Periodic Reporting for period 1 - TORNADO (NEW ROUTES OF SAFE AND SUSTAINABLE BY DESIGN WATER AND OIL REPELLENT BIOBASED COATINGS)
Berichtszeitraum: 2023-01-01 bis 2024-06-30
Due to a variety of unique properties, including excellent water and oil repellence, high thermal stability, the substance class of perfluorinated and polyfluorinated compounds is found in a broad portfolio of coatings. PFAS are a class of thousands of substances that have been produced since the 1940s and used in a broad range of consumer products and industrial applications. PFAS contain both fluoro-carbon and hydro-carbon segments where the non-fluorinated part can degrade and ultimately form perfluorinated PFAS acids, such as PFOA and PFOS. Based on these EU objectives, new toxicity-free coatings with the same functionalities than coatings based on PFAS and minimizing the environmental footprint of the new coatings in particular on climate change, resource use, ecosystems and biodiversity from a life cycle perspective represent a challenge. To identify and fully understand the key challenges and the corresponding research needs TORNADO project aims to contribute to the transition to a safe circular economy by influencing how products should be designed, produced, used or treated at their end-of-life. To achieve the main objective, new organic and hybrid free-toxic coatings with water and oil repellence that are safe and deliver environmental, societal, and/or economical value through their applications (packaging, textile, and kitchenware) will be developed. Moreover, these coatings must accelerate the transition towards a circular economy and climate neutral society and prevent harm to human health and the environment throughout the life cycle, besides enhancing the competitiveness of the European chemical industry and its value chain. TORNADO is going to regain competitiveness for the EU chemical industry bringing sustainable solutions across various sectors, i.e. textiles, packaging and kitchenware, by developing new biobased coatings free of toxic compounds as PFAS
Two new bio-based acrylated bio monomers derived from soybean oil (SO) have been developed by two different chemical routes:
1.- Acrylation of vegetable oils in two consecutive steps.
2.- Acrylation of vegetable oils in one step.
AESO biomonomers has been functionalized with polydimethylsiloxane (PDMS) and polyhedral oligomeric silsesquioxane (POSS). Biomonomers with different molecular weight have been synthesized (750, 1250 and 2500g/mol). A protocol to define the acrylation degree has set up. Scale up trials of PDMS-modified bio-monomer have been carried out (up to 1.5kg).
New waterborne acrylic binders based on commercial biomonomers, TORNADO´s ASO biomonomers and PDMS and POSS functionalized AESO biomonomers have been successfully synthesized by miniemulsion process at lab scale up to 25wt% of biomonomer. PDMS and POSS functinalized AESO have been successfully synthesized by emulsion polymerization processes at lab scale up to 5wt% of biomonomer.
Hybrid sol-gel coatings have been developed. The research has focused on the topcoat.
A template for data collection and elaboration of the LCI has been carried out. A first version of LCI contains laboratory scale data from biomonomer production, functionalization and waterborne and sol-gel coatings has been reached. In addition, end-user information has been requested for the three applications (textile, F&B packaging and kitchenware).
An inventory of available computational tools for predicting both human and ecotoxicity has been performed, as well as computational tools for predicting transformation of the chemicals. The hazard predictions were performed for all the chemicals identified in the Life Cycle Inventories. The hazard properties predicted in silico include environmental fate endpoints such as persistence and bioaccumulation as well as a series of human and eco toxicity endpoints.
1.- Acrylation of vegetable oils in two consecutive steps.
2.- Acrylation of vegetable oils in one step.
AESO biomonomers has been functionalized with polydimethylsiloxane (PDMS) and polyhedral oligomeric silsesquioxane (POSS). Biomonomers with different molecular weight have been synthesized (750, 1250 and 2500g/mol). A protocol to define the acrylation degree has set up. Scale up trials of PDMS-modified bio-monomer have been carried out (up to 1.5kg).
New waterborne acrylic binders based on commercial biomonomers, TORNADO´s ASO biomonomers and PDMS and POSS functionalized AESO biomonomers have been successfully synthesized by miniemulsion process at lab scale up to 25wt% of biomonomer. PDMS and POSS functinalized AESO have been successfully synthesized by emulsion polymerization processes at lab scale up to 5wt% of biomonomer.
Hybrid sol-gel coatings have been developed. The research has focused on the topcoat.
A template for data collection and elaboration of the LCI has been carried out. A first version of LCI contains laboratory scale data from biomonomer production, functionalization and waterborne and sol-gel coatings has been reached. In addition, end-user information has been requested for the three applications (textile, F&B packaging and kitchenware).
An inventory of available computational tools for predicting both human and ecotoxicity has been performed, as well as computational tools for predicting transformation of the chemicals. The hazard predictions were performed for all the chemicals identified in the Life Cycle Inventories. The hazard properties predicted in silico include environmental fate endpoints such as persistence and bioaccumulation as well as a series of human and eco toxicity endpoints.
NEW BIOBASED BIOMONOMERS WITH WATER AND OIL REPELLENCE
New biomonomers have been synthesized by two different chemical routes. The first one has been a two-step process that is the conventional way to obtain acrylated epoxidized soybean oils. To reduce the generation of metal residues, the thermal acrylation process without the use of catalyst has been investigated. It has been found that the reaction of total epoxidezed oil with AA can be successfully carried out by controlling the concentrations of reagents and temperature. Moreover, ASO biomonomers with different acrylation degrees have been synthesized by the direct acrylation route.
Some challenges due to the incompatibility between the silicone based materials and AESO have been get over. Mono-hydride functional polydimethylsiloxane (750 Da, 1250Da and 2500 Da) with very low toxic residual components (D4, D5 and D6) have been synthesized and fully functionalized AESO has been modified. New AESO-PDMS and AESO-POSS biomonomers with one functional double bond have been obtained.
NEW BIOBASED ORGANIC AND HYBRID COATINGS WITH WATER AND OIL REPELLENCE
New waterborne binders to provide novel toxic-free waterborne and biobased binders based on complex acrylic/PDMS and acrylic/POSS chemistries able to build up water and oil repellent coatings for packaging and textiles sectors have been synthesized. Two different chemical routes have been followed, miniemulsion and emulsion polymerization processes. Biocopolymers present up to 25% of biomonomers. A Tg<0º in concordance with the requirements provided by the textile and packaging sector have been developed. Hydrophobic biocopolymer has been obtained WCA>90º and HCA>40º.
Hybrid sol-gel formulations for kitchenware topcoat have been develop. The sol-gel has been applied on metal substrates and the hydrophobicity of the systems characterized being >100º.
DESIGN OF NEW COATINGS FOLLOWING SAFE AND SUSTAINABLE CRITERIA
A preliminary regulatory screening covering the chemicals intended for use as replacements for PFAS in the different products targeted by the TORNADO project. An inventory of available computational tools for predicting both human and eco-toxicity has been compiled, as well as computational tools for predicting the environmental transformation of the chemicals. A number of QSAR based h-phrases prediction models developed in the nationally funded Mistra SafeChem project that has been trained on more dedicated sets of chemicals such as siloxanes have been used.
A first version with relevant data to start LCA studies have been prepared with information from biomonomer production, functionalization and waterborne and sol-gel coatings. LCA has started to analyse the LCI from an environmental and economic point of view in order to support decision making with regard to the different alternatives studied at laboratory scale.
New biomonomers have been synthesized by two different chemical routes. The first one has been a two-step process that is the conventional way to obtain acrylated epoxidized soybean oils. To reduce the generation of metal residues, the thermal acrylation process without the use of catalyst has been investigated. It has been found that the reaction of total epoxidezed oil with AA can be successfully carried out by controlling the concentrations of reagents and temperature. Moreover, ASO biomonomers with different acrylation degrees have been synthesized by the direct acrylation route.
Some challenges due to the incompatibility between the silicone based materials and AESO have been get over. Mono-hydride functional polydimethylsiloxane (750 Da, 1250Da and 2500 Da) with very low toxic residual components (D4, D5 and D6) have been synthesized and fully functionalized AESO has been modified. New AESO-PDMS and AESO-POSS biomonomers with one functional double bond have been obtained.
NEW BIOBASED ORGANIC AND HYBRID COATINGS WITH WATER AND OIL REPELLENCE
New waterborne binders to provide novel toxic-free waterborne and biobased binders based on complex acrylic/PDMS and acrylic/POSS chemistries able to build up water and oil repellent coatings for packaging and textiles sectors have been synthesized. Two different chemical routes have been followed, miniemulsion and emulsion polymerization processes. Biocopolymers present up to 25% of biomonomers. A Tg<0º in concordance with the requirements provided by the textile and packaging sector have been developed. Hydrophobic biocopolymer has been obtained WCA>90º and HCA>40º.
Hybrid sol-gel formulations for kitchenware topcoat have been develop. The sol-gel has been applied on metal substrates and the hydrophobicity of the systems characterized being >100º.
DESIGN OF NEW COATINGS FOLLOWING SAFE AND SUSTAINABLE CRITERIA
A preliminary regulatory screening covering the chemicals intended for use as replacements for PFAS in the different products targeted by the TORNADO project. An inventory of available computational tools for predicting both human and eco-toxicity has been compiled, as well as computational tools for predicting the environmental transformation of the chemicals. A number of QSAR based h-phrases prediction models developed in the nationally funded Mistra SafeChem project that has been trained on more dedicated sets of chemicals such as siloxanes have been used.
A first version with relevant data to start LCA studies have been prepared with information from biomonomer production, functionalization and waterborne and sol-gel coatings. LCA has started to analyse the LCI from an environmental and economic point of view in order to support decision making with regard to the different alternatives studied at laboratory scale.