CA1100686A - Polyamide, polyamide-imide and polyimide polymers and process for their manufacture - Google Patents
Polyamide, polyamide-imide and polyimide polymers and process for their manufactureInfo
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Abstract
Abstract of the Disclosure Polyamide, Polyamide-imide and Polyimide Polymers and Process for their Manufacture Novel polyamides, polyamida-amide-acids or polyamide-acids having structural elements of the formula
Description
`:
:
6-10525/+/B
Polyamide, PolyaMide-imide and Polyimide Polymers and Process for their Manufacture The present invention relates to new polyamide, polyamide-imide and polyimide polymers and a process for their manufacture.
It is known that, in general, polyamides, polyamide-imides and polyimides, and above all aromatic polymers of this type, can be pro-cessed only with difficulty. It is also known that the solubility of such polymers can be somewhat improved if bulky diamines or dianhydri-des containing 3 or more aromatic rings are used for their manufacture (compare, for example, DT-AS 1,595,733 and DT-OS 2,009,739, 2,153,829,
:
6-10525/+/B
Polyamide, PolyaMide-imide and Polyimide Polymers and Process for their Manufacture The present invention relates to new polyamide, polyamide-imide and polyimide polymers and a process for their manufacture.
It is known that, in general, polyamides, polyamide-imides and polyimides, and above all aromatic polymers of this type, can be pro-cessed only with difficulty. It is also known that the solubility of such polymers can be somewhat improved if bulky diamines or dianhydri-des containing 3 or more aromatic rings are used for their manufacture (compare, for example, DT-AS 1,595,733 and DT-OS 2,009,739, 2,153,829,
2,257,996 and 2,321,513). However, these polymers have the disadvantage that they cannot be processed from the melt, or can be processed from the melt only with difficulty. Moreover, the stability to heat and/or - chemical stability of these polymers is inadequate in some cases.
It has been found that polyamides, polyamide-amide-acids and polyamide-acids, and corresponding cyclised (imidised) derivatives, which are readily soluble and can be processed easily and have egcel-lent thermal, electrical and/or mechanical properties can be manufac-tured by using new aromatic diamines.
The present invention therefore relates to new polyamides, polyamide-amide-acids or polyamide~acids which consist of 1 to 100 mol%
of structural elements of formula I
C ~ COOHm~ H ~ (I) HOOCn_l C~ . ;o .~ O \-=o/ _ ,~
6~6 . .
and of O to 99 mol% of structural elements of formula II
- O ~ I
_ _ C ~ COOHm_l (II) HOOC 1 C - NH - Rl - NH - _ ~
in which the NH groups in formula I independently of one another are bonded to the benzene nucleus in the o-, m- or p-position and the indi-vidual m, n, R and Rl independently of one another have the following meanings: m and n denote the number 1 or 2, R denotes an aliphatic radical with at least two carbon atoms or a cycloaliphatic, carbocyclic-aromatic or heterocyclic-aromatic radical, the carbonamide groups and carboxyl groups being bonded to different carbon atoms and, if R deno-tes a cyclic radical and at least one of m and n denotes the number 2, the carboxyl groups each being in the ortho-position relative to a carbonamide group, and Rl denotes an aliphatic radical with a~ least two carbon atoms or a cycloaliphatic, araliphatic, carbocyclic aromatic or heterocyclic-aromatic radical, and also to the corresponding deriva-tives which have been cyclised to the imide.
These polyamides, polyamide-amide-acids or polyamide-acids and the corresponding derivatives which have been cyclised to the imide ; can be manufactured by subjecting 1-100 mol% of a diamine of formula III
'`:
o_ ~
.~ ~. \O
. H ~ o=-. 2 :; in which the NH2 groups independently of one another are in the o-, m- or p-position of the benzene nucleus, and 0-99 mol% of a diamine . .
61~
of formula I~
H2~ ~ Rl NH2 (IV) to a condensation reaction with essentially stoichiometric amounts of a compound of formula V
YOC COX
m-l (V) in which what has been stated under formulae I and II applies in respect of m, n, R and Rl and X, when m and/or n = 2, together with Y, forms the -O- grouping and Y represents a chlorine atom, a hydroxyl group, an unsubstituted or substituted phenoxy group or an alkoxy group with 1-18, and especially 1-12, carbon atoms, or, if m and/or n = 2, Y, to-gether with ~, forms the -O- grouping, the groups -COY and -COX being bonded to different carbon atoms and, if R represents a cyclic radical and m and/or n - 2, the -COY group or groups being in the ortho-posi-tion relative to a -COX group, and optiona].ly subsequently cyclising the resulting polymers, in which m and/or n = 2, to the imide.
The polyamides, polyamide-amide-acids and polyamide-acids accord-ing to the invention in general have an intrinsic viscosity in N,N-di-methylacetamide (DMA) at 25C of about 0.04 to 4.0 d Vg and especially of 0.1 to 2.5 d Vg. The intrinsic viscosity of the cyclised derivatives, that is to say the polyamide-imides and polyimides, in concentrated H2S04 or DMA at 25C is of the same order of size.
The intrinsic viscosity /~ i t i i is calculated according to the following equation ln ~
intrinsic = ~
Jqll6~
.
~ 4 --In this equation: ln denotes the natural logarithm, ~ denotes the visco~
sity of the solution ~0.5% by weight of the polymer in suitable sol-vents, preferably N,N-dimethylacetamide or concentrated sulphuric acid), ~ denotes the viscosity of the solvent and c denotes the concentra-tion of the polymer solution in g of polymer~100 ml of solvent.
The viscosity measurements are carried out at 25C.
The polymers according to the invention can be homopolymers or copolymers which have statistical distribution of the indivicual struc-tural elements of formulae I and II. In the individual structural elements, the m, n, R and Rl can also have different meanings. However, the polymers can also be homopolymers or copolymers which have any desired, and at least in part a block-like arrangement of polyamide, po].ya~.ide amide-acid or polyamide-acid structural elements, according to the definition, of formulae I and II. Homopolymers or copolymers of this type can be obtained, for example, by first allowing a diamine of formula III to react with a slight excess of a specific di-, tri-or tetracarboxylic acid derivative of formula V, for example with a dicarboxylic acid derivative, and then adding another di-, tri- or tetra-carboxylic acid derivative of formula V, a diamine of formula IV
and/or further diamine of the formula III to the reaction mixture.
:~ ;
An additional advantage of the invention is that it is, in general, possible to manufacture copolymers which have the desired improved properties by the addition of relatively small amounts of diamine of formula III.
:
Preferably, the individual m, n, R, Rl, ~ and Y have the same meaning and the NH and NH2 groups in formulae I and III, respectively are both in the same position, especially in the o-position and above all in the p-position of the ben~ene ring.
~IL0~i86 According to a further preference, the polyamides, polyamide-amide-acids or polyamide-acids according to the invention, and the corresponding cyclised derivatives, consist only of structural ele-ments of formula I. However, polymers, accorcLing to the definition, which consist of 5-80 mol% of structural elements of formula I and of 20-95 mol% of structural elements of formula II, and the corresponding cyclised derivatives, are particularly preferred.
If Y represents a substituted phenoxy group, these groups are, in particular, phenoxy groups substituted by nitro groups or alkyl or alXoxy groups with 1 or 2 carbon atoms or by halogen atoms, above all chlorine or fluorine, such as the 2-, 3- or 4-nitrophenoxy group, 2,4- or 3,5-dinitrophenoxy group or 3,5-dichlorophenoxy group or the pentachlorophenoxy, 2-methylphenoxy or 2-methoxyphenoxy group.
Alkoxy groups Y can be straight-chain or branched. Examples which may be mentioned are: the methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert.-butoxy, hexyloxy, octoxy, decyloxy, dodecyloxy, tetra-decyloxy and octadecyloxy group. Unsubstituted phenoxy groups or alkoxy groups with 1-12, and especially 1-4, carbon atoms are preferred.
If R represents an aliphatic radic~l, these radicals are, preferably, unsubstituted, straight-chain or branched alkylene groups with 2-10 carbon atoms.
Cycloaliphatic radicals represented by R are, above all, 5-mem-bered or 6-membered cycloalkylene groups.
If R denotes a carbocyclic-aromatic radical, this preferably contains at least one 6-membered ring; such radicals are, in particu-lar, monocyclic radicals, fused polycyclic radicals or polycyclic radicals which have several cyclic, fused or non-fused systems which cah be linked to one another direct or via bridge members. Examples ~, of suitable bridge members which may be mentioned are -O-, -CU2CH2-, Q
-CH~-, -CH-, -C-, -S-S-, -SO-, -SO2-, -SO2NH-, -CO-, -CO-, -C-C-, .. .. ..
Q Q O O O
Q Q
-CONH-, -NH-CO-NH-, -Si- or -O-Si-O-, in which Q denotes an alkyl group Q Q
with 1-6, and preferably 1-4, carbon atoms or a phenyl group.
. .
If R denotes a heterocyclic-aromatic radical, possible radicals are, in particular, 5-membered or 6-membered heterocyclic-aromatic, optionally benzo-condensed ring systems containing O, N and/or S.
Carbocyclic-aromatic or heterocyclic-aromatic radicals repre-sented by R can also be substituted, for example by nitro groups, alkyl groups with 1~4 carbon atoms, trifluoromethyl groups, halogen ~ atoms, especially chlorine, or silyl, sulphonic acid or sulphamoyl : groups.
: .
Aliphatic, araliphatic, cycloaliphatic, carbocyclic-aromatic or heterocyclic-aromatic radicals represented by Rl can be unsubsti-tuted or substituted, for example by halogen atoms, such as fluorine, chlorine or bromine, or by alkyl or alkoxy groups, each with 1-4 carbon atoms.
~- Possible aliphatic radicals Rl are, above all, straight~chain or branched alkylene groups with 2-12 carbon atoms, it being possible for the alkylene chain also to be interrupted by hetero atoms, such as O, S or N atoms.
In the meaning of a cycloaliphatic radical, Rl represents, for example, the 1,3- or 1,4-cyclohexylene group, the 1,4-bis-(methylene)-cyclohexane group or the dicyclohexyl-methane group, whilst possible araliphatic radicals are, above all, 1,3-, 1,4- or 2,4-bis-alkylene-benzene radicals, 4,~ bis-alkylene-diphenyl radicals and ~,4'-bis-alkylene-diphenyl ether radicals.
If Rl represents a carbocyclic-aromatic radical, such radicals are, preferably, monocyclic aromatic radicals, fused polycyclic aroma-tic radicals or non-fused bicyclic aromatic radicals and in the case of the latter the aromatic nuclei are bonded to one another via a bridge member. Possible bridge members are the groups mentioned in the preceding text when discussing R.
If Rl denotes a heterocyclic-aromatic radical, such radicals are, in particular, heterocyclic-aromatic of 5-membered or 6-membered rings containing 0~ N and/or S. ~dvantageously, R represents an unsub-stituted alkylene group with 4-10 carbon atoms or an unsubsti.tuted monocyclic, a fused bicyclic or a non-fused bicyclic aromatic radical and i.n the case of the latter the aromatic nuclei are bonded to one another via the bridge member -0-, -C0- or -S02-, whilst Rl denotes an unsubstituted alkylene group with 2-10 carbon atoms, a bis-(methy-lene)-cyclohexane group or a monocyclic or non-fused bicyclic aromatic radical which is unsubstituted or substituted by halogen atoms or alkyl or alkoxy groups, each with 1-4 carbon atoms.
Polyamides, polyamide-amide-acids or polyamide-acids, as well as the corresponding derivatives which have been cyclised to the imide, which consist only of structural elements of formula I, in which R
denotes a benzene ring or an unsubstituted alkylene group with 4-10 carbon atoms when m and n = 1, a benzene ring when m = ]. and n = 2 and a benzene ring or the benzophenone ring system when m and n = 2, but especially polyamides, polyamide-amide-acids or polyamide-acids, as well as the corresponding derivatives which have been cyclised to the imide, which consist of 5-80 mol% of structural elements of formula I
and 20-95 mol% of structural elements of formula II and in which m and n each denote the number l, R denotes a benzene ring or an unsubsti-6~36 tuted alkylene group with 4-10 carbon atoms and Rl denotes an unsubsti-tuted alkylene group with 2-12 carbon atoms, but above al] the 1,3- or 1,4-phenylene group, the 4,4'-diphenylmethane radical or the 4,4'-di-phenyl ether radical; m denotes the number 1 and n denotes the number 2, R denotes a benzene ring and Rl denotes an unsubstituted alkylene group with 2-12 carbon atoms, but especially the 1,3- or 1,4-phenylene group, the 4,4'-diphenylmethane radical or the 4,4'-diphenyl ether radical; or m and n denote the number 2, R denotes a benzene ring or the benzophenone ring system and Rl denotes an unsubstituted alkylene group with 2-12 carbon atoms, but preferably the 1,3- or 1,4-phenylene group, the 4,4'-diphenylmethane radical or the 4,4'-diphenyl ether radical, are preferred.
Polymers, accordlng to the definition, and the corresponding derivatives which have been cyclised to the imide, which consist of 5-50 mol% of structural elements of formula I and 50-95 mol% of ~truc-tural elements of formula II and in which Rl denotes the 1,3-phenylene group, the 4,4'-diphenylmethane radical or the 4,4'-diphenyl ether radical, m denotes 1, n denotes 2 and R denotes a benzene ring, or m and n denote 2 and R denotes a benzene ring or the benzophenone ring system, but above all polyamide copolymers which consist of 5-50 mol%
of structural elements of formula I and 50-95 mol% of structural elements of formula II and in which m and n denote the number l, R
denotes a benzene ring and Rl denotes an unsubstituted alkylene group with 4-10 carbon atoms, the 1,3-phenylene group, the 4,4'-diphenyl-methane radical or the 4,4-diphenyl ether radical, are very parti-cularly preferred.
In the above-mentioned preferred polymers, the NH g.oups in formula I are preferably each bonded to the benzene nucleus in the ortho-position and in particular each bonded to the benzene nucleus in the para-position.
~Q~6 The diamines of formula IV and the di-, tri- and tetra-carboxylic acid derivatives of formula V are known or can be manufactured according to methods which are in themselves known. Examples which may be mentioned are:
Diamines of the formula IV
o-, m- and p-phenylenediamine, diaminotoluenes, such as 2,4-di-aminotoluene, 1,4-diamino-2-methoxybenzene, 2,5-diaminoxylene, 17 3-di-amino-4-chlorobenzene, 4,4'-diamino-diphenylmethane, 4,4'-diaminodi-phenyl ether, 4,4'-diamino-diphenyl thioether, 4,4'-diaminodiphenyl-sulphone, 2,2'-diaminobenzophenone, 4,4'-diaminodiphenylurea and 1,~-or 1,5-diaminonaphthalene; 2,6-diaminopyridine, 1,4-piperazine, 2,4-diaminopyrimidine, 2,4-diamino-s-triazine, di-, tri-, tetra-, hexa-, hepta-, octa- and deca-methylenediamine, 2,2-dimethylpropylenediamine, 2,5-dimethylhexamethylenediamine, 4,4-dimethylheptamethylenediamine,
It has been found that polyamides, polyamide-amide-acids and polyamide-acids, and corresponding cyclised (imidised) derivatives, which are readily soluble and can be processed easily and have egcel-lent thermal, electrical and/or mechanical properties can be manufac-tured by using new aromatic diamines.
The present invention therefore relates to new polyamides, polyamide-amide-acids or polyamide~acids which consist of 1 to 100 mol%
of structural elements of formula I
C ~ COOHm~ H ~ (I) HOOCn_l C~ . ;o .~ O \-=o/ _ ,~
6~6 . .
and of O to 99 mol% of structural elements of formula II
- O ~ I
_ _ C ~ COOHm_l (II) HOOC 1 C - NH - Rl - NH - _ ~
in which the NH groups in formula I independently of one another are bonded to the benzene nucleus in the o-, m- or p-position and the indi-vidual m, n, R and Rl independently of one another have the following meanings: m and n denote the number 1 or 2, R denotes an aliphatic radical with at least two carbon atoms or a cycloaliphatic, carbocyclic-aromatic or heterocyclic-aromatic radical, the carbonamide groups and carboxyl groups being bonded to different carbon atoms and, if R deno-tes a cyclic radical and at least one of m and n denotes the number 2, the carboxyl groups each being in the ortho-position relative to a carbonamide group, and Rl denotes an aliphatic radical with a~ least two carbon atoms or a cycloaliphatic, araliphatic, carbocyclic aromatic or heterocyclic-aromatic radical, and also to the corresponding deriva-tives which have been cyclised to the imide.
These polyamides, polyamide-amide-acids or polyamide-acids and the corresponding derivatives which have been cyclised to the imide ; can be manufactured by subjecting 1-100 mol% of a diamine of formula III
'`:
o_ ~
.~ ~. \O
. H ~ o=-. 2 :; in which the NH2 groups independently of one another are in the o-, m- or p-position of the benzene nucleus, and 0-99 mol% of a diamine . .
61~
of formula I~
H2~ ~ Rl NH2 (IV) to a condensation reaction with essentially stoichiometric amounts of a compound of formula V
YOC COX
m-l (V) in which what has been stated under formulae I and II applies in respect of m, n, R and Rl and X, when m and/or n = 2, together with Y, forms the -O- grouping and Y represents a chlorine atom, a hydroxyl group, an unsubstituted or substituted phenoxy group or an alkoxy group with 1-18, and especially 1-12, carbon atoms, or, if m and/or n = 2, Y, to-gether with ~, forms the -O- grouping, the groups -COY and -COX being bonded to different carbon atoms and, if R represents a cyclic radical and m and/or n - 2, the -COY group or groups being in the ortho-posi-tion relative to a -COX group, and optiona].ly subsequently cyclising the resulting polymers, in which m and/or n = 2, to the imide.
The polyamides, polyamide-amide-acids and polyamide-acids accord-ing to the invention in general have an intrinsic viscosity in N,N-di-methylacetamide (DMA) at 25C of about 0.04 to 4.0 d Vg and especially of 0.1 to 2.5 d Vg. The intrinsic viscosity of the cyclised derivatives, that is to say the polyamide-imides and polyimides, in concentrated H2S04 or DMA at 25C is of the same order of size.
The intrinsic viscosity /~ i t i i is calculated according to the following equation ln ~
intrinsic = ~
Jqll6~
.
~ 4 --In this equation: ln denotes the natural logarithm, ~ denotes the visco~
sity of the solution ~0.5% by weight of the polymer in suitable sol-vents, preferably N,N-dimethylacetamide or concentrated sulphuric acid), ~ denotes the viscosity of the solvent and c denotes the concentra-tion of the polymer solution in g of polymer~100 ml of solvent.
The viscosity measurements are carried out at 25C.
The polymers according to the invention can be homopolymers or copolymers which have statistical distribution of the indivicual struc-tural elements of formulae I and II. In the individual structural elements, the m, n, R and Rl can also have different meanings. However, the polymers can also be homopolymers or copolymers which have any desired, and at least in part a block-like arrangement of polyamide, po].ya~.ide amide-acid or polyamide-acid structural elements, according to the definition, of formulae I and II. Homopolymers or copolymers of this type can be obtained, for example, by first allowing a diamine of formula III to react with a slight excess of a specific di-, tri-or tetracarboxylic acid derivative of formula V, for example with a dicarboxylic acid derivative, and then adding another di-, tri- or tetra-carboxylic acid derivative of formula V, a diamine of formula IV
and/or further diamine of the formula III to the reaction mixture.
:~ ;
An additional advantage of the invention is that it is, in general, possible to manufacture copolymers which have the desired improved properties by the addition of relatively small amounts of diamine of formula III.
:
Preferably, the individual m, n, R, Rl, ~ and Y have the same meaning and the NH and NH2 groups in formulae I and III, respectively are both in the same position, especially in the o-position and above all in the p-position of the ben~ene ring.
~IL0~i86 According to a further preference, the polyamides, polyamide-amide-acids or polyamide-acids according to the invention, and the corresponding cyclised derivatives, consist only of structural ele-ments of formula I. However, polymers, accorcLing to the definition, which consist of 5-80 mol% of structural elements of formula I and of 20-95 mol% of structural elements of formula II, and the corresponding cyclised derivatives, are particularly preferred.
If Y represents a substituted phenoxy group, these groups are, in particular, phenoxy groups substituted by nitro groups or alkyl or alXoxy groups with 1 or 2 carbon atoms or by halogen atoms, above all chlorine or fluorine, such as the 2-, 3- or 4-nitrophenoxy group, 2,4- or 3,5-dinitrophenoxy group or 3,5-dichlorophenoxy group or the pentachlorophenoxy, 2-methylphenoxy or 2-methoxyphenoxy group.
Alkoxy groups Y can be straight-chain or branched. Examples which may be mentioned are: the methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert.-butoxy, hexyloxy, octoxy, decyloxy, dodecyloxy, tetra-decyloxy and octadecyloxy group. Unsubstituted phenoxy groups or alkoxy groups with 1-12, and especially 1-4, carbon atoms are preferred.
If R represents an aliphatic radic~l, these radicals are, preferably, unsubstituted, straight-chain or branched alkylene groups with 2-10 carbon atoms.
Cycloaliphatic radicals represented by R are, above all, 5-mem-bered or 6-membered cycloalkylene groups.
If R denotes a carbocyclic-aromatic radical, this preferably contains at least one 6-membered ring; such radicals are, in particu-lar, monocyclic radicals, fused polycyclic radicals or polycyclic radicals which have several cyclic, fused or non-fused systems which cah be linked to one another direct or via bridge members. Examples ~, of suitable bridge members which may be mentioned are -O-, -CU2CH2-, Q
-CH~-, -CH-, -C-, -S-S-, -SO-, -SO2-, -SO2NH-, -CO-, -CO-, -C-C-, .. .. ..
Q Q O O O
Q Q
-CONH-, -NH-CO-NH-, -Si- or -O-Si-O-, in which Q denotes an alkyl group Q Q
with 1-6, and preferably 1-4, carbon atoms or a phenyl group.
. .
If R denotes a heterocyclic-aromatic radical, possible radicals are, in particular, 5-membered or 6-membered heterocyclic-aromatic, optionally benzo-condensed ring systems containing O, N and/or S.
Carbocyclic-aromatic or heterocyclic-aromatic radicals repre-sented by R can also be substituted, for example by nitro groups, alkyl groups with 1~4 carbon atoms, trifluoromethyl groups, halogen ~ atoms, especially chlorine, or silyl, sulphonic acid or sulphamoyl : groups.
: .
Aliphatic, araliphatic, cycloaliphatic, carbocyclic-aromatic or heterocyclic-aromatic radicals represented by Rl can be unsubsti-tuted or substituted, for example by halogen atoms, such as fluorine, chlorine or bromine, or by alkyl or alkoxy groups, each with 1-4 carbon atoms.
~- Possible aliphatic radicals Rl are, above all, straight~chain or branched alkylene groups with 2-12 carbon atoms, it being possible for the alkylene chain also to be interrupted by hetero atoms, such as O, S or N atoms.
In the meaning of a cycloaliphatic radical, Rl represents, for example, the 1,3- or 1,4-cyclohexylene group, the 1,4-bis-(methylene)-cyclohexane group or the dicyclohexyl-methane group, whilst possible araliphatic radicals are, above all, 1,3-, 1,4- or 2,4-bis-alkylene-benzene radicals, 4,~ bis-alkylene-diphenyl radicals and ~,4'-bis-alkylene-diphenyl ether radicals.
If Rl represents a carbocyclic-aromatic radical, such radicals are, preferably, monocyclic aromatic radicals, fused polycyclic aroma-tic radicals or non-fused bicyclic aromatic radicals and in the case of the latter the aromatic nuclei are bonded to one another via a bridge member. Possible bridge members are the groups mentioned in the preceding text when discussing R.
If Rl denotes a heterocyclic-aromatic radical, such radicals are, in particular, heterocyclic-aromatic of 5-membered or 6-membered rings containing 0~ N and/or S. ~dvantageously, R represents an unsub-stituted alkylene group with 4-10 carbon atoms or an unsubsti.tuted monocyclic, a fused bicyclic or a non-fused bicyclic aromatic radical and i.n the case of the latter the aromatic nuclei are bonded to one another via the bridge member -0-, -C0- or -S02-, whilst Rl denotes an unsubstituted alkylene group with 2-10 carbon atoms, a bis-(methy-lene)-cyclohexane group or a monocyclic or non-fused bicyclic aromatic radical which is unsubstituted or substituted by halogen atoms or alkyl or alkoxy groups, each with 1-4 carbon atoms.
Polyamides, polyamide-amide-acids or polyamide-acids, as well as the corresponding derivatives which have been cyclised to the imide, which consist only of structural elements of formula I, in which R
denotes a benzene ring or an unsubstituted alkylene group with 4-10 carbon atoms when m and n = 1, a benzene ring when m = ]. and n = 2 and a benzene ring or the benzophenone ring system when m and n = 2, but especially polyamides, polyamide-amide-acids or polyamide-acids, as well as the corresponding derivatives which have been cyclised to the imide, which consist of 5-80 mol% of structural elements of formula I
and 20-95 mol% of structural elements of formula II and in which m and n each denote the number l, R denotes a benzene ring or an unsubsti-6~36 tuted alkylene group with 4-10 carbon atoms and Rl denotes an unsubsti-tuted alkylene group with 2-12 carbon atoms, but above al] the 1,3- or 1,4-phenylene group, the 4,4'-diphenylmethane radical or the 4,4'-di-phenyl ether radical; m denotes the number 1 and n denotes the number 2, R denotes a benzene ring and Rl denotes an unsubstituted alkylene group with 2-12 carbon atoms, but especially the 1,3- or 1,4-phenylene group, the 4,4'-diphenylmethane radical or the 4,4'-diphenyl ether radical; or m and n denote the number 2, R denotes a benzene ring or the benzophenone ring system and Rl denotes an unsubstituted alkylene group with 2-12 carbon atoms, but preferably the 1,3- or 1,4-phenylene group, the 4,4'-diphenylmethane radical or the 4,4'-diphenyl ether radical, are preferred.
Polymers, accordlng to the definition, and the corresponding derivatives which have been cyclised to the imide, which consist of 5-50 mol% of structural elements of formula I and 50-95 mol% of ~truc-tural elements of formula II and in which Rl denotes the 1,3-phenylene group, the 4,4'-diphenylmethane radical or the 4,4'-diphenyl ether radical, m denotes 1, n denotes 2 and R denotes a benzene ring, or m and n denote 2 and R denotes a benzene ring or the benzophenone ring system, but above all polyamide copolymers which consist of 5-50 mol%
of structural elements of formula I and 50-95 mol% of structural elements of formula II and in which m and n denote the number l, R
denotes a benzene ring and Rl denotes an unsubstituted alkylene group with 4-10 carbon atoms, the 1,3-phenylene group, the 4,4'-diphenyl-methane radical or the 4,4-diphenyl ether radical, are very parti-cularly preferred.
In the above-mentioned preferred polymers, the NH g.oups in formula I are preferably each bonded to the benzene nucleus in the ortho-position and in particular each bonded to the benzene nucleus in the para-position.
~Q~6 The diamines of formula IV and the di-, tri- and tetra-carboxylic acid derivatives of formula V are known or can be manufactured according to methods which are in themselves known. Examples which may be mentioned are:
Diamines of the formula IV
o-, m- and p-phenylenediamine, diaminotoluenes, such as 2,4-di-aminotoluene, 1,4-diamino-2-methoxybenzene, 2,5-diaminoxylene, 17 3-di-amino-4-chlorobenzene, 4,4'-diamino-diphenylmethane, 4,4'-diaminodi-phenyl ether, 4,4'-diamino-diphenyl thioether, 4,4'-diaminodiphenyl-sulphone, 2,2'-diaminobenzophenone, 4,4'-diaminodiphenylurea and 1,~-or 1,5-diaminonaphthalene; 2,6-diaminopyridine, 1,4-piperazine, 2,4-diaminopyrimidine, 2,4-diamino-s-triazine, di-, tri-, tetra-, hexa-, hepta-, octa- and deca-methylenediamine, 2,2-dimethylpropylenediamine, 2,5-dimethylhexamethylenediamine, 4,4-dimethylheptamethylenediamine,
3-methylheptamethylenediamine, 3-methoxyhexamethyldiamine, 2,11-diamino-dodecane, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 1,2-bis~(3-aminopropoxy)-ethane, N,N'-dimethylethylenediamine and N,N'-dimethyl-1,6-diaminohexane as well as the diamines of the formulae 2 2 3 2 2 ( 2)3NH2 and ~2N(CH2)3S(CH2)3NH2; 174-diamin hexane, 1,4-bis-(2-methy1-4-aminopentyl)-benzene and 1,4-bis-(amino-methyl)-benzene.
Compounds of the formula V
Malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid and dodecanedicarboxylic acid, 1,3-cyclopentane-dicarboxylic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, terephthalic acid, isophthalic acid,
Compounds of the formula V
Malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid and dodecanedicarboxylic acid, 1,3-cyclopentane-dicarboxylic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, terephthalic acid, isophthalic acid,
4,4'-dicarboxydiphenylethane, naphthalene-2,6-dicarboxylic acid, thio-phene-2,5-dicarboxylic acid and pyridine-2,3-dicarboxylic acid as well as the corresponding dichlorides and diesters according to the defini-tion; trimellitic acid 1,2-anhydride-chloride (1,3-dioxo-benzo[c]
oxalane-5-carboxylic acid chloride), trimellitic acid anhydride and 6~36 trimelli-tic acid as well as esters according to the definition; pyro-mellitic acid dianhydride, 3,3',4,4'-benzophenone-tetracarboxylic acid dianhydride, 2,3,3',4'-benzophenone-tetracarboxylic acid dianhydride, 2,2',3,3'-benzophenone-tetracarboxylic acid dianhydride, 393',4,4l-di-phenyl-tetracarboxylic acid dianhydride, bis-(2,3-dicarboxyphenyl)-methane dianhydride, bis-(2,5,6-trifluoro-3,4-dicarboxyphenyl)-methane dianhydride, 2,2-bis-(2,3-dicarboxyphenyl)~propane dianhydride, bis-(3,4-dicarboxyphenyl) ether dianhydride, bis-(3,4-dicarboxyphenyl)-sulphone dianhydride, N,N-(3,4-dicarboxyphenyl)-N-methylamine dian-hydride, bis-(3,4-dicarboxyphenyl)-diethylsilane dianhydride, 2,3,6,7-and 1,2,5,6-naphthalene-tetracarboxylic acid dianhydride, 2,6-dichloro-naphthalene-l~4~5~8-tetracarboxylic acid dianhydride, thiophene-2,3,4,5-tetracarboxylic acid dianhydride, pyrazine-2,3,5,6-tetracarboxylic acid dianhydride and pyridine-2,3,5,6-tetracarboxylic acid dianhydride.
Preferred compounds of the formula IV are alkylene-diamines with 2-12, and especially 4-10, carbon atoms and especially 1,3- or 1,4-phenylenediamine, 4,4'-diaminodiphenyl ether and 4,47-diaminodi-phenylmethane.
Acid dichlorides, acid chloride-anhydrides or dianhydrides, and especially those in which R denotes a benzene ring or the benzophenone ring system, are advantageously used as the compounds of the formula V.
The polycondensation reaction of the compounds of the formula III with one or more compounds of the formula V and, optionally, one or more compounds of the formula IV is carried out in a manner which is in itself known, appropriately at temperatures of about -50C to ~300C. The reaction can be carried out in the melt or, preferably, in an inert organic solvent or a solvent mixture. Temperatures of -20C to +50C are preferred for the polycondensation reaction in solu-tion.
' ' :
Examples of suitable organic solvents are: chlorinated aromatic hydrocarbons, such as chlorobenzene and dichlorobenzenes, chlorinated aliphatic hydrocarbons, such as methylene chloride, chloroform, tetra-chloroethane and tetrachloroethylene, aliphatic and cycloaliphatic ketones, such as acetone, methyl ethyl ketone, cyclopentanone and cyclo-hexanone, cyclic ethers, such as tetrahydrofurane, tetrahydropyrane and dioxane, cyclic amides, such as N methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone and N-methyl-~ -caprolactam, N,N-dialkylamides of aliphatic ~onocarboxylic acids with 1-3 carbon atoms in the acid part, such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide and N,N-dimethylmethoxy-acetamide, hexamethylphosphoric acid triamide (hexametapol), N,N,N',N'-tetramethylurea, tetrahydrothiophene dioxide (sulpholane) and dialkylsulphoxides, such as dimethylsulphoxide and diethylsulphoxide.
Preferred solvents are N,N-dialkylamides of aliphatic mono-carboxylic acids with 1-3 carbon atoms in the acid part9 especially N,N-dimethylacetamide, as well as cyclic amides, such as N-methyl-2-pyrrolidone.
The hydrochloric acid obtained during the condensation reaction with compounds of the formula V in which Y represents chlorine can be removed by neutralisation with basic substances, such as calcium hydroxide or triethylamine, or by reaction with an epoxide compound, such as ethylene oxide or propylene oxide, and by washing out with suitable solvents.
The condensation reactions are appropriately carried out with the exclusion of moisture, for example in an inert gas atmosphere, such as nitrogen.
As already mentioned initially, the reaction of the di-, tri-or tetra-carboxylic acid derivatives of the formula V with the diamines -~ l2 -of the formula I~ and~or III can also be carried out stepwise in order to manufacture poly~ers which, at least in part, have a block-type distribution of the structural elements of the formula I or II. It is also possible to link polyamides, polyamide-amide-acids or polyamide-acids which have structural elements of the formula I or VI and have been manufactured separately, with one another and so-called block copolymers are formed by this means. In all of these cases, the reac-tion is carried out in a manner which is in itself l~nown using a slight excess of one or the other reactant in order to obtain prepoly-mers which have end groups suitable for the further reaction, for example amino end groups, acid chloride groups and/or anhydride groups.
.
The optional cyclisation of the polyamide-acids or polyamide-amide-acids (m and/or n = 2) obtained after the condensation reaction is carried out in a manner which is in itself known by chemical means or by means of heat.
The chemical cyclisation is appropriately carried out by treat-ment with a dehydrating agent on its own or as a mixture with a ter-tiary amine. Reagents which can be used are, for example, acetic an-hydride, propionic anhydride and dicyclohexylcarbodiimide or mixtures of acetic anhydride and triethylamine.
The cyclisation by means of heat is carried out by heating to temperatures of about 50C to 300C and preferably of about 150C to 250C and optionally with the addition of an inert organic solvent.
The polyamides, polyamide-amide-acids and polyamide-acids according to the invention, as well as the correspondillg cyclised derivativesJ are suitable for the manufacture of shaped articles of .
very diverse types, such as fibres~ films, sheets, coating composi-tions, foams, laminating resins, composite materials, moulding powders, pres3ed areicles and ehe like, in a mamler which is in ieself hnown, . ~
' .
if desired with the use of customary additives, such as pigments, fil-lers and the iike. The polymers according to t:he invention can also be processed easily from the melt and are distinguished by good mechani-cal, electrical and thermal properties as well as, in general, by good solubility in organic solvents, such as N,N-dimethylacetamide, N,N-di-methylformamide and N-methyl-2-pyrrolidone.
The new diamines of formula III can be manufactured, for example, by either reacting a compound of formula VIa O\M
. (VIa) =~ .=-O M
in a molar ratio of at least 1:2 with a compound of formula VIIa l \ _./ (VIIa) or reacting a compound of formula VIb ~ D_~ (VIb) = O ~ = -in a molar ratio of at least 1:2 with a compound of formula VIIb M+O- ~ ~ 2 (VIIb) in which M denotes a hydrogen, alkaline earth metal or alkali metal cation, a trialkyl-ammonium cation with 3-24, and especially 3-12, carbon atoms, or a quaternary ammonium cation, Zl denotes a halogen atom or, if the nitro group is in the ortho-position relative to Zl' also denotes a nitro group and Z2 denotes a halogen atom, to give a compound of formula VIII
6~3~
1~ -~ ~ 2 o\ ~ \ /
D ~
0~ . (VIII) /
O
N02 =.
in which the two nitro groups independently of one another are in the o-, ~- or p-position of the benzene ring, and subsequently converting the compound of formula VIII into a compound of formula III. Mixtures of two different compounds of the formula VIIa or VIIb can also be used in the above process.
Possible halogen atoms Zl and Z2 are bromine atoms, but especial-ly chlorine atoms and fluorine atoms.
':
If M represents an alkaline earth metal cation or an alkali metal cation, this cation is, for example, the Ba7 Mg, Ca, Li, ~a or K cation. Examples of suitable trialkylammonium cations ~ are the trimethyl-ammonium, triethyl-ammonium, methyldiethyl-ammonium and tri-n-octyl ammonium cation, whilst possible quaternary ammonium cations are, for example, the benzyltrimethyl-ammonium cation and the tetramethyl-ammonium cation. M preferably represents the hydrogen, Na or K cation.
The reaction of the compounds of formula VIa and VIb with the compounds o Eormula VIIa und VIIb can be carried out in an aqueous-organic or organic medium or, alternatively, in the melt.
If M in formula VIa or VIIb represents hydrogen, the reaction is advantageously carried out in an aqueous-organic or organic medium ; and optionally in the presence of an acid-binding agent. Examples of acid-binding agents which can be used are inorganic and organic bases, such as alkaline earth metal hydroxides and carbonates and alkali metal hydroxides and carbonates, especially the hydroxides or carbonates of `'-' :.
.' , . .
'' ' :.
~a or K, and tertiary amines, such as triethylamine, pyridine or pyri-dine bases.
.
The inert organic solvents used are, appropriately, polar aprotic solvents, for example dialkylsulphoxides, such as dime~hylsulphoxide and diethylsulphoxide, tetra~ethylenesulphone or dimethylsulphone.
Compounds oE formula IVa and VIIb in which M represents an alkaline earth metal cation, an alkali metal cation, a trialkyl-ammonium cation or a quaternary ammonium cation are preferred for the reaction in the melt.
The reaction temperatures are generally between about 50C and 150C for the reaction in an organic or aqueous-organic medium and between about 100C and 200C, preferably between about 130C and 160C, for the reaction in the melt.
Compounds of formulae VIb and VIIb, but especially compounds of formulae VIa and VIIa in which M represents the hydrogen cation or an alkali metal cation, especially the sodium cation or potassium cation, and Zl and Z2 represent chlorine or fluorine are preferably used.
' The compounds of formulae VIa, VIb, VIIa and VIIb are prefer-ably employed in stoichiometric amounts. However, the reaction can ; also be carried out with a slight excess of one or the other reactant.
, .
The reduction (hydrogenation) of the compounds of formula VIII
can be carried out in a manner which is in itself known, for example with iron in an acid medium by the Béchamp method, optionally in the presence of neutral salts, such as iron-II sulphate, CaC12 or sodium hydrogen sulphate; with tin or tin-II chloride in the presence of HCl;
with zinc in an acid or neutral medium9 optionally with the addition .~
- of neutral salts, such as CaCl2 and NH4Cl; with lithium aluminium hydride; with hydraæines, such as hydraæine hydrate and phenylhydra zine, if necessary with the addition of Raney nickel catalysts, and with sodium dithionite (Na2S204).
Catalytic reduction is preferred. Examples of suitable catalysts are palladium, palladium-on-charcoal, platinum, platinum black, plati-num oxide and, above all, Raney nickel. The catalytic reduction is appropriately carried out in a suitable inert organic solvent, such as dioxane or methylcellosolve.
The compounds of formulae VIa, VIb9 VIIa and VIIb are known or can be manufactured easily in a manner which is in itself known.
The compounds of formula VIII are also new. Both these compounds and the diamines of the formula III can, after the reaction, be isola-ted, and purified, in a customary manner, for e~ample by washing with water or diethyl ether or by filtering and recrystallising from suit-able solvents, such as methanol or ethanol. The compounds of the for-mulae III and VIII are obtained in the form of white to slightly yellowish crystals.
. :
, . , .- ' ' 6~3~
Example I
HO\ ~2 \ ~ NO
. + 2 i 1 I DMSO
=- H2 OH Cl NO -- ~ O Raney-Ni =.
~ -NH2 . _ . . _ . , = .
. _ . . = . . _ .
.=.
37.2 g (0.2 mol) of 2,2'-dihydroxy-biphenyl and 63 g (0.4 mol) of p-nitrochlorobenzene are dissolved in 160 ml of dimethylsulphoxide (DMSO) in a sulphonation 1ask and the solution is warmed to 80C.
A solution of 26.4 g (0.4 mol) oE 85% strength potassium hydroxide in 20 ml of water is then added dropwise, whilst stirring, and the reac-tion solution is subsequently further stirred for 3 hours at 100-110C.
After coollng, the reaction solution is poured into ice water and the resulting precipitate is washed several times with water. The resulting crude product is then dried for 20 hours under a high vacuum at 70C
and unconverted nitrochlorobenzene sublimes away during drying. The residue is recrystallised twice from ethanol. 12.4 g (15% of theory) of 2,2'-di-(p-nitrophenoxy)-biphenyl are obtained in the form of slightly yellowish crystals; melting point 158C.
Analysis for C24H1606N2 (molecular weight 428.41):
calculated C 67.3% H 3.72% N 6.55%
found C 67.1% H 3.8 % N 6.4 %.
82.5 g of the above 2,2'-di-(p-nitrophenoxy)-biphenyl are hydro-genated with 24 g of Raney nickel in 900 ml of dioxane at 40-50C.
`:
:' .
'.', ' ' ' '' After filtering off the catalyst and evaporating the solvent, 70 g (99% of theory~ of crude 2,2'-di-(p-aminophenoxy)-biphenyl are obtained and this is recrystallised twice from ethanol. After recrystallisation, 51.6 g (73% of theory) of pure 2,2'-di-(p-aminophenoxy)-biphenyl are obtained in the form of slightly yellowish crystals, melting point 15~C.
Analysis for C24H2002N2 (molecular weight 368.44):
calculated C 78.24% H 5.~7% N 7.61%
found C 7~.1 % ~ 5.6 % N 7.~ %
Example 2: 74.4 g (0.4 mol) of 2,2'-dihydroxy-biphenyl are sus-pended in 400 ml of distilled water in a round-bottomed flask and 53.5 g (0.8 mol) of 84% pure solid potassium hydroxide are then added in portions at 20-25C, whilst stirring. The reaction mixture is stirred further until all of the 2,2l-dihydroxy biphenyl has dissolved. The reaction solution is then evaporated to dryness in a rotary evaporator.
315 g (2 mols) of p-nitrochlorobenzene are added to the residue (the dipotassium salt of 2,2'-dihydroxy-biphenyl), the round-bottomed flask is provided with a riser and the reaction mixture is heated to 150C
for 2 hours, whilst stirring. After cooling to about 100C, the result-ing melt is poured into 2 litres of chloroform. The resulting solution is extracted twice with water, dried over potassium carbonate and eva-~- porated in a rotary evaporator. In order to remove excess p-nitrochloro-benzene, the residue is suspended in 2 litres of diethyl ether and the suspension is warmed under reflux for a short time. The reaction mix-ture is then filtered and the material on the filter is rinsed with diethyl ether and, after decolourising with active charcoal, the pro-duct is recrystallised from ethanol. This gives 38.9 g (23% of theory) of the 2,2'-di-(p-nitrophenoxy)-biphenyl (of analytical purity) characterised in Example 1.
`:
The hydrogenation to 2,2'-di-(p-aminophenoxy)-biphenyl is carried out as described in Example 1.
- , :
Example 3: Analogously to the procedure described in Example 2, 37.2 g (0.2 mol~ of 2,2'-dihydroxy-biphenyl are converted into the corresponding dipotassi~m salt using 26.8 g (0.4 mol) of 84% pure solid potassium hydroxide in 200 ml of water. This salt is reacted in the melt with 157 g ~1 mol) of o-chloronitroben~ene, in the manner described in Example 2. The crude product which is obtained after removal of th~
chloroform is dissolved hot in methanol, the solution is decolourised with active charcoal and the product is crystallised. The product is then recrystallised once more from ethanol and 20.3 g (24% of theory) of 2,2'-di-(o-nitrophenoxy)-biphenyl are obtained in the form of pale yellowish crystals; melting point 154C.
Analysis for C24H1606N2 (molecular weight 428.41):
calculated C 67.3% H 3.72% N 6.55%
found C 67.3% H 3.8 % N 6.5 %
27 g of 2,2'-di-(o~nitrophenoxy)-biphenyl are hydrogenated with 3 g of Raney nickel in 270 ml of dioxane at 35-40C. After filtering oEf the catalyst and evaporating the solvent, 23 g (99% of theory) of crude diamine results and this is recrystallised twice from ethanol.
This gives 16.2 g (70% of theory) of 2,2'-di-(o-aminophenoxy)-biphenyl in the form of colourless crystals; melting point 175C.
Analysis for ~24H20o2N2 (molecular weight 368.44):
calculated C 78.25% H 5.47% N 7.61%
found C 78.28% H 5.53% N 7.66%
.
Example 4: 18.62 g (0.1 mol) of 2,2'-dihydroxy-biphenyl and 28.22 g (0.2 mol) of p-nitrofluorobenzene are dissolved in 80 ml of dimethyl-sulphoxide in a sulphonation flask and the solution is warmed to 80C.
A solution of 13.2 g (0.2 mol) of 85% pure potassium hydroxide in lO ml of water is then added dropwise, whilst stirring, and the reac-tion solution is subsequently further stirred for 3 hours at 100-110Co During this time a yellow precipitate forms and after the reaction mixture has cooled this is separated off by decanting off the super-natant liquor and is then washed several times with water. ~fter drying, the crude product is recrystallised from ethanol. 32.86 g (77% oE
theory) of 2,2'-di-(p-nitrophenoxy)-biphenyl of analytlcal purity are obtained in the form of slightly yellowish crystals with a melting point of 158C.
Hydrogenation of the above product by the method described in Example 1 and recrystallisation of the resulting crude product from ethanol gives 2,2'-di-(p-aminophenoxy) biphenyl which is of analytical purity and has a melting point of 157-158C.
;'' Example 5: 18.62 g (0.1 mol) of 2,2~-dihydroxydiphenyl, 23.22 g (0.2 mol) of o-nitrofluoroben~ene, 13.2 g (0.2 mol) of 85% pure solid potassium hydroxide and 10 ml of water are reacted in 80 ml of di-methylsulphoxide according to the procedure described in Example 4.
After washing and recrystallising the resulting precipitata, 28.82 g (67% of theory~ of 2,2'-di-(o-nitrophenoxy)-biphenyl of analytical purity are obtained in the form of slightly yellowish crystals with a melting point of 153-154C.
~ ydrogenation of the above product by the procedure described in Example 3 and recrystallisation of the crude product from ethanol gives 2,2'-di(o-aminophenoxy)-biphenyl which is of analytical purity and has a melting point of 174-175C.
..
Example 6: 5.526 g (0.015 mol) of the 2,2'-di-(p-aminophenoxy)-., biphenyl prepared according to Example 1 are dissolved in 90 ml of ;` anhydrous N,N-dimethylacetamide (DMA) in a sulphonation flask, under a nitrogen atmosphere, and the solution is cooled to 0-5C. 4.83 g (0.015 mol) of 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride in solid form are added in portions to this solution, whilst stirring.
~ The resulting viscous solution is then stirred for a further 30 minu-; tes at 0-5C and subsequently for a further 2 hours at 20-25C. The .:
:
~' ' :
P61~1~
intrinsic viscosity of the polyamide-acid thus formed is 0.75 dl/g (0.5% by weight in DMA at 25C).
Part of this polyamide-acid solution is spread to give a film.
The film is dried in vacuo as follows: l hour at 60~, 1 hour at 100C, 1 hour at 150C and 16 hours at 200C~ A transparellt, flexible film is obtained.
A mixture of 45 ml of acetic anhydride and 30 ml of pyridine is added dropwise to the remainder of the above polyamide-acid solution.
Subsequently, the reaction mixture is stirred for 16 hours at 20-25C
and then poured into water. The precipitate thus formed is washed several times with water and dried in a vacuum drying cabinet for 20 hours at 150C/20 mm Hg and for 20 hours at 200C/0.1 mm Hg. 7.8 g of polyimide in the form of a yellow powder are obtained.
For processing by the compression moulding process, the above polyimide is introduced into a compression mould for circular sheets, which has been prewarmed to 320C, and compression moulded at this temperature for 3 minutes under the contact pressure and for 5 minutes under a pressure of 225 kp/cm2. Strong, transparent mouldings which have good mechanical and electrical properties even at elevated tem-peratures are obtained.
Example 7: Analogously to the procedure described in Example 6, 1.842 g (0.005 mol) of the 2~2'-di-(o-aminophenoxy)-biphenyl prepared according to Example 3, in 37 ml of anhydrous DM~, are reacted with 1.611 g (0.005 mol) of 3,3',4,4'-benzophenone-tetracarboxylic acid di-anhydride. The resulting polyamide-acid has an intrinsic viscosity of 0.20 dl/g (0.5% by weight in DMA at 25C).
. .
.
6~1~
Example 8: 3.68 g (0.01 mol) of 2,2'-di-(p-aminopheno~y)-biphenyl are dissolved in 50 ml of anhydrous D~ in a sulphonation flask, under a nitrogen atmosphere, and the solution is cooled to -15C. 2.03 g (0.01 mol) of isophthalic acid dichloride in the solid form are then added in portions, whilst stirring, in such a way that the temperature of the reaction mixture does not rise above -5C. The reaction mixture is then rinsed with 10 ml of D~ and stirred for a further 1 hour at -5C and then for a further 1 hour at 20-25C. Finally, the reaction mixture is cooled and a solution of 2.02 g (0.02 mol) of triethylamine in 10 ml of DMA is added dropwise at -5C. ~fter stirring for 1 hour at 20-25C, the triethylamine hydrochloride which has precipitated is filtered off.
~- Part of the resulting polyamide solution is cast to give a film and the film is dried in a vacuum oven for 1 hour at 60C, for 1 hour at 100C and for 16 hours at 150C. A transparent film is obtained.
The remainder of the polyamide solution is poured into water.
Thereupon, the polyamide precipitates in the form of a powder and this is dried in vacuo at 150C. The polyamide is soluble in D~ and is pressed in a platen press at 260C to give small, transparent, flexible sheets.
.,,:
- Example 9: 2.210 g (0.006 mol) of 2,2'-di-(p-aminophenoxy)-bi-phenyl and 2.804 g (0.014 mol) of 4,4'-diaminodiphenyl ether are dis-solved in 100 ml of anhydrous D~ in a sulphonation flask, under a nitrogen atmosphere, and the solution is cooled to 15C. 6.445 g (0.02 mol) of 3~3',4,4'-benzophenone-tetracarboxylic acid dianhydride in the solid form are then added in portions and the reaction mixture is stirred for 1 hour at 15C and then for 2 hours at 20-25C.
~' Part of the resulting highly viscous polyamide-acid solution is spread on a glass plate to give a film and the film is dried in a '~. ' '' _ ~3 -vacuum drying cabinet for 1 hour at 60C, for 1 hour at lOO'C and for 16 hours at 200C. A transparent flexible film with good mechanical properties is obtained.
A mixture of 90 ml of acetic anhydride and 60 ml of pyridine is added dropwise to the remainder of the above polyamide-acid solution and the reaction mixture is stirred for 16 hours at 20 25C. The reac-tion mixture is then poured into water. The copolyimide which has pre-cipitated is washed with water and dried for 20 hours at 120C and for 20 hours at 200C in a vacuum drying cabinet. The polymer has an in-trinsic viscosity of 0.48 dl/g ~0.5% by weight in concentrated H2S04 at 25C). Pressing in a platen press at 320C gives transparent flexible sheets with good mechanical properties.
At 320C, it was no~ possible to press a known polyimide, which was prepared by the process described above from 4,4'-diaminodiphenyl ether and 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride (molar ratio 1:1), to flexible sheets.
Example 10: In accordance with the procedure described in Example 9, 2.947 g (0.008 mol) of 2,2'-di-(p-aminophenoxy)-biphenyl in 110 ml of anhydrous DMA are reacted with 2.37 g (0.012 mol) of 4,4'-diaminodi-phenylmethane and 6.445 g (0.02 mol) of 3,3',4,4'-benzophenonetetra-carboxylic acid dianhydride and tlle resulting polyamide-acid is pro-cessed to give films and a polyimide powder. The films are transparent, tough and flexible. The powder has an intrinsic viscosity of 0.4 dl/g (0.5~ by weight in concentrated H2S04 at 25C) and can be pressed at 280C in a platen press to give transparent flexible sheets.
Example 11: In accordance with the procedure described in Example 9, 2.210 g (0.006 mol) of 2,2'-di-(o-aminophenoxy)-biphenyl in 110 ml of anhydrous DMA are reacted with 2.804 g (0.014 mol) of 4,4'-diamino-diphenyl ether and 6.445 g (0.02 mol) of 3,3',4,4'-benzophenonetetra-carboxylic acid dianhydride. The resulting polyamide-acid is processed to give a powder. The copolyimide has an intrinsic viscosity of 0.37 d Vg (0.57~ by weight in concentrated H2S04 at 25C) and can be pressed to transparent sheets at 260C in a platen press.
Example 12: In accordance with the procedure described in Example ~, 1.84 g (O.OQ5 mol) of 2,2'-di-(p-aminophenoxy)-biphenyl are reacted with 4.00 g (0.02 mol) of 4,4'-diaminodiphenyl ether and 5.45 g (0.025 mol) of pyromellitic acid dianhydride in 160 ml of anhydrous DMA and the copolyamide-acid is processed to give transparent flexible films.
Example 13: 3.68 g (0.01 mol) of 2,2'-di-(p-aminophenoxy)-biphenyl and 7.93 g (0.04 mol) of 4,4'-diaminodiphenylmethane are dissolved in 110 ml of anhydrous DMA in a sulphonation flask, under a nitrogen atmosphere, and the solution is cooled to -20C. 10.53 g (0.05 mol) of trimellitic acid anhydridechloride in the solid form are then added, whilst stirring, and the reaction solution is stirred for 15 minutes at -20C and then for 2 hours at 20-25C. Subsequently, the reaction solution is cooled again and a solution of 10.22 g (0.10 mol) of tri-ethylamine in 20 ml of DMA is then added dropwise at -15C. After stirring for 2 hours at 20-25C, the triethylamine hydrochloride which has precipitated is fi]tered off. 60 ml of acetic anhydride are added dropwise to the filtrate. The reaction mixture is stirred for a further 16 hours at 20-25C and is then poured into water. The copolyamide-imide which has precipitated is washed with water and ethanol and dried for 24 hours at 200C/0.1 mm Hg. This gives 18.24 g of the co-polyamide-imide in the form of a yellow powder which is soluble in dimethylacetamide.
For processing by the compression moulding process, the powder is introduced into a compression mould for standard bars, which has been preheated to 300C, and compression moulded at this temperature for 5 minutes under a pressure of 500 kp~cm . Transparent strong mouldings with good mechanical properties are obtained.
Example 14: 7.37 g ~0.02 mol) of 2,2'-di--(p-aminophenoxy)-biphenyland 19.46 g (0.18 mol) of m-phenylenediamine are dissolved in 350 ml of anhydrous D~ in a sulphonation flask, under a nitrogen atmosphere, and the solution is cooled to -20C. 40.6 g (0.2 mol) of isophthalic acid dichloride in the solid form are then added, whilst stirring. The reaction mixture is stirred for a further lS minutes at -20C and then for a further 2 hours at 20-25C and cooled again and a solution of 40.47 g (0.4 mol) of triethylamine in S5 ml of DMA is added dropwise at -15C. The reaction mixture is again stirred for 2 hours at 20-25C.
The resulting highly viscous reaction mixture is then diluted with 300 ml of DMA. The triethylamine hydrochloride which has precipitated is filtered off. The reaction solution is poured into water. The co-polyamide which has precipitated is washed with water and ethanol and dried for 4 hours at 150C/20 mm Hg and for 24 hours at 200C/0.1 mm Hg.
This gives 48 g of copolyamide, which is soluble in dimethylacetamide.
The intrinsic viscosity is 1.24 d Vg (0.5% by weight in DMA at 25C) and the glass transition temperature is 266C.
A 20% strength solution of this polyamide in N,N-dimethylaceta-mide is cast to give films and the films are dried as follows: 3 hours at 80C/20 mm Hg, 1 hour at 150C/0.1 mm Hg and 16 hours at 250C/
0.1 mm Hg. Tough, transparent flexible films are obtained.
For processing by the compression moulding process, the copoly-amide is introduced into a compression mould which has been preheated to 320C and compression moulded at this temperature for 3 minutes under the contact pressure and for 5 minutes under a pressure of 500 kp/cm . Transparent, firm bars or sheets which have excellent mechanical and electrical properties (flexural strength 231 ~Vmm , modulus of elasticity 4,000 N/mm ) are obtained. In comparison with `6~i this, a homopolyamide obtained from m-phenylenediamine and isophthalic acid dichloride from the melt cannot be compression moulded to give shaped articles. Moreover, it is soluble in dimethylacetamide only when lithium chloride is added.
Example 15: In accordance with the procedure described in Example -14, 14.74 g (0.04 mol) of 2,2'-di-(p-aminophenoxy)-biphenyl in 440 ml oE anhydrous DMA are reacted, in the presence of 40.47 g (0.4 mol) of triethylamine with 17.30 g (0.16 mol) of m-phenylenediamine and 40.6 g (0.2 mol) of isophthalic acid dichloride and the polymer is precipitated.
This gives 54 g of copolyamide, which is soluble in DMA. The intrinsic viscosity is 1.11 dl/g (0.5% by weight in D~ at 25C) and the glass transition temperature is 260C (determined by DSC = Differential Scanning Calorimetry).
A 20~ strength solution of this copolyamide in N,N-dimethylacet-amide is processed to f ilms in accordance with E~ample 14. Transparent flexible films with very good mechanical and electrical properties are obtained.
Part of the copolyamide is also processed according to Example 14 by the compression moulding process to transparent shaped articles which have good stability to heat and good mechanical properties.
Example 16: In accordance with Example 147 22.11 g (0.06 mol) of 2,2'-di-(p-aminophenoxy)-biphenyl, 15.14 g (0.14 mol) of m-phenylene-diamine, 40.6 g (0~2 mol) of isophthalic acid dichloride and 40.47 g (0.4 mol) oE triethylamine are reacted in 470 ml of anhydrous D~L~.
The resulting copolyamide is processed to give a powder. The copoly-amide is soluble in DMA; intrinsic viscosity 1.03 dl/g (0.5% by weight in DMA at 25C).
6~
A 20% strength solution of this copolyamide in N,N-dimethyl-acetamide is processed according ~o Example 14 to give transparellt flexibl~ films. The films have good stability to thermo-oxidation and good mechanical properties.
Example 17: In accordance with Example 14, 3.68 g (0.01 mol) of 2,2'-di-(p-aminophenoxy)-biphenyl, 20.55 g (0.19 mol) of m-phenylene-diamine, 40.6 g (0.20 mol) of isophthalic acid dichloride and 40.76 g (0.4 mol) of triethylamine are reacted in 300 ml of anhydrous DMA.
The resulting copolyamide (47 g) is processed to a powder; intrinsic viscosity 1.01 d Vg (0.5% by weight in DMA at 25C).
A 20% strength solution of the copolyamide in D~ is processed to give transparent flexible films which have good mechanical proper-ties and good stability to thermo-oxidation.
Compression moulding of the copolyamide by the compression moulding process at 320C, as described in Example 14, gives strong mouldings which have good mechanical and electrical properties.
Example 1~: In accordance with Example 14, 1.47 g (0.004 mol) of 2,2'-di-(o-aminophenoxy)-biphenyl, 3.89 g (0.036 mol) of m-phenylene-diamine, 8.12 g (0.04 mol) of isophthalic acid dichloride and 8.09 g (0.08 mol) of triethylamine are reacted in 80 ml of anhydrous DMA.
The resulting copolyamide is processed to a powder. This gives 9.6 g oE copolyamide, which is soluble in DMA. The intrinsic viscosity is 0.4 dL/g (0.5% by weight in DMA at 25C).
The copolyamide is compression moulded by the compression mould-ing process at 320C, in accordance with the procedure described in Example 14, to give strong mouldings which have good electrical proper-ties.
..~
Example 19: In accordance with the proceclure described in Example 8, . .
3.68 g ~0.01 mol) of 2,2'-di-(p-aminophenoxy)-biphenyl, 1.16 g (0.01 mol) of hexamethylenediamine, 4.06 g (0 02 mol) of terephthalic acid di-chloride and 4.04 g (0.04 mol) of triethylamine are reacted in 40 ml of anhydrous DMA. The reaction solution is then poured into water.
The product which has precipitated is washed and dried and then pressed in a platen press at 280C to give transparent sheets.
Example 20: In accordance with the procedure described in Example 8, 5.89 g (0.016 mol) of 2~2'-di-(p-aminophenoxy~-biphenyl, 0.80 g (0.004 mol) of 4,4'-diaminodiphenyl ether, 4 78 g (0.02 mol) of sebacic acid dichloride and 4.05 g (0.04 mol) of triethylamine are reacted in 50 ml of anhydrous DMA. Part of the resulting polyamide solution is cast to give a film and the film is dried in a drying cabinet for 16 hours at 70C/20 mm Hg, for 1 hour at 100C/0.1 mm Hg, for 1 hour at 150C/0.1 mm Hg and for 1 hour at 200C/0.1 mm Hg and also for 2 hours at 250C/0.1 mm Hg. Very Elexible films are obtained.
The remainder of the polyamide solution is poured into water.
The polyamide which has precipitated is then dried in vacuo at 80C
and pressed in a platen press at 200C to give transparent, very flexible small sheets.
:
.
oxalane-5-carboxylic acid chloride), trimellitic acid anhydride and 6~36 trimelli-tic acid as well as esters according to the definition; pyro-mellitic acid dianhydride, 3,3',4,4'-benzophenone-tetracarboxylic acid dianhydride, 2,3,3',4'-benzophenone-tetracarboxylic acid dianhydride, 2,2',3,3'-benzophenone-tetracarboxylic acid dianhydride, 393',4,4l-di-phenyl-tetracarboxylic acid dianhydride, bis-(2,3-dicarboxyphenyl)-methane dianhydride, bis-(2,5,6-trifluoro-3,4-dicarboxyphenyl)-methane dianhydride, 2,2-bis-(2,3-dicarboxyphenyl)~propane dianhydride, bis-(3,4-dicarboxyphenyl) ether dianhydride, bis-(3,4-dicarboxyphenyl)-sulphone dianhydride, N,N-(3,4-dicarboxyphenyl)-N-methylamine dian-hydride, bis-(3,4-dicarboxyphenyl)-diethylsilane dianhydride, 2,3,6,7-and 1,2,5,6-naphthalene-tetracarboxylic acid dianhydride, 2,6-dichloro-naphthalene-l~4~5~8-tetracarboxylic acid dianhydride, thiophene-2,3,4,5-tetracarboxylic acid dianhydride, pyrazine-2,3,5,6-tetracarboxylic acid dianhydride and pyridine-2,3,5,6-tetracarboxylic acid dianhydride.
Preferred compounds of the formula IV are alkylene-diamines with 2-12, and especially 4-10, carbon atoms and especially 1,3- or 1,4-phenylenediamine, 4,4'-diaminodiphenyl ether and 4,47-diaminodi-phenylmethane.
Acid dichlorides, acid chloride-anhydrides or dianhydrides, and especially those in which R denotes a benzene ring or the benzophenone ring system, are advantageously used as the compounds of the formula V.
The polycondensation reaction of the compounds of the formula III with one or more compounds of the formula V and, optionally, one or more compounds of the formula IV is carried out in a manner which is in itself known, appropriately at temperatures of about -50C to ~300C. The reaction can be carried out in the melt or, preferably, in an inert organic solvent or a solvent mixture. Temperatures of -20C to +50C are preferred for the polycondensation reaction in solu-tion.
' ' :
Examples of suitable organic solvents are: chlorinated aromatic hydrocarbons, such as chlorobenzene and dichlorobenzenes, chlorinated aliphatic hydrocarbons, such as methylene chloride, chloroform, tetra-chloroethane and tetrachloroethylene, aliphatic and cycloaliphatic ketones, such as acetone, methyl ethyl ketone, cyclopentanone and cyclo-hexanone, cyclic ethers, such as tetrahydrofurane, tetrahydropyrane and dioxane, cyclic amides, such as N methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone and N-methyl-~ -caprolactam, N,N-dialkylamides of aliphatic ~onocarboxylic acids with 1-3 carbon atoms in the acid part, such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide and N,N-dimethylmethoxy-acetamide, hexamethylphosphoric acid triamide (hexametapol), N,N,N',N'-tetramethylurea, tetrahydrothiophene dioxide (sulpholane) and dialkylsulphoxides, such as dimethylsulphoxide and diethylsulphoxide.
Preferred solvents are N,N-dialkylamides of aliphatic mono-carboxylic acids with 1-3 carbon atoms in the acid part9 especially N,N-dimethylacetamide, as well as cyclic amides, such as N-methyl-2-pyrrolidone.
The hydrochloric acid obtained during the condensation reaction with compounds of the formula V in which Y represents chlorine can be removed by neutralisation with basic substances, such as calcium hydroxide or triethylamine, or by reaction with an epoxide compound, such as ethylene oxide or propylene oxide, and by washing out with suitable solvents.
The condensation reactions are appropriately carried out with the exclusion of moisture, for example in an inert gas atmosphere, such as nitrogen.
As already mentioned initially, the reaction of the di-, tri-or tetra-carboxylic acid derivatives of the formula V with the diamines -~ l2 -of the formula I~ and~or III can also be carried out stepwise in order to manufacture poly~ers which, at least in part, have a block-type distribution of the structural elements of the formula I or II. It is also possible to link polyamides, polyamide-amide-acids or polyamide-acids which have structural elements of the formula I or VI and have been manufactured separately, with one another and so-called block copolymers are formed by this means. In all of these cases, the reac-tion is carried out in a manner which is in itself l~nown using a slight excess of one or the other reactant in order to obtain prepoly-mers which have end groups suitable for the further reaction, for example amino end groups, acid chloride groups and/or anhydride groups.
.
The optional cyclisation of the polyamide-acids or polyamide-amide-acids (m and/or n = 2) obtained after the condensation reaction is carried out in a manner which is in itself known by chemical means or by means of heat.
The chemical cyclisation is appropriately carried out by treat-ment with a dehydrating agent on its own or as a mixture with a ter-tiary amine. Reagents which can be used are, for example, acetic an-hydride, propionic anhydride and dicyclohexylcarbodiimide or mixtures of acetic anhydride and triethylamine.
The cyclisation by means of heat is carried out by heating to temperatures of about 50C to 300C and preferably of about 150C to 250C and optionally with the addition of an inert organic solvent.
The polyamides, polyamide-amide-acids and polyamide-acids according to the invention, as well as the correspondillg cyclised derivativesJ are suitable for the manufacture of shaped articles of .
very diverse types, such as fibres~ films, sheets, coating composi-tions, foams, laminating resins, composite materials, moulding powders, pres3ed areicles and ehe like, in a mamler which is in ieself hnown, . ~
' .
if desired with the use of customary additives, such as pigments, fil-lers and the iike. The polymers according to t:he invention can also be processed easily from the melt and are distinguished by good mechani-cal, electrical and thermal properties as well as, in general, by good solubility in organic solvents, such as N,N-dimethylacetamide, N,N-di-methylformamide and N-methyl-2-pyrrolidone.
The new diamines of formula III can be manufactured, for example, by either reacting a compound of formula VIa O\M
. (VIa) =~ .=-O M
in a molar ratio of at least 1:2 with a compound of formula VIIa l \ _./ (VIIa) or reacting a compound of formula VIb ~ D_~ (VIb) = O ~ = -in a molar ratio of at least 1:2 with a compound of formula VIIb M+O- ~ ~ 2 (VIIb) in which M denotes a hydrogen, alkaline earth metal or alkali metal cation, a trialkyl-ammonium cation with 3-24, and especially 3-12, carbon atoms, or a quaternary ammonium cation, Zl denotes a halogen atom or, if the nitro group is in the ortho-position relative to Zl' also denotes a nitro group and Z2 denotes a halogen atom, to give a compound of formula VIII
6~3~
1~ -~ ~ 2 o\ ~ \ /
D ~
0~ . (VIII) /
O
N02 =.
in which the two nitro groups independently of one another are in the o-, ~- or p-position of the benzene ring, and subsequently converting the compound of formula VIII into a compound of formula III. Mixtures of two different compounds of the formula VIIa or VIIb can also be used in the above process.
Possible halogen atoms Zl and Z2 are bromine atoms, but especial-ly chlorine atoms and fluorine atoms.
':
If M represents an alkaline earth metal cation or an alkali metal cation, this cation is, for example, the Ba7 Mg, Ca, Li, ~a or K cation. Examples of suitable trialkylammonium cations ~ are the trimethyl-ammonium, triethyl-ammonium, methyldiethyl-ammonium and tri-n-octyl ammonium cation, whilst possible quaternary ammonium cations are, for example, the benzyltrimethyl-ammonium cation and the tetramethyl-ammonium cation. M preferably represents the hydrogen, Na or K cation.
The reaction of the compounds of formula VIa and VIb with the compounds o Eormula VIIa und VIIb can be carried out in an aqueous-organic or organic medium or, alternatively, in the melt.
If M in formula VIa or VIIb represents hydrogen, the reaction is advantageously carried out in an aqueous-organic or organic medium ; and optionally in the presence of an acid-binding agent. Examples of acid-binding agents which can be used are inorganic and organic bases, such as alkaline earth metal hydroxides and carbonates and alkali metal hydroxides and carbonates, especially the hydroxides or carbonates of `'-' :.
.' , . .
'' ' :.
~a or K, and tertiary amines, such as triethylamine, pyridine or pyri-dine bases.
.
The inert organic solvents used are, appropriately, polar aprotic solvents, for example dialkylsulphoxides, such as dime~hylsulphoxide and diethylsulphoxide, tetra~ethylenesulphone or dimethylsulphone.
Compounds oE formula IVa and VIIb in which M represents an alkaline earth metal cation, an alkali metal cation, a trialkyl-ammonium cation or a quaternary ammonium cation are preferred for the reaction in the melt.
The reaction temperatures are generally between about 50C and 150C for the reaction in an organic or aqueous-organic medium and between about 100C and 200C, preferably between about 130C and 160C, for the reaction in the melt.
Compounds of formulae VIb and VIIb, but especially compounds of formulae VIa and VIIa in which M represents the hydrogen cation or an alkali metal cation, especially the sodium cation or potassium cation, and Zl and Z2 represent chlorine or fluorine are preferably used.
' The compounds of formulae VIa, VIb, VIIa and VIIb are prefer-ably employed in stoichiometric amounts. However, the reaction can ; also be carried out with a slight excess of one or the other reactant.
, .
The reduction (hydrogenation) of the compounds of formula VIII
can be carried out in a manner which is in itself known, for example with iron in an acid medium by the Béchamp method, optionally in the presence of neutral salts, such as iron-II sulphate, CaC12 or sodium hydrogen sulphate; with tin or tin-II chloride in the presence of HCl;
with zinc in an acid or neutral medium9 optionally with the addition .~
- of neutral salts, such as CaCl2 and NH4Cl; with lithium aluminium hydride; with hydraæines, such as hydraæine hydrate and phenylhydra zine, if necessary with the addition of Raney nickel catalysts, and with sodium dithionite (Na2S204).
Catalytic reduction is preferred. Examples of suitable catalysts are palladium, palladium-on-charcoal, platinum, platinum black, plati-num oxide and, above all, Raney nickel. The catalytic reduction is appropriately carried out in a suitable inert organic solvent, such as dioxane or methylcellosolve.
The compounds of formulae VIa, VIb9 VIIa and VIIb are known or can be manufactured easily in a manner which is in itself known.
The compounds of formula VIII are also new. Both these compounds and the diamines of the formula III can, after the reaction, be isola-ted, and purified, in a customary manner, for e~ample by washing with water or diethyl ether or by filtering and recrystallising from suit-able solvents, such as methanol or ethanol. The compounds of the for-mulae III and VIII are obtained in the form of white to slightly yellowish crystals.
. :
, . , .- ' ' 6~3~
Example I
HO\ ~2 \ ~ NO
. + 2 i 1 I DMSO
=- H2 OH Cl NO -- ~ O Raney-Ni =.
~ -NH2 . _ . . _ . , = .
. _ . . = . . _ .
.=.
37.2 g (0.2 mol) of 2,2'-dihydroxy-biphenyl and 63 g (0.4 mol) of p-nitrochlorobenzene are dissolved in 160 ml of dimethylsulphoxide (DMSO) in a sulphonation 1ask and the solution is warmed to 80C.
A solution of 26.4 g (0.4 mol) oE 85% strength potassium hydroxide in 20 ml of water is then added dropwise, whilst stirring, and the reac-tion solution is subsequently further stirred for 3 hours at 100-110C.
After coollng, the reaction solution is poured into ice water and the resulting precipitate is washed several times with water. The resulting crude product is then dried for 20 hours under a high vacuum at 70C
and unconverted nitrochlorobenzene sublimes away during drying. The residue is recrystallised twice from ethanol. 12.4 g (15% of theory) of 2,2'-di-(p-nitrophenoxy)-biphenyl are obtained in the form of slightly yellowish crystals; melting point 158C.
Analysis for C24H1606N2 (molecular weight 428.41):
calculated C 67.3% H 3.72% N 6.55%
found C 67.1% H 3.8 % N 6.4 %.
82.5 g of the above 2,2'-di-(p-nitrophenoxy)-biphenyl are hydro-genated with 24 g of Raney nickel in 900 ml of dioxane at 40-50C.
`:
:' .
'.', ' ' ' '' After filtering off the catalyst and evaporating the solvent, 70 g (99% of theory~ of crude 2,2'-di-(p-aminophenoxy)-biphenyl are obtained and this is recrystallised twice from ethanol. After recrystallisation, 51.6 g (73% of theory) of pure 2,2'-di-(p-aminophenoxy)-biphenyl are obtained in the form of slightly yellowish crystals, melting point 15~C.
Analysis for C24H2002N2 (molecular weight 368.44):
calculated C 78.24% H 5.~7% N 7.61%
found C 7~.1 % ~ 5.6 % N 7.~ %
Example 2: 74.4 g (0.4 mol) of 2,2'-dihydroxy-biphenyl are sus-pended in 400 ml of distilled water in a round-bottomed flask and 53.5 g (0.8 mol) of 84% pure solid potassium hydroxide are then added in portions at 20-25C, whilst stirring. The reaction mixture is stirred further until all of the 2,2l-dihydroxy biphenyl has dissolved. The reaction solution is then evaporated to dryness in a rotary evaporator.
315 g (2 mols) of p-nitrochlorobenzene are added to the residue (the dipotassium salt of 2,2'-dihydroxy-biphenyl), the round-bottomed flask is provided with a riser and the reaction mixture is heated to 150C
for 2 hours, whilst stirring. After cooling to about 100C, the result-ing melt is poured into 2 litres of chloroform. The resulting solution is extracted twice with water, dried over potassium carbonate and eva-~- porated in a rotary evaporator. In order to remove excess p-nitrochloro-benzene, the residue is suspended in 2 litres of diethyl ether and the suspension is warmed under reflux for a short time. The reaction mix-ture is then filtered and the material on the filter is rinsed with diethyl ether and, after decolourising with active charcoal, the pro-duct is recrystallised from ethanol. This gives 38.9 g (23% of theory) of the 2,2'-di-(p-nitrophenoxy)-biphenyl (of analytical purity) characterised in Example 1.
`:
The hydrogenation to 2,2'-di-(p-aminophenoxy)-biphenyl is carried out as described in Example 1.
- , :
Example 3: Analogously to the procedure described in Example 2, 37.2 g (0.2 mol~ of 2,2'-dihydroxy-biphenyl are converted into the corresponding dipotassi~m salt using 26.8 g (0.4 mol) of 84% pure solid potassium hydroxide in 200 ml of water. This salt is reacted in the melt with 157 g ~1 mol) of o-chloronitroben~ene, in the manner described in Example 2. The crude product which is obtained after removal of th~
chloroform is dissolved hot in methanol, the solution is decolourised with active charcoal and the product is crystallised. The product is then recrystallised once more from ethanol and 20.3 g (24% of theory) of 2,2'-di-(o-nitrophenoxy)-biphenyl are obtained in the form of pale yellowish crystals; melting point 154C.
Analysis for C24H1606N2 (molecular weight 428.41):
calculated C 67.3% H 3.72% N 6.55%
found C 67.3% H 3.8 % N 6.5 %
27 g of 2,2'-di-(o~nitrophenoxy)-biphenyl are hydrogenated with 3 g of Raney nickel in 270 ml of dioxane at 35-40C. After filtering oEf the catalyst and evaporating the solvent, 23 g (99% of theory) of crude diamine results and this is recrystallised twice from ethanol.
This gives 16.2 g (70% of theory) of 2,2'-di-(o-aminophenoxy)-biphenyl in the form of colourless crystals; melting point 175C.
Analysis for ~24H20o2N2 (molecular weight 368.44):
calculated C 78.25% H 5.47% N 7.61%
found C 78.28% H 5.53% N 7.66%
.
Example 4: 18.62 g (0.1 mol) of 2,2'-dihydroxy-biphenyl and 28.22 g (0.2 mol) of p-nitrofluorobenzene are dissolved in 80 ml of dimethyl-sulphoxide in a sulphonation flask and the solution is warmed to 80C.
A solution of 13.2 g (0.2 mol) of 85% pure potassium hydroxide in lO ml of water is then added dropwise, whilst stirring, and the reac-tion solution is subsequently further stirred for 3 hours at 100-110Co During this time a yellow precipitate forms and after the reaction mixture has cooled this is separated off by decanting off the super-natant liquor and is then washed several times with water. ~fter drying, the crude product is recrystallised from ethanol. 32.86 g (77% oE
theory) of 2,2'-di-(p-nitrophenoxy)-biphenyl of analytlcal purity are obtained in the form of slightly yellowish crystals with a melting point of 158C.
Hydrogenation of the above product by the method described in Example 1 and recrystallisation of the resulting crude product from ethanol gives 2,2'-di-(p-aminophenoxy) biphenyl which is of analytical purity and has a melting point of 157-158C.
;'' Example 5: 18.62 g (0.1 mol) of 2,2~-dihydroxydiphenyl, 23.22 g (0.2 mol) of o-nitrofluoroben~ene, 13.2 g (0.2 mol) of 85% pure solid potassium hydroxide and 10 ml of water are reacted in 80 ml of di-methylsulphoxide according to the procedure described in Example 4.
After washing and recrystallising the resulting precipitata, 28.82 g (67% of theory~ of 2,2'-di-(o-nitrophenoxy)-biphenyl of analytical purity are obtained in the form of slightly yellowish crystals with a melting point of 153-154C.
~ ydrogenation of the above product by the procedure described in Example 3 and recrystallisation of the crude product from ethanol gives 2,2'-di(o-aminophenoxy)-biphenyl which is of analytical purity and has a melting point of 174-175C.
..
Example 6: 5.526 g (0.015 mol) of the 2,2'-di-(p-aminophenoxy)-., biphenyl prepared according to Example 1 are dissolved in 90 ml of ;` anhydrous N,N-dimethylacetamide (DMA) in a sulphonation flask, under a nitrogen atmosphere, and the solution is cooled to 0-5C. 4.83 g (0.015 mol) of 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride in solid form are added in portions to this solution, whilst stirring.
~ The resulting viscous solution is then stirred for a further 30 minu-; tes at 0-5C and subsequently for a further 2 hours at 20-25C. The .:
:
~' ' :
P61~1~
intrinsic viscosity of the polyamide-acid thus formed is 0.75 dl/g (0.5% by weight in DMA at 25C).
Part of this polyamide-acid solution is spread to give a film.
The film is dried in vacuo as follows: l hour at 60~, 1 hour at 100C, 1 hour at 150C and 16 hours at 200C~ A transparellt, flexible film is obtained.
A mixture of 45 ml of acetic anhydride and 30 ml of pyridine is added dropwise to the remainder of the above polyamide-acid solution.
Subsequently, the reaction mixture is stirred for 16 hours at 20-25C
and then poured into water. The precipitate thus formed is washed several times with water and dried in a vacuum drying cabinet for 20 hours at 150C/20 mm Hg and for 20 hours at 200C/0.1 mm Hg. 7.8 g of polyimide in the form of a yellow powder are obtained.
For processing by the compression moulding process, the above polyimide is introduced into a compression mould for circular sheets, which has been prewarmed to 320C, and compression moulded at this temperature for 3 minutes under the contact pressure and for 5 minutes under a pressure of 225 kp/cm2. Strong, transparent mouldings which have good mechanical and electrical properties even at elevated tem-peratures are obtained.
Example 7: Analogously to the procedure described in Example 6, 1.842 g (0.005 mol) of the 2~2'-di-(o-aminophenoxy)-biphenyl prepared according to Example 3, in 37 ml of anhydrous DM~, are reacted with 1.611 g (0.005 mol) of 3,3',4,4'-benzophenone-tetracarboxylic acid di-anhydride. The resulting polyamide-acid has an intrinsic viscosity of 0.20 dl/g (0.5% by weight in DMA at 25C).
. .
.
6~1~
Example 8: 3.68 g (0.01 mol) of 2,2'-di-(p-aminopheno~y)-biphenyl are dissolved in 50 ml of anhydrous D~ in a sulphonation flask, under a nitrogen atmosphere, and the solution is cooled to -15C. 2.03 g (0.01 mol) of isophthalic acid dichloride in the solid form are then added in portions, whilst stirring, in such a way that the temperature of the reaction mixture does not rise above -5C. The reaction mixture is then rinsed with 10 ml of D~ and stirred for a further 1 hour at -5C and then for a further 1 hour at 20-25C. Finally, the reaction mixture is cooled and a solution of 2.02 g (0.02 mol) of triethylamine in 10 ml of DMA is added dropwise at -5C. ~fter stirring for 1 hour at 20-25C, the triethylamine hydrochloride which has precipitated is filtered off.
~- Part of the resulting polyamide solution is cast to give a film and the film is dried in a vacuum oven for 1 hour at 60C, for 1 hour at 100C and for 16 hours at 150C. A transparent film is obtained.
The remainder of the polyamide solution is poured into water.
Thereupon, the polyamide precipitates in the form of a powder and this is dried in vacuo at 150C. The polyamide is soluble in D~ and is pressed in a platen press at 260C to give small, transparent, flexible sheets.
.,,:
- Example 9: 2.210 g (0.006 mol) of 2,2'-di-(p-aminophenoxy)-bi-phenyl and 2.804 g (0.014 mol) of 4,4'-diaminodiphenyl ether are dis-solved in 100 ml of anhydrous D~ in a sulphonation flask, under a nitrogen atmosphere, and the solution is cooled to 15C. 6.445 g (0.02 mol) of 3~3',4,4'-benzophenone-tetracarboxylic acid dianhydride in the solid form are then added in portions and the reaction mixture is stirred for 1 hour at 15C and then for 2 hours at 20-25C.
~' Part of the resulting highly viscous polyamide-acid solution is spread on a glass plate to give a film and the film is dried in a '~. ' '' _ ~3 -vacuum drying cabinet for 1 hour at 60C, for 1 hour at lOO'C and for 16 hours at 200C. A transparent flexible film with good mechanical properties is obtained.
A mixture of 90 ml of acetic anhydride and 60 ml of pyridine is added dropwise to the remainder of the above polyamide-acid solution and the reaction mixture is stirred for 16 hours at 20 25C. The reac-tion mixture is then poured into water. The copolyimide which has pre-cipitated is washed with water and dried for 20 hours at 120C and for 20 hours at 200C in a vacuum drying cabinet. The polymer has an in-trinsic viscosity of 0.48 dl/g ~0.5% by weight in concentrated H2S04 at 25C). Pressing in a platen press at 320C gives transparent flexible sheets with good mechanical properties.
At 320C, it was no~ possible to press a known polyimide, which was prepared by the process described above from 4,4'-diaminodiphenyl ether and 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride (molar ratio 1:1), to flexible sheets.
Example 10: In accordance with the procedure described in Example 9, 2.947 g (0.008 mol) of 2,2'-di-(p-aminophenoxy)-biphenyl in 110 ml of anhydrous DMA are reacted with 2.37 g (0.012 mol) of 4,4'-diaminodi-phenylmethane and 6.445 g (0.02 mol) of 3,3',4,4'-benzophenonetetra-carboxylic acid dianhydride and tlle resulting polyamide-acid is pro-cessed to give films and a polyimide powder. The films are transparent, tough and flexible. The powder has an intrinsic viscosity of 0.4 dl/g (0.5~ by weight in concentrated H2S04 at 25C) and can be pressed at 280C in a platen press to give transparent flexible sheets.
Example 11: In accordance with the procedure described in Example 9, 2.210 g (0.006 mol) of 2,2'-di-(o-aminophenoxy)-biphenyl in 110 ml of anhydrous DMA are reacted with 2.804 g (0.014 mol) of 4,4'-diamino-diphenyl ether and 6.445 g (0.02 mol) of 3,3',4,4'-benzophenonetetra-carboxylic acid dianhydride. The resulting polyamide-acid is processed to give a powder. The copolyimide has an intrinsic viscosity of 0.37 d Vg (0.57~ by weight in concentrated H2S04 at 25C) and can be pressed to transparent sheets at 260C in a platen press.
Example 12: In accordance with the procedure described in Example ~, 1.84 g (O.OQ5 mol) of 2,2'-di-(p-aminophenoxy)-biphenyl are reacted with 4.00 g (0.02 mol) of 4,4'-diaminodiphenyl ether and 5.45 g (0.025 mol) of pyromellitic acid dianhydride in 160 ml of anhydrous DMA and the copolyamide-acid is processed to give transparent flexible films.
Example 13: 3.68 g (0.01 mol) of 2,2'-di-(p-aminophenoxy)-biphenyl and 7.93 g (0.04 mol) of 4,4'-diaminodiphenylmethane are dissolved in 110 ml of anhydrous DMA in a sulphonation flask, under a nitrogen atmosphere, and the solution is cooled to -20C. 10.53 g (0.05 mol) of trimellitic acid anhydridechloride in the solid form are then added, whilst stirring, and the reaction solution is stirred for 15 minutes at -20C and then for 2 hours at 20-25C. Subsequently, the reaction solution is cooled again and a solution of 10.22 g (0.10 mol) of tri-ethylamine in 20 ml of DMA is then added dropwise at -15C. After stirring for 2 hours at 20-25C, the triethylamine hydrochloride which has precipitated is fi]tered off. 60 ml of acetic anhydride are added dropwise to the filtrate. The reaction mixture is stirred for a further 16 hours at 20-25C and is then poured into water. The copolyamide-imide which has precipitated is washed with water and ethanol and dried for 24 hours at 200C/0.1 mm Hg. This gives 18.24 g of the co-polyamide-imide in the form of a yellow powder which is soluble in dimethylacetamide.
For processing by the compression moulding process, the powder is introduced into a compression mould for standard bars, which has been preheated to 300C, and compression moulded at this temperature for 5 minutes under a pressure of 500 kp~cm . Transparent strong mouldings with good mechanical properties are obtained.
Example 14: 7.37 g ~0.02 mol) of 2,2'-di--(p-aminophenoxy)-biphenyland 19.46 g (0.18 mol) of m-phenylenediamine are dissolved in 350 ml of anhydrous D~ in a sulphonation flask, under a nitrogen atmosphere, and the solution is cooled to -20C. 40.6 g (0.2 mol) of isophthalic acid dichloride in the solid form are then added, whilst stirring. The reaction mixture is stirred for a further lS minutes at -20C and then for a further 2 hours at 20-25C and cooled again and a solution of 40.47 g (0.4 mol) of triethylamine in S5 ml of DMA is added dropwise at -15C. The reaction mixture is again stirred for 2 hours at 20-25C.
The resulting highly viscous reaction mixture is then diluted with 300 ml of DMA. The triethylamine hydrochloride which has precipitated is filtered off. The reaction solution is poured into water. The co-polyamide which has precipitated is washed with water and ethanol and dried for 4 hours at 150C/20 mm Hg and for 24 hours at 200C/0.1 mm Hg.
This gives 48 g of copolyamide, which is soluble in dimethylacetamide.
The intrinsic viscosity is 1.24 d Vg (0.5% by weight in DMA at 25C) and the glass transition temperature is 266C.
A 20% strength solution of this polyamide in N,N-dimethylaceta-mide is cast to give films and the films are dried as follows: 3 hours at 80C/20 mm Hg, 1 hour at 150C/0.1 mm Hg and 16 hours at 250C/
0.1 mm Hg. Tough, transparent flexible films are obtained.
For processing by the compression moulding process, the copoly-amide is introduced into a compression mould which has been preheated to 320C and compression moulded at this temperature for 3 minutes under the contact pressure and for 5 minutes under a pressure of 500 kp/cm . Transparent, firm bars or sheets which have excellent mechanical and electrical properties (flexural strength 231 ~Vmm , modulus of elasticity 4,000 N/mm ) are obtained. In comparison with `6~i this, a homopolyamide obtained from m-phenylenediamine and isophthalic acid dichloride from the melt cannot be compression moulded to give shaped articles. Moreover, it is soluble in dimethylacetamide only when lithium chloride is added.
Example 15: In accordance with the procedure described in Example -14, 14.74 g (0.04 mol) of 2,2'-di-(p-aminophenoxy)-biphenyl in 440 ml oE anhydrous DMA are reacted, in the presence of 40.47 g (0.4 mol) of triethylamine with 17.30 g (0.16 mol) of m-phenylenediamine and 40.6 g (0.2 mol) of isophthalic acid dichloride and the polymer is precipitated.
This gives 54 g of copolyamide, which is soluble in DMA. The intrinsic viscosity is 1.11 dl/g (0.5% by weight in D~ at 25C) and the glass transition temperature is 260C (determined by DSC = Differential Scanning Calorimetry).
A 20~ strength solution of this copolyamide in N,N-dimethylacet-amide is processed to f ilms in accordance with E~ample 14. Transparent flexible films with very good mechanical and electrical properties are obtained.
Part of the copolyamide is also processed according to Example 14 by the compression moulding process to transparent shaped articles which have good stability to heat and good mechanical properties.
Example 16: In accordance with Example 147 22.11 g (0.06 mol) of 2,2'-di-(p-aminophenoxy)-biphenyl, 15.14 g (0.14 mol) of m-phenylene-diamine, 40.6 g (0~2 mol) of isophthalic acid dichloride and 40.47 g (0.4 mol) oE triethylamine are reacted in 470 ml of anhydrous D~L~.
The resulting copolyamide is processed to give a powder. The copoly-amide is soluble in DMA; intrinsic viscosity 1.03 dl/g (0.5% by weight in DMA at 25C).
6~
A 20% strength solution of this copolyamide in N,N-dimethyl-acetamide is processed according ~o Example 14 to give transparellt flexibl~ films. The films have good stability to thermo-oxidation and good mechanical properties.
Example 17: In accordance with Example 14, 3.68 g (0.01 mol) of 2,2'-di-(p-aminophenoxy)-biphenyl, 20.55 g (0.19 mol) of m-phenylene-diamine, 40.6 g (0.20 mol) of isophthalic acid dichloride and 40.76 g (0.4 mol) of triethylamine are reacted in 300 ml of anhydrous DMA.
The resulting copolyamide (47 g) is processed to a powder; intrinsic viscosity 1.01 d Vg (0.5% by weight in DMA at 25C).
A 20% strength solution of the copolyamide in D~ is processed to give transparent flexible films which have good mechanical proper-ties and good stability to thermo-oxidation.
Compression moulding of the copolyamide by the compression moulding process at 320C, as described in Example 14, gives strong mouldings which have good mechanical and electrical properties.
Example 1~: In accordance with Example 14, 1.47 g (0.004 mol) of 2,2'-di-(o-aminophenoxy)-biphenyl, 3.89 g (0.036 mol) of m-phenylene-diamine, 8.12 g (0.04 mol) of isophthalic acid dichloride and 8.09 g (0.08 mol) of triethylamine are reacted in 80 ml of anhydrous DMA.
The resulting copolyamide is processed to a powder. This gives 9.6 g oE copolyamide, which is soluble in DMA. The intrinsic viscosity is 0.4 dL/g (0.5% by weight in DMA at 25C).
The copolyamide is compression moulded by the compression mould-ing process at 320C, in accordance with the procedure described in Example 14, to give strong mouldings which have good electrical proper-ties.
..~
Example 19: In accordance with the proceclure described in Example 8, . .
3.68 g ~0.01 mol) of 2,2'-di-(p-aminophenoxy)-biphenyl, 1.16 g (0.01 mol) of hexamethylenediamine, 4.06 g (0 02 mol) of terephthalic acid di-chloride and 4.04 g (0.04 mol) of triethylamine are reacted in 40 ml of anhydrous DMA. The reaction solution is then poured into water.
The product which has precipitated is washed and dried and then pressed in a platen press at 280C to give transparent sheets.
Example 20: In accordance with the procedure described in Example 8, 5.89 g (0.016 mol) of 2~2'-di-(p-aminophenoxy~-biphenyl, 0.80 g (0.004 mol) of 4,4'-diaminodiphenyl ether, 4 78 g (0.02 mol) of sebacic acid dichloride and 4.05 g (0.04 mol) of triethylamine are reacted in 50 ml of anhydrous DMA. Part of the resulting polyamide solution is cast to give a film and the film is dried in a drying cabinet for 16 hours at 70C/20 mm Hg, for 1 hour at 100C/0.1 mm Hg, for 1 hour at 150C/0.1 mm Hg and for 1 hour at 200C/0.1 mm Hg and also for 2 hours at 250C/0.1 mm Hg. Very Elexible films are obtained.
The remainder of the polyamide solution is poured into water.
The polyamide which has precipitated is then dried in vacuo at 80C
and pressed in a platen press at 200C to give transparent, very flexible small sheets.
:
.
Claims (6)
1. A polyamide, a polyamide-amide-acid or a polyamide-acid which consists of 1 to 100 mol% of structural elements of formula I
(I) and of 0 to 99 mol% of structural elements of formula II
(II) in which the NH groups in formula I independently of one another are bonded to the benzene nucleus in the o-, m- or p-position and the individual m, n, R and R1 independently of one another have the follow-ing meanings: m and n denote the number 1 or 2, R denotes an aliphatic radical with at least two carbon atoms or a cycloaliphatic, carbocyclic-aromatic or heterocyclic-aromatic radical, the carbonamide groups and carboxyl groups being bonded to different carbon atoms and, if R
denotes a cyclic radical and at least one of m and n denotes the number 2, the carboxyl groups each being in the ortho-position relative to a carbonamide group, and R1 denotes an aliphatic radical with at least two carbon atoms or a cycloaliphatic, araliphatic, carbocyclic-aromatic or heterocyclic-aromatic radical, and also the corresponding derivative which has been cyclised to the imide.
(I) and of 0 to 99 mol% of structural elements of formula II
(II) in which the NH groups in formula I independently of one another are bonded to the benzene nucleus in the o-, m- or p-position and the individual m, n, R and R1 independently of one another have the follow-ing meanings: m and n denote the number 1 or 2, R denotes an aliphatic radical with at least two carbon atoms or a cycloaliphatic, carbocyclic-aromatic or heterocyclic-aromatic radical, the carbonamide groups and carboxyl groups being bonded to different carbon atoms and, if R
denotes a cyclic radical and at least one of m and n denotes the number 2, the carboxyl groups each being in the ortho-position relative to a carbonamide group, and R1 denotes an aliphatic radical with at least two carbon atoms or a cycloaliphatic, araliphatic, carbocyclic-aromatic or heterocyclic-aromatic radical, and also the corresponding derivative which has been cyclised to the imide.
2. A polyamide, a polyamide-amide-acid or a polyamide-acid according to Claim 1, which consists of 100 mol% of structural elements of formula I, in which R represents a benzene ring or an unsubstituted alkylene group with 4-10 carbon atoms when m and n = 1, a benzene ring when m = 1 and n - 2 and a benzene ring or the benzophenone ring system when m and n = 2, as well as the corresponding derivative which has been cyclised to the imide.
3. A polyamide, a polyamide-amide-acid or a polyamide-acid accord-ing to Claim 1, which consists of 5-80 mol% of structural elements of formula I and 20-95 mol% of structural elements of the formula II, in which R denotes a benzene ring or an unsubstituted alkylene group with 4-10 carbon atoms when m and n = 1, a benzene ring when m = 1 and n = 2 and a benzene ring or the benzophenone ring system when m and n = 2, and R1 denotes an unsubstituted alkylene group with 2-12 carbon atoms, the 1,3- or 1,4-phenylene group, the 4,4'-diphenyl ether radical or the 4,4'-diphenylmethane radical, as well as the corresponding derivative which has been cyclised to the imide.
4. A polyamide-amide-acid or a polyamide-acid according to Claim 1, which consists of 5-50 mol% of structural elements of formula I and 50-95 mol% of structural elements of formula II, in which m denotes 1, n denotes 2 and R denotes a benzene ring, or m and n denote 2 and R
denotes a benzene ring or the benzophenone ring system, and Rl denotes the 1,3-phenylene group, the 4,4'-diphenyl ether radical or the 4,4'-diphenylmethane radical, as well as the corresponding derivative which has been cyclised to the imide.
denotes a benzene ring or the benzophenone ring system, and Rl denotes the 1,3-phenylene group, the 4,4'-diphenyl ether radical or the 4,4'-diphenylmethane radical, as well as the corresponding derivative which has been cyclised to the imide.
5. A polyamide according to Claim 1, which consists of 5-50 mol%
of structural elements of formula I and 50-95 mol% of structural elements of formula II, in which m and n denote 1, R denotes a benzene ring and R1 denotes the 1,3-phenylene group, an unsubstituted alkylene group with 4-10 carbon atoms, the 4,4'-diphenylmethane radical or the 4,4'-diphenyl ether radical.
of structural elements of formula I and 50-95 mol% of structural elements of formula II, in which m and n denote 1, R denotes a benzene ring and R1 denotes the 1,3-phenylene group, an unsubstituted alkylene group with 4-10 carbon atoms, the 4,4'-diphenylmethane radical or the 4,4'-diphenyl ether radical.
6. A process for the manufacture of a polyamide, a polyamide-amide-acid or a polyamide-acid, and of the corresponding derivative which has been cyclised to the imide, according to Claim 1, wherein 1-100 mol% of a diamine of formula III
(III) , in which the NH2 groups independently of one another are in the o-, m- or p-position of the benzene nucleus, and 0-99 mol% of a diamine of formula IV
H2N - R1 - NH2 (IV) are subjected to a condensation reaction with essentially stoichio-metric amounts of a compound of formula V
(V), in which what has been stated under formulae I and II applies in respect of m, n, R and R1 and X1, when m and/or n = 2, together with Y, forms the -O-grouping and Y represents a chlorine atom, a hydroxyl group, an unsubstituted or substituted phenoxy group or an alkoxy group with 1-18 carbon atoms, or, if m and/or n = 2, Y, together with X, forms the -O-grouping, the groups -COY and -COX being bonded to diffe-rent carbon atoms and, if R represents a cyclic radical and m and/or n = 2, the -COY group or groups being in the ortho-position relative to a -COX group, and the resulting polymer, in which m and/or n = 2, is optionally subsequently cyclised to the imide.
FO 7.3/HO/hl*
(III) , in which the NH2 groups independently of one another are in the o-, m- or p-position of the benzene nucleus, and 0-99 mol% of a diamine of formula IV
H2N - R1 - NH2 (IV) are subjected to a condensation reaction with essentially stoichio-metric amounts of a compound of formula V
(V), in which what has been stated under formulae I and II applies in respect of m, n, R and R1 and X1, when m and/or n = 2, together with Y, forms the -O-grouping and Y represents a chlorine atom, a hydroxyl group, an unsubstituted or substituted phenoxy group or an alkoxy group with 1-18 carbon atoms, or, if m and/or n = 2, Y, together with X, forms the -O-grouping, the groups -COY and -COX being bonded to diffe-rent carbon atoms and, if R represents a cyclic radical and m and/or n = 2, the -COY group or groups being in the ortho-position relative to a -COX group, and the resulting polymer, in which m and/or n = 2, is optionally subsequently cyclised to the imide.
FO 7.3/HO/hl*
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA353,204A CA1100686A (en) | 1976-06-15 | 1980-06-02 | Polyamide, polyamide-imide and polyimide polymers and process for their manufacture |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH7593/76 | 1976-06-05 | ||
| CH759376A CH621768A5 (en) | 1976-06-15 | 1976-06-15 | |
| CA280,393A CA1095083A (en) | 1976-06-15 | 1977-06-13 | Aromatic diamines and process for their manufacture |
| CA353,204A CA1100686A (en) | 1976-06-15 | 1980-06-02 | Polyamide, polyamide-imide and polyimide polymers and process for their manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1100686A true CA1100686A (en) | 1981-05-05 |
Family
ID=27165112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA353,204A Expired CA1100686A (en) | 1976-06-15 | 1980-06-02 | Polyamide, polyamide-imide and polyimide polymers and process for their manufacture |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1100686A (en) |
-
1980
- 1980-06-02 CA CA353,204A patent/CA1100686A/en not_active Expired
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