U.S. patent number RE33,315 [Application Number 07/364,198] was granted by the patent office on 1990-08-28 for wholly aromatic mesomorphic polyester amide imides and the preparation thereof.
This patent grant is currently assigned to BASF Aktiengesellschaft. Invention is credited to Bernd Hisgen, Michael Portugall, Rolf Steinberger.
United States Patent |
RE33,315 |
Hisgen , et al. |
August 28, 1990 |
Wholly aromatic mesomorphic polyester amide imides and the
preparation thereof
Abstract
Wholly aromatic mesomorphic polyester amide imides which form a
liquid-crystalline fiber-forming melt below 320.degree. C. and are
composed of (a) from 5 to 35 mole % of repeat units of the formula
I and/or II ##STR1## where the Xs is the formulae I and II can be
identical or different and each is --O--, --S--, --SO.sub.2 --,
--CO--, --CH.sub.2 -- or .dbd.C(CH).sub.3).sub.2 and n is 0 or 1.
(b) from 0 to 30 mole % of repeat units of the formulae III and/or
IV ##STR2## (c) a molar amount corresponding to the total amount of
components a and b of one or more of the repeat units of the
formulae V, VI, VII, VIII and IX ##STR3## (d) if desired from 5 to
25 mole % of one or more of the repeat units of the formulae X, XI
and XII ##STR4## (e) repeat units of the formula XIII ##STR5## the
mole percentages of components (a), (b), (c), (d) and (e) adding up
to 100 mole % in each case, the preparation thereof and fibers,
films and moldings prepared therefrom.
Inventors: |
Hisgen; Bernd (Limburgerhof,
DE), Portugall; Michael (Wachenheim, DE),
Steinberger; Rolf (Schifferstadt, DE) |
Assignee: |
BASF Aktiengesellschaft
(Ludwigshafen, DE)
|
Family
ID: |
6287546 |
Appl.
No.: |
07/364,198 |
Filed: |
June 9, 1989 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
938057 |
Dec 4, 1986 |
04788272 |
Nov 29, 1988 |
|
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Foreign Application Priority Data
Current U.S.
Class: |
528/170; 528/125;
528/172; 528/183; 528/184; 528/190; 528/193; 528/271 |
Current CPC
Class: |
C08G
73/14 (20130101); C08G 73/16 (20130101); C09K
19/3823 (20130101) |
Current International
Class: |
C08G
73/16 (20060101); C08G 73/14 (20060101); C08G
73/00 (20060101); C09K 19/38 (20060101); C06G
073/16 () |
Field of
Search: |
;528/170,271,125,172,183,184,190,193 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Kight, III; John
Assistant Examiner: Krass; Frederick
Attorney, Agent or Firm: Keil & Weinkauf
Claims
We claim:
1. A wholly aromatic mesomorphic polyester amide imide which forms
a liquid-crystalline fiber-forming melt below 320.degree. C.,
composed of
(a) from 5 to 35 mole % of repeat units of the formula I or II or
mixtures thereof ##STR19## where the Xs in the formulae I and II
are identical or different and each is --O--, --S--, --SO.sub.2 --,
--CO--, --CH.sub.2 -- or --C(CH.sub.3).sub.2 and n is 0 or 1,
(b) from 0 to 30 mole % of repeat units of the .[.formulae.].
.Iadd.formula .Iaddend.III or IV or mixtures thereof ##STR20## (c)
a molar amount corresponding to the total amount of components
.[.a.]. .Iadd.(a) .Iaddend.and .[.b.]. .Iadd.(b) .Iaddend.of repeat
units of the .[.formulae.]. .Iadd.formula .Iaddend.V, VI,
VII.Iadd., VIII .Iaddend.or IX or mixtures thereof, with the
stipulation that a molar quantity greater than zero of V, VI or
mixtures thereof must be present at all times ##STR21## .[.from 5
to 25 mole % of repeat units of the formula X, XI or XII or
mixtures thereof:.]. ##STR22## .Iadd.and .Iaddend.
(e) repeat units of the formula XIII ##STR23## the mole percentages
of components (a), (b) (c).[., (d).]. and (e) adding up to 100 mole
% in each case.
2. A wholly aromatic mesomorphic polyester amide imide as claimed
in claim .[.1.]. .Iadd.11, .Iaddend.composed of
(a) from 7 to 25 mole % of repeat units of the .[.formulae.].
.Iadd.formula .Iaddend.I or II .Iadd.or mixtures thereof
.Iaddend.
(b) from 0 to 20 mole % of repeat units of the .[.formulae.].
.Iadd.formula .Iaddend.III or IV .Iadd.or mixtures thereof
.Iaddend.
(c) a molar amount corresponding to the total amount of components
(a) and (b) of repeat units of the .[.formulae.]. .Iadd.formula
.Iaddend.V, VI, VII, VIII or IX or mixtures thereof with the
proviso that a molar quantity greater than zero of V, VI or
mixtures thereof must be present at all times
(d) from 5 to 20 mole % of repeat units of the .[.formulae.].
.Iadd.formula .Iaddend.X, XI or XII or mixtures thereof and
(e) repeat units of the formula XIII, the mole percentages of
components (a), (b), (c), (d) and (e) adding up to 100 mole % in
each case.
3. A wholly aromatic mesomorphic polyester amide imide as claimed
in claim 1, which contains as component (c) from 5 to 20 mole % of
repeat units of the formula VI or mixtures of 5 to 20 mole % of the
repeat units of the formula VI and 2 to 8 mole % of repeat units of
the formula V and from 5 to 20 mole % of one or more of the repeat
units of the .[.formulae.]. .Iadd.formula .Iaddend.VII, VIII or
IX.
4. A wholly aromatic mesomorphic polyester amide imide as claimed
in claim 1, which contains as component (c) from 5 to 20 mole % of
repeat units of the formula VI and from 5 to 15 mole % of repeat
units of the formula VII and also from 5 to 15 mole % of repeat
units of the formula IX.
5. A wholly aromatic mesomorphic polyester amide imide as claimed
in claim 1, which contains as component (c) from 5 to 20 mole % of
repeat units of the formula VI and from 5 to 15 mole % of repeat
units of the formula VII.
6. A wholly aromatic mesomorphic polyester amide imide as claimed
in claim 1, which contains not less than 10 mole % of repeat units
of the formula XIII.
7. A wholly aromatic mesomorphic polyester amide imide as claimed
in claim 1, which has a glass transition temperature
Tg>140.degree. C.
8. A fiber from a polyester amide imide as claimed in claim 1.
9. A film from a polyester amide imide as claimed in claim 1.
10. A molding from a polyester amide imide as claimed in claim 1.
.Iadd.11. A wholly aromatic mesomorphic polyester amide imide which
forms a liquid-crystalline fiber-forming melt-below 320.degree. C.,
composed of
(a) from 5 to 35 mole % of repeat units of the formula I or II or
mixtures thereof ##STR24## .Iaddend. where the Xs in the formulae I
and II are identical or different and each is --O--, --S--,
--SO.sub.2 --, --CO--, --CH.sub.2 -- or --C(CH.sub.3).sub.2 -- and
n is 0 or 1,
(b) from 0 to 30 mole % of repeat units of the formula III or VI or
mixtures thereof ##STR25## (c) a molar amount corresponding to the
total amount of components (a) and (b) of repeat units of the
formula V, VI, VII, VIII or IX or mixtures thereof, with the
stipulation that a molar quantity greater than zero of V, VI or
mixtures thereof must be present at all times ##STR26## (d) from 5
to 25 mole % of repeat units of the formula X, XI or XII or
mixtures thereof: ##STR27## and (e) repeat units of the formula
XIII ##STR28## the mole percentages of components (a), (b), (c),
(d) and (e) adding up to
100 mole % in each case. .Iadd.12. A wholly aromatic mesomorphic
polyester amide imide as claimed in claim 11, which contains as
component (c) from 5 to 20 mole % of repeat units of the formula VI
or mixtures of 5 to 20 mole % of the repeat units of the formula VI
and 2 to 8 mole % of repeat units of the formula V and from 5 to 20
mole % of one or more of the repeat units of the formula VII, VIII
or IX. .Iaddend. .Iadd.13. A wholly aromatic mesomorphic polyester
amide imide as claimed in claim 11, which contains as component (c)
from 5 to 20 mole % of repeat units of the formula VI and from 5 to
15 mole % of repeat units of the formula VII and also from 5 to 15
mole % of repeat units of the formula IX. .Iaddend. .Iadd.14. A
wholly aromatic mesomorphic polyester amide imide as claimed in
claim 11, which contains as component (c) from 5 to 20 mole % of
repeat units of the formula VI and from 5 to 15 mole % of repeat
units of the formula VII. .Iaddend. .Iadd.15. A wholly aromatic
mesomorphic polyester amide imide as claimed in claim 11, which
contains not less than 10 mole % of repeat units of the formula
XIII. .Iaddend. .Iadd.16. A wholly aromatic mesomorphic polyester
amide imide as claimed in claim 11, which has a glass transition
temperature Tg>140.degree. C. .Iaddend. .Iadd.17. A fiber
from a polyester amide imide as claimed in claim 11. .Iaddend.
.Iadd.18. A film from a polyester amide imide as claimed in claim
11. .Iaddend. .Iadd.19. A molding from a polyester amide imide as
claimed in claim 11. .Iaddend.
Description
The present invention relates to wholly aromatic mesomorphic
polyester amide imides which form a liquid-crystalline
fiber-forming melt below 320.degree. C.
Liquid-crystalline polyester amides and polyester imides are known.
However, these polymers are in need of improvement in heat
distortion resistance, processability, and, in particular, abrasion
resistance. EP Application No. 81,900 discloses polyester amides
which comprise 40% or more coaxial units such as aromatic
dicarboxylic acids, hydroxybenzenecarboxylic acids, bisphenols and
aminophenols and contain an adequate amount of nonlinear radicals
which are derived from aromatic m-amino compounds and 2-nuclear
aromatic sulfones, but does not reveal the composition required to
obtain the desired combination of properties, U.S. Pat. No.
4,176,223 describes polyester imides which are based on
naphthalenedicarboxylic acid, substituted hydroquinones and
4-(4'-carboxyphthalimido)benzoic acid. However, these polymers
require for processing from the melt temperatures of 330.degree. C.
or more. The same is true of the polyester imides known from U.S.
Pat. No. 4,383,105, which are based on hydroxynaphthalenecarboxylic
acid, terephthalic acid, p-hydroxybenzoic acid and
4-(4'-hydroxyphthalimido)phenol.
It is an object of the present invention to provide wholly aromatic
mesomorphic polyester amide imides which form a liquid-crystalline
fiber-forming melt below 320.degree. C. and thus are easy to
process and, in addition, have a high heat distortion resistance, a
high abrasion resistance and a high resilience.
We have found that this object is achieved with wholly aromatic
mesomorphic polyester amide imides which form a liquid-crystalline
fiber-forming melt below 320.degree. C. and are composed of
(a) from 5 to 35 mole % of repeat units of the formula I and/or II
##STR6## where the Xs in the formulae I and II can be identical or
different and each is --O--, --S--, --SO.sub.2 --, --CO--,
--CH.sub.2 -- or --(CH.sub.3).sub.2 and n is 0 or 1,
(b) from 0 to 30 mole % of repeat units of the formulae III and/or
IV ##STR7## (c) a molar amount corresponding to the total amount of
components a and b of one or more of the repeat units of the
formulae V, VI, VII, VIII and IX ##STR8## (d) if desired from 5 to
25 mole % of one or more of the repeat units of the formulae X, XI
and XII ##STR9## (e) repeat units of the formula XIII ##STR10##
mole percentages of components, (a), (b), (c), (d) and (e) adding
up to 100 mole % in each case.
The novel wholly aromatic polyester amide imides have the advantage
of combining a high heat distortion resistance with a smooth
abrasion-resistant surface. The novel polyester amide imides
further have high stiffness, strength and resilience. In addition,
they are substantially resistant to chemicals and of low
flammability and can be processed from the melt at below
320.degree. C.
The liquid-crystalline state of the polyester amide imides can be
detected with a polarization microscope by a method described in
German Published Application DAS No. 2,520,819. Applied in a
thickness of 10 .mu.m between glass plates and viewed between
crossed polarizers, the polymer melts have textures which can be
ascribed to a mesomorphic phase.
The polyester amide imides according to the invention are composed
of
(a) from 5 to 35 mole %, in particular from 7 to 25 mole %, of
repeat units of the formulae I and/or II ##STR11## where the Xs in
the formulae I and II can be identical of different and each is
--O--, --S--, --SO.sub.2 --, --CO--, --CH.sub.2 -- or
.dbd.C(CH.sub.3).sub.2, in particular --O--, --SO.sub.2 -- or
--CH.sub.2 --, and n is 0 or 1, suitable compounds being for
example 4,4'-bis[(4-carboxy)-N-phthalimido]diphenyl ether,
4,4'-bis[(4-carboxy)-N-phthalimido]diphenyl methane,
4,4'-bis[(4-carboxy)-N-phthalimido]diphenyl sulfone,
4,4'-bis[(4-carboxy)-N-phthalimido]diphenyl sulfide,
4,4'-bis[(4-carboxy)-N-phthalimido]diphenyl ketone,
3,4'-bis[(4-carboxy)-N-phthalimido]diphenyl ether,
3,4'-bis[(4-carboxy)-N-phthalimido]diphenyl sulfide,
3,4'-bis[(4-carboxy)-N-phthalimido]diphenyl sulfone,
3,4'-bis[(4-carboxy)-N-phthalimido]diphenyl ketone and
3,4'-bis[(4-carboxy)-N-phthalimido]diphenylmethane.
(Compounds of the formulae I and II are obtainable for example by
the method of J. Polym. Sci. (A-1) 7 (1969), 32-332.)
(b) from 0 to 30 mole %, in particular from 0 to 20 mole %, of
repeat units of the formulae III and/or IV ##STR12## suitable
starting compounds being for example terephthalic acid and
isophthalic acid,
(c) a molar amount corresponding to the total amount of components
(a) and (b) of one or more of the repeat units of the formulae V,
VI, VII, VIII and IX ##STR13## suitable starting materials being
for example p-aminophenol for units of the formulae V,
m-aminophenol for units of the formula VI, hydroquinone for units
of the formula VII, resorcinol for units of the formula VIII and
4,4'-dihydroxybiphenyl for units of the formula IX,
(d) if desired from 5 to 25 mole %, in particular from 5 to 20 mole
%, of one or more of the repeat units of the formulae X, XI and XII
##STR14## suitable starting materials being for example
m-hydroxybenzoic acid for units of the formula X, p-aminobenzoic
acid for units of the formula XI and m-aminobenzoic acid for units
of the formula XII,
(e) repeat units, in particular in an amount of not less than 10
mole %, of the formula XIII ##STR15## a suitable starting compound
being for example p-hydroxybenzoic acid. It will be readily
understood that the mole percentages of components (a), (b), (c),
(d) and (e) add up to 100 mole % in each case.
Advantageously the polyester amide imides according to the
invention contain as component (c) from 5 to 20 mole % of repeat
units of the formula VI and/or from 2 to 8 mole % of repeat units
of the formula V and/or from 5 to 20 mole % of one or more of the
repeat units of the formula VII, VIII or IX.
Particular preference is given to polyester amide imides which
contain as component (c) from 5 to 20 mole % of repeat units of the
formula VI, from 5 to 15 mole % of repeat units of the formula XII
and from 5 to 15 mole % of repeat units of the formula IX.
Other preferred polyester amide imides contain as component (c)
from 5 to 20 mole % of repeat units of the formula VI and from 5 to
15 mole % of repeat units of the formula VII.
Preferred wholly aromatic polyester amide imides according to the
invention have a glass transition temperature of
.gtoreq.140.degree. C., in particular .gtoreq.150.degree. C. The
glass transition temperature is measured by the DSC differential
scanning colorimetry method as described by K. H. Illers et al. in
Makromol. Chemie 127 (1969), 1 ff. The wholly aromatic
liquid-crystalline polyester amide imides of the invention form a
liquid-crystalline fiber-forming melt at below 320.degree. C.
Preference is also given to liquid-crystalline aromatic polyester
amide imides which have partial crystallinity at a temperature
>200.degree. C. and <300.degree. C.
The liquid-crystalline polyester amide imides according to the
invention are obtained in a manner similar to techniques as
described for example in U.S. Pat. Nos. 4,375,530 and
4,118,372.
In an advantageous embodiment, the polyester amide imides according
to the invention are obtained in a single-stage process by
converting the starting materials as underivatized carboxylic
acids, hydroxy compounds or amino compounds using anhydrides of
lower fatty acids, for example fatty acids of 2 to 4 carbon atoms,
in particular acetic anhydride. This conversion may also be
catalyzed with catalysts of the type described for example In
EP-A-131,846 (page 9), used in an amount of from 0.001 to 1% by
weight. In the preferred embodiment, the starting materials are
heated together with a fatty acid anhydride, which is
advantageously present in a molar excess of 5% or more, based on
the hydroxyl and amino groups present, with stirring in an inert
gas atmosphere to a temperature at which reflux occurs.
Advantageously the temperature is raised in stages, for example to
130.degree. to 200.degree. C. in not more than 5 hours, preferably
up to 2 hours, and the temperature is then raised to
250.degree.-350.degree. C., for example in the course of from 2 to
21/2 hours, during which excess fatty acid anhydrides and fatty
acids are distilled off. To complete the reaction it has been found
to be advantageous to employ reduced pressure, for example from 200
to 0.1 mbar, toward the end.
The wholly aromatic liquid-crystalline polyester amide imides thus
obtained can subsequently be further condensed in the solid state,
for example at 150.degree.-250.degree. C. in the solid phase below
the melting point, until the desired viscosity is obtained. This
postcondensation in solid phase can be carried out not only before
but also after thermoplastic processing. Advantageously the
condensation in solid phase is carried out in the presence of
insert gases, for example nitrogen.
It is a remarkable and unforeseeable feature of this single-stage
process that the desired polymers are obtained in a relatively
short time in a trouble-free and complete reaction without
catalysts. This is all the more remarkable as the large number of
chemically different hydroxyl and amino groups would have been
expected to lead to differences in reactivity and hence inadequate
polymer synthesis.
The polyester amide imides according to the invention can contain
customary additives such as stabilizers, oxidation inhibitors,
agents against thermal decomposition and decomposition by
ultraviolet light, lubricants, mold release agents, colorants such
as dyes and pigments, fibrous and pulverulent fillers and
reinforcing agents, plasticizers and nucleating agents in
conventional active amounts.
The stabilizers can be added to the polymers at any stage of
processing or when complete. Preferably the stabilizers are added
early on to prevent the onset of decomposition before the polymers
are protected.
Suitable oxidation inhibitors and heat stabilizers are for example
halides of metals of group I of the periodic table, for example of
sodium, potassium, lithium with copper(I) halides, for example
chloride, bromide or iodide, and also sterically hindered phenols,
hydroquinones, various substituted representatives of these groups
and combinations thereof, in concentrations up to 1% by weight,
based on the polymer.
Suitable UV stabilizers which are employed in amounts of up to 2%
by weight, based on the composition, are for example substituted
resorcinols, salicylates, benzotriazoles or benzophenones.
Further additives are for example organic dyes such as nigrosine or
pigments such as titanium dioxide, cadmium sulfide, cadmium
selenide, phthalocyanines, ultramarine blue or carbon black, which
are employed for example in amounts of up to 5% by weight, based on
the polymer.
Further suitable additives are fibrous or pulverulent fillers and
reinforcing agents such as carbon fibers, glass fibers, amorphous
silica, asbestos, calcium silicate, aluminum silicate, magnesium
carbonate, kaolin, feldspar, chalk, quartz powder or mica, for
example in amounts of up to 70% by weight of the polymer.
Other suitable additives are nucleating agents such as talcum,
calcium fluoride, sodium phenylphosphinate, aluminum oxide or
finely divided polytetrafluoroethylene.
Suitable additives are also plasticizers, for example in amounts of
up to 20% by weight of the polymer, for example dioctyl phthalate,
dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils,
N-n-butylbenzenesulfonamide, and o- and
p-tolueneethylsulfonamide.
The wholly aromatic liquid-crystalline polyester amide imides
according to the invention are suitable for preparing filaments,
fibers, films, foams and industrial moldings by injection molding,
pressing or extruding. The moldings prepared from the polyester
amide imides according to the invention have excellent mechanical
properties such as stiffness, strength and resilience. They are
extremely resistant to chemicals and of low flammability. They also
have a high heat distortion resistance and a smooth,
abrasion-resistant surface. The polyester amide imides according to
the invention are therefore highly suitable for preparing articles
for electrical engineering, data processing, automotive
construction and other industrial sectors. But they can also be
used as coating materials, for example in the form of a pulverulent
dispersion or as a film.
The invention is illustrated by the following examples.
EXAMPLE 1
0.15 mol of terephthalic acid, 0.26 mol of 4-hydroxybenzoic acid,
0.07 mol of hydroquinone, 0.07 mol of dihydroxybiphenyl, 0.06 mol
of 3-aminophenol and 0.05 mol of the compound ##STR16## and 84 ml
of acetic anhydride are heated with stirring under nitrogen from
150.degree. C. to 300.degree. C. in the course of 3 h, while excess
acetic anhydride and acetic acid is distilled off. The pressure is
then reduced to 240 mbar in the course of 1 h 15 min to give a
viscous fiber-forming melt. The polymer melt and the cold polymer
have a pearlescent luster. The polymer has a smooth, hard and
abrasion-resistant surface. DSC differential scanning colorimetry
measurements indicate a glass transition temperature of 150.degree.
C. and a melting point of 260.degree. C. The intrinsic viscosity is
1.00 dl/g, measured at 60.degree. C. in 0.1% strength (wt./vol.)
solution in pentafluorophenol.
EXAMPLE 2
0.10 mol of terephthalic acid, 0.26 ml of 4-hydroxybenzoic acid,
0.07 mol of hydroquinone, 0.03 mol of dihydroxybiphenyl, 0.10 mol
of 3-aminophenol and 0.1 mol of the compound ##STR17## and 84 ml of
acetic anhydride are heated with stirring under nitrogen from
150.degree. C. to 300.degree. C. in the course of 2 hr 45 min,
while excess acetic anhydride and acetic acid is distilled off. The
pressure is then reduced to 80 mbar in the course of 50 min to give
a viscous, pale, fiber-forming melt. The polymer melt and the cold
polymer have a pearlescent luster. The polymer has a smooth, hard
and abrasion-resistant surface. DSC differential scanning
colorimetry measurements indicate a glass transition temperature of
177.degree. C. The intrinsic viscosity is 0.82 dl/g, measured at
60.degree. C. in 0.1% strength (wt./vol.) solution in
pentafluorophenol.
EXAMPLE 3
0.085 mol of terephthalic acid, 0.22 mol of 4-hydroxybenzoic acid,
0.085 mol of hydroquinone, 0.085 mol of 3-aminophenol and 0.085 mol
of the compound ##STR18## and 96 ml of acetic anhydride are heated
with stirring under nitrogen from 150.degree. C. to 300.degree. C.
in the course of 2 hr 50 min, while excess acetic anhydride and
acetic acid is distilled off. The pressure is then reduced to 40
mbar in the course of 20 min to give a viscous fiber-forming melt.
The polymer melt and the cold polymer have a pearlescent luster.
The polymer has a smooth, hard and abrasion-resistant surface. DSC
differential scanning colorimetry measurements indicate a glass
transition temperature of 181.degree. C. The intrinsic viscosity is
0.37 dl/g, measured at 60.degree. C. in a 0.5% strength (wt./vol.)
solution in p-chlorophenol.
* * * * *