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Notes On


Keyur Vasava

The word Polymer comes from the Greek "poly" meaning many, and "meros", parts or units. A polymer is a group of many units. You combine many "monomers" (individual units) to create a polymer. Polymers are substances containing a large number of structural units joined by the same type of linkage. These substances often form into a chain-like structure. Polymers in the natural world have been around since the beginning of time. Starch, cellulose, and rubber all possess polymeric properties.

IUPAC definition: A polymer is a substance composed of molecules characterized by the multiple repetition of one or more species of atoms or groups of atoms linked to each other in amounts sufficient to provide a set of properties that do not vary markedly with the addition of one or a few of the constitutional repeating units.

Polymers are becoming increasingly important in the field of drug delivery. The pharmaceutical applications of polymers range from their use as binders in tablets, for viscosity and flow controlling agents in liquids, suspensions and emulsions. Polymers can be used as film coatings to disguise the unpleasant taste of a drug, to enhance drug stability and to modify drug release characteristics.

Classification of Polymer:
1)Based on origin of Polymers. 2)Based on presence of carbon atom: 3)Based upon the physical property related to heating: 4)Based on microstructure of polymer: 5)Based on reaction mode of polymerization: 6)Based on mechanism of polymerization: 7)Spatially oriented polymers: 8)Based on degradation of polymer:

Based on origin of polymer:

Natural polymers: Protein- silk, collagen, and keratin Carbohydrates -cellulose, starch, glycogen DNA- RNA Other Natural polymers: Rubber (hydrocarbon base) and silicones (alternating silicon and oxygen),Collagen, Albumin, Casein. Semi synthetic polymers : Geletin , fibrinogen chitin &chitoson , dextran, alginate Synthetic polymers: Polyethylene, nylon & PVC.

Based on presence of Carbon Atom:

Organic polymers:Monomers of the polymer contain C and as other atoms mostly H and O.

eg) polypropelen
Inorganic polymers:Monomers of the polymer generally not contain C as an atom. eg)silicon polymer

Based upon physical property related to heating:

Thermoplastic Polymers: material that is plastic or deformable melt to liquid when heated and freezes to breetle. Eg) Polyethylene, pvc, sealing wax . Thermosetting Polymers:Thermosets, which are densely cross-linked in the form of a network, degrade upon heating, while thermoplastics, which do not contain cross-links, melt upon heating. Eg) Asbestos .

Rubbers and Elastomers:Rubbery materials that can stretch many times their original length; they do not melt upon application of heat, they will degrade if heated to high enough temperature.Eg)Natural rubber, synthetic rubber, silicone rubber. Fibers:Nylon, terylene. Liquid resins: sealants Epoxy adhesive,polysulphide

Based on microstructure of polymer:

homopolymers: contain a single kind of monomer. eg) -A-A-A-A-A-A-A-AHomopolymer polystyrene. copolymers: contain more than one kind of monomer(a) random (b) alternating (c) block (d) graft a) -A-B-B-A-B-A-A-BRandom Copolymer b) -A-B-A-B-A-B-A-BAlternating Copolymer c) -A-A-A-A-B-B-B-BBlock copolymer

Based on reaction mode of polymerisation: Addition Polymers: the monomer molecules bond to each other without the loss of any other atoms. Prepared by the Monomers contain one or more double or triple bonds or by the ring opening of cyclic structures. Eg)neoprene.

Condensation Polymers: Usually two different monomers combines with the loss of a small molecules ,usually water Formed by successive reactions of functional groups , and repeating unit of the polymer has fewer atoms than the monomers. Eg)nylon,silk,polyesters.

Based on mechanism of polymerisation:

A) Chain Polymerization Addition polymers Free radical Anionic Cationic Zegler natta Copolymerzation Eg) vinyl acetic acid,acrilic acid polymer (b) Step Growth Polymerization Condensation Polymers eg) potassium vinyl trifluroburate.

Based on spatially oriented polymer:

Random atactic: randomly arranged polymer do not crystallize. Eg) Polyethylene Isotactic: if all the Y units are in the same plane,and isotactic polymer having tendancy to form a helix. eg)polychloroprene. Symmetrical syndiotactic: if a Y unit appears alternatively on top and bottom. Eg)polystyrene

Based on degradation of polymer:

Biodgradable polymers:
It can be defined as polymers comprised of monomers linked to one another through functional group and have unstable linkage in the backbone. And they delivers the drug into body after biodegradation of polymer. eg)Collagen, Albumin,Casein,poly lactate etc.

Solubility Hydrophobicity/Hydrophilicity Glass transition temperature Rheologic Molecular weight analytical

Water soluble polymers: Some polymers are freely soluble in water even though they are of very high molecular weight.Examples of such polymers are: polyvinyl alcohol,Polyethylene oxide etc.

Hydrogels: These are highly hydrophillic polymers that have been crosslinked by means of covalent bonds. Because the polymer cannot dissolve due to covalent crosslinks,water uptake is more than in hydrophillic linear polymer.

According to the nature of the polymer water interactions polymers can be broadly classified into the following categories: Hydrophobic polymers: These are essentially water impermeable and when placed in an aqueous environment, will absorb very little water. Structural parameters that contribute to this property are chain stiffness,high degree of crystallinity and presence of highly hydrophobic groups, These absorb less than 5% of water Hydrophillic polymers: These absorb more than 5% of water. Parametars that contribute to this property are Chain flexibility,absence of Crystallinity and presence of group as amino,Carboxyl and hydroxyl.

Glass Transition Temperature

A parameter of particular interest in synthetic polymer manufacturing is the glass transition temperature (Tg), which describes the temperature at which amorphous polymers undergo a second order phase transition from a rubbery, viscous amorphous solid to a brittle, glassy amorphous solid. The glass transition temperature may be engineered by altering the degree of branching or cross-linking in the polymer or by the addition of plasticizer.

Rheo = flow Viscosity (h, poise) is an expression of the resistance of a fluid to flow. Fluidity (f) = 1/h Newtons theory

Newtons theory
F/A = h dn/dr; h = F/G;
G = dn/dr = velocity gradient/rate of shear F = F/A = shear stress

Rate of shear is directly proportional to shearing stress.

Rheograms of different fluids

Non-newtonian systems
Bingham plastic flow does not begin to flow until a shear stress corresponding to the yield value is exceeded. Flocculated colloid particles 2. Pseudoplastic flow
1. Typically exhibited by polymers in solution (tragacanth, sodium alginate, methylcellulose, NaCMC) Viscosity decreases with the increase of shear rate/shear thinning Caused by the re-alignment of polymer and/or the release of solvents associated with the polymers.


Dilatant flow
Volume increases when sheared Shear-thickening Suspension containing a high concentration of small, deflocculated particles

Molecular weight and Molecular weight Distribution:

The exact molecular weight required for substances to be called polymer. Polymer scientist put the number at about 25,000 g/mol this is minimum molecular weight required for good physical and mechanical property for many important polymers.

The number average molecular weight Mn and the weight average molecular weight Mw important for the polymer distribution which are from different source and molecularily are same . Mn= NiMi/Ni where,Ni number of molecules of molecular wt Mi,

Polydispersity Index (PDI)

The ratio of Mw / Mn called Polydispersity index. Gives information about distribution of polymer Highly branched polymers : PDI > 20 Generally (commercial polymers) : 2 < PDI < 20 Metallocene polyethylene : 1 < PDI < 2