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Polymers

Polymers are compound of very high molecular masses formed by the combination of a large number of simple molecules. The simple molecules which combine to give polymers are called monomers. The process by which the simple molecule (i.e. monomers) are converted into polymers is called polymerisation.

Example : Polyethylene

• All polymers are macromolecule but all macromolecules are not polymers because polymer consist repeating unit of monomer e.g., chlorophyll is a macromolecule but not a polymer.

Classification of polymers

A. Classification based on source of availability

They are classified as

(i) Natural polymers polymers

(ii) Synthetic polymers

(iii) Semi-synthetic

(i) Natural polymers : The polymers obtained from nature (plants and animals) are called natural polymers. These polymers are very essential for life. They are as under.

(a) Starch : It is polymer of glucose and it is food reserve of plant.

(b) Cellulose : It is also a polymer of glucose. It is a chief structural material of the

plant both starch and cellulose photosynthesis.

are made

by

plants from glucose

produced

during

(c) Proteins : These are polymers of a-amino acids, they have generally 20 to 1000 a amino acid joined together in a highly organized arrangement. These are building blocks of animal body and constitute an essential part of our food.

(d) Nucleic acids : These are polymers of various nucleotides. For example RNA and DNA are common nucleotides.

• It may be noted that polymers such as polysaccharides (starch, cellulose), proteins and nucleic acids etc. which control various life processes in plants and animals are also called biopolymers.

(ii) Synthetic polymers : The polymers which are prepared in the laboratories are called synthetic polymers. These are also called man made polymers. For example polyethene, PVC nylon, teflon, bakelite terylene, synthetic rubber etc.

(iii) Semisynthetic polymers : These polymers are mostly derived from naturally occurring polymers by chemical modifications. For example cellulose is naturally occurring polymers, cellulose on acetylation with acetic anhydride in the presence of sulphuric acid forms cellulose diacetate polymers. It is used in making thread and materials like films glasses etc. Vulcanized rubber is also an example of semisynthetic polymers used in making tyres etc. gun cotton which is cellulose nitrate used in making explosive.

• Semi-synthetic polymers : Rayon and other cellulose derivatives like cellulose nitrate, cellulose acetate etc., are semi-synthetic polymers. These are thermoplastic polymers. Viscose rayon in the form of a thin transparent film is known as cellophane. Cellophane is softened with glycerol. Unlike plastic sheets it absorbs water.

• Rayon : Rayon is a man made material which consists of purified cellulose in the form of long fibres. Cellulose is treated with cold NaOH solution to purify it and then treated with CS2 to form a viscose solution. This is why rayon is sometimes called viscose rayon. This solution is allowed to pass through fine pores in metal cylinder, into a dilute solution of H2SO4. This results in the formation of long fibres. Rayon fibre is chemically identical to cotton but has a shine like silk. As such rayon is also known as artificial silk. Rayon is used on a large scale for making textiles, tyre-chord, carpets and surgical dressings. Unlike fully synthetic polymers, it absorbs moisture and is bio-degradable.

  • B. Classification based upon structure

On the basis of structure of polymers these can be classified as

(i) Linear polymers polymers

(ii) Branched chain polymers

(iii) Cross linked

(i) Linear polymers : These are polymers in which monomeric units are linked together to form linear chain. These linear polymers are well packed and have high magnitude of intermolecular forces of attraction and therefore have high densities, high tensile (pulling) strength and high melting points. Some common example of linear polymers are high density polyethylene nylon, polyester, PVC, PAN etc.

(ii) Branched chain polymers : These are polymers in which the monomers are joined to form long chains with side chains or branches of different lengths. These branched chain polymers are irregularly packed and therefore, they have low tensile strength, low density, boiling point and melting points than linear polymers. Some common examples are low density polythene, glycogen, starch etc. (Amylopectin).

(iii) Cross linked polymers : These are polymers in which monomers unit are crosslinked together to form a three dimensional network polymers. These polymers are hard, rigid and brittle because of network structure e.g., Bakelite, malamine formaldehyde resin etc.

  • C. Classification based upon molecular forces

Depending upon the intermolecular forces, the polymers have been classified into four type.

(i) Elastomers

(iii) Thermoplastics

(ii) Fibers

(iv) Thermosetting polymers

(i) Elastomers : The polymers that have elastic character like rubber (a material that can return to its original shape after stretching is said to be elastic) are called elastomers. In elastomers the polymers chains are held together by weak intermolecular forces. Because of the presence of weak forces, the polymers can be easily stretched by applying small stress and regains their original shape when the stress is removed. The most important example of elastomers is natural rubber.

(ii) Fibers : These are the polymers which have strong intermolecular forces between the chain. These forces are either hydrogen bonds or dipole-dipole interaction. Because of strong forces, the chains are closely packed giving them high tensil strength and less elasticity. Therefore, these polymers have sharp melting points. These polymers are long, thin and thread like and can be woven in fabric. Therefore, these are used for making fibers.

Example : Nylon 66, dacron, silk etc.

(iii) Thermoplastics : These are the polymers which can be easily softened repeatedly when heated and hardened when cooled with little change in their properties. The intermolecular forces in these polymers are intermediate between those of elastomers and fibres. There is no cross linking between the chain. The softening occurs as the polymer chain move more and more freely because of absence of cross link. When heated, they melt and form a fluid which can be moulded into any desired shapes and then cooled to get the desired product.

Example : Polythene, polystyrene, PVC, teflon etc.

(iv) Thermosetting polymers : These are the polymers which undergo permanent change on heating. They become hard and infusible on heating. They are generally prepared from low molecular mass semifluid substances. When heated they get highly cross linked to form hard infusible and insoluble products. The cross links hold the molecule in place so that heating does not allow them to move freely. Therefore a thermosetting plastic is cross linked and is permanently rigid.

Example : Bakelite, melamine formaldehyde resin etc.

Difference between thermoplastic and thermosetting polymers

Thermoplastic polymers

Thermosetting polymers

(1)

These

soften

and

melt

on

These do not soften

on heating but

heating.

 

rather become

hard

in

case

 

prolonged heating is done these start burning.

(2) These can be remoulded recast

These

can

not

be

remoulded

or

and reshaped.

reshaped.

 

(3) These are less brittle and soluble in some organic solvents.

These are more brittle and insoluble in organic solvents.

(4)

These are formed

by addition

These are formed by condensation

polymerisation.

 

polymerisation.

(5)

These

usually

have

linear

These have three dimensional cross

structures.

 

linked structures. Ex. Bakelite, urea,

Ex. Polyethylene, PVC, Teflon.

 

formaldehyde, resin.

D. Classification based on Regio and Stereoisomerization in Polymers

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, described in the following diagram, or in a third random manner. Most monomers of this kind, including propylene, vinyl chloride, styrene, acrylonitrile and acrylic esters, prefer to join in a head-to-tail fashion, with some randomness occurring from time to time. The reasons for this regioselectivity will be discussed in the synthetic methods section.

If the polymer chain is drawn in a zig-zag fashion, as shown above,
If the polymer
chain
is
drawn in
a zig-zag fashion,
as shown above,

each of

the

substituent groups (Z) will necessarily be located above or below the plane defined by

the carbon chain. Consequently we can identify three configurational isomers of such polymers.

i.

If

all

the

substituents

lie

on

one

side

of

the chain the configuration is

ii.

called isotactic. If the substituents alternate from one side to another in a regular manner the

iii.

configuration is termed syndiotactic. Finally, a random arrangement of substituent groups is referred to as atactic. Examples of these configurations are shown here.

Symmetrical monomers such as ethylene and tetrafluoroethylene can join together in only one way. Monosubstituted monomers,addition reactions . Many of these addition reactions are known to proceed in a stepwise fashion by way of reactive intermediates , and this is the mechanism followed by most polymerizations. A general diagram illustrating this assembly of linear macromolecules, which supports the name chain growth polymers , is presented here. Since a pi-bond in the monomer is converted to a sigma- bond in the polymer, the polymerization reaction is usually exothermic by 8 to 20 kcal/mol. Indeed, cases of explosively uncontrolled polymerizations have been reported. " id="pdf-obj-3-65" src="pdf-obj-3-65.jpg">

E. Classification based on Polymerization

  • i. Addition Polymers Condensation Polymers

ii.

Addition Polymers

All the monomers from which addition polymers are made are alkenes or functionally substituted alkenes. The most common and thermodynamically favored chemical transformations of alkenes are addition reactions. Many of these addition reactions are known to proceed in a stepwise fashion by way of reactive intermediates, and this is the mechanism followed by most polymerizations. A general diagram illustrating this assembly of linear macromolecules, which supports the name chain growth polymers, is presented here. Since a pi-bond in the monomer is converted to a sigma- bond in the polymer, the polymerization reaction is usually exothermic by 8 to 20 kcal/mol. Indeed, cases of explosively uncontrolled polymerizations have been reported.

It is useful to distinguish four polymerization procedures fitting this general description. • Radical Polymerization The

It is useful to distinguish four polymerization procedures fitting this general description.

• Radical Polymerization The initiator is a radical, and the propagating site of reactivity (*) is a carbon radical. • Cationic Polymerization The initiator is an acid, and the propagating site of reactivity (*) is a carbocation. • Anionic Polymerization The initiator is a nucleophile, and the propagating site of reactivity (*) is a carbanion. • Coordination Catalytic Polymerization The initiator is a transition metal complex, and the propagating site of reactivity (*) is a terminal catalytic complex.

Some Common Addition Polymers Name(s) Properties Uses
Some Common Addition Polymers
Name(s)
Properties
Uses

Formula

Monomer

Polyethylene

low density

(LDPE)

–(CH 2

-CH 2

) n

ethylene CH 2 =CH 2

soft, waxy solid

film wrap, plastic bags

Polyethylene

high

density –(CH 2 -CH 2 ) n

(HDPE)

ethylene CH 2 =CH 2

rigid,

solid

translucent

electrical

insulation

bottles, toys

Polypropylene

(PP)

grades

different

–[CH 2 - CH(CH 3 )] n

propylene CH 2 =CHCH 3

atactic: soft, elastic solid

isotactic:

hard,

strong solid

similar

to

carpet,

upholstery

LDPE

Poly(vinyl

chloride)

(PVC)

–(CH 2 - CHCl) n

vinyl

chloride

CH 2 =CHCl

strong rigid solid

pipes,

flooring

siding,

Poly(vinylidene

chloride)

(Saran A)

–(CH 2

-CCl

2

) n

vinylidene chloride CH 2 =CCl 2

Polystyrene

(PS)

–[CH 2 - CH(C 6 H

5 )]

n

styrene CH 2 =CHC 6 H 5

dense, high-melting solid

seat

films

covers,

hard,

solid

rigid,

clear

soluble

in

solvents

organic

toys,

cabinets

packaging

(foamed)

Polyacrylonitrile

(PAN,

Acrilan)

Orlon,

–(CH 2 - CHCN) n

Polytetrafluoroet

hylene

(PTFE, Teflon)

–(CF 2 -CF 2 ) n

acrylonitrile CH 2 =CHCN

high-melting

soluble

in

solvents

solid

organic

rugs,

clothing

blankets

tetrafluoroethy lene CF 2 =CF 2

resistant,

solid

smooth

non-stick

surfaces

electrical

insulation

Poly(methyl

methacrylate)

(PMMA,

Plexiglas)

Lucite,

–[CH 2 - C(CH 3 )CO 2 C H 3 ] n

methyl

methacrylate

CH 2

=C(CH 3 )CO

2

CH

3

hard,

solid

transparent

lighting

signs

skylights

covers,

Poly(vinyl

 

–(CH 2 -

acetate)

CHOCOCH

(PVAc)

–[CH 2 -

cis-Polyisoprene

natural rubber

CH=C(CH 3

CH 2 ] n

Polychloroprene

–[CH 2 -

(cis

+

trans)

CH=CCl-

(Neoprene)

CH 2 ] n

3 ) n

)-

vinyl

acetate

CH 2 =CHOCOC

H 3

isoprene

CH 2 =CH-

C(CH 3 )=CH 2

chloroprene

CH 2 =CH-

CCl=CH 2

soft, sticky solid

soft, sticky solid

latex

paints,

adhesives

requires

vulcanization

for practical use

tough, rubbery solid synthetic oil resistant rubber

  • 1. Radical Chain-Growth Polymerization

Virtually all of the monomers described above are subject to radical polymerization.

Since this can be initiated by traces of oxygen or other minor impurities, pure samples

of these compounds are often "stabilized" by small amounts of radical inhibitors to

avoid unwanted reaction. When radical polymerization is desired, it must be started by

using a radical initiator, such as a peroxide or certain azo compounds. The formulas

of some common initiators, and equations showing the formation of radical species from

these initiators are presented below.

Poly(vinyl –(CH - acetate) CHOCOCH (PVAc) – –[CH - cis-Polyisoprene natural rubber CH=C(CH CH ] –described above are subject to radical polymerization. Since this can be initiated by traces of oxygen or other minor impurities, pure samples of these compounds are often "stabilized" by small amounts of radical inhibitors to avoid unwanted reaction. When radical polymerization is desired, it must be started by using a radical initiator , such as a peroxide or certain azo compounds. The formulas of some common initiators, and equations showing the formation of radical species from these initiators are presented below. By using small amounts of initiators, a wide variety of monomers can be polymerized. One example of this radical polymerization is the conversion of styrene to polystyrene, shown in the following diagram. The first two equations illustrate the initiation process, and the last two equations are examples of chain propagation . Each monomer unit adds to the growing chain in a manner that generates the most stable radical . Since carbon radicals are stabilized by substituents of many kinds, the preference for head-to- tail regioselectivity in most addition polymerizations is understandable. Because radicals are tolerant of many functional groups and solvents (including water), radical polymerizations are widely used in the chemical industry. " id="pdf-obj-5-166" src="pdf-obj-5-166.jpg">

By using small amounts of initiators, a wide variety of monomers can be polymerized.

One example of this radical polymerization is the conversion of styrene to polystyrene,

shown in the following diagram. The first two equations illustrate the initiation process,

and the last two equations are examples of chain propagation. Each monomer unit

adds to the growing chain in a manner that generates the most stable radical. Since

carbon radicals are stabilized by substituents of many kinds, the preference for head-to-

tail regioselectivity in most addition polymerizations is understandable. Because

radicals are tolerant of many functional groups and solvents (including water), radical

polymerizations are widely used in the chemical industry.

In principle, once started a radical polymerization might be expected to continue unchecked, producing a few

In principle, once started a radical polymerization might be expected to continue

unchecked, producing a few extremely long chain polymers. In practice, larger numbers

of moderately sized chains are formed, indicating that chain-terminating reactions must

be taking place. The most common termination processes are Radical

Combination and Disproportionation. These reactions are illustrated by the

following equations. The growing polymer chains are colored blue and red, and the

hydrogen atom transferred in disproportionation is colored green. Note that in both

types of termination two reactive radical sites are removed by simultaneous conversion

to stable product(s). Since the concentration of radical species in a polymerization

reaction is small relative to other reactants (e.g. monomers, solvents and terminated

chains), the rate at which these radical-radical termination reactions occurs is very

small, and most growing chains achieve moderate length before termination.

In principle, once started a radical polymerization might be expected to continue unchecked, producing a few

The relative importance of these terminations varies with the nature of the monomer

undergoing polymerization. For acrylonitrile and styrene combination is the major

process. However, methyl methacrylate and vinyl acetate are terminated chiefly by

disproportionation.

Another reaction that diverts radical chain-growth polymerizations from producing

linear macromolecules is called chain transfer. As the name implies, this reaction

moves a carbon radical from one location to another by an intermolecular or

intramolecular hydrogen atom transfer (colored green). These possibilities are

demonstrated by the following equations

intramolecular hydrogen atom transfer (colored green). These possibilities are demonstrated by the following equations Chain transfer

Chain transfer reactions are especially prevalent in the high pressure radical

polymerization of ethylene, which is the method used to make LDPE (low density

polyethylene). The 1º-radical at the end of a growing chain is converted to a more

stable 2º-radical by hydrogen atom transfer. Further polymerization at the new radical

site generates a side chain radical, and this may in turn lead to creation of other side

chains by chain transfer reactions. As a result, the morphology of LDPE is an amorphous

network of highly branched macromolecules.

  • 2. 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,

T g = _ 70º C, which is used for inner tubes. This process is similar to radical

polymerization, as demonstrated by the following equations. Chain growth ceases when

the terminal carbocation combines with a nucleophile or loses a proton, giving a

terminal alkene (as shown here).

intramolecular hydrogen atom transfer (colored green). These possibilities are demonstrated by the following equations Chain transfer

Monomers bearing cation stabilizing groups, such as alkyl, phenyl or vinyl can be

polymerized by cationic processes. These are normally initiated at low temperature in

methylene chloride solution. Strong acids, such as HClO 4 , or Lewis acids containing

traces of water (as shown above) serve as initiating reagents. At low temperatures,

chain transfer reactions are rare in such polymerizations, so the resulting polymers are

cleanly linear (unbranched).

3.

Anionic Chain-Growth Polymerization

Treatment of a cold THF solution of styrene with 0.001 equivalents of n-butyllithium

causes an immediate polymerization. This is an example of anionic polymerization, the

course of which is described by the following equations. 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.

3. Anionic Chain-Growth Polymerization Treatment of a cold THF solution of styrene with 0.001 equivalents of1963 Nobel Prize in chemistry . 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. The following diagram presents one mechanism for this useful reaction. Others have been suggested, with changes to accommodate the heterogeneity or homogeneity of the catalyst. Polymerization of propylene through action of the titanium catalyst gives an isotactic product; whereas, a vanadium based catalyst gives a syndiotactic product. " id="pdf-obj-8-21" src="pdf-obj-8-21.jpg">

Species that have been used to initiate anionic polymerization include alkali metals,

alkali amides, alkyl lithiums and various electron sources. A practical application of

anionic polymerization occurs in the use of superglue. This material is methyl 2-

cyanoacrylate, CH 2 =C(CN)CO 2 CH 3 . When exposed to water, amines or other

nucleophiles, a rapid polymerization of this monomer takes place.

  • 4. 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. Their findings permitted,

for the first time, the synthesis of unbranched, high molecular weight polyethylene

(HDPE), laboratory synthesis of natural rubber from isoprene, and configurational

control of polymers from terminal alkenes like propene (e.g. pure isotactic and

syndiotactic polymers). 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 1963 Nobel Prize in chemistry.

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. The following

diagram presents one mechanism for this useful reaction. Others have been suggested,

with changes to accommodate the heterogeneity or homogeneity of the catalyst.

Polymerization of propylene through action of the titanium catalyst gives an isotactic

product; whereas, a vanadium based catalyst gives a syndiotactic product.

Copolymers The synthesis of macromolecules composed of more than one monomeric repeating unit has been explored

Copolymers

The synthesis of macromolecules composed of more than one monomeric repeating

unit has 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 might be 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.

Statistical

Also called random copolymers. Here the monomeric units

Copolymers

are distributed randomly, and sometimes unevenly, in the

polymer chain: ~ABBAAABAABBBABAABA~.

Alternating

Here the monomeric units are distributed in a regular

Copolymers

alternating fashion, with nearly equimolar amounts of each

in the chain: ~ABABABABABABABAB~.

Block Copolymers

Instead of a mixed distribution of monomeric units, a long

sequence or block of one monomer is joined to a block of

the

second

monomer:

~AAAAA-

BBBBBBB~AAAAAAA~BBB~.

Graft Copolymers

As the name suggests, side chains of a given monomer are

attached to the main

chain of

the second monomer:

~AAAAAAA(BBBBBBB~)AAAAAAA(BBBB~)AAA~.

  • 1. Addition Copolymerization

Most direct copolymerizations of equimolar mixtures of different monomers give

statistical copolymers, or if one monomer is much more reactive a nearly homopolymer

of that monomer. The copolymerization of styrene with methyl methacrylate, for

example, proceeds differently depending on the mechanism. Radical polymerization

gives a statistical copolymer. However, the product of cationic polymerization is largely

polystyrene, and anionic polymerization favors formation of poly(methyl methacrylate).

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.

Some Useful Copolymers

Copolymer

Uses

Monomer

 

A

H 2

C=CHC 6 H

5

H 2 C=CHCN

H 2

C=C(CH 3 ) 2

Monomer B

H 2

C=C-

CH=CH

2

H 2 C=C-

CH=CH

2

H 2 C=C-

CH=CH

2

H 2 C=CHCl H 2 C=CCl 2

Saran

films & fibers

SBR

styrene butadiene rubber tires

Nitrile Rubber

adhesives

hoses

Butyl Rubber

inner tubes

F 2 C=CF(CF 3 ) H 2 C=CHF

Viton

gaskets

A terpolymer of acrylonitrile, butadiene and styrene, called ABS rubber, is used for high-

impact containers, pipes and gaskets.

  • 2. Block Copolymerization

Several different techniques for preparing block copolymers have been developed,

many of which use condensation reactions (next section). At this point, our discussion

will be limited to an application of anionic polymerization. In the anionic polymerization

of styrene described above, a reactive site remains at the end of the chain until it is

quenched. The unquenched polymer has been termed a living polymer, and if

additional styrene or a different suitable monomer is added a block polymer will form.

This is illustrated for methyl methacrylate in the following diagram.

Formation of alternating copolymers is favored when the monomers have different polar substituents (e.g. one electrondescribed above , a reactive site remains at the end of the chain until it is quenched. The unquenched polymer has been termed a living polymer , and if additional styrene or a different suitable monomer is added a block polymer will form. This is illustrated for methyl methacrylate in the following diagram. Condensation Polymers A large number of important and useful polymeric materials are not formed by chain- growth processes involving reactive species such as radicals, but proceed instead by conventional functional group transformations of polyfunctional reactants. These 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 " id="pdf-obj-10-151" src="pdf-obj-10-151.jpg">

Condensation Polymers

A large number of important and useful polymeric materials are not formed by chain-

growth processes involving reactive species such as radicals, but proceed instead by

conventional functional group transformations of polyfunctional reactants. These

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. The polyester Dacron and the polyamide Nylon 66, shown here,

are two examples of synthetic condensation polymers, also known as step-

growth polymers. In contrast to chain-growth polymers, most of which grow by carbon-

carbon bond formation, step-growth polymers generally grow by carbon-heteroatom

bond formation (C-O & C-N in Dacron & Nylon respectively). Although polymers of this

kind might be considered to be alternating copolymers, the repeating monomeric unit is

usually defined

as

a

combined

moiety.

Examples of naturally occurring condensation polymers are cellulose, the polypeptide

chains of proteins, and poly(β-hydroxybutyric acid), a polyester synthesized in large

quantity by certain soil and water bacteria. Formulas for these will be displayed below

by clicking on the diagram.

alternating structure. The polyester Dacron and the polyamide Nylon 66, shown here, are two examples of

1.

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. The following examples of condensation

polymers

are

illustrative.

Note that for commercial synthesis the carboxylic acid components may actually be

employed in the form of derivatives such as simple esters. Also, the polymerization

reactions for Nylon 6 and Spandex do not proceed by elimination of water or other small

molecules. Nevertheless, the polymer clearly forms by a step-growth process.

 

Some common Condensation Polymers

 

Formula

Type

Components

 
polyester para HO C-C H -CO H

polyester

para

HO 2 C-C 6 H 4

-CO

2 H

Dacron

HO-CH

2 CH 2

-OH

Mylar

polyester meta HO C-C H -CO H

polyester

meta

HO

2 C-C 6 H 4

-CO

2 H

HO-CH

2 CH 2

-OH

polycarbonat (HO-C H -) C(CH )

polycarbonat

(HO-C 6

H 4 -) 2 C(CH 3 ) 2

 

e

(Bisphenol

 

A)

Lexan

X

2 C=O

 

(X = OCH 3 or Cl)

 
 

polyamide

HO 2 C-(CH 2 ) 4 -CO 2 H

~[CO(CH 2 ) 4

CO-NH(CH 2 ) 6 NH] n ~

Nylon 66

H 2 N-(CH 2 ) 6 -NH 2

 

polyamide

polyamide
 

~[CO(CH 2 ) 5

NH] n ~

Nylon

6

 

Perlon

polyamide para HO C-C H -CO H

polyamide

para HO 2 C-C 6 H 4 -CO 2 H

Kevlar

para H 2 N-C 6 H 4 -NH 2

 
polyamide meta HO C-C H -CO H

polyamide

meta HO 2 C-C 6 H 4 -CO 2 H

Nomex

meta H 2 N-C 6 H 4 -NH 2

 
1. Characteristics of Condensation Polymers Condensation polymers form more slowly than addition polymers, often requiring heat,

polyurethane

Spandex

HOCH 2 CH 2 OH

1. Characteristics of Condensation Polymers Condensation polymers form more slowly than addition polymers, often requiring heat,

Natural rubber

Natural rubber is an elastomer (an elastic hydrocarbon polymer) that was originally derived from a milky colloidal suspension, or latex, found in the sap of some plants. The purified form of natural rubber is the chemical polyisoprene which can also be produced synthetically. Natural rubber is used extensively in many applications and products as is synthetic rubber. The entropy model of rubber was developed in 1934 by Werner Kuhn.

Natural rubber is a polymer of the monomer 2-methylbuta-1,3-diene (isoprene)

Poly(2-methylbuta-1,3-diene) or polyisoprene can exist in two isomeric forms.

Natural rubber is the cis-form 2-Methylbuta-1,3-diene

Chemical makeup

Natural rubber is a polymer of isoprene - most often cis-1,4-polyisoprene - with a molecular weight of 100,000 to 1,000,000. Typically, a few percent of other materials, such as proteins, fatty acids, resins and inorganic materials are found in natural rubber. Polyisoprene is also created synthetically, producing what is sometimes referred to as "synthetic natural rubber". Some natural rubber sources called gutta percha are composed of trans-1,4-polyisoprene, a structural isomer which has similar, but not identical properties. Natural rubber is an elastomer and a thermoplastic. However, it should be noted that as the rubber is vulcanized it will turn into a thermoset. Most rubber in everyday use is vulcanized to a point where it shares properties of both; i.e., if it is heated and cooled, it is degraded but not destroyed.

The list of synthetic polymers includes synthetic rubber, Bakelite, neoprene, nylon, PVC, polystyrene, polyethylene, polypropylene, polyacrylonitrile, PVB, silicone, and many more.

Natural rubber is not a useful polymer because it is too soft and too chemically reactive. The long chain molecules can be coiled twisted and interwined with one another Vulcanization of natural rubber is the chemical process that confers crosslinkage among the polymer chains of rubber, turning natural rubber into a flexible elastic material.

• In the process of vulcanization,1–3 % by mass of sulphur is added to natural rubber and the mixture is heated • Short chains of sulphur atoms (i.e. cross-linkages) are formed between the polymer chains • The sulphur changes rubber into a thermosetting polymer by cross linking the polymer chains through reaction at some of the double bonds as shown:

Natural rubber is an elastomer (an elastic hydrocarbon polymer) that was originally derived from a milky
Natural rubber is an elastomer (an elastic hydrocarbon polymer) that was originally derived from a milky
Natural rubber is an elastomer (an elastic hydrocarbon polymer) that was originally derived from a milky

This makes the rubber harder chemical attrack.

and reduces its susceptibility to oxidation or

other

When vulcanized rubber gets hot,the polymer chains cannot slip across one another since

they are still held together by short chains of sulphur atoms That is why vulcanized rubber does not melt when heated and does not become brittle

when cooled The extent of the cross-linkages formed between the polymer chains affects the properties

of vulcanized rubber If the rubber has few cross-linkages, the rubber is softer, more flexible and more elastic

If the rubber has many cross-linkages, it is stiffer, less flexible and less elastic

Car tyres are made of vulcanized rubber

Because of the presence of cross-linkages among the polymer chains, the rubber does not

melt when it gets hot That is the reason why car tyres do not melt when drivers drive really fast

Degradable Plastics

Natural polymers (e.g. wood and paper) are biodegradable Micro-organisms in water and in the soil use them as food. Synthetic polymers (e.g. plastics) are nonbiodegradable can remain in the environment for a very long time.

In order to tackle the pollution problems caused by the disposal of plastic waste, degradable plastics have been invented

Several types of degradable plastics:

biopolymers

photodegradable plastics

synthetic biodegradable plastics

  • 1. Biopolymers

• Polymers made by living micro-organisms (e.g. paracoccus, bacillus and spirullum) e.g. The biopolymer poly(3-hydroxybutanoic acid) (PHB) is made by certain bacteria from glucose • When PHB is disposed, the micro-organisms found in the soil and natural water sources are able to break it down within 9 months. However, PHB is 15 times more expensive than polyethene

  • 2. Photodegradable Plastics

• Photodegradable plastics have light-sensitive functional groups (e.g. carbonyl groups) incorporated into their polymer chains. • These groups will absorb sunlight use the energy to break the chemical bonds in the polymer to form small fragments

  • 3. Synthetic Biodegradable Plastics

• Made by incorporating starch or cellulose into the polymers during production. Micro- organisms consume starch or cellulose and the plastics are broken down into small pieces • The very small pieces left have a large surface area greatly speeds up their biodegradation.

Drawbacks of this method:

• the products of biodegradation may cause water pollution • the rate of biodegradation is still too low for the large quantity of plastic waste generated • They are much more expensive than ordinary materials. • When buried in landfill, they will not be exposed to sunlight light and may therefore remain unchanged for many years. • Their long term effects on the environment are unknown of any residues. • They may encourage a ‘throwaway is OK’ culture. • They interfere with the present recycle program.