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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



OutlineOutline IntroductionIntroduction Polymer basicsPolymer basics

Polymerization typesPolymerization types

CompositesComposites

MatricesMatrices

Click ChemistryClick Chemistry

Synthesis of azide resinSynthesis of azide resin Alkyne crosslinkersAlkyne crosslinkers

Reactivity differencesReactivity differences

Activation EnergyActivation Energy AverageAverage

Change with conversionChange with conversion Comparison to industry standardComparison to industry standard

ExothermExotherm

AdhesionAdhesion



What is a Polymer? What is a Polymer?

Gasoline= 4 units

Wax= 12 units

Polyethylene= 40,000 units

EthyleneMonomer

CH2 CH2

Polymer- a macromolecule (large molecule) made of many small molecules linked chemically



Polymer ClassificationPolymer Classification

PolymersPolymers

NaturalNatural SyntheticSynthetic

ChainChain

GrowthGrowth

StepStep

GrowthGrowth

FreeFree

RadicalRadicalCationicCationic AnionicAnionic

RingRing

OpeningOpeningCondensationCondensation

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

Step Growth: AA + BB AABB + AABBAA AABBAABBAA . .



Natural PolymersNatural polymeric materials have been used

throughout history for clothing, decoration,shelter, tools, weapons and writing materials

Examples of natural polymeric materials StarchCelluloseProteinHair SilkDNA and RNARubber



Synthetic Polymers

The first fully synthetic polymers werephenol-formaldehyde polymers,Bakelites, manufactured by Bakelandin the 1900s.

The 1930s and 1940s provided the backdrop for the discoveryof many important polymers Melamine Polymers (Formica)

Neoprene Rubber

Polystyrene

Polyethylene Nylon 6,6

Polytetrafluroethylene (Teflon)

Polymethylmethacrylate (Plexiglass)



CondensationCondensation

PolymerizationPolymerization

CH3 O C

O

C O CH3

O

OH CH2 CH2 OH+

CH2 O C

O

C O CH2

O

CH2 O H

dimethly terephthlate ethylene glycol

polyester

2nCH3OHCH2HO

n



Addition Polymerization Addition Polymerization

CH3

O

CH3

O

C C

OO

OO OO CC

CH3

CH3

CH3

CH3

H3C CH3

∆2 H3C C

CH3

CH3

O O C

O

OC

CH3

CH3

H3C2 2CO2+

OC

CH3

CH3

H3C OC

CH3

CH3

H3C

H2

C C

CH3

C

O

CH3

O

OC

CH3

CH3

H3CH2C C

CH3

C

O

CH3

O

CH3

O

CH3

O

H2C C

CH3

O

CH3

O

n

di-t -butly peroxyoxalate carboxyl radicals

methyl methacrylate acrylic radical

growing chain polymethyl methacrylate



Describing PolymersDescribing Polymers

Molecular Weight:Molecular Weight:

Number Average

Mn =ΣniMi

Σni

Weight Average

Mw =ΣniMi

2

ΣniMi

Polydispersity Index

PDI =Mw

Mn

ThermalThermal

Transition:Transition:

Tg

Sharp Tm

Tg

Broad Tm

t e m p e r a

t u re

t e m p e r a

t u re

Crystalline polymer Amorphous polymer



Polymer Applications

Sports Equipment

Military/Police

Protection

Fibers Plastics

Adhesives

Cosmetics

Oil Industry Rubber

Electronics

Textiles/Clothing

Water Treatment

Biomedical

Pharmaceutical

Automotive

Aerospace Coatings

Paper



Medical, PharmaceuticalMedical, PharmaceuticalMedical, PharmaceuticalMedical, Pharmaceutical



Electrical, ElectronicElectrical, ElectronicElectrical, ElectronicElectrical, Electronic

http://www.google.com/products/catalog?hl=en&q=Flat+Screen+TV&ved=0CCIQrQQwAA&cid=11299453432252307421&sa=image



Aerospace, Marine



15

Composites

Composite: consisting of two or more distinctparts, which remainseparate and distinct on

a macroscopic level.



Fiber-Polymer Composites

Matrix Material

Fiber

Types of Fibers:

•Glass

•Graphite

•Boron

•Silica

•Kevlar

Matrix Function:

•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

{ 5-500μm



Polymer Matrices

Thermoplastics High Mw chains

Association through

Hydrogen bonding, van der Waals forces,dipole-dipole, aromatic stacking

Flow upon heating

Polystyrene, polyethylene, nylons,polycarbonate, polyacetals

Thermosets Crosslinked network

Cannot be softened or melted

Epoxides, polyesters,phenolics, ureas, melamine,silicones, polyimides

13700 260 650 110

0Temperature Range °C

Polymer

Composites

Metal

Composites

Glass

Composites

Ceramic &

Carbon-

Carbon

Composites

Tuttle, M. E., Structural Analysis of Polymeric Composite Materials. Marcel Dekker: 2004; p 1-41.



18

Elevated Cure

Initial Cure Post Cure

heat

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

Morgan, P., Carbon Fibers and Their Composites. Taylor and Francis: Boca Raton, 2005; p 501-544



19

Click Reactions

R'

"RO R'OR"

O

R'

Nuc

HO

R'

N

R'

"RO

N

NN

R'

"R

R"-N3

Cu(I)

[O] Nuc

R"O-NH3

Requirements

•easy to perform

•work-up

•high yielding

•tolerant to oxygen & water

•high thermodynamic driving force

(>20 kcal/mol)

Kolb, H. C.; Finn, M. G.; Sharpless, K. B.; Angewandte Chemie International Edition 2001, 40, 2004-2021.

H i



20

N N N

R1

H R2

N

N N

N

N N

R2

R1 R1

R2

+Thermal

Cu(I)

N

N N

R2

R1

1,4 regioisomer 1,5 regioisomer

R-N3 =

1 1a 1b 1c 1d

N

R N N

N

R N NN

R N N

N

R N N

•Proceeds at low temp,

even room temp•Extremely exothermic

•Azides are highlyenergetic,

explosive

•Easily dissociate intonitrene & dinitrogen

Brase, S.; Gil, C.; Knepper, K.; Zimmermann, V., Angew. Chem. Int. Ed. 2005, 44, 5188-5240.

Kolb, H. C.; Finn, M. G.; Sharpless, K. B., Angewandte Chemie International Edition 2001, 40, 2004-2021.

Huisgen1,3-Cycloaddition

i l



Epoxy Triazole CureEpoxy Triazole Cure

(Azido/Alkyne Reaction)(Azido/Alkyne Reaction)

C O

CH2 CH

CH2

O

CH2CH

CH2

CH3

CH3

O O

Na N3+

C O

CH2 CH

CH2

O

CH2CH

CH2

CH3

CH3

O O

NH4Cl

+ H

+ NaCl + NH3

N3 N3

C O

CH2 CH

CH2

O

CH2CH

CH2

CH3

CH3

OH OH

N3 N3

70/30 v/v

2-Ethoxyethanol/H2O ∆ 130 C°

4 h Highly exothermicHighly exothermic

higher crosslinkhigher crosslinkdensity prior todensity prior tovitrificationvitrification

Proceeds at lowProceeds at low

temp, even roomtemp, even roomtemptemp Easy scale-upEasy scale-up



Alkyne Crosslinkers

N

O

N

TPJeff (solid)

n

N

TPA (liquid)

TPEDA (liquid)

N N

OO

O

OO

O

TMBTP (solid)

O

O

O

O

4

TEGDP (liquid)

O

O

4

TEGDPE (liquid)

O

O

O

ODPA (liquid)

OO

O

TMTP (solid)

O

O

O

Amine Propargyl Propiolate



Linear Chain ExtensionLinear Chain Extension

C O

CH2

CH

OO

CH2

CH

N

O

CH3

CH3

N

NN

H

C

NN

H

C O

CH2

CH

H2C

O

CH2

CH

CH2

CH3

CH3

HO OH

N3

N3

CH2

CH2

O

O

CH2

CH2

O

C

C

HC

O

C

C

CH

O

+

O

CH2

CH2

O

O

CH2

CH2

O

C

O

CH2

CH2

C

O

CH2

O

CH2

CH2

C

O

CH2

O

CH2

CH2

C

O

CH2

O

C

HC

CH2

CH2

C

O

CH2

C

CH

O



Propiolate vs. Propargyl

A A i i



Average ActivationEnergies

AE (kJ/mol)

TMBTP 69.21

HDA 70.03

TEGDP 72.28

TMPTP 73.55

DPA 82.32

TMPTPE 82.51

TPDDS 82.62

TEGDPE 83.33TPEDA 84.32

TPA 84.72

TPJeff 85.88

TPTM 86.37

Distinct difference betweenpropiolate x-linkers &amine, propargyl types Resonance structure

N

Amine

O

O

Propargyl

O

Propargyl Ether

O

O

Propiolate



P

3

CuBr

NN

Cu

Cl Cl

Bromotris triphenylphosphine Cu(I)

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

Copper(II) ethylhexonate

H3C O

O

H3C2

Cu2+

Catalysis w/ Cu(I) &Cu(II)

Cu(I) &Cu(II) activity function of solubility,not oxidation state

-2

0

2

4

6

8

10

12

14

16

H e a t F l o w ( W

/ g )

-50 0 50 100 150 200 250 300

Temperature (°C)

un-catalyzed

1 mol % BTTPP

3.5 mol % BTTPP

5 mol % BTTPP

5 mol % CEH

5 mol % DCP

Exo Up Universal V4.3A TA Ins

Ch i A ti ti



Changes in ActivationEnergy

Averaged kinetic data does notaccount for mechanistic changes Temperature, extent of conversion

Problematic for complex systemsEpoxy, catalyst

OOHO

N3

OH

N3

O

O

O

O

3

Tetraethylene glycol dipropiolate (TEGDP)

O

O

3

Tetraethylene glycol diproargyl ether (TEGDPE)

+ or Copper(II) ethylhexonate (CEH)

H3C O

O

H3C 2

Cu2+

Room Temperature5 min

CH3

CH3

A ti ti E



Activation Energy vs.Conversion

0 50 100

68

70

72

74

76

78

80

82

84

86

88

90

92

94

96Catalyzed FWO Model

TEGDP

TEGDPE

E a

( k J / m o l )

α0 50 100

64

66

68

70

72

74

76

78

80

82

84

86

88

90

92

94

96

98

100

102Un-catalyzed FWO Model

TEGDP

TEGDPE

E a

( k J / m o l )

α

0 50 100

70

80

90

100

TEGDPE FWOModel Uncatalyzed

Catalyzed

E a

( k J / m o l )

α

0 50 100

64

66

68

70

72

74 TEGDP FWO ModelUncatalyzed

Catalyzed

E a

( k J / m o l )

α

C i D k



Comparison: Derakane510A-40 to BPA Azide-TMPTP

77.88°C

255.54°C

126.25°C

-0.5

0.0

0.5

1.0

1.5

2.0

H e a t F l o w ( W / g )

0 50 100 150 200 250 300 350

Temperature (°C)

Azide EPON + TMPTP

Control Derakane

Exo Up Universal V4.2E TA Instruments

O

O

O

O

O

O



Comparison: Isothermal 45°C

0.0

0.1

0.2

0.3

0.4

H e a t F l o w ( W / g )

0 20 40 60 80 100 120

Time (min)

Control Derakane

Epon Azide + TMPTP

Exo Up Universal V4.2E TA Instruments



Adhesion to Glass

BPA-Azide

Derakane



ConclusionsExothermic for low

temp cure

Customizable

catalystvariety of alkyne

crosslinkers

Superior adhesion to

glass (qualitative)

Future WorkDetermine

regioisomer linkage

Conduct mechanicaltest on cured resin &composite materials

Quantitativelymeasure adhesion

Synthesis of newazide compounds



School of Polymers & HighSchool of Polymers & HighPerformance MaterialsPerformance Materials

Graduate degrees are in Polymer Science and Engineering

12.9 million in funding

2009-10 enrollment

59 B.S. majors

77 Graduate students23 Postdoctoral fellows

Tuition waived

Up to 25,000 dollar stipend

Health insurance

Preparing for



Preparing forGraduate 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

Visit schools Talk to graduate students

Is there a fit?

Under-classman Consider academic

requirements

Research Experience for

Undergraduates (REU) Graduate school test run

Research experience

Publications

PSC Ph D R dPSC Ph D R d



PSC Ph.D. RoadmapPSC Ph.D. Roadmap

GuidelineGuideline

August2010

December 2014

Select

Advisor

RESEARCH

ResearchProspectus

ResearchProposal Defense

1 2 3 4

Exams

Sh lb F l d ThSh lb F l d Th



Shelby Freland ThamesShelby Freland ThamesPolymer Science ResearchPolymer Science Research

CenterCenter



$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

PSRC AdditionPSRC Addition

I t e tatioInstrumentation



500MHz Multi-Nuclear NMR 500MHz Multi-Nuclear NMR InstrumentationInstrumentation



Composite FabricationComposite Fabrication



Department of Polymer Science founded by Dr. ShelbyF. Thames in 1970

Elevated to School of

Polymers and HighPerformance Materials in 1999

History History



Faculty Research AreasFaculty Research Areas

• Biopolymers and biomimetic

polymers• Pharmaceutical polymers

Polymer Engineering

Coatings and Films

Biomedical Research

Polymer Synthesis

Formulation Science

Water-SolublePolymers

• Polymer composites• Nanoengineered materials• Membranes and fuel cells• Polymer processing and

rheology• Stimuli/-Responsive Systems• High solids, waterborne and

solvent based systems• “Green” coatings• Polymer photochemistry

• Controlled free radical

polymerization• Living polymerization• Functional polymers• Biodegradable materials

• High throughput screening

• Controlled activity• Surface assembly

• Colloid science



l d h

http://www.ge.com/en



Selected Research PartnersSelected Research Partners

Sports and High



http://www.albemarle.com/mainfrm.htm

http://www.pg.com/main.jhtml

http://www.zeonchemicals.com/default.asp

http://www.zeonchemicals.com/default.asp

http://www.energy.gov/index.html

http://www.nsf.gov/


http://www.noveoninc.com/

http://www.bayerpolymers.com/ls/bpo_internet_cms.nsf/ID/Home_DE



Sports and HighPerformance Materials

B i o m

e c h a n i c s &

K i n e s i o l o g y E x e

r c i s e &

H u

m a n

P h y

s i o l o g

y

Polymer Science

SHPM



2010 REU Summer Program

To apply:Online application:

http://www.usm.edu/polymer/Summer_research.php

Official transcriptTwo letters of recommendation

2010 Research Experience for UndergraduatesJune 1st – August 6th, 2010

Deadline: March 19th, 2010



Why Southern Miss?

− Polymer Science & Engineering

− School of Human Performance

− Synergistic Research Opportunity

− Carnegie Research Extensive University

− Leverage DoD Research Relationships



Outdoor Activities

40 mi Paved Trail 41 mi Hiking Trail 12 Golf Courses Canoeing Coast

Desoto NationalForest

Disk Golf Paul B. Johnson

State Park

Zoo Hunting Fishing

Mardi Gras



Mardi Gras

h i b llS h i b ll



Southern Miss FootballSouthern Miss Football

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QUESTIONSQUESTIONS



Anionic Polymerization Anionic Polymerization

KNH2NH3 K + H2N

H2N +

C

H2N

H2C C

CH2

C +

H H

H

H

H2C C

Hn

polystyrene

C

H

H

H H

growing chain

styrene

free ions

carbanion

potassiumamide



Bio InspiredBio Inspired

BiomimeticBiomimetic

Drug DeliveryDrug Delivery

BiopolymersBiopolymersBiocompatibleBiocompatible

Poly-DrugsPoly-Drugs



MarineMarineRoom Temperature Cure MatricesRoom Temperature Cure Matrices

Fire / Flame / Smoke RetardantsFire / Flame / Smoke Retardants

Matrix KineticsMatrix Kinetics

VARTMVARTMCarbon-Fiber CompositesCarbon-Fiber Composites

l



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