Document V30w2ppQgB2z0RMxzZzO6a8mp

. S'- r^7. Status Report SUSPENSION POLY(VINYL CHLORIDE) RESINS: QXPA PROCESS DEVELOPMENT IN PRODUCTION EQUIPMENT WITH "CELLOSIZE" QP-4400 SUSPENDING AGENT author c. Wise J. C. Alexander J. F. Erdmann Group Leader May 26, 1961 FILE NO: B:20:835-S12 Project No: 514X SUMMARY Experimental polymerizations have been performed in the 4600-gallon production autoclave C14, in ord r to develop a process for manufacturing QXPA resin. This resin is needed as a plastisol additive for companion sales with QYNV and QXKV-2 resins, for which considerable sales volumes are dependent upon availability of the additive resin. As a result of this program, a process has been developed for interim manufacture of QXPA resin in quantities sufficient to fill current needs. In this process, agitation is provided by a Pfaudler-type, retreat-curve impeller, th same as is used for standard production of Process 5 resins. The suspending agent is CELLOSIZE QP-4400, which promotes for mation of the glassy beads of polymer which are characteristic of a satisfactory plastisol additive resin. The resin produced by the interim process possess s excellent rheological properties, equal or superior to comp titive resins. The only significant shortcoming is a question able heat stability, which may necessitate a change to a suspending agent other than CELLOSIZE QP-4400. The reproducibility of the interim process was demonstrated by successfully conducting six consecutive produc tion runs, in which the essential features of the polymerization were maintained while several minor conditions were varied. However, some undetected variables which have caused difficul ties in the past have not yet been eliminated and may emerge at any time to override the benefits of recently imposed improvements. Development department Union Carbiqc Chemicals Company SOUTH CHARLESTON. WEST VIRGINIA B:20:835-312 2 During the course of the experimentation, frequ nt inconsistencies in results were observed. These results, upon analysis, provided a basis for a fresh evaluation of the effects of such process variables as agitation, suspending agent concen tration, autoclave charge level, and monomer-to-water ratio. INTRODUCTION The Development Department was called upon to develop a process for the manufacture of QXPA resin in the present facilities of the Suspension Vinyl Resins Unit at Location 514. A considerable urgency was attached to the problem, because a significant volume of sales of QYNV and QXKV-2 resins depends upon the availability of a suitable plastisol additive resin for blending with these dispersion resins by our customers. Obtaining competitive additive resins for resale as a stopgap measure was not desirable, since the known competitive products do not always perform adequately with QYNV and QXKV-2 resins. Thus, the preferred solution of the problem was the rapid development of our ability to produce QXPA resin. The resin sought in this series was one which would perform well as a plastisol additive in decreasing the viscosity while increasing the resin content of the plasticized formula tion. The particle structure known to produce these desirable properties is that of small, spherical, glassy beads of polymer, with low porosity and high apparent density. A resin possessing these properties was produced in production equipment over a year ago. Agitation was provided by Mixco turbines, and Elvanol 50-42 (E88H) was the suspending agent. However, for the current series, use of the Pfaudlertype, retreat-curve impellers was desired by the Production Department, so that equipment changes would not be necessary when shifting production from one type of resin to another. The use of CELLOSIZE QP-4400 as the suspending agent was undertaken on the basis of several completely successful polymerizations in the 600-gallon autoclave E17 (1). This report deals with the operation of production autoclave C14 on an experimental basis to scale up the succ ssfully applied conditions of operation in E17 autoclave for manu facturing QXPA resin. Topics discussed are the present status of the program, the? difficulties involved in reaching the present status, and the effects of variables observed during the experimentation. ucc 039704 B:20: 835-S12 3 DISCUSSION The experimental production of QXPA resin in C14 autoclave was begun under the same conditions which had been employed successfully in the 600-gallon auto clave E17 (1). Early in the program a resin was produced (Table I, Run C14-2-5) which possessed the properties required of a plastisol additive resin. However, the results of that polymerization could not be duplicated in two further attempts at the same conditions (Table I, Runs C14-1-6 and C14-2-16). The discrepancy which changed this experimental series from a simple scale-up to a considerable task was th onset of agglomeration during the latter stages of the polymeri zations. The result of this agglomeration was that, instead of small, glassy beads of polymer (median size 75 to 90 microns), large aggregates (150 to 200 microns) of those beads were obtained. Comparison of the photographs of resin from a successful run (C14-2-5) with an agglomerated run (C14-1-15) in Figure 1 below clearly demonstrates the difference between satisfactory and unsatisfactory resin. The large agglomerat s typified in Run C14-1-15 are wholly unsuited for use as a plas tisol additive. Figure 1 Satisfactory and Unsatisfactory Particle Geometry for Plastisol Additive Resins ucc 039705 B:20:835-S12 4 A great deal of unforeseen effort was expended before this problem of agglomeration was brought under control. The result of this effort was the development of a process for interim manufacture of QXPA resin in quantities sufficient to fulfill immediate needs while a more reproducible and more pro ductive process is developed. The results of all the runs in this series are summarized in Table I and Table II. Photographs of representative resins are presented in Figures 2, 3, and 4. The extent of deviation from run to run is demonstrated again in Figure 5 where photographs of the resin slurry of two runs ar compared at equivalent stages in each polymerization. Status of Development Program The interim process which has emerged from this period of operation has already been published (2), and is pre sented in Appendix A. It provides for use of the Pfaudler-type, retreat-curve impellers which are used for standard production of Process 5 resins at the Suspension Vinyl Resins Unit. The use of CELLOSIZE QP-4400 as the suspending agent, sodium bicar bonate as the buffer salt, and dilauroyl peroxide as the polymerization initiator involves no novel techniques and pro vides a simple, straightforward process. The disadvantage which prohibits the process from being specified for full commercial production is low productivity, resulting from the 50 per cent charge level and from the lengthy, 2-hour mix period prior to heat-up. The resin which is expected from this interim proc ss is equal or superior to competitive resins in the viscosity of blended formulations and in the tensile strength of the resul tant plastics. Disadvantages are two: somewhat inferior heat stability, due probably to the QP grade of CELLOSIZE, and slightly large particle size, which results in graininess in thin film applications, but which can very likely be overcome by moderate adjustment of agitator speed. The reproducibility of the results obtained with this process has been demonstrated (Runs C14-3-23 through C142-28, Table II and Figure 4). It is noteworthy that the major characteristics of the plastisol additive resin were retained in all six of these runs, even though some slight changes in recipe and operation were imposed.- However, the full impor tance of the several process variables, some controllable and some not, has not yet been established, and consequently a vestige of doubt hovers over these seemingly well-established conclusions. ucc 039708 B:20: 835-S12 5 Effects of Variables During the course of this series, many changes were imposed on the process variables in attempting to overcome the problem of agglomeration. Although these changes were insuffi cient to establish definitely the effects of the variables, several tentative interpretations can be made. These are pro posed explanations of observed behavior and are based largely on intuitive reasoning rather than on concrete observations. Agitation The agitation system in which QXPA resin is produced seems to be a primary factor in determining whether a resin will be satisfactory or not. Inadequate agitation does not provide enough turnover in the autoclave to maintain the suspension, and huge agglomerates of resin are formed. Likewise, too much agitation results in formation of very small initial particles and greatly increased surface area of the monomer droplets.. Th suspending agent often is unable to provide adequate protection over this increased area, particularly in the later stages of the polymerization, and agglomeration of the small, glassy beads occurs. The degree of agitation is determined by impeller speed, by the type of baffles installed, and by the relative position of the impeller and the baffles. At the start of this series, C14 autoclave was equipped with pipe baffles, as are the other production autoclaves in use for manufacture of Process 5 resins. The pattern of agitation in this system differed greatly, based on visual observation, from the pattern in E17 autoclave (4). Changes were required; namely, installation of 5-inch flat baffles and relocation of the impeller at a higher position in the autoclave - before the initially successful run (C14-2-5, Table II) could be performed. Then, with basic simi larity in agitation pattern, the impeller speed had to be decreased from 100 rpm to 75 rp^ before the reproducible interim process was found. Concentration of CELLOSIZE QP-4400 After the basic particle size has been set by the agitation, enough suspending agent must be included to protect these monomer globules from coalescing early in the polymeriza tion and from agglomerating later on. Other than in providing this protection, the concentration of the CELLOSIZE QP-4400 has little effect on the size or the nature of the particles. The CELLOSIZE should be used at the lowest possible level, since excessive amounts reduce the polymer heat stability significantly. UCC 0-39707 B:20:835-S12 6 Autoclave Charge Level The 75 per cent charge level which is in standard use in the Suspension Vinyl Resins Unit was initially used in this series as well. However, in order to decrease the distance from the impeller to the surface of the charge, the charge level was later reduced to 50 per cent of capacity. The principle behind this action was that, as compared with E17, the average particle in C14 autoclave had to travel a greater distance from the impeller. The particle thus would lose more energy than its counterpart in the smaller autoclav , and the lower energy level might lead to agglomeration. Increased agitation would impart more energy to the particle, but could lead to agglomeration, as previously pointed out, as a result of lost protection later in the run. The extent of this equipment size effect has not been definitely established, but it may explain why many competitive resins are produc d in autoclaves considerably smaller than those used in our Suspen sion Vinyl Resins Unit. Five of the six successful polymerizations were con ducted with a 50 per cent charge level, and this was specified as a requirement for the interim process. However, since th latest run at 75 per cent of capacity (Run C14-3-26, Table II) produced a resin with satisfactory properties, the permissible charge level may reasonably be expected to increase as famili arity with the interim process is gained. Monomer-to-Water Ratio At one point in the series (Runs C14-1-9, -2-10, and -3-11, Table I) the monomer-to-water ratio was decreased to 30/70, to determine whether greater dilution would prevent agglomeration. The opposite occurred; agglomeration was even worse than when the ratio was 35/65. This was true even when the CELLOSIZE concentration was increased to the point which would provide the same aqueous-phase viscosity present at the 35/65 ratio. Hence, a logical future step would be to increase the monomer-to-water ratio; perhaps the suspending action would be improved, just as it was redu'ced in going the other way. Oxygen Concentration Before charging the vinyl chloride to these runs in C14, a thorough evacuation procedure was carefully followed. The autoclave vapor space was then tested for oxygen content. Within the reliability of the sampling and measuring techniques employed (Analytical Systems Trace Oxygen Analyzer), the oxyg n level was very low (less than 50 ppm) in all the runs included in this report, with the result that the effects of oxygen have not been considered in this series. !JCC 039708 B:20:835-512 7 Buffer Salt The use of sodium bicarbonate as a buffer salt certainly exerts an influence on the polymerization. In bomb polymerizations it increases the tendency to form spherical particles, but also apparently promotes the formation of translucent spheres of polymer, which are of uncertain identity and which contribute significantly to poor heat stability. Isolating these particles, analyzing them, and identifying the role of sodium bicarbonate in their formation are included in prospective plans for future work. Physical Properties of the Polymerizing Mixture Inspection of the autoclave slurry samples taken during the early stages of each polymerization uncovered a phenomenon which may prove of benefit in explaining some of the inconsistent results obtained in this series. Within th first three or four hours of polymerization, the consistency of the resin slurry provided a forecast of the eventual outcome of the run. The slurry from runs which turned out successfully had a "creamy" feel when rolled between the thumb and fore finger. On the other hand, the slurry from unsuccessful runs did not feel "creamy10, but rather it rolled together in th fingers somewhat like wet tissue paper. It seems likely that a difference which could be detected so readily by feeling the resin should also appear as differences in measurable physical properties. Therefore, routine laboratory analyses were performed on filtered auto clave slurry samples to determine viscosity, surface tension, pH, and content of gels and insolubles in the water phase of the slurry. The analyses demonstrated differences from run to run, and from sample to sample, but the variations were essen tially the same for all runs investigated, whether or not a satisfactory resin was produced. As a further test, samples of the aqueous charge to several of the C14 runs were used as the aqueous charge in laboratory polymerizations in 50-ml glass bombs. There was some variation in resin from bomb to bomb, not unusual in polymerization on this scale, but the differences could not be related to the differences observed in the resin from the production runs. Mixing Period In five of the six successful runs, the autoclav charge was agitated at 20"C for two hours before the start of heat-up to the polymerization temperature. This period was O'C'C 039?0g B:20:835-S12 8 added to the standard charging cycle in order to ensure equilibrium between the phases before the start of polymeri zation. The report of a Development Department study of agitation (3) had stated that a considerable amount of time was required for protected suspension systems to achieve equilibrium. The one successful run conducted without the twohour mixing period (Run C14-1-27, Table II) produced a resin of essentially the same properties as were encountered in the runs with the mixing period. The only difference was a slight decrease in the amount of fines, as if starting the polymeriza tion prevented the monomer droplets from reaching their minimum, equilibrium size. Further study along this line is also re quired , and the longer mix period should be continued until it can be proven unnecessary. CONCLUSIONS 1) A process has been defined for interim manufacture of QXPA resin in the 4600-gallon autoclaves of the Suspension Vinyl Resins Unit, Location 514. The process is capable of pro ducing plastisol additive resins which are equal or superior rheologically to competitive products and which at the time of our study were of sufficient quality in other respects to me t competitive materials of similar type. 2) The principal difficulty in scaling up from E17 600-gallon autoclave to C14 4600-gallon autoclave arose from basic differences in agitation, which have been partially accounted for, but which will require additional work in pilot equipment for complete resolution. 3) Developmental effort in C14 autoclave has achieved practically all it can within the present state of knowledge. Further expense for experimental production in th full-scale autoclave is not justifiable; however, the Produc tion Department should be able to gradually improve the process further by employing small, systematic changes (EVOP methods) while producing salable resin. 4) Much of the variability in the results of polymeri zations in this series has not been explained, in spite of all the efforts to maintain uniform conditions and to identify variations which might have occurred. In this regard, the quality of the vinyl chloride monomer is considered a possible source of difficulty, although no proof of its harmfulness has been discovered. ijCC 039710 B:20*835-S12 9 RECOMMENDATIONS The most advantageous use of the results of this series can be obtained if the following recommendations are included in future scheduling. 1) The Production Department should use the interim process, as recommended in Appendix A, for producing required amounts of QXPA resin. 2) During interim production of QXPA resin, the Production Department should keep additional records to permit more effective analysis of operating data. A proposed log sheet to use in recording such necessary information is presented as Appendix B. 3) In general, the Production Department should assume responsibility for and control over the semidevelopmental, semicommercial production of QXPA resin in C14 autoclave. If reproducibility on this operating basis is obtained, implementa tion of a program such as the "random-walk EVOP" would provide a simple, orderly method for process improvement. The Development Department has prepared a specific proposal along this line and will present it separately. 4) If reproducibility should be unattainable at any future point in the production-scale program, the Pfaudler impeller and the present recipe should be abandoned in favor of a return to Mixco agitation and the Elvanol suspending agent system in order to duplicate the conditions under which resin QEX-0125 was produced two years ago. EQUIPMENT AND PROCEDURE C14 autoclave, in which this work was carried out, is a 4600-gallon, stain less steel autoclave equipped with a brine jacket for falling- film cooling. Agitation was provided by a 56-inch diameter, Pfaudler-type, retreat-curve, stainless steel impeller. The impeller was placed on the shaft 28" (one-half the Impeller diameter) above the bottom of the autoclave. Baffling, as previously discussed, was provided initially by two 3-inch pipe baffles which were replaced by four 5-inch flat baffles. In addition to the obvious differences In the two kinds of baffles, the pipe baffles were short and did not extend down to the 1 vel of the impeller, whereas, the flat baffles extended the entire distance of the straight side of the autoclave. The operating procedure comprised (1) charging wat r, suspending agent, buffer salt, and catalyst to the autoclave, (2) evacuating the autoclave vapor space at 50C, (3) charging trichloroethylene molecular weight degrader and vinyl chloride, (4) mixing this charge for two hours at 20C, and (5) conducting the polymerization at 57'C until autoclave pressure had fall n to 70 psig. Specific procedures are presented in the discussion of the interim process in Appendix A. 039711 B:20:835-312 10 FUTURE WORK Although no further experimental work in th production autoclave is intended at this time, considerable experimentation on a smaller scale is planned. 1) Scale-up factors will be investigated by scaling down from the C14 autoclave results in this series to future work in 600-gallon and 10-gallon autoclaves. Such a study, when pursued to a satisfactory conclusion, will provide bases for easing scale-up problems involving many different resins in the future. 2) Additional experiments in glass bombs and in the pilot autoclaves will be undertaken as required to promote less sensitive, more reproducible operation and to improve resin properties found lacking as the resins are evaluated more fully. ACKNOWLEDGMENTS persons: Assistance in conducting these developmental operations was supplied by the following I.The Suspension Resins Department under J. E. Deitzler and D. W. Finn of the Production Department provided the equipment and the personnel for the polymerizations. II. Personnel of the Quality Control Laboratory, under the direction of J. W. Chatfield, performed the routine evaluations included in this report. III. A. F. Rogers, of J. J. Brezinski'g group of the Develop ment Department, conducted those special tests required for evaluation of a plastisol additive resin. Mr o 33971 ; B:20:835-S12 11 BIBLIOGRAPHY (1) Alexander, J. C., Suspension Poly (Vinyl Chloride) Resins: QXPA Polymerization~in the 600-Gallon Autoclave with CELLOSIZE QP-4400, Development Department, April 1961, (B:2<3 : 835-Sd) . (2) Erdmann, J. F., et al., QXPA Resin: Recommendation for Interim Production Process, Development Department, March 6, 1961 (B:2(5:835-Ml 1) . (3) Rodriquez, F., Suspension Process Studies: Effects of Agitation and Suspending Agents in a Model System, Development Department, November 25, 1959 (B:20:240-S2). (4) Erdmann, J. F., and Nelson, W. H., QXPA Resin: Factors in Agitation Scale-up from 600-Gallon to 4600-Gallon Autoclaves, Development Department, in preparation (B:20:835-S13). LABORATORY ACCOUNTS: 81753-0-2156 81753-0-3033 81761-0-3248 PERIOD: November 29, 1960, to February 25, 1961 Attachments: 2 Tables 4 Figures 2 Appendixes jw UC 0397 B:20:835-812 12 TABLE 1 EXPERIMENTAL QXPA POLYMERIZATIONS IN C14 PRODUCTION AUTOCLAVE Operating Temperature: Trichloroethylene concn: Dilauroyl Peroxide concn: Sodium Bicarbonate concn: Autoclave Level: 57"C 1.0 per cent 0.0B per cent 0.15 per cent 75 per cent full r--4 T-4 1 C14 Run No. CELLOSIZE QP-4400 concn, per cent Agitator speed, rpe Monomer-to-mater ratio Specific viscosity Apparent density, lb/cu ft Absorption, per cent Beating loss, per cent Screen analysis, % thru 60 mesh SO " 100 " 140 " 200 " 270 ' Median particle size, microns ICMT Brookfield viscosity, poises (a) 24 hr, 2-1/2 rpn 20 1-4 0.20 120 35:65 0.141 33 29 0.2 100 100 99 80 54 32 70 101 2-5 0.20 100 35:65 0.115 43 15 1.7 100 100 99 95 61 30 65 88 1-6 0.20 100 35:65 0.137 38 23 1.1 100 99 92 78 53 32 80 88 2-16 0.20 100 35:65 0.138 29 34 1.3 74 14 7 3 1 0 205 110 2-7 0.20 90 35:65 0.145 39 20 1.6 95 49 20 10 5 2 185 100 3-8 0.20 90 35:65 0.141 38 21 1.4 99 75 39 24 10 6 155 106 1-9 0.20 100 30:70 0.144 36 24 1.3 99 82 43 25 8 5 145 83 2-10 0.26 100 30:70 0.141 38 20 2.0 100 84 37 23 4 2 145 97 0.26 120 30:70 0.139 41 23 1.0 98 83 39 25 23 22 140 85 1-12 0.20 100 35:65 0.141 36 30 1.9 100 97 84 43 27 23 110 97 2-13 0.30 100 35:65 0.141 39 20 1.5 100 100 97 27 8 7 115 94 3-14 0.30 115 35:65 0.141 38 13 1.4 100 100 36 27 17 16 125 77 1-15 0.20 115 35:65 0.137 35 32 1.6 B6 21 9 5 3 2 210 100 640 135 340 - - _ _ - - - - - - 350 150 300 - - - - (a) These samples mere not sashed In the autoclave B:20:835-S12 - 13 TABLE II EXPERIMENTAL QXPA POLYMERIZATIONS IN C14 PRODUCTION AUTOCLAVE Operating Temperature: Trichloroethylene concn: Dilauroyl Peroxide concn: Sodiua Bicarbonate concn: Monoaer-to-water ratio: 57*C 1.0 per cent 0.09 per cent 0.15 per cent 35:65 C14 Run No. CELLOSIZE QP-4400 concn, per cent Agitator speed, rpa Autoclave level, per cent full Specific viscosity Apparent density, lb/cu ft Absorption, per cent Beating loss, per cent Screen analysis, 1 thru 60 aesb 80 " 100 " 140 " 200 " 270 " Median particle size, nicrons ICMT Brookfield viscosity, poises 24 hr, 2-1/2 rpn 20 rpa 3-17 (a) 1-18 2-19 3-20 1-21 2-22 0.20 0.20 100 100 50 50 0.20 100 50 0.20 100 50 0.20 100 50 0.20 75 50 0.143 0.136 43 37 13 45 1.4 1.2 0.143 35 46 1.6 0.137 37 28 1.4 0.138 38 24 1.6 0.142 40 25 1.3 98 97 94 54 59 13 96 62 46 12 24 4 91 38 28 6 15 2 74 20 15 3 8 1 39 9 9 2 6 - 26 5 6 1 4 - 60 160 185 250 230 390 91 95 93 88 90 95 3-23 (a) 1-24 (a) 2-25 (a) 3-26 (a) 1-27 (a) 2-28 (a) Geoo 202 0.30 75 so 0 .30 75 so 0.30 60 50 0.30 75 75 0.30 75 50 0.30 75 50 - *-- 0.141 45 12 1.6 95 88 83 54 25 18 0. 136 39 17 1.7 100 99 98 87 48 34 0.131 45 13 1.7 93 80 65 33 14 10 0.139 43 15 1.8 93 78 67 46 20 13 0.141 42 16 1.7 96 82 67 42 16 B 0.13 5 40 16 2.1 96 89 76 52 23 15 - - _ - - 95 65 125 120 120 100 90 77 82 B0 88 87 - 228 - - - - - 182 -- 176 272 160 176 160 200 3 66 143 236 126 150 146 146 257 (a) Tbe resin froa these runs was washed In the autoclave by addition of TERGITOL NPX after stripping, CC --J i :,1 DEVELOPMENT DEPARTMENT : 20?835-S12,; lFIGDRE*2? PHOTOMICROGRAPHS ILLUSTRATING AN ACCEPTABI PLASTISOL ADDITIVE RESIN AND THE EFFECTS PROCESS VARIABLES STUDIED AT A 75 PER CENT^^^^^LEVEL'- C14-2-5 100 rpm 0.20 Per Cent CELLOSIZE 35:65 Mon. to Water Ratio C14-2-7 Lower Agitator Speed (90 rpm) C14-2-10 Lower Monomer to Water Ratio r30: 70) C14-2-13 Higher CELLOSIZE QP-4400 Concentration (0.30) ucc 033716 DEVELOEMENTDEPARTMENT B:20:835-S12 FIGURE 4 OTOMICROGRAPHS ILLUSTRATINGIR^RODUCIBILITY *(*, * ' * .'i.fr.aMplHM&Wfc-'' '1-t -- - * AT THE 50 PER CENT CHARGE^LEVEL QEX-0325 Blend of C14-2-25 and C14-3-26 QEX-0327 Blend of C14-1-27 and C14-2-28 QEX-0310 Blend of C14-3-23 and C14-1-24 it, :i: ii DEVELOPMENT DEPARTMENT B:20:835-SI2 FIGURE 5 PHOTOMICROGRAPHS OF RESIN SLURRY SHOWING VARIATIONS IN PROGRESS OF POLYMERIZATION I HOUR 2 HOURS 3 HOURS 5 HOURS T HOURS 9 HOURS II HOURS FINAL B:20:835-S12 APPENDIX A QXPA - STANDARD INSTRUCTIONS FOR INTERIM PROCESS I. Autoclave Preparation 1. Clean autoclave after every third run, including sight glasses and nozzles. 2. Before each run wash out autoclave thoroughly to remove all loose resin remaining from previous runs. 3. Pressure-test autoclave carefully and accurately so that later evacuation will be successful in removing oxygen. 4. Put a new chart on each instrument using 24-hour charts so that we will have a continuous record of each run on a single chart. II. Autoclave Charge - For 50 per cent volume charge in 4600gallon autoclave 1. Water (50C) (to 119-inch rod) (1450 gallons, if water meter is used) 12,100 lb. 2. CELLOSIZE QP-4400 (0.30% of VC1) 19 lb . 8 oz. 3. Sodium bicarbonate (USP) (0.15% of VC1) 4. Dilauroyl peroxide (0.09% of VC1) 5. Trichloroethylene (Hooker) (1.0% of VC1) Liquid level increment on metering tank 6. Vinyl chloride (to provide a ratio of 35/65 vinyl chloride/water, by weight) Counts on Pottermeter III. Charging Procedures 9 lb. 11 oz. 5 lb. 14 oz. 65 lb 2375~ inches 6500 lb. 82S Charge the autoclave in the order listed, observing the following procedures. 1. Add enough water at 50C to fill the bottom head of th autoclave before charging CELLOSIZET. i icc t`"ti on i Vi B:20:835-312 A2 2. CELLOSIZE QP-4400 (dry powder): draw into the autoclave with cold water aspirator. Run the agitator at 30 rpm. Feed carefully to the aspirator to avoid plugging the line. Feed CELLOSIZE rapidly enough to get it all into the autoclave before the water level reaches the end of the rod. Note that cold water should be used in the aspirator since better dispersion of the CELLOSIZE results. 3. Water (50C): after the CELLOSIZE has been added, fill the autoclave to the designated rod level. Be sure agitator is off when filling to rod level. Because of the foam which often forms from the CELLOSIZE, th use of an accurate water meter is preferred to the rod technique, 4. Sodium bicarbonate - add through funnel. 5. Dllauroyl peroxide - add through funnel. 6. Evacuation: a. Blank off rupture disc and stripping header. b. Agitate at 30 rpm. c. Evacuate to 26" vacuum for 1/2-hour at 50C. 7. Purge the VC1 supply line to the atmosphere for a few minutes and close off vacuum line. Break vacuum with VC1 and take to 50 psig autoclave pressure. 8. Remove blanks from rupture disc and stripping header. 9. Cool autoclave contents to 20C; maintain at least 10 psig on the autoclave with VC1 at all times. 10. Make trichloroethylene addition after temperature has fallen to 11. Add vinyl chloride by count on Pottermeter at 20/C. IV. Operating Instructions 1. While charging VC1, purge out lines to oxygen analyzer, and begin measuring the amount of oxygen in the auto clave. Set the analyzer on the 0-500 ppm scale and continue the analysis throughout the run. Label the chart with the run number and time, using a clean chart for each run. Special instructions for use of the analyzer will be issued to all Chief Operators, who will be responsible for the use of this instrument. wo iV'uO'i 7** *7* il B:20:835-S12 A3 2. The oxygen reading is necessary for determining the reproducibility of the evacuation steps, but it is not to be used to stop operation of a given run if a particular level of oxygen is not achieved. 3. When vinyl chloride is added, increase agitator speed to the speed specified for the run. Count by hand to be certain. 4. Hold at 20C for the specified mix period (2 hours). 5. After the mix period, begin heating as fast as possible to operating temperature. 6. Record on charts and log sheets the times of evacuation beginning and end of mix period, and beginning of heat up. (See attached log sheet.) 7. Zero hour is the time when operating temperature is reached. 8. When autoclave pressure has dropped to 70 psig, b gin recovery procedures below. 9. At the 70 psig point, add 1 gallon of TERGITOL NPX by dividing it into four 1-quart portions and diluting each to 1 gallon with HOT WATER before addition. Make sure all the TERGITOL is dissolved in the water (ignore the foam) - this will be greatly helped by using HOT WATER for dilution. Note that the TERGITOL solution must be added against approximately 70 psig autoclave pressure through a double-valve charging system. Continue agitation at operating temperature for 30 minutes; then transfer the autoclave contents into the blowdown tank. V. Resin Recovery 1. Strip off unreacted monomer in the blowdown tank. 2. Fill the tank with water for dilution. 3. Feed the diluted slurry to the Bird slowly and st adily to ensure complete, uniform drying. (Resin must be at least 99.5% 5 before bagging.) 4. Recover in No. 10 flash dryer through the east skin trap as usual. 13372 B:20:83 5-S12 A4 5. Dryer Air Temperatures: First stage outlet 60C Second stage outlet 65C 6. This glassy, bead-like resin particle should be easier to dry than porous resin particles, but probably will require some adjustments of Bird operation and dryer feed because of the smaller particle size. The accept ance of this resin by potential customers depends a great deal upon the dryness of the resin, since more than 0.5% moisture greatly reduces the physical proper ties of the cured materials. uc B:20:835-S12 APPENDIX B QXPA Log Sheet Date Please fill in all information desired as the work progresses. If the data is not available or other problems aris , use back of this sheet to explain your troubles. This information is needed for improved efficiency of this process. Shift 7-3 3-11 11-7 Operator Chief Operator .1 Results of pressure test at psig: Leakage rate psig per hour Time Completed 2. Autoclave charge CELLOSIZE QP-4400 lb. oz. "Water to inch rod Sodium bicarbonate Dilauroyl peroxide lb. oz. .lb. oz 3. Autoclave temperature at end of charging C 4. Evacuation of autoclave Time started vacuum Maximum vacuum on autoclave inches Hg. Time stopped vacuum 5. Breaking vacuum Vinyl chloride used counts on Pottermeter 6. Temperature after cooling C 7. Trichloroethylene inches on metering tank ucc 039724 i > B:20:835~S12 - B2 QXPA Log Sheet (Contd.) Time Compl ted 8. Vinyl chloride _______ counts on Pottermeter NOTE: No. 5 plus No. 8 should equal specified charge. Source of Vinyl Chloride Tank No. at Building 178. What kind of VC1 is it? Synthesis, cracked, mixture of these two, recovered. (Confirm by telephone call to Unit.) or 9. Temperature at start of mix period Agitation speed rpm Temperature at end of mix period C C 10. Start of heat-up End of heat-up (zero hour) 11. Recheck of agitation speed hour rpm at zero A, X X W to m B:20:835-SI2 DISTRIBUTION Mr. W. Adamson, NYO Dr. G. I. Addis, 312 Mr. A. R. Anderson, 515 Mr. G. F. Brant, 514 Mr. J. A. Bruton, NYO Mr. J. W. Chatfield, 514 Mr. L. L. Dintiman, NYO Mr. D. W. Finn, 514 Mr. R. D. Glenn, NYO Mr. G. J. Hanks, Jr., 514 Mr. J. L. Johnson, 514 Dr. T. R. Miller, NYO Mr. D. E. Richardson, 515 Mr. S. H. Rose (2), 511 Mr. M. E. Sutherland, 514 Mr. R. N. Wheeler, 514 Mr. W. R. Wheeler, NYO Mr. J. W. Biddle Dr. J. J. Brezinski Mr. D. L. Engle Mr. G. L. Funk Mr. J. B. Glass Dr. R. I. Hoaglin Dr. G. F. Johnson Mr. P. T. McCoy Mr. A. E. Montagna Mr. A. F. Rogers Mr. C. R. Welter INDEX LIST CELLOSIZE QP-4400 Vinyl Chloride Poly(Vinyl Chloride) Dilauroyl Peroxide Pfaudler Agitation Resin Physical Properties Resin Particle Agglomeration Suspension Polymerization Plastisol Additive Resin X X X 9397: