Atlas of Plastics Additives

566 Pages·2002·24.87 MB·English

by  Dietrich O. Hummel

Dietrich O. Hummel
Atlas of Plastics Additives
Analysis by Spectrometric Methods
With 62 tables and 772 FTIR spectra
Springer
Prof. Dr. Dietrich O. Hummel
Im Lindenhof 15
D-53773 Hennef
ISBN 3-540-42414-8 Springer-Verlag Berlin Heidelberg New York
Library of Congress Cataloging-in-Publication-Data
Hummel, Dieter O.
Atlas of plastics additives : analysis by spectrometric methods / Dieter Hummel.
p.cm.
Includes bibliographical references and index.
ISBN 3540424148 (alk. paper)
1. Plastics--Additives--Analysis. 2. Plastics--Additives--Spectra. I. Title.
TP1142.H86 2002
668.4cn--dc2i
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Preface
Twenty years ago the 2nd edition of the text and spectra volume of Friedrich Scholl on the analysis of plastics additives
was published, it can be found in most laboratories. He deceased shortly after his retirement, and my coworkers and I took
over his heritage. Collecting samples of additives of all kind as well as the measurement of their FTIR spectra was done by
Sigrun Wittmann, Liu Min, Mark Amberg, Vera Brunne, Astrid Baum and myself; my wife Doris digitised the structures. 752
spectra of the more important additives were selected from a total of 1630. To facilitate access for the analyst, the "triplets"
(spectrum with peak table, structure, legend) were arranged according to a decimal system (technological class, chemical
composition). Registers (chemical and trade name, empirical formula) help one to find the desired spectrum.
Literature on (predominantly) spectroscopic methods in the analysis of plastics additives was evaluated until 2001.
Methods and experiments were critically reported; wherever possible the results were compressed in tables. In order to keep
the volume of the book within limits only elementary methods for the separation of additives and matrices were described
(2nd chapter). The chromatographic separation of mixtures had to be omitted; it is amply described in the book of Scholl
and in later monographs. The reason why chapters 3 and 7 are so large is very simple: (FT)IR and mass spectrometries are
by far the most important methods for identification and quantitative determination of additives. They are also suitable for
combination with chromatographic and other analytical methods.
I owe gratitude to my coworkers for their zeal as well as to Stiftung Industrieforschung for generous support of our
research, to many chemical companies for providing samples and to numerous colleagues sending reprints. Many thanks
go to my colleagues B. Schrader (Uni. Essen), K.-W. Brzezinka (BAM, Berlin-Adlershof), K.-J. Eichhorn and D. Fischer (IPF
Dresden) for measuring the Raman spectra of problematic samples. Finally, many thanks go to the editorial staff of Springer
Verlag and to medio Technologies (producer) for skill and carefulness and for their patience with the author.
Dietrich O. Hummel
Summer 2002
Contents
Preface ............................................................................................................................. v
Part A. Theory und Practical Applications
1. Introduction .............................................................................................................................. 3
2. Extraction, Solution Precipitation and Separation of Additives ............................................... 5
2.1 Extraction .............................................................................................................. 5
2.2 Solution Precipitation ............................................................................................. 5
2.3 Separation of Additive Mixtures into Components .................................................. 7
3. Infrared Spectrometry .............................................................................................................. 9
3.1 Fundamentals ........................................................................................................ 9
3.2 Sample Preparation and Measurement .................................................................. 10
3.3 Conventional and Computer-Supported Interpretation of IR Spectra ...................... 12
3.4 Some Aspects of FTIR Spectrometry ..................................................................... 13
3.4.1 Storage of Spectra in the Computer ............................................................... 13
3.4.2 The Search for Similarity and Equality (“Identity”) .......................................... 14
3.5 Recent Work in IR Spectrometry of Additives ........................................................ 17
3.5.1 Additives with Preventive or Curative Properties ............................................ 17
3.5.1.1 Empirical IR Band Assignments ........................................................ 17
3.5.1.2 Separation of Additives and Identification by (FT)IR
Spectrometry ..................................................................................... 18
3.5.1.3 Solubility of Stabilizers and Antioxidants in Polymers ....................... 20
3.5.1.4 ATR Investigation of Rubber Surfaces .............................................. 21
3.5.1.5 Quantitative IRS Analysis of Additives .............................................. 21
3.5.2 Pigments and Fillers ....................................................................................... 22
3.5.2.1 Organic Pigments .............................................................................. 22
3.5.2.2 Inorganic Pigments and Fillers .......................................................... 24
3.5.2.3 Pigments and Other Components in Fine Art and Historical
Objects .............................................................................................. 25
3.5.3 Plasticizers ..................................................................................................... 26

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vii
viii Contents
4. Raman Spectrometry ............................................................................................................... 55
4.1 Fundamentals ........................................................................................................ 55
4.2 Applications of RS in the Field of Plastics Additives ............................................... 55
4.3 RS Combined with Information-Enhancing Techniques for the Identification
of Dyes and Pigments ............................................................................................ 61
4.3.1 Subtracted Shifted Resonance RS ................................................................. 61
4.3.2 RS Combined with Light Microscopy .............................................................. 61
5. Spectrometry in the Ultraviolet and Visible Regions ............................................................... 65
5.1 Fundamentals ........................................................................................................ 65
5.2 Antioxidants ........................................................................................................... 65
5.3 Light Stabilizers ..................................................................................................... 67
5.4 Pigments ................................................................................................................ 67
5.5 Plasticizers ............................................................................................................ 68
6. Nuclear Magnetic Resonance Spectrometry .......................................................................... 71
6.1 Fundamentals ........................................................................................................ 71
6.2 Applications ........................................................................................................... 71
7. Mass Spectrometry .................................................................................................................. 73
7.1 Fundamentals ........................................................................................................ 73
7.1.1 Mass Separation ............................................................................................ 73
7.1.2 Ionization ........................................................................................................ 73
7.1.3 Ion Detection .................................................................................................. 74
7.2 Mass Spectrometry with Electron Impact Ionization (EIMS) ................................... 74
7.3 Mass Spectrometry with Low-Fragmentation Ionization ......................................... 76
7.3.1 (Pyrolysis-) Field Ionization (FI) and Field Desorption Mass
Spectrometry (Py-FIMS, FDMS) ..................................................................... 76
7.3.2 Chemical Ionization Mass Spectrometry (CIMS) ............................................ 80
7.3.3 Fast-Atom Bombardment Mass Spectrometry (FAB-MS) .............................. 82
7.3.4 Laser-Desorption Mass Spectrometry ............................................................ 83
7.3.4.1 Matrix-Assisted Laser-Desorption Ionization Time-of-Flight
(MALDI-TOF) Mass Spectrometry .................................................... 83
7.3.4.2 Laser-Desorption FT-Ion Cyclotron Resonance (LD/FT-ICR)
Mass Spectrometry ........................................................................... 84
7.4 Mass Spectrometry with Pre-Separated Mixtures (GC-, HPLC-, TLC-MS) ............. 87
7.4.1 On-Line Coupling of GC with Mass Spectrometry (GC-MS) .......................... 87
7.4.2 On-Line Coupling of Separation Techniques for Non-Volatile
Substances with Mass Spectrometry ............................................................. 88
7.4.3 A Typical Investigation ................................................................................... 88

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Contents ix
7.5 Mass Spectrometry with a Second Mass Spectrometer as Analyzer
(MS-MS, Tandem MS) ........................................................................................... 89
7.5.1 Fundamentals ................................................................................................. 89
7.5.2 MS-MS of Additives ........................................................................................ 89
8. Structure Analysis by X-Ray Diffraction .................................................................................. 111
8.1 Fundamentals ........................................................................................................ 111
8.2 Inorganic Pigments and Fillers ............................................................................... 111
8.3 Organic Pigments .................................................................................................. 111
9. Elemental Analysis .................................................................................................................. 113
9.1 Atomic Emission Spectroscopy .............................................................................. 113
9.2 Atomic Absorption Spectroscopy ........................................................................... 115
9.3 Analysis of Surfaces: X-Ray Induced Photoelectron Spectroscopy (XPS) ............. 115
10. Bibliography ............................................................................................................................. 117
10.1 Books, Monographs, Reviews ................................................................................ 117
10.2 Contributions in Journals ....................................................................................... 118
10.2.1 Additives in General ....................................................................................... 118
10.2.2 Antioxidants .................................................................................................... 120
10.2.3 Pigments, Fillers ............................................................................................. 121
10.2.4 Plasticizers ..................................................................................................... 123
10.2.5 Stabilizing Agents ........................................................................................... 124
10.2.6 Rubber Chemicals .......................................................................................... 124
10.2.7 Flameproofing and Blowing Agents, Antistatics, Biocides and Other
Additives ......................................................................................................... 125
10.2.8 Computer-Aided Data Evaluation, Special Techniques in Instrumental
Analysis .......................................................................................................... 126
Part B. FTIR Spectral Atlas of Plastics Additives
1. Decimal Classification of Additives .......................................................................................... 133
2. FTIR Spectra of Additives ........................................................................................................ 143
User's Guide .................................................................................................................. 143
Additives with Preventive or Curative Properties ............................................................ 144
Antioxidants, Ageing Inhibitors ................................................................................... 144
PVC Stabilisers and Co-stabilisers ............................................................................ 181
Light Stabilisers .......................................................................................................... 226
Flame Retardants ....................................................................................................... 234
Metal Deactivators ..................................................................................................... 240
Biocides ...................................................................................................................... 241

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x Contents
Pigments, Brightening Agents, Fillers ............................................................................. 245
Inorganic Pigments and Fillers ................................................................................... 245
Organic Pigments ........................................................................................................... 256
Monoazo Pigments .................................................................................................... 256
Disazo Pigments ........................................................................................................ 311
Polycyclic Pigments ................................................................................................... 324
Brightening Agents ......................................................................................................... 366
Stilbene Derivatives ................................................................................................... 366
Fillers ............................................................................................................................. 367
Inorganic .................................................................................................................... 367
Plasticisers, Extenders ................................................................................................... 372
Hydrocarbons, Chloro-Hydrocarbons ......................................................................... 372
CHO-Compounds (Without Esters) ............................................................................ 375
Plasticisers, Esters ......................................................................................................... 377
Esters of Saturated Monocarboxylic Acids ................................................................. 377
Esters of Saturated Di- or Polycarboxylic Acids ......................................................... 382
Esters of Unsaturated Acids, Epoxyesters ................................................................. 396
Sulfur-Containing Esters ............................................................................................ 402
Phthalate Esters ......................................................................................................... 404
Trimellitate Esters ...................................................................................................... 418
Phthalate Polyesters .................................................................................................. 420
Phosphate Esters ....................................................................................................... 422
Plasticisers: Esters, Amides ........................................................................................... 426
Sulfonate Esters, Sulfonamides, Carbonamides ........................................................ 426
Processing Agents, Textile Auxiliaries ............................................................................ 429
Hydrocarbons and Modified Hydrocarbons ................................................................ 429
Fatty Alcohols, -Alcohol Ethers .................................................................................. 434
Carboxylic Acids, Esters, Soaps ................................................................................ 437
Fatty Amines .............................................................................................................. 460
Fatty Amides .............................................................................................................. 461
Adhesion Agents ........................................................................................................ 464
Blowing Agents .......................................................................................................... 466
Textile Auxiliaries ....................................................................................................... 468
Crosslinking Agents, Activators .................................................................................. 477
Vulcanisation Agents, Rubber Auxiliaries ....................................................................... 485
Vulcanisers, Accelerators ........................................................................................... 485
Vulcanisation Activators, Retarders ........................................................................... 502
Rubber Antioxidants, Reinforcing Agents, Peptiser, Others ....................................... 506

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Contents xi
Antiblocking Agents ........................................................................................................ 519
Biocide ....................................................................................................................... 519
Indexes
Chemical Names Index ................................................................................................................. 521
Trivial/Trade Names Index ............................................................................................................ 545
Subject Index ................................................................................................................................. 561

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1
Introduction
About 5xl010kg of polymeric materials are annually con- groups of additives and on the applied analytical methods.
sumed by mankind. Few of these polymers can be used as This allows rapid access to both topics - methods and ma-
produced; examples are intrinsically stabilised polyaromat- terials.
ics like the polypyromellitic imides or inorganic polymers The complete analysis of an industrial polymer follows
like boron nitride or quartz. All organic polymers are this scheme:
subject to oxidative or other kinds of degradation, or they
lack certain properties like elasticity or flame resistance, or 1. Extraction of low-molecular material from polymer
they do not have the colour wanted for a certain application. 2. Separation of additive mixtures into their components
Thermoplastics may degrade during processing, rubber gets 3. Identification of polymer
brittle from ozone attack. 4. Identification of additives
Here enter the additives. However, before going into 5. Quantitative analysis
details it has to be stated that many chemical and physical
properties can be reached by the choice of the proper mate- In this text, only items 1 and 4 will be treated in more de-
rial, by copolymerisation or by polymer blending. None of tail. Item 2 is thoroughly described in the book of Scholl
these materials, however, can withstand sunlight, ionising (Hummel/Scholl vol. 3, Sect. 10.1), chemical analysis (items 4
radiation, heat, the attack of microorganisms, not to men- and 5) in that of Crompton. Recent literature is found in Sect.
tion aggressive chemicals. (Very few may pass for stable, 10.2 and in the 4th edition of Gachter/Muller.
for instance aromatic polypyromellitic imides like Kapton.)
Protective additives, in amounts between 0.02% and about
2%, are able to prolong the lifetime of polymeric materials
by several orders of magnitudes. This means that optical and
mechanical properties - these are the most important ones
- remain almost constant for a long time.
Polymers are the most widely used materials after steel,
and polymeric hydrocarbons1 (polyethylene, polypropyl-
ene, polystyrene) together with polyvinylchloride make
the majority of all industrial polymers. This explains why
antioxidants for polyhydrocarbons and heat- as well as light
stabilisers for PVC are on top of the big family of additives.
To give two figures: the worldwide production of PVC in 1985
was 1.4X1010 kg and that of PVC stabilisers 2.5X108 kg (this
makes an average of 1.8% of stabiliser in PVC). The impor-
tance of all the other industrial polymers and additives is, of
course, no less; this may be shown by the considerable variety
of applications and chemical compositions of the latter.
The following chapters were arranged according to the
instrumental techniques used in additive analysis. The bibli-
ography, on the other hand, presents publications on special
1 We use the term polyolefines only for unsturated polymeric
hydrocarbons like polybutadiene, polyisoprene etc.