• SEVERAL CHARACTERIZATION TECHNIQUES USED TO DEFINE BROAD MOLECULAR PROPERTIES
– – – – GPC: DSC: FTIR: NMR: Molecular Weight Glass Transition Temperature (Tg) Composition Composition
• DESCRIPTIONS / SPECIFICATIONS TEND TO BE BASED ON BULK PHYSICAL PROPERTIES
– – – – – – Ring and Ball Softening Point (ASTM D36-D2398) Melt Viscosity (ASTM D-3236) Cloud Points (Wax/Solution) Color (Gardner/Saybolt/YI) Solubility Parameter Volatility
• TWO TYPES OF POLYMERIZATIONS USED TO MAKE HYDROCARBON RESINS - Cationic Catalysis (Friedel-Crafts) - Thermal
WIDE VARIETY OF MONOMERS FROM STEAM CRACKING
ESCOREZ ® Hydrocarbon Tackifier Resins
Presentation to The Society of Adhesion & Interface, Korea August 2001
ExxonMobil Chemical Korea / B.H. An
1
Content
1. Escorez ® Hydrocarbon Tackifier Resin • What are tackifier resin? • Tackifier History • Petroleum Tackifier Resin Feedstocks Characterization Chemistry & Process Escorez Grade Slate 2. Tape & Label Market • Americas • Europe • Japan • APXJ
VISCOSITY HEAT STABILITY
TACKIFIER RESIN PROPERTIES / ADHESIVE PROPERTIES RELATIONSHIP
Are a Function of Tackifier Resin Properties Process Controls
And Significantly Impact Adhesive Properties
PRIMARY FUNCTIONS OF TACKIFYING RESINS
• Compatible with Adhesive Polymer-- Not a Filler • Lowers Average Molecular Weight-- Viscosity Adjustment • Raises the Blended Tg-- Not a Plasticizer, Improves adhesion
Dilute Isoprene 2-Methyl-1-Butene 2-Methyl-2-Butene IBP-70 C1-C3 C4 Piperylene
C5
C6 C7
Gas Oil C10-C12 Cyclodiene Dimers CDC or DCP
Tar
C7
Crude (Raw) C5
C8-C10 Vinyl Aromatics Heart Cut Distillate (HCD or C9) C10
WHERE DO HYDROCARBON RESINS COME FROM?
• FIRST EXAMPLES FROM COAL TAR DISTILLATES IN 1920’s - Mixed Aromatic Monomers / BF3 Polymerization - Coumarone-Indene Resins • TERPENE BASED RESINS HAVE BEEN AVAILABLE SINCE THE MID-1930’s - Citrus Oils / d-Limonene - Sulfate Turpentine / a -Pinene, b-Pinene, Dipentene • MONOMERS FROM CRACKED PETROLEUM DISTILLATES APPEARED IN 1940’s - Aliphatic Olefins / Diolefins, C5-C6 - Vinyl Aromatics, C8-C10 - Cyclodiene Dimers, C10-C12 • SYNTHETIC AROMATIC MONOMERS ALSO AVAILABLE Styrene Vinyl Toluene Para-Methyl Styrene a-Methyl Styrene
ADHESION INDUSTRY BUSINESS WORLD WIDE
Notre Dame de Gravenchon France Baton Rouge, Louisiana
Machelen, Belgium
Tsurumi,
Japan
Kawasaki,
Japan
PLANT Adhesive Technology
Aliphatic/ Aromatic 8.7 -9.1 Polybutadiene Polystyrene EVA
Desirable Attributes Lower and Lower Color Increased Stability Tuned Polarizability Increased Compositional Variation
WHAT ARE HYDROCARBON RESINS?
•
LOW MOLECULAR WEIGHT, AMORPHOUS, THERMOPLASTIC POLYMERS DERIVED FROM SYNTHETIC OR NATURAL MONOMERS TYPE TYPICAL MONOMERS
Comparator Exxon Method
WAX CLOUD POINT
SOLUTION CLOUD POINT
A MEASUREMENT OF THE HIGH MOLECULAR Exxon WEIGHT END OF RESIN AND/OR COMPOSITIONAL Method DIFFERENCE A MEASURE OF MOLECULAR WEIGHT RESULTING COLOR OF RESIN AFTER HEATING IN AIR UNDER CERTAIN CONDITIONS (5 hrs @ 175 ¡ÆC) Brookfield Exxon Method
Aesthetics Aged Performance
THE IMPACT OF RESIN TYPE ON SOLUBILITY PARAMETER
Cycloaliphatic 8.7 - 8.9
Aliphatic 8.1 - 8.5 Polyethylenebutylene Polyisoprene
THE LANGUAGE OF ESCOREZ RESINS
Instrument SOFTENING POINT COLOR RULE OF THUMB: S.P. = Tg + 50 ¡ÆC (1) YI OF 50% TOLUENE SOLUTION (A) GARDNER SCALE (Gardner ≈ YI/10) PALE YELLOW TO DARK BROWN (B) SAYBOLT SCALE WATER WHITE TO PALE YELLOW (2) MOLTEN COLOR A MEASUREMENT OF COMPATABILITY OF A GIVEN RESIN WITH A POLYMER / WAX SYSTEM Herzog Hunterlab Colorimeter
HYDROCARBON RESIN CHARACTERIZATION
• HYDROCARBON RESINS DIFFICULT TO CHARACTERIZE ON A MOLECULAR LEVEL
– Mixture Of Monomers – Complex Cationic Or Thermal Chemistry – Amorphous Structures
PETROLEUM
trans-Piperylene Styrene 2-Methyl-2-Butene
TERPENE
Limonene β−Pinene
ROSIN
COOH
Abietic Acid
•
BROAD RANGE OF PHYSICAL PROPERTIES - Molecular Weight (Mn): Typically < 2000 g/mol - Glass Transition Temperature: -30-140 ¡ÆC - Color: Water White To Dark Brown
Composition
Feed Molecules
Compatibility
Molecular Weight
Reactor Conditions Feed Molecules
Performance Compatibility
Color/Stability
Feed Molecules Reactor Conditions

CYCLICS
C9