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/ BUSINESS CONFIDENTIAL V \frJj b> MONTHLY REPORT TO: FROM: Dr. J. B. Saunby Mr. W. E. Whitehurst B. J. Hanna DATE: My 31, 1974 Received N. VVHEEia^ib DISPERSION, SOLVENT, AND SPECIALTY VINYL RESINS HIGHLIGHTS VC1 Monomer in Dispersion Resin Latices - In one of th techniques under study to reduce the residual monomer content of dispersion resin latices, a series of batch stripping operations was conducted in the laboratory at temperatures of 30, 60, 70, and 80C with a constant foam level and vacuum increasing with time. Under these conditions the latex, which contained 1.5% monomer initially, yielded values with increasing temperature of 0.25% (50C), 0.03% (60C), 100 ppm (70C), and 10 ppm (80C) with 2.5 hours of stripping. Vinyl Chloride-based Latexes for Can Interiors - Th reproducibility of product and process for the UCC water-born vinyl terpolymer for can Interiors has been demonstrated by con secutive, triplicate polymerizations in a 100-gallon autoclav . The data from these runs are required for the 7DA petition. Th latex will be used for future customer trials. / RESEARCH AND DEVELOPMENT DEPARTMENT CHEMICALS AND PLASTICS UNION CARBIOE CORPORATION SOUTH CHARLESTON, REST VIRGINIA UCC 068379 BUSINESS CONFIDENTIAL -2 - 216H DISPERSION RESINS, OPERATION TEAM , S' 4 T ^ .<*. Ylnyl Chloride Removal from Latices - One method bein^ studled.jpb reduce the residual vinyl chloride In PVC latexes is "2$". to strip ^the latex under vacuum in a batch process. Preliminary. studies ssing a one-liter charge in a jacketed, 2-liter flask yielded the following results. ^' Temperature VC1 Content After 2.5 Hrs. 80C 0.25% 0.03% 100 ppm 10 ppm In each case the vacuum was controlled to maintain a constant f am level of approximately 10 cms. above the liquid surface. The /** - initial residual VC1 content of the latex was about 1.5%.*. In t all of the runs, the stripped latex was found to be acceptaGl. A 2-4 percent increase in total solids was observed. However, if a greater degree of foaming can'be tolerated, or a more effective anti-foam agent can be found, it may be possible to concentrate the latex by operation at a pressure considerably below the vapor pressure of water at the stripping temperatur . In addition to continuing the above study, a continuous falling film stripping operation is being examined. (P. F. Lobo, R. J. Hanna) Use of a Rototherm Thin-Film Evaporator Under Vacuum to Remove VC1 From QYNV Latex Containing 500 ppm Nalco-22-73 Antifoam Agent - The employment of the one quarter-square foot Rototherm evaporator at atmospheric pressure for the removal of VC1 from QYOH latices with and without the use of antifoam ag nts has been previously reported. At temperatures to 85C, 2/3 of the monomer was removed. The results of more recent runs con ducted under vacuum conditions are presented below. ucc 068380 !----------- ii BUSINESS CONFIDENTIAL ucc 068381 Run No. Latex Feed Rate, lbs./hr. Coiftrol A 1 2 19.6 11.7 Control B 3 4 23.1 7.5 Control C 5 6 7 8 -- 10.8 10.7 10.7 10.8 Latex Temp., "C Room Temp. 64-71 74-76 Rooa Temp. 70-72 72-78 Room Temp. 73 68 64 62-64 Absolute Pressure, Hr Latex Increase in Solids, Latex Solids, __2Jt%% Atmospheric 350 340 34.3 35.1 35.4 2 3 Atmospheric 300 300 37.0 38.5 44.3 4 20 Atmospheric 300 215 165 125 37.5 36.7 37.4 38.1 39.2 2 5 TCI in VC1 Reduction Latex, in Lat x, 0.83 0.24 0.10 1.28 0.26 0.06 1.40 0.12 0.07 0.05 0.12 71 88 -- 80 95 __ 91 95 96 91 i u i '-i . BUSINESS CONFIDENTIAL -4 - Under these conditions, removal of 95 percent of th VC1 was approached. Latex samples taken from the B control and Runs 3 sad 4 were spray dried, ground and checked tor rheology..^. No significant difference was noted. The results obtained above used hot oil in the Jacket'of the Rototherm. When steam was used, the heat flux became much higher and difficulty was experienced in avoiding broken latices. With high latex flow rates (30 #/hr.), operation was satisfactory but excessive foaming resulted. At low flow rat s (10 #/hr.) latex stability could not be retained. These pro blems tend to indicate that, like the breakage experienced upon blowing latex from an autoclave, a rapid release of VC1 from a latex particle tends to disrupt the protective layer around each latex particle. The best operation, therefore, results from a low h at flux and long residence time. This, however, would require a large thin-film evaporator. The studies will be continued by Dr. Lobo. (L. G. Reed, R. J. Banna) 320D05 POWDER COATINGS Drying Studies * Sufficient data are now available t make an initial comparison of the various methods of reducing the volatile content of spray dried resin. The favorable econ omics associated with bagged drying suggest that this is pro bably the best method. However, as the volatiles lost are not recoverable, the feasibility of the method would have to be r evaluated in the light of anticipated solvent emission laws. The three auxiliary drying processes studied yield d the following results: Drying System Approximate Drying Time Requir d Microwave augmented drying in an air slide 5-10 minutes Hot air drying in an air slide 3-5 hours Hot air over resin bed 5-10 hours For a given feed rate, the size of a dryer required is lnvers ly proportional to the residence time or drying time and hence th first method appears most favorable. The recovery of volatiles is comparatively easy because of the small amount of air requir d in this method. The drying studies are being continued using \.~*r * * ucc 068382 BUSINESS CONFIDENTIAL -5 - spray dried resin samples of various compositions and volatil contents. ' Vlf' (P. 7. Lobo, B. J. Hanna) Closed Cycle Spray Drying Tests - An additional we of tests on the Niro closed-cycillee~tt<est equipment in Copenhag n has been set for the first week in July. During these tests w intend to evaluate the spray-dry characteristics of GD-7105A, the current ''best choice" for a thermoplastic clear vinyl powder for interior can coatings. Ve also Intend to seek further in formation regarding the necessity of Impregnating the feed: sub stantial process simplification would result if satisfactory performance can be achieved without impregnation. The final item for further examination during the series is the effect of including vinyl acetate monomer in the feed at a level corres ponding to what would be found if a "normal" stripped autoclav varnish were diluted to use as feed to the spray drier. (D. R. Montgomery, B. J. Hanna) 320C17 VINYL CHLORIDE COPOLYMER LATER TOR GAN INTERIORS Polymerization Bate Recent experiments in the one-gallon autoclave hav demonstrated that the magnitude and reproducibility of the poly merization rate for the production of terpolymer latex (QKX2033) can be Improved by the addition of nail quantities of soluble iron to the premix charge. Results of duplicate experi ments, illustrating the Improvement in conversion for a constant polymerization time (23-24 hours), are summarized in the foil wing table (Table I): TABLE I ENHANCEMENT OF POLYMHIIZATION RATE BY THE ADDITION 07 SOLUBLE IRON TO THE FREMIX Soluble Iron Added (ppm of Premix Charge) 0. 0 , 0.19 0.19 0.37 0.37 Latex Total Solids (Percent in 23-24 hrs.) 21.5 22.0 27.1 27.5 37.4 35.9 ucc 068383 BUSINESS CONFIDENTIAL 6 A latex made with 0.75 ppm of soluble Iron added to tb premia charge, i.e. twice the quantity of Iron required for good polymerisation rate, was evaluated by A*. W.I. Wertz. Its per-iaf formance was comparable to standard QEX-2033. (T. L. Dawson) Scale-up - The FDA petition on the water-borne vinyl terpolymer beer can Interiors must contain data to demonstrat reproducible production of the latex in large^cale faclllti s. The only problems encountered In the initial 60/100 gallon scale-up were slow and variable polymerization rates. The use of low concentrations of soluble iron in th premix charge, as described in the proceeding paragraph, has now been employed in a series of polymerizations in the 60/100 gallon autoclaves. Consecutive, triplicate polymerizations (2223 hours) in these larger autoclaves gave latices with total solids on target and near perfect reproducibility of polymeri zation rate. The reproducibility obtained with identical charges (2033 composition) is illustrated in the following table (Tabl XI): TABLE II REPRODUCIBILITY OF QEX-2033 PROCESS IN 60/100 GALLON AUTOCLAVES Run No. (7981-) Soluble Iron Added (ppm of Premix Charge) Latex Total Solids (Percent in 22-23 hrs.) 34 0.37 35 0.37 36 0.37 36.6 35.2 36.0 The latex compositions and coatings properties were also repro duced closely and were on target. The three drums of latex pr pared during these studies will be employed for customer sampling as needed. (T. L. Dawson, R. T. Wood) FDA Petition - The action plan for the vinyl terpolym r latex petition requires that all data be in Dr. W. B. Ackart's hands by July 1. The petition is scheduled to be written and filed by August 1, and the regulation hopefully would issue by February 1, 1975. The current status of the various component parts is as follows: ucc 068384 BUSINESS CONFIDENTIAL 7 I. Total non-volatile extractions at Bound Bxpok. Three solvents have been completed, The fourth is in';/progress and a completed report is planned by June 1. 2. Monomer migration data at South Charleston. Test development work is in progress. The completed report is due July 1. 3. Characterization of extracts. The revised report has been completed. No additional laboratory work is planned. 4. Seven-day rat feeding at Mellon Institute. Polyester sample and low molecular weight terpolym r sample have been shipped to Mellon. Feeding studies are scheduled to begin June 7. The completed report is due on month after receipt of the samples to be fed. There are some additional routine pieces of lnformatl n that must be provided by July 1 if we are to maintain the time table. These are as follows. 1. Identity of the product. \ Common name, chemical name, trade name, empirical formula, structural formula, molecular weights, and methods used to determine. 2. Manufacturing process. Baw materials, BM specifications, and test methods. Polymerization process, recipe, and equations for the re action. 3. Specifications for the copolymer and test methods. 4. Reproducibility of the products. Data for 3 or 4 "coamerdal" batches according to Item 3 above. The data from the consecutive, triplicate 60/100 gallon runs described in a previous section of this report will be used. Ve will also need to file an environmental impact statement with the petition which means that Dr. Ackart will need these data by July. There is some uncertainty about how ucc 068385 BUSINESS CONFIDENTIAL 8 complete the SIS need be because FDA tuts proposed some new, 1 ss stringent requirements. However, st the very least we will n d data identifying the pollutants emitted^durlng manufacture, th applicant* Federal, State, and local emission requirements, anda statement that we are in compliance. In the absence of actual production facilities for the vinyl terpolymer latex (QEX-2033), ^ perhaps we can use environmental data from one of our plants that currently produces other vinyl chloride lAtices. At the worst we will need a full EIS covering manufacture, use, and disposal of the polymer. This implies that we must know in which stat the product will be produced. (W. B. Ackart, J. J. Bresinski, T. L. Dawson, H. Senman, C. S. Veil, V. I. Verts) Protect Review at Glidden - A general review of the status of the vinyl terpolymer latex (QEX-2033) project was held at Strongsville, Ohio on May 10, 1074. The following people attended the netting: Glidden Personnel PCC Personnel Andy Engstron Ed Eubanks John Hafell Bob Moorman Bob Voodruff Jim Woebkenberg Vatson Ackart Bill Buttrick Lowell Comstock Tom Dawson Maynard Sberwin Frank Vllllanson Special emphasis was given to discussions of the IDA status, th odor emission problem, and overspray. IDA Discussion - Dr. V. B. Ackart, UCC Manager of IDA and USDA Liaison for Plastics, gave a summary review of the current and potential problems associated with the recent acti vity related to vinyl chloride monomer. Dr. Ackart pointed out that in addition to IDA we are also concerned about OSHA (manu facture) and EPA (environment) regulations, but that the relevanc of these factors cannot be measured accurately until the regu lations are finalized. These regulations will impact on the total PVC Industry, as well as the water-borne vinyl project. Glidden was advised that this could complicate our ability to supply the latex commercially. Dr. Ackart briefly reviewed our IDA-related laborat ry studies on the terpolymer latex and the results of the pre-petltloo review at FDA. Dr. Ackart expressed the opinion that there ar no technical barriers to FDA approval of the ooatlngs under curr nt regulations, if we can satisfy OSHA and EPA requirements. Our ucc 068386 BUSINESS CONFIDENTIAL -9 - current goal for FDA approval is early 1975, byt final approval will depend on FDA's reaction to our petition. Mr. Andy . Engstrom. Glldden advisor on FDA activities, was optimistic and ? T-Afvi--aided that we should not retard the program because of th ' $ current controversy relating to vinyl chloride monomer. This W? opinion prevailed and it was decided that we should continue the program as planned. The next step at Continental Can is a 13-week pack t st, so Continental has requested a better definition of the potential for FDA approval. Dr. Ackart will write a letter to Nr. Engstrom outlining our plans, our data, and our expectations regarding th FDA status of the vinyl terpolymer. A draft of this letter is currently being circulated internally for approval before it go s to Glldden. Hopefully, this letter will convince Glidden and Continental that we can obtain FDA clearance for the terpolymer. Odor Emission During Baking - Bob Moorman emphasis d that the emission of the "soapy" odor, which was first detected during the baking of the coatings at Continental Can, is of concern be cause they are afraid that it might lead to a problem with OSHA. Brief attempts at Glidden to mask the odor with additives hav not yet been successful. The odor is very characteristic of lauric acid, so we have been investigating the use of a less volatile, reactive surfactant (Avirol POL 40). This FDA-approved surfactant (Avirol POL 40) has be n identified in our laboratory as the ammonium salt of 9,10-dihydroxy stearic acid. A terpolymer latex made with this surfactant gav coatings with blush and adhesion properties similar to those ob tained when ammonium laurate is used as the surfactant. Befor submitting this sample (QEX-2067) to Glidden, Mr. W. I. Wertz conducted and reported the following evaluation of its performanc properties: Three formulations were prepared (1) QEX-2067 + 1 MR Carbopol 940, (2) QEX-2067 + 1 MR Carbopol 940 + 3 MR ammonium laurate (no Avirol was available in Bound Brook), and (3) QEX2067 + 1 MR Carbopol 940 + 3 MR ammonium laurate + 1 MR KRL2774 and 2 FHR Resimene X-735. Systems 1 and 2 were evaluat d n two different samples of Continental Can lubricated budlum st ck at bakes of 4 minutes at 340F and 365F. System #3 was evalu ated on E-81 epoxy and lubricated budlum using a bake of 4 min. at 320F. All films were completely blush free after pasteuriza tion and no adhesion failure occurred. An odor test suggested by Glidden was also conducted by Mr. Wertz using unmodified QEX2033, QEX-2067, and QEX-2067 + 1 FHR Carbopol 940. The con clusion was that QEX-2067 had less and different odor than QEX2033 and that the addition of the Carbopol seemed to reduce the odor even more. In view of these encouraging results, a sample of th terpolymer latex made with Avirol POL 40 (QEX-2067) was given t ucc 008387 BUSINESS CONFIDENTIAL - 10 Bob Woodruff at th m ting on Bay 10. It was,t st d in the Glidden laboratory during the visit. The test confirmed less odor emission from the 2067 latex r--1 -- -*- *-*-- ^-- although some (different) odor was bake of the 2067 coating. Neither name of the Avirol POL 40 surfactant was given to Glidden per sonnel. However, Bob Woodruff was told that it contains hydroxyl groups, so that he would investigate its reactivity in an effort to tie up the surfactant in the coating. Bob was impressed with the inherent improvement in the odor emission, and requested a one-gallon sample for further testing and spray studies. Overspray Problem - Glidden feels that they can solv the overspray problem. It had been suggested earlier that the resin in the overspray be recovered and dissolved in solvent for use as a touch-up lacquer. (T. L. Dawson) 328L PVA OPERATIONS TEAM Recovery of Autoclave Varnish - The current production unit uses a plate dryer to remove the acetone and residual vinyl acetate from the PVA autoclave varnish. In preparation for a new plant for the production of low-profile PVA, a possible im provement was the use of a thin-film evaporator in place of th ponderous plate dryer. Tests in R and D with an Artisan thin-film dryer show d the feasibility of this approach; hence, tests were set up at Artisan and Luwa. These tests, witnessed by Mr. J. V. Carroll of Engineering, did not go well at Artisan because of mechanical problems but did go well at Luwa. The use of a Luwa dryer was, therefore, seriously considered by Engineering for the LP plant design, but finally rejected because of the proven performance of the plate dryer for drying PVA varnish. (J. V. Carroll, R. J. Hanna) REPORTS D. R. Montgomery, Project Report, "Vinyl Solution Polymerizations: Effect of Initiator Type on Lead Content of the Autoclave Varnish," April 10, 1974, File No. 19371. D. R. Montgomery, Project Report, "Vinyl Acetate Polymerizatl n for Low-Profile Additives: Some Studies on the Existing Process," May 10, 1974, File No. 19453. D. R. Montgomery, Project Report, "Vinyl Acetate Polymerization for Low-Profile Additives: Process Studies for Expansion of Capacity," May 21, 1974, File No. 19491. ucc 068388 Number 321H10 32100 32102 335H10 328K 328G 328L 216H 320C17 320D05 R AND D FINANCIAL SUMMARY SOUTH CHARLESTON VINYL RESINS (RJH,' JJB) Title Coatings Dispersion Resins Solution Resins FDA Approval Total Coatings April Expenses. $M 1974 YTD Budgeted 2.1 3.4 0.1 5.6 9.8 19.2 1.8 30.8 25 60 15 100 -/A* ``44 Budget 118 96 36 92 AS and El Dispersion Resins 4.8 22.8 53 129 Operations Team (328) Solution Resins FVEE Resins FVA Total Operations Team 8.5 0.0 3.7 12.2 37.9 0.0 11.2 49.1 140 2 29 171 81 0 116 86 Operations Team (216) Dispersion Resins 15.0 60.2 167 108 Non-Business PVC-Based Latexes Powder Coatings JJB Miscellaneous Total Non-Business 9.0 5.8 0.4 15.2 55.9 23.6 2.7 82.2 107 70 17 194 157 101 48 127 COMPLETE TOTAL 52.8 245.1 685 107 IJCC 068389 Number 216612 897N42 897N47 R AND D FINANCIAL SUMMARY SOUTH CHARLESTON VINYL RESINS, MISCEUJUTEOUS Title ASTM Activities, Suspension Resins AS and El, Sales Travel Tech. Service, UC1 April 0.25 0 0.15 0.40 YTD 2.10 0.16 0.49 2.65 Budgeted 5.0 6.0 6.0 17.0 % Budget 126 8 25 46.5 ucc 068390 ' . BUSINESS CONFIDENTIAL DISTRIBUTION . G. P. Bigelow, NTO-33 . J. L. Carrajal, 514 . J. C. Chaty, 515 . E. F. Goa, 312 . T. L. Dawson, 701 . K. E. Elsenhour, 515 . C. E. Fry, 514 . J. E. Giffin, 514 . R. E. Gulick, NYO-32 . D. E. Hardnan, NTO-33 . G. G. Hinmler, 312 . X. L. Roy, 701 a. Carol Huffaan, 701 (25) . J. V. Koleske, 701 . P. F. Lobo, 701 . V. R. Nanning, 2000 . C. N. Merrian, 312 . D. R. Nontgonery, 701 . G. S. Peacock, 312 . L. G. Reed, 720 . N. H. Reinking, 312 . X. E. Ross, 515 . J. J. Scharf, 514 . P. L. Snith, 701 . R. N. Vheeler, 514 / ucc 068391