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Silicones and Phosphazenes

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 INORGANIC CHEMISTRY

Silicones and Phosphazenes

Prof. Ranjit K. Verma

University Department of Chemistry
Magadh University
Bodh Gaya-824234

(31.07.2006)

CONTENTS
Introduction
Silicones
General introduction
Structural features and synthesis
Interesting properties and uses
Phosphazenes
General introduction
Nature of bonding in triphosphazenes
Uses

Keywords
Polymers, catenation, silicones, halosilanes, silicone oils, silicone elastomers, silicone resins, phosphazenes,
diphosphazenes, polyphosphazenes, bonding in triphosphazenes, homorphic and heteromorphic interactions

1
Introduction
Polymers have revolutionized human civilization. Carbon forms polymers most extensively on
account of its unparalleled catenation property (tendency to form chains). Although to a limited
extent, catenation is exhibited by some other elements in Group 14 and Group 15. For example,
in Group 14, the catenation tendency follows the sequence C >> Si > Ge ~ Sn >>Pb. In Group

15, the NN single bond is so weak that its chain length does not go beyond 3 (in N3ion). The
chain length in case of phosphorus is up to 2 (e.g. in P2H4). Silicon in Group 14 forms polymeric
silanes with difficulty. In conjugation with oxygen however, it makes extensive SiOSi linkages
forming silicones. Similarly, in conjugation with nitrogen, phosphorus shows unique capability
of forming extensive — N = P — bonds in what are called phosphazenes. These two classes of
polymers established Si and P as the second and the third most extensively polymer- forming
elements, respectively and, have revolutionized polymer science on account of their oxidative,
thermal and radiation stabilities. The C = C and C – H bonds in C-based polymers are
susceptible to oxidation and the C-C bonds are prone to cleavage, but these two classes of
silicones and phosphazenes are free from these lacunae. Their good dielectric properties,
excellent water repellency, antistick & antifoam properties, solvent resistance, flame resistance,
sometimes physiological inertness and similar other properties have brought out remarkable
versatility in their applications from engineering goods to items in medical sciences.

Silicones

General introduction
Originally this word was coined by F. S. Kipping to mean a silicon atom substituting carbon in a
ketone (>C=O). But it was soon found that even the first such compound Ph2SiO was a polymer
and it had no chemical resemblance with ketones. Today silicones are well known polymers
having extensive Si-O-Si linkages similar to those in silicates. Silicon is sp3 hybridized and the
tetrahedra undergo permutations and combinations to give large variety of polymeric structures.
But unlike silicates, in which there are terminal oxygens, silicones contain organic moieties (e. g.
CH3, C6H5) attached to silicon and hence Si-C bonds. For this reason they are also called
organosilicon polymers. Such polymeric structures are formed in many ways viz., linear and
cyclic; chains and cross-linked. Depending upon the degree of polymerization the polymer
formed may be a liquid (oils), semisolid (greases), rubber like solid (elastomers) or hard solid
(resins). They are often classified on the basis of physical state as

(a) Linear silicones (silicone oils)

(b) Silicone elastomers
(c) Silicone resins

Some are also called silicone greases.

Structural features and synthesis

Silicones contain Si–O–Si linkages and Si–C bonds. Naturally, the synthetic routes involve
formation of one or both of the two. Formation of Si–O–Si linkage is simple and is achieved
through condensation of two Si–OH bonds (as in the case of formation of silicates from
hydrolysis product of SiCl4). The first step in synthesis of silicones naturally, involves putting
‘R’ groups (R = – CH3, –C6H5) on the tetrahedral Si atom. Care is taken to have at least one ‘X’

2
(X = Cl) on this atom so that it could be substituted by hydrolysis. Subsequent condensation
through Si–OH bonds generate Si–O–Si linkage.

Step 1 - Introduction of Si–C bonds: Preparation of alkyl (or aryl) substituted chlorosilanes:
i) Treating SiCl4 with a Grignard reagent in laboratory gives organosilanes:

SiCl4 + CH3MgCl CH3SiCl3 + MgCl2

Further alkylation will depend upon the molar ratio of the two reactants:

CH3SiCl3 + CH3MgCl (CH3)2SiCl2 + MgCl2

(CH3)2SiCl2 + CH3MgCl (CH3)3SiCl + MgCl2

ii) Industrially, such organosilanes are prepared by direct reaction of alkyl or aryl halides
with Si. A fluidized silicon bed is used in presence of copper catalyst (90% Si ; 10% Cu metal by
weight) :

Cu powder
2CH3Cl + Si (CH3)2 SiCl2
3000C

The reaction proceeds via free radical mechanism and the role of Cu is to form free radical
intermediates such as {CuCl} and {CuCH3}. CuCl halogenates Si and CuCH3 dissociates to give
CH3 . radical. Some mono and trimethyl derivatives are also formed. Adding HCl increases the
yield of the monoderivative and reduces that of the dimethlyl derivative. The reactions in both
the cases are exothermic. Naturally, the heat generated has to be removed. The product is always
a mixture which has to be fractionated to bring desired perfection in polymerization ahead.

Step 2 – Hydrolysis of alkyl / aryl halosilanes :

The substituted halosilanes undergo hydrolysis to corresponding substituted silanols, which on
condensation produce silicones. The properties of these silicones depend upon the degree of
polymerization and stereochemistry. More – OH groups in the silanols naturally, lead to
condensations in more directions. The silanol is usually acidic so it is easily converted to its
sodium salt using a 12 M solution of NaOH:

3
In place of –CH3, there could be a –C6H5. Further condensations lead to higher polymers.

As we have seen, the reaction represented by equation (1) gives linear silicones:

It has structural resemblance with silicates:

To terminate the process of polymerization, appropriate amounts of trimethyl silanols are used:

4
Monoalkyl silanols are used to incorporate in order to achieve desired branching and bridging
groups,

These may give siloxenes (silicone resins)

Thus, for getting a desired variety of silicone, calculated amounts of the mono -, di- and
trihalosubstituted versions of alkyl silanes are used. The following examples may be given as
illustration:

Silicone oils: These are prepared by stirring hexamethyl disiloxane and the cyclo tetramer,
tetrakiscyclo-dimethyl siloxane in suitable ratio with a little of conc. H2SO4. The Si–O bonds are
broken to form esters with H2SO4 :

Thereafter, hydrolysis gives new Si – O bonds and this brings randomness in the Si–O–Si
linkages. The molecular weight, viscosity etc. depend on the initial ratio.

Silicone elastomers: These are prepared by taking the dihaloderivatives only. The dimethyl
polysiloxanes thus obtained are reinforced using fumed silica. The chain blocking precursors
[monohalo derivative which gives (CH3)3Si–O–] and the precursors causing cross-linking are
totally avoided. KOH is used and the linear polymer thus produced is in form of a viscous gum.
For effective use, vulcanization is carried out using benzoyl peroxide etc. This brings about
cross-linking in the polymer:

5
Using catalytic techniques, vulcanization is also effected by introducing acetoxy groups in the
side chain:

Simultaneous condensation through hydroxyl group brings out desired, cross-linking. This
controlled cross-linking (1 in every 100-1000 Si units) brings about unusual flexibility, elasticity,
strength and capacity to bear temperature as high as 2500C and as low as -1000C.

Silicone resins: These are prepared by hydrolyzing methyl and phenyl substituted dichloro and
trichloro silanes in toluene. Introduction of phenyl groups in place of methyl brings about further
heat stability and flexibility. Extensive cross-linking makes them look like bakelite but with
better dielectric properties suitable for use as insulators.

6
The nature of the polymer is determined by the extent of cross-linking and the nature of the
alkyl/aryl substituent.

Interesting properties and uses

All silicones are excellent water repellent, thermally and electrically insulating and chemically
inert. They exhibit antistick, antifoam and flame resistance properties. As such, they have
brought out technological revolutions in all walks of life. A few of their applications are given
below:

(i) Silicone oils: They have extremely high viscosity (ca. 50,000 to 3,00,000 times that of water
depending upon the chain length) which does not change appreciably with temperature. Their
surface tension is low. Chemical inertness and presence non-polar groups make them non-toxic.
They are used:

• As dielectric insulating media e.g. in transformer oils.

• As hydraulic oils
• As compressible fluids for liquid springs
• As antifoaming agents in sewage disposal plants, textile dyeing, cooking oil etc. (ppm
quantities do wonder!)
• As an additive in cosmetics (lipsticks, sun tan lotion, hair oil etc.)

(ii) Silicone greases: Silicone oils are thickened to make silicone greases for use in heavy-duty
steel gears and shafts. For this purpose, methyl phenyl silicone oils are thickened by Li-soaps.

(iii) Silicone rubber: Silicon rubbers are used in making

• Cable insulation
• Static and rotary seals
• Gaskets
• Diaphragms
• Electric tape insulation
• Industrial sealants and adhesives
• Heart valves
• Space suits
• Accurate impressions for dentures
• Masks in cinema.

(iv)Silicone resins: Silicone resins are used in making

• Insulations in electrical equipments

• Laminates and printed circuit boards for electronic equipments
• High temperature paints and coatings on cooking utensils.

7
Phosphazenes

General introduction
Phosphazenes were initially termed phosphonitrilic polymers. Later on, the new term was used to
represent phosphorus, nitrogen (=azo) and P = N double bonds (=ene) which are always present
in these polymers. They are thus ‘unsaturated PN compounds’ containing phosphorus, mostly in
+V state. As is usual with polymers, they may have cyclic or chain structure. The nitrogen in

groups is in 2-coordination and phosphorus in 4-coordination. They contain

R R
the group which is isoelectronic with the
–N=P– –O–Si–

R R
groups of silicones. Their polymers differ in substitution on phosphorus and on the nature of
those substitutents besides the way and the extent, to which polymerization has taken place.
Their water repellent, solvent resistant and flame resistant properties have found new
applications and these have led to many technological innovations during the last few decades.
They are usually classified on the basis of number of phosphazene units that are incorporated in
the structure:

Monophosphazenes: Monophosphazenes are compounds of the type X3P = NR, (X and R = Cl,
OR, NR2, Ar etc.). These are unsaturated compounds and can be prepared as follows:

(a) Reacting an azide (R – N3) with PR3 (R = Ar, OR, Cl, NR2) :

P (C6H5)3 + C6H5–N3 (C6H5)3 – P = N – C6H5

–N2

(b) Reacting dihalotriphenylphosphenes with aromatic amines :-

(C6H5)3PCl2 + C6H5–NH2 (C6H5)3 – P = N – C6H5

–2HCl

Diphosphazenes: These contain two P = N – groups and the P = N and the P – N bonds
are equivalent. These are usually prepared by reacting PCl5 with NH4Cl under mild conditions:
Chlorohydrocarbon solvents
PCl5 + NH4Cl [Cl3P = N – PCl2 = N – PCl3]+Cl–

However, PCl5 undergoes ammonolysis in liq. NH3 :

8
 +
H2N NH2
H2N NH2
2PCl5 + 16NH3(l) P = N–P Cl– + 9NH4Cl
H2N NH2

The disphosphazenes exist both in covalent and ionic forms . Thus

Cl

the halo form can be represented as [Cl –P = N – PCl3] + Cl–

Cl

Polyphosphazenes:
These contain more than two P = N – groups. Polymeric phosphazene dichlorides are
formed when further halogen or halophosphorus substitutions of – NH2 groups in P takes place.
The polymeric phosphazene dichlorides can be represented as
Cl

[Cl – P = N – PCl3] + PCl6–

Cl n

These form chains and cyclic structures having ‘n’ value upto 104. The simple representation of
polyphosphazene dichlorides is made as (NPCl2)n. These are prepared as follows:

Solvent (a halo hydrocarbon)

nPCl5 + nNH4Cl [NPCl2)n] + 4n HCl
120 – 1500C

Cyclic trimer, tetramer etc. are prepared by using different conditions. Separation is done
through fractionation. The cyclic trimer, cyclo – [NPCl2)3 on heating at 150 – 3000C furnishes
polymeric products. But heating at a higher temperature (350 – 3600C) causes cleavage and
depolymerization.

The chlorines in the product may be substituted by nucleophiles and varieties of substituted
polyphosphazenes are obtained having

9
 X

— P = N — units in which X = OCH3,OC6H5, NHPh, N(CH3)2 , R,Ar etc.:

X n

e.g.

Cl CH3

— P = N — + 6CH3MgI — P = N — + 3MgCl2 + 3MgI2

Cl 3 CH3 3

Nature of bonding in triphosphazenes

Bonding in phosphazenes is quite interesting. Diphosphazene contains one P = N and one P – N
bonds both of which are equivalent and the bond length is shorter than single bond. This is easily
explained by resonance

P—N— P

In case of trimer and higher phosphazenes however, things are complex. At first sight, there
seems to be alternate single and double bond conjugate systems through out P – N – P skeleton.
Such conjugate systems are expected to lead to delocalization of the sort of benzene. The cyclic
trimer has an accurately planar 6-membered ring structure but, unlike aromatic systems, it is
difficult to reduce it electrochemically. Also, the spectral evidence of delocalized system
(bathochromic ultraviolet shift) is not found. This is explained by the unique and interesting
structure that triphosphazenes possess.

As in other phosphazenes, triphosphazenes have

(i) Very stable ring

(ii) All the skeletal interatomic distances are equal if all the six substituent groups on
phosphorus are identical.
(iii) A shorter P – N bond length (~ 158 pm) than single bond (~177 pm)
(iv) All the nitrogen atoms weakly basic hence protonable (more so if substituents on P
are electron releasing).

10
The symmetry of the molecule is like that of benzene. It has planar structure with three
nitrogen and three phosphorus atoms situated on alternate corners of the hexagon. The
substitutents (X) on P are placed above and below the plane. If all the substituents are
identical then three of them form together one plane above and three form one plane below
the molecular plane.

Some more features are mentioned below:

• Nitrogen atoms are sp2 hybridized:

Two such hybrid orbitals are involved in σ -bonding

• Similarly, each phosphorus is sp3 hybridized

Three such hybrid orbitals are involved in σ- bonding.

• There is then one ‘in plane’ π-bonding involving the lone pair of N (sp2 orbital) in xy
plane and the vacant dxy or dx2 –y2 orbital of the P — atom.
• There are two ‘out of plane’ interactions:
(i) Heteromorphic interactions: The singly occupied pz1 orbital on the nitrogen
overlaps with the dxzo or dyzO orbital of phosphorus (pπ – dπ bonding).

11
 (ii) Homomorphic interactions: There is a pπ – pπ interaction of pz orbitals of two
nitrogens through the dyz orbital of the phosphorus in between.

• It is believed that the two contributions viz. heteromorphic and homomorphic are
equal. This results in separation of the π orbitals into localized 3-centre orbital
islands. There are 3 such islands with interruptions at the three phosphorus atoms.
These interruptions in the M. O’s. prevent the systems from exhibiting delocalization
of the π-electron.

Uses
Both the cyclic and non-cyclic polyphosphazenes have great oxidative, thermal & radiative
stabilities. Substituents such as –NH2, –OR, –OC6H5 or fluorinated derivatives bring about
further stabilities. Their water repellency, solvent resistance, flame resistance, retention of
flexibility at low temperatures and their dielectric properties make them very useful for a variety
of modern technological purposes. These are used for making:

i) rigid plastics, plastic films, expanded foams

ii) fuel hoses, gaskets
iii) O-ring seals for use in extremely cold climate (e.g. in high flying
aircrafts or in vehicles for Arctic type climate)
iv) metal coatings & wire insulation
v) composite materials together with asbestos, glass or with ordinary
phenolic resins.

Suggested Readings
1. N.N.Greenwood and A.Earnshaw, Chemistry of the Elements, Pergamon
2. J.D.Lee, Concise Inorganic Chemistry, Chapman and Hall
3. S.S. Krisnamurthy, A.C. Sau and M.Woods, “Cyclophosphazenes” in Adv. Inorg. Chem. Radiochem.,
21,41- 112(1978)

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