1) The document investigates the ability of polydiacetylene (PDA) compounds to change color irreversibly upon heating. It studies this property for eicosa-9,11-diyne and 10,12-pentacosadiynoic acid, finding color changes at 45°C and 70°C respectively. 2) A 50/50 mixture of the two compounds changes color between 50-60°C, indicating an intermediate transition temperature. 3) The PDA compounds only polymerize in the solid state on cellulose filter paper under UV light. Solvent effects and functionalization could allow polymerization into films for applications like intelligent labels.

1. Department of Polymer Science
COMMUNICATION
Department of Polymer Science, 2015 | 1
Chemical Communication
Received 13
th
November 2015
Attachment of irreversible thermochromic groups onto cellulose
M. A. Thomson
The ability of polydiacetylene (PDA)-based compounds to change
colour upon heating was investigated in a range of solvents.
Eicosa-9,11-diyne was polymerized via self-assembly upon UV
irradiation and an irreversible colour change from blue to red was
observed at approximately 45 °C. The thermochromic behaviour of
10,12-pentacosadiynoic acid was also investigated and exhibited
an irreversible colour change from blue to red at 70 °C. A 50/50
wt.% mixture of eicosa-9,11-diyne and 10,12-pentacosadiynoic
acid exhibited an irreversible colour change from blue to red
between 50 and 60 ° C.
A diacetylene is a compound which contains two conjugated triple
bonds, allowing for various structural changes upon external stimu-
lus
1
(such as changes in temperature, ionic interaction, electrical
fields or microbial interaction). Upon ultraviolet irradiation, the
diacetylene monomers undergo a self-assembly mechanism to form
polydiacetylenes (PDAs)
2
. The ability to observe the colour change
of the PDA from blue to red with the naked eye is the property
which makes the diacetylenes so versatile
3,4
. An industrial applica-
tion of the PDAs is as an “intelligent” label
5
which changes colour
irreversibly to indicate the thermal history of stored food products.
Eicosa-9,11-diyne (ECD) was synthesized using Hay
6
coupling of
1-decyne (Scheme 1)
1
, which was ordered from Sigma-Aldrich®.
Characterization of the monomer and polymer was done via solu-
tion
1
H NMR and
13
C NMR, and FTIR. 10,12-pentacosadiynoic acid
(PCDA) was ordered from Sigma-Aldrich® and characterized with
FTIR. Solutions of each monomer (0.3 wt.%) were made using a
range of solvents and applied to α-cellulosic filter paper ordered
from Whatman®.
The solvent was allowed to evaporate in a fume hood at room
temperature overnight. The filter paper was placed in a UV box (254
nm, 10 W) for 1 minute. After irradiation the filter paper was heat-
ed on a heating plate and the temperature at which colour change
from blue to red occurred was recorded. Once the thermochromic
temperature of each monomer was determined, a 50/50 wt.% mix-
ture of ECD (0.015 g) and PCDA (0.015 g) in DCM (10 mL) was pre-
pared in attempt to observe an intermediate thermochromic tem-
perature.The solvent effects of a range of classic organic solvents
on the thermochromism of the monomers was investigated.
Both monomers were dissolved in a range of solvents, applied onto
filter paper and the solvent was allowed to evaporate. The colour
change of the filter paper before and after solvent evaporation was
recorded. Each DA monomer was incorporated into a poly(vinyl
alcohol) (PVA) film with a PVA:DA ratio of 1:0.3 (v/v %) in 10 mL
DCM. The films which were cast were then irradiated with UV light
for 1 minute.
*Supplementary experimental procedures can be found in the addi-
tional experimental appendix.
Wang et al.
1
proposed the polymerization mechanism (Scheme
2) via self-assembly of the DA monomer units, which sees the
change from conjugated triple bond structure to a double-triple
bond conjugation in the backbone.
The polymerization of each monomer was attempted in both
solid state and in solution with varying solvents. It was observed
that the self-assembly mechanism was only possible in the solid
state when deposited onto filter paper, due to the fact that in solu-
tion the monomer molecules might have been too dispersed and
isolated for self-assembly to occur
5
. In the solid state, the monomer
units were close enough to one another to allow the self-assembly
mechanism to occur. Therefore the solutions did not exhibit ther-
mochromism after UV irradiation. Each monomer in solution was
characterized using solution NMR and FTIR before and after UV
irradiation and no structural change was observed, therefore
polymerization was unsuccessful in solution.
The monomer in the solid state self-assembled on cellulosic fil-
ter paper upon UV irradiation. The dried monomer was white on
the surface of the filter paper and then after UV exposure a colour
change to blue was observed, indicating that polymerization had
occurred (Fig. 1).
*(NMR and FTIR data can be found in the supplementary appendix).
Department of polymer science, University of Stellenbosch, Private bag X1, Matieland, 7602
Scheme 1: Formation of eicosa-9,11-diyne via Hay
6
coupling of 1-decyne
UV
h𝑣
Fig. 1. Colour change from white to blue of eicosa-9,11,-diyne after UV irradiation
for 1 minute.
UV
h𝑣
Scheme 2: Polymerization of eicosa-9,11-diyne via UV irradiation1
.

2. CHEMICAL COMMUNICATION STELLENBOSCH UNIVERSITY
Department of Polymer Science, 2015 |2
Fig. 4. Colour transition of each PDA from before and after heating past the thermochromic point in a range of
classic organic solvents
Table 1 shows the thermochromic temperatures of ECD and
PCDA which were observed at approximately 45 °C and 70 °C, re-
spectively. The thermochromic temperature of ECD was approxi-
mate and exists as a range of temperatures between 45 °C and 55
°C due to the fact that the conversion of the Hay coupling
6
is ques-
tionable. The greater the conversion of the synthesis, the more
uniform the thermochromic temperature of the polymer. Fig. 2a
shows the colour transition temperature for the ECD polymer, while
Fig. 2b shows PCDA exhibited a specific thermochromic tempera-
ture of 70 °C.
Once the thermochromic temperature of each monomer had
been identified, a mixture of the two monomers could be prepared
in an attempt to program the temperature at which the polymer
would change temperature. Fig. 3 shows that the 50/50 wt.% mix-
ture of each monomer in DCM exhibited partial thermochromism at
approximately 50 °C, and full colour change at 60 °C. This suggests
that either the separate constituents of the mixture changed colour
at their respective temperatures, or an intermediate thermo-
chromic temperature was obtained in between that of each mono-
mer. The temperature range in which colour change occurred was
relatively large, suggesting that the mixture is heterogeneous and
the temperature range is merely the overlapping of the two mono-
mers’ separate colour transitions. A possible solution would be to
produce a graft copolymer of ECD and PCDA, which would improve
the compatibility between the two phases - and thus a single inter-
mediate thermochromic temperature could be obtained rather
than the broad range which was observed.
It was observed that solvent effects caused colour change of the
monomers (i.e. the monomers were solvatochromic
7
). Before the
evaporation of the solvent, the ECD and PCDA were green and red,
respectively. Once the solvent had evaporated completely, the
monomers were both white. After irradiation the change in solvent
caused a change in the shade of blue of the polymer which forms
on the filter paper, indicating that certain solvents allowed for the
self-assembly mechanism better than others.
Fig. 4 shows the characteristic colour change from blue to red
upon heating in a range of classic organic solvents. It was observed
that ECDA exhibited lower solubility (even after sonication) in the
range of classic solvents when compared to PCDA. This was evident
by the degree of aggregation of the ECD in the solvent, resulting in
clumping of solid monomer on the filter paper. Furthermore, it was
observed that the PCDA samples exhibited more saturated/intense
shades of blue and red than the ECD samples. This could possibly be
due to the fact that the PCDA molecules contained polar carboxylic
acid moieties, whereas the ECD molecules were apolar. This al-
lowed the PCDA molecules to anchor onto the cellulose filter paper
via hydrogen bonding between the carboxylic acid and alcohol moi-
eties. Films casted of PVA/DA monomer were exposed to UV radia-
tion and the thermochromic properties observed. The PCDA-
incorporated film exhibited colour change after UV exposure from
clear to blue (Fig. 5), confirming that polymerization had occurred
in the film state. The film changed temperature at 70 °C, which was
expected as the thermochromic temperature of PCDA on filter pa-
per was also 70 °C.
PVA/ECD films did not change colour upon UV exposure, indi-
cating that polymerization did not occur. This could again be at-
tributed to its apolar nature, leaving it unreacted on the PVA sur-
face and thus inhibiting the self-assembly mechanism. Whereas the
PCDA molecules could experience hydrogen bonding with the PVA,
providing sites for self-assembly to occur.
Fig. 2. Colour transition of the DA monomers from blue to red (a) eicosa-9,11-diyne with a
thermochromic temperature range between 45 °C and 55 °C, (b) 10,12-pentacosadiynoic
acid with a thermochromic temperature of 70 °C.
Table 1: Thermochromic temperatures of monomers eicosa-9,11-diyne and 10,12-
pentacosadiynoic acid
Fig. 3. Colour transition of 50 wt.% eicosa-9,11-diyne/10,12-pentacosadiynoic
acid. Partial colour change at 50 °C and complete colour change at 60 °C.

3. CHEMICAL COMMUNICATION STELLENBOSCH UNIVERSITY
Department of Polymer Science, 2015 | 3
In order to incorporate ECD into a film which would then exhibit
thermochromic properties, the DA monomer must be functional-
ized before the polymerization step. The addition of a reactive
group (i.e. carboxylic acid) would improve the compatibility be-
tween the DA and the film, thereby allowing the self-assembly
mechanism to occur. This proves that the production of an “intelli-
gent” label is possible simply by the incorporation of a DA monomer
into a polymer film, provided that the DA monomer can attach onto
the film substrate to allow the self-assembly mechanism to occur.
In conclusion, the polymerization of diacetylenes in the solid
state was possible via UV irradiation, producing the polydiacety-
lenes (PDAs) with the characteristic of changing colour from blue to
red once a specific thermochromic temperature was surpassed. A
50:50 mixture of PCDA and ECD was prepared, which exhibited a
broad thermochromic transition range suggesting that the mole-
cules were not compatible enough to exhibit a single intermediate
thermochromic point in-between that of each monomer. The DA
monomers were solvatochromic, with a difference in colour when
in solution compared to in the solid state. PCDA exhibited strong-
er/more intense colour when compared to ECD due to its strong
interaction with the alcohol groups of the cellulose. Films were
casted of each DA, of which only PCDA underwent polymerization
after UV irradiation. The use of diacetylenes as sensory molecules is
feasible, provided that compatibility exists between the DA and the
substrate on which it is anchored.
Notes and references
* Text marked with an asterisk refers to information which can
be found in the supplementary information appendix.
[1] Wang, M., Wang, F., Wang, Y., Zhang, W. & Chen, X.
Polydiacetylene-based sensor for highly sensitive and
selective Pb2+ detection. Dye. Pigment. 120, 307–313
(2015).
[2] Bloor, D. Topochemical Polymerization: Diynes. Compr.
Polym. Sci. Suppl. 5, 233–249 (1989).
[3] Sun, X., Chen, T., Huang, S., Li, L. & Peng, H. Chromatic
polydiacetylene with novel sensitivity. Chem. Soc. Rev. 39,
4244–57 (2010).
[4] Chanakul, A., Traiphol, N. & Traiphol, R. Controlling the
Reversible Thermochromism of Polydiacetylene/zinc Oxide
Nanocomposites by Varying Alkyl Chain Length. J. Colloid
Interface Sci. 389, 106–114 (2013).
[5] Rougeau, L., Picq, D., Rastello, M. & Frantz, Y. New
irreversible thermochromic polydiacetylenes. Tetrahedron
64, 9430–9436 (2008).
[6] Hay, A. Oxidative Coupling of Acetylenes. II1. J. Org. Chem.
3–4 (1962). doi:10.1021/jo01056a511
[7] Lee, J. et al. A protective layer approach to solvatochromic
sensors. Nat. Commun. 4, 2461 (2013).
Fig. 5. Polymerization of a 1:0.3 (v/v %) PVA/PCDA film via UV irradiation and colour transition from blue to red at 70 °C.
UV ΔH