Document YG99r3djBe6ynwyzDRN6Z7RMD

A. I.Ch.E. 1964 SEMINAR POLYVINYL CHLORIDE MANUFACTURE AND TECHNOLOGY SPONSORED BY THE AMERICAN INSTITUTE OF CHEMICAL ENGINEERS PRESENTED BY THE GENERAL TIRE & RUBBER COMPANY TABLE OF CONTENTS Agenda for Seminar, October 16, 1964 General Introduction History of Polyvinyl Chloride Theory of Polymerization Vinyl Chloride Synthesis General Tire Suspension Process PVC Fabrication and Applications E- E. Gruber Director, Research and Development A. J. Beber Manager, Chemical Pilot Plant R. Milkovich Group Leader, Polymer Research P. R. Sayre Technical Superintendent Ashtabula Plant W. J. Hanlon Technical Manager Chemical Division G. Hackim Vice President - Sales Chemical-Plastics Division AMERICAN INSTITUTE OF CHEMIGU. ENGINEERS TEACHING SEMINAR PRESENTED RY THE GENERAL TIRE & RUBBER COMPANY AGENDA October 16, 1964 8:00 8:30 8:40 8:50 - 8:30 A.M. 8:40 8:50 9:00 9:00 - 9:30 9:30 - 10:00 10:00 - 10:15 10:15 - 10:45 10:45 - 11:15 11:15 - 11:45 11:45 1:30 1:30 P.M. 3: 30 4:30 5:30 6:00 7:00 8:00 Speaker Rema rks 4:30 .. 7:00 8:00 Registration, Conference Hoom Falls-Akron Motel Welcome, J. H. Koffolt for A.I.Ch.E. Welcome, P. E. Jacobs for General Tire Briefing, E- E. Gruber, Director of Research and Development History of PVC, A, J. Beber, Manager, Chemical Pilot Plant Theory of Polymerization, R. Milkovich, Group Leader, Polymer Research Break Vinyl Chloride Synthesis, P. R. Sayre, Tech. Supt. Ashtabula, Chemical Division General Tire Suspension Process, W. J. Hanlon, Technical Manager, Chemical Division PVC Fabrication and Applications, G, Hackim, Vice President - Sales, Chemical-Plastics Division Luncheon, Falls-Akron Motel Buses depart for tours at Pilot Plant and R & D Center Panel discussion at R & D Cafeteria Buses depart for Falls-Akron Motel Buses depart for Women's City Club Social Hour Banque t Welcome, M. G. O'Neil, President, General Tire Sam Salem, President, Chemical-Plastics Division By representative of the A.I.Ch.E. GENERAL INTRODUCTION The program being presented by The General Tire^& Rubber Company for the mem bers of A.I.Ch.E. in this one day seminar is concerned only with-"Polyviny1 Chloride, Manufacture and Technology." The importance of this plastic in the United States is evidenced by a consumption now approaching nearly two billion pounds per year. We have attempted to set up the day's program to carry you through the early history of PVC, present day technology, including vinyl chloride monomer synthesis, polymerization theory, and plant scale manufacturing of polyvinyl chloride resin. Some of the technology used to produce useful end products is discussed. We have tried to make this presentation, which includes much proprietary engineering data, the most up-to-date and comprehensive treat ment of this subject matter available. General Tire entered the plastics fabrication field in the early 1950's on a large scale by acquisition of several manufacturing facilities located in Ohio, Pennsylvania, and Massachusetts. These facilities made General Tire the largest calender operator for vinyl in the United States. Products manufactured in these plastic plants include calendered, printed, and embossed supported and unsupported vinyl film and sheeting for the home furnishings, marine, shoe, and automotive accessory industries. A new plant in Columbus, Mississippi, a multimillion dollar investment in plastic operations, went on stream late in 1963. In 1954, General Tire built a plant at Ashtabula, Ohio, to produce vinyl chloride from acetylene and hydrochloric acid and to produce polyvinyl chloride resins by the suspension polymerization method. This plant is now undergoing its third major expansion. General Tire is thus vertically integrated in the vinyl field from monomer synthesis through polymerization and, finally, is a supplier of all types of plastic end products or accessories to several major industries. General Tire's capabilities in plastic fabrication, in addition to vinyl applications, include reinforced polyester plastics, thermoplastic end products, and poly urethane plastic foam for all kinds of cushioning applications. BIOGRAPHY Dr. Elbert E. Gruber received his B.S. in Chemistry at Xavier University, Cincinnati, Ohio, in 1932. He was awarded degrees of M.S. and Ph.D. in Organic Chemistry in 1934 and 1937 respectively at the University of Illinois where he also served as Graduate Assistant in Chemistry during 1935-1937. Upon completion of his graduate work, Dr. Gruber joined the Research Division of the B. B. Goodrich Company in 1937 advancing to the position of Research Supervisor in 1946. During the war years of 1943-1946 he served on a committee on modifiers in the Copolymer Research Group, Office of Rubber Reserve. In 1950 he joined the Central Research Laboratories of The General Tire & Rubber Company as Head of Plastics Research and in 1955 was named Assistant Director for Exploratory Research, and in 1962 became Director of Research and Develop ment. In addition to his duties at General Tire, Dr. Gruber serves as a mem ber of the Solid Committee of the Large Rocket Committee of the Aerojet-General Corporation, Azusa, California. GEH'O CO0 3 HISTORY OF POLYVINYL CHLORIDK r HISTORY OF POLYVINYL CHLORIDE by A. J. BEBER BIOGRAPHY A. Joseph Beber is a native of Montana. Graduated from Montana State College in 1930 with a Bachelor of Science degree in Chemical Engineering, he received his Master's degree in Chemical Engineering, 1932, and a Ph.D. in Chemistry and Physiology, 1937, from the University of Minnesota. Until 1942, Dr. Beber was associated with Southwest Missouri State College as instructor in General, Analytical, and Organic chemistry. He then joined B. F. Goodrich Company as Research Chemist, working on organic synthesis of rubber chemicals. In 1949, Dr. Beber came to The General Tire & Rubber Company, serving in the analytical and pilot plant sections of research. He now acts as Manager of the Company's chemical pilot plant at Mogadore, Ohio. HISTORY OF POLYVINYLCHLORIDE Tile first bi11ion-pounds-per-year plastic product, polyvinylchloride, is desigr nated by the term "vinyls" or "vinyL resins." It is produced on a global basis and is marketed under many trade names such as PVC, Vinylites, Geons, Corvic, Vinidur, Vinnol, Pliovic, Marvinol, Opalon, and General Tire's Vygens. That PVC has risen to such an important place in the "economies of several nations is due to a great deal of technical work done in this field. The need of a rubber substitute as well as artificial leather and another celluloid started the research in Germany. With the advent of the war, England likewise-was required to find *a rubber substitute, particularly for'the wire and cable industry. The development of special forms of the polymers such as plastisols during the later war years led to the coating of textiles for the manufacturer of leather like cloth products. By the end of the war, good plastisol polymers were available and from 1948 the standard types of PVC suspension, emulsion, polymers and copolymers were being made in increasing tonnage. The period 1950-1955 throughout the world saw the development of improved polymers. Following this period, major price reductions were made and this, together with the improved polymers for special applications and improved process techniques, have all contributed to the amazing growth in consumption over the past twenty years. The early beginnings can be traced back to 1835 when M. V. Regnault^^ published his findings on the reaction of an alcoholic solution of caustic potash on the ethylene dihalides to yield the monomer vinyl chloride according to the following equation: CH2C1-CH2C1 + KOH - CH2 = CHC1 + H20 + KC1 He also observed that when the mixture was allowed to stand for a time, and subsequently heated and exposed to sunlight, a white precipitate formed. Several reviews'^'^'^' have covered in considerable detail the development of polyvinylchloride. M. Kaufman^^ presents an interesting review of the development of polyvinylchloride in England. Almost 40 years later, 1872, Dr. E. Baumannpublished his observations that vinyl bromide as well as vinyl chloride in sealed tubes exposed to sunlight, changed from liquids to light -colored solids. He also observed that these materials were extremely chemically resistant to acids, alkalies, and solvents. The next significant steps are described in papers by I. Ostromislensky. ^ ^^ The first one, published in 1912, was entitled "Concerning the Structure of Polymerized Vinyl Bromide and Its Rubber." He observed the reaction of ultraviolet light on the polymerization of vinyl chloride and vinyl bromide to yield three different modifications, and on the basis of their solubilities, he divided them into alpha, beta, and gamma forms and considered that the degree of polymerization was the highest with the most insoluble or gamma form. The most insoluble or gamma isomer was called Kaupren bromide and Kaupren chloride, and served for the basis of determining the cryoscopic molecular weight and resulted in the empirical formula (C^H^gBr^g) or (C-^H^gCl ) w^ich showed that 16 vinyl halides had been definitely combined. 1 16 ch2 = 0.HC1 -> C32H48C1 16 16 ch2 = CHBr ~> C32H48Br 16 At about the same time, 1912, Os t r omi s 1 en sky and others^) applied for a British Patent entitled "A Process for Obtaining Rubber or Similar. Substances from Polymerized Vinyl Bromide or Polymerized Vinyl Chloride and Their Methyl Homologs." It wcas stated that the polymerized vinyl chloride or vinyl bromide is identical in all its properties with the chloride or bromide of the "Butadiene" rubbers. They also noted the action of sunlight and the absence of oxygen in accelerating this reaction. It was observed that the polymerization could easily be effected in solution, in bromobenzene, toluene, xylene or carbon disulfide. Later Ostromis1ensky11u' received a patent on a process for obtaining vinyl chloride from acetylene. Also in 1929, he received a BritishPatent'^1^ "The Preparat-i-on of PVC and the Application of Plasticizers such as dichlorbenzene, chlorinated naphthalene in order to work the material into plastic masses and films." In 1912, F. Klatte^^) was issued a German Patent for "The Synthesis of Vinyl Chloride by the Reaction of HC1 and Acetylene," In an analogous reaction, he likewise made vinyl acetate. These syntheses still today are the main ones for the commercial production of these monomers. Klatte and others^^ obtained a Patent for the "Processing and Preparation of Horny Materials, Films, Synthetic Fibers, Lacquers, and Working of Plastic Materials." They also recognized at this time that, with or without additives, through pressure or with solvents, PVC could be softened or dissolved so that it could be worked into a desirable shape or form. In 1928, three groups working independently developed vinyl chloride copolymers. The use of vinyl acetate as a copolymer in the polymerization of vinyl chloride greatly increased the use of the vinyl polymers because it solved the processing difficulties of the straight homopolymers. The three groups: E. W. Reid'i4' from Carbide and Carbon, Voss and Dickhauser' 1 from I. G. Far benindustrie, and W. E. Lawson from DuPont,all obtained patents on their processes. A little later, W. L. Semon^^ disclosed that a rubber-like gel structure could be obtained by intimately mixing a high boiling point material like tritolylphosphate into the polymer. This was later followed by other plas ticizers and resulted in a product called "Koroseal"'and has served as a basis for the development of this new class of materials. The first commercial polymerization process of vinyl chloride resulting from technical applications is credited to Lawson and Werntz of E. I. DuPont deNemours'^ who, in the year 1928, showed that peroxide catalysts such as ozone, benzoyl peroxide and barium peroxide could be used. In the earlier patents only the action of light and heat were described. The DuPont process could likewise be used in organic solvents. The application of emulsion processes for vinyl chloride polymerizations resulted in a rapid development of PVC preparation and applications. The oldest emulsion polymerization process of vinyl chloride is that of Mark, Fikentscher, Hengstenberg, and V. Susich.^^ A further advance was the I. G. process of Bappert and Wick'^1' for "Continuous Emulsion Polymerization." o The effect of oxygen or air on the course of the polymerization was later recognized by Schonfeld. '** The oldest suspension process, although not using vinyl chloride, appears to be that of Crawford and McGrath,'' who developed a suspension process for a series of acryl and vinyl esters. The first suspension PVC resins were made by Dr. Berg^^'^^' of Wacker-Chemie in 1935 m which he employed partially saponified polyvinyl acetate (polyvinyl alcohol) as the protective colloid. In the suspension process, the PVC is formed in polymerization into a granular powder in an easi ly-fi11erable form. The future of PVC as well as the past is linked to the appropriate balance of research and development. Further expansion and growth of the PVC industry is dependent on a greater knowledge of its basic behavior and improved processing techniques. Where the industry now stands in this country is shown in the following Tables 1 and 2 of monomer and polyvinyl chloride resin production capacities. Table 1 Estimated Vinyl Monomer, U. S. Capacity, 1964 Capacity*Millions of Pounds Annually B. F. Goodrich Union Carbide Ethyl Corporation Dow Chemical Tenneco (Cary Chemical) Allied Chemical Monochem (Borden & U. S. Rubber) Monsanto Diamond Alkali Goodyear Cumberland Chemical (Airco) General Tire American Chemical 400 280 240 200 170 150 150 150 90 45 60 30 40 2025 Table 2 Estimated Polyvinyl Chloride Resin, U. S. Capacity, 1964 Capacity-Millions of Pounds Annually B. F. Goodrich Uniop Carbide Monsanto Chemical . Cary Chemical Firestone Tire & Rubber Diamond Alkali Air Reduction U. S. Rubber ' Goodyear Tire & Rubber Borden Chemical Thompson Chemical General Tire & Rubber Pantasote Company Dow Chemical Escambia Chemical Atlantic Refining Atlantic Tubing Keysor Chemical Great American Plastics Ame ric an Chemical Rubber Corporation of America Minnesota Mining & Manufacturing , 325 275 ^ 150 140 125 120 115 110 80 80 65 55 50 40 40 25 25 25 15 12 10 5 1887 Literature References (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) M. V. Regnault, Liebigs Ann. Chem. 1_5 ( 1835) 63 C. E. Schildknecht, "Vinyl and Related Polymers," Wiley and Sons (1952) FI Kainer, "Po1yviny 1 ch1orid and Viny1ch1orid-Mischpo1ymerisate, " Springer-Ver1ag (1951) Karl Krekeler and Georg Wick, "Kuntstoff-Handbuch" Band II Teil 1, Karl Hanser-Ver1ag (1963) M. Kaufman, "The First Century of Plastics," P. 74, Plastics Institute, London, 1963 E. Baumann Liebigs Ann. Chem. 163 (1872) 312 I. Ostromis1ensky, J. Russ. Phys, Chem.Ges. 44_ (1912) 204-239, Chem Zentral, 1912, I, 1980 I. Ostromis1ensky, J. Russ. Phys. Chem. Ges. 48 (1916), 1132-51, Chem Zentral, 1923, IV, 606 B. P, No. 6299 (Ostromislensky and Others) (1912) U.S.P. No. 1,541,174 (Ostromis1ensky) (1925) B. P, No. 255,837 (Ostromislensky) (1925) D.R.P. No. 278,249 F. Klatte (1912) D.R.P. No. 281,877 F. Klatte (1913) U.S.P. No. 1,935,577 E. W. Reid (1928) 4 (15) (16) (17) (18) (19) (20) (21) (22) (23) (24) (25) U.S.P. No. 2,012, 177 Voss and Die khauser ( 1935) U.S.P. No. 1,867,014 W. . Lawson (1928) U.S.P. No. 2,188,396 W. L. Semon (1940) U.S.P. No. 1,929,453 W. L. Semon (1933) B. p. No. 319,591 Lawson and Werntz (1928) U.S.P. No. 2,068,424 Mark, Fikentscher, Hengstenberg, and Susich (1. G, Farben ind.) (1937) D.R.P. No. 679,897 Bappert and Wick (1936 U.S.P. No. 2,168,808 Schonfeld (B. F. Goodrich) (1937) U.S.P. No. 2,108,044 Crawford and McGrath, ICI (1933) D.R.P. No. 750,428 Berg (Wacker-Chemie) (1935) D.R.P. No. 755,028 Berg (Wacker-Chemie) (1935)