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GB2172294A - Process for preparing poly(aryl ether ketones) - Google Patents

Process for preparing poly(aryl ether ketones) Download PDF

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Publication number
GB2172294A
GB2172294A GB08605837A GB8605837A GB2172294A GB 2172294 A GB2172294 A GB 2172294A GB 08605837 A GB08605837 A GB 08605837A GB 8605837 A GB8605837 A GB 8605837A GB 2172294 A GB2172294 A GB 2172294A
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Prior art keywords
chloride
bis
carbonyl
naphthalene
diphenyl
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GB08605837A
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GB8605837D0 (en
Inventor
Robert Andrew Clendinning
Louis Michael Maresca
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Union Carbide Corp
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Union Carbide Corp
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/127Macromolecular 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A process for preparing poly(aryl ether ketones) comprising reacting nucleophilic coreactants with electrophilic coreactants under Friedal Crafts polymerization conditions in a solvent comprising 1,2- dichlorethane. Preferably, diphenyl ether is reacted with terephthaloyl chloride and/or isophthaloyl chloride.

Description

SPECIFICATION Process for preparing poly(aryl ether ketones) This invention is directed to an improved process for preparing poly(aryl ether ketones) by reacting a nucleophilic coreactant with an electrophilic coreactant under Friedel-Crafts polymerization conditions, wherein the improvement comprises carrying out the polymerization in a solvent comprising 1,2-dichloroethane.
The preparation of poly(aryl ether ketones) by Friedel-Crafts polymerization techniques is well known in the art. For example, U. S. Patent No. 3,065,205 describes the preparation of aromatic polyketones by Friedel-Crafts polymerization techniques using an organic solvent for the reaction. The solvents used are nitrobenzene, symmetrical tetrachloroethane, dichlorobenzene or carbon disulfide. Nitrobenzene is used as a solvent in all of the examples. The reaction mixture is stated as remaining homogeneous throughout the polymerization. However, the process described in U.S. Patent No. 3,065,205 produces polymers of very low molecular weights and inherent viscosities ranging from 0.13 to 0.18, as measured in concentrated sulfuric acid.
In describing the difficulty in preparing polyketones such as those described in U. S. Patent No. 3,065,205, U.S. Patent No. 3,791,890 states the problem as the relatively intractable nature of the initial polymer-catalyst complex upon formation. The patent states the following in column 1, lines 10 to 20: "Previous attempts to deal with the generally intractable state of the reaction product have included polymerizing the monomers in the presence of a soluble solid material to permit removing the product from the reaction medium and subsequently separating the soluble material by leaching. However, none of these prior techniques has proved entirely satisfac tory." In U. S. Patent No. 3,791,890, an improved process is described in which polyketones are prepared in granular form in a two step process.In the first step diphenyl ether and at least one of terephthalic or isophthalic acid chlorides are reacted in the presence of o-dichlorobenzene, sym-tetrachloroethane, or dichloroethane as a solvent utilizing a Friedel-Crafts catalyst, such as aluminum chloride, at a temperature of from - 1 50C to OOC. All the examples use o-dichlorobenzene as the solvent. The patent states that an initial low reaction temperature is desirable to maintain control over the rate of reaction so that coagulation of the formed polyketone does not occur before dispersion can be effected.In the next step, the reaction mixture produced is dispersed into a fluid medium maintained at a temperature of at least 50"C. The fluid medium is described as any gas or liquid in which the polyketone formed is substantially unreactive at the temperature employed in the process. The dispersion into a heated fluid is stated to segregate the particles of polymer that are beginning to form in the initial reaction mixture and prevent the agglomeration of the particles into a gelatinous mass. A granular polyketone is thus recovered.
However, in this patent no viscosities for the polyketone are reported.
In U.S. Patent No. 3,668,057 describes the preparation of copolyketones with reduced viscosities of about 0.9 dl/g (as measured in concentrated sulfuric acid at 25"C) under Freidel-Crafts polymerization conditions with o-dichlorobenzene as solvent. However, polymers with reduced viscosities of about 0.9dl/g are boarderline with regard to toughness in same end-use applications. Copolyketones with high reduced viscosities are possible using hydrofluoric acid as the solvent and boron trifluoride as the catalyst. However, due to the toxicity of hydrofluoric acid/boron trifluoride it is not a system which is conductive to commercialization.
In the present invention a one step process to prepare high molecular weight poly(aryl ether ketones) has been discovered. It has been found that the use of 1,2-dichloroethane as a solvent in Friedel-Crafts polymerization process produces poly(aryl ether ketones) of high molecular weight in comparison to processes where solvents such as nitrobenzene and o-dichlorobenzene are utilized. The process of this invention prepares higher molecular weight (reduced viscosity) poly (aryl ether ketones) directly without the need of the dispersion step as required in U.S.
Patent No. 3,791,890.
The poly(aryl ether ketones) prepared by the process of this invention have reduced viscosities ranging from about 0.1 dl/g to about 3.0 dl/g, preferably from about 0.5 dl/g to about 2.0 dl/g., as measured in concentrated sulfuric acid at 25"C (concentration of 1g/100ml).
The poly(aryl ether ketones) may be prepared by reacting: (a) a mixture of substantially equimolar amounts of (i) at least one electrophilic aromatic diacyl halide of the formula YOC-Ar-COY where -Ar- is a divalent aromatic radical such as phenylene, diphenylether-4,4'-diyl, diphenyl 4,4'-diyl, naphthalene-diyl, and the like, Y is halogen such as chlorine, bromine or iodine with chlorine being preferred, and COY is an aromatically bound acyl halide group, which diacyl halide is polymerizable with at least one aromatic compound of (a)(ii), and (ii) at least one aromatic nucleophilic compound of the formula H-Ar'-H where -Ar'- is a divalent aromatic radical such as diphenylether-4,4'-diyl, 2,7-dibenzofuranediyl, diphenyl-4,4'-diyl, diphenylmethane-4,4'-diyl, naphthalene-diyl, phenanthrenediyl, and the like, and H is an aromatically bound hydrogen atom, which compound is polymerizable with at least one diacyl halide of (a)(i), and (b) at least one aromatic monoacyl halide of formula H-Ar"-COY where -Ar"- is a divalent aromatic radical such as diphenylether-4,4'-diyl, diphenylmethane -4,4'diyl, naphthalene-diyl, diphenyl-4,4'-diyl, 2,7-dibenzofuranediyl, and the like, and H is an aromatically bound hydrogen atom, Y is as defined above, and COY is an aromatically bound acyl halide group, which monoacyl halide is self-polymerizable, and (c) a combination of (a) and (b).
Specifically, the polyketones may be prepared by reacting one or more of the following nucleophilic coreactants: diphenyl sulfide, dibenzofuran, thianthrene, phenoxathin, phenodioxin, diphenylene, diphenyl, dibenzodioxine, xanthone, 4,4'-diphenoxybiphenyl, 2,2'-diphenoxybiphenyl, 1,2-diphenoxybenzene, 1,3-diphenoxybenzene, 1,4-diphenoxybenzene, 1-phenoxynaphthalene, 1 ,2-diphenoxynaphthalene, diphenyl ether, 1 ,5-diphenoxynapthalene.
Similarly, the following electrophilic aromatic coreactant candidates for polyketone formation may be useful: terephthaloyl chloride, isophthaloyl chloride, thio-bis(4,4'-benzoyl chloride), benzophenone-4,4'-di(carbonyl chloride), oxy-bis(4,4'-benzoyl chloride), oxy-bis(3 ,3'-benzoyl chloride), diphenyl-3,3'-di(carbonyl chloride), carbonyl-bis(3,3'-benzoyl chloride), sulfonyl-bis(4,4'-benzoyl chloride), sulfonyl-bis(3,3'-benzoyl chloride), sulfonyl-bis(3,4'-benzoyl chloride), thio-bis(3,4'-benzoyl chloride), diphenyl-3,4'-di(carbonyl chloride), oxy-bis[4,4'-(2-chlorobenzoyl chloride)], naphthalene-1 ,6-di(carbonyl chloride), naphthalene-1 ,7-di(carbonyl chloride), naphthalene-1 ,5-di(carbonyl chloride), naphthalene-2,6-di(carbonyl chloride), oxy-bis[7,7'-naphthalene-2,2'-di(carbonyl chloride)], thio-bis[8,8'-naphthalene-2,2'-di(carbonyl chloride)], 7,7'-binaphthyl-2,2'-di(carbonyl chloride), diphenyl-4,4'-di(carbonyl chloride), carbonyl bis[7,7'-naphthalene-2,2'-di(carbonyl chloride)], sulfonyl-bis[6,6'-naphthalene-2,2'-di(carbonyl chloride)], dibenzofuran-2,7-di(carbonyl chloride) and the like, or the combination of any of the above.
In addition to the electrophilic aromatic coreactants carbonyl chloride (phosgene), carbonyl dibromide, carbonyl difluoride or oxalyl chloride may be used.
Examples of compounds corresponding to the formula H-Ar"-COY include p-phenoxybenzoyl chloride, p-biphenyloxybenzoyl chloride, 4-(p-phenoxyphenyl) benzoyl chloride, 4-(p-phenoxybenzoyl) benzoyl chloride, 4(p-phenoxyphenoxy) benzoyl chloride 3-chlorocarbinyl dibenzofuran, 1naphthoyl chloride, 2-naphthoyl chloride, and the like.
Preferably, diphenyl ether is reacted with terephthaloyl chloride and/or isophthaloyl chloride.
The preferred Friedel-Crafts catalysts are aluminum chloride, antimony pentachloride and ferric chloride. Other Friedel-Crafts catalysts, such as aluminum bromide, boron trifluoride, zinc chloride, antimony trichloride, ferric bromide and stannic chloride, can also be used.
The reaction may be carried out over a range of temperatures of from about 0 C. to about 160"C. In general, it is preferred to carry out the reaction at a temperature in the range of between 0 and 30"C. However, in some cases it is advantageous to carry out the reaction at temperatures above 30"C. or below 0 C. The reaction is generally carried out at ambient pressure. However, in some instances it may be advantageous to carry out the reaction at pressures greater than atmospheric or at subatmospheric pressures.
The reaction is carried out in a solvent system containing at least 50 percent by weight of 1,2-dichloroethane.
The reaction may be carried out in the presence of a capping agent as described in U. S.
Patent Application Serial No. (D-14604) filed on an even date as this application in the name of L. M. presca and titled, "A Method For Stabilizing Poly(Aryl Ether Ketones)", commonly assigned.
Said application is directed to a method of stabilizing poly(aryl ether ketones) by reacting nucleophilic coreactants with electrophilic coreactants under heterogeneous Friedel-Crafts polymerization conditions by adding a nucleophilic and/or electrophilic capping agent during polymeri zation.
The nucleophilic capping agents are of the general formula:
wherein x is a covalent bond, -0-, -S-, or -CR2- wherein each R is independently hydrogen, an alkyl or fluoroalkyl group, preferably of 1 to 10 carbons, phenyl or an electron withdrawing group substituted phenyl. Preferably, x is a covalent bond, or 0, y is NO2,
or if x is a covalent bond, y can also be hydrogen as well as any of the foregoing, z is halogen, alkyl or alkoxy Specific examples of appropriate nucleophilic capping agents are 4-nitrodiphenyl ether 4-phenoxybenzophenone 4-phenoxydiphenyl sulfone anisole fluorobenzene chlorobenzene biphenyl toluene.
acetyl chloride The electrophilic capping agents correspond to the formula
where w=halogen, alkyl, alkoxy, nitro,
Specific examples of these end capping agents include the following benzoyl chloride p-fluorobenzoyl chloride p-chlorobenzoyl chloride p-methoxybenzoyl chloride benzene sulfonyl chloride p-chlorobenzene sulfonyl chloride p-methylbenzene sulfonyl chloride 4-benzoyl-benzoyl chloride The capping agents may be added anytime during or after the polymerization reaction but preferably are added with the reactants at the beginning of the polymerization reaction.
The polymer of this invention may include mineral fillers such as carbonates including chalk, calcite and dolomite; silicates including mica, talc, wollastonite; silicon dioxide; glass spheres' glass powders; aluminum; clay; quartz; and the like. Also, reinforcing fibers such as fiberglass, carbon fibers, and the like may be used. The polymers may also include additives such as titanium dioxide; thermal stabilizers, ultraviolet light stabilizers, plasticizers, and the like.
The polymers of this invention may be fabricated into any desired shape, i.e., moldings, coatings, films or fibers. They are particularly desirable for use as electrical insulation for electrical conductors.
EXAMPLES The following examples serve to give specific illustrations of the practice of this invention but they are not intended in any way to limit the scope of this invention.
Example I A 2 liter, 3 neck, round bottom flask was equipped with a mechanical stirrer, a nitrogen inlet, condenser and a thermometer. The flask was charged with 14.21 g (0.07 moles) of terephthaloyl chloride, 6.09 9 (0.030 moles) of isophthaloyl chloride, 17.01 9 (0.100 moles) of diphenyl ether and 700 mls of 1,2-dichloroethane. This solution was cooled to 5"C in an ice water bath.
Aluminum chloride (34.76 g, 0.260 moles) was added in portions while maintaining the temperature below 10 C. The resulting reaction mixture was held at 5"-10"C for 6 hours. After 30 minutes a precipitate formed. At the end of 6 hours the ice bath was removed and the reaction mixture was allowed to warm to ambient temperatures (--25"C) where it was held for an additional 16 hours. The reaction mixture was poured into 3 liters of ice water containing 100 ml of concentrated hydrochloric acid. The resulting three phase system was heated to --85"C to distill the 1,2-dichloroethane.The polymer was isolated by filtration, washed with water (2X500 ml) and methanol (2X500 ml) and dried in a vacuum oven at 100"C. The product had a reduced viscosity of 1.62 dl/g as measured in concentrated sulfuric acid at 25"C and a concentration of 9/100 ml.
Comparative Examples A-M Example 1 was repeated using a variety of solvents, including those well known to be useful in Friedel-Crafts reactions. The results are summarized in Table 1.
TABLE 1 Reduced Viscosity of Final Example Solvent Polymer (dl/g) A Carbon Disulfide 0.06 B 1,1,1-Trichloroethane 0.07 C Methylene Chloride 0.50 D Methylene Chloride' 0.92 E Carbon Tetrachloride 0.07 F Trichloroethylene 0.17 G Nitrobenzene 0.18 H O-Dichlorobenzene 0.31 O-Dichlorobenzene2 0.47 J O-Dichlorobenzene3 0.51 K 1,2,4-Trichlorobenzene 0.09 L Trichlorofluoromethane 0.05 M 1,1 ,2-Trichlorotrifluoroethane 0.04 '1% excess of diphenyl ether was used 2Four hours at 80"C instead of 16 hours at 25"C 3Six hours at 80"C instead of 16 hours at 25"C Although relatively high molecular weight polymers can be prepared using methylene chloride, this solvent participates in the reaction resulting in alkylation of the polymer backbone as a major side product. Excess diphenyl ether is needed to obtain high molecular weight product because of this side reaction which consumes diphenyl ether and disrupts the reaction stoichiometry. These alkylated side products lead to polymer instability at elevated temperatures.
Examples 2-7 Example 1 was repeated except that a capping agent was added to control the molecular weight of polymer. The stoichiometry of the primary reactants is shown in the equation:
0 9 0 Cl-C + 04) +2X oC-Ct c-c Act 3 1.2 dichloroethane 5"-25"C ocAoococ3Rowco Reduced viscosity as a function of the end capping agent concentration is shown in Table 2.
TABLE 2 Terephthaloyl Chloride/ Isophthaloyl Reduced Example Chloride X Viscosity 2 90/10 .003 1.21 3 100/0 .003 1.46 4 95/5 .005 .83 5 95/5 .015 .58 6 95/5 .025 .54 7 90/10 .025 .49 8 100/0 .025 .55 9 90/10 .050 .36 10 90/10 .050 .36 11 100/0 .050 .39 12 100/0 .050 .39

Claims (11)

1. A process for preparing a poly(aryl ether ketone) by reacting nucleophilic coreactants with electrophilic coreactants under Friedel-Crafts polymerization conditions, wherein the process is carried out in a solvent comprising 1,2-dichloroethane.
2. A process as claimed in claim 1 wherein the poly(aryl ether ketone) is prepared by reacting one or more of the following nucleophilic coreactants: diphenyl sulfide, dibenzofuran, thianthrene, phenoxathin, phenodioxin, diphenylene, diphenyl, 4,4'-diphenoxybiphenyl, 2,2'-diphenoxylbiphenyl, 1 ,2-diphenoxybenzene, 1 ,3-diphenoxybenzene, 1 ,4-diphenoxybenzene, 1-phenoxy- naphthalene, 1 ,2-diphenoxynaphthalene, diphenyl ether, or 1 ,5-diphenoxynaphthalene.
3. A process as claimed in claim 1 or claim 2 wherein the poly(aryl ether ketone) is prepared by reacting one or more of the following electrophilic coreactants: phosgene, carbonyl difluoride, terephthaloyl chloride, isophthaloyl chloride, thio-bis(4,4'-benzoyl chloride), benzophenone-4,4'-di(carbonyl chloride), oxy-bis(4,4'-benzoyl chloride), oxy-bis(3,3'-benzoyl chloride), diphenyl-3,3'-di(carbonyl chloride), carbonyl-bis(3,3'-benzoyl chloride), sulfonyl-bis(4,4'-benzoyl chloride), sulfonyl-bis(3,3'-benzoyl chloride), sulfonyl-bis(3,4'-benzoyl chloride), thio-bis(3,4'-benzoyl chloride), diphenyl-3,4'-di(carbonyl chloride), diphenyl-4,4'-di(carbonyi chloride), oxy-bis[4,4'-(2-chlorobenzoyl chloride)], naphthalene-1 ,5-di(carbonyl chloride), naphthalene-1 ,6-di(carbonyl chloride), naphthalene-1,7-di(carbonyl chloride), naphthalene-2,6'-di(carbonyl chloride), oxy-bis[7,7'-naphthalene-2,2'-di(carbonyl chloride)], thio-bis[8,8'-naphthalene-2,2'-di(carbonyl chloride)], 7,7'-binaphthyl-2'-di(carbonyl chloride), carbonyl-bis[7,7'-naphthalene-2,2'-di(carbonyl chloride)], sulfonyl-bis[6,6'-naphthalene-2,2'-di(carbo- nyl chloride)], or dibenzofuran-2,7-di(carbonyl chloride).
4. A process as claimed in claim 1 wherein the reactant and/or coreactant is selected from 4-phenoxybenzoyl chloride, 1-phenoxy-1-naphthalene carbonyl chloride, 4-phenoxy-4'-chlorocarbonyl diphenyl or 4-phenoxy-3'-chlorocarbonyl diphenyl ether.
5. A process as claimed in claim 1 wherein diphenyl ether is reacted with terephthaloyl chloride and/or isophthaloyl chloride.
6. A process as claimed in any one of the preceding claims wherein the process is carried out in the presence of a Freidel-Crafts catalyst selected from aluminium chloride, antimony pentachloride or ferric chloride.
7. A process as claimed in any one of the preceding claims wherein the process is carried out at a temperature of from about 0 C to about 25"C.
8. A process as claimed in claim 1 substantially as hereinbefore described in any one of Examples 1 to 7.
9. A poly(aryl ether ketone) whenever prepared by a process as claimed in any one of the preceding claims.
10. Mouldings, coatings, films or fibers whenever made from a poly(aryl ether ketone) as claimed in claim 9.
11. Electrical insulation for electrical conductors whenever comprising a poly(aryl ether ketone) as claimed in claim 9.
GB08605837A 1985-03-11 1986-03-10 Process for preparing poly(aryl ether ketones) Withdrawn GB2172294A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989004848A1 (en) * 1987-11-17 1989-06-01 Raychem Limited Preparation of poly(arylene ether ketones)
US4918237A (en) * 1989-03-13 1990-04-17 E. I. Du Pont De Nemours And Company Process for the manufacture of 1,4-bis(4-phenoxybenzoyl)benzene with certain metal-containing catalysts
EP0315441A3 (en) * 1987-11-04 1990-07-18 Raychem Limited Poly(arylene ether ketones)
EP0390325A3 (en) * 1989-02-27 1991-08-21 Imperial Chemical Industries Plc Polyarylketones
GB2364319A (en) * 2000-07-06 2002-01-23 Gharda Chemicals Ltd Melt processable polyether ether ketone polymer

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WO1991013929A1 (en) * 1990-03-16 1991-09-19 Asahi Kasei Kogyo Kabushiki Kaisha Noncrystalline polymers and production thereof
CN103665368B (en) * 2013-11-28 2017-01-11 张家港祥成医用材料科技有限公司 Method for low-temperature synthesis of polyaryletherketone resin on nanometer/micrometer-scale inorganic seedbed
ES2829265T3 (en) * 2017-05-16 2021-05-31 Arkema France Method for making 1,4-bis (4-phenoxybenzoyl) benzene at an elevated temperature
EP3404011B1 (en) * 2017-05-18 2020-08-26 Arkema France Dissociation of a 1,4-bis(4-phenoxybenzoyl)benzene-lewis acid-complex in an aqueous solution
EP3404012B1 (en) 2017-05-18 2020-09-09 Arkema France Ripening of 1,4-bis (4-phenoxybenzoyl)benzene
KR102262524B1 (en) 2017-11-16 2021-06-07 한화솔루션 주식회사 Method for preparing poly ether ketone ketone
EP3650433B1 (en) 2018-11-09 2024-04-24 Arkema France Method for manufacturing 1,4-bis (4-phenoxybenzoylbenzene) at an elevated temperature
CN119524818A (en) * 2025-01-23 2025-02-28 陕西煤基特种燃料研究院有限公司 A COP@SiO2 solid phase adsorbent based on oil dearomatization, a solid phase extraction column based thereon, and a preparation method and application thereof

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EP0135938A2 (en) * 1983-09-29 1985-04-03 Mitsubishi Kasei Corporation Process for producing aromatic polyether ketones and polythioether ketones

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0315441A3 (en) * 1987-11-04 1990-07-18 Raychem Limited Poly(arylene ether ketones)
US4990589A (en) * 1987-11-04 1991-02-05 Raychem Limited Poly(arylene ether ketones)
WO1989004848A1 (en) * 1987-11-17 1989-06-01 Raychem Limited Preparation of poly(arylene ether ketones)
US5145938A (en) * 1987-11-17 1992-09-08 Raychem Limited Preparation of poly(arylene ether ketones)
EP0390325A3 (en) * 1989-02-27 1991-08-21 Imperial Chemical Industries Plc Polyarylketones
US4918237A (en) * 1989-03-13 1990-04-17 E. I. Du Pont De Nemours And Company Process for the manufacture of 1,4-bis(4-phenoxybenzoyl)benzene with certain metal-containing catalysts
GB2364319A (en) * 2000-07-06 2002-01-23 Gharda Chemicals Ltd Melt processable polyether ether ketone polymer
GB2364319B (en) * 2000-07-06 2003-01-15 Gharda Chemicals Ltd Melt processible polyether ether ketone polymer
US6566484B2 (en) 2000-07-06 2003-05-20 Gharda Chemicals Ltd. Melt processible polyether ether ketone polymer
US6881816B2 (en) 2000-07-06 2005-04-19 Gharda Chemicals Ltd. Melt processible polyether ether ketone polymer

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JPS61211336A (en) 1986-09-19
DE3607902A1 (en) 1986-09-11
GB8605837D0 (en) 1986-04-16
CA1246297A (en) 1988-12-06

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