CA2047381A1 - Polyarylene ethers containing tetraphenylethylene units - Google Patents
Polyarylene ethers containing tetraphenylethylene unitsInfo
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- CA2047381A1 CA2047381A1 CA002047381A CA2047381A CA2047381A1 CA 2047381 A1 CA2047381 A1 CA 2047381A1 CA 002047381 A CA002047381 A CA 002047381A CA 2047381 A CA2047381 A CA 2047381A CA 2047381 A1 CA2047381 A1 CA 2047381A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
Abstract
Polyarylene ethers containing tetraphenylethylene units Abstract Polyarylene ethers which contain, based on the total amount of structural elements present in the polymer, 2-100 mol% of one or more recurring structural elements of the formula Ia, Ib or Ic (Ia), (Ib), (Ic) and 0-98 mol% of a recurring structural element of the formula II
Description
7~
.
Polvarvlene ethers containin~ tetraphenvlethYlene unlts The invention relates to novel, specified polyarylene ethers containing tetraphenylethylene units, to a process for their preparation, and to their use, and to specific diphenol isomer mixtures as the monomer components for the synthesis of polyarylene ethers and to a process for the preparation of these isomer mixtures.
Polyarylene ethers are industrial materials having very good mechanical and therrnal properties and high resistance to conventional organic solvents. For some applications, however, this solvent resistance is undesired. In particular, the modification of thermoset matrix resins requires the use of the most concentrated polymer solutions possible in conventional organic solvents. The object of the present invention was therefore to provide polyarylene ethers having very good solubility in a wide range of organic solvents.
This object is achieved by using bis(4-hydroxyphenyl)diphenylethylene as a monomer component.
The invention accordingly relates to a polyarylene ethers which contain, based on the total amount of structural elements present in the polymer, 2-100 mol% of one or more recurring structural elements of the forrnula Ia, Ib or Ic ¦ O O-Ar1~ _ _ \~ (Ia), )=~ (Ib), L ~ ~ O-Ar~ t 20~7~1 _ o O-Ar1- _ and 0-98 mol% of a recurring structural element of the formula II
~Ar2~ ]
in which Ar2 is a radical of the formula IIIa-IIIg which is unsubstituted or substituted by one or more Cl-C4alkyl groups, Cl-C4aL~coxy groups or halogen atoms:
(Illa), ~ (IIlb), (IIIC), ~3 Z ~ Z ~ (IIId), ~3Z ~3Z ~ (IIIe).
~0~
~IIIg) (III~
where a and b are zero or 1, Z is -CO-, -SO2-, -SO-, -S-, -O-, -C(CH3)2-, -C(CF3)2-, -CH2-or -C(CH3)(C6Hs)-, and Q is -CH2-, -O-, -C(=O)- or a d;rect bond, and Arl is a radical of the formula IVa, IVb or IVc which is unsubstituted or substituted by one or moreCl-C4aLlcyl groups, Cl-C4aLtcoxy groups or halogen atoms:
X ~ X~ (IVa), X ~ X~3 (IVb), CN
~ (IVc), where c is zero, 1 or 2, d is 2 or 3, and X is -CO-, -SO2- or -SO-.
Polyarylene ethers containing a tetraphenylethylene structure are hitherto unknown in the literature.
The only known po!ymers which contain a tetraphenylethylene unit are polyamides and polyimides (Y. Oishi et al., Pol. Mat. Sci. Eng. 1989, 60, 757). The polymers described therein are synthesised starting from 4,4'-diaminotetraphenylethylene; depending on the 4~ Z~0~
coreactant, they are soluble in aprotic, dipolar solvents, such as N-methylpyrrolidone, dimethyl sulfoxide, dimethylacetarnide or pyridine. However, solubility properties of this type are in no way excellent for polyamides or polyimides since other known polymers, for example the polyimides of US Patent 3 856 752 and European Patent Application 92 524, which are derived from diaminotrimethylphenylindane have significantly better solubilities. Further polyamides containing tetraphenylethylene units are described in J. of Polymer Science, Part A, 1991, Vol. 29, 55-61.
It ~vas therefore surprising that the polyarylene ethers according to the invention based on tetraphenylethylene units have particularly good solubilities in conventional organic solvents, such as chlorinated hydrocarbons, cyclic ketones or cyclic ethers.
Other known polyarylene ethers whose monomer component likewise contains four phenyl groups, for example the polyarylene ethers of German Patent Application 3 825 148 which are derived from 4,4'-dihydroxy-3,3'-diphenylbiphenyl do not have the excellent solubility properties of the present compounds.
The polyarylene ethers according to the invention can be prepared by polycondensing one or more diphenols of the forrnula Va, Vb or Vc HO OH HO
)=~ (Va), )=~ (Vb), OH
HO~ ,~OH
Il (Vc) ~3 7~
and, if desired, a diphenol of the fonnula VI
HO-Ar2-OH (VI) with a dihalogen derivative of the forrnula VII
Hal-Arl-Hal (VII) in the presence of an aLlcaline catalyst in a polar aprotic solvent, Arl and Ar2 being as de~ned above, and Hal being halogen, in particular fluorine or chlorine, and the relative amounts of the diphenol of the ~ormula Va IO Vc and of the diphenol of the ~onnula VI
being selec~ed in such a manner that the resultant copolymer contains the amounts defined in claim 1 of the structural elements of the formulae I and II.
The diphenols of the formula V or VI may also be replaced by the corresponding aLkali or alkaline earth metal phenoxides, for example potassium phenoxide or calcium phenoxide.
The polycondensation is usually carried out in approximately equimolar ratios of the diphenols of the forrnulae V and, if used, VIi based on the dihalogen derivative of the formula VII. Approximately equimolar arnounts is taken to mean a molar ratio of 0.8:1.0 to 1.0:0.8; a molar ratio of 0.95:1.00 to 1.00:0.95 is preferred.
The copolymers containing both structural elements of the ~orrnula I and structural elements of the fonnula II can be prepared either in a random manner or in a segmented manner (block copolymers). In the random-type synthesis, a mixture of the phenols V and VI is, for example, condensed with one or more dihalogen derivatives of the fonnula VII.
To prepare a block copolymer, products of the reaction of a diphenol of the forrnula V and a dihalogen derivative of the fonnula VII containing hydroxyl or phenoxide end groups and products of the reaction of a diphenol of the formula VI and a dihalogen derivative of the formula VII containing halogen end groups, or vice versa, are synthesised. This is achieved, as is known, by using an appropriate excess of the diphenol or of the dihalogen derivative in the preparation of the reaction product. An appropriate excess of one of the starting materials is, for example, an excess of from about 1 to 50 mol%. The extent of the excess in each case deterrnines the block length.
- 6 - ;20~
The aL~aline catalyst used in the process according to the invention is generally an alkali metal carbonate or aL~caline earth metal carbonate or a corresponding bicarbonate, such as sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, calcium carbonate or calcium bicarbonate; however, it is also possible to employ other alkaline reagents, such as sodium hydroxide, potassium hydroxide or calcium hydroxide.
Examples of polar aprotic solvents which can be employed for the preparation of the polyarylene ether resins according to the invention are dimethyl sulfoxide, dimethylacetamide, diethylacetamide, tetramethylurea, N-methylcaprolactam, N-methylpyrrolidone and pre~erably diphenyl sulfone.
The reaction is expediently carried out at elevated temperature, preferably up to the reflux temperature of the solvent, for example up to about 350C.
It is frequently advisable concomitantly to use an entrainer, for example chlorobenzene, xylene or toluene, in order to facilitate azeotropic removal from the reaction mixture of the water formed during the reaction.
The compounds of the formula VII are known. Some are commercially available and some can be prepared in a known manner.
Examples of suitable compounds of the formula VII ale 4,4'-dichloro- or4,4'-difluorodiphenyl sulfoxide or-diphenyl sulfone, 4,4'-dichloro- or 4,4'-difluorobenzophenone, 4,4'-dichloroisophthalophenone and 4,4'-dichloroterephthalophenone, or 2,6-difluorobenzonitrile or 2,6-dichlorobenzonitrile.
Preferred compounds of the formula VII are 4,4'-difluorobenzophenone and, in particular, 4,4'-dichlorodiphenyl sulfone.
Compounds of the formula VI are likewise known and commercially available. Examples of suitable compounds of the formula VI are hydroquinone, 4,4'-dihydroxybiphenyl, 2-phenylhydroquinone, 2,6- and 2,7-dihydroxynaphthalene, bisphenol A, bisphenol F, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone and 2,2-bis(4'-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, and the corresponding 204'73Bl C~-C4alkyl-substitu~ed derivatives, for example 3,3',5,5'-tetrarnethyl-4,4'-dihydroxydiphenyl sulfone.
Further suitable compounds are: 2,2'-dihydroxybiphenyl, 9,9-bis(4'-hydroxyphenyl)fluorene and 6,6'-dihydroxy-3,3,3',3'-tetramethyl- 1, l '-spirobiindane.
Preferred compounds of the formula VI are 4,4'-dihydr~xybiphenyl, 4,4'-dihydroxybenzophenone, hydroquinone and bisphenol A.
A particularly preferred compound of the formula VI is 4,4'-dihydroxydiphenyl sulfone.
The diphenols of the formulae Va, Vb and Vc are known or can be prepared in a known manner. A suitable synthetic route for the preparation of 1,2-bis(4'-hydroxyphenyl)-1,2-diphenylethylene is descAbed by R.N. Iyer and K.V.B. Rao in Ind. J. Chem., 16B, 601 (1978). The first step is conversion of 4-methoxybenzophenone into 4-methoxyphenylphenyldichloromethane using PCI5, followed by dimeAsation of the resultant dichloromethane derivative to give the tetrasubstituted ethylene derivative by heating in a solvent in the presence of elemental copper, and subsequently cleavage of the methyl ether by heating with potassium hydroxide in diethylene glycol. An analogous synthesis of tetraphenylethylene derivatives starting from unsubstituted benzophenone is described in Org. Synth. Coll. Vol. II, 573 (1943) and Coll. Vol. IV, 914 (1963~.
It has been found that particularly highly soluble polyarylene ethers are obtained if the diphenol component used in their preparation is a dihydroxytetraphenyl isomer mixture containing the diphenols of the formulae Va, Vb and Vc. This isomer mixture is novel and is likewise a subject-matter of the present invention. Particular preference is given to an isomer mixture containing the diphenols Va, Vb and Vc in a molar ratio of about 2:2:1.
The isomer mixture according to the invention is obtainable, for example, by cleaving the above-described tetraphenylethylenedimethyl ether in a highly acidic medium, forexample using HBr in glacial acetic acid, whereas the corresponding alkaline cleavage described in Ind. J. Chem. 1978, 16 B, 601 gives a mixture containing only two isomers.
This preparation process for the isomer mixture is likewise a subject-matter of the present invention.
The polyarylene ethers according to the invention preferably contain 15-100 mol%, in particular lO-100 mol%, of a recurring structural element of the formula I and 0-95 mol%, in particular Q-90 mol%, of a recurring structural element of the formula r[. Arl and Ar2 in the formulae I and Il are particularly preferably a radical of the forrnula 3 SO2~-, or Arl is a radical of the forrnula SO2~ and Ar2 is a radical of the formula ~3' Particularly preferred polyarylene ethers contain 25-100 mol% of a recurring structural element of the formula I and 0-75 mol% of a recurring structural element of the formula II.
In the formulae IVa and IVb, X is preferably -SO2-. The Arl group is preferably the radical ~3 SO2~ .
Z in the formulae IIId and IIIe is preferably -C(CH3)2-, -CO-, -SO2-, -S- or -O-.
The phenylene groups in the forrnulae IIIa to IIIe and IVa and IVb are preferably 1,3- and in particular 1,4-phenylene groups. Ihe aLIcyl or aLlcoxy substituents of the groups Arl and Ar2 may be straight-chain or branched. Examples of suitable substituents are ethyl, n-propyl, isopropyl, n-butyl and in particular me~yl, and the corresponding alkoxy groups. Preferred groups Arl and Ar2 are unsubstituted.
The Ar2 group of the compounds according to the invention is preferably a radical of the forrnula ,~
3 CH~;--or in particular {3 So2~3 .
The polyarylene ethers according to the invention preferably have a reduced viscosity of from 0.1 to 2.0 dVg, in particular from 0.3 to 1.5 dVg, measured at 25C on a 1% solution in N-methylpyrrolidone (1 g of polymer dissolved in lOQ ml of NMP).
The polyarylene ethers according to the invention can be employed in a manner conventional for thermoplastics and can be converted, for exarnple, into mouldings or films, or can be employed as matrix resins, adhesives or coating compositions. Before the polyarylene ethers, in the form, for example, of a moulding powder, melt or solution, are processed, conventional additives, for example fillers, pigments, stabilisers or reinforcing agents, such as carbon fibres, boron fibres or glass fibres, can be added. The polyarylene ethers according to the invention can also be processed together with other therrnoplastics.
The polyarylene ethers according to the invention are preferably suitable as ma~ix resins for the production of fibre-composite systems, suitable reinforcing fibres being the conventional fibres used to reinforce industrial materials. These may be organic or inorganic fibres, natural fibres or synthetic fibres, such as aramid fibres, and in the forrn of fibre bundles, oriented or nonoriented fibres or continuous fibres. Examples of reinforcing fibres used are glass fibres, boron fibres, carbon fibres and metal fibres.
A further preferred possible use of the polyarylene ethers according to the invention is for Z~3~.
- ]o -the modificadon of other plastics. These plastics may in principle be thermoplasdcs or thermosets. The moclification of thermocurable resins, in particular epoxy resins or bismaleimides, has achieved particulau importance. Polymer systems customised topardcular requirements of this type are described, for example, in US Patent 3,530,087.
Systems of this type have achieved particular importance as matrix resins for the producdon of composite elements. From about 5-1~0 parts by weight, preferably 10-50 parts by weight, of polyarylene ether are usually employed per 100 parts by weight of the plastics to be modified.
The present invention thus also provides mouldings, ~llms, coadngs or adhesive bonds containing a polyarylene ether according to the invendon, and fibre composites containing reinforcing fibres and, as matrix resin, a polyarylene ether according to the invendon.
Specific mendon should be made of both the very good solubility of the polymers according to the invention in a wide range of organic solvents (for example in chlorinated hydrocarbons, cyclic ketones and cyclic ethers) and the very good stability of these solutions. The polymers can thus be processed from solution, for example to give films, or introduced into other systems, for example matrix resins. Solutions containing 1-75 % by weight, preferably 5-40 % by weight, of the polyarylene ethers according to the inventdon in an organic solvent are thus a further subject-matter of the invention. Examples of preferred organic solvents are N-methylpyrrolidone, ~-butyrolactone, dimethylacetamide, dimethyl sulfoxide, cyclohexanone, cyclopentanone, 1,3-dioxolane and methylene chloride. Preferred soludons contain a polyarylene ether containing 5-100 mol%, preferably 10-100 mol%, of a recurring structural element of the forrnula I and 0-95 mol%, preferably 0-90 mol%, of a recurring structural element of the formula II.
The examples below illustrate the invention.
Example 1: SYnthesis of bis(4-hYdroxvphenyl)diphenylethylene (isomer mixture~
a) Bis(4-methoxyphenyl)diphenylethylene A mixture of 212.2 g (1 mol) of 4-methoxybenzophenone and 250 g of PCls in 1.5 l of dry benzene is refluxed ~or 1~ hours. The solvent is subsequently removed by distilladon in a rotary evaporator, 300 ml of benæne are added to the oily residue and the solvent is removed by distillation in a rotary evaporator. This addition and removal of solvent is 2~
repeated 3 times. 1.2 l of benzene and 427 g of copper powder are added to the oily residue which remains, and the mixture is ~efluxed for 24 hours. The hot reaction solution is filte~d, and the filtrate is evaporated in a rotary evaporator. The residue is then recrystallised from 650 ml of glacial acetic acid, the mother liquor is evaporated, and the residue is chromatographed on silica gel (hexane/toluene 3:2).
The amount of bis(4-methoxyphenyl)diphenylethylene obtained after recrystallisation from glacial acetic acid and chromatography is 156 g (79.4 %).
Elemental analysis:
Calculated for C28~242: C: 85.68 H: 6.16 Found: C: 85.02 H: 6.10 b) Bis(4-hydroxyphenYl)diphenylethylene (isomer mixture~
A suspension of 96.6 g (0.246 mol) of bis(4-methoxyphenyl)diphenylethylene in 486 ml of glacial acetic acid and 486 ml of 48 % HBr is refluxed for 24 hours. The reaction solution is cooled to room temperature and poured into 2 1 of water, and the precipitate is filtered off, dried and chromatographed on silica gel (hexane/EtOAc 2:1). Yield of bis(4-hydroxyphenyl)diphenylethylene (isomer mixture): 64.5 g (72 %).
Elemental analysis:
Calculated for C26H20O2: C: 85.69 H: 5.53 Found: C: 85.52 H: 5.54 Titration of the phenol groups: Titration in pyridine using 0.1 N tetrabutylammonium hydroxide in isopropanol: 5.46 meq/g (99.4 % of theoly).
HPLC: Nucleosil C-18 5 llm, CH3CN: H20 7:3 (1 mVmin);
Detection at 254 nm;
Isomer mixture comprising 3 isomers in the ratio 2:2:1.
Example 2: PolYether sulfone made from bis(4-hydroxYphenYl)diphenYlethvlene (isomer mixture) and 4~4'-dichlorodiphenYl sulfone A mixture of 18.34 g (0.0503 mol) of bis(4-hydroxyphenyl)diphenylethylene (isomer mixture), 59.31 g of diphenyl sulfone, 7.30 g (0.0528 mol) of potassium carbonate and 52 g of xylene is heated at a bath temperature of 200C under nitrogen in a round-bottomed flask fitted wi~h stirrer and protective-gas inlet, and a xylene/water mixture is removed by distillation. Towards the end of the distillation operation, a vacoum (2 mbar) is applied briefly. 15.38 g (0.0501 mol) of 4,4'-dichlorodiphenyl sulfone are then added to the reaction mixture, and the temperature is increased to 228C over the course of 15 minutes and kept there for 1 hour. The temperature is then increased to 250C (1 hour~ and subsequently to 280C. This temperature is maintained for 4 hours.
0.040 g (0.0014 mol) of 4,4'-dichlorodiphenyl sulfone are then added at this temperature.
This operation is filtered after 30 minutes and again after 15 minutes. After a further 30 minutes, the viscous reaction mixture is cooled briefly and removed from the reaction flask.
The solidified reaction mixture is powdered, then treated with acetic acid and extracted with water. The polymer is subsequently dissolved in methylene chloride, a small amount of insoluble material is filtered off, and the dissolved product is then precipitated using isopropanol. I he polymer purified in this way is then dried at 240C in a vacuum drying oven. A polyarylene ether sulfone prepared in this way has a reduced viscosity [1 % by weight of polymer in N-methylpyrrolidone (NMP) at 25C] of 0.29 dlJg. The glass transition temperature, determined by DSC, is 215C. The 13C NMR spectrum of thepolyether sulfone shows signals comparable to the monomer (Example lb~ in addition to the diphenyl sulfone unit. In particular, the unchanged presence of the C-C double bond can be seen. The particularly good solubility of this polymer can be seen from the table below.
Solvent NMP DioxaneMethylene chloride Example 1 + + +
+ = soluble Example 3: PolYether sulfone made from bis(4-hydroxvPhenYl)diphenylethylene (isomer mixture), 4,4'-dihvdroxydiphenvl sulfone (1:1) and 4,4'-dichlorodiphenyl sulfone A polymer is prepared analogously to Example 1 from 0.0501 mol of - 13 - 2~
bis(4-hydroxyphenyl~diphenylethylene, 0.0~01 mol of 4,4'-dihydroxydiphenyl sulfone, 0.1000 mol of 4,4'-dichlorodiphenyl sulfone and 0.1052 mol of potassium carbonate (reaction conditions: I h/250C, S h/280C). The resultan~ polymer has a reduced viscosity of 0.42 dl/g and a glass transition temperature of 203C and is soluble in tetrahydrofuran, dioxane, cyclohexanone, cyclopentanone and methylene chloride.
Example 4: Polyether sulfone made from bis(4-hydroxvphenyl)diphenYlethvlene (isomer mixturel,4~4'-dihvdroxydiphenyl sulfone (1:3~ and 4.4'-dichlorodiphenYI sulfone A polymer is prepared as in Exarnple 1 from 0.0504 mol of bis(4-hydroxyphenyl)-diphenylethylene, 0.1510 mol of 4,4'-dihydroxydiphenyl sulfone, 0.2003 mol of 4,4'-dichlorodiphenyl sulfone and 0.2104 mol of potassium carbonate (reaction conditions: 1 h/250C, 5 h/280C). The resultant polymer has a reduced viscosity of 0.46 dVg and a glass transition temperature of 221C and is more than 25 % soluble in methylene chloride.
Example 5: PolYether sulfone made from bis(4-hYdroxyphenvl)diphenYlethylene (isomer mixture)~ 4.4'-dihYdroxydiphenyl sulfone (l :9) and 4.4'-dichlorodiphenyl sulfone A polymer is prepared as in Example 1 frorn 0.0402 mol of bis(4-hydroxyphenyl)-diphenylethylene, 0.3610 mol of 4,4'-dihydroxydiphenyl sulfone, 0.4000 mol of 4,4'-dichlorodiphenyl sulfone and 0.420 of potassium carbonate (reaction conditions:
1 h/250C, 1 h/275C,7 h 10 min/280C). The resultant po~ymer has a reduced viscosity of 0.48 dl/g and a glass transition temperature of 223C and is more than 25 % soluble in methylene chloride.
Example 6. Polyether sulfone made from bis(4-hydroxYphenyl)diphenylethYlene (isomer mixture). 4~4'-dihvdroxYdiphenYI sulfone (1:19) and 4.4'-dichlorodiphenvl sulfone A polymer is prepared analogously to Example 1 from 0.0201 mol of bis(4-hydroxy-phenyl)diphenylethylene, 0.3811 mol of 4,4'-dihydroxydiphenyl sulfone, 0.4000 mol of 4,4'-dichlorodiphenyl sulfone and 0.420 mol of potassium carbonate (reaction conditions:
1 h/250C, 1 h/275C and 4 h/280C). The resultan~ polymer has a reduced viscosity of 0.49 dlJg and a glass transition temperature of 222C and is more than 25 % soluble in methylene chloride.
~0~7 Use Example 7 (polYether sulfone/epoxY blend) A polyether sulfone copolymer prepared as described in Exarnple 5, as a 20 or 30 parts by weight soludon in methylene chloride, is added to a mixture comprising 50 parts of tetraglycidyldiaminodiphenylmethane and 50 parts of triglycidyl-p-aminophenol, and the solven~ is removed in vacuo. 50 parts of p-diaminodiphenyl sulfone are added, and the mixture is cured in a mould for 2 hours at 160C and for 2 hours at 210C. Test specimens are cut out of a sheet produced in this way and used IO determine the flexural strength, outer fibre strain in accordance with ISO 178 and the fracture toughness (GlC by means of "bend notch" according to ASTM E 399).
The following very good values are obtained:
. _ ____ Parts of thennoplasdc . . _ _ . .. _ Flexural strength [N/mm2~: 166 170 Outer fibre strain [% ]: 6.7 6.5 Fracture toughness [J/m2]: 171 300 Example 8: Polyether ketone made from bis(4-hydroxvphenyl)diphenylethYlene (isomer mixture) and 4,4'-difluorobenzophenone A polymer is prepared analogously to Example 1 from 0.0100 mol of bis(4-hydroxyphenyl)diphenylethylene, 0.0100 mol of 4,4'-difluorobenzophenone and 0.0109 mol of potassium carbonate (reaction conditdons: 1 h/226C, 1 h/250C and4 h/278 to 280C). The reacdon mixture is ground and extracted with water containing acetic acid, water and subsequently with a water/acetone (2:1) mixture, the residue is dissolved in methylene chloride, the solution is filtered, and the product is precipitated in isopropanol and dried at up to 200C in a vacuum dIying oven. The resultant polyether ketone has a reduced viscosity of 0.39 dl/g and a glass transition temperature of 190C and is more than 20 % soluble in methylene chloride and N-methylpyrrolidone.
Example 9: Polvether sulfone made from bis(4-hydroxyphenYl)diphenYlethYIene (isomer mixture), 4,4'-dihydroxybiphenyl and 4,4'-dichlorodiphenYI sulfone A polymer is prepared and isolated analogously to Example 8 from 0.0251 mol of bis(4-hydroxyphenyl)diphenylethylene, 0.0251 mol of 4,4'-dihydroxybiphenyl, O.OS00 mol of 4,4'-dichlorodiphenyl sulfone and 0.0526 mol of potassium carbonate (reaction conditions: 1 h/224C, 1 h/250C and 4 h/275 to 280C). The resultant polyether sulfone has a reduced viscosity of 0.23 dUg and a glass transition temperature of 191C
and is more than 20 % soluble in methylene chloride, 1,3-dioxolane, cyclohexanone and N-methylpyrrolidone.
Example 10: Polyether sulfone made from bis(4-hvdroxYphenyl)diphenYlethylene (isomer mixture). uhenYlhydroquinone and 4,4'-dichlorodiphenyl sulfone A polymer is prepared and isolated analogously to Example 8 from 0.0251 mol of bis(4-hydroxyphenyl)diphenylethylene, 0.0251 mol of phenylhydroquinone, O.OS00 mol of 4,4'-dichlorodiphenyl sulfone and 0.0525 mol of potassium carbonate ~reaction conditions: 1 h/226C, 1 h/251C and 4 h/281C). The resultant polyether sulfone has a reduced viscosity of 0.36 dUg and a glass transition temperature of 198C and is more than 20 % soluble in methylene chloride, 1,3-dioxolane, cyclohexanone and N-methylpyrrolidone.
Example 11: Polyether sulfone made from bis(4~hydroxyphenvl)diphenvlethYlene (isomer mixture). hydroquinone. 2,6-dihydroxynaphthalene, 4,4'-dichlorodiphenyl sulfone and 2,6-difluorobenzonitrile A polymer is prepared and isolated analogously to Example 8 from 0.0251 mol of bis(4-hydroxyphenyl)diphenylethylene, 0.0127 mol of hydroquinone, 0.0126 mol of 2,6-dihydroxynaphthalene, 0.0400 mol of 4,4'-dichlorodiphenyl sulfone, 0.0101 mol of 2,6-difluorobenzonitrile and 0.0528 mol of potassium carbonate (reaction condidons:
1 h/225C, 1 h/248C and 2 h 45 min/282C). The resultant polyether sulfone has a reduced viscosity of 1.06 dUg and a glass transition temperature of 216C and is more than 20 % soluble in methylene chloride, 1,3-dioxolane, cyclohexanone and N-methylpyrrolidone.
~o~
Exarnple_12: Polyether sulfone made from bis(4-hvdroxYphenYl)diphenYIethYlene (isomer mixture), 4.4'-dihYdroxybenzophenon, 4~dihYdroxybiphenyl, bisphenol A and 4,4'-dichlorodiphenyl sulfone A polymer is prepared and isolated analogously to Example 8 from 0.0100 mol of bis(4-hydroxyphenyl)diphenylethylene7 0.0101 mol of 4,4'-dihydroxybenzophenone, 0.0201 mol of 4,4'-dihydroxybiphenyl, 0.0101 mol of bisphenol A, 0.0500 mol of 4,4'-dichlorodiphenyl sulfone and 0.052S mol of potassium carbonate (reaction conditions: 1 k~224C, 1 h/251C and 3 h/283 to 285C). The resultant polyether sulfone has a reduced viscosity of 0.23 dVg and a glass transition temperature of 170C and is more than 20 % soluble in methylene chloride, 1,3-dioxolane, cyclohexanone and N-methylpyrrolidone.
Example 13: Polyether sulfone made from bis(4-hvdroxYphenYl)diphenvlethYIene ~1:1 isomer mixture from ether cleava e under basic conditions) and 4~4'-dichlorodiphenyl sulfone A polymer is prepared and isolated analogously to Example 8 from 0.0100 mol of bis(4-hydroxyphenyl)diphenylethylene, 0.0100 mol of 4,4'-dichlorodiphenyl sulfone and 0.010 mol of potassium carbonate (reaction conditions: 1 h/226C, 1 h/248C and 4 h/281C)~ The resultant polyether sulfone has a reduced viscosity of 0.24 dVg and a glass transition temperature of 201C and is more than 20 % soluble in methylenechloride, 1,3-dioxolane, cyclohexanone and N-methylpyrrolidone.
.
Polvarvlene ethers containin~ tetraphenvlethYlene unlts The invention relates to novel, specified polyarylene ethers containing tetraphenylethylene units, to a process for their preparation, and to their use, and to specific diphenol isomer mixtures as the monomer components for the synthesis of polyarylene ethers and to a process for the preparation of these isomer mixtures.
Polyarylene ethers are industrial materials having very good mechanical and therrnal properties and high resistance to conventional organic solvents. For some applications, however, this solvent resistance is undesired. In particular, the modification of thermoset matrix resins requires the use of the most concentrated polymer solutions possible in conventional organic solvents. The object of the present invention was therefore to provide polyarylene ethers having very good solubility in a wide range of organic solvents.
This object is achieved by using bis(4-hydroxyphenyl)diphenylethylene as a monomer component.
The invention accordingly relates to a polyarylene ethers which contain, based on the total amount of structural elements present in the polymer, 2-100 mol% of one or more recurring structural elements of the forrnula Ia, Ib or Ic ¦ O O-Ar1~ _ _ \~ (Ia), )=~ (Ib), L ~ ~ O-Ar~ t 20~7~1 _ o O-Ar1- _ and 0-98 mol% of a recurring structural element of the formula II
~Ar2~ ]
in which Ar2 is a radical of the formula IIIa-IIIg which is unsubstituted or substituted by one or more Cl-C4alkyl groups, Cl-C4aL~coxy groups or halogen atoms:
(Illa), ~ (IIlb), (IIIC), ~3 Z ~ Z ~ (IIId), ~3Z ~3Z ~ (IIIe).
~0~
~IIIg) (III~
where a and b are zero or 1, Z is -CO-, -SO2-, -SO-, -S-, -O-, -C(CH3)2-, -C(CF3)2-, -CH2-or -C(CH3)(C6Hs)-, and Q is -CH2-, -O-, -C(=O)- or a d;rect bond, and Arl is a radical of the formula IVa, IVb or IVc which is unsubstituted or substituted by one or moreCl-C4aLlcyl groups, Cl-C4aLtcoxy groups or halogen atoms:
X ~ X~ (IVa), X ~ X~3 (IVb), CN
~ (IVc), where c is zero, 1 or 2, d is 2 or 3, and X is -CO-, -SO2- or -SO-.
Polyarylene ethers containing a tetraphenylethylene structure are hitherto unknown in the literature.
The only known po!ymers which contain a tetraphenylethylene unit are polyamides and polyimides (Y. Oishi et al., Pol. Mat. Sci. Eng. 1989, 60, 757). The polymers described therein are synthesised starting from 4,4'-diaminotetraphenylethylene; depending on the 4~ Z~0~
coreactant, they are soluble in aprotic, dipolar solvents, such as N-methylpyrrolidone, dimethyl sulfoxide, dimethylacetarnide or pyridine. However, solubility properties of this type are in no way excellent for polyamides or polyimides since other known polymers, for example the polyimides of US Patent 3 856 752 and European Patent Application 92 524, which are derived from diaminotrimethylphenylindane have significantly better solubilities. Further polyamides containing tetraphenylethylene units are described in J. of Polymer Science, Part A, 1991, Vol. 29, 55-61.
It ~vas therefore surprising that the polyarylene ethers according to the invention based on tetraphenylethylene units have particularly good solubilities in conventional organic solvents, such as chlorinated hydrocarbons, cyclic ketones or cyclic ethers.
Other known polyarylene ethers whose monomer component likewise contains four phenyl groups, for example the polyarylene ethers of German Patent Application 3 825 148 which are derived from 4,4'-dihydroxy-3,3'-diphenylbiphenyl do not have the excellent solubility properties of the present compounds.
The polyarylene ethers according to the invention can be prepared by polycondensing one or more diphenols of the forrnula Va, Vb or Vc HO OH HO
)=~ (Va), )=~ (Vb), OH
HO~ ,~OH
Il (Vc) ~3 7~
and, if desired, a diphenol of the fonnula VI
HO-Ar2-OH (VI) with a dihalogen derivative of the forrnula VII
Hal-Arl-Hal (VII) in the presence of an aLlcaline catalyst in a polar aprotic solvent, Arl and Ar2 being as de~ned above, and Hal being halogen, in particular fluorine or chlorine, and the relative amounts of the diphenol of the ~ormula Va IO Vc and of the diphenol of the ~onnula VI
being selec~ed in such a manner that the resultant copolymer contains the amounts defined in claim 1 of the structural elements of the formulae I and II.
The diphenols of the formula V or VI may also be replaced by the corresponding aLkali or alkaline earth metal phenoxides, for example potassium phenoxide or calcium phenoxide.
The polycondensation is usually carried out in approximately equimolar ratios of the diphenols of the forrnulae V and, if used, VIi based on the dihalogen derivative of the formula VII. Approximately equimolar arnounts is taken to mean a molar ratio of 0.8:1.0 to 1.0:0.8; a molar ratio of 0.95:1.00 to 1.00:0.95 is preferred.
The copolymers containing both structural elements of the ~orrnula I and structural elements of the fonnula II can be prepared either in a random manner or in a segmented manner (block copolymers). In the random-type synthesis, a mixture of the phenols V and VI is, for example, condensed with one or more dihalogen derivatives of the fonnula VII.
To prepare a block copolymer, products of the reaction of a diphenol of the forrnula V and a dihalogen derivative of the fonnula VII containing hydroxyl or phenoxide end groups and products of the reaction of a diphenol of the formula VI and a dihalogen derivative of the formula VII containing halogen end groups, or vice versa, are synthesised. This is achieved, as is known, by using an appropriate excess of the diphenol or of the dihalogen derivative in the preparation of the reaction product. An appropriate excess of one of the starting materials is, for example, an excess of from about 1 to 50 mol%. The extent of the excess in each case deterrnines the block length.
- 6 - ;20~
The aL~aline catalyst used in the process according to the invention is generally an alkali metal carbonate or aL~caline earth metal carbonate or a corresponding bicarbonate, such as sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, calcium carbonate or calcium bicarbonate; however, it is also possible to employ other alkaline reagents, such as sodium hydroxide, potassium hydroxide or calcium hydroxide.
Examples of polar aprotic solvents which can be employed for the preparation of the polyarylene ether resins according to the invention are dimethyl sulfoxide, dimethylacetamide, diethylacetamide, tetramethylurea, N-methylcaprolactam, N-methylpyrrolidone and pre~erably diphenyl sulfone.
The reaction is expediently carried out at elevated temperature, preferably up to the reflux temperature of the solvent, for example up to about 350C.
It is frequently advisable concomitantly to use an entrainer, for example chlorobenzene, xylene or toluene, in order to facilitate azeotropic removal from the reaction mixture of the water formed during the reaction.
The compounds of the formula VII are known. Some are commercially available and some can be prepared in a known manner.
Examples of suitable compounds of the formula VII ale 4,4'-dichloro- or4,4'-difluorodiphenyl sulfoxide or-diphenyl sulfone, 4,4'-dichloro- or 4,4'-difluorobenzophenone, 4,4'-dichloroisophthalophenone and 4,4'-dichloroterephthalophenone, or 2,6-difluorobenzonitrile or 2,6-dichlorobenzonitrile.
Preferred compounds of the formula VII are 4,4'-difluorobenzophenone and, in particular, 4,4'-dichlorodiphenyl sulfone.
Compounds of the formula VI are likewise known and commercially available. Examples of suitable compounds of the formula VI are hydroquinone, 4,4'-dihydroxybiphenyl, 2-phenylhydroquinone, 2,6- and 2,7-dihydroxynaphthalene, bisphenol A, bisphenol F, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone and 2,2-bis(4'-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, and the corresponding 204'73Bl C~-C4alkyl-substitu~ed derivatives, for example 3,3',5,5'-tetrarnethyl-4,4'-dihydroxydiphenyl sulfone.
Further suitable compounds are: 2,2'-dihydroxybiphenyl, 9,9-bis(4'-hydroxyphenyl)fluorene and 6,6'-dihydroxy-3,3,3',3'-tetramethyl- 1, l '-spirobiindane.
Preferred compounds of the formula VI are 4,4'-dihydr~xybiphenyl, 4,4'-dihydroxybenzophenone, hydroquinone and bisphenol A.
A particularly preferred compound of the formula VI is 4,4'-dihydroxydiphenyl sulfone.
The diphenols of the formulae Va, Vb and Vc are known or can be prepared in a known manner. A suitable synthetic route for the preparation of 1,2-bis(4'-hydroxyphenyl)-1,2-diphenylethylene is descAbed by R.N. Iyer and K.V.B. Rao in Ind. J. Chem., 16B, 601 (1978). The first step is conversion of 4-methoxybenzophenone into 4-methoxyphenylphenyldichloromethane using PCI5, followed by dimeAsation of the resultant dichloromethane derivative to give the tetrasubstituted ethylene derivative by heating in a solvent in the presence of elemental copper, and subsequently cleavage of the methyl ether by heating with potassium hydroxide in diethylene glycol. An analogous synthesis of tetraphenylethylene derivatives starting from unsubstituted benzophenone is described in Org. Synth. Coll. Vol. II, 573 (1943) and Coll. Vol. IV, 914 (1963~.
It has been found that particularly highly soluble polyarylene ethers are obtained if the diphenol component used in their preparation is a dihydroxytetraphenyl isomer mixture containing the diphenols of the formulae Va, Vb and Vc. This isomer mixture is novel and is likewise a subject-matter of the present invention. Particular preference is given to an isomer mixture containing the diphenols Va, Vb and Vc in a molar ratio of about 2:2:1.
The isomer mixture according to the invention is obtainable, for example, by cleaving the above-described tetraphenylethylenedimethyl ether in a highly acidic medium, forexample using HBr in glacial acetic acid, whereas the corresponding alkaline cleavage described in Ind. J. Chem. 1978, 16 B, 601 gives a mixture containing only two isomers.
This preparation process for the isomer mixture is likewise a subject-matter of the present invention.
The polyarylene ethers according to the invention preferably contain 15-100 mol%, in particular lO-100 mol%, of a recurring structural element of the formula I and 0-95 mol%, in particular Q-90 mol%, of a recurring structural element of the formula r[. Arl and Ar2 in the formulae I and Il are particularly preferably a radical of the forrnula 3 SO2~-, or Arl is a radical of the forrnula SO2~ and Ar2 is a radical of the formula ~3' Particularly preferred polyarylene ethers contain 25-100 mol% of a recurring structural element of the formula I and 0-75 mol% of a recurring structural element of the formula II.
In the formulae IVa and IVb, X is preferably -SO2-. The Arl group is preferably the radical ~3 SO2~ .
Z in the formulae IIId and IIIe is preferably -C(CH3)2-, -CO-, -SO2-, -S- or -O-.
The phenylene groups in the forrnulae IIIa to IIIe and IVa and IVb are preferably 1,3- and in particular 1,4-phenylene groups. Ihe aLIcyl or aLlcoxy substituents of the groups Arl and Ar2 may be straight-chain or branched. Examples of suitable substituents are ethyl, n-propyl, isopropyl, n-butyl and in particular me~yl, and the corresponding alkoxy groups. Preferred groups Arl and Ar2 are unsubstituted.
The Ar2 group of the compounds according to the invention is preferably a radical of the forrnula ,~
3 CH~;--or in particular {3 So2~3 .
The polyarylene ethers according to the invention preferably have a reduced viscosity of from 0.1 to 2.0 dVg, in particular from 0.3 to 1.5 dVg, measured at 25C on a 1% solution in N-methylpyrrolidone (1 g of polymer dissolved in lOQ ml of NMP).
The polyarylene ethers according to the invention can be employed in a manner conventional for thermoplastics and can be converted, for exarnple, into mouldings or films, or can be employed as matrix resins, adhesives or coating compositions. Before the polyarylene ethers, in the form, for example, of a moulding powder, melt or solution, are processed, conventional additives, for example fillers, pigments, stabilisers or reinforcing agents, such as carbon fibres, boron fibres or glass fibres, can be added. The polyarylene ethers according to the invention can also be processed together with other therrnoplastics.
The polyarylene ethers according to the invention are preferably suitable as ma~ix resins for the production of fibre-composite systems, suitable reinforcing fibres being the conventional fibres used to reinforce industrial materials. These may be organic or inorganic fibres, natural fibres or synthetic fibres, such as aramid fibres, and in the forrn of fibre bundles, oriented or nonoriented fibres or continuous fibres. Examples of reinforcing fibres used are glass fibres, boron fibres, carbon fibres and metal fibres.
A further preferred possible use of the polyarylene ethers according to the invention is for Z~3~.
- ]o -the modificadon of other plastics. These plastics may in principle be thermoplasdcs or thermosets. The moclification of thermocurable resins, in particular epoxy resins or bismaleimides, has achieved particulau importance. Polymer systems customised topardcular requirements of this type are described, for example, in US Patent 3,530,087.
Systems of this type have achieved particular importance as matrix resins for the producdon of composite elements. From about 5-1~0 parts by weight, preferably 10-50 parts by weight, of polyarylene ether are usually employed per 100 parts by weight of the plastics to be modified.
The present invention thus also provides mouldings, ~llms, coadngs or adhesive bonds containing a polyarylene ether according to the invendon, and fibre composites containing reinforcing fibres and, as matrix resin, a polyarylene ether according to the invendon.
Specific mendon should be made of both the very good solubility of the polymers according to the invention in a wide range of organic solvents (for example in chlorinated hydrocarbons, cyclic ketones and cyclic ethers) and the very good stability of these solutions. The polymers can thus be processed from solution, for example to give films, or introduced into other systems, for example matrix resins. Solutions containing 1-75 % by weight, preferably 5-40 % by weight, of the polyarylene ethers according to the inventdon in an organic solvent are thus a further subject-matter of the invention. Examples of preferred organic solvents are N-methylpyrrolidone, ~-butyrolactone, dimethylacetamide, dimethyl sulfoxide, cyclohexanone, cyclopentanone, 1,3-dioxolane and methylene chloride. Preferred soludons contain a polyarylene ether containing 5-100 mol%, preferably 10-100 mol%, of a recurring structural element of the forrnula I and 0-95 mol%, preferably 0-90 mol%, of a recurring structural element of the formula II.
The examples below illustrate the invention.
Example 1: SYnthesis of bis(4-hYdroxvphenyl)diphenylethylene (isomer mixture~
a) Bis(4-methoxyphenyl)diphenylethylene A mixture of 212.2 g (1 mol) of 4-methoxybenzophenone and 250 g of PCls in 1.5 l of dry benzene is refluxed ~or 1~ hours. The solvent is subsequently removed by distilladon in a rotary evaporator, 300 ml of benæne are added to the oily residue and the solvent is removed by distillation in a rotary evaporator. This addition and removal of solvent is 2~
repeated 3 times. 1.2 l of benzene and 427 g of copper powder are added to the oily residue which remains, and the mixture is ~efluxed for 24 hours. The hot reaction solution is filte~d, and the filtrate is evaporated in a rotary evaporator. The residue is then recrystallised from 650 ml of glacial acetic acid, the mother liquor is evaporated, and the residue is chromatographed on silica gel (hexane/toluene 3:2).
The amount of bis(4-methoxyphenyl)diphenylethylene obtained after recrystallisation from glacial acetic acid and chromatography is 156 g (79.4 %).
Elemental analysis:
Calculated for C28~242: C: 85.68 H: 6.16 Found: C: 85.02 H: 6.10 b) Bis(4-hydroxyphenYl)diphenylethylene (isomer mixture~
A suspension of 96.6 g (0.246 mol) of bis(4-methoxyphenyl)diphenylethylene in 486 ml of glacial acetic acid and 486 ml of 48 % HBr is refluxed for 24 hours. The reaction solution is cooled to room temperature and poured into 2 1 of water, and the precipitate is filtered off, dried and chromatographed on silica gel (hexane/EtOAc 2:1). Yield of bis(4-hydroxyphenyl)diphenylethylene (isomer mixture): 64.5 g (72 %).
Elemental analysis:
Calculated for C26H20O2: C: 85.69 H: 5.53 Found: C: 85.52 H: 5.54 Titration of the phenol groups: Titration in pyridine using 0.1 N tetrabutylammonium hydroxide in isopropanol: 5.46 meq/g (99.4 % of theoly).
HPLC: Nucleosil C-18 5 llm, CH3CN: H20 7:3 (1 mVmin);
Detection at 254 nm;
Isomer mixture comprising 3 isomers in the ratio 2:2:1.
Example 2: PolYether sulfone made from bis(4-hydroxYphenYl)diphenYlethvlene (isomer mixture) and 4~4'-dichlorodiphenYl sulfone A mixture of 18.34 g (0.0503 mol) of bis(4-hydroxyphenyl)diphenylethylene (isomer mixture), 59.31 g of diphenyl sulfone, 7.30 g (0.0528 mol) of potassium carbonate and 52 g of xylene is heated at a bath temperature of 200C under nitrogen in a round-bottomed flask fitted wi~h stirrer and protective-gas inlet, and a xylene/water mixture is removed by distillation. Towards the end of the distillation operation, a vacoum (2 mbar) is applied briefly. 15.38 g (0.0501 mol) of 4,4'-dichlorodiphenyl sulfone are then added to the reaction mixture, and the temperature is increased to 228C over the course of 15 minutes and kept there for 1 hour. The temperature is then increased to 250C (1 hour~ and subsequently to 280C. This temperature is maintained for 4 hours.
0.040 g (0.0014 mol) of 4,4'-dichlorodiphenyl sulfone are then added at this temperature.
This operation is filtered after 30 minutes and again after 15 minutes. After a further 30 minutes, the viscous reaction mixture is cooled briefly and removed from the reaction flask.
The solidified reaction mixture is powdered, then treated with acetic acid and extracted with water. The polymer is subsequently dissolved in methylene chloride, a small amount of insoluble material is filtered off, and the dissolved product is then precipitated using isopropanol. I he polymer purified in this way is then dried at 240C in a vacuum drying oven. A polyarylene ether sulfone prepared in this way has a reduced viscosity [1 % by weight of polymer in N-methylpyrrolidone (NMP) at 25C] of 0.29 dlJg. The glass transition temperature, determined by DSC, is 215C. The 13C NMR spectrum of thepolyether sulfone shows signals comparable to the monomer (Example lb~ in addition to the diphenyl sulfone unit. In particular, the unchanged presence of the C-C double bond can be seen. The particularly good solubility of this polymer can be seen from the table below.
Solvent NMP DioxaneMethylene chloride Example 1 + + +
+ = soluble Example 3: PolYether sulfone made from bis(4-hydroxvPhenYl)diphenylethylene (isomer mixture), 4,4'-dihvdroxydiphenvl sulfone (1:1) and 4,4'-dichlorodiphenyl sulfone A polymer is prepared analogously to Example 1 from 0.0501 mol of - 13 - 2~
bis(4-hydroxyphenyl~diphenylethylene, 0.0~01 mol of 4,4'-dihydroxydiphenyl sulfone, 0.1000 mol of 4,4'-dichlorodiphenyl sulfone and 0.1052 mol of potassium carbonate (reaction conditions: I h/250C, S h/280C). The resultan~ polymer has a reduced viscosity of 0.42 dl/g and a glass transition temperature of 203C and is soluble in tetrahydrofuran, dioxane, cyclohexanone, cyclopentanone and methylene chloride.
Example 4: Polyether sulfone made from bis(4-hydroxvphenyl)diphenYlethvlene (isomer mixturel,4~4'-dihvdroxydiphenyl sulfone (1:3~ and 4.4'-dichlorodiphenYI sulfone A polymer is prepared as in Exarnple 1 from 0.0504 mol of bis(4-hydroxyphenyl)-diphenylethylene, 0.1510 mol of 4,4'-dihydroxydiphenyl sulfone, 0.2003 mol of 4,4'-dichlorodiphenyl sulfone and 0.2104 mol of potassium carbonate (reaction conditions: 1 h/250C, 5 h/280C). The resultant polymer has a reduced viscosity of 0.46 dVg and a glass transition temperature of 221C and is more than 25 % soluble in methylene chloride.
Example 5: PolYether sulfone made from bis(4-hYdroxyphenvl)diphenYlethylene (isomer mixture)~ 4.4'-dihYdroxydiphenyl sulfone (l :9) and 4.4'-dichlorodiphenyl sulfone A polymer is prepared as in Example 1 frorn 0.0402 mol of bis(4-hydroxyphenyl)-diphenylethylene, 0.3610 mol of 4,4'-dihydroxydiphenyl sulfone, 0.4000 mol of 4,4'-dichlorodiphenyl sulfone and 0.420 of potassium carbonate (reaction conditions:
1 h/250C, 1 h/275C,7 h 10 min/280C). The resultant po~ymer has a reduced viscosity of 0.48 dl/g and a glass transition temperature of 223C and is more than 25 % soluble in methylene chloride.
Example 6. Polyether sulfone made from bis(4-hydroxYphenyl)diphenylethYlene (isomer mixture). 4~4'-dihvdroxYdiphenYI sulfone (1:19) and 4.4'-dichlorodiphenvl sulfone A polymer is prepared analogously to Example 1 from 0.0201 mol of bis(4-hydroxy-phenyl)diphenylethylene, 0.3811 mol of 4,4'-dihydroxydiphenyl sulfone, 0.4000 mol of 4,4'-dichlorodiphenyl sulfone and 0.420 mol of potassium carbonate (reaction conditions:
1 h/250C, 1 h/275C and 4 h/280C). The resultan~ polymer has a reduced viscosity of 0.49 dlJg and a glass transition temperature of 222C and is more than 25 % soluble in methylene chloride.
~0~7 Use Example 7 (polYether sulfone/epoxY blend) A polyether sulfone copolymer prepared as described in Exarnple 5, as a 20 or 30 parts by weight soludon in methylene chloride, is added to a mixture comprising 50 parts of tetraglycidyldiaminodiphenylmethane and 50 parts of triglycidyl-p-aminophenol, and the solven~ is removed in vacuo. 50 parts of p-diaminodiphenyl sulfone are added, and the mixture is cured in a mould for 2 hours at 160C and for 2 hours at 210C. Test specimens are cut out of a sheet produced in this way and used IO determine the flexural strength, outer fibre strain in accordance with ISO 178 and the fracture toughness (GlC by means of "bend notch" according to ASTM E 399).
The following very good values are obtained:
. _ ____ Parts of thennoplasdc . . _ _ . .. _ Flexural strength [N/mm2~: 166 170 Outer fibre strain [% ]: 6.7 6.5 Fracture toughness [J/m2]: 171 300 Example 8: Polyether ketone made from bis(4-hydroxvphenyl)diphenylethYlene (isomer mixture) and 4,4'-difluorobenzophenone A polymer is prepared analogously to Example 1 from 0.0100 mol of bis(4-hydroxyphenyl)diphenylethylene, 0.0100 mol of 4,4'-difluorobenzophenone and 0.0109 mol of potassium carbonate (reaction conditdons: 1 h/226C, 1 h/250C and4 h/278 to 280C). The reacdon mixture is ground and extracted with water containing acetic acid, water and subsequently with a water/acetone (2:1) mixture, the residue is dissolved in methylene chloride, the solution is filtered, and the product is precipitated in isopropanol and dried at up to 200C in a vacuum dIying oven. The resultant polyether ketone has a reduced viscosity of 0.39 dl/g and a glass transition temperature of 190C and is more than 20 % soluble in methylene chloride and N-methylpyrrolidone.
Example 9: Polvether sulfone made from bis(4-hydroxyphenYl)diphenYlethYIene (isomer mixture), 4,4'-dihydroxybiphenyl and 4,4'-dichlorodiphenYI sulfone A polymer is prepared and isolated analogously to Example 8 from 0.0251 mol of bis(4-hydroxyphenyl)diphenylethylene, 0.0251 mol of 4,4'-dihydroxybiphenyl, O.OS00 mol of 4,4'-dichlorodiphenyl sulfone and 0.0526 mol of potassium carbonate (reaction conditions: 1 h/224C, 1 h/250C and 4 h/275 to 280C). The resultant polyether sulfone has a reduced viscosity of 0.23 dUg and a glass transition temperature of 191C
and is more than 20 % soluble in methylene chloride, 1,3-dioxolane, cyclohexanone and N-methylpyrrolidone.
Example 10: Polyether sulfone made from bis(4-hvdroxYphenyl)diphenYlethylene (isomer mixture). uhenYlhydroquinone and 4,4'-dichlorodiphenyl sulfone A polymer is prepared and isolated analogously to Example 8 from 0.0251 mol of bis(4-hydroxyphenyl)diphenylethylene, 0.0251 mol of phenylhydroquinone, O.OS00 mol of 4,4'-dichlorodiphenyl sulfone and 0.0525 mol of potassium carbonate ~reaction conditions: 1 h/226C, 1 h/251C and 4 h/281C). The resultant polyether sulfone has a reduced viscosity of 0.36 dUg and a glass transition temperature of 198C and is more than 20 % soluble in methylene chloride, 1,3-dioxolane, cyclohexanone and N-methylpyrrolidone.
Example 11: Polyether sulfone made from bis(4~hydroxyphenvl)diphenvlethYlene (isomer mixture). hydroquinone. 2,6-dihydroxynaphthalene, 4,4'-dichlorodiphenyl sulfone and 2,6-difluorobenzonitrile A polymer is prepared and isolated analogously to Example 8 from 0.0251 mol of bis(4-hydroxyphenyl)diphenylethylene, 0.0127 mol of hydroquinone, 0.0126 mol of 2,6-dihydroxynaphthalene, 0.0400 mol of 4,4'-dichlorodiphenyl sulfone, 0.0101 mol of 2,6-difluorobenzonitrile and 0.0528 mol of potassium carbonate (reaction condidons:
1 h/225C, 1 h/248C and 2 h 45 min/282C). The resultant polyether sulfone has a reduced viscosity of 1.06 dUg and a glass transition temperature of 216C and is more than 20 % soluble in methylene chloride, 1,3-dioxolane, cyclohexanone and N-methylpyrrolidone.
~o~
Exarnple_12: Polyether sulfone made from bis(4-hvdroxYphenYl)diphenYIethYlene (isomer mixture), 4.4'-dihYdroxybenzophenon, 4~dihYdroxybiphenyl, bisphenol A and 4,4'-dichlorodiphenyl sulfone A polymer is prepared and isolated analogously to Example 8 from 0.0100 mol of bis(4-hydroxyphenyl)diphenylethylene7 0.0101 mol of 4,4'-dihydroxybenzophenone, 0.0201 mol of 4,4'-dihydroxybiphenyl, 0.0101 mol of bisphenol A, 0.0500 mol of 4,4'-dichlorodiphenyl sulfone and 0.052S mol of potassium carbonate (reaction conditions: 1 k~224C, 1 h/251C and 3 h/283 to 285C). The resultant polyether sulfone has a reduced viscosity of 0.23 dVg and a glass transition temperature of 170C and is more than 20 % soluble in methylene chloride, 1,3-dioxolane, cyclohexanone and N-methylpyrrolidone.
Example 13: Polyether sulfone made from bis(4-hvdroxYphenYl)diphenvlethYIene ~1:1 isomer mixture from ether cleava e under basic conditions) and 4~4'-dichlorodiphenyl sulfone A polymer is prepared and isolated analogously to Example 8 from 0.0100 mol of bis(4-hydroxyphenyl)diphenylethylene, 0.0100 mol of 4,4'-dichlorodiphenyl sulfone and 0.010 mol of potassium carbonate (reaction conditions: 1 h/226C, 1 h/248C and 4 h/281C)~ The resultant polyether sulfone has a reduced viscosity of 0.24 dVg and a glass transition temperature of 201C and is more than 20 % soluble in methylenechloride, 1,3-dioxolane, cyclohexanone and N-methylpyrrolidone.
Claims (15)
1. A polyarylene ether which contains, based on the total amount of structural elements present in the polymer, 2-100 mol% of one or more recurring structural elements of the formula Ia, Ib or Ic (Ia), (Ib), (Ic) and 0-98 mol% of a recurring structural element of the formula II
(II) in which Ar2 is a radical of the formula IIIa-IIIg which is unsubstituted or substituted by one or more C1-C4alkyl groups, C1-C4alkoxy groups or halogen atoms:
(IIIa), (IIIb), (IIIc), (IIId), (IIIe), , (IIIf) (IIIg) where a and b are zero or 1, Z is -CO-, -SO2-, -SO-, -S-, -O-, -C(CH3)2-, -C(CF3)2-, -CH2-or -C(CH3)(C6H5)-, and Q is -CH2-, -O-, -C(=O)- or a direct bond, and Ar1 is a radical of the formula IVa, IVb or IVc which is unsubstituted or substituted by one or moreC1-C4alkyl groups, C1-C4alkoxy groups or halogen atoms:
(IVa), (IVb), (IVc), where c is zero, 1 or 2, d is 2 or 3, and X is -CO-, -SO2- or -SO-.
(II) in which Ar2 is a radical of the formula IIIa-IIIg which is unsubstituted or substituted by one or more C1-C4alkyl groups, C1-C4alkoxy groups or halogen atoms:
(IIIa), (IIIb), (IIIc), (IIId), (IIIe), , (IIIf) (IIIg) where a and b are zero or 1, Z is -CO-, -SO2-, -SO-, -S-, -O-, -C(CH3)2-, -C(CF3)2-, -CH2-or -C(CH3)(C6H5)-, and Q is -CH2-, -O-, -C(=O)- or a direct bond, and Ar1 is a radical of the formula IVa, IVb or IVc which is unsubstituted or substituted by one or moreC1-C4alkyl groups, C1-C4alkoxy groups or halogen atoms:
(IVa), (IVb), (IVc), where c is zero, 1 or 2, d is 2 or 3, and X is -CO-, -SO2- or -SO-.
2. A polyarylene ether according to claim 1 having a reduced viscosity of from 0.1 to 2.0 dl/g, preferably from 0.3 to 1.5 dl/g, measured at 25°C on a 1 % by weight solution in N-methylpyrrolidone.
3. A polyarylene ether according to claim 1 or 2, which contains 5-100 mol%, preferably 10-100 mol%, of a recurring structural element of the formula I and 0-95 mol%
preferably 0-90 mol%, of a recurring structural element of the formula II.
preferably 0-90 mol%, of a recurring structural element of the formula II.
4. A polyarylene ether according to claim 3, which contains 25-100 mol% of a recurring structural element of the formula I and 0-75 mol% of a recurring structural element of the formula II.
5. A polyarylene ether according to any one of claims 1 to 4, in which the recurring structural element of the formula I is derived from a bis(4-hydroxyphenyl)diphenylethylene isomer mixture.
6. A polyarylene ether according to claim 1, in which the groups Ar1 and Ar2 areunsubstituted.
7. A polyarylene ether according to claim 1, in which X in the radical of the formula IVa or IVb is -SO2-, in particular a polyarylene ether in which Ar1 is the radical .
8. A polyarylene ether according to claim 1, in which Ar2 is a radical of the formula , , , , , , .
9. A polyarylene ether according to claim 3, in which, in the formulae I and II, Ar1 and Ar2 are a radical of the formula , or Ar1 is a radical of the formula and Ar2 is a radical of the formula .
10. A process for the preparation of a polyarylene ether according to claim 1, which comprises polycondensing one or more diphenols of the formula Va, Vb or Vc (Va), (Vb), (Vc) and, if desired, a diphenol of the formula VI
HO-Ar2-OH (VI) with a dihalogen derivative of the formula VII
Hal-Ar1-Hal (VII) in the presence of an alkaline catalyst in a polar aprotic solvent, Ar1 and Ar2 being defined as in claim 1, and Hal being halogen, in particular fluorine or chlorine, and the relative amounts of the diphenol of the formula Va to Vc and of the diphenol of the formula VI
being selected in such a manner that the resultant copolymer contains the amounts defined in claim 1 of the structural elements of the formulae I and II.
HO-Ar2-OH (VI) with a dihalogen derivative of the formula VII
Hal-Ar1-Hal (VII) in the presence of an alkaline catalyst in a polar aprotic solvent, Ar1 and Ar2 being defined as in claim 1, and Hal being halogen, in particular fluorine or chlorine, and the relative amounts of the diphenol of the formula Va to Vc and of the diphenol of the formula VI
being selected in such a manner that the resultant copolymer contains the amounts defined in claim 1 of the structural elements of the formulae I and II.
11. A process according to claim 10, wherein the diphenols of the formula V or VI are replaced by the corresponding alkali or alkaline earth metal phenoxides.
12. A moulding, film, coating or adhesive bond containing a polyarylene ether according to claim 1.
13. A fibre composite containing reinforcing fibres and, as matrix resin, a polyarylene ether according to claim 1.
14. A solution containing from 1 to 75 % by weight of a polyarylene ether according to claim 1, dissolved in an organic solvent.
15. An isomer mixture containing the diphenols of the formulae Va, Vb and Vc according to claim 10, obtainable by reacting 4-methoxybenzophenone with PCl5 and subsequently dimerising the resultant dichloromethane derivative using elemental copper to give dimethoxytetraphenylethylene, wherein the methyl ether cleavage is carried out in a highly acidic medium.
FD4.3/RU/ac*
FD4.3/RU/ac*
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH241790 | 1990-07-20 | ||
| CH2417/90-6 | 1990-07-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2047381A1 true CA2047381A1 (en) | 1992-01-21 |
Family
ID=4233322
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002047381A Abandoned CA2047381A1 (en) | 1990-07-20 | 1991-07-18 | Polyarylene ethers containing tetraphenylethylene units |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0467847A1 (en) |
| JP (1) | JPH04233939A (en) |
| CA (1) | CA2047381A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100261091A1 (en) * | 2009-04-10 | 2010-10-14 | Hyundai Motor Company | Polysulfone polymers and related polymer electrolyte membranes and fuel cells |
| CN102086265A (en) * | 2009-12-04 | 2011-06-08 | 现代自动车株式会社 | Sulfonated poly (arylene ether) copolymers and related polymer electrolyte membranes and fuel cells |
| US20120309857A1 (en) * | 2011-05-30 | 2012-12-06 | Hyundai Motor Company | Polyarylene-based polymer, preparation method for the same, and polymer electrolyte membrane for fuel cell using the polymer |
| CN103068947A (en) * | 2010-08-10 | 2013-04-24 | 日产化学工业株式会社 | Adhesive composition containing resin having carbon-carbon multiple bond |
| CN103946271A (en) * | 2012-02-09 | 2014-07-23 | 日产化学工业株式会社 | Composition for forming passivation film, including resin having carbon-carbon multiple bond |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100860625B1 (en) * | 2007-05-29 | 2008-09-29 | 한국화학연구원 | Process for the preparation of polyether sulfone by microwave irradiation |
| KR101613260B1 (en) | 2009-02-20 | 2016-04-18 | 주식회사 동진쎄미켐 | Sulfonate based monomer, method for preparing the same, polymer derived from the monomer, polymer electrolyte membrane comprising the polymer, and fuel cell comprising the membrane |
| WO2012020665A1 (en) * | 2010-08-10 | 2012-02-16 | 日産化学工業株式会社 | Adhesive composition comprising aromatic polyether derivative |
| KR101826539B1 (en) * | 2011-05-30 | 2018-02-07 | 현대자동차 주식회사 | Polyarylene-based polymer, preparation method for the same, and polymer electrolyte membrane for fuel cell using the polymer |
| KR101272661B1 (en) * | 2011-08-01 | 2013-06-11 | 건국대학교 산학협력단 | Sulfonated poly(arylene ether) copolymer, method for preparing the saem and use thereof |
| KR101963600B1 (en) * | 2012-08-17 | 2019-04-01 | 주식회사 동진쎄미켐 | Polyarylene-based polymer, process of manufacturing thereof, and the use of the same |
| KR101963599B1 (en) * | 2012-08-17 | 2019-04-01 | 주식회사 동진쎄미켐 | Polyarylene-based polymer, process of manufacturing thereof, and the use of the same |
| JP6311703B2 (en) * | 2013-03-29 | 2018-04-18 | Jsr株式会社 | Composition, method for producing substrate on which pattern is formed, film and method for forming the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2571954A (en) * | 1947-10-25 | 1951-10-16 | Wm S Merrell Co | Tris-phenyl ethylene compounds |
| CH431495A (en) * | 1958-10-30 | 1967-03-15 | Ferrosan Ab | Process for the preparation of substituted bisphenylethylenes |
-
1991
- 1991-07-11 EP EP91810558A patent/EP0467847A1/en not_active Withdrawn
- 1991-07-18 CA CA002047381A patent/CA2047381A1/en not_active Abandoned
- 1991-07-19 JP JP3203412A patent/JPH04233939A/en active Pending
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| US20100261091A1 (en) * | 2009-04-10 | 2010-10-14 | Hyundai Motor Company | Polysulfone polymers and related polymer electrolyte membranes and fuel cells |
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| CN102086265A (en) * | 2009-12-04 | 2011-06-08 | 现代自动车株式会社 | Sulfonated poly (arylene ether) copolymers and related polymer electrolyte membranes and fuel cells |
| US20110136041A1 (en) * | 2009-12-04 | 2011-06-09 | Hyundai Motor Company | Sulfonated poly(arylene ether) copolymers and related polymer electrolyte membranes and fuel cells |
| US8288500B2 (en) * | 2009-12-04 | 2012-10-16 | Hyundai Motor Company | Sulfonated poly(arylene ether) copolymers and related polymer electrolyte membranes and fuel cells |
| CN103068947A (en) * | 2010-08-10 | 2013-04-24 | 日产化学工业株式会社 | Adhesive composition containing resin having carbon-carbon multiple bond |
| CN103068947B (en) * | 2010-08-10 | 2016-06-22 | 日产化学工业株式会社 | Comprise the adhesive composite of the resin with carbon-carbon multiple bond |
| US20120309857A1 (en) * | 2011-05-30 | 2012-12-06 | Hyundai Motor Company | Polyarylene-based polymer, preparation method for the same, and polymer electrolyte membrane for fuel cell using the polymer |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP0467847A1 (en) | 1992-01-22 |
| JPH04233939A (en) | 1992-08-21 |
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