A Concise Introduction to Additives for The r m o p I as t i c Po I y m e rs Johannes Karl Fink Montanuniversitat Leoben, Austria S/c r ive n er @WILEY This Page Intentionally Left Blank A Concise Introduction to Additives for Thermoplastic Polymers Scrivener Publishing 3 Winter Street, Suite 3 Salem, MA 01970 Scrivener Publishing Collections Editors James E. R. Couper Rafiq Islam Pradip Khaladkar Norman Lieberman Peter Martin W. Kent Muhlbauer Andrew Y. C. Nee S. A. Sherif James G. Speight Richard Erdlac Publishers at Scrivener Martin Scrivener (rnartin@scrivenerpublishing.com) Phillip Carmical (pcarmical@scrivenerpublishing.com) A Concise Introduction to Additives for The r m o p I as t i c Po I y m e rs Johannes Karl Fink Montanuniversitat Leoben, Austria S/c r ive n er @WILEY Copyright Q 2010 by Scrivener Publishing, LLC. All rights reserved. Co-published by John Wiley & Sons, Inc., Hoboken, New Jersey and Scrivener Publishing, LLC, Salem, Massachusetts. 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ISBN 978-0-470-60955-2 Printed in the United States of America. 10987654321 Contents Preface xiii 1 Introduction 1.1 Classification References 2 Plasticizers 2.1 Principle of Action 2.2 Principle of Selection 2.3 Characterization 2.4 Risks and Drawbacks 2.4.1 Leaching 2.4.2 Inherent Toxicity 2.5 Classes of Plasticizers 2.5.1 Phthalate Plasticizers 2.5.2 Cyclohexanoic Diesters 2.5.3 Phophate Plasticizers 2.5.4 Aliphatic Esters 2.5.5 Polymeric Plasticizers 2.5.6 Ionic Liquids 2.6 Specific Examples of Application 2.6.1 Heat Shrinkable Films 2.6.2 Adhesive Compositions 2.6.3 Interlayer Films for Safety Glasses 2.6.4 Electrolyte Membranes 2.6.5 Porous Electrodes 2.6.6 Biodegradable Polymers 2.6.7 Plasticizers for Energetic Polymers References 1 1 3 5 6 6 7 8 8 9 9 9 12 13 13 14 15 16 16 17 17 18 18 19 20 21 V vi Contents 3 Fillers 3.1 Surface Modification 3.1.1 Siloxanes 3.1.2 Dispersion and Coupling Additives 3.2 Special Applications 3.2.1 Flame Retardant Fillers 3.2.2 Conductive Fillers 3.2.3 Solder Precoated Fillers 3.2.4 Nan0 Clays 3.2.5 Mixed Matrix Membranes References 4 Colorants 4.1 Physics Behind a Color 4.1.1 Human Eye 4.1.2 Tristimulus Values 4.1.3 Color Spaces 4.2 Color Index 4.3 Test Standards 4.4 Pigments 4.5 Organic Colorants References 5 Optical Brighterners 5.1 Basic Principles 5.2 Measurement 5.3 Inorganic Brighteners 5.4 Organic Optical Brighteners 5.4.1 Reactive Optical Brighteners 5.4.2 Melt Extrusion 5.4.3 Photographic Supports References 6 Antimicrobial Additives 6.1 Modes of Action 6.2 Plasticizers 6.1.1 Types of Irritations 25 25 25 25 29 29 30 32 33 34 34 37 37 37 37 39 40 41 43 43 47 49 50 51 52 52 52 54 55 56 59 59 60 60 Contents vii 6.3 Special Formulations 6.3.1 Contact Lenses 6.3.2 Food Packaging 6.3.3 Polymers with Inherent Antimicrobial Properties References 7 Flame Retardants 7.1 Mechanisms of Flame Retardants 7.2 Smoke Suppressants 7.3 Admixed Additives 7.4 Bonded Additives References 7.1.1 Flame Cooling of Halogens 7.4.1 Examples of Polymers 8 Lubricants 8.1 Principle of Action 8.2 Methods of Incorporation 8.2.1 Conventional Method 8.2.2 Separate Delivery of the Lubricant 8.3 Types of Lubricants 8.3.1 Alcohols 8.3.2 Fatty Acids, Esters and Amides 8.3.3 Waxes 8.3.4 Polymeric Lubricants 8.4.1 PVC 8.4.2 Chlorinated PVC 8.4.3 Electically Conductive Polymers 8.4 Special Applications References 9 Antistatic Additives 9.1 Types of Additives 9.2 Areas of Application 9.3 Additives in Detail 9.3.1 Conventional Additives 9.3.2 Polymeric Additives 65 65 66 67 68 71 71 71 73 74 77 77 83 87 87 88 88 88 89 89 90 90 91 91 91 91 92 92 95 95 96 98 98 100 viii Contents 9.3.3 External Antistatic Additives 9.3.4 Intrinsically Antistatic Compositions 9.3.5 Conductive Fillers References 10 Slip Agents 10.1 Basic Principles of Action 10.2 Compounds 10.3 Special Formulations 10.3.1 Poly(ethy1ene terephthalate) 10.3.2 Formulations for Poly(ethy1ene) References 11 Surface Improvers 11.1 Additives 11.1.1 Fluorocarbon Compounds 11.1.2 Acrylics 11.1.3 Modified Pigments 11.1.4 Organic Salts References 12 Nucleating Agents 12.1 Crystalline Polymers 12.1.1 Crystal Structures 12.1.2 Modification of Properties by Crystallinity 12.2 Experimental Methods 12.2.1 Nucleation Technologies 12.2.2 Characterization of Polymer Crystallization 12.3 Classes of Nucleating Agents 12.3.1 Inorganic Nucleating Agents 12.3.2 Sorbitol Compounds 12.3.3 Phosphates 12.3.4 Carbon Nanotubes 12.3.5 Coupled Nucleating Agents 101 101 101 104 107 107 109 110 110 111 111 113 114 114 114 115 116 116 119 120 120 120 121 121 121 122 122 123 124 124 124 [...]... for Safety Glasses Poly(viny1acetal) (PVAL)based formulations are used as interlayer films for laminated glass, as binders for ceramic forming, as binder for ink or paint and as thermally processable photographic materials (36) Important issues are improved waterproofness and the compatibility with a plasticizer For example, when laminate glass is exposed to high humidity for a long time, it may face... for Thermoplastics Table 1.1:Classification of Additives for Polymers Type Usage for Antioxidant Light stabilizer Acid scavenger Lubricant Processing aid Antiblocking Slip additive Antifogging additive Antistatic additive Antimicrobial agent Flame retardant Blowing agent Modifier Controlled degradation additive Crosslinker Colorant Filler Reinforcement Optical whitener Coupling agent Nucleating agent... into the polymeric matrix, but they will become chemically reactive when they are starting with their protective action The same is mostly true for a flame retardant, but this not a general rule In addition, there is a basic difference between additives for thermoplastic material and additives for thermosetting resins Likewise, a curing agent and an accelerator may be considered as an additive However,... evaporation and degradation of plasticizers have been developed, with the aim of formulating long-lasting flexible plastics and minimizing the ultimate environmental impact of these chemicals Also, fire-retardant plasticizers and plasticizers for use in biodegradable plastics have been developed (2) Several monographs have been prepared with regard to the topic (3-7) Plasticizers are used for several... seems to be a good alternative to phthalates in flexible toys due to its ease of processing, final product performance, low toxicity and fast biodegradation Toxicity tests showed a low acute toxicity and no evidence of reproductive toxicity (2) 2.5 Classes of Plasticizers Plasticizers can be classified according to their chemical structure as shown in Table 2.1 Plasticizers may be also classified into... Flame retardant, not suitable for food applications Phosphates Low viscosity, high gelling capacity, relatively volatile Adipates and extractable, superior low temperature flexibility Good low temperature flexibility, less water sensitive Azelates than adipates Good low temperature performance Sebacates Very low volatility, highly resistant to extraction and Polymers migration Trimellitates Low volatility,... Plasticizers Phosphates have been long known as PVC plasticizers Phosphate based plasticizers are summarized in Table 2.4 Most common is tricresyl phosphate Commercial tricresyl phosphate is a mixture of the ortho, meta, and para isomers Phosphate based plasticizers impart flame retardant properties The flame retardant action arises because they are capable to form polyphosphoric acids by condensation... summarize a few examples of the application and usages of plasticizers in polymeric materials Among all kinds of additives, plasticizers are the most important class of additives for polymers The global demand for plasticizers was 4,647 thousand metric tons in 2000 (31) According to another study, in 2007, the global plastic additives industry grew to 12.2 million tomes This is justified by the rapidly... (multipurpose action), or Commercial importance The most comprehensive classification is the classification with respect to its field of application This kind of classification is summarized in Table 1.1 Additives can be subdivided into chemically inert additives and chemically reactive additives For example, plasticizers, or lubricants are not chemically reactive On the other hand, antioxidants 1 2 Additives for. .. that water may penetrate into it through its edges and it may whiten as its compatibility with plasticizer is not good Special formulations have been developed to overcome these drawbacks When the PVAL is used for interlayer films for laminated glass, a plasticizer may be added to it A preferred plasticizer is triethylene 28 Additives for Thermoplastics glycol For ceramic green sheets, dioctyl phthalate . cants are not chemically reactive. On the other hand, antioxidants 1 2 Additives for Thermoplastics Table 1.1: Classification of Additives for Polymers Type Usage for Antioxidant. between additives for ther- moplastic material and additives for thermosetting resins. Likewise, a curing agent and an accelerator may be considered as an additive. However, these types of additives. teaching material on additives for thermoplastic polymers so I have tried to fill the gap. The goal of the book is to offer a general and concise introduction into plastics additives. For students