1. 1 Chapter 23: Environmental Aspects of Plastics Professor Joe Greene CSU, CHICO

2. 2 Topic Source Reduction Recycling Regeneration Degradation Landfill Incineration Total Product Life Cycle Future Chemical Hazards Sources of Chemical Hazards MSDS

3. 3 Topic Source Reduction –Reduce the amount of material that is used in any application Combine parts into larger parts, e.g., 1 liter soda uses 40% less packaging than (2) 0.5 liters Reduce thickness of plastic part, e.g., trash bags had 0.08mm thickness (0.003 in) with LDPE, was reduced to 0.025mm (0.001 in) thickness with stronger and tougher LLDPE Reduce thickness by process imporvements Substitution of plastics for paper have reduced weight of packaging –1000 grocery bags from paper weighs 140 lbs and stacks 46 inches –1000 grocery bags from plastic weighs 15.6 lbs and stacks 3.5 in –Recycle in house plastic from sprues and runners back into product.

4. 4 Topic Recycling –Collection: plastic listed with recycled number –Codes for plastics 1 PET 2 HDPE 3 Vinyl/PVC 4 LDPE 5PP 6PS 7Other –Handling/Sorting Maximum economic is obtained when each material is sorted Aluminum must be separated from metals since it can’t be readily separated from zinc and brass Plastics are sorted mostly by sight. Machines can sort by light absorption

5. 5 Topic Recycling –Reclamation and Cleaning Plastic is shredded and cleaned –End-Uses- Sorted PCR (Post Consumer Recycle) LDPE for new bags and film PS in insulation and instrument packaging PP in automotive parts, e.g., interior door inner panels, head liners, etc. Mechanical properties drop with use of regrind plastic versus virgin plastic. Max use of 50% regrind, Typical 20%. –End-Uses- Comingled PCR with several plastics regrind Other plastics include thermoset materials, elastomers, and composites Plastic wood with use of comingled PCR that is compression molded and not injeciton molded usually.

6. 6 Topic Regeneration –Process of breaking down polymer molecule into basic chemicals or chemical recycling. –Easiest to regenerate is condensation polymers, PET and nylon. –Under high pressure and heat in the presence of a catalyst the molecule unzips and regenerates the monomers. –Thermoset composites use process of pyrolysys, which is the decomposition of a material using heat in the absence of oxygen. –Advantage of this process is it is more effective for mixed plastics than PCR –Disadvantages is the generation of air and water pollution and large amounts of energy required

7. 7 Topic Landfills –90% of all solid waste (by weight) in US is sanitary landfill. –Plastics comprise 8 % by weight and 20% by volume. –Paper products comprise 40% by weight and 34% by volume. –Percentage of plastics in landfill has not grown in the last 20 years. Inceration –Controlled burning is an option for disposing of a large percentage of municipal solid waste. –Paper, plastic, and other flammables are separtaed from solid waste and pressed into pellets and burned at a separte facility. –Burning generates electricity –Environmental concerns includes creation of toxins (dioxins), ash problems, and carbon dioxode releae for global warming

8. 8 Topic Inceration –Burning generates electricity –Energy content of various solid waste MaterialEnergy Value (BTU/pound) PET10,900 HDPE18,700 Rubber12,800 Newspaper 8,000 Wood 7,300 Yard Waste 2,900 Fuel oil20,900 Coal 9,600

9. 9 Topic Total Product Life Cycle –What is the total impact of a particular product or product type on the environment over the total life cycle of the product from the creation of the product, its use, and disposal impact. –Example, –Polystyrene versus paper cups, Table 23.3

10. 10 Topic Energy Requirements –Example, –Paper sack versus Polyethylene sack, Fig 23.3 –Refrigerators and freezers. Plastics are replace of glass and metal Plastics saved 700 million pounds and require a total of 15.8 trillion BTUs during production versus 23 trillion BTUs for metal and glass. (Savings of 7.2 trillion)

11. 11 Topic Energy Requirements –Plastic pipe More tonnage of plastics hoes into pipe than any other single use. –Weight of pipe was 2 billion pounds versus metal pipe of 17.5 billion pounds. –Energy consumption of plastic was 84 trillion BTUs versus 408 trillion BTUs for metal pipe, Savings of 324 trillion BTUs –Beverage Bottles PET was introduced in mid 1970s to a market full of glass bottles. Energy consumption for plastic is 18.2 trillion BTUs versus 24.2 trillion BTUs for glass. Savings of 16 trillion BTUs, or equivalent to 2.8 millions barrels of crude oil.

12. 12 Chemical Hazards Materials –Resins (See MSDS) Thermoplastic resins- low toxicity and low health hazard Thermoset resins- moderate toxicity and moderate health hazard –Reinforcements- low toxicity and moderate health hazards (dust) –Fillers- low toxicity and moderate health hazards (dust) –Solvents- moderate to high toxicity with moderate to high health hazards –Catalyst- moderate to high toxicity with moderate to high health hazards –Plasticizers- low toxicity and moderate health hazards

13. 13 Material Safety Data Sheet (MSDS) Hazardous materials are common in the plastics industry MSDS are required to accompany any purchased hazardous industrial raw material. Plastics are defined as potentially hazardous because in the course of normal use, plastics may produce dusts, mists, gases, fumes, vapors, or smokes which are dangerous.

14. 14 Material Safety Data Sheet (MSDS) Section I: General Information Section II: Composition Section III: Physical Properties Section IV: Fire and Explosion Hazard Data Section V: Health Hazard Data Section VI: Reactivity Data Section VII: Spill or Leak Procedure Section VIII: Occupational Protective Measures Section IX: Special Precautions Section X: Transportation

15. 15 Section I: General Information Product name Manufacturer’s Identity Emergency telephone numbers Trade name of chemical Chemical family name of the material Example –Lexan –General Electric –1-800-gecares –Lexan PC Resin –Poly(Bisphenol-A carbonate) –Chemical Abstracts Services (CAS) Number- Unambigous identification of materials. Lexan= 25971-65-5 (same as Merlon)

16. 16 Section II: Composition Hazardous Ingredients –Major constituents –hazardous additives, fillers, or colorants –Example for ABS 3 % Carbon black (solid- trapped in polymer) 0.2% residual styrene monomer (gas- released during processing)

17. 17 Section II: Definitions Definitions OSHA- Occupational Safety and Health Administration ACGIH- American Conference of Governmental Industrial Hygienists PEL- Personal Exposure Limits (TWA) TWA- Time weighted average. Exposure level considered acceptable in an 8 hour day as part of a 40 hour week. REL- Recommended exposure TLV- Threshold Limit Value. Recommended by the American congress of Governmental industrial Hygienist. (TWA for 8 hours) STEL- Short term exposure limit. Acceptable exposure for 15 minutes and should not be exceeded any time during the 8 hour work day.

18. 18 Section II: Styrene Styrene as a health hazard Building block for thermoplastic styrenics, e.g., polystyrene, ABS, SAN, and others. Cross-linking building block for thermoset styrenics, e.g., polyesters, vinyl esters. ABS has 0.2 % residual styrene plus other sources (styrenic plastics) One study found a range of 1 to 7 ppm styrene in an injection molding plant Thermosets –Manufacturing of large boat hulls, boats, large tanks, tubs, shower stalls, body panels for cars and trucks. –Polyester is 35% styrene by weight. –Processing methods include fiber spray with resin in stream, handlayup by roller, closed mold RTM operations, compression molding of polyester sheet. Ventilation is essential to keep exposure within limits.

19. 19 Section III: Physical Properties Properties of material as one substance –Evaporation Rate –Melting point –Boiling point –Specific gravity –Solubility in water –Physical form

20. 20 Section IV: Fire and Explosion Hazard Data Section for fire fighting Most plastics are not explosive Upon burning most plastics will yield water and CO 2 Many plastics are self-extinguishing All thermosets are self-extinguishing Water is recommended as the best medium for extinguishing fires Toxic fumes from plastics include –black smoke, CO, hydrogen cyanide, and ammonia Flash point is very high for many plastics

21. 21 Section V: Health Hazard Data Routes of entry of toxic substances –Ingestion Oral LD-50 in rats. Lethal Dose 50 percentile of fatalities in rats Many pelletized plastics are rather inert. Extremely toxic: LD-50 less than 1 mg/kg or 10 ppm Highly toxic: LD-50 less than 50 mg/kg or 100 ppm Moderately toxic: LD-50 less than 500 mg/kg or 1000 ppm Slightly toxic: LD-50 greater than 500 mg/kg or 1000 ppm Example –LD-50 for guinea pig is 264mg/kg (264mg x mass of pig) –Assuming equal response from human: 264mg x 70kg for mass of human = 18480mg or 18.48g to be ingested.

22. 22 Section V: Routes of Entry Routes of entry of toxic substances –Inhalation Thermosets reactants can be inhaled since they are in liquid form and have a vapor pressure that indicates relative volatility. Example: Isocyanates used in polyurethane production –TDI (toluene diisocyanate) used in foams for seats or paints. –MDI (methylene diisocynate) used in RIM body panels or in paints. –Construction projects use foamed polyurethane for interior walls and roofs. –TLV is 0.005 ppm –STEL for TDI is 0.02 ppm. Local and general ventilation are extremely important when working with urethanes Effects are asthma symptoms

23. 23 Section V: Routes of Entry Routes of entry of toxic substances –Inhalation LC for lethal concentration (normally for a vapor or gas) Unlikely for peletized plastics Heated plastics yield hydrocarbons Example –Overheated PET releases acetaldehyde –STEL of 25 ppm –Odor threshold is 0.050 ppm. Example –PVD polymerization uses Vinyl chlorine gas –TLV of 5 ppm –Odor threshold of 3000 ppm (no odor warning) –Known human carcinogen

24. 24 Section V: Routes of Entry Routes of entry of toxic substances –Dermal (Skin) Most pelletized plastics do not affect dermal Isocyanates can cause rashes and blistering of skin Isocyantes can cause discoloring of skin. Hot plastic materials can cause skin burns Catalyst materials can cause skin abrasions Example –Diethylene Triamine (catalyst) CAS# 111-40-0 –ACGIH »TLVSTEL »1 ppm (skin)NE –OSHA »PELSTEL »1 ppmNE

25. 25 Section V: Routes of Entry Routes of entry of toxic substances –Eyes Injured by objects landing in the eye –glass fibers, fillers, additives, colorants, particles of plastic –liquids and gases can cause severe damage –Example »methylene- hardener for epoxy »Causes irreversible blindness in cats and visual impairment in cattle. –Carcinogenicity Pelletized plastics are often not regulated as carcinogenic Residual monomers have links to cancer (vinyl acetate, a residual monomer from PVA and EVA is present at 0.3%) at levels of 600 ppm caused some cancer in some animals (bears A3 notation) Some liquid polymers and catalysts can cause cancer in some animals

26. 26 Section VI: Reactivity Data Pelletized plastics are very stable and non-reactive Thermo-oxidative degradation can yield hazardous gases –PVC: at 100 ºC releases HCl –PMMA: at 100 ºC releases MMA –POM: at 230 ºC releases formaldehyde –Teflon (other fluoroplastics): at 250 ºC release HF –PET: at 300 ºC releases acetaldehyde –Nylons: at 300 ºC nylons release CO and ammonia –Nylon 6: at 340 ºC releases e-caprolactam –Thermoset resin degrade to toxic fumes of CO, formaldehyde, isocynates (for urethanes)

27. 27 Section VI: Reactivity Data _PVC and POM Thermal degradation of PVC –PVC degradation is a serious problem Can decompose catastrophically if overheated in barrel. Remaining materials is tightly packed carbon Fumes contain high concentrations of HCl Response team must wear air respirator, turn off machine, tear down after cooling, remove nozzle and end cap. Thermal degradation of POM (poly actetal or polyoxymethylene) Thermally degrades (>230 ºC )and releases formaldehyde Exposure can occur at purging of machine Local exhaust is essential to minimize exposure Thermal degradation of Phenolics Major uses in adhesive applications (plywood & particleboard) Compression and transfer molding operations Can release small amounts of ammonia, formaldehyde, and phenol

28. 28 Section VI: _Phenolics, Nylon 6, & PMMS Thermal degradation of Phenolics Major uses in adhesive applications (plywood & particleboard) Compression and transfer molding operations Can release small amounts of ammonia, formaldehyde, and phenol –Phenol: TLV of 5 ppm, LD-50 of 414mg/kg, and LC-50 of 821 ppm. –Formaldehyde: ceiling of 0.3 ppm Thermal degradation of Nylon 6 Degrades into monomer_ e-caprolactam, and residual caprolactam –Caprolactam vapor: TLV is 5 ppm, LD-50 (rat) is 2.14 mg/kg –Molding operation release some caprolactam vapor, with more produced during purging and extrusions Thermal degradation of PMMA (acrylic)_ Plexiglass PMMA degrades into MMA (methyl methacrylate) TLV for MMA is 100 ppm (410 mg/m 3 )

29. 29 Section VII: Spill or Leak Procedure Pelletized materials are swept up. Liquid chemicals use absorbent materials For isocyanates the absorbent materials need to allow reaction of the isocyanate with the water in the air. The reacted materials is then disposed of according to specified government regulations. Section VIII: Occupational Protective Measures Workplace protection –Adequate ventilation –Personal protective devices include safety glasses or goggles for eye and face protection gloves, long sleeves, face shields, ear plugs respirators

30. 30 Section IX: Special Precautions Handling Storage Section X: Transportation Special instructions for transporting liquid chemicals Most pelletized plastics have no special restrictions