Thermochromic Polymers and their Structural Dependence

Nowadays, great scientific and technological advances have

completely changed the worldview, improving the performance of

things and so on. One of these discoveries are the thermochromic

polymers, which are materials with special properties that react

to changes in environmental conditions such as temperature. This

kind of materials exhibits change color when they heat or cool.

Also, the structural dependence of thermochromic behavior has

been studied to the control and design strategies of compounds

depending on environmental conditions.

For the design of thermochromic compounds and the analysis

of their properties, it is necessary to consider the composition

and structure of the compounds; this is the main factor for the

phenomenon of thermochromism to occur. These materials can be

designed from organic or inorganic materials. Among the most

used organic materials are thermochromatic liquid crystals,

leuco dyes, papers, and inks. In another hand, cuprous mercury

iodide, silver mercury iodide, and mercury iodide are the most

used inorganic compounds. Also, due to its composition,

thermochromic polymers can be divided into 2 groups, polymers

with inherent properties and doped compounds. The latter is

subdivided into thermochromic polymers based on pigments

aggregation and thermochromic polymers because of additives.

(Seeboth, Lötzsch, Ruhmann, and Muehling, 2014)

Hay and Hollingsworth (1996) studied polymers with inherent

properties, that is to say, materials able to react to

temperature change by their optical characteristics. These

polymers can be classified into liquid crystalline and

conjugated polymers. Liquid crystalline consists of organic

materials that present liquids and solid crystals properties;

and conjugated polymers are mostly organic materials

characterized by a backbone chain. The authors examined the

reaction of samples of liquid crystal polymers at different

active temperature ranges. According to theoretical data, liquid

crystals exhibit several optical properties as crystalline

solids, they show an orientation order but lose the position

order all that lead to fluency.

Additionally, based upon research, Hay and

Hollingsworth(1996)found that these type of compounds in

presence of white light, reflect red color at the end of the

active range at low temperature and blue color at the high end.

Also, above and below the active range, the compound appearance

is colorless. The handling of polymers with inherent properties

requires a careful technique because of the hard control of the

behavior of the physical system under study.

 Regarding polymers based on pigments aggregation, Luthern

and Peredes (2000) studied that in the solid state, 4,4’-

isopropylidenediphenol (bisphenol A; BPA) is a white and weak

acid; and crystal violet lactone (CVL) is a colorless dye. When

these two compounds are heated and form a solution, a blue color

it is exhibited because the dye, which is the responsible for

the color. CVL acts as electron donor and BPA as an electron

acceptor. The authors state that in this reaction, the acid

allows the adoption of a greater degree of a resonance of the

dye, consequently the conjugation is increased and the distance

between the bonding and antibonding pi orbitals decreased. The

increasing of the conjugation of the system causes the change of

color.

Futhermore, Luthern and Peredes (2000)performance a

spectrophotometric analysis of the component for measuring of

the transmittances of light in the sample. This analysis

indicates that the maximum absorbance of BPA/CVL occurs at a

ratio of 4,3/1,00 which means that this system is less

sensitive to bisphenol A concentration relative to crystal

violet lactone concentration. Also, it is found that in the

thermochromic mechanism, the electron acceptor has to overcome

before it is able to efficiently function as an electron

acceptor.
 Seeboth et al.(2014)examined the creation of polymers based

on interactions between a polymer matrix and additives. They

found that physical or chemical interactions between non-

thermochromic polymer matrices and non-thermochromic additives

lead to thermochromism to occur. The experiment was based in the

synthesis of a thermochromic multilayer polymer film composed of

a layer of non-thermoresponsive and thermoresponsive polymers.

In this experiment, the authors discovered that the coaction of

different components with non-thermochromic components originate

the thermoresponsive color effect.

Finally, there are several ways to the preparation and

assembling of thermochromic polymers. The thermochromic effect

has a strength relationship with the structure, and design of

the different materials. Hay and Hollingsworth (1996) developed

a research based on polymers with inherent properties while

Luthern and Peredes (2000) and Seeboth et al.(2014) designed

thermochromic polymers based on the doping and embedding of

pigments and other additives. The advances of science in this

field, have allowed the synthesis of a great variety of

products, from a thermochromic cup to a ring that changes color

according to body temperature, in addition to improving those

that already exist. However, there is still a large field that

needs to be investigated because the thermochromic materials

offer promising properties.

 References

Hay, J. L., & Hollingsworth, D. K. (1996). A comparison of

trichromic systems for use in the calibration of polymer-

dispersed thermochromic liquid crystals. Experimental Thermal

and Fluid Science, 12(1), 1–12. https://doi.org/10.1016/0894-

1777(95)00013-5

Luthern, J., & Peredes, A. (2000). Determination of the

stoichiometry of a thermochromic color complex via Job’s

method. Journal of Materials Science Letters.

https://doi.org/10.1023/A:1006790104175

Seeboth, A., Lötzsch, D., Ruhmann, R., & Muehling, O. (2014).

Thermochromic polymers - Function by design. Chemical

Reviews. https://doi.org/10.1021/cr400462e