Synthesis and Characterization of Polyhydroxyamide ......Kevlar 292 15.2 PC 382 19.3 PE 1558 40.4 Total Heat Release (kJ/g) Heat Release Capacity (J/g ·K) Polymer CUMIRP Cluster F

CUMIRP Cluster F October 18, 2001

Synthesis and Characterization of Polyhydroxyamide/Polymethoxyamides

Arthur J. Gavrin, Eui-Sang Yoo, Richard Farris, E. Bryan Coughlin

CUMIRP Cluster F October 18, 2001

Outline

•Synthesis of PHA/PMeOA “smart”copolymers

•Thermal characterization of the copolymers

•Analysis of their potential to be thermally processed

FAA FAA

FAA

NH

O O

NH

HHOO

nPoly(hydroxy-amide): PHA

NH

O O

NH

H3CCH3OO

nPoly(methoxy-amide): PMeOA

CUMIRP Cluster F October 18, 2001

Synthetic Scheme for PHA/PMeOA “Smart”Fire-Safe Copolymers

H2N

O O

NH2

H3CCH3O

ClO

Cl

NH

O O

NH

H3CCH3OO

NO O

N On

+

NH

O O

NH

RROO

n

N2,pyridineDMAC

1) 0oC, 1h2) RT, 20h

heat+ 2n ROH

H2N

O O

NH2

HH

+1-x x

NH

O OHH

OONH

O O

NH

H3CCH3

CH2

CH2

OONH

O OHH

CH2

CH2

OONH

H2C

H2C

NH

y1-y + ClO

CH2

H2CC

H2

OCl

R' R'

n

PolyBenzoxazole (PBO)

CUMIRP Cluster F October 18, 2001

1H NMR of PMeOA

(ppm)

1.02.03.04.05.06.07.08.09.010.011.0

NH

O O

NH

H3CCH3OO

n

a

bc

d e

f

gh

a

b

c de,f

g,h

H2O

DMSO

CUMIRP Cluster F October 18, 2001

1H NMR of PHA/PMeOA Copolymers

(ppm)

1.02.03.04.05.06.07.08.09.010.011.0

(ppm)

1.02.03.04.05.06.07.08.09.010.011.0

(ppm)

1.02.03.04.05.06.07.08.09.010.011.0

(ppm)

1.02.03.04.05.06.07.08.09.010.011.0

25/75 PHA/PMeOA 25/75 PHA/PMeOA with90/10 IPC/GDC

50/50 PHA/PMeOA PMeOA

Peak found at 10ppm due to PHA hydroxyl group. All in DMSO-d6

CUMIRP Cluster F October 18, 2001

Microcalorimetry Data for Various Polymers

17130PMeOA

113350/50 PHA/PMeOA

20.445025/75/0/100 PHA/PMeOA

16.322425/75/50/50 PHA/PMeOA/IPC/GDC

126625/75/90/10 PHA/PMeOA/IPC/GDC

115025/75/100/0 PHA/PMeOA/IPC/GDC

1042PHA

15.2292Kevlar

19.3382PC

40.41558PE

Total Heat Release (kJ/g)

Heat Release Capacity (J/g ·K)Polymer

CUMIRP Cluster F October 18, 2001

DSC of PHA/PMeOA Copolymers

-2

0

2

4

Hea

t Flo

w (W

/g)

50 100 150 200 250 300 350 400

Temperature (°C)

–––––– 2575_F100_powder_2nd – – – 2575_F50_2ndbatch_2nd–––– · 2575f(5)10powder2nd–– – – 2575powder 2nd–– ––– PHA_2nd–––– – 50_50 powder 2nd– –– – pmeoa4powder 2nd

Exo Up Universal V2.5H TA Ins

Polymer Tg25/75/0/100 PHA/PMeOA/IPC/GDC 150.925/75/50/50 PHA/PMeOA/IPC/GDC 190.025/75/90/10 PHA/PMeOA/IPC/GDC 207.2

25/75 PHA/PMeOA 226.150/50 PHA/PMeOA N/A

PHA N/APMeOA 218.2

CUMIRP Cluster F October 18, 2001

0

20

40

60

80

100

120

Wei

ght (

%)

0 200 400 600 800 1000

Temperature (°C)

–––––– 2575_F50_2ndbatch_3rd – – – 2575_F100_powder–––– · PHA_powder–– – – 25_75_F10 powder–– ––– 25_75 powder(2nd) dried at 160–––– – 50_50 powder– –– – PMEOA powder

Universal V2.5H TA Ins

TGA of PHA/PMeOA Copolymers

CUMIRP Cluster F October 18, 2001

70

80

90

100

110

Wei

ght (

%)

200 250 300 350 400 450

Temperature (°C)

–––––– 2575_F50_2ndbatch_3rd – – – 2575_F100_powder–––– · PHA_powder–– – – 25_75_F10 powder–– ––– 25_75 powder(2nd) dried at 160–––– – 50_50 powder– –– – PMEOA powder

Universal V2.5H TA Ins

TGA of PHA/PMeOA Copolymers

CUMIRP Cluster F October 18, 2001

Thermal Characteristics of PHA/PMeOA Hybrid at different composition

Results from DSC Results from TGA

0 20 40 60 80 100

220

230

240

250

260

270

Tem

pera

ture

(oC

)

PHA Content (%)0 10 20 30 40 50 60 70 80 90 100 110

260

280

300

320

340

360

380

400

Tem

pera

ture

(oC

)

PHA Content (%)

onset for PHA cyclization

Tg

onset for weight loss of PMeOA part

onset for weight loss of PHA part

CUMIRP Cluster F October 18, 2001

Thermal Characteristics of PHA/PMeOA/Flexible Hybrids with different Flexible part contents

Results from DSC Results from TGA

onset for PHA cyclization

Tg

onset for weight loss of PMeOA part

onset for weight loss of PHA part

0 20 40 60 80 100

140

160

180

200

220

240

260

Tem

pera

ture

(oC

)

Content (%)0 10 20 30 40 50 60 70 80 90 100 110

210

240

270

300

330

360

390

Tem

pera

ture

(oC

)

Content (%)

CUMIRP Cluster F October 18, 2001

-5

5

15

25

Dim

ensi

on C

hang

e (%

)

50 100 150 200 250 300

Temperature (°C)

–––––– PMEOA_thin(10/min) – – – 2575_thin(10/min)–––– · 2575_F10_thin(10/min)–– – – 2575_F50_tihn_2ndbatch_radial–– ––– 2575_F100_tihn_radial

Universal V2.5H TA

TMA of PHA/PMeOA Copolymers

CUMIRP Cluster F October 18, 2001

Other Possible Avenues

H2N

CC

NH2

• Crosslinkers• Thermally Induced• Chemically Incorporated

C

C

C

C

O

OO

O

ClCl Cl

Cl

Si

Si

O

O

Si

Si

Si

Si

O

O

O

O

SiO

Si

O

OO

OO

R R

R

RR

R

H2NNH2

Protective Surface Formation

CUMIRP Cluster F October 18, 2001

Future Work and Acknowledgments• Synthesize more flexible

copolymers to optimize processability while retaining low heat release properties

• Optimize synthesis to obtain maximum molecular weight

• Conduct heat treatment studies to determine the effects of solvent and percent cyclization on the physical properties

• Melt spin fibers and examine their physical properties

We would like to thank the following for their financial support for this project:

• Boeing- Commercial Airplane Group

• bp• Federal Aviation Administration• Foster-Miller Inc.• General Electric Co.• Schneller Inc.• Eikos• United States Army• National Institute of Standards and

Technology