Document 4aLLp4eOzxjmN9k5VK3yQjZ41

L.ram MBmmwm Cbemic&i: Commm At Springfield, Massachusetts wen 0 May 24, I960 w a,wa tiGt4 R. A. Coffey F. A. Duston R, K. Perry R. E. Pollard W. P. Willis A. 0. Ericksberg Standards Dept, fteport-_on Limit Procedures: uJ^2-19-l) Effect of FDR-1 Cone. ' 7s*-------L_~W and pH Adjustment i/ P88-42, Addition of Laurie Acid and Maleic Anhydride Subject limited procedures have been reported in "Interim Report: FDR-1 Characterization by Plant Trial" A.P.T./F.A.D., Feb, 25, 1950. In brief, the concentrations of lauric acid, and maleic anhydride normally encountered in raw materials (L2 Og, PDR-1, MGD) do not affect homopolymer quality. PDR-1 concentration changes in homopolymer formulations do influence various properties such as heat stability, bulk density, and particle structure. The optimum PDR-1 concentration is 0.15$. The adjustment of the pH of -the. suspending medium with sulfuric acid or sodium hydroxide offers no FVC quality advantages. J jmy (k. Archie P. Torrensano 4 <- ^ cfb ^ 1* .(n_ , U-v*' - ^ A"'0 ' / rV,y 6 <0 ^v-o. 0J '> It, y ,,W ' t*v" Mf*. (7 // /' 1/4 RSV0024070 SpibLngfield A. 0. Eric Iceberg* p. II. Avon M. 0. Debacher We are returning a copy of the subject report, sent'to us by your Department for approval., for distribution of this report Overseas. Due to the nature of this rjaa&aL__even-JJa.aaigli-JJ2 coven Limited Procedure,1^? Q2-19-1 and P 66-4g_Jbve feel that the contends of this report" are of such a nature that it is not suitable for Overseas distribution. /cvl enc . * Hugh F. Armstrong RSV0024071 MONSANTO CHEMICAL COMPANY PLASTICS DIVISION SPRINGFIELD, MASSACHUSETTS To: F. A. Duston N. E. Aubrey R. A. Coffey 6. P. Cohen D. V. Collins R. I. Dunlap Jl, 0. Ericksberg J. Fantl W. F. Gabel L. E. Louraine 0. L. Smith R. K, Perry ,.R. E. Pollard J. L. Shriver w: PAWillis R. T. Clark Interim Report FDR-1 Characterization by Plant Tial Vinyl Resin Technical Project No. R-51 Work Done During: March, 1959 "to December 1959 Report Prepared By: A. P. Torrenzano Date Typed: February 25, -1959TM t 'iL RSV0024072 Table of Contents I. Introduction II. Summary XII. Conclusions IV. Recommendations V. Work in Progress VI. References VII. Discussion A. Need, for Project B. Review of Previous Work C. Experimental Approach D. Effect of PDR-1 Lots 1. PDR-1 Lots Versus FVC Homopolymer Quality 2. PDR-1 Lots Versus PVC Homopolymer Quality Using EDC Monomer 3. PDR-1 Lots Versus FVC Copolymer Quality E. Correlation F. PDR-1 Specification 1 \ G. PDR-1 Concentration in PVC Formulation H. Acid and Base Addition to PVC Formulation VIII. Operating Procedure IX. Description of Equipement X. Test Procedures XI. Appendix RSV0024073 I. Introduction In May 1959 a FDR-1 characterization study was started with the objective of redefining PDR-1 quality requirements based on performance in plant FVC suspension polymerizations. This project vas prompted by the erratic quality level of suspension homopolymer resins, the simultaneously poor to average performance of PDR-1 lots in the coke bottle acceptance test for copolyer usage, the critically low inventories of acceptable PDR-1, and the general belief that improved PDR-1 quality was needed to produce FVC for a more critical market. The objective of redefining PDR-1 quality requirements imposed these specific problems: 1. To establish significant quality differences in PVC suspension homopolymer and copolymer resins caused by changes in PDR-1 lots. 2. To correlate a PDR-1 physical property with the PVC resin quality. 3. To establish PDR-1 specifications for both Springfield end foreign plants. In addition to recommending a PDR-1 raw material specification, this report will review the plant studies on the effect of PDR-1 concentration changes and addition of acids and base to the PVC formulation. II. Summary , A. Fourteen PDR-1 lots were tested in Standard Opalon 300FM and Opalon 510 polymerizations to establish slgnigicant FVC quality shifts with PDR-1 lot changes. To maximize the probability of PVC quality shifts, the PDR-1 lots were selected to cover a wide range in properties: Seven lots were unacceptable by the coke bottle-copolymer acceptance test; the specific viscosity ranged from 3*9 to 9-2; the PDR-1 conversion ranged from 67 to 85 percent. The polymerization results showed that Opalon 510 copolymer properties . were completely insensitive to changes in the PDR-1 lots, while differences in the PDR-1 lots were responsible for very large shifts in Opalon 30OFM particle size - equal to four times the specification range - and shifts in Opalon 300FM heat stability. The Opalon 300FM particle size results, as measured by the screen analysis factor, correlated with (l) the specific viscosity of purified PDR-1, (2) the specific viscosity of unpurified PDR-1, and (3) the specific conductivity of a PDR-1 (unpurified) water solution. The results of experiments performed during this project and by Research showed that purified PDR-1 specific vis cosity was the prime variable, while unpurified PDR-1 specific viscosity and specific conductivity were secondary variables. This fact was established when post polymerization treatment (purifyir.., and increasing the impurity of PDR-1)did not alter its suspending power. RSV0024074 -2' The Opalon 3OOFM heat stability level correlated with the specific con ductivity of the PDR-1 (unpurified) water solution. A 10# improvement (50 to 55# transmission) in quality was measured for a 500 micromhos decrease in specific conductivity. One anomalous PDR-1 lot was encountered during the project. Three dif ferent samples of PDR-1 lot 222 would not dissolve completely in acetone, during the specific viscosity test, indicating the presence of polyvinyl acetate (insoluble) and VAMA (soluble) polymer with excess vinyl acetate. A VAMA polymer with excess vinyl acetate - instead of an equimolar ratio of vinyl acetate to maleic anhydride - would exhibit a specific viscosity higher than "equimolar" VAMA of the same molecular weight, but not contribute to increasing the suspending power of the polymer. The problem of distin guishing between "equimolar" and "acetate rich" VAMA can be handled by rejecting any PDR-1 lot which contains insoluble polymer, or a high con centration of unreacted maleic anyhdride - via a specific conductivity test, B. Four PDR-1 lots were studied at various concentrations in the FVC formula tion to determine the possibility of improving homopolymer quality and/or compensating for lot to lot variations in PDR-1 quality by optimizing the PDR-1 concentration. The results showed that PDR-1 concentration had little effect on the homopolymer screen analysis and therefore could not be used to compensate for PDR-1 quality differences which had a major effect on resin particle size. PDR-1 concentration changes had a significant effect on the shape and structure of the FVC particle agglomerate. Although the overall size of the agglomerate did not change, as measured by the screen analysis, the low PDR-1 concentration produced a more consistent, spherical agglo merate similar to successful competitive resins. This spherical agglomerate resulted in a resin of higher bulk density and consequently poorer Brabender fusion time. With high PDR-1 concentrations, the individual agglomerates consisted of 10 to 15 small particles fused together into myriad shapes thus resulting in a low bulk density resin and a broader screen analysis distri bution . At low PDR-1 concentrations the resin extrusion grade was affected adversely while the resin heat stability was improved markedly. As a result, the optimum PDR-1 concentration with the present method of operation was 0.120.15#, very close to Standard. Improvements in Brabender fusion time and extrusion grade could be obtained at the 0.18-0.20# PDR-1 concentration provided the "excess" PDR-1 could be removed by more efficient washing in the centrifuge to maintain an acceptable heat stability level. C. Laurie acid and Maleic Anhydride were added to the Opalon 3OQFM formulation to determine tolerable concentrations for these raw material impurties. The results of twelve Opalon 300RM batches showed no significant resin quality differences when Laurie Acid or Maleic Anhydride were present at concentra tions as high as 3.0-12#, based on the weight of Lauroyl peroxide or PDR-1. RSV0024075 -3- D. The possibility of employing a combination of a PDR-l concentration change and. pH adjustment to control resin particle size and distribution -was the subject of a designed 2? batch plant experiment in April, 1956* Sulfuric acid and sodium hydroxide were used to. adjust the pH of the suspending medium to levels ranging from 1.7 to 4.6, while PDR-l was employed at concentrations from 0.06 to 0.26 percent. This experiment was halted after l6 batches when the results of the acidified batches showed a drastic effect on resin heat stability. In general, the results Indicated no practical advantages to pH adjust ment since the acidified batches exhibited poor resin heat stability and extrusion properties, while batches made with sodium hydroxide had a "broad particle size distribution and, as expected, a lower volume resistivity level. The particle size level for the acidified batches was coarse, by comparison to standard batches, with a distribution that was approximately normal for coarse resin. The particle size level for batches with caustic was approximately unchanged, but as mentioned above, the particle size distribution was broadened. III. Conclusions ( A. Opalon 510 copolymer resins are unaffected by PDR-l lot changes ranging in specific viscosity from 4.0 to 9.2. B. An 8.0 minimum PDR-l specific viscosity is required to minimize the effect of PDR-l lot changes on homopolymer particle size. C. Resin heat stability level is dependent on PDR-l specific conductivity (a measure of unreacted monomers) with the present method of washing FVC slurry in the centrifuge. D. PDR-l concentration changes in the FVC formulation cannot be used to com pensate for the effect of low specific viscosity PDR-l on resin particle size. E. With the present method of operation, the optimum PDR-l concentration is the standard 0,15$. However, further work should be directed towards improving centrifuge washing and better defining the various FVC particle parameter requirements. F. In concentrations normally encountered in raw materials,- laurlc acid and maleic anhydride, per se, do not affect homopolymer quality. G. The adjustment of the pH of the suspending medium with sulfuric acid or sodium hydroxide offers no FVC quality advantages. XV. Recommendations A. From the results to-date, the following PDR-l raw material- specifications would be required to insure FVC quality control both for Springfield and foreign plants. RSV0024076 -4- 1. For Homopolymer Usage a. Specific viscosity of purified PDR-l...8.0 min. to *13*0 max. in. water b. Specific conducivlty of e 0.4$ PDR-l wauer solution, micromhos ...................................................................... 1600 Max. c. PDR-l free of polymer insoluble in acetone 2, For Copolymer Usage a. Specific viscosity of purifiedFDR-1.. .6.0 min. to *13.0 max. in water b. PDR-l free of polymer insoluble in acetone c. Master blends for use in copolymer must consist of individual PDR-l lots with a 6.0 minimum specific viscosity. B. The excellent heat level for Opalon 300FM made with low PDR-l concentrations - 0.06$ - suggests this possibility for Opalon 306-69 resin where heat stability is of paramount importance. 0. The present centrifuge washing studies indicate a marked improvement in resin heat stability. This technique may cancel completely the effect of PER-1 specific conductivity and PDR-l concentration on resin heat stability. However, if the washing is not completely successful then PDR-l purification should be evaluated and/or the PDR-l specific conductivity specification lowered. D. If the centrifuge washing permits, it is recommended that a 0.20$ PDR-l concentration be evaluated for captive resins. E. A better definition of desireable, basic FVC particle parameters is required before a superior dry blending resin can be specified or manufactured. A few accurate, meaningful gauges of resin performance unbiased or unconfounded by the test equipment or other FVC variables are necessary. By contrast,-- 1. A variety- of different shaped particles will produce the same screen analysis 2. Resin bulk density changes can be achieved in any one of four ways,particle size level, particle size distribution, particle porosity and particle shape 3. A good Brabender fusion time can be achieved with low bulk density resin, regardless of most other factors. * 4. Dry time results are as much dependent on resin particle size, particle shape, and equipment variables as on resin porosity. * Tentative until work in progress completed. RSV0024077 -5- 5. Resin Fisheye count, regardless of the test equipment, will vary markedly ty small changes in the amount of intensive mixing due to the semi-Fisheye nature of Opalon resin (basically a problem of variable placticizer absorption due to the inconsistency of the FVC particles). In short, the present specifications can be met by a variety of FVC particles that do not necessarily produce good dry blending resins. F. The interesting effect on resin particle shape and structure by changes in the PDR-1 concentration Indicates that two problems are encountered during the polymerization. 1. Controlling the size of the Individual particles which eventually agglomerate. 2. Controlling the manner (shape and number) in which the Individual particles agglomerate Xt would appear rather fortuitous for one suspension system (susp. agents plus agitation) to be the optimum level for both problems. Altering the suspension system during the polymerization would appear necessary to pro duce the desired resin particle agglomerates. V. Work in Progress The following PDR-1 Characterization studies are in progress: A. Effect of high (above 10.0) PDR-1 specific viscosity on resin quality. B. Effect of blending PDR-1 lots of low and high specific viscosity. * C. Effect of PDR-1 solution age on resin quality. In addition, samples of Opalon 300FM will he microscopically Inspected and tested in the porosimeter to better define particle parameters. VI. REFERENCES 1. Suspension Polymerization of Vinyl Chloride, Part B-, M.Baer .May 7,1958,Job. No. 896. " " ~~ 2. Preparation of Vinyl Acetate-Maleic Anhydride Heteropolymer as Suspending Agents for Vinyl Chloride Polymerization, Part A., M. Baer, Job No. 790 3* Process for Manufacturing Vinyl Acetate-Maleic Anhydride HeteropolymersPart B, R.A. Hdmes, Aug. 31,1949 Job No. 790. 4. The Stability of Polymer Suspensions and the Control of Particle Size Dis- trlbution in Vinyl Chloride Polymerization, C.T.Chmiel, Dec. 1,1957> Job No. 18767 ' ' RSV0024078 -65> Studies on the Stability of Polymer Suspensions and the Control of Particle Size Distribution - Fart B., C.T.Chmiel; Feb. 1, 19597 Jt Nos. 1676,19^2. 6. Progress Report on PDB-1 Study; Vinyl PTS Project R-51j A.P.TorrenzanO to F.A.Duston, July 21,1959. 7. Evaluation of PDR-14 Suspending Agent - Opalon 505. L.Vartanian to N.E.Aubrey, June 24,1957. RSV0024079 -7- vii. discussioh A. NEED FOR FROJBCT In May 1959, Vinyl PTS Resin Project R-51 ms initiated to redefine FDR-1 quality requirements for FVC suspension polymerization. The need for this project came from both direct and indirect problems associated with PDR-1 quality. Directly: From January to May 1959 approximately 20 percent of the tested PDR-1 failed to meet product specifications, notably the coke bottle control lab test for PDR-1 acceptance as a suspending agent in Vinyl Chloride vinyl acetate copolymerization. As a result, considerable quantities of unacceptable PDR-1 vere held in inventory while the product was retested repeatedly in the unreproducible coke bottle test. The results of the coke bottle test could not be correlated with any known factors and therefore supplied no direction for improvement of PDR-1. Subsequently, inventories of PDR-1 for use as a copolymer polymerization suspending agent were danger ously low. Indirectly: PDR-1 quality was a suspect in three copolymer coagulated batches and in homopolymer quality control problems. The three coagulated copolymer batches, which required a total of approximately 10 weeks to "Mine" out of the reactors, raised the fear that the entire k kettle line used for copolymer would be lost for a month if the four batches in process coagulated as a result of poor PDR.-l* In homopolymer polymerization, the "poor to average" PDR-1 was not above suspicion for the simultaneously poor and erratic level in FVC blendability, extrusion, and heat stability. Thus, Port Plastic was charged with the responsibility of improving PDR-1 quality level and variability while Springfield was commissioned with the project of determining the relationship between PDR-1 quality and FVC quality in order to redefine PDR-1 specifications. The marked improvement and continuing progress achieved by Port Plastics on this quality problem and of increased PDR-1 productivity had been documented in a series of progress reports by R.J.Grace. The results of work on the Springfield phase of the problem is the subject of this report. B. REVIEW OF PREVIOUS WORK It was considered essential to this present project to review past reports characterizing PDR-1'as a suspending agent for FVC polymerization in order to guide the experimental approach and help interpret results. A few previous reports pertinent to this project were paraphrased below. Messrs. M. Baer and R.A. Holmes (in References 1, 2, and 3 ) defined five characteristics of PDR-1 with good suspending power, based on numerous coke tests and pilot plant studies. 1. Composition of VAMA: The best suspending power (defined by the minimum concentration of suspending agent needed to produce a FVC polymer pass ing a 60 mesh screen) was obtained with PDR-1 made with about equimolar proportions of Vinyl Acetate and partially esterified Maleic Anhydride. RSV0024080 -8- 2. Molecular Weight of VAMA: The suspending power increased with increas ing molecular weight. VAMA of high molecular weight did not necessarily produce FVC of finer particle size than VAMA of lower molecular weight, hut rather lowered the concentration of VAMA in FVC formulation needed to produce the optimum FVC particle size. As an example, 0.08$ PDR-1 (based on the weight of VCM) of 6.0 specific viscosity was sufficient to produce the required FVC particle size, while 0.4 - 0.5$ PDR-1 of 1.64 specific viscosity was required. Only PDR-1 hatches prepared by polymerizing VA-MA in equimolar propor tions can be compared for specific viscosity since small changes in the ratio of the two monomers result in large changes in the viscosity of the resulting heteropolymer. "Effect of Varying Monomer Ratio on the Viscosity of Resulting Heteropolymers" Vac (moIs) 1.0 1.0 1.0 1.0 1.1 1.2 1.4 MA (mols) 1.0 1.1 1.2 1.4 1.0 1.0 1.0 ^Specific Viscosity 2.30 2.12 2.10 1.80 2.64 2..97 4.09 *Note: The above specific viscosity results were for a 0.4$ concern tration in water of unprecipitated PDR-1 made by the solventnon solvent technique. At ratios of higher than 1:1, VA polymerized by itself producing a water insoluble polymer which was emulsified by the VAMA resulting in a cloudy dispersion. Infra-red absorption studies Indicated that two polymers which differed only in their method of preparation had very different absorption spectras. In one of the polymers, the absorption band of the anhydride group was greatly diminished indicating a disappearance on anhydride groups possibly because of lactone formation. Any change in chemical structure of VAMA would, of course, have considerable influence on the viscosity of it's solutions, so that two polymers of identical molecular weight could display widely different specific viscosities. This could explain some discrepancies of results and some unexpected viscosity values. The molecular weight of VAMA affected makedly the bulk density of suspension FVC. This correlation can be seen in the data on the following page. RSV0024081 Specific Vise. (0.4$ in Water) 2.63 2.37 2.30 1.91 1.64 ~9- PVC Bulk Density (of 40 Mesh. Material GR/CC) 0.615 0-554 0.516 0.490 0.35^ 0.294 - mat'l obtained by blending PDR-1 and 1.64 spec, viscosity. Rather surprising was the fact that when two VAMA batches of markedly different viscosities were blended the bulk density of the resulting FVC polymer was not only lower than the average of the bulk densities obtained, but also lower than the bulk density of either individual batch. If two'VAMA. batches of widely different specific viscosities were blended the PVC produced was coarse ,' particle size than that produced by either individual batch. Thi. i._i not take place if the batches had about equal viscosities. Initially PDR-1 was a copolymer of vinyl-acetate - maleic anhydride polymerized by a solvent (benzene) - non solvent technique. With continued development work the suspending action of PDR-1 was improved by modifying the balance of hydrophobic to hydrophilic groups in the polymer by partially esterlfying some of the maleic anhydride with 2-ethyl hexanol prior to polymerization. In addition to the change in polymer composition, further developments improved the suspending action of PDR-1 by defining a modified mass polymerization technique which increased- the level of the VAMA molecular weight than was above that possible with the solvent - non solvent technique and consequently improved suspending action. 3. Purity of PDR-1: Indications were that the more complete the poly merization of the VA-MA monomers the better the suspending action of the PDR-1. Low conversion PDR-1 which had been completely freed from unreacted monomers did not show any improvement in suspending action. Also, the suspending action of a good PDR-1 was not impaired by the addition of vinyl acetate or maleic anhydride in concentrations of those found in PDR-1 batches of poor conversion. It was concluded, therefore, that whatever caused conversion to be incomplete was also the cause for the poor suspending action. (Note: The PDR-1 produced by the recommended modified mass polymerization contained less than 2$ unreacted maleic anhydride and had a specific viscosity greater than 1.7 for 1$ unpurified PDR-1 in cyclohexanone). 4. Concentration of PDR-1 in PVC Pormulatlon: The concentration of PDR-1 needed to produce FVC of desirable particle size depended on the molecular weight of the PDR-1 and the agitation of the PVC reactor. With constant agitation, the suspending action increased with increasing molecular weight. Although the molecular weight of PDR-1 did not determine the fineness of the PVC polymer but only the amount of suspending agent required to optimize FVC particle size, it had been found that PDR-1 of less than 2.0 - 2.5 specific viscosity (0.4$ concentration in water) did not produce PVC polymers of satisfactory particle size. RSV0024082 -10- If the concentration of PDR-1 as a suspending agent was plotted against the particle size of the resulting FVC, a curve showing a minimum was always obtained. The exact shape of the curve and the relative position of the minimum in the curve varied from batch to batch of PDR-1 but a minimum was always present. Three PDR-1 batches having specific vis cosities of 1.6, 2.8, and 6-5 showed a minimum at a concentration of 0.4 - 0.5, 0.3 - O.35, and 0.07 - 0.09 percent respectively. 5. Aging of PDR-1 Aqueous Solutions: On heating and long standing, chemical changes take place which cause the solutions to decrease in viscosity and the pH to drop, probably due to the hydrolysis of some acetate groups in VAMA with the liberation of acetic acid and by formation of lactones, FVC polymerization tests using aged PDR-1 solutions indicated that the suspending properties of PDR-1 became progressively poorer. Age of VAMA Solutions at 50C 0 1.5 hrs. 6.5 hrs. 22.5 hrs. 30.5 hrs. $ PVC Passing 60 Mesh 80 Mesh 97 87 96 77 88 63 86 60 80 52 Based on suspension stability studies in the Laboratory and pilot plant, C. T. Chmiel defined (in Ref. 4 and 5) a procedure to' distinguish between "good" and "poor" suspending agents. In addition, a pH adjustment of the suspending medium was recommended to improve the suspending power of poor PDR-1 lots, and to narrow the particle size distribution of FVC homopoly mer resin. 1- PDR-1 Chacterizatlon by Adsorption on FVC: By carefully dispersing FVC of approximately one micron in size in PDR-1 solutions of known concentration, and then filtering and titrating the filtrate with NaQS, an accurate measurement was obtained on the amount of adsorped PDR-1 on FVC resin. The results indicated that a correlation existed between the amount of suspending agent adsorped and the average particle size of FVC resin prepared in suspension polymerization. The adsorption isotherm for a PDR-1 - PVC system showed for two PIE-1 samples #42 and #46, that up to concentrations of 0.005 N PDR-1 the adsorption characteristics were the same. Beyond this concentration, the adsorption of sample #42 ("poor" PBR-l) decreased sharply whereas for sample #46 ("good" PDR-l) the adsorption remained reasonably constant. At a concentration of 0.0IN PDR-1, which corresponded to the concentration employed for standard vinyl chloride polymerization, the adsorption of #42 was about two thirds that of sample #46. 2 Batch pH Adjustment: Polymerisation studies showed that acidifying the suspending medium with mineral acid to 1-7 pH would improve "poor" suspending agents with a narrowing of the particle size distribution. RSV0024083 -11- With "good' suspending agents, the pH adjustment resulted in an overall coarsening effect and narrowing of the particle size dis tribution. If NaOH was added instead of acid, a coarsening effect was also obtained as the pH increased from 3 to but in general, the particle size distribution was broadened. At still higher pH large hard beads were formed. C. EXPERIMENTAL APPROACH Based on results of past studies it was decided that the objective of redefining PDR-1 specifications to meet the present day PVC requirements imposed three specific problems. 1. To establish signigicant quality differences in PVC suspension homo polymer and copolymer resins caused by changes in PDR-1 batches. In order to maximize the possibility for differences, batches of PDR-1 were selected which were acceptable by the coke bottle test, unacceptable by the coke bottle test, and covering a vide range of specific viscosity and conversion. The PVC properties to be considered were: Opalon 3QQ EM Opalon 510 a. Particle size a. Particle size b. Bulk density b. Dry time c. Melt index c. Bulk density d. Color and heat stability ' e. Extrusion properties f. Brabender fusion time and fisheyes 2. To correlate a PDR-1 physical property with PVC resin quality. The first attempts at correlation were to be with the simpler tests such as (a) PDR-1 specific viscosity, using both purified and unpurified PDR-1, (b) PH and NaCSH neutralization, and (c) conductivity of unpuri fied PDR-1,in water. If further testing was required, determinations could be made with (d) the polarograph for concentrations of free Maleic Anhydride, and (3) infrared analysis. Should these test tech niques fail to correlate with PVC quality, then the suspending charac teristics of PDR-1 could be explored using the adsorption technique developed by Chet Chmlel and lastly, the coke bottle test could be improved and possibly reduced in sensitivety to obtain a correlation. 3* To establish PDR-1 quality requirements for both Springfield and foreign plants. Since the quality problems at Springfield were not necessarily the same as those in foreign plants due to unavoidable basic differences ( such as VCM and water quality) PDR-1 quality specifications different from those required at Springfield could, if economically justified, be utilized to improve PVC quality. Another important phase of study which required simultaneous attention was the possibility of compensating for PDR-1 quality variations or even improving the PVC quality by altering the PDR-1 concentration in the PVC formulation. Conceivably PDR-1 specifications could be defined "to permit an improved PVC quality at a PDR-1 concentration different from standard. RSV0024084 -12- D. RESULTS AT STANDARD OPERATING CONDITIONS The PDR-1 batches employed during this project were listed in Table 1. together with their pertinent data. Different groups,of these 17 listed PDR-1 batches were utilized in a series of ten experiments designed to characterize PDR-1 performance. 1. PDR-I LOTS VERSUS PVC HGMOPOLYMER QUALITY (Exp. #2,#7) PDR-1 lots 22, 225, 36, 237, and 242 (Group A) and later, lots 230, 240, 277, 278, 287, and 242 (Groupd B) were used in the polymerization of 50 acceptable batches of Opalon 300 FM by the X-57 process. Each batch was made in accordance with the Standard Operating Procedure. Any batch failing to adhere to the SOP was rejected and the run repeated. A sample of each batch was taken from the reactor, dried in the labora tory oven and tested for quality level. Since it was not possible to employ the same raw materials other than PDR-1) for the entire project, the comparison of results from one experiment to another, when necessary, was accomplished by using one PDR-1 lot as a control. In this case, Lot 242 was employed in both Groups. In any one experiment all vari ables not under study were held constant, including the lots of GMS, L2O2 and DAM. a. Particle Size: Differences in PDR-1 lots were responsible for very large shifts in particle size level. The severity of the shifts' can best be gauged by inspecting Pig. 1 and noting that the spread of results was approximately four times as great as the Opalon 300FM specification range, which was ca. 90 to l40 SAF. There was no significant difference in particle size variability associated with.any PDR-1 lots. The particle size results for the two groups of PDR-1 were compared on a common basis by adjusting the SAF results of Group B by an amount equal to the difference between lot 242 in Group A and' in Group B. PDR-1 Lot 225 222 242 236 237 Average SAF 47 64 97 99 105 Adjusted Average SAF 47 64 97 99 105 230 63 240 76 287 94 277 118 278 119 242 118 57 67 81 97 . 98 97 RSV0024085 -13- b. Kitchen Mixer Dry Time: There was no change in dry time level with changes in PUR-1 Lots; see Fig. 2. The resin dry time averaged 4'40", with one run above 5'30"- c. Bulk Density: There was no apparent shift in hulk density with PUR-1 lot changes except where PUR-1 coarsened resin particle^ size and consequently increased the bulk density; see Fig. 3 d. Heat Stability: There was a significant (99$) variance in heat stability with changes in PUR-1 lots. The range of results of each PUR-1 were plotted in Pig. 4. e. Extrusion Properties: There was no apparent significant shift in resin extrusion grade or rate with PUR-1 lot change. The extrusion grade ranged predominately between a B and D rating; see Fig. 5- It was rather surprising to encounter a reasonably good level of extrusion grade for the very coarse resin batches made with PUR-1 Lots 222, 225, 230 and 240. It was believed generally that gbod extrusion grades could not be obtained with resin coarser than 9Q-SAF. For the 40 batches tested, 39 batches were within the specifica tion limit of E maximum, with the average level at C. The extrusion rate averaged 145 GFM* f. Brabender Properties: Six of the seven Brabender fusion time results for PUR-1 Lot 287 were the highest values encounteredat standard operating conditions - during this project. As can be seen in Fig. 6, two samples of Opalon 300FM made with - PUR-1 lot 287 did not fuse (20+). The only known difference between lot 287 and the other tested lots of PUR-1 was in the method of manufacturing. Lot 287 waB representative of a series of PUR-1 batches made at Port Plastics to determine the effect of replacing 10$ of the tertiary butyl per benzoate catalyst with benzoyl peroxide. Lot 277 and 278 represented PUR-1 batches made with 5$ benzoyl peroxide, and all other PUR-1 lots tested were manufactured under standard operating conditions. PUR-1 lot 287 was used again in a PUR-1 concentration study, which will be discussed in Section VI E, and showed a fusion time of approximately 25$ higher than batches made with PUR-1 lot 277. It should not be concluded from these data that the 10$ "benzoyl peroxide catalyst system was responsible for the "behavior of lot 287, hut only that further testing of representative PUR-1 lots was warranted if the change to the 10$ benzoyl peroxide catalyst system was considered desirable from a manufacturing point of view. RSV0024086 The Brabender fusion time results obtained when employing Group B PDR-1 lots ranged from ca. 5 to 11 chart units (excluding Lot 287) while Group A ranged from ca. 4 to 8 chart units, implying a change in an uncontrolled FVC process variable or a lack of under standing as to the meaning of Brabender fusion time values. There was no correlation between Brabender Fisheye count and FDR-1 lots, Fig. 7* 2. tor-1 LOTS VERSUS FVC HOMOPOLYMER QUALITY WHEN USING EDC VINYL MONOMER (Exp #4) In an attempt to distinguish differences between PDR-1 lots 236, 237, and 242, which behaved very similarly when tested in Group A, eight batches of Opalon 3^0FM. where manufactured using EDC vinyl chloride monomer. About three months previously, in April 1959, two million pounds of vinyl chloride monomer made from ethylene dichloride, EDC,were received and used in the FVC operations with a simultaneous shift in resin particle size. The shift in particle size was to a coarse ness level that could jiot compensated for by changes in FVC operat ing conditions. As a result, over one million pounds of out-ofspecification FVC was produced with a drastic effect on manufactur ing costs. One tank of EDC monomer containing approximately 100,000 pounds was set aside for use again when the FVC particle size level returned to a normal level. The eight batches of Opalon 30CFM made with the three lots of FDR-1 were again very similar in all properties and comparable to the batches previously made with these lots when tested in Group A. The resin particle size level with the EDC monomer was only slightly coarser than normal production batches (sans EDC); see data sheets for experiment #2 and #4. 3. FDR-1 LOTS VERSUS FVC COPOLYMER QUALITY (EXP. #3 AND #5) After PDR-1 lots 222, 225, 236, 237, and 24-2 had been tested in homopolymer polymerizations, the same five lots where used with the X-26 process to polymerize 18 batches of Opalon 510 copolymer. When no problems were encountered with these five lots of PDR-1, four lots of PDF.-l - 244 , 247, 49, 251 - were tested which did not pass the coke bottle acceptance test but did have an acceptable specific viscosity and specific conductivity. a. Particle Size: Copolymer was unaffected by the changes in the PDR-1 lots tested. See Fig. 8, 9* b. Bulk Density: No shift in bulk deniity with PDR-1 lot changes: See Fig. 10. e. Melt Index: There was no change in melt index with FDR-1 lot changes; see Fig. 10. RSV0024087 -15- E. CORRELATION OF FDR-1 QUALITY AMP FVC QUALITY THe only properties significantly affected by more than one lot of PDR-1 were suspension homopolymer particle size and heat stability. 1. PARTICLE SIZE VERSUS PDR-1 QUALITY After experimenting with PDR-1 lots in Group A, it appeared that the only correlation between particle size and PDR-1 quality was with specific conductivity (Ref. 6). However, after testing samples of the specific drum of PDR-1 used in the experiment and with further data from Group B, PDR-1 lots, it was evident that a significant correlation also existed with both purified and unpurifled PDR -1 specific viscosity. The relationship between resin particle size and purified PDR-1 specific viscosity, Pig. 11, showed that very little change in particle size occurred between a 7*0 - 9*0 specific viscosity level, while below a 7*0 specific viscosity the particle size coarsened rapidly. A very similar relationship, Pig. 12, was obtained between resin particle size and unpurified FDR-1 specific viscosity, with the criti cal point at a 3 specific viscosity. The statement by M. Baer (Section YI, B) that only VAMA polymerized in equimolar proportions of vinyl acetate and maleic anhydride could be compared for specific viscosity was of particular importance in help ing to interpret the experimental results obtained with PDR-1 lot 22. When tested in Group A, PDR-1 lot 222 resulted in very coarse homopoly mer resin - 64 average SAP. This particle size level was inconsistent with the 7*8 specific viscosity resulted obtained for this lot. Two additional samples from the drum of PDR-1 used during the experiment were tested together with a repeat testing of the first sample. The results were inconsistent due to a difference in the PDR-1 quality for each sample tested. Specific Viscosity For Lot 222 Sample Purified Unpurified PDR-1 I-a I-b II III 7.8 6.9 6.1 ? 2*35 ' 1.78 During the specific viscosity test, it was not possible to dissolve the PDR-1 completely in acetone before proceeding with the VAMA precipitation with benzene. It was necessary therefore to filter the mixtrue - removing the polyvinyl acetate solids - before complet ing the test. Samples II, I and III contained increasing amounts of polyvinyl acetate, with sample III producing insufficient quantities of benzene precipitated VAMA to test for specific viscosity. The RSV0024088 -i6- "Acetate Rich" VAMA polymer precipitated with benzene should exhibit a specific viscosity higher than anticipated from resin particle size data and Fig. 11. Therefore the SAP - specific viscosity data point for lot 222 was not added to Fig. 11. To distinguish between "Equimolar" and "Acetate Rich" specific viscosity results would be a control test problem. Obviously any lot of PUR-1 which showed polymer insoluble in acetone should be rejected. Since, according to Ref. 1, VAMA containing as much as 20$ excess vinyl acetate could be dissolved without a sign of polyvinyl acetate insol ubles, and since this material would exhibit a 50$ "higher" specific viscosity (which does not contribute to the suspending power of the VAMA) some additional safeguards were necessary. One solution would be to measure the presence of unreacted maleic anhydride to insure a minimum conversion of this monomer; a specific conductivity test would provide an approximate measurement. Adequate PDR-1 quality control could he expected with an 8.0 minimum specific viscosity, a 1600 micromhos maximum specific conductivity, rejection of PDR-1 lots exhibiting insoluble polymer, and the standard plant trial of one suspension batch. Rote that lot 222 would have been rejected on all four counts. The specific conductivity of a PDR-1 water solution was initailly of considerable interest prior to establishing the specific viscosity correlations. To understand the significance of specific conductivity variations, samples of PDR-1 were purified and tested. The results showed a level of approximately 550 micromhos for VAMA that had been benzene precipitated. In addition, conductivity levels were synthesized by adding vinyl acetate, maleic anhydride, and both vinyl acetate and maleic anhydride to PDR-1 water solutions. These data showed that with only maleic anhydride added, the conductivity was affected as shown in Fig* 13, and the influence (the slope of the line) was approximately 50$ that expected from the general correlation between PUR-1 conversion and specific conductivity in Fig. lb. When added alone vinyl acetate had a negligible effect on conductivity, while when added together with maleic anhydride, the vinyl acetate apparently hydrolyzed to acetic acid and acetaldehyde and contributed to the solution conductiv ity. The conductivity data for the PDR-1 solutions with added maleic anhydride and vinyl acetate showed the same slope as Fig. lb up to a 9$ monomer concentration, with a sharp leveling off as additional monomer was added, Fig. 15. A significant correlation was obtained also between resin particle size and the specific conductivity of a PDR-1 (unpurified) water solution for the various PDR-1 lots tested, Fig. 16. The fact that when maleic anhydride added to the PVC formulation did not influence the resin particle size indicated that the conductivity was not the prime var iable. The same was true for unpurified PDR-1 specific viscosity since research work had shown no change in suspending power when PUR-1 was purified prior to use in PVC polymerizations and no change when PUR-1 was made more "Impure" by adding vinyl acetate and maleic anhydride. It was concluded, therefore, that the prime variable was the molecular weight of the VAMA, which was related to the specific viscosihy of a purified PDR-1. RSV0024089 -17- The secondary correlations with unpurified PUR-1 specific viscosity and specific conductivity were understandable since the polymerisa tion of high molecular weight VAMA was synonymous generally with high monomer conversion. 2. HEAT STABILITY VERSUS FDR-1 QUALITY There was a significant (99$) correlation between resin heat stability and PUk-1 specific conductivity* but not with PUR-1 specific viscosity. This indicated that the unreacted monomers affected the resin heat stability. In figure 17 the calculated correlated curve for all the data was shown with a solid line; the two sigma confidence limits were + 11# transmission. Actually it was suspected that the correlation might be slightly steeper but for the variation in efficiency of washing slurry samples prior to testing. All the samples were washed in the same manner, employing a specified amount of water per specified weight of resin. The coarse resin with less total surface area probably was washed more efficiently than the finer resins. Since .the PUR-1 specific conductivity also was inversely proportional to the resin particle size, it was possible that the heat stability correlation was masked partially. By eliminating the two very high specific conductivity data points - 27^0 and 2355 micromhos - that were associated with very coarse resin and recalculating the correlation for the remaining points, a steeper correlation was obtained that was 99-9$ significant (dotted line on Fig. 17). Further experimentation with additional PUR-1 lots to exploit the accurate correlation was not considered justified since a specific viscosity and specific conductivity specification imposed to insure FVC particle size control would also satisfy the heat stability requirement. Obviously the purification of PUR-1 prior to use in FVC polymerization would warrant consideration if the centrifuge washing studies do not eliminate the resin heat stability dependency on PUR-1 quality and quantity. F. PUR-1 RAW MATERIAL SPECIFICATIONS From the results todate, the following specifications would be required to Insure FVC quality control. 1. FOR HOMOPOLYMER USAGE a. Specific Viscosity of purfied............ 8.0 minimum PUR-1 in water *13*0 maximum. b. Specific conductivity of 0.4$.............. 1600 maximum PUR-1 Water Solution, Micromhos c. No FHR-1 Polymer Insoluble in Acetone RSV0024090 -18- 2. FOR COPOLYMER USAGE a. Specific Viscosity of Purified....................... 6.0 minimum PDR-1 in Water ...................... *13-0 maximum b. No PDR-1 Polymer Insoluble in Acetone c. Master Blends For Use In Copolymer Must Consist of Individual PDR-1 Lots Each. With A 6.0 Minimum Specific Viscosity. The reasons for the homopolymer usage requirements were discussed in the previous section. The safe, 6.0 minimum specific viscosity and blending PUR-1 specifications for copolymer usage were selected to prevent any boarderline PDR-1 quality which might result in coagulated copolymer batches. No attempt was made to distinguish between Springfield and foreign plant requirements for PDR-1 quality. G. PDR-1 CONCENTRATION IN PVC FORMULATION The possibility of improving PVC quality and/or compensating for lot to lot variations'in PDR-1 quality by optimizing the PDR-1 concentration in the PVC homopolymer formulation was explored during this project. Some previously unreported plant work will also be added to the discussion below to support the conclusions. Back in March 1958, a study of PDR-1 concentration was started in 92 Building using Op&lon $00 (X-57) as the subject. It should be noted that the agitative systems in 88 and 92 Buildings differed - and still do - by the type and position of the baffles in the reactor. This difference was pointed out since it was believed that agitation and suspending agent behavior were interrelated and conclusions based, for example, on coke bottle results, pilot plant reactor, or even 92 Build ing results, might not show up in a different agitative system. The influence of baffling of the reactor can be highlighted from the particle size data below which were collected simultaneously in both 88 and $2 Buildings while all other known variables were held constant. 88 Building Agitation: 5^ inch span, retreating type impeller,' rotating at 121 RPM, with twaL-j" x 15" three fingered baffles positioned low in the reactor. RUN NO. 5-81 5-87 5-95 5-102 5-109 5-116 5-123 PARTICLE SIZE 40 60 Bo 100 0 16" 55 22 0 10 46 29 0 10 46 29 . 0 3 32 38 0 11 46 30 0 8 37 35 0 lb 46 28 ON MESS 140 200 11 2 12 2 12 2 23 3 10 1 19 2 12 2 PAN ....T T T T T T T ^Tentative until work in progress completed. SAF "89 93 93 104 91 99 94 Ave. 95 RSV002409] -19- 92 Building Agitation: 54 inch span, retreating type impeller, rotating at 121 REM, with two Sg-" x 2b" two fingered baffles positioned high in the reactor. RUN NO. 8-6409 8-6422 8-6429 8-6437 8-6445 8-6453 8-6460 PARTICLE SIZE, # ON MESH 40 60 80 100 ~I5cT 200 PAN 0 T 7 22 "55 21 0 1 4 20 50 20 4 0 1 5 20 48 22 4 0 1 8 24 45 18 4 T 4 30 32 27 6 0 2 11 29 44 13 T 2 ll 25 4l 17 l 2 4 SAF 15^3 l44 146 i4o 119 132 136 Ave.137 The larger baffles in 92 Building had approximately 408 square inches of surface area as compared to 203 square inches per baffle for the smaller baffles in 88 Building. This factor Increased the baffling efficiency and resulted in a higher agitating intensity, as defined by the "Pfaudler Agitative System"; a 10.5 A.I. for 88 Building and al2.3 A,I. for 92 Buidling. However, when the Agitative Intensity was changed a comparable amount by increasing the impeller speed in 88 Buidling very little ^effect was noted on resin particle size. It could be concluded only that the large baffles, positioned high in the reactor produced a finer resin due to a basic difference in flow pattern which probably provided a higher rate of vertical flow for the agitated fluid. 1. EFFECT OF FDR-1 CONCENTRATION ON 0PAL0N 300 IN 92 BLDG. (Exp.#A) The data in Table 2 were obtained from Opalon 30 batches using different concentrations for FDR-1 tester Blend #35 Excluding runs 12 and 15 which appeared to be influenced by some other variable, these data indicated that PDR-1 concentration changes from 0.03$ to 0.20# had very little effect on resin particle size level or distribution. With PDR-1 concentrations above 0.20#, the resin particle size distribution was broadened. This can be seen in Fig. 18 which shows the PDR-1 coneentratom plotted versus the Geometric Standard Deviation - defined as the slope of the particle size distribution curve when plotted on logarithmic probability paper. Ref. 7* Surpris ing was the fact that as little as 0.03# FDR-1 was sufficient to maintain an adequate suspension. Run 18, which was made using a 0.018# PDR-1 concentration, had over 20# resin of plus 40 mesh size and not tested for other properties. With increasing PDR-1 concentrations the resin bulk density, Reed Mixer dry time, extrusion grade, and extrusion Fisheye count all decreased significantly. See Figures 19, 20, 21, and 22. Unfor tunately no resin heat stability data was obtained during this experiment. RSV0024092 -20- The rather promising resin processing characteristics for a "full conversion" type resin ms pursued further in a study of PDR-1 con centration and hatch pH* which will he discussed in Section VII, H. 2. EFFECT OF PDR-1 CONCENTRATION ON OPALON 30QFM IN 88 BLDG.(Exp.#l) During this present PDR-1 characterization project, further PDR-1 concentration studies were made and this time Opalon 300FM (X-57) in 88 Building was the subject. Sixteen hatches were polymerized in two kettles with slightly different baffle positions using PDR-1 master blend 47 and lot 37 at four levels of concentration - 0.06$, 0.12$, 0.l8$, and 0.24$. a. Particle Size: The particle size data. Fig. 3, for this experiment was "extremely variable and could not be correlated with the vari ables under study, or for that matter, with any other variable. Therefore no useful particle size data was obtained from this experi ment. t b. Dry Time: There was no apparent correlation between PDR-1 concen tration and kitchen mixer dry time results Fig. 24, however the particle size variability could have confounded this relationship. The relationship between the two dependent variables of kitchen mixer dry time and resin particle size can be seen in Fig. 25.. It was hypothesized that the poor dry time levels for fine resins was primarily a result of the poor mixing action of fine resin in the type equipment used in this test and does not necessarily mean fine resin has less total void volume for plasticizer adsorption. The interraction of resin properties-other than the property understudy with test equipment can be extremely misleading especially if indus trial equipment behaves differently. c. Bulk Density; Increasing PDR-1 concentration decreased resin hulk density as seen in Fig. 26. The cause for the hulk density was apparent when samples were examined under a microscope. With low PDR-1 concentrations, the individual FVC agglomerates consisted of 3 to 4 particles fused together into a generally spherical shape; the agglomerates were fairly coarse. With high PDR-1 con centrations, the individual agglomerates consisted of 10 to 15 small particles fused together into myriad shapes thus resulting in a low bulk density. d. Brabender Properties: Increasing the PDR-1 concentration had, in general, the same effect on Brabender fusion time as on bulk density. It was suspected that this again was a case where a dependent variable (bulk density) and test equipemnt were confound ing the significance of fusion time results. See Fig. 7. The Brabender Fisheye count showed no correlation with PDR-1 concentration. Fig. 28. RSV0024093 -21- e. Extrusion Properties: There was no correlation between PDR-1 concentration and Opalon 300PM extrusion grade, Pig. 2$. t. Heat Stability: Kettle slurry samples were washed in the control lab prior to drying and testing. The heat stability of the samples were improved markedly by water washing. Fig. 30- In determining the effect of PDR-1 concentration on heat stability, all samples were washed equally. The results showed that decreas ing the PDR-1 concentration improved resin heat stability, Fig.31. The importance of this correlation will depend on a centrifuge washing study now in progress. It has been established already that the present method of contrifuging Opalon 300FM was equiva lent to approximately "one washing" in the laboratory (see Section VIJljA). Marked improvements were expected by improved washing in the centrifuge such that regardless of the PDR-1 con centration the same high level of heat stability might be attained by removing all excess PDR-1 adsorbed on FVC resin. 3. EFFECT OF PDR-1 CONCENTRATION OF OPALON 300FM in 88 Bldg. (Exp .#8. ) The PDR-1 concentration study was repeated but this time the kettle baffle variable was eliminated and the experiment run in triplicate using PDR-1 lot 277 and lot 287 at four levels of concentration 0.06$, 0.12$, 0.l8$, and 0.24$. PDR-1 lots 277 and 287 were selected since lot 277 represented the highest quality (specific viscosity) PDR-1 available at the time and lot 287 producedsignificantly higher Brabender fusion time results when previously compared in Group B (Section VII,D). Within the range studied, PDR-1 concentration changes showed little effect on the resin particle size level (or more exactly, the screen analysis) except for an indication of a coarsening effect when PDR-1 lot 277 concentration dropped from a 0.12$ to 0.06$ level. No marked difference in screen analysis distribution was encountered at the high PDR-1 concentrations as had "been the case with PDR-1 master blend 35 in 92 Building. With both PDR-1 lots, FVC resin bulk density, B-rabender fusion time and heat stability again showed a dependency on PDR-1 concentration. Results in general, agreed with the data previously obtained on Opalon 300 in 92 Building. See Figures 32,33* 34,35> 3&> and 37. 4. SUMMARY AND CONCLUSIONS PDR-1 concentration changes had a significant effect on the shape and structure of the PVC particle agglomerate. Although the overall size of the agglomerate did not change, as measured by a. screen analysis, the low PDR-1 concentration produced a more consistent, spherical aggolmerate similar to successful competitive resins made by Dow and Goodrich. This spherical agglomerate resulted in a resin of higher bulk density and consequently poorer Brabender fusion time. RSV0024094 -22- Since the more consistent shperlcal particles did not have the total surface area possessed by the varied shaped particles made with high PDR-1 concentration, the dry time for full conversion resin such as Opalon 30Q was high. With the low conversion FM resins the internal void volume became the controlling factor in plasticizer adsorption rates and therefore there was little noticeable difference in dry time results for high and low PDR-1 made batches. The myriad shapes encountered with Opalon 30CFM particles made with high PDR-1 concentrations explained the tendency for a broader screen analysis distribution. The extrusion grades obtained from FVC batches made with various PDR-1 concentration was contrary to what would be expected from the particle shape. Better extrusion grades were obtained from'Opalon''300 as the PDR-1concentration was increased and the particle shape made irregular and inconsistent. With Opalon 300FM a poorer extrusion grade was obtained at very low PDR-1 concentrations, with the more spherical, consistent particles. Possibly, with the large individual particles comprising the agglomerrates (at the low PDR-1 concentration) any impervious particle was readily apparent in an extruded ribbon, while a small impervious particle would be much less noticeable. Resin heat stability level was progessively poorer as the PDR-1 con centration was increased. A higher concentration of adsorbed PDR-1 in the dryed FVC product was the explanation. This undesireable result can be improved by more efficient washing of the FVC polymer during the centrifuging operation. By the present specifications for PVC, improved resin quality could be obtained at the higher PDR-1 concentrations,provided the excess PDR-1 was washed off the FVC resin. Although this approach would improve the FVG quality level as measured by the present specifications, and might also produce a more competitive resin, it was the author's opinion that basically this approach would never produce an excellent dry blending .resin, since a very important requirement for proper performance in extrusion tfas a high bulk density resin (obtained with sperical shape not at a sacrifice of particle porosity) with good dry blend flowing properties. H . ACID AND BASE ADDITIONS TO FVC FORMULATION 1. EFFECT OF PDR-1 CONCENTRATION ARP pH ADJUSTMENT (Exp. 8) Research work (Ref. 4 and 5) had shown that acidifying the suspending medium with mineral acids to a pH of 1.7 would improve poor PDR-1 lots, result in a narrowing of the resin particle size distribution, and a coarsening of the particle size level. If sodium hydroxide was added instead of acid, a coarsening effect would be obtained as the pH was increased from 3 to 5, with the particle size distribution broadened. At still higher pH, large hard particle beads would be formed. RSV0024095 -23- The possibility of employing PDR-1 concentration and pH adjustment to control resin particle size and distribution was the subject of a designed 25 batch plant experiment in April 1958- Sulfuric acid and sodium hydroxide were used to adjust the pH of the suspending medium prior to the addition of VCM - to pH levels of 1.8, 2.4, 3.0, 3.5, and 4.0 while PDR-1 Master Blend 38 was used at concentrations of 0.06, 0.10, 0.15, 0.20, and 0.25 percent. The procedure employed during the experiment consisted of dissolving the specified amount of PDR-1 in the pre-mix tank and after charging to the reactor - which contained the process water - sampling the dilute solution and measuring the pH and titrating with sodium hydroxide. The titer was compared to a PDR-1 concentration - HaOH neutralization, calibration curve for the specific lot of PDR-1 being used. In this manner the exact PDR-1 concentration in the reactor was' measured (Note: With the multi-kettle PDR-1 charging system gains or losses of PDR-1 were possible from one charge to another.) After the pH measurement the amount of 98$ sulfuric acid or 5$ sodium hydroxide required to adjust the pH to the specified level was estimated. The addition to the reactor was made, the reactor contents allowed to agitate for 5 minutes, and then a sample taken. After the polymerization was completed, a slurry sample was taken from the kettle, dewatered and dryed in the laboratory. One very important operation was overlooked during this experiment, that of diluting and washing the slurry samples to simulate plant slurry handling operations. This omission must certainly have been partially responsible for the resin heat stability and volume resistivity results obtained. After manufacturing l6 batches of Opalon ^,00 in 92 Bldg, the experi ment was halted when the feed-back of quality results for the acidified batches showed an unexpected drastic effect on resin heat stability. Possible reasons for the poor heat stability were (l). the catalytic effect on thermal degradation by the sulfuric acid adsorbed on the FVC polymer and (2) the loss of the stabilizing effect of glyceryl mono stearate by an accelerated acid-water hydrolysis of the ester to glycerol and stearic acid. The "loss" of the glyceryl monostearate could also account for the poorer resin extrusion grade of the acidified batches. The quality results were summarized in order of increasing pH in Table 3- a. Particle Size: The addition of sulfuric acid caused a coarsening effect on the resin particle size level. The effect of sulfuric acid on the particle size distribution was negligible, in general, when compared to distributions for other coarse resin such as produced by low viscosity PDR-1. However, an accurate measurement of the screen analysis distribution for coarse resins can not be obtained with the size screens used in the standard test. This was due to the large difference in screen aperatures for the 40 and 60 mesh screens, as compared to the screen aperature difference for the other screens. RSV0024096 U.S. Screen Mesh 4o 60 80 100 i4o 200 Aperature, Microns 420 250 177 149 105 74 As can be seen from the above listing, the difference between a 40 and 60 mesh screen was approximately equal to the difference between a 60 and 200 mesh screen. Since there were three additional screens between the 60 and 200 mesh screens, the impression of a broader distribution was created, s.s shown below. Screens, Mesh____________ Screens, Mesh 40 60 80 100 140 200 PAN 40 60 200 PAN l 84 12 2 1 T T 1 93 3 T 1 1 T T l l4 24 38 18 5 T 8 26 17 23 15 11 1 84 15 T 1 93 5 T T 1 94 5 T 8 81 ll Since there was an Insufficient number of screens between the 40 and 80 znesh fractions, accurate distribution measurements, even with probability paper, were not possible. With the finer resins a more meaningful measurement was possible. Increasing the PDR-1 concentration and/or adding sodium hydroxide had a broadening effect on the particle size distribution as can be seen by the increase in the Geometric Standard Deviation Values in Fig. 38. The effect of adding sodium hydrozide was primarily on the particle size distribution with little change (possibly finer) on the particle size level. Not evident from the screen analysis for the 4.63 pH batch was the fact that this hatch had approximatlly 5$ agglomerated particles of plus 20 mesh size. Quite probably any batch polymerized at a pH of 5* or above would have been a total loss. b. Bulk Density: The lowering of the resin hulk density with inersasing PDR-1 concentration was again quite significant, Fig. 39* c. Volume Resistivity: The expected effect on volume resistivity by the additon of sodium hydroxide was evident from Table 3. The addition of sulfuric acid had no marked influence on VR, with possibly a decrease in VR when the pH was lowered down to the 1.6 - 1.8 range. RSV0024097 -25- d. Extrusion Properties: The extrusion Fisheye count was increased markedly by the addition of sulfuric acid, as can be seen in Fig.40. The limited data plotted could be somewhat misleading implying an improvement in the Fisheye count at low PDR-1 concentrations. It was suspected that additional dataTOuld show a generally worse and more variable level in extrusion properties as the PDR-1 con centration was decreased, with the average level at any one PDR-1 concentration becoming progressively poorer as the batch pH was lowered. The extrusion grade was related directly to the extrusion Fisheye count. e. Heat Stability: The limited data on resin heat stability showed an extremely poor level for the hatches made with sulfuric acid. 2. SUMMARY AND CONCLUSIONS The results indicated no practical advantages to pH adjustment since acidified batches exhibited poor extrusion properties and heat stability, while batches made with sodium hydroxide had a broad particle size distribution and a lower volume resistivity level. The effect on resin particle size level by pH adjustment was of no practical value since low specific viscosity PRD-1 would produce coarse resin comparable to acidified batches, while the effect of sodium hydroxide on resin particle size could be duplicated by increased PDR-1 concentration. 3. ADDITION OF LAURIC ACID AND MALEIC ANHYDRIDE (Exp. #6) There was reason to suspect that the concentration of acidic material in two FVC suspension raw materials was related to changes in homo polymer resin particle size. Previous plant work, had established a correlation between the free fatty acid concentration in nine lots of lauroyl peroxide and changes in resin particle size. In addition, the acidity of methyl glucoside dilaurate was a suspect in the particle size control problem encountered when attempting to use this raw material as a replacement for glyceryl monostearate. Laurie acid was added to the FVC formulation of nine Opalon 300IM batches to determine the maximum tolerable concentration. The follow ing formulation was used during this study, with the reagent grade lauric acid charged to the reactor at the same time as the laurdyl peroxide. RSV0024098 -26- OPALON 300?H> X-g8 PROCESS Raw Material 1. VCM 2. Water 3. PDR-1 4. GMS 5- L202 6. DAM 7* Lauric Acid Weight lOTfHo lbs. 14,820. lbs. 16,5 lbs. 22.0 lbs. 22.0 lbs. 1,600. lbs. 100 to grams Percent 100. 1350.15 0.20 0.20 0.035 1.0 to ! Following this lauric acid series, three batches of Opalon 300FM were made with maleic anhydride added to the formulation - in place of lauric acid - to determine if resin particle size was affected by the presence of unreacted maleic anhydride in PDR-1. Note that .research work during the development of PDR-1 had shown no apparent effect on resin particle size by the purification' of PDR-1 or addition of maleic anhydride to PDR-1 post-polymerization. Monsanto technical grade maleic anhydride was dissolved in one gallon of water and added to the PDR-1 pre-mix tank at the start of the PDR-1 dissolving operation. The amount of maleic anhydride added was sufficient to increase the specific conductivity of a 0.4$ PDR-1 water solution from 1520 to 2700 micromhos. If the presence of unreacted maleic anhydride per se was the cause for the large shifts in homo polymer particle size encountered with different lots of PDR-1, then .the particle size level should be reaated to the specific conductivity as shown in Fig. The particle size results of all the batches made using lauric acid or maleic anhydride showed no significant differences, as shown in Table 4. It was concluded, therefore, that neither lauric acid nor maleic anhydride was theprime variable in the raw material difficul ties mentioned above. VII. OPERATING PROCEIXJRE The standard operating procedures as described in 'Vinyl Chloride Polymeri zation, 92 Bldg., S.O.P., Manual Sections 63O.O through 639-0, Jan.27,1959" were employed during this study except for the defined formulation changes and the handling of the slurry for dewatering and drying. The salient features of the processes were summarized below. A. SUSPENSION H0M0P0LYMER 1. FORMULATION: OPALON 300FM fx-57 process) OPALON 300 Raw Material Parts/100 Parts VCM Weight Parts/lOOParts VCM Vinyl Chloride Monomer 100 10,980. lbs. 100. Water Glyceryl Monostearate 135 0.2 14,820. lbs. 22. lbs. 135. 0.2 Lauroyl Peroxide 0.26 28.5 lbs. 0.26 Diallyl Maleate 0.20 0.20 lbs. 0 *PDR-1 0.15 16.5 lbs. 0.15 Weight 10,980 lbs. 14,820 lbs. 22 lbs. 28.5 lbs 0 16.5 lbs RSV0024099 -27- *Represexited, the amount used under standard operating conditions. 2. REACTION TEMPERATURE: 53 "t c for both products 3* CONVERSION; 0paIon3QQFM was approximately 77$ conversion polymer. To obtain this conversion, 1200 lbs. VCM was " slow vented" over a one hour period starting approximately 10 hours after the VCM charge to the reactor, and 1000 lbs. VCM was "final vented" over a 25 minute period starting at a 90 psig. level during the pressure drop. Approx imately 330 lbs. of VCM were left in the polymer slurry. Opalon 3CO was approximately 91$ conversion polymer, obtained by allowing the polymerization to near completion and then final venting 600 lbs. of VCM starting at a 50 psig. level during the pressure drop. Approximately kOO lbs. of VCM was left in the polymer slurry. 4. DEWATERING AND DRYING: This phase of the operation was performed in the Control Laboratory. A three gallon slurry sample of each PVC batch made was taken from the reactor immediately after the completion of the polymerization. The polymer in the sample was allowed to settle out and the liquid phase was decanted. The polymer was then transferred to porcelain trays and dryed at air temperatures of 50-60C for approx imately 2k - 36 hours (or until dry to the touch). When resin heat stability results were desired a portion (approximately one gallon) of the slurry sample was washed prior to drying. This was performed by decanting off the liquid from the settled out polymer, transferring the polymer to a Buchner funnel (muslin cloth as the filtering media) and allowing to drain. Then a 1000 grams of the wet polymer was reslurried in a clear gallon jar with 1000 milliliters of approximately 20 - 25 C tap water. The slurry, after being hand shakened for approximately 2 minutes, was again filtered in the Buch ner funnel. This operation was termed "one washing", and by repeating the reslurrying of the vet polymer as many washing as specified were obtained. B. SUSPENSION COPOLYMER 1. FORMULATION: OPALON 510 (X-g6 PROCESS) Raw Material Parts/100 Parts VCM+VAc Vinyl Chloride Monomer y; Weight 9,020 lbs. Vinyl Acetate Monomer 18, 1,980 lbs. Water 126. 13 >860 lbs. Lauroyl Peroxide 0.20 22 lbs. Trichloroethylene 1.0 110 lbs. PUR-1 0,127 14 lbs. 2. REACTION TEMPERATURE: 67 + |C RSV0024100 -28- 3* CONVERSION: Opalon 510 was approximately 90 conversion polymer, obtained by allowing the polymerization to proceed until the batch pressure dropped to 25 psig and then cooling the batch (via the jacket water system) as rapidly as possible until the batch pressure reached opsig. 4. DEWATERING AND DRYING: A one gallon sample of the slurry in the reactor was taken to the Control Laboratory for decanting and oven dryed with 40-50eC air. IX. DESCRIPTION OF EQUIPMENT All the Opalon 300 FM experimental batches were polymerized in 88 Bldg, equip ment while the 92 Bldg, equipment was used for the Opalon 300 and Opalon 510 batches. The only known major difference in the equipemnt was the agitative systems for the reactors. AGITATIVE SYSTEMS Type FVC Kettle Impeller Type Baffle Agitative Resin Op. 300 EM Bldg. Bldg. S55iz71e-- Speed 126 RPM Baffles A, A Position X Intensity 12.0 #5, 88 Bldg. 54" #6, 88 Bldg. 54" 126 REM 126 RPM A, B A, A X 12.0 X 12.0 #7, 88 Bldg. 54" 126 RPM A, B Y 12.0 Opalon 300 #5, 92 Bldg. 54" 121 RPM C, C z 12.0 92 Bldg. 54" 121 RPM C, C z 12.0 #7, 92 Bldg. 54" 121 RPM c, c z 12.0 #8, 92 Bldg. 54" 121 RPM c, c z 12.0 Opalon 510 #1, 92 Bldg. 54" 121 RPM c, c z 12.0 #2, 92 Bldg. 54" 121 RPM c, c z 12.0 #3# 92 Bldg. 54" 121 RPM c, c z 12.0 Sk 92 Bldg. 54" 121 RPM c, c z 12.0 Notes A 4#" x 15" three fingered upward deflecting baffle B ki" x 15" three fingered downward deflecting baffle C 8|" x 24" two fingered upward delecting baffle X= Baffle positioned perpendicular to flow. Baffle length into kettle ranged from 100 to 106 inches Y= Baffle positioned perpendicular to flow. Baffle length into kettle rsinged from 78 to 8l inches Z= Baffle positioned perpendicular to flow. Baffle length into kettle was 69 inches Test Procedures The quality results reported, were obtained with the below listed test pro cedures . A. PDR-1 QUALITY RSV0024101 " -29" X. PURIFIED SPECIFIC VISCOSITY...............................................................SDP-508-72 B Prior to testing, the sample was purified by dissolving in acetone (to remove acetone, vinyl acetate, and maleic anhydride) and pre cipitating the polymeric VAMA with benzene, 2. UNFURIFIED SPECIFIC VISCOSITY Same test procedure as above was used, except for the elimination of acetone dissolving - benzene precipitating technique for sample prep aration. The PDR-1 was tested "as is". 3. DILUTE SOLUTION SPECIFIC VISCOSITY The sample was not purified^ Efflux times were measured for a 0.10# PDR-1 water solution at 60C. The two viscosity procedures listed above employed a 1.0# PDR-1 water solution at 25 C. k, # CONVERSION ...........................................................................................SDP-508-72-4 5. SPECIFIC CONDUCTIVITY ......................................................................SDP-508-72-5 B. OPALON 300 FM QUALITY .................. SDP-5O8-I359-IA l. PARTICLE SIZE.........................................................................................SDP-508-1359-1A Note: SAF = (# on 4-0 mesh)(L0)+(# on 60 mesh)(6o)+.. .-f(# on Pan)(250) 100 2. BULK DENSITY............. ........................................................................ SDP-508-1500 A 3. DRY TIME a. Reed................................................................................................ SDP-5O8-I368 b. Kitchen Mixer.............................................................................. SDP-508-I368-I k. HEAT STABILITY................................................................................SDP-5O8-I363A 5 EXTRUSION PROPERTIES................................................................... SDP-508-I366A 6, BRABENDER PROPERTIES As described in "Opalon Technical Service Application Laboratory Report #3: Development of a Test Procedure for Determination of Performance Requirements of Dry Blending Resin", A.B.Bonneville, J.L.Young, Sept. 14, 1959- C. OPALON 510-28 QUALITY I* PARTICLE SIZE.................................................................................... SDP-508-I359-IA Note: SAF for copolymer was calculated the same as above except that the "# on Pan" was multiplied by 300. 2. 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' ______ ,SOt .444 ,5fc4 .450 _^52.5 ! - 2: SO 3:45 2J5B__ LiUS l- - _i - - _________ j . i! 5.15 i i-.is 1- - 2-20 4-.oo - I 4:oo 4.- j6 4'. 45 S'. 00 4-. 30 4:45 LauS-j ,&.i5 .. 4:0ti 4: to - fc'4-5 - 3'lS - Vi? 2:45 _ 4:30 - 4:1S 5-IS 4-`'50 _' 1 5:00 j i` f ` T5 .4 5o4A 5oS5 Sofc4 \ 31 ; 35* i: 5iaf: :. 3 ; 542$ aS ! il.. i;________ i ;> fi mii i l8 i ______ H .440 .440 | .455 " V18 .450 S7t S7Q .585 .520 .S5o 24Z M .555 .455 .545 i i r F 1 --------------------------- 1 2.30 2:lS MS 2:i0 2-45 4:tS inJLJ 3-45 - 4 nS - Sa_, S'. 00 2'4S 4 - IS ____________________________ 2 = VS .2-.bo -j 4--iO 4:45 J_________ -m-- u-- -- feci 5NaT:t-L ~ V- : t> fevl T.nC 4-. 00 7: OO 4: OO uTiSi)3l5X 1 4,5 \2 -3 , 7? J7 i .3 14 ' T ,J4 \7l ; lA3- (4 1 ^1 ..KvLo 4* t 1 1 XT 2TT 1 TT T T T T I6;o0 So:i5 L Q ...\o 4S. tO;oo U'.OO _a____ ___5____ 5 5^60 4'4S lO to to v ____2______ .. 7ng f 1 'V ; t JL. T J43 f is' 4 1 l 1 J A . 5 'i. 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'Cf CN 0 > ^-tssalus 00 ------ = Po . 548 - ..SSS .L -------------- ;1 I \ 1 I4t D 144 ClAUd u 14<! i5t f\ 140 c. fe .stS 145 eu:uCH . 58S .Sta 147 D ISA D _ 150 4s 6 . s so C- . 5S1! 1SI ISO \So c D c_ - l4t c. Stl j i i 1 !. l \ i i "I-------------- 1 i .! 1 ij i j |, ' i! i ii i31r 1! i if i1 t r i! ! ii 1 l! : 1 "T ^ \ ( I i w^ 'F \ - OfcTA SUE.S.T : *8 j / *10 ih lA z\ to zx > Sg H "---7-- ; 8 M \Z ; ; i S' i *( 4 t1 1% 1 i ` Il S i 8i |i ' il il I- it I: ;i ,- s ' f 1 1 3 i: 3.0 g 3 i '; * ! ii >r,; i;: " ?' 6TCU V10` 54IP 5410 544? 54tA ?4t4 S4c4 r-i 4-t> 5*12- s&zs' PDfi-t VoT 377 " P&tt-i CfttJC. .Cf i.7 - ' l[ II 277 .ft. 1 "j 2.87 1 -j " 'I &OVK C Zri&xTi dtc. cersvrt ORv fauvfT> 4*1 .470 .583441 .St? .Soo 4oS .4-18 . 4o4 .-sir . 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S:vS *T cr* 4:50 \t A tSv SilST 5.is 4 30 ' 40 0 3: ** 2'VS a io _ :4f X-AS* __ 4;en> S-.vS 4'iS4: io 4: on i jf | i! i---------------:------------------------- j H t -1 (: t i '' i id i . !i ------------j _ --J *4 PSS.-1 VO'.i a*ji> PtV' iCt>vit.NlV4.ft7104 \iER60i 1 644 .tvioes. j SCR.C. 14 Ki-ltv' OPM-O-O 300*7-1 1 Tme 1a + 10: 4? to: 5 14: 15 7* J 2.0 5 1 %. i? 7:30 AO fe>o ?- \aa 14c X>e ] j T --1--;r f t1 XI 1^--- 02- 11 A Q _ * J it 1 "&> 1 xC& n_l . 4 T 7 xl 31 : 2* 34. T 2 ! x3 t8 ' 33 :y -r 8-2 I 38 `X _ T t 1 4 2.4 ! 37 \5 i t |[ ra. - T r t A- 2>t> 44 14 s ?T 3S 28 : 23 53.V 141 133 nL u4 \ic 12.8 '54nS S:t4> * C'ito 15 _ tMS 1 It-.30 t'4-? \6'4S 9od t.is ? 22. 2'? 12 4* 5$ _ L tS t.:o-o 7 S *5 t + Lib - r j----r fe' T ie> : 5t o'! ; 2i 7 : 2 1 ! r -----.---3-.1--- ax. i fe *3 J \ 2o : 2* \C> 1? T t r V aCo 55 p T 1 ' 3o 27 28 .2; T 2.1 37 1^ 1 t 4 r- 7 it? ' M \*t ' \X . 4- \ J l 3 : V2. 1 3n 24 11- ; > r --4 *r 1 ' 1 i '1 30 is k ^ 7 2 14 18 ti 2i. i V2- ^ T T U \?T 2ml 24 [ It T 10^33 X.O 11 1 4 3t 1 i 2? 24 : 3 0 'I 1 S' \o8 n8 1S2. '7B It. ^4 ux '77 \S3 145 MV M.C. L __ Qtjdl_vTf. en tv . cukve tso 1A S' - G,audo - c - lAt* 147 c ISO . A - 3 - 144 a \48 s - 147 D X 148 C 1 ; IM & Afe A 144 6 1*4 6 4- - 14& C X 108 144 1 *-o '52148 6 c. T> 3 - - ' ttt-vr ^TftAiwTV . 48___ S7 St 58 58 --&.__ At ASS.3 46 __*2___ =-3___ 3 4 II 4o 1 ----------- .. Ao_ 16 12. 1 -VS__,1 --i3_ - 1Ii lf i r) 1 1 i \ \ r | Iw ^ '1 - t[ it t .1. _ _ < ___ 1 j| 1 1 !! il au!':[ i! tl li Si __ ^___1 ______i Tf RSV0024108 TABLE I SUMMARY OF PDR-L LOTS TESTED ircmp PDR-l Lot Specific Visccsty $ Conversion Spec .Conductivity Coke Bottle Acceptance Test A b C _____________ Micrcomhos CopolymerHomopolymer A 222-1,a A 222-1,b A 222-11 A 222-III A 225 A 236 A 237 A 242 B 230 B 240 B 277 B 278 B 287 C 244 c 247 c 249 <^251 MB 35 MB 38 MB 47 7-79 6.90 6.10 ? 3.86 6.79 8.21 8.48 2.35 - >* 1.21 9-97 3-73 3.26 0.60 - 0.28 O.93 1.25 1.11 4.19 4.30 8.90 8.98 5-75 1.25 1.38 4.36 4.77 2.52 - - - - 7.7 9.0 9*2 6.0 - 6.56 5*45 - _ _ _ - 75.1 - - 70.1 82.3 77.0 78.4 67.0 69.0 83.7 85.4 79.9 84.f 86.5 83 81.5 - - - - 1855 2740 1510 1410 1560 2355 1992 887 922 1283 1142 985 1012 1397 - - - NG - v* OK OK OK OK MG MG OK OK MG MG NG MG - - OK -- - - OK OK - OK OK OK OK - - - Notes: Specific Viscosity= PDR-l lots in Group A and B were tested "by the East Control Lab for specific viscosity using three procedures. A = 1$ PDR-l water solution at 25 C, using PDR-l that was purified "by dissolving in acetone and precipitating with benzene. Present S.D.P. test. B = 1$ PDR-l water solution at 25 "C, using unpurified PDR-l, i.e. material as received and used in the plant. C = 0.1$ PDR-l water solution at 60C, using "unpurified" PDR-l. Three different samples of PDR-l Lot 222 would not dissolve completely in acetone, showing a variable amount of insolubles (polyvinyl acetate). There was insufficient precipitated PDR-l - Lot 222 III - to complete the specific viscosity test. RSV0024109 tab; EFFECT OF PDR-1 CONCENTRATION CHANGES ON OFALON 300 RESIN IN 92 BLDG, PDR-1 RUN CONC. MO. SCREEN ANALYSIS . $ ON MESH BULK DENSITY , GR./CC. REED DRY TIME, MIN.: SCC EXTRUSION 4060 80 100. 140 200 PAN SAF RESIN DRY BLEND VISUAL ADJUSTED RATE GRADE FISHEYES .02 18 ' Very coarse .03 14 T 8 31 27 24 6 3 110 .576 .04 16 T 16 4l 23 17 2 1 96 .575 .06 8 T 8 37 32 18 T 3 98 .520 .06 11 T 5 37 33 24 3 T 105 .545 .07 10 T h 36 38 21 2 T 102 .530 .07 13 1 10 38 29 22 1 T 99 - .08 7 1 12 36 31 18 2 T 97 .505 .09 4 0 2 25 36 32 4 1 119 - .12 15 .16 6 1 59 26 9 4 1 T 1 12 42 28 l4 3 T 95 - .17 1 T 3 19 28 35 14 2 107 - .18 12 3 56 18 10 6 5 2 84 .435 .20 17 .21 5 .25 ' 9 .28 2 1 7 31 29 26 5 1 30 32 14 12 10 2 22 34 20 18 6 1 5 19 24 29 20 1 107 .450 T 95 T 98 .415 2 126 - .30 3 1 11 18 15 22 18 l4 145 - * V7I O \J1 .671 .675 .635 .640 .628 ' .650 - .620 .554 .58O - .553 -> i 9:45 8:15 7:15 9:15 8:30 - 8:15 - 4:15 4:15 6:45 - 4:00 - - 9:45 6:15 8:00 6:45 9:00 - 8:00 - 3:30 4:30 4:30 - 4:45 - - 152 150 160 151 156 - 159 150 - 155 152 - 154 - - V IV V III V - V - I Ill III II - - 39 22 43 13 34 40 - 5 12 15 - 13 - - <in / oo to o EFFECT OF PEOR-1 COKCENTRATION AND pH ADJUSTMENT ON OPALON 300 RESIN IN 92 BLDG. pH FDR-1 AMOUNT OF ACID(A) SCREEN ANALYSIS ..'jSon MESH RESIN BULK REED DRY TIME EXTRUSION V.R. HEAT CONC. OR BASEf3)ADDED 40 60 80 100 l40 200 PAN DENSITY,GR./CC MIN: SEC GRADE F.E STABILITY _______________ _________________ ______ _____ j> TRANS. CJ CM CM CM 1.61 1.67 1.88 .070 .185 .128 21# 5 oz. 18# 18# 2.21 2.29 2.30 2-37 .060 .096 .163 .225 3# 12 oz. 4# 5 oz. ^ 8 oz. 1# 4 oz. 2.71 2.76 - 2-74 .124 .l4l .205 .260 0 0 0 1# 8 oz. 3-36 3-51 3-67 -114 .228 .155 1# 3# 2 oz. 1# 15 oz. 3-9]: il03 4.63 .180 ^ 6 oz. it# 8 oz. A T 52 24 8 4 11 T A 38 60 2 T T T T A 1 93 3 T 1 1 T A T 46 36 12 4 1 T A 1 84 12 2 1 T T A T 49 36 11 5 2 T A 8 71 i4 5 4 T T T 3 24 22 38 12 1 T 25 44 22 10 T T T 5 21 19 21 10 22 B 1 17 32 19 18 2 10 B T 1 l4 24 38 18 5 B T 8 26 17 23 15 ll B 9 6 6 10 23 25 19 B T 3 10 18 30 2 37 B 1 16 37 20 16 15 3 533 .472 .500 .544 .493 .470 .465 .465 455 .413 .405 455 .420 435 455 .430 5:15 4:45 8:30 6:30 8:45 12:45 4:45 5:45 10:00 8:00 3 = 30 4:45 8:45 4:30 4:15 4:15 IV 57 IV 52 V 57 57 52 64 IV 27 107 V 54 80 IV 35 94 IV 27 107 III 30 89 IV 25 101 II 13 89 II 8 73 II 12 III 13 II 14 53 18 24 III l4 III 16 12 9 - 0 5 - - 4o 36 - - -- 42 ' A = 98^ Reagent Sulfuric Acid B = 50$ Technical Sodium Hydroxide ILE 4. EFFECT OF IAURIC ACID AMD MALEIC ANHYDRIDE OH OPALON 3QOFM PARTICLE SIZE RUN AMOUNT OF LAURICE ACID (L) PARTICLE SIZE, # ON MESH NO. AND MALEIC ANHYDRIDE(m)ADDED PERCENT* 4o 60 80 100' i4o 200 PAN SAF GRAMS. 3 0 (Control) _ 4 36 29 16 6 2 1 85 7 0 (L) - l 23 47 20 5 2 T 85 8 100 (L) 1.0 1 35 42 17 5 1 1 84 1 200 (L) 2.0 T 30 50 l4 5 3 T 85 5 200 (l) 2.0 1 16 46 25 8 3 1 92 10 2 200 (L) 300 (L) 2.0 1 20 50 20 6 2 T 85 3-0 T 30 48 15 6 1 T 82 4 4oo (L) 4.0 T 9 42 28 16 4 1 100 9 500 (L) 5.0 1 47 37 11 3 1 T 75 11 600 (L) 6.0 1 20 48. 22 5 1 T 81 6 900 (E) 9.0 1 11 42 29 13 4 2 101 2 0 (Control) - T 4 32 35 19 6 2 107 4 0 (Control) - T 1 20 39 28 9 3 120 1 315 - (M) 4.2 T 13 46 27 9 2 l 91 3 630 (M) 8.4 T 9 43 32 11 3 1 96 5 945 (M) 12.6 T 3 30 37 22 5 1 106 * Weight percent for Laurie Acid was computed using the weight of L2O2Q.S the basis, while for Maleic Anhydride, PDR-1 was the basis. RSV0024113 \G. \ io x to T O T H e c m . 3 5 9 -1 4 KC U FrtLL 6 t .H C O . ............... RSV0024114 t<q .? IO * lO T O T M C C M . 3 5 9 -1 4 1/ 4 f.W RSV0024115 F' i. 3 / oi i/i ns e6 Co hj ft hTr * r* oU x0j JAg X RSV0024116 10 X TO T O TVGL C M . 3 5 0 - 1 4 RSV0024117 si' lO X fO T O T H C C H . 3 5 9 - 1 4 K r ,, u r r r L ts & r.ti c o . M *.r ^ u % * j RSV0024119 Cif. "7 c 2 t 5 a o w d- s RSV0024120 D IE T JIIfN ' tU O E N E DIET Z R E N CO-  V RSV0024121 *Ol 3 * 0 * D J E T lG K N G U fc P H A P C R ' O rE T Z O C N C O . Vm) '9 n" X5uui oey h v> c? --V RSV0024122 cinr, i* r. U u " i'. i c: x t, o2 RSV0024123 JL> lX; ':j; r~ 't 6 RSV0024124 crir. I'? \ RSV0024125 1 K 0X l.U T 1 ? 0 f` L T t O t l ? H E $SU* CM C '-\ 9 > D0 Zw* Cf N t- ' c` U2i3? 0aw uL a< a a< UJ or n . \ RSV0024126 iAf to X to TO THE CM. 3 5 9 -1 -4 COrADOCTWtT't C iv 0 . 4 fC PDR.-\ 'W f'iT tP . 5 t> L O T \O t4 . RSV0024127 i \- \ *7 RSV0024128 |iit *%>vL'vV't ' fL. ._!._ j..V\ kt svfst.w m - . ^ _. RSV0024129 'CO iT jfi& j 9 T i- liiH il JJ./\ g RSV0024130 "P *V 71 - r \ -- L_ . J.V'ii. 1-"T 1 . JfiG,.. *2.0 ..^CT.SLC'P.ck.. VP.K-V COtACtrA:EJWft.X\.ULOtaL_J_-.p^L:ipJpp.-;--p_L. Pi lOP.b.!-tOKl 3500 ; PfW TWE . !i. ! i ?!. i;! : i^KPefe-Vn^T --ft:. r . * i -,i.;- '. \ -1 < 4 .*> I,,; r-- fr't '"I-:-;' ' -ptr *; * i *i: *.l--fj . *.... * 'I - -- -tO'OO --^1*0 O T-S:' - V. : 'V,vi''r'-i LeyeL-ft^P VftftAtv^LVT'l' kb ; covic, L Ill', .. ;i ' !. i * --j,TM--" .V --'P-i. , . :' : r. --0--rV-* --h---- * ' Jii-lPP, 'i-'.. a:! *4 1 - TO X pO T O T H E C 'M j 3 5 9 - 1 ^ RSV0024131 VUh ?-0. * O10 l* r; " 07 o- ** af- t'* h0 * Oj x o r* RSV0024132 2A IA1 RSV0024133 fO x K tu r r tt ox T ij :> tt c m . & r.c i*rn <-?>. w 3 5 9 -t'l irti'.s * OII' C1 RSV0024134 "? V. ? . RSY0024135 RSVO024136 RSV0024138 id . -3-4-O n M r> D IC T IO E N C W A P H P A P E R RSV0024139 1% RSV0024140 E U G E N E D IF.TZG E N C U ***`CvK *m '*-** tLOiuO.. . j WKTEJtV i ;.. i .,', ! 4.._ 1::..' ..LEAEvlT?. OF C*. ?><*> Fv\ t-NKtrtl |(H' ' ! ' ' j "i-; ......I"": "]' *7VJETn >/*TH 'SL'47i PW.-l: VKVL<K:~ '..... I : * -I ! -- !- T| i ! i:'--1) ._WftS\^EOi,,.2XKOjV>~ Cx-itLlxi, .>hP -__:J (>Ko.eCT. TiHEi :waH,;ceLt> .vJfcToa, : ; j .. :\>4:COWTOoL- LKE-To OtTe.0.v\\WO- ; --j - - ] : _J _ EFFECr. OW SVjkSAUTV._____ _ OE.SVV)!4NnejS"wH\CiA r " ' WEttE VlASPOc.^- OOE; Tmo VjEfte "too tnt'Cov.oft.E'D To i--- :; ... - T - -; -; -T- b:lL. b:!--:;l, : V ,- , j '! . W, ' ` ^! ! *'%- ! .1. ~--r;",: l"1" ^ ! ; i -* i .. i - _ * f "! '*-" .*:: | . 1 r - : ;'! -1: .: .:;!" i: i . i . . -----:, '' !-- , . * J; J 1 F :: j." j. .:'.!'. . ;'-1 .T'.'.': L ;.... r. . r. ;. U .. ,L .li.--- i:' l bjb :: bTb'bb.j *.b ' -iv-J- = ' ; i \yi ~f~-TM-(--V-4- D IE T ItJ K t'J [if) A n N P A P C M H.I.IM EU 1? . \ za . --- \J~ ' I RSV0024141 so 3 -lO R M P D lf T iS f N n m p u h '.P E .R E U G E N E D IE T J B E N C D . RSV0024143 RSY0024144 0' O -J k o ; *'!' r,, r, :l t 5 , N\fe.T R V C St i ti L P E V a.ISTt O M 14*>1 26- RSV0024145 lO X to TO THE CM . 3 5 9 -T 4 K E U F fr'-U ft c s s n t j C O . I"*LT -n c ' f in 2fj: oc h js 8* oj 0 4J L\4, RSV0024146 F'Cv EFFECT, OF P&R.-1 CC>H t,EKTftW!ON - Otii oInT> 7:70 \j j u1 TP Jh7-i ?* o^ RRV0024147 t j r j ;vn<^.!s7 ; effect of ve>f.-^o<?klq^ aootV\ ! ' EXT^OMoM PAftfeON <*,*.DE, 1 f EKPci.\V\EV^r.; &> i 1 l f 1 J i s. \ 0> n* sU oo XH \%fi fit xo Lr;- .j i aZ.. J .: /; ...At>:..: ri..\.. i:'"; ._iBDR^sv_aoti.cE vkrkt>0*Cw?<. ;__ : !- , i " !. . ! ^ : ! . . f--- - ,,L\ i j.- "j .I _l. RSV0024148 F ' 6 LI ^ X i* v C* 2" x0 b. J a'Lo^etp.vc . 5>'V K \4prp.t>D i^uvr\<m 'j RSV0024149 C-?, - ETUf F E l, ft E S S E . I* C O . RSV0024150 i o: TO X TO T O T H E C M . K C U K FC L A E S S trt CO , f RSV0024151 "4o