formaldehyde 3d edition. acs monograph no. 159

Formaldehyde Tank Cars. Courtesy B. I. Du Poi\t de Nemov,< FORMALDEHYDE By J. FREDERIC WALKER Chemical Research Division, Electrochemicals Department E. I. du Pont de Nemours & Company, Inc. Niagara Falls, JV. Y. American Chemical Society Monograph Series REINHOLD PUBLISHING CORPORATION 330 WEST FORTY-SECOND ST., NEW YORK, XJ. S. A. 1944 Copyright, 1944, by REIXHOLD PUBLISHING CORPORATION All rights reserved \ \ TKIS BOOK / / IS COMPLETE AND UNABRIDGED MAXLTFACTURED UNDER WARTIME jfo&DlTIONS IX CONFORMITY WITH ALI- GOVERNMENT RrGULAT^NS^COZVTROI.JLJr>fGyr^iE USE OF PAPER AXE) OTHER MATERIALS Printed in XT. S. A. by WATrmELT - PRESS, T5TC. GENERAL INTRODUCTION American Chemical Society Series of Scientific and Technologic Monographs By arrangement with the Interallied Conference of Pure and Applied Chemistry, which met in London and Brussels in July, 1919, the American Chemical Society was to undertake the production and publication of Scientific and Technologic monographs on chemical subjects. At the same time it was agreed that the National Research Council, in cooperation with the American Chemical Society and the American Physical Society, should undertake the production and publication of Critical Tables of Chemical and Physical Constants. The American Chemical Society and the National Research Council mutually agreed to care for these two fields of chemical development. The American Chemical Society named as Trustees, to make the necessary arrangements for the publication of the monographs, Charles L. Parsons, secretary of the society, Washington, D. C; the late John E. Teeple : then treasurer of the society, New York; and Professor Gellert Alleman of Swarthmore College. The Trustees arranged for the publication of the A. C. 3. series of (a) Scientific and (b) Technologic Monographs by the Chemical Catalog Company, Inc. (Reinhold Publishing Corporation, successors) of New York. The Council, acting through the Committee on National Policy of the American Chemical Society, appointed editors (the present list of whom appears at the close of this introduction) to have charge of securing authors, ind of considering critically the manuscripts submitted. The editors endeavor to select topics of current interest, and authors recognized as authorities in their respective fields. The development of knowledge in all branches of science, especially in chemistry, has been so rapid during the last fifty years, and the fields covered by this development so varied that it is difficult for any individual to keep in touch with progress in branches of science outside his own speciality. In spite of the facilities for the examination of the literature given by Chemical Abstracts and by such compendia as Beilstein's Hand- buch der Organischen Chemie, Richter's Lexikon, Ostwald's Lehrbueh der Allgemeinen Chemie, Abegg's and Gmelin-Kraut's Handbuch der Anor- .nischen Chemie, Moissan's Traite de Chimie Minerale Generale, Friend's ind Mellor's Textbooks of Inorganic Chemistry and Heilbron's Dictionary •>f Organic Compounds, it often takes a great deal of time^ coordinate die knowledge on a given topic. Consequently when men w™ have spent years in the study of important subjects are willing to coordinate their knowledge arid present it in concise, readable form, they perform a service iii iv FORMALDEHYDE of the highest value. It was with a clear recognition of the usefulness of such work that the American Chemical Society undertook to sponsor the publication of the two series of monographs. . Two distinct purposes are served by these monographs: the first, whose fulfillment probably renders to chemists in general the most important service, is to present the knowledge available upon the chosen topic in a form intelligible to those whose activities may be along a wholly different line. Many chemists fail to realize how closely their investigations may be connected with other work which on the surface appears far afield from their own. These monographs enable such men to form closer contact with work in other lines of research. The second purpose is to promote research in the branch of science covered by the monographs, by furnishing a well-digested survey of the progress already made, and by pointing out directions in which investigation needs to be extended. To facilitate the attainment of this purpose, extended references to the literature enable anyone interested to follow up the subject in more detail. If the literature is so voluminous that a complete bibliography is impracticable, a critical selection is made of those papers which are most important. AMERICAN CHEMICAL SOCIETY BOABD OF EDITOHS F. W. WILLAED, Editor of Monographs Scientific Series:— Technologic Series:— S. C. LIXD, WALTER A, SCHMIDT, W. MAXSHELD CLARE, E. K WEIDLBIN, LINTS C. PAULING, W. G. WHITMAN, L F. FIESEE. C. H. MATHEWSON, THOMAS H. CHILTON, BRUCE K. BKOWN, W.T.READ, ' '"' CHAELES ALLEN THOMAS. Preface The grooving importance of formaldehyde as a commercial chemical, its many unique characteristics, and its varied applications have created a definite need for a svstematk and critical account of formaldehvde chem- istry. This Monograph is presented in the hope of fulfilling this need. Previously no single book dealing with this subject has been available in the English language. In 1908 a book on formaldehyde by Grlov was published in Russia and appeared in a German translation by C. KietabI in 1909 {/'Formaldehyde by J. E. Orlov, translated by C\ KietabI, Verlag von Johann Ambrosius Barth, Leipzig, 1909). More recently, Arthur Menzel edited and revised a treatise on formaldehyde by Vanino and Seitter which was apparently first published in the early years of the twentieth century ("Der Formaldehyde by A. Menzel, Hartleben's Yerlag, Wien und Leipzig, 1927j. Both of these books are now inadequate because of the rapid scientific advances of the last fifteen years. In presenting this Monograph, the writer wishes to express his gratitude to a host of friends without whose help and cooperation its preparation would have been impossible. Special thanks are due to his associates in the Electrochemical* Department of the du Pont Company for their help and inspiration in the initiation, planning, and prosecution of the work. Thanks are also due to Dr. G. C. Bailey and Dr, B. S. Lacy for their assistance in preparing the section dealing with formaldehyde manu- facture. The author is also grateful to Dr. Lacy for his aid in clarifying the problems involved in the analysis and interpretation of physical, chemical and thermodynamic data. It is with pleasure that he acknowl- edges the help and assistance of Mm. Ruth Goodrick and Miss Janet Searles for their loyal aid in editing the manuscript and collaborating in the search for source material. Special thanks for comment, advice, and supplementary information are gratefully acknowledged to J, F. T. Berlinger, T. L. Davis, A. D* Gilbert, AY. k Gordon, J. W. Hill, E. F + Izard, F. L. Koethen, E. R. Laughlin, H, A. Luba,A. M. Neal.R. X.Pease,J. R. Sabina, G. L. Schwartz, Y. B. Sease, and J. R. Weber. J. FEEDBEIC WALKED Niagara Falls, X. Y. April 4, 1944 Introduction Formaldehyde chemistry is complicated by the fact that, although for- maldehyde is well known in the form of its aqueous solution? and solid polymers, it is seldom encountered in pure monomelic form. Substances with which the chemist must deal divide mainly in two groups: (I) com- pounds with the type formula. (CHsOjn and (II) addition compounds or solvates of which the most important are the simple hydrate, methylene glycol (CH^OHV- and the hydrated linear polymers or polyoxymethylene glycols whose type formula is HO-t'CHsOja-H. Group I includes for- maldehyde monomer itself, the relatively little known cyclic polymers, trioxane—1.CH2OJ3 and tetraoxymethylenc—(CHsO)^ and the anhydrous polyoxymethylene which is produced when monomelic formaldehyde polymerizes. Group II includes (A) methylene glycol and the low molecu- lar weight polyoxymethylene glycols present in formaldehyde solutions, (B'l the mixture of solid polyoxymethylene glycols known commercial^ as paraformaldehyde, and (C) the so-called alpha-polyoxymethylenes, HO-(CH^Oj n -H in which n is greater than 100- The anhydrous high molecular weight polymer may be regarded as the end product of this series. Polymeric compounds which are functional derivatives of poly- oxymethylene glycols are also occasionally encountered. All of these hydrates, polymers, and polymer derivatives are reversible and react as formaldehyde, differing only in the readiness with which they split up or hydrolyze to yield formaldehyde or its simple reactive solvates. In discussing formaldehyde chemistry, we shall first give attention to the methods by which it is normally produced. Following this, we shall * deal with the physical and thermodynamic properties of the various for- maldehyde substances: the simple monomer (Chapter II), formaldehyde solutions (Chapters III-VI), and polymers (Chapter VII). Chapters YIII-XV are devoted to the chemical properties of formaldehyde and its reactions with various types of inorganic and organic chemicals. Chapters XVI and XVII deal with formaldehyde detection and analysis. Hexamethylenetetramine (Chapter XVIII), which is produced by the reaction of formaldehyde and ammonia, must receive special consideration in any discussion of formaldehyde substances. Although this compound, (CH-2)eX 4 , is a distinct chemical entity, it plays an important industrial role as a special form of formaldehyde. Chemically it'is an ammono ana- logue of the cyclic formaldehyde polymers in which trivalent nitrogen has replaced bfralent oxygen. The industrial applications of commercial formaldehyde substances, viz. formaldehyde solution, paraformaldehyde, and hexamethylenetetramine vii viu INTRODUCTION are discussed in Chapters 19 and 20. In this connection, it must be pointed out that this Monograph makes no attempt to replace the many excellent works of reference which deal with formaldehyde resins. Al- though the resin industry is the principal formaldehyde consumer and ac- cordingly may not be neglected, it is our purpose to emphasize the many other miscellaneous applications of formaldehyde which have received less attention in previous publications, Unfortunately, the impact of World War II on formaldehyde cannot be treated in this book. Many of the present war-time uses of formaldehyde are simple extensions of the applications here discussed. New uses are of ece*_t*itA (_lirouded in secrecy and must await another time for adequate treatment. J. FREDERIC WALKEB. Niagara Falk, N. F, Sent. 7.19U Page o y GENERAL IxrRODrcTiON iii PREFACE v INTRODUCTION vii CHAPTER 1. FORILALDEHYDE PRODUCTION 1 Production Volume; Commercial Forms of Formaldehyde; Early History; Present Methods of Manufacture; Production of Formaldehyde from Methanol; Production of Formaldehyde from Methane and other Hydro- carbon Gases^ CHAPTER 2. MONOMERIC FORMALDEHYDE 18 Properties of Monomeric Formaldehyde Gas; Heat capacity of Formalde- hyde Gas; Heat of Formation and Free Energy of Gaseous Formaldehyde; Absorption Spectra and Atomic Structure; Properties of Liquid Formalde- hyde; Preparation of Liquid Formaldehyde. CHAPTER 3. STATE OF DISSOLVED FORMALDEHYDE 28 Solutions in Non-Polar Solvents; Solutions in Polar Solvents; State of Formaldehyde in Aqueous Solution; Methylene Glycol; Polymeric Hydrates and Solution Equilibrium; Kinetics of Solution Reactions; Thermo- chemistry of Solution Reactions; Solutions of Formaldehyde in Alcohols. CHAPTER 4* COMMERCIAL FORMALDEHYDE SOLUTIONS 39 Composition of Commercial Solutions; Specifications and Purity; Physical Properties; Storage of Commercial Formaldehyde; Toxicity-Physiological Hazards and Precautions. CHAPTER 5. PHYSICAL PROPERTIES OF PURE AQUEOUS FORMALDE- HYDE SOLUTIONS 48 Introduction; Acidity; Appearance; Boiling and Freezing Points; Density and Refractivity; Heat of Dilution; Heat of Formation and Free Energy; Magnetic Properties; Partial Pressure; Polymer Precipitation; Solvent Properties; Surface Tension; Viscosity. CHAPTER 6. DISTILLATION OP FORMALDEHYDE SOLUTIONS 58 Vacuum Distillation; Pressure Distillation; Atmospheric Pressure Distil- lation; Fractional Condensation; Steam Distillation; Distillation of Formaldehyde Containing Methanol. CHAPTER 7. FORMALDEHYDE POLYMERS 64 Introduction; Linear Polymers: Lower Polyoxymethylene Glycols, Para- formaldehyde, Aipha-Polyoxymethylene, Beta-Polyosymethylene 7 Poly- oxymethylene Glycol Derivatives; Cyclic Polymers: Trioxane, Tetraoxy- methylene. CHAPTER 8. CHEMICAL PROPERTIES OF FORMALDEHYDE 102 Introduction; Chemical Stability and Decomposition; Oxidation and Reduction; Reactions of Formaldehyde with Formaldehyde: C&nrrizzaro Reaction, Tischenko Reaction, Aldol-type Condensations; Type Reactions: Reduction Reactions, Addition or Condensation Reactions, Polymerization Reactions, Reactions of Methylol Derivatives, Reactions Involving Two or More Types. ix CONTENTS Page CHAPTER 9. REACTIONS OF FORMALDEHYDE WITH INORGANIC AGENTS 117 Alkali Met-il*- ^kali snd Alkaline Earth Hydroxides; Metals, Metal Oxide and Hydroxides; Metallic Salts; Ammonia; Ammonium baits; Hydrazine- HvWn^vlamine: Hydrogen Cyanide and Cyanides; Ciirbon Monoxide; Hvdrogeu Peroxide and Peroxides; Hydrogen Sulfide .and Sulfides; Sulfur Dioxide and Sulfites; Acids; Halogens. CHAPTER 10. REACTIONS OF FORMALDEHYDE "WITH ALIPHATIC HYDROXY COMPOUNDS AND MERCAPTAN^ 138 Alcohols; Glvcols and Glycerol; Folyhydroxy Compounds; Sugars; Starch; Cellulose; Joint Pactions of Formaldehyde with Alcohols and Hydrogen Halides. "Reactions of Formaldehyde with Mercaptan*, CHAPTER 11. REACTIONS or FORILILDEKYDE WITH ALDEHYDES AND IvETOXES 150 Reactions with Other Aldehydes: Acetaldehyde—Reactions in Water Solu- tion. Pent aery thritoh Gas-Phase Reactions Involving Formaldehyde and Acetaldehyde' Higher Aliphetie Aldehydes, Aromatic Aldehydes; Ketones: Acetone, Higher Aliphatic Ketones, Cyclic Ketones, Di-Keton.es—Acetyl- acetone, Aryl Aliphatic Ketones. CHAPTER 12. REACTIONS OF FORMALDEHYDE WITH PHENOLS 162 Introduction; Historical; Fundamental Characteristics of Phenol-Formalde- hyde Reactions; Methylol Derivatives; Methylene Derivatives; Phenol Formaldehyde Resins. CHAPTER 13. REACTIONS OF FORMALDEHYDE WITH CARBQXYLIC ACIDS, ACID ANHYDRIDES, ACYL CHLORIDES, AND ESTERS 191 Carboxylic Acids; Acid Anhydrides; Acyl Chlorides; Esters. CHAPTER 14. REACTIONS OF FORMALDEHYDE WITH AMINO AND AMIDO COMPOUNDS 199 Aliphatic Amines; Aromatic Amines; Amides; Irnides; Urethanes (Carba- mates): Thiourea; Aminonitriles-Cyanamide and Cyanamide Polymers; Amino-Acids and Esters; Proteins. CHAPTER 15. REACTIONS OF FORMALDEHYDE WITH HYDROCARBONS AND HYDROCARBON DERIVATIVES 227 Introduction; Reactions with Olefins and Cyclo-Olefins; Halogenated Olefins; Aromatic Hydrocarbons; Acetylenic Hydrocarbons; Organo- Metallic Hydrocarbon Derivatives; Nitro hydro carbons, CHAPTER 16. DETECTION AND ESTIMATION OP SMALL QUANTITIES OF FORMALDEHYDE 244 Introduction; Colorimetrie Procedures; Polarographic Method; Identifica- tion of Formaldehyde; Detection of Acetaldehyde in the Presence of Formal- dehyde ; Detection and Estimation of Small Quantities of Formaldehyde in Air; Detection of Formaldehyde in Foodstuffs; Detection of Formaldehyde in Products -which have been Subjected to Formaldehyde Treatment. CHAPTER 17. QUANTITATIVE ANALYSIS OF FORMALDEHYDE SOLUTIONS AKD POLYMERS 255 Introduction; Physical Methods for Determining Formaldehyde; Chemical Methods; Assay of Commercial Formaldehyde; Assay of Commercial Para- formaldehyde; Determination of Formaldehyde in Special Compositions and m Products Treated with Formaldehyde; Determination of Combined Formaldehyde in Formaldehyde Treated Products [...]... 300°C, as measured by passing mixtures of formaldehyde and air through a heated tube3-23 Although monomeric formaldehyde is obtained whenever formaldehyde solution or its linear polymers are subjected to vaporization, gas having a high formaldehyde concentration is best obtained by the action of heat on paraformaldehyde, which contains 95-96 per cent available formaldehyde, or from the more highly polymerized... anhydrous form of formaldehyde which analyses as containing not less than 95 per cent CH 2 0 Paraformaldehyde is manufactured from formaldehyde solution and is consequently the more expensive form (pages 69-77) Recently, trioxane, (CH20)3: the true cyclic trimer of formaldehyde (pages 94-99) has been publicized14 Hexamethylenetetramine, (CHa^X^ which is formed by the reaction of formaldehyde and ammonia... butyraldehyde, a n d isovaleraldehyde, among others, were discovered before 1860 Formaldehyde, however, remained unknown T h e ease with which m e t h a n o l passes on oxidation from formaldehyde to formic acid a n d thence to carbon dioxide a n d water made the isolation of formaldehyde difficult FORMALDEHYDE PRODUCTION Formaldehyde ^vas first prepared by Butlerov 11 ' 44 in 1859 as the product of... starred the commercial manufacture of formaldehyde in 1889 Shipments of 5-20 kg were made to various factories and to university laboratories Also prepared for the chemical market were such formaldehyde derivatives as paraformaldehyde, hexamethylenetetraroine, and anhydroformaldehyde aniline At approximately this period, investigations were being conducted on the use of formaldehyde as a disinfectant Meister,... Nemours & Co., Inc.) began manufacture of formaldehyde in 1904 In the latter part of the first decade of the twentieth century, the discovery and manufacture of phenol -formaldehyde resins by Dr L H Baekeland increased the demand for formaldehyde When the war began in 1914, the demand for all chemical products increased, and formaldehyde was no exception Since that time formaldehyde production has continued... laboratories, the flammable limits of mixtures of formaldehyde gas and air range from compositions containing approximately 0.37 to 13 volumes of air per volume of formaldehyde gas This means that formaldehyde- air mixtures containing from 7 to 73 per cent formaldehyde should be regarded as potentially explosive The initial combustion temperature of formaldehyde- air mixtures is reported to be approximately... Inorganic and Organic Compounds; Analysis of Hexasiethvlenetetramine CHAPTER 19 USES OF FORUALDEHTDE, FORMALDEHYDE POLBIEES AND HEXAIIETHYLEXETETRAIIINE PART 1 302 Introduction; Uses of Formaldehyde in the Resin Industry; Synthetic Resins; Resins Modified bv Formaldehyde Treatment, CHAPTER 20 USES OP FORMALDEHYDE, FORMALDEHYDE POLBIEES AND HEIUIETHYLEXETETRIMIXE PAET II 318 Introduction; Agriculture; Analysis;... improved formaldehyde unit 37 based on the work reported hy Orlov80,31 In time, the Hokverkohhmgs-Industrie, A G., manufacturer of methanol, also became one of the big producers of formaldehyde I n addition to the above concerns, large dyestuff companies which later amalgamated as the L G Farbenindustrie manufactured formaldehyde for their own consumption Industrial research on t h e manufacture of formaldehyde. .. Klar and Schulze 2 ^ Brochet 9 , and Orlov30'31 CO o to to _ 3 , "Formaldehyde u n i t d e v e l o p e d b y M e r o k l i n and TVteekarm (JTrom liujjgo, G., Cheni A?rp.t 18, 159 (1931).) FORMALDEHYDE PRODUCTION 9 In 1910, O Blank 7 patented the use of a silver catalyst in Germany A year later Le Blanc and Plaschke22 reported that formaldehyde yields obtained with silver catalysts were higher than... production of formaldehyde solution in 1914 was reported to be 8:426,000 lbs; in 1927, 26,447,000 lbs,55 These figures give a representative index of the almost continuous growth of the domestic formaldehyde industry since its beginning in 1901 Commercially) formaldehyde is manufactured and marketed chiefly in the form of an aqueous solution containing 37 per cent by weight dissolved formaldehyde (CH20) . selective, any formaldehyde formed would tend to be com- pletely hydrogenated to methanol, FORMALDEHYDE Production of Formaldehyde from Methanol Reaction Mechanism. The formation of formaldehyde. pointed out that this Monograph makes no attempt to replace the many excellent works of reference which deal with formaldehyde resins. Al- though the resin industry is the principal formaldehyde consumer. Gases^ CHAPTER 2. MONOMERIC FORMALDEHYDE 18 Properties of Monomeric Formaldehyde Gas; Heat capacity of Formalde- hyde Gas; Heat of Formation and Free Energy of Gaseous Formaldehyde; Absorption