ALEA IACTA EST 1st Expertissues Tutorial Course Ischia NA, Italy, July 16 17, 2005

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ALEA IACTA EST1st Expertissues Tutorial
CourseIschia (NA), Italy, July 16 - 17, 2005
POLYMERIC MATERIALS PREPARATION
CHARACTERIZATION
Saturday, July 16, 2005
Emo Chiellini UdR INSTM Dipartimento di Chimica
e Chimica Industriale - Università di Pisa Via
Risorgimento 35 - 56126 Pisa (Italy) Tel 39 050
2219299 - 2219445 / Fax [phone] E-mail
emochie_at_dcci.unipi.it
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Presentation Content

• Hystorical Background on Polymers Production
• Polymers Classification
• Structure Microstructure Features
• Production Processes of Synthetic Polymers
• Controlled Radical Polymerization
• Hydrobiodegradable Polyesters

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Landmarks in Polymer Science Technology
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Annual Production Consumption of Polymeric
Materials Plastics
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Polymeric Materials Classification
MACROMOLECULAR COMPOUNDS
ORGANIC or INORGANIC
SEMISYNTHETIC
NATURAL
SYNTHETIC

• Polysaccharides
• Proteins
• Polynucleotides
• Polyisoprene
• Polyphosphates
• Silica
• Clays

• Proteins
• Rubber
• Polysaccharides
• Silica
• Clays

• Polyvinylics
• Polyesters
• Polyamide
• Polyurethanes
• Polyammides
• Polysulphone
• Polyethers
• Polysiloxanes
• Polyphosphazenes

Chemical Modification
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Typical stress-strain (?-e) plots for a rigid
plastic, a fibre, a flexible plastic, and an
elastomer
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Polymers Structure
Linear
Branched
Crosslinked
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Copolymers
Statistic
Alternating
Block
Repeating Units
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Positional Isomerism
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Microstructure in Chiral Polymers
Isotactic
Syndiotactic
Atactic
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Microstructure of Chiral Polymer in Planar
Zig-Zag Conformation
Isotactic
Syndiotactic
Atactic
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CH3
CH3
CH
O
CH2
CH
O
CH2


PPO
CH3
CH3
CH
C
O
CH
C
O


O
O
PLA
CH3
CH3
CH
C
O
CH
C
O
CH2


O
O
PHB
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Secondary Structure
Fully extended
Helical
Folded chain
Random coil
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Tertiary Structure
Folded chains
Spaghetti
Finged lamellae
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Molecular Weight Distribution in Polymeric
Materials
Polymer
Molecular weight
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Polymerization Processes
Chain Polymerization (Polyaddition)
Free Radical
Ionic Coordinate
Ionic
Anionic
Cationic
Anionic
Cationic
Step-wise Polymerization (Polycondensation)
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Criteria for Chain and Stepwise Reactions in
Polymer Synthesis
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Variation of Molecular Weight vs. Time in
Conventional and Controlled Radical Polymerization
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Polymer Processing Additives

• Physical Properties Modifiers
• Plasticizers
• Lubrificants
• Mold-release agents
• Macromolecular modifiers
• Reinforcing fillers
• Reinforcing agents
• Coupling agents
• Colorants brightening agents
• Chemical physical blowing agents
• Antistatic agents

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Polymer Processing Additives

• Antiaging Additives
• Heat stabilizers
• Antioxidants and metal ion deactivating agents
• Ultraviolet protecing agents
• Flame retardants
• Biocides

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Free Radical Polymerization

• Kinetic Scheme
• Initiation I 2R
• R M RM1
• Propagation RMi-1 M RMi
• Termination RMn RMm
• Chain Transfer Monomer (M), Initiator (I),
  Solvent (S)

ki
slow
k1
kp
ktc
RMn-MmR
ktd
RMn(-H)RMm (H)
I
S
1
1
Cs

CM CI
(?n)o
?n
M
M
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Polymers Produced by Radical Polymerization

• Homopolymers
• Polyethylene (LDPE)
• Polystyrene
• Poly(vinylchloride)
• Poly(vinylacetate)
• Poly(acrylonitrile)
• Poly(acrylamide)
• Poly(alkylacrylate)s
• Poly(vinylfluoride)
• Poly(tetrafluoroethylene)
• Poly(vinylidene fluoride)
• Poly(vinylpirrolydone)
• Poly(chloroprene)

• Copolymers
• Poly(styrene-co-acrylonitrile) (SAN)
• Poly(ethylene-co-vinylacetate) (EVA)
• Poly(styrene-co-butadiene) (SBR)
• Poly(acrylonitrile-co-butadiene) (NBR)
• Poly(styrene-alt-maleic anhydride)
• Poly(ethylene-alt-maleic anhydride)
• Poly(methylmethacrylate-co-methacrylic acid)

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Controlled Radical Polymerization (CRP) or Living
Free Radical Polymerization (LFRP)
P X
P - X
P X
Growing chain transient radical
Controller Persistent radical
Dormant chain
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Proposed Mechanism for TEMPO-Mediated Styrene
Controlled Polymerization Initiated by Benzoyl
Peroxide
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Proposed Mechanism for TEMPO-Mediated Styrene
Controlled Polymerization Initiated by Alkoxyamine
.
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ATOM Transfer Radical Polymerization (ATRP)

• Ingredients
• Monomer, Initiator RX (X CI, Br, SCN)
• Metal Ligand Adduct Me-L (Me Cu, Fe, Ni, Ru L
  Chelating amine)
• Radical Active Species Generated by Reversible
  Redox Process Catalyzed by Me

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Prof. K. Matyjaszewski
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Prof. K. Matyjaszewski
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Prof. K. Matyjaszewski
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Prof. K. Matyjaszewski
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Role of Biomaterials
Role of Biomaterials
Functional
Biostable
Biodegradable
Permanent Implant
Temporary Implant
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Biomaterial Selection Criteria

• Specific Surface Interactions
• Blood Contact
• Need to Bear a Load
• Structural Applications
• Degradation Propensity
• Permeability Responsiveness
• Solubility under Physiological Conditions
• Transparency Need
• Bioenvironmental Responsiveness

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Synthetic Polymeric Materials

• Biodegradable Synthetic Polymers
• Poly(alkylene ester)s
• PLA, PCL, PLGA
• Poly(aromatic/aliphatic ester)s
• Poly(amide-ester)s
• Poly(ester-urethane)s
• Polyanhydrides
• Polyphosphazenes

• Biostable Polymers
• Polyamides
• Polyurethanes
• Polyethylene
• Poly(vinylchloride)
• Poly(hydroxyethylmethacrylate)
• Poly(methylmethacrylate)
• Poly(tetrafluoroethylene)
• Poly(dimethyl siloxane)
• Poly(vinylalcohol)
• Poly(ethylenglycol)

• Stimuli Responsive
• Poly(ethylene oxide-co-propilene oxide)
• Poly(methylvinylether)
• Poly(N-alkyl acrylamide)s
• Poly(phosphazone)s

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Natural Polymeric Materials
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Environmentally Degradable Polymers (EDPs)

• Hydro-Biodegradable
• Functional Fragments
• CO2, H2O, Cell biomass

• Oxo-Biodegradable
• Oxidized Fragments
• CO2, H2O, Cell biomass

H2O - Uptake Enzyme mediated or not
O2 - Uptake Catalyst
Exo-Endo Enzymes
Exo-Endo Enzymes

• Polyesters
• Polyamides
• Polysaccharides

• Polyolefins
• Polyvinylalcohol
• Lignin

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Why Bioresorbable Materials in Medical/Pharmaceuti
cal Applications?

• Reasons for Choice
• No need for surgical removal
• No foreign-body reaction
• Help to regenerate tissues
• Provide better healing
• Conditions for Materials
• Non-toxic and biocompatible
• Processable
• Sterilizable
• Initial strength and dimensional stability
• Completely bioresorbed
• Bioresoption rate/strength decrease controlled

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Microbial Enzymatic Polyesters
Nature Works (PLA)
BIOMAX (PPDT)
BIONOLLE (PAE)
BIOPOL (PHA)
Biotech/Biobased Polyesters
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Biodegradable Functional Polyesters
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Racemic Glyceric Acid Derivatives
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Biodegradable Functional Polyesters
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Functional Polyesters
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Functional Polyesters
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Reactive and Functional Polymers
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Functional Polyesters Polycarbonates
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Functional Glycidyl Ethers
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Poly(esteramide)s
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Poly(b-thioester)s Poly(b-aminoesters)
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Bioresorbable Synthetic Polymers
POLYESTERS
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Conclusions

• A brief outline on what polymeric materials are
  and how they are obtained.
• Discoveries in an apparent mature area like
  polymer science technology have yet to be done.
• Revisiting of consolidate polymerization
  processes at the light of nanoscopic vision of
  matter will offer new challenging opportunities
  for the design and production of tailor-made
  polymeric materials and architectures.
• Blends and composites based on natural and
  synthetic polymers formulated under the vision of
  nanoscale interactions will offer good
  opportunity for the realization of items meant to
  be exploited in a very demanding area such as
  that of Biomaterials.