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 2022.11.17 Tutor 闫毅，姚东东

Experiment 1 Hydrolysis of Polylactic acid

Objectives:
1. Through this experiment to investigate the hydrolysis process of PLA and its
influencing factors
2. By treating PLA particles with different concentrations of alkaline solution
(5/10/20wt%), the effect of alkaline solution concentration on the degree of hydrolysis
of PLA was explored.
3. By using different kinds of alkaline solutions (KOH/NaOH) to treat PLA particles,
exploring the effect of the type of alkaline solution on the degree of hydrolysis
process of PLA.
4. Analyze comparative usage data and draw conclusions by using the method of
controlling variables
Experimental Principle:
The basic principle of this experiment is that PLA is hydrolyzed under alkaline
conditions to generate monomers and oligomers.
In aqueous and alkaline solutions, the hydrolytic degradation of PLA proceeds via
random cleavage of the ester bond, the water molecules attack fragile ester groups in
PLA to break bonds, which caused the degradation.
 Fig 1. Hydrolysis process of PLA
Materials and reagents:
Materials & Reagents Weight & Concentration
Polylactic acid particles 2.0035g
KOH alkaline solution-A 5%wt
KOH alkaline solution-B 10%wt
KOH alkaline solution-C 20%wt
NaOH alkaline solution 10%wt

Experimental Setup:
● Laboratory magnetic stirrer 2.000g
● Type A laboratory magnetic stirrer rotor -
● Electronic laboratory scale -
● 100ml measuring cylinder -
● Glass stirring rod -
● 250ml beaker 50.4195g
● Spatula -
● Filter paper 0.55g
Experimental Procedure:
1．Weigh four groups of polylactic acid particles with a spatula
respectively,Weigh 2.0g of each group and put them into four groups of 250ml
beakers for the experiment.
2．Divide the four groups of polylactic acid particle samples that have been
weighed in the first step into four groups A, B, C, and D for experiments; Then add
100ml of KOH alkaline solution-A with a concentration of 5%wt to the beakers of
group A containing polylactic acid particles for soaking; Similarly, add 100ml of
KOH alkaline solution-B with a concentration of 10%wt to the beakers of group B for
granulation Soaking; add 100ml of KOH alkaline solution-C with a concentration of
20%wt to the beaker of group C for particle soaking; add 100ml of NaOH alkaline
solution with a concentration of 10%wt to the beaker of group D for particle soaking.
3．Put the four groups of Polylactic acid samples A, B, C and D into the
magnetic stirrer at the same time to start the hydrolysis experiment at 80°C, and set
the hydrolysis reaction time to 90 minutes; the four groups of samples were
respectively taken out at 20min, 40min, 60min, 80min and 90min of the reaction and
the sample size, surface morphology, color and weight 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 and size of PLA particles gradually
decreased, and the number decreased slightly.
2. During the experiment, the colour PLA particles gradually changed from milky
white to light yellow.
3. The weight of PLA particles gradually decreased during the experiment.

Fig 2. Actual pictures of PLA at 20min, 40min, and 90min under the hydrolysis
condition of 10%wt KOH alkaline solution
Experimental Results and Data Analysis:
Experimental Results:
Group A---(5%wt KOH alkaline solution/80oC)
Weight of Average
Reaction Polylactic acid Temperature
polylactic particle size Colour
time  particle number (oC)
acid sample (g) (mm)
0 min 2.0271 52 5.18 Milky white 0
20 min 2.0218 52 5.13 Milky white 78.8979

40 min 2.0260 52 5.09 Milky white 75.9540

60 min 2.0001 51 5.03 Milky white 79.5456

80 min 1.9840 50 4.95 Milky white 77.6432

90 min 1.9812 50 4.91 Milky white 67.6743

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

Weight of Average
Reaction Polylactic acid Temperature
polylactic particle size Colour
time  particle number (oC)
acid sample (g) (mm)
0 min 2.0035 50 4.90 Milky white 0
20 min 1.9545 48 4.83 Milky white 78.8979

40 min 1.9438 47 4.77 Milky white 75.9540

60 min 1.9347 45 4.68 Milky white 79.5456

Light milky
80 min 1.9217 44 4.59 77.6432
white
Milky white
90 min 1.9244 44 4.55 67.6743
to yellow
Group C---(20%wt KOH alkaline solution/80oC)
Weight of Average
Reaction Polylactic acid Temperature
polylactic particle size Colour
time  particle number (oC)
acid sample (g) (mm)
0 min 1.9757 53 4.79 Milky white 0
20 min 1.8935 49 4.68 Milky white 78.8979

40 min 1.8275 47 4.55 Milky white 75.9540

Light milky
60 min 1.7779 44 4.43 79.5456
white
 Milky white
80 min 1.6747 41 4.32 77.6432
to yellow
Lightly
90 min 1.6324 39 4.27 67.6743
yellow
Group D---(10%wt NaOH alkaline solution/80oC)
Weight of Average
Reaction Polylactic acid Temperature
polylactic particle size Colour
time  particle number (oC)
acid sample (g) (mm)
0 min 2.0070 49 4.87 Milky white 0
20 min 1.9960 48 4.76 Milky white 78.8979

40 min 1.9817 46 4.64 Milky white 75.9540

60 min 1.9745 46 4.59 Milky white 79.5456

Light milky
80 min 1.9678 45 4.50 77.6432
white
Light milky
90 min 1.9625 45 4.48 67.6743
white

Data Analysis:
By processing the four sets of usage data, The line graph of PLA weight as a function
of hydrolysis time was drawn

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

alkaline solutions on the hydrolysis of PLA
 Fig 4. Lateral comparison of the effects of different alkaline solutions
on the hydrolysis of PLA
Conclusion and Summary:
(1) Through the above experimental process and data analysis, it can be concluded
that the hydrolysis process of PLA is affected by four factors: Temperature,
Alkaline solution weight, Alkaline solution concentration, and Hydrolysis time.
(2) According to the data comparison in Fig 3, By comparing the data in Figure 3, it
can be concluded that the PLA sample treated with 20%wt KOH solution has the
fastest degradation rate, followed by the PLA sample treated with 10%wt KOH
solution, and the PLA sample treated with 5%wt KOH solution. The sample
hydrolysis rate is the slowest, so it can be illustrated that with the increase of the
concentration of the alkaline solution, the hydrolysis rate of PLA showed an
increasing trend with the increase of the concentration of the alkaline solution.
(3) By analyzing the data in Figure 4 and making a horizontal comparison, it can be
concluded that the hydrolysis rate of the PLA sample treated with KOH alkaline
solution is better than that of the NaOH alkaline solution treatment group under
the same conditions, indicating that the type of alkaline solution has an influence
on the hydrolysis rate of PLA.
3 additional questions
1. How to synthesize polylactic acid
PLA is one of the mainstream degradable plastic products. It is a polymer
polymerized from lactic acid as the main raw material. There are two methods for
preparing PLA, namely lactide ring-opening polymerization method and direct
polycondensation method. The lactide ring-opening polymerization method is widely
used currently.

The direct polycondensation method, also known as the one-step method, refers to the
process of preparing PLA by dehydration polycondensation of lactic acid molecules.
The disadvantage of this method is that the reaction system is in a dynamic
equilibrium of polycondensation and depolymerization, and the gradual increase of
the viscosity of the system leads to an increase in the difficulty of removing the by-
product water, and the water that cannot be removed in time will cause the reaction to
proceed in the direction of polymer depolymerization, thereby affecting the PLA.
increase in molecular weight. At the same time, under the reaction conditions of high
temperature and high vacuum, PLA will also undergo depolymerization, coloration
and racemization, which reduces the properties of the product. One-step production of
PLA has a short production process and low cost, but due to the difficulty of
effectively increasing the molecular weight of PLA and the poor mechanical
properties of the product, its industrial application is limited.

The lactide ring-opening polymerization method, also known as the two-step method,
is a process in which lactic acid is first dehydrated to form oligomers, then
depolymerized to form lactide, and then ring-opening polymerization to obtain PLA.
The core technology lies in the synthesis and synthesis of lactide. purification. The
purification of lactide is crucial in the entire ring-opening polymerization process, and
only lactide with high purity can be used to synthesize PLA with high molecular
weight and good physical properties. The two-step method involves the purification
steps of lactide, which is not only complicated in process and high in cost, but can be
achieved by controlling the purity and reaction conditions of lactide to produce PLA
with high molecular weight, controllable chemical structure and better mechanical
properties. , so it is the most widely used method in industry.

Fig 5. Synthesis of PLA from l-and d-lactic acids[1].

2. The difference between the degradation activity of the side chain
ester group and the main chain ester group
Polyesters with ester side groups should follow the principle of Small Molecule
Elimination Reaction Without Main Chain Breakage during the hydrolysis process of
polyester.

In the process of hydrolysis, the ester group in the ROOH group on the side chain is
more active than the ester group on the main chain, so the hydrolysis process starts
with the elimination of the side group, forming a small molecule instead of a
monomer. When the small molecules are eliminated to a certain extent, the weak
points of the main chain ester group increase, and finally the main chain is broken,
and the polymer is fully degraded;
In addition, if the R group in the ROOH group on the side group has higher
electronegativity or molecular weight, it will attract OH- and H2O molecules in the
alkaline solution to attack the ester group on the side chain instead of the main chain
ester group[2].

3. A brief introduction to Professor Chen Xuesi's research in the

direction of PLA
Degradable PLA can be prepared by the ring-opening polymerization of lactide,
which has important application value in the fields of medicine, agriculture and
industry. However, the inherent hydrophobicity and brittleness of such polymers
greatly limit their application range. Therefore, the development of functionalized
PLA materials will have broad application prospects.

Nowadays, Academician Chen Xuesi realized the controllable switch polymerization

of lactide (LA) and 1,3-dioxolane-2,4-dione (OCA) using SalenMn(III)Cl catalyst,
and prepared functionalized blocks Type degradable polyester[3].

Compared with LA, the polymerization process of OCA has a lower Gibbs free
energy, and the CO2 released during the polymerization process will also cause
changes in entropy and enthalpy during the reaction. The SalenMn(III)Cl catalyst has
very special properties. After coexisting with alkylene oxide, it will first generate
SalenMnOR active species, which can rapidly polymerize LA or caprolactone; and
this active species can quickly absorb CO2 to obtain SalenMnOCOR, which is
difficult to polymerize LA, But OCA can be aggregated quickly. The team of
Academician Chen Xuesi realized this controllable switch polymerization reaction by
using a small amount of CO2 generated by OCA polymerization, and then realized the
preparation of block polymers
 Fig 6. The polymerization mechanism of LA and OCA[3]
References
[1] Nanofiller Reinforced Biodegradable PLA/PHA Composites: Current Status and Future Trends
- Scientific Figure on ResearchGate. Available from:
https://www.researchgate.net/figure/Synthesis-of-PLA-from-l-and-d-lactic-acids-Reproduced-
with-permission-from-57_fig1_324992775 [accessed 14 Nov, 2022]
[2] Yan, Zhifeng, et al. “Deeper Insight into Hydrolysis Mechanisms of Polyester/Cotton Blended
Fabrics for Separation by Explicit Solvent Models.” International Journal of Biological
Macromolecules, vol. 154, 2020, pp. 596–605., https://doi.org/10.1016/j.ijbiomac.2020.03.130.
[3] Huang Y, Hu C, Zhou Y, Duan R, Sun Z, Wan P, Xiao C, Pang X, Chen X. Monomer Controlled
Switchable Copolymerization: A Feasible Route for the Functionalization of Poly(lactide). Angew Chem Int
Ed Engl. 2021 Apr 19;60(17):9274-9278. doi: 10.1002/anie.202017088. Epub 2021 Mar 17. PMID:
33580552.