 Industri Polimer & Plastik

 Industri Coating
 Industri Petroleum Processing
 Industri Asam Akrilat
Polymer and Plastics
 What is a Polymer?
Polymers are a large class of materials consisting of many small molecules
(called monomers) that can be linked together to form long chains. A
typical polymer may include tens of thousands of monomers. Because of
their large size, polymers are classified as macromolecules.
Monomer Polymer
Polymerisation

Gas

Solid
 How to make polymers
Addition polymerization – Chain growth polymerisation
All the monomers from which addition polymers are made are alkenes or functionally
substituted alkenes. Addition reactions are known to proceed in a stepwise fashion by way
of reactive intermediates, and this is the mechanism followed by most polymerizations.

Start a chain growing Chain growth Chain stops growing

Initiation Propagation Termination

Condensation Polymerization – Step growth polymerisation

A large number of important and useful polymeric materials are formed by
conventional functional group transformations of polyfunctional reactants.
Two or more monomers random
polymerized together
 random – A and B randomly
vary in chain
 alternating – A and B alternate
in polymer chain
 block – large blocks of A alternating
alternate with large blocks of B
 graft – chains of B grafted on
to A backbone block

A– B–

graft
 Bulk Polymerization
 Solution polymerization
 Suspension polymerization
 Emulsion polymerization
 Bulk Polymerization :
In the reactor: - Liquid monomer
- Initiator
- Inhibitors
- Chain transfer agents
Homogeneous : polymer remains dissolved in monomers.
Ex. PMMA
Heterogeneous : aka. Precipitation polymerization
polymer is insoluble in its monomers.
Ex. Polyacrylonitrile, PVC

Problem : heat transfer not good

Make objects with a desirable shape by polymerization in a mold.

Model of Batch Polymerization
agitator

Monomer

I
I

I
I
Initiator
 Pros & Cons of Bulk Polymerization

Advantage Disadvantage

- Obtain purest possible polymer - Difficult to control

- Conveniently cast to shape - Reaction has to be run slowly

- Obtain highest polymer yield per - Cannot get high rate and high
reactor volume MW at the same time

- Difficult to remove last traces

of unreacted monomer
Polimerisasi bulk stirena secara alir (flow)

Tahap I (80-82 oC):

prepolymerizer, konversi
30—35% 
menghasilkan larutan yg
lebih viscous

Tahap II: larutan

melewati menara dg suhu
yang bertahap meningkat
utk menjaga viskositas
sekaligus meningkatkan
konversi.
 Solution Polymerization
Solution Polymerization : Monomer dissolved into inert-
solvent / inhibitor
- Monomer
- Initiator
- CTA (chain transfer agent)
- Inert solvent
Solvent helps controlling heat transfer from reaction.

Use for : - Thermosetting condensation polymer (stop before gel point)

- Ionic polymerization

- Ziegler-Natta solution process

Model of Solution Polymerization

agitator

Monomer
I

I
I Initiator
I

I
Solvent
 Pros & Cons of Solution Polymerization
Advantage Disadvantage
solvent
- Reduces the tendency toward - Rate [M]  reduce rate,
autoacceleration chain length xn
- Solvent waste
- Increases heat capacity/heat- - Need solvent separation &
transfer recovery
- Have traces of solvent, monomer
- Reduces viscosity
- Lower yield
- Minimize runaway reaction -Solvent may not be really inert
Proses kontinu utk memproduksi polivinil asetat dg viskositas rendah dlm larutan

Vinil asetat

Polymer science & technology, CRC Press

Suspension Polymerization :
Model of suspension polymerization

Suspending agent suspending agents (ex. ionic

detergent, barium sulfate)

(Hydrophobic)
(Hydrophilic)
monomer
+ Water
Initiator

- Ex. Polyvinyl alcohol

- Beads of polymer ( 10-1000 m)
 Advantage Disadvantage

1. Easy heat removal 1. Low yield / reactor volume

and control 2. Traces of suspending agent on

particle surfaces
2. Obtain polymer in a
3. Cannot run continuously
directly useful from
4. Cannot be used for
-condensation polymers
-ionic or Ziegler-Natta
polymerization
 MMA

Polymer science & technology, CRC Press

 Agar monomer dapat terdispersi dalam medium, sifatnya
harus tidak larut/sedikit larut dalam medium.
 Umumnya digunakan polimer yg terpolimerisasi sebagian
(prepolymer) utk menurunkan solubilitas dan meningkatkan
ukuran partikel.
 Suspention agent (0,01 – 0,5% berat monomer) berperan
penting dlm mengontrol proses polimerisasi dan
keseragaman partikel.
◦ Surface-active-agents seperti asam lemak, beberapa garam
anorganik (CaCO3, Ca3(PO4)2, TiO2, Al2O3) utk menurunkan
tegangan permukaan air dan monomer droplet
◦ Polimer yg larut dlm air seperti gelatin, kanji, PAA dan garamnya,
berfungsi sbg protective coatings.
 Emulsion Polymerization
Emulsion Polymerization : Use emulsifier / soap

Initiator Water
Soap monomer (Hydrophilic)

-Reaction occurs in water phase until polymer gets very

hydrophobic and then dissolve back in the monomer region.
Ex. Latex - very very small particle stable in solution
- particle size << 1 m
- can generate very high MW. polymer
Emulsion Polymerization (cont.):

Typical ingredient
100 part (by wt.) monomer (water insoluble)
180 part water
2-5 parts acid soap
0.1-0.5 part water-soluble initiator
0-1 part CTA (monomer soluble)
Tahapan dalam polimerisasi emulsi

Polymer science & technology, CRC Press

Contoh
diagram alir
Polimerisasi
emulsi

Polymer science & technology, CRC Press

 Primary Bond - Covalent Bonding
 Secondary Bonds –
◦ van der Waals
◦ Dipole Bonds
◦ Hydrogen Bonds

secondary
bonding

Linear B ranched Cross-Linked Network

Direction of increasing strength

Improve mechanical properties, processability, durability,
etc.

 Fillers
◦ Added to improve tensile strength & abrasion resistance,
toughness & decrease cost
◦ ex: carbon black, silica gel, wood flour, glass, limestone, talc,
etc.

• Plasticizers
– Added to reduce the glass transition
temperature Tg
– commonly added to PVC - otherwise it is
brittle
Bis(2-ethylhexyl) phthalate
  Stabilizers
◦ Antioxidants
◦ UV protectants

• Lubricants
– Added to allow easier processing
– “slides” through dies easier – ex: Na stearate
• Colorants
– Dyes or pigments
• Flame Retardants
– Cl/F & B
 Thermoplastic –
◦ can be reversibly cooled & reheated, i.e. recycled
◦ heat till soft, shape as desired, then cool
◦ ex: polyethylene, polypropylene, polystyrene, etc.

• Thermoset
– when heated forms a network
– degrades (not melts) when heated
– mold the prepolymer then allow further reaction
– ex: urethane, epoxy
1. Injection Molding (or compression or transfer)
2. Extrusion
3. Thermo-Forming
4. Blow Molding (injection blow molding with
preforms or extrusion blow molding with parison)
5. Rotational Molding (combination of 3 and 4)
 The extrusion machine forms the basis of
nearly all other polymer processes.
 Basically involves melting polymer pellets
and extruding them out through a two
dimensional die.
 Produces long, thin products
◦ Coating for electrical wire
◦ Fishing Line
◦ Tubes, etc.
Nylon
sheaves
 Compression and transfer molding
◦ thermoplastic or thermoset
 Injection molding
◦ thermoplastic & some thermosets
Extrusion Blow Molding

Injection Blow Molding