Document em1MY93DE449OBr0ppn89jykm

n1 Monsanto Company Organic Chemicals Division St. Louis Research Department St, Louis Research Report No. P-1366 TENTATIVE PROCESS FOR PRODUCTION OF PLASTIMER III ETHYLENE/VINYL CHLORIDE COPOLYMER Job No. 2-02-760u01~4733 RSV 0017431 March 25* 1965 Written by: M. E,, Gibbs DO NOT EFPrCTUCE ANY PART CF THIS n FCI'T . EXTRA ClPILS A\:... LAIAT TECH NICAL II.PoRAAIION GROUP OFFICE. Work done by: R- W ,, Bucknell H, Ju Hileman A ,, Alt J - H .. Brown B, Bhatia F. W. Flagg M. E. Gibbs J H. Hahn DISTRIBUTION OF REPORT NO. P-1366 L File 2. H. W. Bucknell H. L. Hubbard 4. Duplicate File 5- Central Reports Library 6. J. F. Quinn 7- M. E. Gibbs 8. J- . Neff - Organic Engineering 9" D. La Wasson - " it 10. T,, Ho Lafferre - " ti ll. Ha Jo Hileman 12. Jo H. Brown 13. 14. 15. 16. J. Ha Hahn Ca Ea Butts - J. P. 1Queeny Plant it it tt it it n u C ,, E. Anagnostopoulos 17 - Extra l8<, Extra 19- Extra 20. Extra This report contains confidential information which is the property of the Monsanto Company and which shall be disclosed only to duly authorized persons. The recipient is held accountable for the filing and safe custody of the report.v which must be returned on demand - RSV 0017432 TABLE OF CONTENTS Page No. INTRODUCTION ............. ................................................................................. . . . 1 SYNOPSIS OF PROCESS ...................................................................................... 1 FLOW SHEETS ............................ -........................................................................... 2 MATERIAL BALANCE .................. ........................................... ..................... . . 4 A, Bill of Materials ............................................-................... - B. Yield............................................................ ............................. . C . Material Balance Sheet .................................................... ... 4 4 4 PROCESS IN DETAIL ......................................................... ............ 6 Ac Summary ............................ .......................................... -*' o B. Reactor Feeds -...................................... ........................................ 6 6 1. Iron-Versene Catalyst ................................................. 2. Aqueous Catalyst Charge .................. .. 3. Reactor Charge .................. .................................. .. 4o Continuous Feeds ..........................*....................8 6 7 7 C - Reactor System ............................................................. ................. 8 D* Coagulation, Washing, and Drying 0 . c. ,, 11 DISCUSSION OF IMPORTANT VARIABLES . ......... ........................ IX A Reactor Charge ....................... .............. .... ......................... 11 1. Persulfate Redox System and Surfactant OODO 2. Oxygen a Retardant . ,,.................- -. 3. pH of Ammonium Persulfate Solution ooooou. 4. Monomer Charge .................. .................................. 12 11 12 12 B Control of Reaction .......... .. * . . . - =. 13 1. Rate ................. 2* Pressure Control 13 13 C . Reaction End Point ....................... . D. Coagulated Solids Formation In Reactor , 0D. B . * ,, 15 15 1. Solids Due to Shear .,,. >. 15 2, Solids as Function of Extent of Completion., 1.5 E . Pressure Letdown ............... *.............................. ... *. F. Coagulation of Latex ........................... ******<> G. Polymer Washing and Drying................................................ H. Reactor Washout ................... -....................... I Materials of Construction . ,, . .* . * ,,.. . . .,,* . 16 16 16 16 17 ccoo > aco: TABLE OF CONTENTS (Cont.) Page No. MATERIALS SPECIFICATIONS, ANALYTICAL METHODS ....................... 17 A. Raw Materials ................................................................................... 17 1* Vinyl Chloride ................ 2. Ethylene ................................................................... -............ Persulfate Redox Catalyst System Materials* 4. D-94 ................................................................................................ 5- Water .................. \......................................... ........................... 17 17 17 19 19 B. Product ..........................*........................................*....................... 19 1 Reactor Latex Product ....................................... * 2. Solid Polymer Product ................................. ................. 19 19 C. Analytical Methods ............ 19 TOXICITY AND HAZARDS ..................................................................................- 21 A . Vinyl Chloride ............. .............................................................. B. Ethylene .............*................. *.................... .............. ................... C. Ammonium Persulfate ............. ..............a............... 21 21 21 POLLUTION CONTROL ....................................... .. *............................ .... 22 REFERENCES .................. ",................. .......... ........................................... .. * - . - 22 ENGINEERING DATA ................................................................. *................. ... 22 ACKNOWLEDGEMENT .............................. ........................... ................................ .. 22 APPENDIX .......... ................... ..................................... ..................... ................. .. . 22 RSV 0017434 Page No. LIST OF FIGURES 1. Plastimer III MaterialBalance Flow Sheet ........ 3 2. Vinyl Chloride Addition Versus Time ............. 9 3. Total Reaction Time as a Function of APS Feed Rate ...................................................................... 14 4. Heat Generation of Plastimer III Reaction as a Function of Batch Time ...................................................... - 23 LIST OF TABLES I. Abbreviations and Molecular Weights ............................ II. Monomer Conversion ........................................................................ III. Plastimer III Material Balance ............................................. IV. Physical Constants Data forEthylene ...... ...... V. Physical Constants Data for Vinyl Chloride Chloroethane ......................... 2 4 5 24 25 APPENDIX A. Laboratory Autoclave ................................................... A-l. RSV 0017435 1. INTRODUCTION Research studies on the ethylene/vinyl chloride reaction were initiated within the Central Research Department, and a recipe was developed for Plastimer III, a copolymer high in vinyl chloride content. Plastimer III was prepared in quantity "by CRD for application and evaluation in floor tile formulations.at Armstrong Cork and Kentile. Preliminary results from these evaluations indicated favorable application properties. As a result, the responsibility of completing the process development was transferred to the Organic Division Research Department in March, 1965. The purpose of this tentative process is to provide a basis for design of manufacturing facilities to produce 1.0-1.5 million pounds per year of Plastimer III copolymer. Work will be continued after this process is issued for the purpose of optimization in certain areas . Amendments for this process will be issued as these optimizations are developed. SYNOPSIS OF PROCESS This process consists of reacting ethylene with vinyl chloride in the presence of a persulfate redox catalyst system. The reaction Is carried out as a semi-batch type reaction in a single reactor at a pressure of 850 psig. and a temperature of 30C. The initial charge to the reactor Includes an aqueous solution of the redox catalyst system, a surfactant, and a buffer; and a mixture of ethylene and vinyl chloride monomers containing 70$ vinyl chloride by weight. Ammonium persulfate fAFS) which serves as an initiator for the catalyst system is continuously added at a constant rate to the reaction mass. Vinyl chloride is added continuously and concurrently with the APS upon demand in order to maintain a constant pressure in the reactor. Ammonium persulfate is added to the reactor in such quantity that the reaction rate approaches zero when sufficient vinyl chloride has been added to give a product latex containing 46.7$ total solids. When all of the vinyl chloride has been added, the VC1 feed stream is stopped and the unreacted monomers in the reactor are vented. When the reactor pressure reaches atmospheric pressure, the latex is drained, frozen in a cold stage at -10C., and subsequently thawed. The two phase liquid-solid mixture Is separated, and the solid phase Is washed with sufficient water and dried at about 4oC. RSV 0017436 2. TABLE I Abbreviations and Molecular Weights Compound Ammonium hydroxide Ammonium persulfate Abbreviation NH40H (NH4)2S20e Molecular Weight .. 35.05 228.20 Ethylene Ferric ammonium sulfate Sodium dodecylbenzene sulfonate c2h* Fe(NH4)(SO4)2I2H2 0 * D-9^ 28.05 484.21 349.49 Sodium formaldehyde sulfoxylate Sodium pyrophosphate SFS SPP 154.12 446.11 Tetrasodium ethylenediamine tetraacetate Na4EDTA 380.2 Vinyl chloride VC1 62.50 Water h2o 18.02 Simplified equations follow: Persulfate Redox System Fe(EDTA)~+ CH20H-S02----- ^Fe(EDTA) + reduction products .... ..(1) Fe(EDTA)~ + S20e_ ------^ Fe(EDTA)"+ SO*- + SO47 . ..(2) Polymerization Reaction 5H2C=CH + H2C=CH2 ------ 1----- 3 1 <C1 /^HaC-CH-CHa-CH-CHa-CH-CHs-CH-CHs-CH-CHa-CHa^?- . . (3) < ||III Cl Cl Cl Cl Cl FLOW SHEETS A schematic flow diagram is given in Figure 1. The material balance in Table III is keyed to this diagram and is based on 100 pounds of polymer solids produced. RgV 0017437 3 : RSV 0017438 4. MATERIAL BALANCE A. Bill of Materials (Basis: 100 pounds of polymer solids; total reactor volume 33*5 gallons.) Material Pounds Consumed Pounds Produced NH*0H (15 N) 1.316 (NH4)2S20s SPP FeNH4(SO.)2I2H2 0 0.422 2.455 0.041 Inorganic salt solids D-94 (43# soap) Na4EDTA SFS CaH4 VC1 H20 Polymer solids Total 12.567 0.065 0.442 30.692 116.753 3116.272 3281.045 9-143 22.101 25.444 3124.357 100.000 3281.045 B. Yield Yield figures are given in Table II as pounds per 100 pounds of polymer solids formed. TABLE II Monomer Monomer Conversion Lbs. Lbs. Charge Unreacted Lbs. Used % Conversion VC1 C2H4 116.753 50.692 Total Monomer 147.445 C. Material Balance Sheet 25.444 22.101 47.545 91.309 8.591 99.900 78.2 28.0 67.7 A detailed material balance sheet is given in Table III. RSV oom39 5 S -i =1 =1 A A 04 o a I O i?'I & <D A (g o o & *-3 -- -9 3 Ck 4 fc- 6 <v RSV 0017440 6. PROCESS IN DETAIL A. Summary A ferric-versene mixture is made up by mixing ferric ammonium sulfate hydrate and tetrasodium ethylene diamine tetraacetate in water under an atmosphere of nitrogen. The ferric versenate is added to an aqueous mix of ammonium hydroxide, sodium pyrophosphate, D-94, and sodium formaldehyde sulfoxylate. The resulting aqueous mixture is fed batchwise to a reactor which has been purged with ethylene and evacuated. A vinyl chloride charge is then added to the reactor followed by a batch charge of ethylene such that the resulting monomer mixture is 70% vinyl chloride by weight and the reactor pressure is 850 psig. at 30C. The contents of the reactor are allowed to equilibrate at 30C. with adequate agitation. Upon temperature and pressure equilibration, the reaction is started by addition of ammonium persulfate (APS). Vinyl chloride is added upon demand during the reaction so as to maintain a constant reactor pressure of 850 psig. at 30C. The APS is fed at a constant rate to achieve a reaction time of 3 hours. When 91% of the required amount of vinyl chloride has been added to the reactor, the addition of APS is stopped. When the vinyl chloride uptake stops, the unreacted monomers are vented off the top of the reactor until the reactor pressure reaches atmospheric pressure. The latex is drained from the reactor by gravity, frozen in a cold stage at -10C., and subsequently thawed. The two phase liquid, solid mixture is separated and the polymer solid is washed and dried at about 40C. B. Reactor Feeds 1. Iron-Versene Catalyst The ferric versene catalyst is made up batchwise from the following charge procedure: Ferric ammonium sulfatehydrate 0.041 lbs. Tetrasodium ethylened'iaminetetraacetate 0.065 Demineralized water 1.719 Total 1.825 lbs. RSV 0017441 7. A nitrogen atmosphere is maintained above the solution while mixing to prevent the solution from being contacted with oxygen which acts as a reaction retarder. 2. Aqueous Catalyst Charge The aqueous catalyst charge is made up batchwise from the following charge procedure in the order given below: Demineralized water Ammonium hydroxide (15 N) Sodium pyrophosphate D-94 (17% soap) Ferric versenate Sodium formaldehyde sulfoxylate 95*575lbs. 1-303 2.455 3i*777 1.825 0.442 Total 151.377 lbs. The sodium dodecylbenzene sulfonate (D-94) is , commercially available as a 57# aqueous solution (43# D-94). Because of its very high viscosity, the 43# solution is diluted with demineralized water to a 17# solution before charging to the aqueous catalyst solution. Per 100 pounds of polymer solid formed, 19.210 pounds of water is added to 12.567 pounds of 43# D-94 to obtain 31.777 pounds of 17# D-94 which then is charged to the aqueous catalyst solution. A nitrogen atmosphere is maintained above the solution while mixing to prevent the solution from being contacted with oxygen. 3. Reactor Charge A 33.5-gallon reactor (based on 100 pounds of polymer solids) is first evacuated, purged with ethylene, and evacuated again. Then 131.377 pounds of aqueous catalyst solution is added, brought to 30C., and 73*907 pounds of vinyl chloride is fed to the reactor without agitation resulting in a reactor pressure of 40 psig. at 30C. Ethylene is added batchwise to the reactor until the reactor pressure reaches 900 psig. At this point, the primary pressure sensing device is shut off from the reactor and the agitation started. The pressure in the RSV 0017442 8. reactor will drop rapidly (to about 400 psig.) when agitation is begun and the contents in the reactor will begin to foam. At this point, reactor pressure is obtained by a gage in the ethylene charge line to the reactor. More ethylene is added with agitation until a reactor pressure of 850 psig. at 30C. is obtained, corresponding to the addition of 30*692 pounds of C2H4. After the addition of all the ethylene, the primary sensing device can be opened to the reactor, allowing the trapped monomers at 900 psig. to blow back into the reactor at 850 psig. and avoiding deposition of foam in the pressure sensing line during charging. The temperature and pressure in the reactor are allowed to equilibrate. (Premixing and emulsifi cation were accomplished in the laboratory 1-gallon autoclave by utilizing an agitator speed of 600 rpm. A more complete description of the agitation system used in process development is given in Appendix A.) Before the reaction is started, the agitation is decreased to a point where complete emulsion is sustained but excessive shear of the reaction mass is eliminated. (This point corresponded to 400 rpm. in the laboratory autoclave.) 4. Continuous Feeds The APS solution is added to the reaction continuously at the rate of 0.74 pounds per hour until 97^ of the vinyl chloride which is to be fed during the reaction has been added (41.5 pounds). Vinyl chloride is added upon demand to maintain a constant pressure in the reactor. A typical vinyl chloride addition curve is shown in Figure 2. The limiting factor governing the maximum VC1 addition rate is the heat removal capacity of the reactor cooling system. Typical reaction time is 3-3*5 hours, although reaction times as short as 2 hours can be achieved and result in satisfactory product. All continuous feeds are fed subsurface. C. Reactor System The reactor consists of a single, backmixed stage, provided with heating (for start-up) and cooling media, and automatic temperature control. A pressure control system is also provided to maintain constant reactor pressure by regulation of vinyl chloride addition rate. RSV 0017443 9- O M 6 S f w:> 3 H i 01 01 v i>i 10. An increase in vinyl chloride monomer concentration in the reactor causes the reactor pressure to increase, and a decrease in vinyl chloride monomer concentration causes pressure to decrease. The operating conditions are: Temperature 30C. controlled to + 0.5C. Pressure- 50 psig. 11 11 + 15 psi. Reactor volume 32-5 gal. " " + 0.2 gal. Agitation sufficient to maintain adequate emulsion but not vigorous enough to cause excessive liquid shear is required. In the 1-gallon process develop ment autoclave equipped with three 4-bladed flat impellers (see Appendix A for details and dimensions), an agitation speed of 400 rpm. was found to maintain satisfactory emulsion. Reaction continues until the solids content of the latex reaches 46-48$. The addition of 42.846 pounds of VC1 during reaction results in a solids content of 46.7$. To terminate the reaction at this point, the APS feed is stopped when 97$ of the vinyl chloride has been added (41.5 pounds). The reaction rate will begin to decrease sharply. When the reaction has stopped, the VG1 feed line is closed and the unreacted monomers vented off the top of the reactor. Venting is started immediately after the reaction has stopped and agitation is used while venting. The gas phase is vented over a 50-35-minute period such that no latex is obtained from the vent. When the reactor pressure has reached atmos pheric pressure, the latex is drained out of the reactor by gravity. The liquid composition after letdown is: Component Weight Percent Water Polymer solids Soap Other solids 53.23 42.80 2.32 1.65 Total 100.00 The reactor off-gas composition is: RSV 0017445 11. Component Mole (Vol.) Percent Ethylene Vinyl chloride Water 65.84 34.02 0.14 Total 100.00 D. Coagulation, Washing, and Drying The liquid latex is coagulated by freezing in a cold stage at -10C. Slow freezing of the latex is required to maintain proper particle size. A freezing rate such that 85-90# of the- polymer crystals are greater than 30 mesh is satisfactory. The cold stage is operated at atmospheric pressure. Subsequent thawing of the frozen latex such that the temperature of the polymer does not exceed 30C. yields a slurry of polymer and other solids in water. The two phase mixture is separated and the solid phase washed with filtered tap water. The washing step requires 3000 pounds of water per 100 pounds of polymer solids for a washing stage having intimate mixing of wash water and polymer solids and a contact time of 1 hour. The washed polymer is dried at 40C. until less than 0.1# moisture is obtained in the product. E. y.*-, -- - DISCUSSION OF IMPORTANT VARIABLES A. Reactor Charge 1. Persulfate Redox System and Surfactant The chemical species serving to initiate monomer and partially reacted polymer thereby causing _ polymerization is the sulfate radical-ion (SO4*). The sulfate radical-ion is formed from the following oxidation-reduction system. Ferric versenate is reduced by SFS to ferrous versenate which serves to decompose persulfate forming a sulfate radical (S04=) and a sulfate radical-ion (SO47). The ferrous versenate is oxidized back to the ferric state, thereby being regenerated. The SFS activates the system; the iron acts as a catalyst; and the persulfate when decomposed serves as an initiator for polymerization. The formation of SO4" from persulfate decomposition occurs only in a limited range of pH. For this reason, sodium RSV 0017446 12. pyrophosphate is used as a buffer to retain the pH of the reaction mass at 9*0~9*5- Sodium dodecylbenzene sulfonate is used as a surfactant or emulsifying agent. Reaction actually takes place in the liquid phase and since the ethylene and VC1 monomers are only slightly soluble in water, it is necessary to emulsify the monomers in the liquid phase. 2. Oxygen a Retardant The presence of a small amount of oxygen in the reactor will inhibit the reaction and prevent it from starting.- To prevent oxygen from getting into the reactor, the aqueous catalyst solution is made up in an atmosphere of nitrogen and charged into a reactor which has been evacuated, purged with ethylene, and evacuated again. Charge lines are also purged and evacuated. 3- pH of Ammonium-Persulfate Solution The APS solution is made up as 20$ APS in water with enough NH4OH added to bring the pH to 7.0. An acidic solution such as an aqueous mixture of APS and water without neutralization will cause the reaction to stop immediately if it is not properly buffered. The appropriate sequence of reactions in the persulfate redox system only exists in a basic media. Reaction inhibition can therefore be caused by inadequate neutralization of the "APS solution. Addition of NH4GH to the APS solution also serves to prevent corrosion to the APS feed system. A 20$ APS-HsO mixture is quite corrosive, even to Jl6 stainless steel, 4. Monomer Charge Because of the nonlinearity of the partial molal' volume of vinyl chloride, the addition of vinyl chloride to ethylene or to a mixture of ethylene and vinyl chloride can cause the pressure of the * mixture to raise or lower depending on conditions. At a concentration of 70$ VC 1 in a mixture of C2H4 and VC1 and a pressure of 850 psig., addition of more VC1 to the mixture causes the total pressure to increase. At low concentrations of VC1, the total pressure will decrease. RSV 0017447 13. Addition of all the C2H4 to the reactor in the initial batch charge before any VC1 is added results in a total reactor pressure of greater than 1000 psig. To avoid exceeding a maximum pressure of 1000 psig., the initial batch charge of VC1 is added first, resulting in a pressure of 40 psig. The ethylene is then added until a reactor pressure of 900 psig. is reached. In the presence of agitation, a significant amount of ethylene will dissolve In the VC1 causing the reactor, pressure to decrease. The line leading to the pressure-sensing device is closed prior to start-up of agitation to prevent the foam caused by agitation to be forced into the pressuresensing line as more ethylene is added. As the remainder of the ethylene is added, the pressure will rise, and at temperature and pressure equi libration a pressure of 850 psig. at 30C. is achieved. The pressure-sensing line can be opened during pressure equilibration allowing monomer to blow from the line back into the reactor leaving the line unplugged by dense foam, B. Control of Reaction 1. Rate The SFS charged in the initial aqueous charge is present in slight excess of the amount needed. The ferric versenate is regenerated as it is used. Therefore, the limiting reagent in the catalyst system is the APS, and the reaction rate is controlled by the amount of unreacted APS in the reactor. Total reaction time as a function of APS feed rate is shown in Figure 3- 2. Pressure Control The appropriate composition of VC1 in the reaction mass is controlled by reactor pressure. As reaction takes place and polymer is formed, the reactor pressure decreases since the product polymer is more dense than the reactant monomer. Reactor pressure is Increased by the addition of VC1 to the reactor. Since VC1 is used in a 5/1 weight ratio to ethylene in the reaction, the addition of pure VC1 to maintain reaction pressure is adequate to retain a sufficiently high concentration of VC1 in the reactor. The Initial RSV 0017448 14. * Mi to TO THE CM J 5 9 M G 15. VC1 composition in the reactor is 70# by weight; the final VC1 composition Is 50-60# by weight. Therefore, total pressure is a sufficiently good control media for control of reaction mass composition. C. Reaction End Point Sufficient reaction is achieved when the solids content of the latex reaches 45-48#. Reaction can proceed beyond this point, but latices with higher solids contents are difficult to vent and result in higher deposits of solids n the reactor. To reach the desired end point, the appropriate amount of APS is added such that the reaction will cease when 42.846 pounds VC1 has been added. The response of reaction rate to APS feed rate is very rapid causing the reaction rate to reach almost zero very shortly , after the APS feed is stopped. If the APS feed is stopped when 97-99# of the total amount of VC1 has been added, the active amount of APS present in the reactor will reach zero when 42.846 pounds VC1 has been added. D. Coagulated Solids Formation in Reactor 1. Solids Due to Shear Coagulated solids may be formed during the reaction or during pressure letdown. An increased amount of coagulum is formed in the latex during the reaction if the reaction is carried out in the presence of high shear agitation. Low shear agitation is desirable and minimizes formation of solids. A flat-bladed turbine type impeller turning at 550-400 rpm. was found satisfactory in process development work using a 1-gallon autoclave. An agitator speed of 600 rpm. was used to premix the initial batch charge but caused an increase in coagulum if used during polymerization. 2. Solids as Function of Extent of Completion The extent of completion of the reaction has an effect upon the amount of coagulated solids formed in the reactor. Above 48-50# total solids in latex, the amount of coagulated solids formed increases rapidly. The variation in total solids from 44-48# causes no significant difference in polymer quality. RSV 0017450 16. E. Pressure Letdown The unreacted monomers are vented from the top of the reactor with agitation as soon as the reaction is completed. The monomers may be vented as rapidly as possible such that no foam or liquid is carried out the vent. The venting will occur rapidly until the pressure in the reactor reaches 50-100 psig. (10-15 minutes) when a great deal of foaming will occur in the reactor. At this point, the agitation is stopped and the venting rate decreased such that foam and latex are still prevented from being vented. To reach atmospheric pressure in the reactor from the point where the venting rate has been decreased takes 20-50 minutes. The reactor pressure must be decreased to atmospheric pressure before the latex can be drained. The latex will coagulate if subjected to even a small pressure gradient. F. Coagulation of I^tex The latex is coagulated by freezing at -10C. The rate of freezing has a pronounced effect upon particle size. Rapid freezing causes formation of small polymer crystals; slower freezing results in larger crystals. Due to a material handling problem in the washing stage, large polymer crystals are desired. For this reason, the rate of freezing should be sufficiently slow to give a particle size such that 85-90# of the particles are larger than 30 mesh and the number of particles smaller than 100 mesh are an absolute minimum. An adequate freezing time for coagulation in a 1.5-2-inch tube is 1-2 hours. All of the latex must be frozen. A mixture of unfrozen latex and thawed coagulum presents a difficult material handling problem. G. Polymer Washing and Drying Little information is known about polymer washing and drying at this time. Amendments to this process will be issued as new techniques and developments are obtained. H. ( Reactor Washout No research has been done on the method or frequency of reactor washout. Current solvents used to clean the reactor are water followed by either acetone or tetrahydrofuran. Amendments will be issued to cover this item. RSV 0017451 17. I. Materials of Construction 316 stainless steel is used for all surfaces exposed to reactants or product latex. No corrosion studies on other types of materials have been done. MATERIAL SPECIFICATIONS, ANALYTICAL METHODS A. Raw Materials 1 Vinyl Chloride Uninhibited or polymerization grade vinyl chloride from the Texas dty Plant is used. It is passed through activated alumina (8-14 mesh) before use (maximum usage of 0.88 pounds alumina per 100 pounds VC1). 2. Ethylene Monsanto Texas City,ethylene is used. It is passed through a charcoal and alumina absorber in series (.01 pound charcoal and .01 pound alumina per 100 pounds C2H4)- 3 Persulfate Redox Catalyst System Materials a. The following compounds from Fisher Scientific were used in process development work. (1) Ferric Ammonium Sulfate /:< Typical analysis: Insoluble matter Chloride Copper Ferrous iron Nitrate Zinc 0.008$ 0.001$ 0.003$ 0.001$ P.T. 0.003$ (2) Tetrasodium Ethylenediamine Tetraacetate Powder, technical with 1 gram chelating 213 mg. of CaC03 at pH 11. (3) Sodium Formaldehyde Sulfoxylate Technical. RSV 0017452 18. b. The following items were obtained from Mallinckrodt Chemical Works. (1) Ammonium Hydroxide 15 N analytical, reagent grade with following typical analysis: Carbon dioxide Chloride Heavy metals Iron Phosphate Residue after ignition Sulfur Assay Specific gravity 0.002# 0.00005# 0.00005# 000...000000220##02# 0.0002# 28.0-30.0# 0.90 (2) Ammonium Persulfate Analytical, reagent grade with following typical analysis: Acidity (as H2S04) 0.20# Chloride and chlorate (as Cl) 0.001# Heavy metals (as Pb) 0.005# Insoluble matter 0.005# Iron 0.001# Manganese 0.00005# Residue after ignition 0.05# Assay (minimum) 98.0# (3) Sodium Pyrophosphate Analytical, reagent grade with following typical analysis: Arsenic Chloride Heavy metals (as Pb) Insoluble matter Iron (Fe) Nitrogen compounds (as N) Sulfate (S04) 0.0005# 0.002# 0.001# 0.010# 0.001# 0.001# 0.005# c. Nitrogen Nitrogen used was obtained from the Air Reduction Company. It Is prepurified nitrogen with a maximum oxygen limit of 5 ppm. A typical analysis is: RSV 0017453 19* PurityDew point Oxygen 99-997# N2 -90P. 2 ppm. 4. D-94 D-94 (sodium dodecylbenzene sulfonate) was obtained from the Richardson Corporation, Chicago, Illinois. The specifications are: Total solids Active SDDBS Alcohol insolubles Unsulfonated oils pH of a 10# solution Iron 46-49$ 44-47$ 1.7$ maximum 2.5# maximum 7-5-8.5 50 ppm. maximum 5. Water Demineralized. B. Product 1 Reactor latex Product latex from the reactor is obtained with the following typical analysis: $ Total solids # Polymer solids Ratio of soap to polymer Latex viscosity 46.7# 42.8# 0.054 9.42 cs. 2. Solid Polymer Product # VC1 Tensile break Elongation break Tr C. Analytical Methods 91.5 7025 psl. 284$ 42.5C. 1. Latex Solids A 10 ml. aliquot of latex is weighed into a tared aluminum foil dish, diluted with 10 ml. of ethanol to prevent foaming and .spattering, and evaporated to dryness in a 105C. oven. RSV 0017454 20. 2 . H The pH is determined directly on the latex with a standard Beckman expanded scale pH meter. 3- Latex Viscosity The latex viscosity is determined by an Ostwald capillary viscometer. Model 150, at 30C. 4. Particle Size A weight average particle size can be obtained by dissymmetry on .a diluted sample of latex. Absolute particle size and size distribution measurements are made by electron microscopy using a special cold stage technique. 5 * Dry Polymer The latex is coagulated by freezing at -10c. After thawing, the coagulum is separated from the aqueous solution, filtered, and washed. The washed coagulum is dried by heating to 65C. at 10 mm. Hg pressure. 6. Specific Viscosity The specific viscosity is obtained with an Ostwald capillary viscometer. Model 50, at 30C. 0.1 gram of solid polymer is dissolved in 100 cc. of tetrahydrofuran and run at 30C. The specific viscosity is equal to the efflux time of the solution divided by the efflux time of the solvent minus 1.0. 7 Vinyl Chloride Content Total chlorine in the dry polymer is obtained by Schoniger combustion and potentiometric titration with silver nitrate. Central Research Department Analytical Laboratory Method No. C-50-61. 8. Mechanical Stability This test subjects a 40.0 gram, filtered sample of E/VC1 copolymer latex suspension to a shearing force exerted by a 1-inch metal disc under a load of 6 kilograms, rotating at 1000 rpm., in contact with RSV 0017455 21. a polyethylene surface. The sample container temperature is held constant at 35C. by circulating water through the jacket. The test if timed for 20 minutes. Following this, the sample is filtered through a 200 mesh screen. About 300 ml. of water is used in transferring the sample and washing the coagulum retained on the filter. The coagulum formed is dried on the screen at 95-100C. for at least 30 minutes. The weight of coagulum is a measure of sample stability. TOXICITY AND HAZARDS A. Vinyl Chloride Vinyl chloride is a flammable liquid and a dangerous fire hazard. Its vapors form flammable mixtures with air at all temperatures down to 20F. The limits of inflammability are 4-22# by volume in air. 10# vinyl chloride is dangerous to life of animals in from 30-60 minutes of exposure, whereas 5# causes symptoms in less than an hour. Vinyl chloride is stored in a cool, ventilated area away from open flame, acute fire hazards, or powerful oxidizing agents. Personnel exposed to it should heed the warning of dizziness and disorientation, and remove,themselves at once from air contaminated with it.^ ' B. Ethylene No appreciable reaction occurs in ethylene at 2,000 atmospheres below 100C. and in ethylene at 250C. below about 300 atmospheres. Nevertheless, even under these conditions, an uncontrollable reaction will propagate if by some mischance it is initiated. Ethylene is only safe from such propagations inside limiting conditions of which the following are examples: Pressure 1,000 atm. 400 atm. 200 atm. Temperature 20C. 100C. 210C . The flammability limits of ethylene with oxygen are 2.9-79*9#,by volume and with air are 2.75-28.6# by volume.13) C. Ammonium Persulfate Contact of ammonium persulfate with other material may cause fire or explosion. RSV 0017456 22 POLLUTION CONTROL The off-gas from the reactor may be recycled to subsequent batches or is flared to eliminate atmospheric pollution and an explosion hazard. Because of the relatively high density of vinyl chloride gas, high concentrations can accumulate near an atmospheric vent without a flare. REFERENCES 1. Bovey, F. A., I. M. Kotthoff, A. I. Medalia, and E. J. Meehan, Emulsion Polymerization, Interscience Publishers, Inc., New York (19551 - 2. Hileman, H. J., Progress Report, Central Research Department, September 1964, E/VC1 Synthesis, Characterization and Applications, Job No. 2601, Issue 7- 5- Renfrew, A., and P. Morgan, Polythene, The Technology and Uses of Polymers, Interscience Publishers, Inc., New York TT957 JT 4. Sax, N. Irving, Handbook of Dangerous Materials, Reinhold Publishing Corporation7 New York "("1951) ENGINEERING DATA Cooling capacity per gallon of reactor volume as a function of reaction time is given in Figure 4. The heat of reaction per pound of polymer is 750 BTU/pound. Physical constants data are given in Tables IV and V. ACKNOWLEDGEMENT The exchange of information and contributions provided by the Central Research Department, notably from the group of Mr. H. J. Hileman, is greatly appreciated. APPENDIX Appendix A. File Copy approved by: M. E. Gibbs R. W. Buckne 11 Date Date" HI IT. Hubbard Mgr. of Res. Date dm RSV 0017457 InL ^ m | JC. 23. 2DIN #1 PHYSICAL CONSTANTS DATA 3UBSTANCE Ethylene STRUCTURAL FORMULA BVCOMPILES M. E. Gibbs NAME Formula Molecular Weight Acnearanre Bo iling Point at 7S0 mm Boiling Point atICO mm Roiling Point i 3Qnm Boiling Point at lOnm Crystallizing Point Melting Point Solution Point Soecific Gravity -10VC . Specific Gravity 9 Pounds per Gal. 9 0 C. Coefficient of Expansion Refractive Index $ n5 Infra Red Spectrum ( }Reference Ultra Violet Spectrum (Reference) Viscosity -1P50,. Viscosity -105WC, Surface Tension Solubility in Water Solubility in Solubility in DATE 3/17/65 CpHa 28.052 CH2 = CH2 &SOURCE DATE Physical Properties IL Drelsbach. R. R. -103-71C .________________ 7 8P. -144.0QC.________________ -153.22 C. -16Q.15C. m 11 11 it 11 0.384 0.345____________________ 11 11 0 . r*s 0.16 CS. 11 Flash Point F (Method) Fire Point C Heat of Combustion at 25"C. Heat of Formation Thermal Stability (cal./kg/min.-) Latent Heat of Fusion B. P . Latent Heat of Van. Van . 300K. Soecific Heat Critical Temoerature Critical Pressure Dissociation Constant Critical Density 316.20 kcal/mole 115.39 cal./e. 0.3725 cal./e. 9.90C. 38380. mm. K. 0.21 e./ml. 11 11 ti 11 11 11 Other Constants Toxicity (Git* Reference) RSV 0017459 NOTE: These data should not be released outside of Monsanto Chemical Company. Use additional sheets if necessary. CD IN SUBSTAnCE- TABLE V 25. PHYSICAL CONSTANTS DATA Vinyl Chloride STRUCTURAL FORMULA Chloroethane TomfMLld by M. E. Gibbs NAME Formula Molecular Weight Adoearanee Boiling Point at 7G0 mm Boiling Poirt atmnrrm Boiling Point * "50mm Boiling Point at 10mm Crystallizing Point Melting Point Solution Point Soecific Gravity -200 . Specific Gravity $ Pounds per Gal. C Coefficient of Expansion Refractive Index ~ 10 w C . n5 infra Red Spectrum (Reference) Ultra Violet Spectrum (Reference) Viscosity -20C. Viscosity -10C. Surface Tension -10"C . Solubility in Water Solubility in Solubility in date 3/17/65 C2H3Cl 52.501 -13.37C. -55.8 r.. -77.qsn. -87.8 C. -153.7QC. 0 * Q83 CH2 = CHC1 ASOURCE DATE Physical Properties II, Drelsbach, R. R. M tr ti 11 ti ir 1.4046 0.2780 cs.____________ 0.2563 cs. 20,88 dvnes/cm. n 11 ti it Flash Point F (Method) Fire Point C Heat of Combustion Heat of Formation Lia. at 25 C. Thermal Stability fcal.Ae/min.) Latent Heat of Fusion Latent Heat of Van. at B.P. Soecific Heat Lia. at 293K. Critical Temperature Critical Pressure Dissociation Constant -78.0C. -lU4.fi Ifnpl /mnlp 18.14 cal./g. 7Q.53 0.38 r.al./.K. 156.5C. UPOfin . mm 11 11 ti 11 ti ir It Other Constants . | ToxicitV (Give Referencel RSV 0017460 ^OTE; These data should not be released outside of Monsanto Chemical Company. Use additional sheets if necessary. APPENDIX A LABORATORY AUTOCLAVE RSV 0017461 APPENDIX A Laboratory Autoclave A-l.