CA2039478A1

CA2039478A1 - Soluble polyarylene ether ketones

Info

Publication number: CA2039478A1
Application number: CA 2039478
Authority: CA
Inventors: Rudolf Pfaendner; Thomas Kainmuller; Kurt Hoffmann; Jean-Pierre Wolf; Andreas Kramer; Friedrich Stockinger
Original assignee: Individual
Current assignee: Novartis AG
Priority date: 1990-04-03
Filing date: 1991-03-28
Publication date: 1991-10-04
Also published as: EP0451104A3; EP0451104A2; JPH0741555A

Abstract

Soluble polyarylene ether ketones Abstract of the Disclosure Polyarylene ether ketones which are soluble in halogenated hydrocarbons and have a reduced viscosity of 0.1 to 2.0 dl/g, measured at 25°C using a 1 % solution of the polymer in N-methylpyrrolidone (NMP), which polyarylene ether ketones contain, based on the total number of structural units present in the polyarylene ether ketone resin, 1-100 mol %
of a recurring structural unit of formula I or II
(I), (II) and 99-0 mol % of a recurring structural unit of formula III
(III) wherein R1 is alkyl, alkoxy, aryl, alkenyl or halogen, and m is 0 or an integer from 1-4, R2 is C1-C4alkyl, C1-C4alkoxy, C6-C12aryl or halogen, and n is 0 or an integer from 1-4, Ar1 is a divalent radical of a bisphenol compound and Ar2 is a divalent radical of an activated dihalo compound which is able to enter into a nucleophilic exchange reaction.

These polyarylene ethers can be readily processed from the solution and are suitable for modifying matrix resins.

Description

20394'78 I

Soluble Polvarvlene ether ketones The present invention relates to polyarylene ether ketones which are soluble in halogenated hydrocarbons and contain 2,2'-bis(benzoyl)biphenyl units, to the preparation thereof, to the mouldings, coatings or sheets made therefrom, and to the use of said polyarylene ether ketones for modifying matrix resins.

Polyarylene ether ketones are industrial materials having very good mechanical and thermal properties which are normally insoluble in halogenated hydrocarbons or form unstable solutions. For example, polyarylene ether ketones containing 4,4'-bis(benzoyl)biphenyl units are disclosed in EP-A-0 194 062. These keto group containing polyethers have especially good resistance to solvents, for example to methylene chloride.

For many utilities, especially for modifying duromer matrix resins, polyether ketones are required which have enhanced solubility properties without any substantial reduction of the thermal properties, such as glass transition temperature. Surprisingly, it has now been found that polyarylene ether ketones containing 2,2'-bis(benzoyl)biphenyl units are readily soluble in customary organic solvents, preferably in halogenated hydrocarbons, and form stable solutions.

Accordingly, the invention relates to polyarylene ether ketones which are soluble in halogenated hydrocarbons and have a reduced viscosity of 0.1 to 2.0 dl/g, measured at 25C using a 1 % solution of the polymer in N-methylpyrrolidone (NMP), which polyarylene ether ketones contain, based on the total number of structural units present in the polyarylene ether ketone resin, 1-100 mol % of a recurring structural unit of formula I
or Il 2~39478 (R2)n (R l)m ~ ~ O--Ar (R2)n (R2)n ~3 ~ 1' ~ o--Ar2-}

(R2)n and 99-0 mol % of a recurring structural unit of formula IlI
~o-Ar2 -o-Arl~ (III) wherein Rl is Cl-C4alkyl, C1-C4alkoxy, C6-C12aryl, C2-C4alkenyl or halogen, and m is O
or an integer from 1-4, R2 is C1-C4alkyl, C1-C4alkoxy, C6-Cl2aryl or halogen, and n is O
or an integer from 1-4, Ar1 is a divalent radical of a bisphenol compound and Ar2 is a divalent radical of an activated dihalo compound which is able to enter into a nucleophilic exchange reaction.

'rhe radical Arl in the structural units of formulae l and lll is preferably a group of formulae IVa to Vg ~ 3~ (IVa), wherein a is O or 1, 2~39478 ~3 (IVb), ~3 (IVc), Z ~ (JVd), wherein b is 1 or 2, ~3 Z ~ Z ~3} (IVe), ~3\/~3/
A (IVf) or )3 (IVg) wherein Z is -CO-, -SO2-, -SO-, -S-, -O-, -C(CH3)2, -C(CF3)2, -CH2-, - IC-CH3 or C6Hs -PO, Q is a direct bond, -O-, -CH2- or -CO-, R3 is Cl-C4alkyl and R4 is Cl-C4alkyl or phenyl, which groups are unsubstituted or substituted by one or more Cl-C4alkyl or Cl-C4alkoxy groups or by halogen atoms.

Preferably Arl is a group of formulae IVa to IVe 2~39478 -~ (TVa), wherein a is O or 1, ~3 ~3 (IVb), ~3 (IVc), Z ~ (IVd), wherein b is 1 or 2, or ~3 Z--~ z ~3} (IVe) wherein Z is -CO-, -SO2-, -SO-, -S-, -O-, -C(CH3)2, -C(CF3)2, -CH2-, or -Cl -CH3, C6Hs which groups are unsubstituted or substituted by one or more Cl-C4alkyl or C~-C4alkoxy groups or by halogen atoms.

The radical Ar2 in the structural units of formulae II and III is preferably a group of formulae IVh bis IVI

~ X ~ X ~3 (IVh), wherein c is O or 1, ~ ~d (IVi), wherein d is 2 or 3 and X is -CO-, -SO2- or -SO-, 2~39478 CN
~ (lVj), (IVk) or N~N
~ (IVl), which groups are unsubstituted or substituted by one or more C1-C4alkyl or Cl-C4alkoxy groups or halogen atoms.
Preferably Ar2 is a group of formulae IVh or IVi ~ X ~ X~ (IVh), wherein c is O or 1, ~ ~d (IVi), wherein d is 2 or 3 and X is -CO-, -SO2- or -SO-, which groups are unsubstituted or substituted by one or more Cl-C4alkyl or Cl-C4alkoxy groups or halogen atoms.

Preferably the polyarylene ether ketones of this invention contain 5-100 mol % of a recurring structural unit of formula I or II and 95-0 mol % of a recurring structural unit formula III.

Most preferably, the polyarylene ether ketones of this invention contain 10-100 mol % of a recurring structural unit of formula I or II and 90-0 mol % of a recurring structural unit of formula III. In the polyarylene ether ketones of this invention, the structural units of formulae I, II and III are preferably unsubstituted.

203~78 Preferred radicals Arl in the structural units of formulae I and nl are typically ~3' ~, ,~3, ~ CH~ , ~ S2~
oCH3 ~C~, ~0~, CF~ ~or o~?

Particularly preferred radicals Arl are those of formulae 20~9~78 ~g or ~So243 Preferred radicals Ar2 in the structural units of formulae II and III are typically CN
~ S2~ ~ \~/ or The polyarylene ether ketones of this invention can be prepared by (a) polycondensing a dihalo compound of formula V
2)n ~3 ~ (R1)m (V)~
(R1)m ~ C ~ Hal (R2)n wherein Rl, R2, m and n are as defined in formula I and Hal is halogen, preferably fluoro or chloro, or a mixture of a dihalo compound of formula V and a dihalo compound of formula VI present therein in an amount of up to 99 mol %
Hal-Ar2-Hal (Vl), 2~39478 wherein Ar2 is as defined for formula II and Hal is halogen, preferably fluoro or chloro, in equimolar amounts, with a diphenol of formula VII

HO-Arl-OH (VII), or the alkali metal phenolate or alkaline earth metal phenolate thereof, wherein Arl is as defined for formula I, in the presence of alkali and in an aprotic solvent, or (b) polycondensing a compound of formula VIII

( R2)n Ho;~3c ~ (R1)m (Rl)m ~C~OH (VIII), (R2)n or the alka]i metal phenolate or alkaline earth metal phenolate thereof, wherein Rl, R2, m and n are as defined in claim 1, or a mixture of a compound of formula VIII and a diphenol of formula VII present therein in an amount of up to 99 mol %, in equimolar amounts, with a dihalo compound of formula VI, in the presence of alkali and in an aprotic solvent, until the polyarylene ether ketone has a reduced viscosity of 0.1 to 2.0 dl/g, measured at 25C using a 1 % solution of the polymer in NMP (1 g of polymer in 100 ml of NMP) The preferred procedure comprises polycondensing (a) a dihalo compound of formula V or a mixture of a dihalo compound of formula V and a dihalo compound of forrnula VIprescnt therein in an amount of up to 95 mol %, preferably of up to 90 mol %, inequimolar amounts, with a diphenol of formula VII, or (b) polycondensing a compo~lnd of formula VIII or a mixt~lre of a compound of formula VIII and a diphenol of formula VII
present therein in an amount of up to 95 mol %, preferably of up to 90 mol %, inequimolar amounts, with a dihalo compound of formula VI, in the presence of alkali alld in an aprotic solvent, until the polyalylene ether ketone has a reduced viscosily of ().15 to 1.8 dl/g, preferably of 0.2-1.5 dl/g.

By equimolar amounts is meant in the context of this invention a molar ratio of dihalo compound of formula V, or of dihalo compounds of formulae V and Vl, to the diphenol of formula VII, or a molar ratio of the compound of forrnula VIII, or of the compounds of formulae VII and VIII, to the dihalo compound of formula VI, of 0.9 to 1.1. The preferred molar ratio is from 0.95 to 1.05.

The alkali used in this process is ordinarily an alkali metal carbonate or alkaline e,u th 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 polyether resins are typically dimethyl sulfoxide, dimethyl acetamide, diethyl acetamide, tetramethylurea, N-methylcaprolactam, N-methylpyrrolidone and, preferably, diphenyl sulfone.

The reaction is conveniently carried out at elevated temperature, preferably at the reflux temperature of the solvent, i.e. in the temperature range up to ca. 350C.

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.

The compounds of formulae V and VIII are known. For example, the preparation of 2,2'-bis(4-fluorobenzoyl)biphenyl is described in the Journal of American Chemical Society 1935,57, page 1095 et seq., and the preparation of 4,4'-dichloro-2,2'-bis(o-chlorobenzoyl)biphenyl is described in the Journal of Organic Chemistry 1984, 49(2), 296-300. The preparation of, for example, 2,2'-bis(4-hydroxybenzoyl)biphenyl is described in the JouMal of Chemical Society, C, 1969, 2388 et seq., and in the Journal of Chemical Society 1938, 1561 et seq. The known processes for the preparation of the compounds of formulae V and VIII give yields of only ca. 30 % of theory.

It has further been found that the compounds of formulae V and VIII are obtained in substantially higher yield by starting from a 2-iodobenzophenone in the synthesis of the 2~39478 biphenyl compounds and heating this compound, in the presence of copper powder, IO C.l.
200C.

Accordingly, the invention also relates to a process for the preparation of compounds of formulae V and VIII, which comprises heating a compound of formula IX

(R2)n (Rl)m ~C~Y (IX), wherein Rl, R2, m and n are as defined for formula V or VIII, and Y is halogen or C1-C4alkoxy, preferably fluoro, chloro or Cl-C2alkoxy, most preferably fluoro or -OCH3, in the presence of a 0.5 to 3-fold amount by weight of copper powder, based on the amount by weight of the compound of formula IX, to a temperature in the ran~,e from 150-250C, to give a compound of formula X

~R2)n 1 m R2) (X) wherein Rl, R2, m, n and Y are as defined for formula IX, and, if Y is C1-C4alkoxy, reacting said compound with AlCl3, in an organic solvent, with stirring, in the temperature range of ca. 60-160C, to a compound of formula VIII, using 3-6 mol of AIC13 per I mol of compound of formula X.

The organic solvent used in this reaction is preferably benzene, toluene, xylene or chlorobenzene.

The compound of formula X can be prepared by reacting a compound of formula XI

ll (R2)n _~ o ~ ~ C--Cl (XI), wherein R2 and n are as defined for formula IX, for example 2-iodobenzoyl chloride, in the presence of a catalytic amount of FeCI3, with a compound of formula XII

(Rl)m ~ (XII), wherein Rl, m and Y are as defined for formula IX, for example fluorobenzene or anisole.

The dihalo compounds of formula VI are known. They are disclosed, for example, in DE-OS 30 14 230 and in EP-A-0 001 879. Suitable dihalo compounds of formula Vl are typically 4,4'-dichlorodiphenylsulfone, 4,4'-difluorodiphenylsulfone, 1,4-bis(4-chloro-phenylsulfonyl)benzene, 4,4'-bis(4-chlorophenylsulfonyl)biphenyl and 2,6-bis(4-chloro-phenylsulfonyl)naphth~lene. 2,6- or 2,7-Bis(p-fluorobenzoyl)naphthalene or 2,6- or 2,7-bis(p-chlorobenzoyl)naphthalene are disclosed in DE-OS 3 804 159 and in POLYMER, 1988, Volume 29, page 358 et seq. Exemplary of further suitable dihalo compounds are 2,6-difluorobenzonitrile or 2,6-dichlorobenzonitrile.

The diphenols of formula VII are also known compounds and most are commercially available Typical examples of suitable divalent phenols of formula VII are hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, 2,5-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-~lihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3',5,5'-tetramethyldiphenylsulfone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl-thioether, 2,2-bis(4-hydroxyp}lenyl)propane or dihydroxynaphthalene. 2,6-Bis(4-}-ydroxy-benzoyl)naphthalene and 2,7-bis(4-hydroxybenzoyl)naphtha-lene are disclosed in DE-OS 38 04 159, and chloro- or methyl-substituted 2,6-bis(4-hydroxyben~oyl)-naphthalene are disclosed in US patent specifications 4 447 592 and 4 275 226. Exemplary of further suitable divalent phenols are 9,9-bis(4-hydroxyphenyl)fluorene and - 12- 2~39~7~

6,6'-dihydroxy-3,3,3',3'-tetramethyl- 1,1 '-spirobiindane.

As mentioned at the outset, the polyarylene ether ketones 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,trichloromethane, dichloroethane, trichloroethane or chlorobenzene. The novel poly-arylene ether sulfones are also soluble in polar aprotic solvents such as N-methyl-pyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide and sulfolane, or usually also in cyclic ethers such as tetrahydrofuran or dioxane, as well as in cyclohexanone orcyclopentanone. On account of their solubility, the polyarylene ether ketones may with advantage be processed to films or incorporated in other matrix systems.

The solutions of the polymers of this invention are stable over several weeks, i.e. no turbidity or precipitation of the polymer occurs. The invention therefore further relates to a solution containing 1 to 75 % by weight, preferably 5 to 50 %, by weight, based on said solution, of a polyarylene ether ketone of this invention.

The polyarylene ether ketones can be used in the conventional manner for thermoplastics and processed to mouldings, films, sheets or coatings. The invention thus also relates to the objects made from the polyarylene ether resins, such as mouldings, coatings, films or sheets.

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

The polyarylene ether ketones may also be used as matrix resins for the fabrication of f1brous composite systems, for which utility it is possible to use as reinforcing fibres the fibres conventionally used for reinforcing industrial materials. These fibres may be organic or inorganic fibres, natural fibres or synthetic fibres, and may be in the form of fibre bundles as oriented or non-oriented fibres or continuous filaments.

A further preferred utility of the polyarylene ether ketones of this invention is, by virtue of their solubility, the modification of other matrix resins. Thus, for example, preferably concentrated solutions of these polymers in customary organic solvents will ordinarily be used for modifying duromer matrix resins with thermoplastics. It must be possible to 2~39478 remove the solvents rapidly after incorporation and they should therefore have as low boiling points and high volatility points as possible.

The invention further relatcs to the use of the novel polyarylene ether ketones for modifying thermoplastic and du}omer matrix resins~

The following Examples illustrate the invention.

Preparation of the monomers 2-Iodo-4'-fluorobenzophenone A solution of 493 g (1.85 mol) of 2-iodobenzoyl chloride in 420 ml of fluorobenzene is added dropwise at room temperature to a suspension of 247 g (1.85 mol) of AlCI3 and a catalytic amount of FeCI3 (1.85 g) in 420 ml of fluorobenzene. The reaction mixture is stirred for 20 hours at room temperature under nitrogen. Excess fluorobenzene is distilled from the reaction mixture, and the residue is poured, with stirring, into S litres of water.
The precipitate is isolated by filtration, washed with water, and dried in a vacuum drier at 40C. Recrystallisation from hexane gives 501 g (83 % of theory) of 2-iodo-4'-fluorobenzophenone which melts at 51-52C.
Elemental analysis calculated for Cl3H8FIO:
cal.: C = 47.88 % found: C = 47.72 %
H= 2.47% H= 2.77%
I = 38.91 % I = 39.00 %.

2,2'-Bis(4-fluorobenzoYl)biphenvl A mixture of 114.3 g (0.35 mol) of 2-iodo-4'-fluorobenzophenone and 343 g of fine copper powder is heated for 30 minutes to 200C. After cooling to 100C, 300 ml of toluene are added and the the solution is filtered hot. The residue is washed thoroughly with hot toluene, and the combined toluene phase is concentrated by evaporation on a rotary evaporator. Recrystallisation of the residue from ethanol gives 54 g (77 % of theory) of 2,2'-bis(4-fluorobenzoyl)biphenyl which melts at 141-142C.
Elemental analysis calculated for C26H16F22:
cal: C = 78.38 % found: C = 78.31 %
H= 4.05% H= 4.18%

2-lodo-4'-methoxybenzophenone A suspension of 493 g (1.85 mol) of 2-iodobenzoyl chloride and a catalytic amount of FeCl3 (6 g) in 1000 ml of anisole is boiled under reflux for 3 hours. The reaction solution is cooled to room temperature and then diluted with 1 litre of toluene and extracted with 2 litres of water. The organic phase is dried over Na2SO4 and concentrated by evaporation on a rotary evaporator. The residue is poured, with stirring, into 2 litres of isopropanol.
The precipitate is isolated by filtration and dried in a vacuum drier at 50C, giving 461 g (74 % of theory) of 2-iodo-4'-methoxybenzophenone which melts at 84-85C.
Elemental analysis calculated for Cl4HllIO2:
cal.: C = 49.73 % found: C = 49.95 %
H = 3.28 % H= 3.28 %
I = 37.53 % I = 37.58 %.

2,2'-Bis(4-methoxvbenzoYl)biphenvl A mixture of 181.2 g (0.535 mol) of 2-iodo-4'-methoxybenzophenone and 362 g of fine copper powder is heated for 1 hour to 200C. After cooling to 100C, 700 ml of toluene are added and the solution is filtered hot. The residue is washed thoroughly with hot toluene and the combined toluene phase is concentrated by evaporation on a rotary evaporator. Recrystallisation of the residue from ethanol gives 90 g (80 % of theory) of 2,2'-bis(4-methoxybenzoyl)biphenyl which melts at 156-158C.
Elemental analysis calculated for C28H224:
cal.: C = 79.60 % found: C = 79.62 %
H= 5.25% H= 5.37%.

2,2'-Bis(4-'hYdroxvbenzoyl)biphenyl 154 g (1.15 mol) of AICI3 are added in small increments at room temperature to a solution of 89 g (0.21 mol) of 2,2'-bis(4-methoxybenzoyl)biphenyl in 1.4 litres of toluene. The suspension is stirred for 16 hours at 80C under nitrogen. After cooling to roomtemperature, the suspension is poured, with stirring, into 2 litres of water. The precipitate is isolated by filtration and washed first with water and then with toluene. The residue is dried in a vacuum drier at 80C, giving 78 g (94 % of theory) of 2,2'-bis(4-hydroxybenzoyl)b~phenyl which melts at 259-261 C.
Elemental analysis calculated for C26H18O4:
cal.: C = 79.17 % found: C = 79.20 %
H= 4.60% H= 4.99%.

Example 1: Polyarylene ether ketone sulfone from 2,2'-bis(4-fluorobenzoyl)biphenyl and ~39478 ,5 4,4'-dihydroxydiphenylsulfone In a round flask with stirrer and inert gas inlet, a mixture of 25.08 g (0.1002 mol) of 4,4'-dihydroxydiphenylsulfone, 97.60 g of diphenylsulfone, 14.60 g (0.1056 mol) of potassium carbonate and 51 g of xylene is heated at a bath temperature of 200C and a xylene/water mixture is distilled from the reaction mixture. Towards the end of the distillation, a vacuum (2 mbar) is briefly applied. Then 39.84 g (0.1000 mol) of2,2'-bis(4-fluorobenzoyl)biphenyl are added to the reaction mixture, the temperature is raised over 25 minutes (min) to 250C and kept for 1 hour (h). The temperature is then raised for 1 h to 275C and thereafter further to 300C. This temperature is kept for 4 h, whereupon the reaction mixture becomes increasingly viscous.

The cooled reaction mixture is taken from the flask and pulverised. After addition of dilute acetic acid and extraction first with water and then with acetone, the polymer is dissolved in methylene chloride. A small amount of insoluble material is isolated by filtration and precipitated from isopropanol. The purified polymer is subsequently dried in a vacuum drier at 240C. A polyarylene ether ketone sulfone so obtained has a reduced viscosity (1 % of the polymer in N-methylpyrrolidone (NMP) at 25C, i.e. 1 g of the polymer in 100 ml of NMP) of 0.67 dl/g. The solubility of the polymer in methylene chloride is 20 %
by weight. The glass transition temperature, measured by differential scanning calorimetry (DSC), is 208C.

Example 2: Polyarylene ether ketone sulfone copolymer of 2,2'-bis(4-fluorobenzoyl)-biphenyl, 4,4'-dichlorodiphenylsulfone and 4,4'-dihydroxydiphenylsulfone In accordance with the general procedure described in Example 1, a polyether ketone sulfone is prepared from 4,4'-dihydroxydiphenylsulfone (0.1001 mol), 2,2-bis(4-fluoro-benzoyl)biphenyl (0.0250 mol) and 4,4'-dichlorodiphenylsulfone (0.0750 mol) withpotassium carbonate (0.1061 mol). Reaction conditions: 1 h/250C, 1 h/275C, 3 h/280C.
The resultant polymer (red. viscosity = 0.33 dl/g) has a glass transition temperature of 218C. The solubility of the polymer in methylene chloride is more than 25 % by weight.

Example 3: Polyarylene ether ketone sulfone copolymer of 2,2'-bis(4-fluorobenzoyl)-biphenyl, 4,4'-dichlorodiphenylsulfone and 4,4'-dihydroxydiphenylsulfone In accordance with the general procedure of Example 1, a polyether ketone sulfone is prepared from 4,4'-dihydroxydiphenylsulfone (0.4015 mol), 2,2'-bis(4-fluorobenzoyl)biphenyl (0.040 mol) and 4,4'-dichlorodiphenylsulfone (0.360 mol) with potassium carbonate (0.420 mol). Reaction conditions: 1 h/250C, 20~9478 1 h/275C and 5.5 h/280C. The resultant polymer (red. viscosity = 0.87 dl/g) has a glass transition temperature of 227C. The solubility of the polymer in methylene chloride is more than 25 %.

Example 4: Polyarylene ether ketone sulfone from 2,2'-bis(4-hydroxybenzoyl)biphenyl and 4,4'-dichlorodiphenylsulfone In accordance with the general procedure of Example 1, a polyether ketone sulfone is prepared from 2,2'-bis(4-hydroxybenzoyl)biphenyl (0.1003 mol) and 4,4'-dichlorodiphen-ylsulfone (0.1002 mol) with potassium carbonate (0.1085 mol). Reaction conditions:
I h/250C, 1 h/273C and 4 h/300C. The resultant polymer (red. viscosity = 0.17 dl/g) has a glass transition temperature of 180C. The solubility of the polymer in methylene chloride is more than 25 %.

Example 5: Polyarylene ether ketone sulfone copolymer of 2,2'-bis(4-hydroxyben~oyl)-biphenyl, 4,4'-dihydroxydiphenylsulfone and 4,4'-dichlorodiphenylsulfone In accordance with the general procedure of Example 1, a polyether ketone sulfone is prepared from 2,2'-bis(4-hydroxybenzoyl)biphenyl (0.0255 mol), 4,4'-dihydroxydiphenylsulfone (0.0754 mol) and 4,4'-dichlorodiphenylsulfone (0.1001 mol) with potassium carbonate (0.1051 mol). Reaction conditions: 1 h/252C, 1 h/278C and 4 h/302C. The resultant polymer (red. viscosity = 0.33 dl/g) has a glass transition temperature of 215C. The solubility of the polymer in methylene chloride is more than 25 %.

Exarnple 6: Polyarylene ether ketone sulfone copolymer of 2,2'-bis(4-hydroxybenzoyl)-biphenyl, 4,4'-dihydroxydiphenylsulfone and 4,4'-dichlorodiphenylsulfone In accordance with the general procedure of Example 1, a polyether ketone sulfone is prepared from 2,2'-bis(4-hydroxybenzoyl)biphenyl (0.0400 mol), 4,4'-dihydroxydiphenylsulfone (0.3615 mol) and 4,4'-dichlorodiphenylsulfone (0.400 mol) with potassium carbonate (0.4200 mol). Reaction conditions: 1 h/250C, 1 h/275C and 4 h 20 min/280C. The resultant polymer (red. viscosity = 0.60 dl/g) has a glass transition temperatwre of 226C. The solubility of the polymer in methylene chloride is more than 25%.

Examples 7-14: The Examples listed in the following Table are carried out in accordance with the general procedure of Example 1.

- 17- 2~3~478 o c~ E~ _ ~ EV v~ oo o ~:i ~ ~ ~.
C .Co .~ l- o V ov V

~o ~ ~oo C~ ~ _ _ :E ~ DO ~o ,~, E ~o E .E E ~ E ~, E E, E
13 ~ ~ o ~ O î~l d~o ~,,o r~

2039~78 ~' ,~
C7~
.:i ~ o o ,o . I_ ~ V C~ C' E~3 ..~ ~ ~ ~o ~ ~ ~o 8 _~ _ ~ ~ .~

.c ~; E . E ~ E E E ~ E ~ E E E E
'~ O ~ O ~ O c~ O ~ 'D O ~i O 'v~ o ~o ~~ Oo ~ ~1 ~
. ~ O
X

~rl ~

::~ c) ~ A A
0~
c 3 ~ cs~

~ E c~
~ _ ~ ~ o .~-~_ C~ ~ V ov~ ~
C~ ~ ~ `1 ~ ~ ~ ~o ~ ~ ~ .c ~ .-. o 2~39478 ~ ~ C~
O ~ A A
.C~

E ~ o ~

~ o o ~ O C~ O
o o ~ o oo o ~
.~ ~ ~ I_ oo ~ U~ oo ~ $ ~ ~ . ~
~ _ _ ~t _ ~ ~

.' ~E E ~ E E E ~ E " E ~ E ~ E E E
o Dg ~ ~ O DO
O ~oO ~~ ~ ~1 d~ ~ ~
_~ ... _._ ~ _.

Example 6: The copolymer prepared according to Example 3 is added in the form of a 2() and 30 parts by weight solution in methylene chloride to a mixture consisting of 50 parts by weight of tetraglycidyl diaminodiphenylmethane and 50 parts by weight of triglycidyl-p-aminophenol and the solvent is removed under vacuum. After addition of 50 parts by weight of p-diaminodiphenylsulfone the mixture is cured for 2 hours at 1 60C and for 2 hours at 210~C. Test specimens are cut from the sheet so obtained and the fracture toughness by bend notch according to ASTM E 399 are dete}mined.

The following values are obtained:

Addition of thermoplastic fracture toughness (parts by weight) Jlm2)

Claims

1. A polyarylene ether ketone which is soluble in halogenated hydrocarbons and has a reduced viscosity of 0.1 to 2.0 dl/g, measured at 25°C using a 1 % solution of the polymer in N-methylpyrrolidone (NMP), which polyarylene ether ketone contains, based on the total number of structural units present in the polyarylene ether ketone resin, 1-100 mol %
of a recurring structural unit of formula I or II

(I), (II) and 99-0 mol % of a recurring structural unit of formula III

(III) wherein R1 is C1-C4alkyl, C1-C4alkoxy, C6-C12aryl, C2-C4alkenyl or halogen, and m is 0 or an integer from 1-4, R2 is C1-C4alkyl, C1-C4alkoxy, C6-C12aryl or halogen, and n is 0 or an integer from 1-4, Ar1 is a divalent radical of a bisphenol compound and Ar2 is a divalent radical of an activated dihalo compound which is able to enter into a nucleophilic exchange reaction.

2. A polyarylene ether ketone according to claim 1, wherein Ar1 in the structural units of formulae I and III is preferably a group of formulae IVa to Vg (IVa), wherein a is 0 or 1, (IVb), (IVc), (IVd), wherein b is 1 or 2, (IVe), (IVf) or (IVg) wherein Z is -CO-, -SO2-, -SO-, -S-, -O-, , ,-CH2-, or , Q is a direct bond, -O-, -CH2- or -CO-, R3 is C1-C4alkyl and R4 is C1-C4alkyl or phenyl, which groups are unsubstituted or substituted by one or more C1-C4alkyl or C1-C4alkoxy groups or halogen atoms.

3. A polyarylene ether ketone according to claim 1, wherein Ar2 in the structural units of formulae II and III is preferably a group of formulae IVh to IVl (IVh), wherein c is 0 or 1, (IVi), wherein d is 2 or 3 and X is -CO-, -SO2- or -SO-, (IVj), (IVk) or (IVl), which groups are unsubstituted or substituted by one or more C1-C4alkyl or C1-C4alkoxy groups or halogen atoms.

4. A polyarylene ether ketone according to claim 1, wherein R1 is C1-C4alkyl, C1-C4alkoxy, C6-C12aryl, C2-C4alkenyl or halogen, and m is 0 or an integer from 1-4, R2 is C1-C4alkyl, C1-C4alkoxy, C6-C12aryl or halogen, and n is 0 or an integer from 1-4, Ar1 is a group of formulae IVa to Ve (IVa), wherein a is 0 or 1, (IVb), (IVc), (IVd), wherein b is 1 or 2, (IVe), wherein Z is -CO-, -SO2-, -SO-, -S-, -O-, , , -CH2- or , which groups are unsubstituted or substituted by one or more C1-C4alkyl or C1-C4alkoxy groups or halogen atoms, and Ar2 is a group of formula IVh or IVli (IVh), wherein c is 0 or 1, (IVi), wherein d is 2 or 3 and X is -CO-, -SO2- or -SO-, which groups are unsubstituted or substituted by one or more C1-C4alkyl or C1-C4alkoxy groups or halogen atoms.

5. A polyarylene ether ketone according to claim 1, which contains 5-100 mol % of a recurring structural unit of formula I or II and 95-0 mol % of a recurring structural unit of formula III.

6. A polyarylene ether ketone according to claim 1, wherein Ar1 in the structural units of formulae I and III is a radical of formula , , , , , or .

7. A polyarylene ether ketone according to claim 1, wherein Ar1 in the structural units of formulae II and III is a radical of formula ,, or .

8. A polyarylene ether ketone according to claim 1, wherein Ar2 in the structural units of formulae II and III is a radical of formula , or .

9. A polyarylene ether ketone according to claim 1, wherein Ar1 and Ar2 in the structural units of formulae I, II and III are the radical .

10. A process for the preparation of a polyarylene ether ketone according to claim 1, which comprises (a) polycondensing a dihalo compound of formula V

(V), wherein R1, R2, m and n are as defined in claim I and Hal is halogen, preferably fluoro or chloro, or a mixture of a dihalo compound of formula V and a dihalo compound of formula VI present therein in an amount of up to 99 mol %
Hal-Ar2-Hal (Vl), wherein Ar2 is as defined in claim 1 and Hal is halogen, preferably fluoro or chloro, in equimolar amounts, with a diphenol of formula VII
HO-Ar1-OH (VII), or the alkali metal phenolate or alkaline earth metal phenolate thereof, wherein Ar1 is as defined in claim 1, in the presence of alkali and in an aprotic solvent, or (b) polycondensing a compound of formula VIII

(VIII), or the alkali metal phenolate or alkaline earth metal phenolate thereof, wherein R1, R2, m and n are as defined in claim 1, or a mixture of a compound of formula VIII and a diphenol of formula VII present therein in an amount of up to 99 mol % in equimolar amounts, with a dihalo compound of formula VI, in the presence of alkali and ill an aprotic solvent, until the polyarylene ether ketone has a reduced viscosity of 0.1 to 2.0 dl/g, measured at 25°C using a 1 % solution of the polymer in NMP.

11. A process for the preparation of a compound of formula V or VIII according to claim 8, which comprises heating a compound of formula IX

(IX), wherein R1, R2, m and n are as defined for formula V or VIII, and Y is halogen or C1-C4alkoxy, preferably fluoro, chloro or C1-C2alkoxy, most preferably fluoro or -OCH3, in the presence of a 0.5 to 3-fold amount by weight of copper powder, based on the amount by weight of the compound of formula IX, to a temperature in the range from 150-250°C, to give a compound of formula X

(X) wherein R1, R2, m, n and Y are as defined for formula IX, and, if Y is C1-C4alkoxy, reacting said compound with AlCl3, in an organic solvent, with stirring, in the temperature range of ca. 60-160°C, to a compound of formula VIII, using 3-6 mol of AlCl3 per 1 mol of compound of formula X.

12. A solution containing 1 to 75 % by weight, based on said solution, of a polymer as claimed in claim 1, dissolved with an organic solvent.

13. A moulded article, coating or sheet comprising a polyarylene ether ketone as claimed in claim 1.

14. A modified thermoplastic and duromer matrix resin comprising as modifying component a polyarylene ether ketone as claimed in claim 1.