"Experience of technology transfer" - INNET" "Networking development project for SMEs: Ecoplastos - Inter-cluster initiative to ...
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“Networking development
project for SMEs: Ecoplastos
INNET”
Francesco Ciardelli,
Macromolecular Science Group
coordinator - University
of Pisa - Department of Chemistry and
Industrial Chemistry (Italy)
“Experience of technology
transfer”
Ideal mechanism for radical functionalization of polyolefins
Generally a PEROXIDE (ROOR)
Polyolefin (PO)
RO
+ RH
M
M
RO = primary radicals
M = functional monomer
A monomer able to graft, generally an unsaturated
polar monomer (i.e., maleic anhydride and its
derivatives)
NOT compatibilized b Compatibilized
Thin interface Large interface
High interfacial tension Low interfacial tension
High diameter of dispersed phase Low diameter of dispersed phase
fPO
f* f f*
Ny Ny
Dipartimento di Chimica e Chimica Industriale
Università di Pisa
Responsabile scientifico: Prof. Mauro Aglietto
Una azione per essere sostenibile deve interessare le
tre dimensioni
By Wikipedia
5
RETENUMA-2 –
PONTEDERA, 26 settembre 2008
Then:
Upgrading the Processability and
Properties of Postconsumer PET
by Reactive Blending with
Functionalized Polyolefins
appeared possible
CATALYSED TRANSESTERIFICATION IN ESTER MODIFIED POLY(ETHYLENE)/ PET BLENDS
Functionalized polyethylene
... ...
O O
OR O CO O H
+ HO CO O H + ROH
OR OR
... O ... O
PE-g-DAS PET Cat.
POgDAS
O
OR Dialkyl maleates are easily grafted on polyethylene and are
sustainable for environment
OR
O
Ti and Zn derivatives
were chosen by considering both transesterification efficiency (as reported
in literature works) and environmental impact
*Efficiency = number of grafted DEM units/moles of DCP
16
EPR + DEM
14
12
SEBS + MAH
LLDPE + DEM
10
Efficiency
8
6 SEBS + DEM
4
PP + DEM
2
5 10 15 20 25 30 35
Monomer/DCP mol/mol
Reactive blending approach
Mixing chamber
Ester functionalized
polyethylene/PET blends were
prepared by melt blending into a
mixer (torque measurements) at
250°C for 10 minutes
rotors
Selective extractions Melt polymer
Determination of the grafting yield by weighting or by an infrared method
grafted PET weight
PET grafting yield = ⋅ 100
PET weight in the feed
Viscosimetric measurements molecular weight of PET
Grafting points number
(moles/µg)
As a SPIN OFF company of the University of Pisa with a strong industrial partnership, SPIN-PET produces innovation in materials based on synthetic and bio-based polymers. With a focus on post-industrial and post-consumer recycled plastics sources, as well as renewable feedstocks, the core activities are aimed at the development of sustainable processes and technical materials, with customized structural and functional properties for different applications. Innovation is targeted at supporting industrial partners and customers in product and process development as well as technology transfer.
COLLABORATIONS Dipartimento di Chimica e Chimica Industriale dell’Università di Pisa (DCCI) CNR-INFM-PolyLab- Laboratorio regionale per le Applicazioni Industriali dei Polimeri Scuola Superiore di Studi e Perfezionamento Sant’Anna (SSSA) di Pisa Dipartimento di Meccanica e Tecnologie Industriali dell’Università di Firenze (DMTI)
COLLABORATIONS
Barcellona, Spagna
Oyonnax, Francia
« Pôle Plasturgie Rhône-Alpes et Franche-Comté »
Rivalta Scrivia - (Tortona - AL)- Italia
Polo di innovazione per i materiali plasticiAUSERPOLIMERI- Pian Di Coreglia (LU) – produzione di compatibilizzanti e antiurtizzanti. STEP snc - Roccastrada (GR): stampaggio componentistica in PC e ABS. EVERY HELMETS srl - Grosseto: realizzazione di caschi per sci, bicicletta, roccia. VEMAR HELMETS srl - Grosseto: realizzazione di caschi per moto. ADACTA srl - Sesto Fiorentino (FI): gestione dati (information & communication technology, ICT) e progettazione e realizzazione di software. FAP srl - Firenze: stampaggio. MPT srl - Calcinaia (PI): costruzione di stampi. TOSCOPLAST srl - Calcinaia (PI): stampaggio componentistica in PP HAPPYPLAST srl - Bientina (PI): stampaggio ad iniezione
Contacts
Web site: http://www.dcci.unipi.it/spinpet/
President: Prof. Francesco Ciardelli
E-mail: fciard@dcci.unipi.it
Tel. +390502219229UNIPI professors (3)
young researchers (3)
freelance entrepreneurs (3)
AUSERPOLIMERI company
20% of the company belongs to University of PisaTHE ACTIVITY
Opportunities for innovation and strategies for developing technical materials with
added value are pursued based on preliminary investigations on the physical and
chemical features of post-consumer or renewable plastics as the main feedstock
1. Physical and chemical analysis of materials
Thermal analysis (DSC and TGA)
Infrared laboratory2. Lab-scale Polymer Processing and Optimizaton
Compression
molding
Laboratory mixers
Injection
Melt flow rate molding3. Evaluation of properties and targeting application
Tensile Impact
12
110
Increase of elongation (% )
elongation at break (% )
10
90
8
70
6
50
4 30
2 10
0
POFPET ZnAc2 ZnO Ti(OBu)4 TiOAc2
-10 Flame
resistance4. Analysis of costs
5. Tailoring of formulations and processing
MAIN
HOPPER
NORMALLY
VENTED
185 200 200 200 200 200 200 200 200 180PE / SEBS-g-DEM / PET ternary system
SEBS-g-DEM was used in place of PE-g-DEM to
minimize the interfacial tension in the immiscible
system and tailor in the ternary system the phase
morphology reported in the picture.
The control of phase morphology developed during the blending allowed to reach
a good yield in copolymer formation by avoiding the cross-linking of
compatibilizer.
PE/PE-g-DEM/PET PE/SEBS-g-DEM/PET
40/40/20 10 mm 40/40/20
+ Ti(OBu)4 + Ti(OBu)4In the Ti(OBu)4 catalysed system the use of SEBS-g-DEM resulted effective for
avoiding the crosslinking side reaction
A suitable phase distribution was obtained and effective formation of SEBS-g-PET
copolymer was revealed
Coltelli et al., Polym. Degr. Stab., 90, 211-223 (2005)Application of compatibilization:toughened blends
PET/PO
blend
d T d The general condition for toughening is that the
inter-particle distance must be smaller than the
critical interpartical distance (Tc).
S. Wu, Pol. Eng. and Sci., 30, 753 (1990)
Use of PET for high impact properties blends CH3
( CH2 CH2 ) (CCH 2 )y O
In PET/ ethylene-propylene rubber (EPM) blends, x
by using a compatibilizer (ethylene-glycidyl COO
methacrylate copolymer [E-GMA]) Tc is E-GMA
established experimentally at 0.1 µm W. Loyens , Polymer, 44, 4929 (2002)Our approach:
Toughened materials from post-consumer LDPE/ post-consumer PET blends by
adding a reactive rubber as compatibilizer precursor.
...
... ...
... HO PET COOH
O O
O O
O O OH
PET COOH
The reaction
ULDPE modified between
by grafting maleic
different anhydride
percentage of modified polyethylene
maleic anhydride
and PET was evidenced by preparing binary blends in a laboratory
mixer and by characterizing them by selective extractions and
FT-IR analysis.
In PET matrix blends more than 30% of fed PET resulted to be
grafted on the functionalized polyolefinPreparation of modified ULDPE
O Modified PE having different content of maleic
O O
anhydride were prepared in a twin screw extruder
..... (Auserpolimeri).
.....
FD A commercial
MAH % by
functionalized weight compatibilizer was used for
PE
comparison O
O O O O
Me
POF0,3 0.3 CH C H2 C H2 C H2 C C H2
FD x y C H3 z
POF0,6 0.6
Lotader
POFD1 1
POFD1,5 1.5Preparation of blends
20
70
10
O
O O
.....
.....
Modified
PET flakes ULDPE LDPE pellets
Twin screw extruder
Blends in pellets
Injection moulded specimensPhase morphology characterization
PET-LDPE The blends contain 10% by weight
of modified ULDPE or Lotader
70 / 30
ref PET-LD-POF0,3
70/20/10
PET-LD-Lotader
FD=0.3
PET- LD-POF1
70/20/10
Lot
FD
FD=1
compatibility PET- LD-POF1.5
70/20/10
FD=1.
5The values of dispersed phase diameter were used to calculate the
interpartical distance by the following equation:
T
d = 1/3
π
−1
6φr
Wu, S., J. Pol. Sci.: Pol. Phis. Edn. 21, 699 (1983)
blends LDPE [% POF ( MAH d (µm) T(µm)
20
1,0
18
by weight] content in POF)
16 [% by weight]
diameter (µm)
0,8
14
ref
12
30 - 12 ± 6 1.0
0,6
10
T (µm)
Dispersed phase
3.8 ± 2.7
8
FD=0.3
0,4 20 10 (0.3) 0.33
6
4
0,2
FD=1
2
20 10 (1.0) 0.9 ± 0.5 0.08
0
0,0
-2
< 0.1
-0,2
FD=1.5
-0,2 0,0
0,0 0,2
0,2 0,4
20
0,4
FD of
FD
0,6
0,6
of m
0,8
0,8
modified
1,0
1,0
ULDPE
odified ULDPE
10
1,2
(1.5)
1,4 1,6
0.7 ± 0.4 0.06
For the last two blends T30/70 recycled LDPE / recycled PET blends
Izod Impact Strength (J/m)
160 TBlends of post-consumer PET and
modified ULDE were prepared. The Injection moulding
90/10 blend showed was used in
injection moulding tests.
Some parts of household appliances
were prepared to study the effects of
injection moulding parameters on the
final properties of pieces
CABLE COVER6. Collaborations, partnerships and consultancy for the design, the development and the production of single parts and prototypes 7. Design and Modeling
t-- con sum er plastics
Pos t
ing
from packag
A VALUABLE MATERIAL:
toughened thermoplastics based on post-consumer PET
Main features :
- Polymeric materials for structural applications in automotive,
household appliances, home automation, sport accessories, etc.
- Price in the range between virgin ABS and reinforced (filled) PP
- Different grades suitable for processing by injection molding, extrusion
and thermoformingInjection-Molding Grades
PET-based compound developed by SPIN-PET : properties
(reinforced 90/5/5 blend with 10% talc)
Compound PET
Unità di misura Modalità di prova
properties 10% talco
Melt flow index (MFI)
g/10 min. 18 ISO 1133
@260°, 2,16 kg
Maximum tensile
N/mm2 41 UNI EN ISO 527
stress
Strain at break % 15 UNI EN ISO 527
Tensile Modulus
N/mm2 2050 UNI EN ISO 527
(23°C)
Flexural Modulus
N/mm2 2100 UNI EN ISO 178
(23°C)
IZOD impact
J/m 77 ASTM D256
toughness (23°C)
Heat deflection
temperature (HDT) °C 71 UNI EN ISO 75
1,8 MPaInjection-Molding Grades
Vacuum cleaner – protopype of
injection molded body parts
ing. Cosimo Bruni Elaborazione grafica: ing. Giovan Gualberto PineiderInjection-Molding Grades
PLASTIMARK® shopping cart
Injection molded structure
Material: glass fiber reinforced PA (Nylon)
elaborato a cura di MPT-Plastica s.r.lInjection-Molding Grades Scuola Superiore Sant’Anna “Dustbot” – prototypes of urban hygiene & floor cleaning robots Within the RIGEPLAST Project, co- funded by Tuscany Region, injection molded body parts will be designed and produced using the plastic material developed by SPIN-PET
Sheet Extrusion and Thermoforming Grades
Main features of the r-PET based sheet-extrusion grade compound
developed by SPIN-PET (PET 80/15/5)
Property Performance Reference materials & performances
Toughness ++ Notched IZOD ≥ 100 J/m (compares with PP)
Elastic Modulus + ~ 1200 MPa (compares with PP)
Elongation ++ ~ 12% (compares with PP)
Fluidity
+++ MFR = 10 (suitable for sheet extrusion)
(MFR @ 260°C, 2.16 Kg)
HDT (Heat Deflection Temp.) Comparable with PET-G (60°C) and
+/-
@ 1,8 MPa Lower than in PP
Exposure to organics (HC fuel) under different
Chemical Resistance ++ enironmental conditions (T, R.H., etc.) does NOT
affect significantly the structural propertiesSheet Extrusion and Thermoforming Grades Profiles for automotive applications, road signalling, …. Excellent impact resistance of the r-PET SE-grade. • Market opportunities as replacement of road signals made of PVC and PP. • Processing & recycling of the r-PET compound poses less challenges than PVC. •poor impact resistance of PP at T
t-- con sum er plastics
Pos t
ing
from packag
PET based films/sheets from a post-industrial stream
Extrusion
PET based
compounds Injection molding
suitable for
Thermoformingost-
t- co n su m er end life
P
ic le s (EL V) plastics
veh
Injection moldable reinforced PP compound based on
r-PP from bumpers
Stabilizers and fillers
Grinded polypropylene from Injection mouldable material with
bumpers properties similar to virgin PP filled with
barium sulfate
Injection moulding of parts of
vehicles or household applianceser W EE E p lastics
t-consum
Post-
Injection moldable PC/WEEE blends
separation fine grinding
and
grinding
analysis
Three main plastic components present in the WEEE plastics.
Two different perspectives have been investigated
• increasing the ductility through addition of compatibilizers
• blending with polycarbonate to match grade requirements for injection moldingTwo flame retardant phosphorous based masterbatches (PEP and PAP) were
then investigated. They resulted in:
test (s) Ttot(s)c Autoextinction
FR wt% class (UL-94)
vertical tests
IPA3 3% ∞ 139.5 HB
IPA20 20% 4.8 14.8 V0
PEP5 2.5% 14.9 24.9 V1
PAP6 2.5% 9.1 9.1 V0
PEP2.5 1.25% 120.2 130.2 HB
PAP3 1.25% 10 20 V1
2200
120
2000
Young Modulus (MPa)
100 1800
Strain at break (%) 1600
80 1400
..and the tensile 1200
60
properties were not 1000
800
worsened…. 40
600
20 400
200
0 0
IPA10 IPA20 PEP5 PEP2.5 PAP6 PAP3stics
bio-based pla
Renewable plastic based materials
PLA pellets
Applications in packaging,
household appliances,
domotics, sports, fashion and composites and blends suitable
agricultural sector for thermoforming, film extrusion
and injection mouldingMelt-processing PBS films
PBS + BBS
200°C milling
50 rpm
10 min
Brabender-type mixer
200°C
melt-process
5 min
Slow cooling to rt
(~5°C/min)
80-100 µm
0.02-0.5 wt.%
Rapid quenching
at 0°CExcimers as probes for film deformation Polypropylene Films
50%
700%
λexc. = 277 nm
PP/BBS-0.5
PP/BBS-0.5: uniaxially drawn at
different strain λexc = 366 nm
Suppression of the excimer band
Emission from green to blue: from excimer to “monomer” fluorescenceStilbene derivative/polypropylene: Fluorescence
Emission sensitive to drawing Taken under irradiation of a long-
range source (366 nm)
Stilbene derivative as stress-strain sensors for PP matrix: potential
application for intelligent and smart polymer object in packaging materialsBBS as thermal sensors in PBS PBSBBS-0.05 q. film: 65 °C
Poly(lactic acid)/poly(butylene succinate) blends as smart biodegradable and responsive
materials for packaging applications
Emission spectra of PLA/PBS blend Emission spectra of PLA/PBS blend
for rigid packaging: effect of thermal stress for flexible packaging: effect of mechanical stress
Pucci A., Di Cuia F., Signori F., Ruggeri G., Journal of Materials Chemistry 17, 783–790 (2007)
Ciardelli F., Pucci A., Signori F., Ruggeri G., Bronco S. Italian Patent 2009, TO2009A000044.Possible European Project on :
new polymer recycled-PET based blends
and composite materials
Thermoformable extruded sheet,
Recycling industries,
Manufactured polymer materials value chain
Low Flammability
TraceabilityYou can also read
