Synthetic of Polymer Products

SYNTHESIS
Stages in polymer production:
1) Polymerisation  synthesize macromolecules from small
ones
2) additive materials  modifie & enhance the properties
3) finishing pieces fashione & shape product

• POLYMERISATION
 monomers are linked together to generate long chains
composed of repeat units
 raw material: derived from coal, natural gas, petroleum
 2 classifications according reaction mechanism: addition &
condensation polymer
 1) Addition polymerization
• Chain reaction polymerization through free radical polymerisation
• unsaturated carbon (organic) molecules react to form a long chain
polymer molecule
• Free radical/ unpaired electron highly reactive, tend to rip electron
from other
• Free radical are created by the division of initiator into two fragment
• Stability of free radical varies depending on the properties of
molecule
• monomer units are attached one by one to an active site to form a
linear macromolecules -Result in exact multiple of original
monomer
• synthesis of polyethylene, polypropylene, PVC
• 3 stages: initiation, propagation & termination  affect MW
• Stages are controlled to ensure degree of polymerization of product
i) Initiation
• Begins when an initiator decomposes into free radical in the
present of monomer.
• The instability of C-C double bond in monomer makes them
susceptible to reaction with the unpaired electron in the radical
• active centre(location of unpaired electron) is formed by reaction
between an initiator (catalyst) species & monomer unit

R•  active initiator; •  unpaired electron

* In free radical polymerisation  the radical attacks one monomer,
and the electron migrates to another part. This newly radical
attack another monomer & the process repeat.
ii) Propagation
• linear growth of polymer chain by sequential addition of monomer
unit to the active growing chain molecule

• 1000 repeat units in 10-2 -10-3 s

• In theory, the propagation continue until the supply of monomers
exhausted
• However, most often the growth of the chain is stopped by the
termination reaction
iii) Termination
• 2 ways:
a) combination
 active end of free electron from 2 growing propagation chain may
link together form 1 molecule

b) disproportionation
free radical strips a hydrogen atom from an active chain
A C-C double bond takes the place of the missing hydrogen
 2) Condensation polimerization
• Stepwise intermolecular chemical reaction that may involve more
than 1 monomer species
• bifunctional monomers react to form a long chain polymer molecule
• By product: small MW (water) that is eliminated (condensed)
• t condensation > t addition polymerisation
• Polysaccharides, protein, thermosetting polyester & phenol-
formaldehyde, nylons, polycarbonates
• intermolecular reaction occurs everytime a repeat unit is formed
Polyesters
• Polyesters form when the -OH
functional group of one
monomer reacts with the -
COOH functional group of
another monomer.
• An ester link (-COO-) is formed
between monomers during the
reaction.
• H2O is eliminated in the
reaction.
• General reaction between a
dicarboxylic acid and a diol:
 POLYMER ADDITIVES
Additives  substances introduce to enhance/modify
properties, thus more serviceable: plasticizers,
stabilizers, colorants, flame retardants, fillers

FILLERS
# to improve tensile & compressive strength, abrasive
resistance, toughness, dimensional, thermal stability etc
# inexpensive materials that replace some vol of more
expensive polymer  reduce cost
# wood flour (sawdust), silica flour, sand, glass, clay etc
PLASTISIZER
- Improve flexibility, toughness; reduce hardness & stiffness
- Plasticizers are usually selected to be nonvolatile materials and
have good compatibility with the desired polymer.
- Small plasticizer molecules occupy positions between large polymer
chain, increase interchain distance with reduction intermolecular
bonding
- Used in brittle materials (Tr): PVC
- Lower Tg  at Tr, polymer may be used with some pliability &
ductility
- (Liquids having low vapor P & low MW)  phtalate ester, adipate
- Application: PVC, thin sheet, film, tubing, raincoats
STABILIZERS
- Additive to counteract deterioration in some polymers
under normal environment  expose to light-UV &
oxidation

# Oxidation
 chemical interaction between oxygen with polymer;
 Stabilizer consume oxygen before it reaches polymer &/
prevent the oxidation reaction that would further damage
# Prevent photochemical degradation  C black
# UV radiation
 interact with & cause severe in covalent bond &
molecular chain
- Approaches to UV stabilization: add UV absorbent & add
material react with broken bond
1) Add UV absorbent material 
- layer at surface as sunscreen
- to block out the radiation before penetrating into &
damage the polymer
2) Add materials that react with bond broken by radiation
before they participate in other reactions  lead more
damage
 Colorants
- give color to polymer
- added as dyes
- molecules dyes dissolve in
polymer
-added as pigment filler
materials that do
- not dissolve, remain
separate phase
- small size & refractive index
near the parent polymers
Flame retardants
- Most all pure polymer are
flammable
- used in textile & toys
- interfere the combustion
process by initiating
different combustion
reaction generate less
heat, reduce T slowing
burning
 Polymer processing
• There are a number of methods for producing polymer shapes,
including molding, extrusion, and manufacture of films and fibers.
• The techniques depend to a large extent on the nature of the polymer
• The greatest variety of techniques are used to form the thermoplastics.
• The polymer is heated to near or above the melting temperature so
that it becomes rubbery or liquid.then formed in a mold or die to
produce the required shape.
BLOW MOLDING
• A hollow preform of a thermoplastic called a parison is introduced
into a die by gas pressure and expanded against the walls of the
die.
• This process is used to produce plastic bottles, containers,
automotive fuel tanks, and other hollow shapes.
EXTRUSION
• This is the most widely used technique for processing thermoplastics.
• Extrusion can serve two purposes: 1) it provides a way to form certain simple
shapes continuously, and 2) extrusion provides an excellent mixer for additives
(e.g., carbon black, fillers, etc.)
• A screw mechanism consisting of one or a pair of screws (twin screw) forces
heated thermoplastic (either solid or liquid) and additives through a die opening
to produce solid shapes, films, sheets, tubes, pipes, and even plastic bags.
• The extruder consist of di¤erent heating or cooling zones. Extrusion can be
used to make film, coat wires and cables with either thermoplastics or
elastomers.
INJECTION MOLD
• Thermoplastics heated above the melting temperature using an
extruder are forced into a closed die to produce a molding.
• This process is similar to die casting of molten metals.
• A plunger or a special screw mechanism applies pressure to force
the hot polymer into the die.
• A wide variety of products, ranging from cups, combs, and gears to
garbage cans, can be produced in this manner.
THERMOFORMING
• Thermoplastic polymer sheets heated to the plastic region can be
formed over a die to produce such diverse products as egg cartons
and decorative panels.
• The forming can be done using matching dies, a vacuum, or air
pressure.

CALENDARING
• molten plastic is poured into a set of rolls with a small opening.
• The rolls, which may be embossed with a pattern, squeeze out a
thin sheet of the polymer—often, polyvinyl chloride. Typical products
include vinyl floor tile and shower curtains.
SPINNING
• Filaments, fibers, and yarns may be produced by spinning.
• The molten thermoplastic polymer is forced through a die containing
many tiny holes.
• The die, called a spinnerette, can rotate and produce a yarn.
• For some materials, including nylon, the fiber may subsequently be
stretched to align the chains parallel to the axis of the fiber; this
process increases the strength of the fibers.
CASTING
• Many polymers can be cast into molds and permitted to solidify.
• The molds may be plate glass for producing individual thick plastic
sheets or moving stainless steel belts for continuous casting of
thinner sheets.
• Rotational molding is a special casting process in which molten
polymer is poured into a mold rotating about two axes.
COMPRESSION MOLDING
• placing the solid material before cross-linking into a heated die
• Application of high pressure and temperature causes the polymer to
melt, fill the die, and immediately begin to harden
• Small electrical housings as well as fenders, hoods, and side panels
for automobiles can be produced by this process
TRANSFER MOLDING
• A double chamber is used in the transfer molding of thermosetting
polymers.
• The polymer is heated under pressure in one chamber.
• After melting, the polymer is injected into the adjoining die cavity.
• This process permits some of the advantages of injection molding to
be used for thermosetting polymers
 Polymer application
Classification is based on end-use: plastics, elastomers, fibers, coating,
adhesive, foams & films.
Particular polymers may be used in more than 1 applications.

1) PLASTICS
 materials that have structural rigidity under load & use for general
purpose application
 Polyethylene, polypropylene, PVC, polystyrene, epoxies
 Some are very rigid, other are flexible exhibit elastic & plastic
deformation when stress, sometimes experiencing deformation
before fracture
 Linear/branched must be used below glass transition T (if
amorphous) or below melting T (semicrystalline)
2) Elastomers  rubbers
 can be stretched to many times their original length, and can
bounce back into their original shape without permanent
deformation.
 include polyisoprene or natural rubber, polybutadiene,
polyisobutylene, and polyurethanes
 Improving mechanical: crosslink structure
• Silicon elastomers:
 have a high degree of flexibility at low T (~90 C);
 stable at T as high as 250 C
 Biocompatible (blood tubing)
• ELASTOMERS (rubber)
3) Fibers
• long filament (L/D)=100:1
• Mostly used in textile industry; woven or knit
• Subjected to stretching, twisting, shearing & abrasion
• high tensile strength, high modulus elastisity & abrasion resistance
high MW to be a strong material; will not break during drawing
• linear structure with regular order
• stable in various environments: acids, base, bleaches, dry cleaning
solvent & sunlight
• relative nonflammable and amenable to drying
 Miscellaneous Applications
COATING
Function:
1) Protect from corrosive/deteriorative reaction
2) Improve appearance
3) Provide electrical insulation
 Organic coaating:paint, varnish, enamel
 Many coating are latex (stable suspension
of small insoluble polymer particle disperse
in water); less organic solvent, less VOC
emission  smog
ADHESIVES
• substances used to bond 2 surfaces of solid material (adherends)
• 2 types of bond: mechanical & chemical
*Mechanical actual penetration of adhesive into surface pores &
crevices
*Chemical  intermolecular forces between adhesive & adherend

• Natural: casein, starch

• Synthetic: polyurethanes, polysiloxanes, epoxies acrylic
Factors to choose adhesive:
1. Materials & porosities to be bond
2. Requires adhesive properties
3. T exposure environment
4. Processing conditions
• Adhesive advantage over other joining technologies:
1. join dissimilar materials & thin components
2. lighter weight
3. better fatigue resistance
4. lower manufacturing cost
• DrawbacksT limitation; maintain mechanical integrity only at low
T, strength decreases with increase in T
• Used in aerospace, automotive, construction etc
FILMS
• Thin layer
• 0.025-0.125 mm thickness
• Packaging, tape
• Characteristic: low density, high
flexibility, high tensile & tear strength,
resistance to moisture & chemical, low
-permeability to some gases (water
vapor)
• polytethylene, polypropylene, cellulose
acetate
FOAMS
• plastic material with high vol of
small pores & trapped gas
bubble
• Thermoplastic & thermosetting:
polyurethane, rubber,
polystyrene
• Cushion, thermal insulation
• Bubbles are generated by
dissolving an inert into molten
polymer (high P); when P
reduce rapidly, the gas comes
out of solution & forms bubbles
& pores that remain in the solid
as it cools