Lab Report for Polymer Degradation

Name 刘哲宁 Student ID 2020304085 Group Member 陈贞儒、李

昊、韩慕一、程帅词、李沐坤
Score Date 2022.12.8 Tutor 闫毅，姚东东

Experiment 3 Hydrolysis of Thermoplastic Polyurethane (TPU)

Objectives:
1．Through this experiment to explore the hydrolysis principle, mechanism and
phenomena of TPU and the related influencing factors of the reaction.
2．By comparing with experimental data and the data of previous two
experiments, obtaining the comparison result of the hydrolytic stability of PLA, PA
and TPU.
3．Analyze the difference in hydrolytic stability between PLA, PA and TPU and
explain the reason that causes the consequence.
Experimental Principle:
The basic principle of PU hydrolysis reaction is that water molecules attack the
amide-peptide bond (-NH-CO-) and ester group (-CO-O-) in the repeating structural
unit of the polyurethane polymer chain and break it to form a small molecular
carboxylic acid to further catalyze the hydrolysis reaction, and finally generate
oilgomers, monomers and CO2.

In aqueous and alkaline solutions, The water molecules preferentially attack the ester
group on the PU main chain and break it to generate carboxylic acid and alcohol. At
the same time, the carboxylic acid acts as a catalyst to further promote the hydrolysis
of the ester group and the amide-peptide bond to form a self-catalyzed reaction. In the
final reaction system, a large amount of carbamic acid and alcohol are generated, and
CO2 is produced at the same time, the specific reaction mechanism has been shown in
the figure below.
 Fig 1. Hydrolysis mechanism of PU
Materials and reagents:
Materials & Reagents Weight & Concentration
Thermoplastic Polyurethane particles 2.0028g
KOH alkaline solution-A 5%wt
KOH alkaline solution-B 10%wt
KOH alkaline solution-C 20%wt

Experimental Setup:
● Laboratory magnetic stirrer 2.000g
● Laboratory high temperature oven -
● Electronic laboratory scale -
● 100ml measuring cylinder -
● Glass stirring rod -
● 250ml beaker 50.4195g
● Spatula -
● Filter paper 0.55g
Experimental Procedure:
1．Initially prepare three groups of polyurethane particle samples with a spatula
respectively, then weigh 2.0g (control the error within 10-3gram) of sample for each
group, then put the sample respectively into three groups of 250ml beakers for the
experiment, make a label for each beaker.
2．Divide the three groups of polyurethane particle samples in the three labeled
beakers into three groups A, B, C for the experiments, Then add 20ml of KOH
alkaline solution-A with a concentration of 5wt% to the beakers of group A containing
PU particles for soaking, meanwhile, add 20ml of KOH alkaline solution-B with a
concentration of 10wt% to the beakers of group B for granulation Soaking, similarly,
add 20ml of KOH alkaline solution-C with a concentration of 20%wt to the beaker of
group C for particle soaking, then mark the group member on the three labels of
beakers respectively.
3．After the preparation step, put the three groups of polyurethane particle
samples A, B and C into the laboratory high temperature oven at the same time and
start the hydrolysis experiment at the condition of T=80°C, at the same time, set the
hydrolysis reaction time to 90 minutes, the three groups of samples were respectively
taken out at 30min, 60min and 90min of the reaction process, Meanwhile, the sample
characteristics (size, surface morphology, color and weight) at each time scale were
recorded.
4．After the 90-minute hydrolysis reaction is over, record the changes in the size,
surface morphology, color and weight of the four groups of Polylactic acid particle
samples, and compare the four groups of experimental data horizontally by the control
variable method to draw the experimental conclusion.
Experimental Notes:
1. During the experiment, the particle size of TPU particles have a slightly change
and almost no reduction of particle amount.
2. During the experiment, the colour TPU particles gradually changed from
translucent/beige to yellow.
3. The weight of TPU particles gradually have a tiny increase during the experiment.
 Fig 2. Actual pictures of TPU particles at 30min and 60min under the hydrolysis
condition of 20%wt KOH alkaline solution
Experimental Results and Data Analysis:
Experimental Results:
Group A---(5%wt KOH alkaline solution/80oC)
Average
Reaction Weight of TPU TPU particle Temperature
particle size Colour
time  sample (g) number (oC)
(mm)
translucent/
0 min 2.0039 65 7.28 0
beige
translucent/
30 min 2.0150 65 7.13 78.8979
beige

60 min 1.9813 64 7.32 beige 79.5456

90 min 1.9666 63 7.25 light yellow 67.6743

Group B---(10%wt KOH alkaline solution/80oC)

Average
Reaction Weight of TPU TPU particle Temperature
particle size Colour
time  sample (g) number (oC)
(mm)
translucent/
0 min 2.0047 62 6.98 0
beige

30 min 1.9834 61 6.54 beige 75.9540

60 min 1.9916 61 6.67 light yellow 79.5456

90 min 1.9978 59 6.75 yellow 67.6743

Group C---(20%wt KOH alkaline solution/80oC)

 Average
Reaction Weight of TPU TPU particle Temperature
particle size Colour
time  sample (g) number (oC)
(mm)
translucent/
0 min 1.9757 60 7.49 0
beige

30 min 1.9906 58 7.85 beige 75.9540

60 min 1.9749 57 7.68 yellow 79.5456

90 min 1.9384 55 7.46 yellow 67.6743

Data Analysis:
By processing the three sets of usage data, The line graph of TPU sample weight
change as a function of hydrolysis time has been drawn as below:

Fig 3. Horizontal comparison of the effects of different concentrations of

alkaline solutions on the hydrolysis of TPU
(1) Through the above experimental process and data analysis, it can be concluded
that the hydrolysis process of TPU is affected by three factors: Temperature,
Alkaline solution concentration, and Hydrolysis time.
(2) By comparing the above experimental data in Figure 3, it can be concluded that
the weight of the TPU sample treated with 5wt% KOH in group A first increased
slightly and then decreased. Similarly, the weight of the TPU sample treated with
20wt% KOH in group C also increased slightly and then decreased, but the rate
of sample weight reduction was much faster than that of group A, and for the
 TPU sample treated with 10wt% KOH in group B, its mass change principle is
opposite to that of the first two groups: the sample weight increases after a small
decrease.
(3) Through data analysis and literature review, it can be found that the abnormality
of the experimental data is related to the hygroscopic performance of the TPU
sample. Since the monomer of the TPU material particles contains polyhydric
alcohol, the alcohol has strong hydrophilicity. Therefore, the molecular structure
of TPU material particles contains many hydrophilic groups. Therefore, at the
beginning of the hydrolysis reaction, the moisture absorption of the TPU sample
caused its weight to increase slightly, but after a period of hydrolysis reaction, the
TPU sample began to degrade, and its weight began to decrease again.
Conclusion and Summary:
1．Through the above experiments, it can be concluded that the reason for the
increase in the mass of the TPU sample during the experiment is that there are many
hydrophilic groups in the TPU monomer, which can enhance its hygroscopicity,
resulting in an increase in the mass of the sample measured in the middle of the
experiment.
2．It can be observed that with the gradual progress of the hydrolysis reaction,
the color of the TPU sample gradually turns yellow. This is because the TPU material
is formed by the co-reaction and polymerization of diisocyanate molecules,
macromolecular polyols, and low molecular polyols (chain extenders). Diisocyanates
are divided into two types: aliphatic and aromatic according to their linking groups,
and the aromatic groups are unsaturated molecular structures. When the TPU material
containing aromatic group structure is hydrolyzed at high temperature, it is easy to
react with anions in the alkaline solution, resulting in aging and discoloration of the
product.
 Fig 4. Discoloration of TPU
3．By comparing with experimental data and the data of previous two
experiments, the hydrolytic stability of PLA, PA and TPU can be compared, which
indicates that hydrolysis stability of the three polymers is TPU>PA>PLA, the reason
is based on the electronegativity of functional groups of the three polymers, because
the electronegativity of Oaton is higher than N atom, so the hydrolysis activity of
PLA(-CO-O-) is higher than PA(-CO-NH-), for TPU, because of its (-O-CO-NH-)
group have a n-Π stable structure, which make the functional group more stable, and
then make TPU has the largest hydrolysis stability.