APCH312 – Materials

Practical 4:
Synthesis and Properties of Polymers

Contents
Aim....................................................................................................................................... 2
Introduction .......................................................................................................................... 3

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Experimental ......................................................................................................................... 4
Part A- Free radical polymerization of styrene(phenylethene) ............................................ 4
Part B: Preparation of a synthetic rubber (Thiokol) ............................................................ 4
Observations/Results ............................................................................................................. 5
Questions .............................................................................................................................. 5
Discussion............................................................................................................................. 7
References ............................................................................................................................ 7

Aim
The sim of this experiment is to synthesis the polymers: polystyrene by a free radical
polymerization reaction and Thiokol by a condensation polymerization reaction. Thereafter
observing the products formed from these reactions.

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Introduction
Polymers are defined as macromolecules formed by a large number of smaller molecules, or
repeating units, termed monomers, that are chemically bonded together. [1] The chemical
reaction that converts monomers into polymers is known as polymerization. There are two
types of polymerization reactions and these reactions depend on the functional groups of the
monomer or the monomer itself used. The types of polymerization reactions include:
• Addition polymerization
A chain reaction, in addition polymerization (also known as chain-growth
polymerization), adds new monomer units to the expanding polymer molecule one by
one by breaking double or triple bonds in the monomer. There are three distinct
processes in the polymerization process: [Error! Reference source not found.]

1. Chain initiation— Typically, the polymerization process is started with the use of
an initiator. This reactive initiation molecule can be a radical (free radical
polymerization), cation (cationic polymerization), anion (anionic polymerization),
and/or organometallic complex (coordination polymerization).

Figure 1: Illustration of the Initiation step in Addition polymerization.

2. Chain propagation— Each new monomer unit adds on to the chain, creating an
active site for the next attachment.

Figure 2: Illustration of the propagation step in Addition polymerization.

3. Chain termination— The radical, cation, or anion is "neutralized," which prevents

the chain from continuing.

Figure 3: Illustration the termination step in Addition polymerization.

• Condensation polymerization
Also known as step-growth, involves the presence of two or more types of functional
groups that can react with one another in such a way that parts of these groups
combine to produce a small molecule (typically H2O) that is removed from the two
pieces. The two monomers' now-empty bonding sites can then be joined together. [3]

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 Figure 4: An example of a Condensation Polymerization reaction.

Properties of Polymers:
• Physical properties
The tensile strength of a polymer increases as chain length and cross-linking
increases. [4]
• Chemical properties
The polymer's flexible nature is due to the dipole-dipole bonding side chains. The
polymer is enabled with hydrogen bonding and ionic bonding, resulting in improved
cross-linking strength when compared to ordinary molecules with distinct side
molecules. [4]

Experimental
Part A- Free radical polymerization of styrene(phenylethene)
Reagents:
• Styrene monomer
• 4M NaOH
• Toluene
• Benzyl peroxide
• Alcohol

Method
10ml of the styrene monomer and 5ml of 4M NaOH were added to a test tube and was
vigorously stirred for one minute. When the solution in the test tube had separated into two
layers, the 5ml of the upper styrene layer had been removed and placed into a measuring
cylinder. The 5ml styrene was then transferred into a clean test tube where 10ml of toluene
was added and mixed, furthermore 0.3g of Benzyl peroxide was also added to the solution.
The test tube containing the solution had then been placed into a 200ml beaker that was half
filled with water. The beaker was placed onto a hot plate and the water had been brought to a
boil, heating had continued for approximately 50minutes. Thereafter, the test tube was
removed from the beaker and placed in a water bath to cool the solution. Once cooled the
solution had been poured into a 400ml beaker that had already contained 200ml of ethanol.
The white precipitate(polystyrene) that had formed on the addition of the solution to the
alcohol was then filtered and blotted dry between filter paper. Over a Bunsen burner a nickel
foil with a small amount of the filtered polystyrene was heated until the white powder had
melted, ensuring that it did not ignite. Once the sample had cooled, observations were
recorded.

Part B: Preparation of a synthetic rubber (Thiokol)

Reagents:

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 • NaOH
• Flowers of sulphur
• Ethylene dichloride (1,2-dichlorethane)

Method
In a beaker 2g of NaOH was dissolved in 50ml of water, afterwards on a hot plate the
solution had gently been brought to a boil. Thereafter,5g of flowers of sulphur was stirred in.
The beaker was removed from the hot plate once the sulphur had dissolved, and the solution
was then cooled in a water bath. The solution had been filtered by vacuum and the yellow-
brown filtrate was collected. To the filtrate 10ml of ethylene dichloride was added and the
mixture had then been heated to 80℃ on a water bath. This temperature was maintained and
the mixture was stirred continuously until white spongy lumps of rubber had separated out.
The excess liquid was filtered off and the rubber residue was washed with water. Any excess
water was squeezed out and the final product had then been observed.

Observations/Results
In Part A, when the white precipitate had been filtered, it had become a fine white powder.
This was then placed on a nickel foil and put over the flame of a Bunsen burner. When the
powder began to melt it became a transparent and viscous mixture similar to glue.

Whilst in part B, when the sodium polysulphides had ethylene dichloride added to it and had
been heated, lumps of white had begun precipitating out and floating towards the top of the
beaker, the more the solution heated the more formed. Once heating and filtration was
complete what was left behind was a semi soft and slightly flexible piece of rubber.

Questions
− Give the reaction for each polymerization carried out
In Part A of the experiment the formation of polystyrene is a Free radical (addition)
polymerization reaction. This reaction is illustrated in Figure 5 and involves the (a)
Initiation: which is the formation of radical that is induced by heat, followed by the
reaction of the radical with the styrene monomer. Thereafter (b) Propagation: which is
the addition of styrene monomers to the polymer chain as it grows, and lastly (c)
Termination: This is the combining or coupling of two radicals to destroy the growth
active centre.

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 Figure 5: Free Radical Polymerization of Styrene
In Part B, the preparation of Thiokol was a condensation polymerization reaction.

− What does the procedure used in Part A imply about the solubility characteristics of
polystyrene?
After the polystyrene had cooled after heating, it was added to 200ml of alcohol.
Where a white precipitate had formed, the white precipitate was separated from the
alcohol by vacuum filtration. As the polystyrene was able to be removed from the
alcohol this indicates that it was insoluble in ethanol. Most chlorinated and aromatic
solvents polystyrene can dissolve, whereas in alcohols it does not. Because
polystyrene is made up entirely of carbon hydrogen bonds, it is nonpolar and will only
dissolve in nonpolar liquids. [5]

− Considering its chemical composition and physical properties explain the function of
the sulphur in the preparation of Thiokol
Sodium polysulphide is made from sulphur and sodium hydroxide (Na2S8). The
elasticity of the rubber is determined by the amount of sulphur in the polysulphide.
The polymer will be elastic if the sulphur content of the polysulphide is equal to or
more than Na2S4; lower sulphur content results in a hard, brittle resin. [6]

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Discussion
In this experiment the polymers polystyrene and Thiokol were synthesised by the respective
free radical polymerization reaction and condensation reaction.

In Part A of the experiment which is the free radical polymerization of styrene, one of the
initial steps in the experimental procedure was to add styrene to sodium hydroxide, this was
done to ensure that the styrene was not contaminated with autopolymerisation by-products.
Therefore, to obtain good results washing with sodium hydroxide is required as it removes
stabilizers. Thereafter toluene which acts as a solvent is added to the pure styrene. The
purpose of using solvent in free radical polymerization is to 1) increase the solubility of the
polymer chain formed and 2) increase heat transfer in the reaction system to ensure that the
polymerization is more "uniform" in terms of molecular weight distribution than bulk
polymerization. Solvents should normally be inert and not a part of the reaction. Following
the toluene is the addition of benzyl peroxide, In the Addition polymerization reaction,
benzoyl peroxide aids in the generation of free radicals in the chain initiation stage, which is
the first step of the reaction. As a result, it functions as a free radical initiator catalyst. The
reaction is then terminated using ethanol as it prevents crosslinking.

In Part B, the preparation of synthetic rubber (Thiokol), begins with mixing of sodium
hydroxide with flowers of sulphur to produce sodium polysulphide. The sulphur present gives
the rubber its elasticity. The sodium polysulphide then reacts with ethylene dichloride, as
both these compounds have different functional groups a condensation reaction is able to take
place, producing water which over heat became vapor as a side product. The resulting rubber
that had formed was a small slightly yellow piece and had minimal elasticity.

References
1. Wexler, P. and Abdollahi, M., 2014. Encyclopedia of toxicology. Amsterdam:
Academic Press, pp.1045-1050.
2. McKeen, L., 2019. The effect of UV light and weather on plastics and elastomers.
Oxford: Elsevier/William Andrew, pp.1-20.
3. Chem.libretexts.org. 2022. 10.5: Condensation Polymers - Chemistry LibreTexts.
[online] Available at:
<https://chem.libretexts.org/Courses/Sacramento_City_College/SCC%3A_CHEM_33
0_-_Adventures_in_Chemistry_(Alviar-
Agnew)/10%3A_Polymers/10.05%3A_Condensation_Polymers> [Accessed 2 May
2022].
4. BYJUS. 2022. Polymers - Classification, Types, Uses, Properties, Polymerization.
[online] Available at: <https://byjus.com/jee/polymers/> [Accessed 2 May 2022].
5. Manufacturing, D., 2022. Material Properites of Polystyrene - a Versatile
Thermoplastic. [online] Dielectric Manufacturing. Available at:
<https://dielectricmfg.com/knowledge-base/polystyrene/> [Accessed 3 May 2022].
6. Baker, E., 1943. The preparation of thiokol: A lecture demonstration. Journal of
Chemical Education, 20, p.427.

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