HOMOGENEOUSLY MIXED ALLOYS COMPRISING AROMATIC POLYAMIDES AND POLY-N-VINYLPYRROLIDONE, PROCESS FOR THEIR PREPARATION, AND THEIR USE

ALLIAGES FORMANT UN MELANGE HOMOGENE, A BASE DE POLYAMIDES AROMATIQUES ET DE POLY(N-VINYLPYRROLIDONE); METHODE DE PREPARATION ET UTILISATION

English Abstract

HOE 89/F 038
-1-
Abstract of the disclosure
Homogeneously mixed alloys comprising aromatic polyamides
and poly-N-vinylpyrrolidone, process for their prepara-
tion, and their use
Alloys of aromatic polyamides with poly-N-vinylpyrroli-
done which are homogeneously mixed and allow the physical
and mechanical properties to be adjusted in a targeted
way, such as for improving the processability and water-
absorption capacity. The PVP, which is water-soluble per
se, is not dissolved out of the allows by water. Futher-
more, a process for the preparation of the alloys, and
their use as molded articles, such as films, coatings or
pressings is described.

Claims

THE EMBODIMENT OF THE INYENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED IS DEFINED AS FOLLOWS:
1. A homogeneously mixed alloy, substantially containing
A) poly-N-vinylpyrrolidone and
B) at least one homo- or copolyaramid containing at
least one recurring structural unit of the formula
(I)
<IMG> (I)
in which E1 and E2 are identical or different and are
selected from the groups
<IMG>
.
-Ar1- or
-Ar1-X-Ar2-,
in which Ar1 a;nd Ar2 are identical or different 1,2
phenylene, 1,3-phenylene or 1,4-phenylene radicals which
are unsubstituted or substituted by (C1-C6)-alkyl, (C1-
C6)-alkoxy, -CF3 or halogen, and the radical X
a) is a direct bond or one of the following divalent
radicals
-O-, -SO2-, -CO-, -C(R1)2- in which R1 is hydrogen,
(C1-C6)-alkyl or fluoroalkyl having 1-4 carbon atoms
in the alkyl group, or
b) -Z-Ar1-Z-, in which Z is the radical -O- or -C(CH3)-2,
or
c) -O-Ar1-Y-Ar2-O-, in which Y is as defined under Xa).
2. An alloy as claimed in claim 1, wherein the group E1 in
the structural units is identical or different and is a

1,3- or 1,4-phenylene radical or the radical
<IMG> or <IMG>
3. An alloy as claimed in claim 1, wherein the group E2 in
the structural units is identical or different and is the
1,4-phenylene radical or the radical
<IMG>
in which R2 is a lower alkyl or alkoxy radical, in each
case having up to 4 carbon atoms in the alkyl group, or
is F, Cl or Br,
or the radical <IMG>
where X' is the group -C(R1)2-, in which R1 is hydrogen or
(C1-C4)-alkyl, or the group <IMG>
4. An alloy as clalmed in claim 1 or 2 or 3, wherein the
halogen radical is fluorine, chlorine or bromine.
5. An alloy as claimed in claim 1 or 2 or 3, wherein the
aromatic polyaramid is in the form of either a random
copolymer or a block or graft copolymer.
6. An alloy as claimed in claim 1 or 2 or 3, containing
a) poly-N-vinylpyrrolidone and
b) at least one copolyaramid containing at least three
randomly recurring structural units of the formula
(I), in which
E1 is a divalent p-phenylene radical,
E2 in the three recurring structural units is once
each a divalent p-phenylene radical,
a radical of the formula
<IMG>

where R2 is CH3, OCH3, F, Cl or Br, and a radical
of the formula
<IMG>
in which X' is as defined above.
7. An alloy as claimed in claim 6, wherein the copolyaramid
contains the recurring structural units
<IMG> and
8. An alloy as claimed in claim 1 or 2 or 3, wherein the
molecular weight of poly-N-vinylpyrrolidone, given as the
weight average, is in the range from 1,000 to 3 million,
and the poly-N-vinylpyrrolidone (component A)) is present
in amounts of from 2 to 98% by weight, relative to the
sum of components A) + B).
9. An alloy as claimed in claim 1 or 2 or 3, wherein the
molecular weight is in the range from 40,000 to 200,000
and component A is present in amounts of from 15 to 85%
by weight.
10. An alloy as claimed in claim 1 or 2 or 3, containing
additives in customary amounts.
11. An alloy as claimed in claim 1 or 2 or 3, wherein, in
addition, polymers are present in amounts of up to 10% by
weight, relative to A) and B).
12. A process for the preparation of a homogeneously miscible

alloy comprising poly-N-vinylpyrrolidone and a poly-
aramid, which comprises
a) adding poly-N-vinylpyrrolidone, dissolved or in the
solid state, to a solution of B) at least one homo- or
copolyaramid containing at least one recurring structural
unit of the formula (I)
<IMG> (I)
obtained by solution, interface or melt condensation,
then removing the solvent from the solution, and where,
in the structural units of the formula (I), E1 and E2 are
identical or different and are selected from the groups
<IMG> or <IMG>
-Ar1- or
-Ar1-X-Ar2-,
in which Ar1 and Ar2 are identical or different 1,2-pheny-
lene, 1,3-phenylene or 1,4-phenylene radicals, which are
unsubstituted or substituted by (C1-C6)-alkyl, (C1-C6)-
alkoxy, -CF3 or halogen, and the radical X
a) is a direct bond or one of the following divalent
radicals
-O-, -SO2-, -CO-, -C(R1)2-, in which R1 is hydrogen,
(C1-C6)-alkyl or fluoroalkyl having 1-4 carbon atoms
in the alkyl group, or
b) -Z-Ar1-Z-, in which Z is the radical -O- or
-C(CH3)-2, or
c) -O-Ar1-Y-Ar2-O-, in which Y is as defined under Xa).
13. The process as claimed in claim 12, wherein, in the case
of the solution condensation, the poly-N-vinylpyrrolidone
is dissolved together with the diamine component, and
this mixture is subjected to the condensation together
with dicarboxylic acid chlorides.

14. The process as claimed in claim 12, wherein the solvent
is removed by evaporation.
15. A molding produced from the alloy as claimed in claim 1.
16. A molding as claimed in claim 15 in the form of films,
castings, coatings or pressings.

17. The homogeneously mixed alloy as claimed in claim 1, and
substantially as described herein.

Description

HOECHST ~RTIENG~SELLSC~AFT ~O~ 89/F 038 Dr.R~St
Descrip~ion
~omogenecusly mi~ed alloy~ Co~pri8illg aromatic poly~mides
and poly-N vinylpyrrolidone~ process for their prepara-
tion, and their u~e
The invention relates ~o homogeneously mixed alloys
compriEing aromatic polyHmides and poly N-vinylpyrroli-
done, a proces~ for ~heir pr~paration, ~nd their use a~
molded articles, ~urh ~ films, co~tlng6 or pressings.
~0 The term ~homogeneously mixed alloy~" inidicate~ that the
components of the alloy are ho~ogeneously mixed with one
another.
Aromatic polyamides (referred ~o as polyaramids below)
are known for theix excell~nt thermal, chemical and
mechanical properties. Therefore, for example, fibers and
films made from raw materials of thi6 type are highly
suitable for industrial area ~of application in par-
ticular for reinforcing plastic~ or a~ filter materials.
Poly-N-vinylpyrrolidone (PVP) i8 commPrcially available
in various molecular weights. Vp to molecular weights of
about one million, PVP i8 801uble even in cold water.
Softening point (gla~s txansition temperature) of PVP in
the fully anhydrous sta e iB 175C. PVP has the following
recurring structural unitss
~ CH2 - CH t-
~F
~he synthesis ~nd properties of PVP are described in
detail in Houben-Weyl: Methoden der Organi~chen Chemie
tMethods of Organic Chemi~try~, Volume XIV/1, pp. 1106
ff. (1961)-

~ 3
-- 2 --
The production of microporous, high tenacity hollowfibers from a stable ~olution of aroma~ic pGlyEulfone
pol~mers or aromatîc polyamide~ as fiber-forming poly-
mers, PVP and suitable 801vent5, ~uch as dLmethyl~ceta
S mide or dLmethylformamide, i~ known (US Pa~ent
4,051,3003. This publication ~t~tes that ths poly~ramid
i~ only compatible with PVP ~o a lLmited extent and that
phase separation occurs during the coagulation proce~s
described.
1~ It is furthermore known to alloy polymers in order to
prepare novel materials which can only ~e ~chieved with
difficu~ty, or not at all, in other ways, for ~xample by
copolymerization. In particular, technologically impor-
tant prGperties, for Qxample thermal stability, ~echani-
cal properties and solvent resistance, can be improved inthis way, and in addition their economic efficieney is
increasedO
However, the prediction of the propertie~ of ~n alloy
from the properties of the individual components i8 far
away, even today. The alloying of polymers th~refore
still remains substantially empirical. In particluar, the
homogeneous miscibility or compstibility of alloys,
specifically those comprising polymers with a strong
interaction, can hitherto not be predicted in spite of a
very large number of experimental and theoretical paper~
in thi~ area. Thus, it i~ known that compatible alloy~ of
polymers are rare (Journal of Polymer Science, Polymer
Physics Edition~ Vol. 21, p. 11 (1983)).
Elsewhere, it is stated that reseaxch activities ha~e
resulted in the discovery of a number of miscible pol~mex
combination~, and that complete miscibility i~ an unusual
property in binary polymer mixtures, which normally tend
to form two-pha~e sy6tems (Polymer~ Yol. 2~, p. 60
(lg83) ~ .
It is al60 known that a con~iderable ma~ority of pair~ of

- 3 ~ 9
polymers form ~wo~phd~e blend6 ~fter mixing, a~ can be
presumed on the ba~is of the low mixin~ entropy for very
lar~e molecules. The~e mixtures ~r~ generally charac-
terized by opacity, differen thermal transitions and
poor mechanical properties (Olabisi, Robe~on~ Shaw:
Polymer-Polymer Mi cibility, Academic Pres~, New York, p.
7 ~197~
In another publication, it ~ stated that the n~mber of
blend systems known to be mi~cible has increa~ed signifi-
cantly in the last d cade. In addition, a nu~ber of
systems have been found which have an upper or lower
critical solution temperature, i.e. complete miscibility
only exi~ts in a limited temperature ran~e. Modern
thermodynamic theories have hitherto only been 6uccessful
to a lLmited ex~ent ~6 far as the predict2bility of
miscibility is concerned. It was therefore doubted
whether any practical theorie~ can be developed which
take into account the real complexities impart~d on the
polymer-polymer interactions by nature (Ma~romolecules,
Vol. 16r p. 753 (1983)).
Alloys of homogeneou~ly mixed polymers are thus very
rare. In addition, miscibility cannot be predicted. On
the other hand, the methods fo.r experLmental determina
tion of the mi~cibility behavior are known (Olabi~i,
Robe~on, Shaw: Polymer-Polymer-Mi~cibility, Academic
Press, New York, pp. 321-327 (1979)).
The following are ~ome of the differentiating feature~:
The clearest criterion for homogeneous miscibility
i8 the appearance of a single gla~s tran~ition
temperature between those of the components used to
prepare the mixture.
The tran~parency of films of polymer alloys is an
indication that the components are homogeneously
mixed.

_ 4 _ 20~
Multiphase alloy~ can u ually be differentiated from
homogeneously mixed alloys by m0an~ of transmi6sion
elec~ron micro~copic ~tudies of thin ~ections.
Scanning elQctron microscopic 6tudie~ of fracture
surfaces or etched surfaces of alloys allow con-
clusions to be made on the mi~cibility of the
components pre~en~.
In industry, there i~ great ~nterest in homo~eneously
mixed polymer alloys, since ~heir properties can be
matched in a specific way to eertain demands by varying
the components ~nd the ~ixing ratios. Due to their
exceptional thermal and mechanical properties, polyamides
are particularly Lmportsnt as an alloy component. For
certain application~, fnr example to improve the proce~-
sibility, a reduction in the glas~ tran~ition temp~r~ture
is advantageous. The adaptation of mechanical properties
in a targeted manner i~ required in practice. Finally, it
is important for many applications to achieve a certain
wa~er-absorption capacity. Since the alloy~ known hi her-
to are usually not up to thece reguirement6, the ob~ect
was thus to find novel polyaramid alloyc who~e components
~re homogeneou~ly mixed and which ~ati~fy the criteria
mentioned.
The ob~ect has been achieved in that certain polyaramids
form surprisingly homogeneou~ly mixed alloys wi~h PVP
which, irrespective of the mixing ratio of the two
components, allow the abovementioned physical properties
to ~e ~et in a tar~eted manner.
The invention relates to a homo~eneou~ly mixed alloy
substantially containing
A) poly-N-vinylpyrrolidone and
B) at least one homo or c~polyaxamid containing at
lea tonerecurringstructuralunit 9f the formula (I)
O O
-~C - E~ E2 NH~ (I~

in which E1 and E2 ~re iden~ical or differcnt 2nd ar
selected from the group~
~3 C~3
,~
~ O~
- AX1~ or
in which Axl and Ar2 are identical or different
1,2-phenylene, 1,3-phenylene or 1,4-phenylene radic~ls
which may be 6ubstituted by (Cl-C6)-alkyl, (Cl-C6)-alkoxy,
each preferably having up tG 4 carbon atoms in the alXyl
qroup~ -CF3 or halogen, for example fluorine, chlorine or
bromine, and the radical ~
a) i~ a direct bond or one vf the ~ollowing divalent
radical~
-O-; -S02-, ~CQ-, -C ( Rl ) 2- ~ in which Rl i~ hydrog~n,
(Cl-C~)-alkyl or ~luoroalkyl having 1-4 ~arbon atoms
I5 in the al]~yl group, such a~ 2- ~ -C (C~33 2- or~
C(CF3)~-, or
b~ _Z_Arl_Z_, in which Z is the radic~l -O- or
-CtCH3)~a/ ~r
c) -C-Ar1-Y-AI2-O-, in which Y is 88 defined under ~a).
The followiny compounds are suitable, fox example, for
the preparation of the polyaramid6 having the recurring
structural units of the formula (I) and re~uired ~ccord-
ing to the invention:
Axomatic dicarboxylic acid derivativefi of th~ formula
~5 Cl-CO-~rl-CO-Cl,
~uch as 4,4' diph~nylsulfone dicarboxylic acid di~
chloride,
4,4'-diphenyl ether dicarboxylic acid dichloride,
4,4~ diphenyldicarboxylic acid dichlori~e,

-- 6 --
2,6~naphthal~nedic~rboxy1ic ~cid dichloride,
i60phthalic acid dichlorid~, but very particularly
terephthalic acid dichloride ~nd ~ubstitut~d
terephthalic acid dichloride, for e~ample
2-chloroterephthalic acid dichloride,
aromatic diamines of the ~tructure ~2N~Arl-NH2, ~uch a~
m~phenylenediamines or substituted phenylene~ismines, for
example 2-chloro-, 2,5-dichloro- or 2-methoxy-p-pheny-
lenedi~mine~ in particular p~phenylenedlamine,
substitu~ed benzidine derivatives of the formula
R2 R2
~2Nr ~ ~H2
in which R2 i~ a lower alkyl or alkoxy radical, in each
case having up to 4 carbon atoms in the alkyl group,
preferably -CH3 or -OCH3~ or i8 F, Cl or ~r,
~uch as 3,3'-di~ethoxy~, 3~3~-dichloro-~ 2,2'~dimethyl-.
and, preferably, 3,3'-dLmethylbenzLdine,
diamine components o ~he formula H2N-Arl-X Ar2-NH2,
~uch as 4,4'-~diaminobenzophenone, bis[4-aminophenyl]
8ul fone,
bis[4-~4/-aminophenoxy)phenyl] sulfone,
1,2-bis r 4'-aminophenoxy]benzene,
~ bis~(4'-aminophenyl)i60propyl]benzene,
2,2' bis[4-(4'-aminophenoxy)phenyl~pxopane,
in particular 1,4-bi~(4'-aminophenoxy)benzene.
It is likewi~e pos~ible to employ mixtures of the dicar~
boxylic acid chloride~ mentioned and/or of the diamines.
The homo- or copolyaramid i8 formed from recurring
~tructuxal units of the formula (I). The individual
~tructural units of the polymers may be different, 80
that E~ and E2 may be different radicals in the copoly-
mers.

~ 7 --
El is preferably a 1,3 or 1,4-phenylene radic~l, the
radical
C~3 ~3~ ~H3
~H
~H3 c~3
and E2 is preferably a 1,4-phenylene radical or the
radical
~2 ~2
in which R2 is a lo~er ~lkyl or alko~y radical, in each
case having up to 4 carbon atom in the alkyl yroup, or
is F, Cl or Br, or the radical
where X' is the group -C(R1)2-, in which Rl is hydrogen or
(Cl C4~-alkyl, or the group
-0~)-~
~n alloy which, beside~ PVP, contains at lea6t one
copolyaramid having at least three randomly recurring
structural units of the formula ~I~ in which
E1 is a divalent p-phenylene radical,
E2 in the three recurring structural unit~ i8 once each a
divalent p-phenylene radical, a radical of the formula
R~ R2
where R2 is CH3, ~CH3, ~ Cl or Br, and a radical of the
formula
~X'~

~ t~3
-- 8 --
in which ~ as defined above, in particular where the
copolyar~mid contains the recurring ~tructural units
~CO~CO~ +
c~3 CH~
--~CO~ CO-NH- ~ NH-t- and
~:0~ CO- N~I~ 0~ 0~ N~l~
Copolyaramids of this composit~on are known from
EP-A 0/l99,090, ko which referPnce i~ hereby m~de.
Polyaramids can generally be prepared in a known manner
by ~olution, interace or melt conden~ation. The way in
which the polycondensation i~ carried out determine~ here
whether random copol~mers, block or graft copolymers are
produced.
Solution condensation of the aromatic dicarboxylic scid
dichlorides with the aromatic diamine~ is carried out in
aprotic, polar 601vent~ of the amide typa, such as
N,N dLmethylacetamide or, in particular, N methyl-2-
pyrrolidone. If nece sary, halide ~alt6 from yroup oneand/or two of the Periodic Table can be added to these
~olvents in a known manner in order to increase the
601vating power or to ~tabilize the polyamide 801ution8.
Preferred additives are calcium chloride and/or lithium
chloride. ~he amount of dicarboxylic sc.Ld dichloride is
selected B0 that the desired 801ution viscogity ih
achieved.
The polycondensation temperatures are usually between -20
and +120~C, preferably between ~10 ~nd ~100C.
Particularly goo~ results are achieved at reaction
temperatures between ~lO and +80C. Polycondensation
reactions are generally carried out so that, when the

~o~
- 9 -
reac~ion i~ complete, 2 to 30, preerably 3.5 to 20, % by
weight of polycondens~te ~ pre~ent in the solution.
The polycondensation can be terminat~d in a cu~ omary
manner, for e~ample by adding monofunctional compounds,
S ~uch a~ benzoyl chloride.
When the polycondensa~ion i8 complete, i.~. when the
polymer ~olution has reached the vi8c08ity necessary for
further proces~ing, the hydrogen chloride produced, which
is 1008ely bvund to the ~mide solvent, i8 neutralized by
adding basic substance~. Examples of ~ub~tances which are
suitable for this purpo~e are lithium hydroxide, calcium
hydroxide, but in particular calcium oxide.
The alloy according to the invention ~an generally b~
prepared in a customary ~anner from a co~mon ~olution of
PVP and a polyaramid in an aprotic organic ~ol~ent, for
example dimethylformamide, dLmethyl sulfo~ide, N methyl-
pyrrolidone or N,N-dLmethylacetamide. The following
possibilities, for example, are available for thi~
purpose~
1. a) Polycondensation of a pclyaramid by ~olution,
interface or melt condensation,
b) difisolution of the resultant polyaramid,
c) dissolution of PVP and
d) ~ub~equent mixing of the PYP 601ution with the
polyaramid solution.
2. a) Solution condensation of a polyaramid and
b) ~ubsequent direct admixing of dry PVP or a PVP
solution directly into the polycondens~tion
batch.
0 3. a) 501ution conden~ation of a polyaramid in the
pre~ence of PVP.
This method al~o gives homogeneous mixture~ of
.the component~. To this end, the diamines are

-- 10 --
dissolved together with PVP and conden~ed by
addition of dicar~oxylio ~cid dichloride~ to form
a PVP/polyaramid solution.
The alloys can be isol~ted by removing the solvent,
preferably by evaporation, or the PVP/poly~r~mid ~olu~
tions obtained are processed further in a known manner to
give shaped s~ructures, ~uch ~s films or pxe~sings. The
alloys have a very wide variety of uses ~ince the com-
ponents mix homogeneous1y.
The molecular weight of the PVP, ~iven as the weight
average, is generally 1,000 ~ 3 t OOO~OOOt preferably
40,000 to 200,000, in particular 50,000 to 100!000.
The components of the alloys according to the invention
are homogeneously mi cible in all ratioR. In part~cular,
the allvys contain PVP in amounts of fxom 2 to 98% by
weîght, prefera~ly 15 to 85% by weight, and particularly
preferably 30 to 7Q% by weight, relative to the 8um of
components (A + B).
The alloys may contain additives in customary amounts,
for example thermsl stabilizers or W ~tabiliz~rs.
Reinforcing fibers can also generally be ~dded in amounts
of up to 50% by weight, for example carbon fibers, aramid
fibers or glass fiberR, also in the form of woven
fabrics. In addition, further polymers, for example
polyLmides or polyesters, may be added, for example in
amounts of up to 10% by weight. The amount ratios in both
cases always relate to the ~um of compon~nts (A + ~).
Depending on the PVP content, the gla~s tran~ition
temperature of the alloy~ according to the invention may
be varied in a targeted manner. In the same way, the
water-ab~orption capacity of ~he alloys can be influ-
enced. The dyeability of aramids can be achieved, for
example, by admixing a colored PVP copolymer. FinallyJ
the use of the alloys according to the invention i8 more

economic than aramids.
The homo~eneou~ miscibility of ~he component~ of the
alloys was proven using ~everal of the above-described
method6. For example, homogeneous alloy~ which cont~in a
polyaramid with a glasæ tran~ition temperature below
decomposition temperature which can be detected by
differential calorLme~y a~hibit a single ~la~s tra~i
tion temperature, determined by diffexen$ial calorimetry,
between that of PVP (175~C) and that of the polyaramid
l~ employed. In addition, it i8 entirely surpri8ing that the
water-soluble PVP i~ not di~olved out of the alloys
according to the invention by water, even by boiling for
several hour~. This is a fur~her indication of the
presence of an alloy comprising homogeneously ~ixed
components.
~x~mples
1) 0.4 mol of 2,2~-bis[4-(4~-aminophenoxy)phenyl]pro-
pane W2S dissolved under nitrogen in 2,000 g of N-methyl-
pyrrolidone (N~P), and 0.4 mol of 5-tert.-buty].iso-
phthalic acid dichloride was added between 15C and 70C
over the cour~e of 60 minutes.
The clear ~olution was ~tirred for about 40 minute~ at
70C and 6ubsequently neutralized with 24.5 g of CaO (96%
purity, i.e. in excess, corresponding to 0.42 mol) and
stirred for a further 30 minutes at 70 DC .
The solution wa~ filtered and coagul~ted in water. The
precipitated polyaramid wa~ wa~hed several times with
water and then with acetone. The polymer wa~ dried at
130~C under reduced pre6sure to constant weight.
According to DSC measurements, the polyaramid obtained
has a glass transition temperature Tg of 255C.

`~0~9~
- 12 -
2~ 5 g of poly~N-vinylpyrrolidone (PVP) were dissolved
in about ~0 g of ~-methylpyrrolidone at rovm temperature
together with 5 g of the polyar~mid d~cribed in Example
1. The mixture was sub~equen~ly fxe~d from solvent at
110C under reduoed pres~ure to con~ant weight. The
resultan~ PVP/pslyaramid alloy exAibit~, ~ccordin~ to DSC
measurements, a single glasQ transi~ion ~emperature of
225C, and was therefore classified a~ homogeneou~ly
mixed.
3) A polyaramid w~s prepared in accor~ance ~ith Example
1 using 0.4 ~ol of the diamine fr~m Example 1 and 0.4 mol
of terephthalic acid dichloride (TPC). Tg 235~C.
The polyhramid obtained was used to px~pare PVP alloy~ of
~ifferent PVP content in accordance with Example 2.
Each of the mixtures obtained exhibit~, according to DSC
measurements, a single glass tran~ition t~mperature
dependent on the composition, and wa& therefore cla~-
~ified as homogeneou~ly mixed (see figure and table
below).
2~
PVP content in
% by weight 0 25 50 75 100
Glass transition
temperature in C235 228 217 200 175
4) 4 g of an alloy described in Example 3, comprising
50~ of PVP and 50% of polyaramid, were ground in a mill
and subsequently pres~ed at 250aC under a pressure of
Q.2 t. This gave a transparent plate which dîd not
sc~tter visible light.
5) 15 g o~ PVP and 15 g of the pclyaramid de6cribed in
Example 3 were di6&01ved together in 170 g of N-methyl-
pyrrolidone at room temperature, and the solution was

~ 13 ~
degassed Rnd c~st to form film~ ~o this ~nd, the mixed
601utien was spread on glass plates at 69~C u~ing a
doctor blade. The cast films were ~ubsequently pre-dried
at 90C for 48 hours and then freed from 801v~nt under
reduced pres~ure at 110~C to con~tant weight~ The film
~hicknesses were between 2 and 100 ~m, depending on the
layer thicknesses applied.
The films ar ~echanically 8~able, non-brittle, colorl~s
and txan~parent. Th~y exhibit a water ab~orption of 9.8~
measured ~t 23C and 8S% rel~tive humidity. ~ilm~ treated
with boiling water for about 120 minu~es exhibit a ~ingl~
gla~s transition temperature of 217C which agre0~ with
the glass transition temperature of thé untreated films.
6) 0.2 mol of p-phenylen0diamine~ O.2 mol of 1,4-
bis~4'-aminophenoxy)benzene and 0.4 mol of 3,3'-dLmethyl~
benzidine were di~solved to~ether in 3.750 g of N-methyl-
pyrrolidone. 0.8 mol of terephthalic acid dichloride was
added in one portion at 16C, and the mixture was heated
to 60C with stirring over the co~r~e of ab~ut 60
minutes. The clear aolution was neutrali2ed using 49 g of
CaO (96%) ~nd s-lbsequently stirr~d for ~bout a further 60
minutes at 709c/ and 268.8 g of dried PVP were added with
stirring. The mixed solution ~a~ filtered and processed
to films in accordance with Example 5.
The films obtained are transparent, colorle~s and
mechanically ~table. According to DSC measurements, they,
like the aramid employed do hOt exhibit a glass
transition tempPrature of below 400C.
Both fracture ~urface~ of films fractured in liquid
nitrogen and ~urfaces etched with various solvents (for
example water or methylene chloride) or oxygen were
examined by scanning ~lectron microscopy. All the photo-
graphs exhibit smooth fracture fiurfaces or surfaces.
Besides the scanning electron micxo~copic studie~,

- ~4 ~ 3
tran~ sion electron micro~copic ~tudie~ were also
carried out both of thin ~ections and of thin ~ections of
the f ilm8 contr~sted with iodine. None of the tran~mis-
~ion electron microscopic picture~ e~hibited any
inhomogeneity of the film~.
The experiment~l re6ul~8 described ~how that the com-
ponents of the alloys are homogeneously mixed.
7) (Polyconden~ation in the pre~ence of PVP) 89.7 g of
dried PvP were di~olved in 734 g of distllled NMP. A
lQ solution of 10.8 g of p-phenylenediamine, 4205 g of 3,3'~
dLmethylbenzidine and 29.2 g of 1,4-bis(4'-aminophenoxy)-
benzene in 1,000 g of distilled N~P was added and the
mixture was cooled to 15C.
78.8 g of tereph~halic a~id dichloride ~TPC) were added
15 t9 this ~olution in one portion with ~tirring. Due to the
heat of reaction, the temperatuxe increafied to about
23C. The vi~cou6 ~olution wa6 warmed to 50C, and
~ufficient further TPC was ~dded until the desired
viscosity had been reach~d. 2.4 g of benzoyl chloride
were then added to convert the remaining amino end
group~. The mia:ture W8S ~tirred for ~bout a ~urther 1/2
hour, and the hydrogen chloride loo~ely bound to NNP was
then neutralized by ~dding 24.5 g of calcium oxide. After
filtration~ the viscous solution i~ directl~ suitable for
the preparation of film8, coatings and the like.
8) - 14) In the individual example~ in the t~ble below,
the starting material~ are listed for the polyaramid~,
furthermore the amounts employed and the glass tran~ition
- temperatures Tg obtained. ~he polyaramid~ ~erQ prepared
as in Example 1, and the alloy~ w~re prepared in cor-
re~ponding manner to Example 2 ~in all cases the
PVP:polyaramid weight ratio i~ 50:50) and the film wa~
produced as in Example 14 (ratio 50:503.

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- 16
C~mparison e~a~ple
5 g of PVP were dissolved at xoom temperature in 90 g of
NMP with 5 ~ of a polyether ~mide ~R~Ultem 1000 (m~nufac-
turer ~eneral Electric Co., Schenectady N.Y., USA) (Tg =
217C), and the sQlvent was sub~equently removed by
evaporation under reduced pres~ure. The alloy sxhibits
the two glass transition temperatures of the starting
materials of 175C and 217C and i~ accordingly not
homogeneously mixed.