Note: Descriptions are shown in the official language in which they were submitted.
~ 15~1~1 RD-7038
BLENDS OF POLYETHERIMIDES AND POLYAMIDEIMIDES
This invention is concerned with blends of polyamideimides
(PAI) and polyetherimides (PEI) use~ul in the coating and mold-
ing arts. More particularly the invention is concerned with a
blend comprising by weight (a) from 5 to 95~ of a polyamideimide
comprising essentially chemically combined units of the formula
o
~0~ \N R
- N - C ~ C
H .,
and (2) from 95 to 5~ of a polyetherimide comprising essentially
chemically combined units of the formula
O O
.. ..
I I . - N~ "
O O
where R is a member selected from the class consisting of
(a) the following divalent organic radicals:
CH3 ~H3 ~CH3
C1~3 ICH3
~<~ ~
CH3 H3
.
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1 15~3.181
C ~ Br ~CH3
~~
~H3Br Br CH3
and L ~ r
\ - C(CH3) ~
Br Br
and (b) divalent organic radicals of the general formula,
(X)~}
where X is -CyH2y~, y is a whole number equal to from 1 to 5
inclusive, and Rl is a divalent organic radical selected from
the class consisting of (a) aromatic hydrocarbon radicals having
from 6-20 carbon atoms and halogenated derivatives thereof,
(b) alkylene radicals and cycloalkylene radicals having from
2-20 carbon atoms, (c) C(2 8) alkylene terminated polydiorgano-
siloxanes,and (d) divalent radicals included by the formula,
~ Q ~ .
where Q is a member selected from the class consisting of
O O
-O-, -C- ,-S-, -S-, and - C H - ,
O x 2 x
and x is a whole number ecual to from 1 to 5, inclusive.
Polyamideimides are known to have good chemical resis-
tance and moderate heat resistance. Although such polyamide-
imides can be dissolved in suitable solvents for coating
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I l S ~
applications, such polyamideimides are quite difficult to mold
and require excessive temperatures and press~res in the mold-
ing cycle. Polyetherimides are known to have good high tem-
perature characteristics and are more amenable to viable mold-
ing cycles, however, it would be advantageous to upgrade thechemical resistance of these polyetherimides and reduce their
cost for molding and coating applications.
We have unexpectedly discovered that blends of polyamide-
imides of formula I and polyetherimides of formula II over a
wide range can be made in which the properties of the blend
show a marked average improvement over the properties of the
components of these blends, and in some instances the improve-
ment in properties are unexpected considering the proportion
of either the polyamideimide or the polyetherimide used. By
making the above-described blends, the utility for both these
members in the blend can be considerably expanded. In addition,
by blending the polyamideimide with polyimides, products can be
obtained which are lower in cost than is usually associated
with the use of the polyetherimides alone without significant
sacrifice (if any) in properties.
The polyetherimides which are employed in the present
invention can be made in accordance with the disclosures and
teachings in U.S. patent 3,847,867 issued November 12, 1974
in the names of Darrell R. Heath and Joseph G. Wirth and
assigned to the same assignee as the present invention. The
polyamideimides employed in the practice of the instant in-
vention can be made in accordance with the disclosures and
teachings in U.S. patent 3,972,902 issued ~ugust 3, 1976.
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A preEerred class of polyetherimides which are included
by formula (II) are polymers consisting essentially of from
about 2 to 5000 or more units and preferably from 5 to 100 units
of the formula
O O
O~OR O~) OR
o o
where Rl is previously defined, and R2 is
Included by the polyetherimides of formula II, are poly-
mers consisting essentially of the following chemically
combined units,
O . O
O R2 ol~~ /
O O
O O
V N ~ NR
O O-R
O
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O O
,. ..
VI~ - N ~ ~ ~ C \ Rl
,. ,
O O -R ----O O
and mixtures thereof, where Rl and R2 are defined above.
The polyetherimides of formulas II-VIcan be made by
effecting reaction between an aromatic bis(etheranhydride~
of the general formula,
O O
VII. o ~ ~ ~ RO ~ O
O O
and an organic diamine of the general formula,
VIII. H NRlNH
where R and Rl are as previously defined.
There can be employed from o,95 to 1.05 mols of aromatic
bis(etheranhydride) per mol of organic diamine. It is preferred
to employ substantially equal molar amounts of bisanhydride and
diamine.
- The polyamideimides employed in the present invention
(which can have from 10 to 5000 or more units of formula I) can
be prepared from acyl halide derivatives of trimellitic an-
hydride. The acyl halide derivative from trimellitic an-
hydride (l,2,4-benzene tricarboxylic acid anhydride) having at
least one acyl halide and that in the 4-ring position, include
'0 derivatives, such as the 4-acid chloride l,4- and 2,4-diacid
RD-7038
~ 15!~181
chloride. The bromide and other reactive halide derivatives
are also suitable. The acyl halide derivativ~ is reacted with
an aromatic diamine having one or more aromatic rings and two
primary amino groups corresponding to general formula VIII.
In making the polyetherimides, there are employed from
0.95 to 1.05 mols of the aromatic dianhydride of formula VII per
mol of the organic diamine of formula VIII. Preferably, one
can employ equal or lower amounts of the bisanhydride and
diamine.
In making the polyamideimide, again one can employ from
0.95 to 1.05 mols of the trimellitic anhydride derivative of the
formula, for example,
o
IX. C1 - C ~ C~
O
per mol of organic diamine of formula ~ Prefexably one
employs substantially equal molar amounts of the trimellitic
anhydride derivative of formula IX and the organic diamine.
Chain stoppers such as aniline or mono-organic acid deri~
vatives or monoanhydrides may be used in making either the poly~
amideimide or polyetherimide~
Generally either the polyetherimideor the polyamideimide
can be obtained by effecting the reaction between the chosen
organic diamine and the particular dianhydride or monoanhydride
in the presence of a dipolar aprotic organic solvent under
ambient conditions to produce a polyamide acid. In both
2' instances, upon further heating the polyamide aci~s convert to
the imidized state comprising the units of formulas I and II.
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~ 1 5 '~
Depencling upon ~he solids content o~ the polyamide acid solutio~
reaction can be completed in from 0.5 to 2 hours or more. ~pon
completion of the reaction, the solution can be cast on a sub-
strate so that evaporation of the orc;anic solvent occurs. By
heating at temperatures of from 150-200C or higher one converts
the polyamlde acid of each polymeric member of the blend to the
polyimide state, so that the blend at this point has good heat
resistance, chemical resistance such as solvent resistance, and
moldability if the desired use of these blends is in molding
applications. Such blends are particularly useful as wire coat-
ing enamels and impart solvent resistance and heat resistance
properties to various substrates.
The aromatic bis(etheranhydride) of formula VII shown in
the above-mentioned U.S. patent 3,847,867, can be prepared from
the hydrolysis followed by dehydration of the reaction product
of the nitrosubstituted phenyl dinit-ile and then reaction with
a dialkali metal salt of a dihydric aryl compound in the
presence of a dipolar aprotic solvent, where the alkali metal
salt has the general formula
X. Alk - 0 - Rl - O - Alk
where Rl has the meanings given above and preferably is the
same as R2 and Alk is an alkali metal ion. Various well known
procedures can be used to convert the resulting tetranitriles
to the corresponding tetracids and diar.hydrides.
Included among the alkali metal salts of the above described
dihydric phenols are sodium and potassium salts of the follow-
ing dihydric phenols:
2,2-bis-(hydroxyphenol)propane;
2,4'-dihydro~ydiphenylmethane;
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~ 15'~181
bis-(2-hydroxyphenyl)-methane;
2,2-bis-(4-hydroxyphenyl)-propane hereinafter iden-
as "bisphenol-A" or "BPA;"
1,1-bis-(4-hydroxyphenyl)-ethane;
1,1-bis-(4-hydroxyphenyl)-propane
3,3-bis-(4-hydroxyphenyl)-pentane;
4,4'-dihydroxybiphenyl;
4,4 7 -dihydroxy-3,3',5,5'-tetramethylbiphenyl;
2,4-dihydroxybenzophenone;
4,4'-dihydroxydiphenyl sulfone;
2,4'-dihydroxydiphenyl sulfone;
4,4'-dihydroxydiphenyl sulfoxide;
4,4'-dihydroxydiphenyl sulfide; etc.
Included by the organic diamines of formula VII
are, for example,
m-phenylenediamine;
p-phenylenediamine;
4,4'-diaminodiphenylpropane;
4,4'-diaminodiphenylmethane;
benzidine;
4,4'-diaminodiphenyl sulfide;
4,4'-diaminodiphenyl sulfone;
4,4'-diaminodiphenyl ether;
1,5-diaminoaphthalene;
3,3'-dimethylbenzidine;
3,3'-dimethoxybenzidine;
2,4-diaminotoluene; 2,6-diaminotoluene;
2,4-bis (~-amino-t-butyl)toluene;
bis(p-~-methyl-o-aminopentyl)benzene;
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~ 1 5 '~
1,3-diamino-4-isopropylbenzene;
1,2-b s(3-aminopropoxy)ethane;
m-xylylenediamine;
p-xylylenediamine;
bis(4-aminocyclohexyl)methane;
3-methylheptamethylenediamine;
4,4-dimethylheptamethylenediamine;
2,11-dodecanediamine;
2,2-dimethylpropylenediamine;
octamethylenediamine;
3-methoxyhexamethylenediamine;
2,5-dimethylhexamethylenediamine;
3~methylheptamethylenediamine;
5-methylnonamethylenediamine;
1,4-cyclohexanediamine;
1.12-octadecanediamine;
bis(3-aminopropyl)sulfide;
N-methyl-bis(3-aminopropyl)amine;
hexamethylenediamine;
nonamethylenediamine; 2,6-diaminotoluene;
bis-(3-aminopropyl)tetramethyldisiloxane, etc.
The polyetherimide-polyamideimide blend can be reinforced
with various particulated fillers such as glass fibers, silica,
fillers, carbon whiskers, up to 50~ or more, by weight, of the
~total blend.
In order that those skilled in the art may better under-
stand how the present invention may be practiced, the following
examples ~re given ~y way of ill~str~t;on and not by way of
limitation. All parts are by weight unless otherwise indicated.
RD-7038
1 1~9181
EXAMPLE 1
Thls e~ample illustrates a method which has been used for
the preparation of the polyetherimide. Other means for making
such imides and use of various substituted ingredients such
as diamino compounds or the dlanhydride are described in the
above-mentioned U.S. patent 3,847,867.
A mixture of 4,4'methylenedianiline (37.344 parts) and
B 2,~-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride
(100 parts), orthodichlorobenzene (1300 parts) and toluene
(50 parts) was stirred and heated to reflux for five hours
under a nitrogen atmosphere. In the course of the reaction,
water formed was removed by azeotropic distillation. Upon
cooling, the reaction mixture was poured into methanol to
isolate the polymer. The yield was 134.7 parts. The intrinsic
viscosity was0.41 dl./g. in dimethylformamide. The glass tran-
sition temperature was 237C. as determined by thermal optical
analysis. The elemental analysis found was: C, 77.8%, H, 4.5%;
N 4 1~. Calculated for (C44H30N2O6)n
N, 4.1%.
By this method of preparation a polyetherimide is obtained
having the formula _
~ O - ~ C(CH3 ~ _ ~ H
where n is a positive integer greater than 1.
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~ ~5~3~83
EXAMPI.E 2
A polyamideimide used in making the blends of our inven-
tion can be prepared in accordance with the disclosures and
teaching~ in the aforesaid U.S. patent 3,573,260. More
particularly, following the directions of this patent (Example
1), a reaction vessel equipped with a nitrogen purge is charged
with 6,055 parts dimethylacetamide and 1,670 parts methylene
dianiline
XII. NH2 - ~ CH~ H2
The mixture is stirred for about 10 minutes after 1,775 parts
of the 4-acid chloride of trimellitic anhydride (formula IX)
is added over a period of 4 hours while maintaining a tem-
perature of around 50C throughout the addition of the tri-
mellitic anhydride acid chloride. The mixture is then heated
lS at 50C for an additional 2-4 hours after which the resulting
polymer can be precipitated by well known means. The polymer
is advantageously washed to remove hydrochloric acid and then
centrifugred to remove excess water. Thereafter the polymer is
dried, e.g., with a rotary drum drier at about 150C.,to give
a polyamideimide of the formula
_ O _
~ y11/ L ~ N - C ~ S ~ ~ ~ ~
m
where m is a whole num~er greater than 1
RD-7038
1 15~31~'1
E~AMPLE 3
In this example, a polyetherimide (PEI~ of formula XI
(prepared as in Example 1), and a polyamidelmide (PAI) of
formula XIII(prepared as in Example 2) were mixed in various
proportions by dissolving the two polymers in a sufficient
amount of N-methylpyrrolidone at about 150C. This yielded a
clear solution which when cooled to room temperature gave a homo-
genous solution. Evaporation of the solvent yielded a clear
yellow film which was difficult to scratch. In other tests,
the two solid polymers were blended at 315C for ten minutes
and thereafter the polymer mixture was cooled to room tem-
perature and compression-molded at 320-330C. for 10 minutes
into thin sheets. The following Table I shows the physical
properties of mixtures of the polymers blended at the elevated
temperatures and then molded using varying amounts of either
the polyetherimide or of the polyamideimide.
Table I
Parts by Weight of
Polymer Ingredients Tensile Strength, Psi Percent Elongation
PEI PAI Yield Ultimate Ultimate
20 lOG 12,300 11,400 19.3
12,500 11,100 20.9~
14,600 13,300 16.8%
- 13,700
11,800 10,800 15.5
0 100 Difficult tO Mold
It will be apparent from an examination of Table I that
with the exception of the test which was carried out on
the polyamideimlde itself which was not moldable at the
specified conditions, unexpectedly the tensile and elongation
12
RD-7038
1 1 5 ~ 3
properties of the blends were quite close despite the varying
amounts of polyetherimide and polyamideimide present in the
blend. It is particularly unexpected to find that whereas the
100~ polyamideimide was not moldable under the conditions of
this test, all the other blends, even those having significant
amounts of the polyamideimide were moldable and in fact the
physical properties were quite comparable to those of the
molded 100~ polyetherimide. Finally, it is found that in the
case of each blend, the solvent resistance, whether in film
form or in the molded state, is enhanced.
EXAMPLE 4
2.1 gm of trimellitic acid chloride (TMAC) and 1.98 gm
of 4,4'-methylene dianiline of formula XII was mixed with
15 cc of N-methylpyrrolidone. After stirring, this mixture
lS exotherm~dto 59C. to give a clear polymeric amic acid amide
identified as solution A.
In another reaction vessel 5.2 g of 2,2-bis[4-(2,3_dicar-
boxyphenoxy) phenyl] propane and 1.98 gm of methylenedianiline
were m~xed with 15 cc of N-methylpyrrolidone to yield after
exotherming to 64C.,a clear polymeric amic acid amide iden-
tified as solution B.
9.5 gm of polymer solution A was mixed with 11.1 gms
of solution B at room temperature and the mixture was stirred
until it was homogeneous. From this solution blend a film was
cast at 280-300C. yielding an imidized polymer film containing
blends of polyamideimide and polyetherimide which had good
abrasion resistance.
RD-7038
1 15'~181
EXAMPLE 5
2.1 gm of TMAC and 2.48 gm of 4,4'-diaminodiphenyl sulfone
in 15 cc N-me'hylpyrrolidone was stirred to yield after exo-
therming to 38C.,a clear polymeric amic acid amide identified
as solution A.
In another reaction vessel, 5.2 g of 2,2-bis[4-(2,3dicar-
boxyphenoxy) phenyll propane and 2.48 gm of the same diamino-
diphenyl sulfone were mixed with 15 cc N-methylpyrrolidone,
to yield after exotherming to 37C., a clear polymeric amic
acid amide identified as solution B.
While stirring,9.8 gm of polymeric solution A was blended
with 11.4 gms of solution B at room temperature until the
mixture was homogeneous. From this solution blend a film was
cast at 280-300C. yielding an imidized polymer film contain-
ing blends of polyamideimide and polyetherimide having goodabrasion resistance.
EXAMPLE 6
2.1 gm of TMAC and 2.0 gm of 4,4'oxydianiline in 15 cc of
N-methylpyrrolidone was stirred to yield, after exotherming to
63C, a clear polymeric amic acid amide identified as solution A.
In another reaction vessel, 5.2 g of 2,3-bis[4-2,3-dicar-
boxyphenoxy) phenyl] propane and 2.0 gm of 4,4'oxydianiline
were stirred in 15 cc N-methylpyrrolidone to yield, after
exotherming to 61C, a clear polymeric amic acid amide identified
as solution B.
9.6 gm of polymeric solution A was blended with stirring
with 11.1 gms of polymeric solution B at room
temperature until the mixture was homogeneous. From this
solution blend a film was cast at 280-300C. yielding an
14
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8 ~
_____
imidized polymer film containing blends of polyamideimide and
polyetherimide having good abrasion resistance.
EXA~PLE 7
2.1 gm of TMAC and 1.08 gm of m-phenylenediamine in 15 cc
N-methylpyrrolidone was stirred to yield, after exotherming
to 43C, a clear polymeric amic acid amide identified as
solution A.
In another reaction vessel, 5.2 g of 2,3-bis[4-(2,3_-licar-
boxyphenoxy) phenyl] propane and 1.08 gm of m-phenylenediamine
wère stirred in 15 cc of N-methylpyrrolidone, to yield after
exotherming to 41C., a clear polymeric amic acid amide, iden-
tified as solution B.
9.1 gm of polymeric solution A was blended with stirring
with 10.7 gms of polymeric solution B at room temperature until
'1-.2 mlxture was homogeneous. From this solution blend, a film
was cast at 280-300C. yielding an i.nidized polymeric film
contai;ling blends of polyamideimide and polyetherimide having
resistance to abrasion.
EXAMPLE 8
2.1 gm of TMAC and 1.08 gm m-phenylenediamine placed
in 15 cc of N-methylpyrrolidone was stirred to yield, after
exotherming to 43C.,a clear polymeric amic acid amide iden-
tified as solution A.
In another reaction vessel, 5.2 g of 2,2-bis[4-(2,3-dicar-
:~oxyphenoxy) phenyl] propane and 1.98 gm of 4,4'-me~h--~lenedi-
aniline were stirred in 15 cc N-methy'pyrrolidone, to yield
after exotherming to 64C.,a clear polymeric amic acid amide
identifed as solution B.
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3 1 8 1
9.1 gms of polymeric solution A was blendecl with stirring
with 11.1 gms of polymeric solution B at room temperature until
the mixture was homogeneous. From this solution blend, a film
was cast at 280-300C. yielding an imidized polymer film
containing blends of polyamideimide and polye~herimide.
The Tg's of the blends in Examples 4-8 (with the solvent
removed) were determined as were the Tg's for the 100% PEI and
100% PAI described in Example 7. The following Table II showed
the results of these tests. It will be noted from Table II
that unexpectedly the Tg's, as exemplified by the results in
Example 7, instead of being an average of the Tg's of the
homopolymers were considerably below the Tg's of the homo-
polymers indicating the unexpected and unobvious results
obtainable by blending polyetherimides with polyamideimides.
The reduction in Tg's (which measures the degree of
softening) improves the moldability of the blends of the
instant invention.
Table II
Example
Number Blend
4 203C.
161C.
7 147C.
7a (100% PEI~ 220C.
7b (100% PAI) 241C.
8 203C.
It will o course b~ apparent to those skilled in the
art that in addition to the diamino compounds used in making
the above blends, other diamino compounds, many examples of
16
RD- 7 0 3 8
~ 1S'~81
which have been recited previously, can be used instea~.
In the same manner, in addition to the bisphenol-A dianhydride
employed in the examples in this application. Other dianhydrides,
many examples of which have been given above, can be employed
to make other types of polyetherimides. Finally, the pro-
portions of the polyamideimide and the polyetherimide
in the blend can be varied widely within the range previously
described without departing from the scope of the invention.
In addition to the two resins comprised in the blend above,
other polymers and resins in amounts ranging from 1 to 50% or
more, by weight, based on the total weight of the blend of
polyamideimide and polyetherimide resins may also be used.
Among such polymers may be added, for instance, polyolefinc,
polystyrene, polyphenylene oxides, such as shown in U.S. patent
3,306,875, epoxy resins, polycarbonate resins, such as shown
in U.S. patent 3,028,365, silicone resins, polyarylene poly-
ethers such as shown in U.S. patent 3,329,909, etc. many of
which are well known in the art.
The compositions of the present invention have application
in a wide variety of physical shapes and forms, including their
use as films, molding compounds, etc. The heat stability and
resistance to deformation at elevated temperature, while at
the same time retaining their properties at elevated tem-
peratures in the imidized state, make hese compositions quite
useful. When used as films or when made into molded products,
these polymers including the lamina'ced productc prepared there-
from not only possess good physical properties at room tem-
perature but they retain their strength and excellent response
to workloading at elevated temperatures for long periods of
17
R.T,_7038
9 l 8 1
time. These blend compositions resist fusion when exposed to
elevate~ temperatures, for extended periods of times while
still retaining an exceptionally high proportion of their
room temperature physical properties.
Films formed from the polymeric blends of this invention
may be used in applications where films have been used pre-
viously. They serve effectively in an extensive variety of
wrapping and packaging applications. Thus, the compositions of
the present invention can be used in automobile and aviation
lO applications for decorative and protective purposes, and as
high temperature electrical insulation for motor slot liners,
in transformers, and as dielectric capacitors.
Alternatively, solutions of the curable compositions
herein described can be coated on electrical conductors such
15 as copper, aluminum, etc. and thereafter the coated con-
ductor can be heated at elevated temperatures to remove the
solvent and to effect curing of the resinous composition there-
on. If desired, an additional overcoat may be applied to such
insulated conductors including the use of polymeric coat-
20 ings, such as polyamides, polyesters, silicones, polyvinyl-
formal resins, epoxy resins, polyimides, polytetrafluoro-
ethylene, etc.
Applications which recommend these resins include their
use as binders for asbestos fibers, carbon fibers, and other
25 fibrous ma-terials in making brakelinings. In addition, grind-
ing wheels and other abrasive articles can be made from such
resins by incorporating abrasive grains such as alundum,
carborundum, diamond dust, etc., and shaping or molding the
18
RD-7038
1 8 1
mixt~re under heat and pressure to obtain the desired condi~-
uration and shape for grinding and abrasive pllrposes.
