Polymers and Applications Dr M V Ramana Professor Arvind Gavali College of Pharmacy Satara

Polymers: Macromolecules formed by the covalent attachment of a set of small molecules termed monomers. Writing Formulas for Polymeric Macromolecules

Many polymeric materials having chain-like structures similar to polyethylene are known. Polymers formed by a straightforward linking together of monomer units, with no loss or gain of material, are called addition polymers or chaingrowth polymers. A listing of some important addition polymers and their monomer precursors is presented in the following table.
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Example of addition polymers

Example of addition polymers

Example of addition polymers

Types of Polymers
Natural Polymers Synthetic polymers
Homopolymers (simple polymer) Copolymers Addition polymers Condensation polymers Biodegradable polymers Non-biodegradable polymers Elastomers Plastics and Fibers Thermoplastics polymers Thermosetting polymers

Synthetic and Biological Polymers

Polymers are classified as: (1) Biological polymer that are found in nature. (2) Man-made or synthetic polymers that are synthesized in the laboratory;

(3)

Semisynthetic polymers: formed by modification of the natural polymers.

Biological polymers: DNA, proteins, carbohydrates Synthetic polymers: nylon, poly-ethylene, poly-styrene Semi-Synthetic polymers: celullose derivatives such as CMC, HPME, EC, MC etc, semisynthetic rubber
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Homopolymers (Simple polymers)

macromolecules composed of a single type of monomeric repeating unit are called as simple polymers. Examples: Polyethylene, polystyrene, Polyvinyl chloride, polytetra fluoroethane (Teflon), etc.

Symmetrical monomers such as ethylene and tetrafluoroethylene can join together in only one way. Monosubstituted monomers, on the other hand, may join together in two organized ways
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Stereoisomerization in Macromolecules
Symmetrical monomers such as ethylene and tetrafluoroethylene can join together in only one way. Monosubstituted monomers, on the other hand, may join together in two organized ways

Stereoisomerization in Macromolecules

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Branched Polymer:

A branched polymer is formed when there are "side chains" attached to a main chain.

Polymers with a high degree of branching are called

dendrimers

branches themselves have branches. This tends to give the molecule an overall spherical shape in three dimensions.

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Copolymers
macromolecules composed of more than one monomeric repeating unit are called as copolymers. These have been explored as a means of controlling the properties of the resulting material. In this respect, it is useful to distinguish several ways in which different monomeric units are incorporated in a polymeric molecule. The following examples refer to a two component system, in which one monomer is designated A and the other B.
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Copolymers
Statistical Copolymers (random copolymers) ~ABBAAABAABBBABAABA~ Alternating Copolymers ~ABABABABABABABAB~. Block Copolymers ~AAAAA-BBBBBBB~AAAAAAA~BBB~. Graft Copolymers ~AAAAAAA(BBBBBBB~)AAAAAAA(BBBB~)AAA~.
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Types of copolymers

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Elastomers and Plastics

Elastomers,or rubbery materials, have a loose cross-linked structure. E.g : natural rubber is a polymer of isoprene Plastics are polymers which, under appropriate conditions of temperature and pressure, can be molded or shaped (such as blowing to form a film). In contrast to elastomers, plastics have a greater stiffness and lack reversible elasticity. Some plastics, such as nylon and cellulose acetate, are formed into fibers
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Thermoplastic Polymers:

Most of the polymers described above are classified as thermoplastic. Above Tg they may be shaped or pressed into molds, spun or cast from melts or dissolved in suitable solvents for later fashioning.

Thermosetting polymers

These polymers, once formed, cannot be reshaped by heating, they are called thermosets . These polymers are characterized by a high degree of cross-linking and resist deformation and solution once their final morphology is achieved. Such polymers are usually prepared in molds that yield the desired object. E.g: Bakelite

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Biodegradable polymers:
Plastics derived from natural materials, such as cellulose, starch and hydroxycarboxylic acids are more easily decomposed when exposed to oxygen, water, soil organisms and sunlight than are most petroleum based polymers. The glycoside linkages in polysaccharides and the ester groups in polyesters represent points of attack by the enzymes of microorganisms that facilitate their decomposition. Such biodegradable materials can be composted, broken down and returned to the earth as useful nutrients. Eg. Carbohydrates, proteins, polyhydroxy butyrate (PHB) etc
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Biodegradable polymers:
Some synthetic polymers such as polylactic acid, poly glycolic acid, copolymers of Polylactic- glycolic acid, careolactone are degraded by the enzymes present in the biological system. PLA materials are currently used in a number of biomedical applications, such as sutures, stents, dialysis media and drug delivery devices. However, one of the drawbacks of polylactides for biomedical applications is their brittleness.

Non-biodegradable polymers

Most of the polymers described are nonbiodegradable. These polymers are not degraded by natural methods (microbial, biological, water, air etc)

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Biodegradable polymer

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Classification of Polymerization Reactions

Basic Requirement for polymerization: Each molecule of monomer must be capable of being linked to 2 (or more) other molecules of monomer by chemical reaction (i.e. monomers must have a functionality of 2 or higher.)
Addition Polymerization: repeat units have identical molecular formulae to those of the monomers from which they are formed.
Condensation Polymerization: repeat units have fewer atoms than present in the monomers.
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Carothers Classification

Classification of Polymerization Reactions

Classification Based on the underlying polymerization mechanisms

Step-growth (Step) Polymerization: polymer chains grow step-wise by reactions that can occur between any two molecular species.

Chain-growth (Chain) Polymerization: polymer chains grow by reaction of monomer with a reactive end-group on the growing chain.

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Classification of Polymerization Reactions

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Classification of Polymerization Reactions

In step polymerizations, the degree of polymerization increases steadily throughout the reaction, but the monomer is rapidly consumed in its early stage. By contrast, in chain polymerizations, high degrees of polymerization are attained at low monomer conversions, the monomer being consumed steadily throughout the reaction.

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Polymerization Reactions Addition polymerization and condensation polymerization Addition polymerization: monomers react to form a polymer without net loss of atoms. Most common form: free radical chain reaction of ethylenes Vinyl chloride (CH2=CHCl )n n monomers one polymer molecule
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Condensation polymerization Condensation polymerization: the polymer grows from monomers by splitting off a small molecule such as water or carbon dioxide. Example: formation of amide links and loss of water Monomers

First unit of polymer + H2O

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Methods for making polymers

Free Radical Polymerization:
Free radicals are often created by the division of a molecule (known as an initiator) into two fragments along a single bond.

benzoyl peroxide

Free radical

The active center is the location of the unpaired electron on the radical because this is where the reaction takes place.

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 In free radical polymerization, the radical attacks one monomer, and the electron migrates to another part of the molecule. This newly formed radical attacks another monomer and the process is repeated. Thus the active center moves down the chain as the polymerization occurs. There are three significant reactions that take place in addition polymerization: initiation (birth), propagation (growth), and termination (death). These separate steps are explained below.

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Initiation
The first step in producing polymers by free radical polymerization is initiation.

This step begins when an initiator decomposes into free radicals in the presence of monomers.

.. RO . ..

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Free-Radical AdditionPolymerization of Ethylene

H2C 200 C 2000 atm CH2 .. RO . ..

CH2

CH2

CH2

CH2

CH2

CH2

CH2

polyethylene

Free-Radical Polymerization of Propene

H2C CHCH3

.. RO . .. CH CH CH
CH3

CH CH3

CH
CH3

CH
CH3

CH
CH3

CH3 CH3

polypropylene

.. RO .. H2C

Initiation

Mechanism

CHCH3

.. RO:
H2C

Initiation

Mechanism

CHCH3

.. RO: H2C CHCH3 H2C CHCH3

Mechanism
Propagation (chain growth)

.. RO: H2C CHCH3 H2C CHCH3

Mechanism
Propagation (chain growth)

.. RO: H2C CHCH3 H2C CHCH3 H2C

Mechanism
Propagation (chain growth)

CHCH3

.. RO: H2C CHCH3 H2C CHCH3 H2C

Mechanism
Propagation (chain growth)

CHCH3

.. RO: H2C CHCH3 H2C CHCH3 H2C

Mechanism
Propagation (chain growth)

CHCH3 H2C

CHCH3

Likewise...
H2C=CHCl
H2C=CHC6H5 F2C=CF2

polyvinyl chloride
polystyrene Teflon

Termination Reaction
Combination:
polymer's growth is stopped by free electrons from two growing chains that join and form a single chain.

Termination Reaction
Disproportionation halts the propagation reaction when a free radical strips a hydrogen atom from an active chain. A carboncarbon double bond takes the place of the missing hydrogen.

Disproportionation can also occur when the radical reacts with an impurity. This is why it is so important that polymerization be carried out under very clean conditions.

Termination Reaction

Cationic Chain-Growth Polymerization

Polymerization of isobutylene (2-methylpropene) by traces of strong acids is an example of cationic polymerization.

The polyisobutylene product is a soft rubbery solid, Tg = _70 C, which is used for inner tubes. This process is similar to radical polymerization.
Chain growth ceases when the terminal carbocation combines with a nucleophile or loses a proton, giving a terminal alkene.

Cationic Chain-Growth Polymerization

Mechanism

Anionic Chain-Growth Polymerization

Treatment of a cold tetrahydrofuran (THF) solution of styrene with 0.001 equivalents of n-butyllithium causes an immediate polymerization. Chain growth may be terminated by water or carbon dioxide, and chain transfer seldom occurs.

Only monomers having anion stabilizing substituents, such as phenyl, cyano or carbonyl are good substrates for this polymerization technique.
Many of the resulting polymers are largely isotactic in configuration, and have high degrees of crystallinity.

Anionic Chain-Growth Polymerization

Ziegler-Natta Catalytic Polymerization

An efficient and stereospecific catalytic polymerization procedure was developed by Karl Ziegler (Germany) and Giulio Natta (Italy) in the 1950's. These methods allowed the synthesis of unbranched, high molecular weight polyethylene (HDPE), synthesis of natural rubber from isoprene In the case of ethylene, rapid polymerization occurred at atmospheric pressure and moderate to low temperature, giving a stronger (more crystalline) product (HDPE) than that from radical polymerization (LDPE). For this important discovery these chemists received the Nobel Prize in chemistry (1963) .

Ziegler-Natta Catalytic Polymerization

Ziegler-Natta catalysts are prepared by reacting certain transition metal halides with organometallic reagents such as alkyl aluminum, lithium and zinc reagents. The catalyst formed by reaction of triethylaluminum with titanium tetrachloride has been widely studied, but other metals (e.g. V & Zr) have also proven effective. Polymerization of propylene through action of the titanium catalyst gives an isotactic product; whereas, a vanadium based catalyst gives a syndiotactic product. (AlEt3TiCl4 or AlBu3TiCl4) are some catalysts studied.

Addition Copolymerization
Most direct copolymerizations of equimolar mixtures of different monomers give statistical copolymers, If one of the monomers is much more reactive, then a homopolymer results.

The copolymerization of styrene with methyl methacrylate, for example, proceeds differently depending on the mechanism. (a) Radical polymerization gives a statistical copolymer. (b) Cationic polymerization gives largely polystyrene, and (c) Anionic polymerization favors formation of poly(methyl methacrylate).
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Condensation Polymers A large number of important and useful polymeric materials are not formed by chain-growth processes involving reactive species such as radicals. Condensation polymerizations often (but not always) occur with loss of a small byproduct, such as water, and generally (but not always) combine two different components in an alternating structure.

Examples of naturally occurring condensation polymers are cellulose, the polypeptide chains of proteins, and poly(-hydroxybutyric acid),
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Proteins: condensation polymers Formed by condensation polymerization of amino acids Monomers: 20 amino acids
NH2 H R CO2H

General structure of an amino acid R is the only variable group

Glycine (R = H) + Glycine

First step toward poly(glycine)

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Characteristics of Condensation Polymers Condensation polymers form more slowly than addition polymers, often requiring heat, and they are generally lower in molecular weight. The terminal functional groups on a chain remain active, so that groups of shorter chains combine into longer chains in the late stages of polymerization. The presence of polar functional groups on the chains often enhances chain-chain attractions, particularly if these involve hydrogen bonding, and thereby crystallinity and tensile strength. E.g. Polyester, polyester, polycarbonate, polyurethane, polyamide (Nylon 66, Nylon 6, Perlon, Kevlar, Nomex) The following examples of condensation polymers are illustrative.

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Polymers with different Tg and Tm are obtained by selecting the suitable monomer and the process of polymerization reaction E.g. The difference in Tg and Tm between the different polyester (completely aliphatic) and the two nylon polyamides shows the effect of intra-chain hydrogen bonding on crystallinity. The high Tg and Tm values for the amorphous polymer Lexan are consistent with its brilliant transparency and glass-like rigidity. Kevlar and Nomex are extremely tough and resistant materials, which find use in bullet-proof vests and fire resistant clothing.

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many polymers form bonds between neighboring chains. These bonds can be formed directly between the neighboring chains, or two chains may bond to a third common molecule. these cross-links have an important effect on the polymer.

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Cross-linking of disulphide bonds in insulin molecule

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One example of crosslinking is vulcanization . In vulcanization, a series of cross-links are introduced into an elastomer to give it strength. This technique is commonly used to strengthen rubber.

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Structural properties of linear polymers: conformational flexibility and strength

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Addition Copolymerization
In cases where the relative reactivities are different, the copolymer composition can sometimes be controlled by continuous introduction of a biased mixture of monomers into the reaction.

Formation of alternating copolymers is favored when the monomers have different polar substituents (e.g. one electron withdrawing and the other electron donating), and both have similar reactivities toward radicals.
For example, styrene and acrylonitrile copolymerize in a largely alternating fashion.

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Addition Copolymerization
Some Useful Copolymers Monomer A H2C=CHCl Monomer B H2C=CCl2 Copolymer Saran SBR styrene butadiene rubber Nitrile Rubber Uses films & fibers

H2C=CHC6H5

H2C=CCH=CH2 H2C=CCH=CH2 H2C=CCH=CH2

H2C=CHF

tires adhesives hoses inner tubes

gaskets
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H2C=CHCN

H2C=C(CH3)2
F2C=CF(CF3)

Butyl Rubber
Viton

Rembember from GChem? Nylon is a condensation polymer made of the monomers adipic acid and hexamethylene diamine.
O OH O

OH

Q ui kTi e and a c m Ph ot o - JPEG d ec om pr ess or ar e nee ded t o s ee t h i pi t ur e . s c

adipic acid
+
NH2 H2N

They're nylons, Benjam

hexamethylene diamine

nylon

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Hydrogen bonds between chains

Supramolecular Structure of nylon

Intermolecular hydrogen bonds give nylon enormous tensile strength

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Biopolymers Nucleic acid polymers (DNA, RNA) Amino acids polymers (Proteins) Sugar polymers (Carbohydrates) Genetic information for the cell: DNA Structural strength and catalysis: Proteins

Energy source: Carbohydrates

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Proteins: amino acid monomers The basic structure of an amino acid monomer
HO O NH2 H R

The difference between amino acids is the R group

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Proteins: condensation polymers Formed by condensation polymerization of amino acids Monomers: 20 essential amino acids
NH2 H R CO2H

General structure of an amino acid R is the only variable group

Glycine (R = H) + Glycine

First step toward poly(glycine)

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Representation of the constitution of a protein

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Three D representation of the structure of a protein

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DNA

Thymine (T) The monomers: Adenine (A) Cytosine (C)

Guanine (G)
PhosphateSugar (backbone) of DNA
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Phosphatesugar backbone holds the DNA macromolecule together

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One strand unwinds to duplicate its complement via a polymerization of the monomers C, G, A and T

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Carbohydrates

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