The Fundamentals of

Advanced Materials: A Novel

Triazole Resin for
Low‑Temperature-Cure
Irene Gorman and Robson Storey
School of Polymers and High Performance Materials
The University of Southern Mississippi
 Outline
 Introduction
 Polymer basics
 Polymerization types
 Composites
 Matrices
 Click Chemistry
 Synthesis of azide resin
 Alkyne crosslinkers
 Reactivity differences
 Activation Energy
 Average
 Change with conversion
 Comparison to industry standard
 Exotherm
 Adhesion
 What is a Polymer?
 Polymer- a macromolecule (large molecule) made of
many small molecules linked chemically

Gasoline= 4 units

CH2 CH2

Ethylene
Monomer Wax= 12 units

Polyethylene= 40,000 units

 Polymer Classification
Polymers

Natural Synthetic

Chain Step
Growth Growth

Free Ring Condensation

Cationic Anionic
Radical Opening

Chain Growth: A* + A AA* + A AAA* . . .

Step Growth: AA + BB AABB + AABBAA AABBAABBAA . .
 Natural Polymers
 Natural polymeric materials have been used
throughout history for clothing, decoration,
shelter, tools, weapons and writing materials
 Examples of natural polymeric materials
 Starch
 Cellulose
 Protein
 Hair
 Silk
 DNA and RNA
 Rubber
 Synthetic Polymers
 The first fully synthetic polymers were
phenol-formaldehyde polymers,
Bakelites, manufactured by Bakeland
in the 1900s.

 The 1930s and 1940s provided the backdrop for the discovery
of many important polymers
 Melamine Polymers (Formica)
 Neoprene Rubber
 Polystyrene
 Polyethylene
 Nylon 6,6
 Polytetrafluroethylene (Teflon)
 Polymethylmethacrylate (Plexiglass)
 Condensation
Polymerization
O O

CH3 O C C O CH3 + OH CH2 CH2 OH

dimethly terephthlate ethylene glycol

O O

HO CH2 CH2 O C C O CH2 CH2 O H 2nCH3OH

n
polyester
Addition Polymerization
CH3 O O CH3 CH3 O CH3

∆
H3C C O O C C O O C CH3 2 H3C C O O C 2 H3C C O + 2CO2

CH3 CH3 CH3 CH3

di-t-butly peroxyoxalate carboxyl radicals

CH3 CH3 CH3

CH3
H2
H3C C O H3C C O C C

O CH3 C O
CH3

O O

CH3 CH3

methyl methacrylate acrylic radical

CH3 CH3 CH3 CH3

H2 H2
H3C C O C C C C

C O O O
CH3

O O O

CH3 CH3 CH3

growing chain polymethyl methacrylate

 Describing Polymers
Molecular Weight:
Number Average Weight Average Polydispersity Index
ΣniMi ΣniMi2 Mw
Mn = Mw = PDI =
Σni ΣniMi Mn

Thermal
Transition:

Sharp Tm Broad Tm
temperature

temperature
Tg Tg

Crystalline polymer Amorphous polymer

Polymer Applications
 Sports Equipment  Electronics
 Military/Police  Textiles/Clothing
Protection  Water Treatment
 Fibers  Biomedical
 Plastics
 Pharmaceutical
 Adhesives
 Automotive
 Cosmetics
 Aerospace
 Oil Industry
 Coatings
 Rubber
 Paper
Medical, Pharmaceutical
Electrical, Electronic
Aerospace, Marine
 Epoxy-Based Marine
Composites via Triazole Cure
 Epoxy resins are the matrix
resin of choice for advanced
carbon-fiber composites
 Advantage: excellent
mechanical and thermal
properties and fiber-matrix
interfacial strength
 Disadvantage: low heat of
cure
 Tg rises as crosslinking You Can’t Fit a Ship in an Autoclave
progresses
 Once Tg surpasses the
temp of the reacting mass,  SOLUTION: Systems that
crosslinking stops create their own heat
 Elevated, post-cure,  Azido/alkyne Huisgen
temperatures are needed “Click” reaction
for high crosslink density
 Composites
 Composite: consisting of
two or more distinct
parts, which remain
separate and distinct on
a macroscopic level.

15
Fiber-Polymer Composites
Types of Fibers:
Matrix Material
•Glass
•Graphite
•Boron
Fiber
•Silica
•Kevlar

Matrix Function:

{
5-500μm
•Bind the fibers together
•Transfer the load to the fibers
•Protect the fibers from environmental damage
•Enable the formation of materials stronger than the individual parts
 Polymer Matrices
 Thermoplastics  Thermosets
 High Mw chains
 Association through  Crosslinked network
 Hydrogen bonding, van der Waals forces,
dipole-dipole, aromatic stacking  Cannot be softened or
 Flow upon heating
 Polystyrene, polyethylene, nylons,
melted
polycarbonate, polyacetals  Epoxides, polyesters,
phenolics, ureas, melamine,
silicones, polyimides

Ceramic &
Glass Carbon-
Polymer Metal Carbon
Composites
Composites Composites Composites
0 260 650 110 1370
Temperature Range °C 0
Tuttle, M. E., Structural Analysis of Polymeric Composite Materials. Marcel Dekker: 2004; p 1-41.
 Elevated Cure
heat

Initial Cure Post Cure

Considerations
•Tg rises as crosslinking progresses
•Once Tg surpasses the temp of the reacting mass, crosslinking stops
•Elevated, post-cure, temperatures are needed for high crosslink density
•If the system’s temp could be increased, by virtue of highly exothermic
crosslinking reaction, then higher crosslink density would be achieved prior to
vitrification
18
Morgan, P., Carbon Fibers and Their Composites. Taylor and Francis: Boca Raton, 2005; p 501-544
 Click Reactions
O
OR"
"RO R'

R'
Requirements
[O] Nuc
•easy to perform
HO
•work-up
•high yielding
R' Nuc
•tolerant to oxygen & water R'
R"-N3
•high thermodynamic driving force
Cu(I) R"O-NH3
(>20 kcal/mol) N
"RO
N N
R'
N
"R R'

19
Kolb, H. C.; Finn, M. G.; Sharpless, K. B.; Angewandte Chemie International Edition 2001, 40, 2004-2021.
 Huisgen
1,3-Cycloaddition
N R1 N
R1 R1
N N N N N N N
Thermal
+
H R2
R2 R2
•Proceeds at low temp,
N
even room temp R1
Cu(I) N N
•Extremely exothermic
•Azides are highly
energetic, R2

explosive 1,4 regioisomer 1,5 regioisomer

•Easily dissociate into
nitrene & dinitrogen
N N N N
N N N N N N N N
R-N3 = R R R R
1 1a 1b 1c 1d

20
Kolb, H. C.; Finn, M. G.; Sharpless, K. B.,Angewandte Chemie International Edition 2001, 40, 2004-2021.
Brase, S.; Gil, C.; Knepper, K.; Zimmermann, V., Angew. Chem. Int. Ed. 2005, 44, 5188-5240.
 Epoxy Triazole Cure
(Azido/Alkyne Reaction)
CH3

O C O
O O
CH CH2 CH3 CH2 CH
CH2 CH2 + Na N3

70/30 v/v NH4Cl

2-Ethoxyethanol/H2O ∆ 130°C
4h
 Highly exothermic
CH3  higher crosslink
O O C O O density prior to
CH CH2 CH2 CH
vitrification
CH3
+ H
 Proceeds at low
N3 CH2 CH2 N3
temp, even room
temp
CH3
 Easy scale-up

OH O C O OH

CH CH2 CH3 CH2 CH + NaCl + NH3

N3 CH2 CH2 N3
Alkyne Crosslinkers
Amine Propargyl Propiolate

O
O
O
O
N N 4 O
n
TEGDPE (liquid) O
4

O TEGDP (liquid) O
TPJeff (solid)

O
N N O O
O

DPA (liquid) O O
O

O O
TPEDA (liquid)
TMBTP (solid)
O O
O

TMTP (solid) O
TPA (liquid)
O O
 Linear Chain Extension
O O O
CH
CH2 C CH2 CH2 O C C CH2 O CH2 C
C O CH2 CH2 C CH2 C O CH2 CH2 O C
HC HC CH
O

CH3

HO O C O OH
CH CH2 CH3 CH2 CH
N3 CH2 H2C N3

CH3

H O O C O O H

O N CH CH2 CH3 CH2 CH N N

N
N N
CH2 C CH2 CH2 O O CH2 CH2 O
O CH2 CH2 C CH2 C CH2 O CH2 C

O O O
 GPC Overlays
O
1 Azide:0.5 DEGDP:0.5 DPA RT CH
1 Azide:0.5 DEGDP:0.5 DPA 100C 2hrs CH2 C CH2 CH2 O C
1 Azide:0.65 DEGDP:0.35 DPA RT C O CH2 CH2 C CH2
CH
O
Dipropargyl adipate
(DPA)

O O

C CH2 O CH2 C
C O CH2 CH2 O C
CH CH
polymerizations Diethylene glycol dipropiolate
(DEGDP)

10 12 14 16 18 20 22 24
Time (min)
Propiolate vs. Propargyl
 Average Activation
Energies
AE (kJ/mol)  Distinct difference between
TMBTP 69.21 propiolate x-linkers &
HDA 70.03 amine, propargyl types
TEGDP 72.28
 Resonance structure
TMPTP 73.55
DPA 82.32 O
TMPTPE 82.51 N
TPDDS 82.62 O
TEGDPE 83.33 Propiolate Amine
TPEDA 84.32 O
TPA 84.72
TPJeff 85.88 O
O
TPTM 86.37 Propargyl Ether Propargyl
 Catalysis w/ Cu(I) &Cu(II)
16
––––––– un-catalyzed
––––––– 1 mol % BTTPP
––––––– 3.5 mol % BTTPP
14 ––––––– 5 mol % BTTPP
––––––– 5 mol % CEH
––––––– 5 mol % DCP

12 CuBr
P

10
Heat Flow (W/g)

3
8
Bromotris triphenylphosphine Cu(I)

2 N
N

Cu
0
Cl Cl

Dichloro (1,10-phenanthroline) Cu(II)

-2
-50 0 50 100 150 200 250 300
O
Exo Up Temperature (°C) Universal V4.3A TA Instruments

H3C O Cu2+
 Cu(I) &Cu(II) activity function of solubility,
not oxidation state H3C
2
Copper(II) ethylhexonate
Changes in Activation
Energy
O

O O
O
3
H3C O Cu2+
O
CH3 Tetraethylene glycol dipropiolate (TEGDP)
H3C
HO O O OH 2

CH3 + or Copper(II) ethylhexonate (CEH)

Room Temperature
N3 N3 5 min
O
O
3
Tetraethylene glycol diproargyl ether (TEGDPE)

Averaged kinetic data does not

account for mechanistic changes
 Temperature, extent of conversion

Problematic for complex systems

Epoxy, catalyst
Activation Energy vs.
Conversion
96 102
Catalyzed FWO Model 100
Un-catalyzed FWO Model
94 TEGDP TEGDP
98 TEGDPE
92 TEGDPE
96
90 94
88 92
90
86
88
84 86
Ea (kJ/mol)

Ea (kJ/mol)
82 84
80
82
80
78
78
76 76
74 74
72
72
70
70 68
68 66
64
0 50 100
0 50 100
α α

TEGDPE FWOModel 74 TEGDP FWO Model

Uncatalyzed
Uncatalyzed
Catalyzed
Catalyzed
100
72

70
90 Ea (kJ/mol)
Ea (kJ/mol)

68

80
66

70 64
0 50 100 0 50 100
α α
 Comparison: Derakane
510A-40 to BPA Azide-TMPTP
2.0
77.88°C ––––––– Azide EPON + TMPTP
–––– Control Derakane

O O

1.5 O

O
Heat Flow (W/g)

1.0 126.25°C

255.54°C

0.5

0.0

-0.5
0 50 100 150 200 250 300 350
Exo Up Temperature (°C) Universal V4.2E TA Instruments
Comparison: Isothermal 45°C
0.4
––––––– Control Derakane
–––– Epon Azide + TMPTP

0.3
Heat Flow (W/g)

0.2

0.1

0.0
0 20 40 60 80 100 120
Exo Up Time (min) Universal V4.2E TA Instruments
 Adhesion to Glass
BPA- Derakane
Azide
 Conclusions
 Exothermic for low  Future Work
temp cure  Determine
 Customizable regioisomer linkage
 Conduct mechanical
 catalyst
test on cured resin &
 variety of alkyne
composite materials
crosslinkers
 Quantitatively
 Superior adhesion to measure adhesion
glass (qualitative)  Synthesis of new
azide compounds
 School of Polymers and High
Performance Materials
Graduate Degrees
Polymer Science and Engineering
 Ph.D. and M.S.
Sports and High Performance
Materials (joint with Health and Human
Performance)
Ph.D. and M.S.
School of Polymers & High
Performance Materials
Graduate degrees are in Polymer Science and Engineering
12.9 million in funding
2009-10 enrollment
 59 B.S. majors
77 Graduate students
23 Postdoctoral fellows
Tuition waived
Up to 25,000 dollar stipend
Health insurance
 Preparing for
Graduate School
Seniors
 Prepare for & take the GRE
 Research graduate programs
 Consider program focus
 Read up on faculty research
 Scholarships/stipends
 Apply
 Letters of recommendation
 Personal statement
Under-classman
 Consider academic
requirements
 Research Experience for
Undergraduates (REU)
 Graduate school test run
 Research experience
 Publications

 Visit schools
 Talk to graduate students
 Is there a fit?
 PSC Ph.D. Roadmap
Guideline
Select
Advisor
Exams
Research Research
Proposal Defense
1
Prospectus 2 3 4

RESEARCH
August December
2010 2014
 Shelby Freland Thames
Polymer Science Research
Center
 PSRC Addition

 $30MM Research Center

 Includes 6.6MM addition that opened April 2004
 104,000 sq. ft.
 Teaching Facilities
 Classrooms, auditorium, conference rooms
 Research laboratories
 Major scientific instrumentation
 Polymer processing and fabrication facility
 Coatings formulation, processing, and
characterization
 Instrumentation
500MHz Multi-Nuclear NMR
Composite Fabrication
 History
 Department of Polymer
Science founded by Dr. Shelby
F. Thames in 1970
 Elevated to School of
Polymers and High
Performance Materials in 1999
Faculty Research Areas
Coatings and Films
• Stimuli/-Responsive Systems
• High solids, waterborne and
solvent based systems
• “Green” coatings
• Polymer photochemistry
Biomedical Research
• Biopolymers and biomimetic
polymers
• Pharmaceutical polymers
Polymer Engineering
• Polymer composites
• Nanoengineered materials
• Membranes and fuel cells Water-Soluble
• Polymer processing and Polymers
rheology • Controlled activity
• Surface assembly
• Colloid science
Formulation Science
• High throughput screening
Polymer
Synthesis
• Controlled free radical
polymerization
• Living polymerization
• Functional polymers
• Biodegradable materials
 Starting Salaries for USM
Polymer Science Graduates
Work Force
 Over 1 million people work directly or indirectly
with polymers
 Over half of all chemists and chemical engineers
are engaged in polymer science and technology
 Annual payroll of $25 billion

Most recent salary range for graduates

in our Ph.D. program is $80-90,000
Selected Research Partners
 Sports and High
Performance Materials

Bi
y
og

om
iol

ec
ys

ha
Ph

nic
n

s&
ma
Hu

Ki
ne
SHPM
&

si o
e
cis

log
er

y
Ex

Polymer Science
2010 REU Summer Program

2010 Research Experience for Undergraduates

June 1st – August 6th, 2010

Deadline: March 19th, 2010

To apply:
 Online application:
http://www.usm.edu/polymer/Summer_research.php
 Official transcript
 Two letters of recommendation
 Why Southern Miss?

− Polymer Science & Engineering

− School of Human Performance

− Synergistic Research Opportunity

− Carnegie Research Extensive University

− Leverage DoD Research Relationships

The University of Southern
Mississippi
Outdoor Activities
 40 mi Paved Trail
 41 mi Hiking Trail
 12 Golf Courses
 Canoeing
 Coast
 Desoto National
Forest
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State Park
 Zoo
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Mardi Gras
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QUESTIONS
Anionic Polymerization
NH3
KNH2 K + H2N
potassium free ions
amide

H
H2
H2 N + C H2N C C

H H H

styrene carbanion

+ H2
C C C C C
H2 H
H H H n

polystyrene
growing chain
Cationic Polymerization
R Cl + 2 TiCl4 R Ti2Cl9
initiator co-initiator ion pair
Lewis Acid

CH3
H CH3
H2
R Ti2Cl9 + C C R C C Ti2Cl9
H CH3 CH3
carbocation
isobutene

CH3 CH3
CH3 H CH3
H2 H2 H2
R C C Ti2Cl9 + C C R C C C C Ti2Cl9
H CH3 CH3
CH3 CH3

growing chain

CH3 H CH3 CH3

C C H2
R C C Ti2Cl9 + C C
H2
H CH3
CH3
CH3
n

polyisobutylene
 Bio Inspired
Biomimetic
Drug Delivery
Biopolymers
Biocompatible
Poly-Drugs
 Aerospace
Resin Synthesis
Composite Fabrication
Failure Analysis
Surface Analysis
Molecular Dynamics
Bonding / Adhesion
Mechanicals
 Marine
Room Temperature Cure Matrices
Room Temperature Cure Matrices
Fire / Flame / Smoke Retardants
Matrix Kinetics
VARTM
Carbon-Fiber Composites
Personal Care