Handbook of Plasticizers

George Wypych

• Publisher: ChemTec Publishing
• Year: 2013
• Print ISBN: 9781895198508
• eBook ISBN: 9781455730025
• Edition: 2
• Topic: Physical Sciences
• Subtopic: Industrial & Technical Chemistry

The second edition of the Handbook of Plasticizers thoroughly reviews information currently available in open literature, such as published scientific papers, information from plasticizer manufacturers, and patent literature.Plasticizers are used in so many products that every library should have this reference source of information on plasticizers readily available for its readers. This book should be used in conjunction with Plasticizer Database, which gives information on the present status and properties of industrial and research plasticizers.The book covers the uses, advantages, and disadvantages of plasticizers, historical and theoretical background, their effects on process conditions, and health, safety, and environmental issues.- The most comprehensive reference work available, covering the properties and applications of plasticizers- Combine scientific background with extensive data and practical engineering techniques- Contains information from the most recent sources and updated information

1

INTRODUCTION

This chapter contains brief summaries of

• historical developments of plasticizers

• expectations from plasticizers

• definitions

• classification

1.1 HISTORICAL DEVELOPMENTS

Many anonymous inventors were the first in their geographic areas to use water as the first plasticizer. Pottery was most likely the first product which was produced with a plasticizer. The short history of pottery on various continents is presented in Table 1.1.

Table 1.1

Short history of pottery

Period	Events
24,000 BC	earliest known clay figurines of fertility images of women found in Europe
7,500 BC	first fired pottery produced in Japan in Jomon period
7,000 BC	the oldest known pottery available in Heiseikan Building of the Tokyo National Museum
5,500 BC	houses are built in Jericho which have a stone foundation, and half meter thick walls built from sun-dried bricks
5,000 BC	oldest pottery in Schleswig-Holstein, Europe
5,000–3,000 BC	Valdivia pottery in Ecuador. So-called Venus of Valdivia resembles Venus of Jomon from Tanabatake, Japan. Each are made from local clays
3,500 BC	pottery produced by neolithic cultures in Tigris and Euphrates river valleys, Middle East
3,150 BC	oldest pottery in Maluku, Indonesia
3,000–2,600 BC	bowls, plates, and platters were produced in Egypt
2,700–2,200 BC	potters wheel was introduced in Egypt
1,600–1,100 BC	pre-Olmec pottery made in Mexico to Honduras, Central America
1,000 BC	oldest pottery found in Colombia, South America
900–500 BC	Etruscan pottery in North-west Italy
550 BC	beginning of potter’s art in Greece

The above chronology of events shows that the development of technology was not evenly spread throughout the world in spite of the fact that some more developed locations were close to each other but some political barriers did not allow for technology exchange. On the other hand, technology could also travel very far for example as seen in Valdivia, Ecuador which may have gotten technology from Japan.

Painting is another example of early application of plasticizers. The following chronological developments show how technology was modified until there was a need to use plasticizers (Table 1.2).

Table 1.2

Technological developments in painting

Period	Event
30,000 BC	imprints of hands (Lascaux Caves in France). In this early period two methods were used: hands were dipped into fluid colorant or surface was coated with greasy material and pigment blown through a tube. Animal fat, urine, blood, eggs, or milk-casein were used as organic binders or dispersants of pigments
6,000 BC	development of secco technique which is painting on dry wall surface with pigment and binder (neolithic period)
2,500 BC	in Egypt arriccio layer to smooth surface and intonaco layer of gypsum plaster form surface on which pigment in binder are applied. Binder is usually gum arabic (referred to as tempera binder) plasticized with honey

Ancient Egypt is also credited with the use of plasticizers to preserve skin. This was practiced in the mummification process in which the body was dried which made dry skin very fragile and thus a mixture of cedar oil, wax, natron, and gum was rubbed to soften the skin and prevent it from cracking.

Preparation of nitrocellulose by Shoenbein and Bottger in 1846 is generally considered as the beginning of the use of plasticizers although plasticizers were not mentioned in their patent and later related discoveries.¹ The first US Patent, which specifically mentioned plasticizer was obtained by Turkington in 1924 for high boiling aldehyde used to plasticize phenol resin.² The second US Patent, which mentioned plasticizers was obtained in 1924 by Lindsay, who used aromatic phosphates to plasticize celluloid.³ The next patents were issued in 1930s for plasticization of zein, gelatin, cellulose acetate, and vinylchloride/vinylacetate copolymers. And these included many known today plasticizers, such as phthalates and phosphates. It is well documented that German scientist Friedrich Klatte was the first to receive patent for PVC in 1913. The patent also included plasticization with many known plasticizers.⁴ 1930s and 1940s were the golden age of plasticizers synthesis and application, whereas 2000–2010 can be credited with elimination of many previously important plasticizers.

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 improve...

Table of contents

• Cover image
• Title page
• Table of Contents
• Copyright
• 1. INTRODUCTION
• 2. PLASTICIZER TYPES
• 3. TYPICAL METHODS OF QUALITY CONTROL OF PLASTICIZERS
• 4. TRANSPORTATION AND STORAGE
• 5. MECHANISMS OF PLASTICIZERS ACTION
• 6. THEORIES OF COMPATIBILITY
• 7. PLASTICIZER MOTION AND DIFFUSION
• 8. EFFECT OF PLASTICIZERS ON OTHER COMPONENTS OF FORMULATION
• 9. PLASTICIZATION STEPS
• 10. EFFECT OF PLASTICIZERS ON PROPERTIES OF PLASTICIZED MATERIALS
• 11. PLASTICIZERS USE AND SELECTION FOR SPECIFIC POLYMERS
• 12. PLASTICIZERS IN POLYMER BLENDS
• 13. PLASTICIZERS IN VARIOUS INDUSTRIAL PRODUCTS
• 14. PLASTICIZERS IN VARIOUS PROCESSING METHODS
• 15. SPECIALIZED ANALYTICAL METHODS IN PLASTICIZER TESTING
• 16. MATHEMATICAL MODELLING IN APPLICATION TO PLASTICIZERS
• 17. HEALTH AND SAFETY ISSUES WITH PLASTICIZERS AND PLASTICIZED MATERIALS
• 18. THE ENVIRONMENTAL FATE OF PLASTICIZERS
• 19. REGULATIONS AND DATA
• 20. PERSONAL PROTECTION
• 21. PLASTICIZER RECOVERY & RECYCLING
• INDEX