PVC Compounders

The packed density is based on the ability of the resin to occupy the smallest space without physical distortion and is usually 10-30% greater than the bulk density. 

Another important consideration is powder flow time as it governs the speed and ease of polymer discharge from a silo or from a mixer. This is influenced by the PVC particle shape, size distribution and compound formulation ingredients. 

Prior to processing, it is necessary for the PVC and formulation additives to be combined intimately together in some form of mixer. The main converting processes are  

The PVC industry consists of resin producers, compounders, additive suppliers and processors. Most processors specialise in processes linked to either PVC-U or PVC-P applications. In some cases, such as pipe and window frame manufacturing, the processed PVC is marketed directly by the processor. In other cases, the processor passes on the PVC in semi-finished form to another company. 

There has been much rationalisation of resin producers in the last twenty years due to consolidation transactions. The major PVC industry participants, as described by EVC International NV, are shown in Table 1 for the year 2000 (166). 

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Cost bilizers. The variety of known costabiHzers for the mixed metal stabilizers is a very long listing. There are, however, a relatively small number of commercially used costabiHzers. Some of these additives can also be added by the PVC compounder or processor ia addition to the stabilizer package to further enhance the desired performance characteristics. The epoxy compounds and phenoHc antioxidants are among the most commonly used costabiHzers with the mixed metal stabilizers. 

The basic metal salts and soaps tend to be less cosdy than the alkyl tin stabilizers for example, in the United States, the market price in 1993 for calcium stearate was about 1.30— 1.60, zinc stearate was 1.70— 2.00, and barium stearate was 2.40— 2.80/kg. Not all of the coadditives are necessary in every PVC compound. Typically, commercial mixed metal stabilizers contain most of the necessary coadditives and usually an epoxy compound and a phosphite are the only additional products that may be added by the processor. The requited costabilizers, however, significantly add to the stabilization costs. Typical phosphites, used in most flexible PVC formulations, are sold for 4.00— 7.50/kg. Typical antioxidants are bisphenol A, selling at 2.00/kg Nnonylphenol at 1.25/kg and BHT at 3.50/kg, respectively. Pricing for ESO is about 2.00— 2.50/kg. Polyols, such as pentaerythritol, used with the barium—cadmium systems, sells at 2.00, whereas the derivative dipentaerythritol costs over three times as much. The P-diketones and specialized dihydropyridines, which are powerful costabilizers for calcium—zinc and barium—zinc systems, are very cosdy. These additives are 10.00 and 20.00/kg, respectively, contributing significantly to the overall stabilizer costs. Hydrotalcites are sold for about 5.00— 7.00/kg. 

In a flexible PVC compound, ingredients in the recipe are chosen based on cost and/or thein contribution to physical and other properties and performance. Typical ingredients (16,17) are stabilizers, fillers, plasticizers, colorants, and lubricants. 

Stabilizers. Heat stabilizers (qv) are included in PVC compounds to counteract the internal generation of hydrogen chloride as well as the external degradative effect of heat. Due to environmental considerations, there is a trend toward decreasing and even avoiding the use of stabilizers based on heavy metals, eg, lead. 

Fillers. These are used to reduce cost in flexible PVC compounds. It is also possible to improve specific properties such as insulation resistance, yellowing in sunlight, scuff resistance, and heat deformation with the use of fillers (qv). Typical filler types used in PVC are calcium carbonate, clays, siHca, titanium dioxide, and carbon black. 

The PVC formulations shown in Table 2 represent typical compounds used by the wine and cable industry. PVC compounders have developed new PVC-based formulations with very good fire and smoke properties (can pass the UL 910 Steiner Tunnel test) that compete with the more expensive fluoropolymers. These can be used in fabricating telecommunication cables usable for plenum area appHcations. 

In the calendering method, a PVC compound which contains plasticizers (qv) (60—120 phr), pigments (qv) (0—10 phr), fillers (qv) (20—60 phr), stabilizers (10—30 phr), and other additives, is kneaded with calender roUs at 150—200°C, followed by extmsion between clearance-adjusted roUs for bonding onto the substrate. This method is employed for products with thick PVC layers, ie, of 0.05—0.75 mm thickness. The main plasticizer used is di-2-ethylhexyl phthalate (DOP). For filler to reduce cost, calcium carbonate is mainly used. A woven or knit fabric made of cotton, rayon, nylon, polyester, and their blend fiber is used as substrate. For foamed vinyl-coated fabrics, the bonded materials are heated in an oven to decompose the foam-blowing... 

Another method is extmsion the PVC compound is kneaded in an extmder, and then extmded through a T-die for bonding onto a substrate. 

Commonly used materials for cable insulation are poly(vinyl chloride) (PVC) compounds, polyamides, polyethylenes, polypropylenes, polyurethanes, and fluoropolymers. PVC compounds possess high dielectric and mechanical strength, flexibiUty, and resistance to flame, water, and abrasion. Polyethylene and polypropylene are used for high speed appHcations that require a low dielectric constant and low loss tangent. At low temperatures, these materials are stiff but bendable without breaking. They are also resistant to moisture, chemical attack, heat, and abrasion. Table 14 gives the mechanical and electrical properties of materials used for cable insulation. 

The dry blend can also be extmded and the extmdate chipped to produce pellets of PVC compound which can then be subsequendy reprocessed to produce the final product. This has the benefit of ease of storage of raw materials since all the formulation ingredients are contained bound in the gelled compound. Many producers of flexible PVC only purchase PVC compound, and many companies exist solely to produce PVC compound rather than a tme end product such as sheet, flooring, or pipe. 

In the formulation of PVC compounds it is not uncommon to replace some of the plasticiser with an extender, a material that is not in itself a plasticiser but which can be tolerated up to a given concentration by a polymer-true plasticiser system. These materials, such as chlorinated waxes and refinery oils, are generally of lower solubility parameter than the true plasticisers and they do not appear to interact with the polymer. However, where the solubility parameter of a mixture of plasticiser and extender is within unity of that of the polymer the mixture of three components will be compatible. It may be shown that... 

Particulate fillers are divided into two types, inert fillers and reinforcing fillers. The term inert filler is something of a misnomer as many properties may be affected by incorporation of such a filler. For example, in a plasticised PVC compound the addition of an inert filler will reduce die swell on extrusion, increase modulus and hardness, may provide a white base for colouring, improve electrical insulation properties and reduce tackiness. Inert fillers will also usually substantially reduce the cost of the compound. Amongst the fillers used are calcium carbonates, china clay, talc, and barium sulphate. For normal uses such fillers should be quite insoluble in any liquids with which the polymer compound is liable to come into contact. 

Calendering processes, of great importance in the production of sheet materials from PVC compounds, are little used with polyethylene because of the difficulty in obtaining a smooth sheet. Commercial products have, however, been made by calendering low-density polymer containing a small amount of a peroxide such as benzoyl peroxide to give a stiff but crinkly sheet (Crinothene) which was suitable for lampshades and other decorative applications. 

In addition to stabilisers, antioxidants and ultra-violent absorbers may also be added to PVC compounds. Amongst antioxidants, trisnonyl phenyl phosphite, mentioned previously, is interesting in that it appears to have additional functions such as a solubiliser or chelator for PVC insoluble metal chlorides formed by reaction of PVC degradation products with metal stabilisers. Since oxidation is both a degradation reaction in its own right and may also accelerate the rate of dehydrochlorination, the use of antioxidants can be beneficial. In addition to the phenyl phosphites, hindered phenols such as octadecyl 3-(3,5-di-tcrt-butyl-4-hydroxyphenyI)propionate and 2,4,6-tris (2,5-di-rcrt-butyl-4-hydroxybenzyl)-1,3,5-trimethylbenzene may be used. 

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. 

Developments in the USA have led to the availability of terephthalate plasticisers, for example dioctyl terephthalate (DOTP). Whilst these materials are very similar to the corresponding o-phthalate esters they are generally less volatile and are best compared with d-phthalates with one or more carbon atom in the alkyl chain. As with the linear dialkyl phthalates the terephthalates show good fogging resistance. This is a phenomenon in which new cars on storage fields awaiting delivery develop misting on the windows due, apparently, to the volatility of additives in PVC compounds used with the car. 

Fillers are commonly employed in opaque PVC compounds in order to reduce cost. They may also be employed for technical reasons such as to increase the hardness of a flooring compound, to reduce tackiness of highly plasticised... 

Figure 12.21. Effect of filler content on the properties of plasticised PVC compounds. (a) Tensile strength, (b) BS softness number.

There are a number of applieations such as bottle and film where tough materials of high elarity are desired. The advent of MBS material has been a significant advance to meet the requirements. It has been found possible here to produce an additive with sufficiently different solubility parameters from the PVC for it to exist in the disperse phase but with a very similar refractive index to the PVC so that light scattering at the interface between the two phases is at a minimum. However, owing to differences in the formulation of PVC compounds, a particular MBS modifier may not have exactly the same refractive index as the PVC eompound. 

When the disperse phase has a slightly higher refractive index the compound tends to be blue when it is lower than that of the PVC the compound tends to be yellow and hazy. In order to overcome this a carefully determined quantity of a second MBS additive, with an appropriate refractive index and whieh is compatible with the PVC compound and hence forms a continuous phase with it, may be added to match the refractive indices. Such a matching operation should be evaluated at the proposed serviee temperature range of the product since the temperature coefficients of the two phases are usually different and a film which is blue at proeessing temperature may become yellow at 20°C. 

Because of the wide range of possible formulations it is difficult to make generalisations about the properties of PVC compounds. This problem is illustrated in Table 12.4, which shows some differenees between three distinct types of eompound. 

Figure 12.23. Routes from raw materials to finished produets illustrating different eompounding teetiniques with PVC compounds- ...

The largest single use area for UPVC is for pipes and fittings. One particular area here is in chemical plant. It is of course necessary to check that all of the components of the PVC compound will be resistant to any of the chemicals with which the plant is liable to come into contact (at the appropriate temperatures) and also that additives will not be leached out by these chemicals. Particular uses are in acid recovery plant and in plant for handling hydrocarbons. 

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