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Polymers and Solgel

The document outlines exercises related to the synthesis and analysis of polymers, specifically focusing on copolymers of vinylphenol and methyl methacrylate, as well as cross-linked network polymer electrolytes based on polysiloxane. It includes questions on polymerization methods, mechanisms, size exclusion chromatography, glass transition temperatures, and the effects of various chemical compounds on ionic conductivity. Additionally, it discusses the relationship between cross-linking density and conductivity in polymer samples.

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2 views4 pages

Polymers and Solgel

The document outlines exercises related to the synthesis and analysis of polymers, specifically focusing on copolymers of vinylphenol and methyl methacrylate, as well as cross-linked network polymer electrolytes based on polysiloxane. It includes questions on polymerization methods, mechanisms, size exclusion chromatography, glass transition temperatures, and the effects of various chemical compounds on ionic conductivity. Additionally, it discusses the relationship between cross-linking density and conductivity in polymer samples.

Uploaded by

armandrovich
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Université Paul Sabatier Master for Energy Storage and Conversion

2008-2009 TU2M

Basics of Polymers and Sol-Gel Chemistry


2h

All the answers have to be argumented.

Exercise 1 : From F.C. Chang et al., Macromolecules, 2005, 38, 6435.

In a recent paper, F.C. Chang et al describe the synthesis of block and random copolymers made of
vinylphenol and methyl methacrylate (PVPh-block-PMMA and PVPh-random-PMMA).
1. Scheme 1 presents a synthetic pathway using a strong base such as sec-BuLi.

PVPh-PMMA

Scheme 1.

a- What is the name of this method of polymerisation ?


b- What are the advantages of such a synthetic method ?
c- What are the drawbacks of such a synthetic method?
d- Write down a possible mechanism for this polymer synthetic pathway, in particular give
the chemical structure of Poly A, Poly B, Poly C,
e- What is the type, block or random, of the obtained polymer PVPh-PMMA ?

2. Poly A and Poly B have been hydrolyzed then analysed by size exclusion chromatography (SEC).
Figure 1 shows the SEC traces. Attribute the traces to Poly A and Poly B.
(1) (2)

Figure 1. SEC traces of Poly A and Poly B

3. The number average molar masses of Poly A and Poly B are respectively 8000 and 16000. Taking
into account your answer and the data in question 2, calculate Mw of Poly A and Poly B.
4. Scheme 2 presents a synthetic pathway using AIBN.

Scheme 2.

a- What is the name of this method of polymerisation ?


b- What is the type, block or random, of the obtained polymer ?

5. The glass transition temperatures (Tg) of PVPh-random-PMMA and PVPh-block-PMMA


copolymers are summarized in Table 1 as a function of the monomers ratio.
a- Explain the increase of Tg as a function of PVPh content.
b- Propose an explanation for the variations of Tg observed between the random and block
copolymers as a function of the monomer ratios.
Table 1. Values of Tg obtained from PVPh-random-PMMA and PVPh-block-PMMA

Exercise 2 : From L.J. Lyons et al., Macromolecules, 2003, 36, 9176.

It is generally admited that the ionic conductivity of polymer electrolytes is enhanced in the
elastomeric amorphous phase by the segmental motion of the polymer chains. According to that,
significant research has been undertaken to develop a polymer structure having a highly flexible
backbone and amorphous character. The present exercise focus on the research of L.J. Lyons et al. for
cross-linked network polymer electrolytes based on a polysiloxane backbone with oligo(oxyethylene)
(EO) side chains doped with LiTFSI. The synthetic pathway is the following :

P0 P1

EO
3
1. The polysiloxane backbone is prepared using the sol-gel method. Propose a chemical structure for
the precursor of the polysiloxane P0.
2. Write all the sequence of reactions involved in the sol-gel preparation of the polysiloxane P0.
3. Polymer P1 is reacted with the following chemical compounds

DVEO
P1

a-Write down a possible chemical representation of the obtained polymer sample noted SPE.
b- What is the role of DVEO ?
c- What is the role of LiTFSI ?

4. By varying the ratio EO/Li+, different polymer samples have been prepared according to the
procedure previously described. Table 2 presents the electrical conductivities of the SPEs samples.
Analyse and explain the variation of the electrical conductivity.

Sample [EO/Li+] Conductivity (S.cm-1)


SPE-1 15/1 8.00x10-5
SPE-2 20/1 1.33x10-4
SPE-3 24/1 1.01x10-4
SPE-4 28/1 8.38x10-5
SPE-5 64/1 5.18x10-5
For all the samples, n/m = 1/30
Table 2. Electrical conductivities of SPE1-5

5. The thermograms of SPE-1, SPE-2 and SPE-3 are represented in Figure 2.


a. Determine the temperatures corresponding to eventual phase transitions for each polymer
sample.
b. Analyse and comment the results.

Figure 2. Thermograms of SPE-1, SPE-2 and SPE-3

6. What is the physical state of these polymers at room temperature (25°C).


7. In the conclusion of their publication, L.J. Lyons et al. claim that the cross-linking density in their
polymer samples (SPE) play an important role in enhancing the conductivity of the polymer
network electrolytes. What is the expected effect ?
8. Same question as previously for the effect of the chain length of EO on the conductivity.

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