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1. POST-MODIFICATION
AND REACTIVE BLENDING OF POLYMERS FOR
THE PREPARATION OF MULTIPHASE, NANOSTRUCTURED AND FUNCTIONAL
MACROMOLECULAR SYSTEMS (E. Passaglia)
Graduate
Research Staff:
Elisa Passaglia, Researcher ICCOM-CNR, UOS Pisa
Francesco Ciardelli,
Full Professor
DCCI, University of Pisa
Serena Coiai, Associate Researcher ICCOM-CNR, UOS Pisa
Francesca Cicogna, Associate Researcher ICCOM-CNR, UOS Pisa
Simona Bronco, Researcher IPCF-CNR,
Pisa
Monica Bertoldo, Researcher IPCF-CNR,
Pisa
Luca Lotti, PhD Student, SNS Pisa
Lucìa Perez, Associate Researcher DCCI, University of Pisa
Stefania Savi,
Technical Personnel
DCCI, University of Pisa
Supported by:
SpecialChem, ATOFINA,
Total, Faraplan, Dow, Crosspolimeri, AuserPolimeri, CAB, Randgate
Companies, and NANOHYBRID STREP PROJECT N°. 516972, MIUR NANOPACK FIRB
2003 D.D.2186 Prot. N. RBNE03R78E and PRIN 2008 PROT. N.. 200898KCKY
Collaborations:
Dipartimento di Fisica dell’Università di Pisa: Prof
Rolla, Dr. Lucchesi, Dr.ssa Andreozzi, Prof. Giordano;
CNR-ICCOM Firenze: Dr. Oberhauser, Dr. Giambastiani;
Dipartimento di Chimica dell’Università di Firenze: Dr. Frediani;
CNR-ISMAC Milano e Genova: Dr.ssa Stagnaro, Dr.ssa Conzatti; IPCF-CNR,
Area di Ricerca, Pisa, Dr. Prevosto: Dr. Tombari, Dr. Pinzino;
Dipartimento di Ingegneria dell’Università di Brescia: Prof. Penco;
Dipartimento di Ingegneria dell’Università di Pisa: Prof. Lazzeri; CEMIN
– Centro di eccellenza Materiali Innovativi Nanostrutturati,
Dipartimento di Chimica, Università di Perugina: Prof. Umbero
Costantino, Dr. Michele Sisani; Dipartimento di Ingegneria Chimica dei
processi e dei Materiali Università di Palermo: Prof. Scaffaro;
Department of Chemical Engineering (Product Technology)of University of
Groningen The Netherlands: Prof Picchioni;
Facultad de Ciencias Quìmica Universidad de
Concepciòn, Chile: Prof Rivas;
Processing and Polymer
Nanomaterials Research Unit, The Petroleum and Petrochemical College,
University of Bangkok: Dr. ssa Muksing,
Prof. ssa Magaraphan;
Instituto de Investigaciones Químicas Universidad de Sevilla-CSIC: Dr.
Juan Cámpora;
Dipartimento di Ingegneria Aerospaziale, Politecnico di Milano: Prof. Di
Landro.; Centro Italiano Packaging (CIP): Dr. Andreotti, Dr.ssa Salmini;
Advanced Catalysis, spin-off Università di Pisa: Dr. Evangelisti, Dr.
Vitulli; SASOL Company Germany GMBH: Dr. Torno; Dow Company: Dr. Bettè,
Dr. Batistini; Atofina Company: Dr. Pradel, Dr. Flat; Auserpolimeri
Company: Ing Bravo.
1.1.
Modification of polyolefins
The radical reactions/reagents are employed as tools to introduce specific
functionalities by controlling macromolecular structure/architecture.
The saturated polyolefin (HDPE, LLDPE, ULDPE, VLDPE,
EPR, EPDM, iPP, PS, SEBS) free radical functionalization is carried out
by promoting the grafting of useful functionalities while suppressing or
lowering the undesidered reactions that generally affect the not
selective radical processes. This purpose is reached through both 1) the
modulation of the feed conditions and 2) the use of designed coagents/radical
species acting as radical trappers and able to control the radicals
reactivity.
In the first case
functionalizing monomers bearing anhydride, acid and esters
functionalities (maleic and itaconic anhydride derivatives) are used in
mixtures to take advantage of the synergic effects of solubility and
diffusion properties in the polymer.. In the latter approach completely
different chemicals
like as derivatives of 3-(2 -furyl) acrylic acid and 3-(2-thienyl)
acrylic acid derivatives have been used alone and in mixture with
conventional reagents.
These reagents
are able to react with
macroradicals in a stoichiometric ratio suppressing radical transfer
mechanisms and thus proving a control and modulation of FD and
macromolecular structure. With the same purpose
funtionalizaed nitroxyl derivatives are also used as macromomolecular
coupling agent for grafting specific functionality in a stoichiometric
ratio. Recently not conventional study of post-modification processes
has been approached by nanostructured
Cobalt nanoparticles dispersed in a stabilized
solution of maleic esters and / or styrene.
The unsaturated polyolefin
(PB, SBR, SBS) free radical functionalization is carried out with thiol
derivatives bearing different functionalities; in particular cysteine
derivatives (and thus natural thiols) are used to produce random or
block copolymers as a function of starting polymer structure, modulation
of feed ratios and specific reactivity of the amino acid derivatives.
Besides, the application of the functionalization
methodology to polar polymer like as polyamide 6 is also employed to
produce highly branched polyamide macromolecules characterized by short
(side chain functional groups) and long (polyamide chains) branching.
References:
1) S. Coiai, S. Augier, C. Pinzino, E. Passaglia, “Control of
degradation of Polypropylene during the radical functionalization with
furan and thiophene derivatives” Polym. Degrad. Stab., 95:
298-305 (2010)
2) E. Passaglia, S. Coiai,
S. Augier “Control of macromolecular architecture during the reactive
functionalization in the melt of olefin polymers” Prog. Polym. Sci.
(Review) 34: 911-947 (2009)
L. Lotti, S. Coiai, F. Ciardelli, M. Galimberti, E. Passaglia “Thiol-ene
Functionalisation of Low Molecular Weight Polybutadiene with L-Cysteine
Derivatives” Macromol Chem Phys 210: 1471–1483 (2009)
3) L. Pérez Amaro, B. L. Rivas, S. Coiai, E. Passaglia, F. Ciardelli “Functionalization
of polypropylene and its potential uses as metal - ion adsorption resin”
J. Appl.
Polym. Sci.,
113: 290–298 (2009)
4) A. Batistini, F.
Ciardelli, F. Cicogna, S.a Coiai, S. Hofmann, E. Passaglia, C. Pinzino,
L. Ricci, I. Tucci. “ Polyethylene functionalization with nitroxyl free
radical” XVII Congresso Nazionale di Chimica Industriale “Energia,
materiali e prodotti da tecnologie e processi eco-sostenibili”, Genova
30 Giugno 3 Luglio 2008, Atti del convegno POL-C09
5) E. Passaglia, F.
Donati, “Functionalization of a Styrene/Butadiene Random Copolymer by
Radical Addition of L-Cysteine Derivatives”, Polymer, 2007, 48, 35-42
6) S. Abbas Mousavi-Saghandikolaei, M. Frounchi, S.n Dadbin, S. Augier,
E. Passaglia, F. Ciardelli, “Modification of isotactic polypropylene by
free radical grafting of trimethylolpropane trimethacrylate (TMPTMA)” J.
Appl. Polym. Sci., 104, 950-958 (2007)
7) M.B. Coltelli, M. Angiuli, E. Passaglia, V. Castelvetro, F. Ciardelli,
“Formation of short and long chain branches during the free radical
functionalization of polyamide
6 in the melt” Macromolecules, 39,
2153-2161 (2006)
8) S. Augier , S. Coiai,
T. Gragnoli, E. Passaglia, J-L.
Pradel, J-J. Flat, “Coagent assisted polypropylene
radical functionalization: monomer grafting modulation and molecular
weight conservation” Polymer, 47
5243-5252 (2006)
9) M.B. Coltelli, M.
Angiuli, E. Passaglia, V. Castelvetro, F. Ciardelli, “Formation of short
and long chain branches during the free radical functionalization of
polyamide 6 in the melt”
Macromolecules,
39, 2153-2161 (2006)
1.2.
Composites and nanocomposites
The occurrence of strong
interaction and/or chemical reactions at the interface between
functionalized polymer materials and inorganic particles is studied and
controlled to prepare nano-structured hybrid materials based onto
thermoplastic materials. Depending on the nature of the filler employed
(amorphous silica, phyllosilicate, organophilic or functional
phyllosicate, organophilic inorganic polyelectrolyte nanoparticles -such
as boehmites and hydrotalcites-, carbon nanotubes) different synthetic
approaches are used: the melt processing by using functionalized
polyolefins and the polymerization in-situ technique of ethylene,
ethylene/CO, styrene, acrylic derivates by using metallocene, Pd
complexes and CuI/CuII (ATRP) catalysts. The
inorganic particles are used also after surface modification to improve
the dispersion and the interphase properties: with this purpose the ATRP
polymerization is used for covering the surface of nanoparticles with
organophilic layers as in the case of boehmites, and cationic/anionic
exchange with suitable surface polarity modifiers are employed for
montmorillonite and hydrotalcites. The interaction degree, in terms of
interphase generation effectiveness, is evaluated by
studying the confinement effects: the analysis of phases structure (amount of bound
rubber), morphology and thermomechanical properties are performed to
understand the phenomena of nano-composites formation either during melt
processing or during the in-situ polymerization.
preparation and
barrier and flame resistance properties are also
investigated.
Most Important and Recent
Publications:
1) S. Coiai, E. Passaglia, A. Hermann, S.
Augier, D. Pratelli, R. C. Streller “The influence of the compatibilizer
on the morphology and thermal properties of polypropylene layered double
hydroxide composites” Polymer Composites In press (2009) DOI
10.1002/pc.20857D. Prevosto, M. Lucchesi, M. Bertoldo, E. Passaglia, F.
Ciardelli, P.o Rolla,” Interfacial effects on the dynamics of
ethylene-propylene copolymer nanocomposite with inorganic clays” Journal
of Non-Crystalline Solids, accepted for publication
2) N. Muksing, S. Coiai, L. Conzatti, E. Passaglia, R. Magaraphan, F.
Ciardelli “Morphology development and stability of polypropylene/organoclay
nanocomposites” Journal of Nanoscience and Nanotechnology. In press
3) M-B. Coltelli, S. Coiai, S. Bronco, E. Passaglia “Nanocomposites
Based on Phyllosilicates: From Petrochemicals to Renewable Thermoplastic
Matrices” chapter 13 in Advanced Nanomaterials. Edited by Kurt E.
Geckeler and Hiroyuki Nishide Copyright © 2010 WILEY-VCH Verlag GmbH &
Co. KGaA, Weinheim ISBN: 978-3-527-31794-3
4) S. Augier, S. Coiai, D. Pratelli, L. Conzatti, E. Passaglia “New
Functionalized Polypropylenes as Controlled Architecture Compatibilizers
for Polypropylene Layered Silicates Nanocomposites” J. Nanosci.
Nanotechnol. 9:4858-4869 (2009)
5) S. Coiai, M. Scatto, M. Bertoldo, L. Conzatti, L. Andreotti, M.
Sterner, E. Passaglia, G. Costa, F. Ciardelli “Study of the compounding
process parameters for morphology control of LDPE/layered silicate
nanocomposites” e-polymers, 2009 n 50
6) Elisa Passaglia, Monica Bertoldo, Serena Coiai, Sylvain Augier,
Stefania Savi, Francesco Ciardelli, “Nanostructured polyolefins/clay
composites: role of the molecular interaction at the interface” Polym.
Adv. Technol. 19: 560-568 (2008).
7) E. Passaglia, M. Bertoldo, S. Ceriegi, R. Sulcis, P. Narducci and L.
Conzatti, “Oxygen and water vapour barrier properties of MMT
nanocomposites from LDPE or EPM with grafted diethylsuccinate groups” J.
Nanosci. Nanotechnol., 8, 1690–1699 (2008)
8) Serena Coiai, Elisa Passaglia, Sylvain Augier, Piero Narducci,
Francesco Ciardelli, “Organophilic boehmite nanoparticles by ATRP
methacrylates polymerization: synthesis, characterization and dispersion
in Polypropylene” J. Nanosci. Nanotechnol., 8, 1803–1811 (2008)
9) F. Ciardelli, S. Coiai, E. Passaglia, A. Pucci, G. Ruggeri “Reactive
Blending of Polyolefins to Nanostructured Functional Thermoplastic
Materials” Polymer International (Review), 57, 805–836 (2008)
10) Elisa Passaglia, Monica Bertoldo, Francesco Ciardelli, Daniele
Prevosto, Mauro Lucchesi “Evidences of macromolecular chains confinement
of ethylene-propylene copolymer in organophilic montmorillonite
nanocomposites” European Polymer Journal 44: 1296-1308 (2008)
11) H.A. Miller, S. Moneti, F. Vizza, E. Passaglia, C. Bianchini, S.
Bronco, S. Ceriegi, R. Sulcis, M. Frediani, F. Ciardelli, G. Costa “Polyketone
Nanocomposites by Palladium-Catalyzed Ethylene-Carbon Monoxide-(Propene)
Co(Ter)polymerization Inside an Unmodified Layered Silicate” e-Polymer
n°3 2006
1.3.
Reactive and reactor polymer blending
Macromolecular reactions
at the interface between functionalized polyolefins and functional
polymers are studied and employed as an effective methodology to attain
compatibilized blends, by creating an active and thick interface thus
stabilizing the morphology.
The reactive blending process between polyolefins containing succinate
groups with poly-e-caprolactam (PA6) or polyethylentereftalate (PET) is
investigated under different conditions: the addition of a
compatibilizing polyolefin precursor (two-steps methodology) and
the addition of low molecular weight reagents (one-step
methodology). The presence of the graft-copolymer,- which constitutes
the compatibilizer formed in-situ and generates the effective
interphase-, its amount and grafting degree rely to the conditions of
process in terms of polymers structure and reagents ratio. The reactor
blending approach is performed by radical or ATRP polymerization
approach onto organic-inorganic hybrid materials constituted by GTR.
Indeed, the accurate characterization of all the products of reaction,
performed after a selective extraction procedure applied to isolate the
different phases, allows to quantify the extent of the interface
reactions and to deepen inside their effect onto morphological, thermal
and mechanical properties of the blends. The use and the effect of
various catalysts is also examined taking into account results obtained
in a model reaction between a low molecular weight amine and succinate
groups used also for developing mathematical models of both the
functionalization and the interpolymer melt reactions.
Most Important and Recent
Publications:
1) M. Penco, S. Della Sciucca, E. Passaglia, G.
Giordani, S. Coiai, L. Di Ladro “Effect of reactive melt mixing on the
morphology and thermal behavior of LLDPE/rubber blends”
J. Appl. Polym. Sci. 109: 1014-1021 (2008)
2) S. Coiai, E. Passaglia, F. Ciardelli, “Gradient density grafted
polymers on round tire rubber particles by atom transfer radical
polymerization” Macromol. Chem. Phys. 207 (24) 2289-2298 (2006)
3) M.-B. Coltelli, E. Passaglia, F. Ciardelli, “One-step
functionalization and reactive blending of polyolefin/polyamide mixtures
(EPM/PA6)” Polymer 47 85-97 (2006)
4) E. Passaglia, M.-B. Coltelli, F. Ciardelli, “Effect of Structure of
Functionalizing Molecule on Inter-Macromolecular Reactions and Blending
of Poly-(ethylene-co-propylene) (EPM) with Poly-(6-amino-hexanoic) Acid
(PA6)” Helv. Chim. Acta, Helv. Chim. Acta, 89, 1596-1609 (2006)
5) E. Passaglia, S. Coiai, G. Giordani, E. Taburoni, L. Fambri, V.
Pagani, M. Penco, "Modulated Crosslinking of Polyolefins through Radical
Processes in the Melt” Macromol. Mater. Eng., 289, 809–817 (2004)
6) D. Sémeril, E. Passaglia, C. Bianchini, M. Davies, H. Miller, F.
Ciardelli, “Reactive Blending of Polyamides with Different Carbobyl
Containing Olefin Polymers” Macromol. Mater. Eng., 288, 475-483, 2003
7) S. Coiai, F. Ciardelli, E. Passaglia, R. Sulcis, E. Resmini, D.
Tirelli, F. Peruzzzotti “Process for manufacturing a thermoplastic
elastomeric material” PCT EP 2004/014313 WO2006063606, Pubblication date
2006-06-22, Application number WO2004EP14313 20041216; US 2008/0132642
A1 (5 Jun 2008)
8) R. Sulcis, E. Passaglia, F. Ciardelli, E. Resmini, D. Tirelli, C.
Bianchini “Process for manufacturing a thermoplastic elastomeric
material” WO/2007/025556, PCT/EP2005/009329 (publication date 3-08-2007)
2. ELECTRO-OPTICAL POLYMERS (G. Ruggeri)
Graduate research staff:
Giacomo Ruggeri, Associate
Professor DCCI, University of Pisa
Francesco Ciardelli, Full
Professor DCCI, University of Pisa
Marco Bernabò, PhD Student DCCI,
University of Pisa
Sagar Kersagar, Grant-Holder, PolyLab-CNR,
Pisa
Vincenzo Liuzzo, Grant-Holder
DCCI,
University of Pisa
Andrea Pucci, Associate Researcher
DCCI,
University
of Pisa
Lucia Ricci, , Grant-Holder
DCCI,
University of
Pisa
Guest Students:
Supported by
MIUR
PRIN 2005 prot. 035119
and MIUR NANOPACK FIRB 2003 D.D.2186 Prot. N. RBNE03R78E
2.1. Electroconductive
polymers, blends and (nano)composites
Electroconducting polymers
have been prepared by polymerization of pyrrole, tiophene, aniline and
some derivatives. In the case of alkylpyrroles polymers Langmuir
Blodgett films and self organized films are prepared and used for
nanowriting under electron-beam irradiation. Fully deuterated
poly(3-n.decylpyrrole) has been prepared and analyzed by Neutron and
x-ray scattering study showing the polymer in the solid state is
arranged in parallel layers and within each layer, neighboring pyrrole
rings maintain a coplanar disposition, whereas the alkyl decane tails
are kinked out of the pyrrole plane.
Thermoplastic conductive materials are prepared by grafting of
polythiofene chains into polyacrylates macromolecules. Nanocomposites
have been formed by polymerization of 3-alkylpyrroles in V2O5
inter-lamellae space. Complexes of polyaniline (emeraldine base) are
blended with sulphonated polystyrene in order to obatin
compatibilization thanks to electrostatic binding at the interfaces.
Collaborations:
1)
N. Costantini, S. Capaccioli, M. Geppi, G. Ruggeri,
"Characterization of electrochemically synthesized alkylpyrroles
intrinsically conducting polymers",
Polymer Adv. Technol ., 11, 27 (2000)
2) F. Huguenin, E.M.
Girotto, G. Ruggeri, R.M. Torresi
"Structural and electrochemical properties of nanocomposites formed by
V2O5 and poly(3-alkylpyrroles)"
Journal of Power Sources, 114, 133 (2003)
3)
A. Orecchini, C. Petrillo, G. Ruggeri,
"Neutron and x-ray scattering study of fully deuterated
poly(3-n.decylpyrrole)",
Journal of Chemical Physics, 118, 7690 (2003)
4) C.R. Martins, G. Ruggeri
, M-A. De Paoli,
"Synthesis in pilot plant scale and physical properties of sulfonated
polystyrene"
J. Brazil. Chem. Soc., 14, 797 (2003)
2.2.
Polymer/metal nanocomposites
The research focused on the role of complexes and metallic
clusters in macromolecular systems. Host-guest systems preparation is
based on the dispersion property, in the macromolecular matrix, of an
organic shell having a metallic core. In particular, as macromolecular
matrices are used thermoplastic materials (i.e., poly(ethylene),
poly(vinyl alcohol) and poly(ethylene)-co-(vinyl alcohol)) while
salicylaldiminate metal complexes, characterized by modulated opto-electronic
properties, and noble metal (Au and Ag) nanoparticles stabilized by
suitable ligands (amines and functionalized thiols) are used as metallic
containing species. This strategy allows to couple the processing
characteristics of the polymer matrix and properties (optical,
catalytic) of the metallic nuclei.
These systems can play a pivotal role in a wide range of technologies
including sensors, optics, fuel cells and catalysis.
Collaborations:
1)
A. Pucci, P. Elvati, G. Ruggeri, V. Liuzzo, N. Tirelli, M. Isola, F.
Ciardelli, “Molecularly controlled blending of metals and organic metals
with polyolefins for the preparation of materials with modulated optical
properties”, Macromol. Symp. 2003, 204, 59-70.
2)
A. Pucci, N. Tirelli, E. A. Willneff, S. L. M. Schroeder, F. Galembeck,
G. Ruggeri, “Evidence and Use of Metal-Chromophore Interactions:
Luminescence Dichroism of Terthiophene-coated Gold Nanoparticles in
Polyethylene Oriented Films” J. Mater. Chem., 2004, 14, 3495.
3)
A. Pucci, V. Liuzzo, G. Ruggeri, F. Ciardelli “Conferring smart
behaviour to polyolefins through molecular blending with metal
complexes”, New Polymeric Materials (Eds. L. S. Korugic-Karasz, W. j.
Macknight, E. Martuscelli) ACS Symposium series n° 916, 2005, chapter 3.
4)
A. Pucci, M. Bernabò, P. Elvati L. I. Meza, F. Galembeck, C. A. de Paula
Leite, N. Tirelli, G.
Ruggeri,
“Photoinduced Formation of Gold Nanoparticles into Vinyl Alcohol based
polymers”, J. Mater. Chem., 2006, 16, 1058-1066.
5)
F. Ciardelli, P. Pertici, G. Vitulli, S. Giaiacopi, G. Ruggeri, A. Pucci,
“Catalytic and Optical Behavior of Polymer Embedded Metal Nanoparticles”,
Macromol. Symp., 2006, 231, 125-133.
6)
M. Boccia, V. Liuzzo , A. Pucci, P. Narducci, G. Ruggeri, “Optical
Properties of M(II) Schiff-base Complexes Dispersed in Ethylene based
Polymers”, Macromol. Symp., 2006, 235, 143-151.
7)
J. de la Venta, A. Pucci, E. F. Pinel, M. A. Garcia, C. De Julian, P.
Crespo, G. Ruggeri, A. Hernando, “Magnetism in polymers with Au
nanoparticles”, Adv. Mater., submitted.
8) F. Ciardelli, O. Pieroni, S. Bronco,
C. Cappelli, G. Ruggeri, A. Pucci, “Modulation of the Superstructure and
Response of Macromolecules through Molecular Interactions and
Nanodispersion”, chapter 27, 435-442, in Functional Nanomaterials (Eds.
Kurt E. Geckeler and E. Rosenberg) American Scientific publisher
(2006).
2.3. Linea polarizers
Host-guest systems based on dipolar chromophors absorbing in the visible
and ultra high molecular weight polyethylene (UHMWPE) have been
submitted to mechanical drawing with consequent orientation of the guest
chromophore molecules parralle to the PE macromolecules. New molecules
having the tertiophene nucleus with electrons push-pull substituents and
long alkyl chains to improve PE compatibility were synthetized and used
as guests.After the orientation films with dichroic ratios high enough
for applications as linear polarizers have been obtained. The dergree of
dispersion of the guest into the host matrix and its effect on optical
properties is subject of study by using different polyethylenes and
different chromophoric structures.
Collaborations:
1)
N.
Tirelli, S. Amabile, C. Cellai, A. Pucci, L. Regoli, G. Ruggeri, F.
Ciardelli, "New terthiophene derivatives for UHMW-polyethylene-based
absorption polarizers", Macromolecules, 24, 2129 (2001)
2)
F. Ciardelli, C. Cellai, A. Pucci, L. Regoli, G. Ruggeri, C. Cardelli,
"Blends of functionalized terthiophenes with polyethylene as materials
for new linear polarizers", Polym. Adv. Technol., 12, 223 (2001)
3)
A. Pucci, L. Moretto, G. Ruggeri, S. Bronco, "Effect of the structure of
the polymer matrix on the terthiophene chromophore dispersion in
dichroic polyethylenes films", Polym. Adv. Technol., 13, 737 (2002)
4)
A. Pucci, L. Moretto, G. Ruggeri, F. Ciardelli, "Effect of the
dispersion of the chromophore on the optical performances of polarizers
from polyethylene and 5”-thio-(3-butyl)nonyl-2,2’:5’,2”-terthiophene",
e-Polymers 2002, no. 015, http://e-polymers.org (2002)
5)
A. Pucci, G. Ruggeri, C. Cardelli, G. Conti, "Influence of processing
method and components molecular structure on the phase behaviour of
polyethylenes/dye blends", Macromol. Symp., 202, 85 (2003)
6)
A. Pucci, P. Elvati, G. Ruggeri, V. Liuzzo, N. Tirelli, M. Isola, F.
Ciardelli, "Molecularly controlled blending of metals and organic metals
with polyolefins for the preparation of materials with modulated optical
properties", Macromol. Symp., 204, 59 (2003)
7)
A. Ambrosio, M. Alderighi, M. Labardi, L. Pardi, F. Fuso, M. Allegrini,
S. Nannizzi, A. Pucci, G. Ruggeri, "Near-field optical microscopy of
polymer-based films with dispersed terthiophene chromophores for
polariser applications", Nanotechnology, 15, S270 (2004)
8)
A. Pucci, S. Nannizzi, G. Pescitelli, L. Di Bari, G. Ruggeri,
“Chiroptical properties of terthiophene chromophores dispersed in
oriented and unoriented polyethylene films”, Macromol. Chem. Phys., 205,
786 (2004)
9)
P. P. Markowicz, M. Samoc, J. Cerne, P. N. Prasad, A. Pucci, G. Ruggeri,
“Modified Z-scan techniques for investigations of nonlinear chirooptic
effects”, Opt. Express, 12, 5209 (2004)
10) A. Pucci, N. Tirelli, G.
Ruggeri, F. Ciardelli, “Dichroism in absorption and emission of
terthiophene chromophores dispersed in oriented polymers”, Macromol.
Chem. Phys., 206, 102 (2005).
11) A. Pucci, C. Cappelli, S. Bronco, G.
Ruggeri, “Dichroic Properties of Bis(benzoxazolyl)stilbene and
Bis(benzoxazolyl)thiophene Dispersed nto Oriented Polyethylene Films: A
Combined Experimental and Density Functional Theory Approach”, J. Phys.
Chem. B, 110, 3127-3134 (2006).
2.4. Molecular sensors
Molecular sensors based on low molecular weight
derivatives of functionalized perilene or stilbene chromophores have
been dispersed into thermoplastic polymer matrices (PE, PP, EVAc,
polyesters) in order to obtain films by solution casting or melt mixing.
The optical response of the dispersed dyes, either in absorption or in
emission, is depending from the nature, morphology and micro-structure
of the polymeric matrix. Modifications of the macromolecular structure
caused by thermal or mechanical stress of the film provide a colour
variation of the dispersed chromophore with a very sensible response.
These properties and behaviour suggest the potential application of
these materials in the field of smart and intelligent packaging.
Collaborations: S. Bronco (activity
line 4.3)
1) A. Pucci, M.
Bertoldo, S. Bronco, “Luminescent Bis-benzoxazolyl-stilbene as Molecular
Probe for Polypropylene Films Deformation”, Macromol. Rapid Commun., 26,
1043, (2005) [cover picture].
2) A. Pucci, T. Biver, G. Ruggeri, L. Itzel
Meza, Y. Pang, “Luminescence Dichroism of Cyano-Containing
Poly[(m-phenylene ethynylene)-alt-(p-phenylene ethynylene)] Aggregates
Dispersed in Oriented Polyethylene”, Polymer, , 46, 11198-11205 (2005).
3) A. Pucci, F. Di Cuia, F. Signori, G.
Ruggeri, “Bis-benzoxazolyl-stilbene Excimers as Temperature and
Deformation Sensors for Biodegradable Poly(1,4-butylene succinate)
Films”, J. Mater. Chem., (2007 in press) DOI: 10.1039/b612033d.
3. SPECIALTY POLYMERS (F.
Ciardelli)
Graduate
Research Staff:
Francesco Ciardelli, Full Professor DCCI, University of Pisa
Angelina Altomare, Researcher DCCI, University of Pisa
Arturo Colligiani, Professor, University of Pisa
Francesco Greco, Grant-Holder DCCI, University of Pisa
Marco Bernabò, PhD Student DCCI, University of Pisa
Andrea Pucci, Associate Researcher DCCI, University of Pisa
Vincenzo Liuzzo, Grant-Holder DCCI, University of Pisa
Guest
Students:
3.1.
Photochromic polymers (A. Altomare)
New photoresponsive polymers are
prepared having a macromolecular structure of vinyl and acrylic type
with photochromic side chains (mainly azobenzene derivatives).
The photoresponse is modulated by varing copolymer structure and
substituents on the chromophore itself. Accordingly materials for non
linear optics are obtained with electrons push/pull substituents in the
para positions. Also with proper spacer liquid crystallinity was
achieved and the material used for olographic applications.
Collaborations:
1) L. Angiolini, D.
Caretti, L. Giorgini, E. Salatelli, A. Altomare, C. Carlini, R. Solaro,
"Optically active polymethacrylates with side-chain L-lactic acid
residues connected to push-pull azobenzene chromophores"Polymer, 41,
4867 (2000)
2) A. Altomare, F. Ciardelli, B. Gallot, M. Mader, R. Solaro, N. Tirelli,
"Synthesis and polymerization of amphiphilic methacrylates containing
permanent dipole azobenzene chromophores" J. Polymer Science: Part A:
Polymer Chem., 39, 2957 (2001)
3) F. Ciardelli, O. Pieroni, "Photoswitchable polypeptides", in "Molecular
Switches", Wiley-VCH, Ed. B.L. Feringa, p. 399 (2001)
4) A. Altomare, F. Ciardelli, G. Faralli, R.
Solaro, "Synthesis of reactive polymeric dyes
as textile auxiliaries"
Macromol. Mater. Eng., 288, 679 (2003)
5) A. Altomare, F. Ciardelli, L. Mellini, R.
Solaro, "Photoactive azobenzene polymers
containing carbazole chromophores",
Macromolecular Chemistry and Physics, 205, 1611 (2004)
3.2.
Photoconductive and photorefractive (A. Colligiani)
Radiation sensitive blends and the possible
use of indole based polymers as photorefractive materials is studied in
comparison to analogous polymers of carbazole. In particular various
macromolecules of vinyl, acryloyl and siloxane backbone with indole side
chains have been prepared. Their composites with plasticizer (indole
derivatives), trinitrofluorenilidene malonitrile as charge transfer
agent and a chromophore with non linear optical (NLO) properties have
been examined for electronic properties, photoelectric response and
photorefractive effect.
Photorefractive and photoconductive characteristics of low molecular
weight (LMW) glasses have been studied by the two-beam asymmetric
coupling (2BC) technique.
Photochromism and photorefractivity of indophenol and indoaniline
derivatives.
Collaborations:
1)
A. Colligiani, F. Brustolin, V. Castelvetro, F. Ciardelli and G.
Ruggeri, “Poly(1-vinylindole) and some of its methyl derivatives as
substrates for photorefractive materials: their synthesis, optical and
electrical characterization”, in Organic Photorefractives,
Photoreceptors, and Nanocomposites, K.L. Lewis, K. Meerholz, eds.,
Proc. SPIE 4104, 71-77 (2000).
2) F. Brustolin, V. Castelvetro, F. Ciardelli,
G. Ruggeri and A. Colligiani, “Synthesis and characterization of
different poly(1-vinylindole)s for photorefractive materials”, J. Polym.
Sci. Part A: Polym. Chem. 39, 253-262 (2001).
3) C. Castè, V. Castelvetro, F. Ciardelli, A.
Colligiani, A. Mazzotta, D. Michelotti, G. Ruggeri and C. A. Veracini,
“Photoconductive films of poly-N-vinylindole-based blends for
high-voltage photorefractive electrooptic cells”, Synth. Met. 138,
341-345 (2003).
4) R. Angelone, C. Castè, V. Castelvetro, F.
Ciardelli, A. Colligiani, F. Greco, A. Mazzotta and G. Ruggeri,
“Synthesis and electrooptical characterization of polysiloxanes
containing indolyl groups acting as photoconductive substrates for
photorefractive materials”, e-Polymers 075, 1-15 (2004).
5) R. Angelone, M. Angiuli, F. Ciardelli, A.
Colligiani, F. Greco, A. Romano, G. Ruggeri, and E. Tombari “An indole-based
low molecular weight glass-former giving materials with high cooperative
photorefractive optical gain”, in Organic Optoelectronics and
Photonics II, P. L. Heremans, M. Muccini, E. A. Meulenkamp, eds.,
Proc. SPIE 6192, 61922M
(2006).
3.3. Polymers for
energy
Polymeric structures are prepared as designed
for specific applications related to energy savings and conversion:
I. Optimization of the synthetic procedure for the preparation of
innovative dispersants for lubricant oils
II. Preparation and characterization of new polymeric membranes with
ionic conduction for fuel cells applications
Collaborations:
1)
A. Pucci, D. Lorenzi, M.B. Coltelli, G. Polimeni, E.
Passaglia, "Controlled degradation by melt
processing with oxygen or peroxide of Ethylene/Propylene copolymers",
J. Appl. Polym. Sci., 94, 372 (2004)
2) A. Pucci, C. Barsocchi, R. Rausa, L. D’Elia, F. Ciardelli, "Alder ene functionalization of polyisobutene oligomer
and styrene-butadiene-styrene triblock copolymer", Polymer, 46,
1497 (2005)
Supported by:
ENI S.p.A. Div. Refining & Marketing (I)
Acta S.p.A. (I)
4. BIOPOLYMERS BASED MATERIALS (S.
Bronco)
NEW: Poster
Prize of Polish Academy of Sciences
Graduate
Research Staff:
Francesco Ciardelli,
Full Professor DCCI, University of Pisa
Simona Bronco, Researcher, PolyLab-CNR, Pisa
Monica Bertoldo, Associate Researcher, PolyLab-CNR, Pisa
Maria-Beatrice Coltelli Associate Researcher, C.I.P., Marghera
Chiara Cappelli, Researcher DCCI, University of Pisa
Valter Castelvetro, Researcher DCCI, University of Pisa
Andrea Pucci, Associate Researcher DCCI, University of Pisa
Francesca Signori, Associate Researcher DCCI,
University of Pisa
Ungraduate
Research Staff:
Claudio Toncelli
Fededrica Cognigni
Guest
Students:
Carlos Chinea from the Escuela de Quìmica of the Universidad
Central de Venezuela, Caracas
Supported by:
NANOPACK FIRB 2003 D.D.2186 Prot. N. RBNE03R78E
PICUS Co-operative Research Project, VI Framework Programme, EC.
Bayer (D)
4.1.
Modification and functionalization of biopolymers
Attempts are performed to prepare new
macromolecular systems from biopolymers by grafting of different
synthetic polymers to the biopolymers backbone. Both modification of
bulk and interfacial properties are pursued. The study includes
molecular modelling of these complex systems to help understanding most
suitable approaches and predict results. Systems under study are at
present collagen and cellulose on which covalent grafting is approached
by free radical reactions in the presence of unsaturated monomers.
Grafting through urethane bonds and hydrogen binding with properly end
capped synthetic macromolecules is also carried out.
References:
1) N. Costantini, F. Ciardelli, A.D. Covington "Studies on the tanning
reactions of zeolite" JALCA, 95, 125 (2000)
2) S. Bronco, V. Bartalini, S. Bocchini, F. Ciardelli, M. Perazzo
"Leather powder as starting material for innovative composites" Modest
2002, 2nd International Conference on Polymer Modification, Degradation
and Stabilization, Budapest (Ungheria), 30 Giugno - 4 Luglio 2002.
3) S. Bronco, C. Cappelli, S. Monti "Understanding the structural and
binding properties of collagen: a theoretical perspective" J. Phys.
Chem. B, 108, 10101-10112 (2004)
4) S. Monti, C. Cappelli, S. Bronco, “Toward
the Supramolecular Structure of Collagen: A Molecular Dynamics Approach”,
J. Phys. Chem. B, 109, 11389-11398 (2005)
5) F. Ciardelli, O. Pieroni, A. Bronco, C. Cappelli, G. Ruggeri, A.
Pucci, “Modulation of the Superstructure and
Response of Macromolecules Through Molecular Interactions and
Nanodispersion”, Functional Nanomaterials, Ed.
K. E. Geckeler and E. Rosenberg, Los Angeles, California, USA, 2006, pp.
435-442.
6) M. Bertoldo, S. Bronco, T. Gragnoli, F. Ciardelli,
“Modification of Gelatine by reaction with 1,6-Diisocyanatehexane”,
Macromol. Bioscience, 2006,
accepted.
4.2.
Bioplastics
The main objective is to obtain polymeric
materials with thermomechanical properties comparable to the most common
commodity plastics and elastomers from macromolecular systems derived
from renewable momomers or from abundant naturally biopolymers .These
materials are based on polymers of lactic acid blended with linear
biodegradable polyester and varying the structure of this last and its
dispersion in the polylactic matrix.Blends of suitable synthetic
polymers with cellulose,collagen and albumin are also under study.
References:
Not available at the moment for confidentiality reasons (EC Project
PICUS)
4.3. Responsive
materials with natural/biodegradable macromolecules
Molecular composites and nanocomposites with
natural or biodegradable/biocompatible synthetic polymers are prepared
to develop responsive materials (biosensors) capable of combining the
specific response of the macromolecule with that of nanodispersed
nanoparticles with delocalized electrons.
Systems under study are linear polyesters with organic chromophores and
nanoclay with polysaccharides.
References:
1) Andrea Pucci, Marco Bernabò, Giacomo Ruggeri, Francesco Ciardelli,
"Dispersione di Sensori Luminescenti Nanostrutturati in Film Polimerici“,
XXII congresso nazionale della Sociatà Chimica Italiana, Firenze,
Settembre 2006
2) Andrea Pucci, Flavia Di Cuia, Francesca Signori, Giacomo Ruggeri,
“Bis-benzoxazolyl-stilbene Excimers as Temperature and Deformation
Sensors for Biodegradable Poly(1,4-butylene succinate) Films”,
Journal of Materials Chemistry, submitted 2006
5. CONTROLLED ARCHITECTURES, SURFACES AND
INTERFACES (V. Castelvetro)
Graduate
Research Staff:
Valter Castelvetro, Researcher DCCI,
University of Pisa
Francesco Ciardelli,
Full Professor DCCI, University of Pisa
Monica Bertoldo, Associate Researcher, PolyLab-CNR, Pisa
Sabrina Bianchi, Grant-Holder DCCI, University of Pisa
Simona Bronco, Researcher, PolyLab-CNR, Pisa
Chiara Cappelli, Researcher DCCI, University of Pisa
Giacomo Giannini, Grant-Holder DCCI, University of Pisa
Antonella Manariti, Grant-Holder DCCI, University of Pisa
Giacomo Ruggeri, Associate Professor DCCI, University of Pisa
Supported by:
5.1.
Waterborne polymers
Water-borne dispersions of functional
polymers are synthesized either directly, by emulsion polymerization, or
by action of suitably selected surfactants on polymeric materials
produced by conventional solution or bulk polymerization. Emulsion and
miniemulsion polymerization techniques are investigated as means to
produce reactive and/or highly compatibilized multicomponent colloidal
polymer dispersions. Morphology and stability of the resulting polymer
latexes, as well as their film-forming behavior and the surface, thermal
and mechanical properties of the resulting films are characterized.
Specifically designed partially fluorinated latexes are being developed,
with the aim of improving the performances of water-based,
environmentally friendly formulations for metal, wood, stone, leather
and textile coating applications. Reactive polymer latexes are also
being developed as self-curing or surface-specific coating and
remediation materials.
1)
V. Castelvetro, F. Ciardelli, G. Francini, P. Baglioni "On the surface
properties of waterborne fluorinated coating polymers" Macromol. Mat.
Eng., 278, 6 (2000)
2)
C. De Vita, V. Castelvetro, F. Ciardelli, S. Scola "Reactive hybrid
macromolecular dispersions in aqueous media as binders for porous stone
materials" 3rd World Congress on Emulsions, Lyon, 24-27 September
2002-03-05
3)
V. Castelvetro, C. De Vita, G. Giannini, M. Malvaldi "Alkoxysilane
functional acrylic latexes: influence of copolymer composition on
self-curing behavior and film properties" Macromol. Symp. (submitted)
5.2.
Polymers for surface finishing
The surface properties and appearance of
various substrates, from packaging plastics to textile fibers, are
modified by deposition or direct grafting of polymer structures. The
polymer modifiers are produced either in separate synthetic steps or
directly on the substrate by surface-graft polymerization processes
induced by high energy (e.g. plasma) or chemical activation.
Multifunctional polymer structures with conventional and photochromic
dyestuffs, ammonium-type or fluorinated groups are synthesized, and
their photochemical behaviour, biocide/biostatic activity or
hydrophobicity, respectively, are investigated. Additional functional
groups are introduced in the macromolecular structure for improved
adhesion, water dispersibility, self-crosslinking, etc. The surface
finish is applied by conventional technique (e.g. from solution or
water-borne dispersions), by chemical grafting or by free radical
polymerization at (photoinitiated) or from (graft polymerization) the
solid surface.
Fluorinated acrylic-based copolymers for coating applications are
prepared starting from commercial and new fluorinated acrylates.
Tailoring of the macromolecular architecture is aimed at improving the
material properties for the required application. Water-borne
dispersions of nanostructured partially fluorinated polymer particles
are also prepared and their film-forming behavior investigated. The
fluorinated materials are developed as protective coatings for stone,
textile, leather and other porous substrates, with particular attention
to their water repellency, filmability, adhesion, hydrolytic and
photooxidative stability. The latter properties are specifically
investigated for their relevance in the field of cultural heritage
protection. Characterization of the surface energy and of its dynamic
behavior is carried out to improve the chemical and physical stability
of the hydrophobic coatings
1)
V. Castelvetro, G. Francini, G. Ciardelli, M. Ceccato
"Evaluating fluorinated acrylic latices as textile water and oil
repellent finishes" Textile Res. J., 71, 399 (2001).
2) M. Lazzari, O. Chiantore, V. Castelvetro,
M. Aglietto "Photochemical stability of partially fluorinated acrylic
protective coatings II. Copolymers of 1H,1H,2H,2H-perfluorodecyl
methacrylate with unfluorinated acrylic esters" Chem. Mater., 13, 2843
(2001).
3) T.S. Berzina, V.I. Troitsky, V. Castelvetro,
M.P. Fontana "Electron beam sensitive LB films of fluorocarbon polymer"
Mat. Sci. Eng., C 22, 295 (2002).
4) V. Castelvetro, M. Aglietto, F. Ciardelli,
O. Chiantore, L. Toniolo "Structure control, coating properties, and
durability of fluorinated acrylic-based polymers" Journal of Coatings
Technology, 74, no. 928, 57 (2002)
5) G. Ciardelli, L. Corsi, M. Faetti, E. Fatarella, F. Zulli "Free
radical generation upon plasma-treatment of cotton fibers and their
initiation efficiency in surface-graft polymerization" J. Polym. Sci.
Polym. Phys. Ed. (submitted)
5.3. Surface
modification of polymeric substrates
The surfaces of polyolefin films having
thickness in the 50¸150 mm range are modified by physical and chemical
methods. In particular, plasma treatments and UV initiated chemical
reactions are exploited to improve functional properties such as surface
wettability, catalytic ability or resistance upon UV degradation also
for packaging application. Deposition of catalytic species by spray
coating and migration of additives to the surface are method also
investigated.
1) S. Bronco, M.
Bertoldo, E. Taburoni, C. Cepek, M. Sancrotti "The effects of cold
plasma treatments on LDPE wettability and curing kinetic of a
polyurethane adhesive" Macromol. Symp. in press.
2) L. Andreotti, M. Sterner, G. Trani, G. Schiavon, C.A. Zaggia, M.
Mazzetti, M. Bertoldo, S. Bronco, C. Cappelli, V. Liuzzo "Composti
particolarmente catalizzatori di poliuretani" Italian Patent Application
PD2004A000138, 28 may 2004
3) F. Fallani, G. Ruggeri, S. Bronco, M. Bertoldo "Modification of
surface and mechanical properties of polyethylene by photoinitiated
reactions" Polym. Degrad. Stab., 82, 257 (2003)
4) M. Bertoldo, S. Bronco, C. Cappelli, T. Gragnoli, L. Andreotti "Combining
theory and experiment to study the photo-oxidation of polyethylene and
polypropylene" J. Chem. Phys., 107, 11880 (2003)
5) M. Bertoldo, F. Ciardelli "Water extraction and degradation of a
sterically hindered phenolic antioxidant in polypropylene films" Polymer,
in press
5.4. Controlled polymer architectures
Block and Multiarm Polymer Structu res by Controlled
Polymerization (PSUF Several polymeric systems and polymerization
processes are studied, with the purpose of devising new material
properties by controlled macromolecular synthesis. Polymer-based
colloidal hybrids are being developed as coatings and binders for porous
organic and inorganic substrates and as precursors for ceramic
nanoporous membranes. The newly developed aqueous dispersions of
nanostructured particles are obtained by either mixed polymerization and
sol-gel techniques or emulsion polymerization in the presence of
preformed inorganic nanoparticles, such Polymers with well-defined
macromolecular architecture, such as block, multi-arm, or simply
monodispersed homopolymer structures are prepared by living (cationic,
anionic) or controlled (free-radical mechanism based on the ATRP or RAFT
technique) chain polymerization. Various polymerization processes are
selected to suit the final goal. Thus the polymerizations are run either
in homogeneous (solvent or bulk) or heterogeneous (dispersed phase,
surface-graft polymerization) phase, and the ultimate product can be a
lipophilic or hydrophilic polymer, a self-assembling amphiphilic block
copolymer or a polymeric graft grown from a solid surfaceas synthetic
metal oxides and natural or synthetic lamellar silicates.
1) V. Castelvetro, C. De Vita "Nanostructured hybrid materials from
aqueous polymer dispersions" Adv. Colloid Interface Sci., 108-109C, 167
(2004).
2) V. Castelvetro, C. De Vita, M. Geppi, S. Giaiacopi, O. Chiantore, D.
Scalarone, G. Costa "Synthetic approaches to inorganically modified
aqueous polymer dispersions: from reactive acrylic latexes to
nanostructured hybrids with either spherical or lamellar inorganic phase"
Abstract Book, “Polymers in Dispersed Media”, Lyon, april 4-8 2004, p.
78-80.
3) G. Chessa, A. Scrivanti, U. Matteoli, V. Castelvetro "Synthesis of
three- and six-arms polymers via living controlled free radical
polymerisation" Polymer, 42, 9347 (2001).
4) V. Castelvetro, G. Bontà Pittaluga, F. Ciardelli "Multifunctional
poly(vinyl ethers) by controlled cationic polymerisation in fluorinated
solvent" Macromol. Chem. Phys., 202, 2093 (2001).
5) L. Andreozzi, M. Faetti, M. Giordano, F. Zulli, V. Castelvetro "Crossover
region and entanglement in nearly monodisperse poly(ethyl acrylates)
studied with electron spin resonance spectroscopy" Philos. Mag., 84,
1555 (2004).
6. POLYMERS AND ENVIRONMENT (M.
Aglietto)
Graduate
Research Staff:
Mauro Aglietto, Associate Professor DCCI, University of Pisa
Francesco Ciardelli,
Full Professor DCCI, University of Pisa
Maria-Beatrice Coltelli, Associate researcher C.I.P.,
Marghera
Guido Giordani, Grant-Holder DCCI, University of Pisa
Irene della Maggiore, Grant-Holder DCCI, University of Pisa
Stefania Savi, Post-Doc
DCCI, University of Pisa
Supported by:
6.1.
Analysis of polymer materials
Complex materials based on polymeric blends, polymer/inorganic
composites, chemically modified natural polymers and synthetic/natural
polymer mixtures have been analyzed.
The polymeric blends examined were commercially available and
post-consumer materials based on synthetic polymers, such as mono and
multilayer films, fibres, coatings, etc; the modified natural polymers
were cellulose, collagen and gelatine; the synthetic/natural mixtures
were based on natural materials such as wood, paper, leather and textile
fibres mixed, coated or impregnated with synthetic polymers.
On one hand, such analysis had the purpose to investigate the materials
in the bulk and to evaluate their chemical composition, the properties
of the solid matrix, such as mechanical (stiffness and ductility by
stress-strain behaviour), structural, thermal and rheological properties.
On the other hand, some of the surface properties of
the materials were also examined: chemical and morphological properties,
adhesion properties of different solid materials (multilayer films,
coatings, etc.), wetting properties of liquids on solid surfaces and
solid-vapour surface tension.
6.2.
Recycling
The use of plastics coming from the separate collection of solid
waste to obtain blends provides a suitable method for waste recycling by
allowing the preparation of new materials with an added value with
respect to the recovered polymers. Post-consumer polymeric compounds
are prepared by melt blending and characterized by Scanning Electron
Microscopy (SEM), FT-IR techniques, thermal analysis (TGA and DSC),
tensile and impact tests to focus the correlations between structural,
morphological and final properties of materials. In this framework, the
reactive blending of post-consumer PET and functionalized polyolefins (POF)
is studied to tailor engineering materials with modulated properties, as
a consequence of the attractive balance of mechanical and barrier
properties and of the improved processability. PET/POF blends properties
can be modulated acting on the composition (weight ratio of polymeric
components, use of nucleating agents, chain extenders and crosslinking
agents), the processing conditions and the degree of compatibility. The
recycling of post-consumer polypropylene (PP) coming from the automotive
industry is also investigated. In particular car bumpers, air ducts and
instrument panels can be recovered to produce new raw materials. The
processability of these materials is studied as a function of mixing
parameters and presence of stabilizers. Moreover
different amounts of fillers were added for modulating the melt
viscosity and stress-strain properties of the obtained material.
6.3. Industrial
ecology of materials
Many industrial processes, in terms of flows of raw materials, products
and wastes, were investigated in order to develop new strategies for the
recovery of sources and the purification of waste streams by applying
the general rules of industrial ecology.
In different kinds of industries polymeric wastes are produced, such as
in leather (collagene and gelatine), paper (cellulose) and moulding (synthetic
polymer scraps) industries. The proper modification of such materials
and preparation of composites with specific properties can allow the
recovery of wastes as industrial sources, with the final aim of
optimising and innovating industrial cycles and reducing the consumption
of both matter and energy.
Moreover the interaction of properly tailored polymeric materials with
waste streams of various anthropic activities with the aim of properties
improvement, depuration or recovery of chemicals was also kept into
account.
1) M.-B. Coltelli, S. Bianchi, S.
Savi, V. Liuzzo, M. Aglietto, Metal catalysis to improve compatibility
at PO/PET blends interfaces, Macromol. Symp., 204, 227-236 (2003)
2) M. Aglietto, M.-B. Coltelli, S. Savi, F. Lochiatto, F. Ciardelli,
Post-consumer Polyethylene Terephthalate (PET)/Polyolefin blends through
reactive processing, J. Material Cycles and Waste Management 6, 13-19
(2004)
3) M.-B. Coltelli, S. Savi, I. Della Maggiore, V. Liuzzo, M. Aglietto,
F. Ciardelli, A model study of Ti(OBu)4 catalysed reactions during
reactive blending of polyethylene (PE) and poly(ethylene terephthalate)
(PET), Macromol. Mat. Eng., 289, 400-412, 2004 (2005)
4) M. Aglietto, M.-B. Coltelli, S. Savi, I. Della Maggiore, Reuse of
post-consumer poly(ethylene terephthalate) (PET) in toughened blends, in
Feedstock Recycling of Plastics, M. Muller-Hagedom, H. Bockhom (eds),
Universitatsverlag Karlsruhe, 2005, p. 503-508
5) M.-B. Coltelli, I. Della Maggiore, S. Savi, M. Aglietto, F. Ciardelli,
Modified styrene-b-ethylene-co-1-butene-b-styrene triblock copolymer as
compatibiliser precursor in polyethylene/poly(ethylene terephthalate)
blends , Polymer Degradation and Stability, 90 (2) 211-223(2005);
erratum 91, 987 (2006)
6) M.-B. Coltelli, M. Aglietto, Miscele poliesteri/poliolefine
modificate da plastiche post-consumo, in “Leghe e formulati polimerici:
miscelazione fisica e reattiva”, Pacini Editore, 2006, p.347-366
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