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The New Generation of Green Plastics

How New? How Green?

Laura Park, DFO Newfoundland and Labrador

Presentation Outline Brief overview of conventional plastics and associated environmental concerns. Overview of major types of green plastics. Comparison of green plastics and conventional plastics in relation to major environmental concerns. Presentation of original data on conventional and green plastics in relation to buoyancy and degradation in sea water, acute toxicity of leachate, MFO induction.

Conventional Plastics
Polyethylene terephthalate (PETE) High density Polyethylene (HDPE) Polyvinylchloride (PVC) Low density Polyethylene (LDPE) Polypropylene (PP) Polystyrene (PS) Nylons Polymethyl methacrylate ABS plastic
O T H E R

Clear bottles for beverages, cooking oil, cleaners Toys, plastic bags, food & beverage bottles and tubs Pipes, well liners, IV bags, food & beverage bottles Shopping bags, trash bags, film packaging, bottles Tupperware, rope, food tubs & bottles Hard plastic, insulation, cutlery, clear trays, packaging Fabric, rope, netting Hard, clear plastic Plexiglas Pipes, car parts, toys, LEGO

Polytetrafluoroethylene Teflon" Polyvinylacetate Melamine-formaldehyde Silicone/Synthetic Rubber (various types) Nalgene polycarbonate Urea-formaldehyde resins

No stick pans, stain resistant coatings on carpet,


textiles, leather, Goretex, tents, dental floss Films and coatings Resins & laminates like Formica Sealants, gaskets, toys, shoes, teething rings, nipples, snorkels, tires, gaskets, shoes Baby bottles, microwave cookware, syringes, test tubes, dental products, compact discs, water cooler bottles Used in fiberglass and particle board

Many others, and literally thousands of variations and polymer blends

Conventional PlasticsEnvironmental Concerns: Persistence


Conventional plastics dont biodegrade, which means they cant be used as a food source by any living creature or even softened by the digestion process. All large food molecules must be broken down into small molecules before animals can absorb them. This is accomplished by specific enzymes which have evolved over billions of years. Plastic biodegradation is hampered by a number of factors: Plastics are giant molecules chains (polymers) of millions of small molecules (monomers). Specific plastic degrading enzymes have not evolved. Plastic polymers are incompatible with water. Most plastics will start to biodegrade to some extent once the polymer chain length is reduced to ~5,000 units. If degradation products are polar, degradability improves.

Conventional PlasticsEnvironmental Concerns: Persistence


Heat, UV radiation and mechanical stress can cause degradation of the plastic polymer:
Heat melting/burning temperature varies with plastic type. Some plastics are more brittle than others effects of mechanical stress vary. Plastizers are common additives. Catalysts and other trace components of plastic absorb UV radiation initiating oxidative degradation of the polymers UV stabilizers are common additives.

Over time, these processes lead to embrittlement, fragmentation and eventual biodegradation of plastics, but the process takes centuries. As a result, persistent plastic is accumulating in our landfills, oceans, soils and food chain. Persistence plastic debris has major impacts on the marine ecosystem.

Conventional Plastics-Environmental Concerns: Toxicity

Conventional Plastics-Environmental Concerns: Toxicity


Burning plastic can release toxic chemicals: PVC Dioxins & HCL (acid rain)

Teflon releases toxic chemicals when heated. Toxic releases during plastic production. Small molecules can leach out of the plastic: Unreacted monomers some (styrene, vinyl chloride) are toxic Production chemicals - may include solvents, catalysts, lubricants, additives which speed setting time, etc. Additives Can make up as much as 50% of the final product Not part of the polymer structure - loosely bound and can leach out. Most of these additives are not well tested or regulated. These include dyes, plasticizers, stabilizers, anti-static agents, flame retardants, etc.

Toxicity of Conventional Plastics


# Plastic Type Polyethylene terephthalate (PETE) High density Polyethylene (HDPE) Polyvinylchloride (PVC) Low density Polyethylene (LDPE) Polypropylene (PP) Polystyrene (PS) Components of Concern Acetaldehyde BHT, Chimassorb 81, irganox PS 800,1076, and 1010 Lead, cadmium, mercury, nonylphenol, Diethylhexyl phthalate, Bisphenol A BHT, Chimassorb 81, irganox PS 800,1076, and 1010 BHT, Chimassorb 81, irganox PS 800,1076, and 1010 Styrene, Deca-BDE (related to PCBs)

Polycarbonate (Nalgene) Bisphenol A (BPA) Teflon pans, stain Perfleurochemicals (PFCs) resistant coatings

Conventional Plastics - Environmental Concerns: Use of non-renewable fossil fuels


Conventional plastics are made from dwindling nonrenewable fossil fuels mostly natural gas 4% of worlds oil production is used as raw material for plastics. Plastics are the worlds most used material an estimated 350 billion pounds of new plastic is produced annually, and this number is growing. Only a small percentage of plastic is recycled and most recycled products (plastic lumber, clothing) are not recycled. Impediments to recycling include Quality Control issues, health risk (food packaging), very labour intensive, thermoset plastics cannot be melted grind up as filler.

Major Concerns Conventional plastics: Greenhouse gas emissions:


An estimated 4% of the worlds oil production is used to produce plastic. This could be avoided by using renewable energy sources. Conventional plastics act as a carbon sink, but so did the crude oil when we left it in the ground so there is no real net gain.

What makes a plastic green?


Should degrade completely (to carbon dioxide, methane, water, inorganic compounds) in a range of natural environments (compost, soil, marine and fresh water/sediments). Should be non-toxic and leave no toxic or persistent residues (i.e. metals, plastic particles). Should disappear rapidly (3-6 months). Should ideally be produced from a renewable resource.
Is natural source genetically modified? Is it competing with food production?

To be a viable alternative, green plastics must: Possess and maintain appropriate performance properties during anticipated life of the product. Be processed using existing technology/equipment. Be produced at a competitive price.

Overview of major types of green plastics


Biodegradable plastic from natural polymers Cellulose-based plastics: Cellophane was the first biodegradable plastic initially produced in 1908. Cellulose is also the basis for rayon, and celluloid. The rapid growth of plastics from fossil fuels largely replace cellulose-base products, although still used for some applications celluloid table tennis balls. As interest in biodegradable plastics increased in recent years, difficulty processing cellulose-based plastic using current technology has restricted interest in this polymer.

Overview of major types of green plastics


Biodegradable plastic from natural polymers Starch-based plastics: Thermoplastic starch-based polymers made of at least 90% starch from renewable resources such as corn, potato, wheat or tapioca are now on the market. By using specific plasticizing solvents, gelatinized starch can be converted into a thermoplastic material. To improve some of the properties of the plastic, the biopolymer may be modified, and blended with additives such as plasticizers, but no synthetic polymers are added. Examples: Novon, Eco-FOAM, Paragon Fully biodegradable, renewable source, non-toxic.

Overview of major types of green plastics


Biodegradable plastic polymers produced by microbes: Various types of bacteria synthesize polymers as an energy storage molecule (similar to starch). Some of these are useful for plastic production. Polyhydroxybutyrate (PHB) is the most common - brittle, has poor thermal stability, difficult to process. In 2000, cost was 10x more than traditional plastic, largely due to cost of the glucose. Cheaper feed stock options are being explored including whey. Polyhydroxyvalerate (PHV) - small amounts improve properties of PHB eg. Biopol (copolymer PHB/PHV with addition of a softener (triacetine/estaflex) and titanium dioxide and boron nitrate.

Overview of major types of green plastics


Biodegradable plastic polymers produced by microbes: These products are not widely available Still trying to work the bugs out of the process.

E. coli bacteria have been genetically modified (GM)


produce PHB more efficiently.

Corn has been genetically modified to produce PHB in their cells.

Overview of major types of green plastics


Biodegradable plastic from natural monomers: PLA Polylactic Acid
eg.

Lacea, Lucty, Galactic

Lactic acid is produced by fermentation of sugar. A solvent-free melt process is used to synthesize a lactic acid polymer. Fully degradable, but degrades poorly at
less than 60C (ocean) Non-toxic and can be recycled

Generally good performance characteristics: PLA is naturally clear, and can be formulated to be rigid or flexible and formed using most conventional techniques and equipment (films, sheets, fibers, molds)

Production cost has been prohibitive, but with oil prices on the rise, and recent innovations leading to reduced costs, interest in this polymer has increased Large plant recently constructed in Nebraska (300 million lbs PLA/yr.)

Overview of major types of green plastics


Biodegradable plastic synthesized from fossil fuels:

Polycaprolactone (PCL)
fully biodegradable, degrades in human body (used for sutures), non-toxic Compatible with starch and a range of other resins used as a plasticizer for PVC A number of other related products from fossil fuels mostly produced in Japan/Korea.

Polyvinyl alcohol and ethylene vinyl alcohol


Water soluble Vinex, Elvanol (made in USA)

Overview of major types of green plastics


Degradable plastics made from conventional polymers with additives which promote degradation: Typically polyethylene or polypropylene with a thermal and/or UV prodegradant additive oxo-degradable Once the material is discarded, oxidative degradation is initiated by heat, UV light or mechanical stress in presence of oxygen. Metals are frequently used to promote oxidation. Degradation products are more water soluble, which improves biodegradability. e.g. BIO-SOLO (used for compost collection in PEI) Recycled PE + additives. (cobalt) degradation activated by heat and oxygen - Probably will not degrade in a cold ocean Other examples include EcoSafe, BioMax, TDPA, PDQ, Addiflex, DegradeTM, Totally Degradable PlasticTM and Entec.

Overview of major types of green plastics


Blends of natural and/or synthetic polymers 5-50% starch blended with synthetic polymers such as polyethylene, polypropylene or polystyrene. The starch portion degrades and the plastic disintegrates into small particles that will persist, but are not visible. e.g. Earthstrength, Polystarch, Entec and MEBI Thermoplastic starch blended with polyvinyl alcohol e.g. Plantic (Australia)

Overview of major types of green plastics


Blends of natural and synthetic polymers Thermoplastic starch blended with biodegradable polymers from renewable or non-renewable sources

NatureWorksTM - Starch/PLA
Fully biodegradable, non-toxic, renewable source

Mater-BiTM, BioFlexTM - Starch/PCL or PVA


Fully biodegradable, non-toxic, renewable and nonrenewable sources.

Capron
Blend of Polyhydroxybutyrate (PHB) with Polycaprolactone (PCL)

Green plastics Vs traditional plastics


Type
Traditional

Source
Nonrenewable

Toxicity

Persistence

Toxicity a 400-600 years or Concern more Some say never!


Compost 4-8 weeks Ocean 20-30 weeks off Australia (temp dependent) Compost 2-6 weeks Ocean unknown - degrades poorly at temp< 60C Compost 4 weeks Ocean- unknown but may be digestible Compost 2-6 weeks Ocean 8 weeks 6 weeks to disintegrate in compost, 3-5 years in dry landfill, biodegradation 5-10 years. Ocean unknown

Starch-based PLA PHB/V PCL

Renewable Non-toxic Renewable Non-toxic Renewable Non-toxic Nonrenewable Non-toxic Unknown

Prodegradant Nonadditives renewable

Impacts of floating plastic debris in the ocean


Floating plastic moves long distances on ocean currents causing serious environmental problems: Degradation of distant beaches, fouling of fishing gear Entanglement of sea creatures feeding in the pelagic environment (birds, sea turtles, baleen whale, fish) Mortality/morbidity resulting from ingestion Entanglement of ship propellers and other marine equipment. Clogging of water intakes, oil spill response equipment, etc

Buoyancy of Traditional Plastics


# Type Polyethylene terephthalate (PETE) High density Polyethylene (HDPE) Polyvinylchloride (PVC) Low density Polyethylene (LDPE) Polypropylene (PP) High Density Polystyrene (PS) Polystyrene foam
Density of seawater varies from 1.020-1.029

Density
g/cm3

Buoyancy Sinks Floats Sinks Floats Floats Sinks, but may remain in water column Floats
Extremely buoyant

1.370 0.941 1.380 0.910.925 0.850.95 1.050

0.0017 and up

PCL + starch Mater-bi BioBag

PCL + starch Mater-bi BioBag

PE Sobeys bag

PE + UV Prodegradant

PE + starch

Distilled H2O

Six months at room temperature

Buoyancy and degradation of Green plastics in seawater

BioSak (Mater-Bi) - two months at 0-4 C

Mixed Function Oxidase (MFO) Induction:


A general purpose detoxification enzyme system which inactivates a wide range of fat soluble toxic substances. MFO enzyme levels increase (induction) in response to exposure of the animal to a toxin Used by researchers as an indicator of the toxicity of a substance. Chronic induction is associated with a range of pathology. In preliminary studies 1 week old cod larvae exposed to leachate from black PE garbage bags (10g/L) showed an increase in MFO:
17 pooled larvae /group pmol/mg/min

Exposed Control

4.35 0.07

Work conducted by Jacqueline Guiney, Anne Mathieu (Oceans Ltd.) & St. Johns ACAP

Polystyrene test tubes PE + starch Control 2 PE + UV Prodegradant

Control 1

PVC shower curtain

PCL + starch Mater-bi BioBag

Black Polyethylene garbage bag

100g plastic in 5 L seawater for 10 days at 4-8 C

Specific Activity (pmol/mg/min)


0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

Biodeg radable Photod egrada b le

Contro l1 Contro l2 Biosac k Polysty rene Polyeth ylene

EROD in cod larvae exposed to various plastics

Conclusions More research is needed on all plastics, particularly in relation to their toxicity and fate in the environment. Conventional plastics are a serious environmental concern and green plastics offer a good alternative for many applications.

Green plastics are a rapidly evolving industry

Wide range of products being marketed as green. Need to evaluate based on more than the companys promotional material. There is strong disagreement on whether conventional plastics can ever completely biodegrade, even in the presence of prodegradant additives.

Some useful References:


The Impacts of degradable plastic bags in Australia (2003) Final report to Department of Environment and Heritage, ExcelPlas Australia Environment Australia, Biodegradable Plastics Development and Environmental Impacts (2002) ExcelPlas Australia

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