Polyurethanes E-Book

Mark F. Sonnenschein

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Serie: Wiley Series on Plastics Engineering and Technology
• Sprache: Englisch

Seitenzahl: 771

Veröffentlichungsjahr: 2020

Beschreibung

This book, cohesively written by an expert author with supreme breadth and depth of perspective on polyurethanes, provides a comprehensive overview of all aspects of the science and technology on one of the most commonly produced plastics. * Covers the applications, manufacture, and markets for polyurethanes, and discusses analytical methods, reaction mechanisms, morphology, and synthetic routes * Provides an up-to-date view of the current markets and trend analysis based on patent activity and updates chapters to include new research * Includes two new chapters on PU recycling and PU hybrids, covering the opportunities and challenges in both

Leseprobe

Table of Contents

COVER

TITLE PAGE

COPYRIGHT PAGE

DEDICATION PAGE

PREFACE

ACKNOWLEDGMENTS

1 INTRODUCTION

REFERENCES

2 POLYURETHANE BUILDING BLOCKS

2.1 POLYOLS

2.2 ISOCYANATES

2.3 CHAIN EXTENDERS

REFERENCES

3 INTRODUCTION TO POLYURETHANE CHEMISTRY

3.1 INTRODUCTION

3.2 MECHANISM AND CATALYSIS OF URETHANE FORMATION

3.3 REACTIONS OF ISOCYANATES WITH ACTIVE HYDROGEN COMPOUNDS

REFERENCES

4 THEORETICAL CONCEPTS AND TECHNIQUES IN POLYURETHANE SCIENCE

4.1 FORMATION OF POLYURETHANE STRUCTURE

4.2 PROPERTIES OF POLYURETHANES

REFERENCES

5 ANALYTICAL CHARACTERIZATION OF POLYURETHANES

5.1 ANALYSIS OF REAGENTS FOR MAKING POLYURETHANES

5.2 INSTRUMENTAL ANALYSIS OF POLYURETHANES

5.3 MECHANICAL ANALYSIS

5.4 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY

5.5 FOAM SCREENING: FOAMAT®

REFERENCES

6 POLYURETHANE FLEXIBLE FOAMS

6.1 MAKING POLYURETHANE FOAMS

6.2 FOAM PROCESSES

6.3 FLEXIBLE FOAM FORMULATION AND STRUCTURE–PROPERTY RELATIONSHIPS

REFERENCES

7 POLYURETHANE FLEXIBLE FOAMS

7.1 APPLICATIONS

7.2 TRENDS IN MOLDED FOAM TECHNOLOGY AND MARKETS

REFERENCES

8 POLYURETHANE RIGID FOAMS

8.1 REGIONAL MARKET DYNAMICS

8.2 APPLICATIONS

8.3 BLOWING AGENTS AND INSULATION FUNDAMENTALS

8.4 INSULATION FUNDAMENTALS

8.5 TRENDS IN RIGID FOAMS TECHNOLOGY

REFERENCES

9 POLYURETHANE ELASTOMERS

9.1 REGIONAL MARKET DYNAMICS

9.2 APPLICATIONS

9.3 TRENDS IN POLYURETHANE ELASTOMERS

REFERENCES

10 POLYURETHANE ADHESIVES AND COATINGS

10.1 ADHESIVES AND COATINGS INDUSTRIES: SIMILARITIES AND DIFFERENCES

10.2 ADHESIVES

10.3 TRENDS IN POLYURETHANE ADHESIVES

10.4 COATINGS

REFERENCES

11 SPECIAL TOPIC

11.1 MARKETS AND PARTICIPANTS

11.2 TECHNOLOGY

11.3 FUTURE TRENDS

REFERENCES

12 SPECIAL TOPIC

12.1 GOVERNMENTAL REGULATION OF ISOCYANATES

12.2 NONISOCYANATE ROUTES TO POLYURETHANES

REFERENCES

13 POLYURETHANE HYBRID POLYMERS

13.1 INTRODUCTION

13.2 POLYURETHANE–ACRYLATE HYBRIDS

13.3 URETHANE–EPOXY HYBRIDS

13.4 URETHANE–SILICONE HYBRIDS

13.5 POLYURETHANE–POLYOLEFIN HYBRIDS

13.6 HYBRIDIZATION VIA TRANSURETHANIFICATION

REFERENCES

14 RECYCLING OF POLYURETHANES

14.1 INTRODUCTION

14.2 GLYCOLYSIS, HYDROLYSIS, AMINOLYSIS, AND ACIDOLYSIS

14.3 PYROLYSIS

14.4 RECYCLE FOR FUEL VALUE

14.5 REGRINDING AND INCORPORATION

REFERENCES

INDEX

END USER LICENSE AGREEMENT

List of Tables

Chapter 2

TABLE 2.1 Comparison of polyol general polyol properties

TABLE 2.2 Common polymerization starters or initiators for polyether polymerizati...

TABLE 2.3 Structures of acids and alcohols common to polyester polyol synthesis f...

TABLE 2.4 Properties of selected polyester polyols useful in polyurethane synthes...

TABLE 2.5 Comparison of polyols used for rigid appliance foam and rigid construct...

TABLE 2.6 Example of an aromatic polyester polyol for construction application

TABLE 2.7 Raw materials and unit ratios for two commercial aromatic polyester pol...

TABLE 2.8 Properties of rigid polyurethane foams with aromatic polyester polyols ...

TABLE 2.9 Select polycarbonate polyols (based on diol variation) and the differen...

TABLE 2.10 Fatty acid composition of common seed oils used for polyester polyol s...

TABLE 2.11 Effect of process variable ratios on relative production of monomeric ...

TABLE 2.12 Effect of process variable ratios on the production of desired MDI and...

TABLE 2.13 Structure and properties of common chain extenders used in urethane ch...

Chapter 3

TABLE 3.1 Enthalpy of urethane formation (kcal/mol) of various isocyanates with v...

TABLE 3.2 Approximate reversion temperatures of urethane product back to constitu...

TABLE 3.3 Reactivity of several common diisocyanates relative to MDI

TABLE 3.4 Reactivity of the isocyanates of TDI isomers relative to the para posit...

TABLE 3.5 Relative reaction rates of isocyanates with varying reaction partners

Chapter 4

TABLE 4.1 Examples of solubility parameters calculated by the method of Bicerano

a

Chapter 5

TABLE 5.1 Conventional polyol specifications and ASTM procedures for measurement...

TABLE 5.2 Critical evaluation of the ASTM method‐derived property value in Table ...

TABLE 5.3 Conventional isocyanate specifications and ASTM procedures for measurem...

TABLE 5.4 Critical evaluation of the ASTM method‐derived property value in Table ...

TABLE 5.5 Reference for resonance frequencies for functional groups commonly enco...

TABLE 5.6 Data derived from a Porod analysis of Figure 5.17

TABLE 5.7 Conventional polyurethane mechanical tests and ASTM procedures for meas...

Chapter 6

TABLE 6.1 Representative slab foam formulations

TABLE 6.2 Alternative methods of describing the hard‐segment content of a polyure...

TABLE 6.3 Property range of a conventional slabstock foam made from the formulati...

TABLE 6.4 HR foam formulation and its representative properties

TABLE 6.5 Representative formulations for making a “hot mold” molded foam of two ...

TABLE 6.6 Representative formulation for a HR “cold mold” molded foam....

TABLE 6.7 Representative formulation for a HR “cold mold” molded foam using blend...

TABLE 6.8 Representative formulation for a HR “cold mold” molded foam using pMDI...

TABLE 6.9 Effects of foam raw material structure variation on foaming and foam pr...

TABLE 6.10 The effects of catalyst strength on the polyurethane foam process and ...

TABLE 6.11 Effects of silicone surfactant variables on foam processes and propert...

Chapter 7

TABLE 7.1 Simplified formulation and representative properties for high‐resilienc...

TABLE 7.2 Representative formulations and property ranges for viscoelastic foams ...

TABLE 7.3 Representative formulation, molding conditions, and properties of a hig...

TABLE 7.4 Representative formulation, molding conditions, and properties of a hig...

TABLE 7.5 General formulation guidelines for high resilience (HR) transportation ...

TABLE 7.6 General structure–property relationships for flexible molded polyuretha...

Chapter 8

TABLE 8.1 Polyisocyanurate (PIR) foam formulations and properties for making insu...

TABLE 8.2 Formulation for producing spray foams

TABLE 8.3 Formulations for froth foam that might be use as a window sealant (Form...

TABLE 8.4 Comparison of typical properties of high‐pressure spray foam and froth ...

TABLE 8.5 Formulations and properties for three pour‐in‐place applications...

TABLE 8.6 List of standard tests and descriptions relevant to the polyurethane ri...

TABLE 8.7 Formulations and properties for use in appliance insulation application...

TABLE 8.8 Typical range of rigid polyurethane foams for appliances and the direct...

TABLE 8.9 Properties of rigid polyurethane foam blowing agents, several of which ...

TABLE 8.10 Promulgation of regulations for blowing agents previously used for pol...

TABLE 8.11 Status of acceptability/unacceptability for a variety of foam blowing ...

Chapter 9

TABLE 9.1 Comparison of a polybutylene adipate ester and an ethylene oxide‐capped...

TABLE 9.2 Representative standard tests for characterizing, comparing, and rankin...

TABLE 9.3 Design guidelines for the effect of a change in material property on we...

TABLE 9.4 Example shoe sole formulation based on a polyester quasi‐prepolymer and...

TABLE 9.5 Example polyether polyol shoe sole formulation based on a polyether sof...

TABLE 9.6 A representative listing of polyurethane elastomer applications

TABLE 9.7 Characteristics of the types of commercially available polyurethane pre...

TABLE 9.8 Differences between quasi‐prepolymer and full prepolymer systems and re...

TABLE 9.9 Prepolymer formed at between 70 °C and 80 °C under N2 at desired NCO co...

TABLE 9.10 Applications defined by the typical Shore A hardness required

TABLE 9.11 Comparison of properties for typical thermoplastic elastomer classes

TABLE 9.12 Example formulations for TPUs of various hardnesses (modulus) and from...

TABLE 9.13 Comparison of properties obtained for various plastic composites

TABLE 9.14 A modified S‐RIM formulation that could be scaled for making an automo...

Chapter 10

TABLE 10.1 Major applications for polyurethane adhesives as a function of format...

TABLE 10.2 ASTM standard methods for testing adhesives

TABLE 10.3 Example formulation and properties of a one‐part solvent‐borne polyure...

TABLE 10.4 Formulation and properties of a nonreactive polyurethane hot‐melt adhe...

TABLE 10.5 Formulation and properties of a reactive polyurethane hot‐melt adhesiv...

TABLE 10.6 Composition and properties of a PUD adhesive

TABLE 10.7 ASTM classification of polyurethane coatings based on format and metho...

TABLE 10.8 Abridged list of standardized tests and methods for characterizing coa...

TABLE 10.9 Formulation and properties of a two‐part solvent‐borne polyurethane co...

TABLE 10.10 Illustrative properties for a water‐borne polyurethane coating obtain...

TABLE 10.11 Composition and coating properties of a blend of acrylic and polyuret...

TABLE 10.12 Properties of UV‐curable polyurethane coatings tested before and afte...

TABLE 10.13 Structures of chemical blocking agents and their deblocking temperatu...

TABLE 10.14 Formulation of an illustrative polyurethane powder coating

TABLE 10.15 Properties of the polyurethane powder coating in Table 10.14

Chapter 11

TABLE 11.1 Formulation and properties of thermoplastic polyurethane commonly empl...

TABLE 11.2 Solubility parameters of representative solvents useful for determinin...

TABLE 11.3 Composition of a polyurethane prepolymer/curative that could be made i...

Chapter 13

TABLE 13.1 Cross‐linking agents for copolymer hybridization of urethanes and acry...

TABLE 13.2 Comparison of material performance attributes of polyurethanes and epo...

TABLE 13.3 Property comparison (10 high to 0 low) of polyurethane, silicone, and ...

Chapter 14

TABLE 14.1 Reversion temperatures of commonly occurring polyurethane bonds

TABLE 14.2 Comparison of properties of cold‐mold methylene diphenyl diisocyanate ...

TABLE 14.3 Comparison of properties of a reaction injection molded (RIM) polyuret...

List of Illustrations

Chapter 1

FIGURE 1.1 Percentage global consumption of plastics in 2018. Polyethylene e...

FIGURE 1.2 Illustrative structures of high‐volume commodity polymers.

FIGURE 1.3 The urethane unit within a polyurethane polymer chain.

FIGURE 1.4 Chemical structures of isocyanate, polyester, and polyether. To m...

FIGURE 1.5 Structures of urea, ester, amide, and urethane functionalities.

FIGURE 1.6 Publication activity focused on commodity plastics for (a) 1954–2...

FIGURE 1.7 Publication activity in polyurethane science by language from (a)...

FIGURE 1.8 Types of publication (all languages) where the focus of the work ...

FIGURE 1.9 Analysis of (a) patented polyurethane topics during 2013–2019 and...

FIGURE 1.10 Percentage isocyanate plant capacity utilization. The triangle d...

Chapter 2

FIGURE 2.1 Relative volumes of polyols produced in 2017. Within the error of...

FIGURE 2.2 Comparison of basic polyol structures.

FIGURE 2.3 Building blocks for polyether polyol synthesis.

FIGURE 2.4 Synthesis of butylene oxide via the chlorohydrin route.

FIGURE 2.5 Synthesis of propylene oxide via the hydrogen peroxide (HPPO) pro...

FIGURE 2.6 Volume of PO produced by the numerous routes available in 2018. C...

FIGURE 2.7 Production of THF via dehydration of butanediol.

FIGURE 2.8 Production of polypropylene oxide via base‐catalyzed ring‐opening...

FIGURE 2.9 Possible pathways by which PO polymerization can traverse to prod...

FIGURE 2.10 Mechanism for formation of unsaturation in polyether polyols. PE...

FIGURE 2.11 The effect of monol on polyol functionality. The calculated actu...

FIGURE 2.12 Proposed coordination–insertion mechanism for activity of DMC ca...

FIGURE 2.13 Proposed acid–base coordination mechanism for activity of DMC ca...

FIGURE 2.14 Difference in measured polyol functionality attained by KOH and ...

FIGURE 2.15 Measured unsaturation levels by titration of three polyols for a...

FIGURE 2.16 Simplified block diagram for a small polyol production of a glyc...

FIGURE 2.17 Acid‐catalyzed polymerization of THF to make polytetramethylene ...

FIGURE 2.18 Process for preparation of PTMEG by reaction of THF with acetic ...

FIGURE 2.19 Simplified block diagram for production of PTMEG using the aceti...

FIGURE 2.20 Cartoon representations of the types of comonomer organization a...

FIGURE 2.21 Fractional consumption of polyester polyols in 2017. (a) USA; (b...

FIGURE 2.22 Polymerization of polyesters via esterification reaction between...

FIGURE 2.23 Accepted mechanism for coordination–insertion ring‐opening polym...

FIGURE 2.24 (a) Melting point and enthalpy of melting of polyester polyols d...

FIGURE 2.25 (a) Weight and (b) mole fraction distributions of oligomer sizes...

FIGURE 2.26 Unit ratios for diacids or diesters used in preparation of aroma...

FIGURE 2.27 Production of terephthalic acid and phthalic anhydride.

FIGURE 2.28 Comparison of lowest energy conformations of aromatic polyester ...

FIGURE 2.29 Preparation of polycarbonate polyols from phosgene (not recommen...

FIGURE 2.30 Preparation of polycarbonate polyols using an elevated pressure ...

FIGURE 2.31 Preparation of polycarbonate polyol using an alkoxylate.

FIGURE 2.32 Polycarbonate polyols from alkoxylates and the structural variat...

FIGURE 2.33 Example preparation of an acrylic polyol.

FIGURE 2.34 Polymerization of SAN using azobisisobutyronitrile (AIBN) as an ...

FIGURE 2.35 Generation of a carbon‐centered radical on a propylene oxide pol...

FIGURE 2.36 Examples of macromer structures.

FIGURE 2.37 Scanning electron microscope image of SAN particles formed in co...

FIGURE 2.38 Preparation of a PIPA polyol.

FIGURE 2.39 Structure of fatty acid components of seed oils.

FIGURE 2.40 Illustrative triglyceride structure showing oleic, stearic, and ...

FIGURE 2.41 Oxidation of an illustrative triglyceride to the epoxidized form...

FIGURE 2.42 Simplified ozonolysis of oleic acid. Other products are also pos...

FIGURE 2.43 Procedure for formation of polymerizable ester alcohols from see...

FIGURE 2.44 Illustrative procedure of olefin metathesis reactions and metath...

FIGURE 2.45 General preparation of a TDI–polypropylene oxide prepolymer.

FIGURE 2.46 The isocyanate function.

FIGURE 2.47 Assembling the reactants into a transition state geometry for ur...

FIGURE 2.48 World (a) capacity and (b) production of isocyanates for polyure...

FIGURE 2.49 World toluene production and portion used for manufacturing TDI ...

FIGURE 2.50 Simplified block diagram for TDI production.

FIGURE 2.51 Preparation of nitrotoluenes from toluene and nitric acid with a...

FIGURE 2.52 Pathways and product distributions of dinitrotoluene from mononi...

FIGURE 2.53 Preparation of toluenediamines from nitrotoluenes by catalytic h...

FIGURE 2.54 Phosgenation of toluene diamines to produce toluene diisocyanate...

FIGURE 2.55 First step of the phosgenation process forming the dicarbamoyl c...

FIGURE 2.56 Thermolysis of the dicarbamoyl chloride to form the isocyanate a...

FIGURE 2.57 Preparation of TDI by reaction of toluene diamines with dimethyl...

FIGURE 2.58 Preparation of dimethyl carbonate.

FIGURE 2.59 Process for reductive decarbonylation for nonphosgene production...

FIGURE 2.60 Simplified proposed mechanism for Pd‐catalyzed reductive carbony...

FIGURE 2.61 Nonphosgene preparation of isocyanates via the Curtius rearrange...

FIGURE 2.62 Illustrative structures of MDI and pMDI.

FIGURE 2.63 Nitration of benzene to nitrobenzene followed by hydrogenation t...

FIGURE 2.64 Global usage of aniline in 2018. The vast majority is used for m...

FIGURE 2.65 Simplified block diagram for the production of monomeric, polyme...

FIGURE 2.66 Structures of 4,4′‐methylene bisphenyldiamine and the MDA polyme...

FIGURE 2.67 Mechanism for the production of polymeric and monomeric MDA by r...

FIGURE 2.68 1,3,5‐Triphenylhexahydritriazine formed by trimerization of the ...

FIGURE 2.69 Phosgenation of MDA and pMDA to form MDI and pMDI.

FIGURE 2.70 Side reaction in MDI production between MDA and MDI to form a ur...

FIGURE 2.71 Formation of APA – a common impurity in pMDI, usually quantified...

FIGURE 2.72 Formation of uretdione, a common undesired side reaction resulti...

FIGURE 2.73 Measured percentage molar conversion of MDI monomer to dimer

per

...

FIGURE 2.74 Oxidation processes of isocyanates leading to color in polymers....

FIGURE 2.75 Global consumption of major commercial aliphatic isocyanate in 2...

FIGURE 2.76 Structures of common and commercially available aliphatic isocya...

FIGURE 2.77 Process to produce hexamethylene diamine from adiponitrile.

FIGURE 2.78 Phosgenation of hexamethylene diamine to hexane diisocyanates.

FIGURE 2.79 Trimerization of acetone to form isophone [161].

FIGURE 2.80 Conversion of isophorone to isophorone nitrile, hydrogenation to...

FIGURE 2.81 Conversion of MDA to hydrogenated MDA.

FIGURE 2.82 Trimerization of aliphatic isocyanates commonly preceding their ...

FIGURE 2.83 Conversion of isophorone diamine to isophorone diisocyanates usi...

FIGURE 2.84 Ethylene glycol chain extender (in boxes) linking isocyanates th...

FIGURE 2.85 Hydrogen bonding between chain‐extended urethane hard segments. ...

FIGURE 2.86 Illustration of the origin of the greater stabilization of hard ...

Chapter 3

FIGURE 3.1 Urethane structure.

FIGURE 3.2 Generally accepted transition state for the uncatalyzed formation...

FIGURE 3.3 FTIR spectroscopy of a polyetherpolyol focusing on the OH stretch...

FIGURE 3.4 Common catalysts for urethane and urea formation. Trade names are...

FIGURE 3.5 Examples of bond polarization mechanisms of catalyst action.

FIGURE 3.6 Proposed mechanism of Lewis acid catalysis of urethane formation....

FIGURE 3.7 Proposed mechanism of Bismuth carboxylate urethane catalysis. Coo...

FIGURE 3.8 Energy‐minimized interaction between water and pentamethylene dip...

FIGURE 3.9 Trimerization of isocyanate to isocyanurate.

FIGURE 3.10 Proposed mechanism of isocyanurate formation using highly nucleo...

FIGURE 3.11 Dynamic mechanical analysis of an aromatic polyurethane showing ...

FIGURE 3.12 The reaction of isocyanate and water, forming an amine.

FIGURE 3.13 The reaction of amine with an isocyanate to form a urea.

FIGURE 3.14 Formation of an allophanate by reaction of a urethane with an is...

FIGURE 3.15 Formation of a biuret linkage by reaction of urea with isocyanat...

FIGURE 3.16 Dimerization of isocyanate to form the uretdione.

FIGURE 3.17 Catalyzed dimerization of isocyanate to form carbodiimide.

FIGURE 3.18 Phospholene‐catalyzed formation of carbodiimide.

FIGURE 3.19 Proposed trimerization of carbodiimide occurring during high‐tem...

FIGURE 3.20 Proposed reaction of carbodiimide to form a six‐member ring duri...

FIGURE 3.21 Reaction of carbodiimide and isocyanate to form the industrially...

FIGURE 3.22 Reaction of aliphatic isocyanate and carboxylic acid to form the...

Chapter 4

FIGURE 4.1 Hard and soft polyurethane segments make for a multiblock copolym...

FIGURE 4.2 Representations of polyurethane final structures. (a) An idealize...

FIGURE 4.3 Scanning electron micrograph of a 20%/80% (w/w) blend of cross‐li...

FIGURE 4.4 Tapping‐mode atomic force microscopy of a thermoplastic polyureth...

FIGURE 4.5 Polyurethane elastomer of the same composition as the polyurethan...

FIGURE 4.6 Illustrative phase diagram of a polyurethane capable of exhibitin...

FIGURE 4.7 Illustrative phase diagram for polyurethane phase decomposition t...

FIGURE 4.8 Transmission electron microscopy of a cast polyurethane elastomer...

FIGURE 4.9 Graphical representations of the Kerner and Davies equations usin...

FIGURE 4.10 Graphical representation of the Budiansky equation using a soft‐...

FIGURE 4.11 Graphical representation of the Halpin–Tsai equation (Equation 4...

FIGURE 4.12 Graphical representation of the modulus predictions based on a p...

FIGURE 4.13 Diagram of the categories of phase‐separated polyurethanes that ...

FIGURE 4.14 Illustrative stress–strain curve for a polyurethane elastomer ch...

FIGURE 4.15 Illustrative stress–strain curves for polyurethane elastomers of...

FIGURE 4.16 Illustrative stress–strain curve for a polyurethane elastomer wi...

FIGURE 4.17 The equivalent box model for calculating large strain properties...

FIGURE 4.18 Graphical representation of Equation 4.17 calculating the maximu...

FIGURE 4.19 Graphical representations of Equations 4.18 and 4.24 showing the...

FIGURE 4.20 Graphical representation of the Fox equation (Equation 4.25) rel...

FIGURE 4.21 Graphical representation of the Gordon–Taylor equation for varyi...

FIGURE 4.22 Graphical representation of the Kwei equation, keeping

k

at or n...

Chapter 5

FIGURE 5.1 Anhydride derivatization of polyols prior to titration of acid en...

FIGURE 5.2 ATR Fourier transform infrared (FTIR) spectroscopy of polyethylen...

FIGURE 5.3 Integrated OH absorbance versus percentage OH measured. Example c...

FIGURE 5.4 Cast polyurethane elastomer: dark areas are hard segment. See Fig...

FIGURE 5.5 Illustrative scanning electron micrographs of (a) open cell polyu...

FIGURE 5.6 Illustrative TEM images of polyurethanes. (a) Oriented rod‐like h...

FIGURE 5.7 Simplified illustration showing sample and signal detection contr...

FIGURE 5.8 Potential diagram of attractive and repulsive forces influencing ...

FIGURE 5.9 A piece of the foam was embedded in epoxy and then cured. The cur...

FIGURE 5.10 ATR‐FTIR spectroscopy of isocyanurate foam. These foams are made...

FIGURE 5.11 ATR‐FTIR spectroscopy of flexible foams showing the sensitivity ...

FIGURE 5.12 Transmission FTIR spectroscopy of TDI–polyurethane flexible foam...

FIGURE 5.13 Relationship of the sample to the detector for WAXS analysis.

FIGURE 5.14 WAXS data for polyurethane elastomers with polybutylene succinat...

FIGURE 5.15 WAXS from a polyurethane foam with a polyurea hard segment.

FIGURE 5.16 Relationship of sample to detector for SAXS analysis. Compare wi...

FIGURE 5.17 SAXS data for a polyurethane foam. Inset are the 2D data.

FIGURE 5.18 (a) SAXS data for a molded polyurethane foam and (b) the derived...

FIGURE 5.19 SAXS data for a TDI flexible slab foam. The d‐spacing determinat...

FIGURE 5.20 Illustration of a conventional tensile measurement configuration...

FIGURE 5.21 Representative stress–strain data for a polyurethane elastomer s...

FIGURE 5.22 Useful fixtures for mechanical testing of polyurethanes. (a) Sta...

FIGURE 5.23 A technician measuring a film sample using a tensile testing mac...

FIGURE 5.24 Hysteresis loop of a polyurethane elastomer with 45% hard segmen...

FIGURE 5.25 Representative DMA for a polyurethane elastomer. (a) Storage (so...

FIGURE 5.26 DMA fixtures. (a) Parallel plate fixture for measurement of thin...

FIGURE 5.27 A technician preparing a DMA for analysis using a cup‐and‐plate ...

FIGURE 5.28 Example of rheokinetic data obtainable with DMA for a two‐part r...

FIGURE 5.29 (a) Representative stack‐plot of

1

H MAS NMR spectra of a polyure...

FIGURE 5.30 The FOAMAT® foam qualification system for quantifying the physic...

Chapter 6

FIGURE 6.1 Slab foam process. The image does not show the feed tanks, ventil...

FIGURE 6.2 The structure of the common polyurethane foam cross‐linking agent...

FIGURE 6.3 Molded foam operations. (a) Raw material handling. (b) Foam fabri...

FIGURE 6.4 Timeline for the physical and chemical processes occurring in pol...

FIGURE 6.5 Scanning electron microscope images of flexible foams. (a) An ope...

FIGURE 6.6 A useful experimental technique for evaluating the timing of urea...

FIGURE 6.7 Examples of reactive catalyst structures. The tertiary amines are...

FIGURE 6.8 (a) Example reaction for making a catalytic polyol. The reaction ...

FIGURE 6.9 General structure of a silicone surfactant, as might be used for ...

FIGURE 6.10 Suggested polyhedral structures found in polyurethane foams base...

FIGURE 6.11 Measured properties from small‐scale polyurethane foam screening...

FIGURE 6.12 Compression set for three molded foams measured following 75% co...

FIGURE 6.13 Lack of correlation of 75% humid aged compression set (HACS) wit...

FIGURE 6.14 Correlation of humid aged load loss (HALL), a test that ages the...

FIGURE 6.15 Correlation of humid aged load loss (HALL) with the d‐spacing, w...

FIGURE 6.16 Lack of correlation of diethanolamine (DEOA; a cross‐linking age...

Chapter 7

FIGURE 7.1 Approximate volume breakdown for the production (a) of polyuretha...

FIGURE 7.2 Approximate breakdown for the volume usage of flexible polyuretha...

FIGURE 7.3 Approximate split for the polyurethane flexible slabstock and fle...

FIGURE 7.4 Test fixture and sample geometry for testing flexible foam IFD, a...

FIGURE 7.5 Approximate breakdown for the types of foams used in the manufact...

FIGURE 7.6 Approximate breakdown of the flexible foam market based on foam d...

FIGURE 7.7 Illustration of the delayed recovery response of a polyurethane v...

FIGURE 7.8 Shear modulus and tan (

δ

) (tan delta) spectrum of (a) a visc...

FIGURE 7.9 Scanning electron microscope image of a typical viscoelastic poly...

FIGURE 7.10 Unique commercial relationships among suppliers to the transport...

FIGURE 7.11 Patent activities within the flexible polyurethane foam category...

FIGURE 7.12 (a) Data from Figure 7.11 with the “foam property” category remo...

Chapter 8

FIGURE 8.1 Relative performance of common insulation materials and construct...

FIGURE 8.2 Proportional production of rigid foams in 2015 by geographical re...

FIGURE 8.3 Ratio of production and consumption volume in the Asia Pacific re...

FIGURE 8.4 Approximate European (a) construction and (b) appliance market si...

FIGURE 8.5 Approximate breakdown for 2015 of the North American rigid foam m...

FIGURE 8.6 Proportional consumption of polyurethane rigid foams in 2015 in (...

FIGURE 8.7 Trimerization of isocyanate functionality to form an isocyanurate...

FIGURE 8.8 (a) Photograph of an isocyanurate boardstock and (b) a scanning e...

FIGURE 8.9 Measured flexural moduli of isocyanurate board properties using 6...

FIGURE 8.10 Measured

R

‐value (ASTM C518) as a function of board thickness fo...

FIGURE 8.11 Schematic of the process for making isocyanurate boardstock. A t...

FIGURE 8.12 Typical process for developing a polyurethane spray foam formula...

FIGURE 8.13 Schematic of the components for application of a spray foam.

FIGURE 8.14 Process for the production of Mannich polyols for use in spray f...

FIGURE 8.15 Drawings of (a) the external view of a froth foam gun and nozzle...

FIGURE 8.16 Form (a) of a purchased froth foam system and function (b) of a ...

FIGURE 8.17 Pour‐in‐place (PIP) application segments (nonappliance) in 2015....

FIGURE 8.18 Global segmentation of rigid construction foams globally in 2015...

FIGURE 8.19 Segmentation of the polyurethane rigid foams for construction ma...

FIGURE 8.20 Percentage consumption of polyurethane rigid foams for appliance...

FIGURE 8.21 Illustration of the concepts in a reverse heat loss test for ref...

FIGURE 8.22 Relationship between measured blowing agent thermal conductivity...

FIGURE 8.23 Nanocellular polyurethane foam produced using supercritical CO

2

....

FIGURE 8.24 Relative patent activity by three large polyurethane chemical pr...

FIGURE 8.25 Patent activity of three large polyurethane chemical producers a...

Chapter 9

FIGURE 9.1 Approximate volume relationships between polyurethane elastomers ...

FIGURE 9.2 Approximate volume relationships between polyurethane thermosetti...

FIGURE 9.3 Approximate geographical industrial consumption of polyurethane e...

FIGURE 9.4 Chinese global exports of monomeric and polymeric methylene diphe...

FIGURE 9.5 Capacity utilization for isocyanate production in (a) Western Eur...

FIGURE 9.6 Regional industrial consumption of polyurethane elastomers for (a...

FIGURE 9.7 Volume fraction industrial usage of polyurethane elastomer in (a)...

FIGURE 9.8 Consumption of microcellular polyurethane elastomer primarily use...

FIGURE 9.9 Approximate volume fraction consumption of thermoset versus therm...

FIGURE 9.10 Styrene–butadiene–styrene triblock copolymer, the major componen...

FIGURE 9.11 Segmentation of polyurethane elastomers not including footwear. ...

FIGURE 9.12 A simplified representation of polyurethane elastomer market pos...

FIGURE 9.13 The prepolymer production concept.

FIGURE 9.14 Example of the quasi‐prepolymer concept.

FIGURE 9.15 North American consumption of prepolymers by type. LF, low free ...

FIGURE 9.16 Simplified diagram of a cast elastomer molding system with two t...

FIGURE 9.17 Global segmentation of the 2016 TPU market by consumption volume...

FIGURE 9.18 Segmentation of the 2016 global TPU market by region.

FIGURE 9.19 Simplified diagram of the commercial relationships between manuf...

FIGURE 9.20 Simplified illustration of reactive extrusion of TPUs.

FIGURE 9.21 Volume production of polyurethane building blocks for RIM applic...

FIGURE 9.22 Geographical segmentation of RIM production in 2016.

FIGURE 9.23 Industrial consumption of polyurethane elastomeric fiber.

FIGURE 9.24 Synthesis of the prepolymer for making spandex. The soft segment...

FIGURE 9.25 Preparation of spandex polyurethane urea polymer from prepolymer...

FIGURE 9.26 Hard‐segment structure stabilization through germinal hydrogen b...

FIGURE 9.27 Trend of increasing applied for and granted patents on polyureth...

FIGURE 9.28 (a) Patent activity of companies having at least 10 patents from...

FIGURE 9.29 Pie chart of patent activity filed from 2015 to 2019 of top 18 a...

FIGURE 9.30 Normalized patent activity during 2015–2019 based on application...

Chapter 10

FIGURE 10.1 Technology structure of polyurethane coatings and adhesives by f...

FIGURE 10.2 Relative volume of polyurethane (a) volume and (b) value used in...

FIGURE 10.3 Consumption of polyurethane resins in coatings relative to other...

FIGURE 10.4 Distribution of global consumption of polyurethane chemicals in ...

FIGURE 10.5 Global consumption of polyurethane adhesives by (a) total formul...

FIGURE 10.6 Global consumption of polyurethane in polyurethane adhesives.

FIGURE 10.7 Global consumption of (a) isocyanates and (b) polyols for polyur...

FIGURE 10.8 Growth in PUD patent activity since development in the early 196...

FIGURE 10.9 Synthesis of ionomeric prepolymer for PUD based on DMPA.

FIGURE 10.10 Batch process for PUD production.

FIGURE 10.11 Block diagram for a continuous process for making PUDs via a hi...

FIGURE 10.12 Patent activities from (a) 2000–2014 and (b) 2015–2019 of major...

FIGURE 10.13 Global patent activity for polyurethane adhesives for companies...

FIGURE 10.14 Adhesive patent activity subject based on protecting specific p...

FIGURE 10.15 Analysis of polyurethane adhesive applications patent activity ...

FIGURE 10.16 Distribution of patents based on their delivery format and gene...

FIGURE 10.17 (a) Distribution of polyol consumption in polyurethane coatings...

FIGURE 10.18 Distribution of industrial applications employing polyurethane ...

FIGURE 10.19 Simplified supply chain and commercial relationships among poly...

FIGURE 10.20 Structure of aliphatic isocyanate trimers (a) isophorone diisoc...

FIGURE 10.21 Illustrative composition of building blocks for making a UV‐cur...

FIGURE 10.22 Operations to a powder‐coated item. The components of the powde...

FIGURE 10.23 Dimerization of a polyisocyanate to a blocked uretdione structu...

FIGURE 10.24 Patent activity for (a) 2000–2014 and (b) 2015–2019 by large mu...

FIGURE 10.25 Covestro’s (formerly Bayer) activity during 2000–2014 on polyur...

FIGURE 10.26 Patent activity for 2015–2019 by filing language as a proxy for...

FIGURE 10.27 Distribution of subject matter from filed patent documents on p...

Chapter 11

FIGURE 11.1 Patent activity from 1990 to 2014 of various industrial polyuret...

FIGURE 11.2 Distribution of patents from 1990 to 2014 filed on biomedical us...

FIGURE 11.3 Patent activity for Medtronic plc for 1994–2013 by (a) technolog...

FIGURE 11.4 Patent activity for Bayer AG for 1994–2013 by (a) technology seg...

FIGURE 11.5 Number of patents filed in the Chinese language from 1991 to 201...

FIGURE 11.6 Structure of lactic acid and the derived biorenewable and biodeg...

FIGURE 11.7 Copolymer of polycaprolactone and polylactic acid, as might be p...

FIGURE 11.8 Preparation of a polyester–anilide and subsequent conversion to ...

FIGURE 11.9 Structure of the polyamine lysine and the derived biodegradable ...

FIGURE 11.10 Simplified process flow for making medical films such as examin...

FIGURE 11.11 Ratio of published patents to journal articles in 2014–2019 on ...

FIGURE 11.12 Analysis of open literature (English language only) topics wher...

FIGURE 11.13 Analysis of the patent literature (USA only) subject matter whe...

Chapter 12

FIGURE 12.1 Growth in public documents exploring or protecting the productio...

FIGURE 12.2 Patent activity of top filers of polycyclic carbonate to polyure...

FIGURE 12.3 (a) Activity intensity of research on the production of polyuret...

FIGURE 12.4 (a) A nonisocyanate‐containing final product with reactive end g...

FIGURE 12.5 Direct transformation of polyoxirane (epoxy) to a polycyclic car...

FIGURE 12.6 Illustrative reaction of a polycyclic carbonate with a polyamine...

FIGURE 12.7 Illustrative reaction of aziridine with super critical CO

2

to ma...

FIGURE 12.8 Two potential mechanisms for formation of the polyurethane–amine...

FIGURE 12.9 Conversion of amine to carbamate by reaction with CO

2

and subseq...

FIGURE 12.10 Reaction of an amine with CO

2

to make urethane via an ‐onium sa...

FIGURE 12.11 Reaction of amine with CO

2

to form urethane using Mitsunobu rea...

FIGURE 12.12 Reaction of urea and methanol to form methyl carbamate.

FIGURE 12.13 Reaction of methyl carbamate and formaldehyde to make the hemia...

FIGURE 12.14 Reaction of a polyol with methyl carbamate or urea to produce a...

FIGURE 12.15 Reaction of a dimethyl ester with hydroxylamine hydrochloride t...

FIGURE 12.16 Reaction of the polyhydroxamic acid with dimethyl carbonate, re...

FIGURE 12.17 Illustrative reaction of a hydroxylamine and diphenyl carbonate...

FIGURE 12.18 Direct reaction of ethanolamine and carbon dioxide to form oxaz...

Chapter 13

FIGURE 13.1 Growth in total documents where the primary focus of the work is...

FIGURE 13.2 Documents (both patent and open literature) where the subject is...

FIGURE 13.3 Distribution of polymers networked or copolymerized with polyure...

FIGURE 13.4 Relative importance of polyurethane IPN and copolymer hybrid app...

FIGURE 13.5 Possible rearrangement during utilization of glycidol to compati...

FIGURE 13.6 Reaction of diglycidyl ether of bisphenol A with a diphenolic fo...

FIGURE 13.7 Hydrolysis of a diketamine to produce the latent amine, which ca...

FIGURE 13.8 Reaction pathway to produce methoxysilanes grafted onto a polyol...

FIGURE 13.9 Hydrolysis of alkoxysilanes for cross‐linked network formation....

FIGURE 13.10 An isocyanato‐alkoxysilane for forming a polyurethane–silicone ...

FIGURE 13.11 Reaction scheme for preparation of a polyurethane–PDMS diblock ...

FIGURE 13.12 A reaction scheme for making a polyurethane–PDMS hybrid using p...

FIGURE 13.13 An illustration of a POSS structure and examples of the kinds o...

FIGURE 13.14 Structure of maleic anhydride‐modified polyethylene and its rea...

FIGURE 13.15 Transmission electron micrograph of maleic anhydride polyethyle...

FIGURE 13.16 A polyurethane and polyester backbone in position to facilitate...

FIGURE 13.17 Atomic force microscopy showing the very high dispersion of pol...

Chapter 14

FIGURE 14.1 Environmental fate of consumer waste in (a) the USA for 2017

FIGURE 14.2 Total number of documents produced for 2000–2019 on the subject ...

FIGURE 14.3 Analysis of documents detailing the mode of recycle in all langu...

FIGURE 14.4 Language of document publication for those in Figure 14.3.

FIGURE 14.5 Companies patenting, and their number of patents, for 2010–2019 ...

FIGURE 14.6 Simplified classification of manner of polyurethane recycle.

FIGURE 14.7 Chemistry of glycolysis. The large desirable polyol moiety is su...

FIGURE 14.8 Chemistry of hydrolysis. The large desirable polyol moiety is su...

FIGURE 14.9 Chemistry of aminolysis. The large desirable polyol moiety is su...

FIGURE 14.10 Chemistry of acidolysis. The dicarboxylic acid progressively de...

FIGURE 14.11 Polyurethane decomposition reactions occurring between 200 °C a...

Guide

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WILEY SERIES ON POLYMER ENGINEERING AND TECHNOLOGYRichard F. Grossman and Domasius Nwabunma, Series Editors

Polyolefin Blends / Edited by Domasius Nwabunma and Thein Kyu

Polyolefin Composites / Edited by Domasius Nwabunma and Thein Kyu

Handbook of Vinyl Formulating, Second Edition / Edited by Richard F. Grossman

Total Quality Process Control for Injection Molding, Second Edition / M. Joseph Gordon, Jr.

Microcellular Injection Molding / Jingyi Xu

Poly(lactic acid): Synthesis, Structures, Properties, Processing, and Applications / Edited by Rafael Auras, Loong‐Tak Lim, Susan E.M. Selke, and Hideto Tsuji

Hyperbranched Polymers: Synthesis, Properties, and Applications / Edited by Deyue Yan, Chao Gao, and Holger Frey

Advanced Thermoforming: Methods, Machines and Materials, Applications and Automation / Sven Engelmann

Biopolymer Nanocomposites: Processing, Properties and Applications / Alain Dufresne, Sabu Thomas, Laly A. Pothan

Polymers for PEM Fuel Cells / Hongting Pu

Polyurethanes: Science, Technology, Markets, and Trends / Mark F. Sonnenschein

Functional Polymer Coatings: Principles, Methods, and Applications / Edited by Limin Wu and Jamil Baghdachi

Polyurethanes: Science, Technology, Markets, and Trends, Second Edition / Mark F. Sonnenschein

POLYURETHANES

Science, Technology, Markets, and Trends

SECOND EDITION

MARK F. SONNENSCHEIN, Ph.D.

The Dow Chemical CompanyMidland, MI, USA

This edition first published 2021© 2021 John Wiley & Sons, Inc.

Edition HistoryJohn Wiley & Sons (1e, 2014)

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Library of Congress Cataloging‐in‐Publication Data

Names: Sonnenschein, Mark F., author.Title: Polyurethanes : science, technology, markets, and trends / Mark F. Sonnenschein, Ph.D., The Dow Chemical Company, Midland, Michigan, US.Description: Second edition. | Hoboken : Wiley, 2021. | Series: Wiley series on polymer engineering and technology | Includes bibliographical references and index.Identifiers: LCCN 2020024254 (print) | LCCN 2020024255 (ebook) | ISBN9781119669418 (hardback) | ISBN 9781119669463 (adobe pdf) | ISBN 9781119669470 (epub)Subjects: LCSH: Polyurethanes.Classification: LCC TP1180.P8 S56 2021 (print) | LCC TP1180.P8 (ebook) | DDC 668.4/239–dc23LC record available at https://lccn.loc.gov/2020024254LC ebook record available at https://lccn.loc.gov/2020024255

Cover Design: WileyCover Image: Courtesy of The Dow Chemical Company

Dedicated to my wife, Geraldine Franklin Sonnenschein, for her beauty, kindness, and endless support and to my children, Matthew, Anne, and Susan, for the inspiration and the laughs. My canines, Arlo, Lark, Bugle, and Sprite, are acknowledged for patiently and cheerfully keeping me company throughout the writing process.

PREFACE

I want to begin by thanking the people and organizations that bought the first edition of Polyurethanes: Science, Technology, Markets, and Trends. I have received many encouraging and constructive comments since it appeared at the end of 2014. At the same time I have also had a certain amount of angst about the number of errors in the book, most of them typographical, but not all of them! In addition, I have been acutely aware as time has passed, even over just 6 years, that the polyurethane industry is continuously changing and evolving. The “Science” and “Technology” parts of the first edition title have changed somewhat, but the “Markets” and “Trends” components of the first edition were badly in need of updating. What was also striking was how third‐party industry forecasts made in 2014 about subsequent years were in most cases wrong, demonstrating how poorly crystal ball analyses of economic activity perform. In this second edition there is much less attention paid to these prognostications.

An interesting macrotrend at the time of this writing is the rapid expansion of global capacity with only moderate growth occurring now and in the future. This assures that producer prices will remain under pressure and help maintain low price inflation for the foreseeable future. This may also result in additional consolidation in the polyurethanes industry, or the spinning out of polyurethane businesses from chemical conglomerates as was see when Bayer AG spun off its polyurethane assets into a separate company called Covestro AG. An additional market complication is the introduction of large chemical concerns that represent and depend on national subsidies, such as those appearing in China and Saudi Arabia. As a statement of a societal commitment apart from market forces, they are capable of distorting market supply and pricing. Whether by consolidation or spinning out of assets, the ability of the surviving companies to efficiently and effectively allocate and spend capital in the prevailing economic environment could be a continuing element in the polyurethanes industry story.

This edition adds two new special chapters at the end: Chapter 13 on polyurethane hybrid polymers and Chapter 14 on polyurethane recycle. As the reader will see, both topics cover nascent technologies in terms of the scientific progress and industrial intent to commercialize in these technology fields. Polymer hybrids are often conceived in the belief that if two different polymers are good, then their combination (or hybridization) will be even better. While this has not historically been found true for a number of reasons, there are a number of instances for polyurethanes where polymer backbone hybridizations are beneficial, making this technology area potentially ripe for growth in the future.

Polyurethane recycle – the subject of Chapter 14 – is a subset of the much larger topic of plastics recycle. However, unlike soda straws, water bottles, and disposable food packaging, polyurethanes are usually not found in articles that are commonly thrown away. There is no developed municipal collection and distribution system for acquiring polyurethanes, separating them from the objects they are a part of, and readying them for chemical cleanup and reversion back to useful building blocks. However, regulations, especially those emanating from the European Union, requiring end‐of‐life stewardship of things such as mattresses and automotive seats – containing significant volumes of polyurethanes – are forcing producers to develop technology and commercial partnerships. This industrial evolution will permit polyurethane recycle either through low‐value physical incorporation or by chemical transformation of the polyurethane polymer into useable feedstocks for making new materials. If governmental regulations create price inelastic demand for these materials, then the methods of their production and the value they bring will become a topic of increasing importance into the future.

Mark F. SonnenscheinMidland, MI

ACKNOWLEDGMENTS

I would like to express my deep gratitude to the people who have helped me through the years and provided fertile ground for growth. Particularly I would like to mention my colleagues whom I have worked with in the field of polyurethanes over the past 20 years. First, I would like to mention my constant collaborator Benjamin Wendt, who has worked with me closely in the lab for many years and excelled at making hard things work easily. Many people have provided guidance, encouragement, and excellent collaboration over the years. Especially I would like to mention Dr. Alan Schrock, Dr. Justin Virgili, Dr. Mark Cox, Dr. Jack Kruper, Dr. Chris Christenson, Dr. Valeriy Ginzburg, Dr. Jozef Bicerano, Mr. Will Koonce, Dr. Juan‐Carlos Medina, Prof. Tony Ryan, Dr. David Babb, Dr. Robbyn Prange, Dr. Nelson Rondan, Dr. Maria Pollard, Dr. Jai Venkatesan, Dr. David Bem, Dr. Florian Schattenmann, Dr. Andre Argenton, Dr. Jorge Jimenez, Dr. Kaoru Aou, Dr. Kshitish Patankar, Dr. Steve Guillaudeu, Dr. Cecile Boyer, Dr. Steve Montgomery, Dr. Brian Landes, Dr. Steve Webb, Dr. Phillipe Knaub, Dr. Hamdy Khalil, Dr. Tirtha Chatterjee, Dr. Lotus Huang, Dr. Cathy Tway, Dr. Shawn Feist, Prof. John Klier, Prof. Craig Hawker, and Dr. John Kramer.

I would also like to recognize the great support I received from The Dow Chemical Company in writing this book by giving me the encouragement, time, resources, and freedom to realize this vision.

I would be remiss to not acknowledge the contributions of my copy‐editor, Lindsey Williams. Her patient and meticulous contributions have made this a more readable and useful text.

Lastly, I would like to acknowledge the people who gave me my scientific foundations and inspired in me a love of experiment and a respect for theory. Particularly I would like to mention Prof. Richard G. Weiss (Georgetown University), Dr. C. Michael Roland (The United States Naval Research Lab), and Prof. Gordon Johnson (Kenyon College) for putting up with me in my early years.