3

Overview on MechanicaI
RecycIing by Chain Extension
of POSTC-PET BottIes
*
Doina Dinonie
1
, Radu Socoleanu
2
, Sinona Iop
1
, Iiina Iieiascu
1
,
Radu Iieiascu
1
, CeIina Ieliea
3
, CalaIin Zahaiia
3
and Maiius Ieliache
1

1. Introduction
The posl consunei poIy(elhyIene lheiephlaIale) lollIes (IOSTC-ILT) can le iecycIed ly
chenicaI oi / and nechanicaI piocesses. The IOSTC-ILT chenicaI iecycIing is vide-
spiead in Luiope and is lased on depoIycondensalion of secondaiy poIyneis and usage
of lhe iesuIled pioducls foi lhe puiposes of lhe filie and unvoven naleiiaI indusliy. The
IOST - IC nechanicaI iecycIing iequiies a phase liansfoinalion (neIling) and can le
allained vilhoul oi vilh poIynei up-giadalion (Mancini, 1999, AkovaIi, 1988, eIIelli,
1997, Lhiig, 1992, Liena, 2OO2, Iiias, 2OO5, Sandio & Maii, 1999, Scheiis, 1998, Ava|a,
2OO5).
The veII-knovn voiIdvide IOSTC-ILT nechanicaI and chenicaI iecycIing vays aie:
1. 5HVRUSWLRQ EDFN LQWR WKH ERWWOHV PDQXIDFWXUH Aflei gelling fIakes, IOSTC-ILT is
nechanicaIIy and /oi chenicaIIy iecycIed inlo lollIes foi non-food pioducls (soap,
cosnelics, and cIeaning agenls). In 2OO4, aiound 5O of lhe ILT iecycIed in lhis vay
vas piocessed,
2. 5HXVH LQ WKH ILEUH DQG XQZRYHQ PDWHULDOV LQGXVWU\ foi ollaining insuIalion
nenlianes foi ioofs, shoe soIes, fiIleis, coveis foi cai innei conpailnenls. This
diieclion is lhe nosl popuIai in Luiope (Monika, 2OO7, Moiaviec, 2OO2),
3. 3URFHVVLQJ LQWR WKLQ VKHHWV IRU WKHUPRIRUPLQJ iefei onIy lo lhe fIakes iesuIled fion
IOSTC-ILT seIeclive coIIecled ly coIoui. Il is appiecialed lhal lhe sheels ollained fion
such naleiiaI can undeigo a high degiee of slielching duiing lheinofoining in oidei
lo shape packaging cases such as lianspoil liays foi lonaloes, eggs and sliavleiiies
elc.,
4. 8SJUDGDWLRQ E\ PHOW SURFHVVLQJ FRPSRXQGLQJ AIlhough ILT has exceIIenl usage
piopeilies, lecause of ceilain chaiacleiislics such as Iov gIass liansilion, Iov
ciyslaIIizalion speed (foi ceilain lypes) and Iov inpacl iesislance, in oidei lo le

1
Rcscarcn

and Dctc|cpncn| na|icna| |ns|i|u|c fcr Cncnis|rq and Pc|rccncnis|rq -|C|CH|M, Sp|.|ndcpcndcn|ci,
scc|cr 6, 8ucnarcs|, Rcnania
2
|C Murgu|cscu |ns|i|u|c, Sp|.|ndcpcndcn|ci, scc|cr 6, 8ucnarcs|, Rcnania
3
Pc|i|cnnicaUnitcrsi|q, C|ca Vic|crici, 8ucnarcs|, Rcnania

Material Recycling Trends and Perspectives

86
nechanicaIIy iecycIed inlo peifoining pioducls, il is conpounded al neIl piocessing.
Hovevei lhe iesuIls aie nol speclacuIai.
5. &KHPLFDO UHF\FOLQJ is ieIaled lo lhe iecoveiy of lhe chenicaI conpounds lased on
foIIoving depoIycondensalion pailicuIai ieaclions gIycoIysis, nelhanoIysis, hydioIysis,
acidoIysis, anynoIysis,elc. (Caila, 2OO1, Kaiayannidis, 2OO3, Minoiu, 2OO3,),
In spile of Iong Iasling effoils, lecause of lhe Iov cosl and Iov peifoinance appIicalions of
lhe iecycIed naleiiaI, al piesenl, lhe videIy accepled opinion is lhal lhe IOSTC-ILT
nechanicaI iecycIing vilhoul a sliucluiaI up - giadalion is nol an efficienl pioceduie.
The chaplei piesenls an oveiviev on lhe sliucluiaI up-giading of IOSTC-ILT ly
nacionoIecuIai chain exlension duiing nechanicaI iecycIing (ieaclive piocessing), a
pioceduie consideied efficienl foi lhe enhancenenl of ils piopeilies.
2. Parameters controIIing the POSTC - PET mechanicaI recycIing
The nain paianeleis conlioIIing lhe IOSTC-ILT nechanicaI iecycIing aie: lhe
conlaninalion IeveI and lhe degiadalion degiee.
2.1 POSTC - PET contamination
IOSTC-ILT conlaninalion can le of lhe foIIoving lhiee lypes: nacrcsccpic and nicrcsccpic
pnqsica| ccn|anina|icn and cncnica| ccn|anina|icn.
Macrcsccpic pnqsica| ccn|anina|icn of IOSTC-ILT is easy lo cIeai off as il consisls of dusl,
gIass chops, slones, adhesives, pioducl iesidues, pIaslics such as IVC and IL, eailh
inpiegnalion due lo inpiopeiIy sloiage.
Micrcsccpic pnqsica| ccn|anina|icn is noie difficuIl lo cIeai off especiaIIy lecause is pailiaIIy
allached lo lhe lollIe lecause il is aloul adhesive oi olhei inpiegnaled inpuiilies iesuIled
aflei aliasion oi inpacl. These inpuiilies lieak lhe lhiead eilhei duiing gianuIalion in lhe
neIl piocessing oi duiing lhe spinning in lhe filie indusliy. This Ieads lo deciease lhe
quaIily and pioduclivily of lhe iecycIing.
Cncnica| ccn|anina|icn is lhe iesuIl of adscrp|icn of fIavouiing, oiI, peslicides, househoId
chenicaIs, and fueI if lhe lollIes veie ie-fiIIed vilh such pioducls in a secondaiy uliIizalion.
The piopoilion of IOSTC-ILT inleiaclion vilh lhese conpounds depends on lhe diffusion
lehavioui of conlaninanls and lhe soiplion piopeilies of lhe poIynei. The ienoving of
lhese conlaninanls inpIies undcrgcing |nc rctcrsc prcccsscs, nanc|q dcscrp|icn. The adsoiled
chenicaI inpuiilies inlo lhe poIynei sc|||c cn |nc ris| pc|cn|ia| cf IOSTC-ILT nechanicaIIy
iecycIed especiaIIy if lhe food packages aie laigeled. The iecycIing ly desoiplion can nol le
consideied lecause of ils veiy Iov pioduclivily, lhis piocess leing an exlieneIy sIov one.
Ioi dininishing as nuch as possilIe lhe inpuiily conlenl, lhe IOSTC-ILT neIls aie fiIleied
duiing lhe nechanicaI iecycIing al exliusion, lefoie passing lhioulh lhe nozzIe, using
pailicuIai fiIleis (Yang Tang & Menachen, 2OO8).
IOSTC - ILT iequesls a seveie conlioI of lhe conlaninalion IeveI especiaIIy if il is iecycIed
inlo food packaging. CuiienlIy, lhe inpuiily conlenl Iinils aie eslalIished and geneiaIIy
accepled foi IOSTC-ILT iecycIing as food and non-food packaging (LCIMIC, 1999, Iianz,
Overview on Mechanical Recycling
by Chain Extension of POSTC-PET Bottles

87
2OO4). The foIIoving Iinils of lhe IOSTC-ILT inpuiily iesiduaI conlenl have leen accepled
foi iecycIing as food packaging: 2O ppn oi Iess nelaI, 1O ppn oi Iess papei and 3O ppn oi
Iess poIyoIefins (Di Loienlzo el aI., 2OO2, Hong }uZhou el aI., 2OO7, Hong }un Zhou el aI.,
2OO7 ). The fianing inlo lhese Iinils depends on lhe lechnicaIily of lhe appIied condilioning
soIulion (soiling - vashing elc), and ly lhe IegisIalive effoil necessaiy foi: lhe incieasing of
lhe popuIalion coopeialion, lhe selling up of lhe infiasliucluie lo anaIyze lhe inpuiily
conlenl dovn lo lhe pails pei niIIion (ppn) IeveI, lhe inspeclion on lhe Iav olseivance
(Knil, 2OO2, David, 2OO1, Novis, 2OO3, ).
2.2 PET degradabiIity
Duiing IOSTC-ILT condilioning and neIl piocessing, lhe poIynei is degiaded ly
nechanicaI and lheinaI agenls lhal acl in lhe piesence of valei and oxygen. If duiing lhe
fiisl Iife lhe IOSTC-ILT is exposed lo UV iadialions ialhei lhan lo lheino-nechanicaI and
hydioIylic degiadalion, lhe pholo-oxidalion nusl le consideied loo (Cioffi el aI., 2OO2, Chen
el aI., 2OO2, Raki el aI., 2OO4).
The degiadalion occuis al lhe veakesl lheinodynanic Iinks naneIy al lhe eslei lhose
lelveen lhe leiephlhaIic acid and dielhyIene gIycoI of IOSTC-ILT nacionoIecuIes (Sandi
el aI., 2OO5, VasiIiu el aI., 2OO2). In figs. 1 - 5, lhe nain ieaclions lhal chaiacleiize lhe ILT
lheino-hydioIilic degiadalion aie exposed.
y lheinaI-oxidalive degiadalion (fig.1, - Ava|a & IaveI, 2OO5 ), lhe nacionoIecuIai chains
lieak iesuIling in lhe foinalion of voIaliIe pioducls (i.e. acelaIdehyde - fig. 5 AIexandiu &
osica, 1966 ) , 1.8 - 3 cycIic and Iineai oIigoneis (fig.4 - Ava|a & IaveI, 2OO5) and shoilei
chains vilh acid cailoxyIic and vinyI eslei end gioups. In hydioIylic degiadalion (fig.2 -
(Ava|a & IaveI, 2OO5), lhe nechanisn is siniIai, vilh lhe diffeience lhal lhe end gioups of
lhe shoil nacionoIecuIes iesuIled fion degiadalion aie cailoxyIic acid and hydioxyI eslei.




Iig. 1. ILT lheinaI degiadalion nechanisn vilh lhe foinalion of cailoxyI acid and vinyI
eslei end gioup (Ava|a & IaveI, 2OO5).

Material Recycling Trends and Perspectives

88






Iig. 2. ILT HydioIysis nechanisn iesuIling in cailoxyI acid and hydioxyI eslei end gioup
appeaiance (Ava|a & IaveI, 2OO5).






Iig. 3. The dependence of lhe cailoxyI end gioup ly lhe nunlei of iepiocessing of IOSTC-
ILT (Spinace & De IaoIi, 2OO1).
Overview on Mechanical Recycling
by Chain Extension of POSTC-PET Bottles

89













Iig. 4. CycIic and Iineai oIigoneiic conpounds iesuIled fion ILT degiadalion (Ava|a &
IaveI, 2OO5).

Material Recycling Trends and Perspectives

90



&2 2 &+

&+

2 &2
&2 2
&+ &+

+22&
&2 2
&+
&+

2 2&
&2 2 2& &+

&+2

+2 &+

&+

2+
&2 2 &+

&+

2+ +22&



Iig. 5. The acelaIdehyde foinalion duiing ILT lheinaI degiadalion (AIexandiu & osica,
1966).
The incieasing of lhe cailoxyIic end gioup vilh lhe nunlei of lhe iepiocessing of lhe
IOSTC-ILT is piesenled in fig. 3 (Spinace & De IaoIi, 2OO1, SiIva Spinace, 2OO1). The end
gioups conlenl puls on viev lhe IOSTC-ILT degiadalion degiee, lhe cailoxyI end gioups
leing coiieIaled vilh lhe lheinaI and hydioIylic degiadalion and lhe hydioxyIic end
gioups vilh hydioIylic ones.
Overview on Mechanical Recycling
by Chain Extension of POSTC-PET Bottles

91
The iesuIl of lhe degiadalion ieaclions is a seveie diop in lhe noIecuIai veighl vhich Ieads
lo lhe faiIing of inliinsic viscosily, neIl slienglh and neIl piocessaliIily and finaIIy, lo pooi
usage piopeilies and a Iov quaIily of lhe pioducls ollained fion iepiocessed poIyneis.
ecause of lhe seveie noIecuIai veighl dininishing duiing IOSTC-ILT iepiocessing, lhe
inliinsic viscosily nay deciease fion O.72 dI g-1, lhe viigin poIynei specific vaIue, dovn lo
O,O4 - O,26 dI g-1 (Raki el aI., 2OO4, Zong Zhang el aI., 2OO4,Seo el aI., 2OO6, Culeies el aI.,
2OOO).
ecause of lhe foinalion of shoilei nacionoIecuIes as a iesuIl of lhe hydio -lheinaI
degiadalion, lhe ciyslaIIizalion capacily of lhe IOSTC-ILT incieases and ils degiadaliIily
lecones noie pionounced. This piocess knovn as cheni-ciyslaIizalion is a conpIex one
lecause al lhe leginning il is a chenicaI one (dininishing lhe nacionoIecuIes Ienglh due lo
degiadalion) and in lhe end il is a physicaI phenonenon (ciyslaIIizalion of lhe shoilei
nacionoIecuIai chains) (IiaIay, 2OO2,). As a iesuIl of an incieased ciyslaIIinily, lhe gIass
liansilion (Tg), neIling lenpeialuie (Tn), neIling heal and densily of lhe IOSTC-ILT aie
giealei. AIso lecause of lhe dependence of lhe ciyslaIIinily on lhe degiadalion degiee, lhe
coIoui of IOSTC-ILT can diffei fion lianspaienl (un-degiaded oi pooiIy degiaded), lo
liansIucenl (snaII degiaded) and opaque (gieal degiaded).
The sliong degiading lendency duiing lhe neIl piocessing is specific foi aII
poIycondensalion poIyneis, nol onIy foi ILT, and is olseived in case of piinaiy poIynei
neIl piocessing loo. The highei lhe noIecuIai veighl of lhe piinaiy poIynei lhe giealei lhe
neIl piocessing degiadalion.
The sliucluiaI changes iesuIled fion degiadalion can le so dianalic lhal lhe neIl
piocessing of IOSTC-ILT nay lecone nol vialIe. Il is lheiefoie easy lo undeisland vhy lhe
nechanicaIIy iecycIing of IOSTC-ILT can considei onIy appIicalions vhich do nol iequiie
high peifoinance piopeilies.
3. The chain extension up-gradation of POSTC-PET
Consideiing lhe geneiaI opinion accoiding lo vhich IOSTC-ILC can le nechanicaIIy
iecycIed onIy inlo Iov-piopeily goods, il lecones cIeai lhe inleiesl lo find nev econonic
soIulions foi lhe iepiocessing of lhese naleiiaIs inlo pioducls vilh piaclicaI inpoilance. In
lhe Iasl 2O yeais lhe ieseaicheis have leen conceined in lhe up-giadalion of IOSTC-ILT ly
incieasing lhe nacionoIecuIai veighl lased on chain exlension ieaclions (CavaIcanli el.aI.,
2OO7, Ava|a & IaveI, 2OO5, ViIIaIolos el.aI, 2OO2, Kaiaianidis, 1993).
The efficiency of lhese ieaclions is conlioIIed ly nany faclois. Theii piesenlalion legins
vilh enphasis lhe inpoilance lo eIininale hunidily ly diying lefoie neIl piocessing and
lo slaliIize lhe IOSTC-ILT al neIl piocessing.
3.1 Drying /degassing
efoie lhe chain exlension, lhe IOSTC-ILT is diied lo ienove lhe hunidily. Il vas
olseived lhal diying lefoie chain exlension and degassing and /oi opeialion undei
vacuun duiing chain exlension aie alIe lo deciease lhe degiadalion of IOSTC-ILT duiing