NanoHybridpolymerer Interessante muligheter for termo og herdeplaster Ferdinand Mnnle, Monika Pilz,

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Nano-HybridpolymererInteressante muligheter for
termo- og herdeplaster Ferdinand Männle,
Monika Pilz, Christian R. Simon, Susannah L.
Trevor, Huaitian Bu and Bjørn S. TanemSINTEF
Materials and Chemistry, P.O. Box 124 Blindern,
N-0373 Oslo, NorwayFerdinand.Mannle_at_sintef.no
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Content

• Organic inorganic hybrid polymers
• Synthesis
• Functionalisation
• Characterisation
• Application to polymer materials
• Modifier for epoxy products and coatings
• Barrier coatings
• Nanocomposites
• Summary
• Cost estimations
• Patents
• Outlook

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Content

• Organic inorganic hybrid polymers
• Synthesis
• Functionalisation
• Characterisation
• Application to polymer materials
• Modifier for epoxy products and coatings
• Barrier coatings
• Nanocomposites
• Summary
• Cost estimations
• Patents
• Outlook

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Organic Inorganic Hybrid Polymers
N
H
N
H
2
N
H
2
2
OEt
N
H
N
H
H
O
2
2
SiO
2
N
H
Si
OEt
1.5
2
N
H
N
H
- EtOH
2
OEt
2
N
H
N
H
Nanoparticles with amine groups (HAPS)
2
N
H
2
2
N
H
.
N
H
.
2
N
H
.
2
2
N
H
N
H
.
.

2
2
SiO
SiO
1.5
N
H
1.5
N
H
.
.
2
2
modification
N
H
N
H
.
.
N
H
2
2
.
2
Nanoparticles with modified amine goups (MHAPS)
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Synthesis of primary organic inorganic nano sized
hybridpolymer (HAPS)

• Controlled sol-gel reaction of 3-aminopropyl
  triethoxysilane (?-APS)

Hydrolysis Condensation
(?-APS)
HAPS SiO1.5X-NH2
(X -CH2CH2CH2-)
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Synthesis of modified organic inorganic nano
sized hybridpolymer (MHAPS)

• Functionalisation by modification

• Amine modified nanoparticles (HAPS)

• The building blocks of the nanoparticle
• A silica-based core
• An organic functional group
• The different building blocks may be varied in a
  number of ways depending on the application

SiO
Amide modified nanoparticles (MHAPS)
O
C
N
H
SiO
OH
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Function of hybridpolymers

• Cross-linker
• Adhesion promoter
• Lubricant

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Kind of hybridpolymers

• Selected qualities of MHAPS

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Characterisation of HAPS

• Particle size and size distribution
• average particle size of 3 nm
• nanoparticles

Nanosizer-ZS from Malvern Instruments Ltd.
measurements based on dynamic light scattering
(DLS)
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Characterisation of HAPS and MHAPS

• Molecular weight determination
• Gel Permeation Chromatography (GPC)
• or Size Exclusion Chromatography (SEC)

Mixture of fatty acids
r gyration radius nm M molecular weight
Da
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Characterisation of MHAPS

• TGA analysis
• of MHAPS-1

14wt loss due to residual solvent
30wt mineralized residue SiO2
hexanoic acid
Promising temperature stability up to 400
ºC indicates possibility to high temperature
applications (polymer processing)
TGA 10 mg heated from 30C to 190C at 20C/min
under N2 atmosphere 120 min at 190C then
heated from 190C to 900C at 20C/min. At 770C
atmosphere change to air
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Characterisation of MHAPS

• UV absorbing properties
• of MHAPS-3

transmittance spectra
salicylic acid
Visible light up to 430 nm is absorbed by
MHAPS preventing polymers from degradation
Quartz cell with 1 cm light path
length UV-Visible spectrophotometer in the
wavelength range from 300 to 800 nm
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Content

• Organic inorganic hybrid polymers
• Synthesis
• Functionalisation
• Characterisation
• Application to polymer materials
• Modifier for epoxy products and coatings
• Barrier coatings
• Nanocomposites
• Summary
• Cost estimations
• Patents
• Outlook

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Accelerating functional groups
Curing of epoxy products

• amide functional groups
• act as catalyst

• Addition of accelerating functional groups can
  increase reaction development
• improving the cure kinetics
• in epoxy resin systems

O
C
N
H
SiO
OH
Being bound into the networks minimises the
problems associated with such small molecules
such as leaching as is observed with commercially
used accelerators
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Multifunctional crosslinker
The amine functional groups act as crosslinking
sites
Convential crosslinker
Multi crosslinker
Increased functionality (f ) increased curing
rate
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Experimental procedures
salicylic acid

• During the curing
• Monitoring of thermal changes - gelation
  kinetics process rheometry - the complex
  viscosity and gel point

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Evolution of heat during curingunder adiabatic
conditions
Gelation Kinetics

• A insulated volume
• to retain exothermic reaction heat
• Addition of hardener with amine modified
  nanoparticles HAPS increases exothermic reaction
  extent and rate
• Greater extent of reaction with the addition of
  amide modified nanoparticles MHAPS
• Increase reactivity for fast cure applications

16g material in an insulated 30ml PP
container Thermocouple and temperature logging
device measured the heat evolution over 250 min
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Complex viscosity determination during
curingunder 26ºC, isothermal conditions
Gelation kinetics

• Thin layer at ambient temperature
• Significant reduction in gelation rate with
  addition of amide modified nanoparticles HAPS
• and greater rate of viscosity increase
• Increased reactivity for fast cure under low
  temperature (ambient) conditions

• Rheometry used to measure the shear elastic and
  loss moduli and complex viscosity of a thin layer
  of material between two parallel plates

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How to improve scratch resistance in coatings

• Improved cross-link of cure coatings
• Improved cross-link of inorganic nanoparticles
  and coating
• Improved adhesion between coating and
  thermoplastic by chosing the appropriate
  functionality
• Fatty acid modified hybridpolymer as lubricant

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Modification of epoxy coatings
Conventional epoxy
HAPS-modified epoxy
Nanoparticle modifier
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Modified epoxy coatings

• Wear and Scratch Resistance
• Light Stability

salicylic acid
High improvements in scratch resistance (pencil
hardness) light stability (yellowing
resistance)
Pencil hardness by Erichsen 318S Yellowing index
by Byk Gardner spectro-guide
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Nanoparticles as barrier layers

• Nanoparticles as barrier layers on thermoplastics
• Prohibit leakage of additives
• Reduce oxygen permeation
• Hinder oxidative degradation
• Provide UV protection
• Hinder hydrolysis
• Approved for indirect food contact
• Recyclable wihout separating coating and
  thermoplastic

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Barrier coatings on thermoplastics

• Development of nanoparticle-modified coatings
• applied on polymer-based packaging
• high industrial applicability due to good gas
  barrier, transparency, wear, photostability and
  cost efficiency

barrier coating
.
salicylic acid
20 µm
glycidyl methylacrylate
OTR cm3 O2/ m2day
150
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HDPE
120 µm
Compression moulded HDPE films Curing after
application of a barrier coating film 48h / 60
ºC OTR at standard conditions (23C/50RH) with
OX-TRAN Model 2/10
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Compounding into the thermoplastics

• Nanocomposites
• Improved cross-link triggered by a post-converter
  process (moisture, light, heat)
• Retention of dye-stuff, stabilizers and other
  functional additives
• Improved adhesion to coatings by compounds
  containing small amounts of hybridpolymer
• Fatty acid modified hybridpolymer as lubricant
  (self-lubrication)

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Application in thermoplastic polymers

• Thermal properties
• of hybridpolymer MHAPS-4 only
• of doped ethylene-octene copolymer film (50µm)

compounded in a Clextral extruder and extruded to
a tape
DSC melting endotherms / phase transitions
.
.
.
.
.
93ºC
ethylene-octene copolymer
SiO
.
1.5
.
.
.
.
35ºC salicylic amide groups
salicylic acid
behenic acid
60ºC behenic amide groups

• thermoplastic behaviour of the hybridpolymer

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Content

• Organic inorganic hybrid polymers
• Synthesis
• Functionalisation
• Characterisation
• Application to polymer materials
• Modifier for epoxy products and coatings
• Barrier coatings
• Nanocomposites
• Summary
• Cost estimations
• Patents
• Outlook

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Whats about the manufacturing costs?

• Main cost contribution caused by the silane
  about 10 EUR/kg. 1 kg silane yields about 0.5 kg
  HAPS
• Modification to MHAPS is done with low cost
  organic raw materials. Mass ratio between primary
  particles and organic modifiers usually 12 or
  higher.
• A typical modification of 0.5 kg primary
  nanoparticles (10 EUR) with 1 kg organic modifier
  (2-3 EUR) yields 1.5 kg modified nanoparticles
  for about 9 EUR/kg (including process costs)

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Patented technology

• EPOXY RESIN CURING AGENT FOR ENHANCED WEAR
  RESISTANCE AND WEATHERABILITY OF CURED MATERIALS
  
• Publication number WO2004035675
• Publication date 2004-04-29
• Inventor SIMON CHRISTIAN (FR) MAENNLE
  FERDINAND (DE) BEYLICH JEST (NO)
• GAARDER RUNE H (NO) WINDSLAND KJELL (NO)
  REDFORD KEITH (UK)
• METHOD FOR THE MANUFACTURE OF POLYBRANCHED
  ORGANIC/INORGANIC HYBRID POLYMERS
• Publication number WO2005100450
• Publication date 2005-10-27
• Inventor MAENNLE FERDINAND (DE) SIMON
  CHRISTIAN (FR) BEYLICH JEST (NO) REDFORD KEITH
  (UK) SOMMER BRITT (NO) HINRICHSEN EINAR (NO)
  ANDREASSEN ERIK (NO) OLAFSEN KJELL (NO)
  DIDRIKSEN TERJE (NO)
• POLYBRANCHED, ORGANIC / INORGANIC HYBRID POLYMER
  AND METHOD FOR ITS MANUFACTURE
• Publication number WO2005100449
• Publication date 2005-10-27
• Inventor MAENNLE FERDINAND (DE) SIMON
  CHRISTIAN (FR) BEYLICH JEST (NO) REDFORD KEITH
  (UK)

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Patented technology

• POLYMER COMPOSITION
• Publication number WO2005100469
• Publication date 2005-10-27
• Inventor MAENNLE FERDINAND (DE) SIMON
  CHRISTIAN (FR) BEYLICH JEST (NO) HAUGE ROGER
  (NO) KLEPPE EMIL ARNE (NO) ROEDSETH KAARE ROGER
  (NO) LARSEN AAGE GELLEIN (NO)
• LIGHT PROTECTIVE ADDITIVE BASED ON ORGANIC/
  INORGANIC HYBRID POLYMER, METHOD FOR ITS
  MANUFACTURE AND USE THEREOF
• Publication number WO2007053024
• Publication date 2007-05-10
• Inventor MAENNLE FERDINAND (DE) ROEDSETH KAARE
  ROGER (NO) BU HUAITIAN (CN)

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Outlook

• Hybridpolymer can be a valuable tool for
  improving properties of polymer composites
• Hybridpolymers will act as multifunctinal
  crosslinker in epoxy coatings by improving
  reactivity
• Hybridpolymers can be applied in coatings for
  thermoplastics or directly in thermoplastics
• The tool has to be adjusted for the targeted
  applications
• It is NOT a finished product or ready-to-use
  additive
• This technology will provide cost-effective
  solutions for large bulk polymer products