CA2054125A1

CA2054125A1 - Soluble polyarylene ethers

Info

Publication number: CA2054125A1
Application number: CA 2054125
Authority: CA
Inventors: Andreas Kramer; Christian Vonlanthen
Original assignee: Individual
Current assignee: Novartis AG
Priority date: 1990-10-26
Filing date: 1991-10-24
Publication date: 1992-04-27
Also published as: EP0483066A3; JPH04266926A; EP0483066A2

Abstract

Soluble polyarylene ethers Abstract of the Disclosure Amino group containing polyarylene ethers which are soluble in organic solvents and have an inherent viscosity (?inh) Of 0.02 to 1.0, measured in a 1 % by weight solution of the polymer in N-methylpyrrolidone at 25°C, which polyarylene ethers, based on the total amount of structural units present in the polymer, contain 100 to 5 mol % of a structural repeating unit of formula I or II

(I) or (II) and 95 to 0 mol % of a structural repeating unit of formual III

(III) wherein X is -SO2- or -CO-, and Ar is a group of formula IVa to IVe (IVa), wherein a is 0 or 1, (IVb), (IVc), (IVd), wherein b is 1 or 2, or (IVe) wherein Z is -CO-,-SO2-,-SO-,-S-,-O-, -?(CH3)2, -?(CF3)2, -CH2- or

Description

,c,~ ; rJ~

Soluble po~yarvlene ethers The present invention relates to polyarylene ethers which are soluble in organic solvents and contain amino groups in the polymer chain, to their preparation and to the use thereof for modifying duromer materials, especially as hardeners or modifiers for maleimide and epoxy resins.

Amino-terminated polymers, such as amino-terminated polysulfones or polyarylene ethers, are known and disclosed, inter alia, in US patent 3 895 064 and EP-~-0 311 349.
Such amino-terminated polymers are suitable for flexibilising epoxy resins, and the moulding materials made therefrom usually exhibit a more or less substantial drop in the Tg value, as phase separation occurs during the cure, as reported, for example, by R.B. Bauer et al. at 35th International SAMPE Symposium, April 2-5, 1990, pages 395 to 403.

The polyarylene ether prepared from bisphenol A and 1,3-dichloro-4-nitrobenzene in Exarnple 23 of US patent 4 108 837 is used for making films from the melt.

In the publication "Die Angewandte Makromolekulare Chemie" 119 (1983), pages 105-123, it is reported ~hat the polymer prepared from bisphenol A and 1,3-dichloro-4-nitrobenzene (2,4-dichloronitrobenzene) is only incompletely chemically hydrogenated with Raney nickel and hydrazine, and that the reaction product isolated after the reduction is insoluble in organic solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetrahydrofuran, petroleum ether and dimethyl acetamide. In order that no premature crisslinking may occur after termination of the hydrogenation conditions, the amino groups are provided with protective groups.

It has now been found that catalytic hydrogenation of a nitro group containing polycondensate of 1,3-dichloro-4-nitrobenzene and bisphenol A with hydrogen, under pressure and in the presence of Pd/C, gives an amino group containing polymer which is very readily soluble in organic solvents such as methylene chloride, tetrahydrofuran, dimethyl formamide or N-methylpyrrolidone, and which forms very stable solutions in '~

" 20~412~

these solvents.

Specifically, the invention relates to amino group containing polyarylene ethers which are soluble in organic solvents and have an inherent viscosity (lli,~h) of 0.02 to 1.0, measured in a 1 % by weight solution of the polymer in N-methylpylrolidone at 25C, whichpolyarylene ethers, based on the total amount of structural units present in the polymer, contain 100 to 5 mol % of a structural repeating unit of formula I or II

O--Ar--o ~ (I) or ~hlH_ ~ , and 95 to 0 mol % of a structural repeating unit of formual m ~} X ~ - Ar- O ~ (III) wherein X is -SO2- or -CO-, and Ar is a group of formula IVa to IVe (IVa), wherein a is 0 or 1, ~3 (IVb), ~ (IVc), , .

wnereln X is -SO2- or -CO-, and Ar is a group of forrnula IVa to IVe ~IVa), wherein a is O or 1, ~3 (IVb), ~ (IVc), 2 ~

~ Z ~ (IVd), wherein b is 1 or 2, or - 4 ~

~CH 3 ~s02 3 More particularly, the radical Ar in the structural units of formulae I and III is a radical of formula ~ 3 ~ C 3 or ~so2~3.

The polyarylene ethers of this invention may typically be prepared by polycondensing 1,3-dichloro-4-nitrobenzene or a mixture of 1,3-dichloro-4-nitrobenzene and a dihalo compound of formula Hal ~ X ~3 Hal (V), present therein in an amount of up to 95 mol %, preferably 90 mol %, wherein Hal is a halogen atom, preferably a chlorine or fluorine atom, and X is as defined above, with a diphenol of formula VI

~IO-Ar-OH (VI), , wherein Ar is as defined above, or by polycondensing 2,4-bis(4-hydroxyphenoxy~aniline or a mixture of 2,4-bis(4-hydroxyphenoxy)aniline and a diphenol of formula VI present therein in an amount of up to 95 mol %, preferably 90 mol %, with a halogen compound of formula V, in the presence of akali and in an aprotic solvent, until the resultant polyarylene ether has a ~ h Of 0.02 to 1.0, and subsequently converting the nitro group 2 ~

containing polyarylene ether by complete catalytic reduction of the nitro groups into an amino group containing polyarylene ether of this invention.

In the process of this invention it is preferred to use the diphenol of formula VI or the mixture of 2,4-bis(4-hydroxyphenoxy)aniline and a diphenol of formula VI in equivalent excess.

The alkali used in this process is ordinarily an alkali metal carbonate or alkaline earth metal carbonate such as sodium, potassium or calcium carbonate. But other alkaline reagents such as sodium hydroxide, potassium hydroxide or calcium hydroxide can also be used.

Polar aprotic solvents which can be used in the process of this invention for the preparation of the novel polyarylene ether resins are typically, diethyl acetamide, tetramethylurea, N-methylcaprolactam, and preferably dimethyl acetamide or N-methyl-pyrrolidone.

The reaction is conveniently carried out at elevated temperature, preferably at the reilux temperature of the solvent, i.e. in the temperature range up to c. 250C.

The concurrent use of an entrainer such as chlorobenzene, xylene or toluene is often expedient in order to be able to remove the water of reaction from the reaction mixture as an azeotrope.

1,3-Dichloro-4-nitrobenzene is known and commercially available, for example from Fluka Chemie AG, Buchs, CH.

The dihalo compounds of formula V are likewise known. They are disclosed, for example, in DE-OS 30 14 230 and in EP-A-0 001 879. Suitable dihalo compounds of formula V are typically 4,4'-dichlorodiphenylsulfone, 4,4'-difluorodiphenylsulfone, 4,4'-dichloro-benzophenone and 4,4'-difluorobenzophenone.

The diphenols of formula Vl are also known compounds and most are commercially available. Typical examples of suitable divalent phenols of formula VI are hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, 2,5-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3',5,5'-tetramethyldiphenylsulfone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylthioe,her, 2,2-bis(4-hydroxyphenyl)propane or dihydroxynaphthalene. Further, 2,6-bis(4-hydroxybenzoyl)naphthalene and 2,7-bis-(4-hydroxybenzoyl)naphthalene are disclosed in DE-OS 38 04 159, and chloro- or methyl-substituted 2,6-bis(4-hydroxybenzoyl)naphthalene is disclosed in US patents 4 447 592 and 4 275 226.

2,4-Bis(4-hydroxyphenoxy)aniline, which is also used for the preparation of the polyarylene ethers of the invention, has not been described in the literature and may be prepared by reacting excess hydroquinone monobenzyl ether in the presence of alkali and in an aprotic solvent, such as N-methylpyrrolidone, and hydrogenating the resultant nitro compound in known manner to 2,4-bis(4-hydroxyphenoxy)aniline. Hence the starting2,4-bis(4-hydroxyphenoxy)aniline for the preparation of the novel polyarylene ethers likewise constitutes an object of the invention.

As mentioned at the outset, the polyarylene ethers of this invention are soluble in customary organic solvents, preferably in halogenated, i,.e. chlorinated or fluorinated, hydrocarbons, especially in chlorinated hydrocarbons such as methylene chloride, tri- or tetrachloromethane or dichloroethane. The novel polyarylene ethers are also soluble in polar aprotic solvents such as N-methylpyrrolidone, N,N-dimethylformamide and dimethyl sulfoxide, or also in cyclic ethers such as tetrahydrofuran or dioxane, as well as in cyclohexanone. On account of their solubility, the polyarylene ethers may with advantage be processed from a solution to films or incorporated in other matrix systems.
The solutions of the polyarylene ethers are stable for several weeks, i.e. no turbidity, precipitation or deposition of the polymer occurs.

Prior to processing, for example as melt or, more particularly, as solution, the po'yarylene ethers may be blended with customary modifiers such as fillers, pigments, stabilisers or reinforcing agents such as carbon, boron, metal or glass fibres.

The novel polyarylene ethers can be used for curing and modifying maleimide or epoxy resins, especially epoxy resins. Thus utility constitutes a further object of the invention.

The use of polyamines for curing or modifying maleimide resins such as mono- or polymaleimides is known, for example from FR patent 1 555 564 or DE-OS 2 350 471.
Typical suitable maleimide resins which can be cured or modified with the novel polyarylene ethers are compounds of formula VII
o C--C~
C ~ - A (VII), R ' ~ C
O n wherein Rl and R2 are each independently of the other a hydrogen atom or a linear or branched alkyl group of 1 to 4 carbon atoms and A is a n-valent aliphatic radical of 2 to 30 carbon atoms, a cycloaliphatic, an aromatic, a heterocyclic or an araliphatic radical, and n is 1, 2, 3 or 4, or, if n is 2, A is also a direct bond.

The following maleimides are particularly suitable:
N,N'-ethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-m-phenylene-bismaleimide, N,N'-p-phenylenebismaleimide, N,N'-4,4'-diphenylmethanebismaleimide, N,N'-4,4'-3,3'-dichlorodiphenylmethanebismaleimide, N,N'-diphenylethanebismaleimide, N,N'-4,4'-diphenylsulfonebismaleimide, N,N'-m-xylylenebismaleimide, N,N'-p-xylylenebismaleimide, N,N'-4,4'-2,2-diphenylpropanebismaleimide, the N,N'-bismaleimide 4,4'-diaminotriphenylphosphate, the N,N'-bismaleimide of 4,4'-diaminotriphenylphosphite, the N,N'-bismaleimide of 4,4'-diaminotriphenylthiophosphate, the N,N',N"-trismaleimide of tris(4-arninophenyl)-phosphate, the N,N',N"-trismaleimide of tris(4-aminophenyl)phosphite and the N,N',N"-trismaleimide of tris(4-aminophenyl)thiophosphate.

Polyarnines are known hardeners and modifiers for epoxy resins. The novel polyarylene ethers, which are readily compatible with epoxy resins and form a homogeneous monophase system, are preferably used for hardening or modified epoxy resins to achieve a flexibilisation of the cured epoxy resins with only a relatively small fall in the Tg value.
Accordingly, the invention also relates to a curable mixture comprising (a) an epoxy resin containing more than one epoxide group in the molecule and (b) a novel polyarylene ether in an amnount sufficient to effect a full cure of the epoxy resin.

Suitable epoxy resins (a) are all types of epoxy resins, such as those which contain groups of formula VIII, 3 ~ ~ 2 '~

--CH--C--CH (VIII), wherein either R3 and Rs are each a hydrogen atom, in which case R4 is a hydrogen atom or a methyl group, or R3 and R5, when taken together, are -CH2CH2- or -CH2CH2CH2-, in which case R4 is a hydrogen atom, which groups are attached direct to oxygen, nitrogen or oxygen atoms.

Typical examples of such resins are polyglycidyl esters and poly-(,s-methylglycidyl) esters, which can be obtained by reaction of a compound containing two or more carboxylic acid g,roups per molecule with epichlorohydrin, glycerol dichlorohydrin or ~-methylepichlorohydrin in the presence of an alkali. Such polyglycidyl esters can be derived from aliphatic polycarboxylic acids, for example oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerized or trimerized linoleic acid, from cycloaliphatic polycarboxylic acids, such as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid and 4-methylhexahydrophthalic acid, and from aromatic polycarboxylic acids, such as phthalic acid, isophthalic acid and terephthalic acid.

Other examples are polyglycidyl ethers and poly-(,s-methylglycidyl) ethers which are obtainable by reaction of a compound containing at least two free alcoholic and/or phenolic hydroxyl groups per molecule with the corresponding epichlorohydrin under alkaline conditions, or alternately in the presence of an acid catalyst, and subsequent treatment with an alkali. These ethers can be prepared with poly(epichlorohydrin) from acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly(oxyethylene) glycols, 1,2-propanediol and poly(oxypropylene) glycols, 1,3-propanediol, 1,4-butanediol, poly(oxytetramethylene) glycols, 1,5-pentanediol, 1,6-hexanediol, 2,4,6-hexanetriol, glycerol, 1,1,1-trimethylolpropane, pentaerythritol and sorbitol, from cycloaliphatic alcohols, such as resorcitol, quinitol, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane and l,l-bis(hydroxymethyl)cyclohex-3-ene, and from alcohols having aromatic nuclei, such as N,N-bis(2-hydroxyethyl)aniline and p,p'-bis(2-hydroxyethylamino)diphenylmethane. They can furthermore be prepared from mononuclear phenols, such as resorcinol and hydroquinone, as well as polynuclearphenols, such as bis(4-hydroxyphenyl)methane, 4,4-dihydroxydiphenyl, bis(4-hydroxy-phenyl)sulfone, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-2 ~ 2 ~

phenyl)propane (otherwise known as bisphenol A) and 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, as well as novolaks formed from aldehydes, such as formaldehyde, acetaldehyde, chloral and furfurol, with phenols, such as phenol itself and phenol which is substituted on the ring by chlorine atoms or alkyl groups having in each case up to nine carbon atoms, such as 4-chlorophenol, 2-methylphenol and 4-tert-butylphenol.

Poly-(N-glycidyl) compounds include typically triglycidyl isocyanurate~N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetraglycidyl-3,3'-dialkyl-4,4'-diaminodiphenylmethane and N,N'-diglycidyl derivatives of cyclic alkyleneureas, such as ethyleneurea and 1,3-propyleneurea, and hydantoins, such as 5,5-dimethylhydantoin.

Poly-(S-glycidyl) compounds are typically the di-S-glycidyl derivatives of dithiols, such as e~ane-1,2-dithiol and bis(4-mercaptomethylphenyl) ether.

Examples of epoxy resins containing groups of the formula VIII in which R3 and R5 togçther are a -CH2-CH2- group are bis(2,3-epoxycyclopentyl) ether, 2,3-epoxycyclo-pentyl glycidyl ether, 1,2-bis-(2,3-epoxycyclopentyloxy)-ethane and 3,4-epoxycyclo-hexylmethyl 2',4'-epoxycyclohexanecarboxylate.

Also suitable are epoxy resins in which the 1,2-epoxide groups are bonded to different types of lletero atoms, for example the N,N,O-triglycidyl derivative of 4-aminophenol, the glycidyl ether/glycidyl ester of salicylic acid or p-hydroxybenzoic acid, N-glycidyl-N'-(2-glycidyloxypropyl)-5,5-dimethylhydantoin and 2-glycidyloxy-1,3-bis(5,5-di-methyl- 1 -glycidyl-3-hydantoinyl)propane.

Particularly preferred resins are aromatic epoxy resins such as novolak epoxy resins, diglycidyl ethers of bisphenols or tetraglycidyl compounds of aromatic diamines.
The novel polyarylene ethers (b) are present in the curable epoxy resin mixture in an amount suitable for a effecting a full cure when the mixture contains c. 0.8 to 1.2 equivalents of active hydrogen bound to amino nitrogen atoms.

As previously mentioned, the novel polyarylene ethers can be used for modifying epoxy resins. In this case, the epoxy resin mixture of (a) and (b) contains a further epoxy resin 2 ~

hardener (c) which differs from (b), with the proviso that, on the one hand, (b) and (c) together are prçsent in an amount sufficient to cure the epoxy resin or, on the other hand, only (c) is present in an amount sufficient to cure the epoxy resin and the polyarylene ether (b) is present in an amount of up to 50 % by weight, based on the amount of (a) and (c). Epoxy resin hardeners which differ from (b) may typically be other amines, including aliphatic, cycloaliphatic, aromatic and heterocyclic amines, such as m- and p-phenylenediamine, bis(4-aminophenyl)methane, aniline/formaldehyde resin, bis(4-aminophenyl)sulfone, ethylenediamine, 1,2-propanediarnine, 1,3-propanediarnine, N,N-diethylethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N-(2-hydroxyethyl)-, N-(2-hydroxypropyl)-, and N-(2-cyanoethyl)diethylenetriamine, 2,2,4-trimethylhexane-1,6-diamine, 2,3,3-trimethylhexane-1,6-diamine, m-xylylenediamine, N,N-dimethyl- and N,N-diethyl-propane-1,3-diamine, ethanolamine, bis(4-aminocyclohexyl)methane, 2,2-bis(4-amino-cyclohexyl)propane, 2,2-bis(4-amino-3-methylcyclohexyl)propane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine), and N-(2-arninoethyl)piperazine; as well as dicyandiamide; polyarninoamides, such as those from aliphatic polyamines and dirnerised or trimerised fatty acids, from amine adducts prepared from amines with a stoichiometric less than e~uivalent amount of polyepoxides; isocyanates and isothiocyanates; polyphenols, such as resorcinol, hydroquinone, 2,2-bis(4-hydroxyphenyl)-propane, phenol/aldehyde resins and oil-modified phenoValdehyde resins, phosphoric acid, polythiols, such as those commercially obtainable as "Thiokols", polycarboxylic acids and their anhydrides, such as phthalic anhydride, tetrahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, nonenylsuccinic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, hexachloroendomethylenetetrahydrophthalic anhydride and endomethylenetetrahydrophthalic anhydride and their mixtures, maleic anhydride, succinic anhydride, pyromellitic anhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, polysebacic anhydride, polyazelaic anhydride, the acid of the aforementioned anhyrides as well as isophthalic acid, terephthalic acid, citric acid and mellitic acid.
Particularly preferred polycarboxylic acids or anhydrides are those which are liquid at temperatures below 60C. Catalytic hardeners can also be used, such as ter~iary amines (e.g. 2,4,6-tris(dimethylaminoethyl)phenol and other Mannich bases, N-benzyldimethyl-amine and triethanolamine); alkali metal alkoxides of alcohols (for example the sodium alcoholate of 2,4-dihydroxy-3-hydroxymethylpentane), tin salts of aLkanoic acids (e.g. tin octanoate), Friedel-Crafts catalysts, such as boron trifluoride and its complexes and chelates, which may be obtained by reacting boron trifluoride with 1,3-diketones.

2 ~

With the hardeners it is also possible to use the suitable curing catalysts. When using poly(arninoamides), dicyandiamides, polythiols or polycarboxylic acid anhydrides, the catalysts may be tertiary amines or their salts, quaternary ammonium compounds or alkali metal alkoxides. Illustrative examples of specific catalysts are N-benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, imidazoles and triamylammonium phenoxide.
If the hardener is a polycarboxylic acid or the anhydride thereof, then normally 0.6 to 1.1 equivalents of carboxyl group or anhydride group will be used per 1 equivalent of epoxide group. When using polyphenols as hardeners, it is convenient to use 0.75 to 1.25 equivalents of phenolic hydroxyl groups per 1 epoxide equivalent. Catalytichardeners are normally used in amounts of 1 to 40 parts by weight per 100 parts by weight of epoxy resin.

Depending on the nature of the hardener, the cure may be carried out at room temperature or more elevated temperatures.

If the hardener employed is a mixture of hardeners, the expert in the epoxy resin art will know how to determine what amounts of hardener and what curing temperatures are necessary to effect a full cure of the epoxy resin.

The curable compositions of this invention may also contain further known modifiers commonly used in the art of polymerisable materials. Exemplary of such modifiers are pigments, dyes, fillers and reinforcing agents, flame retardants, antistatic agents, adhesive promoters, flow control agents, antioxidants and light stabilisers. Suitable fillers are mineral and fibrous fillers such as quartz powder, fused silica, alumina, glass powder, mica, kaolin, dolomite, graphite, carbon black and carbon fibres and textile fibres.
Preferred fillers are quartz powder, fused silica, alumina or dolomite.

The compositions of the invention may be used quite generally for making cured products and can be used in a formulation adapted to suit each specific end use as coating compounds, paints, compression moulding materials, dipping resins, casting resins, impregnating resins, laminating resins, one- or two-component adhesives or matrix resins.

To cure the compositions of the invention the temperatures will normally be in the range from 60 to 250C, preferably from 80 to 220C and, most preferably, from 100 to 200C.

?~ ~

The compositions of the invention can first be precured at low temperature until the curable composition gels, followed by a final cure at higher temperature.

. The products prepared from the compositions of this invention are distinguished in particular by a high deflection temperature under load.

Preparation of 2t4-bis(hydroxyphenoxy)aniline ;

a) In a 2.5 litre sulfonation flask, 348.3 g (1.73 mol) of hydroquinone monobenzyl ether and 167 g (0.87 mol) of 1,3-dichloro-4-nitrobenzene are reacted in the presence of 293 g (1.90 mol) of potassium carbonate (anhydrous) in 870 ml of N-methyl-2-pyrrolidone (N~P) and 700 ml of xylene at 147C, and the water of reaction is removed as an azeotrope from the system over 8 hours under nitrogen. The xylene is then removed from the reactor by distillation and the residual suspension is cooled to room temperature and poured into 10 litres of water. The brown precipitate is isolated by filtration, suspended in 4 litres of methanol, isolated by filtration and dried at 80C under vacuum. The crude product is recrystallised from 2.5 litres of isopropanol, giving 280 g (S2 % of theory) of a pale brown crystalline powder with a melting point of 113-115C.

Elemental analysis: calculated found 73.98 % C 73.79 % C
4.85%H 4.88%H
2.70%H 2.54%N.

b) 256 g of the nitro compound described in a) are hydrogenated in a suspension of 25 g of 5 % Pd/C in 2.5 Iitres of dimethyl formamide for 14 hours at 37C in the presence of hydrogen (normal pressure). The reaction solution is filtered and the filtrate is concentrated on a rotary evaporator at 100C. The residue is extracted in 2 x 500 ml of methanol and the extract is dried under vacuum at 70C, affording in quantitative yield a violet powder with a phenol content of 6.28 equivalents/kg (theory: 6.47 equivalents/kg) and an amine value of 3.07 equivalents/kg (theory: 3.32 equivalents/kg).
Elemental analysis: calculated found 69.89 % C 68.53 % C
4.89%H 4.96%H
4.53%H 4.34%N.

, Example 1:
a) In a 750 ml sulfonation flask equipped with stirrer, thermometer, water separator, condenser and gas inlet tube, 96 g (0.5 mol) of 1,3-dichloro-4-nitrobenzene, 114 g (0.5 mol) of bisphenol A, 152 g (1.1 mol) of anhydrous pulverised potassium carbonate, 300 ml of NMP and 180 ml of xylene are heated to reflux and the water of reaction is removed from the system as an azeotrope under nitrogen over 6-20 hours. The xylene is then removed from the reactor by distillation and the cooled residual suspension is poured into 3 litres of water. The precipitate is isolated by filtration, mixed a second time with S
litres of water, isolated by filtration, thoroughly washed with water and dried under vacuum at 100C, giving 155 g of a beige powder which dissolves in methylene chloride to form a clear solution and which has a number average molecular weight (Mn) of 8 660 and a weight average molecular weight (Mw) of 55 570, determined by gel permeation chromatography (in tetrahydrofuran).

b) 100 g of the nitro compound described in a) are hydrogenated in a suspension of 4 g of 10 % Pd/C in 500 ml of dimethyl formamide for 20 hours at 65C in the presence of hydrogen (normal pressure). The reaction solution is filtered and the filtrate is precipitated in S litres of water. The precipitate is isolated by filtration, mixed a second time with S litres of water, isolated by filtration and dried under vacuum at 80C, affording 76 g of a violet powder with an amine value of 2.7 equivalents/kg which is readily soluble in methylene chloride (Mn: 600, Mw: 5 5700).

Example 2:
a) In accordance with the general procedure of Example 1, 144 g (0.75 mol) of 1,3-dichloro-4-nitrobenzene, 110.1 g (1 mol) of resorcinol, 290 g (2.1 mol) of anhydrous pulverised potassium carbonat, 350 ml of NMP and 700 ml of toluene are reacted to give 185 g of a brown powder which dissolves in methylene chloride to form a clear solution and which has a molecular weight of 670 (Mn) and 1 110 (Mw), deteremined by gel permeation chromatography (in tetrahydrofuran).

b) 160 g of the nitro compound obtained in a) are reduced with hydrogen to the amine as described in Exarnple lb). Yield: 95 g of a dark brown powder with an amine value of 3.3 equivalents/kg, a Mn of 646 and Mw of 1052 and a phenol value of 2.8 equivalents/kg.

2~S~12~

.
Example 3:
a) 221 g (0.77 mol) of dichlorodiphenylsulfone, 191.5 g (0.84 mol) of bisphenol A, 9.6 g (0.05 mol) of 1,3-dichloro-4-nitrobenzene, 261 g (1.9 mol) of anhydrous potassium carbonate, 800 ml of dimethyl acetamide and 400 ml of xylene are reacted and worked up in accordance with the general procedure described in Example 1 a), affording 309 g of a yellow powder which is readily soluble in methylene chloride.
Gel permeation chromatography: Mn = 8050; MW = 28 400.

b) 300 g of the nitro compound described in a) are hydrogenated in a suspension of 30 g of 10 % Pd/C in 2500 rnl of dimethyl formarnide for 3 hours at 35C in the presence of hydrogen (normal pressure). The reaction solution is filtered and the filtrate is precipitated in 15 litres of water. The precipitate is isolated by filtration, mixed a second time with 10 litres of water, isolated by filtration and dried under vacuum at 80C, affording 242 g of a violet powder with an amine value of 0.13 equivalentlkg which is readily soluble in methylene chloride and has a ~ h of 0.28.
Gel permeation chromatography: Mn = 8100; MW = 27 800.

Example 4:
a) 224 g (0.775 mol~ of dichlorodiphenylsulfone, 239.4 g (1.05 mol) of bisphenol A, 48.0 g (0.25 mol) of 1,3-dichloro-4-nitrobenæne, 325.8 g (2.36 mol) of anhydrouspotassium carbonate, 1 litre of dimethyl acetamide and 400 ml of xylene are reacted and worked up in accordance with the general procedure described in Example la), affording 408 g of a yellow powder which is readily soluble in methylene chloride and has a ~ h of 0.20.
Gel permeation chromatography: Mn = 6670; MW = 17 260.

b) 380 g of the nitro compound obtained in 4a) are reduced with hydrogen to the amine as described in Example 3b). Yield: 167 g of a violet powder with an amine value of0.41 equivalents/kg and a ~ of 0.25.
Gel permeation chromatography: Mn = 6500; MW = 17 800.

Example 5: In a 750 ml sulfonation flask 57.2 g (0.20 mol) of dichlorodiphenylsulfone, 39.9 g (0.175 mol) bisphenol A, 7.96 g (0.025 mol) of 2,4-bis(4-hydroxyphenoxy)aniline, 33.1 g (0.24 mol) of anhydrous potassium carbonate, 400 ml of dimethyl acetarnide and 200 ml of xylene are reacted at 146C and the wate} of reaction is removed from the system as an azeotrope. After 12 hours the xylene is removed from the reactor by :. r ' 2~ 5 distillation and the residual suspension is cooled to room temperature and poured into 3 litres of water. The precipitate is isolated by filtration, mixed a second time with 3 litres of water, isolated by filtration and thoroughly washed with water and dried under vacuum at 100C, giving 74.8 g of a violet powder which has an amine value of 0.27 equivalent~g, dissolves readily in methylene chloride and has a ~i"h f 0.64.
Gel permeation chromatography: Mn = 11 S00; MW = 17 300.

Example 6:
a) In a 2.5 litre sulfonation flask, 196.1 g (0.86 mol) of bisphenol A, 38.4 g (0.20 mol) of 1,3-dichloro-4-nitrobenæne, 255.4 g (1.84 mol) of anhydrous potassium carbonate,1.2 litres of dimethyl acetamide and 400 ml of toluene are reacted at 140C and the water of reaction is removed continuously from the system as an azeotrope. After 4 hours the reaction mixture is cooled to lOO~C and 139.5 g (0.64 mol) of difluorobenzene are added.
The temperature is increased again to 140C and the batch is allowed to react for 12 hours.
The xylene is then removed from the reaction mixture by distillation and the residual suspension is cooled to room temperature and poured into 10 litres of water. Theprecipitate is isolated by f1ltration, mixed a second time with 10 litres of water and isolated by filtration. The filter product is washed thoroughly with water and dried under vacuum at 100C, affording 295 g of a pale yellow powder which dissolves in methylene chloride to form a clear solution and has a molecular weight of 9000 (Mn) and 45 550 (MW).11ir,h = 0-34-b) 280 g of the nitro compound described in a) are hydrogenated in a suspension of 86 g of5 % Pd/C in 5 litres of dimethyl formamide for 10 hours at room temperature in the presence of hydrogen (normal pressure). The reaction solution is filtered and the filtrate is precipitated in 20 litres of water. The precipitate is isolated by filtration, mixed a second time with 5 litres of water, filtered and dried under vacuum at 80C, affording 260 g of a violet powder with an amine value of 0.43 equivalent/kg which is readily soluble in methylene chloride and has a ~ h of 0-37-Gel permeation chromatography: Mn = 8600; MW = 38 500.
Use Examples Example I: 10 g or 20 g of of the polymer of Example 3b) are added to an epoxy resin/hardener combination comprising S0 g of N,N,N',N'-tetraglycidyl-p-diaminodiphen-ylmethane, S0 g of N,N,O-triglycidyl-p-aminophenol and 50 g of 2~412~

p-diaminodiphenylsulfone, dissolved in 100 ml of methylene chloride. The solvent is then removed by distillation on a rotary evaporator. The resin mixture, which is readily curable at 150C, is poured into a 4 mm metal mo~ld and hardened for 2 hours at 160C and for 2 hours at 210C. The reddish brown transparent sheet which is removed from the mould has the following properties:

Polymer of Example 3b) lOg 20g __ Tg (TMA) 246C 244C
flexural strength ( ISO 178) 138 MPa 150 MPa edge fibre elongation ( ISO 178) 4.2 % 5.0 %
fracture toughness ( ASTM E 399-789) 100 J/m2 164 J/m2 Example II: 10 g or 30 g of of the polymer of Example 4b) are added to an epoxy resin/hardener combination comprising 50 g of N1N,N',N'-tetraglycidyl-p-diarninodiphen-ylmethane, 50 g of N,N,O-triglycidyl-p-arninophenol and 50 g of p-diaminodiphenyl-sulfone, dissolved in 100 ml of methylene chloride. The solvent is then removed by distillation on a rotary evaporator. The resin mixture, which is readily curable at 150C, is poured into a 4 mm metal mould and hardened for 2 hours at 160C and for 2 hours at 210C. The reddish brown transparent sheet which is removed from the mould has the following polymer properties:

Polymer of Example 4b) lOg 30g . __ Tg (TMA) 246C 239C
flexural strength ( ISO 178) 156 MPa 146 MPa edge fibre elongation ( ISC) 178) 5,5 % 5.1 %
fracture toughness ( ASTM E 399-789) 164 J/m2 219 J/m2 Example III: 10 g or 30 g of of the polymer of Example 4b) are added to an epoxyresin/hardener combination comprising 50 g of N,N,N',N'-tetraglycidyl-4,4'-dian~ino-3,3'-diethyldiphenylmethane and 45 g of p-diaminodiphenylsulfone, dissolved in 100 ml of methylene chloride. The solvent is then removed by distillation on a rotary evaporator.
The resin mixture, which is readily curable at 150C, is poured into a 4 mm metal mould 2 ~ 2 ~

and hardened for 4 hours at 1 80C. The reddish brown transparent sheet which is removed from the mould has the following polymer properties:

Polymer of Example 4b) lOg 30g Tg (TMA) 212C 192C
flexural strength ( ISO 178) 112 MPa 120 MPa edge f1bre elongation ( ISO 178) 3.3 % 3.9 %

ExamPle IV: 8 g of the polymer of Example 6b) are added to an epoxy resin/hardener combination comprising 40 g of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 40 g of N,N,O-triglycidyl p-aminophenol and 36 g of p-diaminodiphenylmethane, dissolved in 100 ml of methylene chloride. The solvent is then removed by distillation on a rotary evaporator at 120C. The resin mixture, which is readily curable at 150C, is poured into a 4 mm metal mould and hardened for 2 hours at 160C and for 2 hours at 210C. The reddish brown transparent sheet which is removed from the mould has the following properties:

Polymer of Example 6b) 8g Tg (~MA) 230C
flexural strength ( ISO 178) 115 MPa edge fibre elongation ( ISO 178) 3.9 %
fracture toughness (ASTM E 399-789) 176 J/m2 ,

Claims

1. An amino group containing polyarylene ether which is soluble in organic solvents and has an inherent viscosity (?inh) of 0.02 to 1.0, measured in a 1 % by weight solution of the polymer in N-methylpyrrolidone at 25°C, which polyarylene ether, based on the total amount of structural units present in the polymer, contains 100 to 5 mol % of a structural repeating unit of forrnula I or II

(I) or (II) and 95 to 0 mol % of a structural repeating unit of formula III

(III) wherein X is -SO2- or -CO-, and Ar is a group of formula IVa to IVe (IVa), wherein a is 0 or 1, (IVb), (IVc), (IVd), wherein b is 1 or 2, oder (IVe) wherein Z is -CO-, -SO2-, -SO-, -S-, -O-, -C(CH3)2, -C(CF3)2, -CH2- or -?1-CH3, which group is unsubstituted or substituted by one or more members selected from the group consisting of C1-C4alkyl, C1-C4alkoxy or halogen.

2. A polyarylene ether according to claim 1, comprising 100 to 5 mol % of a structural repeating unit of formula I and 95 to 5 mol % of a structural repeating unit of formula III.

3. A polyarylene ether according to claim 1, wherein Ar in formulae I and III is an unsubstituted group of formulae IVa to IVe.

4. A polyarylene ether according to claim 1, wherein Ar in formulae I and III is a radical of formula , , , or

5. A polyarylene ether according to claim 1, wherein Ar in formulae I and III is a radical of formula , , or

6.A process for the preparation of a polyarylene ether according to claim 1, which comprises polycondensing, for example, 1,3-dichloro-4-nitrobenzene or a mixture of 1,3-dichloro-4-nitrobenzene and a dihalo compound of formula (V), present therein in an amount of up to 95 mol %, preferably 90 mol %, wherein Hal is a halogen atom, preferably a chlorine or fluorine atom, and X is as defined above, with a diphenol of formula VI
HO-Ar-OH (VI), wherein Ar is as defined above, or by polycondensing 2,4-bis(4-hydroxyphenoxy)aniline or a mixture of 2,4-bis(4-hydroxyphenoxy)aniline and a diphenol of formula VI present therein in an amount of up to 95 mol %, preferably 90 mol %, with a halogen compound of formula V, in the presence of akali and in an aprotic solvent, until the resultant polyarylene ether has a ?inh of 0.02 to 1.0, and subsequently converting the nitro group containing polyarylene ether by complete catalytic reduction of the nitro groups into an amino group containing polyarylene ether as claimed in claim 1.

7.2,4-Bis(4-hydroxyphenoxy)aniline.

8. A curable mixture comprising (a) an epoxy resin containing more than one epoxy resin in the molecule and (b) a polyarylene ether according to claim 1 in an amount sufficient to effect a full cure of the epoxy resin.

9. A curable mixture according to claim 8, which further comprises an epoxy resin hardener (c) which differs from (b), with the proviso that, on the one hand, (b) and (c) together are present in an amount sufficient to effect a full cure of the epoxy resin.

10. A curable mixture according to claim 8, which comprises components (a), (b) and (c), the hardener (c) being present in an amount sufficient to effect a full cure of the epoxy resin and the polyarylene ether (b) being present in an amount of up to 50 % by weight, based on the amount of (a) and (c).

FD4.3/STA/bg*