Polymers

Polymers are long chain giant organic molecules are assembled from many smaller molecules called monomers. Polymers consist of many repeating monomer units in long chains. A polymer is analogous to a necklace made from many small beads (monomers).

Another common name for many synthetic polymers is plastic which comes from the Greek word "plastikos", suitable for molding or shaping. Many objects in daily use from packing, wrapping, and building materials include half of all polymers synthesized.
Other uses include textiles, TV's, CD's, automobiles, and many other all are made from polymers. A quarter of the solid waste from homes is plastic materials - some of which may be recycled as shown in the table on the left.

Classification of Polymers:
Homopolymers - consist of Copolymers - consist of chains chains with identical bonding with two or more linkages linkages to each monomer unit. usually implying two or more This usually implies that the different types of monomer polymer is made from all units. identical monomer molecules.
These may be represented as : [A-A-A-A-A-A]These may be represented as : [A-B-A-B-A-B]-

Polymers are further classified by the reaction mode of polymerization, these include:
Condensation Polymers Addition Polymers - the usually two different monomer monomer molecules bond to combine with the loss of a each other without the loss of small molecule, usually water. any other atoms. Polyesters and polyamides Alkene monomers are the (nylon) are in this class of biggest groups of polymers in polymers. this class. Polyurethane Foam in graphic.

Classification based upon the physical property related to heating:

Natural Gas Liquids (Ethane, Propane) or Naphtha (from Crude Oil)

Steam Cracking Ethylene, Propylene

Other Polymers

Chemicals

POLYETHYLENE

polyethylene is created through the polymerization of ethylene (i.e., ethene). Polyethene, Polythene, PE, LDPE, HDPE, MDPE, LLDPE

Types of Polyethylene

HDPE (0.940-0.965) High Density

LLDPE (0.860-0.926) Linear Low Density

O C-OH O

O
O O O

O
O

O O

LDPE (0.915-0.930) Low Density

High Pressure Copolymers (AA, VA, MA, EA)

Low-density polyethylene (LDPE) is a thermoplastic made from the monomer ethylene

Imperial Chemical Industries first discovered low-density polyethylene in 1933. Its first commercial use came during World War II, when it was used as insulation on radar cables.

LDPE (Low Density Polyethylene) is defined by a density range of 0.910 - 0.940 g/cm3. It has a high degree of short and long chain branching, which means that the chains do not pack into the crystal structure as well. It has therefore less strong intermolecular forces as the instantaneous-dipole induceddipole attraction is less. This results in a lower tensile strength and increased ductility. LDPE is created by free radical polymerization.

The high degree of branches with long chains gives molten LDPE unique and desirable flow properties.

The SPI resin identification coding system is a set of symbols placed on plastics to identify the polymer type. It was developed by the Society of the Plastics Industry (SPI) in 1988, and is used internationally. The primary purpose of the codes is to allow efficient separation of different polymer types for recycling. Separation must be efficient because the plastics must be recycled separately. Even one item of the wrong type of resin can ruin a mix.

Recycling number
1

Image

Abbreviation
PETE or PET

2
3 4 5 6 7

HDPE
PVC or V LDPE PP PS OTHER or O

Injection
The injection blow moulding machine is based on an extruder barrel and screw assembly which melts the polymer. The molten polymer is fed into a manifold where it is injected through nozzles into a hollow, heated preform mould. The preform mould forms the external shape and is clamped around a mandrel (the core rod) which forms the internal shape of the preform. The preform consists of a fully formed bottle/jar neck with a thick tube of polymer attached, which will form the body.

Blowing
The preform mould opens and the core rod is rotated and clamped into the hollow, chilled blow mould. The core rod opens and allows compressed air into the preform, which inflates it to the finished article shape.

Ejection
After a cooling period the blow mould opens and the core rod is rotated to the ejection position. The finished article is stripped off the core rod and leak-tested prior to packing. The preform and blow mould can have many cavities, typically three to sixteen depending on the article size and the required output. There are three sets of core rods, which allow concurrent preform injection, blow moulding and ejection.

1 8

2 3

Process steps of Injection Blow Moulding

The blow moulding machine is based on a standard extruder barrel and screw assembly to plasticise the polymer. The molten polymer is led through a right angle and through a die to emerge as a hollow (usually circular) pipe section called a parison. When the parison has reached a sufficient length a hollow mould is closed around it. The mould mates closely at its bottom edge thus forming a seal. The parison is cut at the top by a knife prior to the mould being moved sideways to a second position where air is blown into the parison to inflate it to the shape of the mould. After a cooling period the mould is opened and the final article is ejected. To speed production several identical moulds may be fed in cycle by the same extruder unit. The process is not unlike that used for producing glass bottles, in that the molten material is forced into a mould under air pressure.

One of the most common methods of film manufacture is Blown Film (also referred to as the Tubular Film) Extrusion. The process involves extrusion of a plastic through a circular die, followed by "bubble-like" expansion. The principal advantages of manufacturing film by this process include the ability to: Produce tubing (both flat and gussetted) in a single operation Regulation of film width and thichness by control of the volume of air in the bubble, the output of the extruder and the speed of the haul-off Eliminate end effects such as edge bead trim and non uniform temperature that can result from flat die film extrusion Capability of biaxial orientation (allowing uniformity of mechanical properties) Blown Film Extrusion can be used for the manufacture of co-extruded, multi-layer films for high barrier applications such as food packaging.

3 layer die head with air ring and internal bubble cooling

Film bubble going into a collapsing frame

Control panel graphic from an automated blown film line

Taking an edge trim from film web

The lay flat tube is separated into 2 single sheets

Blow Film Line In Action

Applications
Blown film can be used either in tube form (e.g. for plastic bags and sacks) or the tube can be slit to form a sheet. - Industry packaging (e.g. shrink film, stretch film, bag film or container liners), - Consumer packaging (e.g. packaging film for frozen products, shrink film for transport packaging, food wrap film, packaging bags, or form, fill and seal packaging film), - Laminating film (e.g. laminating of aluminium or paper used for packaging for example milk or coffee), - Barrier film (e.g. film made of raw materials such as polyamides and EVOH acting as an aroma or oxygen barrier used for packaging food, e. g. cold meats and cheese), - films for the packaging of medical products, Agricultural film (e.g. greenhouse film, crop forcing film, silage film, silage stretch film).

PE Demand by Conversion Process

Food Packaging
Film 51%

Hygiene & Medical Consumer & Ind. Liners Stretch Films Agricultural Films HDSS

Plastics and rubbers are used in different packaging materials and dosing devices These materials are in direct contact with the Pharmaceutical product The final use of the product determines the risk of possible interactions with the product Extractables and leachables can be harmful and can possibly alter the pharmaceutical product

Extractable :

Compounds that can be extracted from packaging (i.e. elastomeric, plastic components or coating of the container and closure system) when in the presence of selected solvent or process
Leachable : Compounds that leach from packaging as a result of direct contact with the formulation of the drug product and thus could potentially be dosed to a patient.

Can also get interaction with a product component to produce an impurity that requires stability monitoring.

Container/ Film

=>

Potential Sources of Extractables from elastomeric or plastic components: Additives and processing aids, e.g. antioxidants, stabilizers, plasticizers, emulsifiers etc. Trace level contaminants and reaction products contained in additives Monomers Secondary reaction products from processing Pigments Contaminants and/ or reaction products from storage/shipping Conduct risk assessment based on this information regarding the identity and amounts of ingredients

Based on Extractable study suitable test methods for testing of potential leachables in drug product have to be developed Recovery of reference compounds could be optimized by spiking into a drug product formulation matrix. Based on Toxicological Expertise limits for potential leachables have to be defined Validate the analytical methods Methods for leachables studies are specific to the finished product Determine shelf-life acceptance criteria for leachables based on the toxicological risk assessment

Chemical Properties Aesthetic Properties

Impart Color Odorants Add fragrance Deodorants Development of Odor

Dyes & Colors

light stability Anti Oxidants Prevent Oxidative degradation Biocides Prevent Mildews

UV Stabilizers Improve

Surface Properties Lubricants Prevent sticky to machine Slip & Blocking Agent Prevent film & sheet sticky Anti Static Agent Prevent static charges on surface Coupling Agent Improve bonding between polymer & filler Welty Agent Stabilize dispersion of Fillers Anti Fogging Agent Disperse moisture droplets on film

Mechanical Properties
Plasticizers Flexibility Impact Modifier Improves impact strength Reinforcy fillers Increase Strength Nucleatic agent Modify Crystalling Morphology

By virtue of their insulting nature, polymers of all types allow static charge to build up on their surfaces, and films have large surface area to volume ratio. Such static charge build up leads to several undesirable consequences in the final products. Built up static charge can attract dust on to a food package, which is undesirable aesthetically. It cause several processing problems such as winding of films, agglomeration of powders during transport, adhesion of film during processing, etc.. It can be avoided by using masterbatches containing anti-static agents which will used internally with polymer.

Internal antistats are migratory in nature. The strongly polar hydrophilic end adsorbs water molecules which eliminates static charges by ionic conduction. The long hydrocarbon chain length constitutes the hydrophobic group and controls the rate of diffusion of the antistat to the surface of the polymer product.

Esters
Glycerol mono-Stearate is commonly used as an antstatic agent for PE It is useful for only short term performance of about 1-2 months.

Amines Amides
Usually Ethoxylated products & useful for long term ant-static performance. Usually Ethoxylated products & useful for long term ant-static performance.

It is FDA approved at any level of Concentration

Commonly used in making electronic circuit boards It has limited FDA approval

It has limited FDA approval

1. If the other additives are also migratory, they compete with the antistats for diffusion through the polymer matrix & also compete with the antistats for surface coverage. Slips are a common example of this type of additive, which may exert adverse influenced on anti-static properties.
2. Amine & Amide type antistats are basic(Alkaline) in nature, which may react with some acidic flame retardants, which can result in reduction of anti-static properties.