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Polymer an Insight in to the learning topics
Classification of polymers:
  Thermoplastics- PE, PS, PVC, PTFE, ABS, PMMA, Synthetic Rubber

   Thermosetting plastics -        properties and industrial applications
                                   of Bakelite, Melamine Resin, Epoxy Resin,
   Polyurethane (PU), Polyamide (nylon Series), Polyester (PET), PC, Silicon
   Polymer

   Moulding of plastics into articles:
                                Compression,
                                injection,
                                transfer and extrusion methods.
                                                       methods
   Conducting polymers:         Properties and applications
   Biodegradable polymers       Properties and applications

 11/11/12                                                                      1
 A word polymer is a combination of two Greek words,
  “Poly” means “many” and “Meros” meaning “parts or
  units”.
 A polymer is a large molecule of which is formed by
  repeated linking of the small molecules called
  “monomers”.

  n(CH2-CH2)               (-CH2-CH2-)n
   ethylene                polyethylene
The number of repeating units in the chains of which
 a polymer is made up is called degree of a
 polymerization (n).

Polymers with high degree of polymerization are
 called the “High Polymer”, and those with low degree
 of polymerization are called “Oligopolymers”.

High polymers have very high molecular mass (10000
 to 1000000 u) and are called macromolecules.
Degree of Polymerization (P) = M/m;
  Where, M= Mass of Polymer; m = mass of monomeric unit


                       Polymerisation
    3      CH2 CH2                          CH2 CH2
                                                           3

           Ethylene
                                            polyethylene


Degree of polymerisation (P) = 3

 Mass of this polymer M = (28 x 3) = 84Da




11/11/12                                                       4
A macromolecule may consist of monomer of
 identical or different chemical structure and
 accordingly they are called Homopolymers or
 copolymers (or Heteropolymers).

       A     A       A      A       … Homopolymers



       A     A       B      A        … Copolymers
Tacticity- Plane representation of polypropylene polymer

   1. Isotactic polymers
           H        H       H          H         H
           CH2 C CH2 C CH2 C CH2       C CH2 C
                                                         Functional groups on the
              CH3   CH3     CH3        CH3       CH3     same side of the main carbon
                                                         skeleton

 2. Syndiotactic polymers
              H     CH3    H       CH3       H
                                                       Functional groups arranged
       CH2 C CH2 C CH2 C CH2       C CH2 C             in the alternate fashion of the
                                                       main carbon skeleton
              CH3   H      CH3     H         CH3

   3.Atactic polymers
              H     CH3     CH3    H         H
                                                        Functional groups arranged
       CH2 C CH2 C CH2 C CH2       C CH2 C              in a random manner around
                                                        the main carbon skeleton
              CH3   H       H      CH3       CH3

11/11/12                                                                                 6
Polymers can be linear, branched or cross-linked.
 The monomer may be arranged in the chain at
 random or regularly.

                      (LINEAR POLYMER)
   A    A   A   A   … …      B    B   B

    A       A       A     A     A         A


            A             A      A        A   A


            A             A      A

                (BRANCHED POLYMER)
A               A

    A            A               A

A   A        A       A       A           A

A            A                           A

A   A        A       A       A       A


        (CROSS-LINKED POLYMER)
Functionality
     The number of reactive sites present in a monomer is called functionality

1.

                                                                            O
     Linear chain polymer is formed if the functionality of the       HO C CH2 NH2
     monomer is only two (Bifunctional)

2.                                                                        Ex. Glycine

                                                                              O
                                                 O
                                                                       HO C CH2 NH2
                                OH CH2 CH C OH
                                           NH2

                                      Ex. Serine
                                                     O
                                  OH CH2 CH C OH                  Cross linked chain polymer is
                                                                  formed if the functionality of the
                                              NH2                 monomer is more than two
                                                                  (multifunctional)
 11/11/12                                 Glycine                                                 9
Classification of Polymers
Classification based on Source
1. Natural polymers
 E.g., Proteins, Cellulose, Starch, Rubber

2. Semi-synthetic polymers
 E.g., Cellulose derivatives - Cellulose acetate
  (Rayon)

3. Synthetic polymers
 E.g., Buna-S, Buna-R, Nylon, Polythene, Polyester.
Classification based on Structure
1. Linear polymers
   consist of long and straight chains. E.g., Polyvinyl chloride




2. Branched chain polymers
   contain linear chains having some branches, e.g., low density polymer.




3. Cross-linked or Network polymers
    formed from bi-functional and tri-functional monomers and contain
   strong covalent bonds e.g. bakelite, melamine,
Classification based on Molecular Forces
 1. Elastomers
   eg. Buna-S, Buna-N, neoprene
2. Fibers
   eg. Polyesters, Polyamides.
3. Thermoplastic polymers
   eg. Polythene, Polystyrene, PVC.
4. Thermosetting polymers
   eg. Bakelite, urea-formaldelyde resins

Order of strength :-
Thermosetting > Fibres > Thermoplastics > Elastomers
Classification based on mode of Polymerization
1. Addition polymers
 formed by the repeated addition of monomer molecules
 possessing double or triple bonds
   n(CH2=CH2)                      -(CH2 -CH2 )-
    Ethylene                         polyethylene

2. Condensation polymers
 formed by repeated condensation reaction between two
 different bi-functional or tri-functional monomeric units.
 eg. terylene (dacron), nylon 6, 6, nylon 6.

n(H2N(CH2)6 NH2) + n(HOOC(CH2)4COOH)
                   [-NH(CH2)6NHCO(CH2)4CO-]n + nH2O
 (Nylon 6:6)
Polymerization is of two types;


 Addition or chain polymerization
 Condensation polymer
1. Free radical mechanism:- Alkenes or dienes and their derivatives are
  polymerized in the presence of a free radical generating initiator (catalyst)
  like benzoyl peroxide, acetyl peroxide, t-bu peroxide, etc.

This process involves in 3 steps –
a) Chain initiation step - addition of phenyl free radical formed by the
  peroxide to the ethene double bond ,thereby forming a larger radical.

b) Chain propagation step - repetition of this sequence with new and bigger
   radicals.

c) Chain terminating step - the product radical thus formed reacts
   with another radical to form the polymerized product.

Some of polymers formed by this process are-
Polytetrafluroethene (Teflon), Polyacrylonitrile, Polyethylene, etc.
 In addition polymers , the polymer is formed from the
 monomer, without the loss of any material, and the
 product is the exact multiple of the original
 monomeric molecule.

   CH2=CH2              -CH2-CH2-              POLYMERIZATION   (-CH2-CH2-)n
  Ethylene monomer   Molecular Rearrangement                      Polyethylene
Addition polymerization proceeds by the initial
formation of some reactive species such as free
radicals or ions and by the addition of the reactive
species to the other molecule, with the regeneration
of the reactive feature.
Chain polymerization occur in three steps:-

•Chain initiation step
•Chain propagation step
•Chain termination step
In chain initiation step, a free radical is first generated
as a result of physical or chemical effect, which is
responsible for the further continuation of the chain
polymerization
The primary free radical react with the double bond of
an unexcited monomer molecule and adds to it
forming a new radical capable of further interaction
with the initial monomers.
The most common termination processes are Radical
Combination and Disproportionate.
These reactions are illustrated by the following equations.
In condensation polymerization, the chain growth is
accompanied by the elimination of small
molecules.
The molecules are in the form of the water molecule
H2O ; methanol molecule CH3OH ,etc.
Step Growth polymerization:- It involves a repetitive condensation
reaction between two bi-functional monomers.
Eg. Formation of Nylon 6,6
nHOOC(CH2)4COOH + nH2N(CH2)6 NH2        553K

                                         High pressure


                                        [-N-(CH2) 6-N-C(CH2)4-C-]n


                                          H              O     O
                                                  Nylon6,6
Copolymerisation:- is a polymerization reaction in which a mixture
of more than one monomeric species is allowed to polymerize and
form
a copolymer. For example, a mixture of 1, 3 – butadiene and styrene
can form a copolymer.
Examples of Daily Use Polymers
Plastics
 Plastics are high molecular weight organic materials
   which can be moulded into any desired shape by the
   application of heat and pressure in the presence of
   catalyst.

Constituents of plastics:
1. Resins
2. Plasticizers
3. Fillers or Extenders
4. Lubricants
5. Stabilizers
6. Pigments
7. Anti-oxidants
8. Catalysts or Accelerators
Resins:
They are basic binding materials and hold the constituents
 together.
They are generally linear polymers with low molecular weight
 to enhance fusibility and mouldability.
It is then converted into crosslinked form during moulding in
 the presence of a catalyst.
E.g. Thermoplastic resins and thermosetting resins.

Plasticizers:
They improve flow for processing by reducing the
  intermolecular force of attraction
E.g. Dioctylphthalate, oleate and organic phosphates

Fillers:
They increase the tensile and compressive strength of
  plastics.
They also reduce the shrinkage during setting of the plastics.
E.g. Mica, quartz, limestone, acrylics
Lubricants:
 They makes the moulding process easier and also provide glossy
  finish to the final product.
 E.g. Waxes, oils and soaps

Stabilizers:
 They increase the thermal stability during processing.
 E.g. Stearates of lead, barium and cadmium.

Pigments:
 They provide colours to the plastics
 TiO2, ZnO – White; Cr2O3 – Green, Carbon black – black, Red lead -
  Red
 Anti-oxidants: They protect against oxidative degradation
 E.g. Phenyl p-napthyl amine, diphenyl p-phenylene diamine

Catalysts:
 They are added to accelerate the polymerization of fusible resin into
  cross-linked infusible form especially for thermosetting plastics.
 E.g. H2O2, benzoyl peroxide
Definition
These are linear or slightly branched long chain
 polymers, which can be softened on heating &
 reversibly hardened on cooling repeatedly.
Their hardness is a temporary property & varies with
 temperature.
 It can be reprocessed, so sometimes also referred as
 green plastics.
Structure
 Thermoplastics possess weak intermolecular
 forces(e.g. Van der Waal) & don’t have crosslinks.
Examples
 Cellulose derivatives
      - 1) Cellulose acetate
      - Cellulose nitrate
 Polyethenic/vinyl resins
      - 2) Polyethylene
      - 3) Polypropylene
      - 4) Polyvinyl acetate
      - 5) Polyvinyl chloride
      - 6) Polystyrene
      - 7) Teflon
      - 8) Acrylic
      - 9) Polysulfone
      - 10) Polyester
Polyethylene(PE)/Polythene
  There are mainly two types of polythene:
  Low density polythene(density range of 0.910–0.940
   g/cm3):It is obtained by the polymerisation of ethene
   under high pressure of 1000-2000 atm at a
   temperature of 350-570 K in the presence of traces of
   oxygen or a peroxide initiator.
  It is created by free radical polymerization.
 Properties:
1. High degree of short and long chain branching.
2. intermolecular forces is less.
3. Tough but highly flexible & ductile.
4.Chemically inert.


 Uses: Insulation of electricity carrying wires and
 manufacture of squeeze bottles, toys and flexible
 pipes.
 High density polythene(density >= 0.941 g/cm3):
   formed when addition polymerisation of ethene takes
   place in a hydrocarbon solvent in the presence of a
   catalyst such as triethylaluminium and titanium
   tetrachloride (Ziegler-Natta catalyst) at a
   temperature of 333-343 K and under a pressure of 6-7
   atm.
 Properties:
1. low degree of branching(lack of branching is ensured
   by an appropriate choice of catalyst & reaction
   conditions).
2. stronger intermolecular forces and tensile strength,
3. Chemically inert.
 Uses:for manufacturing buckets, dustbins, bottles,
 water pipes etc.




 Environmental issue
  Although polyethylene can be recycled, most of the
 commercial polyethylene ends up in landfills, and in
 the oceans such as the Great Pacific Garbage Patch.
 Polyethylene is not considered biodegradable, except
 when it is exposed to UV from sunlight. Under UV
 lights tertiary carbon bonds in the chain structures
 are the centres of attack. The UV rays activate such
 bonds to form free radicals, which then react further
 with oxygen in the atmosphere, producing carbonyl
 groups in the main chain.
Polystyrene
Polystyrene is actually an aromatic polymer that
 is made from the monomer styrene. It is a long
 hydrocarbon chain that has a phenyl group
 attached to every carbon atom. Styrene is an
 aromatic monomer, commercially manufactured
 from petroleum. Polystyrene is a vinyl polymer,
 manufactured from the styrene monomer by free
 radical vinyl polymerization.
Properties
Polystyrene is generally flexible and can come in the
 form of moldable solids or viscous liquids.
The force of attraction in polystyrene is mainly due to
 short range van der Waals attractions between chains.
Uses
The outside housing of computer, housings of
 most kitchen appliances, model cars and
 airoplanes, toys, molded parts in car are all made
 of polystyrene.
It is also made in the form of foam that is used
 for packaging and insulating.
Polystyrene is generally flexible and can come in
 the form of moldable solids or viscous liquids.
Polyvinyl chloride of repeating vinyl
It is a vinyl polymer constructed
 groups (ethenyls) having one of their hydrogens
 replaced with a chloride group.




 Obtained by heating a water emulsion of vinyl
 chloride in presence of benzyl peroxide/ hydrogen
 peroxide in an autoclave under high pressure.
 Properties:
1. Colurless & odourless
2. Non-inflammable & chemically inert
3. Resistant to light,O2, inorganic acid & alkalis.
4.Greater stiffness & rigidity than polyethylene but
 brittle.
Uses: Third most widely produced plastic
 Unplasticized PVC: Highly rigid but brittle, for
   making sheets, tank lining, helmets ,mudguards etc.
 Plasticized PVC(by adding plasticizers e.g.
   phthalates): Making continuous sheets of varying
   thickness, hoses, pipes, construction, table covers,
   conveyor belts etc.
Polytetrafluoroethylene (TEFLON)
 • It is obtained by polymerization of water-
 emulsion of tetrafluoro ethylene, under pressure
 and in the presence of benzoyl peroxide as a
 catalyst.
Properties of high electronegative fluorine in
Due to presence
 structure of TEFLON, strong interchain forces are
 present which make it extremely tough.
High softening point (350°c).
It has high chemical resistance.
It has good mechanical and electrical
 properties(high-performance substitute for
 polyethylene)
Uses
 It is used in insulating motor, transformers.
 It is used in making wires.
 Non-stick cookware coatings are made
  from TEFLON for eg. In frying pan.
 Also used for making gaskets, tank linings, pipes and
  tubes for chemical industries.
 Used for making non lubricating bearings.
 one of the lowest coefficients of friction against any solid.
Poly(methyl methacrylate)
Is a transparent thermoplastic, often used as a light or
 shatter-resistant alternative to glass. Synthetic
 polymer of methyl methacrylate. Can be made by all
 types of moulding processes.
 Properties:
1. Strong & light weight
2. Good impact strength ,higher than both glass &
   polystyrene.
3. Transmits up to 92% of light & filters UV lights.
4.coefficient of thermal expansion is relatively high.
5. Its properties can be modified to suit requirements.
Uses: Making aquarium glasses; automobile
 headlights; spectator protection(e.g.- in ice hockey
 rinks); Aircraft windows; Helmet visors; making
 acrylic paints; bone cement, contact lenses etc.
AcrylonitrileButadieeneStyrene

•Monomers:-Acrylonitrile , Butadieene, Styrene
•Formula :-(C8H8·C4H6·C3H3N)n

•Production :-Copolymer made by polymerizing styrene and acrylonitrile in the
presence of polybutadiene. The proportions can vary from 15 to 35% acrylonitrile,
5 to 30% butadiene and 40 to 60% styrene.

•Properties :-The styrene gives the plastic a shiny, impervious surface. The
butadiene, a rubbery substance, provides resilience even at low
temperatures.Mechanical properties vary with temperature.

•Application :-
1.Used to make light, rigid, molded products such as piping .
2.Musical Instruments such as plastic clarinet.
3.Golf club heads :- Used due to its good shock absorbance
4.Used as a colorant in tattoo inks.
Bakelite, a phenol-formaldehyde polymer, was the first
completely synthetic plastic, first made by Leo Baekeland
in 1907. Baekeland and an assistant started their research
in 1904 looking for a synthetic substitute for shellac.
Bakelite was commercially introduced in 1909. Bakelite
was first used to make billiard balls, but, later, was used to
make molded insulation, valve parts, knobs, buttons, knife
handles, many types of molded plastic containers for
radios and electronic instruments, and more.
Phenolic reins set to rigid, hard, scratch resistant, infusible, water resistant, insoluble
solids, which are resistant to non-oxidizing acids, salts and many organic solvents,
but are attacked by alkalis, because of the presence of free hydroxyl group in their
structures, They posses excellent electrical insulating character.




Phenol - formaldehyde polymers are the oldest synthetic polymers. These are
obtained by the condensation reaction of phenol with formaldehyde in the
presence of either an acid or a base catalyst. The reaction starts with the initial
formation of o-and/or
p-hydroxymethylphenol derivatives, which further react with phenol to form
compounds having rings joined to each other through –CH2 groups. The initial
product could be a linear product – Novolac used in paints.
Novolac on heating with formaldehyde undergoes cross linking to form an infusible
solid mass called bakelite.
1.Plastic items like telephone parts,cabinets,heater handles.
2.Phonograph records
3.Electrical switches and berings used in propeller shafts in paper industry.
4.Soft bakelite used as binding glue for
   laminated,wooden plants and in varnishes
5.Sulphonated bakelite are used as ion exchange resins.
6.For impregating fabrics,wood and paper.




        valve parts, knobs, buttons,                  Phonograph records
Melamine resin or melamine formaldehyde  (also shortened to melamine) is a
hard, thermosetting plastic material made from melamine and
formaldehyde by polymerization at 80°C.



 Melamine formaldehyde resin gives water white products,have good tensile strength,
 good electrical insulation, good chemical resistance, great hardness and good
 abrasion resistance.
The resin is formed by condensation co-polymerisation of melamine and formaldehyde.
It is a quite hard polymer and is used widely for making plastic crockery
under the name Melamine. The articles made from melamine polymer do
not break even dropped from considerable height. They are also used as
laminates and for making decorative items. In paper industry to improve
wet strength of paper. In fabric treatment as finishing agent.
Polyurethanes are made from a dialcohol and diisocyanate monomers. The isocyanate
compounds contain the functional group (O=C=N-). A rearrangement reaction leads to
the formation of the urethane linkage. Technically polyurethane is not a condensation
polymer since no molecules are lost, but the functional group does rearrange.
 For example, Perlon-U (a crystalline polymer) is obtained by the reaction of 1,4-
butane diol with 1,6-hexane diisocynate
1.Polyurethanes are less stable than polyamides(nylons) at elevated temperature.
2.They are characterized by excellent resistance to abrasion and solvents.




 Polyuraethenes are used as coatings, films, foams,adhesives and elastomers.
 Resilient polyurethene fibres (spandex) are used for foundation garments and swim
 suits.They also find use as a leather substutute(corfoam). They are used to cast to
 produce gaskets, and seals.
Silicone polymers do not have carbon as part of the backbone structure. The although
silicon is in the same group as carbon in the periodic table, it has quite different
chemistry.
Many silanes are known which are analogous to the hydrocarbons with Si-Si bonds.
These compounds are not very stable and hence not very useful.
Silicones on the other hand have an alternating -Si-O- type structure. This basic
structural unit is found in many rocks and minerals in nature including common sand.
Various organic groups such as methyl or the benzene ring may be bonded to the
silicon as shown in the graphic on the bottom.
Silicones are water repellent, heat stable, and very resistant to chemical
attack. They find many uses in oils, greases, and rubberlike materials.
Silicone oils are very desirable since they do not decompose at high
temperature and do not become viscous. Other silicones are used in
hydraulic fluids, electrical insulators and moisture proofing agent in fabrics.
Silicones have a number of medical applications because they are chemically
inert. A good deal of controversy has involved the the use of silicone in
polyurethane bags as breast implants. Again they were used because they
were thought to be very inert and resistant to dissolving or other reactions.
Reports have cited increased cancer risk and severe immune responses from
possible leakage of the silicone from the implants.
EPOXY RESIN
THE ORIGIN OF EPOXY RESINS

The first commercial attempts to prepare resins from
epichlorohydrin were made in 1927 in the United States.
Credit for the first synthesis of bisphenol-A-based epoxy resins
is shared by Dr. Pierre Castan of Switzerland and Dr. S.O.
Greenlee of the United States in 1936. Dr. Castan's work was
licensed by Ciba, Ltd. of Switzerland, which went on to
become one of the three major epoxy resin producers
worldwide. Ciba's epoxy business was spun off and later sold
in the late 1990s and is now the advanced materials
business unit of Huntsman Corporation of the United States.
Dr. Greenlee's work was for the firm of Devoe-Reynolds of the
United States. Devoe-Reynolds, which was active in the early
days of the epoxy resin industry, was sold to Shell Chemical
(now Hexion, formerly Resolution Polymers and others).
A new method of synthesis of high molecular weight epoxy resins is
presented. All reactions were performed in a multi-mode microwave
reactor “Plazmatronika” (microwave frequency - 2,45GHz, maximum
of microwave power - 300W). Shortening of the reaction time for all
processes performed in the microwave reactor, in comparison to
conventional heating, was observed.

Synthesis of high molecular weight epoxy resins under
microwave irradiation
PROPERTIES
Epoxy is a copolymer; that is, it is formed from two different
chemicals. These are referred to as the "resin" and the "hardener".
The resin consists of monomers or short chain polymers with an
epoxide group at either end. Most common epoxy resins are
produced from a reaction between epichlorohydrin and bisphenol-A,
though the latter may be replaced by similar chemicals. The hardener
consists of polyamine monomers, for example Triethylenetetramine
(TETA). When these compounds are mixed together, the amine
groups react with the epoxide groups to form a covalent bond. Each
NH group can react with an epoxide group, so that the resulting
polymer is heavily crosslinked, and is thus rigid and strong.
The process of polymerization is called "curing", and can be controlled
through temperature and choice of resin and hardener compounds;
the process can take minutes to hours. Some formulations benefit
from heating during the cure period, whereas others simply require
time, and ambient temperatures.
APPLICATION
The applications for epoxy-based materials are extensive and include
coatings, adhesives and composite materials such as those using
carbon fiber and fiberglass reinforcements (although polyester, vinyl
ester, and other thermosetting resins are also used for glass-
reinforced plastic). The chemistry of epoxies and the range of
commercially available variations allows cure polymers to be
produced with a very broad range of properties. In general, epoxies
are known for their excellent adhesion, chemical and heat resistance,
good-to-excellent mechanical properties and very good electrical
insulating properties. Many properties of epoxies can be modified (for
example silver-filled epoxies with good electrical conductivity are
available, although epoxies are typically electrically insulating).
Variations offering high thermal insulation, or thermal conductivity
combined with high electrical resistance for electronics applications,
Wind Energy applications
 Epoxy resin is used in manufacturing the rotor blades of wind turbines. The resin is
 infused in the core materials (balsa wood, foam) and the reinforcing media (glass,
 fabric). The process is called VARTM, i.e. Vacuum Assisted Resin Transfer Moulding.
 Due to excellent properties and good finish, epoxy is the most favoured resin for
 composites.




erospace applications




ectrical systems and electronics
Paints and coatings

         Adhesives




dustrial tooling and composites




onsumer and marine applications
Nylon is used as general name for all synthetic fiber forming polyamides,
i.e., having a protein like structure. These are the condensation polymers of
diamines and dibasic acids A number is usually suffixed with the
Nylon which refers to the number of carbon atoms present in the diamine
and the dibasic acids respectively.



Nylon-6,6 is obtained by the polymerisation of adipic acid with hexamethylene
diamine.
It is produced by the self condensation of caprolactum.




                    Beckmann Rearrangement
1.They are translucent,whitish,horny,high melting polymers .
2.They posses high temperature stability and high abrasion resistance.
3.They are insoluble in common organic solvents(like methylated spirit,benzene
and Acetone), and soluble in phenol and formic acid.
4.Their mouldings and extrusions have good physical strengths(especially high
  impact strength) and self lubricating properties.




1.They are light, horny, and high melting.
2.They are insoluble in common solvents.
3.They have good strength.
4.They absorb little moisture ; and are thus ’drip-dry’ in nature.
5.They are very flexible and retain original shape after use.
6.They are resistant to abrasion.
7.On blending with wool, the strength and abrasion resistance of the latter increases.
1.Nylon-6,6 is primarily used for fibres, which find use in making socks, ladies hoses,
dresses, carpets,etc.
2.Nylon-6 is mainly used for moulding purposes for gears, bearings, electrical
mountings, etc. These bearings and gears work quietly without any lubrication.
3.They are also used for making filaments for ropes, bristles for tooth brushes and
films, tyre cords,etc.
POLYCARBONATE
   S
Repeating chemical structure
unit of
Polycarbonate made from
bisphenol A
Structure
Polycarbonates received their name because they are
polymers containing carbonate groups (-O-(C=O)-O-). Most
polycarbonates of commercial interest are derived from
rigid monomers. A balance of useful features including
temperature resistance, impact resistance and optical
properties position polycarbonates between commodity
plastics and engineering plastics
SYNTHESIS
•The main polycarbonate material is producted by the reaction of
bisphenol A and phosgene (COCl2). The first step involves treatment
of bisphenol A with sodium hydroxide, which deprotonates the
hydroxyl groups of the bisphenol A.

   (HOC6H4)2CMe2 + 2 NaOH → (NaOC6H4)2CMe2 + 2 H2O

•The diphenoxide ((NaOC6H4)2CMe2) reacts with phosgene to give a
chloroformate, which subsequently is attacked by another phenoxide.
The net reaction from the diphenoxide is:

 (NaOC6H4)2CMe2 + COCl2 → 1/n [OC(OC6H4)2CMe2]n + 2 NaCl

 In this way, approximately one billion kilograms of
polycarbonate is produced annually
Uses of polycarbonates
 1) Domestic wares
2) Electrical insulator in electronic industries
3)Other uses for polycarbonate
   include greenhouse enclosures, automobile
   headlights, outdoor fixtures, and medical
   industry applications, though the list is virtually
   endless.
Processing (or) moulding (or) compounding of plastics

Compounding or moulding is a process by which the polymer resins are
mixed with some additives like fillers, plasticizers, stabilizers etc to impart
some special properties to the moulded final product.

 Ingredients of a plastic

Additives       Examples                  Function/Importance
1. Resins       Thermoplastic and         Basic binding materials and holds the
                thermosetting resins      constituents together. Major part of
                                          the plastics. Thermosetting resins
                                          transferred in to crosslinked plastics
                                          during moulding in presence of a
                                          catalyst
2. Plasticizers Dioctylphthalate (DOP)    To improve the elasticity and to
                Adipate, Oleate,          reduce the brittleness of the plastics.
                Organic Phosphate         Also improves the flow of polymer
                                          during the process



 11/11/12                                                                           77
Additives          Examples                       Function/Importance

 3. Fillers (or)    Mica, quartz, Limestone,       Increases the tensile and compressive
 Extenders          Nylon                          strength of plastics. They reduce the
                                                   shrinkage during the process of setting

 4. Lubricants      Waxes, Oils, soaps             To make the moulding process smooth and
                                                   give the glossy finish to the final product

                                                   To increase the thermal stability of a
 5. Stabilizers     Stearates of Pb, Ba and Cd
                                                   polymer

 6. Pigments        TiO2, ZnO (white), chromium
                    oxide (green), carbon black,   To provide colours to the moilded articles
                    Read Lead

                    Phenyl, n-napthyal amine,      Protection against oxidation
 7. Anti-Oxidants
                    Diphenyl-p-
                    phenylenedimaine

 8. Catalyst        H2O2 and Benzoyl peroxide      Added only in the case of thermosetting
                                                   resins to increase the rate of polymerisation




11/11/12                                                                                         78
Different types of Moulding technique


The moulding is different for various polymer depends on their thermal
behaviour and nature of the resins.

 1. Compression moulding                       Used for moulding the
 2. Transfer moulding                          thermosetting polymers


 3. Injection moulding                         Used for moulding      the
                                               thermo polymers
 4. Extension moulding and


                                               Used for moulding the
 5. Blow moulding
                                               bottle type articles which
                                               has narrow neck




 11/11/12                                                                   79
Pressure   •   The process of molding a material in a confined
Pressure = 70 kg/cm      2
                                               shape by applying pressure and usually heat.
                                           •   Almost exclusively for thermoset materials
                                           •   Used to produce mainly electrical products

                                                   Top moulding part of the die
                                                   (plunger)
                                                             •A force of 2900psi is usually
                                                             required for moldings up to 1inch
                                                             (25 mm) thick.
                                               Guide pins •An added 725psi should be
                                                             provided for each 1inch (25 mm)
                                                             increase.


                                                          Molten polymer with ingredients
                                                          in the cavity at 200oC

                                                Bottom moulding part of the die with cavity
                                                (the shape of the cavity decides the shape
                                                of the final product)

               Extraction pin
                                                           Pressed plastic
                                                           material
    11/11/12                                                                                80
This is exclusively used for thermosetting plastics. The resin ingredients mixture is preheated in a
preheating chamber. When the moulding mixture becomes plastic then it is forced through a orifice into
the hot mould by using the plunger. After setting time it is taken out. Complicated shapes can be made.

                                                                                 Heaters

                                                                                Plunger (top molding
                                                                                part)


                                                                              Charger (plastic ingredients)


                                                                                Sprue

                                                                               Molding Cavity

                                                                              Bottom molding part
                                       Ejector pin


A process of forming articles by fusing a plastic material in a
chamber then forcing the whole mass into a hot mold to
solidify.
Used to make products such as electrical wall receptacles and
circuit breakers                                                                              Molded
                                                                                              plastic

    11/11/12                                                                                         81
Clamping   Molding part             Injection part




       *
                          Cavity
                                                    Hopper      Hydraulic
                                                                screw
                                         Barrel                 drive




                                     Heater bands




11/11/12                                                               82
Pressing of molten polymer using die and plunger in Injection Molding




                                                                        The feeding or injection of
                                                                        hot plastic



                                                                                        This method is generally used for
                                                                                        thermoplastics.

                                                                                Die     The moulding composition is heated in
                                                                                        a suitable chamber connected by a
                                                                                        duct leading to the mould.
                                                                                        The hot softened plastic is then forced
                                                                                        under high pressure into the relatively
                                 The cavity in which the molten
                                                                                        cool mould cavity where it is set by
                                 plastic will be fed and pressed
     Plunger                                                                            cooling and the moulded object is then
                                                                                        ejected.
                                                                                        The temperature range used is 90 to
                                                                                        260oC.




*11/11/12 http://www.idsa-mp.org/proc/plastic/injection/injection_process.htm
  Source:                                                                                                                83
It is a process in which the molten plastic material is forced through a die
  which produces a continuous extrudate (product) in the form of final product.
  This process is used mainly for the production of films tubes, rods, hoses.
  It also used for the coating cables with PVC and other plastics.


                       Raw materials
                                          Molten
                                          polymer       Die




                                                                              Extruded pipe




           Screw                       Heater
           conveyer                                           Cooling of
                                                              final product


11/11/12                                                                                84
Unit iii polymers

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Unit iii polymers

  • 1. Polymer an Insight in to the learning topics Classification of polymers: Thermoplastics- PE, PS, PVC, PTFE, ABS, PMMA, Synthetic Rubber Thermosetting plastics - properties and industrial applications of Bakelite, Melamine Resin, Epoxy Resin, Polyurethane (PU), Polyamide (nylon Series), Polyester (PET), PC, Silicon Polymer Moulding of plastics into articles: Compression, injection, transfer and extrusion methods. methods Conducting polymers: Properties and applications Biodegradable polymers Properties and applications 11/11/12 1
  • 2.  A word polymer is a combination of two Greek words, “Poly” means “many” and “Meros” meaning “parts or units”.  A polymer is a large molecule of which is formed by repeated linking of the small molecules called “monomers”. n(CH2-CH2) (-CH2-CH2-)n ethylene polyethylene
  • 3. The number of repeating units in the chains of which a polymer is made up is called degree of a polymerization (n). Polymers with high degree of polymerization are called the “High Polymer”, and those with low degree of polymerization are called “Oligopolymers”. High polymers have very high molecular mass (10000 to 1000000 u) and are called macromolecules.
  • 4. Degree of Polymerization (P) = M/m; Where, M= Mass of Polymer; m = mass of monomeric unit Polymerisation 3 CH2 CH2 CH2 CH2 3 Ethylene polyethylene Degree of polymerisation (P) = 3 Mass of this polymer M = (28 x 3) = 84Da 11/11/12 4
  • 5. A macromolecule may consist of monomer of identical or different chemical structure and accordingly they are called Homopolymers or copolymers (or Heteropolymers). A A A A … Homopolymers A A B A … Copolymers
  • 6. Tacticity- Plane representation of polypropylene polymer 1. Isotactic polymers H H H H H CH2 C CH2 C CH2 C CH2 C CH2 C Functional groups on the CH3 CH3 CH3 CH3 CH3 same side of the main carbon skeleton 2. Syndiotactic polymers H CH3 H CH3 H Functional groups arranged CH2 C CH2 C CH2 C CH2 C CH2 C in the alternate fashion of the main carbon skeleton CH3 H CH3 H CH3 3.Atactic polymers H CH3 CH3 H H Functional groups arranged CH2 C CH2 C CH2 C CH2 C CH2 C in a random manner around the main carbon skeleton CH3 H H CH3 CH3 11/11/12 6
  • 7. Polymers can be linear, branched or cross-linked. The monomer may be arranged in the chain at random or regularly. (LINEAR POLYMER) A A A A … … B B B A A A A A A A A A A A A A A (BRANCHED POLYMER)
  • 8. A A A A A A A A A A A A A A A A A A A A (CROSS-LINKED POLYMER)
  • 9. Functionality The number of reactive sites present in a monomer is called functionality 1. O Linear chain polymer is formed if the functionality of the HO C CH2 NH2 monomer is only two (Bifunctional) 2. Ex. Glycine O O HO C CH2 NH2 OH CH2 CH C OH NH2 Ex. Serine O OH CH2 CH C OH Cross linked chain polymer is formed if the functionality of the NH2 monomer is more than two (multifunctional) 11/11/12 Glycine 9
  • 10. Classification of Polymers Classification based on Source 1. Natural polymers E.g., Proteins, Cellulose, Starch, Rubber 2. Semi-synthetic polymers E.g., Cellulose derivatives - Cellulose acetate (Rayon) 3. Synthetic polymers E.g., Buna-S, Buna-R, Nylon, Polythene, Polyester.
  • 11. Classification based on Structure 1. Linear polymers consist of long and straight chains. E.g., Polyvinyl chloride 2. Branched chain polymers contain linear chains having some branches, e.g., low density polymer. 3. Cross-linked or Network polymers formed from bi-functional and tri-functional monomers and contain strong covalent bonds e.g. bakelite, melamine,
  • 12. Classification based on Molecular Forces 1. Elastomers eg. Buna-S, Buna-N, neoprene 2. Fibers eg. Polyesters, Polyamides. 3. Thermoplastic polymers eg. Polythene, Polystyrene, PVC. 4. Thermosetting polymers eg. Bakelite, urea-formaldelyde resins Order of strength :- Thermosetting > Fibres > Thermoplastics > Elastomers
  • 13. Classification based on mode of Polymerization 1. Addition polymers formed by the repeated addition of monomer molecules possessing double or triple bonds n(CH2=CH2) -(CH2 -CH2 )- Ethylene polyethylene 2. Condensation polymers formed by repeated condensation reaction between two different bi-functional or tri-functional monomeric units. eg. terylene (dacron), nylon 6, 6, nylon 6. n(H2N(CH2)6 NH2) + n(HOOC(CH2)4COOH) [-NH(CH2)6NHCO(CH2)4CO-]n + nH2O (Nylon 6:6)
  • 14. Polymerization is of two types;  Addition or chain polymerization  Condensation polymer
  • 15. 1. Free radical mechanism:- Alkenes or dienes and their derivatives are polymerized in the presence of a free radical generating initiator (catalyst) like benzoyl peroxide, acetyl peroxide, t-bu peroxide, etc. This process involves in 3 steps – a) Chain initiation step - addition of phenyl free radical formed by the peroxide to the ethene double bond ,thereby forming a larger radical. b) Chain propagation step - repetition of this sequence with new and bigger radicals. c) Chain terminating step - the product radical thus formed reacts with another radical to form the polymerized product. Some of polymers formed by this process are- Polytetrafluroethene (Teflon), Polyacrylonitrile, Polyethylene, etc.
  • 16.  In addition polymers , the polymer is formed from the monomer, without the loss of any material, and the product is the exact multiple of the original monomeric molecule. CH2=CH2 -CH2-CH2- POLYMERIZATION (-CH2-CH2-)n Ethylene monomer Molecular Rearrangement Polyethylene
  • 17. Addition polymerization proceeds by the initial formation of some reactive species such as free radicals or ions and by the addition of the reactive species to the other molecule, with the regeneration of the reactive feature.
  • 18. Chain polymerization occur in three steps:- •Chain initiation step •Chain propagation step •Chain termination step
  • 19. In chain initiation step, a free radical is first generated as a result of physical or chemical effect, which is responsible for the further continuation of the chain polymerization
  • 20. The primary free radical react with the double bond of an unexcited monomer molecule and adds to it forming a new radical capable of further interaction with the initial monomers.
  • 21. The most common termination processes are Radical Combination and Disproportionate. These reactions are illustrated by the following equations.
  • 22. In condensation polymerization, the chain growth is accompanied by the elimination of small molecules. The molecules are in the form of the water molecule H2O ; methanol molecule CH3OH ,etc.
  • 23. Step Growth polymerization:- It involves a repetitive condensation reaction between two bi-functional monomers. Eg. Formation of Nylon 6,6 nHOOC(CH2)4COOH + nH2N(CH2)6 NH2 553K High pressure [-N-(CH2) 6-N-C(CH2)4-C-]n H O O Nylon6,6
  • 24. Copolymerisation:- is a polymerization reaction in which a mixture of more than one monomeric species is allowed to polymerize and form a copolymer. For example, a mixture of 1, 3 – butadiene and styrene can form a copolymer.
  • 25. Examples of Daily Use Polymers
  • 26. Plastics  Plastics are high molecular weight organic materials which can be moulded into any desired shape by the application of heat and pressure in the presence of catalyst. Constituents of plastics: 1. Resins 2. Plasticizers 3. Fillers or Extenders 4. Lubricants 5. Stabilizers 6. Pigments 7. Anti-oxidants 8. Catalysts or Accelerators
  • 27. Resins: They are basic binding materials and hold the constituents together. They are generally linear polymers with low molecular weight to enhance fusibility and mouldability. It is then converted into crosslinked form during moulding in the presence of a catalyst. E.g. Thermoplastic resins and thermosetting resins. Plasticizers: They improve flow for processing by reducing the intermolecular force of attraction E.g. Dioctylphthalate, oleate and organic phosphates Fillers: They increase the tensile and compressive strength of plastics. They also reduce the shrinkage during setting of the plastics. E.g. Mica, quartz, limestone, acrylics
  • 28. Lubricants:  They makes the moulding process easier and also provide glossy finish to the final product.  E.g. Waxes, oils and soaps Stabilizers:  They increase the thermal stability during processing.  E.g. Stearates of lead, barium and cadmium. Pigments:  They provide colours to the plastics  TiO2, ZnO – White; Cr2O3 – Green, Carbon black – black, Red lead - Red  Anti-oxidants: They protect against oxidative degradation  E.g. Phenyl p-napthyl amine, diphenyl p-phenylene diamine Catalysts:  They are added to accelerate the polymerization of fusible resin into cross-linked infusible form especially for thermosetting plastics.  E.g. H2O2, benzoyl peroxide
  • 29.
  • 30. Definition These are linear or slightly branched long chain polymers, which can be softened on heating & reversibly hardened on cooling repeatedly. Their hardness is a temporary property & varies with temperature. It can be reprocessed, so sometimes also referred as green plastics.
  • 31. Structure  Thermoplastics possess weak intermolecular forces(e.g. Van der Waal) & don’t have crosslinks.
  • 32. Examples  Cellulose derivatives - 1) Cellulose acetate - Cellulose nitrate  Polyethenic/vinyl resins - 2) Polyethylene - 3) Polypropylene - 4) Polyvinyl acetate - 5) Polyvinyl chloride - 6) Polystyrene - 7) Teflon - 8) Acrylic - 9) Polysulfone - 10) Polyester
  • 33. Polyethylene(PE)/Polythene  There are mainly two types of polythene:  Low density polythene(density range of 0.910–0.940 g/cm3):It is obtained by the polymerisation of ethene under high pressure of 1000-2000 atm at a temperature of 350-570 K in the presence of traces of oxygen or a peroxide initiator.  It is created by free radical polymerization.
  • 34.  Properties: 1. High degree of short and long chain branching. 2. intermolecular forces is less. 3. Tough but highly flexible & ductile. 4.Chemically inert.  Uses: Insulation of electricity carrying wires and manufacture of squeeze bottles, toys and flexible pipes.
  • 35.  High density polythene(density >= 0.941 g/cm3): formed when addition polymerisation of ethene takes place in a hydrocarbon solvent in the presence of a catalyst such as triethylaluminium and titanium tetrachloride (Ziegler-Natta catalyst) at a temperature of 333-343 K and under a pressure of 6-7 atm.  Properties: 1. low degree of branching(lack of branching is ensured by an appropriate choice of catalyst & reaction conditions). 2. stronger intermolecular forces and tensile strength, 3. Chemically inert.
  • 36.  Uses:for manufacturing buckets, dustbins, bottles, water pipes etc.  Environmental issue Although polyethylene can be recycled, most of the commercial polyethylene ends up in landfills, and in the oceans such as the Great Pacific Garbage Patch. Polyethylene is not considered biodegradable, except when it is exposed to UV from sunlight. Under UV lights tertiary carbon bonds in the chain structures are the centres of attack. The UV rays activate such bonds to form free radicals, which then react further with oxygen in the atmosphere, producing carbonyl groups in the main chain.
  • 37. Polystyrene Polystyrene is actually an aromatic polymer that is made from the monomer styrene. It is a long hydrocarbon chain that has a phenyl group attached to every carbon atom. Styrene is an aromatic monomer, commercially manufactured from petroleum. Polystyrene is a vinyl polymer, manufactured from the styrene monomer by free radical vinyl polymerization.
  • 38. Properties Polystyrene is generally flexible and can come in the form of moldable solids or viscous liquids. The force of attraction in polystyrene is mainly due to short range van der Waals attractions between chains.
  • 39. Uses The outside housing of computer, housings of most kitchen appliances, model cars and airoplanes, toys, molded parts in car are all made of polystyrene. It is also made in the form of foam that is used for packaging and insulating. Polystyrene is generally flexible and can come in the form of moldable solids or viscous liquids.
  • 40. Polyvinyl chloride of repeating vinyl It is a vinyl polymer constructed groups (ethenyls) having one of their hydrogens replaced with a chloride group.  Obtained by heating a water emulsion of vinyl chloride in presence of benzyl peroxide/ hydrogen peroxide in an autoclave under high pressure.
  • 41.  Properties: 1. Colurless & odourless 2. Non-inflammable & chemically inert 3. Resistant to light,O2, inorganic acid & alkalis. 4.Greater stiffness & rigidity than polyethylene but brittle.
  • 42. Uses: Third most widely produced plastic  Unplasticized PVC: Highly rigid but brittle, for making sheets, tank lining, helmets ,mudguards etc.  Plasticized PVC(by adding plasticizers e.g. phthalates): Making continuous sheets of varying thickness, hoses, pipes, construction, table covers, conveyor belts etc.
  • 43. Polytetrafluoroethylene (TEFLON) • It is obtained by polymerization of water- emulsion of tetrafluoro ethylene, under pressure and in the presence of benzoyl peroxide as a catalyst.
  • 44. Properties of high electronegative fluorine in Due to presence structure of TEFLON, strong interchain forces are present which make it extremely tough. High softening point (350°c). It has high chemical resistance. It has good mechanical and electrical properties(high-performance substitute for polyethylene)
  • 45. Uses  It is used in insulating motor, transformers.  It is used in making wires.  Non-stick cookware coatings are made from TEFLON for eg. In frying pan.  Also used for making gaskets, tank linings, pipes and tubes for chemical industries.  Used for making non lubricating bearings.  one of the lowest coefficients of friction against any solid.
  • 46. Poly(methyl methacrylate) Is a transparent thermoplastic, often used as a light or shatter-resistant alternative to glass. Synthetic polymer of methyl methacrylate. Can be made by all types of moulding processes.
  • 47.  Properties: 1. Strong & light weight 2. Good impact strength ,higher than both glass & polystyrene. 3. Transmits up to 92% of light & filters UV lights. 4.coefficient of thermal expansion is relatively high. 5. Its properties can be modified to suit requirements.
  • 48. Uses: Making aquarium glasses; automobile headlights; spectator protection(e.g.- in ice hockey rinks); Aircraft windows; Helmet visors; making acrylic paints; bone cement, contact lenses etc.
  • 49. AcrylonitrileButadieeneStyrene •Monomers:-Acrylonitrile , Butadieene, Styrene •Formula :-(C8H8·C4H6·C3H3N)n •Production :-Copolymer made by polymerizing styrene and acrylonitrile in the presence of polybutadiene. The proportions can vary from 15 to 35% acrylonitrile, 5 to 30% butadiene and 40 to 60% styrene. •Properties :-The styrene gives the plastic a shiny, impervious surface. The butadiene, a rubbery substance, provides resilience even at low temperatures.Mechanical properties vary with temperature. •Application :- 1.Used to make light, rigid, molded products such as piping . 2.Musical Instruments such as plastic clarinet. 3.Golf club heads :- Used due to its good shock absorbance 4.Used as a colorant in tattoo inks.
  • 50.
  • 51. Bakelite, a phenol-formaldehyde polymer, was the first completely synthetic plastic, first made by Leo Baekeland in 1907. Baekeland and an assistant started their research in 1904 looking for a synthetic substitute for shellac. Bakelite was commercially introduced in 1909. Bakelite was first used to make billiard balls, but, later, was used to make molded insulation, valve parts, knobs, buttons, knife handles, many types of molded plastic containers for radios and electronic instruments, and more.
  • 52. Phenolic reins set to rigid, hard, scratch resistant, infusible, water resistant, insoluble solids, which are resistant to non-oxidizing acids, salts and many organic solvents, but are attacked by alkalis, because of the presence of free hydroxyl group in their structures, They posses excellent electrical insulating character. Phenol - formaldehyde polymers are the oldest synthetic polymers. These are obtained by the condensation reaction of phenol with formaldehyde in the presence of either an acid or a base catalyst. The reaction starts with the initial formation of o-and/or p-hydroxymethylphenol derivatives, which further react with phenol to form compounds having rings joined to each other through –CH2 groups. The initial product could be a linear product – Novolac used in paints.
  • 53. Novolac on heating with formaldehyde undergoes cross linking to form an infusible solid mass called bakelite.
  • 54. 1.Plastic items like telephone parts,cabinets,heater handles. 2.Phonograph records 3.Electrical switches and berings used in propeller shafts in paper industry. 4.Soft bakelite used as binding glue for laminated,wooden plants and in varnishes 5.Sulphonated bakelite are used as ion exchange resins. 6.For impregating fabrics,wood and paper. valve parts, knobs, buttons, Phonograph records
  • 55. Melamine resin or melamine formaldehyde  (also shortened to melamine) is a hard, thermosetting plastic material made from melamine and formaldehyde by polymerization at 80°C. Melamine formaldehyde resin gives water white products,have good tensile strength, good electrical insulation, good chemical resistance, great hardness and good abrasion resistance.
  • 56. The resin is formed by condensation co-polymerisation of melamine and formaldehyde.
  • 57. It is a quite hard polymer and is used widely for making plastic crockery under the name Melamine. The articles made from melamine polymer do not break even dropped from considerable height. They are also used as laminates and for making decorative items. In paper industry to improve wet strength of paper. In fabric treatment as finishing agent.
  • 58. Polyurethanes are made from a dialcohol and diisocyanate monomers. The isocyanate compounds contain the functional group (O=C=N-). A rearrangement reaction leads to the formation of the urethane linkage. Technically polyurethane is not a condensation polymer since no molecules are lost, but the functional group does rearrange. For example, Perlon-U (a crystalline polymer) is obtained by the reaction of 1,4- butane diol with 1,6-hexane diisocynate
  • 59. 1.Polyurethanes are less stable than polyamides(nylons) at elevated temperature. 2.They are characterized by excellent resistance to abrasion and solvents. Polyuraethenes are used as coatings, films, foams,adhesives and elastomers. Resilient polyurethene fibres (spandex) are used for foundation garments and swim suits.They also find use as a leather substutute(corfoam). They are used to cast to produce gaskets, and seals.
  • 60. Silicone polymers do not have carbon as part of the backbone structure. The although silicon is in the same group as carbon in the periodic table, it has quite different chemistry. Many silanes are known which are analogous to the hydrocarbons with Si-Si bonds. These compounds are not very stable and hence not very useful. Silicones on the other hand have an alternating -Si-O- type structure. This basic structural unit is found in many rocks and minerals in nature including common sand. Various organic groups such as methyl or the benzene ring may be bonded to the silicon as shown in the graphic on the bottom.
  • 61. Silicones are water repellent, heat stable, and very resistant to chemical attack. They find many uses in oils, greases, and rubberlike materials. Silicone oils are very desirable since they do not decompose at high temperature and do not become viscous. Other silicones are used in hydraulic fluids, electrical insulators and moisture proofing agent in fabrics. Silicones have a number of medical applications because they are chemically inert. A good deal of controversy has involved the the use of silicone in polyurethane bags as breast implants. Again they were used because they were thought to be very inert and resistant to dissolving or other reactions. Reports have cited increased cancer risk and severe immune responses from possible leakage of the silicone from the implants.
  • 63. THE ORIGIN OF EPOXY RESINS The first commercial attempts to prepare resins from epichlorohydrin were made in 1927 in the United States. Credit for the first synthesis of bisphenol-A-based epoxy resins is shared by Dr. Pierre Castan of Switzerland and Dr. S.O. Greenlee of the United States in 1936. Dr. Castan's work was licensed by Ciba, Ltd. of Switzerland, which went on to become one of the three major epoxy resin producers worldwide. Ciba's epoxy business was spun off and later sold in the late 1990s and is now the advanced materials business unit of Huntsman Corporation of the United States. Dr. Greenlee's work was for the firm of Devoe-Reynolds of the United States. Devoe-Reynolds, which was active in the early days of the epoxy resin industry, was sold to Shell Chemical (now Hexion, formerly Resolution Polymers and others).
  • 64. A new method of synthesis of high molecular weight epoxy resins is presented. All reactions were performed in a multi-mode microwave reactor “Plazmatronika” (microwave frequency - 2,45GHz, maximum of microwave power - 300W). Shortening of the reaction time for all processes performed in the microwave reactor, in comparison to conventional heating, was observed. Synthesis of high molecular weight epoxy resins under microwave irradiation
  • 65. PROPERTIES Epoxy is a copolymer; that is, it is formed from two different chemicals. These are referred to as the "resin" and the "hardener". The resin consists of monomers or short chain polymers with an epoxide group at either end. Most common epoxy resins are produced from a reaction between epichlorohydrin and bisphenol-A, though the latter may be replaced by similar chemicals. The hardener consists of polyamine monomers, for example Triethylenetetramine (TETA). When these compounds are mixed together, the amine groups react with the epoxide groups to form a covalent bond. Each NH group can react with an epoxide group, so that the resulting polymer is heavily crosslinked, and is thus rigid and strong. The process of polymerization is called "curing", and can be controlled through temperature and choice of resin and hardener compounds; the process can take minutes to hours. Some formulations benefit from heating during the cure period, whereas others simply require time, and ambient temperatures.
  • 66. APPLICATION The applications for epoxy-based materials are extensive and include coatings, adhesives and composite materials such as those using carbon fiber and fiberglass reinforcements (although polyester, vinyl ester, and other thermosetting resins are also used for glass- reinforced plastic). The chemistry of epoxies and the range of commercially available variations allows cure polymers to be produced with a very broad range of properties. In general, epoxies are known for their excellent adhesion, chemical and heat resistance, good-to-excellent mechanical properties and very good electrical insulating properties. Many properties of epoxies can be modified (for example silver-filled epoxies with good electrical conductivity are available, although epoxies are typically electrically insulating). Variations offering high thermal insulation, or thermal conductivity combined with high electrical resistance for electronics applications,
  • 67. Wind Energy applications Epoxy resin is used in manufacturing the rotor blades of wind turbines. The resin is infused in the core materials (balsa wood, foam) and the reinforcing media (glass, fabric). The process is called VARTM, i.e. Vacuum Assisted Resin Transfer Moulding. Due to excellent properties and good finish, epoxy is the most favoured resin for composites. erospace applications ectrical systems and electronics
  • 68. Paints and coatings Adhesives dustrial tooling and composites onsumer and marine applications
  • 69. Nylon is used as general name for all synthetic fiber forming polyamides, i.e., having a protein like structure. These are the condensation polymers of diamines and dibasic acids A number is usually suffixed with the Nylon which refers to the number of carbon atoms present in the diamine and the dibasic acids respectively. Nylon-6,6 is obtained by the polymerisation of adipic acid with hexamethylene diamine.
  • 70. It is produced by the self condensation of caprolactum. Beckmann Rearrangement
  • 71. 1.They are translucent,whitish,horny,high melting polymers . 2.They posses high temperature stability and high abrasion resistance. 3.They are insoluble in common organic solvents(like methylated spirit,benzene and Acetone), and soluble in phenol and formic acid. 4.Their mouldings and extrusions have good physical strengths(especially high impact strength) and self lubricating properties. 1.They are light, horny, and high melting. 2.They are insoluble in common solvents. 3.They have good strength. 4.They absorb little moisture ; and are thus ’drip-dry’ in nature. 5.They are very flexible and retain original shape after use. 6.They are resistant to abrasion. 7.On blending with wool, the strength and abrasion resistance of the latter increases.
  • 72. 1.Nylon-6,6 is primarily used for fibres, which find use in making socks, ladies hoses, dresses, carpets,etc. 2.Nylon-6 is mainly used for moulding purposes for gears, bearings, electrical mountings, etc. These bearings and gears work quietly without any lubrication. 3.They are also used for making filaments for ropes, bristles for tooth brushes and films, tyre cords,etc.
  • 73. POLYCARBONATE S Repeating chemical structure unit of Polycarbonate made from bisphenol A
  • 74. Structure Polycarbonates received their name because they are polymers containing carbonate groups (-O-(C=O)-O-). Most polycarbonates of commercial interest are derived from rigid monomers. A balance of useful features including temperature resistance, impact resistance and optical properties position polycarbonates between commodity plastics and engineering plastics
  • 75. SYNTHESIS •The main polycarbonate material is producted by the reaction of bisphenol A and phosgene (COCl2). The first step involves treatment of bisphenol A with sodium hydroxide, which deprotonates the hydroxyl groups of the bisphenol A. (HOC6H4)2CMe2 + 2 NaOH → (NaOC6H4)2CMe2 + 2 H2O •The diphenoxide ((NaOC6H4)2CMe2) reacts with phosgene to give a chloroformate, which subsequently is attacked by another phenoxide. The net reaction from the diphenoxide is: (NaOC6H4)2CMe2 + COCl2 → 1/n [OC(OC6H4)2CMe2]n + 2 NaCl  In this way, approximately one billion kilograms of polycarbonate is produced annually
  • 76. Uses of polycarbonates 1) Domestic wares 2) Electrical insulator in electronic industries 3)Other uses for polycarbonate include greenhouse enclosures, automobile headlights, outdoor fixtures, and medical industry applications, though the list is virtually endless.
  • 77. Processing (or) moulding (or) compounding of plastics Compounding or moulding is a process by which the polymer resins are mixed with some additives like fillers, plasticizers, stabilizers etc to impart some special properties to the moulded final product. Ingredients of a plastic Additives Examples Function/Importance 1. Resins Thermoplastic and Basic binding materials and holds the thermosetting resins constituents together. Major part of the plastics. Thermosetting resins transferred in to crosslinked plastics during moulding in presence of a catalyst 2. Plasticizers Dioctylphthalate (DOP) To improve the elasticity and to Adipate, Oleate, reduce the brittleness of the plastics. Organic Phosphate Also improves the flow of polymer during the process 11/11/12 77
  • 78. Additives Examples Function/Importance 3. Fillers (or) Mica, quartz, Limestone, Increases the tensile and compressive Extenders Nylon strength of plastics. They reduce the shrinkage during the process of setting 4. Lubricants Waxes, Oils, soaps To make the moulding process smooth and give the glossy finish to the final product To increase the thermal stability of a 5. Stabilizers Stearates of Pb, Ba and Cd polymer 6. Pigments TiO2, ZnO (white), chromium oxide (green), carbon black, To provide colours to the moilded articles Read Lead Phenyl, n-napthyal amine, Protection against oxidation 7. Anti-Oxidants Diphenyl-p- phenylenedimaine 8. Catalyst H2O2 and Benzoyl peroxide Added only in the case of thermosetting resins to increase the rate of polymerisation 11/11/12 78
  • 79. Different types of Moulding technique The moulding is different for various polymer depends on their thermal behaviour and nature of the resins. 1. Compression moulding Used for moulding the 2. Transfer moulding thermosetting polymers 3. Injection moulding Used for moulding the thermo polymers 4. Extension moulding and Used for moulding the 5. Blow moulding bottle type articles which has narrow neck 11/11/12 79
  • 80. Pressure • The process of molding a material in a confined Pressure = 70 kg/cm 2 shape by applying pressure and usually heat. • Almost exclusively for thermoset materials • Used to produce mainly electrical products Top moulding part of the die (plunger) •A force of 2900psi is usually required for moldings up to 1inch (25 mm) thick. Guide pins •An added 725psi should be provided for each 1inch (25 mm) increase. Molten polymer with ingredients in the cavity at 200oC Bottom moulding part of the die with cavity (the shape of the cavity decides the shape of the final product) Extraction pin Pressed plastic material 11/11/12 80
  • 81. This is exclusively used for thermosetting plastics. The resin ingredients mixture is preheated in a preheating chamber. When the moulding mixture becomes plastic then it is forced through a orifice into the hot mould by using the plunger. After setting time it is taken out. Complicated shapes can be made. Heaters Plunger (top molding part) Charger (plastic ingredients) Sprue Molding Cavity Bottom molding part Ejector pin A process of forming articles by fusing a plastic material in a chamber then forcing the whole mass into a hot mold to solidify. Used to make products such as electrical wall receptacles and circuit breakers Molded plastic 11/11/12 81
  • 82. Clamping Molding part Injection part * Cavity Hopper Hydraulic screw Barrel drive Heater bands 11/11/12 82
  • 83. Pressing of molten polymer using die and plunger in Injection Molding The feeding or injection of hot plastic This method is generally used for thermoplastics. Die The moulding composition is heated in a suitable chamber connected by a duct leading to the mould. The hot softened plastic is then forced under high pressure into the relatively The cavity in which the molten cool mould cavity where it is set by plastic will be fed and pressed Plunger cooling and the moulded object is then ejected. The temperature range used is 90 to 260oC. *11/11/12 http://www.idsa-mp.org/proc/plastic/injection/injection_process.htm Source: 83
  • 84. It is a process in which the molten plastic material is forced through a die which produces a continuous extrudate (product) in the form of final product. This process is used mainly for the production of films tubes, rods, hoses. It also used for the coating cables with PVC and other plastics. Raw materials Molten polymer Die Extruded pipe Screw Heater conveyer Cooling of final product 11/11/12 84