Plastics additives : a Rapra market report

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 1.6 Terminology...................................................................................................................................... 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 – CaCO3 ..............................................................................................44 4.8.4.2 Carbon................................................................................................................................45 4.8.4.3 Glass...................................................................................................................................464.8.4.4 Kaolin................................................................................................................................ 46 4.8.4.5 Mica – KMg (AlSi3O10)(OH)2............................................................................................ 47 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 – Mg3Si4O10(OH)2 ...................................................................................................... 47 4.8.4.7 Wollastonite – CaSiO3 ....................................................................................................... 47 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................................................................................................................................ 764.14 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 ...........................................................................................................1175.10.8 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.......................................................................................................