GB2116990A - Production of aromatic polyketones - Google Patents
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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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/127—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from carbon dioxide, carbonyl halide, carboxylic acids or their derivatives
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Abstract
Production of thermoplastic aromatic polyketones by reacting the following reactant classes in the presence of fluoroalkane sulphonic acid (such as CF3SO2OH): (a) a selected aromatic monocarboxylic acid (such as 4,-(4-phenoxy) phenoxy benzoic acid), (b) a selected aromatic dicarboxylic acid (such as 1,4-di (4-carboxy)- phenoxybenzene or diphenyl -4,4'- dicarboxylic acid) and a selected aromatic compound (such as 1,4- diphenoxybenzene), and (c) a combination of (a) and (b). The monocarboxylic acids have the formula <IMAGE> the dicarboxylic acids have the formula <IMAGE> and the aromatic compounds have the formula <IMAGE> where Ar is an aromatic radical other than -Ch-CO-Ph- or -PH-SO2-Ph (Ph being phenylene) when y is 1, Y is a direct link, -O-, -S- or -NAr- (Ar' being an aromatic radical), -X- and -X'- are direct links -O-, -S- or -NAr'-, -Z- is -O- or adjacent link, y is 1 to 3, n is 1 or more and m is 0 or 1 or more.
Description
SPECIFICATION
Production of aromatic polyketones
The present invention relates to a process for the production of thermoplastic aromatic polyketones.
Thermoplastic aromatic polyketones are polymers which are well known to the art. They are of significant commercial utility in view of their excellent electrical insulating and mechanical properties at high temperatures, their high strength and toughness and their excellent resistance to fire and chemicals.
It is known to produce aromatic polyketones by electrophilic aroylation processes which utilize a reaction between a mixture of an aromatic diacyl halide and an aromatic compound with at least two aromatically bound hydrogen atoms, or a self-reaction of an aromatic monoacyl halide containing at least one aromatically bound hydrogen atom, or a reaction involving the use of all three types of compound, in the presence of a suitable Friedel
Crafts catalyst, e.g. an Fe salt or a BF3/liquid HF mixture. Examples of such processes are described in British Patents 1 086 021 and 1164817.
Aromatic mono- or diacyi halides tend to be expensive starting materials which means that processes using them tend to be costly to operate.
It has been discovered, as described in European
Patent Publication No. 0 049 070, that it is possible to produce thermoplastic aromatic polysulphones in a fairly general reaction starting from an aromatic monosulphonic acid containing at least one aromatically bound hydrogen atom, or a mixture of an aromatic compound containing at least two aromatically bound hydrogen atoms and an aromatic disulphonic acid, or a combination of both, by effecting the polycondensation in the presence of a fluoroalkane sulphonic acid, such as trifluoromethane sulphonic acid. For example, it is possible to produce an aromatic polyethersulphone of repeat unit:
by polycondensing diphenyl ether-4-sulphonic acid in the presence of trifluoromethane sulphonic acid.
It would be advantageous to apply this chemistry to the somewhat analogous production of aromatic polyotherketones, i.e. employing aromatic mono- or dicarboxylic acids as starting materials instead of aromatic mono- or diacyl halides. Aromatic carboxytic acids are, generally speaking, less expensive than aromatic acyl halides, so that processes employing them may allow a more economical production of aromatic polyketones to be realised. However, we have found that it is not possible to apply the technique discovered for aromatic polysulphone production (discussed above) in such a general manner when it comes to aromatic polyketone production.For example, diphenyl ether - 4 - carboxylic acid reacts only very slowly in the presence of trifluoromethane sulphonic acid at ambient temperature, and even at higher temperatures yields only low molecular weight products in the presence of this reagent.
Nevertheless, we have discovered that it is possible to produce certain aromatic polyketones using the above-discussed technique provided only certain selected aromatic mono- or dicarboxylic acids are used.
According to the present invention there is provided a process for the production of a thermoplastic aromatic polyketone which process comprises reacting in the presence of a fluoroalkane sulphonic acid the reactants selected from the following class:
(a) at least one aromatic monocarboxylic acid of formula:
where -Y- is a direct link, -0-, -S-, -NAr'- where
Ar' is a monovalent aromatic radical (preferably phenyl);Ar is a divalent aromatic radical but must not be -Ph-CO-Ph- or-Ph-SO2-Ph- (where -Ph- is phenylene) when y is 1 (and is preferably phenylene, biphenylene, terphenylene, -pPh-O-OpPh-CO-pPh- O-pPh-, or- pPh - O - pPh - SO2 - pPh - O - pPh - where-pPh- is p-phenylene); and n is an integer of > 1 (preferably 1 to 3) andy is an integer of 1 to 3;
(b) a mixture of at least one aromatic dicarboxylic acid of formula:
where-X-and-X'-are independently a direct link -O-, -S-, -NAr'- where Ar' is as defined in (a); mis O or an integer of > 1 (preferably 1 to 3); and Ar is as defined in (a); and at least one aromatic compound of formula:
where -Z- is - or a direct link; and Ar, n, andy are as defined in (a); and
(c) a combination of (a) and (b).
The presence of the fluoroalkane sulphonic acid in the process of the invention is a crucial feature, and it is thought that this reagent acts as a Brönsted Acid. The preferred fluoroalkane sulphonic acid is trifluoromethane sulphonic acid CF3SO20H. Other fluoroalkane sulphonic acids which may be used are the higher members of a series of fluoroaikane sulphonic acids containing 1 to 18 carbon atoms (which maybefullyfluorinated as described in GB 758467 or partially fluorinated), e.g. the fluoroethane and fluoropropane sulphonic acids such as CF2HCF2SO20H, CF3CF2SO20H and
CF3CF2CF2SO20H. It is convenient to adjust the amount of fluoroalkane sulphonic acid used so that the acid, acts as the reaction solvent.The use of a reaction system which comprises a more catalytic (i.e. much smaller) quantity ofthefluoroalkane sulphonic acid is not, however, excluded from the scope of the invention.
The reaction is preferably effected under substantially anhydrous conditions, i.e. ensuring that free moisture is substantially excluded from the reaction mixture both before and during the reaction. Of course, water is produced as the reaction proceeds but it is thought that this is substantially removed by the fluoroalkane sulphonic acid. A dehydrating agent may also be used if desired to improve the removal of water.
In the reactant sub-class (a) of the invention, a single aromatic monocarboxylic acid (as defined) may be used in the preparation of the aromatic polyketone to produce a polymer consisting solely of units derived from this compound; alternatively two or more such aromatic monocarboxylic acids may be employed to produce a copolymer consisting of units derived from these compounds.
in the reactant sub-class (b) of the invention a single aromatic dicarboxylic acid (as defined) and a single aromatic compound (as defined) may be used in the preparation of the aromatic polyketone to produce a polymer consisting solely of units derived from these compounds; alternatively two or more such aromatic dicarboxylic acids and/or two or more such aromatic compounds may be employed to produce a copolymer containing units derived from these compounds. It is preferably to employ substantially equimolar quantities of the at least one aromatic dicarboxylic acid and the at least one
aromatic compound. However the proportions may
be varied slightly from equimolar quantities in order to modify the molecular weight of the product.
In reactant sub-class (a) of the invention, the at
least one aromatic monocarboxylic acid preferably
has the formula:
in which -Y- is a direct link or-O-; and Ar is phenylene, biphenylene orterphenylene (each having an all para bond arrangement).
Examples of aromatic carboxylic acids in sub-class (a) which may be used are as follows:
Of these, 4 - (4 - phenoxy)phenoxy benzoic acid is particularly preferred since polymerisation according to the invention yields a polymer having the same repeat unit as that of a currently commercially available aromatic polyketone, viz.
or, rewritten,
In reactant sub-class (b) of the invention, the at least one aromatic dicarboxylic acid preferably has the formula:
in which -X- and -X'- are independently a direct link or-O-; Aries phenylene, biphenyleneorterpheny- lene (each having an all para bond arrangement); andmisOor1.
Examples of aromatic dicarboxylic acids in subclass (b) which may be used are as follows:
In reactant sub-class (b), the at least one aromatic compound preferably has the formula:
in which Ar is phenylene, biphenylene and terphenylene, (each having an all para bond arrangement), pPh -O- pPh - CO - pPh - 0 - pPh -, or- pPh - 0 - pPhSO2- pPh - O- pPh -; n is 1 to 3; and y is 1 or 2.
Examples of aromatic compounds in sub-class (b) which may be used are as follows:
The aromatic polyketones produced by the process of the present invention are normally of high molecular weight, usually having, e.g. a reduced viscosity (RV) of at least 1.0 and more usually at least 2.0 and iess than 7. (RV in this specification is measured at 25"C on a solution of the polymer in trifluoromethane sulphonic acid, said solution containing 1 g of polymer per 100 cm3 of solution).
The conditions required for the polymerisation reaction (for example, inter alia, reaction temperature and time) to produce the aromatic polyketone should be determined by experiment as they will vary with the nature of the starting monomer (or monomers) used and with the desired properties of the polymer being manufactured. Conveniently the pressure employed may be atmospheric pressure. A normal reaction temperature range is ambient temperature to 200"C.
The invention is now illustrated by the following
Examples.
EXAMPLE 1
4 - (4 - phenoxy)phenoxy benzoic acid (10 g) was disolved in 100 ml of trifluoromethane sulphonic acid in a conical flask (capacity 250 ml), and the clear red solution allowed to stand at ambient temperature for 48 hours. The highly viscous solution produced was allowed to pass, dropwise in a current of nitrogen, down a glass tube into stirred 10% aqueous NaOH solution. The resulting pink pellets were stirred overnight in this solution, filtered off, boiled in 10% aqueous Na2CO3 solution for 7 hours, then in deionised water until no base residues remained, and finally dried at 150 C under vacuum.
The white pellets of polymer could be moulded at 400"C to give tough, flexible films. The RV of the polymer was 2.28, its glass transition temperature (Tg) was 152"C and its melting point (Tm) was 330"C.
The yield of polymer was essentially quantitative, and the 13C nmr spectrum (sharp peaks at 202.5, 171.4, 154.2,142.4, 126.9, 126.2, 121.0 parts per million) showed it to consist entirely of repeat units having the formula:
The nmr spectrum was identical with that of the commercially available aromatic polyketone produced bythe nucleophilicpolycondensation of hydroquinone and 4,4' - difluorobenzophenone as described in European Patent Pubiication No. 001 879.
EXAMPLE 2
1,4- diphenoxybenzene (1.5 g) and 1,4 - di(4 carboxy)phenoxy benzene (2.0 g) were dissolved in 17.5 ml of trifluoromethane sulphonic acid, and the clear red-brown solution was allowed to stand at ambient temperature for 18 hours. The resulting viscous solution was treated as in Example 1 to give a white, tough, polymer having a 13 C nmr spectrum which showed it to possess a repeat unit identical to that of the polymer of Example 1. The polymer had a
Tg of 152"C and a Tm of 334"C.
EXAMPLE 3
1,4 - diphenoxybenzene (2 g) and diphenyl - 4,4' dicarboxylic acid (1.85 g) were dissolved in 19 ml of trifluoromethane sulphonic acid, and the resulting solution was allowed to stand at ambient temperature for 144 hours. The viscous red-brown solution was allowed to run, as a thin filament, into 10% aqueous NaOH solution. Further treatment, as per
Example 1, gave a fibrous mass of ivory-coloured polymer which was dried at 150"C under vacuum.
The polymer had a Tg of 192"C and a Tm of 428"C. Its 13C nmrspectrum (peaks at 203.5,171.7,152.6, 149.2,142.6,137.0, 132.4,130.8,125.4 and 120.5 parts per million) showed it to consist essentially of repeat units of formula:
EXAMPLE 4
4 - (4 - Phenoxy)phenyl benzoic acid (1.0 g) was dissolved in 5 ml of trifluoromethane sulphonic acid and the deep red-brown solution was allowed to stand at ambient temperature for 46 hours. The extremely viscous solution was diluted with a further 8 ml of trifluoromethane sulphonic acid, and then poured, as a thin filament, into stirred 10% aqueous
NaOH solution.The resulting fibrous polymer was treated with boiling 10% aqueous Na2CO3 solution, then with boiling water, and finally with acetone, before drying under vacuum at 150"C. The tough white polymer had RV of 6.54, a Tg of 216"C and a
Tm of 486"C and consisted essentially of repeat units offormula
EXAMPLE 5
Diphenyl ether - 4,4' - dicarboxylic acid (1.97 g) and 1,4- diphenoxybenzene (2.0 g) were dissolved in 19 ml trifluoromethane sulphonic acid, and the dark red solution was allowed to stand at ambient temperature for 140 hours.The resulting solution was treated as in Example 3 to give a white polymer of RV 2.68 having a Tg of 151"C and a Tm of 345"C, and consisting essentially of repeat units of formula
EXAMPLE 6 {COMPARATIVE)
Terephthalic acid (1.66 g) and 1,4 - diphenoxybenzene (2.85 g) were dissolved in 20 ml trifluoromethane sulphonic acid and the solution was allowed to stand at ambient temperature for 48 hours. No increase in viscosity was observed, and the solution was then heated to 90"C for 5 hours. A slight increase in viscosity occurred, but on pouring the solution into 10% aqueous NaOH solution only brittle, powdery material was precipitated. High polymer was clearly not formed in this reaction.
EXAMPLE 7 (COMPARATIVE)
4-Phenoxy benzoic acid (1.0 g) was dissolved in 5 ml trifluoromethane sulphonic acid and this solution was allowed to stand at ambient temperature for 100 hours. Periodic examination of the solution by 1H nmr spectroscopy showed that a slow reaction was occurring, but polymer was not formed.
EXAMPLE 8 (COMPARATIVE)
4,4' - Diphenoxy - benzophenone (0.37 g) and diphenyl - 4,4' - dicarboxylic acid (0.24 g) were dissolved in 5 ml trifluoromethane sulphonic acid and the solution was heated at 80"C for 4 hours. On pouring into water only brittle, low molecular weight material was obtained.
EXAMPLE 9
4 - (4 - Phenoxy)phenoxy benzoic acid (1.0 g) and 4 - (4 - phenoxy)phenyl benzoic acid (0.95 g) were dissolved in 23 ml of trifluoromethane sulphonic acid, and the resulting deep red-brown solution was observed to become very viscous over 6 hours at ambient temperature. After 24 hours the solution was run, as a fine filament, into 10% aqueous NaOH solution, and the precipitated fibrous copolymer, having the repeat units of formulae
was treated as in Example 1. This material had a Tg of 167"C and a Tm of 334"C.
EXAMPLE 10
4,4' - diphenoxybiphenyl (1.93 g) and 1,4 - di(4 carboxy) phenoxy benzene (2.00 g) were dissolved in 45 ml of trifluoromethane sulphonic acid, and the solution was allowed to stand at ambient temperature for 24 hours. After this time a clear red-brown gel had formed, which was cut into small pieces and treated with 10% aqueous NaOH at 100 Cfor4 hours. The fragments of polymer were then suspended in refluxing 10% sodium carbonate solution for 48 hours, washed and finally extracted successively with N,N - dimethyl formamide, water, and acetone. The resulting polymer, after drying at 1 50"C under vacuum, had a Tg of 173"C and a Tm of 370"C.
A material of the same composition, but of lower molecular weight, was obtained by stopping the polymerisation after 21/2 hours, and the 13C nmr spectrum of this polymer indicated repeating units of the formula
EXAMPLE ii 4,4' - Diphenoxybiphenyl (2.40 g) and diphenyl 4,4' - dicarboxylic acid (1.72 g) were dissolved in 46.4 ml of trifluoromethane sulphonic acid, and the deep brown solution was allowed to stand at ambient temperature for 120 hours. The viscous solution was treated as in Example 1, to give a tough, pale brown polymer, having the repeat units of formula
which had Tg 209 C and Tm 414 C.
EXAMPLE 12 4,4' - Diphenoxybiphenyl (2.00 g) and diphenyl ether - 4,4' - dicarboxylic acid (1.53 g) were dissolved
in trifluoromethane sulphonic acid (39.7 ml), and the
solution was allowed to stand at ambient tempera
ture for 72 hours. Dropwise addition of this solution
to 10% aqueous sodium hydroxide gave pellets of
polymer which were treated as in Example 1. The Tg of this material was 172"C and Tm was 374"C. The 13C nmr spectrum indicated that the polymer con
sisted essentially of repeating units of the formula
EXAMPLE 13 4 - (4 - Phenoxy)phenoxybiphenyl (2.40 g) and diphsnyl - 4,4' - dicarboxylic acid (1.72 g) were dissolved in 46 ml of trifluoromethane sulphonic acid, and the solution was allowed to stand at ambient temperature for 360 hours. The resulting deep red viscous solution was treated as in Example 1 to give pellets of cream-coloured polymer having
Tg 200"C and Tm 407 C. The 13C nmr spectrum was consistent with a structure having repeating units of the formula
EXAMPLE 14 4 - (4 - Phenoxy)phenoxybiphenyl (2.49 g) and 4,4' - dicarboxydiphenyl ether (1.90 g) were dissolved in 49 ml of trifluoromethane sulphonic acid, and the solution was a!lowed to stand at ambient temperature for 17 hours. Treatment of this solution, as in
Example 1, gave pellets of a polymer which had Tg 1650C and Tm 348"C. The 13C nmr spectrum of this material was consistent with a structure having repeating units of the formula
Claims (16)
1. A process for the production of a thermoplastic aromatic polyketone characterised in that said process comprises reacting in the presence of a fluoroalkane sulphonic acid the reactants selected from the following class:
(a) at least one aromatic monocarboxylic acid of formula:
where-Y- is a directlink,-O-,-S-,-NAr'-where Ar' is a monovalent aromatic radical;Ar is a divalent aromatic radical but must not be-Ph-COPh-or -Ph-SO2-Ph- (where-Ph- is phenylene) when y is 1; and n is an integer of > 1 andy is an integer of 1 to 3;
(b) a mixture of at least one aromatic dicarboxylic acid of formula:
where -X- and -X'- are independently a direct link -O-,-S,-NAr'-whereAr' is as defined in (a); mis O or an integer of 1; and Ar is as defined in (a); and at least one aromatic compound of formula:
where-Z- is -0- or a direct link; and Ar, n, andy are as defined in (a); and
(c) a combination of (a) and (b).
2. A process according to claim 1 characterised in that Ar is phenylene, biphenylene, terphenylene, pPh - 0 - pPh - CO- pPh - O- pPh - or- pPh - 0 - pPh - SO2- pPh - 0 - pPh - where pPh is p-phenylene.
3. A process according to either claim 1 or claim 2 characterised in that sub-classes (a) and (b) n is an integer of 1 to 3.
4. A process according to any one of the preceding claims characterised in that in sub-class (a) the at least one aromatic monocarboxylic acid has the formula
wherein -V- is further limited by being a direct link or -0- and -Ar- is further limited by being phenylene, biphenylene or terphenylene (each having an all para bond arrangement).
5. A process according to claim 4 characterised in that said at least one aromatic monocarboxylic acid is selected from
6. A process according to any one of the preceding claims characterised in that in sub-class (b) m is
O or an integer of 1 to 3.
7. A process according to claim 6 characterised in that in sub-class (b) the at least one aromatic dicarboxylic acid has the formula
wherein -X- and -X'- are further limited by being independently a direct link or-0-; -Ar- is further limited by being phenylene, biphenylene or terphenylene (each having an all para bond arrangement); and m is further limited by being 0 or 1.
8. A process according to claim 7 characterised in that said at least one aromatic dicarboxylic is selected from
9. A process according to any one of the preceding claims characterised in that in sub-class (b) the at least one aromatic compound has the formula
wherein -Ar- is further limited by being phenylene, biphenylene, orterphenylene (each having an all para bond arrangement), - pPh - 0 - pPh - CO - pPh - 0 - pPh -, or - pPh - 0 - pPh - SO2 - pPh - 0 - pPh -; n is an integer of 1 to 3; andy is further limited by being 1 or 2.
10. A process according to claim 9 characterised in that said at least one aromatic compound is selected from
11. A process according to any one of the preceding claims characterised in that the fluoroalkane sulphonic acid used is trifluoromethane sulphonic acid.
12. A process according to any one of the preceding claims characterised in that the fluoroalkane sulphonic acid acts as the reaction solvent.
13. An aromatic polyetherketone characterised by being produced by a process according to any one of the preceding claims.
14. An aromatic polyetherketone according to claim 13 characterised by having an RV of at least 1.0.
15. An aromatic polyetherketone according to either claim 12 or claim 13 characterised in that it has repeat units of formula
alone or with other repeat units.
16. An aromatic polyetherketone according to any one of claims 13 to 15 characterised in that it has repeat units of at least one or more of the following formulae
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08305042A GB2116990B (en) | 1982-03-17 | 1983-02-23 | Production of aromatic polyketones |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8207783 | 1982-03-17 | ||
| GB08305042A GB2116990B (en) | 1982-03-17 | 1983-02-23 | Production of aromatic polyketones |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8305042D0 GB8305042D0 (en) | 1983-03-30 |
| GB2116990A true GB2116990A (en) | 1983-10-05 |
| GB2116990B GB2116990B (en) | 1985-11-06 |
Family
ID=26282268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08305042A Expired GB2116990B (en) | 1982-03-17 | 1983-02-23 | Production of aromatic polyketones |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2116990B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0176988A1 (en) * | 1984-09-28 | 1986-04-09 | Amoco Corporation | An article molded from a blend of a poly(aryl ether ketone)and a poly(aryl ether sulfone) |
| EP0176989A1 (en) * | 1984-09-28 | 1986-04-09 | Amoco Corporation | Molded articles manufactured from blends of a biphenyl containing poly(aryl ether sulfone) and a poly(aryl ether ketone) |
| US4820792A (en) * | 1986-04-11 | 1989-04-11 | Raychem Limited | Preparation of aromatic polyketones using a strong acid catalyst with a weaker acid solvent |
| US4839459A (en) * | 1988-06-27 | 1989-06-13 | Eastman Kodak Company | Process for the preparation of poly(ether-ketone) polymers |
| WO1992001662A1 (en) * | 1990-07-23 | 1992-02-06 | Eastman Kodak Company | Process for preparing diketones and keto-acids |
| WO1994005618A1 (en) * | 1992-08-31 | 1994-03-17 | Eastman Kodak Company | Process for the production of diiodoketones |
| US5338881A (en) * | 1990-07-23 | 1994-08-16 | Eastman Chemical Company | Process for preparing diketones |
| GB2355464A (en) * | 2000-02-11 | 2001-04-25 | Victrex Mfg Ltd | Aromatic polyetherketones |
| EP1170318A1 (en) * | 2000-07-06 | 2002-01-09 | Gharda Chemicals Limited | Melt processible polyether ether ketone polymer |
| JP2013053194A (en) * | 2011-09-01 | 2013-03-21 | Yamagata Univ | Method of producing aromatic polyketone, and aromatic polyketone |
-
1983
- 1983-02-23 GB GB08305042A patent/GB2116990B/en not_active Expired
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0176988A1 (en) * | 1984-09-28 | 1986-04-09 | Amoco Corporation | An article molded from a blend of a poly(aryl ether ketone)and a poly(aryl ether sulfone) |
| EP0176989A1 (en) * | 1984-09-28 | 1986-04-09 | Amoco Corporation | Molded articles manufactured from blends of a biphenyl containing poly(aryl ether sulfone) and a poly(aryl ether ketone) |
| US4820792A (en) * | 1986-04-11 | 1989-04-11 | Raychem Limited | Preparation of aromatic polyketones using a strong acid catalyst with a weaker acid solvent |
| US4839459A (en) * | 1988-06-27 | 1989-06-13 | Eastman Kodak Company | Process for the preparation of poly(ether-ketone) polymers |
| WO1992001662A1 (en) * | 1990-07-23 | 1992-02-06 | Eastman Kodak Company | Process for preparing diketones and keto-acids |
| US5107029A (en) * | 1990-07-23 | 1992-04-21 | Eastman Kodak Company | Process for preparing diketones and keto-acids |
| US5338881A (en) * | 1990-07-23 | 1994-08-16 | Eastman Chemical Company | Process for preparing diketones |
| WO1994005618A1 (en) * | 1992-08-31 | 1994-03-17 | Eastman Kodak Company | Process for the production of diiodoketones |
| GB2355464A (en) * | 2000-02-11 | 2001-04-25 | Victrex Mfg Ltd | Aromatic polyetherketones |
| EP1263836A1 (en) | 2000-02-11 | 2002-12-11 | Victrex Manufacturing Limited | Aromatic polyetherketones |
| GB2355464B (en) * | 2000-02-11 | 2004-08-11 | Victrex Mfg Ltd | Aromatic polyetherketones |
| US6909015B2 (en) | 2000-02-11 | 2005-06-21 | Victrex Manufacturing Limited | Aromatic polyetherketones |
| EP1170318A1 (en) * | 2000-07-06 | 2002-01-09 | Gharda Chemicals Limited | Melt processible polyether ether ketone polymer |
| US6566484B2 (en) | 2000-07-06 | 2003-05-20 | Gharda Chemicals Ltd. | Melt processible polyether ether ketone polymer |
| EP1473314A1 (en) * | 2000-07-06 | 2004-11-03 | Gharda Chemicals Limited | Melt processible polyether ether ketone polymer |
| US6881816B2 (en) | 2000-07-06 | 2005-04-19 | Gharda Chemicals Ltd. | Melt processible polyether ether ketone polymer |
| JP2013053194A (en) * | 2011-09-01 | 2013-03-21 | Yamagata Univ | Method of producing aromatic polyketone, and aromatic polyketone |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2116990B (en) | 1985-11-06 |
| GB8305042D0 (en) | 1983-03-30 |
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