POLYMER ADDITIVES INTRODUCTION Polymers in their pure form, as obtained from the manufacturing plants after isolation and

purification are called virgin polymers. Virgin Polymers as such may not be amenable for processing straightaway. The following is a list of some of the important additives to a polymer: Fillers and reinforcements Plasticizers UV-stabilizers and absorbers Anti oxidants Heat stabilizers Anti-agingAgents Antistatic Agents Flame retardants Blowing agents Lubricants Cross-linking agents Coupling agents Colouring agents Biocides

Fillers and Reinforcements Many plastics are virtually useless alone but are converted into highly serviceable products by combining them with particulate or fibrous solids termed as fillers. Typical examples of fillers are wood, flour, fibre, cellulose and powdered mica. The principle purpose of adding fillers is most often to reduce the cost of the overall material. Fillers usually cost much less than the plastic and therefore any combination of plastic and filler will be less costly in terms of total weight or total volume than the pure plastic material itself. Reinforcing fillers are used to improve some mechanical properties, such as modulus, tensile or tear strength, abrasion resistance and fatigue strength. Thus there are two objectives of adding fillers to a polymer i) improvement of physical properties. ii) making the material cost less. Particulate fillers such as carbon black or silica are widely used to improve the strength and abrasion resistance of commercial polymers. Mica can be used to modify the polymers electrical and heat insulating properties. FRP In recent years the use of mineral fillers has increased markedly, with emphasis on calcium carbonate which dominates the market.

Plasticizers On addition of plasticizers the polymer which is hard rigid solid at room temperature becomes a rubber like material. Plastsizers are low molecular weight non-volatile substances (mostly liquids) which when added to a polymer, improves its flexibility, processibility and hence utility. The plasticizer substantially reduces the brittleness of many amorphous polymers because its addition even in small quantities markedly reduce the Tg ( glass transition temperature- ie the temperature at which the amorphous polymer passes from the glassy state to a rubbery state) of the polymer. This effect is due to the reduction in cohesive forces of attraction between polymer chains. Plasticizer molecules (being relatively small in size as compared to polymer molecules) penetrate into the polymer matrix and establish polar attractive forces between it and the chain segments. These attractive forces reduce the cohesive forces between polymer chains and increase segmental mobility, thereby reducing the Tg value. The basic requirements that must be met by a plasticizer are compatibility and permanence. The Plasticizer must be miscible with the polymer. Permanence requirements demand low diffusion rate of the plasticizer within the polymer. Plasticizer containment still remains a major problem, particularly for periods of extended use. For instance, most plastic floor tiles become brittle with extended use, mainly due to leaching out of plasticizer(plasticizer that has migrated to the surface of plastic gets rubbed or washed away). This is being overcome by surface treatment of polymer products. Typical plasticizers used for PVC (poly vinyl chloride-the most commonly used plastic material) include the esters of common organic acids like dioctyl pthalate (DOP), dioctyl adipate (DOA) and phosphates. Table 1 Common plasticizers Plasticizer Chemical structure Dioctyl adipate Dioctyl pthalate Trialkyl phosphate Examples DOA DOP TCP

Plasticizer efficiency-the reduction in Tg per unit weight of plasticizer added. The problem with high efficiency plasticizer- they will diffuse out of the polymer in time due to their low missibility with the polymer.( called low permanence plasticizers) loss of plasticizer will lead to a gradual increase in brittleness and Tg will rise. External plasticization-adding plasticizer with low Tg tp polymer ie by compounding a polymer with a low Tg compound. Internal plasticization- copolymerizing the polymer with a monmer of low Tg polymer such as poly vinyl acetate.

UV-stabilizers and absorbers While much of the suns high-energy radiation is absorbed by the atmosphere, a part of the UV radiations in the wavelength range 280-400 nm reaches the earth surface. This is associated with the energy of 100-72 kcal and is strong enough to cleave covalent bonds and thus causes yellowing and embrittlement of organic polymers. UV-stabilizers are added to protect the polymers from the deteriorating effects of high energy UV radiations from sun. The function of the photo stabilizer is to absorb the UV radiations and dissipate the energy thus absorbed to the environment in some harmless form. (longer wavelength, having lesser energy). Carbon black can function as UV absorber but is restricted to articles where colour is not a criterion of choice. As an example carbon black, is widely used in tire manufacture, it provides good absorption in the UVrange as well as provides abrasion resistance and serves as a low-cost filler. Transparent plastics can be protected against yellowing and embrittlement by using stabilizers like hydroxy benzophenones.

H O O C

o-hydroxy benzophenone UV stabilizers can also act by deactivating free radicals as they are formed. eg : 4 methyl 2,6 tert btyl phenol

Antioxidants Antioxidants retard oxidative degradation of polymers. Free radicals are generated in polymer systemsdue to exposure of polymer to heat, mechanical shear, UV-radiations. These free radicals in the presence and combination of oxygen attack other polymer molecules and initiate a chain reaction which results in the degradation of the polymer. The sequence of reactions may be represented as follows: RH Polymer R + H free radicals

The radical combines with oxygen to form peroxide radical R + O2 ROO Peroxide free radical

The peroxide free radical then attacks another polymer molecule ROO + Peroxide RH ROOH + R Polymer dead polymer free radical

The chain continues to be, until it is terminated or disrupted in someway. An antioxidant is an agent that brings about the break in the chain reaction and stops degradation. As per the manner in which this interruption is brought about, the agents are classed into two groups- the preventive antioxidant and chain-breaking antioxidant. The preventive type prevents the formation of radicals, while the chain- breaking type interrupts the propagation sequence. Many naturally occurring antioxidants are derivatives of phenol Charles carraher Pg 533

As shown by the following equation, the antioxidant acts as a chain transfer agent to produce a dead polymer and a stable free radical that does not initiate chain radical degradation. However it may react with other free radicals to produce a quinine derivative. Heat stabilizer Heat stabilizers are added to polymer materials which are employed under conditions where they are exposed to heat. In chlorine containing polymers such as PVC a type of degradation known as dehydro-halogenation occurs when PVC is exposed to heat. As shown by the following equation, when pVC gets heated it may lose hydrogen chloride and formconjugated polyene structure which are unstable, the degradation continues as an unzipping type of chain reaction. Carriher pg 534

Toxic lead and barium and calcium salts act as scavengers for hydrogen chloride and may be used as heat stabilizers, such as wire coating. Anti-agingAgents When polymers are kept in service conditions for considerable length of time, it has often been noticed that the properties and characteristics of the polymer change for the worse. The reason behind this phenomenon is the structural changes and modifications that the polymer undergoes in theservice conditions. The structural changes may set in due to any of the following four reasons: i) Chain rupture may lower the molecular weight and hence, the strength. ii) Cross-linking may lead to rigidity, brittleness and difference in solubility. iii) Chromophoric groups may form, giving colour to the polymer. iv) Polar groups may develop, bringing down the electrical insulation property. The structural modifications are due to some chemical reactions, of which the principle ones are oxidation, ozone effect, UV-light attack and dehydrochlorination. To stop or deter the oxidation and ozone effect process, preventive type of antioxidants and antiozonants are added. For resisting the attack of UV-light, absorbers or chelating agents are added. Antistatic Agents Since most polymers are poor electrical conductors, static electrical charges can form on the surface of plastics. Such static charge build up can present problems such as dust collection and sparking. Hygroscopic additives called antistats are effective for dissipating static electrical charges. The antistatic agents are slightly incompatible with the polymer due to which they slowly migrate to the surface and give a protective layer such that no static charge can build up. Antistats belong to either of two categories- external or internal. External antistats are applied by spraying, wiping or dipping the plastic surface, while internal antistats are compounded with the plastic during processing. In the case of internal antistats the additive diffuses to the surface of the plastic where the hygroscopic additive absorbs moisture and thereby, provides a conductive layer of water. Examples of antistatic agents include phosphate and fattyacid esters, quantenary ammonium compounds. Flame retardants Since some polymers are used as shelter and clothing and in household furnishing, it is essential that they have good flame resistance. Flammability of polymeric materials may lead to undesirable consequences in some applications. For example if a carpet of polyacrylonitrile catches fire at night due to a spark caused by a faulty electrical connection, it would release HCN gas, which may lead to fatal situation for those who are sleeping in the room. Hence for such applications it is desirable to add a flame retardant to the polymer, which would discourage burning of the material. Flame retardants are added to resist the burning process in according to one or more of he following mechanisms: i) They may interfere in the flame propagation reaction and help extinguish the fire. ii) Being with the polymer, it may produce volumes of incombustible gas which would decrease oxygen concentration around the flame, thus forcing it to go out. iii) It may provide an endothermic type of reaction, which would lower the heat so that the flame may not get sustained. iv) It may produce a layer of ash, cutting off the supply of oxygen to the point of fire.

Blowing agents Many plastics are foamed to provide insulating properties or flexible products for seat cushions and other application. In order to do so blowing agents are added as additives to polymers. The formation of cellular polymeric product is possible by the help of blowing agents. The additives which are used to generate sufficient amount of gases by their decomposition inside he polymer matrix tp obtain cellular or foam product are known as chemical blowing agents. These additives are decomposed or volatilized at final stage of polymer processing Following 3 characteristics are important 1) The generation of gases should occur within a narrow and well defined range, which must be lower than the decomposition temperature of the used polymer and other additives in the system. 2) They should be stable while their storage and handling 3) The generated gases should not be toxic Eg:

The blowing agent may be solid liquid or gas. Whatever its state, the agent must, at the manufacturing temperature, turn to a gaseous form to pervade the mass of the polymer. When the gas bubbles through the polymerizing substance or the molten polymer, it gives a cellular structure to the material. Physical blowing agent- include volatile liquids such as pentanes, hexanes and heptanes, fluorocarbons and gases such as nitrogen, carbondioxide and air that are added during processing. Chemical blowing agents (CBA) hydrazine derivatives are solid additives that generate gases when decomposed at processing temperatures. Lubricants and flow promoters Lubricants are added to improve the flow characteristics of a material during its processing. They operate by reducing the melt viscosity or by decreasing adhesion between the metallic surfaces of the processing equipment and the material being processed. Examples of lubricants are waxes, amides, esters, acids and metal stearates.

Coupling agents- To get the advantages of two semicompatible or incompatible compounds or materials like filler with polymer, the interaction between the two need to be improved by the incorporation of coupling agents. These agents are usually bifunctional compounds, where one of the functionalities interact with one component (say filler) and other functionality with the other (say polymer). Thus the two such components are bonded physicochemically through the coupling agent.. Eg: tri etoxy vinyl silane Amino propyl triethoxy silane

Colourants- The reason for adding colours to polymers may be i) to have aesthetic appeal, ii) to give a means of identification, to improve visibility iii) For imitating the appearance of a natural, conventional article. There are 4 methods of imparting colour a) Coating the surface b) Dyeing the surface c) Incorporation of materials which would provide chromophoric groups in the polymer d) Mass colouration method Colorants are of 2 types 1) dyes 2) pigments Dyes promote colour by dissolving in the polymer. Pigments remains dispersed throughout the polymer. Dyed plastics often hold their colour much better against fading than pigmented plastics. Dyes are heat sensitive Pigments are light sensitive Inorganic pigments Rutile titanium oxide Lead chromate Ferri/ferro cyanide Carbon black White colour Yellow colour Prussian blue black

Organic pigments- pthalocyanines-blue colour Dyes-azo dyes, anthra quinines Biocide- Polymers or any other additives present in the matrix may be attacked by micro organisms such as bacteria, fungi, algae, etc. These micro organism attack may cause loss of viscosity, discolouration of he polymer by degradation. Thus biocide that is antibiotic like Cu, Sn, Sb As containing compounds are largely used for this purpose, particularly marine applications of polymers. Cross-linking agents For polymers such as rubbers , the elastic property needs to be controlled. For this vulcanization is done. Vulcanization is a cross linking process. Cross-linking agents are those