SILICONE POLYMERS: SYNTHESIS OF SILLY PUTTY

: Cross-linked [(CH
3
)
2
SiO]
x
1



Chemistry 2400 Experiment 2 Bowdoin College, 2014

Background
2 ,3



Silicon and its many compounds can be found everywhere, from the sand on the beaches, to
the cement in the sidewalks, to the microprocessor chips in computers, to the Silly Putty

available in most toy stores. Approximately 25% of the earth's crust contains silicon in its
various compounds, mainly as silica and silicate minerals, (SiO
4
4
tetrahedra, linked through
the oxygens to other silicons, with metal ions such as Na
+
, K
+
, Ca
2+
, Mg
2+
, Al
3+
, Fe
2+
, etc., to
balance the charge). Variations in cations and the linkage of the tetrahedra result in different
structures, from the plates that mica forms to the complex 3-D linkages that make up feldspar.
Most of the common minerals, including gemstones, are silicates. Clays (weathered minerals)
result from loss of some of the cations that help to bind together the SiO
4
4
tetrahedra. Silica
(sand, quartz) has the empirical formula SiO
2
, but in fact exists as a covalently bonded network
of Si and O atoms, each Si bridged by 4 O atoms to still more Si atoms (see Chang, Covalent
Crystals in Sect. 11.6 and Table 11.4, and on Blackboard, Greenwood and Earnshaw, 364-366).
SiO
2
is more properly written as (SiO
2
)
n.


Historically, silicon compounds have been used since the Stone Age, when humans made tools,
ceramics and weapons out of silica. However, the actual element Si, was not identified until
1823. Silicon is a member of the carbon family of elements, and is often called a metalloid. A
metalloid is a compound that looks like a metal but does not possess the physical and chemical
properties of a metal. Because of the position of silicon relative to carbon, much of the early
work with silicon was modeled after organic chemistry.


J. Berzelius (1779-1848) performed much of the early chemistry of silicon by reacting crude
silicon with halogen gases as shown in Equation 1:


Si + 2Cl
2
! SiCl
4
(1)


In 1854, F. Whler set out to synthesize silane, SiH
4
, the silicon analog to methane. One of
Whler's major curiosities was whether the biochemistry of living creatures was actually based
on silicon rather than carbon as was believed at the time. Whler succeeded in synthesizing
silane, and found silane had similar properties to methane. However, a major difference
between the two compounds was that silane slowly reacted with water to form SiO
2
as shown
in Equation 2, while CH
4
is inert to water.

SiH
4
+ 2H
2
O ! SiO
2
+ 4H
2
(2)


The results of this experiment confirmed that the biochemistry of living creatures on Earth is
based on carbon! Who knows about life on other planets. One Star Trek episode postulated a
life form based on silicon.

As new silicon compounds were synthesized and studied, many differences were found

1

Szafran, Z.; Pike, R. M.; Singh, M. M. Microscale Inorganic Chemistry: A Comprehensive Laboratory Experience; Wiley: New York, 1991; pp 176-181.


2

Rochow, E. G. Silicon and Silicones; Springer-Verlag: Berlin, 1987.


3

Stark, F. O.; Fallender, J. R.; Wright, A. P. In Comprehensive Organometallic Chemistry; Wilkinson, G.; Stone, F. G. A.; Abel, W. Eds.; Pergamon:
Oxford, 1982; Vol. 2, p 305.


2
between silicon and carbon analogs. For example, silicon and oxygen have a strong affinity for
each other and form very strong chemical bonds. Silicon is also very reactive at high
temperature, yet slow to react at room temperature. Most importantly, the covalent
compounds formed of silicon and hydrogen or halides were not stable toward air or water like
covalent compounds of carbon. This reactivity of silicon is due to its large size which allows it
to expand its coordination number above four, even though many silicon compounds are only
four coordinate. In fact, the geometry of (SiO
2
)
n
is tetrahedral, with silicon in the center and
four oxygen atoms at the corners of a tetrahedron, each oxygen bridging to another silicon.


The strength of the Si-O bond, 466 kJ/mol, is greater than expected for a single bond between
these atoms. X-ray crystallography data shows relatively short Si-O bond lengths. Only
recently has the first compound containing an Si=Si bond been synthesized, in contrast to the
many well known alkene (C=C) and alkyne (C=C) compounds of carbon.
4

In 1865, C. Friedel and J. Crafts synthesized the first silicon compounds with organic groups
directly attached to the silicon center. Unlike the halogenated compounds synthesized by
Berzelius, tetraethylsilane, Si(CH
2
CH
3
)
4
, was found to be stable in both air and water. A
comparison of SiCl
4
with Si(CH
2
CH
3
)
4
shows that the presence of electron-donating (ethyl)
groups attached to the silicon results in thermally stable and inert compounds, while electron-
withdrawing (chloro) groups result in more reactive silicon compounds.


F. S. Kipping was the next chemist to devote his career to the study of silicon compounds.
Even though the chemistry of carbon and silicon often differed, Kipping was determined to
continue to synthesize, study and compare silicon compounds with the analogous carbon
compounds. Kipping's research focused on preparing halo-organic silicon compounds. With
the use of Grignard reagents (product of reaction 3 below), Kipping succeeded in his task as
shown in Equations 3 and 4 below.


Mg + CH
3
CH
2
Br !

CH
3
CH
2
MgBr (3)


2CH
3
CH
2
MgBr + SiCl
4
! (CH
3
CH
2
)
2
SiCl
2
+ 2MgBrCl (4)


The synthesis resulted in a mixture of productsmono-, di-, and tri-chloro-substituted silanes.
Repeated distillation of the resulting oily solution gave the desired product. After isolating
(CH
3
CH
2
)
2
SiCl
2
, Kipping found it easily hydrolyzed in water to form (CH
3
CH
2
)
2
Si(OH)
2
,
silicohol. Kipping was hoping that loss of H
2
O from silicohol would yield (CH
3
CH
2
)
2
Si=O,
analogous to a ketone, but the products were always linear or cyclic polymeric silicon
complexes as shown in Figure 1. Even though the resulting polymeric products were not
ketone analogs of silicon, Kipping (circa 1901) called them silicones. They are more properly
named organopolysiloxanes, or just polysiloxanes.


The next major breakthrough in silicone chemistry was made by J. F. Hyde of Corning. Hyde
synthesized ethylphenylsilicone, similar to the polymers shown in Fig. 1, where R represents
ethyl and phenyl groups. Hyde found that above 200 C, the ethyl groups were oxidized by air
and replaced by oxygen, resulting in cross-linked polymer chains as shown in Fig. 2.

4 West. B. Pure Appl. Chem. 1984, 56, 163.




3


Figure 1. Linear and cyclic silicone polymers. (R = methy, ethyl, phenyl)


This new silicone polymer bound to glass fibers was called Fiberglass, and is used
extensively today as insulation for wires, motors and generators. The synthesis of these
compounds still posed some problems as the use of a Grignard reagent generated a mix of
products in the formation of the halo-organo silanes, and the hydrolysis of the silane gave
many linear and cyclic silicone polymers, which could be separated only by careful distillation .

Another major breakthrough in silicone chemistry occurred in 1940 when E. G. Rochow
developed the synthesis of methylsilicone without the use of a Grignard reagent as shown in
Equations 5 ( (CH
3
)
2
SiCl
2
, dichlorodimethylsilane product), 6 (hydrolysis of silane to silicohol
monomer), and 7 (polymerization of silicohol to linear silicone polymer with terminal OH
groups). Reactions 6 and 7 tend to occur simultaneously, as the heat of the hydrolysis causes
polymerization to occur. A monomer unit is added to a chain by losing an H from the chain
and an OH from the monomer, forming H
2
O.



(5)

(CH
3
)
2
SiCl
2
+ H
2
O ! (CH
3
)
2
Si(OH)
2
+ heat (not balanced) (6)


x (CH
3
)
2
Si(OH)
2
+ heat ! HO[(CH
3
)
2
SiO]xH + x-1 H
2
O (7)


Si
R
R
O
x
Si
R
R
HO O Si
R
R
OH
O
Si
O
Si
O
Si
R
R
R
R
R
R
R
2 CH
3
Cl + Si

(CH
3
)
2
SiCl
2
+ heat

Cu
300
o
C


4
Methylsilicones are the major silicones in use today. Much of the flexibility of silicones is due
to the weak intermolecular attractions between neighboring methyl groups.
5
Linear silicone
polymers of low molar mass with a Si(CH
3
)
3
group in the terminal position instead of OH are
called silicone oils. These silicone oils are waterproof, have a wide melting point range and
exhibit little change in viscosity with varying temperature. Silicone oils are used in lotions,
cosmetics, varnishes and the food industry, and also as the liquid phase in many GC columns.
Longer chain silicon polymers are called silicone resins. Silicone resins are high molar mass
compounds with a rigid body used for electrical insulation, coatings for engine parts,
lamination of mica and paint additives to protect steel structures. Finally, silicone elastomers
(rubber) are silicones of very high molar mass that are strategically cross-linked to provide
flexibility to the material over a wide range of temperatures. Silicone rubber is used in many
rubber parts, including tubing, O-rings, catheters and implant material for medical purposes
and parts that are in contact with food. Because Si is believed to be non-toxic, silicon
compounds are widely used in the food and medical industry. There is some controversy
surrounding the use of silicone rubber as breast implant material, however.


In today's lab, you will investigate the chemistry of silicones by synthesizing Silly Putty, a
bouncy, stretchy crosslinked silicone polymer. You will start with dichlorodimethylsilane,
hydrolyzing it at reflux (solvent is boiling and recondensing) in diethyl ether to form the linear
silicone polymer (reactions 6 and 7, product of 7 looks like linear polymer in Fig. 1 with R =
CH
3
, see also Polydimethlsiloxane, p. 366 of Greenwood and Earnshaw, on BB). The linear
polymer can be represented as HO[Si(CH
3
)
2
O]
x
H. Once the hydrolysis and polymerization are
finished, the HCl generated is neutralized with aqueous sodium hydrogen carbonate,
NaHCO
3
. The linear polymer is extracted into the ether layer. The ether/polymer solution
layer is dried and any ionic species (Na
+
, Cl

, HCO
3

) are removed by passing the solution

through a column of silica gel and sodium sulfate. The ether is evaporated, leaving pure liquid
linear polymer. Addition of boric acid, B(OH)
3
, with heating will generate -O-B(OH)-O-
linkages between silicons in adjacent chains by displacing CH
3
groups, forming a gummy resin
known as Silly Putty

. (It will not break the very strong SiO bonds - think quartz.) This
would be similar to Fig. 2 with R = R' = CH
3
and OB(OH)O linkages instead of oxygen from
air (O" in Fig. 2). Assuming one boric acid links 2 Si atoms (one in each chain), for each such
linkage, a CH
3
group is lost from a silicon in each chain, an H atom is lost from each linking
OH of B(OH)
3

and the OB(OH)O linkage forms a bridge between the two Si atoms. The
formula of Silly Putty is best represented as HO[Si(CH
3
)
2
O]
x
H chains crosslinked at
intervals by OB(OH)O linkages between 2 Si (with loss of one CH
3
per Si linked) but see
Question 2 at end.

Terms to know for this experiment:
Network compound (covalent solid), polymer, hydrolyze, viscosity, elute (verb), eluate (noun)


Before you come to lab (write out in notebook) - Heading, Purpose, Chemicals, Reference.

! Consult the Safety Data Sheet (SDS) for Dichlorodimethylsilane on Blackboard. ! Find its
CAS number. ! In the Hazards Identification Section, list the OSHA Hazards and the GHS
classifications and categories. Go to http://www.osha.gov/dsg/hazcom/ghs.html, then scroll

5
Rochow, E. G. Modern Descriptive Chemistry; Saunders: Philadelphia, 1977.




5
to Sections 3.1 and 3.2. ! For each of the GHS classifications and categories assigned for this
chemical, record what the classification/category means (e.g., Acute Toxicity, Inhalation (use
Gases), Cat. 1 means it has an LC50 of ! 100 ppm). ! From Section 10 of the SDS, list the
Conditions to Avoid. ! Which one of these conditions do we actually use with the
dichlorodimethylsilane in the experiment?

! Write the neutralization reaction between HCl and NaHCO
3
. ! Why are bubbles produced?


! Look up the mass density (g/mL) of (CH
3
)
2
SiCl
2
, dichlorodimethylsilane. Cite reference (in
the Aldrich catalog, the density value is preceded by "d"). ! From the volume used (see
Procedure), what amount (in moles) is used? ! How many moles of Si is this? All other
reagents are added in excess. ! What is the theoretical yield of linear polymer? (one mole of
Si yields one mole of (CH
3
)
2
-Si-O-, the polymer unit, with MM = 74.1 g per unit - terminal H,
OH may be ignored (there is 1 of each for X (CH
3
)
2
-Si-O-) units and X is very large).


! Boric acid is added to the linear silicone polymer in a 1:20 mass ratio. This comes to a 1:16.7
mole ratio of B(OH)
3
to (CH
3
)
2
-Si-O- (B to Si). ! If we assume the role of boric acid is to tie
two chains of [-(CH
3
)
2
-Si-O-]
x
together by bridging 2 Si atoms, is there enough B(OH)
3
to link
all the Si atoms (for every 16.7 Si in the ratio above, how many Si are bridged)? ! What does
this tell you about the frequency of the Si-O-B(OH)-O-Si linkages?

! Read Chang Section 11.6 and Table 11.4, and the section on Compounds in the Language
of Chemistry (LoC) document on Blackboard. ! Sketch the structure of solid (SiO
2
)
n
. !
Each Si is bonded to how many O? ! Sketch the structure of CO
2
.
! Each C

is bonded to
how many O? ! State 3 physical properties of quartz and carbon dioxide that demonstrate
their differences (see Chang, Table 11.4). ! Relate the differences in the properties of (SiO
2
)
n

(e.g., quartz) and CO
2
to the differences in their structures. Hint - what is the "basic structural
unit" of each compound?


! Sketch the following 3 setups in your notebook.


water in
water out
water-jacketed
condenser
round-bottomed
flask
magnetic
stir bar
stir motor
Apparatus for reflux reaction
Column chromatography
sodium
sulfate
silica
collect
ether
beaker
of
warm
water
Apparatus for evaporating
ether.
Nitrogen in


6
POST LAB WRITING
Informal Section in Notebook see Lab Guide, p. 7 need 1a, 1b (characterization results)
and 3 no discussion (pretty much covered by questions (below). Also a couple of items at the
end of the Procedure handout.

Questions answer in notebook (dont need to rewrite question, just number and answer).

1. The prelab exercises assumed that each B(OH)
3
was linking two Si in two linear polymer
chains (SiOB(OH)OSi bridges). ! Draw the structure showing two chains linked in
this fashion You may use zigzag lines (backbone) for structures but write in the Si, O and B
atoms. ! Would all the links on these chains necessarily be to the other chain (ladder-
fashion)? ! What else could happen?


2. ! What did we assume each B(OH)
3
is displacing from each chain in order to link them?
! What does the B(OH)
3
lose? ! What unused group is left on the B? ! Could this group
react similarly? ! How would that affect the frequency of SiOBOSi linkages (the number
of linked Si)? ! From our results, can we tell which has actually happened?


3. ! What do you think might be different about the product if too much B(OH)
3
was added,
assuming it all reacted? ! Explain.


4. ! Look up dilatant at www.nationmaster.com/encyclopedia/Complex-fluid. Under
Power-law fluids, what are the properties of dilatant materials? Click the dilatant link and
record what this means (in plain English) for Silly Putty

.


5. ! What feature makes the linear polymers soluble in ether and insoluble in water (this is
one of the reasons Silly Putty is waterproof)? ! Why? (Hint: Examine the intermolecular
forces between the outside atoms of the polymers and 1) water and 2) diethyl ether. Review
LoC/Solubility and InterpretData (both on Blackboard).

Recommended more on Silly Putty

go to http://people.howstuffworks.com/silly-putty2.htm
http://www.ehow.com/about_5512818_silly-putty-experiments.html
http://chemistry.about.com/od/everydaychemistry/a/sillyputty.htm - can you find a
(probable) error in How Silly Putty Works (related to its insolubility in water)?

If you look at these, does the information confirm or conflict with any of your observations
(give an example).

FORMAL SECTION - Experimental Methods see Lab Guide p. 8-9. See example in
NotebookReportExamples on Blackboard. Do not need to include reactions. Be sure to relate
your observations to the chemistry that is occuring.