GB1563224A - Aromatic polyethers - Google Patents

Aromatic polyethers Download PDF

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GB1563224A
GB1563224A GB517476A GB517476A GB1563224A GB 1563224 A GB1563224 A GB 1563224A GB 517476 A GB517476 A GB 517476A GB 517476 A GB517476 A GB 517476A GB 1563224 A GB1563224 A GB 1563224A
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process according
dihalo
formula
mol
sulphone
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Imperial Chemical Industries Ltd
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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
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)

Description

(54) AROMATIC POLYETHERS (71) We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, Imperial Chemical House, Millbank, London SW1P 3JF, a British Company, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to aromatic polyethers and in particular to aromatic polyetherketones, polyetheresulphones and ethereketone/sulphone copolymers.
Such aromatic polyethers are useful plastic materials generally having high softening temperatures which enable the polymers to be used for applications wherein the polymer may be subject to a high service temperature.
Such polvmers may be made by the polycondensation of one or more dihalo compounds of general formula
where X is halogen, Q is -CO- or -502-, n is 1, 2 or 3, and m is 0, 1, 2 or 3, with an approximately equimolar amount of one or more alkali metal bisphenates of general formula
where M is alkali metal, Q' is -CO- or 502-, n' is 1, 2 or 3, and m' is 0, 1, 2 or 3.
The polymers resulting from this reaction contain the repeat unit
It has been proposed in U.K. patent specification 1 414421 to make polyetherketones and etherketone/sulphone copolymers from certain aromatic dihalo compounds and alkali metal bisphenates under certain conditions. We have now found that polymers containing repeat units I may conveniently be made by the procedure of that patent specification using the appropriate dihalo compounds and alkali metal bisphenates.
Accordingly we provide a process for the production of aromatic polyethers comprising heating, at temperatures between 2500C and 400 C, 50 to 51% molar of at least one dihalo compound of formula
where X is halogen, Q is -CO- or -502-, n is 1, 2 or 3 and m is 0, 1, 2 or 3, with 50 to 49% molar of at least one alkali metal bisphenate of formula
(at least 95% of the -OM groups being in the para position) where M=alkali metal, Q' is -CO- or -502-, n' is 1, 2 or 3 and m' is 4 1, 2 or 3, said at least sne bisphenate being in the form of a suspension in an aromatic sulphone of formula
in which Y is a direct link, an oxygen atom, or two hydrogen atoms (one attached to each benzene ring) and Z and Z' are hydrogen atoms or phenyl groups and may be the same or different, at least some of the dihalo compound having the structure
and/or at least some of the bisphenate having the structure
Examples of suitable dihalo compounds are the following: 4,4' - dichlorobenzophenone (X = Cl, Q=CO, m=O) 4,4' - difluoroberizophenone (X=F, Q=CO, m=O) 4,4' - dichlorodiphenylsulphone (X=CI, Q=SO2, m=O) 1,4 (and 1,3) bis - (4 - chlorobenzoyl) benzene (X=C1, Q=CO, m=l, n=l) 4,4' - bis - (4 - chlorobenzoyl) biphenyl (x=Cl, Q=CO, m=l, n=2) 4,4" - bis - (4 - chlorobenzoyl) p - terphenyl (x=cl, Q=CO, m=1, n=3) 4,4' - his - (4 - chlorophenylsulphonyl) biphenyl (X=CI, Q= SO2, m= 1, n=2) bis- [4' - (4 - chlorophenylsulphonyl) biphenylyl] sulphone (X=C1, Q=S02, m=n=2) 4 - [4' - (4 - chlorophenylsulphonyl) biphenylyl] sulphonyl - 4' - (4 - fluorophenylsulphonyl) biphenyl (one X=CI, Q= SO2, the other X=F, m=n=2) 4,4' - bis[4' - (4 - chlorophenylsulphonyl) biphenylyl sulphonyl] biphenyl (X= Cl, Q=SO2, m=3, n=2) 4,4" - bis - (4 - chlorophenylsulphonyl) p - terphenyl (X= Cl, Q= SO2, m=l, n=3).
Examples of suitable bisphenates are the dialkali metal salts of the bisphenols corresponding to the above dihalo compounds in which the halogen atoms are replaced by hydroxy groups.
The preferred dihalo compounds are selected from 4,4' - dihalobenzophenone, 4,4' - dihalodiphenylsulphone and 1,4 (and 1,3) bis - (4 - halobenzoyl) benzene.
The preferred bisphenates are the dialkali metal salts of 4,4' - dihydroxy (benzo- phenone), 4,4' - dihydroxydiphenylsulphone and 1,4 and 1,3 - bis - (4 - hydroxybenzoyl) benzene.
At least some of the dihalo compound and/or bisphenate must be of the formula
respectively.
It is preferred that it is the dihalo compound that has this formula and that, in this compound, Q is -CO-.
A particularly preferred combination of reactants is
alone or in conjunction with and ii)
The bis-(4-halobenzoyl) benzene reactant is preferably the 1,4-isomer.
In this process we prefer that 3 to 25% of the linking -CO- and -S 0,- groups are -SO2. The appropriate amount of -S 02- linkages may be provided by the use of a mire of
as the bisphenate component and/or by the use of the dihalo compound
as all or part of a dihalo reactant
used in conjunction with the dihalo reactant
A particularly preferred process is to employ the mixture
where the sum of the molar amounts of a) and b) is 50 to 51% of the sum of a)+ b) +c) and the molar amount of b) is 10 to 50% of the sum of a) +b).
The halogen atoms X in the dihalo compounds are preferably chlorine or fluorine.
The fluorine derivatives are generally more reactive and enable the displacement of alkali metal halide to be carried out more quickly, but are more expensive. Bromine derivatives are also relatively expensive and, although they resemble the chlorine derivatives in performance they usually offer no advantages. Iodine derivatives are generally less satisfactory.
The dihalo compounds having the formula
may be made by Friedel-Crafts condensation of 2 moles of a halobenzene, e.g. chlorobenzene, with the appropriate phthaloyl chloride isomer, e.g. terephthaloyl chloride.
Other dihalo compounds of the formula
may be made by the methods described in United Kingdom patent specifications 1 308 139, 1 352 137 and 1414421.
The alkali metal in the bisphenate is conveniently potassium or sodium.
The polymerisation procedure is as described in United Kingdom patent specification 1 414 421.
The solvent employed is preferably diphenyl sulphone. One important feature of the process is that the bisphenate is only very slightly soluble in the solvent at the polymerisation temperature. The bisphenate is mostly present in the reaction mixture in the form of a suspension and for this reason should be added in finely divided form.
Polymers made from the preferred monomer mixture, i.e.
in which 10 to 50 mol % of the sum of a) +b), is reactant b) are particularly useful products. They are crystalline polymers having melting points of the order of 340 to 370"C that however can be melt fabricated without excessive cross-linking occurring.
Polymers containing lesser amounts of sulphone linkages tend to have higher melting points and be less readily processed without incurring the onset of crosslinking. On the other hand, polymers containing a greater amount of sulphone linkages tend to be less readily crystallised and in some cases are wholly amorphous.
The polymers are of particular utility for wire insulation where the insulation is required to remain intact under conditions of high service temperature, often in contact with organic liquids, for example hydraulic fluids.
To be of practical utility, the polymers preferably have a reduced viscosity of at least 0.8, particularly at least 1.0. [Reduced viscosities are measured herein at 250C on a solution of polymer in concentrated sulphuric acid (specific gravity 1.84) containing 1 g of polymer in 100 cm2 of solution.] The polymer also preferably has a low absorbance, particularly below 0.35.
[Absorbances are measured herein at a wavelength of 550 nm in a 1 cm cell using a solution of polymer in concentrated sulphuric acid as used for reduced viscosity measurements.] A low absorbance is indicative of relative freedom from structural irregularities such as chain branching. For polymers of a given reduced viscosity, those having a low absorbance tend to give tougher films than those of higher absorbance.
The invention is illustrated by the following examples.
EXAMPLE 1.
A sample of hydrated dipotassium salt of 4,4'-dihydroxybenzophenone, finely ground to pass through a sieve having a mesh opening of 500 ,am, was estimated by titration against a standard solution of sulphuric acid in a mixture of equal volumes of methanol and water. Accordingly a sample (0.0648 mol) of the ground hydrated dipotassium salt was weighed into a glass flask of capacity 250 cm3 fitted with a stirrer, nitrogen purge and an air condenser. Diphenyl sulphone (40 g; melting point 124 to 125.5 CC, recrystallised from methanol) was introduced into the flask and powder blended with the dipotassium salt The flask was flushed with nitrogen and heated on a solder bath at 2300C. As the diphenyl sulphone melted, the stirrer was started, the nitrogen purge commenced, and the pressure in the flask reduced slowly to 50 torr. Water distilled from the mixture and a lemon-yellow slurry of the dipotassium salt in diphenyl sulphone remained in the flask. Care was taken to ensure that the diphenyl sulphone did not boil and hence did not splash the dipotassium salt on to the upper walls of the flask. The apparatus was then filled with nitrogen and the pressure therein increased to atmospheric.
1,4 - bis - (4 - chlorobenzoyl) benzene (13.8898 g; 0.0391 mol); 4,4' - dichlorodiphenylsulphone (7.4858 g; 0.0261 mol); and recrystallised diphenyl sulphone (9 g) were added to the flask.
[The dihalo compounds comprised 50.15 mol % of the condensants (i.e. dihalo compounds plus bisphenate) charged, and the 4,4'-dichlorodiphenylsulphone 40 mol % of the dihalo compounds.] A bubbler was fitted to the air condenser and the slurry was heated under nitrogen with stirring for 2 hours at 230 C, then 18 hours at 2600C and finally 1+ hours at 3200 C. To end stop the reaction 4,4'-dichlorodiphenyl sulphone (1 g) was then added to the solution which was then stirred at 320"C for a further hour. The reaction mixture was cooled to room temperature, ground, extracted by boiling twice with acetone, once with 1% acetic acid, once with water, then with a mixture of equal volumes of methanol and acetone, and finally dried at 140 C for 24 hours at 100 torr.
A sample of the polymer was dissolved in concentrated sulphuric acid to give a pale orange solution (absorbance of 0.21; reduced viscosity 2.40) that was free from gelatinous material.
The polymer consisted of units of the formula
in the molar ratio 3:2, and so about 15.4% of the -CO- and the -SO linking groups were -SO,-.
The polymer powder was pressed, using an electrically heated press at 4000C and 20 tonnes pressure on a 10 cm diameter ram, into an opaque, tough film.
The crystalline melting point, Tm, was 341"C and the glass/rubber transition temperature, Tg, was 1740 C.
[Tm and Tg are measured herein by differential scanning calorimetry using a heating rate of 160C per minute.] EXAMPLE 2.
Example 1 was repeated but using 0.0656 mol of the hydrated dipotassium salt of 4,4' - dihydroxybenzophenone; 18.7352 g (0.0527 mol) of 1,4 - bis - (4 - chlorobenzoyl) benzene; 3.7864 g (0.0132 mol) of 4,4' - dichlorodiphenyl sulphone; and a total of 51 g diphenyl sulphone. [The dihalo compounds comprised 50.11 mol % of the condensants charged and the 4,4' - dichlorodiphenylsulphone 20 mol % of the dihalo compounds.] The resultant polymer contained the repeat units
the molar ratio 4:1 and so about 7.1% of the -CO- and -SO,- linking groups vere -502-. The polymer had a reduced viscosity of 1.41, and an absorbance of 0.27. The polymer could be pressed as in Example 1 into tough film. The crystalline melting point, Tm, was 360"C while the glass/rubber transition temperature, Tg, was 1650C.
EXAMPLE 3.
Example 1 was repeated but using 0.0667 mol of the hydrated dipotassium salt of 4,4' dihydroxybenzophenone; 11.9027 g (0.0335 mol) of 1,4 - bis - (4 - chlorobenzoyl) benzene; and 9.6224 (0.0335 mol) of 4,4' - dichlorodiphenylsulphone; and a total of 50 g of diphenyl sulphone. [The dihalo compounds comprised 50.11 mol % of the condensants charged and the 4,4' - dichlorodiphenylsulphone 50 mol % of the dihalo compounds.] The resultant polymer contained the repeat units
in the molar ratio 1:1, and so about 20% of the -CO- and --5 0,- linking groups were -SO,-.
The polymer had a reduced viscosity of 1.85 and an absorbance of 0.22, and could be pressed, as in Example 1, into tough films.
The crystalline melting point, Tm, was 333"C while the glass/rubber transition temperature, Tg, was 1770C.
EXAMPLE 4.
25.4604 g (0.0828 mol) of a hydrated dipotassium salt of 4,4' - dihydroxy benzophenone was dehydrated and polymerised with 29.5793 g (0.0833 mol) of 1,4bis - (4 - chlorobenzoyl) benzene as the sole dihalo compound by a procedure similar to that of Example 1, employing a total of 64 g of diphenyl sulphone.
[The dihalo compound comprised 50.15 mole % of the condensants charged.] The prepolymerisation was conducted for seven hours at 230"C and polymerisation for four hours at 320 to 3500 C; the temperature being increased to 350 C as polymerisation ensued to maintain the polymer in solution.
No end stopping reagent was added and the polymerisation terminated by cooling the reaction mixture. The cooled reaction mixture was milled to a particle size of less than 1 mm and worked up by boiling three times with acetone (500 ml; 10 min); once with dilute aqueous acetic acid (500 ml water + 10 ml acetic acid; 20 min); once with water (500 ml; 20 min); and finally once with acetone (500 ml; 15 min).
The resultant polymer powder was dried at 140"C for 24 hours at 100 torr.
The polymer consisted of repeat units of formula
and dissolved in concentrated sulphuric acid to give a red solution (absorbance > 1.0; reduced viscosity 1.19) containing gel.
Film made by the procedure of Example 1, and slow cooled from 400"C, was crystalline, opaque and brittle. The crystalline melting point, Tm, was 3840C.
EXAMPLE 5.
26.4713 g (0.0710 mol) of a hydrated dipotassium salt of 4,4' - dihydroxy- diphenyl sulphone was dehydrated and polymerised with 25.3641 g (0.0714 mol) of 1,4 - bis - (4 - chlorobenzoyl) benzene as the sole dihalo compound by a procedure similar to that of Example 1, employing a total of 62 g of diphenyl sulphone.
[The dihalo compound comprised 50.14 mol % of the condensants charged.] The prepolymerisation was conducted for seven hours at 260"C and polymerisation for one hour at 3200 C. No end stopping reagent was added and the polymerisation terminated by cooling the reaction mixture. The cooled reaction mixture was milled to a particle size of less than 1 mm and worked up by boiling twice with acetone (500 ml; 10 min); once with dilute aqueous acetic acid (500 ml water + 5 ml acetic acid; 10 min); once with water (500 ml; 30 min); and finally once with acetone (500 ml; 10 min). The resultant polymer powder was dried at 1400C for 24 hours at 50 torr.
The polymer consisted of repeat units of formula
and had an absorbance of 0.25 and a reduced viscosity of 1.83. The polymer powder was of moderately low crystallinity and had a crystalline melting point, - Tm, of 2840C.
Film made by the technique of Example 1 with slow cooling from 4000C to 2000C was amorphous, transparent and very tough having a Tg of 185 C. It became opaque when boiled in xylene for 30 min and then exhibited poor crystallinity (Tm 2730C).
EXAMPLE 6.
30.1680 g (0.0899 mol) of a hydrated mixture of equimolar amounts of the dipotassium salts of 4,4' - dihydroxybenzophenone and 4,4' - dihydroxydiphenyl sulphone was dehydrated and polymerised with 32.0879 g (0.0903 mol) of 1,4 - bis (4 - chlorobenzoyl) benzene as the sole dihalo compound by a procedure similar to that of Example 1 employing a total of 75 g of diphenyl sulphone.
[The dihalo compound comprised 50.11 mole % of the condensants charged.] The reactants were prepolymerised for 15+ hours at 240"C and polymerised for 39 hours at 300 to 3200C (the temperature was increased to keep the polymer in solution as polymerisation proceeded). The polymerisation was terminated by adding 2 g of 4,4' - dichlorodiphenyl sulphone and heating at 3200C for a further i hour.
After cooling and grinding the reaction mixture, it was worked up by boiling twice with acetone (500 ml), once with dilute aqueous acetic acid (500 ml water + 5 ml acetic acid), once with water (500 ml), and then with methanol (500 ml). The resultant product was then Soxhlet extracted for 17 hours with acetone and then seven hours with methanol and then dried at 140"C for 24 hours at 100 torr.
A sample of the polymer was dissolved in concentrated sulphuric acid to give an orange solution (absorbance 0.30; reduced viscosity 1.00).
The polymer consisted of units of the formula
in the molar ratio 1:1 and so about 16.7% of the -CO- and -SO2- linking groups were -SO.
The melt stability of the polymer, stabilised with 0.2% by weight triphenyl phosphate, was assessed by melt extrusion at a shear rate of 125 se'. At 3800C no increase in melt viscosity (0.83 kNsm2) was observed over a period of 40 minutes whereas at 400"C the melt viscosity increased from 0.42 to 2.18 kNsm2 over a period of 40 minutes.
EXAMPLE 7.
Example 6 was repeated using a mixture of 3.4949 g (0.01076 mol) of a hydrated dipotassium salt of 4,4' - dihydroxybenzophenone and 12.0275 g (0.03228 mol) of a hydrated dipotassium salt of 4,4' - dihydroxydiphenyl sulphone in place of the equimolar mixture thereof. 15.3658 g (0.04326 mol) of 1,4 - bis - (4 - chlorobenzoyl) benzene and a total of 37 g of diphenyl sulphone were employed.
[The dihalo compound comprised 50.13 mol % of the condensants charged.] Prepolymerisation was conducted for four hours at 2300C and polymerisation 2i hours at 3200 C. The resultant polymer which consisted of the units
in the molar ratio 1:3 (and thus about 25% of the -CO- and -SO,- links were -S 02-) had an absorbance of 0.48 and a reduced viscosity of 1.16.
Film made as in Example 1, with rapid cooling from 4000C to 1500C was tough and transparent but became opaque, i.e. crystalline, upon annealing at 2600C.
EXAMPLE 8.
19.4556 g (0.0447 mol) of a hydrated dipotassium salt of 1,4 - bis - (4hydroxybenzoyl) benzene was dehydrated and polymerised with 15.9768 g (0.0450 mol) of 1,4 - bis - (4 - chlorobenzoyl) benzene as the sole dihalo compound by a procedure similar to that of Example 1, employing a total of 43 g of diphenyl sulphone.
[The dihalo compound comprised 50.17 mol % of the condensants charged.] The reaction mixture was prepolymerised for 22 hours at 2300C to give a thick unstirrable brown paste and then polymerised for two hours at 320 to 3600C; the temperature being gradually raised to 360"C as polymerisation ensued to keep the polymer in solution. No end stopping reagent was added and the polymerisation terminated by cooling the mixture.
The cooled reaction mixture was ground and worked up by the procedure of Example 4.
The polymer, which consisted of units of the formula
was pressed, as in Example 1, with slow cooling from 400"C to give a crystalline opaque brittle film. The film, which could not be made amorphous, had a Tm of 3840C.
A solution of the polymer in concentrated sulphuric acid contained gel and was unfilterable.
EXAMPLE 9.
The procedure of Example 8 was repeated but using 19.5911 g (0.0451 mol) of a hydrated dipotassium salt of 1,4 - bis - (4 - hydroxybenzoyl) benzene and a mixture of 8.0438 g (0.0226 mol) of 1,4 - bis - (4 - chlorobenzoyl) benzene and 6.5028 g (0.0226 mol) of 4,4' - dichlorodiphenyl sulphone as the condensants. The total amount of diphenyl sulphone employed was 41 g.
[The dihalo compounds comprised 50.06 mol % of the condensants charged; and 4,4' - dichlorodiphenyl sulphone 50 mol % of the dihalo compounds.] The prepolymerisation period at 2300C was 21 hours and the polymerisation period was 4 hours at 320"C increasing to 328"C.
The resultant polymer consisted of units of the formula
in the molar ratio 1:1 and so about 14% of the -502- and -CO- links were -SO,-. The polymer dissolved in concentrated sulphuric acid to give a deep red solution (absorbance approximately 1.0; reduced viscosity 1.84).
Film prepared by the technique of Example 1 employing slow cooling from 400 C was crystalline, opaque and brittle. Tm was 359"C.
Attention is hereby drawn to the fact that the subject matter of this application overlaps with that described and claimed in our copending U.K. Application No.
5173/76 (Serial No. 1 563 223).
WHAT WE CLAIM IS: 1. A process for the production of aromatic polyethers comprising heating, at temperatures between 250"C and 400 C, 50 to 51% molar of at least one dihalo compound of formula
where X is a halogen, Q is -CO- or -SO,-, n is 1, 2 or 3 and m is 0, 1, 2 or 3, with 50 to 49% molar of at least one alkali metal bisphenate of formula
(at least 95% of the -OM groups being in the para position) where M is an alkali metal, Q' is -CO- or -SO,-, n' is 1, 2 or 3 and m' is 0, 1, 2 or 3, said at least one bisphenate being in the form of a suspension in an aromatic sulphone of formula
in which Y is a direct link, an oxygen atom, or two hydrogen atoms (one attached to each benzene ring) and Z and Z' are hydrogen atoms or phenyl groups and may be the same or different, at least some of the dihalo compound having the structure
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (16)

  1. **WARNING** start of CLMS field may overlap end of DESC **.
    was pressed, as in Example 1, with slow cooling from 400"C to give a crystalline opaque brittle film. The film, which could not be made amorphous, had a Tm of 3840C.
    A solution of the polymer in concentrated sulphuric acid contained gel and was unfilterable.
    EXAMPLE 9.
    The procedure of Example 8 was repeated but using 19.5911 g (0.0451 mol) of a hydrated dipotassium salt of 1,4 - bis - (4 - hydroxybenzoyl) benzene and a mixture of 8.0438 g (0.0226 mol) of 1,4 - bis - (4 - chlorobenzoyl) benzene and 6.5028 g (0.0226 mol) of 4,4' - dichlorodiphenyl sulphone as the condensants. The total amount of diphenyl sulphone employed was 41 g.
    [The dihalo compounds comprised 50.06 mol % of the condensants charged; and 4,4' - dichlorodiphenyl sulphone 50 mol % of the dihalo compounds.] The prepolymerisation period at 2300C was 21 hours and the polymerisation period was 4 hours at 320"C increasing to 328"C.
    The resultant polymer consisted of units of the formula
    in the molar ratio 1:1 and so about 14% of the -502- and -CO- links were -SO,-. The polymer dissolved in concentrated sulphuric acid to give a deep red solution (absorbance approximately 1.0; reduced viscosity 1.84).
    Film prepared by the technique of Example 1 employing slow cooling from 400 C was crystalline, opaque and brittle. Tm was 359"C.
    Attention is hereby drawn to the fact that the subject matter of this application overlaps with that described and claimed in our copending U.K. Application No.
    5173/76 (Serial No. 1 563 223).
    WHAT WE CLAIM IS: 1. A process for the production of aromatic polyethers comprising heating, at temperatures between 250"C and 400 C, 50 to 51% molar of at least one dihalo compound of formula
    where X is a halogen, Q is -CO- or -SO,-, n is 1, 2 or 3 and m is 0, 1, 2 or 3, with 50 to 49% molar of at least one alkali metal bisphenate of formula
    (at least 95% of the -OM groups being in the para position) where M is an alkali metal, Q' is -CO- or -SO,-, n' is 1, 2 or 3 and m' is 0, 1, 2 or 3, said at least one bisphenate being in the form of a suspension in an aromatic sulphone of formula
    in which Y is a direct link, an oxygen atom, or two hydrogen atoms (one attached to each benzene ring) and Z and Z' are hydrogen atoms or phenyl groups and may be the same or different, at least some of the dihalo compound having the structure
    and/or at least some of the bisphenate having the structure
  2. 2. A process according to Claim 1 in which at least some of the dihalo compound has the formula
  3. 3. A process according to Claim 2 wherein in the dihalo compound of formula
    Q is -CO-.
  4. 4. A process according to Claim 3 wherein at least some of the dihalo compound is 1,4 - bis(4 - halobenzoyl) - benzene.
  5. 5. A process according to any one of Claims 1 to 4 in which at least some of the dihalo compound is selected from a 4,4' - dihalobenzophenone and/or a 4,4' - dihalodiphenyl sulphone.
  6. 6. A process according to any one of Claims 1 to 5 in which the bisphenate is selected from dialkali metal salts of at least one 4,4' - dihydroxy (benzophenone), 4,4'dihydroxy - diphenylsulphone and 1,4 and 1,3 - bis(4 - hydroxybenzoyl)benzene.
  7. 7. A process according to Claim 3 wherein the dihalo compound is
    alone or in conjunction with
    and the bisphenate has the formula
  8. 8. A process according to Claim 7 wherein 3 to 25% of the linking -CO and -SO,- groups are -SO2-.
  9. 9. A process according to Claim 7 or Claim 8 wherein the bisphenate is a mixture of
  10. 10. A process according to any one of Claims 7 to 9 wherein the dihalo reactant contains a compound of formula
    as all or part of a dihalo reactant
    used in conjunction with the dihalo reactant
  11. 11. A process according Claim 10 wherein the reactants consist of a mixture of the compounds
    where the sum of the molar amounts of a) and b) is 50 to 51% of the sum of a)+ b) +c) and the molar mount of b) is 10 to 50% of the sum of a) +b).
  12. 12. A process according to any one of Claims 1 to 11 wherein the halogen atoms X are chlorine or fluorine.
  13. 13. A process according to any one of Claims 1 to 12 wherein the alkali metal M is selected from sodium and potassium.
  14. 14. A process according to any one of Claims 1 to 13 wherein the solvent is diphenyl sulphone.
  15. 15. A process according to Claim 1 substantially as hereinbefore described and with particular reference to any one of the Examples.
  16. 16. Polymers whenever prepared by a process according to any one of Claims 1 to 15.
GB517476A 1977-02-10 1977-02-10 Aromatic polyethers Expired GB1563224A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0194062A2 (en) * 1985-03-05 1986-09-10 Imperial Chemical Industries Plc Polyarylether
EP0327980A2 (en) * 1988-02-12 1989-08-16 BASF Aktiengesellschaft High-temperature-resistant polyaryl ether having an enhanced processability
WO2019002620A1 (en) * 2017-06-30 2019-01-03 Solvay Specialty Polymers Usa, Llc Poly(ether ketone ketone) polymer powder having a low volatiles content

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0194062A2 (en) * 1985-03-05 1986-09-10 Imperial Chemical Industries Plc Polyarylether
EP0194062A3 (en) * 1985-03-05 1986-11-20 Imperial Chemical Industries Plc Polyarylether
AU574900B2 (en) * 1985-03-05 1988-07-14 Imperial Chemical Industries Plc Polyaryl ether
EP0327980A2 (en) * 1988-02-12 1989-08-16 BASF Aktiengesellschaft High-temperature-resistant polyaryl ether having an enhanced processability
US4997902A (en) * 1988-02-12 1991-03-05 Basf Aktiengesellschaft Polyaryl ethers which are stable at high temperatures and have improved processibility
EP0327980A3 (en) * 1988-02-12 1991-07-03 BASF Aktiengesellschaft High-temperature-resistant polyaryl ether having an enhanced processability
WO2019002620A1 (en) * 2017-06-30 2019-01-03 Solvay Specialty Polymers Usa, Llc Poly(ether ketone ketone) polymer powder having a low volatiles content
US11851526B2 (en) 2017-06-30 2023-12-26 Solvay Specialty Polymers Usa, Llc Poly(ether ketone ketone) polymer powder having a low volatiles content

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