Water Extr. 85-95C Lot 4 Water Extr. 85-95C, KHs Wash Lot 4 H2S04 Extr. 85-95C, Water Wash vDkto 170:100 130:100 109:100 100:100 107:100 Y12D12 vDi8 Lot 7 Dried "As Is" Lot 7 Water Wash, Ms Wash Lot 7 Water Extr, 85-950, NHa Wash Lot 7 NaOH Extr. 85-99V, Water Wash Dkio Dfcpo Dkx8 Dki8 106:100 104:100 100:100 100:100 Y8 D8 Y6 D8 Y8 D8 Y12D10 In addition, laboratory finishing of the plant solvent breached material in the laboratory corrected the weakness (Table - WEM-4). TABLE - WEM-4 Lab Finishing of Plant Solvent Breached Product Rubout vs. GT-SOS-D* Lot 00062 Lot 4 Lot 5 Lot 6 vLtgo vDk^Q vDk20 100:100 Str. 100:100 Y10D10 B Y6 D6 Lot 7 vLt35 106:100 Y15X12 It was decided to finish the lots "as is" at Newark, {See Newark Finishing of Lot 4* 6, 8a 7 - page 70 }. DUP050028018 ~y~ V., PRESET WORK (Cont>d) G. Solvent Breaching Lots 8, 9? 10 & XX (Cont8d) (KEoraisoryj'". Lots 8s 9 und 10 v/ere weak and all four lots were dull via laboratory solvent breaching and rubout. Pre-extractions5 premilling,, and variations in the solvent breaching procedure were tried to improve the quality. The two most potent changes were made in solvent breaching. Increasing the 2-ethoxyethanol made a considerable improvement in strength. Increasing both the 2-ethoxyethanol and o-dichloro benzene in proportion to the water in the presscake produced the strongest product. Wo way was found to significantly reduce the dullness. TABLE - WBM-5 Green Y - Solvent Breaching Variations Lot Procedure 8 Standard 8 Increase 2-ethoxyetlianol 8 Incr. 2-ethoxy, -f 0DCB/H20 9 Standard 9 Increase 2-ethoxyethanol 9 Incr. 2-ethoxy + ODCB/HaO 10 Standard 10 Increase 2-ethoxyethanol 10 Incr. 2-ethoxy + ODCB/HaO 11 Standard ii Increase 2-ethoxyethanol ii Incr. 2-ethoxy -F ODCB/HaO Rubout vs. GT-805-D Lot 00062 vDkc^Q vDkSo vDk45 vDkifO vDkgo vsDk5 DIC55 Dkgo t>k3o 0k35 Dk40 Dkio 118:100 105:100 97:100 108:100 103:100 93:100 109:100 97:100 96:100 98:100 96:100 92:100 VD25 YlkDi7 Yl60l4 Y18O17 sY8 Dio y12D12 B20D30 B20D22 I18D17 B15D18 B15D9 B10D12 Composite samples of Lots 8,, 9^ 10 and 11 finished by the above breaching procedures were evaluated in 32J. Results showed the products to be better in trans- parency3 essentially equal in "flip-flop"., but weak and dull in tint compared to GT-805-P Lot 00062. Initial tests at Chestnut Run indicated that quality could be significantly varied by changing milling condi tions but subsequent extensive testing has proved other wise. There is some improvement in gloss and strength with increased milling time but no more than would be expected with other pigments. There were no significant changes due to variation in pigment/binder or pigment/ solvent ratios, DUP050028019  o3~ ,V. ERESENT WORK (Cont'd) G. Solvent Breaching Lots 6, 9 .10 & 11 (plant) The crude lots were combined in equal proportions to make three solvent Preachings In the Preachings3 both the 2-ethoxyethanol and the o-dichlorobensene were Increased in proportion to the water in the presscake (26l lbs. 2-ethoxyethanol and 339 lbs, ODCB per 1*000 lbs. of water). The first batch was 1*000 pounds. The last two breachings were made at double the standard batch size or 2*000 pounds with no operating difficulties. TABLE - WEM-6 Plant Solvent Breachings Eiibout v.s, GT^-805-Ds Lot 00062 Lot 8 Lot 9 Lot 10 Dk99B99 Bk99B29 Dk99B29 92:100 86:100 89:100 B15B29 B10D99 B99 Plant breached vs. laboratory breaches indicated approximately 15 points of blueness and dullness picked up during plant solvent breaching. Solvent Breaching Lots 12? 13 14 & 15 - Standardization The four Orchem cohalogenatlons were combined into three 2*000 lb, solvent breachings at Newport. Batches 11* 12 and 13, The breachings were run using 150$ 2~ethoxyethanol {785 lbs. 2-ethoxyethanol per 1*000 lbs. of dry pigment) and o-dichlorobenzene based on the amount of water in the presscake (339 lbs. o-dichlorobenzene per 1*000 lbs, of water), Newport yield and quality results are shown in Table - WEM-7. H. Newark Finishing of Green Y* Lot No. 3 (Semi-Works) The plant Solvent-Breached (0SB) Green Y* Lot No. 3 was checked in the lab for optimum finishing treatments* based on previous work on lab solvent-breached (OSB) Green Y. These results are given in Table XVII and Table XVIII. The best results in 32J acrylic were obtained by treatments with 2$ Emcol P-10-59 + H2SO4 + A and with 3$ Barium Trimellitate (BaTM), Best results in vinyl plastic were obtained with a finishing treatment with 2% Aluminum Benzoate , DUP050028020 YIELD AMD QUALITY AFTER SOLVENT BREACHING AT NEWPORT- AIoooSL o\o\ HCCOMM HCOCVMJ p mm PoSi f3it 0* IP 0X00I1 oroH ooHfr CI'M-VION oOvVeCnn %% 0\0\ Xp Xp vo in cncn .>R. ww oin H J-l Tta) _Pp WX rmOH TJ rH . QH> X OVO0CVX0) ` rcHncrHn CM * VO co Hin HoinXto oorH oorH cHoAQoCico4nMnvvcAHPeiiCocnniMnn CM X coco CO CM a*}-VO1 oo "6-4 HN- XvXXX XX oO QO H X* MCcCcMnMn HOccCnMn XpconvXecnn co in n Xcn Xo XH X VO VO o C0M\0CVO p * 00 ' co xin ocn CcMn* CcMn CM VO cn P . ss P& r-Ii TinS ^ COO -H m=j- cn cncn co in VO XH vo in CM: CO VO r-l COCO wPtOoCPs o c3n- i aj +3 T\0 O O pJ; m& rl S3; oo oo x- CO aj<XmH XX mn VO x-x- X Xr CM xXX CO o X-CO *? CM VO CO CM CO X in CO CO x in co 30 XH cn co H VO VO P co co oo oo men ft pp in o CM H X- H <a m CM CM HH HH Pffl P fe: S: covo LfSO CHO H nccnn H t XfH aj- Olin -Hi- nf|cHn H ^ H1OI0 T>tHoJ CO* CM no men CO W COUOi -P OinPin iCnM co incM 4 NCM-OCO OO CinM cvoo in h Ps 3 xol fCiJi pto 6os* ar-fl inn' o on cHm Hm tn^j- H CO CO VO H -H0o=}V\ cn*cM. cCoM OCO oo no n ft xCM cJ--oI nrH >a CoO mm X3 a o 'x H rH CM rH XCO | i i DUP050028021 -65- TABLE XVII PERFORMANCE Off PLANT SOLVENT BREACHED GREEK Y IK 32J - 24 HR. TINTS* Treatment None Ca-H* (pH9) 2$ CaSx (pH 9} kfo CaSx (pH 10) 2fo AlBs (pH 3) 2fa BaXS (pH 9) 4$ BaXS (pH 10) BaXS (pH 9) 2$ BaSx + BaXS (pH 9) 3fo BaBl (pH 4) Sfo BaBl (pH 4} 2% Emcol P-10-59 -2- ifeSO* .+ A 3% BaXS (pH 4,5) y? BaTM (pH 4, 5) 3% BaSal (pH 4,5) 3% Ba Gyanamer (pH 6) 8$ Ba Cyanamor (pH 6} Homogenization -f HaSO^ Homogenisation + Ca+4` (pH 9} Homogenization -f 2% CaSx (pH 9) Homogenization + 4$ BaXS (pH 10) Homogenisation Jr 5$ AlBs (pH 3) Sue GA 4818, #64706 Spray Sir, 120 115 107 115 115 108 118 120 115 115 125 95 103 95 112 118 125 106 10? 108 105 107 100 Floe. Res. 11 11 11 11 12 11 11 11 9 9 10 8 3 10 12 11 11 11 12 12 9 11 14 Shade b io BO B5 - B8 Bo B9 b8 B9 - = B B Bio %0 B10 B4 B8 i1 Int, BlO DO D5 D8 d8 d9 d8 d9 ~ D10 D10 D D D5 Q5 d5 H4 D8 vl' *GaSx = Calcium Staybelite., Albs BaXS = Barium Xylene Sulfonate BaBl = Barium Blacolate, BaTM BaSal = Barium Salicylate = Aluminum Benzoate, Barium Trimellitates Vj DUP050028022 TABLE XVIII PERFORMANCE OF PLANT BREACHED GREEK Y IN Vim Treatment Ca++ (pH 9) 2/o CaSx (PH 9) 4-/o CaSx (PH 10) 2Jo A1B3 (pH 3) Homog, + 5Jo AlBs (pH 3) 4$ BaXS (PH 9) None Saco GA 48l8 5 C7f64706 dtrenftca 5 Cutis 13 Oats Predispersed 120 80 * 110 90 102 105 85 102 100 75 100 110 SO 104 ISO 90 - 130 90 - 300 100 100 DUP050028023 -67. V. PRESENT WORK (ConVd) H, Newark Finishing of Green Y, Lot No, 3 {Serai-Works) (Cont*d) Two semi-works finishings of the solvent-breached (OSB) Green Y were made. Semi-works finishing was preferred at this time because of the limited amount of Green Y (N-9^9) available but primarily to avoid contamination with regular Green B or Green G or CPC Blue which is likely to occur in the plant. The first used a treatment with 2$ Emcol + HaSO^, and heat* giving a product coded GT-804-D* Lot 00061* designed for use in paint. This run of about 200 pounds showed no operating difficulties except that a too rapid steam sparging gave some foam overflow. A low speed pulverization in the 8" semi-works mill was used. The second finishing was with 2% Aluminum Benzoate giving a product coded GT-305-D* Lot 00062-R* designed for use in plastics. This run of about 164 pounds yield showed no operating difficulties. This product was pulverized lot; speed in the 8" semi-works mill* but was improved by a repulverization* giving signifi cantly improved dispersibility in vinyl. Quality of Semi-Works Finished Green Y Paint In 32J acrylic with 24 hr. grinds* quality was as follows; TABLE XIX Tints ITT"" Str. Res. Shade Int. GT-304, Lot 0006l 100 GT-805* Lot OOO62-R 110 12 Btj 12 B5 D4 D5 Suco GA48i 8* C#64706 100 14 nJ/ J/ 10/90 Met, Flip Sh. Flop Eq. Better Dkg Eq. Better Eq. "jk v si/ 50/50 Met. Over- Stripe Bleed I3 98 None None 100 None DUP050028024 gm -68- TABLE XIX (Cont'd) In High Gloss Lucite - 24 Hr. Grinds GT-804, Lot.00061 Tints FI, Str. Res. Shade Iht, 10/90 Metallic Flip Sh, Flop< 1iw'iimimdw Bep, 102 11 Bi(. D4 Bl Better Dk2 50/50 Metalllcs "Flip Sh. Int, nNaW-w^ma> Str, >waiKK>inpuy Flop Bi I3 98 Better GT-.805, Lot 00062* 100 11 B4 D4 Suco GA48i 8, C# 64706 100 14 4' '4'' ^Pulverized Only Once. Bl Better Dkg 4" V B1 h v* 98 Better 100 In general, in paint 5 the tints are a little on the weak side but the metalllcs, especially the high metallics, are not weak and give better flip-flop than Suca GA 48l8. The intensity in metallies is also good compared to Suco* but not in tint. An outdoor exposure series to test durability of Green Y in 32J and High Gloss Lucite has been started. Previous tests were in 30<I vehicle and indicated "Monastral" type lightfastness at 12 months exposure. Vinyl Plastie III! I Willi > -- --W*. The results of the Ease of Dispersion test and Migration test are as follows 5 TABLE XX 5 15 PreCuts Cuts dispersed Migration GT-304-D, Lot OOO6I 325 110 .102 Hone GT-305-0, Lot 00062-R 290 85 104 None Suco GA 4318, Cy 64/06 300 100 100 Hone This shows the improved dispersibility of GT-805-D over GT-804-D. The re pulverization of Lot 00062-R was necessary to improve dispersibility in vinyl although no change was evident by a rubout dispersibility test. The method of pulverization., i.e. mill size and speed, was found to greatly influence dispersibility as shown by the following Table. DUP050028025 -69- V. PRESENT WORK (Cant'd) TABLE EXI Method of Strength Pulverization 5 Guts 15 Oats Pred. Suco GA4813 300 100 100 Lot 00061 8" RS 325 110 102 Lot 00062-H 8" RS 300 100 102 Lot 00062-R Lot 00062-R 8W R8 (Twice)290 5" RS 290 85 104 80 102 Lot 00062-R 5" HS 200 75 103 Best results v;ere with the 5" mill at High Speed (HS) but this size mill cannot be used except for very small samples. Future lots of the code for plastics., GT-805"Ds will be pulverised once at high speed. Quality of C-T~805-D, Lot 00062-R, for plastics was significantly poorer than the corresponding laboratory product (lSOO -IE). "This difference was not only the result of a different pulverization {8" RS Bill for semi-works material vs. 5" HS mill for the lab product) since a similar pulverization of the semi-works dry, lump, material in the 5" BS mill did not bring quality up to that of the lab product. Ho explanation was immediately evident for this difference. Different drying temperatures have been checked in the lab, but this does not appear to be the explanation. Samples of GT-8o4-D, Lot 00051 and GT-805-D, Lot 00062-H were sent to Chestnut Run for their evaluation in May, 1965- {iSoo-l, 12, 19) Preliminary reports have indicated that GT-805-D is preferred for both paint and. plastics over GT-804-D,, Aluminum Benzoate Lake of Green Y for F&F A 2 Eg, sample of a product (labelled 1800-19G) was sent to Chesnut Run for testing and sampling to F&F in May, 1969. The lake may be preferable to the toner for their use to avoid any ''plating out" problem in their circulating system for "Lucite" acrylic resins. This product was made in an analogous way to GL~76l~D and analyzes for a 42.9$ toner content. DUP050028026 -70- v* b b s s b n t v o s k (contM) H. Newark Finishing of Lots 4, 6 & 7 (Plant) Ba.sed on the lab finishing results, lots 4' and 7 and Lot 6 and the Balance of Lot 3, were combined and finished at Newark as GT-805-D, The quality results are shorn in Table - 3H-8 TABLE - WEK-8 Plant Finishing as GT-805-B iiiHiirn<ifHiiriiriiT~-r|-i`i" irirrirnii--rin~nTimn nr^iiln n iiiii i' larniWum.l ~HTiirM,-|VHl,iitTntrtt GT-805-D 36743 (Lots km) vs, ffiC-805-3>, lot 00062: By Bubout: Lt^g 118:100 ^igPlB 32Ji 115:100 D39 GT-805 36765 (Bal-. Lot 3 & Lot 6) vs. GW-805-D* Lot 00062; By Bubout: B^YlOBlO 104:100 XJ15 32Jj 108:100 B29 <3T-.805-D, Lot 36743 and Lot 36765 were inferior to the semi-works standard., Lot 00062, In 32J, both plant lots showed evidence of flocculation with Lot 36743 being the worst. Tinting strength of the plant lots as 50-50 metallies was also weaker. All four lots of 1-949 used in making the plant finished GT-S05-L smelled strongly of CDOB. Lot M of N-949s which appeared to be the worst, contained 9% 0DC3 bn a CFG basis. Previous laboratory work indicated that this can have an adverse affect on quality. Based on reboot results, GT-805-0 appeared to be a very hard textured pigment. To determine if this was a factor in the weakness of the plant lots, a miniraum-meudmira rubout test was used: vs. 7.:s. 50 (1! G-805-I>, L-36743 (Hf-805-D, L-36765 GT-805-B, L~00062 109 - 100 104 * 100 103 100 Although the plant lots were somewhat worse, texture probably isnft a significant factor in the differences between the semi-works and plant GT-805-D. DUP050028027 ~?1- ER1SENT WORK (Cont?d) H. Newark Finishing of Newport Solvent Breached Lops 61 gHTlQ... Two GT~805~B hatches5 Lot 394X9 and Lot 39*0^ were made from the three Newport solvent breached Lots 8, 9a and 10. Rubout and 323F paint results are shown in Table 9 - i&t, TABLE - WSM--9 Plant Finishing as GT-805-3) QT-80$- Lot 394:19 vs. OT-805-53 Lot 00062 By Rubout: Dkqg 103:100 SUXI99 32J 5 lias stone - Bark, Dull Flip-Flop - Sot as good as GT-805-D Lot 00062 but better than Suco m-48l8 Tint - Weak and Dull GT-805-D Lot 39434 vs, GT-805-D Lot 00062 By Rubouts Dk<S0 1031100 BiueigBull50 32.J: Masstone ~ Bark, Dull. Flip-Flop - Hot as good as GT-805-D Lot 00062 but better than Suco SA~4Sl8 Tint - Weak and Dull These .lots were so close ttoetorially, they were combined and blended. This bland, GT-805-D Lot 85922-I, was evaluated in 32J sand mill grinds vs. GT-805-B m 00062 at Chestnut Run. Lot 85922-1 was dark and less intense in metallic, and weak and less intense in tint . It was slightly superior to SW 00062 in metalie ''flip-flop'^however, this ad vantage would not compensate for the generally low color intensity and weakness. Finishing of Newport Solvent Breached Lots 1.1, 12 <: 1.3 - BPandardi^auion Run Three GT-S05-D batches were made from the three solvent breechings. These were held in lump form to permit a pulverisation study before proceeding. Rubout quality of the lump material versus the semi-works goal is shown in Table - WEM-10. DUP050028028 GT-805-D Lot Ho. 41104 41124 41144 tmm - 0T-GG5-P Lump vs. Gl-oOo-L Lot 00062 H-949 Lot Ho. Rubout *"ST$U' 11-J 3 B435B15 85:100 12A BkgoBlS 94:100 131 B435B35I18 92:100 *1F1 XJ5TT . myhrv-.awtP> Bi b D 1,2 Y8X6 Lot 4-1104 was split into three parts for a pulveriza tion study - one part was held as lump, one part. Lot 43.293, was low speed pulverised and one part. Lot 41294, was high speed pulverised. Rubout and paint test results are shown in Table - TO-XX. TABLE - WSM-11 Lot Ho. *#?.*irl*>.'*n*.***n!* -<r--v...Wi*y ,v?-vr nr,rw&r*'Z&t+)i.:*; vs. Lot Ho. Rubout 41293 (ISP) 4.1293 {LSP) 4.1294 (HB?) 41294 (HSP) 41104 (Lump) 41104 (Lump) Die B Ltg Lthpli 321 100:100 100:100 100:100 Y2X2 B2D4 B^Dg 5/95 Tint 41293 (LSP) 4-1294 (BSP) 100:100 vsig 32J 10/90 Metallic 41293 (LSP) 41294 (HSP) Equal Dx8 As the pulverization study did not indicate major differences, the two remaining lots were lot? speed pul verised and tested .in 32?X ball mill grinds. These results are tabulated in Table - HEM-12. XiO'G Ho. 41104 .{LSP) 4.112.4 (LSP) 41144 (LSP) TABLE * HBM-12 GT-S05-B Low Speed Pulverised 321 Ball Mill Grinds Vs. GT-805-D Lot 0062 10/90 Metallic 5/95 Tint B15S-5.5 B.8 B32 B3 B22 104:100 .108:100 108:100 BX2B20 B12D2O DUP050 -73- V. PRESENT WORK (Cont?d) Lot 41124, Lot 41144 and approximately 500 lbs. of Lot 4ll04 all low speed pulverised* were blended as a candidate standard. Lot 86509s and submitted to Chestnut Run for evaluation, Newark and Chestnut Run results are summarized in Table - BM-*13. TABLE - WEI4-13 GT-805-I3 Lot 86509-2 - Proposed Standard Evaluation Newark Results GT-805-B Lot 86509-2 vs. GT-805-D S 00062 Rubout Mass'- Masstone tone Wet Dry Bk2^B2g ^-2929 Finish Drawdown sB Finish Wet s High Finish Dry High Str. Wet 90:100 (Add.) 91:100 Pi>&/ Dry jMw (Add . ) 93:100 94:100 Tint Wl sl"6 12 y q Ii YQ D15 Lithe Label Stock Wet s High Dry Equal Bond Paper Wet High Dry High Opacity - Black Lined gaper Masstone W1et-H-- * 5SC Equal Equal Light Stability Drawdown Wet Dry Trans parent Trans parent Masstone Drawdown Strength Equal Equal vs Better DUP050028030 74- |||||, V. PRESENT WORK (Cant'd) 'XiABXJB - WEM-13 (Cant'd) Newark Results (Cont'd) Solvent Bleed Test (TF 7201) Butyl Cellosolve -45 T-36712 -45 Xylol -10 Alcohol -50 Water 50 Lot 86509-2 vs, 3W00062 Equal Lot 86509-2 vs. Blank SW 00062 vs. Blank Worse Worse PlCTient Characteristics ws Worse ws Worse ginger Fineness Color Comparison "(TP 7601) Lot 86509-2 vs. SW 00062 Dry Coarse Oil Ab s 03?pbion Dk290ull20 Specific pH Moisture Water Soluble Salts TF 7401 Lot 86509-2 SW 00062 OK OK 25.25 23.50 2,69 2.62 4.4 0.40 4.3 0.40 Chestnut Him Results (Ref. Work Request No, NC-66-21) 0.20 0.15 32<T Sand Mill Grinds Lot 86509-2 vs. SW 00062 Lot 86509-2 VS, Suco 48l8 (CS-66046) Metallic s. superior flop vs, less int. ws. Yellow less int. s. superior flop s. It, Tint 575)5 s. less int. -2.5^* less int. -5$* ^Estimated strength. DUP050028031 -T>- V. PRSSEMT WORK (Coat'd) H. Chestnut Run Results (Cont'd) It was concluded that GT-805-D, as represented by Lot 86509-2 was a satisfactory match for semiworks Lot 00062. Although slightly weak and less intense, it could he effectively promoted against Suco's GA~48l8 because of superior transparency. Based on the above results lot 86509-2 was approved as the f,Monastr&l!( Green Y, GT-805-D, standard. I. Comparison of Physical Properties of Green Y 1. Elemental Compos ition Y:iWdrTt^ry^HaTysXr*of Suco GA-4818 (various samples) shows a close analytical control: TABLE XXIX Elemental Analysis of Sued --------- $Cu C# 59377 3-52,3.78 C# 59411 3.48 C# 594X6 3.60,3.75 f&v 59.1 59.6 59. S 5051 5.89 5.67 5,53 sr~~""01T--TTcEaT 11.82 12.0 12,14 2,66 2.58 2.53 14.5 14,6 14.7 Our Green Y runs, which have given goal composi tion, tend to a higher bromine content, ranging from 12.9 to 14.0. Green Y has also been checked for the presence of Aluminum {0% to 0.05$) and Iron (0.04$). These amounts are close to the limits of detection. 2. si Absorption in the visible light region (350-700 m/A V tras measured for Green Y and Suco GA-4818 in 32J acrylic vehicle thinned with Toluene, these materials being ball milled. The A mast, was 668 h ma for both Green Y and Suco, and the general shapes of the absorption curves were Identical. Absorption indices are given in the following table. DUP050028032 PRESENT WORK (<Jont'*d) I. 2. Optical Bensity (Cant'd) TABLE KXJ.XX , Absorption Indices of Very Yellow Shade Greens in 32J Acrylic Vehicle Sample Green Y (TSC-IO6-29F) Ratio Homog./ Homogenized Hot Homogenized Hot Homog, 26.26 21.78 ,1.208 Green Y (TSC-106-42A-2) 25.77 20.56 1.254 Sueo GA-4818 C# 64706 24.82 21.20 I.I72 The higher optical densities for the Green Y products indicates additional strength, confirming the rub out strength advantage of 3~5$, but all samples were very close in ultimate particle size. The higher ratio of Homog./Hot Homog. for these samples corresponded with a greater tendency for these particular samples of Green Y, to flocculate in 32J vehicle. {TSC-106-45} 3. Surface Area These measurements 3 made on the Sorptometer, gave values as follows: Sueo GA-48l3j C# 64'fo6 Gf~804~I)9 hot 0006l SfZg..:. 40 54 These figures indicate a considerably smaller particle size, but do not accord with the fact that strength on the dry xubout is only slightly greater for Green Y. (1800-21) 4. Electron Micrographs Green Y and Sueo OA-4818 in 32J vehicle thinned with Toluene were prepared by Fullam spraying. This is a method of spraying a droplet of the 32J vehicle ball milled dispersion with Freon gas so that no appreciable aggregation occurs. Green Y samples gave DUP050028033 -77- V PRESENT mm (Cont'd) I* 4, Electron Micrographs (Confd) pictures showing very small rounded particles with just a few large bar-shaped pieces, Suco, on the other handj shows a large number of bar-shaped particles, some of which consist of individual units. Apparently the small rounded particles in Green Y may have a greater tendency to cause flocculation in 32J vehicle than the (more) bar-like particles in Suco. (1800-21) 5. Spectrophotometrie Absorption in H2SO4 Solution of CFG Greens oF^aFious'WoSl7e^ontent~~w*,~~~" If the resolution of the spectrophotometer is good enough, the curve for absorption of CPC Greens exhibits two absorption peaks in the 650-950 range. If the resolution is not too good, e.g., if the slit width on the DK-2 Beckman is too wide, then the doublet is not resolved. The Cary (Process Research) and the DK-2A (Elastomers Control Lab) at Orchem Chambers Works adequately resolved the doublet. The DK-2 instrument at Hewark must use a minimum slit width In order to do this. The position of the doublet and-Xmax.) appears, from a limited experience, to roughly parallel the Bromine content and yellowness (as pigments) of the completely halogenated CFG Greens. (See Section VI-C). TABLE XXIV Correlation of Absorption Doublet of CPC Greens In BoT~'s'olution wi^H^Br^Sne^TFent - -- . ... p--|----t -t ~ 1-- n-~;-ir-r -i -fii rrr~~-*rr inTiimimiiw n h mi--11 ni < mawi ii-riiniinir>ii Atoms of Br P\Min. Polychlor-CKJ 0 8l0 854 Heliogen Viridine Y C# 57538 Eaiuon G-54.00, C# 59107 3.7 815 859 8.3 823 870 Suco GA-4818, C# 59461 Green Y, Lot Ho. 3 12 833 880 12.9 834 879 There may be a slight shift in absorption peaks (e.g., 5 mjJ-) because of different calibrations of different instruments. DUP050028034 78- ?. PRESENT WORK (Cont'd) I, 5* Spectrophotometrie Absorption in HaSO^ Solution of^Tc^i,eHs'~o:?~'WS':lous Bromine ConoinF'T^pnir?*d.) A quantitative relationship was measured for various samples of very yellow shade Greens by using the HaSO<t solution absorption curves. These curves were taken on the DK-2 .Beckman instrument, which did not however, resolve the doublet. Results were as follows; % Cohalogenated CPC Suco GA-4818, C# 64706 Green Y, XOP-295 Packlot Green Y, TSC-106-42A (Solvent washed) 100 102.5 103,7 Care was taken during the measurementsto keep the %S0a solutions cool since it was shown that heating of these solutions gave decomposition. <1800-14) Since the pigment content was greater for Green Y, it was concluded that any weakness of Green Ys e.g., in 32u tint, was due to floccula tion and/or aggregation in the particular system involved, 6, Reflectance Curves for Very Yellow Shade Greens <i -- r~ilTin j|~'iiyi>iiinmf~iln<i<nriiilt'TiriTiTimii'~itritfnmm mrmwiwmi i< i>iiriiiinif 11 ii rmnoiy nrrmii' onwimii i|iii. Wi.nniiii<ii|iiinin.iri.<n>l----'hit These curves are given in Figure 17 for Green Y, Lot No, 4 and for Suco GA-4818. The curves corre late with the slightly greater yellowness and greater dullness of the particular lot of Green Y. ?, X-ray Diffraction Spectra Suco GA-4818 and Green Y, Lot No, 3 show similar diffraction spectra. Each spectrum appears smeared out with a maximum, very broad peak in the range of 25-26 (2) and a lesser peak at 16,7 (20). This behaviour contrasts with that of polychlor CPC (GT-751) which shows a sharp, maximum peak at 26.7 (2) together lesser peaks rather clearly defined. J Preparation of Hexadecabromo - CPC A brominated CPC containing 16 bromine atoms was desired for comparison of shade and intensity with those products containing 12 or 13 bromine atoms. The preparation of hexadecabromp-CPC had previously been tried starting from tetrabromophthalic anhydride DUP050028035 400 20 DUP050028036 -80- Y, PRESET? WORK (Ccnt'd) I. Preparation of Hexadecabromo - CPC (ContM) (HB 1624-23* 275 31}, but the product obtained analysed high for Copper and Nitrogen. The present procedure used a eutectic melt of AlBr3, NaBr, KBr and CuBra + CPC at 200C for 27 hr* with a large excess of bromine. The product (15 g.) was purified by dissolving in a mixture of 100 cc Cone'd HaSO^ * 85 ce 30$ Oleum*, and filtering thru sintered glass, and then acid pasting. The hard, blue, crystalline product gave analyses as follows: Formula; Cgg&r^gNS Cu $ Theory Found Average CU 3.45 N 6,09 C 20.9 Br 69.6 2.91* 2.84, 2.71, 2.71 5.92, 5.92 22.13, 22.24 69.41, 69.36 2. BO 5.92 22.19 69.36 Since the Cu analyses were low, it was thought that some metal-free complex may be present. it was found possible to insert copper metal into the molecule by the following treatment; Dissolving in HaSO^-Oleum mixture, acid paste into water, transferring the slurry to IMS' and then heating with CuBra at the reflux tempera ture of DMF. This product then analysed for 3.14$ average) Cu. The appearance of the product was also changed from a very dark crystalline blue to a soft green powder by this procedure. Not enough of this metallized product was available for evaluation as a pigment, but the precursor (analysing for 2.80$ Cu) vrhen solvent breached and compared to Suco GA-4818 was quite dull, somewhat yellower, about equal strength. Apparently the utility of CPC Br^g as a pigment is still an open question. There is an apparent ten dency toward demetallization during the bromination which might be overcome by use of larger amounts of CuBra in the eutectic melt. If a product much yellower than Suco GA-4818, 'with 12 Bromine atoms is eventually desired, such as one with 14.5 to 15 Bromine atoms, then some changes in the eutectic bromination might be needed to obtain maximum intensity. DUP050028037 VI COSTING 8l VERY YELLOW SHADE GREEN COSTS (At 280M Lbs,/Mo. Production Rate) Newport CN-949) Ingredients & Packages Out-of-Pocket Mill Cost VCWT. 256.23 289.O2 313.86 Newark (GT-805-D) Ingredients & packages Out-of-Pocket Mill Cost Total Cost Selling Price 322.43 344.57 357.30 403.73 450,00 fo Return on Sales % Contribution to Burden and Profit 10.3 23.4 DUP050028038 "82- vtl. PATBHT SITUATION Conclusions have been drawn by A, J, Stratton^*12)3 as follows; 1, PolybroMo CFG is an old product fully disclosed in U,,3, 2,276,860 which is now expired. 2. Bromination of CFG in an Aicis-Haci melt in the presence of catalysts is disclosed in u.S, 2,247,758, owned by DuPont and now expired. 3 The steps of isolating the pigment by treating with an emulsion of ODCB in the presence of an alkali and of a fatty substance such as stearic acid is disclosed in' U,S 2,833,782 owned by DuPont. 4. Competitive V. S. patents concerned with bromination of CPC do not specifically claim any steps presently used by us. On the basis of the above conclusions, it is.the opinion of A. J, Stratton and confirmed by Legal that DuPont is free to manufacture and sell Green Y as presently contemplated. (1) Letter RLS to AJS 9/29/64 (25 Letter AJS to AAB 10/10/64 (3) Letter J. P. Hancock to AJS 4/28/65 DUP050028039 -83VIJI, FUTURE WORK A few -things need to be done to improve economy in the eohaXogenation at Chambers Works. Primarily these involve changes in equipment, especially the installation of a condenser on the kettle in order to prevent loss of the elemental Bromine through the stack. These equipment changes are described by W. E. Miller in a letter W. E. Miller to J. W. Minnich (Appendix B), Better performance of the finished Green Y product in acrylic tints where they are weak vs. Suco GA-4818 would also be desirable. Greater dispersibility in plastics appears to be definitely attainable since the plant product GT-805-D, Lot 000.62R was considerably poorer in dispersibility than the corresponding lab product, Longer range projects could explore the possibility of making a product of even greater yellowness than GT-805-B, but with equal intensity. DUP050028040 84- IX. APPENDICES A. Literature Abstracts go Bromlnated Phthalocyanines The following patents and articles are abstracted: B.P. 461,268 I.C.I, B.P, 470,079 I.G. Parben Barrett, Bradbrook, pent & Linstead. J. Chem. Soc. 1820 (1939) XI. S. 2,195,984 XC. I, U.S. 2.247,752 DuPont u.s. 2,276,860 U.S. 2,549,842 B. Klailber, Thesis Gen, Aniline St 3d, Ultramarine Tech. Hochschule u.s, 2,873,279 B.P. 850,237 P.P. 1,263,272 Bel. 601,218 Gen. Aniline I.C.I* Materieres Colorantes Sandoz P.P. 1,273,802 Ciba U.S. 3,041,192 P.P. 1,282,308 Gen. Aniline I.C.I, P.P. 1,286,156 Bayer B.P. 925,379 B.P. 926,978 P.P. 1,309,505 B.P. 933, 242 Can. 695,548 Geigy Geigy I.C.I, Gen, Aniline Gen. Aniline Bel. 646,970 Geigy Feb. 15, 1937 Aug.. 9, 1937 April 2, 1940 July 1, 1941 March 17, 1942 April 24, 1951 Stuttgart, 1959 Feb. 10, 1959 Oct, 5, I960 March 2, 1961 March 10, I96I Oct. 4, 1961 June 26, 1962 Dec. 11, 1961 Jan, 22, 1962 May 9, 1962 May 22, 1963 Oct. 8, 1962 Aug. 8, 1963 Oct. 6, 1964 April 24, 1963 DUP050028041  *3.5- IX. APPENDICES A. Literature Abstracts B.P. 4.61,268 Linstead & Dent to l.C.X Feb. 15, 1937 (U.S. 2,214,469, P,P, 809,6X6, S. 194,195) Brominated metal-free phthalocyanines were obtained by heating either metal-free phthalocyanine or copper phthalocyanine with elemental Br2 in sealed vessels up to 300C. The products contain from 11-12.6 atoms of bromine per molecule. Metal-free phthalocyanine is more readily haloganated than the metal phthalocyanines. CPC is demetallized during the bromination to give brominated MF-phthalocyanine. (No source of copper was used in the reaction), Brominated Nickel and Zinc phthalocyanines were also made but in these cases demetallization was not complete. The Nickel compound, with 9.7 Br atoms was "bluish green", the Zinc compound, with 12,3 Bromine atoms, was "yellowish green". The MF-PC with 11 Br atoms was described as "bright green" and 11 very fast to light". Chlorinations were also conducted, either with elemental chlorine or in media such as SOCI3, sulfur chloride or sulfuryl chloride and with aluminum chloride. No yields given in any examples. B.P. 470,079 (P.P. 816,692) I.G. Farben Aug. 9, 1937 Simultaneous synthesis And halogenation of phtha locyanines are achieved by heating phthaXonitrile in a solvent such as nitrobenzene or OBCB with bromine or chlorine under pressure. Copper salts, A1C13, or ZnCla may also be used. No analyses of the brominated phthalocyanines are given, but chlorinated products are described containing 8 atoms of chlorine. P, B. Barett, E. F. Bradbrook, C. E. Dent & R,,P. Linstead J. Chem. Soc, (1939) 1820 Treatment of phthalocyanine with Brs gives addition products, which, on further treatment, e.g,, heating, yield substituted phthalocyanines. Products containing from 4.9 up to about 13 Bromine atoms were made, 13 atoms appearing to be the upper limit of substitution. Lower temperatures give less highly brominated products. DUP050028042 -86- IX* APPENDICES (Coat'd) A, Literature Abstracts (Cont'd) C.S. 2,195,984 Dent & Silvester to X.C.I. Apr. 2, 1940 (B. 478,256, g, 809,616, S. 202,861) Disclosed use of molten phthalie anhydride or chlorinated phthalie anhydrides for chlorination or bromination Of phthalocyanines. A product was made from CPC in which Bromine was passed, in a Na stream, into molten phthalie anhydride, SbCl$ + CPC at 250~26osC. The product contained 48$ Br and 'was a bright bluish green shade. Also, chlorinated metal-free, Nickel and Aluminum phthalocyanines were made by this method, U.S. 2,247,752 Pox to DuPont July 1, 1941 Orchem's basic eutectic process for chlorination or bromination of CPC or other metal phthalocyanines reaction uses: Aids - 450 Pis, Bad - 110 Pts, CcmuCla - 20 Pts. 60 Pts. SbCls - Optional with Cla being passed into the molten mass at 200C. CuCla is stated to exert a catalytic effect. Two examples on bromination given. Ex. 8 uses 400 Pts, Bra in addition to the above, giving an analysis: This product was somewhat bluer than polychlor-CPC. By passing the Bra into the melt via a stream of nitrogen (Ex. 9) a product was obtained with 11 Br and 3 01 atoms, described as ''much yellovrer than" "has been possible to obtain by the use of chlorine alone." DUP050028043 APPBKOICES (Cosnt'd) A * Literature Abstracts (Cont!d) U.S. 2,276,860 Hiemann, Schmidt, Muelbauer ^ Wiest to general Aniline March 17* 1942 Uses a variety of halogenatirg agents* e.g., POOla* PCX5, POOI5, SOS la and media, e.g., CHCXs, CCI4, GHsCI'I* CaH^GU* SQa for haXogen&tion of phthaiocy&nines, either metal-free, Copper* li, Al, Cu, Sn or Zn compounds. Examples of Brorain&tion: Ex. 2; CFG + Cu salts in CXaCOOH Heat to l4oG.., add Bra* continue heating. Product contains Br, Ex. 5* CPC t ZnCla in nitrobenzene at l85C, Add Bra in nitrobenzene Heat 185*0* 2 hr. Filter. Product is green compared to initial CPC. Ex . 13 s CPC + Aids + Had Heat to 130C . .add Bra Lead Cla into melt for 5 hr.-, hydrolyze-. Product is CPG Br8 016 Claims & CPC containing over 8 halogens... U.S. 2*549*842 Moser to Standard Ultramarine Apr. 24, 1951 Processes for synthesis of chlorinated and brcmln&ted CPG or other jietal phthalocyanines from the corresponding h&lo-phthaXie anhydrides, using the ''urea method" of phthalocyanine synthesis. Large amounts of urea must he used, along with an ancillary agent, e.g., halide or oxyhaXi.des of Zr, 'll, Sn, Sh and As. High yields are claimed.. SOB is used as the solvent. Mixed halogen-CPO products were made using both tetrachlor and tetrabroaip phthalic anhydrides, but the Br in the products was lower, and the Cl in the products was higher than anticipated. Products were: CPC Bra 01x4 CPC Br Clx5' A polybrom CPC was made in Ex. IS: 50 grams Urea 58 g. TBPA 19 g. CuBra 630 . TCB 20 g. SnBr<. Heat 175"l8oc. 3 hr. Yield 65 g. Crude or 36 g. purified copper poly'oromo phthalocyanine DUP050028044 -88 IX, APPENDICES1*rtrmnmu. , v.iin '('6C' ent 5d) / A, Literatur-e Abstracts (Cent rd) B. Xlaiber, Thesis s Tech, Hochsehule Stuttgart., 1969 CPC 3 g. in jZ^ROa 100 cc with 1 gCu powder and 5-10 cc Br, *..Heat at 1801S0*C 6 hr. Product contains 46% Br {10 atoms Br/molecule) Bromination of CPC with iron Reduction ,,>r,,.,^...^.. y-, - - ^ 3 g. CPC 0.3 g Iron Reduction 5" 10 ec Big la 100 cc 0OS Heat 6 hr. at in sealed tube. Pour runs gave 53#> 53#* 57#* 60# (11.5, 12, 12.5, 13 Atoms Br) {Recheched calculations: 53# 8$ 57# * 9.5* o0#' 10,7 Br atoms) Bromination of CPC in rZ^Br and CbH^Brs '"'*" *' - --t.-r--,^r>--^--,-i`----r-----nn--y-hrf.n <1--r---!-- > - r inri I" in-rTVTit'- i TfrnnirriM> rfi in.mum This gave Br contents less than 10$ with 0 Br with p-Dibromobensene. 52 g, C5HBr 3 g, CPC . 1 g. FeBrs .10 cc Br Heat 200-205*0 5 hr. Product is greenish blue with 47# Br, (10 Atoms Br) Brominatlon of CPC in AlBrs 3 g. c p c 0,5 g. Ferrum Reduction 60 g, AlBr3 Heat at 60C 2 hr. Add more AlBrs and Bra Heat at X80*C. 3 hr. Product is light green, and contains 67.8# Br (15 Br atoms), The yield, is small. Wo copper analysis is given. DUP050028045 -39- IX. APPENDICES (Cont'd) A. Literature Abstracts (Cont'd) 13.S, 2,873,279 (B,P. 8187831) Randall & Taras to Gen, Aniline Feb.10, 1959 Processes for halogenation phthalocyanines in a medium of AlCla and inorganic compounds of sulfur e.g., SOa.3 SOClas sulfuryl chloride. Sulfur chloride is left out. Ex. 13 describes a cohalogenation vrith AICI3, SOClai CPC and Bra at 115-120*0, The product is claimed to contain 13 Br atoms and 2 Cl atoms but the analysis indicates only 11 Br atoms and 0,9 Cl atoms. Claims are limited to treating with elemental chlorine, B,P. 850237 Kershaw & Fazackerley to I.C.I, Oct, 5, I960 Eutectic process for cohalogenation of CPC similar to that in U.S. 2,24?,752 to Fox (DuPont), using AICI3, NaCI, CPC3 Brs and a CI2 stream. Ratios of ingredients, e. g.: AICI3 - 391*1 NaCI - 82,5 CPC - 9^ are somewhat different, this using a higher ratio of CPC to Aids. Another difference is that no CuCla is used here. Also the temperature is slightly lower. Basically there is little new here over U.S, 2,247,752, Products made are, e.g,; CPC Bri.4 Cl14,5 CPC Bra.9 C112.7 High bromine utilization is obtained. DUP050028046 -90 IX. APPENDICES (Centsd) A. Literature Abstracts (Cent?d) French 1,263,272 Woerth & Chabrier Mar. 2, 1961 to Comp. Fr des Matieres Colorantes Cohalogenated CPC is made to a eutectic melt of Aids, NaCl and NaBr with no other source of 'bromine. Ex. 3? AlCla - 420 g. NaCl - 90 Heat to 150, stir Add a mixture of 100 g. CPC Heat to 195* Pass in Cla Hydrolyze Product is CPC Brg,5 CI11.3 6? g. NaBr The calculated bromine utilization efficiency is 67#. Bel. 601,218 Geiger & Geiger to Sandoz (F.P. :i,2833566) Mar. 10, 1961 Eutectic process similar to that in U.S* 2,247,752 or B.P. 850,237 for eohalogenation of copper phthalocyanine or nickel phthalocyanine, yielding products containing about 35$ 3r, 25# Cl, A high degree of bromine utiliza tion efficiency is claimed.. The end of the substitution is said to be "easily recognized by the liberation of bromine atoms already introduced into {the CPC ring) by the excess chlorine, giving an evolving of bromine vapors which is characteristic." Ex, 1; AICI3 - 1200 g. NaCl ~ 260 g. Heat to 195 Add CuCl2 - 75 g. cpc - 315 g. Add simultaneously, in the course of 5-6 hr. Brs - 270 g. Cla ** 30 g Pass in, during 10 hr., 100 g. Cla Reduce temp, to l6o, add 80 g. Cla in 8 hr. Then pass in 270 g. Cla over 11 hr. more Hydrolyze -- product contains 32.5$ Br, 25# Cl Ex. 4 is a hromination of octachloro-CPC. Cohalogenated iron and zinc phthalocyanines are mentioned. DUP050028047 .~91** lx. APPBIfDXCES (ConVd) A. literature Abstracts (Cent5 d) F.P. 1,273,802 Ciba October 4, 1961 (B.P. 910,137) (Indian Appl. #T4099) (Belgium 597,220) Canadian 686,227 Eutectic process for cohalogenation of- CPC which uses no elemental cis. The addition of chiorosulfonic acid or other compounds to the eutectic mixture appar ently frees elemental Ola for use in the cohalogenation. Coahlogenated CPC containing high amounts of Bromine were made in this way. The process uses a high ratio of Alois to CPC (18) compared to other usage \Gf,, US. 2,247,752 which uses a ratio of about 8)* Ex. Is AlCls Nad CPC 180 g. 40 g. 10 g. Heat to 120C. , add 17.8 g. CISOsH Stir 1 Hr. at 120 Stir 1 Hr. at l4o Cool to 120 Add 25 g. Bra Stir 12 Hr. at 120C. - hydrolyze Product is CPC Brg^j Glg^ Ex. 5s AlCls IffaCl CPC 180 g 40 g. 10 g. Heat to 120C Add 25 g. Br& Add 25 g. CISOsH Stir 1 Hr. at 120 Stir 1/2 Hr. at 140 Stir - 1-1/2 Hr. at l60 - hydrolyze Product is CPC BrxQ^ Cl^ 0 The calculated bromine utilization efficiency is 60#. In addition to CISOsH. the following compounds can be used; Methane sulfonic acid chloride Methyl-sulfuric acid chloride Pluorosulfonic acid Perchloro indane Sulfuryl chloride DUP050028048 -92- IX, APPENDICES (Cont*d) A. Literature Abstracts (ConVd) French 1,282, 308 ICX December 11, 1961 CoUaXoget%s,1?^{i CPC is made in a eutectic melt of AICX3, HaCX and NaBr. Additional Bra in the elemental form may or may not be added, This patent is very similar to .F,P. 1,253,272 to Comp, Fr, des Matieres Colorantes. This patent, however, makes more highly brominated products in its examples, e.g., Ex. 7s Alda - 723.5 pts, Mr - 270 pts, c p c - 94 pts. Heat to 160, add 52.4 pts. Bra in 2 Hr. with temp erature rising to l80C. Pass in 194 pts, GXa in 24 Hr. at a8<rX90C, Hydrolyze Product is claimed to be CPC Bt ^q OIq ^ Ho copper analysis is given. The Bromine Utilization Efficiency for this sample is 75$. In view of the fact that no copper source is used in any of the examples, it might be expected that some replacement of copper In 0BC by aluminum might have taken place with subsequent increas in Br content because of lowered molecular weight, DUP050028049 -93- XX, APPENDICES (Cent5 d) A, Literature Abstracts (Cont*d) U*S. 3,041,192 Brouillard & Kate to Gen. Aniline .Tune 26, 1962 Method for conditioning polychlor or eohaloganated CPC so as to obtain strong and yellow-shade greens by the use of certain organic esters in the hydrolysis, e.g., butyl benzyl phthalate, dimethyl phthalate, butyl eyelohexyiphthalate . Ex. 6: AlCls laCl CuClg CPC 450 g. 1X0 g. 20 g. 60 g. Heat to l6oC . Add 65 g. Brs by passing Ola gas over the Bra and into the flask. Heat at 2QO-2XOo0, and add Cla for 3 more hours. Pour Slowly into 2000 g. of vigorously agitated water containing 25 g. butyl benzyl phthalate. Stir 1 Hr., Filter, Hash, Mix presscake with 340 g, pigment grade CaC03. Dry at 120-1300C, "Compared to similar phthalocyanine green lakes of similar composition, it is very much yellower and distinctly brighter", The phthalocyanine in this product is CPC Brg.^Clxi.ij.* The calculated bromine utilization efficiency is 37$. DUP050028050 Literature Abstracts (Cont*d) FP 1 -`56 B.F Canadian 6?9*018 dP. 1,178^537 January 22s 1962 February 19, 1964 September 24* 1964 C ohalogenation of CPC is done in a media of pyrosulfuryl chloride 00 0 - s 01 u II 0 and thionyl chloride- The pyrosulfurylchloride is made by reacting CISOsH and SOCla. Bromine is used in the elementary form. NaESOs is used in the hydroly sis water. Products are 3 e.g.s CPC Brj,,% 1$e1 CPC Brxo.9 ci2.i w t > 1 *500 Kne; b IK 932,9^3 ICX October 8; 1962 Eutectic processes for cohalogenatlon of CPC in Aide ~ EaCl melt. Bromine is added as a liquid 5 and is also passed into the melt in a stream of nitrogen and/or chlorine gas. nothing particularly new is revealed. Hold temperatures are 160~1700. in all cases. Sigh bromine utilization claimed. Ex, 6? 72 pts. CPC 120 pts. Ml 547 pts. Aid Heat to 1600170C.s pass 62 pts. Cla into 200 pts. liquid Bra at 35 and pass this mixture into the melt at l60o170oC during 17 hr. Then pass in CI2 (8 pts3 or until the weight no longer increases) during 3 hr. Product is CPC Br-j^o dQ g Critiques This uses a 25$ excess of Bra. Ex. 7 uses a 13$ Bra xs and a very much smaller amount of CuCl than was used in our Runs at Chambers Works. DUP050028051 IX. APPESBXOSS (Cont*d) -95 A. Literature Abstracts {Cont!d) BB. 926, 978 Geigy May 22, 1963 Processes are described for chlorination and cohalogenation of phthalocyanines in pyrosulphuryl chloride MtSi alumintua chloride and sodium chloride and/or aluminum bromide and sodium, bromide at temperatures of 120--l600* (Pyrolsulphuryl chloride is " . Wo elemental halogen is used. BP, 925,379 Geigy May 8, 1963 Sulfur monochloride with sulfuryl chloride are used for chlorine supply in processes for chlorination and cohalogenation of CPC. The former is used with Aids or AlBrs and EaCX or NaBr, CaBra, MgBre. Mo free halogen is used. Bel. 646,970 Geigy April 24, 1963 Processes for halogenation of CPC in AlClo ~b MaCl with Ola and/or Bra* Byrosulfuryl chloride or thionyl chloride and/or sulfur monochloride is also added while the eutectic melt is hot (140 - l60C) , Advantages claimed are a shorter reaction time and the fact that the crude products are easily made pigmen tary in particle size by treating with a solvent, e.g., nitrobenzene, Products containing halogens such as: 6.2% Cl 11.8# Cl 1.6# Cl 99-5# Br 53.6# Br 63.4# Br The finishing treatment is illustrated; ^/25 g. Chlor (9.7#) - Bromo {54.6#} CPC 10 g.^SOa 0.6 g. HaOH 0.3 g. Oleic Acid Heat and steam distill off the mN02, filter, wash, dry, ' DUP050028052 IX. APPENDICES (Contsd) 96- A* Literature Abstracts (Cont*d) BoP* 5*33*242 &en. Aniline August 8, 1963 This patent uses HaBr in a eutectic melt to supply Bromine for cohalogenation of CPC. nothing new over F.F. 1,202,308 to IC1 of F.P. 1,273,272 to Comp. Fr. des Matieres Colorantes. Can. 695,548 Tullsen et al to Gen. Aniline October 6, 1964 Method of conditioning eohalogenated CPGfs by kneading the crude in a dough mixer with toluene sulfonic acid or Coneid. HaSO^ or butyl earbitol to give soft, strong pigments. DUP050028053 *97" IX. APPENDICES (Coattd) B * latter WEM to JWM Page i J. W. MXOTICH (4) NEWPORT ec : E. Goniclc - Wilmington E. N, Kramer - " A. A* Brizzolara - Newark R, X,* Sweet - " K* H Gyorgy - Newport Technical Pile ~ 11 Newport, Delaware April 15, 1964 TEST lEOm GREEN CPC MANUFACfTUBS AT CUMBERS WORKS Summarized below are two latemate process descriptions for the manufacture of very yellow shade green crude. These are the processes for which 7we would like Orehem to estimate manu facturing costs at the 40-80M lbs./year level. Brominated CPC Process X Kettle clean and empty. Charge the following ingredients% Aluminum Chloride, anhydrous-- 2300 lb. NaCX--396 lb* 180 ib, CuCl~~---------------------------------------- 45 lb. FeCls, Anhydrous------9 lb, CPC Crude----550 lb. Heat to 170C., hold 1/3 hour or as long as necessary to fluidise the melt* Cool to 150C* ;t50., hold and stir. Add Bromine-------2680 lb, through leg in 22 hours Add Chlorine----- ----through leg in 3 hours 134 lb, Prepare T~24 tank with 1000 gal. water> cooled to < 5C . Drown into T-24 tank in two stages, stir 1 hour, filter wash acidfree to Congo Red, Blow press dry and dump to Permaplex containers. Approx, yield ~ 1500 lb. DUP050028054 -98EC. APFEHDICES (ContM) B. Letter WEM to JHM - Page 2 Process II - 35$ Bromine Excess with Calculated Chlorine Kettle clean and empty* Charge the following ingredientss Aluminum Chloride, anhydrous lyad-- Cud"* "* ---- CPC Crude 2500 lb. 486 lb* 70 lb* 550 lb. Heat to 3.70C., hold 1/2 hour or as long as necessary to fluidize the melt. Cool to l40C. +5C ., hold and stir. Add Bromine---- - ---------~~ 1654 lb. through leg in 10 hours Add Chlorine (M* *-** - Ml .IS MA*(.' > M MM *! through leg in 2? hours 600 lb. Prepare T-24 tank with 1000 gal, water, cooled to <5C. Brown into T~24 in two stages, stir 1 hour, filter wash acid-free to Congo Red. Blow press dry and dump to Permaplex containers. Approx, yield - 1500 lb. Manufacture would be in the eutectic melt process equipment in the HMonastr&ln Building at Chambers Works where four previous trial batches were made. With minor revisions for increasing effi ciency and reducing costs, the equipment is adequate. The proposed changes and a brief explanation of the need for each are tabulated belowx 1. Seal the Reactor The reactor is currently operated under a negative pressure preventing leakage of chlorine or bromine into the working area* To reduce losses of bromine, it is desirable to operate the Very yellow Shade green process at essentially atmospheric pressure (slightly positive). To do this, requires the following revisions: (a) Provide unused reactor nozzles with bolted blank flanges, (b) Make naeessa-ry changes to the reactor agitator packing gland to insure a tight seal. .(c) Provide a positive closing mechanism for the charging chute. (d) Provide a rupture disc line. (e) Alter vent lines to prevent leakage. DUP050028055 XX. APPENDICES (Cont Jd) B. Letter HEM to JM - Page 3 2. Improve Bromine Addition Facilities In previous experimental runs at Changers Works, long delays were experienced in waiting for the bromine portable tanks to be filled and transported to the "Monastral,! operating area. As a minimum proposal, it is recommended that an adequate number of portable tanks be furnished to prevent delays. Also it is suggested a dual piping and scale set-up be provided to reduce the time required to switch bromine tanks. Bromine was charged via a straight pipeline under the surface. Addition rate was controlled by adjustment of flow through a bullseye and by scale weight difference. It is recommended that bromine be added by a rotameter (0-500 ee/minute). The scale would still be used for cheeking addition rate. 3 * Improve Chlorine Addition Facilities A 150 lb. cylinder equipped with a Calrod heating coil was used for adding chlorine during the experi mental runs. The Calrod heating coil was inadequate and it was necessary for the operator to play live steam on the cylinder to maintain the pressure. It is recommended that a heating mantle be purchased into which the cylinder can be laced. A scale, pressure gauges, needle valve and rotameter (oTM100 lbs./hr.) are required for proper control of addi tion rate. As an alternative, the existing chlorine system used for chlorination of greens, could be adapted for the smaller addition rate, ^, Bromine Condenser To minimise bromine addition time, bromine is added in excess. To keep bromine losses to a minimum, it is recommended that a condenser be installed in the vent line to return bromine to the reactor. It should be a single pass. Monel condenser with 130 square feet of heat transfer area. The vapors would be vented through a jacketed section of vent piping down three the con denser, Bromine would be returned to the reactor and non-condensables vented to the stack, A by-pass should be provided around the condenser to permit cleaning. WEM/tmj /s/ W. E. MILLER TECHNICAL SECTION DUP050028056 100- IX. APPENDICES (CcntM) C. Sulfuric Acid Completion Test rainy.--...Iw'.nim'i t ii.iiiiiHi .i< I.i--.wv .. Sample the mass by Immersing a rod into the melt. Withdraw the rod and immerse it into a Jar of cold water. Stir until completely dispersed. Filter on a sintered glass, Gooch crucible (Coming medium porosity) to obtain a filter cake about 1 mm thick. Wash tvxiee with water by filling the crucible about 3/4 full of water each time. Suck down and follow x/ith two acetone washes. Place in oven (100C.) for about five minutes to complete drying. Weigh 50 mg. of the dry color and place in a 50 ml. beaker containing 25 ml. 90$ sulfuric acid (jr 0.1$). Mix well and filter through a sintered crucible, collecting the filtrate in a test tube set in a filter flask with the adaptor positioned so that it will discharge into the test tube. The filtrate should be a pale straw color if the chlorination is complete. If the charge is underehlorin&ted, the filtrate will be a reddish brown. If overchlorinated, the filtrate will have & green fluorescence. DUP050028057 d e s eiu es & c wz<mm& mMMMmr . .. IK. APPENDICES 101 Letter BM to P. Dowd cc; M. 0-lem - Chambers Whs. S. Brandt - ,} P. L, Rslg - Newport : J. W. Minnich - Essearch File - " Newport, Delaware December 27* 1965 P. DOWD CHAMBERS WORKS RESEARCH - COLORS - 42 jams m 10 PHOfCggSiRig ABSORPIM Iff -SMTOX0 ACID S0tW3t Whs carve for absorption of CPC greens exhibits two absorption peaks in the 650-950 m/*-7 range. The position of the doublet parallels the bromine content and yellowness (as pigments') of the completely halogenated CPC greens. The endpoint is a max, value between 878 and 882 m/^ At this max. value the PVmtrn should be between 835 and 840 sis's-'1 To obtain this endpoint on the 580 pound, 10 crude batch size, approximately 2,900 pounds of bromine is added at the 120 .lb,/hr, rate. This should give a/'imax, value of 865 or above. Then add chlorine at the rate of 50 lbs./hr, for 4 hours. After4the chlorine addition,, return to adding bromine at a slow rate (approx. 20 lbs./hr,) until the spectrophoto- saetric curve is obtained, This should give the -desired {p\ max. 8?8 to 882 m/r' and /\ sdn between 835-840 } If the Z' max, value is low, add bromine at the 120 lbs.,/hr. rate until the endpoint is reached (up to 400 lbs.). Buns 9 end .10 of the last campaign were made at the 560 pound ,LG crude batch size and should be considered typi cal m there were no unusual operating problems. The readings at the points mentioned above 'are tabulated below; Run 9 1st Bromins^addition / \ max., min. 2895# 868, 828 2920# 86?, 827 1st Chlorine -addition ZN max. 5 7^min. 2nd Bromine_ addition p\ max., min.. A 175# 880, 835 225# 878, 835 CO t CO 00 ^ CM CQ CO DUP050028058 IX. APPENDICES fCone hi) 2- - Attached are graphs showing the brooaine and chlorine addition rates and spectrophotoaetrie absorption results for Huns 9 and 10, Also enclosed are spectrophotos&etric absorp tion curves for Huns. 9 and 10. If there are any questions or any problems during the run, do not hesitate to call. WEM/mc Atteh, BEsmaoH Brrxsxoif Newport Plant Phone Wilin, Hone Phone PB~-4~9488 PO-4-4203 Alternates if X cannot be reached; Newport Plant Fnone Wllm* Home Phone PE-A-9231 *0-4-5627 DUP050028059 -103- '} DUP050028060 -104- .* J DUP050028061 DUP050028062 <? iS'O DUP050028063 n . DK-2 47-'" .r i i ii 107- DUP050028064 t t.i h i ri r' ; Mr*.rs ins .jf**. , t*i* u> # \ * -iob- i, i DUP050028065 UCtMAN t*C HH.UtTQK.CMlf.. U 5 1 I ' ,-109- i i !i i CM CO'.C *' r X" I V >' - rt.'f i rss __ v/ \ i ** ? > !1 DUPO 50028066 % DUP050028068 "HfR`>1n O s0'* ' , -'-T-vxv sPV *T '.nr tutifiiwp r*uf. K,\ it -113- 1 /& S' DUP050028070 s. t,, m p o s t si mmm & comm p io s e mj s iMvmomm XX. APPEilBICES (Cent?d) E, Letter.WHS to GMo Loughran/F.H Odell- BssJM ', ~ eei H. Ariioul (2) ~ 0* B* Struve' " A* A* BrisscX&rs W, A, Jenkins A. 3X folk M H. Wet&si -Hf H# Gyorgy ~ j.i Ms, Mismlefe SU It Smet ~, Ee-sesrcih. File - ftewTa? rk n Newport ?# fewark Newport Sswports Delaware October 10, 1966 o. m* x.ooaam f , if,, a>m (3) EBSlMlgg 001,ORa ~ "igtlKmil? ~ OPC SECTS, i TBAISIXTHAL ^W.TOaf smi>s gHEM (8~949) M.s of this date, responsibility for the manufacture of 'Very Yellow Shade -(frees is transferred from Hese&reb to dperati, This process ms established on the basis of obtaining -a green product in the very yellow shade range to meet and eurpst.se comps1'v erve offerings. She crude* designated ^Monastml1' Fast Green 4T, is made by eohclcge cooper pMfe&lceyaniiie with bros&ae and ch.ls.rine via the eutectic melt, process at Chambers Work. The desired compositicm is 12-13 atoss of brasajae m& a total halogen content of at least I4,,3 atorss per CBS molecule. las crude is snipped to Ifewporh -where it is rtsolvent breached1' by refluxing with o-dicl&orobemtehe, S-ethoxyethanol, and sodium staybalitei Tbs o-diekisr.Gbenzene is recovered via steam distilla tion, The bi*eachsd slurry is treated with a surfactant and acid extracted, fke pigment is then pressed, washed and repulped for shipment to where it is treated with alial.num bensoate, dried, micropolverlsed end peeked as :GS-.805-!>. &X-805-B is the yellowest green in our line mid is as yellow and more transparent 'than caapetitioa. Its primary use is in automotive metallic^ where transparency is important. 'Lot 86509-2 has been set up aa standard, M/mc Attc-h, W, E. M2LLEB RSSMBCH BiFXSXO!? DUP050028071 IX. APMDICSS (ContM) Page 115 Ifawpori, fteltonure October 10, 1966 o k ? -' imm' M-9^9. gHQOKSS IQIISS Attached, 111. Critical ^Proe-egg^. ' X;; A, Crude :HKom-strai" Fast Oreen / Crude "Wet is manufactured at the Chambers Worka. Finished product quality ear* bs bo better than the quality of the' c.ruc.s. Our specifications for the crude are based, on spectra- Ikiotometrlc &'.bc;-*rpt? or ct the green dissolved lit auifuric aolcL Fhe curve- Cox' Osorptlon of CPC .greens eaMHita two Sibco'cpticsx i.cola !n the 650-950 m^>s< range. i'h pool- tiou of the douP;-::t purttlXela the broalna content and jellomess (at pig; so .is} of the ,co?letely Iial.ogeBated. $Bp .greens, Ihe n-ict is a /*) s&&su value between 8?8 sad 3&2 ,V,; Xlsy/max, value-,, the;ain falls 'between 835 and 8%0 * Meeting the specification gu'-rer-tees proper bra&iSiS eoutsat ' and 'hue but does not insure chrcc*. .1 Gf-reyal. Me iltUi is a very yellow e;acl Intense product, emtimimtlon with blues or other -greens will result in "ciunes and Stillness. 2 > Bre&clrlng a. She quantity of o-dichlorobensene required is based m the emouiit of water In the pres.seaS:e. foo little CfiifiS can result in wslsj&sg,. Corrected Figure 1300-------- X?,e _stsuda:M u,: ..:-yVLty of OBPB Is l>2-5 gal. |l74^q.-T0B,^ bcesd oa a preseoahe":whieh is 33$ eelidei,s^ 2,000 3b. 'dry pigment, 6*000 ?bs- net weight. Far lower .solids" press--cakes, the 0B1B a-ast be increased in proportion to fchs assart of we Os.v in the presses!;/ The calculation is as fallowst DUP050028072 2, Solvent .fgonfc^aj a, laont^-gt The aaouat of QBCB to Be added in Step 8 w let, weight of preaeeakg - dry weight '(g5OQQ lbs, std. 000-lbs* Cetds asount of imtex*- S pres@oa&e| JC 125 sala tsta* asotmt of 0UCB) lasts 65 gal* of =DDGB used in the St&ybelite m.ts*uo, i. It io inspoirtant to minimise vapor .leaks during tiie long reflux cycle to imintaic proper ratios* 3 B^tr&ction Brcmlimtsd CPC is very .heavy and settles rapidly once the volume is he!ow the agitator, Thfe flushes specified are essential to prevent leaving large .heels, % * gassing,,.. gaadlM #nd aepnlping Washing of the.presseake is essential for :-:s>ov&I of sulfuric acid sad soluble cctitaainants,. cepulped Blurry has tvs he alkaline to prevent corrosion of drums* T1X* ^rou-vpa _ '^viahls*^for tf,. J?i>ntrol .A, In gsasmlj, the more bromine substituted in the CHJ molecule^ the ycllo&sr the product. fheso products arc eorrespondiiigly wester because of higher molecular weights if B, Reduction in o-dlohlcrobenzene or too little 2-ethoxy*sttmaol produce wsateer products. &* a corollary in cm of -srcakness in the pleats higher euantliice of these ingredients should he tried., Xifv Eputipe. Wegtlog A. "Sloivaotgro.!^ gasf green 4 gyu4% 1, Chsiahsra. tWorks a, $ .solids,, t>, Spec irostiobosstrio Absorption in sulfuric acid, 2, d-T.-rpc-rt a, gaborstory Solvent Brs&chtng - The Istcrsiovy ^}^iHC^^Iscl^5B^pr S5i(3uri, Is. attached, ductl. correlation has been obtained between laboratory end plant processed aaraplec, DUP050028073 Page 117 2* Mewporb a. Laboratory Solvent Breaching (Cont^d) laboratory breaching can be used to cheek crude equality and to determine bow to combine or the order to run batches in the Plant, b. Baeklot X, $ Solids. 2. pH fSutraetsd solids* . Butsout versus the Areas, for farther standard, Lot B490 A, Bitch SISB The present process should be studied with the goal of increasing the batch size to the capacity of the' press or 2*BOO lbs, crude (dry weight) B* Syele Time Seduction in the 1.6 hour reflux cycle May be possible sad should be studied* 1. Y&eM laprovement Because of high weight per unit volumes volumetric losses equivalent to other processes result in higher yield losses- therefore* particular care must be'taken with this code to prevent mechanical losses.. XL -Ogembility Problems 1.. Dumping gyasseake to the still * The present method M*Vsmove:C:iH'g^preSicEI^'Wom dl-ums to the still is laborious and time consuming, An improved method of charging the still is required. A minlMum requirsiaent is a third floor charging chute to the still designed to handle presscake* 2` - 3US to she viscous nature of Aiftcoi. 1-10-59, addition down the long;, bending chute from the third floor to the first floor extraction tank is undesirable, A line directly trm & drum cm a .scale oh 'the second floor is suggested. E.. Bag^.Mateylal.Eatios The g-cthcacyethifmol was increased during tbs course of development of this product from 1,045 lbs., to 1,570 lbs. Intermediate amounts should be evaluated. If .sales DUP050028074 S, Ea: Jferial Patios tCoixtM] of mz,y yelXosr sty-ole green substantial: a 2sBmm of roe serening, tfce 2~ttio3(yeiJm; Befeyeaaea a. HofefeoofeBj Ml! WISM JO 101.8 TSC ?8o 86, St's 3.06 Eessm-e-h 1800 3162 - 0 34-3?* %o 3183 ~ p i$s'2o, o?i. : 317? - v 9-11? 16-2-4 ,, 520:1 - p x~xs? i!>--4:u 3209 - p x~3 m, 295. 309 0 1001,, ;'!S?.6PI!. f:KQ/J3P to 00 ^loraotrsl Green 4f I-., g.ooOl'P.Zsr:cr^s .yiv.so,., i'WW. 'tv .. vr. jh%v^:*s:.-Na.vVj.v\v.'.>\-i. I.-962 SivO ~ 9 MO, )W , 1963 $S0'- 9 87s 69* 3.04, IBSs XTTa 20? X964 m - >? 33? 8.5* 168 1965 Hea. Colors - 169, 288 1.966 , Solars ~ P 96 V0 ~ ~ U-gA. .`l-'. - M&gfrly Co-lmlogeB&teo. CrO 0-refeD.s and 'Olomatrai5* Green f (To be isoner) DUP050028075 gage 219 SewporM $el#*are October'X03 1966 iw j m$x m mmm msm BzSi UBm^mx cm MB Bistilling Flask* 2 1* 3 necks 4/40Joint* center l5/50J^t Seating MasafcXe, 2 1 Allllm Condenser* J; 24/40 Offset .Adapter,. 7n length, 'ff 24/40 Blstlllimg Beetlrer* SO Stopcock* tjT 24/40 fbeimorali MaMer/if 24Ao Timrmsm%&T3 Eimige 0-~X5Q'*C., 8" iammXm firoimd 3c$sib Stopper* $ 24/40 Stirring fled* f^rex# "Tetlm Saddle 03:,nd for 10 tm agitator abaft,.^45/50 iiiCi'.OJtrtB 1. AM 100 g My weight of i:S>maa:trsXf! Fast Orsen 4f crude in standard, breaking sst^up. 2,. If tb.a pyoaAaafes 1 above 33$ solids* a4<t^_sal rater to adjust to 3$ $ solids? -m-rrw,-,TM** m3, fks0 to add 300gr - net weight of pressea&e (g) 3 > AM is orders 84 wl *-etbo3Eyeiriasol 12 ret 30$ sodium hydroMAe 4 Agitate for 10 rclnutss * Be sure well tsixed before i>;:;ocsedi.sg, 5- mtsolTS 3-I/B g wSti?^eXitew in ml Sm, mi 0B0B -- 52 ml CDCB (atd,) I Bressca&e pet wt(g) - .100 g My. wt L gQO S KaQ in 'pressoafee 6, Adi MiaybelMM solution from burette at 3-5 ml/min* to slurry y^&gy agitation,. DUP050028076 P&gjG 120 (Ooirl? *1} a tot;ex Kg l>vSS ?i, 8, $}. 10, XK X?>, 13t.t-., XK, xS,v if* 1-3, .:;.gg Sst gy iia&te for reflux* S&gt to mtiri &ac! .rsfltw for 2Q hours* AAM 20 ml ot ~mtex" Sot X'ltisls. ftjr IOC Six? listill, off XXKX5 , FKooKi 003B rSK:rxea- lil la a tl>,n strs&ca X:,a XO0 li of ^&ie;e, 30 ill o<x\ceKura.i-&c| ^ulfKric said SIK -5 xinxigs, .lit Kcl g Ilggil r-KX-39- Dilute' to 1*000 ?&X, ;< :&.& to Sg-ii^C gold at tggg>e.xatxxefor8 logr-s,: liifcax xai rail oKK fr~& gash to O^gOO otg&g:, lave <m oxhe :fc KgKKf assled icttlo, Iry sisll yoxilon ox XO~0 .for yoioi'l > grlgS'l -rxxxrg tho K Igx 0tllXdl3.ri_, So>t Olg IK DUP050028077 ' ?i'KLX * S i : . i'> ;'XS'iLS.i Jl.X_j;' ) { gage 121 DUP050028078 Page 122 ad;a J,ly 3C:g.fc i.B 2bO\r sali4f;. !.,.... .gal..! aati&ir. to acquit Cl B&iw. of HaO added * :2Cj 2' ? .'* '4 n i :'* A 53 *U` '* A-W \ f a./ ; *. <:. V ' ..v:o 1 3?. . /' -a . h,, " . - > v ,, ....... Agitate ten- Mi 30p{ cattle to 23 stiXl - 2 full ... * 5 t!. ' v`i v` . IMMli ;?M 20 * *' - i " ,~ i oner 25 Xian puMcii (Ses asaJM-rm Xiiatg^ytdona M eul of 'Intel card!, Ms . J* 5 _ . .pel ) OiBB teged a ............ co o ... un ~!o '< ; o Mu tool;. 125 Cal, 01C2 ,',Bed.} k ,, ,, .*}i` : , > ^ O 1Op , MY ft, I wclJO0 >0 !,rr ' ',2: S 2;5 |pu . M1B oaM 1:. MaplM i~ cclio' 3D . K p&s'lto] , to : > I c . Close uMMs ecrar axil Bolt, Ofeeclt Oo .see l>mi stiQX. "is tot for refluo. uSee slate u qpnodsl 5iMiiMB.csis sitaehad), ChscB to oca u&por 11$ mlT$ it open szC vo-Mu is an OMD u o M-mmo , O.V.- lin-pUUlS gtciiS v''Xl?U full OpOIi., iai; aidXI iu,:qguuk:,ne qusetss cpM, u .-or -..o; g vru '/.'.a L-e neovcM. ynlves? a.re e?* to cutoca tie- uulno}., le!,t to ic-Ulou: (c.'ipooeciciitelp* 100*0), loot: at MllM u?o in us turn line? foe uniunatto oM.v-nCM" to siMM C ~:>Uk >Xv '5 Menu ,,i ,, min 1 ?30 tail . . lol. sian. 1 'U.Ul L act , DUP050028079 Koflex for 15 Boros, ..... i,.Jt! Mci Y Bet grill for 0D1B irire'orri (oos ale tel aoa sg-ecruit lzejte.-m.dd6as attacfoB)* Boors&se aiere to fist!7.1 off ;;?;it;i| sa qudollif ee rrorriMs w&ilrovt eol-or S.r dirrliXItia,. SteriM color Be earrieu, Brer ir. ant dlBltllAtca rsr.ro la color Be atilt ''. . v'- eelnt nrsir atex Diet rus rXerre idicmcl distillril on Baer every 13 00,00'2 so o -s .l cr,. trot lit till a ir ;:ovrrXoo alow Sfce OBli :Bi 3iKk;<i Irtvi. rriolr,: conti;;for fO oiiait, lette mn .r*aer|;u.ri. l.f tie nnriszyld i& air arrfo rota (ilftivirilp..7.l-vr. .to- 7- ' . Bo;.. *]..... ... ^ ! B'' ,:, : -- Y................ v' ; ..... ; ................Yolor B.B 1 0,0 .YlBitiBLievvto ;t:v, l nor iBOCE7/fB,ri!.B.otcrvvfca.ri 1..... .. 7"'*'........................... P "...".............................. ' :: I i DUP050028080 MS. 10" f/aaa.c to 225 still, taiIda 'So x It .ainiStn., Chock 131. tail s^pM ana cilia, &,mqs %c ill charge to S3I islt, I lisa six, alii lon oX mix Cisca r',111 sxYtxf and XXX MMM Xix sji 231 tank to 65s* wlt'ii A2ter, .igltaio X5 Xxie.x Xii xtHlx ox sX Xl (1100 dess,} (,. u.: n . . ~ i-.-; Xx. .; ' xccii flex oaifxi aeid teacl taits* xXiie fax' 1 Ms x x x o .b , Clxi: X >xS repaid, SIxM 'fe 2 &c loxx If icX alee! ft narvrUaa, ici 93 Ha ,. - . . x ; > X x - ;1 isnf, 1x1 ecXxH-t f 931- XX 0 83X$X- So: MX i a x I S>'9XH iVoi-aK Hi arxx xl a 23 frixsx Xxl ilXex :tltx *- should !>s ^iptf nci H.xx Install ll.asi gate., tHat gi\iH,Dg Ha h ; to ill press HliX pxxiH, eXAgx Itff' tx>i lilt. 25:> xleiA Hi; tf Hi XXX, HI f. s.xcoi Hf caX; flail to MM, IfSC 1;C iHrl xii x?H:y xx? linage deals, Tif Ha;x i.xl< >aaccKat catt at Hit Hm An. C-OXa /.AAA A. ! u S3" 2`! i _:s lai-l ' ^ pH i S3 Ibsi jn-/ ! i ; DUP050028081 rise l Ct>x- tA&'ZZ Vk 41.0.35 m*u5. 1Z ,. w y. S4'\ ] Start variisg 241 press, Wssli for 20 hours siaimoru 4. supervise Record pK .rflsr 2500 Qtm&i Mrs, !....'pK "'"oipp O'hSCH rpi'blOi'i; naxoip H100XH 9s sapty .and c leers M. llnxurp arses charts to pixer, 49, Frsssas&e foil /ies, Iols fi.mi or olopp-f h'hrth'sio bp o:t::i:H.ios} flush props rlpfe xith riniffiijm mricrit Of K hf0,4, 91. if aecer'SKrpb. rci! 'oator to strop to foolli-t-atr jprrrlog of slurry, ;:ta. " * d 1 . `10 Pc? of .rixi'ar;,, to rot use sir .Jet, Baoord t *H- If tolcrf pH 7, of-)us'i mth eawtori-rr Hpdr';s..fao, 7 13 Birr4 drurm-dap fra eaxer, Itee ner drurs,- .54 lifer 2-~<|p.s.rt ss.3:pla prefeirg out, folliot ore li^jrie Ires:? Href of arch Aro/p rim dror is ropi`crdjrleif 1/2 full. 59 llorori fees of ,cr i-or. Alt Ilf,. ^iteyjxlpd ftp 4 Ho, Of Drums.. 'feet Isld. V v>t\ ,.' , ~v v. icH-r, ioij Hot will !Bs.rs i%tsu ;m o b c u ferry, Hole IH-949 floeo ml 0.09 or A orrrcule ting lire , :!;, r O 0 0 . DUP050028082 -6- K*-X Ut'L- ' v 'O 'tt . 1" ' *0 v to six task oil 3rd floor. add go11 (65 Gala.) alrgln OMB * St-art agitator. fluers aM 60 tbs-, pracrushsd S ia^belifai5 rosin,- Gontiime to stir trntil ros:Ui 1ms &iaaalx-A uatlX s-2*dy fox- clmrgljti into otfli* Page 126 ~6,u.cuffty7v~" 3 jgsgord rf^TTistiir * 20* 70 ibsJ lbs-. DUP050028083 g; ? >>?? oH-V;' K wsmsm & co. musz DUP050028084