Thermally stable, glassy polymeric materials were prepared from maleimide-acetylene terminated monomeric materials by several methods. The monomers were heated to self-polymerize. The A-B structure of the monomer allowed it to polymerize with either bismaleimide monomers/oligomers or bis-acetylene monomers/oligomers. Copolymerization can also take place by mixing bismaleimide and bisacetylene monomers/oligomers with the maleimide-acetylene terminated monomers to yield homogenous glassy polymers

Gerber, Margaret K.

St.clair, Terry L.

English

NASA Technical Reports Server

IIIIII 1l11111 Ill 11111 11111 11111 11111 1ll11 lllll l111111111111111111 
US005189129A 
United States Patent 1191 [ i l l  Patent Number: 5,189,129 
Gerber et al. [45] Date of Patent: Feb. 23, 1993 
HIGH TEMPERATURE POLYMER FROM 
MONOMERS 
Inventors: Margaret I(. Gerber, Cincinnati, 
MALEIMIDE-ACETYLENE TERMINATED 
Ohio; Terry L. St. Clair, Poquoson, 
Va. 
The United States of America as 
represented by the Administra tor of 
the National Aeronautics and Space. 
Administration, Washington, D.C. 
Assignee: 
Appl. NO.: 801,868 
Filed: Dec. 3,1991 
Related U.S. Application Data 
Continuation-in-part of Ser. No. 528,666, May 18, 
1990, abandoned. 
Int. ( 3 . 5  ............................................ C08F 222/40 
U.S. Cl. .................................... 526/262; 526/285; 
528/322 
Field of Search ................. 526/262, 285; 528/322 
1561 References Cited 
U.S. PATENT DOCUMENTS 
3,819,349 4/1915 Bilow et al. ........................... 260/41 
4,108,836 8/1918 Bilow .................................. 528/128 
4,216,407 6/1981 Bilow et  al. ......................... 528/212 
4,365,034 12/1982 Grimes et al. ...................... 524/256 
Primary Examiner-Harold D. Anderson 
Attorney, Agent, or Firm-George F. Helfrich 
Thermally stable, glassy polymeric materials were pre- 
pared from maleimideacetylene terminated monomeric 
materials by several methods. The monomers were 
heated to self-polymerize. The A-B structure of the 
monomer allowed it to polymerize with either bismalei- 
mide monomers/oligomers or bis-acetylene monomers- 
/oligomers. Copolymerization can also take place by 
mixing bismaleimide and bisacetylene monomers/oli- 
gomers with the maleimide-acetylene terminated mono- 
mers to yield homogenous glassy polymers. 
1571 ABSTRACT 
31 Claims, No Drawings 
https://ntrs.nasa.gov/search.jsp?R=19930010138 2020-03-24T07:30:03+00:00Z
5.189.129 
1 
HIGH TEMPERATURE POLYMER FROM 
MALEIMIDE-ACETYLENE TERMINATED 
MONOMERS 5 
2 
ORIGIN OF THE INVENTION 
The invention described herein was made in the per- 
formance of work under a NASA contract and is sub- 10 
ject to the provisions of Section 305 of the National 
Aeronautics and Space Act of 1958, as amended, Public 
Law 85-568(72 Stat. 435; 42 USC 2457). 
CROSS-REFERENCE 15 
This application is a continuation-in-part of copend- 
ing application Ser. No. 528,666, fded May 18, 1990, 
now abandoned. 
20 
BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates generally to polyimides 
which are suitable for high temperature applications as 25 
a result of their high or nondetectable glass transition 
temperature and their high themooxidative stabilities. 
It relates particularly to three series or types of polyi- 
mides which are prepared from maleimide-acetylene 30 
terminated monomers. 
2. Description of Related Art 
Polyimides that are prepared from the reaction of 
organic compounds containing pendant acetylene 
groups or organic oligomers containing pendant acety- 
lene groups are well known for their thermooxidative 
stability and exceptionally high glass transition temper- 
atures. Likewise, organic compounds or oligomers con- 
taining activated carbon-carbon double bonds can be 
used to prepare polymers which are thermally stable if 
these compounds or oligomers contain imide moieties 
(Le. maleimides). 
However, polymers prepared from these compounds 
are often brittle and difficult to process. Bilow et al. 
(US. Pat. No. 4,108,836) developed a process for pre- 
paring alcohol soluble polyimide precursors which can 
be imidized in situ and cured through acetylene end 
groups. In a later invention, Bilow et al. (US. Pat. No. 
4,276,407) invented a phenylacetylene terminated oligo- 
mer which melts at low temperatures. Grimes and Rein- 
hart (U.S. Pat. No. 4,365,034) patented a new composi- 
tion of matter comprising an acetylene-terminated poly- 
imide oligomer and a cure rate inhibitor. Bilow et al. 
(U.S. Pat. No. 3,879,349) prepared polyimide polymers 
from the homopolymerization of acetylene substituted 
polyimide oligomers which could be processed into 
useful articles at moderate temperatures and pressures. 
SUMMARY OF THE INVENTION 
Mixtures of maleimide-acetylene terminated mono- 
mers have the following general primary structure: 
35 
40 
45 
50 
55 
60 
65 
II 0 0  0 
where R, Y, and Z are any aromatic moiety as set forth 
in detail below. 
The two types of unsaturation (double and triple- 
bonded carbons) allows for the formation of a co-con- 
tinuous network by polymerizing these monomers with 
themselves, bismaleimide monomers or oligomers, bis- 
acetylene monomers or monomers, or mixtures thereof. 
The maleimide-acetylene terminated oligomeric mate- 
rial is not pure or isolated, but is instead a mixture con- 
taining a statistical distribution of bismaleimide, bis-ace- 
tylene, and maleimide-acetylene terminated monomers. 
This mixture offers several advantages over current 
isolated (or pure) monomer systems which are polymer- 
ized with pure bis-acetylene or bismaleimide monomers 
or oligomers. The mixture allows for lower melting 
temperatures and easier processing. Another advantage 
is an increase in compatibility with bis-acetylene and 
bismaleimide monomers or oligomers in the melt. This 
results in an overall reduction in the amount of phase 
separation and allows for a homogeneous polymer. The 
resulting polymers from these monomers are more flexi- 
ble than polymers made from previous maleimide-ace- 
tylene monomers. 
An object of the present invention is to provide a 
high temperature polymer which is easier to process 
and more flexibel by heating a maleimide-acetylene 
terminated monomeric material to a temperature where 
it reacts or exotherms. 
Another object is to provide high temperature poly- 
mers by mixing the maleimide-acetylene terminated 
monomeric material with acetylenecontaining com- 
pounds and/or oligomers and heating them to a temper- 
ature where they react. 
Another object is to provide high temperature poly- 
mers by mixing the maleimide-acetylene terminated 
monomeric material with maleimide containing mono- 
mers or oligomers and heating them to a temperature 
where they react. 
Another object is to provide high temperature poly- 
mers by mixing the maleimide-acetylene terminated 
monomeric material with compounds such as N-(3ethy- 
nyl-pheny1)maleimide (NEPMI) and heating them to a 
temperature where they react. 
Another object is to provide homogeneous high tem- 
perature polymers by mixing the maleimide-acetylene 
terminated monomeric material with mixtures of malei- 
mide monomers or oligomers and acetylene monomers 
or oligomers. 
DESCRIPTION OF THE PREFERRED 
EMBODIMENTS 
Maleimide-acetylene terminated monomeric materi- 
als were prepared and then heated in an open pan at 
various rates using a DuPont 1090 thermal analyzer to 
produce high temperature polymers. The monomers 
were prepared according to the following procedure: 
3 
5,189,129 
4 
organic v II 
solvent n -
organic 
Byproducts such as bismaleimides, bis-acetylenes, and then vacuum dried for approximately 12 hours at 
and monomers with either maleimide or acetylene ter- 100" C. Approximately 71 g of the material were iso- 
minations were left in with the primary product. This 25 lated. The resulting monomeric material had the follow- 
mixture offers several advantages over current isolated ing primary structure: 
monomer systems which are polymerized with pure 
bis-acetylene or bismaleimide monomers. The mixture 
allows for lower melting temperatures and easier pro- 
cessing due to a broad processing window. Another 
advantage is an increase in compatibility with bis-acety- 
lene and bismaleimide monomers or oligomers in the 
melt as a result of the A-B structure of the monomer. 
This results in a reduction in the phase separation of the 
polymer. The monomeric structure also allows for an 
increase in flexibility and a reduction in the amount of 
shrinkage of the polymer as compared to polymers 
made with the previous acetylene-maleimide termi- 
nated monomer. 
EXAMPLES 
EXAMPLE 1 
A solution of 0.1 moles (24.83 g/mole) 3,3'- 
diaminodiphenylsulfone (3,3'-DDS) and 0.1 moles 
(98.06 g/mole) maleic anhydride (MA) in 100 ml N- 
dimethyacetamide @MAC) was prepared. A second 
solution of 0.1 moles (358.29 &mole) 3,3',4,4'-sul- 
fonediphthalic anhydride (SOIDPA) and 0.1 moles 
(1 17.1512 g/mole) 3-aminophenyl acetylene (APA) in 
100 ml DMAc was also prepared. The two solutions 
were poured together and stirred at room temperature 
for several hours. Then, 0.2500 g of nickelous acetate 
and 200 ml of acetic anhydride were added and stirring 
of the solution was maintained for several hours in 
order to cyclodehydrate the compound. The malei- 
mide-acetylene terminated monomeric material was 
isolated from the solution by pouring the solution into a 
blender half full of ice water. A fine white precipitate 
was filtered and washed 3 times with deionized water 
40 
A 5 mg sample of the monomeric material was ther- 
45 mally polymerized by heating in open pans in a thermal 
analyzer at rates of lo", 20', 50' and loo' C./min. Melt- 
ing transitions were observed between 140'-155' C. 
depending on the heating rate. After melting, an exo- 
therm, which increased in intensity as the heating rate 
50 was increased, was observed at approximately 
250'-285' C. and the temperature for the exotherm 
increased with the heating rate. No glass transition 
temperatures were observed after heating the polymers 
to 400" c. 
EXAMPLE 2 
The maleimide-acetylene terminated monomeric ma- 
terial prepared in Example l was blended at a 1:l molar 
ratio with NEPMI and was thermally polymerized at 
60 10' and 50' C./min. Melt transitions were observed at 
127' and 137' C. at lo' and 50' C./min respectively. 
After the melt, an exotherm, which increased in inten- 
sity as the heating rate was increased, was observed at 
225" and 260" C. respectively. No glass transition tem- 
65 peratures were observed after heating the polymer to 
400" C. Although NEPMI was the monomer used in 
this example, any monomer having the following struc- 
ture can also be used: 
55  
5 
5,189,129 
6 
mine (p-PDA) and 0.05 moles (98.06 g/mol) MA in 50 
ml DMAc. The two solutions were blended, cyclized, 
filtered, and dried as in Example 1. The resulting mono- 
meric material had the following primary structure: 
0 0 0 
0 c N ~ N w N a c = c H  II 11 
0 
11 
0 0 
CN-- .=cH EXAMPLE 5 
Each of the three previously prepared maleimide- 
acetylene terminated monomeric materials were ad- 
mixed at a 1:l ratio with a sample of a maleimide of 
methylene dianiline @MI) and heated to 300" C. A 
2o polymeric glass resulted. Although, BMI was used in 
this example, any monomer or oligomer of the follow- 
ing general 
15 
II 
0 
where Ar is any aromatic moiety. 
EXAMPLE 3 
A malehide-acetylene terminated monomeric mate- 
rial was prepared. A solution of 0.05 moles (200.242 
g/mol) maleic anhydride (MA) in 50 ml of DMAc was 
combined with a solution of 0.05 moles (322.234 g/mol) 25 
benzophenonetetrawboxylic dianhydride (BTDA) 
and 0.05 moles (117.1512 &mol) APA in 50 ml DMAc. 
can also be used: 
g/mol) 4,4'-oxydianiline (ODA) and 0.05 moles (98.06 0 0 
c N ; - N >  
The solutions were blended, cyclized, filtered, and I1 11 
dried as in Example 1. The resulting monomeric mate- 0 
30 rial had the following primary structure: 
0 0 
When heated at lo" and 50" C./min, the compound 
exhibited a strong broad exotherm from 240"-280" C. 
and 250"-320' C. respectively. No melt transitions were 
observed nor were any glass transitions noted for the 
resulting polymer. 
EXAMPLE 4 
45 
A maleimide-acetylene terminated monomeric mate- 
where Ar is any aromatic moiety and n= 1-50. 
EXAMPLE 6 
Each of the three previously prepared maleimide- 
acetylene terminated monomeric materials were ad- 
mixed with a sample of a bis-acetylene terminated oligo- 
mer, Thermid 600@ which is available commercially 
from National Starch and has the structure: 
rial was prepared from a solution of 0.05 moles (218.123 
g/mol) of pyromellitic dianhydride (PMDA) and 0.05 
moles (117.1512 g/mol) APA in 50 ml DMAc and a 
solution of 0.05 moles (108.144 g/mol) p-phenylene-dia- where n= 1-10 
5,189,129 
7 8 
The mixture was heated to 300" C. and a polymeric 
acetylene terminated oligomer used in this example, 
other bis-acetylene terminated oligomers having the 
0 0  
glass resulted. Although Thermid 600Q was the bis- 
following general structure may also be used. 
where n= 1-50 and Ar is any aromatic moiety. 
0 
5 
HCrC-(Ar) , -CrCH 
I1 II 
0 0  II 0 
10 where R, Y, and Z are any aromatic moiety. EXAMPLE 7 
Each of the three previously prepared maleimide- 
acetylene terminated monomeric materials are blended 
with a mixture of Thermid 600Q and BMI. The mix- 
2. A thermally stable, glassy polymer according to 
claim 1, wherein (I) has the following primary struc- 
tural formula: 
0 0 0 
c N - @  II 
S O 2 0  N b  ' O 2 & N 0 C G  CH. 
II 
0 
II 
0 
II 
0 
ture is heated to 300" C. to yield a homogenous poly- 
meric glass. 
These thermally stable, glassy polymers are formed 
3. A thermally stable, glassy polymeric material ac- 
z5 cording to claim 1, wherein (I) has the following pn- 
mary structural formula: 
from monomers and oligomers that melt and polymer- 
ize without the evolution of volatiles. They are easy to 
process because of their lower melting temperatures. 
4. A thermally stable, glassy polymer according to 
claim 1, wherein (I) has the following structural for- 
mula: 
0 0 0 
5. A thermally stable, glassy polymer according to 
claim 2, wherein the monomer composition additionally 
at least one (v) ethynylimide havins the 
fol1O-g general formula: 
They exhibit no glass transition Up to 400" c. because Of 
their high crosslink densities. Despite their high cross- 
link densities, the polymers formed from the maleimide- 
acetylene terminated monomers are more flexible and 55 
undergo less shrinkage than those formed from previous 
maleimide-acetylene monomers. Their A-B structure 
increases compatibility when they are polymerized with 
mers. These polymers are useful as high temperature 60 
0 03 
bis-acetylene and bismaleimide monomers and oligo- C N -  Ar -CGCH 
composite matrix resins for supersonic aircraft struc- 
tures in mainframe and engine applications. 
II 
0 
What is claimed as new and desired to be secured by 
1. A thermally stable, glassy polymer prepared from 65 
Letters Patent of the United States is: 
a monomer composition comprising at least one (I) 
ethynyl maleimide having the following general pri- 
mary structural formula: 
where Ar is any aromatic moiety. 
6. A thermally stable, glassy polymer according to 
claim 3, wherein the monomer composition additionally 
comprises at least one (V) ethynylimide having the 
following general formula: 
9 
5,189,129 
10 
(V) 
5 
where Ar is any aromatic moiety. 10 
7. A thermally stable, glassy polymer according to 
claim 4, wherein the monomer composition additionally 
comprises at least one (V) ethynylimide having the 
following general formula: 
15 
0 
20 
0 
where Ar is any aromatic moiety. 
claim 5, wherein (V) has the formula: 
8. A thermally stable, glassy polymer according to 25 
0 
It 
(NEPMI) 
30 
35 
9. A thermally stable, glassy polymer according to 
claim 6, wherein (V) has the formula: 
0 
II 
(NEPMI) 
40 
0 45 
10. A thermally stable, glassy polymer according to 
claim 7, wherein (V) has the formula: 
comprises at least one (VI) bisimide having the general 
formula: 
n=  1-50 
where Ar is any aromatic moiety. 
15. A thermally stable, glassy polymer according to 
claim 3, wherein the monomer composition additionally 
comprises at least one (VI) bisimide having the general 
formula: 
n= 1-50 
where Ar is any aromatic moiety. 
16. A thermally stable, glassy polymer according to 
claim 4, wherein the monomer composition additionally 
comprises at least one (VI) bisimide having the general 
formula: 
55 
n= 1-50 
17. A thermally stable, glassy polymer according to 
where Ar is any aromatic moiety. 
claim 14, wherein (VI) has the following structure: 
11. A thermally stable, glassy polymer according to 
claim 2, wherein the monomer composition consists of 
12. A thermally stable, glassy polymer according to 
claim 3, wherein the monomer composition consists of 
13. A thermally stable, glassy polymer according to 
claim 4, wherein the monomer composition consists of 65 
14. A thermally stable, glassy polymer according to 
claim 2, wherein the monomer composition additionally 
01). 60 
(111). 
0V). 
0 0 
18. A thermally stable, glassy polymer according to 
claim 15, wherein (VI) has the following structure: 
n 0 
I I  
0 
11 
0 
19. A thermally stable, glassy polymer according to 
claim 16, wherein (VI) has the following structure: 
11 
0 
5,189,129 
12 
comprises at least one (VII) bisacetylene having the 
following general formula: 
II 
HC-C--(Ar),-C=CH (VW 
n= 1-50 
where Ar is any aromatic moiety. 
22. A thermally stable, glassy polymer according to 
claim 4, wherein the monomer composition additionally 
20. A thermally stable, glassy polymer according to 10 comprises at least one (VII) bisacetylene having the 
following general formula: 
II 
0 
II 
0 
claim 2, wherein the monomer composition additionally 
comprises at least one (VII) bisacetylene having the 
following general formula: HC=C-(Ar).-CrCH WII) 
n= 1-50 
where Ar is any aromatic moiety. 
WII) 15 n=1-50 
where Ar is any aromatic moiety. 
claim 20, wherein (VII) has the following structure: 
23. A thermally stable, glassy polymer according to 
where n = 1-10. 
21. A thermally stable, glassy polymer according to 
claim 3, wherein the monomer composition additionally 
24. A thermally stable, glassy polymer according to 
claim 21, wherein (VII) has the following structure: 
where n = 1-10, 
25. A thermally stable, glassy polymer according to 
claim 22, wherein (VII) has the following structure: 
5,189,129 
13 14 
0 0 0 
where n = 1-10 
26. A thermally stable, homogenous, glassy polymer 2o 
a) an acetylene-maleimide terminated monomer hav- 
where n= 1-50 and Ar is any aromatic moiety; and 
c) a bis-acetylene terminated monomer having the 
following general structural formula: 
prepared from 
ing the following general structural formula: 
HCrC+Ar)n-CrCH 
0 0  
c N - y - N v R v N - z - c E c H  A A
2s where n= 1-50 and Ar is any aromatic moiety. 0 
27. A thermally stable, homogenous, glassy polymer 
according to claim 26, wherein said acetylene-malei- 
mide terminated monomer has the following primary 
I1 structure: I1 0 0 
0 0 0 
C N O  S O 2 0 . a  s o 2 & N 0 C = C H .  II 
0 
I1 
0 0 
28. A thermally stable, homogenous, glassy polymer 
40 according to claim 26, wherein said acetylene-malei- 
mide terminated monomer has the following primary 
structure: 
where R, Y, and Z are any aromatic moiety; 
b) a bismaleimide terminated monomer having the 
following general structural formula: 29. A thermally stable, homogeneous, glassy polymer 
according to claim 26, wherein said acetylene-malei- 
mide terminated monomer has the following primary 
structure: 
5,189,129 
15 
30. A thermally stable, homogeneous, glassy polymer 
according to claim 26, wherein said bismaleimide termi- 
nated monomer has the following structure: 
16 
0 0 @MI) 
0 0 
10 31. A thermally stable, homogenous, glassy polymer 
according to claim 26, wherein said bis-acetylene termi- 
nated monomer has the following structure: 
35 
40 
45 
50 
55 
60 
65 


High temperature polymer from maleimide-acetylene terminated monomers

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