Plastic Monomers, Additives, and Processing Aids Helene Wiesinger wiesinger@ifu.baug.ethz.ch What are Plastics? • Greek: plastikos = capable of being shaped or molded • Plastics vs. polymers  Plastics are composed of organic polymers (macromolecules that are composed of many repeated sub-units – monomers) and additives  All plastics are polymers and are often named after the polymer matrix, but not all polymers are plastics. 24.11.2022 2 Polymer matrix Additives Different Grouping Methods of Plastics According to their cost and performance: 1. Commodity plastics (or standard/bulk plastics): produced in great amounts at low cost. e.g. PVC, HDPE, LDPE, LLDPE, VLDPE, PP, PS, EPS, PET 2. Engineering plastics (or technical plastics): plastics with improved mechanical properties and dimensional stability compared to commodity plastics. e.g. PP, PET, PBT, PA, PC, POM, PMMA, SAN, ABS, HIPS, PPO-PS, POM-PUR, PCABS, etc. 3. High-performance plastics (or specialty plastics): engineering plastics with even more improved mechanical properties. e.g. liquid cystal polymers (LCPs), polyetheretherketone (PEEK), fluoropolymers 24.11.2022 3 Different Grouping Methods of Plastics 24.11.2022 4 According to their hardening processes: • Thermoplastics: harden through simple cooling of a polymer melt (a physical process) and soften while being heated. e.g., PE, PP, ABS, PVC, etc. • Thermosets: harden through chemical cross-linking reactions between polymer molecules; when heated, they do not soften but decompose chemically. e.g., alkyd, phenolic, amino, epoxy, unsaturated polyesters, polyurethane, and allylic resins Different Grouping Methods of Plastics • According to the origin of feedstock: fossilvs. bio-based plastic • According to the biodegradability: biodegradable vs. non-biodegradable plastics 24.11.2022 5 Plastics – Production overview 24.11.2022 6 Global production (2021): 390 Mt/y European use by sector [1] 1 Plastics Europe (2022), Plastics – the facts 2022. https://plasticseurope.org/resources/market-data/ 24.11.2022 7 In 2015, 4% of the global greenhouse gas emissions were caused by plastics. [1] 1 Zheng, J., Suh, S., 2019. Strategies to reduce the global carbon footprint of plastics. Nat. Clim. Chang. 2 Cabernard, L. et al., 2022. Growing environmental footprint of plastics driven by coal combustion. Nat. Sustain. 3 Klotz, M. et al., 2022. Limited utilization option for secondary plastics may restrict their circularity. doi.org/10.1016/j.wasman.2022.01.002 main causes for climate change impact of plastics: production and waste incineration [2, 3] 🔻 A Wide Range of Chemicals are Present in Plastics • Unreacted monomers, residual processing aids and additives can be released during the production, use, disposal and recycling of plastics. 24.11.2022 8 Additives and Processing aids 24.11.2022 9 Global production: ~18 Mt / y Major types: [2]  Plasticizers: 7.5 Mt/y  Fillers  Flame retardants: 2.1 Mt/y  Heat stabilizers: 1.2 Mt/y  Impact modifiers: 1.0 Mt/y  Lubricants: 0.8 Mt/y  Antioxidants: 0.5 Mt/y •Antioxidants prevents oxidative degradation •Light stabilizers prevents degradation by sunlight •Heat stabilizers prevents degradation by heat Stabilization •Biocides prevents growth of microbes •Colorants imparts color •Fillers increase strength, lower costs •Flame retardants reduce flammability, smoke generation •Impact modifiers improve impacts strength •Nucleating agents promote crystallinity •Odor agents add fragrance, repress objectionable odors •Plasticizers increase flexibility, reduce melt viscosity Functionalization •Antistatic agents prevents static charge build-up •Blowing agents decompose during processing to create foamed plastic •Catalysts enable polymerization reaction •Initiators start or regulate chain growth during polymerization •Lubricants reduces friction between polymer and processing surface •Solvents dissolves monomers, polymers and additives for mixing •Viscosity modifiers modifies melt flow viscosity Processing aids 1 Ullmann (2018). Plastic Additives. https://doi.org/10.1002/14356007.a20_459.pub2 2 IHS Markit (2018). Plastics additives - Specialty Chemicals Update Program. https://www.spglobal.com/commodityinsights/en/ci/products/chemical-plastics-additives-scup.html Concerns about Chemical Release from Plastics 24.11.2022 10 Recyling Challenges Associated with PlasticMAP They may influence recycled plastics in the following ways:  Interfere with recycling or sorting process  Reduce the (actual) recyclability including aesthetics in mechanical recycling o Reduction of mechanical properties: pro-degradant/pro-oxidant metal additives (Aldas et al. 2018, 10.1155/2018/2474176), mixing of additives o Color-changes through colorants, carbon black, PbS (black) in recycled PVC o Odor changes  Reduce the safety of secondary materials o heavy metals, halogenated flame retardants, phthalates, etc. 24.11.2022 11 ?chemicals used in plastics potential hazards ? 24.11.2022 12 Plastic Monomers, Addtives and Processing Aids Database 24.11.2022 13 Monomers, additives and processing aids are highly diverse  ECHA + industry: over 400 plastic additives registered under REACH at above 100 tonnes/year  Groh et al. (2018): over 3’000 additives in plastic packaging  SpecialChem additives database: over 30’000 commercially available formulations Only few substances are regularly discussed in scientific literature  Need for an overview of their chemical identities and priority setting Methods 1. Identification of relevant data sources 3. Categorization of substance types and use patterns industry science regulatory b) categorize sources based on content c) retrieve and harmonize data b) verify CASRNs using SciFinder preliminary categorization a) define categories and respective keywords fulfilled function industrial sector substance type compatible polymers matching PBT hazard criteria under EU REACH? high production volume? a) find substances with concerning properties 4. Identification of substances of (potential) concern d) include further information hazard data regulatory status regional use status tonnage data irrelevant substances, irrelevant information a) identify relevant substances relevant substances (Name, CASRN, SMILES) use data b) categorize substances by keywords c) check for and eliminate errors updated keywords b) check legal status & scientific references wrong CASRN ambiguous content A … B XXX C … A … low B YYY medium C … high legal status substances of (potential) concern yes no • search for plastics-related keywords • find CASRNs information sources c) assign confidence irrelevant content 2. Inclusion of relevant substances&information high medium low no yes missing data high medium low unknownlevel of concern • update keywords • repeat from b) number of scientific references a) select plasticrelevant sources final categorization with confidence scores 24.11.2022 14 190 63 Wiesinger et al. 2021. ES&T, 10.1021/acs.est.1c00976 Methods – Inclusion of relevant substances and information a) Identify relevant substances  Search for plastic-related keywords  Search for CASRNs b) Verify CASRNs using SciFinder c) Assign confidence to sources and substances d) Include further information 24.11.2022 15 hazard data legal status regional use status tonnage data Global: - Stockholm Convention - Montreal Protocol - Rotterdam Convention Others: - OECD High production volume chemicals Results – Overview of the Substances 24.11.2022 16 * Substances are found in sources of all mentioned types ** These active CASRNs are associated with 24 901 deleted CASRNs and 22 alternate CASRNs *** Substances of unknown or variable composition, complex reaction products and biological materials Confidence in their use in plastics Information sources Substance types Regulatory 2 572 Scientific 2 238 Industrial 1 457 High 8 567 Medium 1 398 Low: 582 Plastic monomers, additives & processing aids 10 547 active CASRNs** UVCBs***, mixtures and polymers 2 703 Individual compounds 7 561 Other aromatics 1 484 Other organics 1 693 Uncategorizable: 283 Inorganics 1 049 Organohalogens 1 189 Organosulfur: 418 Organophosphor: 228 Metalorganics, organometallics & organic metal salts: 1 268 Regulatory & Scientific* 2 072 Regulatory & Industrial*: 375 Scientific & Industrial*: 327 Regulatory, Scientific & Industrial* 1 506 Organosilicons: 232 Wiesinger et al. 2021. ES&T, 10.1021/acs.est.1c00976 Results – Use Patterns Many substances  fulfill several functions  are compatible with several polymer types  are used in several industrial sectors 3’282 Uncategorizable Additives Monomers 2’508 659 157 871 1’482 1’355 233 Processing aids 0 2000 4000 6000 8000 10000 Colorant Other Processing Aids Filler Intermediates Lubricant Biocide Monomer Crosslinking Agent Plasticizer Odor Agent Light Stabilizer Catalyst Antioxidant Initiator Flame Retardent Heat Stabilizer Antistatic Agent Viscosity Modifier Blowing Agent Solvent Impact Modifier Nucleating Agent Uncategorizable Number of subtances Function 0 2000 4000 6000 8000 10000 PA LDPE PET HDPE PVC PP PUR PS ABS PC HIPS EPS Other - Thermoplastic Other - Rubber Other - Bioplastic Uncategorizable Number of subtances Polymer type 24.11.2022 17 Results – Use Patterns 24.11.2022 18 Wiesinger et al. 2021. ES&T, 10.1021/acs.est.1c00976 Results – Regional relevance  10–80% of substances registered in inventories from different parts of the world  the commercial status, extent of use and concentrations in plastic articles remain unknown 79% 25% 19% 77% 66% 60% 59% 52% 49% 25% 10% 69% 51% 22% 41% 0 2’000 4’000 6’000 8’000 10’000 EU Russia Turkey Taiwan China Vietnam South Korea Philippines Japan Thailand Malaysia USA Canada Mexico New Zealand Number of substances Regional registrations Europe Asia North America Australia & Oceania 24.11.2022 19 Results – Substances of Potential Concern  more than 2’400 substances = 25% of the identified substances  about 900 substances of potential concern are also approved for use in food-contact plastics 24.11.2022 20 HAZARD TYPE TOTAL HPVC NOT REGULATED1 NOT RESEARCHED2 PBT Persistent, bioaccumulative & toxic 22 7 7 2 vPvB Very persistent & very bioaccumulative 35 19 3 8 CMR Carcinogenic, mutagenic, reproductive toxic 951 501 350 91 ED Endocrine disrupting 30 17 3 3 AqTox Chronic aquatic toxicity 1’646 754 897 188 STOT_RE Specific target organ toxicity 891 562 331 57 TOTAL 2’486 1’254 1’327 266 1 regulated by international regulatory lists or in the EU, USA, Japan or Republic of Korea 2 no scientific references according to SciFinder Wiesinger et al. 2021. ES&T, 10.1021/acs.est.1c00976 Results – Examples of Unregulated Substances of Potential Concern 24.11.2022 21 Chloroalkanes, C14-17 Lubricant, flame retardant, plasticizers… CASRN: 85535-85-9 POP candidates Benzene, 1,1'-(1,1-dimethyl-3- methylene-1,3-propanediyl)bisPolymerization control agent CASRN: 6362-80-7 Skin Sens. 1, STOT RE 2 Aquatic Acute 1, Aquatic Chronic 1 1-Propanol, 2-methoxy-, 1-acetate Solvent, used in colorants, … CASRN: 70657-70-4 Repr. 1B Thioperoxydicarbonic diamide ([(H2N)C(S)]2S2), N,N,N',N'-tetraethylCrosslinking Agent CASRN: 97-77-8 Skin Sens. 1, STOT RE 2 Aquatic Acute 1, Aquatic Acute 2 Phosphoric acid, tris(methylphenyl) ester Flame retardant,.. CASRN: 1330-78-5 Skin Sens. 1, Repr. 2 STOT RE 2, Aquatic Acute 1 Aquatic Chronic 1 2-(2H-Benzotriazol-2-yl)-4,6-ditert-pentylphenol (Tinuvin 328) Antioxidant CASRN: 25973-55-1 STOT RE 2 Wiesinger et al. 2021. ES&T, 10.1021/acs.est.1c00976 Results – Examples of Inconsistently Regulated Substances • 901 substances of potential concern are approved for use in food-contact plastics  265 substances of potential concern are restricted/banned in other use areas 24.11.2022 22 Terphenyl, hydrogenated Colorant, other processing aid,… CASRN: 61788-32-7 SVHC (vPvB) Ethanol, 2-chloro-, 1,1',1''-phosphate Flame retardant, other processing aid… CASRN: 115-96-8 SVHC (Repro) 1,2-Benzenedicarboxylic acid, 1,2-bis(2-ethylhexyl) ester Colorant, plasticizer, … CASRN: 117-81-7 SVHC (Repro, EDC) Ethane, 1,1,1-trichloroAntioxidant, stabilizer, lubricant,… CASRN: 26523-78-4 SVHC (EDC) Wiesinger et al. 2021. ES&T, 10.1021/acs.est.1c00976 Discussion – Data Availability & Uncertainties Critical data and knowledge gaps: - Regulator-harmonized hazard data - Use details and concentration ranges Our numbers may still well be underestimates, due to focuses on: - digitized sources (vs. print sources) - sources where assigned CASRNs are provided (vs. sources where no assigned CASRNs provided) - intentionally added substances (vs. NIAS) - existing GHS hazard data (vs. literature values) 24.11.2022 23 0 2000 4000 6000 8000 10000 Regional use Function Any hazard data Production volume Industrial Sector Polymer Type Regulator-harmonized hazard data Number of subtances Data Availability available data missing data Wiesinger et al. 2021. ES&T, 10.1021/acs.est.1c00976 Discussion – Possible Ways Forward • Establishing a centralized knowledge base  e.g. through public-private partnerships and corporate social responsibility; harmonizing information exchange standards • Ensuring transition to a safe and sustainable circular plastic economy  e.g. developing standardized approaches to assessing the sustainable circularity of plastics and chemicals therein; avoiding hazardous substances, reducing product complexity and embedding sustainable circularity in the design phase; fostering innovative and enabling business models and practices • Expanding and harmonizing regulatory efforts  e.g. group- or class-based approaches; one substance, one assessment; complementary market-based policy instruments to internalize externalities 24.11.2022 24 Wiesinger et al. 2021. ES&T, https://pubs.acs.org/doi/10.1021/acs.est.1c00976 Wang et al. 2021. https://pubs.acs.org/doi/abs/10.1021/acssuschemeng.1c00243 Take-Home Messages • A messy situation regarding intentionally added chemicals in plastics  Thousands of diverse substances (potentially) used  25% having concerning properties, and only a part researched and regulated (including conflicting regulations in different domains)  A general lack of transparency on their actual occurrence in products and hazards • Concerted efforts from all actors are urgently need to ensure transition to a safe and sustainable circular economy, starting from the design phase! 24.11.2022 25 Outlook Following policy actions are urgently needed  Design for recycling – also on the chemical level  Supply chain transparency  Expand focus of research, regulation and monitoring Research needs and opportunities  Target list for non-targeted analysis  Support alternatives assessment  New research foci  Need for analytical standards  Need for standardized terminology regarding chemicals Publication of paper and database soon “Clean Cycle” Strategy Key components of the strategy (1) Phase-out of hazardous chemicals in primary materials (2) Separation of contaminated used materials (3) Safe treatment/disposal of contaminated materials  ”Clean Cycle” Project @ETHZ 24.11.2022 27 (1) (2) (3) Clean Cycle Project @ETHZ 24.11.2022 28 PlasticAdditives andHuman Exposure PlasticMaterial Flowsand Environmental Assessment  identify and prioritize hazardous chemicals used in plastics  quantify current levels of target hazardous chemicals in target plastic flows  Map and model current plastic flows in Switzerland  Model future scenarios of plastic flows in Switzerland  model the current and future levels of human exposure to selected hazardous chemicals via plastics and the associated risks to human health  model environmental impacts of the current and potential future plastic recycling systems  develop strategies to maximize the resource efficiency of plastics with minimized risks to human health  inform policy- and decision-makers Current research – Measurements of chemicals in plastics Goal: Fill the data gaps from PlasticMAP regarding concentrations and actual uses  Which chemicals are actually present in plastics samples?  Which concentrations are relevant for different products?  Where are hot/blind-spots in plastic screening literature? 24.11.2022 29 ATR-IR XRF LC/GC-MS Measured concentrations Claimed inputs Production, market & waste Chemicals B&C case study Literature review PlasticMAP Database Current research – B&C case study 24.11.2022 30 150 Building & Construction samples, PVC ATR-IR GC-MS polymer type, phthalate screening XRF elemental composition phthalate concentration DF: 26% presence of other substances Bioassays biological activity DiNP DEHP DiDP DEP DiBP DNOP DCHP BBP DBP DEHT DEHA DINCH Br EHPhP TPhP MTT ROS Ames UmuC YES A-YES YAS Y-YAS n.d. n.d n.d n.d. n.d. n.d. n.d. n.d. n.d. 0 0 0 12 0 0 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.40 0 0 0 0 0 0 0 0 0 215958 0 0 0 0 0 0 n.d. 3 0 1 0 137 1 0 0 0 0 0 0 0 0 55176 0 0 0 0 1 0 0.5 2 n.d. n.d. n.d. n.d.35 0 0 0 0 0 0 0 0 0 348209 0 0 0 0 0 0 0 2 n.d. n.d. n.d. n.d.33 0 8 0 0 0 0 0 0 0 0 0 16 0 0 1 1 n.d. n.d. 0 1 0 125 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.18 0 0 0 0 0 1 0 0 0 8729484 0 26 0 0 1 0 n.d. n.d. 0 1 0 117 1 0 0 0 0 0 0 0 0 8153 0 0 0 0 1 0 n.d. 2 n.d. n.d. n.d. n.d.16 1 1 0 0 0 1 0 0 0 8804335 0 0 0 0 0 0 n.d. 1 n.d. n.d. n.d. n.d.14 0 4 0 0 0 0 0 0 0 92932 0 0 7945 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.11 0 0 0 0 0 0 0 0 0 0 0 tbm 0 0 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.9 0 2 0 0 0 0 0 0 0 178676 0 0 1185 0 2 1 n.d. 1 n.d. n.d. n.d. n.d.5 0 2 0 0 0 0 0 0 0 99053 0 tbm 0 0 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.5 0 28 0 0 0 0 0 0 0 0 0 0 0 0 1 0 n.d. 2 1 1 0 15 0 0 0 0 0 0 0 0 0 65088 0 tbm 0 0 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.3 0 2 0 0 0 0 0 0 0 5043 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n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 7377570 0 0 tbm 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 7377817 0 0 0 21892 3183 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 7461665 0 0 0 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 7753501 0 0 91 0 0 1 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 7896039 0 0 42 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 8459985 0 0 0 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 8496634 0 0 0 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 8526099 0 0 83 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 8833033 0 0 11 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 9276366 0 0 13 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 9347651 0 0 20 0 0 1 1 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 9413798 0 0 0 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 9615106 0 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 9791661 336819 0 0 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 9862404 0 0 0 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 9909234 0 0 34 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 10481361 0 0 12 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 10838502 0 0 13 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 11426144 0 0 0 19890 0 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 11847176 0 0 46 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 12057624 0 0 0 48851 7453 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 12167780 0 0 0 0 0 0 0 n.d. n.d. 0 0 0 00 0 0 0 0 0 0 0 0 12687252 0 0 22 0 0 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 13029179 0 0 0 28128 2780 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 13089630 0 0 0 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 13102149 0 0 0 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 14586109 0 0 0 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 14747412 0 0 56 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 15129409 0 0 56 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 15383066 0 0 0 47653 7269 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 15659419 0 0 0 48968 7381 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 16005348 0 0 0 43419 5122 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 16271305 0 0 13 0 0 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 17033472 0 0 0 34585 4257 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 17640462 0 0 0 38552 4310 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 0 0 0 0 18943294 0 0 0 69303 10428 0 0 n.d. n.d. n.d. n.d. n.d. n.d.0 0 0 0 0 19 0 0 0 18956841 0 0 0 0 0 0 0 n.d. n.d. 1 0 0 0 plasticizers flame retardants bioassays samples Further, I thank for the support from: • the Clean Cycle project team: Magdalena Klotz, Dr. Zhanyun Wang, Dr. Melanie Haupt, Prof. Stefanie Hellweg • the Swiss Federal Office for the Environment (FOEN), the Swiss Federal Office of Public Health (FOPH) and Canton of Zurich‘s Office of Waste, Water, Energy and Air (AWEL). Acknowledgement 24.11.2022 31 Thank you very much for your attention! Thanks to RECETOX and Ondřej and Peter for the invitation!