Experiment 2: Inorganic Polymers

CH3500: Inorganic Chemistry, Plymouth State University

Adapted from "Inorganic Polymers," Chemistry Across the Periodic Table : Chemistry 311 Laboratory Manual, Chad C.
Wilkinson, University of Wisconsin at Madison (2010).

Introduction:
Silicones are a class of inorganic polymer with the general formula
[R2SiO]x. The name silicone was applied to these compounds by Wohler in
1857 because their empirical formula is analogous to that of organic ketones,
R2CO. The similarities between these two classes of compounds do not extend
farther than their names, however. Ketones are discrete molecules wherein the
group IV atom (carbon) is double bonded to a single oxygen. The valence p-
orbitals of silicon do not lie at an energy level that supports -bonding to
oxygen. Therefore, SiO bonds are single bonds, not double bonds. There is
extensive silicon oxygen single bond chemistry that leads to network solids
called silicates. Silicate minerals, where each silicon atom is bonded to 4
oxygen atoms, are among the most abundant materials on earth. Figure 1:
Silicones, more properly named as organopolysiloxanes, are formed by dichlorodimethylsilane
hydrolysis and polymerization of dialkyldichlorosilanes such as
dichlorodimethylsilane (Figure 1). The term silane refers to the molecule SiH4 and is derived from
the ane suffix applied to the alkane carbon analog. When treated with water, the chloro substituents
are hydrolyzed off and replaced by hydroxyl substituents (Reaction 1).

Reaction 1: Hydrolysis of dichlorodimethylsilane

The silanol molecules then condense of their own accord to produce chains or rings (Reaction. 2).

Reaction 2: Polymerization of silanols

Compared to other polymers you may be familiar with, this polymerization process generally
results in shorter chained molecules, producing an oily substance. The properties of this silicone oil
can be adjusted by changing reaction conditions, using monomers with different alkyl side chains, and

Copyright Plymouth State University and Jeremiah Duncan. May be distributed freely for education purposes only. 1
adding cross-linkers, resulting in polymers of varying side chains, chain length, branching, and cross-
linking.
Hydrolysis of dichlorodimethylsilane in dilute ether solution gives good yields of small, cyclic
polysiloxanes (3 6 units), which can then be cross linked by heating in the presence of boric acid,
B(OH)3. The boric acid carries out condensation reactions with the hydroxyl terminus of any linear
chain polymers. Upon heating and treatment with acids or bases, the ring polymers undergo an
equilibration process where the Si-O bonds open and re-form as the system attempts to reach the most
thermodynamically stable state (in terms of the ring size distribution). Boric acid molecules react with
these open Si-O linkages, causing the rings to revert to chains. Since each boric acid molecule can bond
to three separate silicone chains, a network structure called a silicone gum--essentially the same as the
silly putty you can buy in a toy store.
In this lab, you will synthesize and investigate the properties of a silicone polymer gum. You may
take your sample of silicone gum home with you, but remember the admonition that appears on the
packages of silly putty in the stores: Do Not Eat!

Safety Considerations:
Dichloro-dimethylsilane is air sensitive. Perform any manipulations with it quickly and in the
hood.
Do NOT dispense volatile liquids (i.e. ether or dichloro-dimethylsilane) outside the hood
HCl gas is generated in the initial step. Perform this step in a hood, and keep your head out!
Properly dispose of organic solvents (e.g. ether) in the Organic Waste container.
Dispose of dichlorodimethylsilane in Halogenated Organic Waste

Procedure
You will work with a partner for this lab. You may wish to divide up the tasks!
Remember to record what you do (including exact masses weighted out), data collected, and
observations at each step in the procedure.
A. Reaction to Produce Silicone Oil
1. Assemble a reflux apparatus in the hood on top of a 250 mL round bottom flask. Remember:
water in the bottom, water out the top.
2. Position an ice/water bath on top of a magnetic stirrer so the round bottom flask sits inside the
bath.
3. Raise the condenser and measure 40 mL of diethyl ether (graduated cylinder) into the flask. Add
a magnetic stirring bar
4. Using an air-free syringe and proper air-sensitive techniques, measure out and transfer 20 mL of
dichlorodimethylsilane into the flask. Re-attach the condenser. Note: Dichloro-dimethylsilane
is air sensitive. You will be shown the proper technique for handling this material in lab.
Perform this transfer quickly but carefully!
5. Begin rapid magnetic stirring.
6. Measure 40 mL of deionized water (grad. cylinder). Proceed to add the water dropwise (slowly
at first) through the top of the condenser using a pipet. (Note: The reaction is exothermic
enough to cause the ether to boil the reflux condenser will minimize solvent loss, and the ice

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 batch should act as a heat- sink, but monitor the temperature of the flask to make sure that you
do not boil the ether.) The first 20 mL of water should be added over the course of ~10 mins.
The remaining 20 mL can be added over ~5 mins. ). HCl gas is generated as a reaction by-
product. Keep your head out of the hood!
7. Continue stirring for 10 minutes after adding all the water. Use this time to
a) Prepare your vacuum filtration setup see below.
b) In a hood in the Gen Chem lab, turn on a hotplate and adjust it so that a small beaker of
water will remain at approximately 45C. One hotplate may be set up for use by several
groups.
c) In a hood in the Inorganic Chem lab, turn on a hotplate and adjust it so that a small beaker
of water will remain at approximately 75C. You will use this hotplate exclusively.
B. Neutralization
1. Once the flask is cool to the touch, remove the condenser and transfer the contents of the flask to
a separatory funnel. Remove as much of the aqueous (lower) layer as possible. (Caution this
waste material will be acidic and should be properly disposed of).
2. Run the ether portion back into the reaction flask. Do not worry if some water remains. Reattach
the condenser to the flask and begin stirring. Measure out ca. 20 mL of 10% sodium bicarbonate
solution. Add the bicarbonate solution dropwise through the condenser until bubbling stops. The
bicarbonate will neutralize any residual HCl in solution. This reaction produces CO2 gas, so the
reaction mixture will froth. Add the bicarbonate slowly enough to prevent the froth from
reaching the top of the flask.
3. Remove the condenser and return the reaction mixture to the separatory funnel. Remove the
aqueous layer. Test this aqueous solution with pH paper to determine whether it is acidic.
4. Repeat the neutralization step in the separatory funnel until the pH paper tests neutral or slightly
basic. Be sure to vent the funnel during the initial swirling after each addition of bicarbonate
solution.
5. Once the aqueous portion tests neutral or basic, add 30 mL of deionized water to the ether
solution, shake and vent the funnel, then remove the aqueous layer. Get as much of the water
out as you can. At this point it is better to lose a few drops of ether than keep a few drops of
water.
6. Continuing to work in the hood, transfer the ether layer to a 250 mL beaker. Dry the ether
solution by adding anhydrous sodium sulfate. Add a spatula-full at a time, then swirl. The
solution is dry when newly added sodium sulfate no longer appears to clump.
7. Decant the liquid portion into a beaker. Add a 10 mL portion of ether to the sodium sulfate, stir
with a stirring rod or spatula, allow the solids to settle, and decant again. Add this rinse to the
ether portion already recovered. Do not be concerned if a little solid sodium sulfate is
transferred too; any solids will be filtered in the following steps.
8. Place the beaker containing the sodium sulfate in a hood and allow it to sit there until the end of
the lab period. This allows the remaining ether to evaporate away. Dispose of the waste sodium
sulfate in the solid chemical waste container.
9. Set up a vacuum filtration apparatus using a 500 mL vacuum flask in ice as a vapor trap, a 250
mL vacuum flask to collect the filtrate, and a 30 mL medium porosity glass fritted filter funnel.
Secure the 250 mL flask with a ring stand and clamp.

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 10. Add about in of diatomaceous earth or silica gel to the filter.
11. Add your reaction solution (Step 7) to fill the filter funnel about halfway. Stir or swirl the
funnel to get an evenly distributed slurry.
12. With both lab partners working in unison, turn on the vacuum and begin pouring the rest of the
reaction solution into the filter funnel. To the extend possible, pour at a rate that maintains the
liquid level in the funnel. Try not to let the funnel run dry until you have poured all of the
solution through it.
13. Rinse the beaker twice with a minimal amount of (<10 mL) of ether and filter the rinses
through the funnel.
14. Let the vacuum continue running for 30-60 sec to help dry the filter power. Then turn off the
vacuum in the following manner:
a) Carefully break the seal between the filter funnel and the vacuum flask. Remove the funnel
completely.
b) Turn off the vacuum. Using this sequence prevents the filtrate from splashing out of the
flask, prevents vacuum oil from being sucked into the filtration apparatus, and extends the
lifetime of the pump.
15. Weigh a clean, dry 250 mL beaker.
16. Pour the filtrate into the beaker. Rinse the vacuum flask twice with a minimal amount of ether
(<10 mL) and add the rinses to the beaker.
17. Place the beaker on the hotplate (previously heated to 45C) in a hood. Run a slow stream of
nitrogen over the surface of the solution to evaporate off the solvent. Once all the ether has
evaporated off (give it a sniff to ascertain this), leaving a clear oil, weigh the beaker.
C. Cross-linking the polymer
18. Measure out an amount of boric acid equal to 5% of the mass of your silicone oil.
19. Transfer your beaker to the 75C hotplate. Add the boric acid to the oil with stirring (glass rod)
for 5 minutes at ~70-80C. (Note: The boric acid may not dissolve well.)
20. Increase the temperature to ~120C for an additional 5 minutes with stirring. Increase the
temperature to ~175C. The mixture will bubble and begin to look crystalline. Use the glass rod
to scrape the bottom and sides, then allow the heating to continue until very little or no oil
remains. This takes approximately ten minutes.
21. Allow to cool for a few minutes. Scrape the product out of the beaker with the stirring rod; it
may appear crystalline and brittle at first, but kneading it with your fingers will convert it into
the putty consistency desired after a period of manipulation.

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Analysis (Lab Notebook)
The following must be completed in your lab notebook before you can turn in your Notebook Report:
1. Roll the putty into a ball and bounce it on a hard surface (be gentle, and watch it closely).
2. Pull the putty apart quickly. What happens?
3. Pull the putty apart slowly. What happens?

Analysis and Conclusions (Lab Report)

Your lab report is due by lecture a week from Friday, . Your report must be handed in BOTH
electronically (via Moodle) and in hard copy form. See the document "InorgChem-
LabReportGuide.pdf" on the course website for guidelines on writing your report.
1. Assuming all of the dichlorodimethylsilane and boric acid reacted, calculate the degree of cross-
linking in the polymer as a ratio of B to Si.
2. Discuss the properties of the silicone oil and the final product. Explain how cross-linking gives
rise to the change in properties.

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