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UNIT 1: Polymers

Syllabus: Introduction, classification, properties, advantages and application of polymers in

formulation of controlled release drug delivery systems.

Introduction
Polymers are high molecular weight compounds obtained by repeated union of simple
molecules (Monomers). Ex: Starch, Polyvinyl chloride, Polyethylene, Nylon etc. The word ‘
Polymer’ is coined from two Greek words: poly means many and mer means unit or part.
The term polymer is defined as very large molecules having high molecular mass. These are
also referred to as macromolecules, which are formed by joining of repeating structural units
on a large scale. The repeating structural units are derived from some simple and reactive
molecules known as monomers and are linked to each other by covalent bonds.
This process of formation of polymers from respective monomers is called polymerization. The
transformation of ethene to polythene and interaction of hexamethylene diamine and adipic
acid leading to the formation of Nylon are examples of two different types of polymerization
reactions.

Monomers
The monomer is a simple repetitive unit that when joined together in large numbers gives rise
to a polymer. These are the building blocks of Polymer
Ex: Vinyl chloride, Ethene, Propylene etc.

The number of repeating units (n) in the chain so formed is called the Degree of
polymerization (DP=n). Polymers with a high degree of polymerization are called High
polymers and those with low degree of polymerization are called Oligo polymers.
Degree of polymerization (DP)
Degree of polymerization is a number, which indicates the number of repetitive units
(monomers) present in the polymer. By knowing the value of DP, the molecular weight of the
polymer can be calculated.

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Molecular weight of the polymer= DP x Molecular weight of each monomer.

DP is represented as ‘n’.
Ex: (CH2-CH2)n ………………….Polythene
Here ‘n’ is the DP.
i) Calculate the molecular weight of the polythene polymer given DP is 100. Molecular weight
of the polythene = DP X Molecular weight of Polythene
= 100 X 28=2800.
Basic Concepts
1.Functionality
2. Nomenclature of Polymers
3. Tacticity
1. Functionality
The functionality of a monomer is the number of sites it has for bonding to other monomers
under the given conditions of the polymerization reaction. Thus, a bifunctional monomer, i.e.,
monomer with functionality two, can link to two other molecules under suitable conditions.
A polyfunctional monomer is one that can react with more than two molecules under the
conditions of the polymerization reactions.
Ex: The double bond in vinyl monomers (CH2 = CHX) can be considered as a site for two
free valencies. When the double bond is broken, two single bonds become available for
combination.
H2C=CHX → --- CH2 – CHX ------
2. Nomenclature of Polymers
Polymers are classified in to four types
a) Homo Polymers b) Hetero polymers c) Homo chain Polymers d) Hetero chain polymers
a) Homo Polymers : Polymers made up of with same type of monomers are called homo
polymers eg: Poly ethylene, PVC

b) Hetero polymers : Polymers made up of with different type of monomers are called hetero
polymers eg: Hemicellulose

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c) Homo chain Polymers : If the main chain consists of only one type of atoms called Homo
chain Polymers eg: polyethylene

d) Hetero chain polymers: If the main chain consists of different type of atoms called Hetero
chain Polymers
eg: Nylon

3. Tacticity – The difference in configuration due to the orientation of different functional

groups with respect to the main chain is called tacticity. It is of three types
a) Isotactic – If all the functional groups are arranged on the same side of main chain is called
isotactic
b) Syndiotactic - If all the functional groups are arranged in the alternative fashion of main
chain is called Syndiotactic
c) Atactic - If all the functional groups are arranged in random of main chain is called atactic

Classification of polymers
[1] by Source [2] by Backbone of the chain [3] by Structure [4] by Compostion [5] by Mode
of Polymerization [6] by Molecular force
1. Classification Based on Source
[A] Natural Polymers
These polymers are found in plants and animals. Alginate, chitosan, starch, guar gum, xanthan
gum, gellan gum
[B] Semi-synthetic Polymers
They are derived from naturally occurring polymers and undergo further chemical
modification. cellulose nitrate and cellulose acetate.
[C] Synthetic Polymers

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These are human-made polymers. Plastic is the most common and widely used synthetic
polymer. It is used in industries and various dairy products. For example, nylon, polyether, etc.
2. Classification Based on Backbone of the polymer chain
(A) Organic Polymers
A polymer whose backbone chain is essentially made of carbon atoms is termed as organic
polymer. The atoms attached to the side valencies of the backbone carbon atoms are, however,
usually those of hydrogen, oxygen, nitrogen, etc.

(B) Inorganic Polymers

On the other hand, generally chain backbone contains no carbon atom is called inorganic
polymers. silicone polymer are examples of it.

3. Classification Based on Structure of Polymers

4. Classification Based on Composition of Polymers

[1] Homopolymer
A polymer resulting from the polymerization of a single monomer; a polymer consisting
substantially of a single type of repeating unit.

[2] Copolymer

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When two different types of monomers are joined in the same polymer chain, the polymer is
called a copolymer.

5. Classification Based on Mode of Polymerisation

(a) Addition Polymers and (b) Condensation Polymers.
(a) Addition Polymers
The addition polymers are formed by the repeated addition of monomer molecules possessing
double or triple bonds, e.g., the formation of polythene from ethene and polypropene from
propene.
However, the addition polymers formed by the polymerisation of a single monomeric species
are known as homopolymer, e.g., polythene.

The polymers made by addition polymerisation from two different monomers are termed as
copolymers, e.g., Buna-S.

(b) Condensation Polymers

A condensation reaction combines two molecules into a single molecule with the loss of a
small molecule such as water, ethanol or water.
The condensation polymers are formed by repeated condensation reaction between two
different bi- functional or tri- functional monomeric units. In these polymerisation reactions,
the elimination of small molecules such as water, alcohol, hydrogen chloride, etc. take place.
The examples are terylene (dacron), nylon, etc.

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6. Classification Based on Molecular Forces

The mechanical properties of polymers are governed by intermolecular forces, e.g., van der
Waals forces and hydrogen bonds, present in the polymer. These forces also bind the polymer
chains.
Under this category, the polymers are classified into the following groups on the basis of
magnitude of intermolecular forces present in them. They are
(i) Elastomers
(ii) Fibers
(iii) Liquid resins
(iv) Plastics [(a) Thermoplastic and (b) thermosetting plastic].
(i) Elastomers
These are rubber – like solids with elastic properties. In these elastomeric polymers, the
polymer chains are held together by the weakest intermolecular forces. These weak binding
forces permit the polymer to be stretched.

A few ‘crosslinks’ are introduced in between the chains, which help the polymer to retract to
its original position after the force is released as in vulcanised rubber.
ii) Fibers
Fibres are the thread forming solids which possess high tensile strength and high modulus.
These characteristics can be attributed to the strong intermolecular forces like hydrogen
bonding. These strong forces also lead to close packing of chains and thus impart crystalline
nature.
Examples are polyamides (nylon).

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The carbonyl oxygen and amide hydrogens can hydrogen bond with each other. This allows
the chains to line up in an orderly fashion to form fibers.
iii) Liquid Resins
Polymers used as adhesives in a liquid form are described liquid resins. Examples are epoxy
adhesives and polysulphide sealants.

(iv) Plastics [(a) Thermoplastic and (b) thermosetting plastic]

A polymer is shaped into hard and tough utility articles by the application of heat and
pressure called ‘plastic’. Typical examples are polystyrene, PVC and polymethyl
methacrylate.
They are two types (a) thermoplastic and (b) thermosetting plastic.
Thermoplastic Polymers
Some polymers soften on heating and can be converted into any shape that they can retain on
cooling. The process of heating, reshaping and retaining the same on cooling can be repeated
several times. Polyethylene, PVC, nylon and sealing wax are examples of thermoplastic
polymers.
Thermosetting Polymers
Some polymers, on the other hand, undergo some chemical change on heating and convert
themselves into an infusible mass.

These polymers are cross linked or heavily branched molecules, which on heating undergo
extensive cross linking in moulds and again become infusible. These cannot be reused. Some
common examples are bakelite, urea- formaldelyde resins, etc.

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Average molecular weight

The polymer molecules are not identical but are a mixture of many species with different
degrees of polymerization, that is, with different molecular weights. Therefore, in the case of
polymers we talk about the average values of molecular weights.
The molecular weight of a polymer is given by the product of the molecular weight of the
repeat unit (the ‘‘mer”) and the number of repeat units. Molecular weight distribution has one,
two or more peaks, are respectively referred to mono-modal distribution, bimodal or
multimodal. The molar mass can be measured by exclusion chromatography or by determining
the intrinsic viscosity in the solution (rheological measurements).
There are two ways to calculate the average molecular weight:
A) The number-averaged molecular weight (Mn) of a polymer is the total weight of all of
the polymer’s chains divided by the total number of chains.
Mn = (Total weight of all of the polymer chains)/(Total number of chains)
Number of chains = N1, N2, N3,…………….Ni
Molecular weight of chains = M1, M2, M3,………Mi
Total weight of chains or number of monomers
= N1M1+N2M2+N3M3+…………..+NiMi
𝑁1 𝑀1 +𝑁2 𝑀2 +⋯……………….+𝑁𝑖 𝑀𝑖 ∑ 𝑀𝑖 𝑁𝑖
𝑀𝑛 = = ∑ 𝑁𝑖
……………………………………………….(1)
𝑁1 +𝑁2 +⋯………………+𝑁𝑖

B) The weight-averaged molecular weight (Mw) is the sum of the square of the total
molecular weight divided by the total molecular weight.
∑ 𝑊𝑖 𝑀𝑖 𝑊1 𝑀1 +𝑊2 𝑀2 …… 𝑁1 𝑀1 𝑀1 +𝑁2 𝑀2 𝑀2 +⋯. 𝑁 𝑀2 +𝑁 𝑀2 …… ∑ 𝑁𝑖 𝑀𝑖2
𝑀𝑤 = ∑ 𝑊𝑖
= = = 𝑁 1𝑀 1+𝑁 2𝑀 2……… = ∑ 𝑁𝑖 𝑀𝑖
……………(2)
𝑊1 +𝑊2 …………. 𝑁1 𝑀1 +𝑁2 𝑀2 +⋯.. 1 1 2 2

(Mn<Mw)

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C) Polydispersity/ heterogeneity index(PDI)

PDI = Mw/Mn
Monodisperse: Molecules have the same size, shape or mass.
Mw=Mn
PDI = 1
Polydisperse: Mixture have an inconsistent size, shape, and mass distribution.
Mw>Mn
PDI > 1
Polymer hydrophobicity
CDDS exposes the polymers to the aqueous environment which absorbs water. The polymer
and water interaction is important in CDDS. Nature of polymer-water interactions, polymers
can be classified as
1. Hydrophobic polymer 2. Hydrophilic polymer 3. Water soluble polymer 4. Hydrogels
1. Hydrophobic polymer
a) Water impermeable
b) water absorption less than 5%
c) structural properties like
 chain stiffness
 high degree of crystallinity
 presence of highly hydrophobic groups
d) example: PEG-PLA
2. Hydrophilic polymer
a) Water permeable
b) water absorption more than 5%
c) structural properties like---chain flexibility, absence of crystallinity, presence of amino,
carboxyl, hydroxyl etc. groups d) example: CMC
3. Water soluble polymer
a) Water soluble
b) water soluble polymers have the capacity to increase the viscosity of solvents
c) example: PVA, PVP,
4. Hydrogels
a) Highly hydrophilic/water soluble
b) cross-linked by covalent bonds
c) water absorption more
d) example: cross-linked CMC
Viscosity
The dissolved macromolecules have the ability to build up the relative viscosity of their
solution. Factors affecting: temperature, salinity, polymer concentration, molecular weight.

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Solubility
Water soluble polymers interact with water and increase the viscosity and or swells. Lower the
molecular weight of a polymer, the greater its solubility in a solvent. Polymers that are
sufficiently polar will be able to interact with the water to provide energy to remove individual
polymer chains from the solid state. The greater the degree of crystallinity of the polymer, the
lower the rate of solution. In CDDS, if the polymer solution rate is too slow, then soluble drug
is leached out with little retardation.

Solubility depends on
 crystallinity
 molecular weight
 branching
 polarity
 cross-linking degree
Polymer Crystallinity: Crystalline and Amorphous Polymers
The polymeric chains being very large are found in the polymer in two forms as follows:
1. Lamellar crystalline form in which the chains fold and make lamellar structure
2. Arranged in the regular manner and amorphous form in which the chains are in the irregular
manner.
The lamellae are embedded in the amorphous part and can communicate with other lamellae
via tie molecules.
Polymer may be amorphous or semi-crystalline in nature.

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A typical range of crystallinity can be defined as amorphous (0%) to highly crystalline

(>90%). The polymers having simple structural chains as linear chains and slow cooling rate
will result in good crystallinity as expected.

In slow cooling, sufficient time is available for crystallization to take place. Polymers having
high degree of crystallinity are rigid and have high melting point, but their impact resistance
is low. However, amorphous polymers are soft and have lower melting points.
Solvent penetrates the amorphous part more easily than the crystalline part. Examples of
amorphous polymers: polystyrene and poly (methyl methacrylate). Examples of crystalline
polymers: polyethylene, and PET polyester.
Spherulites
If the molten polymer is cooled down, then the crystalline lamellae grow in radial direction
from a nucleus along the three dimensions leading to a spherical structure called spherulite.

The amorphous region is in between the crystalline lamellae. Spherulite formation and its
diameter depend on various parameters such as the number of nucleation sites, polymer

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molecule structure and rate of cooling. Due to highly ordered lamellae in the spherulite, it
shows higher density, hardness, tensile strength, and Young’s modulus.
THERMAL PROPERTIES OF POLYMERS
In the amorphous region of the polymer, at lower temperature, the molecules of the
polymer are in, say, frozen state, where the molecules can vibrate slightly but are not able to
move significantly. This state is referred as the glassy state. In this state, the polymer is brittle,
hard and rigid analogous to glass. Hence the name glassy state. The glassy state is similar to a
supercooled liquid where the molecular motion is in the frozen state. The glassy state shows
hard, rigid, and brittle nature analogous to a crystalline solid with molecular disorder as a liquid.
Now, when the polymer is heated, the polymer chains are able to wiggle around each other,
and the polymer becomes soft and flexible similar to rubber. This state is called the rubbery
state. The temperature at which the glassy state makes a transition to rubbery state is called the
glass transition temperature Tg. Note that the glass transition occurs only in the amorphous
region, and the crystalline region remains unaffected during the glass transition in the semi-
crystalline polymer.
Glass Transition Temperature and Melting Point
The glass transition temperature is the property of the amorphous region of the polymer,
whereas the crystalline region is characterized by the melting point. The semi-crystalline
polymer shows both the transitions corresponding to their crystalline and amorphous regions.
Thus, the semi-crystalline polymers have true melting temperatures (Tm) at which the ordered
phase turns to disordered phase, whereas the amorphous regions soften over a temperature
range known as the glass transition (Tg).

The polymer melting point Tm is increased if the double bonds, aromatic groups, bulky or large
side groups are present in the polymer chain, because they restrict the flexibility of the chain.
The branching of chains causes the reduction of melting point, as defects are produced because
of the branching.
Factors Affecting the Glass Transition Temperature (Tg)
The glass transition temperature depends on the mobility and flexibility (ease of the chain
segment to rotate along the chain backbone) of the polymeric chains. If the polymeric chains
can move easily, then the glassy state can be converted to the rubbery state at lower

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temperature, that is, the glass transition temperature is lower. If somehow the mobility of the
chains is restricted, then the glassy state is more stable, and it is difficult to break the
restriction causing the immobility of the polymer chains at the lower temperature, because
more energy is required to make the chains free. Thus, in this case, the glass transition
temperature is raised.
I.Intermolecular Forces
Strong intermolecular forces cause higher Tg. For example, PVC (Tg = 80 ∘C) has stronger
intermolecular forces than polypropylene (Tg = −18 ∘C) because of the dipole–dipole forces
from the C—Cl bond.
II. Chain Stiffness
The presence of the stiffening groups (such as amide, sulfone, carbonyl, p-phenylene etc.) in
the polymer chain reduces the flexibility of the chain, leading to higher glass transition
temperature.
For example, polyethyleneterephthalete is stiffer than polyethylene adipate due to the presence
of benzene ring. Therefore, Tg value is higher for polyethyleneterephthalate.

III. Cross-Linking
The cross-links between chains restrict rotational motion and raise the glass transition
temperature. Hence, higher cross-linked molecule will show higher Tg than that with lower
cross-linked molecule.
IV. Pendant groups
The presence of pendent group can change the glass transition temperature.
(a) Bulky pendant groups: the presence of bulky pendant group, such as a benzene ring, can
restrict rotational freedom, leading to higher glass transition temperature. As in polystyrene,
the presence of benzene ring increases the Tg. In polypropylene, there is no benzene ring that
leads to lower Tg value.

(b) Flexible pendant groups

The presence of flexible pendant groups, for example, aliphatic chains, limits the packing of
the chains and hence increases the rotational motion, tending to less Tg value. In
polybutylmethacrylate, the presence of large aliphatic chain reduces the Tg value when
compared with that of polymethylmethacrylate.

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V. Plasticizers
Plasticizers are low molecular weight and non-volatile materials added to polymers to increase
their chain flexibility. They reduce the intermolecular cohesive forces between the polymer
chains, which in turn decrease Tg.
VI. Molecular Weight
The glass transition temperature is also affected by the molecular weight of the polymer. Tg is
increased with the molecular weight. The molecular weight is related to the glass transition
temperature by the Fox–Flory Equation:

where Tg,∞ is the glass transition temperature at the molecular weight of infinity, and K is the
empirical parameter called Fox–Flory parameter related to the free volume inside the polymer.
It is observed that Tg is increased up to the molecular weight of approximately 20,000, and
after this limit, the Tg is not affected appreciably.

Mechanical Properties Of Polymers

It is of great importance to be familiar with some basic mechanical properties of the material
before its application in any field, such as
 how much it can be stretched,
 how much it can be bent,
 how hard or soft it is,
 how it behaves on the application of repeated load and so on.
Strength
In simple words, the strength is the stress required to break the sample. There are several types
of the strength, namely tensile (stretching of the polymer), compressional (compressing the
polymer), flexural (bending of the polymer), torsional (twisting of the polymer), impact
(hammering) and so on.
The polymers follow the following order of increasing strength:

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linear < branched < cross-linked < network

Factors Affecting the Strength of Polymers:
1. Molecular Weight
The tensile strength of the polymer rises with increase in molecular weight and reaches the
saturation level at some value of the molecular weight. The tensile strength is related to
molecular weight by the following equation:

𝜎∞ is the tensile strength of the polymer with molecular weight of infinity. A is some constant,
and M is the molecular weight.

At lower molecular weight, the polymer chains are loosely bonded by weak van der Waals
forces and the chains can move easily, responsible for low strength. In case of large
molecular weight polymer, the chains become large and hence are crosslinked, giving
strength to the polymer.
2. Cross-linking: The cross-linking restricts the motion of the chains and increases the strength
of the polymer.
3. Crystallinity: The crystallinity of the polymer increases strength, because in the crystalline
phase, the intermolecular bonding is more significant.
b. Percent Elongation to Break (Ultimate Elongation)
It is the strain in the material on its breakage. It measures the percentage change in the length
of the material before fracture. It is a measure of ductility.

 Ceramics have very low (<1%),

 metals have moderate (1–50%)
 thermoplastic (>100%),

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 thermosets (<5%) value

of elongation to break.
c. Young’s Modulus (Modulus of Elasticity or Tensile Modulus)
Young’s Modulus is the ratio of stress to the strain in the linearly elastic region. Elastic
modulus is a measure of the stiffness of the material.

d. Toughness
The toughness of a material is given by the area under a stress–strain curve.

The toughness measures the energy absorbed by the material before it breaks. A typical stress–
strain curve is shown, which compares the stress–strain behavior of different types of materials.
The rigid materials possess high Young’s modulus (such as brittle polymers),

Ductile polymers also possess similar elastic modulus, but with higher fracture toughness.
However, elastomers Have low values of Young’s modulus and are rubbery in nature.
The yield strength of the plastic polymer is the corresponding stress where the elastic region
(linear portion of the curve) ends (Fig. A). The tensile strength is the stress corresponding to

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the fracture of the polymer. The tensile strength may be higher or lower than the yield strength
(Fig. A).

The mechanical properties of the polymer are strongly affected by the temperature. A typical
plot of stress versus strain is shown in (Fig. b). From the plot, it is clear that with increase in
the temperature, the elastic modulus and tensile strength are decreased, but the ductility is
enhanced.
e. Viscoelasticity
There are two types of deformations: elastic and viscous. Consider the constant stress level
applied to a material as shown in the Fig. A. In the elastic deformation (Fig. B), the strain is
generated at the moment the constant load (or stress) is applied, and this strain is maintained
until the stress is not released. On removal of the stress, the material recovers its original
dimensions completely, that is the deformation is reversible (Fig. B), that is: where E is the
elastic modulus, 𝜎 is applied stress, and 𝜖 is the strain developed.

However, in viscous deformation (Fig. C), the strain generated is not instantaneous and it is
time dependent. The strain keeps on increasing with time on application of the constant load,
that is, the recovery process is delayed. When the load is removed, the material does not return
to its original dimensions completely, that is, this deformation is irreversible (Fig. C). where

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Usually, polymers show a combined behavior of elastic and plastic deformation (Fig. D)
depending on the temperature and strain rate. At low temperature and high strain rate, elastic
behavior is observed, and at high temperature but low strain rate, the viscous behavior is
observed. The combined behavior of viscosity and elasticity is observed at intermediate
temperature and strain rate values. This behavior is termed as viscoelasticity, and the polymer
is termed as viscoelastic.

Advantages and application of polymers in formulation of controlled release drug

delivery systems
Advantages of polymers
Polymers are the most promising option for controlled drug administration because of their
attractive, flexible features and ease of production at industrial scale, and potential for
further modification. Polymer therapeutics include linear or branched polymer chains that act
as a bioactive molecule, such as polymeric drugs, or as an inert carrier for a drug.
Polymers play an important part in the advancement of drug delivery technology by targeted
and controlled release of medicine. Rheumatoid arthritis, diabetes, hepatitis B and C, cancer,
and ischemia have all been targeted with polymer conjugates.
Application of polymers
APPLICATIONS OF POLYMERS IN SOLID DOSAGE FORMS
IN TABLETS
Polymers like methyl cellulose, hydroxyl ethyl cellulose, hydroxyl ethyl methyl cellulose are
used as binders. Polymers like carboxyl methyl cellulose sodium is used as disintegrating
agent.
Polymers like all the cellulose derivative are used as coating materials. Polymers like cellulose
acetate phthalate, hydroxyl propyl methyl cellulose phthalate, polyvinyl acetate phthalate are
used as enteric coating material.
IN CAPSULES
Gelatin, a natural polymer which is the major ingredient in the manufacturing of capsules
APPLICATIONS OF POLYMERS IN LIQUID DOSAGE FORMS

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IN SUSPENSIONS
Polymers like Acacia, Tragacanth, Cellulose derivative, Xanthum gum are used as suspending
agents. They should be selected based on their characters like PH, solubility & concentration.
They enhances the dispersion of solids in liquids.
IN EMULSIONS
Polymers like Tragacanth, Spans, Tweens are used as emulsifying agents.
In controlled release drug delivery system
The Ocuserts System
The use of conventional drug delivery systems, such as drops and ointments, to transport
therapeutic agents to the eye for the treatment of eye problems (e.g., glaucoma), is an
inefficient process. The use of polymeric implants inserted under the lower cul- de-sac of the
eye improves the efficiency of ocular medication delivery.

Pilocarpine is distributed within an alginic acid matrix in this system, which is sandwiched
between two polymer layers (ethylene-co-vinyl acetate). Following implantation, it is
designed to release either 20 mg/h or 40 mg/h of a therapeutic drug for seven days.
Transdermal Patches
Transdermal medication delivery entails the drug diffusing through the skin and eventually
being absorbed into the systemic circulation.

The drug delivery system is made up of many layers, including a metallic backing layer that
prevents drug loss by being resistant to drug diffusion, a drug containing reservoir, a rate
controlling membrane, and an adhesive layer. The medicine is dissolved or disseminated in
the matrix using a solid polymer (acrylate copolymer).

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Dr. Tapan Kumar Giri, Department of Pharmaceutical Technology, Jadavpur University