INTRODUCTION

tances. Although this compound, (CHz) sNa, , it plays an important industrial role as a

Chemically it is an ammono analogue of ers in which trivalent nitrogen has replaced

ons of commercial formaldehyde substances, , formaldehyde polymers, and hexamethylene-

Chapter 20. In this connection, it must be graph makes no attempt to replace the ma'ny

ce which deal with formaldehyde resin tech- industry is a major formaldehyde consumer neglected, it is our purpose to emphasize the

e which have received less attention in previous

J. FREDERIC WALKER

Contents

Preface to 'third Edition

Preface to Second Edition

Preface to First Edition

Introduction

FORMALDEHYDE PRODUCTION Growth of Formaldehyde Industry Early History of Formaldehyde Methods of Production

Reduction of Carbon Oxides Production of Formaldehyde from Methanol

Manufacture of Formaldehyde from Methanol Production of Formaldehyde from Hydrocarbon

Oxidation of Methane Oxidation of Higher Hydrocarbon Gases

Purification of Formaldehyde Solutions Special Formaldehyde Solutions Shipping Formaldehyde

MONOMERIC FORMALDEHYDE Formaldehyde Gas

Properties Preparation

Liquid Formaldehyde Properties Preparation

STATE OF DISSOLVED FORMALDEHYDE Solutions in Nonpolar Solvents Solutions in Polar Solvents

xv

vii

xiii

1 2 4 7 7 8

16 Gases 25

25 27 29 32 32

AdministratorText Box547.436 WAL 3rd ed.

xvi CONTENTS I CONTENTS I 3. STATE OF DISSOLVED FORMALDEHYDE (Continued)

Water Solutions of Formaldehyde State of Formaldehyde in Aqueous Solutions

Methylene Glycol Determination of Methylene Glycol

Unhydrated Formaldehyde in Aqueous Solution Polymeric Hydrates and Solution Equilibrium Relation of Formaldehyde Partial Pressure

to Solution Composition Kinetics of Changes in Solution Equilibrium

Thermochemistry of Changes in Solution Equilibrium Solutions of Formaldehyde in Alcohols

4. COMMERCIAL FORMALDEHYDE SOLUTIONS Specifications and Purity Commercial Alcoholic Solutions of Formaldehyde Physical Properties of Aqueous Commercial Formaldehyde

Density and Refractivity Expansion Coefficients Flash Point Partial Pressure of Formaldehyde Resistivity Viscosity

Storage of Commercial Formaldehyde Precipitation of Polymer Reactions Leading to the Chemical Loss.of Formaldehyde

on Storage Materials of Construction for Formaldehyde Storage

Toxicity: Physiological Hazards and Precautions Safe Handling and First Aid

5. PHYSICAL PROPERTIES OF AQUEOUS FORMALDEHYDE Acidity Appearance Boiling Points and Freezing Points Density and Refractivity Dielectric Constant Freezing Points Heat of Dilution Heat of Formation and Free Energy Magnetic Properties

Partial Pressure Polymer Precipitation Refractivity Solvent Properties Surface Tension Viscosity

6. DISTILLATION OF FORMALDEHYDE SOLU Vacuum Distillation Pressure Distillation Atmospheric Pressure Distillation

i Fractional Condensation Fractionation ~ t ' eam Distillation Miscellaneous Purification Processes Distillation of Alcoholic Formaldehyde

7. FORMALDEHYDE POLYMERS Linear Polymers Lower Polyoxymethylene Glycols Paraformaldehyde

Early History Composition and Structure Thermochemistry Properties Paraformaldehyde Manufacture Mechanism of Paraformaldehyde Pro

Alpha-Polyoxymethylene Properties Preparation

Beta-Polyoxymethylene Polyoxymethylene Glycol Derivatives Polyoxymethylene Diacetates

Structure Properties Preparation

Polyoxymethylene Dimethyl Ethers Structure Properties Preparation

in Aqueous Solutions

in Aqueous Solution

EHYDE SOLUTIONS

the Chemical Loss.of Formaldeh

ction for Formaldehyde Storage Hazards and Precautions

OF AQUEOUS FORMALDEHYDE

CONTENTS

Partial Pressure Polymer Precipitation Refractivity Solvent Properties Surface Tension Viscosity

6. DISI'ILLKTION OF FORMALDEHYDE SOLU'I'IONS Vacuum Distillation Pressure Distillation Atmospheric Pressure Distillation Fractional Condensation lh-actionation Steam Distillation Miscellaneous Purification Processes Distillation of Alcoholic Formaldehyde Solutions

7. FORMALDEHYDE POLYMERS Linear Polymers Lower Polyoxymethylene Glycols Paraformaldehyde

Early History Composition and Structure Thermochemistry Properties Paraformaldehyde Manufacture Mechanism of Paraformaldehyde Production

Alpha-Polyoxymethylene Properties Preparation

Beta-Polyoxymethylene Polyoxymethylene Glycol Derivatives Polyoxymethylene Diacetates

Structure Properties Preparation

Polyoxymethylene Dimethyl Ethers Structure Properties Preparation

xvii

xviii C O N T E N T S CONTENTS I 7. FORMALDEHYDE POLYMERS (Continued)

Gamma-Polyoxymethylene Preparation

Delta-Polyoxymethylene Structure Properties Preparation

Epsilon-Polyoxymethylene High Molecular Weight Polyoxymethylenes

History Structure Properties Partial Pressure and Thermodynamic Properties Preparation Preparation from Monomer Preparation from Trioxane Preparation from Aqueous and Alcoholic Solutions Polyoxylllethylene Copolymers

Acetal Resins End-capping Stabilization Agents

Cyclic Polymers Trioxane Structure Physical Properties Thermodynamic Properties Hydrolysis and Depolymerization Physiological Properties Preparation

Tetraoxane

8. CHEMICAL PROPERTIES OF FORMALDEHYDE Chemical Stability and Decomposition Oxidation and Reduction Isotope Formaldehydes Reactions of Formaldehyde with Formaldehyde

Polylnerization Reactions Cannizzaro Reaction Tischenko Reaction ~ ldol - type Condensations

Type Reactions Reduction Reactions Addition or Condensation Reactions Trans-hydroxymethylation Polymerization Reactions

Reactions of Methyl01 Derivatives Decomposition with Liberation of For Trans-hydroxymethylation

I Pol condensation Condensation with other Compounds

1 Dehydration to Double-Bonded Methy 1 Addition Reactions

Reduction to Methyl Derivatives I I Reactions Involving Two or More Types

REACTIONS OF FORMALDEHYDE WITH II Alkali Metals Alkali and Alkaline-Earth. Hydroxides Metals, Metal Oxides, and Hydroxides Metallic Salts Ammonia Ammonium Salts Sulfamide Hydrazine Hydroxylamine Hydrogen Cyanide and Cyanides Cyanogen Carbon Monoxide Hydrogen Peroxide and Peroxides Hydrogen Sulfide and Sulfides Sulfur Dioxide and Sulfites Acids

Sulfuric Phosphoric Acid Nitric Acid Nitrous Acid Hydrohalogen Acids

Phosphine and Phosphorus Halides Silicon Tetrachloride Halogens

C O N T E N T S I CONTENTS xix

t Polyoxymethylenes

Thermodynamic Properties

OF FORMALDEHYDE

de with Formaldehyde

Type Reactions Reduction Reactions Addition or Condensation Reactions Trans-hydroxymethylation Polymerization Reactions

Reactions of Methyl01 Derivatives Decomposition with Liberation of Formaldehyde Trans-hydroxymethylation Polycondensation Condensation with other Compounds Dehydration to Double-Bonded Methylene Derivatives Addition Reactions Reduction to Methyl 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 Sulfamide Hydrazine Hydroxylamine Hydrogen Cyanide and Cyanides Cyanogen Carbon Monoxide Hydrogen Peroxide and Peroxides Hydrogen Sulfide and Sulfides Sulfur Dioxide and Sulfites Acids

Sulfuric Phosphoric Acid Nitric Acid Nitrous Acid Hydrohalogen Acids

Phosphine and Phosphorus Halides Silicon Tetrachloride Halogens

xx C O N T E N T S

10. REACTIONS OF FORMALDEHYDE WlTH ALIPHATIC HYDROXY COMPOUNDS AND MERCAPTANS

Alcohols Glycols and Glycerols Polyhydroxy Compounds Sugars Starch Cellulose Joint Reactions of Formaldehyde with Alcohols and

Hydrogen Halides Reactions of Formaldehyde with Mercaptans

1 1. REACTIONS OF FORMALDEHYDE WlTH ALDEHYDES AND KETONES

Reactions of Formaldehyde with Other Aldehydes Acetaldehyde: Reactions in Water Solution Pentaerythritol Gas-Phase Reactions Involving Formaldehyde and

Acetaldehyde Copolymerization Reactions Higher Aliphatic Aldehydes Aromatic Aldehydes

Reactions of Formaldehyde with Ketones Acetone Higher Aliphatic Ketones Cyclic Ketones DiKetones Aryl Aliphatic Ketones

12. REACTIONS OF FORMALDEHYDE WlTH PHENOLS Historical

Fundamental Characteristics of Phenol-Formaldehyde Reactions

Influence of Phenolic Structure Effect of Catalyst

Methylol Derivatives Phenol Alcohols Saligenin and Methylophenols Cresol and Xylenol Derivatives Miscellaneous Substituted Phenols . Polyhydric Phenols

8 CONTENTS

Derivatives of Methylol Phenols Methylene Derivatives

Phenols and Cresols Xylenol Mesitol Durenol Chlorophenols Naphthols Nitrophenols Salicylic Acid Polyhydric Phenols

Phenol-Formaldehyde Resins Fusible Resins : Novolaks

I

! Infusible Resins

REACTIONS OF FORMALDEHYDE WlTH ACID ANHYDRIDES, KETENE, ACYL (

Aliphatic Acids Aromatic Acids Acid Anhydrides Acyl Chlorides Ketene Esters

/ 14. REACTIONS OF FORMALDEHYDE WlTH AND NITRILES Aliphatic Amines The Mannich Reaction Aromatic Amines Amides

Monoamides Urea Urea-Formaldehyde Resins Substituted Ureas

Diamides j Poly amides 1 Imides Urethanes (Carbamates)

i i

Thiourea Aminonitriles, Cyanamide and Cyanamid4 Amino Acids and Esters

I CONTENTS I C O N T E N T S xxi I Derivatives of Methyl01 Phenols 317

AND MERCAPTANS 264 Methylene Derivatives 321 264 Phenols and Cresols 322 267 Xylenol 329 270 Mesitol 330 27 1 Durenol 331 272 Chlorophenols 332 274 Naphthols 332

Nitrophenols 332 276 Salicylic Acid 333 279 Polyhydric Phenols 334

Phenol-Formaldehyde Resins 335 LDEHYDE WITH ALDEHYDES Fusible Resins: Novolaks 337

285 Infusible Resins 338 285 285 13. REAC'I'IONS OF FORMALDEHYDE WITH CARBOXYLIC ACIDS, 287 ACID ANHYDRIDES, KETENE, ACYL CHLORIDES, AND ESTERS 345

8 Involving Formaldehyde and Aliphatic Acids 345 290 Aromatic Acids 349 290 Acid Anhydrides 350 290 Acyl Chlorides 351 294 Ketene 351 294 Esters 352 294 297 14. REACTIONS OF FORMALDEHYDE WITH AMINES, AMIDES 298 AND NITRILES 359 299 Aliphatic Amines 359 299 The Mannich Reaction 365

Aromatic Amines 369 LDEHYDE WITH PHENOLS 304 Amides 373

305 Monoamides 374 ristics of Phenol-Formaldehyde Urea 377

305 Urea-Formaldehyde Resins 382 308 Substituted Ureas 385 309 Diamides 388 310 Polyamides 389 3 10 Imides 390 312 Urethanes (Carbamates) 391 313 Thiourea 39 1 314 i Aminonitriles, Cyanamide and Cyanamide Polymers 393 316 Amino Acids and Esters 395

I

xxii C O N T E X T S CONTENTS I 14. REACTIONS OF FORMALDEHYDE WlTH AMINES, AMIDES

AND NITRILES (Continued) Nucleic Acids Proteins

Nitriles

15. REACTIONS OF FORMALDEHYDE WlTH HYDROCARBONS AND HYDROCARBON DERIVATIVES

Saturated Aliphatic Hydrocarbons Olcfins and Cyclic Olefins Halogenated Olefins Diolefins Acetylenic Hydrocarbons Aromatic Hydrocarbons

Halomethylation Reactions Formation of Diarylmethanes and Hydrocarbon Resins

Organometallic Hydrocarbon Derivatives Nitro-hydrocarbons

16. REACTIONS OF FORMALDEHYDE WlTH HETEROCYCLIC COMPOUNDS

Furans Tetrahydrofurans Thiophcnes

T11iana1)hthene Pyrroles Pyrazoles Pyrrolidine Pyridines

Alkyl Pyridines Piperidine Indolc Quinolines

17. DETECTION AND ESTIMATION OF SMALL QUANTITIES OF FORMALDEHYDE Colorimetric Procedures Eegriwe's or Chromotropic Acid Method Hantzsch Reaction Method Miscellaneous Color Tests

Polarographic Method Gas Chromatographic Method

Detection of Higher Aldehydes in the Prese: Detection and Estimation of Small Quantit

in Air Detection of Formaldehyde in Foodstuffs Detection of Formaldehyde in Products w

Subjected to Formaldehyde Treatme

18. QUANTITATIVE ANALYSIS OF FORMALDEH Physical Methods for Determining Form Chemical Methods

I Sodium Sulfite Method Alkaline Peroxide Method Iodimetric Method Ammonium Chloride Method Mercurimetric Method Potassium Cyanide Method Hydroxylamine Method Methone or Diinedon Method

Assay of Commercial Formaldehyde Assay of Commercial Paraformaldehyde

b

t Determination of Formaldehyde in specid 1

I in Products Treated with Formaldehyd( i Determination of Free Formaldehyde in Aqt

Analysis of Amino-Formaldehyde Resins Phenol and Phenol-Formaldehyde Condens4 Medicinal Soaps

I Dusting Powders Fungicides and Seed-Conserving Agents Determination of Combined Formaldehyde ! 19. HEXAMETHYLENETETRAMINE

Chemical Structure Mechanism of Hexamethylenetetramine Manufacture of Hexamethylenetetraminl Commercial Grades of Hexamethylenetei

Properties of Hexamethylenetetramine Physiological Properties of Hexamethyle

Chemical Reactions of Hexamethylenetetri

CONTENTS

EHYDE WlTH AMINES, AMIDES

DEHYDE WlTH HYDROCARBONS

ethanes and Hydrocarbon Resii rbon Derivatives

LDEHYDE WlTH HETEROCYCLIC

TlON OF SMALL QUANTITIES

otropic Acid Method

i C O N T E N T S Polarographic Method

Gas Chromatographic Method Detection of Higher Aldehydes in the Presence of Formaldehyde Detection and Estimation of Small Quantities of Formaldehyde

I in Air Detection of Formaldehyde in Foodstuffs Detection of Formaldehyde in Products which have been

Subjected to Formaldehyde Treatment

18. QUANTITATIVE ANALYSIS OF FORMALDEHYDE Physical Methods for Determining Formaldehyde Chemical Methods

Sodium Sulfite Method Alkaline Peroxide Method Iodimetric Method Ammonium Chloride Method Mercurimetric Method Potassium Cyanide Method Hydroxylamine Method Methone or Diinedon Method

Assay of Commercial Formaldehyde Assay of Commercial Paraformaldehyde Determination of Formaldehyde in Special Compositions and

in Products Treated with Formaldehyde Determination of Free Formaldehyde in Aqueous Mixtures Analysis of Amino-Formaldehyde Resins Phenol and Phenol-Formaldehyde Condensates Medicinal Soaps Dusting Powders Fungicides and Seed-Conserving Agents Determination of Combined Formaldehyde in Formals

19. HEXAMETHYLENETETRAMINE Chemical Structure Mechanism of Hexarnethylenetetramine Formation Manufacture of Hexarnethylenetetramine Commercial Grades of Hexarnethylenetetramine

Properties of Hexamethylenetetramine Physiological Properties of Hexarnethylenetetramine

Chemical Reactions of Hexarnethylenetetramine

xxiii

xxiv CONTENTS

19. HEXAMETHYLENETETRAMINE (Continued) Reactions with Inorganic Compounds Reduction of Metal Compounds Reactions with Organic Compounds

Analysis of Hexamethylenetetramine Detection and Identification Quantitative Determination of Hexamethylenetetramine Determination of Impurities in Hexamet,hylenetetramine

20. USES O F FORMALDEHYDE PRODUCTS ,, /" Acetal Resins Agriculture

Seed, Bulb and Root Treatment Soil Disinfection Prevention of Storage Rots and Infections Fertilizers

Analysis Catalysts Concrete, Plaster and Related Products Cosmetics Deodorization Disinfection and Fumigation Dyes and Dyehouse Chemicals Embalming and Preserving Explosives Fireproofing Fuels Gas Absorbents Hydrocarbon Products

Oil Well Operations Refining of Hydrocarbons Stabilization Addition Agents

Insecticides Leather

Formaldehyde as a Tanning Agent Syntans Miscellaneous Uses of Formaldehyde in the Leather

and Hide Industry Formaldehyde Treatment of Fur and Hair

t CONTENTS I Medicine

Vaccines Detoxifying Action Vitamins Bactericides and Bacteriostats Drug Synthesis and Modification Hexamethylenetetramine Formaldehyde Resins

Metal Industries Use of Formaldehyde and its Derivati

Addition Agents I Control of Hydrogen Sulfide Corrosion o L

I Mirrors I Uranium

Electroplating Metal Sequestering Agents

Paper Direct Treatment of Paper and Paper

Formaldehyde Treatment of Paper with Formaldeh Indirect Methods of Formaldehyde Coated Papers

I Photography ,

i Proteins r Rubber I

Rubber Latex Vulcanization and Modification of Ru Accelerators Antioxidants Synthetic Rubber

Solvents and Plasticizers Stabilizers Starch Surface-active Agents

Preparation of Surface-active Agents Textiles

Treatment of Cellulosic Fabrics Direct Treatment of Cellulosic Fabrics. Treatment of Cellulosic Fabrics with N-1 Water Repellency Improvements Relating to Dyeing and 1

I CONTENTS CONTENTS xxv I

ation of Hexamethylenetetramine rities in Hexamethylenetetramine

DE PRODUCTS ,. '

ge Rots and Infections

Related Products

nt of Fur and Hair

Medicine 60 1 Vaccines 601 Detoxifying Action 603 Vitamins 604 Bactericides and Bacteriostats 604 Drug Synthesis and Modification 604 Hexamethylenetetramine 605 Formaldehyde Resins 605

Metal Industries 607 Use of Formaldehyde and its Derivatives as Pickling

Addition Agents 607 Control of Hydrogen Sulfide Corrosion of Oil Well Equipment 609 Mirrors 6 10 Uranium 61 1 Electroplating 611 Metal Sequestering Agents 612

Paper 613 Direct Treatment of Paper and Paper Pulp with

Formaldehyde 614 Treatment of Paper with Formaldehyde and Proteins 615 Indirect Methods of Formaldehyde Treatment of Paper 616 Coated Papers 617

Photography 620 Proteins 626

+ Rubber 628 Rubber Latex 628 Vulcanization and Modification of Rubber 630 Accelerators 631 Antioxidants 632 Synthetic Rubber 632

Solvents and Plasticizers 634 Stabilizers 636 Starch 637 Surface-active Agents 638

Preparation of Surface-active Agents 638 Textiles 639

Treatment of Cellulosic Fabrics 640 Direct Treatment of Cellulosic Fabrics with Formaldehyde 642 Treatment of Cellulosic Fabrics with N-Methyl01 Compounds 645 Water Repellency 647 Improvements Relating to Dyeing and Dyed Fabrics 647

xxvi CONTENTS

USES OF FORMALDEHYDE PRODUCTS (Continued) Flameproofing Miscellaneous Effects Treatment of Protein Fibers Wool Artificial Fibers from Natural Proteins Nylon Polyvinyl Alcohol Fibers

Wood Formaldehyde Treatment of Wood

Author Index

Subject Index

Since its discovery in the la century, formaldehyde has become an industri importance. It is estimated that production i reached a total of about 2600 million pounds commercial solution in 1963.

Commercially, formaldehyde is marketed chi solutions containing about 36 to 50 per cent b dehyde ( C H 2 0 ) . The standard 37 per cent U. cient methanol (7 to 15 per cent by weight) polymer under ordinary conditions of tran tions containing about 1 per cent methanol formaldehyde are preferred for large-scal such solutions must be kept warm to preve favor the use of these solutions, and new m it possible to maintain solution at relative1

For special purposes, formaldehyde is ha solutions containing urea and melamine an methanol and other low molecular weight a

Commercial forms of formaldehyde also in paraformaldehyde, HO- (CH20) ,.OH. This as a solid form of formaldehyde. Trioxane of formaldehyde is commercially available. are normally manufactured from the aqueous expensive forms. (Chapter 7)

Hexamethylenetetramine, (CH2)eN4, which of formaldehyde and ammonia (Cf. Chapter in many instances and therefore may be re formaldehyde from the standpoint of use.