Chemistry
Certificate
Investigatory
Project
S.UDAYATHKIRAN
12-C
1
Acknowledgements
2
TABLE OF CONTENTS
Sr.No Contents Pg.No
1 Certificate 2
2 Acknowledgement 3
3 Topic 5
4 Introduction 6
6 Reaction Chemistry 8
7 Aim 11
8 Apparatus 11
9 Chemicals 11
10 Experimental procedure 12
11 Discussion 14
12 Conclusion 14
13 Precaution 15
14 Bibiliography 15
3
Topic
TO PREPARE UREA FORMALDEHYDE RESIN
(HARD PLASTIC)
4
Introduction
One classification of polymers divides them into thermoplastic
and thermosetting resins. Most amorphous linear polymers (e.g.
polystyrene, polyethylene, poly(ethylene terephthalate) are
thermoplastics. The mobility of the polymer increases as the
temperature increases. If a linear polymer is cross-linked, a three-
dimensional network is formed, and translational motion is
inhibited or even prohibited. Cross-linkable polymers are
generally referred to as thermosets, or thermosetting resins. From
a processing point of view, the above distinction of thermoplastic
and thermoset implies that the former can, in principle, be
extruded and molded many times, while the latter can be
processed at high temperature only once before cross-linking
reactions render the polymer hard and solid. The shape of the
polymer is thermally set. Thermosets are generally insoluble, even
when the degree of cross-linking is low (~ 2%). For example,
natural rubber (gutta percha, all cis-1,4-polyisoprene) is normally
used as a thermoplastic. Cross-linking with about 2% sulfur
produces an insoluble, swellable elastic material. At 10-15% cross-
linking density, the polymer becomes stiffer, and can be used to
make articles such as combs. At higher (25-35%) cross-link density,
the rubber becomes extremely hard, and is used to make bowling
balls. An important group of thermosetting resins is the
aminoplasts, or amino resins, of which about 80% are urea-
5
formaldehyde (UF) resins, and 20% are melamine-formaldehyde
(MF) resins. A small proportion of amino resins contain other
aldehydes or other amines. Amino resins are water soluble before
curing, colourless (which allows unlimited colourability), have
excellent solvent resistance once cured, outstanding hardness and
abrasion resistance, and good heat resistance. A drawback of
these materials is the potential release of formaldehyde during
and after cure, and poor weatherability. Melamine mouldings
have somewhat better weatherability than the urea mouldings. A
major application of amino resins is in the area of adhesives,
primarily for the plywood, chipboard, and sawdust board
markets. Amino resins are also used in textile processing (to
impart wash and wear quality), automobile tires (to improve
adhesion between rubber and tire cord), and paper processing (to
improve the wet strength).
6
Reaction Chemistry
The raw materials for amino resins are urea, melamine, and
formaldehyde. Formaldehyde is generally marketed as a 37%
aqueous solution known as formalin. Gaseous formaldehyde
dissolves readily in water, and reacts to form methylene glycol,
The other major form of formaldehyde is solid (flake or powder)
paraformaldehyde, which is a mixture of poly(oxymethylene
glycols), HO(CH2O)nH, where n = 8 - 10. These chains readily
regenerate formaldehyde when mixed with water. There are two
main reactions in UF and MF condensations. The first one,
hydroxymethylation, can be catalyzed by either acid or base. The
other major form of formaldehyde is solid (flake or powder)
paraformaldehyde, which is a mixture of poly(oxymethylene
glycols), HO(CH2O)nH, where n = 8 - 10. These chains readily
regenerate formaldehyde when mixed with water. There are two
main reactions in UF and MF condensations. The first one,
hydroxymethylation, can be catalyzed by either acid or base.
This is generally the first step in UF polymer formation, and these
methylol compounds are prepared under neutral or alkaline
conditions. The second important reaction is methylene bridge
formation, and is only catalyzed by acid. Methylene bridge
formation
7
This reaction results in dimer, polymer chain, or network
formation. Thus, the stable resin intermediate formed in
hydroxymethylation can be converted to solid cross-linked
polymer by addition of an acid catalyst. During crosslinking, two
main reactions are believed to occur. The first involves the
formation of dimethylene ether linkages,
and the second is a rearrangement reaction, leading to
diaminomethylene bridge formation,
The resulting matrix is depicted below for melamine-
formaldehyde. These four basic reactions account for much of the
reaction chemistry of UF and MF resins, and their precise control
8
is still the subject of intense industrial and academic research.
9
Aim
To prepare Urea Formaldehyde-resin
Apparatus
500-mL reaction kettle 1
4-neck lid 1
clamp 1
glassrod stirrer 1
jacketed collar for stirrer 1
heating mantle 1
overhead stirrer 1
50-mL Erlenmeyer flasks 2
125-mL Erlenmeyer flasks 2
250-mL Erlenmeyer flasks 2
condenser with tubing 1
Buchner funnel 1
Barrett distillation trap 1
250-mL beaker 2 600-mL beaker
2
Chemicals
Urea,
formalin (37%)
ethanol
NaOH solutions 0.5N
H2SO4
Wood flour
calcium phosphate
ammonium chloride
furfuryl alcohol
10
triethanolamine
Experimental Procedure
1. Preparation of monomethylolurea
During the laboratory period two weeks prior to
performing this experiment, add 5 g urea and 6 mL
formalin to a small flask. Adjust the pH of the mixture
between 7 and 8 (indicator paper), and stir the mixture
until solution is effected. Let the flask stand at room
temperature for 2 - 4 hours, and then store it in the
refrigerator until the next laboratory period.
After two weeks, remove the flask from the fridge, and
filter the mixture by suction. Wash the residue with
ethanol and dry it in an oven at 50oC. Determine the
melting point and the water solubility of the crude
product. (Tm of monomethylolurea = 110 oC).
2. Preparation of a urea-formaldehyde
adhesive Sixty grams (1 mole) of urea and 137 g (1.7 mole)
formalin are charged into a 500-mL reaction kettle
equipped with a mechanical stirrer and a reflux condenser.
The pH of the mixture is adjusted with 2M NaOH to
between 7 and 8 as determined by universal indicator
paper, and the mixture is refluxed for 2 hours using a
heating mantle as the heat source. After the mixture has
11
been refluxed for 2 hours, a Barrett receiving trap is
introduced between the flask and the reflux condenser.
The distillation is continued until about 40 mL of water is
distilled into the trap and discarded. [See Senior
Demonstrator or TA for assistance]. The solution is
acidified with 5 drops of glacial acetic acid; 44 g of furfuryl
alcohol and 0.55 g triethanolamine are introduced into the
reaction mixture, and the solution is heated at 90 oC for 15
minutes. The mixture is then cooled to room temperature.
A 15-g sample of the resin is removed and is mixed with a
hardener composed of 1 g of wood flour, 0.05 g calcium
phosphate, and 0.2 g ammonium chloride. The mixture is
set aside to harden at room temperature. The remaining
resin to which the hardener has not been added is placed
in a vial.
3. Preparation of UF resin under acidic conditions
In order to demonstrate the rapidity of the reaction of
urea with formaldehyde under acidic conditions, mix 5 g of
urea with 6 ml of formalin in a test tube, and shake the
test tube until the urea has dissolved. Adjust the pH of the
solution to 4 by addition of 4 drops of 0.5N H2SO4, and
observe the time required for precipitation to occur.
Remove part of the precipitate and compare its solubility
12
in water with the sample of monomethylolurea prepared
in Part 1 above.
Discussion
In your report, describe the materials that you prepared,
and compare them to each other. Also, answer the
following questions. 1. Describe, with reactions, the
formation of formaldehyde from poly(oxymethylene
glycol) under acidic and basic conditions, respectively. 2.
What role do the furfuryl alcohol and triethanolamine play
in the preparation of the UF adhesive?
Conclusion:
This study shows that the free formaldehyde content in
resin system plays a role in pH changes by reacting with
NH4Cl. The pH of UF resins decreases with increasing
NH4C1 content, but this effect becomes limited to
nonexistent with further NH4Cl addition as most of the
free formaldehyde reacts with NH4C1. The main effect of
NH4C| on UF-resin curing is catalyzing the reactants in UF-
resin systems, in addition to releasing HCl. The gel time of
UF resins decreases with increasing catalyst and resin solid
contents and decreasing pH.
13
Precautions
1. While adding concentrated H2SO4, it is better to stay
little away from the beaker since the reaction sometimes
becomes vigorous.
2. The reaction mixture should be stirred continuously.
Bibiliography
WATERLOO CHEM LAB EXP 2 PDF
14
