CA2029713A1

CA2029713A1 - Ordered polyether ketone sulfones

Info

Publication number: CA2029713A1
Application number: CA002029713A
Authority: CA
Inventors: Rudolf Pfaendner; Friedrich Stockinger
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1989-11-14
Filing date: 1990-11-09
Publication date: 1991-05-15
Also published as: EP0428484A2; EP0428484A3; JPH03188125A

Abstract

Ordered polyether ketone sulfones Abstract of the Disclosure Ordered polyether ketone sulfones which contain, based on the total amount of structural units present in the polymer, 40-100 mol% of a recurring structural unit of formula I

(I) and 0-60 mol% of a recurring structural unit of formula II

Description

2 ~ '7 ~ ~
- 1 . .

K-17827/+/C~GM 362 ~ . , ,, C)rdered polyether ketone sulfones The present invention relates to specific ordered polyether ketone sulfones, to a process for their preparadon, and to the use thereof.

Polyarylene ether ketones are partially crystalline industrial moulding materia1s with good mechanical properties and having very good resistance to almost aU organic solvents.
Polyarylene ether sulfones are less resistant to organic solvents, but have higher glass transition temperatures than corresponding ketones. A combination of properties is obtained with polymers which contain both groupings, i.e. polymers which, compared with polyarylene ether ketones, have a somewhat reduced solvent stability but have enhanced themlal properties.

Such known polyether ketone sulfones are described e.g. by C.K. Sham et al., in British Polymer Journal 20,149-155 (1988). They are obtained by reacting a diphenol with a mixture of two halogen derivatives, for example from 4,4'~ichlo~diphenylsulfone and 4,4~ifluorobenzophenone, in the presence of a basic catalyst. In the polymers soobtained, the ketone and sulfone groups are randomly distributed along the polymer chain.
In Polymer Prepr. ~A.CS.), 26(2), 277-280 (1985), S.D. Wu et al. ckscribe in addition to random polyether ketone sulfones also segmented copolymers which are pepared from hydroxyl-terrninated polysulfone oligomers and 4,4t-difluorobenzophenone in the presence of a base. It is only possibk to process these polymers at temperatures above the melt temperature, i.e. at well above 300C.

Thc present inventdon has for its object to provide polyether ketone sulfones which are suitable for use as industnal moulding matedals and which have enhanced properdes compared with known polyether ketone sulfones. Surpdsingly, this object can be achieved by synthesising specific ordered polyether ketone sulfones.

Accordingly, the present invendon relates to ordered polyether ketones which contain, based on the total amount of structural units present in the polymer, 4~100, preferably 50-100, mol% of a recu~Ting structural unit of formula I

~9~3 ~o~o~s~o~o~ a) .

and 0-60, preferably 0-50, mol% of a recurring structural unit of formula II
~OArl-O-Ar2 ~ (Il) :
wherein Arl is a group of formula IIIa or IIIb ~X~X~ (ma), d ~X ~X~d (IIIb), and Ar2 is a group of formulae IVa-IVd (IVa), ~ (IVb), (IVc)or ~z~- (IVd), in which X is -CO~, -SO2- or -S~ and Z is a direct bond, -CHr, -C(CH3)2-, -C(CF3)2-, ' -CO-, -SO2-, -S~, -S- or ~-, R is a Cl-C4alky~1 group, a is 0, 1 or 2, b is 2 or 3, and c is 1, 2 or 3, and d is a whole number from O to 4, e is a whole number from O to 5, and f is a whole number from O to 3.

The polymers of this invendon are characterised by the structural unit of formula I in which the ketone and sulfone groups are predominantly distributed in ordered manner, i.e.
alternately distributed, along the polymer chain. They have better mechanical properties than comparable random polymers and better thermal properties (higher glass transidon ~` '''~' ""~ " r,` , , ; ~: ,, " . , :; ~

3 ~ 7 ~ 3 temperature) and are more readily processed (lower processing temperature) than segmented copolymers. According to DSC investigations, the copolymers of this invention are essentially amorphous compounds. The properties of a polymer normally derive from the structure, i.e. the bonds and units employed. The ordered polymers of this invention are based on the same kind and number of structures as the random polymers. It is therefore surprising that the polymers of this invention have better properties.
The structural unit of formula I can be prepared, for example, by polycondensation of 4,4'-bis(4"-hydroxyphenoxy)diphenylsulfone and 4,4'-dihalobenzophenone or of 4,4'-bis(4"-hydroxyphenoxy)benzophenone and 4,4'-dihalodiphenylsulfone. The starting compounds, 4,4'-dihalobenzophenone and 4,4-dihalodiphenylsulfone, are comrnercially available. 4,4'-Bis(4"-hydroxyphenoxy)diphenylsulfone can be prepared, for example, from 4,4'-dich10rodiphenylsulfone and hydroquinone monomethyl ether, as described by P.M. Undley et al. in A.C.S. Symp. Ser. 282, 31-42 (1985). 4,4'-bis(4"-hydroxy-phenoxy)benzophenone can be prepared, for example, from p-tert-butoxyphenol and 4,4'-dichlorobenzophenone according to German Offenlegungsschrift 3 700 809, andsubsequent ether cleavage.

The structural units of formula II can also be prepared in the same way as the structural units of formula I.

The present invention also relates to a process for the preparation of the novel polyether ketone sulfones by (al) polycondensing either a dihalo derivative of formula V

H~l ~ }~ }H~l (V) with a diphenol of formula VI

HO~,}o~S(~O ~OH (Vl) or a dihalo derivative of formula VII
H~l ~}S02~}H I (VII) with a diphenol of formula vm - 4 - 2 ~ 7 ~ 3 NO~ }~o~OH (VIII) in the presence of an aLlcaline catalyst in a polar aprodc solvent, and, if appropriate, (a2) polycondensing a dihalo derivadve of formula IX
Hal-Arl-Hal (IX) with a diphenol of formula X
HO-Ar2~H (X) in the presence of an aLlcaline catalyst in a polar aprotic solvent, and (b) subsequently in an optional additional step further polycondensing the reaction product of reaction (al) with the reacdon product of the reacdon (a2) with each other in the presence of an alkaline catalyst in a polar aprotic solvent, in which formulae V, VII and IX above Hal is halogen, preferably fluoro or chloro, Arl and Ar2 are as defined above, the reladve amounts of the reaction product (al) and the reacdon product (a2) being so chosen that the resultant copolyrner contains the above defined amounts of the structural units of formula I and formula II.

In place of the dipheno!s of formulae VI or VIII and X it is also possible to use the corresponding alkali metal or alkaline earth metal phenolates, for example the potassium or calcium phenolates.
. . .
The polycondensation is ordinarily carried out using approximately e~quimolar amounts of the compounds of formulae V and VI or VII and VIII or XI and X. Approximately equimolar amounts will be understood as meaning in this context a molar ratio of 0.8:1.0 to1.0:0.8,preferablyof0.95:1.0to1.0:0.95.

The synthesis of the copolymers which contain structural units of formula I as well as structural units of formula II may be carried out not only in stadsdcal but also in segmented manner (block copolymers). When synthesising random polymers, typically a mixture of phenols VIII and X is condensed with one or more dihalo derivatives of formula IX.

A block copolymer is prepared by synthesing reacdon products of reaction (al) carrying hydroxyl or phenolate end groups and the reacdon products of reaction (a2) carrying halogen end groups or conversely. This is done in known manner by using a suitable excess of the diphenol or of the dihalo derivadve in the synthesis of the reacdon product -s 2~2~

(al) or (a2) respectively. A suitable excess of one of the educts is typically an excess of ca. 1 to 50 mol%. The arnount of the excess is governed in each case by the length of the block.

The alkaline catalyst used in the process of this invention is normally an alkali metal carbonate or aL~aline earth metal carbonate or a corresponding hydrogencarbonate such as sodium, potassium or calcium carbonate or hydrogencarbonate. However, other alkaline reagents such as sodium hydroxide, potassium hydroxide or calcium hydroxide may also be used.

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

The reaction is conveniently carned out at elevated temperature, preferably in the l~nge up to the reflux temperature of thc solvent, i.e. up to ca. 350C.

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

The compounds of formulae IX and X are known. Some are commercially available or can be prepared in known manner.

Illustradve examples of suitable compounds of formula IX are 4,4-dichloro- or 4,4'-difluorodiphenylsulfoxide or -diphenylsulfone, or 4,4' dichloro- or 4,4'-difluorobenzo-phenone, 4,4'-dichloroisophthalophenone and 4,4'-dichloroterephthalophenone.

Preferred compounds of formula IX are 4,4'-dichlorodiphenylsulfone and 4,4'-difluoro-be,nzophenone.

Illustrative examples of suitable compounds of formula X are hydroquinone, 4,4'-dihydroxybiphenyl, 2-phenylhydroquinone, 2,7 dihydroxynaphthalene, bisphenol A, bisphenol F, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfide, 4,4-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenyl-.. . .. . ...
: - :~ ,, - 6- 2 ~

sulfone or 2,2-bis(4'-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane and the corresponding Cl-C4alkyl-substituted derivatives such as 3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenylsulfone.

Preferred compounds of formula X are 4,4'-dihydroxydiphenylsulfone, hydr~quinone and 4,4'-dihydroxybiphenyl.

The polyether ketone sulfones of this invention preferably contain 75-100 mol% of a recurring structural unit of formula I and ~25 mol% of a recurring structural unit of formula IL

Particularly preferred polyether ketone sulfones contain 90 100 mol% of a recurring shuctural unit of formula I and 0-10 mol% of a recurring structural unit of formula II.

The preferred meaning of X in formulae lIIa and IIIb is -CO- or -SOr. ' The preferred meaning of Z in formula IVd is a direct bond, -C(CH3)2-, -CO, -SO2-, -S-or -O .

The preferred meaning of a in formula llIa is 0.
: . . .
The phenylene groups in formulae IIla, IIIb, IVa, IVb and IVd are preferably 1,3- and, more particularly, 1,4-phenylene groups. The substituents R in formulae IIIa, IIIb and IVa to IVd may be s~aight chain or branched. Exemplary of suitable substituents are ethyl, n-propyl, isopropyl, n-butyl and, preferably, methyl.

The preferred meaning of d in formulae IIIa, IlIb and IVa, IVb and IVd is 2 or 0. The preferred meaning of e in formula IVb is 1 or 0. The preferred meaning of f in formula IVc is 3 or 0. The radicals of formulae lIIa, IIIb and IVa to IVd, wherein d, e and f are each 0, are most preferred.

The polyether ketone sulfones of this invention preferably have a reduced viscosity of 0.1 to 2.0 dVg, rnost preferab1y of 0.3 to 1.5 dUg, measured at 25C in a 1% solution (1 g of polymer in 100 ml of N-methylpyrrolidone).

The polyether ketone sulfone resins of this invention can be used in the conventional 7 2 ~

manner for thermoplastics and processed, for example, to mouldings or sheets, or they can be used as matrix resins, adhesives or coating compounds. Prior to the processing of the polyether ketone sulfone resins obtained in the form, for example, of moulding powders, melts or solutions, customary modifiers such as fillers, pigments, stabilisers or reinforcing agents such as carbon, boron or glass fibres, can be added. The polyether ketone sulfones of this invention can be processed together with other thermoplastics.

Preferably the polyether ketone sulfones of this invention are suitable for use as matnx resins for the production of fibrous composite systems, for which utility it is possible to use as reinforcing fibres the fibres conventionally used for reinforcing industrial moulding materia1s. These fibres may be organic or inorganic fibres, natural fibres or syn thetic fibres such as aramide fibres, and be in the form of fibre bundles, as oriented or non- oriented fibres or as continuous filaments. The reinforcing fibres used are typically glass, asbestos, boron, carbon and metal fibres.

A further preferred utility of the polyether ketone sulfones is for modifying other plastics materials. These plastics materials can be in principle thermoplasdcs or duromers. The modificatdon of heat-curable resins, especially of epoxy resins or bismaleimides, is of particu1ar importance. Such polymer systems which are adapted to special needs are disclosed, for example, in US patent specification 3 530 087. Such systems are of special importance as matrix resins which are used for the producdon of sandwich structures.
Normally ca 5-100, preferably 10-80, parts by wdght of polyether ketone sulfone are used per 100 parts by weight of plastdcs rnaterial to be modified.

Hence the present invention also relates to moulW ardcles, sheets, coatings or bonds containing a novel polyether ketone sulfone as well as fibrous composite structures containing reinforcing fibres and, as matrix resin, a novel polyether ketone sulfone.

The invention further relates to the use of the polyether ketone sulfones for modifying plastics materials.

The unexpectedly good mechanical and thermal properties of the polyether ketone sulfones of the invention merit special mention.

-8- 2~7~ 3 Example 1: In a round flask equipped with stirrer and inert gas inlet, a mixture of 21.72 g (0.0500 mol) of 4,4'-bis(4"-hydroxyphenoxy)diphenylsulfone,49.57 g of diphenylsulfone, 8.12 g (0.0588 mol) of potassium carbonate and 59 g of xylene are heated under nitrogen at a bath temperature of 200C, and a mixture of xylene/water is removed by disdlladon.
Towards the end of the disdllation, a vacuum (0.6 kPa) is applied briefly. Then 10.95 g (0.0502 mol) of 4,4'-difluorobenzophenone are added to the reaction mixture and the temperature is raised to 250C over 25 minutes and kept for 1 hour. The temperature is i ~ ;
subsequently raised to 275C over 30 minutes and then further raised to 320C. This temperature is kept for 3 hours, during which time the reaction mixture becomes increasingly viscous.
:
The cooled reaction mixture is removed from the flask, pulverised and, after addidon of acetic acid, extracted first with water and then with acetone. The purified polymer is then dried in a vacuum drier up to a temperature of 240C. The polyether ether ketone sulfone -so obtained has a reduced viscosity (1 % of polymer in NMP at 25C) of 0.53 dl/g.

A sample of the polymer is ground and pressed to a transparent film in a sheet press (280C, 3 t,5 min). The film (glass transition temperature: 174C, DSC) has a tensile strength of 65 N/mm2 and an elongation at break of 10.0 % (DIN 53 455). .

Example 2: In accordance with the procedure described in Example 1, a copo1ymer of 0.0751 mol of 4,4'-bis(4-hydroxyphenoxy)diphenylsulfone,0.0252 mol of 4,4'-dihydroxy-diphenylsulfone and 0.1001 mol of 4,4'-difluorobenzophenone with 0.1072 mol of potassium carbonate is prepared (reacdon conditions 1 h/228C, 1 h/250C, 1 h/282C and 2 h/305C). The polymer has a reduced viscosity (1 g in 100 ml of NMP) of 0.70 dVg and a glass transidon temperature of 174C

Example 3: In accordance with the procedure described in Example 1, a copolymer of 0.0251 mol of 4,4'-bis(4-hydroxyphenoxy)diphenylsulfone, 0.0251 mol of 4,4'-dihydroxy-diphenylsulfone and 0.0502 mol of 4,4'-difluorobenzophenone with 0.0542 mol of potassium carbonate is prepared (reacdon condidons 1 h/222C, 1 h/246C, 1 h/278C and 3 h/305C). The polymer has a reduced viscosity (I g in 100 ml of NMP) of 0.25 dVg and a glass transidon temperature of 158C

9 2~2~

Example 4: In accordance with the procedure described in Example 1, a copolymer of 0.0501 mol of 4,4'-bis(4-hydroxyphenoxy)diphenylsulfone, 0.0251 mol of 4,4'-dichloro diphenylsulfone and 0.0251 mol of 4,4'-difluorobenzophenone with 0.0501 mol of potassium carbonate is prepared (reaction conditions 1 h/226C, 1 h/253C, 1 h/281C and 2 h/302C). The polymer has a reduced viscosity (1 g in 100 ml of NMP) of 0.51 dVg and a glass transition temperature of 187C.

Claims

1. An ordered polyether ketone sulfone which contains, based on the total amount of structural units present in the polymer, 40-100 mol% of a recurring structural unit of formula I

(I) and 0-60 mol% of a recurring structural unit of formula II
(II) wherein Ar1 is a group of formula IIIa or IIIb (IIIa), (IIIb), and Ar2 is a group of formulae IVa-IVd (IVa), (IVb), (IVc) or (IVd), in which X is -CO-, -SO2- or -SO- and Z is a direct bond, -CH2-, -C(CH3)2-, -C(CF3)2-, -CO-, -SO2-, -SO-, -S- or -O-, R is a C1-C4alkyl group, a is 0, 1 or 2, b is 2 or 3, and c is 1,

2 or 3, and d is a whole number from 0 to 4, e is a whole number from 0 to 5, and f is a whole number from 0 to 3.

2. A polyether ketone sulfone according to claim 1, which contains 75-100 mol% of a recurring structural unit of formula I and 0-25 mol% of a recurring structural unit of formula I.

3. A polyether ketone sulfone according to claim I, which contains 90-100 mol% of a recurring structural unit of formula I and 0-10 mol% of a recurring structural unit of formula II.

4. A polyether ketone sulfone according to claim 1, wherein X in formulae IIIa and IIIb is -CO- or -SO2-.

5. A polyether ketone sulfone according to claim 1, wherein Z in formula IVd is a direct bond, -C(CH3)2-, -CO-, -SO2-, -S- or -O-.

6. A polyether ketone sulfone according to claim 1, wherein R in formulae ma, IIIb and IVa-IVd is methyl.

7. A polyether ketone sulfone according to claim 1, wherein d,e and f in formulae IIIa, IIIb and IVa-IVd are each 0.

8. A polyethcr ketone sulfone according to claim 1, which has a reduced viscosity of 0.1 to 2.0 dl/g, measured at 25°C in a 1% solution (1 g/100 ml) in N-methylpyrrolidone.

9. A polyether ketone sulfone according to claim 8, which has a reduced viscosity of 0.3 to 1.5 dl/g, measured at 25°C in a 1 % soludon (1 g/100 ml) in N-methylpyrrolidone.

10. A process for the preparation of a polyether ketone sulfone as claimed in claim 1, which comprises (a1) polycondensing either a dihalo derivative of formula V

(V) with a diphenol of formula VI

(V1) or a dihalo derivative of formula VII
(VII) with a diphenol of formula VIII

(VIII) in the presence of an alkaline catalyst in a polar aprotic solvent, and, if appropriate, (a2) polycondensing a dihalo derivative of formula IX
Hal-Ar1-Hal (IX) with a diphenol of folmula X
HO-Ar2-OH (X) in the presence of an alkaline catalyst in a polar aprodc solvent, and (b) subsequendy in an optional additional step further polycondensing the reacdon product of reaction (a1) with the reaction product of thc reaction (a2) with each other in the presence of an alkaline catalyst in a polar aprotic solvent, in which formulae V, VII and IX above Hal is halogen, Ar1 and Ar2 are as defined above, the relative amounts of the reaction product (a1) and the reaction product (a2) being so chosen that the resultant copolymer contains the above defined amounts of the structural units of formula I and formula II.

11. A process according to claim 10, wherein a corresponding alkali metal or alkaline earth metal phenolate is used in place of the diphenol of formula VI or VIII and X.

12. A moulded article, sheet, coadng or bond which contains a polyether ketone sulfone as claimed in claim 1.

13. A composite fibrous structure which contains reinforcing fibres and, as matrix resin, a polyedher ketone sulfone as claimcd in claim 1.

14. A method of modifying plasdcs materials by admixing a polyether ketone sulfone as claimed in claim 1 with said plasdcs material.