Document ZBVRor6K8bbgJQnExq4zaXgZZ

tennecoiNTER-OFf ICE MEMO CHEMICALS, INC. To W.C. Champion FROM F.W. Kanzler subject X-315 Set-Up Batches AT Burlington At Burlington Date March 19, 1975 Copy to W, Miringoff J.W, Poarch G.I. Rozand P,R, Scarito A r. Siegel bcc 1. Young In the attempt to expand copolymer production at the Burlington facil ity, two reactors of the Homopolymer Plant were utilized for the initial plant trials. In December, 1974 the first 315 batches were run in re actors 10 and 11. After fifteen batches, reactor 11 set-up and reactor 10 showed floaters, followed by a set-up batch in this reactor. In early February, another trial run of 315 resin was attempted. Again, a set-up occurred after the third batch charged. As a result, Burlington Analytical Services attempted, together with R&D Piscataway, to characterize the problem on hand and to possibly make sug gestions to eliminate the reoccurrence of set-ups when running T-315 copolymer. Attached is a detailed summary by E. Young of the work performed in Burl ington and the conclusions resulting from this work. It may be advantageous to investigate the possibility to install an inprocess pH monitoring system in a reactor to check pH fluctuations of in-plant conditions. Attachment FWK/jst F.W, Kanzler COLOR!TE 010427 TENNECOINTER-OFTICE MEMO CHEMICALS, INC. To F.W. Kanzler AT Burlington From E. Young AT Burlington Subject Investigation of Set-Up Batches date March 19, 1975 Copy to File I. Set-Up - December, 1974 The gelatin used in the set-up batch was submitted to General Foods for analysis to determine if the gelatin met all specifica tions. The results of General Foods' analysis (contained in a letter from James E. Foley, Jr. dated 1/3/75) are summarized be low. Analysis #1 is the initial analysis of the gelatin as reported to Mr. Champion on 12/16/74 by General Foods. Analysis #2 is the analysis of General Foods' retained sample. Analysis #3 is the sample we submitted to General Foods. Sample #1 Sample #2 Sample #3 bloom viscosity pH ash moisture 275 gms 52.0 mps 4.45 0.29% 6.85% 265 gms 53.5 mps 4.45 0.29% 6.85% 265 gms 51.5 mps 4.30 0.21% 7.36% Mr. Foley went on to state that the gelatins used in this blend had a bloom range of 270 - 285 and a viscosity of 49.0 - 55.5. General Foods also evaluated water samples we submitted for gelatin content with the following results: reactor 10, batch 5195 - 0.14% reactor 10, batch 5187 and reactor 11 - 0.10% Analysis on mother liquors were also done in the Flemington labor atories (3721), submitted by R.S. Miller and analyzed by C.W. Johnston. The Flemington analysis showed the following results: reactor 10 - 0.15% reactor 11-0.09% control - 0.15% The gelatin values between laboratories showed excellent correlation. These levels are in the range expected. Further work at Flemington confirmed the presence of gelatin in the mother liquors and show this gelatin was qualitatively similar to the gelatin submitted. These tests also showed the mother liquors con tained no significant amounts of Methocel. These results show nothing unusual in the mother liquors. COLORITE 010428 Page 2 The resin in reactors 10 and 11 were analyzed for bound acetate content which is shown as follows: Sample 315 Specification Round Acetate Analytical Number reactor 10 reactor 11 13.5.-15.5 14.3% 11.5% 19399 19407 Reactor 11 is out of spec low, most likely due to a set-up early in the reaction. Reactor 10, being in-spec, is most likely due to the reaction almost running to completion prior to set-up. II. Set-Up - February, 1975 Since nothing unusual was found in the mother liquor - the presence of gelatin was confirmed; it was noted that there are two major dif ferences between making copolymer in the Copolymer Plant versus making copolymer in the Homopolymer Plant. First is in agitation, the co polymer reactors agitate at 110 rpm and the homopolymer reactors at ' 117 rpm - the second difference is in the way the components are charged. In the Copolymer Plant, the components are "pre-mixed". In the homopolymer side, the components are added "sequentially", By "pre-mixed" we mean that the VCM, MVAc and TCE are mixed with each other prior to being charged into the reactor. By "sequential" we mean that first the MVAc is charged to the reactor, then the TCE, then the VCM. We were not able to examine the effect of different agitation on the reaction. We were, however, able to design an experiment which evaluated the differences between "pre-mix" and "sequential" charging. Two experiments were run in the Analytical Laboratory to aid in the determination of the reason for the set-up in reactor 10, The first was a determination of the pH changes during the additions of the re action components. The second was a bottle polymerization to determine the differences in "sequential" and "pre-mix" additions of the monomers to the reaction vessel. A. pH Study The pH study was run in the following manner: The demineralized water was preheated to 135F. The gelatin and L2O2 were charged simultaneously. The pH was studied for twenty minutes, the TCE charged, the pH studied for ten minutes, the VAcM was charged and the pH was studied for five minutes. During the run, the tempera ture was maintained between 130 - 140F. The following was the amounts of each constituent used in the synthetic reactor charge: demineralized gelatin (type L2O2 TCE VAcM water "A") - 331 gms - 0,88 gms - 0,34 gms - 2.1 gms - 4.0 gms The experiment was run in duplicate. The pH decreased steadily through the addition of TCE. Upon the addition of MVAc, the pH showed a marked increase during both runs. COLOR!TE 010429 Page 3 B. Bottle Polymerization Two bottle polymerizations were run; the first without TCE and the second with TCE; 1. Bottle Polymerization Without TCE The following formulation was used during this run: 2% solution gelatin type "A" ~ 80 gms demineralized water - 70 gms L2O2 - 0.1 gms VAcM - 12 gms VCM - 68 gms Bottles #1, #2 and #3 were charged "sequentially". All of the substituents except VCM were added. The bottles were placed in the freezer overnight. The VCM was then added and the polymerization was run for twenty hours at 157F, Bottles #4, #5 and #6 were charged "pre-mixed". All of the substituents except VCM and VAcM were added. The bottles were placed in a freezer overnight. The VCM was added, then the VAcM, which had been chilled, was added. The polymeriza tion was run for twenty hours at 157F. Results: Bottles #1 and #2 formed bb's approximately 1 cm in diameter, with some set-up resin in the neck of the bottles. The supernate was relatively clear. Bottle #3 formed some good resin with agglomerates present. Coarse particles were also present in bottle #3. The supernate, while more turbid than #1 and #2, was less turbid than #4, #5 and #6. Bottles #4, #5 and #6 formed good resin. The gelatin in the supernate of these bottles was de termined in the following manner: The supernate was filtered through #1 Whatman filter paper and the total solids of the filtrate was taken to be gelatin. 2. Bottle Polymerization With TCE The following formulation was used during this run: 2% solution gelatin type "A" - 80 gms demineralized water - 70 gms VAcM - 12 gms L2O2 - 0.1 gms TCE -0.65 gms VCM - 68 gms Bottles #1 and #2 were charged "sequentially". All substitu ents were added to bottles #1 and #2 except VCM. The bottles were placed in a freezer overnight. The VCM was added. The COLORITE 010430 Page 4 polymerization was run at 157F for twenty hours. Bottles $3 and $4 were charged "pre-mixed". All substituents except TCE, VAcM and VCM were added to bottles $3 and #4. The bottles were placed in a freezer overnight. The VCM was added, then chilled TCE-VAcM mix ture was added. The polymerization was run at 157UF for twenty hours. During this run, the batch was overheated to 165F during the third hour of the run. Results: Bottles #1 and #2 formed very coarse resin particles with a small amount of set-up resin in the neck of bottle #1. Bottles #3 and #4 contained good resin. The supernate of bottles #3 and #4 were more turbid than the supernate of bottles #1 and #2. 1 The most likely reason we did not get bb's or more set-up in bottles during this run is the overheat. This overheat probably resulted in a reduction of catalyst activity. Also, based on observation of the amount of monomer vented after the runs, this second run had a lower yield than the first run, a~ gain because of the reduction of catalyst activity due to the overheat. This experiment indicates that ''sequential" addition of the monomers in the making of 315 copolymer will lead to set-ups. We think that the pH change follow ing the addition of VAcM may affect the suspension properties of the gelatin-water solution. We recommend that a more detailed study of the effect of pH upon the suspension properties of gelatin "A" be done. Attachments (3) EY/jst E. Young COLORITE 0X0431 Component Gelatin "A" and L2O2 TCE VAcM pH STUDY SYNTHETIC 315 CHARGE Time (minutes) 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 1st Run - 4.43 4,42 4.42 4.42 4.42 4.41 4,40 4.40 4.40 4.39 4.39 4.38 4.38 4.35 4.35 4.33 4.32 4.31 4.30 4.30 - 4.30 4.28 4.23 4.21 4.20 4.19 4.18 -- 4.18 4.16 - 4.30 4.30 4.30 4.30 4.29 - 2nd Run 4.2C 4.19 4.18 4,18 4.17 4.17 4.17 4.17 4.15 4.15 4.14 4.12 4.12 4.12 4.12 4.12 4.11 4.10 4.10 4.10 - 4.10 4.08 4.05 4.03 4.02 4.02 4.02 - 4.01 4.00 - 4.12 4.18 4.18 4.15 4.15 4.12 COLORITE 010432 gelatin determination BOTTLE POLYMERIZATION - REN A Bottle Numbers 1 2 3 4 5 6 x, 1, 2, 3 x, 4, 5, 6 Gelatin (%) 1.07 1.09 1.10 1.70 1.82 1.60 1.08 1.71 E. Young 3/18/75 COLOR!TE 010433 20 X 20 TO THE INCH 46 1242 7 X IO INCHES M*pc in u .A. KEUFFtc a esse* co. COLORITE 010434