DEPARTMENT OF CHEMISTRY

FACULTY OF SCIENCE AND MATHEMATICS

UNIVERSITI PENDIDIKAN SULTAN IDRIS

LABORATORY REPORT
SKU3043: POLYMER CHEMISTRY
Semester I Session 2019/2020

ID NO AND NAME 1. Abdul Rahim Bin Md Saad (D20162075593)

2. Mohd Khairy Izzuan Bin Mohd Yusof (D20162075594)
LECTURER Prof. Madya Dr. Ismail Zainol
EXPERIMENT NO. 1
TITLE Cross-Linked Polymer
DATE & DAY 26th September 2019

CHECK LIST (Please tick)

Title
Objective(s)
Introduction
Methods (in diagram)
Observations (in table)
Data & calculation
Discussions
Questions & answers (if appropriate)
Conclusion(s)
References (at least 2)
Experiment 1
CROSS-LINKED POLYMER

1. Objectives
Upon completion of this experiment, we should be able to:

1.1. prepare a cross-linked polymer.

1.2. examine the physical properties of the cross-linked polymer.

2. Introduction
Poly(vinyl alcohol) or PVA is a type of polymer that is an odourless and tasteless, translucent,
white or cream coloured granular powder. (Saxena, 2003) It is soluble in water. The structure
of poly(vinyl alcohol) (partially hydrolysed) is given below:

Borax [Na2B407.10H2O], the salt of a strong base and a weak acid, hydrolyses in water solution
to form a boric acid-borate buffer having a pH of around 9 (Casassa, Sarquis, & Van Dyke,
1986)

The buffer equilibrium is written as:

When borax is added to a solution of PVA the polar -OH groups on borax and PVA cross-link.
Crosslinking is a process of forming a three-dimensional network structure from a linear
polymer by a chemical or physical method. Chemical methods produce covalently bonded
networks, which is, chemical gels. (Subramanian, 2017)

In this experiment, PVA cross-linked by a hydrated borax molecule.

3. Method
3.1. Apparatus used:
3.1.1. Wooden stir stick / plastic stir rod
3.1.2. Graduated cylinder
3.1.3. Beaker
3.1.4. Heater
3.2. Material used:
3.2.1. Poly(vinyl alcohol)(Mn 70,000 and Mn 31,000)
3.2.2. Borax (Na2B4O7.10H2O)
3.2.3. Distilled water
3.3. Procedure:
3.3.1. Part A:
Firstly, different concentrations of poly(vinyl alcohol)(PVA) and borax solutions
was prepared using distilled water as the solvents. The solutions prepared according
to Table 1. After that, PVA and borax acid was reacted inside a beaker as per
reaction in Table 1. Immediately after the two chemicals added, the solution was
stirred and any changes occurred as the reaction proceeds was observed and
recorded. After the slime(gel) was formed, the slime is then kneaded until desired
consistency was reached.

Reaction Poly(vinyl alcohol) (PVA) Borax

Types of Concentration Volume Concentration Volume

PVA (g/ml), % (ml) (g/ml), % (ml)
1 (M
70000
n) 2.5 / 50 , 5% 10.0 1 / 20 , 5% 1.0
2 70000 2.5 / 50 , 5% 10.0 2 / 20 , 10% 1.0
3 70000 5.0 / 50 , 10% 10.0 1 / 20 , 5% 1.0
4 31000 2.5 / 50 , 5% 10.0 1 / 20 , 5% 1.0
5 31000 5.0 / 50 , 10% 10.0 1 / 20 , 5% 1.0
6 31000 5.0 / 50 , 10% 10.0 2 / 20 , 10% 1.0

Table 1: Reactants for cross-linking in polymer

 3.3.2. Part B
The physical properties of the formed gel were compared based on:

(a) stretching effect

(b) pressure effect
(c) gravity effect

4. Result & Calculation

Reaction Stretching Pressure Gravity

1

Best Worst Best

Very good Very poor Very good

Good Good Poor

 4

Poor Poor Good

Worst Best Worst

Very poor Very good Very poor

5. Discussion
In the first part of the experiment, we prepared a cross-linked polymer. Crosslinking is a
process of forming a three-dimensional network structure from a linear polymer by a chemical
or physical method. Chemical methods produce covalently bonded networks, which is known
as chemical gels. (Subramanian, 2017)

Boric acid is such a weak acid that it actually does not give up H+ but rather accepts an OH-
from the water. At low concentrations, both boric acid and borate ion are present as the
monomeric species having, respectively, the structures
 (Cheng, ATY; Rodriguez, F, 1981)

PVA contains, the polymer polyvinyl alcohol (also called polyethenol). Poly(vinyl alcohol)
has the structure:

(Gohil, Bhattacharya, & Ray, 2006)

The borate ion can make weak bonds with the OH groups in the polymer chains so it can link
the chains together. Borate ion is tetrafunctional in interaction with alcohol -OH group, and,
thus, is particularly effective in creating three-dimensional gel networks from poly(vinyl
alcohol) as shown below.

(McLaughlin, Wyffels, Jentz, & Keenan, 1997)

Crosslinking is also broadly used method for the modification of polymer properties. The
formation of tri-dimensional structures, gels, causing substantial changes in material
properties. (Subramanian, 2017) In this experiment, 6 type of gel was produced by using 2 type
of molecular weight of poly (vinyl alcohol), with differences concentration and difference
concentration of crosslinking agent (borax). The physical properties of the gel were tested with
3 physical test which are stretching effect, pressure effect, and gravity effect. The test of
stretching and gravity effect mainly to test the viscosity of the gel and pressure effect is to test
the elasticity of the gel. The term “viscous” implies that they deform slowly when exposed to
an external force. The term “elastic” implies that once a deforming force has been removed the
material will return to its original configuration. (Gould, Jesunathadas, Nazarenko, & Piland,
2019) From the result we can see that, first reaction gel is the least viscous and the least elastic
while the most viscous and the most elastic is the fifth reaction gel.

Crosslinking process tends to reduce the specific volume of the polymer because it increases
the extent of branching or in other words, the density of the gel component. (Ochiai,
Fukushima, Fujikawa, & Yamamura, 1976)The gel from 1st reaction contain higher molecular
weight than the gel from 4th reaction with the same concentration of PVA and borax. Longer
chain molecule will attract more water making the gel less viscous and less elastic. The gel
from 2nd reaction contain same molecular weight with the gel from 1st reaction with the
different concentration borax. Increasing the borax concentration, will increase the amount of
cross linking between the PVA. Higher crosslink density is the result of more linkages per
length of polymer chain, resulting in larger property changes. (Maitra & Shukla, 2014) Higher
branching density, as with side groups, restricts mobility because the free volume is reduced
and the molecular motion becomes more difficult. With a low number of branches, free volume
increased. (Ochiai, Fukushima, Fujikawa, & Yamamura, 1976) Therefore, we can see that 2nd
reaction gel is more viscous and more elastic than 1st reaction gel.

There are several precautions that we must make when carrying out the experiment. Firstly,
when preparing PVA, the temperatures must not be above 90°C because it may result in
decomposition of the PVA. (Maitra & Shukla, 2014) Secondly, the gel should be tested
immediately after obtained because repeated stress to the gel may gradually decrease its ability
to expand or stretch due to the deformation of the branch after experiencing repeated stress.
Water in the gel may also be loss if exposed too much to the air and lost it flexibility. (Casassa,
Sarquis, & Van Dyke, 1986)
6. Questions
(i) Draw the structure and write the chemical equation for the production of cross-linked
poly(vinyl alcohol).

(ii) Explained why the properties of poly(vinyl alcohol) network are totally different than
vulcanized rubber.

The borate cross-linkages in poly(vinyl alcohol) are not fixed but break and reform
easily or in other word that the system is said to be in a state of dynamic equilibrium.
The bonding created by the cross-links are so weak and are made and unmade so readily
due to hydrogen bonding interactions between the interlinkage polymer. Vulcanized
rubber on the other hand form permanent cross-links by carbon-sulphur-carbon
covalent bonds between chains.

(iii) Differentiate the physical properties of cross-linked polymer, linear polymer and
branched polymer.
A linear polymer is simply a chain in which all of the carbon-carbon bonds exist in a
single straight line. Linear polymer flow when heated and can be moulded into a variety
of shapes which they retain when they cool. Linear polymer is the most soft between
the three polymer

Branched polymers occur when groups of units branch off from the long polymer chain.
This can make the polymer strong in the ideal temperature range. Branched polymers
also flow when heated and can be moulded into a variety of shapes which they retain
when they cool. Branched polymer is harder than linear polymer but softer than
crosslinked polymer.
 The cross-linked polymer forms long chains, either branched or linear, that can form
covalent bonds between the polymer molecules. Because cross-linked polymers form
covalent bonds that are much stronger than the intermolecular forces that attract other
polymer chains, the result is a stronger and more stable material. It is the hardest
polymer among the three.

7. Conclusion
From the experiment, we are able to prepare several cross-linked polymers with PVA
crosslinked with borax. The physical properties of the cross-linked polymer are also
successfully examined. With higher concentration of PVA and borax, more rigid and viscous
gel are formed due to the high amount of crosslinking between the polymer. Higher molecular
weight polymer yield less elastic gel due to the higher amount of water trapped between the
crosslinked polymer.

8. References
Casassa, E., Sarquis, A., & Van Dyke, C. (1986). The gelation of polyvinyl alcohol with borax: A
novel class participation experiment involving the preparation and properties of a" slime".
Journal of Chemical Education, 63(1), 57.

Cheng, ATY; Rodriguez, F. (1981). Journal of Applied Polymer Science, 3895-3908.

Gohil, J., Bhattacharya, A., & Ray, P. (2006). Studies on the crosslinking of poly (vinyl alcohol).
Journal of polymer research, 161-169.

Gould, T. E., Jesunathadas, M., Nazarenko, S., & Piland, S. G. (2019). Mouth protection in sports.
In T. E. Gould, M. Jesunathadas, S. Nazarenko, & S. G. Piland, Materials in sports
equipment (pp. 199-231). Elsevier.

Maitra, J., & Shukla, V. K. (2014). Cross-linking in hydrogels-a review. Am. J. Polym. Sci, 25-31.

McLaughlin, K., Wyffels, N., Jentz, A., & Keenan, M. (1997). The gelation of poly (vinyl alcohol)
with Na2B4O7 10H2O: killing slime. Journal of chemical education, 74(1), 97.

Ochiai, H., Fukushima, S., Fujikawa, M., & Yamamura, H. (1976). Mechanical and thermal
properties of poly (vinyl alcohol) crosslinked by borax. Polymer Journal, 131.
Saxena, S. (2003). Polyvinyl Alcohol (PVA) Chemical and Technical Assessment. 61st Meeting
The Joint FAO/WHO Expert Committee on Food Additives (pp. 10-19). Rome: Food and
Agriculture Organization of the United Nations.

Subramanian, M. N. (2017). Polymer blends and composites: chemistry and technology. New
Jersey: John Wiley & Sons.