design of macromolecules and nanostructured … · 9 researchers/ 5 technicians ... cr p cl p n h...

Istituto per lo Studio delle Macromolecole ISMAC – Milano9 researchers/ 5 technicians8 students/felloship holders

Istituto per lo Studio delle Macromolecole ISMAC – Genova3 researchers / 3 technicians2 students/felloship holders

Design of macromolecules and nanostructuredmaterials with controlled architecture

for functional applications

Istituto per lo Studio delle Macromolecole

Aim: through the design and development of novel polymerization catalysts, to create new macromolecular architecture or polymers with newfunctionalities. The "taylor made“ functional and nanostructured materialswill be evaluated for potential applications in specific fields, such as packaging, optical devices, automotive industry and rubbers

Dipartimento Progettazione Molecolare: Progetto 2 Commessa 096 Macro

Catalysis and polymerizations of α-olefins

ISMAC-Milano

Catalysis and polymerizations of diolefins

ISMAC-Milano

CompoundingMorphological characterisation of new

polymeric materialsISMAC-Genova

ProcessingMolecular, thermal, reological characterization

ISMAC-Milano

Studies on polymer microstructure / polymerization mechanismsNMR Analysis, conformational analysis, molecular modeling

ISMAC-Milano

Human resource distribution


CatalysisISMAC-MilanoCatalysis

ISMACISMAC--MilanoMilano

CrP

Cl

PN

H

Cl

NRNCo

Cl Cl

n

n

m z

Si

N

TiClCl

/ MAO

/ MAO

R =S

S

(CH2)n

(CH 2)nR

MtCl 2

R

x y

Si

N

TiCl2

ZrCl2


O

NiN

N

R R

RR

PMe3

mn

l

OH

Vreactor= 250ml

Vreactor= 2.0l

PolymerizationISMAC-Milano

PolymerizationPolymerizationISMACISMAC--MilanoMilano

Polymerization

NMR- microstruttural analysis


SCALE - UPSCALE SCALE -- UPUP

CompoundingISMAC-GenovaCompoundingISMACISMAC--GenovaGenova


Twin-screw extruder 40D

(matrix, amount of filler, surface modification, processing time)

Elastomer based composites

(matrix, mixed filler)

Elastomer based nanocomposites

(matrix, compunding systems, surface modification)

Nanocomposites based on different polymer matrices

In situ composites obtained through reactiveblending of technopolymers with LCP

Brabender Plasti-Corder®

Morphological Characterisation by Electron Microscopy and Image Analysis

Chemical, Physical and Mechanical Characterisation


TEM

SEM micrograph of aPE-TOPAS blend

400nmTEM micrograph of aPE-based nanocompisite

ProcessingISMAC - Milano

ProcessingProcessingISMAC ISMAC -- MilanoMilano

Rheological Characterization


SEC Characterization

ProcessingISMAC - Milano

ProcessingProcessingISMAC ISMAC -- MilanoMilano

Extrusion

Film production


FLEXIBLE PACKAGINGFLEXIBLE PACKAGING NANOCOMPOSITESNANOCOMPOSITES

PROGETTO Regione Lombardia 2005“Materiali poliolefinici per imballaggi flessibili con prestazioni modulabili ed alta riciclabilità”PROGETTO Regione Lombardia 2006“Film polimerici innovativi con proprietà modulate, funzionali al mantenimento della qualità dei prodotti alimentari”

PROGETTO CARIPLO 2005-2007“Imballaggi plastici per alimenti: additivi macromolecolari a basso coefficiente di diffusione e basso rischio di contaminazione”

FIRB MIUR NANOPACK 2005-2008 “Nuovi materiali e film polimerici nanostrutturali a ridotto impacco ambientale, con proprietà di risposta verso agenti chimici e fisici, per il packaging flessibile”

α-Olefines

STREP NANOHYBRID2005-2008 “Designed Nanostructure HybridPolymers: Polymerization Catalysis and TectonAssembly”

NOE IDECAT 2005-2011 “Integrated Design of Catalytic Nanomaterials for a SustainableProduction”

Diolefines

PROGETTO CARIPLO 2005-2006“Progettazione di nanocompositi a matrice elastomerica funzionalizzata”

FIRB MIUR 2007-2010“Studio delle interazionicarica-polimero, attraverso indagini morfometriche e analisi dinamico-meccaniche, di compositi e nanocompositi a matrice elastomerica”

MAIN PROJECTSMAIN PROJECTSMAIN PROJECTS

“Materiali poliolefinici per imballaggi flessibili con prestazioni modulabili ed alta

riciclabilità”

Regione Lombardia


“Film polimerici innovativi con proprietà modulate, funzionali al mantenimento della qualità dei prodotti

alimentari”

AimInnovative polymeric films with modulated properties, functional

to maintain food quality

The guide ideaNowadays it is necessary to go over the simple concept of high barrier package and to finalize the research efforts rather to modulate the film properties, in particular the permeability, in function of the specific requirements of the different foods

Proposed activity: Permeability will be tuned by acting on polymer microstructure, mainly through the choice of comonomers in copolymers of ethylene. The wide possibility of varying length, branching and structure of olefin comonomers is finalized to the modulation of polymer free volume with consequent variation of barrier properties

Advantages: Polyolefin materials are easily recycled. The innovation proposed is in full accordance with the desire to avoid aluminum and chlorine in packaging as well as plesticizers as additives, that are increasingly perceived as environmentally unfriendly

Tuning permeability through the use of branched comonomers

Expected result: increase polymer free volume, higher permeability

Traditional comonomers

ethylene/1-butene

ethylene/1-hexene


Non traditional comonomers

ethylene/3-methyl-1-butene

ethylene/4-methyl-1- pentene

ethylene/4-methyl-1-pentene/1-hexene terpolymer

Expected result : higher barrier, high trasparency film, high rigidity and strength

Random copolymermainly alternating

Tg = till to 120°C

Blocky copolymer

Tg = 150-194°C

Tuning permeability through the use cyclic comonomers

FLEXIBLE PACKAGING NANOCOMPOSITES




α-Olefines



Diolefines




“Imballaggi plastici per alimenti: additivi macromolecolari a basso coefficiente

di diffusione e basso rischio di contaminazione”

Progetto Fondazione CARIPLO“Promuovere la valorizzazione della conoscenza attraversoil sostegno di progetti di ricerca applicata a tecnologie abilitanti”


Aim: macromolecular additives with low diffusioncoefficient for plastic food packaging

The guide ideaDue to their peculiar sealing properties, their low cost and lowreactivity, polyolefins are the plastics most frequently used asfood contact materials.Even if polyolefins are actually safe, the migration of anti-oxidant and of other small molecules used as lubricants or slip agent, represents a risk of food contamination and might lead tosome risk of allergenic phenomena

Proposed activityTo design new polymeric materials which include in their macromolecular structure the anti-oxidant and lubricatingfunctions, normally devoted to small molecules added to the polymer bulk

From Commercial Antioxidants toto FunctionalizedFunctionalized Comonomers Comonomers

O

HO

3 3 3

2,5,7,8-tetrametil-2-(4',8',12'-trimetiltridecil)-6-cromanolo


OH

O

OH

O

OH

O

OH

O

2,6-di-tert-butil-4-metossi-fenolo (BHA)Vitamin E

O

SH O

O

ZrCl2

Ethylene

OH

O

** n

k


N N

iPr

iPr

Pri

iPr

Br BrNi

OH

O

**

n

Ethylene

Chain microstructure depends on the type of catalyst

OH

Ok

Linear copolymeranti-oxidant function

Branched copolymeranti-oxidant and lubricating function

OH

Ok

FLEXIBLE PACKAGING NANOCOMPOSITES




α-Olefines



Diolefines




Major Objective: Learning from nature

Mainobjectives

Designed Nanostructured Hybrid Polymers: Polymerisation Catalysis and Tecton Assembly

Polyolefins

60% of the total polymerproduction

FP6 STREP Project: NMP3- CT-2005-516972

Expected improvement of: stiffness,

strength,

toughness,

barrier performance,

heat distortion

temperature

paintability,

transparence

Why Nano ?

Very small amount (a few weight-percent) of nanometer-scaled anisotropic tectons is expected to be sufficient to modify polymer properties because most polymer is located at the nanofiller interface.

This conversion of bulk into interfacial polymer shall be the key to improved property profiles.

The current polyolefin-based nanocomposites encounter difficulties withdispersion of tectons in the matrix (polyolefins are non-polar).

from Mülhaupt

Design and development of nanostructured hybrids

Activities

1. Synthesis of nanostructured hybrids by use of block copolymers

2. Synthesis of nanocomposites via “in situ” coordination polymerization

3. Preparation of nanocomposites by melt processing

+

Filler Block copolymer polymer matrix

POLAR APOLAR

+

Filler Block Embedding in polymer matrix

Filler Mt

Mt

MtM

t

Mt

Mt

Mt

Mt

catalyst

Mt

monomerFiller

PolymerCatalyst

Filler Mt

Mt

MtM

t

Mt

Mt

Mt

MtMt

Mt

MtM

t

Mt

Mt

Mt

Mt

catalyst

MtMt

monomerFiller

PolymerCatalyst


Significant research is conducted to develop strategies for efficient livingpolymerisation and to develop catalysts switchable between insertion and controlled radical chain propagation mechanisms.

The beneficial effect of the novel polar and apolar diblock (AB) copolymers to obtain

stable organic inorganic interphase of novel hybrid polyolefins;

1. 1. SynthesisSynthesis of of functionalizedfunctionalized polymerspolymers

A)

B)

C)P

P

PRandom copolymers with functional group (P)Random copolymers with functional group (P)

Block copolymersBlock copolymers Apolar - Polar

Polymers with terminal (P) polar groupsP

+ FILLER

Melt Blending

Effects on the stability of nanocomposites, on the exfoliation of clays and on final properties of polyolefin

nanocomposites

Some Results in Catalysis

RWTH Okuda, Spaniol, Hitzbleck e.g

Living Isospecific Styrene Polymerization

ISMAC Ravasio, Zampa,Tritto, Boggioni

Living Ethylene-Norbornene

Polymerization

R2

S

R2

S

R1

R1

O

O

TiCH2PhCH2Ph

n2n

B(C6F5)3 / AlR3isotacticMw/Mn < 1.2

SiMe2R

Scthf

CH2SiMe3

CH2SiMe3

[Ph3C][B(C6F5)4]

excess

X

l m n l' m' n'

SinthesisSinthesis of block of block copolymerscopolymers withwith functionalfunctionalgroupsgroups

N

ON

RR

RR

PMe3

M

M = Ni, PdR = Me, i-Pr

OH

l m n

OH

Maximum content of polar monomer

+

late transition metal catalystactivated with [Ni(COD)2].

SiMe3

Scthf

CH2SiMe3

Me3SiCH2

[Ph3C][B(C6F5)4] activator

Catalyst supportation on the tectons for in situ (filling)

polymerisation;

to produce nanoparticles coated with polymer as easy-to-disperse intermediates for novel nanohybrids with high inorganic content

Sasol Nanocyl

CarbonNanotubes

Catalyst supportation on the tectons for in situ (filling)

polymerisation;

to produce nanoparticles coated with polymer as easy-to-disperse intermediates for novel nanohybrids with high inorganic content

Zr

R

R

XX

X = e.g.O

O R

X

, -OHISMAC L. Boggioni, I Tritto

UMH P. Dubois

MAO cocatalystETHYLENEMETALLOCENE

IMMOBILIZATION OF COCATALYST ADDITION OF METALLOCENE

FILLER

NANOCOMPOSITE

AlCH3

OX n

MtR

in situ POLYMERIZATION

UMH P. Dubois

« Polymerization FillingTechnique »

Ethylene-NorborneneCopolymerization

with Metallocene Catalysts

n

n

n

n

n

n

E-N copolymer Properties • High transparency • High rigidity and strength • Excellent biocompatibility • Very good resistance to acids and alkalis and polar organic solvents • Low density • Low birefringence

Highly performant materials withmuch improved properties (barrier,

thermal, mechanical, flame retardant, rheological,…)

In situ Ethylene-NorborneneCopolymerization

on Multi Wall Carbon Nanotube (MWCNT)

+

Strategy

OurOur aimaim

Some Results in Nacomposites byin situ polymerizations

UMH Dubois, Bredeau, Alexander

PE-coated MWNTs by surface-catalyzed/initiated polymerizations

ISMAC

PE-N coated MWNTs by surface-catalyzed/initiated polymerizations

MAO ethylenemetallocene

Cocatalystimmobilization

Addition of the metallocene catalyst which remains

immobilizedclay

A

Polimerization

B

Organo-clay

Solvent

CatalystSwelling

Cocatalyst

MAOMAO

MAOMAO

MAO

MAO-cat

MAO-catMAO-cat

MAO-cat

Monomer

C

Organo-clayMAO

CatalystSolvent Monomer

One-step

Cocatalyst

masterbatch process : masterbatch process : nanocompositesnanocomposites

Clay or CNT / Polymer

nanocompositeswith 3 wt% of

loading

In situ homo-copolymerization1.1. Highly filled (e.g. 50

wt%) Clay or CNT/ Polymer

nanocomposite

Preformed polymer

(commercial matrix)2.2. Melt blending

Metal Catalyst

Block Co-PolymerPolymer Matrix

Tecton

12

34

A

BCD

Pola

r par

t

Apol

arpa

rt

MtMt

Embedding in the polymer matrix 5

This illustration summarises the main steps that will create the bondingin the ‘standard’ process investigated by Nanohybrid.

ObjectivesApplication-oriented property enhancement, thanks to

nanostructured hybrid polyolefins

Through the development of fundamental knowledge and the understanding of phenomena linked to nanostructured hybrid polyolefins, various applications are targeted in the long term. Early exploration will take place in the project in order to assess the capabilities of theNANOHYBRID material, and in view of further adaptation to these industrialprocesses.

• Design for automotive parts.• Advanced functional materials for high performance elastomers. • Polymer MEMS (micro-electro mechanical system) components for optical and

biological applications. • Materials design for packaging. • Nanocomposite polyolefin fibres for textile and technical applications

No Name Short name Country

1 Istituto per lo Studio delle Macromolecole -Consiglio Nazionale Delle Ricerche

ISMAC-CNR Italy

2 Istituto di Chimica dei Composti Organometallici Consiglio Nazionale Delle Ricerche

ICCOM-CNR Italy

3 Centro Di Cultura per l’Ingegneria delle Materie Plastiche

CDCMP Italy

4 University of Mons-Hainaut UMH Belgium 5 Albert – Ludwigs- University Freiburg FMF Germany 6 Aachen University RWTH Germany 7 Commissariat à l’Energie Atomique CEA France 8 Slovak University of Technology in

Bratislava STUBA Slovakia

9 Sasol Olefins & Surfactants GmbH SASOL Germany 10 Basell Poliolefine Italia S.p.A BASELL Italy 11 CEBAL S.A.S. France CEBAL France 12 C.R.F. Societa Consortile per Azioni CRF Italy 13 NANOCYL S.A. NANOCYL Belgium 14 ALMA CONSULTING GROUP ALMA France

List of participants

design of macromolecules and nanostructured … · 9 researchers/ 5 technicians ... cr p cl p n h...

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