Elemental silicon on which the entire technology is based is typically obtained by reduction of the

mineral silica with carbon at high temperatures

The silicon is then converted directly to tetrachlorosilane by the reaction

Tetrachlorosilane can be used to form an organosilane by the Grignard reaction

This relatively complicated reaction has been replaced by the so-called Direct Process or Rochow
Process, which starts from elemental silicon as is illustrated by the reaction

This process also yield RSiCl3 and R3SiCl, which can be removed by distilation. Compounds of
formula R2SiCl2 are extremely important as intermediates to a variety of substances having both
organic and inorganic character. Hydrolysis gives dihydroxy structures, which can condense to give
the basic [-SiR2O-] repeat unit. The nature of the product obtained depends greatly on the reaction
conditions. Basic catalysts and higher temperatures favor higher molecular weight linear polymer
Acidic catalysts tend to produce cyclic small molecules or low molecular weight polymer.

The hydrolysus approach to polysiloxane synthesis has been largely replaced by ring-opening
polumerization of organolisicon cyclic trimers and tetramers, with ionik initiation. These cyclic
monomer are produced by the hydrolysis of dimethuldichlorosilane. Under the right condition, at
least 50 wt % og the products arep cyclic oligomers. The desired cyclic species arep separated from
the mixture for use in ring-opening polymerizations such as those descripbed inthe following
section.

In addition, ‘click’ chemistru has been developed for new synthesis techiques in general, and
polymerization in particular. These approaches have been used to prepare polysiloxane elastomers
and polydimethylsiloxane (PDMS) copolymers that can function as thermoplastic elastomers. New
synthetic strategies for structured silicones, based on B(C6F5)3 have alse been developed. Another
new approach involves enzymes, such as the lupase enzymatically catalyzed synthesis of silicone
aromatic polyesters and silicone aromatic polyamides.

2.2 Ring-Opening Polymerizations

Cyclic siloxane can undero a ring-opening chain growth polymerization. Free radical are not useful as
initiator species, because of the nature of the siloxane bond, but cationic initiator are veru effective.
The reaction is illustrated using the most common cyclic oligomes, the timer
hexamethylcyclotrisiloxane, or the tetramer octamethylcyclotetrasiloxane.

(SiR2O)3,4 -> [-SiR2O-]

Where R can be alkyl or aryl and x is the degree of polymerization. In principle, the reaction is
reversible, but in practice i tis made essentially irreversible by the choice of monomer, initiator, and
polymerization conditions. Because of this potential reveribility however i tis important to remove
all initiator from the finished product, typically done by neutralization of the acidic or basic terminal
chain residues. Alternatively, some initiators can be removed by volatilization or thermolysis. End
blocking is frequently used to place groups on chainc ends that invrease thermal stability and preven
re-requilibration.

Because i tis frequently impossible to remove all trace of active species, some reorganization is
almost inveitable. In these processes, siloxane bond interchage to bring about variation in both
molevular weight and in the relative amounts of cyclic and linear species. At equilibrium, a Gaussian
distribution of molecular weight exist. The cyclic oligomers that occur most frequently are D4
through D6. The amount obtained depend greatly on the ‘monomer’ and on the polymerization
conditions. D4 through d6 are typically present to the extent of 10-15 wt %. The lower molecular
weight products are generally removed from the polymer berfore its used in comercial application.

The low molecural weight products are also of interest grom fundamental scientific point of view in
two respects. First, the extent to which such products are formed can be used as a measure of chain
flexibility.

Second, the various cyclic species formed can be purified useing standard separation techniques,
and then used to test theoretical predictions regarding the differences between otherwise identical
cyclic and linear molecules.
 Silikon Silikon adalah anorganik dan semi-anorganik polimer, dibedakan dengan
adanya link siloxane berulang (-Si-O-) dalam struktur molekul. Perumusan tipikal
menggabungkan radikal metil (CH3) dengan (SiO) di berbagai proporsi untuk memperoleh unit
berulang - ((CH3)m-SiO) -, di mana m menetapkan proporsionalitas. Dengan variasi komposisi
dan pengolahan, Polisiloksan dapat diproduksi dalam tiga bentuk:

Cairan

Elastomer

Resin termoseting

Cairan yang rendah berat molekul polimer yang digunakan untuk pelumas, pemoles,
wax. Silikon elastomer dan termoseting Silikon, dirawat di sini, cross-linked. Ketika cross-
linked, bentuk resin Polisiloksan sistem yang digunakan untuk cat, pernis, dan pelapis dan
laminasi lainnya seperti Printed Circuit boads menjadi kaku. Mereka juga digunakan sebagai
bahan cetakan bagian listrik. Curing dilakukan dengan pemanasan atau dengan membiarkan
pelarut yang mengandung polimer untuk menguap. Silikon terkenal akan tahan panas yang baik
dan air repelensi, tetapi kekuatan mekanik tidak begitu besar sebagai cross-linked polimer.

Data dalam Tabel 10,4 (f) adalah untuk silikon polimer termosetting yang khas.

TABEL 10,4 (lanjutan) (f). resin silicon termosetting

Contoh kimia : [(CH3)6-SiO]n

Metode polimerisasi : Langkah (kondensasi), biasanya
Kekuatan tarik : 4000 Ib/in2 (30 MPa)
Pemanjangan : 0%
Gravitasi spesifik : 1,65
Perkiraan pangsa pasar : Kurang dari 1%