JPS63500666A - Poly(aryletherketone) with extended molecular class - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Poly(aryletherketone) with extended molecular chain The present invention provides a new method containing segments of crystalline poly(aryletherketone). It has normal crystallinity and has molecular chains that form extended polymers. This new substance; much easier to detect. It exhibits excellent toughness and processability and very good high temperature and solvent resistance.

Immunity IJ Conventionally, the formation and properties of poly(aryl ether) (hereinafter referred to as "PAE") have been A large body of patents and other literature has been developed to address the issue. Some of the earliest works, e.g. Bonner U.S. Pat. No. 3.065.205 describes aromatic diacyl halogenation Electron aromatics between compounds and unsubstituted aromatic compounds, such as diphenyl ether. Aromatic substitution reactions (e.g., Friedel-Crafts) catalytic reactions). Johnson (, 1ohnson) and others 1. tou rnalof Polymer 5science-A - Volume 1, 5, 1967 , pp. 24+5-2427, Johnson et al., U.S. Pat. ．． 108°837 and 4.175.175, these have a wide range of PA Expanded to E. , l　o　　n　s　n　nOthers have a very wide range of PA Nuclear aromatic substitution reaction between E-activated aromatic dihalides and aromatic diols (condensation reaction). This method allows Johnson ( johnson) Others: A broader class of poly(aryletherketones) A large number of new PAEs were created, including ``PAEK'').

Recently, Dahl-U.S. Patent No. 3.953.400, Dahl l) Others, U.S. Patent No. 3.956.240, Dahl, U.S. Pat. No. 4.247.682, Rose et al., U.S. Patent No. 4.320 ．． No. 224, Maresca, U.S. Patent No. 4.339.568; Atwood et al., August issue, pp. 953-958, Atwood ( At-・00d) Others, Pol.

ymer Preprints, 20 Ken, No. 1, April issue, 1979, +91- 194 pages, Rueda et al., Pol>1Iler Communi Cat, 1onS, 1983, Vol. 24, September issue, pp. 258-260. As can be seen, interest in PAEK is increasing. Early 1970s ■ In the middle of ~Yo, Raychem Corp. commercially introduced r　A　E　K　J to be combined with rsTILANTMJ2 The acronym for the polymer is r　P　E　K　J, and each ether group and keto group is 1 ．． Separated by 4-phenylene units. 1978, Imperial Ch. chemical Industries PLC (ICI) is a trademark r V Commercialized rPAEKJ under ictrex peekJ. r　P AE K As J is an acronym for poly(aryletherketone), rPE EKJ is a poly(ether enylene) with a 1,4-phenylene unit in its structural formula. It is an acronym for ter ketone.

PAEK is thus well known. It can be synthesized from various starting materials and Can be adjusted to melting point or molecular weight. Its P A E K is crystalline, Dahl and D At sufficiently high molecular weights, as shown by the patents of ahl et al. (supra), It can be strong. That is, in the tensile impact test (AST MD-1822) shows a high value (>50ft-1bs/1n2).

Although it may have a wide range of uses, it is expensive to manufacture and therefore , it is an expensive polymer.

Its favorable properties classify it as an upper Pt layer of engineering resins. .

PAEK is an aromatic diaphragm, as described, for example, in U.S. Pat. No. 3,065,205. Syl halides and unsubstituted aromatic compounds such as diphenyl ether By a Friedel-Craft (Fiecle-Craft, s) contact reaction with This method is generally cheaper, but Dahl et al. (supra) say that polymers are brittle and thermally unstable. states. Dahl's patent (above) is based on Friedelkraft's (Fi edel-Crafts) catalyst to make superior PAEK. It is said that he preaches the law. On the other hand, it is produced by nucleophilic aromatic substitution reaction. For example, PEEK has v1 mechanical properties which can be generally recognized as good toughness. Show quality.

friend The present invention is directed to poly(aryletherketone) polymers with extended molecular chains. Ru. Preparation of starting poly(aryletherketone) segments and their subsequent Both couplings with diphenols take place by the nuclear route. i.e. base Excellent toughness when done using a neutral solvent.1. Good processability and excellent melt resistance A product with chemical properties and heat resistance is obtained.

The polymer of the present invention can be prepared by the method shown in the following reaction formula. It is made with a molecular weight of The more the hydroquinone reactant is in excess, the more The molecular weight of the precursor is low. In the second step, the dihydroxy-terminated precursor (3) is The desired high molecular weight poly(aryleyl -terketone (5). ! II Chi base In the above formula, X represents chlorine, halogen such as fluorine or bromine, or nitro, and Ar is Ar can be a residue of 1,4-bis(varfluorobenzoyl)henzene Ortho and or hetero to halogen or nitro functional groups, provided that there are no It is a 2ffi aromatic residue containing an electron-withdrawing group at the position.

The steps delineated by reaction schemes (1) and (II) are the isolation of intermediate (3) or the precursor This is then coupled to the final copolymer (5) in a one-pot operation. It can be done either in rotation. Obviously two or more couplings of formula (4) Mixtures of agents can also be used in the method of the invention.

Any dihalobenzenoid or dinitrobenzenoid compound or mixture thereof objects are used in this invention. The compound or compounds are halogen or nitro having an electron-withdrawing group in at least one of the ortho and distal positions relative to the group , has two halogen or nitro groups bonded to the benzene ring. This dihaloben Zenoid or dinitrobenzenoid compounds are ortho- or As long as there is an activated electron-withdrawing group in the rose position, benzenes with the same halogen or nitro group benzenoids that are mononuclear or different when attached to a noid ring It is either polynuclear when attached to a ring. Fluorine and chlorine replacement Benzenoid reactants are preferred. Due to the fast reactivity of fluorine compounds, chlorine compounds are Fluorine-substituted benzenoid compounds are most preferred, preferred because they are inexpensive. , especially when traces of water are present in the polymerization reaction system. Shi・Kashiko water content 1 is preferably kept below about 1% and for best results below 0.5%. It's a place where you can be.

Electron-withdrawing groups are used as activating groups in these compounds. Of course it is a reaction condition. It should be inert under certain conditions, but otherwise the structure is critical. Not. Preferred are 4,4'-dichlorodiphenyl sulfone and 4.4 ’-difluorodiphenylsulfone with two halogen or nitro substituted benzenes It is preferred to bind the noid ring, although other strongly attractive groups, which will be discussed later, can be easily used as well. Can be used.

The stronger of the electron-withdrawing groups: gives the fastest reaction and is therefore preferred.

The ring does not contain an electron-donating group on the same benzenoid nucleus as a halogen or nitro group. is preferred, but other groups may be present in the nucleus or in the residue of the compound. preferred or all of the substituents on the benzenoid nucleus are hydrogen (zero electron withdrawing), or , G.F. Bunnett (,1,F, Bunnett), Chetn, R ev, 11273 (1951) and Quart, Rev, u, 1 (195 8) any other group with a positive sigma value as mentioned in . Matata Taft's Organic Chemis Steric Effects in try), John Wi ley & 5ons (195G), Chapter 13; Cheat, Rev, and , 222:, lAc5. Ll, 3120 and JAC5,,,7J, See 4231.

Activating groups are basically one of two types:

(a) Other nitro or halo groups, phenylsulfone or alkylsulfone, cyano , trifluoromethyl, nitroso, and pyridine, such as trifluoromethyl, nitroso, and pyridine, the same Monovalent group that activates - or more halogen or nitro groups on the ring (b) a group of 2i that can activate substitution of halogen or nitro groups on two different rings; . For example, sulfonic oropenzoquinone, 1.4- or 1.5- or 1.8-diph Halogen or nitro on the same or adjacent rings as in the case of fluoroanthraquinone etc. Activating group in the nucleus that can activate functional groups.

Preferred coupling agents are those of formulas (6), (7) and (8), where m is 1 to 3.

The most preferred coupling agents are selected from difluoro compounds (6) and (7).

The molecular weight of precursor (3) varies from dimer (i.e. n=20) to about io, ooo sell.

glIi instead of coupled poly(aryletherketone) of the present invention ! The method involves dihalo-terminated precursor (9) base (m) The molecular weight of (9) is determined in a manner similar to that used for adjusting the molecular weight of (3). It is adjusted by

Precursor (9) can be diphenol or diphenol after isolation and preparation or immediately after preparation. One reaction scheme (■) for condensation with a mixture of polymers to give the final copolymer.

In the above formula, the group Ar' is the residue of a diphenol different from hydroquinone. Jifu The phenol is, for example, dihydroxydiphenylalkane or its nuclear halogenated derivative. conductors, such as 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis (4-hydroxyphenyl)2-phenylethane, bis(4-hydroxyphenyl) ) Methane, or salts thereof containing IB or two chlorines on each aromatic ring It is a purified derivative.

“Other materials, correctly named bisphenols, are also very valuable and preferred. stomach. These materials are bisphenols with groups that bind pairwise or asymmetrically. , the asymmetrically bonding group is, for example, an ether acid cyst group (-0-), a phenolic nucleus is Hydrocarbohydrate residues are attached to the same or different carbon atoms of the residues.

Such a dinuclear phenol has the structural formula where Ar is an aromatic group, preferably a phenyl group. is a ren group, and AI and Ar are the same or different inert substituents, such as carbon atoms. Alkyl groups having 1 to 4 halogen atoms such as fluorine, chlorine, bromine or iodine R is an alkoxy group having 1 to 4 carbon atoms, and a and b are 0 including 0.4. -4, R1 is a dihydroxydiphenyl group, for example 4.4', 3°3 ', or an aromatic carbon atom such as in a 4,3'-dihydroxydiphenyl group It represents a bond between children or is a divalent group, e.g. Hydrogen residues, such as alkylene groups, alkylidene groups, cycloalkylene groups, cyclo an alkylidene group, or a halogen, alkyl, aryl or similar substituted alkyl group; Includes kylene, alkylidene, and cycloaliphatic or aromatic groups. its fragrance A group group may also represent a ring fused to both Ar groups.

Certain dihydric polynuclear phenols are inter alia bis- (Hydroxyphenyl)alkanes, such as 2,2-bis-(4-hydroxyphenyl) phenyl)propane, 2,4'-dihydroxydiphenylmethane, bis-(2-hyperoxypropane) Droxyphenyl)methane, bis-(4-hydroxyphenyl)methane, bis= (4-hydroxy-2,6-dimethe-3-methoxyphenyl)methane, 1,1 -bis-(4-hydroxyphenyl)ethane, 1,2-bis-(toberyloxy) phenyl)ethane, 1,1-bis-(4-hydroxy-2-chlorophenyl)ethane Tan, 1.1-bis=(3-methyl-4-hydroxyphenyl)propane, 1 ．． 3-bis-(3-methyl-4-hydroxyphenyl)propane, 2,2-bis -(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis-(3- Isopropyl hydroxyphenyl>propane, 2,2-bis-(2-isopropyl) Lopyl-4-hydroxyphenyl)propane, 2,2-bis-(4-hydroxy naphthyl)propane, 2,2-bis-(4-hydroxyphenyl)pentane, 3 , 3-bis-(4-hydroxyphenyl)pentane, 2.2-bis-(4-hydro roxyphenyl)pebutane, bis-(4-hydroxyphenyl>phenylmethane) , 2.2-bis-(4-hydroxyphenyl)-1-phenyl-propane, 2, 2-bis-(4-hydroxyphenyl) 1. ! ,! , 3゜3.3-hexaflu Olopropane and di(hydroxyphenyl)sulfones such as bis-(4-hyroxyphenyl) droxyphenyl) sulfone, 2,4'-dihydroxyphenyl sulfone, 5- Chloro-2,4'-dihydroxydiphenylsulfone, 5'-chloro-4,4 ’-dihydroxydiphenyl sulfone, etc. e.g. bis-(4-hydroxyphenyl)ether, 4.3'-14,2' -12,2'-12,3'-dihydroxydiphenyl ether, 4,4'-dihydrophenyl ether Droxy-2,6-dimethyl diphenyl ether, bis-(4-hydroxy-3 -isobutylphenyl)ether, bis-(4-hydroxy-3-isopropyl) phenyl)ether, bis-(4-hydroxy-3-chlorophenyl)ether , bis(4-hydroxy-3-fluorophenyl) ether, bis(4-hydroxy-3-fluorophenyl)ether, Droxy-3-bromophenyl ether, bis-(4-hydroxynaphthyl) ether, bis-(4-hydroxy-3-chloronaphthyl)ether and 4, 4°-Dihydroxy-3,6-dimethoxydiphenyl ether Phenylketones, such as 4,3'-14,4'-14,2'-12,2'- and 2.3'-dihydroxybenzophenone: dihydroxydiketone e.g. 1.4- Bis(4′-hydroxybenzoyl)henzen, 4.4′-bis(4″-hydro xybenzoyl) diphenyl ether, 1,3-bis(4'-hydroxybenzo Il) Hensen: Mononuclear diphenols such as resorcinol; fused ring polynuclear diphenols such as dihydroxynaphthalene, dihydroxyanthra7ane and dihydro Contains xyphenanthrene.

A preferred diphenolic coupling agent corresponds to the following formula.

Compounds (13), (16) and (17) are most preferred for the purposes of this invention.

The molecular weight of the precursor (10) ranges from the lowest to that of a dimer (i.e. when n=2) to the highest of molecular weights. It changes from about io to ooo.

Both the precursor and the final polymer are made in solution using a nucleophilic polycondensation reaction.

The reaction involves mixing a mixture of the above monomers or precursors with a suitable monomer. Both are carried out by heating at temperatures of about 100 to about 400'C. The reaction is It is carried out in the presence of an alkali metal carbonate or bicarbonate. Preferably an alkali metal If a mixture of carbonates or bicarbonates is used, the mixture of alkali metal carbonates or bicarbonates is When a compound is used, the mixture contains sodium carbonate or sodium bicarbonate and a second alkali metal carbonate or bicarbonate, in which case the carbonate or bicarbonate in Box 2 Alkali metals have atomic numbers higher than that of sodium. second alkali The amount of metal carbonate or bicarbonate is the amount of secondary alkali metal per gram atom of sodium. is 0.001 to 0.20 gram atoms.

Higher alkali metal carbonates or bicarbonates are thus potassium, rubidium and carbonates and bicarbonates of cesium. preferred mating Sodium carbonate or sodium bicarbonate with potassium carbonate or cesium carbonate It is mu.

Alkali metal carbonates or bicarbonates are anhydrous, but if hydrated salts are used If the polymerization temperature is relatively low, e.g. The particles should be removed by heating under reduced pressure before the polymerization temperature is reached.

If high polymerization temperatures (>250°C) are used, any water will be absorbed during the course of the polymerization reaction. Carbonate or bicarbonate should be added first as it will be quickly expelled before any adverse effects can occur. There is no need to dehydrate. The total amount of alkali metal carbonate or bicarbonate used is In such an amount that there is at least one atom of alkali metal per phenol group. be. Therefore, when using the monomeric or oligomeric diphenols of the present invention, aromatic At least 1 mole of carbonate per mole of group diol, or i! There are 2 moles of bicarbonate It's difficult.

An excess of carbonate or bicarbonate may be used. Alkali metal per phenolic group There may be 1 to 1.2 atoms.

Using an excess of carbonate or bicarbonate will result in a faster reaction, especially at high temperatures and and/or the risk of polymer cleavage occurring when using more active carbonates. be.

As mentioned above, the second (higher) alkali metal carbonate or bicarbonate used The amount of salt is the alkali metal of higher atomic number per gram atom of sodium o, o oi to about 0.2 gram atoms are present.

Thus, when using a mixture of carbonates, such as sodium carbonate and cesium carbonate, the sodium carbonate There should be from 0.1 to about 20 moles of cesium carbonate per 100 moles of thorium.

Similarly, use a mixture of bicarbonates and carbonates, such as sodium bicarbonate and potassium carbonate. When 0.05 to 10 moles of potassium carbonate per 100 moles of sodium bicarbonate It is a certain place.

For example, a mixed carbonate such as sodium carbonate and potassium carbonate can be mixed with a second alkali metal. Can be used as carbonate. In this case, one of the alkali metal atoms in the mixed carbonate is If thorium, the amount of sodium in the mixed carbonate should be used When determining the amount of salt, add it to the amount of sodium in thorium carbonate. .

Preferably a second alkali metal carbonate or bicarbonate per gram atom of sodium. 0.005 to 0.1 gram atom of the alkali metal is used.

Oligomeric bisphenols or oligomeric dihalopenzenoite compounds are used. When used, they are used in substantially equimolar amounts between the monomeric chain extenders. It is a good place to go. If used in excess, low molecular weight products will be produced. but A slight excess of a given number of reactants, up to 5 mole percent, may be used if desired.

The reaction is carried out in the presence of an inert solvent.

Preferably, the solvent used is an aliphatic or aromatic sulfoxide or sulfoxide of the formula It is.

R-5(0)λ-R' In the formula, X is 1 or 2, and R and R' are alkyl or aryl groups and are the same Or something different. R and R' together form a divalent radical. good Preferred solvents include dimethyl sulfoxide, dimethyl sulfone, sulfolane (1, l-dioxothiolane) or aromatic sulfones of the formula. In the formula, R2 is directly or an oxygen atom or two hydrogen atoms (each in a Hensen ring.The above aromatic Examples of group sulfones include diphenylsulfone, dibenzothiophenedioxy), and fluorine. Dioxide containing enoxathiin dioxide and 4-phenylsulfonylbiphenyl Phenylsulfone is a preferred solvent. Other solvents that may be used include N, N ’-dimethylacetamide, N,N-dimethylformamide and UN-methyl- Contains 2-pyrrolidone.

The temperature ranges from about 100°C to about 400°C, depending on the reactants and depending on the nature of the solvent. A preferred temperature is 270°C or higher. The reaction is Generally carried out under atmospheric pressure. However, higher or lower pressures can also be used.

For a certain polymer production, the polymerization is started at a temperature, e.g. between 200°C and 250°C. , it may be desirable to increase the temperature as the polymerization continues. This is especially true This is necessary when making polymers that have low solubility in solvents.

Thus, as the molecular weight increases, the temperature is progressively increased to keep the polymer in solution. Preferably.

In order to minimize the splitting reaction, it is preferable that the maximum polymerization temperature is 350°C or less. stomach.

The polymerization reaction is carried out using a suitable end-capping agent, such as methyl chloride, tert-butyl chloride. Alternatively, 4-dichlorodiphenylsulfone is mixed with the reaction mixture at the polymerization temperature and Heat for a period of up to 1 hour at a heating temperature and then stop by interrupting the heating. I can do that.

This invention also combines potassium fluoride alone or with sodium carbonate or sodium bicarbonate. than using a combination of alkali metal carbonates or bicarbonates with a higher atomic number of 2. Improvements in making chain-extended polymers within a relatively short overall reaction time It also takes time to understand how it was done.

In particular, this method uses hydroquinone (to make the precursor) and 1,4-bis(bara). - forming a chain-extended polymer with a fluorobenzoyl)bendi) precursor; or sodium carbonate and/or sodium bicarbonate and potassium, rubidium or is an alkali selected from cesium fluoride or chloride or their combinations. Precursor for making one or both chain extension polymers in the presence of a potash metal halide Allow your body to react.

The reaction involves monomer reactants or block precursors and about 100 to about 400 monomers. It is carried out by heating at temperatures up to ℃. The reaction is added sodium carbonate and/or fluorination of sodium and potassium bicarbonate, rubidium, or cesium. It is carried out in the presence of compounds or chlorides.

Sodium carbonate or sodium bicarbonate and the above salts (arium and fluoride salts are anhydrous) It is a good place to go. However, hydrated salts are used and the reaction temperature is relatively low, e.g. At 250°C, the water can be heated, for example, under reduced pressure before reaching the reaction temperature. It is difficult to remove it.

If high reaction temperatures (>250”C) are used, the carbonate or bicarbonate is first dehydrated. There is no need to do so because any water can adversely affect the reaction process. for they will be expelled immediately. Optionally, for example, toluene, Azeotropic organic media such as silene and chlorobenzene can be used to remove water from the reaction. I can do that.

Sodium carbonate or bicarbonate and potassium or rubidium used or the total amount of cesium fluoride, chloride, or mixtures thereof with respect to the anion. (regardless of carbonate, bicarbonate or chloride), total The amount should be such that there is at least 1 atom of alkali metal.

Preferably, about 1 to about 1.2 atoms of sodium are used for each phenolic group. Ru. In other preferred embodiments, from o, ooi to about 0.5 for each phenolic group. derived from atomic alkali metals (chlorides of higher atomic number alkali metals V) things) are used.

Sodium carbonate or bicarbonate and potassium fluoride are The ratio of potassium to

0.01 to about 0.5, preferably about 0.01 to about 0.25, most preferably A ratio of about 0.02 to about 0.20 is used.

The sum of alkali metals may be used in excess. Therefore, alkali per phenol group About 1 to about 1.7 atoms of the metal may be present. If you use a large excess of alkali metal, Although this can lead to a faster reaction, there is a risk that the resulting polymer will split. especially high temperature This is the case when using highly and/or more active alkali metal salts. Of course it's cesium. It is well known to those skilled in the art that potassium is the less active metal. less cesium and more sodium is used. more salt Since chloride salts are less active than fluoride salts, more chloride and less fluoride can be used. used.

In the chain extension process, when calculating the maximum molecular weight, bisphenol and dihalobenzene are dinitrobenzenoid (or dinitrobenzenoid) compounds, one of which is an oligomeric ) are used in substantially equimolar amounts. 〃) However, a small amount of any of the reactants An excess of (up to 5 mole %) may be used if desired. one thing against the other An excess of will lead to the production of low molecular weight products.

The reaction is carried out in the presence of an inert solvent.

The reaction temperature 1 ranges from about 100°C to about 400°C, depending on the nature of the reactants and solvent. Exists. A preferred temperature is 250°C or higher. The reaction is carried out at ambient pressure. preferable. However, higher or lower pressures may also be used. Generally carried out in an inert atmosphere.

The production of some chain-extended polymers involves running the reaction at one temperature, e.g., 200°C and 250°C. It is desirable to start between 0.degree. C. and increase the temperature as the reaction continues to occur. this is particularly useful when making relatively high molecular weight polymers that have low solubility in solvents. is necessary. thus keeping the polymer in solution as the molecular weight of the polymer increases. Therefore, it is desirable to increase the temperature little by little.

The polymers of the present invention are carbonates including chalk, calcite and dolomite; silicates silicon dioxide including mother, talc and wolstonite; vitreous bulbs; vitreous Powder: May contain inorganic fillers such as aluminum quartz and quartz.

Further, reinforcing fibers such as glass fibers and carbon fibers may be used. The polymer also contains nitrogen dioxide. Additives such as tans, heat stabilizers, UV stabilizers and plasticizers may also be included.

The polymers of the present invention include polyarylate, polysulfone, polyetherimide, polyester Amidimide, polyimide, polyphenylene sulfide, polyester, poly Carbonate, polyamide!・One or more of polyhydroxyethers, etc.” It can be mixed with other polymers.

The polymer of the present invention can be fabricated into a desired shape, i.e. a molded article, a coating, a film or a fiber. It can be engineered. They are particularly desirable for use in electrical insulation for electrical conductors.

The polymers can also be spun into monofilament yarns, as exemplified by U.S. Pat. No. 4,359,501. This is then shaped into industrial textiles using the IU method. It can be accomplished.

Furthermore, the polymer can be used for mold gears, hair rings, etc.

dog”L example The following examples serve to provide specific illustrations of the practice of the invention, but in no way It is not intended to limit the scope of the invention.

Thick] L plexus” 2 Inclined side arm with Claisen arm, nitrogen inlet tube, thermocouple probe, condenser 1.4 in 2501, 3-necked flask with condenser and stainless steel stirrer -bis(bara-fluorobenzoyl)-benzene (0,1104 mol, 35.5 8g), hydroquinone (0,115 mol, 12.66g), sodium carbonate (0,1173 mol, 12.43 g, crushed and dried), anhydrous potassium fluoride (0,0293 mol, 1.70 g) and diphenylsulfone (100 g ), deaerate the AI position, top of the condenser ζ; connected Firestone valve Fill with argon by Start the flow of high purity nitrogen to the Firestone valve Replace the connection with a bubbler. Carefully pour the contents of the flask into the heating mantle and heat. Stir the reaction mixture to melt the diphenyl sulfone by heating with a temperature controller. Then heat to 200°C and keep at that temperature for 30 minutes. Then it was heated to 250℃ for 1 hour. Finally, keep at 270℃ for 2 hours. Pour the anti-IZ’ fH compound from the reaction flask. The sample was washed, cooled, and ground into a fine powder. The sample was then refluxed twice in acetone and then diluted with 2% hydrochloric acid. Once with water, then rinse thoroughly with acetone. Then vacuum it ( Discuss the chemistry of zero reactants dried to constant weight at 120°C under about 20+ am Based on this, this oligomer had the structure (3) depicted above.

Supporting company Oligomers are made substantially as described in the previous examples. 2 o'clock at 270℃ When the heating period ended, 4,4'-difluorohensiphenone (0,005 8 mol, 1.27 g) was stirred with 8.0 g of diphenyl sulfone. The reaction mixture was then heated to 290°C and held for 30 minutes, then Heat to 320°C. After 1.6 hours, the viscous reaction mixture was removed from the flask and cooled. Instead, grind it. The reaction product was washed in succession (500 ml, 1 hour) with acetone (twice), Reflux with water, 2% hydrochloric acid, water, and acetone in a vacuum oven overnight (approximately 1 5 hours) Dry at 110-120°C.

The polymer was compression molded and the film (20 mil) was graded AS for tensile strength and elastic modulus. ASTM-D-6 for yield elongation and elongation at break according to TM-D-638. Tested according to ASTM-D-256 for pendulum impact strength according to do. Excellent quality is recorded.

branch land yunyu Haloゝ-+　S”　E-ray　...1 standing 11L The experimental method is the same as that used in the above examples.

The results are summarized in Table 1.

Table 1 Molar ratio Lx Kotatsu 111 1.4-fluorocarbon 3　1.02　1.4-Heath (H0 Seahitoro Bird Shihen Soil) 4 1 ．． 05 4.4'-Heath Phenol 5 1.04 4,4'-C 1:)-o 1 sea 7 x 2 A ln*shiro 1.03 4,4’- sea! Do ON Sissy - I to 7 tl-9n7 1.05. 4.4'-Shicht 0 xyhensohenosi In all cases, polymers of good quality are obtained.

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Claims (1)

[Claims] 1. Poly(aryletherketone) of the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Ar is a residue of 1,4-bis(p-fluorobenzoyl)benzene. bond to the ether function, provided that this is not possible and that y is greater than 1. 2 containing an electron-withdrawing group ortho and/or distal to the carbon aromatic residues). 2. Ar is ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ one or a combination of the following, and m is 1 to 3: poly(aryletherketone). 3. Ar′ is different from the residue of hydroquinone, y is larger than 1, and The following formula ▲ number is the residue of a diphenol provided that n is at least 2 There are formulas, chemical formulas, tables, etc.▼ or a combination of the following: ether ketone). 5. (a) Remove excess hydroquinone from 4,4'-dihydrogen in a neutral solvent in the presence of a base. hydroxyl-terminated intermediates are produced by reacting with dinitrodiketones , (b) converting the intermediate obtained in step (a) to 1,4bis(p-halobenzoyl)ben Activation different from Zen01 or 1,4-bis(p-nitrobenzoyl)benzene Further chain spreading with aromatic dihalo or dinitro compounds in a neutral solvent and in the presence of a base. Preparation of poly(aryletherketone) of the following formula with chain extension consisting of Law. ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Ar is a residue of 1,4-bis(p-fluorobenzoyl)benzene. bond to the ether function, provided that it cannot be and that y is greater than 1. 2 containing an electron-withdrawing group in the ortho and/or para position to the carbon aromatic residues). 6. (a) 1,4-bis(p-halobenzoyl)benzene or 1,4-bis(p- Nitrobenzoyl)benzene is reacted with hydroquinone in the presence of a base in a neutral solvent. Correspondingly, a dihalo- or dinitro-terminated intermediate is formed, and (b) the reaction between a base and a neutral solvent The intermediate obtained in step (a) in the presence of an aromatic diacetate different from hydroquinone The chain-extended polymer of the following formula consists of further chain extension with a hydroxy compound. Method for producing ly(aryl ether)ketone ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Ar′ is different from the residue of hydroquinone, and y is larger than 1 and n is the residue of a diphenol, provided that n is at least 2). 7. alkali metal carbonates and/or alkali metal bicarbonates or mixtures thereof A method as defined in claims 5 and 6, carried out in the presence of 8. The alkali metal carbonate is sodium carbonate or sodium bicarbonate and potassium carbonate. or cesium carbonate, or a mixture thereof, as defined in claim 7. How to be defined. 9. The reaction is sodium carbonate and/or sodium bicarbonate and potassium, rubidium Claim 7, which is carried out in the presence of fluoride or chloride of cesium or cesium The method defined in 10. Neutral solvent is aliphatic or aromatic sulfoxide, sulfone or mixture thereof A method as defined in claim 5 or 6, wherein the method is a product. 11. A method as defined in claim 5 or 6 carried out in step 1.