Overview On Pharmaceutical Polymers

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OVERVIEW ON PHARMACEUTICAL POLYMERS
Article in World Journal of Pharmacy and Pharmaceutical Sciences · May 2021

DOI: 10.20959/wjpps20215-18964
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WORLD JOURNAL OF PHARMACY AND PHARMACEUTICAL SCIENCES
Pravin et al. World Journal of Pharmacy and Pharmaceutical Sciences
SJIF Impact Factor 7.632
Volume 10, Issue 5, 953-975 Review Article ISSN 2278 – 4357
OVERVIEW ON PHARMACEUTICAL POLYMERS
Pravin S.*, Ayyappan T.1 and Vetrichelvan T.2
1
Department of Pharmaceutics, Adhiparasakthi College of Pharmacy, Melmaruvathur,
Chengalpattu, Tamil Nadu, India, 603319.
2
Department of Pharmaceutical Analysis, Adhiparasakthi College of Pharmacy,
Melmaruvathur, Chengalpattu, Tamil Nadu, India, 603319.
Article Received on
ABSTRACT
12 March 2021, Pharmaceutical Polymers are the heart of Pharmaceutical formulations
Revised on 02 April 2021,
Accepted on 23 April 2021 either in conventional and novel drug delivery system. The drug
DOI: 10.20959/wjpps20215-18964 release is sustaining, extending, modifying, controlling and targeting
based on the use of polymer in different dosage forms and drug
*Corresponding Author
delivery system. A proper selection of surface and bulk properties can
Pravin S. help in the designing of polymers for various applications in pharmacy.
Department of These are widely used as pharmaceutical aids (Binder, suspending
Pharmaceutics,
agent, emulsifying agent, coating agent, adjuvant etc), packaging
Adhiparasakthi College of
materials and medical devices both in conventional and controlled drug
Pharmacy, Melmaruvathur,
Chengalpattu, Tamil Nadu, delivery system. In this article briefly review Pharmaceutical polymers
India, 603319. and their classification, properties, mechanism of drug release and
applications of polymers drug delivery system.
KEYWORDS: Polymers, Pharmaceutical aid, Conventional Dosage forms, Controlled drug
delivery system, Packaging materials, Medical devices.
INTRODUCTION[6][7]
“Polymer” word is derived from Greek roots “Poly” meaning many and “Meros” meaning
parts. Polymers have very large molecular weights made up of repeating units (or monomers)
throughout their chains. Polymers are considered to be a subset of macromolecules. A
monomer is a small molecule that combines with other molecules of the same or different
types to form a polymer. If two, three, four, or five monomers are attached to each other, the
product is known as a dimer, trimer, tetramer, or pentamer, respectively. An oligomer
contains from 30 to 100 monomeric units. Products containing more than 200 monomers are
www.wjpps.com │ Vol 10, Issue 5, 2021. │ ISO 9001:2015 Certified Journal │ 953
simply called a polymer. From the structural prospective, monomers are generally classified
as functional (containing reactive functional groups) and olefinic (containing double bond).
Polymers can have different chemical structures, physical properties, mechanical behavior,
thermal characteristics.[8]
The pharmaceutical applications of polymers range from their use as binders in tablets to
viscosity and flow controlling agents in liquids, suspensions and emulsions. Polymers can be
used as film coatings to disguise/mask the unpleasant taste of a drug, to enhance drug
stability and to modify drug release characteristics. Pharmaceutical polymers are widely used
to achieve taste masking; controlled release (e.g. extended, pulsatile and targeted) enhanced
stability and improved bioavailability. Monolithic delivery devices are systems in which a
drug is dispersed within a polymer matrix and released by diffusion. The rate of the drug
release from a matrix product depends on the initial drug concentration and relaxation of the
polymer chains which overall displays a sustained release characteristic.[9]
Classification of Polymers
Polymers can have different chemical structures, physical properties, mechanical behavior,
thermal characteristics and can be classified in different ways by following below are,
1. Based on the origin[1]

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[1]
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)[2]

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[3]

On this basis, polymers can be classified into two classes.
Homoplymer: 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[3]

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.
But there were some polymers that didn’t fit into either of the strict categories proposed
above. Therefore, these terms were modified by H.F. Mark on the basis of kinetics of
polymerization (1950) as
(i) Chain polymerization
(ii) Step polymerization
Chain growth polymer: Chain polymers are the products of self addition reaction of
monomer molecules through a chain reaction. No by-product is formed in this reaction, the
molecular weight of the polymer is the exact multiple of the molecular weight of monomer,
e.g., all the vinyl monomers.
Step growth polymers: A step growth polymers is the product of a reaction that involves a
random reaction of two molecules that may be any combination of a monomer, oligomer or a
long chain molecule. It proceeds by step-wise fashion. Some of the examples of step growth
polymers are nylons, polyurethanes
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.[3]
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.,
comblike polymers, star polymers, dendrimers, low density polyethylene, graft copolymers
etc.[3]
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.[3,6]
7. Based on thermal characteristics / thermo response[3,7]

Polymers can be classified into two categories on the basis of their behavior 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 cannotbe recycled as a chemical change occurs in thermoset
polymers as a result of heating. For example, crosslinked epoxy resins,

polydicyclopentadiene, polycarbonates, polyisoprene, etc.
8. Based on interaction with water[10]

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

Stimuli are commonly classified in three categories: physical, chemical, or biological.[26,27]
Physical stimuli (light, temperature, ultrasound, magnetic, mechanical, electrical) usually
modify chain dynamics, i.e. the energy level of the polymer/solvent system, while chemical
stimuli (solvent, ionic strength, electrochemical, pH) modulate molecular interactions,
whether between polymer and solvent molecules, or between polymer chains.[28] Biological
stimuli (enzymes, receptors) relate to the actual functioning of molecules: enzymatic
reactions, receptor recognition of molecules.[29]
Photoresponsive polymers: PAA[30,31], PHPMAm[32, 33], and PNIPAM.[34,35]
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).[43,44]
Inflammation responsive polymers: Hyaluronic acid.[3]

Temperature responsive polymers: Poly(N-alkyl substituted acrylamides): e.g. poly(N-
isopropylacrylamide) (PNiPAAm)[19,20], Poly (N-vinylalkylamides): e.g. poly(N-
[21]
vinylcaprolactam) (PNVC) , and copolymers such as poly (L-lactic acid)-poly(ethylene
glycol)-poly(L-lactic acid) (PLLA-PEG-PLLA) triblock copolymers[22], and poly (ethylene
oxide)-poly(propylene oxide)-poly (ethylene oxide) (PEO–PPO–PEO) copolymers.[23]
Electro-Responsive Polymers: Polythiophene (PT) or sulphonated-polystyrene (PSS).[24,25]
Redox-Responsive Polymers: Acid labile moieties inside polyanhydrides[45,46],
poly(lactic/glycolic acid) (PLGA)[47], and poly(b-amino esters) (PbAEs)[48] induce redox
responsiveness.
Enzyme-Responsive Polymers: Pectin, chitosan, amylase/amylopectin, cyclodextrin and
dextrin.[49,50,51]
10. Based on Morphology[6]

Crystalline Polymers: e.g, syndiotactic polypropylene.
Amorphous polymers: e.g., atactic polypropylene.
11. Based on tacticity[3]

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.
12. Based on Charge[10]

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[10]

Covalent: PVP, scleroglucan
Hydrogen bond: Cyanoacrylate
14. Based on bioadhesive forces[10]

Electrostatic interaction: Acrylate (hydroxylated methacrylate), poly (methacrylic acid),
CP, PC, PVA, chitosan.
15. Based on Physical properties[7]

Elastomers: e.g., Natural rubbers, synthetic rubber.
Plastic : e.g., polyethylene, polystyrene.
Fibres : e.g., saran, vinyon, orlan.
Ideal Charaters of polymers[18]

It should be inert and compatible with the environment.
It should be non- toxic and physiologically inert. It should be easily administrable.
It should be easy to fabricate and must be inexpensive.
It should have good mechanical strength.
It must have compatibility with most of the drugs.
It must not adversely affect the rate of release of the drug.
It must not have tendency to retain in tissue and must be a good biodegradable material.
PROPERTIES OF POLYMERS
Crystallinity
Partial alignment of molecular chains is associated with the process of crystallization of
polymers. Lamellae are those which are having chain fold together and form ordered regions,
which compose spherulities. Dyeing of polymers get affected by crystallinity. Amorphous
form is much more prone to dyeing as compared to crystalline form because the dye
molecular penetrate much easier through amorphous regions. These are being classified as-
Crystalline Polymers: - Light scattering between crystalline and amorphous regions usually
causes polymer to be opaque and called as crystalline polymers. Either for law (amorphous
polymer) or high (crystalline) degree of crystallinity the transparency is higher as because
density of such boundaries is lower. For example, atactic polypropylene is usually amorphous
and transparent while syndiotactic polypropylene, which has crystallinity ~50%, is opaque.
Semi crystalline Polymers

Highly ordered molecular structures with sharp melting point are possessed by semi
crystalline materials. Semi crystalline material rapidly change to low viscosity fluid when
given quantity of heat gets absorbed and they remain in solid form. Softens does not vary
with temperature increases. Direction flow us transverse to flow causes less shrinking and
thus material is anisotropic in flow. Chemical resistance is excellent. Beyond their glass
transition temperature. Semi crystalline exhibit substantial improvement in HDT’s which
reinforced and retain useful levels of strength and stiffness.
Amorphous Polymers: During x-ray or electron scattering experiments polymer do not

exhibit any crystalline structure and those polymers were called as amorphous polymers. E.g.
– using straining-induced contrast enhancement in TEM. Formation of localised deformation
zones, such as crazes, deformation bands, or shear bands, which are characterised by
representative HVTEM micrographs, shows micromechanical behavior of amorphous

polymer.
Viscosity
The presence in solution of large macromolecular solutes may have an appreciable effect.
Viscosity increases, the sustained drug release is prolonged.
Polymer complexes
Polymers provide ample opportunity for the formation of complexes in solution, e.g, when an
aqueous solution of high molecular weight polyacid is mixed with polyglycol. The viscosity
and pH of the solution of the equimolar mixture of polyacid and glycol remains the same with
increase increase in oligomer chain length up to a critical point. This occurs only when the
poly(ethylene glycol) moleculeas are reached a certain size. Such macromolecular reaction
are highly selective and strongly dependent and molecular size, conformation heat etc.
Biological macromolecule undergo complex reactions, which are often vital to their activity.
The studies have estabilished a specific interacteraction between hyaluronic acid and the
proteoglycans the intracellular matrix in cartilage. Calcium is coordinated between certain
uronic acid- containing polysaccharides, which can explain the tight binding of calcium and
other multivalent ions in polysaccharide structures, and also how bivalent ions can induce gel
formation in acidic polysaccharide such as alginic acid solutions. It has been found such
interaction have dietary significance.[1]
Syneresis
The separation of liquid from a swollen gel is known as syneresis. This is a form of instability
in aqueous and non-aqueous gels. Separation of a solvent phase is thought to occur because
of the elastic contraction of the polymeric molecules. In the swelling process during gel
formation the macromolecules involved become stretched and the elastic forces increase as
swelling proceeds. At equilibrium the restoring force of the macromolecules is balanced by
the swelling forces, determined by the osmotic pressure.[1]
Adsorption of macromolecules
The ability of some macromolecules to absorb at interfaces is being exploited in suspension
and emulsion stabilization. Gelatin, acacia and proteins absorb at interface. Sometimes such
adsorption is unwanted, e.g. insulin adsorption on to glass infusion bottles. Addition of
albumin to prevent adsorption is now common practice. The albumin adsorbs at the glass or
plastic surface and presents a more polar surface to the solution, thus reducing, but not
always preventing, adsorption of the protein (e.g. insulin). The binding is considered to be a
non-specific phenomenon, which may occur on other inert materials, such as polythene and
glass. The adsorption of macromolecules at interfaces may be the reason why molecules such
as those of hyaluronic acid can act as biological lubricants in joint fluids.[1]
Bioadhesivity of water- soluble polymers

Adhesion between a biological surface and a biological surface and a surface of a hydrophilic
polymers or a surface to which a hydrophilic polymer has been grafted or adsorbed, arises
from interactions between the polymer chains and the macromolecules on the mucosal
surface.To achieve maximum adhesion there should be maximum interaction between the
polymer chains of the bioadhesive and the mucus. The charge on the molecules will be
important and for two anionic polymers maximum interaction will occur when they are not
charged. Penetration and association pH must be balanced. The adhesive performance of
polymers can be excellent (e.g. carboxymethylcellulose), good (Carbopal), fair (gelatin) or
poor (povidone). Anionic poly(acrylic acid) (carbophil) derivatives and the cationic cationic
chitosans have been approved by the FDA. Polycarbophil and carbomer (carbopol 934P)
have pKa values of about 4.5 and display maximum mucoadheivity at pH where they are
undissociated.[1]
Polymer dissolution
Polymer dissolution in solvents is an important are of interest in polymer science and
engineering because of its many applications in industry such as microlithography, membrane
science, plastics recycling and the drug delivery. Unlike non-polymeric materials, polymers
do not dissolve instantaneously, and the dissolution is controlled by either the
disentanglement of the polymer chains or by the diffusion of the chains through a boundary
layer adjacent to the polymer-solvent interface.[1]
MECHANISM OF DRUG RELEASE BY POLYMERS

DISSOLUTION
When drug release by dissolving of polymer by penetration of dissolution fluid. In Sustained
or controlled drug delivery system, drug is dispersed (matrix system) or encapsulated
(individual drug particles) with slowly dissolving polymers. The rate of penetration of the
dissolution fluid into matrix determines the drug dissolution and subsequent release. The
penetration of dissolution fluid is however, dictated by the matrix, porosity, presence of
hydrophobic additives and the wettability of system and surface of particle. In encapsulated
system, the coat thickness and its aqueous solubility determine the time required for
dissolution of coat one can formulate a repeat action or sustained release product by using a
narrow or a wide spectrum of coated particles of varying thickness, respectively (Figure 1).[4]
Figure 1: Drug release by dissolution controlled mechanism of polymer.
Diffusion
Diffusion occurs when the drug passes from the polymer matrix into the external
environment. In controlled drug delivery system, drug is homogenously dispersed in a
polymer matrix (monolithic matrix system) or drug (solid, dilute solution or highly
concentrated solution) within a polymer matrix and surrounded by thin film (reservoir
system). Diffusion occurs when the drug passes from the polymer matrix into the external
environment. With the passage of time and continous drug release, the delivery rate normally
decreases in these type of system since the bioactive agent has to traverse a long distance
progressively and thereby requires a longer diffusion time for ultimate delivery of drug(s). In
swelling controlled drug delivery system, drug release by swelling of polymer followed by
diffusion of drug with or without dissolution (Figure 2).[4]
Figure 2: Drug release by diffusion controlled mechanism of polymer.
Dissolution and Diffusion

Drug release by dissolution of polymer followed by diffusion of drug. In controlled drug
delivery system consist of the drug core enclosed in partially soluble membrane. Dissolution
of part of outer membrane leads to facilated diffusion of the contained drug through pores in
the coating by dissolution and diffusion controlled relase mechanism of polymer.[4]
Erosion[52]
A) The active agent is covalently attached to the polymer backbone and is released as its
attachment to the backbone cleaves by hydrolysis of bond A. Because it is not desirable to
release active agent molecules with polymer fragments still attached, reactivity of bond A
should be significantly higher than reactivity of bond B (Figure 3).
Figure 3: Drug release mechanism by erosion.
B) The active agent is contained in a core surrounded by a bioerodible rate-controlling

membrane. Such a system combines the attributes of a rate-controlling polymer membrane,
which provides a constant rate of drug release from a reservoir-type device, with erodibility,
which results in bioerosion and makes surgical removal of the drug-depleted device
unnecessary. Because constancy of drug release demands that the bioerodible polymer
membrane remain essentially unchanged during the delivery regime, significant bioerosion
must not occur until after drug delivery has been completed. Thus, polymer capsules will
remain in the tissue for varying lengths of time after completion of therapy (Figure 4).
Figure 4: Drug release mechanism by erosion with diffusion.
C) The active agent is homogeneously dispersed in a polymer and drug release from this
monolith is controlled by diffusion, by a combination of diffusion and erosion, or by erosion
(Figure 5).
Figure 5: Drug release mechanism by erosion.
Ion exchange[3]
Drug release by reversible exchange of ions (in drug-ion exchange resin complex). Ion
exchange resins are used to sustain the effects of drugs based on the concept that negatively
or positively charged drug moieties combine with appropriate resins producing insoluble
polysalt resonates. Where R-SO3-H+ and R-NH3+OH- represents cationic and anionic resins,
respectively, whereas H2N-A and HOOC-B depicts basic and acidic drug respectively.
Where administered orally resins come in contact HCl with pH 1.2 following reaction take
place.
R-SO3-H+ + H2N-A → R-SO3- + H3N+ -A
R-N+H3- + HOOC-B → R-N+H3-OOC-B + H2O
Subsequently, when the system reaches intestine, where it is exposed to a fluid of slightly
alkaline pH, following reactions occur.
R-SO3-H3N+-A + HCl → R-SO3-H+ + A-N+H3Cl-
R-N+H3-OOC-B + HCl → R-N+H3-Cl- + B-COOH
R-SO3-H3N+-A + NaCl → R-SO3-Na+ + A-N+H3Cl-
R-N+H3-OOC-B + NaCl → R-N+H3Cl- + B-COO-Na+
Applications of Polymers in Drug Delivery System

Tablets
Tablets are the most commonly used dosage form for pharmaceutical preparations meant to
be taken orally. Release of drug from the tablet can be controlled by altering the design and
content of the formulation. In tablet the polymer are used as a Disintegrants and Binder. E.g.
Starch, cellulose, Alginates, polyvinylpyrrolidine, sodium CMC etc are used as disintegrants.
Polymers used as binders are Glucose, Starch, HPMC, Gelatin, Alginic acid,
polyvinylpyrrolidine, Sucrose, Ethyl cellulose. Polymers are also used to mask the unpleasant
taste of the drug and also for enteric coating of tablets e.g. Shellac and zein. MCC enhances
compressibility of tablet.[8]
Capsules
Capsule are generally composed of gelatin. The composition of gelatin get varied so gelatin
re of two types that is hard gelatin and soft gelatin. Fillers such as MCC and starches are used
to fill up the volume in capsule. To overcome problem of aggregation various polymers such
as starch and sodium starch glycolate are mixed with capsule container.[14][15][16]
Polymers in Parenteral
In Parenteral the various polymer like Methacrylic acid act as an Interferon inductor which
induce to the interferon in cancer like disease. Methacrylic acid alkyl amide is act as plasma
expander which increase the plasma level in body when admixture of drug with polymer
present in body. Some Vaccines are transpired by using polymer because which disintegrate
in GIT tract, example Methyl methacrylate.[8]
Polymers in Disperse systems

Various synthetic and natural hydrophilic polymers are extensively used to enhance the
physical stability of pharmaceutical disperse systems. Examples of these include alginates,
acacia, carrageenan and xanthan gum, whereas a wide range of synthetic polymers has also
been used for this purpose, e.g., cellulose ethers, poly(acrylic acid), PVP and PVA.[8]
Polymers in Gels
Gel system consist of physical or chemical cross-linked between adjust polymer chain restrict
chain mobility. Gel has rheological properties. Cross-linked gels are most commonly known
as hydrogels. They are also known a s smart polymers because they shows different gelling
properties in different environment of water. Most commonly used hydrogels are poly
(hydroxyethyl methacrylate), poly (methacry1ic acid) and poly (acrylamide). In
pharmaceutical industries cross-linked gels are primarily use for local drug delivery of drugs
to skin, oral cavity, vagina and rectum.[11]
Swelling Controlled Release Systems

In many drug delivery systems, the dimensions of the dosage form will change during the
course of drug release due to swelling of the polymer matrix. Although the mechanism for
drug release is diffusion, Examples of systemsb that exhibit swelling controlled release are
physically crosslinked and chemically crosslinked gels. In terms of controlled drug release,
chemically Crosslinked hydrogels e.g., poly(hydroxyethylmethacrylate), have been used to
provide controlled drug release from medical devices, whereas swelling controlled physical
hydrogels may be easily manufactured by directly compression of drug with a hydrophilic
polymer, e.g., HPMC.[8]
Temperature Responsive Drug Release

Several reports have been published on the design and application of controlled systems for
the administration of drugs that use the temperature as an external stimulus. The polymers
used to obtain such release properties are referred to as thermoresponsive polymeric systems.
Typically, the homo and copolymers of N-substituted acrylic and methacrylate amides [e.g.
poly (isopropyl acrylamide)], are used for this purpose. More specifically, there are two types
of thermoresponsive polymer systems namely those that exhibit positive and negative
temperature dependency. Polymers in the former category display an upper critical solution
temperature below which polymer contraction occurs upon cooling. Conversely, negative
temperature dependent polymers have a lower critical solution temperature and will contract
upon heating above the lower critical solution temperature.[8]
pH Responsive Drug Release

In the design of dosage forms, a specific goal may be to obtain the release of the drug in the
sites that guarantee maximum therapeutic benefits. Within the gastrointestinal tract a range of
pH values exist, ranging from about one in the stomach to neutrality within the intestine.
Targeting drug release within certain regions of the gastrointestinal tract as a method to
enhance drug stability within acidic fluids or to reduce the irritant effects of certain drugs has
been used for several decades. For example, enteric polymers have been used as tablet
coatings for this purpose, examples of which include cellulose acetate phthalate and cellulose
acetate butyrate. These polymers are insoluble in low pH environments; however they are
soluble in the less acid regions of the gastrointestinal tract. Following dissolution of the
enteric coating, the tablet and hence the drug will dissolve, thereby facilitating drug
absorption. Due to this pH dependent solubility, enteric polymers may be described as pH
responsive polymers.[8]
Transdermal drug delivery system

Transdermal system dependent ostensibly on rate-controlling membranes are available for the
delivery of nitroglycerin, scopolamine, oestradiol (estradiol), fentanyl, clonidine and other
drugs. The barrier properties of skin are so variable, however, that one advantage of rate-
controlling system generally consist of a reservoir, a rate-controlling membrane and an
adhesive layer. Diffusion of the active principle through the controlling membrane governs
release rate. The active principle is usually present in suspended form; liquids and gels are
used as dispersion media. In matrix system the active principle is dispersed in a matrix, which
consist either of a gel or of an adhesive film. In Transiderm Nitro, the rate- controlling
membrane is composed of a poly-ethylene/ vinyl acetate copolymer having a thin adhesive
layer (membrane type). Motion sickness: Transderm-Scop (Scopolamine), Hypertension:
Catapress-ITS (Clonidine Polyisobutylene), Oestrogen theraphy: Estraderm (Oestradiol),
Smoking cessation: Nicotinell (Nicotine) etc.[4,5]
Microcapsules and microspheres

Microencapsulation is a technique, which involves the encapsulation of small particles of
drug or solution of drug, in a polymer film or coat. Microspheres on the other hand are solid,
but not necessarily homogenous particles which can entrap drug. Microspheres can be
prepared by a variety of techniques, e.g. coacervation, spray coating etc. Desolvation of water
insoluble macromolecules in non-aqueous solvents would lead to the deposition of a
coacervate layer around aqueous or solid disperse droplets. The various water-soluble and
water-insoluble macromolecules, which have been used in coacervation processes, are
arabinogalactan, cellulose acetate phthalate, carboxy methyl cellulose, cellulose nitrate,
gelatin, ethyl cellulose, gum Arabic (acacia), poly(ethylene vinylacetate), hydroxyl ethyl
cellulose, poly(methyl methacrylate), poly(acrylic acid), polyethyleneimine, poly(vinyl
alchol),poly vinyl pyrrolidone, methyl cellulose, starch etc. Desolvation, and thus
coacervation, can be induced thermally and this is the basis of some preparative techniques.
The conditions for phase separation are best obtained using phase diagram.[6]
Ocular drug delivery system

Improving the ocular contact time of solutions utilizes the incorporation of polymers into an
aqueous medium such as polyvinyl alchol (PVA), polyvinylpyrrolidone (PVP),
methylcellulose, carboxymethylcellulose (CMC) and hydroxypropyl cellulose (HPC). The
increased solution viscosity reduces the solution drainage. Increasing the solution viscosity of
pilocarpine solution from 1to 100 cps through the incorporation of methyl cellulose reduced
the solution drainage rate constant 10 times while only 2-fold increase in pilocarpine
concentration in the aqueous humour was obtained. Ocusert has the drug reservoir as a thin
disc of pilocarpine-alginate complex sandwiched between two transparent discs of
microporous membrane fabricated from ethylene-vinyl, acetate copolymer. The microporous
membranes permit the tear fluid to penetrate into the drug reservoir compartment to dissolve
pilocarpine molecules are then released at a constant rate of 20 or 40 mg/hr for a hour to
seven day management.[5,6]
Buccal Drug delivery system

Buccal tablets- The use of cellulosic or acrylic polymers generally offers almost immediate,
high adhesion performance for prolonged period of time, even with high drug content.
Different polymers can be used for the development of laminated and hydrogel systems
including cellulose derivatives (methylcellulose, sodium carboxy methylcellulose and
hydroxyl ethyl cellulose), natural gums (guar gum, karaya gum and agarose), poly acrylates
(poly(acrylic acid), poly (vinyl pyrrolidone) and poly (ethylene glycol)) and gelatin. These
polymer exhibit mucoadhesive properties in the presence of water. Poly (acrylic acid) based
patches have been successfully for the delivery of opiod analgesics. Chewing gum
formulations consist generally of a gum base of cellulosic or acrylic polymer. The polymer is
blended with sugar as well as drug. Drug release from chewing gum formulations is generally
rapid but not as immediate as in the case for the fast dissolving tablets.[4]
Progestasart system
Progestasart intra-uterine device is the example of controlled drug delivery system medicated
implant use for contraceptive purpose. The drug release from progestasart occurs by diffusion
polymer act as a rate controlling membrane for drug release. Polyethylene and
poly(ethyleneco-vinyl acetate) are used in such system.[15]
Polymers in drug conjugates

It is one of the strategy for improved delivery of therapeutic agent. The conjugate of polymer
and drug composed of drug that is bound covalently to polymer. Strategy of polymer drug
conjugate use especially in the field of cancer therapy which is known as„ polymer
therapeutics‟. Biodegradable polymer are preferred although non-biodegradable synthetic
polymer such as PEG and poly (hydroxylpropylmethacrylate) preferred mostly. The easiest
way of attaching drug to macromolecule by direct attachment without spacer. HPMA
doxorubicin and HPMA-paclitaxel undergone in clinical trials.[15,17]
Current Status and Future Prospects Of New Drug Delivery System

With the progress in all spheres of science and technology, the dosage forms have evolved
from simple mixtures and pills to the highly sophisticated technology intensive drug delivery
systems, which are known as Novel Drug Delivery Systems (NDDS). Quest for New Drug
Delivery System (NDDS) has got new impetus since early eighties to have improved
therapeutic outcome from the same drug, because the NDDS have several advantages over
the conventional dosage form. Since then several NDDS have been developed and it
constitute a sizable portion of the global market.[13]
Types of Novel Drug Delivery Systems

There are multiple schemes of classification of types and techniques of NDDS - based on
therapeutic group of drugs loaded, physical form, intended application route, mechanism of
delivery or action, etc. and none would be complete.[13]
Microparticulate Drug Delivery Systems

Drugs encapsulated within polymeric beads in order to control the release, mask taste,
prevent degradation from atmospheric moisture and to ensure proper delivery as desired.
These multi-unit dosage forms are mainly intended for oral delivery, though parenteral and
other routes of administration have also found commercial and clinical success. Different
systems implement various rate controlling mechanism including nonerodible mechanical
barrier for diffusion controlled release, microporous membrane systems, water swellable and
hydrogel systems, pH sensitive polymer coated systems, gastric floatation systems,
mucoadhesive systems, colon-specific delivery systems, etc. a large spectrum of drug have
been modulated for release and other properties, e.g. cardiovascular drugs, antipsychotics,
antibacterial and chemotherapeutic agents. The selection of polymer for a particular
multiparticulate system is crucial and a wide variety of polymers such as cellulose derivatives
(methyl, ethyl, hydroxypropyl, hydroxypropyl methyl cellulose), acrylic polymers,
biodegradable polymers (Polylactide coglycollic acid, poly lactic acid, polyglycollic acid,
etc.) and natural polymers (sodium alginate, albumin, other proteins, chitosan, etc.) are used
depending on the requirement of the particular system to be developed.[12,13]
Nanoparticles
These are colloidal drug delivery systems in the nanometer size range having wide
application potential at present. They have got all characteristics of the liposomes minus the
stability problems. They have been utilized to deliver and control the release of drug
molecules from suitable polymeric nanoparticles/ nanospheres. Usually FDA approved
biocompatible polymers such as poly (L-lactide - D-glycollic acid) have been used, though
other polymers such as polyepsilon-caprolactone, chitosan and polyalkyl cyanoacrylates have
been also used. Their most promising area of application is tumor targeting capability.
Nanoparticles are not only suitable for parenteral administration, but also they have been
exploited as advanced systems for drug delivery through cornea, skin, bronchioles and oral
routes.[12,13]
Aquasome
These are carbohydrate stabilized nanoparticles of ceramics / calcium phosphate having
water-like properties that help to protect and preserve the fragile biological molecules. They
are comprised of a solid nano-crystalline core coated with oligomeric film to which the drug
moieties or biochemically active molecules are adsorbed with or without modification. There
three layered structures are self assembled by non-covalent and ionic bonds. Their intended
route of administration is parenteral and with advancement of research in this field, other
routes might be contemplated.[12,13]
Dendrimers
In search for novel biomaterials for controlled and targeted delivery of bioactives, Starburst
Dendrimers are the latest stars that bear promising properties for the delivery of drugs,
vaccine, metals or genes to the desired sites. In spite of being polymers they bear similarity
with vesicular structures such as micelles, liposomes and globular proteins. The dendrimers
are three-dimensional branched structures like trees and hence the name "Dendrimer". They
possess a very large number of chain ends and synthesized chemically. Into the branches of
dendrimers drugs and other biologically active molecules could be entrapped for controlled
and/or targeted delivery initially via parenteral route and subsequently other routes could be
tried.[12,13]
Microemulsions
Microemulsions are transparent thermodynamically stable systems of colloidal nature that are
formed from classical emulsions, but at specific phase-volume ratios. They afford
solubilization of water-insoluble molecules, thereby improving their bioavailability as well as
applicability and reduced ADME problems. A widely used immunosuppressant, Cyclosporin,
have been formulated commercially as a microemulsion for increased solubility and
bioavailability. Proteins and peptides may also be formulated as oral microemulsions, such as
oral insulin systems, and also scope exists in developing oral vaccines through this
system.[12,13]
Liposomes
These are uni-/multilamellar phospholipid vesicles composed of concentric spherical layers
of aqueous zones sandwiched between phospholipid membranes. Both water and oil soluble
drugs can be encapsulated in the liposomes either in the aqueous zone or the lipid-bilayers
according to their solubility. They are often referred to as "artificial cells" as they resemble
one in almost all practical aspects. They showed immense potential in delivery of anti-tumor
therapeutics as well as anti-fungals. Drugs such as Amphotericin B, Doxorubicin and
Daunorubicin have been successfully launched in market as liposomes.[12,13]
Niosomes
These are vesicles like liposomes, but made up of nonionic surfactants and like liposomes.
They can also entrap hydrophilic as well as lipophilic drugs. They have better stability than
liposomes and hence have greater interest for industrial adoption. The non-ionic surfactant
systems make niosomes inherently target-specific to tumor, liver and brain. They have been
reported to be useful as targeting systems of drugs for treatment of cancer and in therapy of
microbial diseases caused particularly by virus and parasites. Tumor targeting of
Methotrexate in mice model have been highly successful. Since no special handling / storage
precautions are required for niosomes, their commercial exploitation would be easier. They
are biodegradable and reduce systemic toxicity of various antitumor and antimicrobial agents
by localizing the drug to specific sites of action.[12,13]
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OVERVIEW ON PHARMACEUTICAL POLYMERS

Article in World Journal of Pharmacy and Pharmaceutical Sciences · May 2021

The user has requested enhancement of the downloaded file.

Volume 10, Issue 5, 953-975 Review Article ISSN 2278 – 4357

OVERVIEW ON PHARMACEUTICAL POLYMERS

Pravin S.*, Ayyappan T.1 and Vetrichelvan T.2

1. Based on the origin[1]

ii) Synthetic Polymers

iii) Semi-synthetic Polymer: Hydrogenated natural rubber,Cellulose nitrate,methyl cellulose

3. Based on the presence of carbon (organic and inorganic)[2]

4. Based on the types of monomer[3]

Homoplymer: A polymer containing a single type of repeat units is called a homopolymer,

5. Based on the Polymerization process[3]

Addition polymers: Addition polymerization reaction is responsible for formation of

Condensation polymers: Condensation polymerization reaction is responsible for the

6. Based on the Line structure

7. Based on thermal characteristics / thermo response[3,7]

Thermosetting polymers: Conversion of polymers into an infusible mass is because of

polymers as a result of heating. For example, crosslinked epoxy resins,

8. Based on interaction with water[10]

9. Based on stimuli response

Inflammation responsive polymers: Hyaluronic acid.[3]

10. Based on Morphology[6]

11. Based on tacticity[3]

12. Based on Charge[10]

13. Based on Potential[10]

14. Based on bioadhesive forces[10]

15. Based on Physical properties[7]

Ideal Charaters of polymers[18]

Semi crystalline Polymers

Amorphous Polymers: During x-ray or electron scattering experiments polymer do not

representative HVTEM micrographs, shows micromechanical behavior of amorphous

Bioadhesivity of water- soluble polymers

MECHANISM OF DRUG RELEASE BY POLYMERS

Figure 1: Drug release by dissolution controlled mechanism of polymer.

Figure 2: Drug release by diffusion controlled mechanism of polymer.

Dissolution and Diffusion

Figure 3: Drug release mechanism by erosion.

B) The active agent is contained in a core surrounded by a bioerodible rate-controlling

Figure 4: Drug release mechanism by erosion with diffusion.

Figure 5: Drug release mechanism by erosion.

Applications of Polymers in Drug Delivery System

Polymers in Disperse systems

Swelling Controlled Release Systems

Temperature Responsive Drug Release

pH Responsive Drug Release

Transdermal drug delivery system

Microcapsules and microspheres

Ocular drug delivery system

Buccal Drug delivery system

Polymers in drug conjugates

Current Status and Future Prospects Of New Drug Delivery System

Types of Novel Drug Delivery Systems

Microparticulate Drug Delivery Systems

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