Determination of Additives in Polymers and Rubbers

Determination of Additives in Polymers and Rubbers

Author: T.R. Crompton
ISBN 978-1-84735-000-8 

Hard and Soft-backed,

Pages 450


Powerful new analytical tools have been made available to the chemist by a combination of various chromatographic techniques with methods of identifying separated additives and their degradation products by techniques based on infrared and mass spectrometry. In particular supercritical fluid chromatography combined with mass spectrometry has come to the fore. Combinations of polymer pyrolysis with gas chromatography with mass spectrometric identification of the pyrolysis products is throwing new light on what happens to antioxidants and other polymer additives during polymer processing and a products' life. Similarly evolved gas analysis and then thermogravimetry and dynamic scanning calorimetry is proving very useful in antioxidant loss studies.

The book is an up-to-date coverage of the present state of knowledge on the subject of polymer additive systems and as such should be extremely useful to workers in the field.

1 Direct Determination of Additives in Polymers and Rubbers
1.1 Infrared Spectroscopic Methods
1.2 Ultraviolet Spectroscopy
1.3 Raman Spectroscopy
1.4 Mass Spectrometry
1.5 X-ray Photoelectron Spectroscopy (XPS)
1.6 Thermal Methods of Analysis
1.6.1 Differential Scanning Calorimetry
1.6.2 Differential Thermal Analysis
1.6.3 Thermogravimetric Analyses
1.7 Vapour Phase Ultraviolet Spectroscopy
1.8 X-Ray Fluorescence Analysis
1.9 Nuclear Magnetic Resonance Spectroscopy

2 Extraction Techniques for Additives in Polymers
2.1 Introduction
2.2 Solvent Extraction
2.2.1 Polyolefins
2.2.2 Polystyrene
2.2.3 Acrylic Polymers
2.2.4 PVC
2.2.5 Rubbers
2.2.6 Polyacrylamide
2.2.7 Polyurethane
2.2.8 Vinyl Chloride, Butadiene, Acrylonitrile, Styrene, Ethylhexyl Acrylate Copolymers
2.2.9 Other Polymers
2.3 Fractional Precipitation
2.4 Fractional Extraction
2.5 Separation by Diffusion Methods
2.6 Dialysis or Electrodialysis
2.7 Vacuum Thermal Displacement Extraction Method
2.7.1 Effects of Polymer Milling on Extraction
2.8 Solvent Extraction – Infrared Spectrometry
2.9 Solvent Extraction – Ultraviolet Spectroscopy
2.9.1 Ionol in Polyolefins
2.9.2 Santonox R In Polyolefins
2.9.3 Styrene Monomer
2.10 Solvent Extraction – Visible Spectroscopy
2.10.1 Phenol Antioxidants
2.10.2 Amine Antioxidants
2.10.3 Tris Nonyl (Phenylated Phenyl) Phosphite
2.11 Solvent Extraction Spectrofluorimetry
2.11.1 Perkin-Elmer LS-2B Microfilter Fluorimeter
2.11.2 Antioxidants
2.12 Solvent Extraction – Mass Spectrometry
2.12.1 Ultraviolet Absorbers
2.13 Solvent Extracts – Electrochemical Methods
2.13.1 Acrylamide Polarography
2.13.2 Antioxidants
2.13.3 Organic Peroxides
2.13.4 Procedure
2.13.5 Calculations
2.13.6 Acrylonitrile
2.13.7 Determination of Styrene
2.13.8 Determination of Acrylonitrile
2.13.9 Organometallic Stabilisers
2.14 Chronopotentiometry
2.15 Anodic Voltammetry
2.16 Solvent Extraction – Nuclear Magnetic Resonance Spectroscopy (NMR)

3 Liquid Chromatography
3.1 Introduction
3.1.1 The Isocratic System
3.1.2 Basic Gradient System
3.1.3 Advanced Gradient System
3.1.4 The Inert System
3.2 Chromatographic Detectors
3.2.1 Post-Column Derivatisation - Fluorescence Detectors
3.2.2 Diode Array Detectors
3.2.3 Electrochemical Detectors
3.3 Antioxidants
3.3.1 Instrumentation
3.3.2 Applications
3.4 Oligomers
3.5 Acrylic Acid Monomer
3.6 Acrylamide Monomer
3.7 Amines
3.8 Plasticisers
3.9 Additive Mixtures
3.10 High Performance Liquid Chromatography – Infrared Spectroscopy
3.11 Gel Permeation Chromatography

4 Gas Chromatography
4.1 Antioxidants
4.1.1 Secondary Antioxidants
4.2 Volatile Compounds
4.3 Monomers
4.4 Oligomers
4.5 Hindered Amine Light Stabilisers (HALS)
4.6 Plasticisers
4.7 Organic Peroxides
4.8 Rubber Antidegradants
4.9 Miscellaneous Polymer Additives
4.10 Identification of Additives by a Combination of GC and Infrared Spectroscopy
4.11 Identification of Additives by a Combination of GC and Mass Spectrometry
4.12 Pyrolysis GC

5 Thin-Layer Chromatography
5.1 Experimental
5.1.1 Preparation of Thin-layer Plates for Analysis
5.1.2 Application of Polymer Extract to Plate
5.1.3 Selection of Chromatographic Solvent
5.1.4 Detection of Separated Compounds on the Plate
5.1.5 Evaluation of Developed Plates
5.1.6 Spectroscopic Methods
5.1.7 Optical Densiometric Analysis
5.1.8 Methods Based on Spot Size
5.2 Antioxidants
5.2.1 Determination of Santonox R
5.3 Ultraviolet Stabilisers
5.4 Plasticisers
5.5 Organotin Stabilisers
5.6 Epoxy and Other Heat Stabilisers
5.7 Optical Whiteners
5.8 Amine and Phenolic Antioxidants and Antidegradants, Guanidines and Accelerators in Rubber
5.9 Miscellaneous Additives
5.10 Combination of Thin-Layer Chromatography with Infrared Spectroscopy
5.10.1 Premigration of Plates
5.10.2 Removal of Separated Compounds from the Plate
5.10.3 Extraction of Pure Polymer Additives from Separated Adsorbent Bands
5.10.4 Preparation of Infrared Spectra Separated Additives
5.10.5 Preparation of UV Spectra of Separated Additives

6 Paper Gel Permeation Chromatography

7 Supercritical Fluid Chromatography
7.1 Antioxidants
7.2 Oligomers
7.3 Supercritical Fluid Chromatography-Mass Spectrometry (SFC-MS)

8 Headspace Analysis - Volatiles
8.1 Volatiles
8.2 Monomers
8.3 Oligomers
8.4 Miscellaneous

9 Thermal Methods
9.1 Pyrolysis-Gas Chromatography-Mass Spectrometry
9.2 Evolved Gas Analysis

10 Determination of Water

11 Determination of Metals
11.1 Destructive Techniques
11.1.1 Atomic Absorption Spectrometry
11.1.2 Graphite Furnace Atomic Absorption Spectrometry
11.1.3 Atom Trapping Technique
11.1.4 Vapour Generation Atomic Absorption Spectrometry
11.1.5 Zeeman Atomic Absorption Spectrometry
11.1.6 Inductively Coupled Plasma Atomic Emission Spectrometry
11.1.7 Hybrid Inductively Coupled Plasma Techniques
11.1.8 Inductively Coupled Plasma Optical Emission Spectrometry-Mass Spectrometry
11.1.9 Pre-concentration Atomic Absorption Spectrometry Techniques
11.1.10 Microprocessors
11.1.11 Autosamplers
11.1.12 Applications: Atomic Absorption Spectrometric Determination of Metals
11.1.13 Visible and UV Spectroscopy
11.1.14 Polarography and Voltammetry
11.2 Non-destructive Methods
11.2.1 X-ray Fluorescence Spectrometry
11.2.2 Neutron Activation Analysis
11.2.3 Metal Stearate Stabilisers

12 Non-metallic Elements
12.1 Instrumentation
12.1.1 Furnace Combustion Methods
12.1.2 Oxygen Flask Combustion Methods
12.2 Acid Digestions of Polymers
12.2.1 Chlorine
12.2.2 Nitrogen
12.2.3 Phosphorus
12.2.4 Silica
12.3 X-ray Fluorescence Spectroscopy
12.4 Antec 9000 Nitrogen/Sulfur Analyser
Appendix 1

Roy Crompton was Head of the polymer analysis research department of a major international polymer producer for some 15 years. In the early fifties he was heavily engaged in the development of methods of analysis for low-pressure polyolefins produced by the Ziegler-Natta route, including work on high-density polyethylene and polypropylene. He was responsible for the development of methods of analysis of the organoaluminum catalysts used for the synthesis of these polymers. He was also responsible for the development of thin-layer chromatography for the determination of various types of additives in polymers and did pioneering work on the use of TLC to separate polymer additives and to examine the separated additives by infrared and mass spectrometry. He retired in 1988 and has since been engaged as a consultant in the field of analytical chemistry and has written extensively on this subject, with some 20 books published.