Note: Descriptions are shown in the official language in which they were submitted.
1082400
This application is divided from applicants copending application
Serial No. 243,546 which relates to soluble polyamide-imides which are useful
because of their solubility in non-polar volatile solvents.
This present invention relates to novel polyamide amic acid inter-
mediates in the preparation of said polyamide-imides derived from phenylindane
dl amlnes .
In accordance with the present invention there is provided a
soluble polyamide-amic acid consisting essentially of the recurring unit
having the formula
O O
NHC ,~ CNH-Y
~ ' ~ CO H _
._ _
wherein Y is a divalent organic radical selected from carbocyclic-aromaticJ
aliphatic, araliphatic, cycloaliphatic, and heterocyclic radicals, combination
of these, and radicals with heteroatom-containing bridging groups where the
heteroatom in the bridge is oxygen, sulfur, nitrogen, silicon or phosphorus,
provided that, out of the total number of polyamide-imide recurring units,
1 to 100 percent of such units have Y equal to a phenylindane radical of the
structural formula R2
R3 R4
CH3
~herein
-- 1 --
:
: . :
1082400
Rl is hydrogen or lower alkyl, and
R2, R3, R4 and R5 are independently hydrogen, halogen or lower
alkyl.
In another aspect, there is provided a process for the manufacture
of said polyamide amic acid defined above characterized in that process for
the manufacture of a soluble polyamide amic acid consisting essentially of
the recurring unit having the formula R2
~ R3
wherein Rl is hydrogen or lower alkyl, and R2, R3, R4 and R5 are independent-
ly hydrogen, halogen, or lower alkyl.
It is well known that aromatic polyamide-imides are tough, thermally
stable and flame resistant. The existing polyamide-imide polymers, however,
have found only limited commercial acceptance due to certain undesirable
properties. For example, in coating applications it is highly desirable for
the polymer to be soluble in relatively non-polar volatile solvents so that
solvent removal may be easily accomplished. Most high molecular weight poly-
amide-imides, however, are insoluble or only marginally soluble and only in
highly polar, non-volatile, expensive solvents.Furthermore, these solutions
generally are not stable.
Special tedious methods have been developed to fabricate these
polyamide-imides. One such method involves utilizing the more soluble
polyamide-amic acid precursor and thermally imidizing this material after
application. This procedure, however, releases volatiles at high tempera-
tures and leaves voids in the polymer. In wire coating applications this
1082400
necessitates making multiple coatings of thin films and imidizing the amic
acid between coats. This process is expensive and inefficient; it would
be desirable for the polyamide-imide to be sufficiently coated in one
application. Furthermore, polyamide-amic acids are not stable at ordinary
temperatures, especially when dissolved, and are extremely sensitive to
hydrolysis by small amounts of water.
Another method developed to produce soluble polyamide-imides is to
utilize isocyanate derivatives of the diamines in the reaction with trimel-
litic acid. This method, however, generally affords unstable solutions that
advance in viscosity with time.
Another method that claims to afford soluble polyamide-imides is
to perform the imide ring in the monomer before polymerization. This method
involves a multiple sequence of steps, including performing the imide ring,
and is undesirable from an economic standpoint. This invention is thus
directed at providing the polyamide-amic acid intermediates for the manu-
facture of aromatic polyamide-imides capable of forming stable solutions in
relatively non-polar solvents.
The polyamide-imides derived in whole or in part from diamines
containing a phenylindane nucleus in accordance with aforementioned applica-
tion Serial No. 243,546 are characterized by a recurring unit having the
following structural formula:
. _ _ .
--NH-C ~ N y _ _
wherein Y is a divalent organic radical selected from carbocyclic-aromatic,
aliphatic, araliphatic, cycloaliphatic, and heterocyclic radicals, combina-
tions of these, and radicals with heteroatom containing bridging groups
-- 3 --
- , ' - ,.
1~)8Z400
where the heteroatom in the bridge is oxygen, sulphur, nitrogen, silicon
or phosphorus, provided that, out of the total number of polyamide-imide
recurring units, 1 to 100 percent, preferably 10 to 100 percent of such
units, have Y equal to a phenylindane radical of the structural formula
~2
~ ~ R
wherein
Rl is hydrogen or lower alkyl, preferably lower alkyl of 1 to 5
carbon atoms, and R2, R3, R4 and R5 are independently hydrogen, halogen,
or lower alkyl, preferably lower alkyl of l.to 4 carbon atoms, and either
aromatic ring of the unsymmetrical phenylindane radical may be bounded to
an amide or imide nitrogen.
The phe~ylindane diamine component of the soluble polyamide-imide
can consist of any combination of the isomeric or substituted isomeric
diamino compounds represented by the structural formula
H2N ~ ~ J ~ ~ NH2
R3 Rl CH3
For example, the phenylindane diamine component can comprise from 0 to 100%
of 5-amino-1-~4'-aminophenyl)-1~3,3-trimethylindane in combination with from
- 4 -
~V8;~400
100 to 0% of 6-a~ino-1-(4'-aminophenyl)-1,3,3-trimethylindane. Further,
either or both of these isomers can be substituted over the entire range
from 0 to 100% by any of the substituted diamine isomers represented by
formula I without impairing the novel soluble nature of these polyamide-
imides Examples of such substituted diamino isomers are S-amino-6-methyl-
1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylindane, 5-amino-1-(4'-amino-Ar',
Ar'-dichlorophenyl)-Ar, Ar-dichloro-1,3,3-trimethylindane, 6-amino-1-(4'-
amino'-Ar', Ar'-dichlorophenyl)-Ar,Ar-dichloro-1,3,3-trimethylindane,
4-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethyl-indane and
Ar-amino-l-(Ar'amino-2',4'-dimethylphenyl)-1,3,3,4,6-pentamethylindane.
The prefixes Ar and Ar' in the above formulas indicate indefinite positions
for the given substituents in the phenyl rings.
Among the phenylindane diamines of the formula I, those are
preferred in which Rl is hydrogen or methyl, R2 and R3 independently of one
another are hydrogen, methyl, chloro or bromo and R4 and R5 independently of
one another are hydrogen, chloro or bromo. More preferred phenylindane
diamines of the formula I are those in which Rl is hydrogen or methyl, R2
and R3 independently of one another are hydrogen, methyl, chloro or bromo,
R4 and R5 independently of one another are hydrogen, chloro or bromo,
and the amino groups are at positions 5, 6, or 7 and at positions 3' or 4'.
Among the phenylindane diamines of the formula I those are most preferred
in which Rl is hydrogen or methyl, R2, R3, R4 and R5 are hydrogen, and the
amino groups are at positions 5 or 6 and at position 4'.
The phenylindane diamines may be prepared by various synthetic
routes. The most preferable method of preparation is through the acid-
catalyzed dimerization of styrene or substituted styrenes to produce the
given phenylindane. Then, by subse~uent nitration and reduction of the
phenylindanes, the phenylindane diamines are produced. One method of
- 5 -
~ ~ .
lV82400
achieving alkyl substitution on the aromatic rings of the phenylindane
diamines is by subjecting alkyl substituted compounds such as benzaldehyde,
acetophenone and the like to a Grignard reaction, followed by water removal
to produce the alkyl substituted styrene compound. Dimerization, nitration
and reduction can then be effected as mentioned above. Additionally, it
has been found that chlorine gas effects direct chlorine substitution on
the aromatic rings of diamino-1,3,3-trimethyl-1-phenylindane dihydro-
chloride to produce chlorinated diaminophenylindanes.
Characteristic of the solubilizing effect of the phenylindane
diamines is their property of imparting solubility to systems derived in
part from aromatic diamines through partial replacement of the diamine
portion. Such solubilizing effect may be less pronounced in the case of some
difficultly soluble polyamide-imides. However, in such systems, solubility
may still be achieved at a suitably high phenylindane diamine/non-phenyl-
indane diamine ratio.
The group Y of the non-phenylindane diamines may be selected from
alkylene groups containing from 2 to 12 carbon atoms; cycloalkylene groups
containing from 4 to 6 carbon atoms; a xylyene group, arylene groups
selected from ortho, meta or para-phenylene, xylyene, tolylene, biphenylene,
napthylene or anthrylene; a substituted arylene group of the formula
76 lR7
~W~
wherein W is a covalent bond, carbonyl, -N~,-N- (lower)alkyl, -0-,-S-,-SS-,
-N-phenyl, sulfonyl, a linear or branched alkylene group of from 1 to 3
carbon atoms; arylene, especially phenylene group; or a dialkyl or diaryl
silyl group; R6 and R7 are independent and each is hydrogen; halogen;
especially chloro or bromo; lower alkyl, preferably lower alkyl of from
1 to 5 carbon atoms, especially methyl; lower alkoxy, preferably lower alkoxy
-- 6 --
1~)82400
containing from 1 to 5 carbon atoms, especially methoxy; or aryl, especially
phenyl.
More preferably, Y embraces groups which are derived from the
aromatic diamines disclosed in the immediately preceding paragraph. Most
preferably, Y is a group having the formula
~W ~
wherein W is a covalent bond, methylene, sulfur, oxygen, or sulfone, and
R6 and R7 are independently hydrogen, halogen, or lower alkyl, preferably
lower alkyl of from 1 to 5 carbon atoms, especially methyl, or a group having
lQ the formula
R8~
wherein R8 is hydrogen, halogen or lower alkyl, preferably lower alkyl of
from 1 to 5 carbon atoms, especially methyl.
Among the non-phenylindane diamines that can be employed in the
preparation of the polyamide-imides of this invention are diamines as
illustrated bel~w:
4,4'-methylenebis(o-chloroaniline)
3,3'-dichlorobenzidine
3,3'-sulfonyldianniline
4,4'-diaminobenzophenone
1,5-diaminoaphthalene
bis(4-aminophenyl)diethyl silane
bis(4-aminophenyl~diphenyl silane
bis(4-aminophenyl)ethyl phosphine oxide
N-~bis(4-aminophenyl)]N-methyl amine
1()82400
N-~bis(4-aminophenyl)]N-phenyl amine
4,4'-methylenebis(2-methylaniline)
4,4'-methylenebis(2-methoxyaniline)
4,4'-methylenebis(2-methylaniline)
4,4'-oxybis(2-methoxyaniline)
4,4'-oxybis(2-chloroaniline)
4,4'-thiobis(2-methylaniline)
4,4'-thiobis(2-methoxyaniline)
4,4'-thiobis~2-chloroaniline)
4,4'-sulfonylbis(2-methylaniline)
4,4'-sulfonylbis(2-ethoxyaniline)
4,4'-sulfonylbis(2-chloroaniline)
3,3'-dimethyl-4,4'-diaminobenzophenone
3,31-dimethoxy-4,4'-diaminobenzophenone
3,3'-dichloro-4,4'-diaminobenzophenone
4,4'-diaminobiphenyl
m-phenylenediamine
p-phenylenediamine
4,4'-methylenedianiline
4,4'-oxydianiline
4,4'-thiodianiline
4,4'-sulfonyldianiline
4,4'-isopropylidenedianiline
3,3'-dimethylbenzidine
3,3'-dimethoxybenzidine
3,3'-dicarboxybenzidine
di~minotoluene
2,6-diaminopyridine
-- 8 --
108;i~400
m-xylylene diamine
p-xylylene diamine
bis-(4-aminocyclohexyl)methane
hexamethylene diamine
heptamethylene diamine
octamethylene diamine
nonamethylene diamine
decamethylene diamine
3-methylheptamethylene diamine
4,4-dimethylheptamethylene diamine
2,11-diaminododecane
1,2-bis~3-aminopropoxy~ethane
2,2-dimethylpropylene diamine
3-methoxyhexamethylene diamine
2,5-dimethylhexamethylene diamine
2,5-dimethylheptamethylene diamine
5-methylnonamethylene diamine
1-4 diaminocyclohexane
1J 12-diamino-octadecane
H2N(CH2)20-(cH)2o(cH2)2NH2
H2N(CH2)3s~cH2)3NH2
2N(cH2)3N(cH3)(cH2)3NH2
The polyamide-imides of copending application Serial No. 243,546
can be prepared by conventional methods. Thus, e.g., by reacting trimellitic
anhydride or a derivative thereof having the formula
O O
~C(j,
g _
, ' ' : - .
~082400
wherein Xl denotes hydroxyl, halogen, alkoxy group having 1 to 4 C-atoms,
or a phenoxy group in a solvent at a temperature below 100C with about
equimolar amounts of a diamine or a mixture of diamines of the formula
X2-NH-Y-NH-X3
wherein Y has the same meaning as indicated above and X2 and X3 independently
denote hydrogen or anacetoxy group, preferably hydrogen, to the polyamide-amic
acids of the present invention having an inherent viscosity of at least 0.1
and consisting essentially of the recurring unit having the formula
O O
- - NH-I - r~ C NH-Y - _
wherein Y has the same meaning as above and the arrows indicate isomerism,
and following by dehydration of thepolyamidamic acids to the corresponding
polyamide-imides. In this process the diamines are preferably reacted with
trimellitic anhydride acid chloride at a temperature below 100C, preferably
at or below room temperature, in an organic reaction medium which is a
solvent for at least one of the reactants, preferably under substantially
anhydrous conditions, and in presence of an acid acceptor to afford the
polyamide-amic acids of the above formula.
These polyamide-amic acids have a molecular weight such that their
inherent viscosity is at least 0.1, preferably 0 3-5Ø The inherent vis-
cosity is measured at 25C at a concentration of 0.5% by weight of the
polymer in a suitable solvent, e.g., N,N-dimethyl-acetamide, N-methyl-
pyrrolidone, dimethylformamide, etc.
The polyamide-amic acids must be dehydrated ~imidized) to the
polyamide-imide form to impart the thermal stability and extraordinary
physical prq~ertie~ characteristic of the polymers of this invention.
- 10 -
'
- ~ .
Depending upon the final application or end use of the polymer one of the
following methods may be employed to imidize the polyamide-amic acid:
a) Chemical Imidization: The polyamide-amic acid is treated with
a chemical dehydrating agent such as acetic anhydride in a suitable solvent,
preferably the same reaction medium used to prepare the amic acid. The amic
acid is contacted with the dehydrating agent for about 24 hours at room
temperature or 3-4 hours at 50-60C in the presence of a basic catalyst
such as pyridine and isolated by precipitation into a non-solvent.
b) Thermal Imidization. In one aspect of this method the amic
acid is heated in a suitable solvent such as nitrobenzene until imidization
is complete and isolated by precipitation into a non-solvent or by distilla-
tion of the solvent. With some solvents it is possible to isolate the product
by simple filtration. Alternately, thermal imidization may be carried out
by isolating the polyamide-amic acid and heating the neat polymer in an oven
until the water of imidization is removed.
Thermal imidization may also be performed after application of the
polyamide-amic acid to a substrate.
It is possible to alter the properties of the polyamide-imide by
incorporating into the polymer dicarboxylic acids or dianhydrides, or both,
as e.g., a portion of the trimellitic acid may be substituted by benzophenone
tetracarboxylic acid dianhydride to attain a greater percentage of imide
groups and thereby improve the thermal stability of the polymer. In the
extreme case, all of the trimellitic acid component could be replaced by a
dianhydride and diacid to give said polyamide-imide. Such polyamide-imide
systems may be prepared by methods well known in the art.
Polyamide-imides heretofore known to the art have generally been
extremely insoluble, and have not been shapeable after conversion from the
polyamide-amic acid state to the polyamide-imide form. The polyamide-imides
prepared from the polyamide-amic acids of the present invention are extremely
- 11 -
:
10l3;~400
useful in that they can be dissolved in certain solvents, in relatively high
concentration, and the solutions can be employed for further fabrication of
the polyamide-imides. In this way, it is possible to produce polyamide-imide
films, coatings, laminates and the like without the necessity of using a
polyamide-amic acid intermediate with a follow-on conversion step. This is
highly advantageous, because it permits the application of polyamide-imide
coatings to articles which might be damaged by heating or chemical conversion
techniques heretofore necessary.
The soluble polyamide-imides display excellent physical, chemical
and electrical properties which render them capable of being used as adhesives,
laminating resins, especially for printed circuit boards, fibers, coatings,
especially for decorative and electrical purposes, films, wire enamels, molding
compounds and engineering materials. Solutions of the phenylindane polyamide-
imides of this invention can be used to impregnate reinforcing fibers and
fabrics like glass, boron, metal oxide whiskers and graphite. These prepregs
can then be cured to form rigid polyamide-imide laminates or composites or to
form strong thermally resistant structural adhesive bonds between aluminum,
stainless steel, titanium or other metals.
These polyamide-imides have very good solubility in common organic
solvents. Examples of such organic solvents are the following:
N,N-dimethylformamide
N,N-dimethylacetamide
N-methyl-2-pyrrolidone
N,N-diethylf~rmamide
N,N-diethylacetamide
N-methylca~x~lactam
dioxane
dimethylsulfoxide
_ 12 -
,
~'
108~400
tetramethylurea
pyridine
dimethylsulfone
hexamethylpho~phoramide
tetramethylene sulfone
formamide
~-methylformamide
r -butyrQlactone
tetrahydrofuran
m-cresol
2-~ethaxyethyl acetate
1,2-dimethoxyethane
bis~2-methoxyethyl) ether
chloroform
nitro~enzene.
The solvents can be used alone, in combinations of solvents, or in
combination with poor solvents such as benzene, benzonitrile, xylene, toluene
and cyclohexane.
More specifically, these polyamide-imides have been found to be
soluble up to more than 60% in these solvents. The particular solubility
achieved depends on various factors such as the nature of the solvent, the
nature of the diamine employed and the extent of any replacement of the
phenylindane diamines of the invention by other diamines. The solubilities
attained are unique because the phenylindane moieties contained in the novel
soluble polyamide-imides are themselves aromatic in character and might be
expected to impart to their polyamide-imides the generally found characteris-
tic of insolubility amQng aromatic polyamide-imides. Thus, it is most
unusual that these phenylindane diamines can be reacted with trimellitic
_ 13 -
,
,: ~
'' '
108Z400
anhydride acid chloride and with aromatic diamines to produce the instant
soluble polyamide-imides.
The soluble polyamide-imides can be precipitated from their
solutions by use of methanol, water, acetone, spray drying and the like. The
resulting granular material can be molded or redissolved in a suitable sol-
vent to yield a film-forming or varnish type composition. Other appropriate
ingredients can be added to the polyamide-imide solutions or molding powders
including fillers, dyes, pigments, thermal stabilizers and reinforcing agents,
such as glass fiber, carbon, boron and the like, depending on the end use.
These polyamide-imides have exceptionally high glass transition
temperatures (Tg) and thermal stabilities which permit their use in high
temperature applications. Wire coating and motor varnish are two
important applications for which these materials are particularly suited.
A partial list of specific applications for these materials is as follows:
l. Mold liners and containers for casting lower melting materials,
including metals.
2. High temperature electrical insulation~ such as slat liners,
magnet wire, motor varnish.
3. Packaging of items to be exposed to hlgh temperature or high
energy radiation while still within package.
4. Laminated structures where the films are bonded to sheets or
foil.
5. Capacitors.
6. Dry transfQrmers.
7. Printed circuits.
8. Tape fQr hot pipe over~rapping.
9. Aircraft radoms.
To further illustrate the nature of this invention, the following
- examples are given below.
- 14 -
108Z400
Example 1
1,3,3-Trimethyl-l-phenylindane
To 6.0 kg of 62% sulfuric acid at 50C was added l.Q kg. of
~-methyl-styrene over a S minute period. The mixture was refluxed (145C)
for 2Q hours. After cooling, the lower acid phase was drawn off and discarded.
The organic phase was washed with sulfuric acid several times and then with
water several times. The product was recrystallized from methanol which
afforded 750 g of white crystals with a melting point of 50.5C-52.0C.
The yield was 75%.
By essentially following the above procedure and substituting
,3,4-trimethylstyrene for -methyl-styrene there is obtained a mixture of
tetramethyl phenylindanes in 95% yield.
Example 2
5~6)-Amino-1-(4'-aminophenyl)-1,3,3-trimethylindane
(a) Preparation of 5,4'-dinitro- and 6,4'- dinitro-1,3,3-
trimethyl-l-phenylindane isomers
To a solution of 236 g ~1.0 mole) 1,3~3-trimethyl-1-phenylindane
(~-methylstyrene dimer) in 750 ml chloroform at 2-8C was added a previously
mixed solution of 396 ml sulfuric acid and 132 ml nitric acid dropwise over
a 2.5 hour period. The two phase reaction mixture was allowed to stir an
additional 4 hours at 5C. The chloroform phase was isolated and washed with
aqueous sodium bicarbonate until neutral and then with distilled water.
A light yellow oil was obtained after drying and stripping the chloroform
solution. Two triturations in hexane at room temperature afforded 295 g light
yellow powder, melting point 109- 125. This material was shown to be a
mixture of the 5,4'-dinitro- and 6,4'-dinitro-1,3,3-trimethyl-1-pheny~ndane
îsomers by NMR analysis.
lysi~ Qr C18~18N24
- 15 -
1()8:i~400
% Calculated: CJ 66.25; H, 5.55; N, 8.58
% Found: C, 66.13; H, 5.50; N, 8.42
~b) Preparation of 5~6)-Amino-1-~4'-amino-
phenyl)-1,3,3-trimethylindane
A mixture of 250 g ~0.767 mole) of the dinitro isomers and 250 g
~4.60 g - atoms) reduced iron powder in 1 liter 50% a~ueous ethanol was brought
to reflux and a previously prepared solution of 60 ml concentrated hydro-
chloric acid in 400 ml 50% aqueous ethanol was added over a 1 hour period.
Reflux was continued an additional 3 hours, the reaction cooled to 50 and
5Q ml concentratedhydrochloric acid added. The reaction mixture was filtered.
The filtrate was made basic with 20% NaOH and extracted with ether, dried and
stripped under vacuum to afford 145 g (71%) of a clear brown glassy solid
melting point 47-54 . NMR analysis indicated the product was 62% 6-amino-
and 38% 5-amino-1-~4'-aminophenyl)-1,3,3-trimethylindane.
Analysis for C18H22N2:
% Calculated: C, 81.18; H, 8.32; N, 10.52
% Found: C, 81.27; H, 8.20; N, 10.48
Preparation of Polyamide-imide from 4,4'-Methylenedianiline
and Trimellitic Anhydride Acid Chloride
To a 300 ml. flask fitted with mechanical stirrer, nitrogen inlet
and cooling bath was added 5.00 grams (0.0252 mole) 4,4'-methylened aniline
and 65 ml. N,N-dimethylacetamide. The reaction mixture was stirred until
solution was achieved and 2.57 grams (0.0254 mole) triethylamine was added. The
reaction mixture was then cooled with ice and 5.~1 grams (0.0252 mole) trimel-
litic anhydride acid chloride was added all at once. Cooling was continued
until the trimellitic anhydride acid chloride had dissolved. The cooling
- l6 -
lV8;~400
bath was removed and the reaction was continued for 3 hours at room tempera-
ture during which time the triethylamine hydrochloride precipitated as a
crystalline solid. The polyamic acid was precipitated into rapidly stirring
cold water, recovered by filtration, washed thoroughly and dried at 50C/50
mm.Hg vacuum. The polyamic acid was a fibrous, yellow solid.
The polyamide-imide was prepared by treating 2 grams of the poly-
amic acid, partially dissolved in 20 ml. N-methyl-2-pyrrolidone, with 3 grams
(0.03 mole) acetic anhydride and 1 gram (0.01 mole) pyridine at room tempera-
ture. The polyamide-imide gelled almost immediately after addition of the
acetic anhydride and pyridine.
Example 4
Preparation of Polyamide-imide from 5~6~-Amino-1(4'-amino-
1-(4'-aminophenyl)-1,3,3-trimethylindane and Trimellitic
Anhydride Acid Chloride
Solution Method
To a 500 ml. flask fitted with mechanical stirrer and nitrogen
inlet was added 20.20 grams (0.0758 mole) 5(6)-amino-1-(4'-aminophenyl)-1,3,3-
trimethylindane and 260 ml. N,N-dimethylacetamide. The reaction mixture was
stirred until solution was achieved and 7.73 grams (0.0763 mole) triethylamine
was added. The reaction mixture was then cooled using an ice bath and 15.97
grams (0,0758 mole) trimellitic anhydride acid chloride was added all at
once. The ice bath was removed after the trimellitic anhydride acid chloride
had dissolved. Reaction was continued for 3 hours at room temperature during
which time triethylamine hydrochloride precipitated as a crystalline solid.
The polyamic acid was precipitated by adding the reaction mixture to rapidly
stirring cold water. The polyamic acid was then recovered by filtration,
washed thoroughly and dried at 50C/50 mm.Hg vacuum. The polyamic acid,
a white powdery solid, had an inherent viscosity of 0.22 (0.5% in N-methyl-2-
pyrrolidone).
- 17 -
108;~400
The polyamide-imide was prepared by treating 25 grams of the
polyamic acid, dissolved in 150 ml. N-methyl-2-pyrrolidone, with 30 grams
(0.3 mole) acetic anhydride and 3 grams (0.04 mole) pyridine at room tempera-
ture for 18 hours. The polyamide-imide was precipitated into water, recovered
by filtration, washed thoroughly and dried at 80C/50 mm.Hg vacuum. The poly-
amide-imide, a yellow powdery solid, had an inherent viscosity of 0.29 (0.5%
solution in N-methyl-2-pyrrolidone at 25C).
Example 5
Preparation of Polyamide-imide from 5(6)-Amino-1-~4'-
aminophenyl)-1,3,3-tri~ethylindane and Trimellitic
Anhydride Acid Chloride
Interfacial Method
To a 1 quart commercial blender ~as added a solution consisting
of 5.4901 grams (0.0206 mole) 5(6)-amino-1-~4'-aminophenyl)-1,3,3-trimethyl-
indane, 36.1 grams acetone, 10.3 grams water and 2.17 grams (0.0214 mole)
triethylamine. This solution was mixed at medium speed and a solution con-
sisting of 4.3399 grams (0.0206 mole) trimellitic anhydride acid chloride
and 15.5 grams acetone was added all at once. A gelatinous precipitate
formed almost immediately and the stirring speed was increased to maximum.
The reaction was continued for 15 minutes at which time 500 ml. of hot water
was added to precipitate the polyamic acid. The polyamic acid was recovered
by filtration, washed thoroughly and dried at 50 C/50 mm.Hg vacuum. The
polyamic acid was a yellow, powdery solid. The inherent viscosity of the
polyamic acid was 0.39 (0.5% in N-methyl-2-pyrrolidone at 25C).
The polyamide-imide was prepared by treating a solution of 6 grams
polyamic acid in 34 ml of N-methyl-2-pyrrolidone with 7 grams (0.07 mole)
acetic anhydride and 1 gram (0.01 mole) pyridine at 80C for 2 hours. The
polyamide-imide was precipitated into cold water, recovered by filtration,
washed thoroughly and dried at 80C/50 mm.Hg vacuum. The dried polyamide-
- 18 -
lV~Z400
imide, a yellow powdery solid, had an inherent viscosity of 0.45 (0.5% in N-
methyl-2-pyrrolidone at 25C) and was 40% soluhle in dimethylformamide,
N,N-dimethylacetamide, N-methyl-2-pyrrolidone, m-cresol, tetrahydrofuran,
dioxane, glyme, diglyme, and cyclohexanone, The polyamide-imide had a glass
transition temperature (Tg) of 350C (by torsional braid analysis).
Example 6
Preparation of Polyamide-imide Copolymers
By essentially following the procedures described in Examples
4 and 5, the following polyamide-imide copolymers of 5(6)-amino-1-(4'-amino-
phenyl)-1,3,3-trimethylindane (PIDA) and 4,4'-methylenedianinline ~MDA)
with trimellitic anhydride were prepared:
- 19 -
l()~Z400
o o o
~,_ a
,, ~ o o g o o o o ,~
D ~ ~ ~ J ~ ~ ~1 o~
:5 o~ ~ S O
_~ O ~
O t~ O O O O O O O ~ O
cd
O
~ ~ _I oo O t~ / h
O ~ ~ t" ~ ~ ~ r~
,l O O O O O O O
., ~ ~
~,~ ~ ~
u7 ~ Z ~
O ¢ ~ h
O O O O O O O I Z L~
C~
~ ~ .~ ~
~ O
".~ ~h
~ $~
¢ ¢ ¢ ¢ ¢ ¢ C~ ¢ O o
~o ~ ~ ~ ~ ~ a~ ~ ~ 5 ~
,,~ 0~O 0~O 0~O 0~O 0~O0~O0~O 0~O ~ ~
o o o ~O 00 ~ o
o ¢ ¢ ¢ ¢ ¢ ¢ ¢ a~
~ a a a a a a a ~ ~
~ 1--( H 1~ 1 H 1~11~
~O~ 1:14 ~ D~ ~ ~ ~ ~ ~ ~rl O
o\ o\ o\ o~O o~Oo~Oo~O
O O 0' 0 0 0 0
- 20 -
`: ', ' : ',
~:
1()~;~400
Example 7
By essentially following the procedure described in Example 4,
soluble polyamide-imides are obtained by reacting equivalent amounts of tri-
mellic anhydride acid chloride and of each of the following aromatic diamine
mixtures:
~ a) 5~ male % 5(6~-amino-1(4'-aminophenyl)-1,3,3-trimethylindane
(PIDA) and 50 mole % 4,4'-methylenebis-(o-chloroaniline)
(b) 50 mole % PIDA and 50 mole % 4,4'-sulfonyldianiline
(c) 50 mole % PIDA and 50 mole % m-phenylenediamine
~d) 5a mole % PIDA and 50 mole % p-phenylenediamine
Example 8
By essentially following the procedure of Example 4, and replacing
the 5(6)-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane reacted in that
example by the following arQmatic diamines:
(a) 5-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethyl-
indane; and
Cb) an isomeric mixture of 5-amino-1-(4'-amino-Ar', Ar'-dichloro-
phenyl)-Ar,Ar-dichloro-1,3,3-trimethylindane and 6-amino-1-(4'-amino-Ar',Ar'-
dichlorophenyl)-Ar,Ar-dichloro-1,3,3-trimethylindane, there are obtained
soluble polyamides.
- 21 -
:
