(b)Silicone Fluids :

(i) Preparation : Silicone fluids are prepared by hydrolysis of dimethyl

dichloro silane in presence of strongly acidic aqueous solution .The low molecular
weight product is produced by adding trimethychlorosilane during
polymerization.The added silane serves as an end site blocker to stop further
growth.

(ii) Properties :

1. Silicone fluids have high spreading power so that a thin protective type of
film can be spread over plastics , metals , ceramics etc.

2. All possess high water repellant properties.

3. All are stable in air up to 1500C, at higher temperature they get

crosslinked to produce viscous fluids.

(iii) Uses :

1. Silicone fluids are used to prevent cracking of organic /inorganic

powder .A thin coat of polymer on such compounds is helpful.

2. They are used to polish automobiles , cars etc .They are used to treat
interior part of avail for storing aqueous suspension of penicillin.

3. Used for lining moulds of rubber tyres ,plastics casting etc.

4. Silicone fluids with varying viscosities are used as damping and

hydraulic fluids.

5. They are used as antifoaming agents in petroleum oils.

6. They are used as fluids for capacitors ,transformers since they have
excellent water resistance and dielectric properties.

7. They are used as high temperature bath oils which are used for heat
sterilization of dental and surgical instruments.

(C) Silicone Compounds :

 (i) Preparation :

The silicon compounds are formulated from dimethyl fluids by adding finely
divided silica. Addition of fillers like lithium soaps , carbon etc. give compounds
called silicon greases.

(ii)Properties :

Consistency of silicone greases varies from free flowing to heavy ointment .The
blend retains all properties of dimethyl silicones.
(iii) Uses :
1) Silicone greases are widely used as water repellent ,as sealing agents in
aviation type spark plugs ,as lubricants ,as moisture proof seals , corrosion
inhibitors .
2) They are used as insulators in electrical connections , X –ray
equipments , marine engine ignition system ,battery cases.
3) They are used for water proofing , preventation of leather and
rubber diaphragms etc.
4) They find uses in lubricating ball bearings ,working in chemical and
corrosive environments and those under light to moderate loads at
low temperatures .Carbon based grease is moderate loads at low
temperatures .Carbon based grease is used as heat resistant grease
for : conveyor belts and oven doors.
.
(d) Silicons Resins :
(i) Preparation :

Hydrolysis and condensation of bi-functional and tri-funcational silanes under

carefuiiy controlled conditions(relative amount ofreactint, additives etc) followed
by adding terminators produce resins.Usually resins are cured at a temperature
somewhat higher than at which it is likely to be used.
(ii) Properties :

1. Silicone resins are highly resistant to water and heat.

2. They have excellent adhesion property .

3. They however ,show poor resistance to water vapour since the films
have high water vapour permeability.

4. They have no action on strong acids , and bases but are easily attacked by
aplihatic ,aromatic and chlorinated hydrocarbons.

5. Coatings of silicon resins are nontoxic and shown non stickiness.

(iii) Uses :

1. Silicone resins are used as protective coatings on motors, turbines

,boilers ,steam pipes , refrigerators , washing machines and other
household equipments.

2. As a water resistant resins , in masonry and concrete.

3. As thermal and electrical insulators , they are used as firewall structure, high
temperature vibration dampers etc.

4. Usd to coat the food handling equipments.

Bonding in Silicones :An Overview

Chemistry of poly siloxane is much dependent on stepwise reactions;

however , it differs from reactions of carbon compounds .The difference is due to
the presence of vacant d orbitals on Si atoms (the first row elements like C,do not
have d orbitals ). The d orbitals can participate in valence bonding giving penta
and hexa co-ordination .It can also interact with electron rich atoms like oxygen to
produce double bonds. As a result , the bonding becomes unexpectedly strong.This
is the reason for the higher stability of silicone polymers than organic polymers.

Availability of d orbitals on Si atom increases the reactivity of the silicone

compounds for example, Si –Cl bond can be hydrolyzed unlike to C-Cl bond to
produce silanol. The silanol are highly unstable, two of such silanol condense to
produce Si-O-Si –linkage (siloxane) even in presence of water.The siloxanes are
stable towards hydrolysis.The polysiloxanes are highly stable.The stability is
attributed to relatively high bond length as comparaed to corresponding carbon
compounds .Si-O bonds are more stable then C-O bonds by about 98 kJ/
mole.Table 3.2 dispalys the vatious bond energies of some carbon and silicon
linkages with H ,halogens, oxygen ect.However Si-Si bonds are
thermodynamically less stable than C-Cbonds.Si-O linkage is more stable due to
higher bond energy .The bond energy is higher due to presence of dΠ-P Π - Π
bonding between Si and oxygen.

Table 3.2 Bond Energies

Bond Bond Energy in Bond Bond Energy in

KJ/mole KJ/mole
Si=Si 310 C=C 602
Si-Si 222 C-C 346
Si-F 565 C-F 485
Si-O 452 C-O 358
Si- Cl 381 C-Cl 327
Si-h 318 C-H 411

The water repellant property and nonstickiness of polysiloxanes are mainly due to
the formation of hydrophobic sheath of organic substituents around the polymer
backbone .Si-O-Si linkages are ionic in nature Si-O-Si linkages from getting
hydrolyzed.
Silicon atoms in Polymers are linked with oxygen and subsituents
trtrahedrally.The various infinite structures like single chains, rings double chains
,layered and cross linkings are possible depending upon the number of shared Si
atom with the other atoms. The dipole- dipole interaction of electropositive Si
atoms with electronegative atoms in neighboring chain is negligible due to higher
bond angle between Si –O-Si .The close packing in polysiloxane is not possible
when the substituents at Si are bulky because they will occupy large effective
volumes.
3.7.2 Phosphonitrilic Polymers
 Phosphonitrilic polymers are a group of linear or cyclic compounds containing
structura units of unsaturated –N =P-linkages

(a) Preparation :
The cyclic phosphonitrilic chlorides and their derivatives are the starting materials
for preparation of various kinds of phosphonitrilic polymers.They are obtained by
ammonialysis of PCL5in a solvent (e.g.s-tetra ethane ) at high temperature.

Refux150o

PCl5 +NH4Cl → 1/n(PNCl2)n+4HCl

(Tetrachloroethane) (where n=3to8)

According to conditions prevailing at the time of reaction,the products are cyclic or
linear polymers .The product resembles organic niitriles R-CN therefore they are
called phosphonitriles. However the reaction products are usually cyclic,which
resemble benzene so they are also termed as phosphazene.
The mechanism of the reaction which gives both cyclic and liner polymers is yet
not fully understood .It is believed that PCl5 reacts in its ionic from [PCl4]+[PCl6]-
.The anionic part is attacked by ammonia with elimination of HCl to produce
NH = PCl 3

PCl6-+NH4+ → NH4PCl6 → HN=PCl3+3HCl

HN=PCl3 act as nucleophil towords either itself or PCl5.

HN=PCl3+[PCL4]+[PCl6]- → [Cl3P=N-PCl3]+[PCl6]-+ HCl

The product [Cl3P= N-PCl3]+ [PCl6]- is an intermediate, precipated out in early part
of reaction. The cations portion of this intermidate futher attacks on ammonia to
produce another linkage.
[CL3=N-PCl3]+[PCl6]-+ NH4Cl→[Cl3P=N-PCl2=N-PCl3]+ Cl-+4HCl
 .. 29....
.

This continues with increase in chain length.The ionic linear species

[Cl3P=N-(PCl2)n-1 PCl3]+ Cl- formed in the reaction are the main precursors wich
undergo intermolecular elimination of PCl4+ (cyclization ) to produce cyclic
compounds having various ring sizes. .

Cyclic trimer

Usually two types of products ,cyclic polymer of the type (NPCl2)n and liner
polymer of the type – (NPCl2)n PCl4 are produced .Their proportion can be varied
by adjusting reaction conditions.For example , if excess PCl5 is used ,liner
polymer predominates .If PCl5 is added slowly to reaction mixture the polymer is
wholly cyclic .Typically they are (NPCl2)n where n = 3 to 12 (around 80 % cyclic
and 20 % linear )

2HCl
[Cl3P-N=PCl2-N=PCl3]+Cl- +NH4Cl-→
 The separation of product is carried out by distillation of the solvents and
treating residue with petroleum ether.Cyclic polymer get dissolved in petrolem
ether while insoluble part contains a mixture of linear polymer with end group PCl 5
The soluble part contains cyclic polymer (dimer ,trimer , tetramer ,penta ,hexa ,
hepta and octa )etc which can be separated by distillation and solvent extraction.
Trimeric (NPCl2)3 was first prepared by Liebig in 1834 while stokes
obtained a series of (NPCl2)n compounds in 1897.
Use of PBr5 and NH4Br instead of PCl5 and NH4Cl also give similar type of
products. However fluoride derivatives connot be used to produce these polymer
since it results in the stable NH4PF6 Therefore , such polymers are obtained by
fluorination of cyclic chloro compounds by replacement reaction.
By using differently substituted P compounds and ammonium halides it is
possible to prepare other phosphonitrilic derivatives.
Chlorophosphazenes are weak bases due to delocalized pi system and
therefore , suffer electrophilic attack (i.e. they are acting as nucleophiles ) .Typical
reaction includes nucleophilic displacement of Cl- ion from chloro phosphazenes
,on account of inductive effect.Tetramer phosphonitrilic chloride is more readily
hydrolyzed to produce acids .The protonation usually occurs at more negative
nitrogen.Such type of reactions can be used to produce a number of salts.
For examples : H2O

1. (NPCl2)3————————[NP(OH)2]3

CH3ONa

2. (NPCl2)3————————[(NP(OCH)3)2]3

C5H10N

3. (NPCl2)3————————[(NP(C5H10N)3)2]3

PhMgBr

4. (NPCl2)3————————[(NP(ph)2]3

KSO2F

5. (NPCl2)3————————[(NPF2]3
 3000C

6. (NPCl2)3————————{(NPCl)2)}3

Bonding in Phosphonitrilc Compounds : An Overview

The extent of delocalization, nature of bonding and aromaticity has been

debated for many years.Carbocyclic compounds like benzene involving (d-p)
bonding obey Huckel’s rule . Unlike benzene cyclophosphazenes involve (d-p)
bonding.The bonding in polyphosphazenes is best described by two models
,namely Criag and paddock Model and Island (Dewar ) Model.

According to Criag and paddock model.the bonding involved in cyclic

polymers has alternate P an N atoms ,which can best be described by used of
hybrid and atomic orbitals.

The electronic configuration of P atom is

(Ground State )

(Excited State )

They hybridization on P atom is sp3 and the four lobes are directed towards four
corners of a tetrachdron.

The electronic configuration of P atom is

(Ground State )

(Excited State )

The hybridization in N atom is sp 2 and the three lobes are disposed triangular in
grometry .One sp2 hybrid orbital orital out of three contains one nontaining an
electron .Two of sp3 HOs of P atoms are uned informing exo - cyclic bonds with
the substituents while remaining two sp3 HOs are used in forming ring bonds
with two adjacent N atoms which use sp2 hydrid orbitals .Thus a ring structure
results with substituents lying opposite sides of the ring.The remaining two
orbitals on N an sp3 HO containing lone pair of election in the plane of ring and
a.p.atomic orbital (unhybridized ) containing an unpaired electron in a plane
perpendicular to the ring plane are available for bond formation with 3 d orbitals
of phosphorus.Thus two mutually perpendicular systems are present in the
phosphazene , the first in the ring plane and the second perpendicular to this plane.
A system in the plane of a phosphazene ring is derives from sp 2 HOs of N and
dx2-y2 orbital on P atoms (Fig 3.1 ) However dxy is also known to contribute is
bonding (See Fig 3.2 ) the sign of wave functions of combining orbitals is same for
both the situations therefore the system is called homomrphic system.

Another system ( heteromorphic ) located in the plane perpendicular to

phosphazene ring is derived chiefly from pz ss (unhybridized) atomic orbital of N
and dxz orbital on P atoms .(However , dyz is also known to contribute in
bonding ) pz – d xz type of overlap has a node due to inevitable mismatch in the
sign of orbital wave function which reduces the stability of delocalized system
(Fig 3.3 ) such type of system is called heteromorphic system.(In a delocalized
ring system the orbital should be inverted in symmetry in pairs tohave minimum
energy since P orbital is symmetric .In pz –dxz the nodes are introduced between
each pairs of d and p orbitals which represent a confinement and thus high energy
.However pz –dyz type of overlap do not give nodal surface (Fig 3.4)

Another approach to explain pi bonding is called Inland approach (Dewar

model ) It considers the hybridization of d xz and d yz orbitals to give two hybrid
orbitals which are directed towards the nitrogen atoms in the palne so that
formation of three centre bond about each N atom could occur.This type of
bonding gives a node at each O atom since two .See Fig 3.5 Both the theories
predict the presence of delocalized system which imparts stability to tetramer.

Localized d p orbital extends over whole structure of rings P being more

electropositive than N has partial positive charge while independent of ring size
and of equal length but shorter than that of single bond .Presence of negative
substituents on P makes d orbital more compact favouring lateral overlap.The
problems regarding d p p p bonding occurs and rings are planar .The
presence of two mutually perpendicular systems have approximately cylindrical
symmetry as in acetylene therefore they have little resistance to tortional motion
they are flexible and have temperature coefficient of viscosity .
 Geometrical isomers are exhibited due to different ways of distribution of
attached groups above and below the ring or bonded singly or in [airs to
phosphorus. (i.e. P atoms are unsymmetrically substituted ) Tetramer like (NPF2)
4 is approximations planar hexagonal and exhibit a considerable range of
conformations like tub , crown saddle ,planar boat chair etc of which boat (K-form
) and chair (L-form) are important .See fig 3.6

While for (NPMe2)4 and {(NP(NMe2)2)}4 only boat from is observed .For
P6N7Cl9 a fused ring structure is observed which is non planar.

Most of the cyclic phosphonitrilic polymers are crystalline.

(b) Properties :

Phosphazene have some interesting properties over carbon basedpolymers .

1.A trimeric polymers with bulky substituents at N can bemade in vatious
forms like elastomers plastic films and fiber .The materials show
flexibitliy even at low temperatures.Theyhave excellent water resistant
and fire resistant properties.

2. Some of the fluoro alkoxysubstitued phosphazenes are execellent water

repellant so that they do not interact with the living tissues .

3. Cholorophoshazenes extensively get cross linked on heating to a rubber

like polymer (n = 15,000) However, this is susceptible for nucleophilic
attack and displacement. .If is soluble in common organic solvents.
4. Poly phosphazenes can be attached to drugs steroids and act as a slow
drug releasing agents in human body due to their hydrolytic instability
 .The slow hydrolyses would provides these frugs in a therapeutic steady
state.

5. Most of the phosphazene polymers are having useful optical electrical

and thermal properties.

(C) Applications :

The Commercial applications are not as well established as silicones

.Some of the important applications are given below.
1. Fluoro alkoxy sunbstituted phosphazenes ,due to their excellent water
repellant properties find use in making the artificial blood vessels and
prosthetic devies.
2. Polyphosphazene attached to durgs , steroids can be used as a slow
drug releasing agent in human body.The slow hydrolysis of
phosphazenes linked to drugs antibiotics ,steroids would provide
these drugs in therapeutic steady state.
3. Poly (phosphazenes ) are being explored for use as precursors to
produce ceramics.

QUESTIONS

(A)Objective Type Questions

1.Select the most appropriate alternative for the following :

i) A polymer contains a number a number of …………..joined together

via covalent bonds .

(a) Simple molecules (b) big molecules (c) monomer (d) atoms

ii) Monomers having at least …………..functional group is only capable

to forming polymers. .

(a) two (b) three (c) one (d) four

iii) The process by which thousands of monomers of the same of different

kinds are joined together is called …………..reaction.
 (a) addition polymerization (b) condensation polymerization

(c) chain polymerization (d) polymerization

iv) Normally …………..bond is present in a polymer .

(a) ionic (b) covalent (c) co-ordinate (d) hydrogen

v) The basic structural chainin an inorganic polymers is made up of …. .

(a) C-C linkages only (b) C-H linkages

(c) non-metals ,metals excluding ‘C’ (d) metals only

Vi ) …………..polymerization incolves three distinct steps viz. initiation

propagation and termination .

(a) Condensation (b) Addition (c) Chain (d) Ring opening

vii) The …………..polymer offers agreater resistance to oxidation and

pyrolysis.

(a) natural (b) synthetic (c) organic (d) inorganic

viii) An example of thermosetting polymers is …………..

(a) Nylon (b) Polyethylene (c) Bakelite (d) PVC

xi) Homoatiomic Polymer contain the skelecton of ……………in the

backbone .

(a) same kind of atoms (b) different kind of atoms

(c) carbons only (d) non metals only

x) A …………..modification of P contains discrete P4 tetrahedra .

(a) Orthorhombic (b) red (c) black (d) white

xi) …………..were the two who placed the polymer chemistry on the
firm footing .

(a) Staudinger and corothers (b) Friedal and Craft

(c) Liebig and Stokes (d) Criag and Paddock.

Xii ) The backbones in fluorocarbons consist of structural units of

…………..

(a) –C-C (b) F-F (c) C-H (d) –C-F

xiv) Silicone …………..retains its flexibility in – 900to 1500C temperature

range.

(a) rubbers (b) resins (c) fluids (d) compounds

xv) Fluorocarbons are obtained by fluorination of appropriate alkene is

presence of …………..

(a) inert solvents (b) oxygen (c) nitrogen (d) vacuum

xvi) Phosphonitrilic polymers contain structural units of unsaturated

…………..

(a) –C-N (b) –B-N- (c) –P=N- (d) –P-C

xvii) The hybridization involved on P atom in phosphonitrilic polymer is

…………..

(a) sp3 (b) sp2 (c) sp (d) dsp2

{Ans : (i) –c .(ii) –a ,(iii) –d ,(iv) –b , (v) –c , (vi) –b , (vii) –d ,(viii)-c ,(ix)
–a ,(x) -d ,(xi) - a , (xii)-a,(xiii)-a , (xiv) – a , (xv) –c , (xvi) –c , (xvii) –a }

2. State whether the following statements are True of False :

(i) The first polymer substance was synthesized in 1920 by H

Staudinger.
 (ii) Bakelite is an example of copolymer.

(iii) Addition polymerization reaction accompany with formation of

byproducts like water KCL .NH3 etc.

(iv) Addition polymerization reaction requires an initiator to start

reaction.

(v) Monomers having more than two functional froups can also give
polymer.

(vi) A polymer containing –Si-Si –linkages is called homoatomic

polymer.

(vii) PTFE is an example of a heteroatomic polymer .

(viii) C –F bond is fluorocarbons have greater energy .than C- C bonds.

(ix) Cyclic tetramer of siloxane is quite stable.

(x) Cyclophosphazene involves d p boning between P an N.

{Ans : (i) – T (ii) –T ,(iii) –F ,(iv) –T , (v) –T , (vi) –T , (vill) –F , (ix) -

T , (x) -T }

3.Fill in the blanks with proper word.

(i) The –C-F- bond energy is ……………..kj/mole

(ii) A……..modification if P is amorphous with a high degree of

polymerization.

(iv) A………modification of P contains the corrugated layers made up of

two halves separated by 228 pm distance.

(v) PTFE is ……………..

(vi) The polymers containing –Si-O-Si – linkages are called ………

(vii) The Si-O bond is more stable than C-O bond by about ……kj/mole.

(viii) Trimeric (PNCl2)3 was first synthesized by …….in 1834.

{Ans : (-480, (ii) – (CH2-CF2)n , (iii) – red , (iv) – black , (v)

Polyterafluoroethylene , (vi) – siloxanes , (vill) -98 , (viii) – Liebeg }
4.Define the following :
(i) Polmerization reaction (ii) Inorfanic polymers

(iii) Monomers (iv) Addition polymers

(v) Condensation polymerization

(vi) Polymer backbones (vii) Homoatomic polymers
(viii) Heteroatmic polymer (ix) Florocarbons

(x) Silicones (xi) siloxane

(xii) Phosphonitrilic polymers.

5.Match the following :

1) Polyethylene (a) Synthetic fibers
2) Bakelite (b) Thermoplastics

3) Nylons (c) Poly tetrafluoroethylene

4) –C-C – linkages (d) Thermosetting plastics

5) –Si-O- linkages (e) polysiloxane

6) –Si-O-Si- linkages (f) polyvinlinylidine fluoride

7) (RP)n (g) Monomers

8) (CF2 –CF2)n (h) Cyclo polphosphines

9) Cotton (i) Heteroatomic polymer

10) (CH2-CHCl)n (j) Natural polymer
 11) CH2=CHCl (i) Homoatomic polymer

{Ans : 1-b,2-d,3-a,4-k,5-I,6-e,7-f, 8-c,9-j,10-h 11-g}

(B) Short Answer Type Questions

1. What are polymers ? Comment on the number of functional groups

required for a monomer in order to get linear and crosslinked polymers .

2. What do yo mean by the term polymerization ? Explain addition

polymerization reaction with suitable example.

3. What are inorganic polymers ? How are they superior to organic

polymers

4. What is polymer backbone ?Give the types of polymer backbones.

5. Distinguish between :

(i) Organic polymers and Heteroatomic polymers.

(ii) Homoatomic backbone and Heteroatomic backbone=

(iii) Thermoplastics and Thermosetting polymers.

(iv) Homoatomic polymers and Heteroatomic polymers.

6. Outline in brief the classification scheme of polmers.

7. What are fluorocarbons ? Give preparation and uses of polyvinyl

fluoride.

8 .What is PTFE ? Mention important properties and uses of PTFE.

9. What are silicones ? Give nomenclature system of silicones with suitable

examples .

10 .Give various methods used to prepare intermediates required for synthesis

of silicones.
11. What are siloxanes ? Dis cuss any one method of preparation.

12 What are various allotropes of phosphorus ? Comment on their

structures.

13. What are cyclic silicone tetramers ? How can we use them for
synthesis of silicone polymers ?

14. Discuss in brief the types of silicones .

15. Descrube bonding present in phosphonitrilic polymers on the basis

of criag and paddock model.

16.Give reasons :

(i) Fluorocarbons are prepared by controlled fluorination reaction.

(ii) Fluorocarbons are homoatomic polymers.

(iii) Phosphponitrilic polymers contain structural units of unsaturated –

N=P- linkages.

(iv) PTFE is stable even at high temperatures.

(v) Organic nitriles R-CN are not considered as organic polumers.

(C) Long Answer Type Questions

1. What is meant by the term polymer? Discuss various type of

polymerization reactions with suitable examples.

2. What do you mean by backbones ? Discuss various methods of

illustrative examples the types of backbones.

3 What are fluorocarbons ? Discuss various methods of preparation

of polyvinylidine and polyvinyl fluorides .Why the preparation is
always carried out in an inert atmosphere?

4. What is PTFE? Describe the preparation properties and uses of PTFE.

5. What are the methods of preparation of linear and crosslinked
silicone polymers ?
6. What are phosphontrilic polymers ? Describe the mechanism of
cyclic phosphonitrilic chloride formation. .How these are useful for
preparation of linear polymers?
7. Discuss the structure and bonding present in cyclic phosphonitrilic
polymer on the basis of Dewar model.