WRITTEN REPORT ABOUT POLYMERS Submitted by : CUA, NEIL DE LEON JOANA DY, PAULO ESPERAS, RUSSELL 3CHEA

SUBMITTED TO: PROF. NATALIA DIMAANO

POLYMERS Engineering polymers include natural materials such as rubber and synthetic materials such as plastics and elastomers. Polymers are very useful materials because their structures can be altered and tailored to produce materials 1) with a range of mechanical properties 2) in a wide spectrum of colors and 3) with different transparent properties. Mers A polymer is composed of many Mer simple molecules that are repeating The repeating unit in a polymer chain structural units called monomers. A Monomer single polymer molecule may consist A single mer unit (n=1) of hundreds to a million monomers Polymer and may have a linear, branched, or Many mer-units along a chain (n=103 or more) network structure. Covalent bonds Degree of Polymerization hold the atoms in the polymer The average number of mer-units in a chain. molecules together and secondary bonds then hold groups of polymer chains together to form the polymeric material. Copolymers are polymers composed of two or more different types of monomers. Polymer Chains (Thermoplastics and Thermosets) A polymer is an organic material and the backbone of every organic material is a chain of carbon atoms. The carbon atom has four electrons in the outer shell. Each of these valence electrons can form a covalent bond to another carbon atom or to a foreign atom. The key to the polymer structure is that two carbon atoms can have up to three common bonds and still bond with other atoms. The elements found most frequently in polymers and their valence numbers are: H, F, Cl, Bf, and I with 1 valence electron; O and S with 2 valence electrons; n with 3 valence electrons and C and Si with 4 valence electrons. The ability for molecules to form long chains is a vital to producing polymers. Consider the material polyethylene, which is made from ethane gas, C2H6. Ethane gas has a two carbon atoms in the chain and each of the two carbon atoms share two valence electrons with the other. If two molecules of ethane are brought together, one of the carbon bonds in each molecule can be broken and the two molecules can be joined with a carbon to carbon bond. After the two mers are joined, there are still two free valence electrons at each end of the chain for joining other mers or polymer chains. The process can continue liking more mers and polymers together until it is stopped by the addition of anther chemical (a terminator), that fills the available bond at each end of the molecule. This is called a linear polymer and is building block for thermoplastic polymers.

The polymer chain is often shown in two dimensions, but it should be noted that they have a three dimensional structure. Each bond is at 109 to the next and, therefore, the carbon backbone extends through space like a twisted chain of TinkerToys. When stress is applied, these chains stretch and the elongation of polymers can be thousands of times greater than it is in crystalline structures. The length of the polymer chain is very important. As the number of carbon atoms in the chain is increased to beyond several hundred, the material will pass through the liquid state and become a waxy solid. When the number of carbon atoms in the chain is over 1,000, the solid material polyethylene, with its characteristics of strength, flexibility and toughness, is obtained. The change in state occurs because as the length of the molecules increases, the total binding forces between molecules also increases. It should also be noted that the molecules are not generally straight but are a tangled mass. Thermoplastic materials, such as polyethylene, can be pictured as a mass of intertwined worms randomly thrown into a pail. The binding forces are the result of van der Waals forces between molecules and mechanical entanglement between the chains. When thermoplastics are heated, there is more molecular movement and the bonds between molecules can be easily broken. This is why thermoplastic materials can be remelted. There is another group of polymers in which a single large network, instead of many molecules is formed during polymerization. Since polymerization is initially accomplished by heating the raw materials and brining them together, this group is called thermosetting polymers or plastics. For this type of network structure to form, the mers must have more than two places for boning to occur; otherwise, only a linear structure is possible. These chains form jointed structures and rings, and may fold back and forth to take on a partially crystalline structure. Since these materials are essentially comprised of one giant molecule, there is no movement between molecules once the mass has set. Thermosetting polymers are more rigid and generally have higher strength than thermoplastic polymers. Also, since there is no opportunity for motion between molecules in a thermosetting polymer, they will not become plastic when heated. Classification of Polymers: Homopolymers - consist of chains with identical bonding linkages to each monomer unit. This usually implies that the polymer is made from all identical monomer molecules. These may be represented as : -[A-A-A-A-A-A]-Copolymers - consist of chains with two or more linkages usually implying two or more different types of monomer units. These may be represented as : -[A-B-A-B-A-B]-

Polymers are further classified by the reaction mode of polymerization, these include:

Addition Polymers - the monomer molecules bond to each other without the loss of any other atoms. Alkene monomers are the biggest groups of polymers in this class.

Condensation Polymers - usually two different monomer combine with the loss of a small molecule, usually water. Polyesters and polyamides (nylon) are in this class of polymers. Polyurethane Foam in graphic.

Classification based upon the physical property related to heating:

Thermoplastics - plastics that soften when heated and become firm again when cooled. This is the more popular type of plastic because the heating and cooling may be repeated.

Thermosets - plastics that soften when heated and can be molded, but harden permanently. They will decompose when reheated. An example is Bakelite, which is used in toasters, handles for pots and pans, dishes, electrical outlets and billiard balls.

Types of polymers o Commodity plastics PE = Polyethylene PS = Polystyrene PP = Polypropylene PVC = Poly(vinyl chloride) PET = Poly(ethylene terephthalate) o Specialty or Engineering Plastics Teflon (PTFE) = Poly(tetrafluoroethylene) PC = Polycarbonate (Lexan) Polyesters and Polyamides (Nylon)

Properties of Macromolecules A comparison of the properties of polyethylene (both LDPE & HDPE) with the natural polymers rubber and cellulose is instructive. As noted above, synthetic HDPE macromolecules have masses ranging from 105 to 106 amu (LDPE molecules are more than a hundred times smaller). Rubber and cellulose molecules have similar mass ranges, but fewer monomer units because of the monomer's larger size. The physical properties of these three polymeric substances differ from each other, and of course from their monomers.

HDPE is a rigid translucent solid which softens on heating above 100 C, and can be fashioned into various forms including films. It is not as easily stretched and deformed as is LDPE. HDPE is insoluble in water and most organic solvents, although some swelling may occur on immersion in the latter. HDPE is an excellent electrical insulator. LDPE is a soft translucent solid which deforms badly above 75 C. Films made from LDPE stretch easily and are commonly used for wrapping. LDPE is insoluble in water, but softens and swells on exposure to hydrocarbon solvents. Both LDPE and HDPE become brittle at very low temperatures (below -80 C). Ethylene, the common monomer for these polymers, is a low boiling (-104 C) gas. Natural (latex) rubber is an opaque, soft, easily deformable solid that becomes sticky when heated (above. 60 C), and brittle when cooled below -50 C. It swells to more than double its size in nonpolar organic solvents like toluene, eventually dissolving, but is impermeable to water. The C5H8 monomer isoprene is a volatile liquid (b.p. 34 C).

 Pure cellulose, in the form of cotton, is a soft flexible fiber, essentially unchanged by variations in temperature ranging from -70 to 80 C. Cotton absorbs water readily, but is unaffected by immersion in toluene or most other organic solvents. Cellulose fibers may be bent and twisted, but do not stretch much before breaking. The monomer of cellulose is the C6H12O6 aldohexose D-glucose. Glucose is a water soluble solid melting below 150 C.

To account for the differences noted here we need to consider the nature of the aggregate macromolecular structure, or morphology, of each substance. Because polymer molecules are so large, they generally pack together in a non-uniform fashion, with ordered or crystalline-like regions mixed together with disordered or amorphous domains. In some cases the entire solid may be amorphous, composed entirely of coiled and tangled macromolecular chains. Crystallinity occurs when linear polymer chains are structurally oriented in a uniform three-dimensional matrix. In the diagram on the right, crystalline domains are colored blue. Increased crystallinity is associated with an increase in rigidity, tensile strength and opacity (due to light scattering). Amorphous polymers are usually less rigid, weaker and more easily deformed. They are often transparent.

Three factors that influence the degree of crystallinity are: i) Chain length ii) Chain branching iii) Interchain bonding

The importance of the first two factors is nicely illustrated by the differences between LDPE and HDPE. As noted earlier, HDPE is composed of very long unbranched hydrocarbon chains. These pack together easily in crystalline domains that alternate with amorphous segments, and the resulting material, while relatively strong and stiff, retains a degree of flexibility. In contrast, LDPE is composed of smaller and more highly branched chains which do not easily adopt crystalline structures. This material is therefore softer, weaker, less dense and more easily deformed than HDPE. As a rule,

mechanical properties such as ductility, tensile strength, and hardness rise and eventually level off with increasing chain length.

The nature of cellulose supports the above analysis and demonstrates the importance of the third factor (iii). To begin with, cellulose chains easily adopt a stable rod-like conformation. These molecules align themselves side by side into fibers that are stabilized by inter-chain hydrogen bonding between the three hydroxyl groups on each monomer unit. Consequently, crystallinity is high and the cellulose molecules do not move or slip relative to each other. The high concentration of hydroxyl groups also accounts for the facile absorption of water that is characteristic of cotton.

Natural rubber is a completely amorphous polymer. Unfortunately, the potentially useful properties of raw latex rubber are limited by temperature dependence; however, these properties can be modified by chemical change. The cis-double bonds in the hydrocarbon chain provide planar segments that stiffen, but do not straighten the chain. If these rigid segments are completely removed by hydrogenation (H2 & Pt catalyst), the chains lose all constrainment, and the product is a low melting paraffin-like semisolid of little value. If instead, the chains of rubber molecules are slightly cross-linked by sulfur atoms, a process called vulcanization which was discovered by Charles Goodyear in 1839, the desirable elastomeric properties of rubber are substantially improved. At 2 to 3% crosslinking a useful soft rubber, that no longer suffers stickiness and brittleness problems on heating and cooling, is obtained. At 25 to 35% crosslinking a rigid hard rubber product is formed. The following illustration shows a cross-linked section of amorphous rubber. By clicking on the diagram it will change to a display of the corresponding stretched section. The more highly-ordered chains in the stretched conformation are entropically unstable and return to their original coiled state when allowed to relax.