FORMALDEHYDE by J. FREDERIC WALKER C h e m i c a l R e s e a r c h Division, E l e c t r o c h e m i c a l s D e p a r t m e n t , E. I. d u P o n t de N e m o u r s & C o m p a n y , Niagara Falls, Ν. Υ .
AMERICAN CHEMICAL SOCIETY MONOGRAPH NO. 98 A b o u t a n y p r o d u c t of g r e a t t e c h n i c a l a n d i n d u s t r i a l i m p o r t a n c e , having a n e x t r e m e variety of u s e s , a g r e a t d e a l of m i s i n f o r m a t i o n a n d confusion is a l m o s t c e r t a i n to a c c u m u l a t e over t h e y e a r s . I n few cases h a s t h e n e e d for c r i t i c a l survey a n d i n t e g r a t i o n b e e n more c o m p e l l i n g t h a n i n t h a t of f o r m a l d e h y d e . T h i s v o l u m e is t h e first serious a t t e m p t t o sift a n d a n a l y z e t h e vast l i t e r a t u r e w i t h a view t o p r e s e n t i n g i t s e s s e n t i a l facts i n c o m p a c t a n d c o m p r e h e n s i b l e f o r m . Y e a r s of experience i n t h i s field h a v e e n a b l e d Dr. Walker t o review a n d e v a l u a t e t h e m a s s of m a t e r i a l p u b l i s h e d on f o r m a l d e h y d e . S o m e idea of t h e m a g n i t u d e of this t a s k is given b y t h e f a c t t h a t if h e h a d m e n t i o n e d all t h e references, h e w o u l d have p r o d u c e d twenty v o l u m e s i n s t e a d of o n e ! H e h a s i n d e e d p e r f o r m e d a r e m a r k a b l e service t o t h e c h e m i c a l industries i n successfully c a r r y i n g o u t t h i s difficult a n d i m p o r t a n t i n v e s t i g a t i o n . His r e s u l t s comprise a v o l u m e t h a t will b e a s t a n d a r d of reference for years t o c o m e . C O N T E N T S GENERAL INTRODUCTION. PREFACE. INTRODUCTION. FORMALDEHYDE PRODUCTION — Production Volume; Commer cial Forms of Formaldehyde; Early History; Present Methods of Manu facture; Production of Formaldehyde from Methanol; Production of Formaldehyde from Methane and other Hydrocarbon Gases. MONOMERIC FORMALDEHYDE — Properties of Monomeric For maldehyde Gas; Heat capacity of Formaldehyde Gas; Heat of Formation and Free Energy of Gaseous Formaldehyde; Absorption Spectra and Atomic Structure; Properties of Liquid Formaldehyde; Preparation of Liquid Formaldehyde. STATE OF DISSOLVED FORMALDEHYDE — Solutions in Non-Polar Solvents; Solutions in Polar Solvents; State of Formaldehyde in Aqueous Solution; Methylene Glycol; Polymeric Hydrates and Solution Equilib rium; Kinetics of Solution Reactions; Thermochemistry of Solution Reactions; Solutions of Formaldehyde in Alcohols. COMMERCIAL FORMALDEHYDE SOLUTIONS — Composition of Commercial Solutions; Specifications and Purity; Physical Properties; Storage of Commercial Formaldehyde; Toxicity-Physiological Hazards and Precautions. PHYSICAL PROPERTIES OF PURE AQUEOUS FORMALDEHYDE SOLUTIONS — Introduction; Acidity; Appearance; Boiling and Freez ing Points; Density and Refractivity; Heat of Dilution; Heat of Forma tion and Free Energy; Magnetic Properties; Partial Pressure; Polymer Precipitation; Solvent Properties; Surface Tension; Viscosity. DISTILLATION OF FORMALDEHYDE SOLUTIONS — Vacuum Distillation; Pressure Distillation; Atmospheric Pressure Distillation; Fractional Condensation; Steam Distillation; Distillation of Formalde hyde Containing Methanol. FORMALDEHYDE POLYMERS — Introduction; Linear Polymers: Lower Polyoxymothylene Glycols, Paraformaldehyde, Alpha-Polyoxynielhylene, Beta-Polyoxymethylene, Polyoxymethylene Glycol Deriva tives; Cyclic Polymers: Trioxane, Tetraoxymethylene. CHEMICAL PROPERTIES OF FORMALDEHYDE — Introduction; Chemical Stability and Decomposition; Oxidation and Reduction; Re actions of Formaldehyde with Formaldehyde: Cannizzaro Reaction.. Tischenko Reaction, Aldol-typc Condensations: Typo Reactions: Reduc tion Reactions, Addition or Condensation Reactions, Polymerization Reactions, Reactions of Methylol Derivatives, Reactions Involving Two or More Types. REACTIONS OF FORMALDEHYDE WITH INORGANIC AGENTS— Alkali Metals; Alkali and Alkaline Earth Hydroxides; Metals, Metal Oxides and Hydroxides; Metallic Salts; Ammonia; Ammonium Salts; Hydrazine; Hydroxylamine; Hydrogen Cyanide and Cyanides; Carbon Monoxide; Hydrogen Peroxide and Peroxides; Hydrogen Sulfide and Sulfides; Sulfur Dioxide and Sulfites; Acids; Halogens. REACTIONS OF FORMALDEHYDE WITH ALIPHATIC HYDROXY COMPOUNDS AND MERCAPTANS — Alcohols; Glycols and Glycerol; Polyhydroxy Compounds; Sugars; Starch; Cellulose; Joint Reactions of Formaldehyde with Alcohols and Hydrogen Halides. Reactions of For maldehyde with Mercaptans.
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REACTIONS OF FORMALDEHYDE WITH ALDEHYDES A N D KETONES — Reactions with Other Aldehydes: Acetaldehyde — Reac tions in Water Solution, Pentaerythritol, Gas-Phase Reactions Involving Formaldehyde and Acetaldehyde, Higher Aliphatic Aldehydes, Aromatic Aldehydes; Ketones: Acetone, Higher Aliphatic Ketones, Cyclic Ketones, Di-Ketones — Acetylacetone, Aryl Aliphatic Ketones. REACTIONS OF FORMALDEHYDE WITH PHENOLS — Introduc tion; ^Historical; Fundamental Characteristics of Phenol-Formaldehyde Reactions; Methylol Derivatives; Methylene Derivatives; Phenol Formaldehyde Resins. REACTIONS OF FORMALDEHYDE WITH CARBOXYLIC ACIDS, ACID ANHYDRIDES, ACYL CHLORIDES, AND ESTERS — Carboxylic Acids; Acid Anhydrides; Acyl Chlorides; Esters. REACTIONS OF FORMALDEHYDE WITH AMINO AND AMIDO COMPOUNDS — Aliphatic Amines; Aromatic Amines; Amides; Imides; Urethanes (Carbamates) Thiourea; Aminonitriles-Cyanamide and Cyanamide Polymers; Amino-Acids and Esters ; Proteins. REACTIONS OF FORMALDEHYDE WITH HYDROCARBONS AND HYDROCARBON DERIVATIVES —Introduction; Reactions with Olefins and Cyclo-Olefins; Halogenatcd Olefins; Aromatic Hydro carbons; Acetylenic Hydrocarbons; Organo-Metallic Hydrocarbon De rivatives; Nitrohydrocarbons. DETECTION A N D ESTIMATION O F SMALL QUANTITIES OF FORMALDEHYDE—Introduction; Colorimetric Procedures; Polarographic Method; Identification of Formaldehyde; Detection of Acetalde hyde in the Presence of Formaldehyde; Detection and Estimation of Small Quantities of Formaldehyde in Air; Detection of Formaldehyde in Food stuffs; Detection of Formaldehyde in Products which have been Subjected to Formaldehyde Treatment. QUANTITATIVE ANALYSIS OF FORMALDEHYDE SOLUTIONS AND POLYMERS — Introduction; Physical Methods for Determining Formaldehyde; Chemical Methods; Assay of Commercial Formaldehyde; Assay of Commercial Paraformaldehyde; Determination of Formaldehyde in Special Compositions and in Products Treated with Formaldehyde; Determination of Combined Formaldehyde in Formaldehyde Treated Products. HEXAMETHYLENETETRAMINE—Introduction; Chemical Struc ture; Mechanism of Hexamethylenetotramine Formation; Manufacture; Properties; Physiological Properties; Chemical Reactions with Inorganic and Organic Compounds; Analysis of lEexamethylenctetramine. USES OF FORMALDEHYDE, FORMALDEHYDE POLYMERS AND HEXAMETHYLENETETRAMINE. PART I — Introduction; Uses of Formaldehyde in the Resin Industry; Synthetic Resins; Resins Modified by Formaldehyde Treatment. USES OF FORMALDEHYDE, FORMALDEHYDE POLYMERS AND HEXAMETHYLENETETRAMINE. PART II—Introduction; Agriculture; Analysis; Concrete, Plaster, and Related Products; Cos metics; Deodorization; Disinfection and Fumigation; Dies and Dyehouse Chemicals; Embalming and Preserving; Explosives; Fertilizers; Fireproofing; Fuel Specialties; Gas Absorbents; Hydrocarbon Products; Insecticides; Leather; Medicinal Uses; Metal Industries; Paper Photog raphy; Rubber; Solvents and Plasticizers; Surface Active Agents; Textiles; Wood. INDEX.
400 M>aa«*9 20 Chapter*—Muni
rated—Price
It ΕΙΛΙΙΟΜ» P U B L I S H I N G CORP. VOLUME
2 2, N O .
21.NOVEMBER
10,
1944
ST. G Ο 330 WEST 42nd STREET NEW YORK 18, Ν. Υ.
1949
