TECHNOLOGY TUTORIAL

The Chemistry of Norbornene Monomers and Polymers and Products and Application Areas Overview

¾ What is Norbornene? ¾ What are Functionalized Norbornene Monomers? ¾ How are Norbornenes Polymerized? ¾ Promerus Proprietary Catalysts ¾ Customization of Polynorbornene Polymers ¾ Products and Application Areas Promerus LLC is a Leader in Polycyclic Olefins

¾ We have 25+ years of Polynorbornene R&D and commercialization experience ¾ Our research and development efforts include: 9 Catalysis Research 9 Monomer Synthesis and Production 9 Polymerization Activities 9 Formulation Development 9 Application Validation ¾ We deliver a unique platform of materials for electronics packaging and other applications What Is Norbornene?

Norbornene is a bicyclic olefin.

Norbornene possesses ring strain, so the molecule contains a highly reactive double bond.

Norbornene is manufactured via the Diels-Alder reaction of cyclopentadiene and ethylene.

Norbornene is a colorless substance that melts at 46°C.

Norbornene finds use in many different applications: 9 Cyclic Olefin Copolymers (COC) 9 Pharmaceutical intermediates 9 Pesticide Compounds 9 Specialty Fragrances 9 General Organic Synthesis What are Functionalized Norbornenes? Functionalized norbornene monomers are typically prepared via either high or low temperature Diels-Alder-reactions, and via derivatization.

High purity, functionalized norbornenes can be as reactive as norbornene.

Functionalized norbornene molecules exist as two isomers: endo (major) and exo (minor). X Many high purity, functionalized norbornenes are liquids. endo isomer Functionalized norbornenes contain many different types of reactive and non-reactive groups. Example substituents include: 9 Acetate (OC(O)R) 9 Alcohol (OH) 9 Alkyl (R) X 9 Aldehyde (C(O)H) 9 Anhydride (RC(O)O(CO)R)

9 Epoxide (CH2C(O)CH) 9 Ester (CO2R) 9 Ether (OR) 9 Ketone (C(O)R) 9 Nitrile (C≡N) exo isomer 9 Silyl Ether (Si(OR)3) 9 Phenyl (Ar) Diels-Alder Chemistry is Used to Prepare Norbornene Monomers

X

Y

Natural Gas X Ethylene X

Propane, Propylene Δ X Butane, X Butadiene Y Y Dicyclopentadiene (DCPD) C1 C2 C3 C4 Z Q C5

+ Norbornene Derivatives - Examples

CMe O 3 Δ O 1-hexene O O

Butylnorbornene tert-Butylester norbornene Styrene

Double Bond Shift

Si(OMe)3 Phenylnorbornene Vinylnorbornene Ethylidene norbornene

Si(OMe)3

Trimethoxysilylnorbornene One Key to our Success is our Monomers

¾ High Purity ¾ Ease of Handling ¾ Multitude of Polycyclic Olefinic Building Blocks ¾ Huge Variety of Functional Groups ¾ Crosslinking Monomers ¾ Ring Strain Drives Polymerization How is Norbornene Polymerized?

n n Ring-Opening Metathesis Ethylene Norbornene Polymerization Co-Polymerization (ROMP) n

n n Vinyl- or Addition- Radical or Cationic Polymerization AP and ROMP Catalysts Yield Different Polymers

Addition Polymerization (AP) - Saturated

M H MH MH n

Ring-Opening Metathesis Polymerization (ROMP) - Unsaturated

R R MC MC H H R M n H Several Transition Metal Initiators Can Be Used to Polymerize Norbornene

n Ti, Ta, Mo, W, Re, Ru, Os, Ir, Co Ring-Opening Metathesis Polymerization (ROMP) n

Ti, Zr, Cr, Co, Ni, Pd n

Vinyl-Addition

Predominant Transition Metals Employed in Bold Our Catalysts have Many Benefits

¾ High Activity, Single Component ¾ Low Residue in Purified Polymer ¾ Well-controlled Molecular Weight ¾ Functional Group Tolerance, e.g., 9 Alkyl 9 Aryl 9 Ester 9 Epoxide 9 Ether 9 Silyl ether 9 Carboxylic Acid 9 Alcohol Some of our Catalysts are Well-defined Initiator Cationic Species + ¾ Hydrocarbyl (or Hydride) Initiating Site Ni ¾ “Naked” Cationic Metal Center ¾ Nickel and Palladium are Most Active + ¾ Weakly Coordinating Anion 9 BF - Pd 4 - 9 PF6 - 9 B(C6F5)4 We Can Achieve Molecular Weight Control Via Chain Transfer

+ PNB

Chain Transfer Ni (β−Hydride Elimination) "Ni-H+"

PNB H

Ni Propagation (Chain Growth)

Olefin Insertion PNB Ni H Chain Transfer Not Possible H (No β−Hydride Elimination) Promerus Polymers Have High Tg

Cymetech, LLC Metton-America Ticona Nippon Zeon Mitsui

Ring Opening Metathesis Polymerization (ROMP)

Addition Copolymerization

H2

Increasing Tg Promerus, LLC JSR Nippon Zeon Addition Homopolymerization Polymer Properties Are Controlled by Changing the Functional Group

Glass Transition Toughness Temperature Coefficient of Thermal Modulus & Elongation Expansion (CTE)

X

Solubility Optical Loss

Refractive Index Crosslink Density Adhesion Why Use Promerus Polycyclic Olefin Polymers?

Amorphous Polyolefin • Wide Spectral Window X • Low Moisture Absorption • Low Dielectric Constant • Chemical Resistance X • Low Birefringence X • Low Dielectric Loss • High Breakdown Voltage X Rigid Polycyclic Backbone

• High Tg X

Tailoring Polymer via Functional Group (X) • Adhesion • Refractive Index • Latent Reactivity Promerus Materials Can Be Processed in Many Ways

Solution Mass Polymerization ƒ Spin Coating ƒ Casting ƒ Solvent Casting ƒ Resin Transfer Molding (RTM) ƒ Reaction Injection Molding (RIM) Post Treatment ƒ Screen-Printing ƒ Photodefinable ƒ Thixotropic Materials ƒ Latent Crosslinking ƒ Composites ƒ Thermal Decomposition ƒ Surface Property Enhancement Promerus Materials Are Useful in Many Applications

¾ Avatrel® Dielectric Polymers 9 For Electronic Packaging and Redistribution Layers ¾ Unity® Sacrificial Materials 9 For MEMS WLP, Protective Coatings and Temporary Wafer Bonding ¾ DUVCOR™ Photoresist Polymers ¾ Appear™ Optical Polymers ¾ Enestra® Optical Encapsulant ¾ Aprima® Adhesives