Synthesis and photopolymerisation of new fluorinated macromonomers for the obtaining of high performance fluoropolymers

Project Information

PhotoFluo

Grant agreement ID: 690917

DOI

10.3030/690917

Project closed

EC signature date 21 December 2015

Start date 1 February 2016

End date 31 January 2020

Funded under

• EXCELLENT SCIENCE - Marie Skłodowska-Curie Actions

Total cost

€ 238 500,00

EU contribution

€ 139 500,00

Coordinated by

POLITECNICO DI TORINO
Italy

Periodic Reporting for period 2 - PhotoFluo (Synthesis and photopolymerisation of new fluorinated macromonomers for the obtaining of high performance fluoropolymers)

Reporting period: 2018-02-01 to 2020-01-31

Summary of the context and overall objectives of the project

OBJECTIVES OF THE PROJECT AND ISSUES ADDRESSED

PhotoFluo is a Marie Skłodowska-Curie Research and Innovation Staff Exchange (RISE) project started on 1st February 2016. It consists of a consortium of three teams (two from Europe and one from Canada):
1. Politecnico di Torino (POLITO), Italy – Coordinator Organisation
2. Ecole Nationale Supérieure De Chimie De Montpellier (ENSCM), France – Beneficiary Organisation
3. Trinity Western University (TWU), Canada – Beneficiary Organisation.

PhotoFluo project aims at developing novel high-performance fluoropolymers, suitable for optical and electronic devices, membranes for fuel cells and Li batteries, microfluidics, and biomaterials. This ambitious goal will be achieved starting from designing new perfluoropolyalkylether (PFPAE) building blocks with improved safety (not bioaccumulative as the perfluoroalkyl structure currently employed) and showing chemical inertness, flexibility in a wide temperature range, very low refractive index and wettability.

PFPAE monomers will be properly modified and functionalized to tune the material final properties and make these precursors suitable for crosslinking. The fluoropolymers will be synthesized starting from the new monomers by photoinduced polymerization, chosen as an efficient and eco-friendly process: the polymer formation is fast (no more than minutes compared to hours requested by thermal processes), is solvent free, is carried out at room temperature consuming low amount of energy, permits spatial resolution, as it mainly occurs in the illuminated areas. After obtaining an original portfolio of PFPAE polymers, they will be fully characterized and tested in view of innovate applications.

IMPACT ON RESEARCHERS' CAREER AND ON SOCIETY

PhotoFluo project provides a window of opportunity for the researchers to work in challenging environments and acquire new skills and knowledge in chemistry and material science. In particular young researchers will exceptionally benefit from the project, as working with an interdisciplinary approach in an international team gives new career perspectives.
The development of safer fluoropolymers will impact different industrial fields. In fact polymers made of PFPAE building blocks have the advantage of not being bioaccumulative, unlike perfluoroalkyl chains which caused concerns and the banning in different applications.

For the implementation of the program, the three research partner teams have been selected as they have a relevant scientific record in the fields of:
1. fluorochemistry (TWU)
2. photopolymerization (POLITO and ENSCM)
3. polymer science (POLITO and ENSCM).

Secondments of 11 Early Stage Researchers (ESRs) and Experienced Researchers (ERs) are scheduled to exploit the complementarities of the different expertises of each group, to share them and to reinforce young researchers career. The project includes a strong dissemination plan to report on the results, not only to the scientific community, but also to potential users and non-specialized audience.

Work performed from the beginning of the project to the end of the period covered by the report and main results achieved so far

OVERVIEW OF THE RESULTS

During the four years of research, researchers from Italy, France and Canada were able to implement the work planned and to successfully reach the main goals of the project.

The scientific results achieved are:

1) The team designed and synthesised new compounds containing perfluoropolyalkylether (PFPAE) building blocks having the characteristics of highly fluorinated products, i.e. chemical inertness, thermal resistance, low glass transition (i.e. liquid in a wide temperature range), very low refractive index and low surface tension. Such products are preferred to perfluoroalkyl structures currently employed as they are not bioaccumulative and guarantee improved safety.

2) The team explored the use of the new PFPAE compounds for the making of polymers and copolymers: to this aim the process chosen was the photoinduced polymerisation. It is a green polymerisation process that uses no solvent, does not need the heating of the reactive compounds, shows extremely high reaction rate and thus is very fast (i.e. assuring the obtaining of a solid material in minutes or even in seconds).

3) The team obtained a variety of polymers and copolymers characterised by chemical and thermal resistance, mechanical flexibility in a wide temperature range, very low wettability towards polar and non-polar liquids (i.e. showing strong hydrophobicity and remarkable oleophobicity).

4) The team demonstrated that some of the new PFPAE polymers can be used in high-tech applications, in particular for separation membranes for energy devices (batteries) and for microfluidic reactors. By swelling the polymer with the appropriate electrolytic solution, membranes for ionic conduction can be obtained; by photolithographic techniques, appropriate patterning of the polymers can be produced opening the way to the fabrication of devices. Once the scaling up of the synthesis of the precursors is made and larger amounts of PFPAE chemicals are available, one can certainly propose their use for additive manufacturing.

All these results are reported in 7 publications on peer-reviewed journals and 24 oral presentations and 3 poster presentations to international conferences, to most of which the entire team contributed.

Other relevant results are:

1) 17 communications events reaching also the large public;

2) training of 6 young scientists (ESRs) assuring transfer of both scientific knowledge and soft skills, such as communication, dissemination, project management;

3) implementing the project management skills of the experienced researchers and their technical knowledge by an interdisciplinary approach;

3) building of a small but strong research team, actively willing to exploit the benefits of the past work continuing the collaboration.

Exploitation of the results through the submission of a patent concerning the synthesis of the PFPAE products is in progress. Three more papers are in preparation.

Progress beyond the state of the art and expected potential impact (including the socio-economic impact and the wider societal implications of the project so far)

The main results obtained by the PhotoFluo project concern the synthesis of new highly fluorinated products suitable for polymerisation processes: at present a platform of chemicals is available, although at a laboratory scale. This set of products is unique: they have in common a fluorinated building block, the perfluoropolyalkylether (PFPAE) chain, which provides the properties of most fluorochemical, but is non-bioaccumulative and non-toxic; they are diversified by a variety of reactive end-groups guaranteeing their use in polymerisation even in tha absence of a photoinitiator (as demonstrated by the work conducted) and their exploitation in other chemistries. This is an undoubtful step beyond the state of the art and a milestone for changing the present applications of fluorochemicals. Therefore, there is the potential for a socio-economic impact benefiting industries and society, at least in terms of safety and environmental concern.

Prove of this potential is that the PFPAE building blocks obtained and their synthetic procedures are under evaluation for the submission of a patent. Once the patent is assigned, the impact of the project will be quantified.

ACTIVITIES AND RESULTS OF PHOTOFLUO IN ONE SHOT