SCHOOL OF INDUSTRIAL TECHNOLOGY

SEMESTER I 2023/2024

IWA281 - COATINGS TECHNOLOGY LABORATORY I

EXPERIMENT A
STEP GROWTH POLYMERIZATION: PREPARATION OF UNSATURATED
POLYESTER RESIN

PREPARED BY: GROUP 7

PREPARED FOR: DR. AZNIWATI BINTI ABD AZIZ

DR. MOHAMMED DANISH

LAB ASSISTANT: MR. SHAMSUL ZOOLKIFLI

SUBMISSION DATE: 13/12/2023

NO NAME OF GROUP MEMBERS MATRIX Roles of Lab Report

. NO.

1. MUHAMMAD IMAN DANIAL BIN MOHD RASHIDI 162290 Result, Appendix

2. MUHAMMAD SYABBATUL AL HAMDI BIN 160813 Discussion

MUSTAFFA ALBAKRI

3. MOHD FAUDZY BIN SANI 163783 Result

4. NUR SYAMILA BINTI HAYAZI 162714 Abstract,Introduction

,Objective,Method

5. NADHIRAH BINTI AHMAD HISHAM 164597 Abstract,Introduction,

Objective,Method

6. AFIQAH ADLINA BINTI MOHAMAD ADNAN 145593 Conclusion,Discussion

NO NAME OF GROUP MEMBERS MATRIX Roles of Experiment
. NO.
1. MUHAMMAD IMAN DANIAL BIN MOHD 162290 ● Find and weight
RASHIDI apparatus and
chemical
● Prepare reaction
flask
● Prepare water bath
● Prepare
unsaturated
polyester resin
● Titration of
standardisation of
KOH
● Titration of
unsaturated
polyester resin
with KOH
● Record reading
2. MUHAMMAD SYABBATUL AL HAMDI BIN 160813 ● Find and weight
MUSTAFFA ALBAKRI apparatus and
chemical
● Prepare reaction
flask
● Prepare water bath
● Prepare
unsaturated
polyester resin
● Titration of
standardisation of
KOH
● Titration of
unsaturated
polyester resin
with KOH
● Record reading
3. MOHD FAUDZY BIN SANI 163783 ● Find and weight
apparatus and
chemical
● Prepare reaction
flask
● Prepare water bath
 ● Prepare
unsaturated
polyester resin
● Titration of
standardisation of
KOH
● Titration of
unsaturated
polyester resin
with KOH
● Record reading
4. NUR SYAMILA BINTI HAYAZI 162714 ● Find and weight
apparatus and
chemical
● Prepare reaction
flask
● Prepare water bath
● Prepare
unsaturated
polyester resin
● Titration of
standardisation of
KOH
● Curing of
unsaturated
polyester
● Record reading
5. NADHIRAH BINTI AHMAD HISHAM 164597 ● Find and weight
apparatus and
chemical
● Prepare reaction
flask
● Prepare water bath
● Prepare
unsaturated
polyester resin
● Titration of
standardisation of
KOH
● Curing of
unsaturated
polyester
● Record reading
1.0 ABSTRACT

Unsaturated polyester is produced by diol and unsaturated dibasic acid. This

experiment is divided into two sections . First, the experiment prepares unsaturated polyester
resin with materials such as maleic anhydride, phthalic anhydride, propylene glycol,
hydroquinone, xylene, and toluene. Second, the experiment determines the measurement of
acid number with materials such as potassium hydrogen phthalate, potassium hydroxide,
phenolphthalein indicator, ethanol, styrene, cobalt octanoate, methyl ethyl ketone peroxide,
and glass fibre. Results were split into the respective categories mentioned according to each
task. Every chemical had important functions in producing the experiment.
2.0 INTRODUCTION

Polyester is the reaction product between a dibasic acid and a polyhydroxy substance.
Polyester can be classified into two types namely unsaturated and linear polyester saturated
polyester. This experiment will use unsaturated polyester. Not saturated polyester is the third
largest class of thermoset moulding resin.Unsaturated polyesters are synthesised in the
laboratory by the condensation of saturated and unsaturated anhydrides with glycols. The
condensate obtained is mixed with styrene monomer to get an unsaturated polyester resin
formulation. Unsaturated polyester is produced by diols and unsaturated dibasic acids. This
type of polyester has a double bond along the polymer backbone. It consists of low molecular
weight polymers. Using vinyl monomer with suitable organic peroxide to absorb it and pour
or form the final product and then convert by applying heat into a thermoset to cure it
completely.

Polyester resin is thermosetting which is a polymeric material that must undergo some
chemical reaction after coatings are applied to form useful films. These cross-linking or
curing reactions fundamentally connect comparatively smaller polymer chains, resulting in an
increase in molecular weight and the production of a crosslinked or network polymer
structure. Thus, the structure of the polymer in the cured films of thermosetting systems,
unlike thermoplastic ones, is formed by strong chemical linkages connecting polymer chains,
making these films strong and resistant to chemical and solvent attack.

During curing and production of crosslinked polymers are obtained by reacting the
polyester resin with an unsaturated monomer usually styrene in the presence of a peroxide
initiator. The type of polyester is used in surface coatings, casting, and the production of
fibre-reinforced polyester (FRP). Saturated polyester is obtained from a reaction between
saturated dibasic acid and diol but does not contain double bonds in the polymer backbone.
This type of polyester also can be used in the coatings industry.

The characteristics of unsaturated polyester are heat resistance, high tensile and
compressive strength, high bending strength, resistance to chemical corrosion, excellent
dielectric properties and good fluidity when heated. Other than that, the characteristics of
saturated polyester are versatility and weather resistance, prominent hardness and toughness,
resistance to dirt and suitability for general requirements which is cost-effective.
3.0 OBJECTIVE

The objective of this experiment is to learn the preparation of unsaturated polyester resin ,
understand the kinetics of step-growth polymerization (or condensation) involved and study
on how fibre-reinforced polyester (FRP) is produced .

4.0 MATERIALS & METHODOLOGY

4.1 Chemical Required

● maleic anhydride

● phthalic anhydride

● propylene glycol

● ethylene glycol

● hydroquinone

● xylene

● toluene

4.1.2 Apparatus required

● Flanged reaction flask fitted with stirrer

● dean and stark trap

● thermometer

● thermocouple

● heating mantle

● beaker
 ● measuring cylinder

● nitrogen inlet tube

4.1.3 Method

First week

Preparation of unsaturated polyester resin

1. 76g(1 mole) of propylene glycol and 21.7g(0.35 mole ) of ethylene glycol were
weighed and put in the reaction flask .followed by adding 50 ml of toluene
2. The above flask was heated until it reached 150-175 degree celsius and maintained for
15 minutes . The heating was carried out with string and moderate nitrogen flow .
3. All water in the water collector has been removed . Then distillation was continued
until all 50 ml of toluene was recovered .
4. The apparatus was allowed to cool to room temperature . The flask was cooled by
water .
5. 73.5 g (0.75 mole) of maleic anhydride , 74 g (0.5 mole) of phthalic acid and 25 ml
xylene were put in the flask .
6. 10 ml xylene was put in the water collector . The temperature of the flask was
increasing rapidly until it reached 200 c .Then , the nitrogen gas was allowed to flow
into the heating mixture in a moderate and stable manner .
7. Volume of the water collector for every minute of the first 10 minutes and every 5
minutes has been determined . removed the water in the collector if needed , then the
same volume of xylene was replaced through the condenser .
8. When the volume of the water collector has attained a constant level ,the content of
the water collector has been removed and the flow of nitrogen has increased .
9. 0.03 g (0.02%) of hydroquinone was cooled and added to unsaturated polyester resin
prepared in order to retain any crosslinking reaction that may occur .
Second week

Measurement of acid number

1. Standardization of potassium hydroxide (KOH)

0.56 g KOH was dissolved with distilled water in a 100 mL volumetric flask also, 2.04g of
potassium hydroxide phthalate (KHP) was dissolved with distilled water in 100mL
volumetric flask (standard solution). 10mL KOH was pipetted with 5 drops of
phenolphthalein indicator (use Erlenmeyer cone ), followed by titration with a known
concentration of KHP solution (standard solution) .

2. Titration of unsaturated polyester resin with standardized KOH

0.5 grams of unsaturated polyester resin was dissolved with 20mL ethanol in conical flask. 5
drops of phenolpthalein indicator were put into the flask and titrated with standardized KOH
solution. The solution colour would change from colourless to red .For blank titration, 5
drops of phenolphthalein indicator was put in 20mL ethanol and titrate with 20mL of
standardized KOH.

3. Curing of unsaturated polyester

20 g of resin was dissolve with 40-48%(9g) styrene. 0,03%(0.09g) cobalt octanoate was
mixed slowly and followed by adding 1-2% (0.58g) of methyl ethyl ketone peroxide
(MEKP).the result mixture was put on glass fiber . The glass fiber was allowed to become
hard (curing occurred at room temperature ).
5.0 RESULT

5.1 Volume of Water Produced

Data for first 10 minutes

First 10 minutes

1 minutes 1.2 ml 6 minutes 4.8 ml

2 minutes 2.2ml 7 minutes 4.4 ml

3 minutes 3.0ml 8 minutes 2.8 ml

4 minutes 3.4 ml 9 minutes 2.6 ml

5 minutes 4.4 ml 10 minutes 1.7 ml

Table 3.1 shown volume of water produce for first 10 minutes

Data for every next 5 minutes

Time Volume of water produced

5 minutes 1.2 ml

10 minutes 1.0 ml

15 minutes 1.0 ml

20 minutes 1.2 ml

25 minutes 1.2 ml

Table 3.2 shown volume of water produce for every next 5 minutes

● Graph for water produce against time

● Percentage of Polyester resin produce
 Weight of beaker and polyester 256.65
resin(g)

Weight of empty beaker (g) 137.55

Weight of Polyester resin (g) 119.10

Table 3.3 shown weight of polyester produced

Chemical Equation that Involved

n HOOC-R-COOH + n HO-R-OH→ H [-OOC-R-COO-R] n OH + (2n-1) H2O

(A) Experimental results

(119.10g) / (245.2g) x 100%

= 48.57%

(B) Theoretical result

Number of mole= mass/ relative molecular mass

Mass= Relative molecular mass x number of moles

Anhydride= 147.5g (1.25 moles)

Glycol= 97.7g (1.35 moles)

 Mass of total anhydrides = 147.5g/mol x 1.25 mol

= 184.38g

Mass of total glycol = 97.7g/mol x 1.35 mol

= 131.90g

Total mass of chemical used calculated from chemical equation:

=184.38g + 131.90g =316.28g

Theoretical value (180.73/ 316.28) x 100 = 57.14%

Acid Number

a) Standardization potassium hydroxide (KOH)

Titration Readings
1 2 3
Initial volume 50 41.6 36.2
(mL)
Final volume (mL) 41.6 36.2 30.2
Volume of KPH 8.4 5.4 6.0
used (mL)
Average 6.6

Titration of KPH with KOH

Average volume of KHP used (ml) = (8.4+5.4+6.0) / 3 = 6.6 ml

Weight of KOH used = 0.56g

Molecular weight of KOH = 56.1 g/mol

Volume of KOH solution that used, YKOH = 10ml

Chemical equation = KOH + C8H5O4K —> C8H4O4K2 + H20

The molarity of KOH = (0.10 x 6.6) / 10 = 0.066 M

Titration Readings
1 2 3
Initial volume 50 45.4 30
(mL)
Final volume (mL) 16.5 15.7 16.4
Volume of KPH 33.5 29.7 13.6
used (mL)
Average 25.6

Titration of unsaturated polyester resin with KOH

Average volume of KOH used (ml) = (33.5+29.7+13.6) / 3 = 25.6 ml

Titration

Initial volume (mL) 50

Final volume (mL) 57.4

Volume of KPH used (mL) 2.6

Titration of KOH with ethanol (blank)

Volume of KOH that used for titration of resin = (25.6 – 2.6) ml = 23 mL

Number of mole KOH = (0.066 M x 23 ml) / 1000 = 1.518 x 10-3 mol

Weight of KOH = (1.518 x 10-3 mol) (56.1 g/mol) = 4.82332 g

Acid number is equal to mg KOH which is needed to neutralize 1g of resin. Based on the

experiment result, 0.05502g of KOH is needed to neutralize 1g of resin.

Acid number (mg KOH / 1 g of unsaturated polyester resin)

Acid value (mg KOH/g) = Titre value x Molarity of KOH x Molecular weight of KOH

Weight of sample (g)

= (23mL) (0.066M) (56.1g/mol)

119.10g

= 0.715028g

=715.03mg

Average molecular weight

Number of moles = Mass

𝑅𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑚𝑎𝑠𝑠

Therefore, the average molecular weight of resin

= 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑢𝑛𝑠𝑎𝑡𝑢𝑟𝑎𝑡𝑒𝑑 𝑝𝑜𝑙𝑦mer

𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙

= 0.5 / [(1.518 x 10-3)/2]

= 658.7615 g/mol
6.0 DISCUSSION

6.1 Experimental discussion

In this experiment, the chemical equation involved is:

Anhydride (maleic and phthalic anhydride) + Glycol (ethylene and propylene glycol)

Unsaturated polyester resin + water (side product)

The resultant unsaturated polyester resin sample displays the predicted light yellow color and
viscosity. Since the reaction is reversible, a substantial amount of reactants may persist,
leading to a diminished resin yield. To counteract this, excess propylene glycol is introduced
to shift the equilibrium favourably, potentially enhancing resin production and yield. The
generation of water as a byproduct is undesirable, prompting the need to eliminate it to ensure
optimal resin yield. Various polyester resin samples exhibit differing quantities of carboxylic
acid end groups, with the free carboxylic acid content evaluated volumetrically through
titration with potassium hydroxide (KOH). The resin's acidity is expressed as an acid number,
a standard measure determined by the milligrams of KOH needed to neutralise the acids.

Acid number is measured in this example by the milligrams of potassium hydroxide

(KOH) required to neutralise the acid in 1g of unsaturated polyester resin. In a blank titration,
a fixed and known concentration of titrant (KOH) is titrated into a solvent (ethanol) with no
analyte (unsaturated polyester resin). This is done to ensure that either there are no substances
in the solvent which can react with the titrant, or to estimate the amount of titrant that would
react with the pure solvent. In this way, we can estimate the error that can be produced when
the actual titration experiment is conducted. In this experiment, potassium hydrogen phthalate
(KHP) is used as the standard in standardization of potassium hydroxide (KOH). KHP is used
as the standard because it is stable as a solid and in solution, it is soluble in water but not
hygroscopic and is easily dried and its molecular mass (≈200 g/mol). This will make the
determined masses of the substance for making a solution accurately.

Xylene and toluene are used in this experiment to assist in the removal of water
using azeotropic distillation. Azeotropic distillation is a distillation method that adds other
light chemicals to generate a new, lower-boiling azeotrope that is heterogeneous so that we
can separate the liquid mixture. The unwanted side product of water may be readily removed
since the water will combine with the xylene or toluene to create a lower-boiling azeotrope.
As a result, removing water from the reaction will be easy. After mixing propylene glycol
with ethylene glycol and toluene, heat the reaction flask to 150-175°C and keep it there for 15
minutes. Since the standard for ethylene glycol as a dehydration agent is that it acts
efficiently at 175°C as it approaches its vapour pressure, 175°C was chosen for the
experiment.

The water produced in the experiment is 30.5mL which is different from the
theoretical value which is 27.0mL. This situation happened because when the water in the
collector is removed, the same volume of xylene is not replaced. When removing the water,
some xylene also is removed. In the titration of potassium hydroxide (KOH) by the potassium
hydrogen phthalate (KHP), the volume of KHP is larger than the expected value as the KHP
did not prepare well. After KHP solid is diluted, it should have been shaken first before using
it but this step is skipped. . For the titration of polyester resin and ethanol by potassium
hydroxide (KOH), there is an outlier value. This might be due to the mass of resin that is used
is not accurate as the actual value needed (0.5g). Besides, the KOH is not pure enough as
some of the KOH is reused after rinsing the pipette. Hence, the acid number that was
calculated from the experiment is not accurate as the actual value as there are some errors.
6.2 Chemicals functions

Used to manufacture resins, dyes,

medicines, and agricultural products.

Maleic anhydride

A commonly employed commercial

chemical, extensively used as a raw
material for producing other
chemicals, including plasticizers,
polyester, alkyd resins, pigments,
and dyes. It is present in tobacco
smoke, oak smoke, and various
Phthalic anhydride combustion products.

A plasticizer commonly used in aqueous

film-coating formulations.

Propylene glycol

Utilized as antifreeze in heating and

cooling systems, hydraulic braking
fluids, industrial humectant, safety
Ethylene glycol explosives manufacturing,
plasticizers, synthetic fibers
(Terylene, Dacron), synthetic waxes,
 and solvent in paint and plastics
industries.

Used as a chemical intermediary in the

production of inhibitors for monomers,
paints, varnishes, motor lubricants, and
fuels, as well as a rust inhibitor in cooling
towers.

Hydroquinone

Used in the printing, rubber, paint, and

leather industries as a solvent.

Xylene

A major commercial chemical that is

utilised as a gasoline additive as well as in
the manufacture of other chemicals, nylon
and plastics, explosives, paints and lacquers,
and inks, dyes, and perfumes.

Toluene

A commonly used commercial chemical,

employed in agriculture for synthetic
rubber, polymers, resins, and various
chemicals. Certified for use in
manufacturing food containers and
disposable cups in the food industry.

Styrene
 Facilitates the bonding of molecules to a
surface. Numerous traditional adhesives and
binding agents are also accessible for
diverse applications.
Potassium hydroxide

Employed as a crosslinking agent for

unsaturated polyester resins in adhesives,
serving as a curing agent.

Methyl ethyl ketone peroxide

6.3 Industry and General Use of Polyester Resin

Polyester resin, a thermosetting unsaturated polymer, results from the reaction between
organic acids and alcohols. Derived from the polymerization of specific compounds or even
trees, it exhibits limited thermal stability, chemical resistance, and processability. These
features find applications in various domestic and industrial uses.

In construction materials, polyester resin strengthens prefabricated items like shower

stalls and closet fixtures. It's combined with acrylic for decorative metal pieces, columns, and
balustrades, offering strength, weatherproofing, and matching decor. In transportation, its
adhesive property bonds fiberglass layers for lightweight body panels in automobiles,
airplanes, and boats. However, epoxy resin is replacing it in boat construction due to better
water resistance. Polyester resin is also used in luggage and packaging for its transparent
film-forming ability.

For decorative purposes, steel body panels receive a polyester resin-based colorant.
Additionally, polyester resin reinforces the interiors of "wet" appliances like dishwashers and
washing machines, offering advantages over stainless steel. Its lightweight strength makes it
ideal for manufacturing waterproof, weather-resistant, and cost-effective patio furniture.
7.0 CONCLUSION

The experiment successfully prepared unsaturated polyester resin using key chemicals, such
as maleic anhydride and phthalic anhydride. The procedures were smooth, and we
encountered no issues with responses or results. Careful handling of chemicals was essential
due to their potential harm to humans and the environment. The produced polyester resin
averaged 48.57%, with an acid number of 715.03 mg and an average molecular weight of
658.7615 g/mol. Additionally, we gained insights into the kinetics of step-growth
polymerization.

This experiment illustrated the formation of unsaturated polyester as a condensation

polymer, where smaller molecules are released as by-products. Over two days, we explored
the production of fiber-reinforced polyester (FRP). Unsaturated polyester resin serves as a
matrix for FRP, offering cost-effectiveness and various grades for specific applications. The
resin is derived from the reaction of aliphatic diols with unsaturated and saturated acids.

In conclusion, the experiment deepened our understanding of laboratory-based

unsaturated polyester resin production, emphasising the suitability of maleic anhydride,
phthalic anhydride, propylene glycol, and ethylene glycol. This hands-on experience
provided valuable insights not readily available in standard study materials.
8.0 REFERENCES

1. Cherian, B., & Thachil, E. T. (2004). SYNTHESIS OF UNSATURATED

POLYESTER RESIN—EFFECT OF CHOICE OF REACTANTS AND THEIR

RELATIVE PROPORTIONS. International Journal of Polymeric Materials and

Polymeric Biomaterials, 53(10), 829–845.

https://doi.org/10.1080/00914030490502364

2. Libretexts. (2020, July 14). 24.6: Step-Growth Polymers—Condensation polymers.

Chemistry LibreTexts.

https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Map%3A_Organic_Che

mistry_(Smith)/24%3A_Synthetic_Polymers/24.06%3A_Step-Growth_PolymersCon

densation_Polymers

3. Wikimedia Foundation. (2021, October 10). Step-growth polymerization. Wikipedia.

Retrieved January 11, 2022, from
https://en.wikipedia.org/wiki/Step-growth_polymerization
4. Polyester Resin. (n.d.). Retrieved December 21, 2020, from
https://www.sciencedirect.com/topics/chemical-engineering/polyester-resin
5. “Uses and Applications of Polyester Resin - Science Struck.”
https://sciencestruck.com/polyester-resin (accessed Dec. 22, 2020).
6. “The Uses of Polyester Resin | eHow.”
https://www.ehow.com/list_6376795_uses-polyester-resin.html (accessed Dec. 22,
2020).
9.0 APPENDICES

Picture 1 shown of reading of titration

Picture 2 shown the reading of measuring cylinder
Picture 3 shown result after drying process
Picture 4 shown process of titration