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Published by ChemTec Publishing

38 Earswick Drive, Toronto, Ontario M1E 1C6, Canada

ISBN 978-1-895198-97-3 (hard copy); 978-1-927885-16-1 (epub)

Cover design: Anita Wypych

All rights reserved. No part of this publication may be reproduced, stored or transmitted in any form or by any means without written permission of copyright owner. No responsibility is assumed by the Author and the Publisher for any injury or/and damage to persons or properties as a matter of products liability, negligence, use, or operation of any methods, product ideas, or instructions published or suggested in this book.

Library and Archives Canada Cataloguing in Publication

Handbook of plasticizers / George Wypych, editor. -- 3rd edition.

Includes bibliographical references and index.

Issued in print and electronic formats.

ISBN 978-1-895198-97-3 (hardcover).--ISBN 978-1-927885-16-1 (PDF)

1. Plasticizers--Handbooks, manuals, etc. I. Wypych, George, editor

II. Title: Plasticizers.

TP247.7.H33 2017668.4'11

C2016-907344-0 C2016-907345-9

Printed in Australia, United Kingdom and United States of America

10.17 Plasticizer effect on contact with other materials

10.18 Influence of plasticizers on swelling of crosslinked elastomers

Vasiliy V. Tereshatov, Valery Yu. Senichev

10.18.1 Change of elastic properties of elastomers on swelling in liquids of different polarity 286

10.18.2 Influence of swelling on viscoelastic properties of crosslinked amorphous elastomers 291

10.18.3 Influence of swelling on tensile strength and critical strain of elastic materials 292

10.19 The swelling of nano-heterogeneous coatings in plasticizers

Vasiliy V. Tereshatov, Valery Yu. Senichev, Marina A. Makarova

10.20 Peculiarities of plasticization of polyurethanes by binary plasticizers

Vasiliy V. Tereshatov, Valery Yu. Senichev, Vladimir N. Strel'nikov, Elsa N. Tereshatova, Marina A. Makarova

10.21 Stability of physico-mechanical properties of plasticized polyetherurethane in a humid medium

M. A. Makarova, V. V. Tereshatov, A. I .Slobodinyuk, V. Yu. Senichev, Zh. A. Vnutskikh

10.22

V. V. Tereshatov, V. Yu. Senichev

V. V. Tereshatov, Zh. A. Vnutskikh, V. Yu. Senichev, A. I. Slobodinyuk

Vasiliy V. Tereshatov, Valery Yu. Senichev, Elsa N. Tereshatova, Marina A. Makarova

William R.

All these examples from past show that new technological developments were dictated by requirements of processing or a need to soften material. There was little exchange of information during these early technological developments.

1.2 EXPECTATIONS FROM PLASTICIZERS

A large number of applications of plasticizers are driven by even larger number of expectations of improvement of original properties of polymers and products into which these polymers are formulated with the use of plasticizers. A list below shows the most important expectations of plasticizer influence on the development of desired properties:

•decrease the glass transition temperature of the polymer the most typical reason for plasticizer use. This expectation is frequently related to and explained by mechanism of plasticizer action

•making material more flexible the influence related to the changes in polymer structure frequently measured by decrease in glass transition temperature

•increased elongation and decreased tensile strength are typical results from glass transition decrease on addition of plasticizers, although in some polymers or products specific results are also observed, especially when the plasticizer concentration in material varies

•decrease in ductility of materials and improvement of its impact resistance

•low temperature properties of many materials are improved by different types and concentrations of plasticizers

•viscosity control plasticizers are low viscosity liquids, which reduce viscosity of polymer solutions and improve workability of complex industrial formulations. There are numerous cases reported wherein viscosity also increases due to polymer solubility in the plasticizer (e.g., PVC plastisols) or interaction with other liquid components present in formulation (e.g., water in water-based products in which formation of water-in-oil emulsion causes viscosity to increase)

•modification of rheological properties most products, especially products having high polymer content are non-Newtonian liquids. Their apparent viscosity is a function of shear rate. This, in turn, causes a complex rheological behavior

•effect on chemical reactivity lower viscosity makes molecules to move and thus interact and chemically react. At the same time, addition of plasticizer dilutes reacting components, making plasticizer influence on reactivity a composite influence of both dilution and mobility

•decrease of the temperature of dissolution gelation temperature, coalescence temperature are the most frequently affected parameters but many other effects are discovered in various products (e.g., improved smoothness of coating, decreased temperature of adhesive application, etc.)

•effect on processability. In addition to lowering fusion and gelation temperatures, plasticizers lower melting temperature. Addition of plasticizers frequently opens new possibilities of material processing (lower degradation rate, allows for processing on different types of equipment, reduces pressure of extrusion, etc.). Mixing time is reduced in the presence of plasticizers

•modification of interaction with water by products containing plasticizers. Hydrophobic plasticizers reduce water sensitivity of some products and hydrophilic plasticizers increase water absorption, which may increase curing rate in

water-reactive systems, decrease skin time, decrease or increase tackiness, cause swelling, etc.

•assist dispersion of liquid and solid additives (liquid additives especially benefit if they are easily soluble in a plasticizer; predispersion of fillers, pigments and solubilization of other liquid additives improves their incorporation)

•effect on electric conductivity depends on electric properties of plasticizers which may act as additional conductors or insulators

•fire behavior most plasticizers generally increase susceptibility of material to burn, drip during burning, and produce smoke but some plasticizers (phosphates and chloroparaffins) reduce burneability of materials and smoke production

•resistance to biological degradation most plasticizers increase potential of biological attack and some products containing plasticizers must be protected by biocides. In biodegradable materials, selected plasticizers are deliberately added to increase biodegradation rate

•improvement of sound blocking and vibration damping properties

•improvement of optical clarity by homogenizing system components

•effect on volatilization of product components. Plasticizers generally reduce amount of VOC by helping to replace some solvents but slow diffusion and evaporation also cause release of liquid component leading to the so-called fogging and indoor pollution

•effect on crystallization is generally towards reduction of crystallinity but in many cases crystallizing ability can be substantially increased by increased mobility of crystallizing polymer chains or their segments

•increased compatibility between additives, polymer with additives, and polymers in blends

•improvement of photorefractive properties of some compositions

•migration of low molecular substances into the product and out of the product is increased. This is especially important in pharmaceutical products in which coating containing a plasticizer regulates drug release rate but it is also essential in textile dyeing and many other applications

•increase in gas permeability

In addition, to the above listed expectations based on physical chemical properties of plasticizers and their effect on other materials, namely polymers, we also have several socio-political factors and expectations, which are the trademark of our present times. These include:

•renewable resources (as a source of raw materials used in the production of plasticizers)

•biodegradable (up a certain degree of biodegradability, considering that it does not harm either performance or lifetime of the final products)

•non-phthalate (even though some of the so-called “non-phthalate plasticizers” are also phthalates but tere- rather than ortho- or cyclohexane derivatives, similar in structure to ortho-phthalates)

Several chapters (17-21) discuss specificity of these issues, which are frequently based on legitimate concerns, but sometimes are based on campaigns by various consumer groups. Some of these concerns have no foundation in science but were so widely dis-

Plasticizer Types

2.1 INTRODUCTION

Table 2.1 shows consumption of plastics additives by type in the USA in 1999.1

Table 2.1. Consumption of plastics additives in 1999 in the USA by type. [Data from Kattas L N, Gastrock F, The Individual Additives Dynamics of Change. Retec 2000.]

Plasticizers are by far the most common additives. They are also less expensive than other additives used in the polymers processing and applications. Consumption of additives in Europe is given in the table 2.2.

Table 2.2. Consumption of additives in 2006 Europe by type. [Data from Mueller, S. Plastic Additives The European Market in the Global Envirionment. Addcon 2007.]

Table 2.6 compares shares of different phthalates in 1990s in European Union and global shares of different phthalates in 2008.

Table 2.6. Shares in percents of different phthalates. [Data from Peijnenburg W J G M, Phthalates in Encyclopedia of Ecology, Elsevier, 2008, p. 2733-38 and Bisig M D, Plasticizer Update, SPI 20th Vinyl Compounding Conference, July 19-21, 2009.]

Plasticizer

In the past production, the largest use among phthalates belonged to di-(2-ethylhexyl) phthalate (51%), diisodecyl phthalate (21%), and diisononyl phthalate (11%). This varied from country to country. In Russia, which manufactured 300,000 tons of plasticizers (Europe manufactured over 1,300,000 tons of various plasticizers),6,8-9 di(2-ethylhexyl) phthalate constituted 65.1% of total production and the total phthalates constituted 98% of all plasticizers.4 The use of plasticizers changed recently because of reported findings and regulations (see Chapters 18-21). Phthalates and some chloroparaffins are the most affected groups. Production of phthalic anhydride, which is principally used for production of phthalic esters, slightly decreased.10 Table 2.6 shows that the use of DOP was drastically reduced (it will be even more reduced if not for high consumption of DOP in China, where it constitutes 65% of the total plasticizer use).3 In Europe and the USA, DOP was replaced by longer chain phthalates and non-phthalate plasticizes.3

This may signalize that further changes in the produced types of plasticizers are to be expected. Implication of plasticizers in health and safety issues caused some market analysts and manufacturers to report additives growth with the exclusion of plasticizers11 to display a higher growth. The plasticizers’ growth until 2006 was expected to be 2.7%, which is at about an average of additives’ growth.7 Now, plasticizer growth is forecasted at 3-4%. The demand on plasticizers is driven by the growth in PVC market (4-5%).3 There is no shortage of plasticizer capacity. About 100 producers manufacture plasticizers and their capacity is utilized in 70%.3 Plasticizers or usually produced locally but there is some importation of alcohols used for plasticizer production.3 In the future production, still further changes can be expected, mainly because of the global economy and uniformity of regulations. Goods exported from China will need to use similar set of plasticizers as goods manufactured in North America and Europe. In addition, many products will make use of non-phthalate plasticizers, and biodegradable plasticizers and bioplasticizers. In the next section, plasticizers are discussed in thirty-two sections (some sections are still divided into subsections). Thirty sections are based on chemical similarity and two are based on applications (explosives and cementitious products) because chemical compositions of these plasticizers are very different than the plasticizers used in other markets. The discussion in the next section is designed to find common features of plasticizers within the same chemical group and to provide information that is suitable for comparison of properties of plasticizers from different chemical groups. This section does not contain information on specific plasticizers. Information on specific plasticizers is included in a special electronic publication on CD-ROM.12 The first edition of CD-ROM database published in 2004 contained specific data on over 1272 product including commercial plasticizers (1215) as supplied by manufacturers as well as some data on chemical compounds

TLV-TWA 8 h, OSHA, mg/m3 not determined

NIOSH-IDHL, mg/m3 not determined

Figure 2.2. Effect of molecular weight of adipates on their Hildebrand solubility parameters.

Esters of adipic acid constitute an important group of plasticizers. Two major applications of these plasticizers include products which perform at low temperatures and cling film.

A few comparative studies14-16 on adipates and some other plasticizers and data available on commercial products help in generating information on the effect of chemical structure on physical properties of plasticizers. Figure 2.1 shows that melting temperature (and freezing temperature) decreases with molecular weight. Boiling point of adipates increases with increase in their molecular weight. These data show benefits of increasing molecular weight of alcohol in the plasticizer considering that these plasticizers are expected to be permanent additives that decrease temperature of service of plasticized articles. Figure 2.2 shows that the solubility parameter slightly decreases with an increase in molecular weight of a plasticizer. Similarly, dielectric constant of adipates decreases with

Figure 2.1. Effect of molecular