Much of the polyimide research at Langley Research Center has focused on isomeric modification of the diamine component; polyimides having considerably improved processability and adhesion have resulted. The present structure-property study was designed to investigate how isomeric attachment of the three oxydiphthalic anhydride (ODPA) polyimides affects their properties. Each dianhydride, 3,4,3',4'-oxydiphthalic anhydride (4,4'-OPDA,I), 2,3,2',3'-oxydiphthalic anhydride (3,3'-ODPA,II), and 2,3,3',4'-oxydiphthalic anhydride (3,4'-OPDA,III), was reacted with p-phenylenediamine, 4,4'-oxydianiline, 3,3'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, and 4,4'-bis(3-aminophenoxy)benzophenone in DMAc. The inherent viscosities of the resulting poly(amic acids) were determined. Thermally imidized films were studied for their creasability and solubility, as well as by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and wide angle X-ray scattering (WAXS). A comparison of these properties will be made

Gerber, Margaret K.

Pratt, J. Richard

Stclair, Terry L.

English

NASA Technical Reports Server

NASA Technical Memorandum 101525 
I S M R I C  O X Y D I P H T H A L I C  A N H Y D R I D E  POLY IMIDES 
ZARGARET i < ,  GERBER, J,  R I C H A R D  FRATT AND TEREY L I  ST, C L A I L  
{ U S & - T B -  10 15 2 5 )  IS0 IPS3.C C 1 P D I E H T H A L I C  
A P H Y i i b l D E  F O t Y X B l E E S  (EASA) 1 4  F CSCL 118 
Unclas 
63/27 0 I852 19 
NClVErEIBER 1968 
National Aeronautics and 
Space Administration 
Langley Research Center 
Hampton, Virginia 23665-5225 
https://ntrs.nasa.gov/search.jsp?R=19890005885 2020-03-20T04:49:08+00:00Z
ISOMERIC OXYDIPHTHALIC ANHYDRIDE POLYIMIDES 
M. K. GERBER,* J. R. P R A T  AND T. L. ST. CLAIR 
NASA LANGLEY RESEARCH CENTER 
HAMPTON, VA 23665-5225 
INTRODUCTION 
The objective of this structure-property study was to investigate 
the effect of isomeric attachment of the three oxydiphthalic anhydride 
(ODPA) polyimides on various polymer properties such as film forming 
ability, glass transition temperature (Tg), crystallinity and 
thennooxidative stability. Polyimides were prepared from these three 
anhydrides and characterized by various methods. Polyimides 
containing the 4.4'-ODPA isomer are known1.2; however, the 
synthesis and polymerization of the 3,3'-ODPA and 3,4'-ODPA isomers 
have not yet been reported. 
EXPERIMENTAL 
Chemicals were received from commercial sources except the 
3.4'-ODPA and 1.3-bis (4-aminophenoxy-4'-benzoyl)benzene which 
were synthesized in-house. See Figure 1 for the structures of the 
*PRC SYSTEMS SERVICES WORKING AT NASA LANGLEY RESEARCH 
CENTER 
2 
dianhydrides and Figures 2 and 7 for the diamine structures. The 
name, acronym, source, DTA maximum melting point 
and method of purification are as follows: 2,3,2',3'-oxydiphthalic 
anhydride (3,3'-ODPA), experimental sample from Occidental 
Chemical Corporation, 237OC. recrystallized from acetic anhydride: 
3,4,3'4'-oxydiphthalic anhydride (4,4'-ODPA), experimental sample 
purchased from Occidental Chemical Corporation, 22 l0C, used as 
received: 4,4'-bis(3-aminophenoxy)benzophenone, Mitsui Toatsu 
Chemical Corporation, 14 l0C, used as received; 3.3'- 
diaminobenzophenone (3.3'-DABP), Ash Stevens, Inc., 15 l0C, used as 
received: 3,3'-diaminodiphenylsulfone (3.3'-DDS02), FIC Corporation, 
173OC. recrystallized from water: 4,4'-oxydianiline (4,4'-0DA). 
Kennedy and Klim, Inc., 187OC. used as received: p-phenylenediamine 
(p-PDA), Aldrich Chemical Corporation, 136OC, used as received: N,N- 
dimethylacetamide (DMAc), used as received from Fluka Chemical 
Corporation: 1,3-bis(4-aminophenoxy-4'-benzoyl)benzene (1,3-BABB),3 
experimental sample prepared by Dr. Steve Havens of this laboratory, 
165OC, used as received: 1,4-bis(3-arninophenoxy-4'-benzoyl)benzene, 
Mitsui Toatsu Chemical Corp., 156OC. used as received: and 1,3-bis(3- 
aminophenoxy-4'-benzoyl)benzene, Mitsui Toatsu Chemical Corp., 
148OC, used as received. 2,3,3',4'-Oxydiphthalic anhydride (3.4'- 
ODPA) was synthesized via the following method. (Figure 3) 
4-Hvdroxv-N-ethvl~h thalimide 
4-Hydroxyphthalic anhydride was prepared from 4- 
hydroxyphthalic acid (Lancaster Synthesis, Ltd., England) in 88% yield 
by heating in a vacuum oven 0.75 h at 18OoC, then slowly cooled 
, 
. 
3 
overnight. A small amount of product sublimed onto the glass wall of 
the oven. The m.p. was 162°C. Lit. reports m.p. 171-3OC.4 
4-Hydroxyphthalic anhydride (5.48 g, 0.0334 mol) and 
ethylamine (2.22 ml, 0.0337 mol) were refluxed for 2 h in 30 ml 
DMAc. On cooling the product was precipitated in a blender from 
deionized water, filtered, reslurried in additional water and vacuum 
dried to afford 4.86 g (76.1%). m.p. 194°C. (DTA onset m.p.) Anal. 
Calcd. for C10HgN03: C, 62.82: H, 4.74: N, 7.33. Found: C, 62.83: H, 
4.70: N, 7.33%. FUR (KBr): 3279 (phenolic OH): 3063 (aromatic 
C-H): 2986 (aliphatic C-H): 1762 and 1688 (imide I doublet): 1384 
(imide 11); 1078 (imide 111): 720 cm-1 (imide rV). 
3-Fluoro~hthalic anhvdride was prepared by reacting 3- 
nitrophthalic anhydride with C12 in the melt. followed by fluorination 
of the resulting 3-chlorophthalic anhydride with anhyd. KF.5 The 
melting points of the 3-chloro- and 3-fluorophthalic anhydrides were 
125°C and 157°C respectively. 
2.3.3'.4'-0xvdi~hthalic Anhvdride (3.4'-ODPA) 
4-Hydroxy-N-ethylphthalimide (4.60 g, 0.024 1 mol) and aqueous 
NaOH (1.90 g, 0.0241 mol of 50.7%) were heated with 30 ml DMSO 
and 35 ml toluene. A Dean-Stark trap was used to remove the toluene- 
water azeotrope for 2 h until clear. After cooling to room temperature 
3-fluorophthalic anhydride (4.00 g, 0.0241 mol) was added and the 
resulting solution was heated for 1 h at  73-75OC, then 1 h at 90-95°C 
before precipitation from water in a blender. Vacuum drying afforded 
3.58 g (44.1%) of unrecrystallized anhydride-imide, DTA m.p. 197°C 
(slightly broad). IR (KE3r): 1852 and 1790 (anhydride doublet): 1772 
and 1710 (imide I doublet); 1260 cm-1 (aryl ether). No carboxylic 
4 
acid absorbtion was detected. The entire sample was hydrolyzed in a 
refluxing solution of 6.66 g of 50.7% aqueous NaOH and 25 ml water 
for 20 h and filtered cold. The filtrate was acidified with excess 6 N  
HCl and a white collodial product was removed by centrifugation and 
rinsed with a small amount of water. Two additional crops were taken 
after the filtrate was evaporated under the hood for several weeks. 
Vacuum drying at 110°C afforded 3.65 g (45.0%) of crude 
tetracarboxylic acid, m.p. 198-2 13°C (visual). IR (IU3r): 2300-3500 
(-C02H dimer): 1692 (carboxylic carbonyl): 1288 cm- 1 (arom. ether). 
Cyclization with acetic anhydride toluene for 1 h at reflux afforded 
3,4'-ODPA in 65.5% yield, m.p. 170°C. Anal. Calcd. for C16H607: C, 
61.95; H, 1.95: 0, 36.11. Found: C, 61.83: H, 2.13; 0, 36.33%. FTIR 
(KBr): 1852, 1777 (anhyd. carbonyl): 1257 cm-1 (arom. ether). 
Polvmer Svnthesis 
Polymerizations were conducted a t  15% solids in DMAc. The 
diamine was dissolved in the DMAc in an  oven-dried serum bottle. 
Stirring was accomplished with a magnetic stirrer. Anhydride was 
added to the dissolved diamine, and the solution was allowed to stir a t  
room temperature (RT) overnight (Figure 4). . The poly(amic acid) was 
cast on a soda-lime glass plate a t  approximately 20 mil wet thickness, 
dried at  RT to a tack-free film in a dust proof chamber and cured in a 
forced air oven 1 h each at 100°C, 200°C, and 300°C unless otherwise 
indicated. Cooled films were removed from plates using a razor blade. 
Characterization Methodology 
Inherent viscosities were determined for the poly(amic acid) 
solutions in DMAc at  0.5% (wt./vol.) and 35°C. Differential scanning 
calorimetry (DSC) was performed on fully imidized films using a 
5 
DuPont 990 Thermal Analyzer at 20°C/min. Torsional braid analysis 
(TBA) was conducted at  a heating rate of 3"C/min in air over the 
temperature range 50°C to 400°C. 
Films were characterized as "creasable" when they could 
withstand a 180" fold followed by a 360" fold with a finger crease; 
"brittle" films snapped or tore a t  the crease line. Those that could not 
be removed from the glass plate in one piece were termed "brittle 
pi e ce s . I' 
Imidized films were tested for solubility a t  RT at approximately 
1% by weight in methylene chloride, DMAc, and m-cresol. Films that 
were insoluble at 25°C in these solvents after several hours were also 
tested at  the boiling point of each solvent for 15 minutes. 
Wide Angle X-ray Scattering (WAXS) was performed on a Philips 
N D  3600, XRG 3100 at 45 kV and 40 mA using copper radiation with 
a flat sample holder and a graphite monochromator. Isothermal 
thermogravimetric analysis (ITGA) was performed on a Perkin Elmer 
TGS-2 thermogravimetric system at  325°C in flowing air for 100 h. 
Thermogravimetric analysis (TGA) was performed at a programmed 
heating rate of 2.5"C/min from 100°C to about 610°C. 
RESULTS AND DISCUSSION 
Table I lists the inherent viscosities of the various polymer 
systems, Tg of the imidized films by DSC and film characteristics. The 
3,3'-ODPA polyimides produced brittle films, while inherent 
viscosities of the corresponding poly(amic acids) ranged from 0.23 to 
0.59 dl/g. Glass transition temperatures ranged from 198"-294"C. All 
6 
of these films examined by WAXS were amorphous. Three of the 3.4'- 
ODPA polyimides produced creasable films and the corresponding 
poly(amic acids) had viscosities of 0.97 to 1.45 dl/g. ?bo films were 
brittle and lower viscosities, 0.35 and 0.55 dl/g, were observed for 
these poly(amic acids). The 3,4'-ODPA-p-PDA polyimide film required 
a curc to 350°C in air to complete imidization. Glass transition 
temperatures were higher than in the corresponding 3,3'-ODPA 
polyimides and ranged from 207°C to 313°C. All of these films 
examined by WAXS were amorphous. The 4,4'-ODPA polyimide films 
were all creasable when fully imidized and the corresponding 
poly(amic acid) viscosities ranged from 0.34 to 0.95 dl/g. Glass 
transition temperatures which ranged from 204°C to 268°C showed an 
increase from the 3.3'-ODPA and 3.4'-ODPA polyimides in all but two 
cases, however, this may be a function of molecular weight as these 
two poly(amic acids) had unusually high viscosities. No Tg was 
observed by DSC or TBA for the 4,4'-ODPA-p-PDA polyimide, which 
was semicrystalline by WAXS. 
Table I1 contains solubility data of the isomeric ODPA polyimides 
in three solvents. The 3,3'-ODPA polyimides appear to be the most 
soluble and the 4.4'-ODPA polyimides appear the least soluble. 
The 100 h, 325°C isothermal thermogravimetric analysis (ITGA), 
of the three isomeric ODPA polyimides polymerized with 4,4'-bis(3- 
aminophenoxy)benzophenone (similar viscosities) is presented in 
Figure 5. The 3,3'-ODPA and 3,4'-ODPA polyimides showed 8.07% and 
8.37% weight loss, respectively, after 100 h compared with the 4.4'- 
ODPA polyimide which experienced only 3.64% weight loss. 
7 
Dynamic TGA (Figure 6) showed a similar weight loss correlation 
to the ITGA curves. Once again the 4,4'-ODPA polyimide appeared 
most thcrniooxidatively stable. 
Three additional polymers were synthesized using 3,3'-ODPA 
and three longer chain bis(aminophenoxy benzoy1)benzene isomers 
(Figure 7 compounds A, B and C). Two of these polyimides gave filnis 
that were creasable, indicating higher molecular weight. The inherent 
viscosities of these two poly(amic acids) were 0.82 and 0.48 dl/g, 
respectively. Cured films exhibited Tgs at 214°C and 194OC, 
respectively. However, the polyimide film synthesized from lt4-bis(3- 
aminophenoxy-4'-benzoyl)benzene prduced a brittle film. The 
inherent viscosity of its poly(amic acid) was 0.58 dl/g and the cured 
film had a Tg of 197°C. The long chain nature of the diamine s e e m  to 
be an  important component in producing high molecular weight 
creasable films in the 3,3' ODPA system. 
SUMMARY AND CONCLUSIONS 
Two isomers of ODPA were procured as experimental samples, 
and one was synthesized in house for a structure - property study. 
Evaluation of polymers synthesized from the three isomers of ODPA 
indicated that all 4,4'-ODPA compositions produced high molecular 
weight creasable films; other isomeric ODPA compositions containing 
the 3-substituted ether linkage varied from low to high molecular 
weight as judged by their solution viscosities and flexibilities. A 
comparison of Tgs exhibited no significant trends. Polyimides based 
on 4.4'-ODPA were the least soluble in a range of organic solvents 
8 
while polyimides based on 3.3'-ODPA were the most soluble. The 4.4'- 
ODPA/ 4,4'- bis (3- aminop henoxy) benzophenone polyimide exhibited 
the highest thermooxidative stability by dynamic TGA and 325°C -1TGA 
when compared with the other ODPA isomers. Additional polymers 
synthesized from 3.3'-ODPA and diamines with an increased chain 
length produced two flexible films. 
1. 
2. 
3. 
4. 
5. 
REFERENCES 
St. Clair, T. L., St. Clair, A. K. and Smith, E. N., Structure-Solubilitv 
Relationships in Polvmers, Academic Press, 199 (1977). 
St. Clair, A. K., St. Clair, T. L., Polvmers for High Technolom, ACS 
Symposium Series 346. 437 (1987). 
Hergenrother, P. M., Wakelyn, N. T. and Havens, S .  J., "Polyimides 
Containing Carbonyl and Ether Connecting Groups," Journal of 
Polvmer Science: Part A: Polvmer Chemistry, 25, 1093 (1987). 
Heilbron, I., "Dictionary of Organic Compounds," 3, Fourth 
Edition, 1797 ( 1965). 
Heller, A., "Preparation of 3-Fluorophthalic Anhydride," Journal of 
Organic Chemistry, 25, 834 (1960). 
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Report Documentation Page 
17. Key Words (Suggested by AuthorWJ 
1. Report No. i 2 Government Accession No 
__ i NASA TM-101525 
4 Title and Subtitle 
18. Distribution Statement 
I someri c Oxydi phthal  i c Anhydri de Pol y i  m i  des 
19. Security Classif. (of this report) 120. Securiw Classif (of this page) 
I 
7. Authorls) 
21 No. of pages 22. Price 
Margaret K.  Gerber, J .  Richard P r a t t  and Te r ry  L .  
S t .  C l a i r  
9. Performing Organization Name and Address 
NASA Langley Research Center 
Hampton, VA 23665-5225 
- 
2. Sponsoring Agency Name and Address 
Nat iona l  Aeronaut ics  and Space Admin i s t ra t i on  
Washington, DC 20546-0001 
3 Recipient's C,italog No. 
5 Report Date 
___ November 1988 
6 Performing Organization Code 
~- 
8. Performing-Organization Report No. 
--____ 
10. Work Unit No. 
506-43 -1 1-01 
11. Contract or Grant No. 
13. Type of Report and Period Covered 
Technical  Memorandum 
14. Sponsoring bgency Code 
5. Supplementary Notes 
Use o f  t rade  names o r  names o f  manufacturer< does n o t  c o n s t i t u t e  an o f f i c i a l  
endorsement o f  such products  o r  manufacturers,  e i t h e r  expressed o r  imp1 ied ,  by 
t h e  Nat iona l  Aeronaut ics  and Space Admin i s t ra t i on .  
~ ~~~ 
6 Abstract 
Much o f  t he  po ly imide  research a t  Langley Research Center has focused on 
i someric modi f i c a t i  on o f  the d i  ami ne component; p o l y i m i  des having 
cons iderab ly  improved p r o c e s s a b i l i t y  and adhesion have resu l ted .  The 
present  s t ruc tu re -p roper t y  study was designed t o  i n v e s t i g a t e  how isomer ic  
at tachment o f  the th ree  oxydiphthal  i c  anhydride (ODPA) poly imides a f f e c t s  
t h e i r  p r o p e r t i e s .  Each dianhydr ide,  3,4,3' ,4 ' -oxydiphal  i c  anhydride 
(4,4'-ODPA, I )  2,3,2' ,3 ' -oxyd iph tha l i c  anhydr ide (3,3'-ODPA, 111, and 
2,3,3' , 4 ' -oxyd iph tha l i c  anhydride (3,4'-ODPA, 1111, was reacted wi th 
p-phenylenediamine, 4 ,4 ' -oxyd ian i l ine ,  3,3 ' -d iaminodiphenyl  sul fone, 
3,3'-diaminobenzophenone, and 4,4'-bis(3-aminophenoxy)benzophenone i n  DMAc. 
The i n h e r e n t  v i s c o s i t i e s  o f  the  r e s u l t i n g  poly(amic a c i d s )  were determined. 
Thermal ly im id i zed  f i l m s  were s tud ied  f o r  t h e i r  c r e a s a b i l i t y  and s o l u b i l i t y ,  
as we1 1 as by d i f f e r e n t i a l  scanning ca lo r ime t ry  (DSC), thermograv imetr ic  
ana lys i s  (TGA) and wide angle x-ray s c a t t e r i n g  (WAXS). 
these p r o p e r t i e s  w i  11 be made. 
A comparison o f  
lo1 ymer F i 1 ms 
'01 v imi  des 
I 1 Subject  Category - 27 
Jncl ass i  f i ed 1 U n c l a s s i f i e d  I 18 I A02 
NASA FORM 1626 OCT 86 


Isomeric oxydiphthalic anhydride polyimides

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