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NXER-OFFICE MEMO TENNECO CHEMICALS, INC To F.W. Kanzler "kt Burlington From E. Young at Burlington Subject Evaluation of Deionized Gelatin v* Date August 18, 1975 copy to W. C. Champion W. Miringoff J.W. Poarch Four samples of deionized gelatin were evaluated in the Analytical labor atory. The samples were studied for pH and were also evaluated using the bottle polymerizer. For the purposes of this report, the following notation will be used: "A" ,7B77 "Al" "A2" "B-*-77 1TB2,f - current type "A" now being used - current type 77B77 now being used - deionized type t,Art gelatin, lot S12510A - deionized type "A" gelatin, lot 7514402 - deionized type ''B" gelatin, lot 7503902 - deionized type "B" gelatin, lot K515902B Summary The pH studies of the deionized gelatin indicate the pH of the deionized "A" type gelatin solutions will have a pH before polymerization of about .3 to .6 pH units higher than the "A" type gelatin currently being used. The deionized ,,A"/,,B" combinations also are higher than the current "A"/'']!1 type being used, about .1 to .2 pH units. Bottle polymerization studies indicate the deionized "A" type to be more reliable in avoiding set-ups than the current "A" type now being used. None of the bottles using the deionized "A" type set up while one of the bottles using the currentlyused ''A" type was bb's. All the nA"/"B" systems yielded good resin. Screen analyses of the resin shows the current "A"/'HP7 type resins yielded a finer resin in the bottle polymerization than the deionized gelatin. Relative viscosity measurements showed no significant differences between the gelatins currently being used and the deionized type.' I. pH Studies The following formulation was used for this study: demineralized water - 325.2 gms L22 - 0.26 gms total gelatin TCE - 0.66 gms - 1.78 gms MVAc -- 33.4 gms temperature - 135F 5 The gelatin used for each study is the type specified. Where two gela tins were used, 0.33 gms of each type were used. The same raw materials were used for all of these studies. A. Gelatin "A1" The initial pH of this solution was about 0.6 pH units higher than the previous studies made using gelatin "A77. The pH prior to the COLORITE 009937 Page 2 addition of TCE was about 0.3 units higher than the previous studies. After the addition of TCE, the pH difference is only about 0.2 units. Five minutes after the addition of MVAc, the pH differences is only about 0.1 units. This seems to indicate that the pH differences of the final mixture prior to the addition of VCM are quite small, B. Gelatin "A2'' This study followed the same patterns as Study I except the pH"s ran about 0.1 pH units higher. So the differences are 0.1 units greater than those recorded above. The pH difference of the solu tion prior to addition of VCM is 0.2 units. In earlier studies of type "A" gelatin using a slightly different formulation, a final difference of about 0.1 units was found on duplicate runs. These results will give slightly higher pH's than the type "A" now being used. C. ,,Alt,/"B1" Gelatin The pH's levels in this study ran about 0.4 higher initially than type "A^". The final pH is about 0.2 pH units higher than the study for type "A ". ; D. "A2"/'^1" Gelatin This study follows a similar pattern to "A^"/"B^"''. The pH's are less than 0.1 units higher than "A^"/'^". E. "A2"/'#" Gelatin The study is similar to the two abboove, however, the pH's run about 0.1 pH units higher than "A^"/"B'L". F, "A2/''B2" Gelatin IThis study is similar to the three above while the pH's are less than tt^ltt rtg2 ti These studies show that the "A"/"B" combinations have pH's about 0.3 to 0.4 higher than deionized "A" used by itself. Also, type "A^" when used in combinations with "B^"/"B2rr yield a pH of about 0.1 units higher. This follows the sane patterns as the studies above, where "A2" was slightly higher in final pH than "A^". "B2" yields a final ph about 0.5 units higher than "B1" in combinations with "A^" or "A2". II. Bottle Polymerization Studies Three bottle polymerization runs of six bottles each were run; Bottle Gelatin Type Result 1 "A" bb's 2 "A" resin 3 maJ" resin 4 resin 5 "A2" resin 6 resin COLORITE 009938 Run Bottle Gelatin Type Result 21 2 3 4 5 6 "A"/"B" 'A"/''B'' VpXv/ TTgJ-tT "a}-"/"B2" ,,AL,,/"B2" resin resin resin resin resin resin "A"/"B" resin 2 resin 3 A;"/"Bj-" resin 4 "a;"/"bJ" resin 5 "A" "/"B," resin 6 resin This study seems to indicate that the deionized gelatins are more reliable than the current "A" type. In study I, all of the deionized gelatin bot tles had resin, half the "A" type currently used made bb's. Also, the "A"/"B" combination bottles made resin in all twelve bottles run. The bottles all had gelatinous spherical particles of resin which floated. These are thought to be soft spheres of resin with monomer trapped inside. These spheres appeared to be most abundant in bottles made using type "B2" gelatin. The resin, when dried, showed white fibrous particles of resin and also hard glassy spheres of resin. These runs show the reliability of an T,Art/''B11 suspension system versus the ,TAt? type by itself. None of the "A''/''B'' bottles set up. The pH's of the mother liquors of the "A "/''B" run were measured and are on Table II. These results indicate the range of pH's over which this system gives colloidial protection. Screen analysis of resin from Polymerization The copolymer from the seventeen bottles which yielded "good" resin was analyzed for particle size distribution. The results are tabulated on Table III. The screen analysis was done using 50 gms of resin and 2.5 gins of graphite. The results indicate that the ''A''/''B'* type gelatin now in use gives a finer resin than the deionized types, This is most evident,in the bot t-i-e--s- --r-u--n- --w---i-t-h- type -Jr- "A^" -- bhyy -i-t-s--e---l-f-----o-- r iin c--o--m---b--in--a--t-i-o-n- w---i-t-h- "B- ^" o--r "B"a2i None of the bottles made with type "A'4" had resin finer than 200 mesh. The presence of a resin smaller than 200 mesh in the bottles using type "A^" by itself or in combination with "B1" or "B2" indicates that this type is a candidate for further evaluation. Only one bottle, an "Al"/ "B2'' combination, showed no resin finer than 200 mesh. It is felt that a Pilot Plant run would give a better indication as to actual plant be havior. Relative Viscosity of Bottle Resin The relative viscosity of the resin made in the bottle polymerization was measured. With the exception of bottles 2-3 (relative viscosity of 1.51), COLORITE 009939 Page 4 all the results are in the range of 1.56 to 1.60. The viscosities show no dramatic changes from gelatin type to gelatin type. This indicates that in bottle polymerization, the types of gelatin used in this study will have no great effect upon the relative viscosity and hence, the molecular weight. The screen and viscosity data should be considered, however, with caution. The writer was able to find no other screen or viscosity data for copoly mer made in bottles. Therefore, it is not known if any of the values found are typical or "fluxes". It is also not known what the correlation is between the physical properties of bottle resin and plant resin. If a bench scale reactor had been available, the writer feels that the data would be more meaningful. A bench scale reactor would better dup licate actual plant conditions which would give a better picture of what would happen in the plant. If studies similar to the one described in this report are planned in the future, such equipment should be acquired. EY/gs Attachments (9) E. Young COLOR!TE 009940 TABLE 1-1 pH STUDY USING GELATIN "A1" Addition of L9O9 and Gelatin "A1" Min PH 1 4.90 2 4.90 3 4.90 4 4.90 5 4.90 6 4.89 7 4.90 8 4.90 9 4.90 10 4.90 11 4.90 12 4.90 13 4.90 14 4.90 15 4.90 16 4.90 17 4.90 18 4.90 19 4.90 20 4.90 Addition of TCE Min PH 1 4.90 2 4.90 3 4.89 4 4.88 5 4.88 6 4.85 7 4.83 8 4.82 9 4.81 10 4.80 Addition of MVAc Min PH 1 4.75 2 4.72 3 4.70 4 4.69 5 4.66 COLORITE 009941 TABLE 1-2 2 pH STUDY USING GELATIN "A " Addition of L7O9 and Gelatin "A2" Addition of TCE Min PH 1 4.95 Min PH 1 5.00 2 5.00 2 4.99 3 5.01 4 5.00 5 5.00 6 5.00 7 5.00 3 4.98 4 4.95 5 4.92 6 4.91 7 4.90 8 5.00 8 4.89 9 5.00 10 5.00 9 4.88 10 4.88 11 5.00 12 5.00 13 5.00 14 5.00 15 5.00 16 5.00 17 5.00 18 5.00 19 5.00 20 5.00 Addition of MVAc Min PH 1 4.80 2 4.81 3 4.80 4 4.80 5 4.78 COLORITE 009942 TABLE 1-3 pH STUDY USING GELATIN "A1" AND "B1" Addition of L9O2 and Gelatin "A1 and "B1" Min 1 2 3 4 5 6 7 8 9 10 U 12 13 14 15 16 17 18 19 20 pH 5.22 5.30 5.30 5.30 5.30 5.30 5.29 5.29 5.29 5.29 5.29 5.29 5.29 5.29 5.29 5.30 5.29 5.29 5,29 5.30 Addition of TCE Min PH 1 5.30 2 5.30 3 5.30 4 5.29 5 5.29 6 5.28 7 5.26 8 5,24 9 5.22 10 5.22 Addition of MVAc Min PH 1 5.10 2 5.02 3 5.00 4 4,98 5 4,92 COLORITE 009943 TABLE 1-4 pH STUDY USING GELATIN "A1" and "B2" Addition of L9O9 and Gelatin ,TA^'" and "B^" Addition of TCE Min 1 2 3 4 5 6 7 8 9 10 11 pH 5,32 5.38 5.38 5.36 5.35 5.37 5.35 5.34 5.33 5.33 5,33 Min 1 2 3 4 5 6 7 8 9 10 pH 5.32 5.33 5.35 5.32 5.32 5.31 5.30 5.30 5.30 5.30 12 5.35 13 5.33 14 5.32 15 5.32 16 5.32 17 5.32 18 5.32 19 5.33 20 5.34 Addition of MVAc Min pH 1 5.10 2 5.09 3 5.05 4 5.00 5 4.99 COLORITE 009944 TABLE 1-5 pH STUDY USING GELATIN "A2" AND "B1" Addition of L9O9 and Gelatin "A2" and "B1" Min PH 1 5.43 2 5.48 3 5.48 4 5.48 5 5.48 6 5.48 7 5.48 8 5.46 9 5.48 10 5.48 11 5.48 12 5.48 13 5.48 14 5.46 15 5.48 16 5.45 17 5.45 18 5.45 19 5.44 20 5.45 Addition of TOE Min PH 1 5.48 2 5.46 3 5.45 4 5,43 5 5.42 6 5.41 7 5.41 8 5.40 9 5.40 10 5.40 Addition of MVAc Min PH 1 5.18 2 5.14 3 5.10 4 5.06 5 5.20 COLORITE 009945 TABLE 1-6 pH STUDY USING GELATIN "A2" AND "B2" Addition of L9O9 and Gelatin "A2" and "B2" Min pH 1 5.60 2 5.59 3 5.55 4 5.52 5 5.52 6 5.52 7 5.52 8 5.52 9 5.52 10 5.51 11 5.52 12 5.51 13 5.52 14 5.51 15 5.50 16 5.51 17 5.52 18 5.51 19 5.51 20 5.51 Addition of TCE Min pH 1 5.52 2 5.52 3 5.51 4 5.50 5 5.50 6 5.50 7 5.49 8 5.48 9 5.48 10 5.46 Addition of MVAc Min pH 1 5.23 2 5.18 3 5.13 4 5.09 5 5.05 COLORITE 009946 TABLE 2 pH OF MOTHER LIQUOR IN BOTTLES FORM RUNS 2 & 3 TITLE 2-1 2-2 GELATIN "A" & "B" "A" & "B" PH 3.78 3.65 2-3 "A1" & "B1" 3.96 2-4 "A1" & "B1" 4.20 2-5 "A1" & "B2" 3.62 2-6 "A1" & "B2" 3.92 3-1 "A" & "B" 4.01 3-2 "A" & "B" 3.95 3-3 "A2" & "B1" 4.20 3-4 ''A2" & "B1" 3.98 3-5 "A2" & "B2" 3.80 3-6 "A2" & "B2" 3.98 COLORITE 009947 Bottle 1-1 1-2 1-3 1-4 1-5 1-6 2-1 2-2 2-3 2-4 2-5 2-6 3-1 3-2 3--3 3-4 3-5 3-6 TABLE 3 SCREEN ANALYSIS Mesh Gelatin 35 60 80 100 140 200 Thru "A" 6 18 48 64 76 96 4 "A" tt^ltt Bee Bees 12 34 56 68 80 96 4 llffi Tl "A2" 4 22 56 66 72 98 2 6 34 64 76 86 100 0 10 40 72 84 94 100 0 "A" & "B" "A" & "B" A1" & T,BrL "A'*'" & tgltt 6 24 46 58 26 42 56 ' 66 20 44 64 78 10 26 56 70 62 90 10 74 94 6 84 96 4 76 96 4 "A1" & "B2" "A1" & "B2" 2 34 68 80 84 100 0 4 34 68 80 82 96 4 "A" & "B" 4 16 36 50 62 90 10 "A" &."B" 2i "A M & "B-1-" "A2" & "B1" A2" & "B2" "A2" & "B2" 2 10 32 48 78 96 4 8 32 66 78 88 100 0 6 32 64 82 86 100 0 4 40 54 86 90 100 0 6 36 66 78 80 100 0 COLORITE 009948 TABLE 4 RELATIVE VISCOSITY Sample Viscosity 1-1 1.59 1-2 Bee Bee's 1-3 1.60 1-4 1t .59 1-5 1.59 1-6 1.57 2-1 1.58 2-2 1.57 2-3 1.51 2-4 1.58 2-5 1.57 2-6 1.59 3-1 1.57 3-2 1.58 3-3 1.57 3-4 1.56 3-5 1.58 3-6 1.58 COLORITE 009949