Laura Park

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The New Genera t ion of

GreenPlast ics

How New ? How Green?

Laura Park, DFONewfoundland and Labrador

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Presenta t ion Out l ine

Br ief overv iew o f convent ional p last ic sand assoc ia ted env i ronment a l c oncerns .

Overv iew o f m a jor types o f greenp las t i cs .

Com par ison of greenp last ic s and c onvent iona l

p las t ic s in re lat ion t o m a jor env i ronm enta lconcerns .

Presenta t ion o f or ig ina l dat a on c onvent iona l

and greenp last ic s in rela t ion t o buoyanc y anddegradat ion in sea w a te r , acu t e t ox ic i t y o fleac hat e , MFO induc t ion.

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Many o thers , and l i te ra l ly t housands o f var ia t ions and po lym er b lends

Used in f iberglass and part ic le boardUrea-form aldehyde resins

Baby bot t les , mic row ave cookw are, syr inges, tes t tubes,denta l p roduc t s , compac t d i scs , w a te r coo le r bo t t l es

Na lgene po lyca rbona te

Sealant s, gaskets, toys, shoes, teet h ing r ings, n ipples,snorkel s, t i r es, gasket s, shoes

Si l icone/Synthet i c Rubber (var ioustypes)

Res ins & lam inates l i ke Formic aMelamine-formaldehyde

Fi lms and c oat ingsPolyv iny laceta te

No st i c k pans, s ta in res is tant c oat ings on carpet ,tex t i les , lea ther , Goretex , t en ts , denta l f loss

Poly te t ra f luoroethy lene Tef lon"

Pipes, car part s, toys, LEGOABS plast ic

Hard, c lear p las t ic P lex ig lasPo lymethy l methacry la te

Fabr ic , rope, net t ingNylons

OTHER

Hard p las t ic , insu la t ion , cu t le ry , c lear t rays , packag ingPolyst yrene (PS)

Tupperw are, rope, food tubs & bot t lesPolypropyl ene (PP)

Shopping bags, t r ash bags, f i lm pac kaging, bot t lesLow densi t y Polyethylene (LDPE)

Pipes, w el l l iners, IV bags, food & beverage bot t lesPolyvinylchlor ide (PVC)

Toys, p las t ic bags, food & beverage bot t les and tubsHigh densi t y Polyethylene (HDPE)

Clear bot t les for beverages, cook ing o i l , c leaner sPolyethy lene terephtha la te (PETE)

Convent iona l P last ic s

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Convent iona l p las t ic s don t b iodegrade, w h ic h means t heyc an t be used as a food source by any l i v ing c reat ure oreven sof t ened by t he d igest ion process.

Convent ional Plast ic sEnvironm ent a l Conc erns:

Pers is tence

Plas t ic b iodegradat ion is ham pered by a num ber o f fac t ors :

A l l la rge food mo lecu les mus t be b rok en dow n in to sm a l lm olec u les before an imals can absorb t hem . Th is isacc ompl i shed by spec i f i c enzymes w h ich have evo lved overb i l l ions of years.

Plas t i c s a re giant m o lecu les cha ins (po lymers) o f m i l l ionsof smal l m olecu les (m onomers) .

Pl as t i c po lymers are i ncompa t i bl e w i t h w a te r.

Spec i f i c p las t i c degrad ing enzymes have no t evo lved .

Mos t p l as t i c s w i l l st a r t t o b iodegrade t o some ex ten t oncet he po lymer c ha in lengt h is reduced t o ~5,000 un i ts . I fdegradat ion produc t s are po lar , degradab il i t y im proves.

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Convent ional Plast ic sEnvironm ent a l Conc erns:

Pers is tenceHeat , UV radia t ion and mec han ic a l s t ress can c ausedegradat ion o f the p las t i c po lym er :

As a resu l t , pers is ten t p last i c i s acc umula t ing in ourlandf i l ls , oc eans, so i ls and food chain. Pers is t enc e p last ic

debri s has ma jo r impac t s on the mar ine ecosyst em.

Over t im e, t hese p rocesses lead to em br i t t l ement ,f ragment at ion and eventua l b iodegradat ion o f p las t ic s , butt he process tak es c en tu r ies .

Heat me l t ing /bu rn ing temperatu re va r ies w i th p last i c t ype . Some p last i c s a re more b ri t t l e t han o thers e ff ec t s o fm echan ica l s t ress vary. Plas t izers are com m on add it i ves.

Ca ta lysts and othe r t race c omponen ts o f plast i c absorb UV

rad iat ion ini t ia t ing ox ida t ive degradat ion o f t he polymers UVstab i l i ze rs a re c omm on add i t i ves .

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Convent ional Plast ic s-Envi ronm ent a l Conc erns:

Tox i c i t y

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Tox ic re leases dur ing p las t i c p roduc t ion .

Unreac ted m onom ers som e (s ty rene , v iny l ch lo r ide) a re t ox i c

Pr od uc t i on c h e m ic a ls - m a y in c lu de s ol ve nt s , c a t a ly st s ,lubri can t s , add it i ves w h ich speed se t t ing t ime, e tc .

Addi t i ves Can make up as much as 50% of the f ina l p roduc t Not par t o f the po lymer s t ruc t u re - loose ly bound and can leac hout . Mos t o f t hese add i t i ves a re no t w e l l tes t ed o r regu lat ed .

These inc lude dyes, plas t ic izers , st ab i l i zers , ant i -s t a t ic agents ,f l ame re ta rdan ts , e tc .

Convent ional Plast ic s-Envi ronm ent a l Conc erns:

Tox i c i t yBurning p last i c c an release tox ic c hemic a ls :

PVC Diox ins & HCL (ac id ra in)

Te f lon re leases t ox ic c hemic a ls w hen heated .

Sm al l mo lecu les can leac h ou t o f the p las t i c :

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St yren e, Dec a-BDE (relat edt o PCBs)

Polyst yren e (PS)

B ispheno l A (BPA)

Per f leuroc hemic a ls (PFCs)

Polycarbonate (Nalgene)Tef lon pans, s t a in

res is tan t c oa t ings

BHT, Ch imassorb 81, i rganoxPS 800,1076 , and 10 10

BHT, Ch imassorb 81, i rganoxPS 800,1076 , and 10 10

Lead, cadmium , mercury ,nonylphenol , Diet hy lhex y lph tha la te , B i spheno l A

BHT, Ch imassorb 81, i rganox

PS 800,1076 , and 10 10

Aceta ldehyde

Com ponents o f ConcernPlas t ic Type#

Polypr opy lene (PP)

Low densi t yPolyethylene (LDPE)

Polyv iny lch lor ide(PVC)

High densi t y

Polyethylene (HDPE)

Polyethy lenet e reph tha la te (PETE)

Tox ic i t y o f Convent iona l Plas t ic s

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Convent iona l p last ic s are m ade f rom dw ind l ing non-renew ab le fossi l fue ls m ost l y na tu ra l gas 4% o f w or lds

o i l produc t ion is used as raw m ater ia l for p las t i c s.

Plas t i c s are the w or lds mos t used mat er ial anes t im ated 350 b i l l i on pounds of new p last i c i s p roduced

annual ly, and th is num ber is grow ing.

Convent iona l Plas t ic s - Env ironment a l Concerns :

Use of non-renew able foss i l fue ls

Only a sm al l perc ent age o f p las t ic i s recyc led andm ost recyc led p roduc t s (p last i c lumber , c lo th ing) a renot recyc led .

Imped iment s t o rec yc l ing inc lude Qua li t y Cont ro lissues, heal t h r isk ( food pac k aging), very labourint ens i ve , t he rm ose t p las t i cs canno t be m e lt ed g r ind

up as f i l ler .

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Greenhouse gas em iss ions:

Major Concerns Convent iona l p last ic s :

An es t im ated 4% o f the w or lds o i l produc t ion is

used to produc e p las t ic . Th is cou ld be avo ided byus ing renew able energy sourc es.

Convent iona l p las t ic s ac t as a c arbon sink , but sod id the c rude o il w hen w e le ft i t i n t he g round sot here is no rea l net ga in .

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What m ak es a plast ic green?

Should degrade com ple t e ly (t o carbon d iox ide,m et hane, w at er , inorgan ic c om pounds) in a range o fnat ura l env i ronm ent s (c om post , so il , m ar ine and f reshwater /sed iments) .

Shou ld be non-t ox ic and leave no t ox ic orpers is tent res idues (i .e . m et a ls , p las t ic par t i c les).

Should d isappear rap id ly (3-6 m ont hs).

To be a v iab le a l te rnat ive , green plas t ic s must :

Possess and m a int a in appropr iate pe rfo rmanceproper t ies dur ing an t i c ipa ted l i fe o f the p roduc t .

Be p rocessed us ing ex is t ing t echno logy/equ ipment .

Be p roduced a t a compe t i t i ve pr ice .

Should ideal ly be produc ed f rom a renew able resourc e.I s nat ura l source genet ica l ly mod i f ied? Is i t c ompet ing w i th foodproduct ion?

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Overview o f m a jor t ypes o f greenp las t i cs

Cel lu lose-based p last ic s :

Ce l lophane w as the f i rs t b iodegradab le p las t ic in i t ia l l y produc ed in 1908.

Cel lu lose is a lso t he bas is for rayon, and c e l lu lo id .

Biodegradab le p las t ic f rom nat ura l po lymers

The rapid grow t h o f p las t ic s f rom foss i l fue ls la rge lyrep lace c e l lu lose-base product s , a l t hough s t i l l usedfo r some appl i ca t ions c e l lu lo id t ab le t enn is ba l l s.

As in teres t in b iodegradab le p las t ic s increased inrec ent years , d i f f i cu l t y proc ess ing ce l lu lose-basedp last i c us ing c ur ren t t echno logy has res t r i c t edin te res t i n t h i s polymer .

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Overview o f m a jor t ypes o f greenp las t i cs

Thermoplas t ic s t arc h-based po lymers m ade of a t leas t90% st a rch f rom renew ab le resources such as c orn ,po ta to , w hea t o r t apioca a re now on the marke t .

By us ing spec i f i c p las t ic izing so lvents , ge lat in ized

s ta rc h can be c onver ted in to a thermop las t i cmater ia l .

To improve some o f t he p roper t ies of the p last i c , t heb iopo lym er may be modi f ied , and b lended w i t hadd i t i ves such as p las t ic izers , but no synt het icpo lymers are added.

Ex am ples: N ovon, Ec o-FOAM, Paragon

Fu l l y b iodegradab le , renew ab le source , non-t ox ic .

Biodegradab le p las t ic f rom nat ura l po lymers

St arc h-based p las t ic s :

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Overview o f m a jor types o f greenp las t i cs

Var ious types o f bac t er ia synthes ize po lymers as anenergy s t orage m olecu le (s imi la r to st arc h). Som e of

t hese are usefu l fo r p las t ic produc t ion.

Biodegradab le p las t ic po lymers produced by m ic robes :

Po lyhydroxybu ty ra te (PHB) i s the mos t c omm on - b ri t t l e,has poor t herm al s tab i l i t y , d i f f i cu l t t o process. In 2000,

c os t w as 10x m ore than t rad i t i ona l plas t i c , l a rge ly duet o c os t o f t he g luc ose . Cheaper feed s toc k op t ions a rebe ing ex p lo red inc lud ing w hey .

Po lyhydroxyvale ra te (PHV) - sma l l amounts improveproper t ies of PHB

eg. B iopo l (c opo lymer PHB/PHV w i t h addi t ion of asof tener (t r iac et ine/es t a f lex) and t i t an ium d iox ide and

boron n i t ra t e .

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Biodegradab le p las t ic po lymers produced by m ic robes :

E. c ol i bac t er ia have been genet ic a l l y m odi f ied (GM)

produce PHB more e f f i c ient ly .

Corn has been genet ic a l l y m odi f ied to produc e PHB int he i r ce l l s.

These p roduc t s a re no t w ide ly avai lab le St i l l t r y ing

t o w ork t he bugs ou t o f t he p rocess .

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Biodegradable p las t i c f rom na tu ra l m onomers :

PLA Po ly lac t i c Ac id eg. Lac ea, Luc t y , Galac t ic

PL A i s n at u ra ll y c l ea r, a nd c an be fo rm u la t ed t o b er ig id or f lex ib le and formed us ing most c onvent iona l

t ec hn iques and equ ipm ent (f i lms, sheet s , f ibers , m olds)

Lac t i c ac id i s p roduced by fe rmenta t ion o f sugar . A

so lvent -f ree mel t p roc ess is used t o synthes ize a lac t icac id po lymer .

Ful ly degradabl e, but degrades poor ly atless t han 60C (oc ean)

N on -t o x i c an d c a n b e r ec y c l edGenera l l y good per fo rmance c harac t e r i st i cs :

Produc t ion cos t has been proh ib i t i ve , bu t w i th o i l p r ic es ont he r ise , and rec ent innovat ions lead ing t o reduc ed cost s ,in te res t i n t h i s po lymer has inc reased Large p lan t

rec ent ly c onst ruc t ed in Nebraska (300 m i l l ion lbs PLA/yr .)

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Overv iew o f major t ypes o f greenp las t i cs

Biodegradable p las t ic synt hes ized f rom foss i l fue ls :Po lycaprolac t one (PCL)

fu l ly b iodegradable, degrades in hum an body(used for sut ures), non-t ox ic

Compat ib le w i th s t a rch and a range o f o therres ins used as a plas t ic izer fo r PVC

Polyv inyl a lc oho l and e t hy lene v inyl a lc oho l Wa t e r s ol ub le

V inex , El vano l (made i n USA)

A number o f o t her re la ted p roduc t s f rom fossi lfue ls most ly produced in J apan/K orea.

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Degradable p las t ic s made f rom c onvent iona l

po lym ers w i th add it i ves w h ich p rom ote degradat ion :

e.g. BIO-SOLO (used fo r c om post c ol lec t ion in PEI)Rec yc led PE + addi t ives. (c obal t )

degradat i on ac t i va ted by hea t and ox ygen - Probab ly w i l lno t degrade in a c o ld ocean

Typ ic a l l y polye thy lene o r po lypropylene w i th a t herma l

and /o r UV prodegradant add it i ve oxo-degradable

Ot her ex am ples in c lude Ec oSafe, BioMa x , TDPA, PDQ,

Addi f lex , Degrade TM, Tot a l ly Degradable Plast ic TM and Ent ec .

Onc e the m at er ia l is d iscarded, ox idat ive degradat ion isin it i a ted by hea t , UV l i gh t o r mec han ic a l s t ress inpresence o f ox ygen. Met a ls are f requent ly used t o

promot e ox ida t ion . Degradat ion p roduc t s a re m ore w aterso lub le, w h ic h improves b iodegradab i l it y .

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Blends o f nat ura l and/or synthet ic po lymers5-50% st a rch b lended w i th syn t he t i c po lym ers such

as po lyet hy lene, po lypropylene or po lys ty rene.

The s ta rc h por t ion degrades and the p las t i cd is in tegra tes in to sma l l part i c les tha t w i l l persis t ,but are not v is ib le .

e .g . Ear t hs t rength , Po lys tarc h, Ent ec and MEBI

Therm op las t i c s ta rc h b lended w i th po lyv iny l al coho l

e .g . Plan t i c (Aus t ra l ia)

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Blends o f na tu ra l and synt he t i c po lym ersTherm op las t i c s ta rc h b lended w i th b iodegradab le

po lymers f rom renew able or non-renew able sources

NatureWorksTM - St arch /PLA

Ful ly b iodegradab le , non-t ox ic , renew able sourc e

Mater-BiTM, BioFlex TM - St arc h/PCL or PVA

Ful ly b iodegradable, non-t ox ic , renew able and non-

renew ab le sources .

Capron

Blend o f Po lyhydrox ybuty ra te (PHB) w i th Polycapro-

l ac t one (PCL)

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6 weeks t o d is in tegra te incom post , 3-5 years in drylandf i l l , b iodegradat ion 5-10

years . Ocean unknown

U n k n o w nNon-renewab le

Prodegradantadd i t i ves

Compost 2 -6 w eeksOcean 8 weeksNon-tox icNon-

renewab lePCL

Compost 4 w eeks

Ocean- unknow n but m ay bed igest ib le

Non-tox icRenewab lePHB/V

Compost 2 -6 w eeks

Oc e an u nk n ow n - d eg ra de spoor ly at tem p< 60C

Non-tox icRenewab lePLA

Compost 4 -8 w eeks

Ocean 20-30 w eeks of fAust ra l ia (tem p dependent )

Non-tox icRenewab leStarch-based

400-600 ye ars ormore Some say

never !

Tox i c i t y aConcern

Non-renewab le

Trad i t iona l

Pers is tenceTox i c i t ySourceType

Greenp las t ic s Vs t rad i t iona l p last ic s

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Im pact s of f loa t ing p last ic debr is in the ocean

Floa t ing p last i c m oves long d ist ances on oc eanc urrents c aus ing ser ious env i ronment a l p rob lems:

Degradat ion o f d is tant beaches, fou ling o f f i sh ing gear

Ent ang lement o f sea c reatures feed ing in thepe lag ic env i ronment (b i rds , sea t ur t les , ba leenw hale , f i sh)

Mor ta l i t y /m orb id i ty resu l t ing f rom ingest ion

Ent ang lement o f sh ip prope l le rs and o ther m ar ine

equ ipment .

Clogg ing o f w at er in tak es, o i l sp i l l response

equ ipment , e tc

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0.0017and up

1.050

0.85-0.95

0.910-

.925

1.380

0.941

1.370

Densi tyg/cm 3 BuoyancyType#

FloatsExt remely buoyant

Polyst yrene foam

Sink s , but m ay

rema in i n w a te rco lumn

High Densi t y Polyst yrene

(PS)

FloatsPolypr opy len e (PP)

FloatsLow dens i ty Po lyethy lene

(LDPE)

SinksPolyvi nylc hlor ide (PVC)

FloatsHigh dens i ty Po lyethy lene(HDPE)

SinksPolyethy lene terephtha la te(PETE)

Buoyancy o f Trad i t iona l Plast ic s

Densi ty of seaw ater var ies f rom 1.020-1.029

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Buoyanc y and degradat ion o f Greenp las t i csin seaw ate r

PCL + st arch

Mat er-b i BioBag

PCL + starc h

Mat er-b i BioBag

PE Sobeysbag

PE + UVProdegradant

PE + st arc h Dist i l led H2O

Six mon ths a t room tem pera tu re

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BioSak (Mat e r-B i) - t w o mon ths at 0 -4 C

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Mixed Funct ion Ox idase (MFO) Induc t ion :

A general purpose detox i f i ca t ion enzym e sys temw hich inac t i vat es a w ide range o f fa t so luble tox icsubs tances .

MFO enzym e levels inc rease (induc t ion) inresponse t o exposure of t he an im a l to a t ox in Used by researchers as an ind ica t o r o f the t ox ic i t yo f a substanc e. Chron ic induct ion is assoc ia t edw i th a range of pa tho logy.

In p rel im inary st ud ies 1 w eek o ld c od la rvaeex posed t o leachat e f rom b lac k PE garbage bags(10g/L) show ed an inc rease in M FO:

0.07Control

4.35Exposedpmol/mg/min17 pooled larvae /group

Work c onduc ted by J ac quel ine Guiney, Anne Math ieu (Oc eans Ltd. ) & St . J ohns ACAP

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PE + starc h

PE + UV Prodegr adant

Contro l 1

Contro l 2

PCL + st arch Mat er-b i BioBag

Polys tyrene tes t t ubes

Black Polyethylene garbage bag

PVC show er cur t a in

100g p last ic in 5 L seaw at er fo r 10 days a t 4-8 C

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0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

Bio

deg

rad

able

Ph

otod

eg

rad

able

Co

ntr

ol1

Co

ntr

ol2

B

iosac

k

Polys

tyrene

Po

lyeth

yle

ne

Sp

ecificActivity(pmo

l/mg/min)

EROD in cod larvae exposed to various plastics

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Conclus ions

Convent iona l p las t ic s are a ser iousenvi ronm enta l c oncern and greenp last ic s o ffe ra good al t e rna t ive for m any app l ic a t ions.

Greenplast ic s are a rapid ly evo lving indust ry Wide range o f product s be ing m ark et ed asgreen. Need to eva luat e based on m ore than t hec om pany s p rom ot ional m at er ial .

There is st rong d isagreem ent on w hetherc onvent iona l p last ic s can ever c om plet e lyb iodegrade, even in t he presenc e ofp rodegradan t add it i ves.

More researc h is needed on a l l p last ic s ,par t i c u lar l y in relat ion t o t hei r t ox ic i t y and fat ein the env ironm ent .

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Som e usefu l Referenc es:

The Impac t s o f degradab le p las t i c bags in

Aust ra l ia (2003) Fina l repor t t o Depar tm ent o fEnv ironment and Her i tage , Ex c e lPlas Aus t ra l ia

Env i ronment Aust ra l ia , B iodegradab le Plas t ic s

Deve lopment and Env i ronment a l Impac t s (2002)Exc e lPlas Aus t ral ia

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Laura Park