Polymers

• Greek “Poly” meaning many and “Meros” meaning parts

• Their consequently large molecular mass, relative to small molecule
compounds, produces unique physical properties including toughness,
viscoelasticity, and a tendency to form glasses and semi crystalline
structures rather than crystals
Classification of Polymers
• Based on the origin
• i) Natural Polymers
Protein-based: Albumin, Collagen, gelatin etc.
Polysaccharides: Agarose, alginate, carrageenan, chitosan,
cyclodextrins, dextran, hyaluronic acid, polysialic acid etc.
• ii) Synthetic Polymers
• Biodegradable
• Polyesters: Poly(lactic acid) (PLA), poly (glycolic acid) (PGA), poly (hydroxyl
butyrate) (PHB), poly (Ɛ-caprolactone) (PCL), poly(β-malic acid) (PMA),
poly(dioxanones) (PDA) etc.
• Polyanhydrides: Poly(sebacic acid) (PSBA), poly(adipic acid) (PAPA),
poly(terphthalic acid) (PTA) and various copolymers etc.
• Polyamides: Poly(imino carbonates) (PIC), polyamino acids (PAA) etc.
• Phosphorus-based: Polyphosphates, polyphosphonates, polyphosphazens etc.
• Others: Poly(cyano acrylates) (PCA), polyurethanes, polyortho esters,
polydihydropyrans,polyacetals etc.
• Non-biodegradable
• Cellulose derivatives: Carboxymethyl cellulose (CMC), ethylcellulose (EC),
cellulose acetate (CA), cellulose acetate propionate (CAP), hydroxypropyl
methylcellulose (HPMC) etc.
• Silicones: Polydimethylsiloxane (PDS), Colloidal silica etc.
• Acrylic polymers: Polymethacrylates (PMA), poly(methyl methacrylate)
(PMMA), poly hydro(ethyl methacrylate) (PHEM) etc.
• Others: Polyvinyl pyrrolidone (PVP), ethyl vinyl acetate (EVA), poloxamers,
poloxamines etc.
• iii) Semi-synthetic Polymer: Hydrogenated natural rubber,Cellulose
nitrate,methyl cellulose etc are chemically modified polymers.
2. BASED ON BACKBONE

• Polymers with carbon chain backbone: Polyethylene, polypropylene,

polystyrene, poly(vinyl chloride), polytetrafluoroethylene,
polyacrylonitrile, poly(vinyl alchol), poly(vinyl acetate),
polyacrylamide, poly(methyl methacrylate), polyvinylpyrrolidone, etc.
• Polymers with hetero chain backbone: Poly(ethylene oxide),
poly(propylene oxide), cellulose (poly –glucoside,β →1,4), amylase
(poly-glucoside, alpha → 1,4) (component of starch), pectinic acid
(polygalacturonoside), polyethylene glycol terphthalate,
polydimethylsiloxane etc.
3. Based on the presence of carbon (organic and inorganic)

• Organic Polymers: Polymer whose backbone chain is essentially made

of carbon atoms is termed an organic polymer.
• The atoms attached to the side valencies of the backbone carbon
atoms are, however, usually those of hydrogen, oxygen, nitrogen, etc.
The majority of synthetic polymers is organic and they are extensively
studied.
• Inorganic Polymers: The molecules of inorganic polymers, on the
other hand, generally contain no carbon atom in their chain
backbone.
• Glass and silicone rubber are examples of inorganic polymers.
4. Based on the types of monomer

• On this basis, polymers can be classified into two classes.

• Homopolymer: A polymer containing a single type of repeat units is called
a homopolymer, e.g., polystyrene.
• Copolymer: If a polymer is made up of two different monomers then it is
called copolymer, e.g., styrene butadiene (SBS) rubber and Sty-co-An.
5. Based on the Polymerization process
• Carothers in 1929 classified polymers into two types on the basis of
mechanism of polymerization reaction:
• (i) Addition polymers
• (ii) Condensation polymers
• Addition polymers: Addition polymerization reaction is responsible for formation
of polymer. Double and triple bonds are possessed by these monomer
molecules. E.g., polythene, polypropene, polystyrene, polyvinyl chloride etc.
• Condensation polymers:
• Condensation polymerization reaction is responsible for the formation of
polymers.
• Elimination of small molecule such as water, alchol, hydrogen chloride etc takes
place by this polymerization reaction.
• It possesses bi functional or poly functional monomers.
• The reaction can take place between two similar or different monomers.Nylon-6,
6 Nylon-6, Terylene, glyptal etc are the examples of condensation polymers.
6. Based on the Line structure

• The monomer units in a polymer may be present in linear, branched or crosslinked fashion.
• Linear Polymer: A straight chain species i.e., the units are connected to each other in a chain
arrangements.
• Linear polymers may be represented by a chain with two ends, e.g., high density polyethylene.
• Branched Polymer: The main chains of polymer molecules have small branches of the same or
different molecules.
• Branched polymers have side chains, or branches of significant length which are bonded to the main
chain at branched points, and are characterized in terms of the number and size of the branches.
• Polymers with well controlled modes of branching, e.g., comb like polymers, star polymers,
dendrimers, low density polyethylene, graft copolymers etc
• Cross-linked Polymer: Those polymers in which two linear chains are joined together by covalent
bonds i.e, the chains are crosslinked.
• E.g., Bakelite. Vulcanized rubber Novolac, melamine-formaldehyde.
7. Based on thermal characteristics / thermo response

• Polymers can be classified into two categories on the basis of their behaviour towards
temperature:
• Thermoplastic polymers: They are those polymers which can be softened on heating and
hardened on cooling, e.g., linear polymers.
• Since no chemical change occurs in the structure of the polymer molecule as a result of
heating, therefore these polymers can be recycled many times. Examples of such polymers
are Polyolefins, nylons, linear polyesters and polyether’s, PVC, sealing wax etc
• Thermosetting polymers: Conversion of polymers into an infusible mass is because of
chemical changes.
• Production of giant molecules and cross-linking of polymer chain molecules and the curing
or setting process involves chemical reaction leading to further growth.
• They cannot be softened once get solidified either by heating or by curing agents.
• Thermosetting polymers can notbe recycled as a chemical change occurs in thermoset
8. Based on interaction with water

• Non‐biodegradable hydrophobic Polymers: E.g. Polyvinyl chloride

• Soluble Polymers: CP, HEC, HPC, HPMC, PEG, PAA, sodium CMC, sodium
alginate
• Insoluble polymers: Chitosan (soluble in dilute acids), ethyl cellulose, PC
• Hydro gels: Polyvinyl pyrrolidone
9. Based on stimuli response
• Photo responsive polymers: PAA[30,31], PHPMAm[32, 33], and PNIPAM.
• pH responsive polymers: Chitosan[36], albumin[37], gelatin[38], poly(acrylic
acid) (PAAc)/chitosan IPN[39], poly(methacrylic acid-g-ethylene glycol) [P(MAA-
g-EG)][40,41], poly(ethylene imine) (PEI)[42], poly(N,N-diakylamino
ethylmethacrylates) (PDAAEMA), and poly(lysine) (PL).
• Inflammation responsive polymers: Hyaluronic acid.
• Temperature responsive polymers: Poly(N-alkyl substituted acrylamides): e.g.
poly(N-isopropylacrylamide) (PNiPAAm), Poly (N-vinylalkylamides): e.g. poly(N-
vinylcaprolactam) (PNVC), and copolymers such as poly (L-lactic acid)-poly(ethylene
glycol)-poly(L-lactic acid) (PLLA-PEG-PLLA) triblock copolymers, and poly (ethylene
oxide)-poly(propylene oxide)-poly (ethylene oxide) (PEO–PPO–PEO) copolymers.
• Electro-Responsive Polymers: Polythiophene (PT) or sulphonated-polystyrene (PSS)
• Redox-Responsive Polymers: Acid labile moieties inside polyanhydrides,
poly(lactic/glycolic acid) (PLGA), and poly(b-amino esters) (PbAEs) induce redox
responsiveness.
• Enzyme-Responsive Polymers: Pectin, chitosan, amylase/amylopectin, cyclodextrin
and dextrin.
10. Based on Morphology

• Crystalline Polymers: e.g, syndiotactic polypropylene.

• Amorphous polymers: e.g., atactic polypropylene
11. Based on tacticity
• With respect to main chain (back bone) of the polymer, the polymer posses geometric
arrangement of characteristic group of monomer units which is called as tacticity. It classified into
three groups as following:
• Isotactic polymers: A polymer in which substitents group is located on one side of plane of
carbon-carbon chain, i.e., every chiral carbon has the same co figuration, is called isotactic.. E.g:
Isotactic polypropene.
• Syndiotactic polymers: A polymer, in which substituents group is attached alternatively above and
below the plane of carbon-carbon chain, is called syndiotactic. E.g., syndiotactic polypropylene
• Atactic polymers: A polymer, in which there is no systematic configuration is called atactic
polymers, e.g., atactic polypropylene. It has proper strength and more elasticity.
Based on Charge
• Cationic: Aminodextran, chitosan, (DEAE)- dextran, TMC
• Anionic: Chitosan-EDTA, CP, CMC, pectin, PAA, PC, sodium alginate,
sodium CMC, xanthan gum
• Non-ionic: Hydroxy ethyl starch, HPC, poly (ethylene oxide), PVA
13. Based on Potential
• Covalent: PVP, scleroglucan
• Hydrogen bond: Cyanoacrylate
14. Based on bioadhesive forces
• Electrostatic interaction: Acrylate (hydroxylated methacrylate), poly
(methacrylic acid), CP, PC, PVA, chitosan.
15. Based on Physical properties
• Elastomers: e.g., Natural rubbers, synthetic rubber.
• Plastic : e.g., polyethylene, polystyrene.
• Fibres : e.g., saran, vinyon, orlan
CHARACTERISTICS OF IDEAL
POLYMER
Low Density.
Low coefficient of friction.
Good corrosion resistance.
Good mould ability.
Excellent surface finish can be obtained.
Can be produced with close dimensional tolerances.
Economical.
Poor tensile strength.
Low mechanical properties.
Poor temperature resistance.
Can be produced transparent or in different colours
SOME COMMON ADDITION POLYMERS
SOME CONDENSATION POLYMER
GENERAL MECHANISM OF DRUG
RELEASE
FROM POLYMER
• Diffusion
• degradation
• water penetration(Swelling)
DRUG RELEASE FROM POLYMER BY
DIFFUSION
• Drug release from polymer by diffusion-Rate limiting step is diffusion
of drug through inert water insoluble membrane barrier. There are
two types,
a) Reservoir
b) Matrix
RESERVOIR DIFFUSION SYSTEM
• In membrane-controlled reservoir devices, the drug is contained in a
core, which is surrounded by a polymer membrane, and it is released
by diffusion through the rate controlling membrane e.g. Poly(Nvinyl
pyrrolidone),Poly(ethylene-co-vinyl acetate).
MATRIX DIFFUSION SYSTEM
• In these devices, the drug is released either by passing through the
pores or between polymer chains, and these are the processes that
control the release rate. Such as polyethylene , polyvinyl acetate
DEGRADATION
• The drug molecules, which are initially dispersed in the polymer, are
released as the polymer starts eroding or degrading. The four most
commonly used biodegradable polymers in drug delivery systems are
poly(lactic acid), poly(lactic-co-glycolic acid), polyanhydrides,
poly(ortho esters), and poly(phosphoesters)
WATER PENETRATION (SWELLING)
This type of systems are initially dry and when placed in body, absorb
water or other fluid and it swells. Swelling increases aq. solvent content
within the formulation as well as the polymer mesh size, enabling the
drug to diffuse through the swollen network into external environment.
E.g (N-isopro-pylacrylamide), Ethylene-vinyl alcohol
PROPERTIES OF POLYMERS
• Crystallinity
• Viscosity
• Polymer complexes
• Syneresis
• Adsorption of macromolecules
• Bioadhesivity of water- soluble polymers
• Polymer dissolution