Plasticisers purpose

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). 

It has already been mentioned in Chapter 5 that plasticisers are often replaced in part by extenders, materials which in themselves are not plasticisers but which can be tolerated up to a given concentration in a polymer-plasticiser system. Refinery oils and chlorinated waxes are widely used in PVC for this purpose with the prime aim of reducing cost although the chlorinated waxes may also be of use as flame retardants (q.v.). 

In the early days of the commercial development of PVC, emulsion polymers were preferred for general purpose applications. This was because these materials exist in the form of the fine primary particles of diameter of the order of 0.1-1.0 p,m, which in the case of some commercial grades aggregate into hollow secondary particles or cenospheres with diameters of 30-100 p,m. These emulsion polymer particles have a high surface/volume ratio and fluxing and gelation with plasticisers is rapid. The use of such polymers was, however, restricted because of the presence of large quantities of soaps and other additives necessary to emulsion polymerisation which adversely affect clarity and electrical insulation properties. 

Until comparatively recently the bulk of general purpose phthaiate plasticisers have been based on the branched alcohols because of low cost of such raw material. Suitable linear alcohols at comparative prices have become available from petroleum refineries and good all-round plasticisers are produced with the additional advantage of conferring good low-temperature flexibility and high room temperature resistance to plasticised PVC compounds. A typical material (Pliabrac 810) is prepared from a blend of straight chain octyl and decyl alcohols. 

For electrical insulation china clay is commonly employed whilst various calcium carbonates (whiting, ground limestone, precipitated calcium carbonate, and coated calcium carbonate) are used for general purpose work. Also occasionally employed are talc, light magnesium carbonate, barytes (barium sulphate) and the silicas and silicates. For flooring applications asbestos has been an important filler. The effect of fillers on some properties of plasticised PVC are shown in Figure 12.21 (a-d). 

The polymer may be plasticised by polar liquids capable of forming hydrogen bonds with the hydroxyl groups. Glycerin has been used for this purpose. 

Blending of ABS with other polymers is not restricted to the aim of raising the distortion temperature. Blends with PVC are made for various purposes. For example, 80 20 ABS/PVC blends are used to produce fire-retarding ABS-type materials, as already mentioned, while 10 90 blends are considered as impact-modified forms of unplasticised PVC. ABS materials have also been blended with plasticised PVC to give a crashpad sheet material. 

In some moulding compositions other special purpose ingredients may be incorporated. For example, naphthalene, furfural and dibutyl phthalate are occasionally used as plasticisers or more strictly as flow promoters. They are particularly useful where powders with a low moulding shrinkage are required. In such formulations a highly condensed resin is used so that there will be less reaction, and hence less shrinkage, during cure. The plasticiser is incorporated to... 

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. 

Chlorinated rubber is extensively employed in industrial corrosion-resistant surface coatings, for which purpose it is marketed by ICI under the trade name Alloprene. Although thermoplastic moulding compositions have been made by plasticising with the common ester plasticisers such as tritolyl phosphate they are of no commercial importance. 

If polypropylene is too hard for the purpose envisaged, then the user should consider, progressively, polyethylene, ethylene-vinyl acetate and plasticised PVC. If more rubberiness is required, then a vulcanising rubber such as natural rubber or SBR or a thermoplastic polyolefin elastomer may be considered. If the material requires to be rubbery and oil and/or heat resistant, vulcanising rubbers such as the polychloroprenes, nitrile rubbers, acrylic rubbers or hydrin rubbers or a thermoplastic elastomer such as a thermoplastic polyester elastomer, thermoplastic polyurethane elastomer or thermoplastic polyamide elastomer may be considered. Where it is important that the elastomer remain rubbery at very low temperatures, then NR, SBR, BR or TPO rubbers may be considered where oil resistance is not a consideration. If, however, oil resistance is important, a polypropylene oxide or hydrin rubber may be preferred. Where a wide temperature service range is paramount, a silicone rubber may be indicated. The selection of rubbery materials has been dealt with by the author elsewhere. ... 

The main features of PC are low cost, need for small sample amount, high level of resolution, ease of detection and quantitation, simplicity of apparatus and use, difficult reproducibility (because of variation in fibres) and susceptibility to chemical attack. Identification of the separated components is facilitated by the reproducible Rj values. Detection methods in PC have been reviewed [368]. Fluorescence has been used for many years as a means of locating the components of a mixture separated by PC or TLC. However, also ATR-IR and SERS are useful. Preparative PC is unsuitable for trace analysis because filter paper inevitably contains contaminants (e.g. phthalate esters, plasticisers) [369]. For that purpose an acceptable substitute is glass-fibre paper [28]. 

In other experiments, PVC/plasticiser extracts (n-hexane) were separated by SEC using THF or chloroform as the mobile phase. Similarly, PE film was immersed in THF for several hours and the extract was concentrated by a factor of 20 prior to injection into a SEC system [51]. However, use of extraction techniques followed by injection into a SEC system for separation of low-MW additives is not the most obvious analytical approach in view of the relatively low resolution of conventional SEC in the low molecular mass range. For this purpose efficient column packing materials with small pore sizes are to be used. 

Pure PETN is too sensitive to friction and impact for direct application for military purposes. It can usefully be mixed with plasticised nitrocellulose, or with synthetic rubbers to obtain plastic or mouldable explosives. The commonest application, however, is in conjunction with TNT in the form of pentolites. Pentolites are usually obtained by incorporating PETN into molten TNT. A small amount of the PETN goes into solution, but the bulk remains suspended in the liquid and the whole mix can suitably be used in preparing cast charges. Pentolites containing 20-50% PETN are the commonest in practice. 

Polymer additives may be classified into five groups (although some additives can serve more than one purpose, e.g., plasticisers, carbon black) ... 

The term plasticiser is most commonly reserved for the synthetic liquids added for the purpose of depressing the Tg. A variety of plasticisers with molecular structures containing polar groups are used, most of these being esters. 

As well as aiding processing, a major function of plasticisers is to extend the operating temperature range by improving low temperature flexibility. The majority of demand in CR and NBR is satisfied by general purpose phthalate plasticisers di-2-ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP) and diisodecyl phthalate (DIDP). However, a wide variety of speciality plasticisers, mainly esters, are marketed within the rubber industry. The majority of these have linear molecular structures giving them better low temperature performance than the phthalates. Examples of such plasticisers are di-2-ethylhexyl adipate (DOA), butyl carbitol adipate, di(butoxyethoxyethyl) adipate (BCA), and di-2-ethylhexyl sebacate (DOS). 

The decision by the European Commission to impose an immediate ban on the sale of PVC toys and teethers containing phthalate plasticisers has drawn criticism from both within and outside of the plasticiser industry. The Commission says its decision was taken only after its scientific advisors reported that plasticiser release tests are unreliable for control purposes. 

Phthalate plasticisers have historically served as the preferred plasticisers to impart flexibility to PVC and several other polar polymers. They provide a desirable balance of cost and performance properties. Their acceptable and safe use is unmatched in medical appliances, food processing and packaging applications, as well as many other end uses. Potential alternatives do not have the historical record of acceptable performance found with phthalate plasticisers. Nevertheless, the Precautionary Principle has caused certain segments of society to clamour for alternatives to phthalate plasticisers. Known non-phthalate plasticisers are reviewed, and comparisons to the traditional General Purpose (GP) phthalate plasticisers are provided General Purpose plasticisers are those that impart optimum overall performance properties in PVC at lowest cost. 6 refs. USA... 

The purpose of plasticisation is to decrease hardness and to increase flexibility and elongation. Phthlates (e.g. butyl benzyl phthalate, dioctyl phthalate and butyl phthalate) are used as external plasticisers. Externally plasticised systems have a migratory tendency with ageing. In order to overcome this drawback, systems are being internally plasticised. This process involves the use of comonomers (e.g. acrylates and higher alkyl... 

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