Plastics Additives: A Rapra Market Report

210 Pages·2008·3.16 MB·English

by  Geoffrey Pritchard

Plastics Additives
Rapra Market Report
by Geoffrey Pritchard

Plastics Additives
A Rapra Market Report
by
Professor Geoffrey Pritchard
March 2005
Rapra Technology Limited
Shawbury, Shrewsbury, Shropshire SY4 4NR, UK
Tel: [phone] Fax: [phone] http://www.rapra.net
The right of G. Pritchard to be identified as the author of this work has been asserted by him in
accordance with Sections 77 and 78 of the Copyright, Designs and Patents Act 1988.
© 2005, Rapra Technology Limited
ISBN: 1-85957-499-8
All rights reserved. No part of this publication may be reproduced, stored in a retrieval system,
or transmitted in any form or by any means – electronic, mechanical, photocopying, recording or
otherwise - without the prior permission of the publisher, Rapra Technology Limited, Shawbury,
Shrewsbury, Shropshire, SY4 4NR, UK.
Typeset, printed and bound by Rapra Technology Limited
Contents
1 Introduction..............................................................................................................................1
1.1 Why This Report Has Been Written..................................................................................................1
1.2 Geographical Focus...........................................................................................................................1
1.3 Period Under Review.........................................................................................................................1
1.4 Additives Covered.............................................................................................................................2
1.5 Structure of the Report.......................................................................................................................2
1.6Terminology.......................................................................................................................................2
1.7 Author................................................................................................................................................3
1.8 Sources of Information......................................................................................................................3
2 Executive Summary and Conclusions....................................................................................5
3 Background to the Additives Business...................................................................................9
3.1 Factors Determining the Level of Demand for Additives..................................................................9
3.2 Polymers...........................................................................................................................................10
3.3 Markets.............................................................................................................................................11
3.3.1 Packaging...................................................................................................................................11
3.3.2 Building and Construction.........................................................................................................13
3.3.3 Automotive................................................................................................................................15
3.3.4 Electrical and Electronic Equipment..........................................................................................17
3.3.5 Other Markets for Plastics..........................................................................................................19
3.4 Compounders....................................................................................................................................19
3.5 Global Economies and their Significance for the Plastics Industry..................................................20
4 Technology..............................................................................................................................23
4.1 Antiblocking Agents.........................................................................................................................23
4.1.1 Film Haze and Clarity................................................................................................................24
4.1.2 Slip Agents.................................................................................................................................24
4.2 Biocides............................................................................................................................................25
4.2.1 Why Biocides Are Used in Plastics...........................................................................................25
4.2.2 Applications of Antimicrobials in Microorganism-Resistant Products......................................26
4.2.3 Active Ingredients of Antimicrobial Additives..........................................................................26
4.2.4 Test Methods..............................................................................................................................27
4.3 Antioxidants......................................................................................................................................27
4.3.1 The Need for Polymers to be Protected Against Oxidation.......................................................27
4.3.2 Free Radicals..............................................................................................................................28
4.3.3 Primary and Secondary Antioxidants........................................................................................28
4.3.4 Acceptor and Donor Types of Antioxidant................................................................................30
4.4 Antistatic Agents...............................................................................................................................30
4.4.1 Introduction................................................................................................................................30
4.4.2 Blooming Antistatic Agents.......................................................................................................31
4.4.3 Compatibility.............................................................................................................................32
4.4.4 Carbon Black and Similar Fillers...............................................................................................33
4.4.5 Permanent Antistatic Agents......................................................................................................33
4.5 Blowing (or Foaming) Agents..........................................................................................................33
4.5.1 Introduction................................................................................................................................33
4.5.2 Chemical Blowing Agents (CBA).............................................................................................34
4.5.3 Physical Blowing Agents...........................................................................................................35
4.5.3.1 HFCs...................................................................................................................................36
4.5.3.2 Hydrocarbons......................................................................................................................37
4.6 Clarifying and Nucleating Agents.....................................................................................................38
4.7 Compatibilisers.................................................................................................................................39
4.8 Fillers (Including Nanofillers)..........................................................................................................40
4.8.1 Why Fillers Are Added To Plastics...........................................................................................40
4.8.2 Physical Properties of Fillers.....................................................................................................41
4.8.3 Effects of Fillers on Polymer Properties....................................................................................41
4.8.4 Commercially Important Fillers.................................................................................................44
4.8.4.1 Calcium Carbonate – CaCO ..............................................................................................44
3
4.8.4.2 Carbon.................................................................................................................................45
4.8.4.3 Glass....................................................................................................................................46
4.8.4.4 Kaolin.................................................................................................................................46
4.8.4.5 Mica – KMg (AlSi O )(OH) ............................................................................................47
3 10 2
Mica is an aluminosilicate mineral, extracted from rocks along with quartz and
sometimes feldspar. The name mica is a simplification as it actually represents a group of
about 37 phyllosilicate minerals, although they all have the same characteristic layered
structure........................................................................................................................................47
4.8.4.6 Talc – MgSi O (OH) ......................................................................................................47
3 4 10 2
4.8.4.7 Wollastonite – CaSiO .......................................................................................................47
3
4.8.5 Surface Treatment of Fillers by Coupling Agents and Wetting Agents....................................48
4.8.6 Nanofillers and Nanocomposites..............................................................................................49
4.8.6.1 Preparation of Nanocomposites..........................................................................................50
4.9 Flame Retardants and Smoke Suppressants.....................................................................................51
4.9.1 Introduction...............................................................................................................................51
4.9.2 Mode of Action.........................................................................................................................52
4.9.3 Halogenated Flame Retardants..................................................................................................53
4.9.4 Mechanism of Action................................................................................................................54
4.9.5 Antimony Trioxide....................................................................................................................54
4.9.6 Phosphorus Compounds............................................................................................................55
4.9.7 Intumescent Phosphorus Systems.............................................................................................55
4.9.8 Aluminium Trihydroxide (Alumina Trihydrate, ATH).............................................................56
4.9.9 Magnesium Hydroxide..............................................................................................................57
4.9.10 Borates....................................................................................................................................57
4.9.11 Nitrogen Compounds..............................................................................................................58
4.9.12 Tin...........................................................................................................................................58
4.9.13 Other Compounds...................................................................................................................59
4.10 Heat Stabilisers..............................................................................................................................59
4.10.1 Degradation of PVC................................................................................................................59
4.10.2 Mode of Action of Stabilisers.................................................................................................60
4.10.3 Lead Stabilisers.......................................................................................................................60
4.10.4 Mixed Metal Stabilisers (Ba-Zn, Ca-Zn, Ca-Ba-Zn)...............................................................61
4.10.5 Co-stabilisers...........................................................................................................................62
4.10.6 Organotin Stabilisers...............................................................................................................62
4.11 Impact Modifiers............................................................................................................................63
4.11.1 Brittle Failure in Polymers......................................................................................................63
4.11.2 Mechanisms of Toughening....................................................................................................64
4.11.2.1 Crazing.............................................................................................................................65
4.11.2.2 Shear Yielding..................................................................................................................65
4.11.2.3 Crazing Combined With Shear Yielding..........................................................................65
4.11.3 Types of Impact Modifier.......................................................................................................66
4.11.4 Toughened Thermoplastics.....................................................................................................67
4.11.4.1 Polystyrene.......................................................................................................................67
4.11.4.2 PVC..................................................................................................................................68
4.11.4.3 Polyolefins........................................................................................................................68
4.11.4.4 Engineering Plastics.........................................................................................................68
4.11.5 Thermosets..............................................................................................................................68
4.12 Lubricants and Process Aids..........................................................................................................69
4.12.1 Multiple Roles.........................................................................................................................69
4.12.2 External Lubricants.................................................................................................................69
4.12.3 Internal Lubricants..................................................................................................................69
4.12.4 Lubricants for PVC.................................................................................................................70
4.12.5 Lubricants For Polymers Other Than PVC.............................................................................70
4.12.6 Process Aids............................................................................................................................71
4.13 Plasticisers......................................................................................................................................72
4.13.1 Why Plasticisers Are Used......................................................................................................72
4.13.2 Basic Requirements of a Plasticiser........................................................................................73
4.13.3 Phthalates................................................................................................................................74
4.13.4 Relationship Between Phthalate Type and Flexible PVC Properties......................................74
4.13.5 Non-phthalate Plasticisers.......................................................................................................74
4.13.6 Plasticisers for Non-PVC Polymers........................................................................................75
4.13.7 Extenders.................................................................................................................................76
4.14 UV and Visible Light Stabilisers....................................................................................................76
4.14.1 Why Light Stabilisers Are Used..............................................................................................76
4.14.2 Light Absorption and Reflection..............................................................................................76
4.14.3 Types of Light Stabiliser..........................................................................................................78
4.14.3.1 Light-Absorbing Fillers.....................................................................................................78
4.14.3.2 Organic UV Absorbers......................................................................................................79
4.14.3.3 Excited State Quenchers...................................................................................................80
4.14.3.4 Incorporation of Photoantioxidants Such As Hindered Amine Stabilisers (Derivatives of
2,2,6,6-Tetramethylpiperidine).......................................................................................................80
4.14.4 Measuring the Effectiveness of Light Stabilisers.....................................................................81
4.15 Miscellaneous Additives.................................................................................................................81
5 Products and Markets...........................................................................................................83
5.1 Introduction.......................................................................................................................................83
5.2 Antiblocking Agents.........................................................................................................................83
5.3 Antimicrobials (Biocides).................................................................................................................85
5.3.1 Replacement of Arsenic Compounds.........................................................................................86
5.3.2 Biocides Containing Metal Atoms.............................................................................................87
5.3.3 Silver Compounds......................................................................................................................88
5.3.4 Permanence of Biocides.............................................................................................................88
5.3.5 SARS and MRSA......................................................................................................................89
5.4 Antioxidants......................................................................................................................................89
5.4.1 Protection Against High Temperatures......................................................................................89
5.4.2 Permanence................................................................................................................................90
5.4.3 Other Products...........................................................................................................................91
5.4.4 New Technology........................................................................................................................91
5.5 Antistatic, Electromagnetic Interference (EMI) and Radio Frequency Interference (RFI) Agents...92
5.5.1 Current Sources of Demand.......................................................................................................92
5.5.2 Technical Objectives..................................................................................................................92
5.5.3 Types of Blooming Antistatic Agent.........................................................................................92
5.5.4 Food Contact..............................................................................................................................92
5.5.5 Carbon........................................................................................................................................93
5.5.6 Other Fillers...............................................................................................................................94
5.5.7 New Types.................................................................................................................................94
5.6 Blowing Agents................................................................................................................................95
5.6.1 Demand for Foamed Plastics.....................................................................................................95
5.6.2 Changes in the Types of Physical Blowing Agents Used..........................................................96
5.6.3 Chemical Blowing Agents.........................................................................................................99
5.6.4 High Temperature Blowing Agents...........................................................................................99
5.7 Clarifying and Nucleating Agents...................................................................................................100
5.7.1 Competition Between PP and Other Polymers........................................................................100
5.7.2 Nucleating Agents....................................................................................................................101
5.8 Compatibilisers...............................................................................................................................102
5.8.1 Wood-Plastics Compatibilisers................................................................................................103
5.8.2 Compatibilisers For Mixed Waste...........................................................................................104
5.8.3 Other Developments................................................................................................................104
5.9 Fillers..............................................................................................................................................104
5.9.1 Applications.............................................................................................................................105
5.9.2 Calcium Carbonate...................................................................................................................105
5.9.3 Talc..........................................................................................................................................106
5.9.4 Carbon......................................................................................................................................106
5.9.5 Other Fillers.............................................................................................................................107
5.9.6 Nanofillers...............................................................................................................................109
5.10 Flame Retardants and Smoke Suppressants..................................................................................112
5.10.1 Introduction............................................................................................................................112
5.10.2 Regulation..............................................................................................................................112
5.10.3 Side Effects of FRs................................................................................................................113
5.10.4 Metal Hydroxides...................................................................................................................113
5.10.5 Brominated FRs.....................................................................................................................114
5.10.6 Chlorinated FRs.....................................................................................................................116
5.10.7 Antimony Compounds...........................................................................................................117
5.10.8 Phosphorus FRs.....................................................................................................................118
5.10.9 Red Phosphorus FRs.............................................................................................................119
5.10.10 Nitrogen-based FRs, With or Without Phosphorus Compounds.........................................119
5.10.11 Borate FRs...........................................................................................................................120
5.10.12 Expandable Graphite...........................................................................................................121
5.10.13 Silicone FRs........................................................................................................................121
5.10.14 New Ideas............................................................................................................................121
5.10.15 FRs for Foam......................................................................................................................122
5.10.16 Smoke Suppressants............................................................................................................122
5.11 Heat Stabilisers............................................................................................................................123
5.11.1 Phase Out of Lead Compounds.............................................................................................123
5.11.2 Mixed Metal Soaps...............................................................................................................123
5.11.3 Volatile Emissions................................................................................................................124
5.11.4 Organic Stabilisers................................................................................................................125
5.11.5 Tin Compounds.....................................................................................................................126
5.11.6 Co-stabilisers.........................................................................................................................127
5.12 Impact Modifiers..........................................................................................................................127
5.12.1 Achieving a Balance of Properties........................................................................................127
5.12.2 Acrylic Modifiers..................................................................................................................128
5.12.3 Chlorinated Polyethylene.................................................................................................129
5.12.4 Low Temperature Impact Strength........................................................................................129
5.12.5 Inorganic Additives...............................................................................................................129
5.12.6 Modifying Thermosets..........................................................................................................129
5.13 Lubricants and Process Aids........................................................................................................130
5.13.1 Lubricants..............................................................................................................................130
5.13.2 Process Aids..........................................................................................................................131
5.13.3 Inorganic Process Aids..........................................................................................................133
5.14 Plasticisers....................................................................................................................................133
5.14.1 Markets..................................................................................................................................133
5.14.2 Health and Safety Controversy.............................................................................................134
5.14.3 Medical Applications............................................................................................................135
5.14.4 Minimising Plasticiser Loss..................................................................................................135
5.14.5 Other Alternatives to Phthalates............................................................................................136
5.14.6 Plasticisers for Biodegradable Plastics..................................................................................137
5.14.7 Medium Chain Length Chlorinated Paraffins.......................................................................137
5.15 Ultraviolet and Visible Light Stabilisers......................................................................................138
5.15.1 Polyolefin Stabilisation.........................................................................................................138
5.15.2 Interference Between Additives............................................................................................138
5.15.3 Minimising Stabiliser Loss....................................................................................................139
5.15.4 Protecting Contents of Packaging.........................................................................................139
5.15.5 Agricultural Film...................................................................................................................139
5.15.6 Other Developments..............................................................................................................141
6 Supply and Demand.............................................................................................................143
6.1 Trends Affecting the Demand for Additives for Plastics...............................................................143
6.2 The Global Economic Situation and its Effect on Plastics Sales....................................................143
6.3 Factors Influencing Additive Sales When Plastic Sales Remain Constant....................................144
6.4 Consumption of Plastics and the Implications for Additives.........................................................145
6.4.1 Trends in the Consumption of PVC........................................................................................146
6.4.2 Polyolefins..............................................................................................................................146
6.4.3 Other Polymers.......................................................................................................................147
6.5 Consumption of Additives.............................................................................................................149
6.5.1 Recent Estimates of Market Size............................................................................................149
6.5.2 Future Prospects......................................................................................................................151
6.5.2.1 Antimicrobials..................................................................................................................152
6.5.2.2 Antioxidants.....................................................................................................................152
6.5.2.3 Antistatic Agents..............................................................................................................152
6.5.2.4 Blowing Agents................................................................................................................153
6.5.2.5 Fillers...............................................................................................................................153
6.5.2.6 Coupling Agents...............................................................................................................154
6.5.2.7 Nanofillers........................................................................................................................154
6.5.2.8 Flame Retardants..............................................................................................................155
6.5.2.9 Heat Stabilisers.................................................................................................................157
6.5.2.10 Impact Modifiers.............................................................................................................158
6.5.2.11 Lubricants.......................................................................................................................159
6.5.2.12 Plasticisers......................................................................................................................159
6.5.2.13 Light Stabilisers..............................................................................................................160
6.6 Additive Suppliers..........................................................................................................................162
6.6.1 Types of Company...................................................................................................................162
6.6.1.1 Illustrative List of Suppliers..............................................................................................163
6.6.2 Suppliers of Specific Additives................................................................................................163
6.6.2.1 Antiblocking Agents.........................................................................................................163
6.6.2.2 Antimicrobial Agents........................................................................................................164
6.6.2.3 Antioxidants......................................................................................................................164
6.6.2.4 Antistatic Agents...............................................................................................................164
6.6.2 5 Blowing Agents................................................................................................................164
6.6.2.6 Clarifying and Nucleating Agents.....................................................................................164
6.6.2.7 Compatibilisers.................................................................................................................164
6.6.2.8 Fillers and Nanofillers.......................................................................................................164
6.6.2.9 Flame Retardants..............................................................................................................166
6.6.2.9 Heat Stabilisers.................................................................................................................167
6.6.2.10 Impact Modifiers.............................................................................................................167
6.6.2.11 Lubricants and Process Aids...........................................................................................167
6.6.2.12 Plasticisers......................................................................................................................167
6.6.2.13 UV and Light Stabilisers.................................................................................................167
6.6.3 Some Specific Additive Suppliers...........................................................................................167
6.6.3.1 Akcros Chemicals (Headquarters: Eccles, Manchester, UK)............................................168
6.6.3.2 Albemarle (Headquarters: Richmond, VA, USA).............................................................168
6.6.3.3 Baerlocher (Headquarters: Unterschleissheim, near Munich, Germany)..........................168
6.6.3.4 Chemson AG (Headquarters: Arnoldstein, Austria).........................................................169
6.6.3.5 Ciba Specialty Chemicals (Headquarters: Basel, Switzerland).........................................169
6.6.3.6 Clariant (Headquarters: Muttenz, Switzerland).................................................................169
6.6.3.7 Crompton Corp. (Headquarters: Middlebury, CT, USA)..................................................170
6.6.3.8 Cytec Industries (Headquarters: West Paterson, NJ, USA)..............................................171
6.6.3.9 Dead Sea Bromine Group (Headquarters: Beer Sheva, Israel).........................................171
6.6.3.10 Dover (Headquarters: Dover, OH, USA)........................................................................171
6.6.3.11 Dyneon (Headquarters: Oakdale, MN, USA).................................................................171
6.6.3.12 Eliokem (Headquarters: Villejust, Courtaboeuf, France)................................................172
6.6.3.13 Ferro (Headquarters: Cleveland, OH, USA)...................................................................172
6.6.3.14 Great Lakes Chemical Corporation (Headquarters: Indianapolis, IN, USA)..................172
6.6.3.15 Rohm and Haas (Headquarters: Philadelphia, PA, USA)...............................................173
6.6.4 Reorganisations, Mergers and Acquisitions.............................................................................173
6.6.4.1 Mergers and Acquisitions.................................................................................................174
6.6.5 Co-operative Agreements........................................................................................................176
6.6.6 Prices........................................................................................................................................178
6.6.7 Profitability..............................................................................................................................179
6.7 New Plant Capacity........................................................................................................................181
7 Environmental and Regulatory Developments..................................................................185
7.1 REACH...........................................................................................................................................185
7.2 End-of-Life Disposal......................................................................................................................186
7.3 Concerns About Specific Substances..............................................................................................187
7.3.1 Phenols.....................................................................................................................................187
7.3.2 Phthalates.................................................................................................................................187
7.3.3 Heavy Metals...........................................................................................................................188
7.3.4 PVC..........................................................................................................................................189
7.3.5 Nanofillers...............................................................................................................................189
7.4 Biocides..........................................................................................................................................189
7.5 Flame Retardants............................................................................................................................189
7.6 Food Contact Legislation................................................................................................................190
Glossary of Abbreviations and Acronyms............................................................................193
Appendix – Some Sources of Further Information..............................................................197