Department of Pharmacy (Pharmaceutics) | Sagar savale

Polymer

Mr. Sagar Kishor savale

[Department of Pharmacy (Pharmaceutics)]
avengersagar16@gmail.com
17-12-2015
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 Contents
I

1. Introduction
2. IUPAC Definition
3. Common Polymers
4. Polymer Recycling Codes
5. The number code indicates the polymer type
6. Polymer
7. Characteristics of polymer
8. Classification of Polymer
9. Polymerization Techniques
10. Poloxamer
11. Biocompatibility Testing of Polymers
12. Biodegradable Polymer
13. Factors
14. Characterizations
15. Polymer used in drug Delivery system
16. Applications
17. Reference
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 1. Introduction
 A word polymer is a combination of two Greek words, “Poly” means “many”
and “Meros” meaning “parts or units”.
 A polymer is a large molecule of which is formed by repeated linking of the
small molecules called “monomers”.
 More monomer molecules joined in units of long polymer.

n(CH2-CH2) (-CH2-CH2-)n
ethylene polyethylene

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• Polymer - a long chain molecule made up of many small identical units of
Monomer is known as Polymer.

• Monomer - the smallest repeating unit is known as Monomer.

• Polymer is a molecule is obtained by natural and synthetic origin having

group of Smallest repeating unit is known as polymer.

• Polymer is important for increasing the stability of drug molecule, it is

important to influencing the solubility of drug molecule, it is important to
maintain the Physicochemical properties, it is important to maintain the
prolong stability of drug molecule in extended period of time, it is important
for influencing the Bioavailability of drug.
• Polymer is important for Pharmaceutical industries and research purpose.
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 2. 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
(constitutional repeating units) 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.”

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 3. Common Polymers
• Polymers are common in nature. Wood, rubber, cotton, silk, proteins, enzymes,
and cellulose are all examples of polymers
• A wide variety of synthetic polymers have been produced, largely from
petroleum based raw materials. These include polyurethane, teflon,
polyethylene, polystyrene, and nylon.

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 4. Polymer Recycling Codes

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 5. The number code indicates the polymer type

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 6. Polymer

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 7. Characteristics of polymer
1. Low Density.
2. Low coefficient of friction.
3. Good corrosion resistance.
4. Good mould ability.
5. Excellent surface finish can be obtained.
6. Can be produced with close dimensional tolerances.
7. Economical.
8. Poor tensile strength.
9. Low mechanical properties.
10. Poor temperature resistance.
11. Can be produced transparent or in different colours

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 8. Classification of Polymer
1. classification based on source
2. classification based on structure
3. classification based on polymerisation
4. classification based on molecular force

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 1. Classification based on source
1. Natural polymers - The definition of a natural polymer is a polymer that
results from only raw materials that are found in nature. Example - Proteins,
Cellulose, Starch, Rubber.

2. Semi-synthesis polymers – The polymer can obtained both Natural as well as

Synthetic origin is known as Semisynthetic polymer. Example - Cellulose
derivatives - Cellulose acetate (Rayon).

3. Synthesis polymers - This are the polymer was prepared by Laboratory is

known as Synthetic Polymer. Example - Buna-S, Buna-R, Nylon, Polythene,
Polyester.
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 2. Classification based on structure
1. Linear polymers - the smallest repeating unit arrange in straight line
path is known as Linear polymer. Example - pvc.

2. Branched chain polymers - contain linear chains having some branches,

Example - low density polymer.

3. Cross linked chain polymers - formed from bi-functional and tri-functional

monomers and contain strong covalent bonds. Example - bakelite, melamine.

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 Cross linked chain polymers
Linear polymers

Branched chain polymers

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 3. Classification based on polymerization
• Addition polymers
formed by the repeated addition of monomer molecules possessing double or triple bonds
n(CH2=CH2) -(CH2 -CH2 )-
Ethylene polyethylene
One from of polymer is converted into anther from of polymer loss of atoms, ion, from Molecule.
• Condensation polymers
formed by repeated condensation reaction between two different bi-functional or tri-functional
monomeric units.
e.g. terylene (dacron), nylon 6, 6, nylon 6.

n(H2N(CH2)6 NH2) + n(HOOC(CH2)4COOH) [-NH(CH2)6NHCO(CH2)4CO-]n + nH2O

(Nylon 6:6)
One polymer can converted into anther from of polymer without loss of atoms, ion, from molecule.
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 Addition polymers Condensation polymers

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 Mechanism of addition polymeriasation
1. Free radical mechanism - Alkenes or dienes and their derivatives are polymerized in the presence
of a free radical generating initiator (catalyst) like benzoyl peroxide, acetyl peroxide, t-bu peroxide, etc.
This process involves three steps,
1. Chain initiation step - addition of phenyl free radical formed by the peroxide to the ethane double bond ,thereby
forming a larger radical.
2. Chain propagation step - repetition of this sequence with new and bigger radicals.
3. Chain terminating step - the product radical thus formed reacts with another radical to form the polymerized product.

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 Condensation Polymerization
• The resin is formed by condensation co-polymerization of melamine and
formaldehyde.

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 4. Classification based on molecular force
1. Nylon :- Nylon is used as general name for all synthetic fiber forming polyamides,i.e., having a protein like
structure. These are the condensation polymers of diamine and dibasic acids A number is usually suffixed with
the Nylon which refers to the number of carbon atoms present in the diamine and the dibasic acids respectively.
example: nylon 6,6, nylon-6,6: Nylon-6,6 is obtained by the polymerization of adipic acid with hex methylene
diamine.

n(H2N(CH2)6 NH2) + n(HOOC(CH2)4COOH) [-NH(CH2)6NHCO(CH2)4CO-]n + nH2O

(Nylon 6:6)

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 2. Thermoplastic Polymers
• These are linear or slightly branched long chain polymers, which can be softened on heating
& reversibly hardened on cooling repeatedly. Their hardness is a temporary property & varies
with temperature.
• The polymer under heating it can convert one stare to anther state and after cooling it can
again convert its original state.

Example:- polyvinyl chloride.

Polyvinyl chloride:- It is a vinyl polymer constructed of repeating vinyl groups (ethenyls) having one of
their hydrogen's replaced with a chloride group.

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 3. Thermosetting polymers
• Initial Mixture of Reactive, Low Molar Mass Compounds Reacts Upon Heating In The Mold To Form An
Insoluble, Infusible Network.
Example: Bakelite
Bakelite: Bakelite Is Formed of Phenol And Form-aldehyde Polymerization.

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Polymerization Techniques

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 9. Polymerization Techniques
1. Addition polymerization
1. Bulk polymerization
2. Solution polymerization
3. Suspension polymerization
4. Emulsion polymerization
2. Condensation polymerization
1. Melt polycondensation
2. Solution polycondensation

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 9.1 Bulk polymerization
1. Mass or block polymerization: Polymerization of the undiluted monomer.
2. carried out by adding a soluble initiator to pure monomer (in liquid state).
3. The mixture is constantly agitated & heated to polymerization temperature.
4. Once the reaction starts, heating is stopped as the reaction is exothermic.
5. The heat generated is dissipated by circulating water jacket.
6. Viscosity increases dramatically during conversion.
7. The method is used for the polymerization of liquid state monomers.
8. It is usually adopted to produce polystyrene, polyvinyl chloride, polymethyl
methacrylate and low density polyethylene.

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• Advantages
1. The system is simple and requires thermal insulation.
2. The polymer is obtained pure.
3. Large castings may be prepared directly.
4. Molecular weight distribution can be easily changed with the use of a chain transfer
agent.
• Disadvantages
1. Heat transfer and mixing become difficult as the viscosity of reaction mass increases.
2. Highly exothermic.
3. The polymerization is obtained with a broad molecular weight distribution due to the
high viscosity and lack of good heat transfer.
4. Very low molecular weights are obtained.

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 9.2 Solution polymerization
1. Some disadvantages of bulk polymerization are eliminated in solution polymerization.
2. Monomer along with initiator dissolved in solvent, formed polymer stays dissolved.
3. The mixture is kept at polymerizaion temperature & constantly agitated.
4. Depending on concentration of monomer the viscosity of solution does not increase.
5. After the reaction is over, the polymer is used as such in the form of polymer solution or the
polymer is isolated by evaporating the solvent.
6. Polymer so formed can be used for surface coating.
7. It is used for the production of Polyacrylonitrile, PVC, Polyacrylic acid, Polyacrylamide,
Polyvinyl alcohol, PMMA, Polybutadiene, etc

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• Advantages
1. The solvent acts as a diluent & helps in facilitating continuous transfer of heat of polymerization. Therefore
temperature control is easy.
2. The solvent allows easy stirring as it decreases the viscosity of reaction mixture.
3. Solvent also facilitates the ease of removal of polymer from the reactor.
4. Viscosity build up is negligible.
• Disadvantages
1. To get pure polymer, evaporation of solvent is required additional technology, so it is essential to separate &
recover the solvent.
2. The method is costly since it uses costly solvents.
3. Polymers of high molecular weight polymers cannot be formed as the solvent molecules may act as chain
terminators.
4. The technique gives a smaller yield of polymer per reactor volume, as the solvent waste the reactor space.
5. The purity of product is also not as high as that of bulk polymerization. Removal of last traces of solvent is
difficult.

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 9.3 Suspension polymerization
1. Liquid or dissolved monomer suspended in liquid phase like water.
2. Initiators used are monomer soluble e.g. dibenzoyl peroxide.
3. Thus, polymer is produced in heterogeneous medium.
4. Initiator, The size of monomer droplets is 50-200 µm in diameter.
5. The dispersion is maintained by continuous agitation and the droplets are prevented to coalesce (unite or
merge) by adding small quantity of stabilizers ; The stabilizers used are PVA, gelatin, cellulose are used along
with inorganic stabilizers such as kaolin, magnesium silicate, aluminum hydroxide, calcium/magnesium
phosphate, etc if necessary.
6. As it concerns with droplets, each droplet is tiny bulk reactor. The polymerization takes place inside the
droplet & product formed being insoluble in water. The product separated out in the form of spherical pearls or
beads of polymer. Hence the technique is also known as Pearl polymerization / Granular polymerization /
Bead polymerization. The products are small uniform spheres. They can be used directly for some applications
as precursors of ion exchange resins otherwise they can be extruded & chopped to form larger, easily moulded
pallets. They can be dissolved in a suitable medium for use as adhesives & coatings. This technique is used to
form PVC, Polyvinyl acetate, Polystyrene, Styrene-di-vinyl benzene copolymer beads (used for ion exchange)
etc.
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• Advantages
1. The process is comparatively cheap as it involves only water instead of solvents.
2. Viscosity increase is negligible.
3. Agitation & temperature control is easy.
4. Product isolation is easy since the product is insoluble in water.
• Disadvantages
1. The method can be adopted only for water insoluble monomers.
2. It is difficult to control polymer size.
3. Polymer purity is low due to the presence of suspending & stabilizing additives that are
difficult to remove completely.
4. Suspension polymerization reaction is highly agitation sensitive.
5. Larger volume of reactor is taken up by water.
6. The method cannot be used for tacky polymers such as elastomers because of the tendency
for agglomeration of polymer particles.
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 9.4 Emulsion polymerization
1. The technique is used for the production of large number of commercial plastics & elastomers.
2. The system consists of water insoluble monomer, dispersion medium & emulsifying agents or
surfactants (soaps and detergents) and a water soluble initiator (potassium persulphate / H2O2, etc).
3. The monomer is dispersed in the aqueous phase, not as a discrete droplets, but as a uniform
emulsion.
4. The size of monomer droplet is around 0.5 to 10 μm in diameter depending upon the polymerization
temperature & rate of agitation.
5. The emulsion of monomer in water is stabilized by a surfactant.
6. A surfactant has a hydrophilic and hydrophobic end in its structure.
7. When it is put into a water, the surfactant molecules gather together into aggregates called micelles.
8. The hydrocarbon tails (hydrophobic) orient inwards & heads (hydrophilic) orient outwards into
water.
9. The monomer molecules diffuse from monomer droplets to water & from water to the hydrocarbon
center of micelles.

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Examples:
• Synthetic rubber-styrene-butadiene (SBR), Polybutadiene, Polychloroprene.
• Plastics-PVC, polystyrene, Acrylonitrile-butadiene-styrene terpolymer (ABS).
• Dispersions-polyvinyl acetate, polyvinyl acetate copolymers, latexacrylic paint, Styrene-
butadiene, VAE

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• Advantages
1. High molecular weight polymers
2. fast polymerization rates.
3. allows removal of heat from the system.
4. viscosity remains close to that of water and is not dependent on molecular weight.
5. The final product can be used as such ,does not need to be altered or processed
• Disadvantages
1. Surfactants and polymerization adjuvants -difficult to remove
2. For dry (isolated) polymers, water removal is an energy-intensive process
3. Designed to operate at high conversion of monomer to polymer. This can result in
significant chain transfer to polymer.
4. Can not be used for condensation, ionic or Ziegler-Natta polymerization.

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 10. Poloxamer
 The word "Poloxamer" was coined by the inventor, Irving Schmolka, who received the patent for these materials in 1973
 Poloxamers are nonionic triblock copolymer composed of a central hydrophobic chain of polyoxypropylene
(poly(propylene oxide)) flanked by two hydrophilic chains of polyoxyethylene (poly(ethylene oxide)).
 Poloxamers are also known by the trade name Pluronics.

a’ represents ethylene oxide portion

‘b’ represents propylene oxide portion.

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 Properties
1. Poloxamers generally occur as white, waxy, free-flowing prilled granules.

2. They are practically odorless and tasteless.

3. At room temperature, Poloxamer 124 occurs as a colorless liquid.

4. Synonyms - Pluronic, Poloxalkol.

5. Chemical Name - α-Hydro-hydropoly(oxyethylene) poly(oxypropylene), poly(oxyethylene) block coploymer.

6. Empirical formula - HO(C2H4O)a(C3H6O)b(C2H4O)a H

7. Functional Category - Dispersing agent, emulsifying agent, solubilizing agent, tablet lubricant, wetting agent,
stabilizing agent.

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8. Acidity/ Alkalinity - pH =5.0-7.4 for a 2.5% w/v aq. Solution

9. Cloud Point - >1000C for 1% w/v aqueous solution, and 10% w/v aqueous
solution of Poloxamer 188.

10. Density - 1.06g/cm3 at 250C

11. Flash Point - 2600 C

12. Flow ability - solid Poloxamers are free flowing.

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 11. Biocompatibility Testing of Polymers
1. Cytotoxicity test
2. Sensitization
3. Intracutaneous Reactivity
4. Irritation
5. Systemic Toxicity (Acute Toxicity)
6. Sub chronic Toxicity (Sub acute Toxicity)
7. Chronic Toxicity.
8. Implantation
9. Haemocompatibility
10. Genotoxicity
11. Carcinogenicity
12. Reproductive & Developmental Toxicity
13. Biodegradation
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 12. Biodegradable Polymer

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 13. Factors
1. Molecular Structure
2. Molecular Weight
3. Viscosity
4. Molecular Shape
5. Solubility
6. Polymer Crystslinity
7. Glass transition temperature

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 14. Characterizations
1.Spectroscopy and spectrometry methods
Nuclear Magnetic Resonance (NMR), Infra-red (IR) and Raman, Ultra-violet-visible (UV-VIS), Fluorescence, Chirality, Optical
rotation, Circular dichroism (CD), X-ray diffraction, and Mass spectrometry
2.Scattering techniques
Small angle X-ray scattering (SAXS), Small angle neutron scattering (SANS), and Laser light scattering (LLS)
3.Electrical techniques
` Electron paramagnetic resonance (EPR), Electrochemistry, and Electrophoresis
4.Size exclusion chromatography (SEC)
5.Microscopy
Transmission electron microscopy, Scanning electron microscopy and atomic force microscopy
6.Rheology, physical properties
Intrinsic viscosity, Differential Scanning Calorimetry (DSC), and Dielectric spectroscopy (DS)
7.Miscellaneous
X-ray Photoelectron Spectroscopy (XPS), measurements of dipole moments, titrimetric, glass transition temperature etc.

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 15. Polymer used in drug Delivery system

• Polymer used in,

1. Oral drug delivery system
2. Parenteral drug delivery system
3. Ophthalmic drug delivery system
4. Mucosal drug delivery system
5. Intranasal drug delivery system
6. Pulmonary drug delivery system
7. Vaginal drug delivery system
8. Transdermal drug delivery system
9. New drug delivery system

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 16. Applications
• It is important to maintain the physicochemical properties.
• It is Non toxic, Non irritant, Non reactive.
• It can increases the stability.
• Reduced toxicity.
• It should be stable in formulation or preparation , it can not affect original active drug.
• It is Thermodynamically stable.
• It is important to reduced dosing frequency.
• It can give sustained and prolonged released activity.
• It is important to increases the solubility of poorly water soluble drug.
• It is important to prevent the Biodegradation.
• It is important increases the dissolution rate as well as absorption rate of drug.
• It is important to increasing the Bioavailability of drug.

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Polymeric materials are used in and on soil to improve aeration, provide mulch, and promote plant growth and health.
• Medicine - Many biomaterials, especially heart valve replacements and blood vessels, are made of polymers like
Dacron, Teflon and polyurethane.
• Consumer Science - Plastic containers of all shapes and sizes are light weight and economically less expensive
than the more traditional containers. Clothing, floor coverings, garbage disposal bags, and packaging are other
polymer applications.
• Industry - Automobile parts, windshields for fighter planes, pipes, tanks, packing materials, insulation, wood
substitutes, adhesives, matrix for composites, and elastomers are all polymer applications used in the industrial
market.
• Sports - Playground equipment, various balls, golf clubs, swimming pools, and protective helmets are often
produced from polymers.

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 17. Reference
• Controlled and Novel Drug Delivery by N. K. Jain; pg no: 27-51.
• Controlled Drug Delivery Concepts and Advances by S.P.Vyas Roop K.Khar; pg no:97-155.
• Design of Controlled Release Drug Delivery System by Xiaoling Li, Bhaskara R. Jasti; pg no:271-303.
• Biodegradable Polymer as drug delivery system; “Synthetic polysaccharides”; edited by-Mark Chasin, Robert Langer Vol- 45; Page No-
43-49, 71-90,121-160.
• Advanced Drug Delivery reviews;56(2004);pg no: 1453-1466 by Gesine winzenburg et. al.
• N.K. Jain, Pharmaceutical Product Development, second edition : 2011, CVS Publishers PVT. LTD, New Delhi. Pg.No.701-741.
• Anderson BC et al. Understanding drug release from poly(ethylene oxide)-b-(propylene oxide)-b-poly(ethlene oxide) gels. J Control
Release 2001; 70: 157–167.
• Moore T et al. Experimental investigation and mathematical modelling of Pluromic F127 gel dissolution: drug release in stirred systems. J
Control Release 2000; 67: 191–202.
• Sweet DV, ed. Registry of Toxic Effects of Chemical Substances. Cincinnati: US Department of Health, 1987.
• Dumortier G et al. A review of poloxamer 407 pharmaceutical and pharmacological characteristics. Pharm Res 2006; 23(12): 2709–2728.
• Csaba N et al. PLGA: poloxamer and PLGA:poloxamine blend nanoparticles: new carriers for gene delivery. Biomacromolecules 2005;
6(1): 271–278.
• Food Chemicals Codex, 6th edn. Bethesda, MD: United States Pharmacopeia, 2008; 768–770.

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• Novel drug delivery systems – Y.W.Chien – Dekker 50
• Bio–adhesive drug delivery system –
Dekker 98
• Encyclopedia of controlled drug delivery systems.
• www.google.com
• Design of Controlled Release Drug Delivery System by Xiaoling Li, Bhaskara R. Jasti; pg
no:271-303.

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