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Polymer science
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DEFINITION A Polymer is a substance composed of molecules with a large molecular mass of repeating structural units or monomers connected by covalent chemical bonds.
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Types Of Linking In Polymers
Linear Polymers: A polymer in which the molecules form long chains without branches or cross-linked structures. examples: nylon, polyester, PVC etc. Branched Polymer: A polymer chain having branch points that connect three or more chain segments. Examples: polythene, glycogen, starch etc Cross linked Polymer: Cross-links are bonds that link one polymer chain to another. They can be covalent bonds or ionic bonds. Examples: malamine formaldehyde resin etc Linear & Branched Polymers are know as thermoplastic materials. Cross linked Polymer are know as thermosetting materials. 4
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Polymer classes include
Bio polymer Conductive polymer Co polymer Fluoro polymer In organic polymer Poly ester rubber silicone Synthetic rubber Vinyl polymer
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Classification of polymers
A. Depending on response to heat a. Thermoplastic : linear or slightly branched Solid melt solid resolidification Weak attractive forces hence, can be remolded. Eg :PE, PVP,PVC etc.
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Classification of polymers
a.Depending on response to heat b.Thermosetting: Extensive cross linking covalently Solid Decomposed solid Chains cannot be easily broken. Eg : Epoxy resin, Poly urethane.
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Classification of polymers (b)Based on chemical reaction
Condensation polymerisation Addition polymerisation
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Classification of polymers
Addition polymerization Condensation polymerisation
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Classification of polymers (C.) Based on repeating units
Homo polymer: [A-A-A-A] Co polymer : [A-B-A-B-A-B] Alternating copolymers : [A-B-A-A-B-A-B-B] Random copolymers [A-B-B-B-A-B-B-B] Block copolymers:
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Classification of polymers (D.)Based on origin of polymer
(i )Natural polymers Eg:Gelatin, Xantum gum , Sodium alginate etc. (ii.)Semi synthetic polymers Eg: Methyl cellulose, HPC, HPMC, etc. (iii.)Synthetic polymers Eg ;carbopol, PVA, PVP, PEG,etc.
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Classification of polymers (E). Based on degradation properties
Non bio degradable Eg:EC, PVC. Bio degradable Bulk eroding polymer eg:PLGA Surface eroding polymers eg:Polyanhydrides
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Classification of polymers
Natural and synthetic polymers cotton., silk ,wool PVC, nylon ethylene Organic and inorganic polymers Glass , silicone, rubber Thermoplastic Thermoplastic & Poly ethylene, sealing wax. Plastics,Elastomers, Fibers, Liquid Resins PVC, polystyrene,PMC Nylon terelene
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Molecular weight There are different ways that molecular weights of a polymer can be expressed: By number of chains By the weight of chains By viscosity The two most common ways are Number(Mn) And weight average calculations
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Molecular weight determination
1. Number Average Molecular Weight Molecular weight is determined by calculating the total molecular weight of monomer and total number of monomer. Mi- total molecular weight of monomer. Ni- number of monomer molecules. Mn- number average molecular weight.
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Molecular weight determination
2. Weight Average Molecular Weight M - weight average molecular weight. Mi- total molecular weight of monomer. Ni- number of monomer molecules.
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Characteristics of ideal polymer
Inert Non toxic Good mechanical strength Easily administered
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CRITERIA FOLLOWED IN POLYMER SELECTION
The polymer should be soluble and easy to synthesis It should have finite molecular weight It should be compatible with biological environment It should be biodegradable It should provide good drug polymer linkage
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Preparation of polymer solution
Upon contact , the solvent molecules diffuses into the solid particles swell them and then into gel particles The solvated polymer molecule diffuses out into the solvent . By stirring it reduces the thickness of the stagnant liquid layer surrounding each particle Powders or grains are added to solvent. Stirring done inorder to prevent aggregation that forms lumps. Eg: MC should be dispersed with high shear in about 1/4th the total amount of water heated to 80 Cto 90 c If particles are wetted and dispersed the rest of water is added cold to about 50 c. Swells and dissolves the dispersed paticles fast with moderate shear.Eg:HPC,HPMC o o o
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Conti………………. Eg:PVA &SCMC are soluble in hot than in cold water.
So dipersed in ice cold water followed by dissolution at 90oc Eg: Dissolved in 80% toulene &20%ethyl alcohol . First toulene is added , the alcohol is then added to effect prompt dissolution. Cellulose derivatives are stored for 48 hours after dissolution to promote full hydration , viscosity, & clarity.
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Thermodynamics of polymer solutions
For the dissolution of a polymer in the solvent at a temperature T , the Gibbs free energy of mixing is ΔG = ΔH - TΔS The important points to be considered in thermodynamics of polymer solution are Heat of mixing Entropy of mixing Free energy of mixing
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Phase seperation This technique is used in micro encapsulation of drugs by using high molecular weight long chain flexible polymers. These polymers are used for their rate retarding properties Phase seperation-coacervation Core(drug) Coat(polymer) LMV(liquid manufacturing vehicle)
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Cont……………… Rigidisation of micro capsules
To achieve this phase seperation different methods employed are Changing in temperature Addition of incompatible polymer Non solvent addition Salt addition Polymer polymer interactions How the deposition of coat over core materials occurs? Rigidisation of micro capsules Formed embryo microcapsules are gets hardened by various methods like Thermal linking Cross linking
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Polymers in solid state
Solid polymers depends on: Mechanical , permeability, electric, thermal, optical properties. These factors determine the flexibility and strength of the polymers For amorphous polymers cross linking or the fillers may be desirable.
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Properties of polymers
A.Physical properties of polymers The properties of polymer depends on many factors including inter and intrachain bonding Presence of additives Chain size and geometry Molecular weght distribution Polymers do not boil
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a.Physical properties Glass transition temperature(Tg) (Tg)
Vinyl polymers (Tg)Below room temperature flexible Rubber &plastic Glass transition temperature(Tg) (Tg) Condensation polymers (Tg) above room temperature Hard plastics Many polymers brittle at room temperature. To become liable plasticizers added that allow segmental mobility Eg: PVC, & poly styrene
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a. Physical properties conti…………
Inflexible region Hard Flexible region Soft Urethane portion Hydrogen bonding Hard Polyether portion Flexible Soft Poly urethanes Room temperature
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b.Chemical properties Different side groups on the polymer can lend to: Ionic bonding Hydrogen bonding Polymers containing amide or carbonyl groups can form hydrogen bonds between adjacent chains. Polyesters have dipole –dipole bonding between the oxygen atoms in C=Ogroups and the hydrogen ato.ms in C-H groups. Dipole bonding is not as strong as hydrogen bonding
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c. Mechanical properties
Depending on their structure , molecular weight , and intermolecular forces, polymers resist differently when they are stressed. For elastic materials the stress and strain correlation is linear upto the failure point For fibres and highlt cross linked polymers the slope of the stress and strain line is steeper. Energy is needed to break the polymer . The area under the stress/strain measures it. The larger the area, is the tougher the polymer.
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Tacticity Tacticity describes the relative steriochemistry of chiral centers in neighbouring structural units within a macromolecule. There are three types : Iso tactic A tactic Syndiotactic
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Thermal characterisation
Thermal analysis of the polymers is the important phenomenon to study the stability and degradation of polymers. Method :- a) TGA b) DSC c) Thermo mechanical analysis
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THERMOGRAVIMETRICAL ANALYSIS (TGA)
This method provides indication for thermal stability and upper limit of thermal degradation where loss of sample begins. This method only measures loss of volatile content from the polymer. This method has limitation that it can not detect temperature at chain cleavage of chain takes place.
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Differential Scanning Calorimetry (DSC)
parameters measured- Glass transition temperature (Tg) Crystalline melting point Heat of fusion Heat of crystallization It requires placing of Reference and test sample for the continuous monitoring in the heating chamber.
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Differential scanning calorimetry
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Thermo Mechanical Analysis (TMA)
This method is used for determination of deformation of polymer sample as a function of temperature placed on platform in contact with probe. It measures transition from glassy to a rubbery polymer and gives idea about softening temperature.
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Pharmaceutical applications of polymers
1.Biomaterials for delivery systems Polyurethanes Polysiloxanes Poly methyl methacrylate Poly vinyl alcohol Polyethylene Poly vinyl pyrrolidone
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Biomaterials for delivery systems
Currently being used polymers Polymers which degrade in body poly (2-hydroxy ethyl methacrylate). Poly( acrylic acid) Poly(N-vinyl pyrrolidone) Poly(methyl methcrylate) Poly vinyl alcohol Poly acryl amide Poly(methacrylic acid). PEG Polyethylene-co-vinyl acetate Poly actides Polyglycolides Poly (lactide-co-glycolides) Poly anhydrides Poly orthoesters
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Polymers in controlled drug delivery
Micrograph of particles used to carry drugs to the lung Drug levels in the blood with Traditional drug dosing Controlled delivery dosing
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Controlled release mechanisms
Drug delivery from a typical matrix drug delivery system Drug delivery from typical reservoir devices: Implantable or oral systems Trans dermal systems
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Bio degradable systems
Drug delivery from : Bulk eroding and Surface eroding bio degradable systems Bio degradabl micro particles of 60:40 lactide :glycolide PLGA Bio degradable micro particle of 75:25 lactide:glycolide PLGA after 133 days of degradation in water
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Applications of polymers
Dental Ophthalmic orthopedic Sutures Drug delivery Drugs Tablets Liquids For controlling the flow semi solids
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References Bio pharmaceutics and pharmacokinetics by: D.M.Bharmankar, Sunil.B. Jaiswal. Govariker V. R., Viswanathan N. V., Sreedhar J., “Polymer Science”, New age publications, Jain N.K., Controlled and novel drug delivery, CBS Publisher,New delhi, Martin A., Swarbrick J., Commarata A., Physical pharmacy, K.M.varghese company, Bombay, Sinko P.J.,Physical pharmacy and pharmaceutical sciences, fifth edition, lippincot williams & wikins co.,
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