Plastic Plasticisation

A further account of plastics, plasticisers, PVC and connected health issues is presented in Chapter 5. 

Figure 7.9 SEM images of cross sections of soy plastic sheets plasticized with different amounts of acetamide.Liu, D. and L. Zhang Structure and properties of soy protein plastics plasticised with acetamide. Macromolecular Materials and Engineering 2006, 291, 820-828. Copyright Wiley-VCH Verlag GmbH Co. KGaA. Reproduced with permission.

Solubility Parameters of Plastics, Plasticisers and Typical Solvents... 

The term plasticized (also spelt plasticised ) simply means that there is plasticizer (plasticiser) present in the injection molding material but, it does not mean that there are no other additives mixed in with the polyvinyl chloride resin (PVC). Additives are essential in PVC technology as without them the plastic is useless as it cannot be successfully processed. Some additives enhance the properties of the base PVC and permit its use in a wider range of applications. 

In the case of poly(vinyl chloride) plastics, the FWA is mixed dry with the PVC powder before processing or dissolved in the plasticising agent (see Vinyl polymers). Polystyrene, acrylonitrile—butadiene—styrene (ABS), and polyolefin granulates are powdered with FWA prior to extmsion (2,78) (see... 

D. F. Cadogan, Plasticisers N Consideration of Their Impact on Health and the Environment, Plasticizers Sector Group, CEFIC, Brussels, Belgium, 1992. 

Non-ionic surfactants used in detergents, paints, herbicides, pesticides and plastics. Breakdown products, such as nonylphenol and octylphenol, are found in sewage and industrial efffuents Products of combustion of many materials Widely used as plasticisers for PVC. Common environmental pollutants... 

RITCHIE, p. D. (Ed,), Plasticisers, Stabilisers, and Fillers, Iliffe (published for The Plastics Institute), London (1972)... 

It has been common practice to blend plasticisers with certain polymers since the early days of the plastics industry when Alexander Parkes introduced Parkesine. When they were first used their function was primarily to act as spacers between the polymer molecules. Less energy was therefore required for molecular bond rotation and polymers became capable of flow at temperatures below their decomposition temperature. It was subsequently found that plasticisers could serve two additional purposes, to lower the melt viscosity and to change physical properties of the product such as to increase softness and flexibility and decrease the cold flex temperature (a measure of the temperature below which the polymer compound loses its flexibility). 

In the rubber industry hydrocarbon oils are often used to reduce the softness and facilitate the processing of hydrocarbon rubbers. These appear to have a small interaction with the polymer but spacing effects predominate. Such materials are generally referred to as softeners. The rubber industry, like the plastics industry, commonly uses the term plasticisers to describe the phthalates, phosphates and sebacates which are more commonly used with the more polar rubbers. 

The very low density materials (VLDPEs) introduced in the mid-1980s are generally considered as alternatives to plasticised PVC (Chapter 12) and ethylene-vinyl acetate (EVA) plastics (see Chapter 11). They have no volatile or extractable plasticisers as in plasticised PVC nor do they have the odour or moulding problems associated with EVA. Whilst VLDPE materials can match the flexibility of EVA they also have better environmental stress cracking resistance, improved toughness and a higher softening point. 

The tonnage of plasticisers consumed each year exceeds the annual tonnage consumption of most plastics materials. Only PVC, the polyolefins, the styrene polymers, the aminoplastics and, possibly, the phenolics are used in large quantity. 

Whilst vinyl acetate is reluctant to copolymerise it is in fact usually used today in copolymers. Two of particular interest to the plastics industry are ethylene-vinyl acetate (Chapter 11) and vinyl chloride-vinyl acetate copolymers (Chapter 12). In surface coatings internal plasticisation to bring the Tg to below ambient temperatures and thus facilitate film forming is achieved by the use of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and dialkyl maleates and fumarates. 

In the late 1970s several developments occurred causing renewed interest in poly(ethylene terephthalate) as a plastics material. These included the development of a new mouldable grade by ICI (Melinar) and the development of a blow moulding technique to produce biaxially oriented PET bottles. In addition there appeared a glass-fibre filled, ionomer nucleated, dibenzoate plasticised material by Du Pont (Rynite) (see Chapter 26). 

Although acetylation thus renders the cellulosic structure soluble, cellulose acetate will still decompose below its softening point. It is thus necessary to compound cellulose acetate with plasticisers in order to obtain plastics materials of suitable flow properties. Other ingredients are also added at the same time. 

As a result of development work between the Battelle Institute in Frankfurt and a German candle-making company, Aetema, biodegradable cellulose acetate compounds have been available since 1991 from the Rhone-Poulenc subsidiary Tubize Plastics. They are marketed under the trade names Bioceta and Biocellat. The system is centred round the use of an additive which acts both as a plasticiser and a biodegrading agent, causing the cellulose ester to decompose within 6-24 months. 

Plastics materials may be produced from casein by plasticising with water, extrusion and then cross-linking with formaldehyde (formolisation). The resultant products have a pleasant horn-like texture and are useful for decorative purposes. The amount of casein produced has decreased since World War n but was still one of the preferred materials for use in the decorative button industry until quite recently. 

Plasticisers. Plasticisers are low molecular weight materials which alter the properties and forming characteristics of the plastic. An important example is the production of flexible grades of polyvinyl chloride by the use of plasticisers. 

Other factors which can affect impact behaviour are fabrication defects such as internal voids, inclusions and additives such as pigments, all of which can cause stress concentrations within the material. In addition, internal welds caused by the fusion of partially cooled melt fronts usually turn out to be areas of weakness. The environment may also affect impact behaviour. Plastics exposed to sunlight and weathering for prolonged periods tend to become embrittled due to degradation. Alternatively if the plastic is in the vicinity of a fluid which attacks it, then the crack initiation energy may be reduced. Some plastics are affected by very simple fluids e.g. domestic heating oils act as plasticisers for polyethylene. The effect which water can have on the impact behaviour of nylon is also spectacular as illustrated in Fig. 2.80. 

However, nowadays this type of machine is seldom used because it is considerably more complicated and more expensive than necessary. One area of application where it is still in use is for large mouldings because a large volume of plastic can be plasticised prior to injection using the primary cylinder plunger. 

Barrels and Heaters These are also similar to those in extruder machines. In recent years, vented barrels have become available to facilitate the moulding of water sensitive plastics without the need for pre-drying. Water sensitivity in plastics can take several forms. If the plastic absorbs water then dimensional changes will occur, just as with wood or paper. The plastic will also be plasticised by the water so that there will be property changes such as a reduction in modulus and an increase in toughness. All these effects produced by water absorption are reversible. 

Plasticised amorphous thermoplastics Certain plastics may be mixed with high-boiling low-volatility liquids to give products of lower T. The most important example occurs with p.v.c. which is often mixed with liquids such as di-iso-octyl phthalate, tritolyl phosphate or other diesters to bring the below room temperature. The resultant plasticised p.v.c. is flexible and to some degree quite rubbery. Other commonly plasticised materials are cellulose acetate and cellulose nitrate. 

It is essential to appreciate that such plasticisers will considerably modify the chemical properties of the plastics material since the plasticiser may be readily extracted by certain chemicals and chemically attacked by others whilst the base polymer may be unaffected. 

The chloride ion is the most frequent cause of contact corrosion, since chlorine is present in the many chlorinated plastics, and is also frequently retained in residual amounts from reactive intermediates used in manufacture. Thus epoxides usually contain chloride derived from the epichlor-hydin used as the precursor of the epoxide. In addition to the contaminants referred to in Table 18.18, various metal and ammonium cations, inorganic anions and long-chain fatty acids (present as stabilisers, release agents or derived from plasticisers) may corrode metals on contact. 

Copper alloys are particularly prone to attack by long-chain fatty acids which are often present in sealing compositions, temporary protectives and as trace additives in many plastics under acid conditions ester plasticisers may saponify in the presence of copper giving rapid corrosion of the copper and accelerating degradation of the polymer. 

Plastic containers often have residual mould release agents and can leach nutritious plasticisers into the product filled into them. 

It is a well-known fact that specific plastic materials like flexible PVC, Polyurethane or Silicone may be easily attacked by microorganisms leading to discoloration or mechanical failures.14 This susceptibility to microbial attack is mainly attributed to the plasticiser content of the material as well as other ingredients such as stabiliser or antioxidants.5,6 The predominant organisms on the surface of those plastics are fungi and actinomycetes and it is said that by the action of their extracellular enzymes other organisms such as bacteria may be able to grow on the material.7... 

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