Upload
toine-dinnissen
View
776
Download
5
Embed Size (px)
Citation preview
EPOXY PRODUCTS FOR HIGHEPOXY PRODUCTS FOR HIGHPERFORMANCE COMPOSITESPERFORMANCE COMPOSITES
KompozytKompozyt--expo 25expo 25--26 November 2015;26 November 2015; KrakowieKrakowie
Toine Dinnissen; Technical Service Manager CEE, CIS and ItalyToine Dinnissen; Technical Service Manager CEE, CIS and ItalyToine Dinnissen; Technical Service Manager CEE, CIS and ItalyToine Dinnissen; Technical Service Manager CEE, CIS and Italy
[email protected]@OlinBC.com
™ Trademark of Olin Corporation
OUTLINEOUTLINEOlin CorporationOlin Corporation
Composites; Why and What ?Composites; Why and What ?Composites; Why and What ?Composites; Why and What ?
BisphenolBisphenol--A Epoxy ResinsA Epoxy Resins
AccelerationAcceleration
High Glass TransitionHigh Glass Transition
Epoxy Novolac ResinsEpoxy Novolac Resins
New Epoxy Novolac ResinNew Epoxy Novolac Resin
“Burning“Burning--topic” ???topic” ???
™ Trademark of Olin Corporation
New Olin
BLUE CUBEBLUE CUBE
EpoxyСhlor.Org
Cl, NaOH in US
Chlor-Alkali productschlorine, caustic, bleach etc.
Chemical DistributionWinchester ammunitionCl, NaOH in US Winchester ammunition
™ Trademark of Olin Corporation
New Olin
Olin / Blue Cube “merger” will triple Olin’s annual revenues
™ Trademark of Olin Corporation
Integrated Business Model
HardenersCausticCaustic
WaterTreatmentPolymers Civil Engineering
Dis
trib
uto
rs
AllylChloride EPI
LiquidEpoxy
SpecialtyEpoxies
Blends
Hardeners
Solid/SolidSolutions
Brominated
CumeneCumene
AcetoneBenzeneBenzene
Phenol BPA
CausticCaustic
PropylenePropylene
ChlorineChlorine
Adhesives
Coatings.
Composites
Electronics
Poly-carbonate
Dis
trib
uto
rsF
orm
ula
tors
BrominatedEpoxies
BenzeneBenzene Electronics
Olin upstream and downstream of epoxies
Core Olin epoxy products
External downstream
Fo
rmu
lato
rs
™ Trademark of Olin Corporation
Global Epoxy Business
Pisticci
Rheinmuenster
Stade
Baltringen
Gumi
ShanghaiFreeport
Zhangjiagang
Horgen
Roberta
Epoxy Manufacturing Site
R&D Center
Technical Service Center
Guaruja
Zhangjiagang
Sao Paulo
™ Trademark of Olin Corporation
COMPOSITESCOMPOSITESCOMPOSITESCOMPOSITESWhy and WhatWhy and What
™ Trademark of Olin Corporation
Mechanical Properties Comparison
Black Steel Stainless Steel316
Hastelloy® C GRP
(Mat & Roving)
Density [gr/cm3] 7.8 7.9 8.9 1.5
Tensile Modulus [GPa] 207 193 180 10-15
Tensile Strength [MPa] 450 590 550 120-250Tensile Strength [MPa] 450 590 550 120-250
Heat Conductivity [W/mºC] 46 15 12 0.2
Thermal ExpansionCoefficient
[mm/mm ºC]x10-6
12 16 12 23
PE PP PVC PVDF GRP
Density [gr/cm3] 0.95 0.90 1.4 1.75 1.5Density [gr/cm ] 0.95 0.90 1.4 1.75 1.5
Tensile Modulus [MPa] 80 80-130 300-350 1200 10,000-15,000
Tensile Strength [MPa] 30 30 60 50 120-250
Heat Distortion
Temperature [ºC]
40 45 75-100 90 100-200
All data are typical data and not to be construed as specifications
™ Trademark of Olin Corporation
Fibre Reinforced Composites
Property Epoxy Unsaturated Polyester (UPR) andEpoxy Vinyl Ester Resin (EVER)
Phenolic
Cure mechanism Polymerization of resinplus hardener
Catalyticcopolymerization
CondensationPolymerization
(produces water)
Wet impregnation, typicalsystem
Liquid resins plus amineor other hardeners
Styrene-modified resins plus peroxidecatalysts
Liquid phenolics plus acidcatalysts
Cure temperature (°C) 25-150 25-100 25-170
Typical cure time (min) 60-180 10-60 60-180
Stability of resin (alone) Excellent Fair Poor
Cure-shrinkage of system Low (2-3%) High (6-8%) High
Adhesion to metal Excellent Fair Fair
Physical properties of Excellent Excellent Excellent/Bad (best heatPhysical properties ofcured laminate
Excellent Excellent Excellent/Bad (best heatresistance, most brittle)
All data are typical dataand not to be construedas specifications
™ Trademark of Olin Corporation
Epoxy versus Polyester
• In all high performance Fiber Reinforced Plastic applications EPOXY binders are the“state of the art” (Aircraft, Aerospace, Racing boats/kayaks/cars/surf/snow-boards, skies, largewindmill blades,…..)
• WHY ? Best value for money !–(cost of the binder is relatively small versus cost of the finished object)
• EP binder systems have Performance Advantages over PE in 5 major areas:
better adhesion,
best mechanical properties (particularly strength and stiffness),
improved resistance to fatigue and micro cracking, improved resistance to fatigue and micro cracking,
low degradation (diminution of properties) from water penetration,
best resistance to osmosis (surface degradation due to water permeability)
™ Trademark of Olin Corporation
Adhesion
Epoxy Resin have far better adhesion than unsaturated Polyesters
* polar hydroxyl- (for each epoxy group) and ether-groups improve adhesion
* low shrinkage* low shrinkage
More homogeneous bond between fibers and binder and better transfer of loadbetween different components
High adhesion is very important in resisting micro-cracking
Bond between core and binder is usually the weak link
™ Trademark of Olin Corporation
Mechanical Properties
• Tensile Strength and Stiffness Data freely available ex. INTERnet
Room temperature cured Epoxy = 20-30% stronger than Polyester. After post-curethe difference becomes even bigger. Polyester boats typically are not post-curedthe difference becomes even bigger. Polyester boats typically are not post-curedwhereas epoxy boats are. Polyester boats often “post-cure” in service.
Consequences;• Initial almost double strength of post-cured EP boats versus non Post Cured PE• Cosmetics;
•Volume shrinkage epoxy about 2 % immediately•PE volume shrinkage up to 7% over longer period, print through effect
™ Trademark of Olin Corporation
Fatigue Resistance & Micro-cracking
• Maximum Strength is not the sole criteria,such load is seldom applied to for instancea hull.
• Micro-cracking occurs well before reachingultimate strengthultimate strength
• Loss of adhesion between binder andfibers
• Cracking away from the fibers = transversemicro-cracking
• Strain that a composite can take beforemicro-cracking will depend on adhesionand toughness
Typical binder Stress/Strain curves(Post-cured for 5 hours at 80 °C)
• Superior ability to withstand cyclic loadingis THE main advantage of Epoxy bindersystems over Polyester binder system. Thisis the reason that in high demandingapplication exclusively epoxy binders areused.
™ Trademark of Olin Corporation
Degradation from Water
• All resin will absorb moisture
• increase of weight
• affects resin-fiber bonds = gradual /long term loss of mechanical properties
• Polyester (and vinyl-ester) give hydrolysis of ester linkages
• thin PE laminates retains only 65% of its inter-laminar shear strength over a period of one year• thin PE laminates retains only 65% of its inter-laminar shear strength over a period of one year
• epoxy resins under similar conditions will retain >90% of its initial properties.
™ Trademark of Olin Corporation
Osmosis
• All resin will absorb moisture that will;
• react with hydrolysable components,
• dissolves un-reacted components (catalysts,…)
• Tiny “cells” of concentrated solution are formed.
• Osmotic pressure “pull” extra water to the cells (to dilute the salts)• Osmotic pressure “pull” extra water to the cells (to dilute the salts)
• Pressure in the cells will increase
– Chicken-pox (=blistering)
• Polyester (and vinyl-ester) give high risk hydrolysis of ester linkages
• Epoxy has low water transmission rate and high water resistance
™ Trademark of Olin Corporation
Epoxy versus Polyester
•Epoxy Resin
•Bonding Strength 2000 psi
•Tough Binder
•Low moisture absorption
•Epoxy Vinylester Resin
•Bonding Strength 500 psi
•Intermediate moisture absorption
•Unsaturated Polyester•Bonding Strength <<500 psi•Not tough, fractures easily = micro-cracking
•High moisture absorption•Low moisture absorption(low osmotic blistering)
•Low Shrinkage (very goodappearance)
•Very high adhesion to all sorts offibers (glass, carbon, kevlar,…)
•Intermediate moisture absorption
•Contains Styrene (EH&S)
•Cure sensitive to moisture andtemperature
•Difficulties bonding dissimilar or
•High moisture absorption(high osmotic blistering)
•Highest shrinkage
•Bonding to glass, not for carbon,•Very high adhesion to all sorts offibers (glass, carbon, kevlar,…)
•Very good bonding to dissimilar oralready cured material (repairsystems)
•Versatile and “State of the Art”
•Difficulties bonding dissimilar oralready cured material. (good forglass, less for carbon, kevlar,…)
•Cheaper than Epoxy
•Bonding to glass, not for carbon,kevlar,…
•Cheapest Resin•“Cheap Stuff”
™ Trademark of Olin Corporation
Epoxy Products in Composites
• Features:
– Excellent adhesion to many (difficult) substrates
– Low shrinkage upon cure
– Excellent Chemical Resistance– Excellent Chemical Resistance
– Excellent Mechanical Properties
– Good Heat Resistance
– …
• Often used to produce light weight composite parts that can replace metalarticles.
• e.g. FRP pipes, automotive parts, storage tanks, wind-mill blades, ….• e.g. FRP pipes, automotive parts, storage tanks, wind-mill blades, ….
™ Trademark of Olin Corporation
BISPHENOLBISPHENOL--A EPOXY RESINA EPOXY RESINBISPHENOLBISPHENOL--A EPOXY RESINA EPOXY RESINDescriptionDescription
PortfolioPortfolio
Fast CureFast Cure
High Temperature ResistanceHigh Temperature Resistance
™ Trademark of Olin Corporation
Crude Oil Brine Salt
Naphta Electrolysis
Epoxy Resin Route
Benzene Propylene CL2 NaOH
Cumene Allylchloride
Acetone Phenol
EpichlorohydrinBisphenol-A
OH O
OHHO
OOH
HOClCa(OH)2
C l
ClO
EpichlorohydrinBisphenol-A
Polycarbonate Epoxy Resins
OHHO ClO
™ Trademark of Olin Corporation
Standard Bisphenol-A epoxy resin
Bisphenol A(A = Acetone)
Epichlorohydrin
OCl
Epichlorohydrin
OCl
OHHO
(A = Acetone)
OOO O
DGEBA = Diglycidylether of Bisphenol A
BADGE = Bisphenol-A Diglycidylether
LER = standard liquid epoxy resin D.E.R.™ 33X-series
Viscosity = ± 4000 mPa.s
O O
™ Trademark of Olin Corporation
High Molecular Weight Species
ClO
+
OHHO
Diglycidyl ether of bisphenol A (DGEBA)
Resin n=0
NaOHOO
O O
OOO
OO
Typically between 5 and 15%
Diglycidyl ether of bisphenol A - Oligomer
NaOH
n=1,2,3...
Increase in viscosity
OO
OHO
OOO
n
™ Trademark of Olin Corporation
Mono-Hydrolyzed Resin (alpha-glycol)
Diglycidyl ether of bisphenol A (DGEBA)
OOO O
O OHCl
O
O H
Monohydrolyzed Resin (MHR)
H2O
1,2-Diol / α-GlycolfunctionOO
OH
OHO
Monohydrolyzed Resin (MHR)
Increase in viscosityIncrease in OH groups – can have impact on wetting, adhesion and reactivityDecrease in Epoxy Functionality
Typically between 0.1 and 5%
™ Trademark of Olin Corporation
Depending on the process conditions used, theLER will have different composition and properties.Side reactions will decrease the epoxy contentreduced functionality !) and affect resin properties
Liquid Epoxy Resin Composition
reduced functionality !) and affect resin propertiessuch as viscosity, reactivity, wetting, adhesion.
Side reactions/products include:
•Higher oligomer formation•Hydrolysis of epoxy groups (MHR)•Total Chlorine•Total Chlorine
•Epichlorohydrin•Ionic chloride•incomplete dehydrochlorination (HyCl)•formation of bound chlorides
™ Trademark of Olin Corporation
Bisphenol-A Liquid Epoxy Resins
D.E.R.™ 332Epoxy Resin
D.E.R. 330Epoxy Resin
D.E.R. 331™Epoxy Resin
Epoxide Equivalent Weight [gr/eq]A.S.T.M. D-1652
171 – 175 176 - 185 182 – 192
Viscosity @ 25 °C [mPa.s] 4000 – 6000 7000 - 10000 11000 - 14000Viscosity @ 25 °C [mPa.s]A.S.T.M. D-445
4000 – 6000 7000 - 10000 11000 - 14000
340 / average EEW 1.97 1.89 1.82
Mix with D.E.H.™ 24 hardener [phr] 14.0 13.5 13.0
Mix-viscosity @ 25 °C [mPa.s] 900 1250 2250
Time to gel, 500 grams [min] 43 40 25
Heat Deflection Temperature [°C] 107 104 111
with Nadic-Methyl-Anhydride [°C] 156
with BF3-MEA [°C] 168
™ Trademark of Olin Corporation
Bisphenol-A Liquid Epoxy Resins
Resin D.E.R.™ 330 Epoxy Resin D.E.R. 331™ Epoxy Resin
D.E.H.™ 24 Hardener wt% Change wt% Change
Days; 7 28 120 7 28 120
Sulfuric Acid (30%) 0.56 1.24 2.85 0.69 1.80 3.10Sulfuric Acid (30%) 0.56 1.24 2.85 0.69 1.80 3.10
Acetone 0.17 0.74 4.48 0.45 2.10 7.70
Sodium Hydroxide (50%) 0.00 -0.06 -0.11 0.00 0.04 0.02
Jet-fuel 0.03 -0.01 0.09 0.02 -0,01 0.09
Distilled Water 0.40 0.79 1.68 0.41 0.88 1.70
Thermal Degradation
Hours 100 200 300 500 100 200 300 500Hours 100 200 300 500 100 200 300 500
weight loss @ 160 °C 0.95 0.95 1.32 1.41 0.71 1.00 1.40 1.60
weight loss @ 210 °C 2.11 3.77 7.39 3.40 5.40 6.80 7.80
™ Trademark of Olin Corporation
NEW INNOVATIONNEW INNOVATIONNEW INNOVATIONNEW INNOVATIONFast CureFast Cure
™ Trademark of Olin Corporation
Accelerated Epoxy Resins
EEW onsolids
[gr/eq]
Viscosity @25 °C
[mPa.s]
Description
D.E.R.™ 3411 epoxy resin 185 – 205 4500 – 5500 Very fast curing modified bisphenol-A/F liquid epoxy resinD.E.R.™ 3411 epoxy resin 185 – 205 4500 – 5500 Very fast curing modified bisphenol-A/F liquid epoxy resinwithout reactive diluent. Is suitable for fast setting, lowtemperature curing systems as crystallization resistant startingbase resin.
D.E.R. 3412 epoxy resin 187 – 207 850 – 1150 Very fast curing di-functional reactive diluent modifiedbisphenol-A/F liquid epoxy resin. Is suitable for crystallizationresistant, fast setting, low temperature curing epoxy bindersystems.
D.E.R. 3414 epoxy resin 190 – 210 2500 – 4500 Master-batch accelerated Bisphenol-A epoxy resin. Activationabove 50°C. Designed for fast, heat curing composites.
D.E.R. 3415 epoxy resin 190 – 210 2500 – 4500 Master-batch accelerated Bisphenol-A epoxy resin. Active atroom temperature. Especially suitable for low temperaturecuring epoxy binder systems in civil engineering and coatingapplications or for fast curing composites.
™ Trademark of Olin Corporation
D.E.R.™ 3414 epoxy resin
70
80
90
100
100% D.E.R.™ 330 epoxy resin
95% D.E.R. 330 + 5% D.E.R. 3414
90% D.E.R. 330 + 10% D.E.R. 3414
22
0
10
20
30
40
50
60
70
%F.S
.
90% D.E.R. 330 + 10% D.E.R. 3414
80% D.E.R. 330 + 20% D.E.R. 3414
00 50 100 150 200 250 300
Gel-time [min]
Gel-times; resp. 262, 69, 39 and 22 minutes
at Room Temperature with IPD
™ Trademark of Olin Corporation
Formulations [pbw] A B C
D.E.R.™ 330 epoxy resin 85 70 55
D.E.R. 3415 epoxy resin 15 30 45
D.E.R.™ 3414 epoxy resin
IPDA (not optimized level) 27 27 27
Tg, °C (4.5 min @ 90 °C) 38 47 49
Tg, °C (5.5 min @ 90 °C) 45 51 53
Tg, °C (6.5 min @ 90 °C) 55 62 63
Tg, °C (7.5 min @ 90 °C) 58 63 67
• D.E.R. 3415 is a bisphenol-A based epoxy resin modified with a catalyst which can be activated• D.E.R. 3415 is a bisphenol-A based epoxy resin modified with a catalyst which can be activatedat temperature above 50°C while maintaining very good pot life at ambient temperature
• It can be blended with any other epoxy resins (either aromatic and aliphatic)
• It is compatible with most of the amine curing agents (aromatic and aliphatic amines)
• It can be used to adjust the reactivity of different amine curing systems by adding differentlevels into the curing systems
™ Trademark of Olin Corporation
NEW INNOVATIONNEW INNOVATIONNEW INNOVATIONNEW INNOVATIONHigh TemperatureHigh Temperature
™ Trademark of Olin Corporation
High(er) Temperature Resistance
4,4'-Methylenedianiline (MDA) is a suspectedcarcinogen. It is included in the "substances of veryhigh concern" list of the European Chemicals Agency(ECHA).
Pure methylenedianiline is a highly toxic, colorless solid.
May be fatal if swallowed, inhaled or absorbed
DiethyleneTolueneDiamine
May be fatal if swallowed, inhaled or absorbedthrough skin. Causes irritation to the skin, eyes andrespiratory tract. Combustible solid or liquid when heated.May cause methemoglobinemia. Affects blood,cardiovascular system, central nervous system, liver andkidneys and may cause cancer.
Ancamine DL-50 (MDA-blend)Highly viscous / solid = light to dark brown @ 50,000 - 55,000 mPa.s (AHEW = 51 gr/eq)
DETDALow viscosity liquid = clear amber liquid @ 100 - 200 mPa.s (AHEW = 46 gr/eq)
Need 10% less per 100 kilo epoxyMuch lower viscosity = allows blending and use at muchlower temperatures (room temperature)
™ Trademark of Olin Corporation
D.E.H.™ 650 Curing Agent
™ Trademark of Olin Corporation
Labeling according to EC Directives:Hazard Symbol: Xn - Harmful
N - Dangerous to the EnvironmentRisk Phrases: R 21/22 - Harmful in contact with skin and if swallowed.
R 48/22 - Harmful: danger of serious damage to health by prolonged exposure if swallowedR 36 - Irritating to eyes.R 50/5 - very toxic to aquatic organisms, may cause long-term adverse effect in aquatic environment
D.E.H.™ 650 Curing Agent
ASTM D-7903 point Flex
MDA Ref. D.E.H.™ 650
Tg (DSC, °C) 167 178
Flexural Strength[MPa]
110 116
Modulus [MPa] 2707 3137
Strain [%] 8.3 6.3
D.E.H.™ 650 hardener @ 37 °C
Strain [%] 8.3 6.3
Stress @ Break[MPa]
106 116
K1c FractureToughness
0.76 0.61
Pot-life 150 grams
MDA-reference @ 57 °C
™ Trademark of Olin Corporation
EPOXY NOVOLAC RESINSEPOXY NOVOLAC RESINSEPOXY NOVOLAC RESINSEPOXY NOVOLAC RESINSHigh Temperature and ChemicalHigh Temperature and ChemicalResistance CompositesResistance Composites
™ Trademark of Olin Corporation
Bisphenol-F epoxy resin and Epoxy Novolac
Liquid bisphenol A epoxy resin
A ≡ Acetone
Liquid bisphenol F epoxy resin
F ≡ Formaldehyde
OO
OO
OOO O O
bisphenol A bisphenol-Fepoxy resin epoxy resin
Mw 340 312
EEW 170 156
Viscosity 10,000 4,000
O O O
O
O
O
O
ortho - para
O
O
O
O
ortho - ortho
O O O
n
OO
OHO
OOO
bisphenol A bisphenol-Fresin resin
Mw for n = 1 624 442
EEW 312 147
Average Functionality ???
™ Trademark of Olin Corporation
Dow Epoxy Novolac Resins
Epoxy Novolac Resins EEWon solids[gr/eq]
Viscosity@ 25 °C[mPa.s]
Description
D.E.N.™ 425 Epoxy Novolac 169 – 175 9500 – 12500 D.E.N. 425 liquid epoxy novolac resin fills the gap between bisphenol F epoxyresins and viscous epoxy novolac resins. Its multi-functionality (± 2.5) producesa tightly cross-linked network, yielding improved resistance against variousa tightly cross-linked network, yielding improved resistance against variouschemicals. Unlike other epoxy novolac resins, this grade does not necessarilyrequire post cure.
D.E.N. 431 Epoxy Novolac 172 – 179 1100 – 1700@ 51.7°C
D.E.N. 431 epoxy novolac resin has multi-epoxy functionality (± 2.8) whichmakes it useful in adhesives, electrical and structural laminates, coatings andcastings for elevated temperature service. Where the higher viscosity of D.E.N.438 epoxy novolac resin cannot be tolerated.
D.E.N. 438™ Epoxy Novolac 176 – 181 31000 – 40000@ 51.7 °C
D.E.N. 438 epoxy novolac resin is a widely used general purpose epoxy novolacresin. It is recognized as a standard for high temperature applications. D.E.N.438 has multi- epoxy functionality (± 3.6) and exhibits high chemicalresistance and excellent elevated temperature performance. Adhesives basedon D.E.N. 431 are ideal binders for abrasives in grinding and polishing products.
D.E.N. 439 Epoxy Novolac 191 – 210 15000 – 35000 D.E.N. 439 epoxy novolac resin is a widely used general purpose epoxy novolacD.E.N. 439 Epoxy Novolac 191 – 210 15000 – 35000@ 71°C
D.E.N. 439 epoxy novolac resin is a widely used general purpose epoxy novolacresin. D.E.N. 439 has multi-epoxy functionality (±3.8) which is slightly morereactive than D.E.N. 438 epoxy novolac resin.
D.E.N. 440 Epoxy Novolac 186 – 192 35000 – 70000@ 71°C
D.E.N. 440 epoxy novolac resin is an extremely high functional (± 4.4) epoxynovolac resin. Offers highest performance in this product group with regards tomechanical, temperature and chemical resistance properties.
™ Trademark of Olin Corporation
Higher epoxy functionality ===> Higher crosslink densityExcellent solvent/chemical resistance.Higher Temperature ResistanceGel at lower conversion
D.E.N.™ 438™ Epoxy Novolac Resin
Resin
NMA
days 7 28 120 7 28 120
Sulfuric Acid (30%) 0.44 0.68 0.77 0.33 0.83 0.55
Hydrochloric Acid (36%) 0.24 0.60 1.50 0.32 0.56 1.36
Nitric Acid (40%) 0.59 1.37 3.11 0.40 1.10 1.70
Ammonium Hydroxide (28%) 0.77 1.31 1.92 0.67 1.24 1.84
D.E.N.™438™ D.E.R.™ 331™
(wt% change) (wt% change)
For high temperatureand /or chemicalresistance propertiesAmmonium Hydroxide (28%) 0.77 1.31 1.92 0.67 1.24 1.84
Acetic Acid (25%) 0.57 0.93 1.12 0.46 0.73 0.90
Acetone 0.24 1.15 5.07 4.80 13.00 22.30
Toluene 0.07 0.14 0.32 0.06 0.09 0.28
Sodium Hydroxide (10%) 0.42 0.64 0.64 0.37 0.51 0.50
JP4 Fuel 0.00 0.01 0.12 0.02 0.02 0.16
Distilled water 0.55 0.97 1.13 0.52 0.82 0.87
resistance propertiesDow Epoxy Novolacresins are the bestchoice.
D.E.N.™438™ Epoxy Novolac Resin
All data are typical data and not to be construed as specifications
D.E.N.™438™ Epoxy Novolac Resin
Epoxy Equivalent Weight [gr/eq] 176 - 181Viscosity @ 52°C [mPa.s] 31000 - 40000
™ Trademark of Olin Corporation
300
Glass Transition Temperature
MTPHA
Resin D.E.N.™438™ D.E.R.™331™
Curing Agent
Temperature Hours
160 °C 100 0.11 0.36
200 0.08 0.48
300 0.10 0.71
BF3 * MEA
% Weight LossAll data are typical dataand not to be construedas specifications
D.E.N.™ 438™ Epoxy Novolac Resin
100
150
200
250
[°C]
MTPHA
DiCy
NMA
DETDA
DDS
BF3*MEA
300 0.10 0.71
500 0.05 0.86
210 °C 100 1.73 2.60
200 2.97 4.00
300 3.82 4.90
500 5.02 5.50
260 °C 100 11.30 19.60
200 13.15 D
0
50
D.E.R.™330 D.E.N.™438™
™ Trademark of Olin Corporation
MTHPA versus DETDA
D.E.H.™ 70 curing agent D.E.H. 650 curing agent
Resin D.E.R.™ 330 D.E.N.™ 438™ D.E.R.™ 330 D.E.N.™ 438™
EEW [gr/eq] 176 – 185 176 - 181 176 – 185 176 - 181
Mix-ratio [phr] D.E.H. 70 / MI85 / 1
D.E.H. 70 / MI85 / 1
26.0 26.385 / 1 85 / 1
Cure Schedule; Hours @ °C 2 hrs @ 85 °C3 hrs @ 150 °C
2 hrs @ 85 °C2 hrs @ 150°C2 hrs @ 200 °C
2 hrs @ 120 °C2 hrs @ 177 °C
2 hrs @ 120 °C2 hrs @ 177°C2 hrs @ 225 °C
Glass Transition Temperature [°C] 148 149 182 220
Coefficient of Linear Expansion [ppm/°C] 70 66 74 69
Water Absorption, 2 weeks boil [%] 1.45 1.49 2.35 2.47
Flexural Strength [MPa] 128 138 108 110
Flexural Modulus [GPa] 3.27 3.51 2.64 3.06
Strain @ Yield [%] 6.7 6.7 6.9 6.1
Cured density [gr/cm3] 1.190 1.224 1.140 1.210
™ Trademark of Olin Corporation
• Gelation is Controlled by Functionality
Carothers: % Cure @ Gel Ξ 2 / favg
Flory: % Cure @ Gel Ξ 1
[1 + (f-2)]1/2
Gel-point can be Predicted
• Gelation is Controlled by Functionality
react 3 moles of D.E.R.™330 epoxy resin = 6 reactive groupswith 2 moles of amino-ethyl piperazine = 6 reactive groupsaverage functionality = 12 groups / 5 mole = 2.4
Gel Point ~ 2/2.4 ~ 83% cure at Gel
react 7 moles of D.E.R.™330 epoxy resin = 14 reactive groupswith 2 moles of tetra-ethylene-pentamine = 14 reactive groupsaverage functionality = 28 groups / 9 mole = 3.11
Gel Point ~ 2/3.11 ~ 64% cure at GelGel Point ~ 2/3.11 ~ 64% cure at Gel
react 14 moles of D.E.N.™425 epoxy resin = 35 reactive groupswith 5 moles of tetra-ethylene-pentamine = 35 reactive groupsaverage functionality = 70 groups / 19 mole = 3.68
Gel Point ~ 2/3.68 ~ 54% cure at Gel
Higher Functionality is Early Mould Release
™ Trademark of Olin Corporation
NEW INNOVATIONNEW INNOVATIONNEW INNOVATIONNEW INNOVATIONEven Higher…Even Higher…
™ Trademark of Olin Corporation
Opportunity Statement
D.E.N.™ 440 epoxy novolac resin, a differentiated Epoxy Phenol Novolac designed for improved hightemperature applications. The product offers higher functionality (F±4.5) to form tightly cross linkednetwork that shows higher Tg and improved chemical resistance. Hot melt (solvent-free) prepreg andadhesive makers will also benefit from its’ low melt viscosity and improved tackiness.
Technical Hypothesis: Higher Tg leads to higher heat deflection temperature (HDT), which isgenerally desired in hotmelt prepreg to reduce production-cycle time. Low melt viscosityand improved tackiness enhance the process-ability.
™ Trademark of Olin Corporation
D.E.N.™ 438™ Epoxy Novolac Resinversus
D.E.N. 440 Epoxy Novolac Resin
Part A D.E.N.™ 438™ Epoxy Novolac D.E.N. 440 Epoxy Novolac
Epoxy Resin 80.2 80.2Epoxy Resin 80.2 80.2
Part B
D.E.N. 431 Epoxy Novolac 19.8 19.8
DICY 5.6 5.6
UREA 2.8 2.8
Uncured rheology properties
η* @ 80oC (Pa*s) 1.5 6.4
G* @ 1rad/s (MPa@25°C)) 0.005 0.21
Cured polymer propertiesCured polymer properties
Tonset (oC) 117 117
Tg (oC)160oC cured 193 215Flexure Modulus (GPa) *2.93 *3.53
KIC (MPa*m0.5) *0.58 *0.52
™ Trademark of Olin Corporation
D.E.N.™ 440 Epoxy Novolac Resin vs e-BPAN
Part ABisphenol A resin eBPAN
D.E.N.™ 440Epoxy Novolac
Variable resin 16 16
D.E.R™ 383 Liquid Epoxy Resin 32.1 25.7 25.7
D.E.R. 662 Solid Epoxy Resin 48.1 38.5 38.5D.E.R. 662 Solid Epoxy Resin 48.1 38.5 38.5
Part B
D.E.N. 431 Epoxy Novolac Resin 19.8 19.8 19.8
DICY 5.6 5.6 5.6
UREA 2.8 2.8 2.8
Uncured rheology properties
G* @ 1rad/s (MPa@ 25°C)) 0.07 0.22 0.07
η* @ 80oC (Pa*s) 9.2 11.4 7.4
Cured polymer propertiesCured polymer properties
Tonset (oC) 118 117 118
Tg (oC)140oC cured 136 152 149
Flexure Modulus (GPa) 3.14 3.08 3.27
KIC (MPa*m0.5) 1.02 0.85 0.85
™ Trademark of Olin Corporation
Competitive Situation
• DEN 440 shows higher Tg than that ofEOCN and DEN 438, but similar to eBPAN
• Epon SU8 is one of the eBPANs which ispopular in NA, while presence of KEB 3165is mainly in APAC. Viscosity is very highis mainly in APAC. Viscosity is very high
• THPEGE shows superior performance withhigher price (>2 times).
Materials Suppliers Comments
EOCN-
1020-55Nippon Epoxy Cresol Novolac
Epalloy-
9000CVC
Tris-Hydroxy Phenyl
Ethane Triglycidyl Ether9000
CVC Ethane Triglycidyl Ether
(THPE-GE)
Epon SU-8 Hexion Epoxy Bis-Phenol A
Novolac, (eBPAN) high
functionality SERKEB-3165 Kolon
™ Trademark of Olin Corporation
NEW INNOVATIONNEW INNOVATIONNEW INNOVATIONNEW INNOVATIONBurning hot development…Burning hot development…
™ Trademark of Olin Corporation
Flame Retardancy
• Aluminum Trihydrate
• Phosphorous Compounds
VE1021224M3 VE102124M1
Viscosity @ 25 °C [mPa.s] 9100 1400• Phosphorous Compounds
• need a lot and give high viscosity
• Brominated Epoxy Resins
• Solid (about 40% Bromine)
• Solid in Solution (about 20% Bromine)
EEW [gr/eq] 199 164
% Bromine 24.5 15.2
• NEW Liquid Brominated Epoxy Resin
™ Trademark of Olin Corporation
Olin Epoxy Portfolio comprises;
The Epoxy business of the Olin Corporation is Committed and Reliable partners for our Clients
• High Quality standard Raw Materials
• D.E.R™ 33x epoxy resins
• D.E.N.™ 43x epoxy novolac resins
• D.E.H.™ curing agents (incl. D.E.H. 70 anhydride hardener)• D.E.H.™ curing agents (incl. D.E.H. 70 anhydride hardener)
• Higher Temperature Performance
• D.E.H. 650 curing agent
• D.E.N. 440 epoxy novolac resin
• Viscosity
• Diluents (mono-, di- or multi-functional); D.E.R.™ 7xx series
• Bisphenol-F epoxy resin(s); D.E.R. 354, 351, 352
• Cure rate• Cure rate
• Room temperature / Latent accelerated resins; D.E.R. 34xx
• Long(er) pot-life amines (D.E.H™ 23 or 2132 curing agent)
• Flexibility
• Amines (e.g. D.E.H. 23), diluents (e.g. D.E.R. 732P) orD.E.R. 3913 Flexible epoxy resins
• Flame Retardancy
™ Trademark of Olin Corporation
Page 49
Thank You !!!
Univar Poland Sp. z.o.o.
Meet us for face-to-face discussion at the EXPO; Booth W06
Univar Poland Sp. z.o.o.
Katarzyna Izbaner-Jasnikowska
+48 (0) 516177351
Joanna Radzikowska
+48 (0) 502531653
[email protected]@univareurope.com
Olin Corporation
Toine Dinnissen
™ Trademark of Olin Corporation
Page 51
Isophoronediamine
Product / Formulation 1 2 3 4 5
D.E.R.™ 330 epoxy resinEEW = 185 gr/eq
100 100 100 100 100
Isophorone diamineAHEW = 43 gr/eq
22 23 24 25 26
Liquid properties
Reactivity at 25°CReactivity at 25°C
Gel time [min] 161 158 156 152 151
Time to peak [min] 315 303 321 321 332
Exotherm [°C] 42 57 46 43 50
Reactivity at 50°C
Gel time [min] - 48 47 - -
Time to peak [min] - 51 50 - -
Exotherm [°C] - ca. 250 ca. 250 - -
Physical properties 2)
Tg (by DMA) after 1 h [°C] 161.5 167.2 170.5 167.4 166.1 166
168
170
172
174
Tg (by DMA) after 2 h [°C] 161.4 167.6 170.6 167.6 167.5
Tg (by DMA) after 3 h [°C] 164.4 170.4 172 170.5 167.6
Tensile test @ 1 h at 150 °C cure
Stress [MPa] 76.9 73.4 80.2 74.5 73.3
Modulus [GPa] 2.8 2.79 2.62 2.69 2.54
Strain [%] 4.19 4.14 5.7 4.51 5.27
160
162
164
166
21 22 23 24 25 26 27
1 hour
2 hours
3 hours
Theoretical mixing Ratio : 23.0 phr D.E.R. 330 epoxy resinEmpirical mixing ratio : 24.0 phr D.E.R. 330 epoxy resin
™ Trademark of Olin Corporation
Recent Innovation – More FlexibilityColor 30 APHAAmine number 472 mg KOH/gViscosity 15 mPa.s @ 25 °CDensity 0.96 g/cm3Mol. Weight 230AHEW 63 gr/eq
D.E.R.™ 330 epoxy resin 100 100
D.E.H.™ 23 amine hardener 32 25
IPDA - 5D.E.H. 23
60
70
80
90
100
Mix-viscosity [mPa.s @ 23°C] 320 620
Tg [°C]; DSC 90 98
Flexural Strength [MPa] 102 131
Flexural Modulus [GPa] 3.14 3.38
Tensile Strength [MPa] 66.9 73.8
Izod impact Strength [cm-kg/cm] 7.08 8.17
Elongation at Break [%] 10.0 8.0
20
30
40
50
60
20 24 28 32 36 40 44
Glass Transition Temperature [°C]
Heat Deflection Temperature [°C]
Theoretical mixing Ratio : 31.1 phr D.E.R. 330 epoxy resinEmpirical mixing ratio : 32.0 phr D.E.R. 330 epoxy resin
Elongation at Break [%] 10.0 8.0
™ Trademark of Olin Corporation
Glass Transition Temperature, TgTg = The Temperature Range where a polymer changes
from Glass to Rubber
* Secondary Bonds are Broken* Molecular Mobility Increases* Free Volume Increases* Strength Decreases
Tg = The Temperature Range where a polymer changesfrom Glass to Rubber
* Secondary Bonds are Broken* Molecular Mobility Increases* Free Volume Increases* Strength Decreases
20
25
30
* Strength Decreases* Flexibility Increases* Internal Stress is Relieved
* Strength Decreases* Flexibility Increases* Internal Stress is Relieved
Vitrification
Slow Cure
Fast Cure
Tg = Cure Temp.
Cure is diffusion controlledGlassy
0
5
10
15
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
Cure Time
Tg = Cure Temp.
When the Tg of the Growing Polymer Reaches the CureTemperature, The Polymer VitrifiesExtend of cure is determined by the Tg, Average Functionality
Liquid /Rubber
Cure isKineticallyControlled
™ Trademark of Olin Corporation
Tg versus Cured Property
Tg < Service TemperatureTg > Service Temperature
Epoxy-Cycloaliphatic AmineCured @ 100°C
Epoxy-PolyamideCured @ 25°CCured @ 100°C
Tg = 110°CService Temperature 80°C
Cured @ 25°CTg = 30°CService Temperature 40°C
Glassy, RigidLow Impact ResistanceHigh Internal StressHigher Barrier Properties
Rubbery, ToughHigh Impact ResistanceLow Internal StressLower Barrier Properties
Functionality Gel PointCrosslinkingFunctionality TgGel PointCrosslinking
Gel PointDry TimePot Life
ChemicalResistanceStrength
RheologyChemicalResistanceShrinkage
% CureGlass/RubberInternal Stress
Reactivity
™ Trademark of Olin Corporation
Gelation
∞Covalently Bonded Polymer Network
Molecular Weight Infinitely High∞
Polymer Properties develop at Gel-Point
Sol Gel
Gel = “One” macromolecule
Sol = Low molecular weight fraction
Solvent SolubleNo Physical StrengthFluid Behavior50% of Shrinkage
Solvent In-solublePhysical StrengthElastic Behavior50% of Shrinkage
Gel Point
Monomers
™ Trademark of Olin Corporation
Gelation versus Functionality
Active Groups per Molecule 2 Functional Epoxy Groups
OOO
OOO
5 Functional Amine-Hydrogen Groups
OHO O
n
Functionality ≤ 2 Linear Molecular Weight Build
A A B B A A B BB B A A B B
AB
No Cross linking
Functionality > 2 Cross Linking
Cross linking leads to gelation
™ Trademark of Olin Corporation
Gel-point can be Predicted
Carothers: % Cure @ Gel Ξ 2 / favg
Flory: % Cure @ Gel Ξ 1
[1 + (f-2)]1/2
• Gelation is Controlled by Functionality
react 3 moles of D.E.R.™330 epoxy resin = 6 reactive groupswith 2 moles of amino-ethyl piperazine = 6 reactive groupsaverage functionality = 12 groups / 5 mole = 2.4
Gel Point ~ 2/2.4 ~ 83% cure at Gel
react 7 moles of D.E.R.™330 epoxy resin = 14 reactive groupswith 2 moles of tetra-ethylene-pentamine = 14 reactive groupsaverage functionality = 28 groups / 9 mole = 3.11
Gel Point ~ 2/3.11 ~ 64% cure at Gel
react 14 moles of D.E.N.™425 epoxy resin = 35 reactive groupswith 5 moles of tetra-ethylene-pentamine = 35 reactive groupsaverage functionality = 70 groups / 19 mole = 3.68
Gel Point ~ 2/3.68 ~ 54% cure at Gel
Higher Functionality is Early Mould Release
™ Trademark of Olin Corporation
Crosslink Density:
High Crosslink DensityHigh Crosslink DensityHigh Chemical & Heat ResistanceStrong, RigidHeat Cure Needed
D.E.N.™438™
Low Crosslink DensityLow Crosslink Density
D.E.R.™324
Low Crosslink DensityLow Crosslink DensityModerate Chemical & Heat ResistanceFlexible, ToughCure at Lower Temperatures
High X-Link DensityD.E.R.™ 331 / Imicure(1) EMI 24Cure @ 150 °C
Flexural Strength 21,000 psiFlexural Modulus 540,000 psiElongation @ Break 2 %Cure @ 150 °C
Low X-Link DensityD.E.R.™ 331 / Jeffamine(2) D-400Cure @ 30 °C
Glass Transition 160 °C3 hr acetone boil 1 %wt gain
Flexural Strength 11,200 psiFlexural Modulus 406,000 psiElongation @ Break 60 %Glass Transition 30 °C3 hr acetone boil 29 %wt gain
™ Trademark of Olin Corporation