Note: Descriptions are shown in the official language in which they were submitted.
-1- 8CU-3310
_OLYETHERIMIDE BLENDS
This invention relates -to a class of poly-
etherimide blends. The blends exhibi-t a high glass
transition temperature, e.g., from abou-t 125 to 210 C,
which makes -the blends particularly suitable for auto-
motive and appliance applications. Preferred blends
compri,se an aliphatic polyetherimide and an aroma-tic
polyetherimide, i.e., blends of a polyetherimide formed
from an aliphatic diami,ne and a polye-therimide formed
from an aromatic diamine.
The blends of the invention include a
polyetherimide of the formula:
O O
11 ij
_ ~ N A - O --- Z - O- --A N - R- __
\C/ \C /
~ O
L a
where a represents a whole number in excess of 1, e~g.,
]5 10 to 10,000 or more, the group -O-A~ is selected from:
~ _0/~ --0'/'~ '~
~ 3 8CU-331()
Rl being hydrogen, lower alkyl or lower alkoxy,
preferably a polye-therimide includes the latter -O-A~
group where Rl is hydrogen such -that -the polye-therimide
is oE the fo:rmu].a:
O O
- - N ~ ~ _ O - Z--- -~- C ~ ,N--- R - __
O O
_ _ a
and -the divalent bonds of the -O-Z-O- radical are in the
3,3'; 3,4'; 4,3' or the 4,4' position;
Z is a member of the class consisting of (1)
~ ~ ~ 3 ~ 3
CH CE-I3 CH CH~ Br Br
~ ~ ~ ~ { ~ ~ ( 3 2 C
and (2) divalent organic radicals of the general formula:
(0~ (X)q ,~
CU-3310
--3--
where x is a member selected from the class consis-tiny
of divalent radicals of -the formulas,
O O
-C H2~-, -C-, -S~, -O-- and -S-,
o
where q is 0 or 1, y is a whole number from 1 to 5, and
:R is a divalent organic radical selected from -the class
consisting of (]) aromatic hydrocarbon radicals having
from 6-20 carbon atoms and halogena-ted derivatives
-thereof, (2) alkylene radical.s and cycloalkylene radicals
having from 2-20 carbon atoms, C(2_8) alkylene terminated
polydiorganosiloxane, and (3) divalent radicals included
by the formula
~ ~ Q ~
where Q is a member selec-ted from the class consisting of
O O
-O-, -C-, -S-, -S- and -CXH2 -
o
where x is a whole number from 1 to 5 inclusive.
Particularly preferred polye-therimides for the purposes
of the present inven-tion include -those where -O-A~ and
Z respectively are:
. ) \
CH3
~ 8CU-331
and R is selec-ted from hexame-thylene.
~ - CH2 _~ ~ )> _
C112 ~ 2 \~ O
and polyetherimides containing two or more of the R groups.
Po]yetherimides can be obtained by any of the
methods well known to those skilled in the art including
-the reaction o-f any aromatic bis(ether anhydrides) of -the
formula
O O
o\ ~Jo_ z_o r- /O
o o
where Z is as defined hereinbefore with an organic diamine
of the formula
2 R NH2
where R is as defined hereinbefore
Aromatic bis(ether anhydride)s of the above
formula include, for example,
2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]-propane
dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether
dianhydride, l/3-bis(2,3-dicarboxyphenoxy)benzene
dianhydride; 4 J 4'-bis(2l3-dicarboxyphenoxy)diphenyl
sulfide dianhydride; 1,4-bis(2,3-dicarboxyphenoxy)benzene
dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl
~e~
- 5 -- 8CU-3310
sulfone dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxy)
phenyl]propane dianhydride; 4,4'-bis(3,4-dicarboxy-
phenoxy) diphenyl ether dianhydride; 4,4'-bis(3,4-
dicarboxyphenoxy) diphenyl sulfide dianhydride; 1,3-
bis(3,4-dicarboxyphenoxy) benzene dianhydride; 1,4-
bis(3,4-dicarboxyphenoxy)benzene dianhydride; 4,4-
bis(3,4-dicarboxyphenoxy)benzophenone dianhydride;
4-(2,3-dicarboxyphenoxy)-4-(3,4-dicarboxyphenoxy)diphenyl
2,2-propane dianhydride; etc., and mixture of such
dianhydrides.
In addi-tion, aromatic bis(ether anhydride)s
also included by the above formula are shown by
Koton, M.M.; Florinski, F.S.; Bessonov, M.I.;
Rudakov, A.P. (Insti-tute of Heteroorganic compounds,
Academy o-f Sciences, U S.S.R.), ~.S.S.R. Pa-ten-t No.
257,010, NGvember 11, 1969, Appl. May 3, 1967.
Organic diamines of -the above formula
include, for example, m-phenylenediamine, p-phenyler-e-
diamine, A,4'-diaminodiphenylpropane, ~,4'-diamino-
diphenylmethane benzidine, 4,4'-diaminodiphenyl sulfide,
~,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl
ether, l,5-diaminonaphthalene, 3,3'-dimenthylbenzidine,
3,3'-dime-thoxybenzidine, 2,4-bis(~ -amino-t-bu-tyl)-
-toluene, bis(p-~ -amino-t-butylphenyl)ether, bis(p-~ -
methyl-o-aminopentyl)benzene, 1,3-diamino-4-isopropyl-
benzene, 1,2-bis(3-aminopropoxy)ethane, m-xylylenediamine,
p-xylylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene,
bis(4-aminocyclohexyl)me-thane, 3-methylhep-tame-thylene-
diamine, 4,4-dimethylheptame-thylenediamine, 2,11-
dodecanediamine, 2,2-dimethylolpropylenediamine,
octamethylenediamine, 3-methoxyhexamethylenediamine,
2,5-dimethylhexamethylenediamine, 2,5-dime-thylhepta-
methylenediamine, 3-methylheptamethylenediamine,
5-methylnonamethylenediamine, 1,4-cyclohexanediamine,
8CU-3310
--6--
1,12-octadecanediamine, bis(3-aminopropyl)sulfide,
N-methyl-bis(3-aminopropyl)amine, hexamethylenediamine,
heptame-thylenediamine, nc,namethylenediamine,
decame-thylenecliamine, his(3-aminoprc,pyl)
tetrarnethylclisiloxarle, bis(~-aminobu-tyl)
tetramethyLdis:iloxane, and the like.
The aromatic bis(ether anhydricle) used in making
-the above-mentioned preferred polye-therimides is 2,2-
bis[~-(3,4-dicarboxy phenoxy)phenyl]propane dianhydride
(bisphenol A bisph-thalic anhydride) and -the diamines used
are hexamethylene diamine, m-phenylene diamine, m-xylylene
diamine, ~,~'-diaminocliphenylmethane and diamino
diphenylsulfone~
In general, -the reactions can be advantageously
carried out employing well-known solvents, e.g., o~
dichlorobenzene, m-cresol/-toluene, N-methyl-pyrrolidone,
etc., in which to effect interaction between -the
dianhydrides and the diamines, at -tempera-tures of from
about 100 to abou-t 250C. Alternatively, the polyether-
imides can be prepared by melt polymeriza-tion of any of
-the above dianhydrides with any of the above diamine com-
pounds while hea-ting the mixture of -the ingredients at
elevated temperatures with concurrent intermixing.
Generallyl mel-t polymerization temperatures be-tween abou-t
200 to ~00C. and preferably 230 to 300C. can be emp~loyed.
The conditions of -the reac-tion and the proportions of
ingredien-ts can be varied widely depending on the desired
molecular weight, in-trinsic viscosity, and solvent
resistance. In general~ equimolar amounts of diamine and
dianhydride are employed for high molecular weigh-t
polyetherimicles, however, in certain instances, a slight
molar excess (about 1 to 5 mol percent) of diamine can be
employed resulting in the produc-tion of polyetherimides
having terminal amine groups. Monofunc-tional organic
amines such as aniline, or organic anhydrides such as
phthalic anhydride and maleic anhydride provide molecular
weigh-t control. Low molecular weight polyetherimide can
~q~
8CU-3310
--7--
be employed to -form copolymers. From 0.l to 50 mole
percen-t of comonomers based on the to-tal moles of
reac-tants can he employed. ~,enerally, use-Eul poly-
.~, e-therimides have an in-tri.nsic viscGsity [~/~] grea-ter
-than 0.2 deciliters per gram, preferably 0.35 to 0.60,
or 0.7 deciii.ters per gram or even higher when measured
in m-cresol a-t 25 C.
Included amon~ the many me-thods of making -the
polye-therir,lides are those disclosed in U.S. Paten-t Nos.
3,8A7,867, issued November 12, 1974 to Heath et al,
3,847,869, issued No~ember 12, 1974 to Williams,
3,850,885, issued November 26, 1974 to Take]coshi e-t al,
3,852,242, issued November 26, 1974 -to White and
3l855,178, issued December 17, 197~ -to Whi-te, e-tc.
]5 In accordance with the present invention,
blends of the polyetherimides are generally obtainable
in all propor-tions of the polyetherimides relative to
each o-ther. Consequently, blends comprising from abou-t
1 to about 99%~ by wei.gh-t of one polye-therimide and from
abou-t 99 to abou-t 1%, by weight of another polye-therimide
are included within -the scope of the invention as well as
blends of three or more different polye-therimides
containing a-t ieast about 1% by weight of each of -the
contained polyetherimides. By controlling the proportions
of the various polyetherimides relative to each other,
blends having certain predetermined proper-ties which are
improved over those of one or more components of -the
blend alone may be readily obtained. In general, blends
of polyetherimides have a good appearance and exhibit a
high glass -transition -temperature such as from 125 to
210C
I-t is contemplated tha-t the polye-therimide blends
of the present invention may also include additive
materials such as fillers, stabilizers/ plasticizers,
flexibilizers, surfac-tant agents, pigments, dyes, rein-
forcements, flame retardants and diluents in conventional
amounts .
3CU-3310
--8--
Methods for forming polyether:Lmide blends may
vary considerably Prior art blending -techniques are
generally satisfactory. A preferred method comprises
blending the polymers and additives such as reinforce-lnents
in powder, granular or filamentous form, extruding the
blencl, ancl choppinq -the ex-trudate into pellets sui-table
for molding by means conventionally used -to mold normally
solid thermoplastic composi-tions.
The polyetherimide blends of the presen-t
invention have application in a wide variety of physical
shapes and forms~ including -the use as films, molding
compounds, coatings, etc. When used as films or when
made in-to molded produc-ts, these blends, including
laminated products prepared therefrom, not only possess
good physical properties at room -tempera-ture bu-t they
re-tain -their strength and excellent response to work-
loading at eleva-ted temperatures for long periods of -time.
Films formed from -the blends of -this inven-tion may be used
in applica-tion where films have been used previously.
Thus, the blends of the presen-t inven-tion can be used
in automobile and aviation applications for decorative
and protective purposes, and as high -tempera-ture electrical
insulation for motor slot liners, transformers, dielectric
capaci-tors, cable and coil wrappings (form wound coil
insulation for motors), and for containers and con-tainer
linings. The blends can also be used in laminated
struc-tures where films or solutions of the blend are
applied -to various heat-resis-tan-t or other type of materials
such as asbestos, mica, glass fiber and the like, the
shee-ts superimposed one upon -the other, and thereafter
subjecting the sheets to elevated tempera-tures and
pressures to effect flow and cure of the resinous binder
to yield cohesive laminated structures. Films made from
the subject polyetherimide blends can also serve in
printed circuit applications.
8CU-3310
_ g_
Al-ternatively, solutions of -the blends herein
described can be coa-ted on elec-trical conduc-tors such as
copper, aluminum, etc. and thereafter tl~e coa-te~ conductor
can be hea-ted at elevated tempera-tures to remove the
sol.vent and p:rovide a con-tinuous resinous composition
-thereon. I:E desired, an additional overcoa-t may be
applied -to such insula-ted conductors including -the use
of polymeric coa-tings, such as polyamides, polyes-ters,
silicones, polyvinylformal. resins, epoxy resins,
polyimides, polytetrafluoroethylene, etc. The use of the
blends of the presen-t inven-tion as overcoa-ts on other -types
of insula-tion is no-t precluded.
O-ther applications which are con-templated for
these blends include -their use as binders for asbestos
fibers, carbon fibers, and o-ther fibrous ma-terials in
making brake lininys In addition, moldi.ng compositions
and molded articles may be formed from the polymeric
blends of the invention by incorporating such fillers as
asbes-tos, glass fibers, talc, clay, quar-tz powder, finely
divded carbon, and metals, silica and the like into the
blends prior to molding. Shaped ar-ticles may be molded
under heat, or under heat and pressure, in accordance
wi-th practices well known in the art.
The following examples illustrate specific
polye-therimide blends in accordance with -the presen-t
invention. It should be understood that the examples
are given for the purpose of illus-tration and do not
limit the invention. In -the examples, all parts and
percentages are by weight unless o-therwise specified.
E MPLE I_
Binary polyetherimide blends according to -the
invention ~"ere prepared, formed into blend films and then
-tested for glass transition -tempera-ture.
A firs-t polyetherimide was prepared from -the
reaction productof essentially equimolar amounts of
2,2-bis[4-(3,4-dicarboxy phenoxy)phenylj propane dianhydride
8CU-3310
-10-
and m-phenylene diamine produced at elevated temperature
of abou-t 250 to about 300 C. and under nitrogen
a-tmosphere. A test specimen for glass transition
-temperature and the results are set :Eor-th in the
:EoLlowin-~ '['able I.
A seconcl polyetherimide was prepared from the
reac-tion product of hexamethylenediamine and 2,2-bis[4-
(3,~--di.carboxy phenoxy)phenyl~ propane dianhydride and
-Eormed in-to a test specimen as above. The glass
transi.tion -temperature of this polyetherimide is also
set forth in Table I.
About 90 parts of the firs-t polyetherimide in a
N-methylpyrrolidone solution were mixed with abou-t 10 parts
of -the second polye-therimide in a N-methylpyrrolidone
solution and the polymer mixture was then solution cas-t
-to form a fi.lm. The glass transition temperature of the
blend film was measured and is given in Table I.
The above blending procedure was -then repeated
so as to produce six additional blends having varying
amounts of the first polyetherimide rela-tive -to the second
polye-therimide. The glass transition tempera-ture for each
of the additional blends is also se-t forth in Table I.
From the data, i-t can be observed -that blends containing
from 50 to 70% of the firs-t polyetherimide and 50 to
30% of the second polyetherimide have a glass transition
temperature in -the range of 165 to 190 C. which makes
these blends particularly adap-table for autornotive and
appliance applications.
. .
.
8CU-3310
--11--
TABLE I
_ ____ __
~irs-t Second Glass
PolyetherirflidePolyetherimide Transition
Con-tent Con-tent Temperature
t%) (%) (C)
___ __ ___. ___.__ __ ___
100 0 222
210
~20 1l 198
130 1 189
,40 ~ 180
1 50 167
138
190 128
0 I100 12
EXAMPLE II
Binary polyetherimide blends according -to -the
invention were prepared, formed into blend films and then
-tes-ted for glass -transi-tion temperature.
A firs-t polyetherimide was prepared from -the
reaction product of essentially equimolar amounts of
2l2-bis[4-(3,4-dicarboxy phenoxy)phenyl] propane dianhydride
and m-phenylene diamine produced a-t elevated tempera-ture
of about 250 to about 300C. and under nitrogen atmosphere.
A tes-t specimen solution coated in the form of a film was
tested for glass -transition tempera-ture and the resul-ts are
set forth in the following Table II.
A second polyetherimide was prepared from the
reaction product of m-xylene diamine and 2,2-bis[4-(3,4-
dicarboxy phenoxy)phenyl] propane dianhydride and formed
into a test specimen as above. The glass transitlon
tempera-ture of -this polye-therimide is also set for-th in
Table II.
8CU-3310
-12-
~ second polyetherimide was prepared from -the
reaction product of m-xylene diamine and 2,2-bis[4-(3,4-
dicarboxy phenoxy)phenyll propane dianhydride and formed
into a -test specimen as above, The glass transition
temperature of this polye~,herimide is also set for-th in
Table II.
About 90 parts oE -the first ~polyetherimide in a
N-methylpyrrolidone solution were mixed with about 10
parts of the second polyetherimide in a N-methylpyrrolidone
solution and the polymer mixture was then solution cas-t to
form a film. The glass transition temperature of the blend
was measured and is given in Table II.
The above blending procedure was then repeated
so as -to produce six additional blends having varying
amounts of the first polyetherimide relative to the second
polye-therimide. The glass transition -temperature for each
of the additional blends is also set for-th in Table II.
From -the data~ it can be observed -tha-t blends containing
from 10 to 60% of the firs-t polyetherimide and 90 to 40%
oE -the second polye-therimide have a glass transition
temperature in the range of 170 to 195C. which also ma~es
-these blends par-ticularly adap-table for automo-tive and
appliance applica-tions.
"~
.... _ _ . . _ _ .. _ _ . _ _ . _ _ _ _ _ _ _ _ .. _ _ . _ _ _ _ _ _ _ . ~ _ _ _ -- . ..... .. ., . _ . .. . .
8CU-33lO
13-
TAsLE II
First Seconcl Glass
Polyetherimide Polyetherimide Transi-tion
Content Content Tempera-ture
5 (%) (%) (C)
._ _ ~ ~_ _ 222
211
208
204
1060 40 196
185
185
171
O 100 168
15 EXAMPLE I I I
Polyetherimide blends accorcding to -the invention
were prepared from a polyetherimide homopolymer and a
polyetherimide copolymer. The blends were formed into
blend films and then tested for glass -transi-tlon temperature.
The polye-therimide homopolymer was prepared from
the reaction product of essentially equimolar amounts of
2,2-bis[4-(3,4-dicarboxy phenoxy)phenyl~ propane dianhydride
and m-phenylene diamine produced at elevated temperature
of about 250 to about 300 C. and under nit.rogen atmosphere.
A test specimen solution coated in the form of a film was
tested for glass transition -tempera-ture and the results are
set forth in Table III.
The polyetheri~ide copolymer was prepared from
the reaction product of essentially equimolar amounts of
30 2,2-bis[4-(3,4-dicarboxy phenoxy)phenyl] propane
dianhydride and a mixture of equimolar amounts of
8CU~3310
-14-
m-phenylene diamine and hexamethylene diamine. About
50 parts of the polyetherirnide homopolymer were mixed
in solution with abou-t 50 parts o-E -the polyetherimide
copo].ymer and -the polymer mixture was then solution
cast to form a film. The glass transition -temperature
of the blencl :Eilm was measured and is given in Table III.
Ano-ther polyetherimide copolymer was prepared
as above excep-t -that the molar ra-tio of m-phenylene
diamine -to hexamethylene diamine was about three -to
one. About 75 parts oE the polyetherimide homopolymer
were mixed in solution with about 25 parts of the
polyetherimide copolymer and the polymer mix-ture was
then solution cas-t to Eorm a blend film. The glass
transition tempera-ture oE the blend was measured and
is given in Table III.
A iurther polyetherimide copolymer was
prepared as above with the exception that the molar
ratio oE m-phenylene diamine to hexame-thylene diamine
was about one -to three. About 25 parts of the
polyetherimide homopolymer were mixed in solution
with about 75 par-ts of -the second polyetherimide copolymer
and the polymer mixture was then solution cast to ~orm a
blend film~ The glass transition temperature of the
blend was measured and is given in Table III.
From the data presented in Table II, it can be
observed that the polyetherimide homopolymer-copolymer
blends have an excep-tionally high glass transition
tempera-ture even at high aliphatic amine concentrations,
i.e., at high hexamethylene diamine ratios. These high
glass transition temperatures give the blends utility as
coatings and insulation and as compression and injection
molding compounds.
8CU-3310
-15-
TABLE III
Polye-therimide Polye-therimide Ratio of G'ass
Homopolymer Copolymer m-phenylene d:iamine Transi-tion
Content Content to hex.~me-thylene diamine Temperature
_ ( QO ) _ ( % ) __ to prepare copolymer tPo)
100 _ 223
25 3:1 211
50 1:1 203
75 1:3 19~3
~ ___~__ ~ __~
Suhstitution of other polyetherimides for the
polyetherimides of the blends of the above examples may
result in the formulation of polyetherimide polymer blends
having similar characteristics.
While -the present invention has been described
with reference -to particular embodiments thereof, it will
be unders-tood that numerous modifications may be made by
those skilled in the art wi-thout actually departing from
the spirit and scope of the invention as deEined in the
appended claims.
