COPOLYMERES SEQUENCES D'AMIDE-ETHER-IMIDE

AMIDE ETHER IMIDE BLOCK COPOLYMERS

Abrégé anglais

AMIDE ETHER IMIDE BLOCK COPOLYMERS
ABSTRACT OF THE DISCLOSURE
Amide ether imide block copolymers having
excellent glass transition temperatures suitable for
manufacture of fibres, films, coating and moulding
compounds and a method for their preparation, are
described.

Revendications

- 18 -
The embodiments of the invention in which an
exclusive property or privilege is claimed are defined
as follows:
1. An amide ether imide block copolymer
wherein the block copolymer consists essentially of
polymeric units of the formulas:
<IMG> I.
II.
<IMG>
where "a" represents a whole number in excess of 1,
and Z is a member of the class consisting of (1)
<IMG>

- 19 -
Claim 1 continued:
<IMG> and <IMG>
and (2) divalent organic radicals of the general formula:
<IMG>
where X is a member selected from the class consisting
of divalent radicals of the formulas: -CyH2y-,
?, ?, -O- and -S- where q is 0 or 1, y is a whole
number from 1 to 5, the divalent bonds of the -O-Z-O-
radical are situated on the phthalic anhydride-derived
units, in the 3,3'-, 3,4'-, 4,3'- or the 4,4'- positions,
and R1, R2 and R3 are divalent organic radicals
independently selected from the class consisting of
(a) aromatic hydrocarbon radicals having from 6 to about
20 carbon atoms and halogenated derivatives thereof,
(b) alkylene radicals and cycloalkylene radicals having
from 2 to about 20 carbon atoms, C(2-8) alkylene
terminated polydiorganosiloxane, and (c) divalent radicals
included by the formula:
<IMG>
where Q is a member selected from the class consisting
of: -O-, ?, ?, -S-, and -CxH2x, and x is a whole
number from 1 to 5 inclusive.

- 20 -
2. The block copolymer of claim 1 wherein the
polymeric unit of Formula I is from about 5 to about 95
mole percent of the block copolymer.
3. The block copolymer of claim 1, wherein
the polymeric unit of Formula I is from about 10 to
about 90 mole percent of the block copolymer.
4. The block copolymer of claim 1, wherein
the polymeric units of Formula I is from about 20 to 80
mole percent of the block copolymer.
5. The block copolymer of claim 1 wherein
R2 is an alkylene radical having from 2 to about 20
carbon atoms.
6. The block copolymer of claim 1 wherein
R2 is an aromatic radical having from 6 to about 20
carbon atoms.
7. The block copolymer of claim 1 wherein R1
is an alkylene radical having from 2 to about 20 carbon
atoms.
8. The block copolymer of claim 7 wherein
R1 is an aromatic radical having from 6 to about 20
carbon atoms.
9. The block copolymer of claim 1 where
Z is of the formula:
<IMG>
where y is a whole number from 1 to 5.
10. The block copolymer of claim 9, wherein
R3 is metaphenylene and Z is a group of the formula :
<IMG>

- 21 -
11. A process for the production of an amide
ether imide block copolymer comprising reacting an acid
chloride of the formula:
<IMG> V.
with at least a molar equivalent of an organic diamine
of the formula:
H2N - R1 - NH2 III.
under polymerization conditions to form an amine terminated
polyamide of the formula,
VII.
<IMG>
thereafter reacting said amine terminated amide with an
aromatic bis(ether anhydride) of the formula:
VI.
<IMG>
to form an amide ether imide block copolymer; where
Z is a member of the class consisting of (1)
<IMG>

- 22 -
Claim 11 continued:
<IMG>
and (2) divalent organic radicals of the general formul:
<IMG>
where X is a member selected from the class consisting
of divalent radicals of the formulas: -CyH2y-.
-?-, -?-, -O- and -S- where q is 0 or 1, y is a whole
number from 1 to 5, the divalent bonds of the -O-Z-O-
radical are situated on the phthalic anhydride-derived
units, in the 3,3'-, 3,4'-, 4,3'- or 4,4'- positions,
and R1 and R2 are divalent organic radicals selected
from the class consisting of (a) aromatic hydrocarbon
radicals having from 6 to about 20 carbon atoms and
halogenated derivatives thereof, (b) alkylene radicals
and cycloalkylene radicals having from 2 to about 20
carbon atoms, C(2-8) alkylene terminated polydiorgano-
siloxane, and (c) divalent radicals included by the
formula:

- 23 -
<IMG>
where Q is a member selected from the class consisting
of: -O-, ?, ?, -S-, and -CxH2x-, and x is a whole
number from 1 to 5 inclusive.
12. A process for the production of an amide
ether imide copolymer comprising polymerizing an
organic diamine of the formula,
H2N - R1 - NH2
with an acid chloride of the formula,
<IMG>
and polymerizing the reaction product with an aromatic
bis(ether anhydride) of the formula,
VI.
<IMG>
where the number of moles of diamine reacted is equal
to the total moles of acid chloride and aromatic
bis(ether anhydride) combined and Z is a member of the
class consisting of (1):
<IMG>

Claim 12 continued: - 24 -
<IMG>
and (2) divalent organic radicals of the general formula:
<IMG>
where X is a member selected from the class consisting
of divalent radicals of the formulas: -CyH2y-,
-?-, -?-, -O- and -S where q is 0 or 1, y is a whole
number from 1 to 5, the divalent bonds of the -O-Z-O-
radical are situated on the phthalic anhydride-derived
units, in the 3,3'-, 3,4'-, 4,3'- or 4,4'- positions,
and R1 and R2 are divalent organic radicals selected.
from the class consisting of (a) aromatic hydrocarbon
radicals having from 6-20 carbon atoms and halogenated
derivatives thereof, (b) alkylene radicals and cyclo-
alkylene radicals having from 2-20 carbon atoms,
C(2-8) alkylene terminated polydiorganosiloxane, and
(c) divalent radicals included by the formula:
<IMG>

- 25 -
Claim 12 continued:
where Q is a member selected from the class consisting
of:
-O-, < IMG >, < IMG >, -S-, and CxH2x-, and x is a whole number
from 1 to 5 inclusive.

Description

S~9
8CU-03527
AMIDE ETHER IMIDE
BLOCK COPOLYMERS
BACKGROUND OF THE INVENTION
The present invention relates to novel copolymers.
More particularly, the invention concerns novel block
copolymers which contain polyetherimide polymeric units
Polyetherimides are amorphous, high-performance
engineering thermoplastics. The chain structure of these
polymers features rigid aromatic imide functionality and
provides for high rigidity, creep resistance and high
heat deflection temperatures. Polyetherimides exhibit
high glass transition temperatures, and accordingly are
generally processed at relatively high temperatures.
Polyamides or nylons are melt processible thermo-
plastics whose chain structure features repeating amide
groups. They are generally semicrystalline with melting
points ranging from 175 to 275C. Unfortunately, nylons
have low glass transitlon temperatures which render them
unsuitable for many applications.
There exists a need for a polymer that exhibits
moderate glass transition temperatures and has advan-
tageous properties of both polyamides and polyether-
imides.
SUMMARY_OF_THE INVENTION
In accordance with this invention, disclosed herein
are amide ether imide block copolymers and methods for
their preparation. The novel block copolymers contain
polymeric units of the formulas:
O O
11 11
- -HN-C-R2-C-NH-Rl-- _ I.
a
and

~;275~
2 8cu-03527
O O
_--N I- Z N R3- _
C C II.
11 11
O O a
where a represents a whole number in excess of 1, e.g,.,
10 to 10~000 or more and Z is a member of the class
consisting of
L CH3
S C \~
CH3 CH3 CH3\ CH3
c~3 c~3
CH3\ Elr Br CH3 Br Br
\/ ( 3 2 C
CH3/ Br Br c~3 8r Br
and ( 2) divalent organic radicals o the general ormula:
~O~(X)q--\0~/--
10 where X is a member selected from the class consisting of
divalent radicals of the formulas:

t7~
O O
Il 11
CyH2y , C-, -S-, -O- and -S-
o
where q is 0 or 1, y is a whole number from I to 5, the
divalent bonds ox the -O-Z-O- radical are situated on the
phthalic anhydride-derived unitst e..g., in the 3 ,3 1_,
3,4'-,4,3'=or the 4,4'-positions, and R1~ R2 and R3 ye
divalent organic radicals independently selected from the
class consisting of (a) aromatic hydrocarbon radicals
having from 6 to about 20 carbon atoms and halogenated
derivatives thereof, (b) alkylene radicals and cyclo-
10 alkylene radicals having from 2 to about 20 carbon atoms,C(2_g) alkylene terminated polydiorganosiloxane, and (~)
divalen!t radicals included by the formula:
Q
where Q is a member selected from the class consisting
ox:
O
Il 11
-O-, O S-, and -CXH2x-,
and x is a whole number from 1 to 5 inclusive.
DETAILED DESCRIPTION
The novel copolymers of the present invention are
20 prepared by the polymerization of a reactive polycar-
boxylic group-containing compound, preferably an acid
chloride, with an organic diamine to yield an amine
terminated polyamide. To this reaction product is
further added an aromatic bis(ether anhydride and
.
...

~L2~759V
optionally an organic diamine. These components are
reacted under polymerization conditions to produce the
blsck copolymer of the present invention.
The organic diamines that are included are of the
formula:
H2N-R1-N~2 III., and
H2N-R3-NH2 IV.
where R1 and R3 are as def ined hereinabove. Organic
diamines of Formulas III and It include, for example,
m-phenylenediamine,
p-phenylenediamine,
4,4'-diaminodiphenylpropane,
4,4'-diaminodiphenylmethane,
benzidine,
15 4, 4 ' -d i aminodiphenyl sulfide,
4,4' diaminodiphenyl sulfone,
4,4'-diaminodiphenyl ether,
1,5-diaminonaphthalene,
3,3'-dimethylbenzidine,
2 0 3, 3 ' d imethoxybenz id i ne,
2,4-bis(~ amino~t-butyl)toluene,
bis(p~ amino~t-butylphenyl)ether,
bis(p-~-methyl-o-aminopentyl)benzene,
1,3-diamino-4-isopropylbenzene,
1,2-bis(3-aminopropoxy)ethane,
m-xylylenediamine,
p-xylylenediamine,
2,4-diaminotoluene,
2,6-diaminotoluene,
bis(4-aminocyclohexyl)methane,
3-methylheptamethylenediamine,

5~
4,4-dimethylheptamethylenediamine,
2,11-dodecanediamine,
2,2-dimethylpropylenediamine,
octamethylenediaminef
3-methoxyhexamethylenediamine,
2,5~dimethylhexamethylenediamine,
2,5-dimethylheptamethylenediamine,
3-methylheptamethylenediamine,
5-methylnonamethylenediamine,
1,4-cyclohexanediamine,
1,12-octadecanediamine,
bis(3-aminopropyl)sulfide,
N-methyl-bis(3-aminopropyl)amine,
hexamethylenediamine,
heptamethylenediamine,
nonamethylenediamine,
decamethylenediamine,
bis(3aminopropyl)tetramethyldisiloxane,
bis(4-aminobutyl)tetramethyldisiloxane, etc.,
and mixtures of such diamines.
The reactive polycarboxylic group-containing
compounds employed in making the copolymers of this
invention include, for example, polycarboxylic acids,
anhydrides and acid halides. Preferred polycarboxylic
group-containing compounds are acid chlorides that
represented by the formula:
O O
Cl-C-R2~ Cl V.
where R2 is as defined hereinabove. Acid chlorides of
Formula V include for example,
adipylchloride,
malonyl chloride,

'7S~
succinyl chloride,
glutaryl chloride,
pimelic acid dichloride,
suberic acid dichloride,
azelaic acid dichloride,
sebacic avid dichloride,
dodecaned~oic acid dichlorides
phthaloyl chloride,
isophthaloyl chloride,
terephthaloyl chloride,
1,4-naphthalene dicarboxylic acid dichloride,
4,4'-diphenylether dicarboxylic acid dichloride and thy
like.
The aromatic bis(ether dianhydride)s that are sub-
sequently reacted with the reaction product of the
diamine and reactive polycarboxylic group-containing
compound are of the formula,
O o
Il 11
0/ ~-o-æ-o '~/C~o
`\ ' --I\ /
C VI.
Il 11
O O
where Z is as defined hereinbefore. Aromatic bis(ether
anhydride)s of Formula VI include, for example,
2,2-bis[4-~2,3-dicarboxyphenoxy)phenyl]propane
dianhydride;
4,4'-bis~2,3-dicarboxyphenoxy)diphenyl ether
dianhydride;
2S 1,3-bis(2,3-dicarboxyphenoxy~benzene dianhydride;
4,4'~bis(2,3-dicarboxyphenoxy)diphenyl sulfide
dianhydride;

7~
t,4-bis (2,3-dicarboxyphenoxy)benzene dianhydride;
4,4'-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride;
4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfone
dianhydride;
2,2~bis~4-(3,4-dicarboxyphenoxy)phenyl]propane
dianhydride;
4j4'-bis(3,4-dicarboxyphenoxy)diphenyl ether
dianhydride;
4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide
dianhydride;
1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride;
t,4-bist3,4-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 mixtures of such dianhydrides.
The reaction between the diamine and the reactive
polycarboxylic group~containing compound is conducted
under polyamide-forming conditions. Generally, equimolar
amounts of the acid chloride and diamine can be employed,
however, a molar excess o diamine is preferred in order
to produce an amine terminated polyamide of the formula,
o ol
H N~-R1-NH-~R2-C NH-R1-N~2
n
where R1 and R2 are as defined hereinabove, and n is an
integer from about 1 to about 20 preferably prom about 1
to about 4. These reactions are advantageously conducted
under substantially anhydrous conditions in a basic,
nonreactive solvent, such as N-methylpyrrolidone,
pyridine, or the like. Synthetic methods or preparing
polyamides are well known, and the copolymers of the
,

~75~C~
present invention are not limited to any particular
synthetic prodcedureD
After the above reactants have been polymerized, the
aromatic bis(ether anhydride) and optionally additional
organic diamine are added In general, equimolar amounts
of the total diamine (i. e . am3 ne-terminated polyamide
plus additional organic diamine) and the aromatic
bis(ether anhydride) are combined. Depending on the
desired proportion of polymeric units, the molar ratio of
the amine terminated polyamide and aromatic bis(ether
anhydride) can vary. The mole ratio of amine terminated
polyamide to anhydride can range from 1 to 99 mole
percent polyamide to 99 to 1 mole percent aromatic
bis(ether anhydride).
The reaction between the anhydride, the amine
terminated polyamide and organic diamine can be advan-
tageously carried out employing well-known solvents,
e.g., o-dichlorobenzene, m-cresol/toluene, etc., in whiz
to effect interaction between the reactants, at temper-
atures of prom about 100C to about 250C. Alterna-
tively, the block copolymers can be prepared by melt
polymerization while heating the mixture of the ingredi-
ents at elevated temperatures with concurrent inter-
mixing. Generally, melt polymerization temperatures
between about 200C to 400C and preferably 230C to
300C can be employed. Any order of addition of chain
stoppers ordinarily employed in melt polymerization can
be employed. The conditions of the reaction and the
proportions of ingredients can be varied widely dependlng
- 30 on the desired molecular weight, intrinsic viscos-ity, and
solvent resistance.
As used herein and in the appended claims, the
amount or weight percent of each polymeric unit, as
defined by Formula I and II, can vary. The amount of
each polymeric unit are controlled my the methods o

7~
g
preparation The polymeric unit of Formula I can be from
5 to 95 mole percent of the block copolymers, with the
balance being the polymeric unit of Formula II.
Preferred polymers are those in which the polymeric unit
of Formula I is from 10 to 90 mole percent of the block
copolymer, most preferably from about 20 to ~0 mole
percent of the block copolymer.
By controlling the proportions of the polymeric
units, each having predetermined properties, a block
copolymer can be formed having certain superior prop-
erties over a polyamide or polyetherimide~ In general
the higher the proportion of polymeric units of Formula I
will result in a block copolymer having lower glass tran-
sition temperatures, for example 60C. On the other
hand, a block copolymer having a lower proportion of the
polymeric units of Formula I will have a higher glass
transition temperature, for example, 100C.
The invention is further illustrated by the
following examples which are not intended to be
limiting.
EXAMPLE I
Several aliphatic amide ether imide block copolymers
were prepared. To a suitable reaction vessel was charged
15cc of N-methyl pyrrolidone (NMP). Hexamethylene
diamine ~HMDA) was added to the NMP. Adipylchloride was
then added and mixed in an amount such that the mixture
contained a 10~ molar excess of ~MDA. Additional
HMDA was added with equivalent moles of 2,2-bis[4 (2~3-
dicarboxyphenoxy)phenyl]-propane dianhydride ~BPADA).
The polymer solutions were cast and films were obtained
after heating at 250-290C. The table below lists the
varying amounts of reactants. Also listed are the
respective glass transition temperatures (Tg's) of the
product block copolymer. The Tg's were determined on the
films using a differential spanning calorimeter at a 40CC

5~C~
- 10
per minute heating rate, taking a midpoint transition
after a second rapid cool.
For purposes of comparison, polyamide and poly-
etherimide, were produced and tested
\

~75 91~
I o o o ,
5J' us o -- o
I` O
Us O er 0
, O o o o _
_, o o o o o o
o o o o o
o o S
, ......
o o t, o .~ _
u~l o o o g _ 0~
, o o o o o o
o o C o o o
l DO~C~C' SZ
I
o ,-
l oz
o o o o o O .
.
ED or co 51
I,., . . . . . .
_ o o o o
us r u
.~ _ o o O o o o I
_I o o o o o o I
o o o o o o
V
.~ us S
_ _ _ o ô o

5~(~
12
Ex ampl e I was repe ated w i th the e x cop i on that all
the HMDA was added to the reaction vessel containing the
NMP. The adipyl chloride was then added and the react-
5 ants were mixed. The BP~DA was then subsequently added.~he Table below lists the amount of reactants and the
Tg's o the respective block copolymers.
\

5~
D ¦ O i I f ~`J
L) or o
U~l 0
MU l o
a
C SZ '
x
H
1-1 ,
. ~U~ _ OZ
O O
S T
O o o o
on O I
:~ Io,C~oooo
o o o o o o
ED O er :0 O-
I or Ln
1 o -- or

'7~9~
EXAMPLE II
Several additional block copolymers were formed.
These blook copolymers were aromatic aliphatic amide
ether imide block copolymersr The copolymers were made
S by the sequential addition of isophthaloyl chloride to
hexame'chylene diamine followed by s oichiometric addition
of BPADA in NMP. The polymer solutions were cast and
films were obtained after heating at 250-290C. The
cable below lists the varying amounts ox reactants. Also
listed are the respective Tg's of the product block
copolymer. For purposes of comparison, polyamide and
polyetherimide homopolymers were produced and tested.

-~;z759~
C
I) .. us r-
_ In up I_
.~
s
SF
Us o o o o o o o ox
a) _ _ _ _ _ _ _
I:: O o o o o o o o
W o . . . . .
o o o o o o o
SZ
_ _ _ _ _
H
us o a OZ
' g 0, O
~3 O Sl
1 0 o
us O I
a I o O g o
o o o o o o
. o , o S
o _ I
at o
`. i

:~2~59~
16
As illustrated by the above data, block copolymers
having improved properties are obtained where the polymer
chain contains both structural units of Formula I and
II~
The block copolymers of the present invention have
application in a wide variety of physical shapes and
form, including the use as films molding compounds,
filaments, fibers, coatings, etc. When used as films or
when made into molded products, these polymers, including
laminated products prepared therefrom, not only possess
good physical properties at room temperature but they
retain their strength and excellent response to worn-
loading at elevated temperatures for long periods of
time. Films formed from the polymeric compositions of
this invention may be used in applications where films
have been used previously. Thus, the compositions of the
present invent.ion can be used in automobile and aviation
applications for decorative and protective purposes, and
as high temperature electrical insulation for motor slot
liners, in transformers, as dielectric capacitors, as
coil and cable wrappings (form wound coil insulation for
motors), for containers and container linings, in lamin-
ating structures where films of the present composition
or where solutions of the claimed compositions of matter
are applied to various heat-resistant or other types of
materials such as asbestos, mica, glass fiber and the
like and superimposing the sheets one upon the other and
thereafter subjecting them to elevated temperatures and
pressures to effect flow and cure of the resinous binder
to yield cohesive laminated structures. Films made from
these compositions of matter can also serve in printed
circuit applications.
Alternatively, solutions of the compositions herein
described can be coated on electrical conductors such as

5~
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 compo-
sition thereon. If desired, an additional overcoat may
be applied to such insulated conductors including the use
of polymeric coatin~sr such as polyamides, polyesters,
silicones polyvinylformal resins, epoxy resins, poly-
imides, polytetrafluoroethylene, etc. The use of the
curable compositions of the present invention as over-
coats on other types of insulation is not precluded.
Applications which recommend these resins includetheir use as binders for asbestos fibers, carbon fibers,
and other fibrous materials in making brake linings. In
addition, molding compositions and molded articles may be
formed prom the polymeric compositions in this invention
by incorporating such fillers as asbestos, glass fibers,
talc, quartz, powder, wood flour, finely divided carbon,
silica, into such compositions prior to molding. Shaped
articles are formed under heat, or under heat and
pressure in accordance with practices well-known in the
art. In addition, various heat-resistant pigments and
dyes may be incorporated as well as various types of
inhibitors depending on the application intended.
While certain representative embodiments and details
have been shown for purposes of illustrating the inven-
tion, it will be apparent to those skilled in the art
that various changes and modifications may be made
therein without departing from the scope of the inven-
tion.