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HOMOGENEOUS HETEROGENEOUS
SYSTEM SYSTEM
BULK SUSPENSION POLYMERIZATION
POLYMERIZATION
EMULSION POLYMERIZATION
SOLUTION
POLYMERIZATION
PRECIPITATION
POLYMERIZATION
polymer
• Low viscosity at the beginning
• high viscosities at later stages of the reaction
Solution
the viscosity
• In solution polymerization, the monomer,
initiator, and resulting polymer are all soluble in
the solvent.
• Solution polymerization may involve a simple
process in which a monomer, catalyst, and
solvent are stirred together to form a solution
that reacts without the need for heating or
cooling or any special handling.
• On the other hand, elaborate equipment may
be required.
• For example, a synthetic rubber process using a
coordination catalyst requires rigorous
exclusion of air (to less than 10 ppm); moisture;
carbon dioxide; and other catalyst deactivators
from the monomer, solvent, and any other
ingredient with which the catalyst will come in
contact before the reaction.
• In addition, exclusion of air prevents the
tendency to form dangerous peroxides.
• To avoid product contamination and
discoloration, materials of construction also
need to be selected with the greatest care.
• Polymerization is performed in solution either
batchwise or continuously.
• The batch may be mixed and held at a constant
temperature while running for a given time, or
for a time dictated by tests made during the
progress of the run.
• A continuous reaction train, consists of a
number of reactors, usually up to about ten,
with the earlier ones overflowing into the next
and the later ones on level control, with
transfer from one to the next by pump.
• As the reaction progresses, solution polymerization
generally involves a pronounced increase in
viscosity and evolution of heat.
• The viscosity increase demands higher power and
stronger design for pumps and agitators.
• The reactor design depends largely on how the
heat evolved is dissipated.
• Reactors in solution polymerization service use
jackets; internal or external coils; evaporative
cooling with or without compression of the vapor
or simple reflux-cooling facilities, a pumped
recirculation loop through external heat exchanger;
and combinations of these.
ADVANTAGES OF SOLUTION POLYMERIZATION
• The catalyst is not coated by polymer so that its
efficiency is sustained and removal of catalyst
residues from the polymer, when required, is
simplified.
• Solution polymerization is one way of reducing the
heat transfer problems encountered in bulk
polymerization.
• The solvent acts as an inert diluent, increasing
overall heat capacity without contributing to heat
generation.
• By conducting the polymerization at the reflux
temperature of the reaction mass, the heat of
polymerization can be conveniently and efficiently
removed.
• Furthermore, relative to bulk polymerization,
mixing is facilitated because the presence of the
solvent reduces the rate of increase of reaction
medium viscosity as the reaction progresses.
DRAWBACKS OF SOLUTION POLYMERIZATION
0% 10 – 20% 75 – 80%
Aglomerasi
Kontrol temperatur
sangat penting
Reaktor Reaktor
dengan jaket dengan baffle
Hati-hati! Dead volume
Sistem
refrijerasi
• Jika ukuran reaktor berjaket diperbesar, timbul
masalah luas perpindahan panas.
PENYESAIAN:
Masalah utama dalam reaktor untuk polmerisasi
suspensi adalah terbentuknya kerak polimer. Jika kerak
terbentuk di antara coil-coil pendingin, maka
pembersihannya akan sangat sulit.
• Polimerisasi emulsi saat ini banyak dimanfaat-
kan secara komersial untuk memproduksi ber-
bagai jenis polimer.
2) Viskositas
Viskositas pada polimer emulsi menunjukkan kekentalan dan
kemampuan emulsi dalam mengalir. Polimer yang bercabang akan
lebih kental dibandingkan dengan polimer rantai lurus dengan berat
molekul yang sama.
Distribusi Komponen
R
Jika sejumlah kecil sabun dimasukkan ke air, maka
akan terionisasi:
O O
O
Hydrophilic
[CH3 (CH2)16 C O–] group
Hydrophobic
group
First addition More addition More addition
of surfactant of surfactant of surfactant
• Konsentrasi surfactant
• Temperatur
• Kekuatan ion
• Keberadaaan molekul lain
LOKASI POLIMERISASI
panas
S2O8– 2 SO4–
Anion radikal yang larut dalam air akan bereaksi
dengan monomer terlarut dalam fasa air mem-
bentuk radikal bebas tipe sabun:
50 – 60C
SO4– + (n + 1) M
– S2O4– (CH2 – CX2)n – CH2 – CX2
Lokasi polimerisasi
Alasan mengapa reaksi polimerisasi terjadi dalam
micelle:
Sebelum inisiasi:
• Dispersing medium, biasanya air, yang
mengandung sedikit sabun (emulsifier) dan
monomer.
• Tetesan monomer dengan ukuran 10.000 Å
terpisah akibat stabilisasi oleh molekul emulsifier.
• Konsentrasi tetesan monomer 1010–1011 per ml.
• Jika CMC terlampaui, 50 –100 molekul
emulsifier akan membentuk micelle yang
berbentuk bola dengan ukuran 40 – 50 Å;
2. Teknik Seeding
Pada polimerisasi emulsi dengan teknik seeding, sebagian
air, monomer dan surfaktan dimasukkan ke dalam reaktor
kemudian dilakukan penambahan inisiator secara langsung
(shot). Setelah semua inisiator selesai ditambahkan,
dilakukan feeding sisa air, monomer dan surfaktan.
Keunggulan dari polimerisasi cara ini adalah dapat
menghasilkan ukuran partikel yang relatif besar.
3. Teknik Kontinu
Teknik polimerisasi secara kontinu adalah teknik dimana semua
komponen yang terlibat dalam proses polimerisasi ditambahkan
bersamaan secara terus-menerus. Teknik ini memiliki keunggulan
dalam pengontrolan suhu karena monomer yang ditambahkan
sedikit demi sedikit.
4. Teknik Semikontinu
Pada teknik semikontinu, sebagian air dan surfaktan dicampurkan
dan kemudian dimasukkan ke dalam reaktor. Selanjutnya ke dalam
campuran yang disebut initial charge ini dimasukkan pre-emulsi
monomer dan larutan inisiator secara terus-menerus ditambahkan
sampai habis. Teknik semikontinu merupakan teknik polimerisasi
yang paling banyak digunakan di industri polimer khususnya yang
menghasilkan partikel polimer bergugus fungsi.