Inventory of additives in epoxy resins/ composites

Grant Agreement number: 101058371 Project acronym: ESTELLA Project title: Design of bio-based thermoset polymer with recycling capability by dynamic bonds for bio-composite manufacturing Grant Agreement number: 101058371 Project acronym: ESTELLA Project title: Design of bio-based thermoset polymer with recycling capability by dynamic bonds for bio-composite manufacturing DELIVERABLE 1.1 Inventory of additives in epoxy resins/composites Contractual Date of Delivery: 01 09 2022 Actual Date of Delivery: 29 09 2022 Lead contractor for this deliverable: SINTEF Author(s): J. Comerford, R. Gaarder, K. Olafsen Participants(s): Tonje Heggeset, Anders Brunsvik WP contributing to the deliverable: WP 1 Nature: Internal report for Consortium Version V. 4 Grant Agreement 101058371 – Project ESTELLA ESTELLA_D1.1 ©ESTELLA - This is the property of ESTELLA Parties: shall not be distributed/reproduced without formal approval of ESTELLA General Assembly. This reflects only the author’s views. The Community is not liable for any use that may be made of the information contained therein. REVISION TABLE Document version Date Modified sections - Details V1 27.09.22 Internal review by SINTEF V2 28.09.22 Internal review by CID V3 29.09.22 Edited version V4 29.09.22 ICSO & CID quality control - Edited Grant Agreement 101058371 – Project ESTELLA ESTELLA_D1.1 ©ESTELLA - This is the property of ESTELLA Parties: shall not be distributed/reproduced without formal approval of ESTELLA General Assembly. This reflects only the author’s views. The Community is not liable for any use that may be made of the information contained therein. Table of Contents TABLE OF CONTENTS .................................................................................................................... 3 ABBREVIATIONS ........................................................................................................................... 4 EXECUTIVE SUMMARY .................................................................................................................. 5 1. APPLICATION SPECIFIC ADDITIVES .................................................................................... 6 1.1. WINDOW FRAMES MADE WITH COMPOSITE MATERIALS ...............................................................6 1.2. CONTINUOUS FIBRE COMPOSITE MATERIALS ........................................................................... 10 1.3. SUMMARY ........................................................................................................................... 15 2. CHEMICAL SPECIES USED IN SYNTHESIS OF THE CAN POLYMERS ................................. 16 2.1. SUMMARY ........................................................................................................................... 22 3. BIO-BASED UV STABILISATION .......................................................................................... 25 BIBLIOGRAPHY ........................................................................................................................... 27 Grant Agreement 101058371 – Project ESTELLA ESTELLA_D1.1 ©ESTELLA - This is the property of ESTELLA Parties: shall not be distributed/reproduced without formal approval of ESTELLA General Assembly. This reflects only the author’s views. The Community is not liable for any use that may be made of the information contained therein. Abbreviations ATBN : Amine-terminated butadiene acrylonitrile BHT : 2,6-di-tert-butyl-pcresol CTBN : Carboxyl terminated butadiene–acrylonitrile rubber DADPS : Diamino diphenyl sulfone DGEBA : Bisphenol A diglycidyl ether DGEBF : Bisphenol F diglicidyl ether ECH : Epichlorohydrin EEW : Epoxy equivalent weight FAME : Fatty Acid Methyl Esters HALS : Hindered amine light stabilizers REACH : Registration Evaluation and Authorisation of Chemicals Micro-CT : Micro computed tomography NBR : Nitrile butadiene rubber PESU : Polyether sulfone Phr : Parts per hundred PVC : Polyvinylchloride SVHC : Substance of very high concern TGAP : Tri-functional triglycidyl p-amino phenol TGDDM : Tetraglycidyl-4,4′-diaminodipehnylmethane Grant Agreement 101058371 – Project ESTELLA ESTELLA_D1.1 ©ESTELLA - This is the property of ESTELLA Parties: shall not be distributed/reproduced without formal approval of ESTELLA General Assembly. This reflects only the author’s views. The Community is not liable for any use that may be made of the information contained therein. Executive Summary Deliverable D1.1 is designed to provide the consortium with an overview of what types of additives are commonly used in epoxy type composites, highlight risks associated with these and therefore identify which are suitable for substitution to future proof materials developed in the ESTELLA project. As the project is at an early stage of development, it has been difficult to shortlist additives that will be used, as such, this document is aimed at assessing: a) Typical additives used in the ESTELLA target applications: window frames and scooter platform b) Reagents being used for the synthesis and development of the CAN materials (as suggested by partners - National Institute of Chemistry, Kemijski inštitut, Slovenija and Wageningen University & Research, The Netherlands) c) UV stabilisers to protect furan moieties used in the ESTELLA polymers Sustainability is a very broad term so each additive will be assessed using the following criteria: a) REACH registration: i. Is the additive REACH registered? ii. Is it restricted in any way? iii. Are there any toxicological issues that should be considered? iv. What are the registered volumes? b) Bio-based feedstocks: is there a possibility that the additive can be manufactured from a bio-based feedstock? This D1.1 deliverable has fully met its objectives. There has been a delay in delivery compared to what was agreed in the grant agreement due to staff illness and timing of the holiday period but that this has not affected the progress of the project. Grant Agreement 101058371 – Project ESTELLA ESTELLA_D1.1 ©ESTELLA - This is the property of ESTELLA Parties: shall not be distributed/reproduced without formal approval of ESTELLA General Assembly. This reflects only the author’s views. The Community is not liable for any use that may be made of the information contained therein. 1. Application specific additives To narrow the search parameters, the proceeding sections are focussed on typical types of additives that are incorporated into the target applications of the ESTELLA project – namely window frames and hockey sticks. Sections 1.1 and 1.2 are then summarised in 1.3. 1.1. Window frames made with composite materials The thermoset reinforced fibre materials and high-output and costefficient production technologies used for composite window and door frames are well proven and highly recognised in the building industry. They offer certain advantages compared to other solutions made from wood, PVC, aluminium, or a combination of these. The production method used for the profiles making up the frame is known as pultrusion and is quite similar to the method for extrusion of PVC and aluminium profiles. However, in pultrusion the finished product is pulled through a tool where the resin/reinforcement is shaped, heated and fully cured. Since the product is highly sensitive to the cost of manufacturing, the output measured in meters of profile per hour is important, which dictates much of the requirements of the constituents from which the product is made. Some typical requirements for the thermoset resin system in pultrusion of building products are:  High fibre loading in order to ensure dimensional stability and to allow moulding of thin parts in the profiles  Rapid and consistent wetting of the fibrous reinforcement with no dry spots in the bulk as well as in the surface It must also tolerate loadings of other additives which are used as:  Viscosity adjusters  Pigments  Low-profile additives to improve dimensional stability and avoid cracks due to very high temperatures (high peak exotherm – rapid cure) and high temperature gradients causing thermal residual stresses and strains  Fast and consistent wetting and release of entrapped air in a separate impregnation unit (often impregnation of fibres in a resin bath with pins/cylinders) or in a separate cavity in the resininjection pultrusion tool (fully closes production process)  Fire retardants  Release agents (internal)  Surface which is paintable or able to attach foils with no or as little preparation as possible Grant Agreement 101058371 – Project ESTELLA ESTELLA_D1.1 ©ESTELLA - This is the property of ESTELLA Parties: shall not be distributed/reproduced without formal approval of ESTELLA General Assembly. This reflects only the author’s views. The Community is not liable for any use that may be made of the information contained therein.  Meet minimum critical strain limits without causing microcracking when loaded with operational loads  Meet surface finish targets (surface finish class), as produced and during the expected life, which tailors the additives for improved e.g., environmental resistance (UV,…) As price is very important, most pultruded profiles for windows and doors are made using cheaper polyester resins. Other, and more expensive resins are used where product specifications require better chemical resistance or mechanical properties. Below is an assessment table (table 1) containing a list of example additive families which are commonly used in such applications. Often additives are combined into a larger formulation and where this is the case, we have attempted to itemise the constituent parts and assess these individually. Table 1: Additives used in window type composites Additive examples REACH legislation Bio-based potential? EC / List no. Concerns, listed in Annex XVII or in SVHC list? Annual limit (tonnes p/a) Viscosity reduction and/or increased filler load BYK-W1 985 (solution/ mixture) Acidic polyester No, polymers are exempt from registration - - Carbonyl based species can often be isolated from a bio-based feedstock, but specifics needed Solvent naphtha Yes 265-199-0 Substance may be fatal if swallowed and enters airways, may cause genetic defects and may cause cancer. Carcinogenic and mutagenic ≥ 1 mill Roughly 150,000 tonnes of bio-based naphtha produced p/a2 Phosphori c acid esters (methyl ester found) Yes, little information 603-247-8 Can hydrolyse to corrosive acid None stated None found 2methoxy1methyleth yl acetate Yes 203-603-9 Flammable liquid and vapour, may cause drowsiness or ≥ 10k to < 100k Possible but not obvious – acetyl could be derived from acetic acid. 1methoxy-propan-2ol could be Grant Agreement 101058371 – Project ESTELLA ESTELLA_D1.1 ©ESTELLA - This is the property of ESTELLA Parties: shall not be distributed/reproduced without formal approval of ESTELLA General Assembly. This reflects only the author’s views. The Community is not liable for any use that may be made of the information contained therein. dizziness synthesised from methanol and chlorinated propan2-ol Pigmentation, (BYK-9076) Alkylamm o-nium salt (of a high molecular weight copolyme r) (Alkylolam monium salt) Yes for the ammonium salt 812-737-2 GHS09: Hazardous to the environment, GHS08: serious health effects, GHS07 health hazard None stated Possible but unlikely Antiseparation (RHEOBYK-D 410) Solution of modified urea, lithium chloride Not found Manufacturing limit in EU <1 None found Lithium chloride Yes 231-212-3 May damage fertility or the unborn child, is harmful in contact with skin, is harmful if inhaled and may cause respiratory irritation ≥ 1k to < 10k No Antisedimentatio n (ANTI-TERRA204) Solution of Poly carboxylic acid salt of polyamin e amides No, exempt - - Carbonyl based species can often be source from a bio-based feedstock, but specifics needed Fatty acids, C18, unsatd., dimers, reaction products with N,Ndimethyl1,3propane diamine and 1,3propane diamine Yes 605-296-0 A majority of data submitters agree this substance is Skin sensitising ≥ 100 to < 1k Yes – fatty acids Solvent naphta Yes 265-199-0 As above - serious health hazard, carcinogenic ≥ 1 mill Roughly 150,000 tonnes of bio-based naphtha produced p/a1 Air-release, (BYK-P 9920) Mixture of oligomeri No Manufacturing limit in EU <1 More information needed Grant Agreement 101058371 – Project ESTELLA ESTELLA_D1.1 ©ESTELLA - This is the property of ESTELLA Parties: shall not be distributed/reproduced without formal approval of ESTELLA General Assembly. This reflects only the author’s views. The Community is not liable for any use that may be made of the information contained therein. c substance s with wetting agents Oxirane, mono [(C1214alkyloxy)m ethyl] derivs. Yes 271-846-8 This substance causes skin irritation and may cause an allergic skin reaction ≥ 1k to < 10k Possibly from fatty acids feedstock 2,6-di-tertbutylpcresol Yes 204-881-4 Under assessment as Endocrine Disrupting ≥ 10k to < 100k Possible but very unlikely to have economic route Fibre wetting (glass fibre, BYK-P 9920) oxirane, mono[(C1 214alkyloxy) methyl] Derivs, 2,6-di-tertbutyl-pcresol No Likely to have similar health concerns as with 2,6-di-tert-butylpcresol - None found Processing (BYK-P 9065) Fatty acids, C18unsatd, dimers Yes 500-148-0 Serious eye irritation, is harmful to aquatic life with long lasting effects and causes skin irritation ≥ 10k to < 100k Yes Fatty acids, talloil, 2ethylhexyl esters Yes 269-811-7 None listed None listed Yes 2,6-di-tertbutylpcresol (BHT) Yes 204-881-4 Under assessment as Endocrine Disrupting ≥ 10k to < 100k Possible but very unlikely to have economic route Mechanical properties (BYK-C 8001) Copolym er with surface active groups No, exempt - - - 3- (trimethox ysilyl)prop yl amine Yes 237-511-5 Causes severe skin burns and eye damage ≥ 1k to < 10k Possible but very unlikely to have economic route Methanol Yes 200-659-6 Toxic if swallowed, is toxic in contact with skin, is toxic if inhaled, causes damage to organs and is a highly flammable liquid and vapour. Some uses of this ≥ 10 mill to < 100 mill Yes, 43 mill tpa3, 27 Grant Agreement 101058371 – Project ESTELLA ESTELLA_D1.1 ©ESTELLA - This is the property of ESTELLA Parties: shall not be distributed/reproduced without formal approval of ESTELLA General Assembly. This reflects only the author’s views. The Community is not liable for any use that may be made of the information contained therein.  The weight percentage of molecules containing three monomer units or above should exceed 50%;  The weight percentage of any molecule of the same molecular weight shall not exceed 50%. If material or material additives meet this requirement then currently, they will not face legislative issues regarding REACH. However, whilst polymers aren't covered by REACH, the European Commission is developing a proposal on which polymers to register and how this should be done 8 . 2. Chemical species used in synthesis of the CAN polymers To assist in the overall sustainability the ESTELLA project, a list of reagents, starting materials and catalysts that are to be used in material development were shortlisted by two consortium partners, the National Institute of Chemistry, Kemijski inštitut, Slovenija and Wageningen University & Research, The Netherlands and then reviewed by SINTEF. Production limits and bio-based supply of these chemicals was also reviewed. The assessment tables can be seen below and are grouped by chemical family. Table 3: Carboxylic acids Additive and REACH Stage REACH legislation Bio-based potential? EC / List no. Concerns, listed in Annex XVII or in SVHC list? Annual limit (tonnes p/a) Tannic acid (Tannins) Yes 215-753-2 Harmful to aquatic life with long lasting effects and causes serious eye irritation 1 - 10 Yes - derivatives found in nutgalls, bark and other plant parts, especially oak bark. Gallic acid Yes 205-749-9 Causes serious eye and skin irritation, may cause respiratory irritation ≥ 10 to < 100 Yes Citric acid Yes 201-069-1 Serious eye irritation and may cause respiratory irritation, serious eye damage and causes skin irritation ≥ 100k Yes - high concentrations in citrus fruit. 2 mill tonnes p/a9,27 (±) Tartaric acid Yes 205-105-7 Suspected hazardous to the aquatic environment 1 - 10 Yes - Tartaric acid, which is naturally produced in grapes, can be recovered from winery waste streams as a by-product of wine industry10 Malonic acid Yes 205-503-0 Causes serious eye damage, harmful if swallowed, causes skin ≥ 100 to < 1 k Yes – 20,000 tonnes per year expected by 202411,27 Grant Agreement 101058371 – Project ESTELLA ESTELLA_D1.1 ©ESTELLA - This is the property of ESTELLA Parties: shall not be distributed/reproduced without formal approval of ESTELLA General Assembly. This reflects only the author’s views. The Community is not liable for any use that may be made of the information contained therein. irritation and may cause respiratory irritation Oxalic acid Yes 205-634-3 Harmful if swallowed and is harmful in contact with skin, causes serious eye damage, cause damage to organs through prolonged or repeated exposure and causes skin irritation ≥ 10k to < 100k Yes – Avantium pipeline production27 Glutaric acid Yes 203-817-2 Causes severe skin burns and eye damage and causes serious eye damage ≥ 100 to < 1 k Yes – but no industrial methods found12 Sebacic Yes 203-845-5 According to the notifications provided by companies to ECHA in REACH registrations no hazards have been classified ≥ 10 k Yes – 200k tpa13,27 Fumaric Yes 203-743-0 Causes serious eye irritation ≥ 10 k < 100 k Yes – can be made from succinic acid which is produced at 34,000 tpa14,27 fatty acids C16-18 Yes 266-928-5 There is no harmonised classification and there are no notified hazards by manufacturers, importers or downstream users for this substance ≥ 100 k to < 1 mill Yes15 Pripol type - Fatty acids, C18-unsatd., dimers, hydrogenated (PRIPOL 1006 PRIPOL 1009 PRIPOL 1025) Yes 500-231-1 According to the notifications provided by companies to ECHA in REACH registrations no hazards have been classified. ≥ 1k to < 10k Yes – as above Grant Agreement 101058371 – Project ESTELLA ESTELLA_D1.1 ©ESTELLA - This is the property of ESTELLA Parties: shall not be distributed/reproduced without formal approval of ESTELLA General Assembly. This reflects only the author’s views. The Community is not liable for any use that may be made of the information contained therein. Table 4: Anhydrides Additive and REACH Stage REACH legislation Bio-based potential? EC / List no. Concerns, listed in Annex XVII or in SVHC list? Annual limit (tonnes p/a) Maleic anhydride Yes 203-571-6 Causes damage to organs through prolonged or repeated exposure, is harmful if swallowed, causes serious eye damage, may cause an allergic skin reaction and may cause allergy or asthma symptoms or breathing difficulties if inhaled. ≥ 100 k Potentially, but succinic acid is the bio-based alternative Rosin, maleated Yes 232-480-4 Toxic to aquatic life with long lasting effects, causes serious eye damage and may cause an allergic skin reaction. ≥ 1k to < 10 k Yes – the base material is a resin obtained from pines and some other plants Terpene-based anhydrides No Manufacturing limit in EU - - Succinic anhydride Yes 203-570-0 Causes severe skin burns and serious eye damage, is harmful if swallowed, may cause an allergic skin reaction and may cause allergy or asthma symptoms or breathing difficulties if inhaled ≥ 1 k to < 10 k Yes – made from the acid, 34,000 tonnes per year16,27 Glutaric anhydride Yes 203-593-6 Harmful if swallowed, causes serious eye damage and causes skin irritation Manufactured in and / or imported to the European Economic Area, for intermediate use only. Yes – from the acid, but no commercial routes found Terephthalaldehyde Yes 210-784-8 Toxic in contact with skin, is toxic if inhaled, is harmful if swallowed, causes skin irritation and may cause respiratory irritation, causes serious eye irritation. ≥ 10 k to < 100k Possible – commercial processes to terephthalate in the pipeline17,27 Grant Agreement 101058371 – Project ESTELLA ESTELLA_D1.1 ©ESTELLA - This is the property of ESTELLA Parties: shall not be distributed/reproduced without formal approval of ESTELLA General Assembly. This reflects only the author’s views. The Community is not liable for any use that may be made of the information contained therein. Table 5: Amines Additive and REACH Stage REACH legislation Bio-based potential? EC / List no. Concerns, listed in Annex XVII or in SVHC list? Annual limit (tonnes p/a) Butylamine Yes 203-699-2 Causes severe skin burns and eye damage, is a highly flammable liquid and vapour, is fatal if inhaled and may be corrosive to metals. ≥ 10 Possible but not commercial 18 Dibutylamine Yes 203-921-8 Substance is a flammable liquid and vapour, is harmful if swallowed, is harmful in contact with skin, is fatal if inhaled, is toxic if swallowed, is toxic in contact with skin, causes severe skin burns and eye damage and causes serious eye damage. ≥ 1 k < 10 k None found Octylamine Yes 203-916-0 Substance is toxic if swallowed, causes severe skin burns and eye damage, is toxic in contact with skin, is very toxic to aquatic life, is a flammable liquid and vapour, causes serious eye damage, is harmful if inhaled and may cause respiratory irritation. ≥ 1 k to < 10 k None found Dodecylamine Yes 204-690-6 Substance may be fatal if swallowed and enters airways, causes severe skin burns and eye damage, is very toxic to aquatic life with long lasting effects, may cause damage to organs through prolonged or repeated exposure and may cause respiratory irritation. ≥ 1 k to < 10 k None found m-xylenediamine Yes 216-032-5 Causes severe skin burns and eye damage, is harmful if swallowed, causes serious eye damage, is harmful to aquatic life with long lasting effects and may cause an allergic skin reaction. Fatal if inhaled. <1 None found 5,5'- methylenedifurfuryla mine No Manufacturing limit in EU <1 None found 5,5'- ethylidenedifurfirylami ne No Manufacturing limit in EU <1 None found Cardanol-based amines None found Manufacturing limit in EU <1 - 2,5-bis(aminomethyl) furan Yes 867-665-4 Corrosive, respiratory hazard <1 Likely from a hydroxymethylfurfural based feedstock Grant Agreement 101058371 – Project ESTELLA ESTELLA_D1.1 ©ESTELLA - This is the property of ESTELLA Parties: shall not be distributed/reproduced without formal approval of ESTELLA General Assembly. This reflects only the author’s views. The Community is not liable for any use that may be made of the information contained therein. Bis(furfurylamine)-A (([5-(aminomethyl) furan-2-yl]) methanamine) Yes 867-665-4 Manufacturing limit in EU <1 Likely from a hydroxymethylfurfural based feedstock Tryptophan (L-tryptophan) Yes 200-795-6 According to the notifications provided by companies to ECHA in REACH registrations no hazards have been classified ≥ 100 to < 1 k Yes Phenalkamine derived from cardanol Not found Manufacturing limit in EU <1 Yes, at least partly Table 6: Alcohols Additive REACH legislation Bio-based potential? EC / List no. Concerns, listed in Annex XVII or in SVHC list? Annual limit Cardanol 1) Cashew, nutshell liq. Yes 232-355-4 A majority of data submitters agree this substance is Skin sensitising Likely to be <1 Yes Cardanol 2) Distilled CNSL liquid Yes 609-405-2 Registration not complete Likely to be <1 Yes Lysinol (2,6-diamino-1hexanol) No Manufacturing limit in EU <1 Yes19 Eugenol Yes 202-589-1 A majority of data submitters agree this substance is Skin sensitising ≥ 1 k to < 10 k Yes, no commercial production found however Glycols (decompositions solvents): a) ethylene glycol Yes 203-473-3 Harmful if swallowed, may cause damage to organs through prolonged or repeated exposure ≥ 1 mill to < 10 mill Yes, from sugar via ethanol, ethylene and ethylene oxide. 40,000 tpa20,27 b) 1, 3Propylene glycol Yes 207-997-3 Causes skin irritation ≥ 1 k to < 10 k Yes, 77,000 tpa21,27 c) Glycerol Yes 200-289-5 According to the notifications provided by companies to ECHA in REACH registrations no hazards have been classified ≥ 1 k to < 10 k Yes, 1,500,000 tpa22,27 Oxo alcohols (decompositions solvents): a) N-Butanol Yes 200-751-6 Flammable liquid and vapour, is harmful if swallowed, causes serious eye damage, causes skin irritation, may cause respiratory irritation and may cause drowsiness or dizziness. ≥ 100 k to < 1 000 k Yes, 10,000 tpa23,27 b) Iso-Butanol Yes 201-148-0 Flammable liquid and vapour, causes serious eye damage, causes skin irritation, may cause respiratory irritation and may cause drowsiness or dizziness. ≥ 10 k to < 100 k Yes, 6,000 – 9,000 tpa24,27 c) 2-Ethylhexanol Yes 203-234-3 Serious eye irritation, is harmful if inhaled, causes skin irritation and may cause respiratory irritation. ≥ 100 k to < 1 mill Yes25,27 Grant Agreement 101058371 – Project ESTELLA ESTELLA_D1.1 ©ESTELLA - This is the property of ESTELLA Parties: shall not be distributed/reproduced without formal approval of ESTELLA General Assembly. This reflects only the author’s views. The Community is not liable for any use that may be made of the information contained therein. Table 7: Reactive dilutents and other species Additive REACH legislation Bio-based potential? EC / List no. Concerns, listed in Annex XVII or in SVHC list? Annual limit Epichlorohydrin Yes 203-439-8 Toxic if swallowed, is toxic in contact with skin, causes severe skin burns and eye damage, is toxic if inhaled, may cause cancer, is a flammable liquid and vapour and may cause an allergic skin reaction. Carcinogenic, Skin sensitising ≥ 100 000 tonnes Yes, 540,000 tpa26,27 Tetrabutylammonium bromide Yes 216-699-2 Harmful if swallowed, causes serious eye irritation, is harmful to aquatic life with long lasting effects, is suspected of damaging fertility or the unborn child, may cause damage to organs through prolonged or repeated exposure and causes skin irritation. ≥ 1 000 to < 10 000 None found Glycidyl ethers of alcohols: a) 1,4butanediol diglycidyl ether Yes 219-371-7 Harmful in contact with skin, causes serious eye irritation, is harmful if inhaled, causes skin irritation and may cause an allergic skin reaction. Skin sensitising ≥ 1 000 to < 10 000 Yes, but no commercial route exists Epoxidized plant oils: 1) Soybean oil Yes 232-391-0 According to the notifications provided by companies to ECHA in REACH registrations no hazards have been classified ≥ 10 000 to < 100 000 Yes Epoxidized plant oils: 2) Linseed oil Yes 232-401-3 Causes serious eye irritation, is harmful if swallowed, is harmful in contact with skin, is harmful if inhaled, may cause an allergic skin reaction, causes skin irritation and may cause respiratory irritation ≥ 1 000 to < 10 000 Yes Lignin Yes 232-682-2 According to the majority of notifications provided by companies to ECHA in CLP notifications no hazards have been classified N/A Yes Grant Agreement 101058371 – Project ESTELLA ESTELLA_D1.1 ©ESTELLA - This is the property of ESTELLA Parties: shall not be distributed/reproduced without formal approval of ESTELLA General Assembly. This reflects only the author’s views. The Community is not liable for any use that may be made of the information contained therein. Table 8: Catalysts Additive REACH legislation Bio-based potential? EC / List no. Concerns, listed in Annex XVII or in SVHC list? Annual limit (tonnes p/a) Zinc acetate Yes 209-170-2 Toxic to aquatic life with long lasting effects, is harmful if swallowed and causes serious eye damage. ≥ 100 to < 1 k Partly – acetate source Tin compounds: a) Tin bis(2ethylhexanoate) Yes 206-108-6 Toxic to aquatic life with long lasting effects, causes serious eye damage, is suspected of damaging fertility or the unborn child, may cause an allergic skin reaction, causes skin irritation and may cause respiratory irritation. ≥ 100 to < 1 k No route found Peroxides: a) hydrogen peroxide Yes 231-765-0 Causes severe skin burns and eye damage, may cause fire or explosion (strong oxidiser), is harmful if swallowed and is harmful if inhaled, substance may intensify fire (oxidiser). ≥ 1 mill to < 10 mill Yes b) Dibenzoyl peroxide Yes 202-327-6 Causes serious eye irritation, if heated may cause a fire or explosion and may cause an allergic skin reaction', is very toxic to aquatic life with long lasting effects, is explosive (mass explosion hazard). ≥ 1 k to < 10 k Possible to synthesise from bio-based benzoic anhydride 2-methylimidazole Yes 211-765-7 May damage the unborn child and is suspected of damaging fertility, causes severe skin burns and eye damage and is suspected of causing cancer. Substance of very high concern (SVHC) and included in the candidate list for authorisation. ≥ 100 to < 1 k Possibly, the base unit imidazole can be obtained from biomass fractionation and delignification. However, bio-based routes not found 2,4,6tris(dimethylaminom ethyl)phenol Yes 202-013-9 Harmful if swallowed, causes serious eye irritation and causes skin irritation, causes severe skin burns and eye damage and causes serious eye damage, harmful to aquatic life with long lasting effects and may cause an allergic skin reaction. ≥ 1 k to < 10 k Bio-based route not obvious 2.1. Summary The previously highlighted chemical families (tables 3-8) are common reagents used in the synthesis of polyester materials, where (di and tri) carboxylic acids, anhydrides, dialcohols and some of the reactive dilutants form the core polymer structure and the catalysts allow the synthesis to occur at an increased rate of a chemical reaction. Grant Agreement 101058371 – Project ESTELLA ESTELLA_D1.1 ©ESTELLA - This is the property of ESTELLA Parties: shall not be distributed/reproduced without formal approval of ESTELLA General Assembly. This reflects only the author’s views. The Community is not liable for any use that may be made of the information contained therein. Carboxylic acids None of the listed carboxylic acids were found to be listed in REACH Annex XVII or highlighted as a SVHC, nor were any of them recorded to exhibit risk of severe long term health effects (e.g., carcinogenic, mutagenic, or endocrine disrupting species). All expect tannic acid and (±) tartaric acid have REACH approval to be made at >10,000 tonnes per year, per manufacturer, with bio-based citric, malonic and sebacic acid being produced at commercial quantities. 27 Fatty acids, C18unsaturated (dimers, hydrogenated), fumaric acid, sebacic acid, oxalic acid and citric acid have concluded Compliance Check Evaluation and no serious issues were highlighted. The compliance check focuses on eight key endpoints: genotoxicity, repeated-dose toxicity, pre-natal developmental toxicity, reproduction toxicity, carcinogenicity, long-term aquatic toxicity, biodegradation and bioaccumulation. Further testing will apply to tannic acid, (±) tartaric acid and glutaric acid, but is not expected to cause any issue to growth and supply. Anhydrides Similarly, none of the listed anhydrides were found to be listed in REACH Annex XVII or highlighted as a SVHC, nor exhibited severe health risks. However, due to the anhydride moiety it should be noted that they are generally much more reactive than their carboxylic acid counterparts. All except rosin (maleated) are registered for production above 1,000 tonnes per year. Glutaric anhydride is typically used in formulation or repacking and at industrial sites and is not permitted to be isolated and used. No terpene-based anhydrides were found to be REACH registered and as such, it can be expected that there will be a maximum limit of 1 tonne production within the EU (or exported into the EU). Succinic acid (the anhydride precursor) is currently produced at commercial quantities of around 34,000 tonnes per year. Amines 5,5'-methylenedifurfurylamine, 5,5'-ethylidenedifurfirylamine and any cardanol-based amines were not found to be REACH registered. As such, they have a maximum production and importation limit of 1 tonne per year in the EU, per manufacturing company. Bis(furfurylamine)-A although registered, has received not testing and according the ECHA REACH database, appears to be still limited to a 1 tonne annual production limit within the EU. None of the amines listed were found in either REACH Annex XVII or highlighted as a SVHC. No commercial routes from a bio-based feedstock were found. Grant Agreement 101058371 – Project ESTELLA ESTELLA_D1.1 ©ESTELLA - This is the property of ESTELLA Parties: shall not be distributed/reproduced without formal approval of ESTELLA General Assembly. This reflects only the author’s views. The Community is not liable for any use that may be made of the information contained therein. Alcohols Many of the alcohols listed in table 6 have approval to be produced at significant quantities, including eugenol, ethylene glycol, 1, 3propylene glycol, glycerol, n-butanol, iso-butanol and 2-ethylhexanol. Lysinol, a potential alternative to petrochemical based polyamines and amino alcohols, was the only 'alcohol' found not to be REACH registered and as such, its production is limited to 1 tonne per annum. None of the alcohols listed were found in either REACH Annex XVII or highlighted as a SVHC. Many of these were found to be currently produced at a commercial scale27 including ethylene glycol (175,000 tpa), 1,3-propylene glycol (77,000 tpa), glycerol (1,500,000 tpa), n-butanol (10,000 tpa) and isobutanol (6,000-9,000 tpa). Reactive dilutants and other species Of the species listed in table 7, epichlorohydrin is the most hazardous being a probable carcinogen and mutagen. Despite its toxicity, there is huge demand as it is used in the production of epoxy resins (roughly 90% of all ECH produced globally is used for this purpose). 28 As such it has approval for production at ≥ 100 000 tonnes per annum, per company, with an estimated 540,000 tonnes of biobased ECH being produced per year. 27 As alternative materials and chemistry evolves, it is likely that such high risk chemical species will receive increased pressure for restricted use or banning. Tetrabutylammonium bromide and 1,4-butanediol diglycidyl ether were not reported to have significant health impacts, however, no bio-based commercial production of these compounds could be found. Soybean oil, linseed oil and lignin all have growing production in the bioeconomy along with negligible health risks. None of the species listed in table 7 were found in either REACH Annex XVII or highlighted as a SVHC. Catalysts 2-methyl imidazole was found to be listed as a substance of very high concern (SVHC) and is included in the candidate list for authorisation due to it being toxic for reproduction. As such, any process or material development in the ESTELLA project should not include this compound. None of the other species listed in table 8 were found in either REACH Annex XVII or highlighted as a SVHC. However, although a common and cheap catalyst, zinc acetate should be considered at risk as zinc is widely acknowledged as a critical element 29 . Many tin compounds have been listed as SVHA and included in the candidate list for authorisation, examples include, dioctyltin dilaurate, dibutyltin dichloride, and bis(tributyltin) oxide. Tin arsenide, lead tin trioxide, tin alloy, dibutyltin hydrogen borate, nickel tin trioxide are listed in Annex XVII and are Grant Agreement 101058371 – Project ESTELLA ESTELLA_D1.1 ©ESTELLA - This is the property of ESTELLA Parties: shall not be distributed/reproduced without formal approval of ESTELLA General Assembly. This reflects only the author’s views. The Community is not liable for any use that may be made of the information contained therein. therefore restricted. Whilst tin bis(2-ethylhexanoate) is not listed as a SVHC, tin compounds should be avoided where possible due to their associated toxicity and the fact that the catalyst remains in the materials after synthesis. For polytransesterification type chemistry alternative titanium compounds should be considered. Both dibenzoyl peroxide and 2,4,6-tris(dimethylaminomethyl)phenol were found to be damaging to aquatic life, with the peroxide carrying the obvious stability risk. Further information has been requested by ECHA for dibenzoyl peroxide for subchronic toxicity and pre-natal developmental toxicity which may lead to restrictions of use in future. 3. Bio-based UV stabilisation Due to the potentially high furan content of the CAN materials developed in the ESTELLA project, UV stabilisers were reviewed to ensure protection of this moiety whilst retaining high potential bio-based content and/or low toxicity of the additives where possible. It should be noted that typically such additives are not incorporated into the polymer matrix when used with the target ESTELLA applications, instead they are applied as a protective coating. Different bio-based additives for thermoplastics have been reviewed. 30 A commercially available UV stabilizer in 2019 was Caplig 770™ from Nanjing Capatue Chemical CO, China. This stabilizer consists of bis (2,2,6,6-tetramethyl-4 piperidyl) sebacate and is produced from sebacic acid where castor oil is the raw material (this has good availability and can be bought from Sigma Aldrich). It should be noted however, that the suitability of this UV stabilizer for epoxy products has not been reported. The same authors mention that lignin has been used as light stabilizer for rubber acting as a UV filter in the same way as carbon black. Another biobased heat and light stabilizer is Akcrostab LT-4803 from Valtris, 31 speciality chemical, USA. This is a mixed metal epoxidized soybean oil blend, but this product seems to be intended for use in PVC. A UV stabiliser consisting of nanoclay (halloysite nanotubes) loaded with lignin was studied by Nikafshar et al 32 . This stabiliser showed promising UV stability when tested in an epoxy coating. Non-bio-based but low toxicity UV stabilizers approved for food contact can were reviewed. Key examples include Uvinul 5050 H (BASF, Germany), which is a sterically hindered amine (HALS) and Tinuvin 326 (BASF) which consists of 2-(2-hydroxyphenyl)-benzotriazole. The latter is