Promerus has developed a unique catalytic system that enables photo-polymerization of various cyclic olefins, which enables a new class of photopolymers for various applications.
1. Latent, UV-activated ROMP catalyst system
Oleksandr (Sasha) Burtovyy1, Linda Zhang 1, Leah Langsdorf1, Alex Niemiec1, Dan
Gastaldo1, Doug Skilskyj1, Krzysztof Skowerski2 and Larry Rhodes1
1 Promerus LLC, (Brecksville, OH USA) 2 Apeiron Synthesis, (Wrocław, Poland)
UV light
over 4 sec
2. Global leader in Polycyclic Olefin (Norbornene) Technology
Product Development Group for Sumitomo Bakelite Co., Ltd. (SB)
Formerly BFGoodrich Electronic Materials (acquired by SB in 2001)
Includes monomer and polymer production
Main Application Areas:
Semiconductor Materials
High Performance Electronics and Display Materials
Membrane Materials
Emerging applications
~30 Employees
Location
Brecksville, OH, USA
2
Promerus is a Leader in Cyclic Olefin Polymer (COP)
Technology
3. 3
• Adhesion
• Coefficient of Thermal Expansion
• Elongation
• Glass Transition Temperature
• Modulus
• Refractive Index
• Surface Energy
• Transparency
• Impact resistance
Our team of experts has the ability
to tailor the functional groups of
polymer properties. These include:
4. 4
Literature overview
Photo-ROMP of cyclooctene
1. Latency – <1% conversion in 24h at 35 °C (in
the dark)
2. Reactivity – 94% conversion in 1h irradiation
in solution at 35 °C (350 nm)
Y. Ginzburg, A. Anaby, Y. Vidavsky, C. E. Diesendruck, A. Ben-Asuly, I. Goldberg and N. G. Lemcoff. Organometallics 2011
PAG
Photo-ROMP of cyclooctene
1. Latency – not reported
2. Reactivity – 95% conversion in 2h irradiation
in solution (300 nm)
B. K. Keitz and R. H. Grubbs. JACS 2009, 131, 2038
Photo-ROMP of DCPD
1. Latency – <5% conversion in 24h (in the
dark)
2. Reactivity – 95% conversion in 15 min
irradiation in solution (440 nm)
C. Theunissen, M. A. Ashley and T. Rovis. JACS 2019, 141, 6791
Short Review: Or Eivgi and N. Gabriel Lemcoff. Synthesis 2018, 50, 49-53
5. 5
Current issues
Issue Current status Requirements
Latency Several days
Weeks or
months
Photo-speed and
conversion
10 min – 2h of irradiation
Residual monomer
< 1 min
100% reactive
Solvent-less
Use of solvent to
improve solubility of
catalyst and/or co-
catalyst
Neat
formulation (no
solvent)
6. 6
Schematic mechanism of our UV-activated
ROMP catalyst system
UV-only curable formulation
Ru-catalyst
active
UV/N2
Photoactivator
r.t.Ru-catalyst
non-active
UV/O2
Photoactivator ROMP
No reaction
Cyclic Olefin Monomer
+
8. 8
QUICK PHOTOCURE
Fast process time
Environment
friendly
No mixing needed
Long pot-life
Easy to transfer
SOLVENT-LESS
ONE-PART
LATENT
LOW VISCOSITY
Advantages of Promerus’ unique system
9. 9
Our ROMP photopolymers have fast and
complete cure after UV exposure
light on at t=9.0 sec
light off at t=13.0 sec
50% conversion at t=15 sec (∆t = 6 sec) *
99% conversion at t=39 sec (∆t = 30 sec)*
Integral, %DSC, mW/mg
* - calculated based on total heat released
Area: 275 J/g
Exposure conditions: 3 J/cm2 of 395 nm UV light in 4 sec at
30 °C
10. Our ROMP photopolymers have fast and complete
cure after UV exposure
10
TGA of cured sample (after 3 J/cm2 in 4 sec) 10 °C/min ramp in N2
11. 11
One-part solvent-free formulations are stable
and r.t. for weeks
0
50
100
150
200
250
300
0
5
10
15
20
25
30
35
40
45
50
0 5 10 15 20
Heatofreaction,J/g
Viscosity,cP
Time, days
Latency
12. 12
Thermo-mechanical properties can be tuned
by changing monomer compositions
Elongation-to-break
100 % 3000 %
Glass transition temperature
- 20 °C 220 °C
Young’s Modulus
0.001 GPa 2.0 GPa
Impact resistance
20 J/m 800 J/m
Formulation A: 200 % 122 °C (HDT - 91 °C) 0.9 GPa 600 J/m
13. 13
Digital Light Projection: Selective
exposure to light by projectorFlashforge Hunter DLP 3D Printer
Promerus new photopolymer formulations can
be 3D-printed using DLP technology.
14. 14
Conclusions
Promerus has developed a unique catalytic system that
enables photo-polymerization of various cyclic olefins, which
enables a new class of photopolymers for various applications.
Our low-odor photocurable formulations offer several
advantages, including low viscosity and long pot life resulting
in polymers with a unique combination of high elongation-to-
break, high Tg and high impact resistance.
UV light
over 4 sec