GB2235195A - Durene derivatives - Google Patents
Durene derivatives Download PDFInfo
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- GB2235195A GB2235195A GB9002640A GB9002640A GB2235195A GB 2235195 A GB2235195 A GB 2235195A GB 9002640 A GB9002640 A GB 9002640A GB 9002640 A GB9002640 A GB 9002640A GB 2235195 A GB2235195 A GB 2235195A
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- arl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
- C07C49/813—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen polycyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/14—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
- C07C49/784—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic with all keto groups bound to a non-condensed ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/82—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups
- C07C49/83—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups polycyclic
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Compounds of formulae <IMAGE> wherein:- A and A<1> are SO, SO2 or CO and may not be the @same; Ar and Ar<1> are divalent aromatic groups and may or may @not be the same; and X and X<1> are halogen, OH or SH, preferably Cl or F, and <IMAGE> wherein A and A<1> are SO, SO2 or CO and may not be the same when A is ortho or meta to A<1> and wherein A and A<1> are SO or SO2 and may not be the same when A is para to A<1>, may be used in the preparation of polyarylethers suitably containing the unit ArADA<1>Ar<1>, wherein D is a residue of durene or of a monomer terminating with durene units, connected by either and/or thioether linkages to itself and/or thioether linkages to itself and/or to other units.
Description
Aromatic Compounds
This invention relates to aromatic compounds including aromatic ketones and sulphones and to processes for making them. The ketones and sulphones of the invention find particular, but not exclusive, use in preparation of polyarylethers containing ketone and sulphone linkages.
This invention further relates to such polyarylethers and to processes for their preparation.
According to a first aspect of the invention, there is provided an aromatic compound of formula I:
wherein: - A and A1 are SO, S02 or CO and may or may not be the same;
Ar and Arl are divalent aromatic groups and may or may not be the
same; and
X and X1 are halogen, OH or SH.
Preferably, X and X1 are C1 or F.
According to a second aspect of the invention, a process for making a compound of formula I comprises reacting:a) durene with a compound of formula IIA and/or IIB:
YAArX IIA
YA1ArlX1 IIB wherein A, A1, Ar, Arl X and X1 are as hereinbefore defined and Y
is halogen; or b) durene with a polyoxybenzoyl and/or a polyoxybenzenesulphonyl,
whereby a product monomer of formula I in which X e X1 = OH is
obtained; reactions a) and b) each being carried out in the presence of an acid capable of activating the reaction.
According to a third aspect of the invention, there is provided an aromatic compound of formula III:
wherein A and A1 are as hereinbefore defined when A is ortho or meta to
A1 and wherein A and A1 are SO or S02 and may or may not be the same when A is para to A1.
According to a fourth aspect of the invention, a process for making a compound of formula III comprises reacting durene with a compound of formula IV:
wherein A and A1 are as hereinbefore defined in the preceding paragraph and B is halogen, in the presence of an acid capable of activating the reaction.
According to a fifth aspect of the invention, a polyarylether is characterised by containing the unit V:
- Ar A D A1 Arl - V connected by ether and/or thioether linkages to itself and/or to other units, wherein A, A1, Ar and Arl are as hereinbefore defined and D is a residue of durene or of a monomer terminating with durene units.
Groups Ar and Arl preferably have the general formula
Ar2 (A2Ar3)n wherein: - Ar2 and Ar3 are arylene and may be the same or different;
A2 is a direct link or S02, SO, CO, O, S or CR2 where R is
hydrogen, C1 to C4 alkyl, phenyl or the two groups R (which
otherwise may be the same or different) are joined externally to
form a cycloaliphatic ring; and
n - O to 3.
Groups Ar2 and Ar3 can be single-ring or fused ring arylenes. They are linked to A2 preferably at obtuse angles, especially at para positions or (for naphthylene) at 2,6 or 2,7 or 1,4 or 1,5 positions).
In useful polymers, and utilising readily accessible monomers, Ar and Arl are 1,4-phenylene.
If other units are present, they preferably are defined in the same way as the Ar and Arl linked through A and A1, but can be the same as or different from such Ar and Arl. The proportion of such units to unit I is suitably in the ranges 10:90 to 90:10, especially 40:60 to 60:40.
Preferably, in unit I, A and A1 are both CO, Ar and Arl are both 1,4-phenylene and the other units, when present, are typically selected from 2, 2-bis (4-hydroxyphenyl )propane, 4,4"-dihydroxydiphenylsulphone, hydroquinone, resorcinol, 4,4'-dihydroxybenzophenone, thiophenols, 4,49-difluorodiphenylsulphone, 4,4, -dichlorodiphenylsulphone, 4,4'-difluorobenzophenone and 4,4'-dichlorobenzophenone.
Such polymers may exhibit crystallinity when made, but they are recoverable in amorphous form by dissolving in for example concentrated sulphuric acid or orthochlorophenol and precipitating by pouring into water or methanol, respectively.
The invention further provides, processes for making the polymer.
In particular, according to a sixth aspect of the inventions a process comprises reacting a monomer of formula I:
with itself and/or with one or more other compounds represented by that formula andlor with one or more other nucleophilic reactants, in the presence of a base, the halogen and total amount of OH and SB combined being selected to be in approximate molar equivalence, the reaction proceeding by a nucleophilic substitution mechanism.
This process embraces the following possibilities:
a) when both X and X1 are halogen, a compound of formula I is reacted with a bisphenol which can be the corresponding compound of formula I, or a different compound of formula I in which compound both X and X1 are OH or SH or X is OH and X1 is SH, and/or can be one or more other bisphenols or bisthiophenols and/or phenollthiophenols; b) when one of X and X1 is halogen and the other is OH and/or SH, a compound of formula I is reacted with itself and/or a different compound of formula I and/or one or more other halophenols and/or halothiophenolsr c) a) and b) can be operated simultaneously or sequentially.
In this nucleophilic substitution process, the base can be one or more alkali metal hydroxides which may, if desired, be pre-reacted with phenol and/or thiophenol reactants. More conveniently it is introduced as one or more salts of weak acids, especially carbonates and/or bicarbonates but possibly carboxylates. The alkali metal preferably is, or includes at least 1Z molar of, potassium, rubidium or caesium. Any balance of base can be provided by basic compounds of one or more of sodium, lithium or alkaline earth metals. The total base used should be at least equivalent to the halogen to be reacted and is preferably up to 20D, especially up to SZ, molar excess.
According to a seventh aspect of the invention, a process comprises reacting durene, or a monomer terminating with durene units, with at least one compound of formula VI:
Y - A - Ar - Z - Arl - A1 - yl VI wherein: - A, A11 Ar and Arl are as hereinbefore defined;
Y and yl is halogen, OH or SH; and
Z is O or S; in presence of an acid capable of activating the reaction, the reaction proceeding by an electrophilic substitution mechanism.
The process can be carried out in a single stage or in two stages, in the first of which the intermediate of formula VII:
D - A - Ar - Z - Arl - A1 - Y VII wherein D is durene or a monomer terminating with durene units, is formed and in the second of which that intermediate is caused to selfcondense.
If the process is carried out in two stages, two different catalysts can be used.
Preferably the acid used in the processes according to the invention is a Lewis acid which functions as a Friedel-Crafts catalyst, suitable compounds being A1C13, BF3, FeC13 or ZnC12; or the acid is a superacid such as a fluoroalkanesulphonic acid, eg trifluoromethanesulphonic acid, or HF/BF3; but preferably the acid is aluminium chloride.
The invention will now be illustrated by reference to the following Examples.
Example 1
Aluminium chloride (337g, 2.53 mole) was added slowly to 4-fluorobenzoyl chloride (665g, 4.19 mole), the mixture being heated to ca 800C-1000C during the addition and being maintained within this temperature range until the aluminium chloride had completely dissolved.
Powdered durene (56.2g, 0.42 mole) was slowly added to the stirred solution over 5 minutes resulting in a dark brown, viscous solution.
The mixture was then stirred at 1200C-1600C for 1 hour, the excess 4-fluorobenzoyl chloride being distilled off under reduced pressure, ca 250g, being recovered. The semi-solid residue was added to crushed ice (2.5 kg) and the mixture made strongly acidic with concentrated hydrochloric acid. The product was extracted with dichloromethane (1.21), the aqueous layer being re-extracted and the combined extracts being reduced to ca half volume, washed with sodium carbonate solution, then three times with water and once with saturated sodium chloride solution. After a further evaporation (to ca 400 ml), the extract was dried with sodium sulphate and evaporated.The brown residue, following recrystallisation from benzene, was identified by elemental analysis and nmr spectroscopy as bis(4-fluorobenzoyl)durene (105g, 64Z yield), ie:
having a melting point of 2300C.
The product was further purified to polymerisation grade material by recrystallisation from 190ml of toluene and 670ml of propan-2-ol following decolourisation by activated carbon.
Examnle 2
Bis(4-chlorobenzoyl)durene (61.6g, 52X yield), ie:
having a melting point of 2360C-2370C, was prepared and identified in accordance with the method described in Example 1, the reactants being aluminium chloride (226g, 1.69 mole), 4-chlorobenzoyl chloride (493g, 2.8 mole) and durene (37.7g, 0.28 mole).
The product was further purified to polymerisation grade material by recrystallisation from 950ml of toluene and 670ml of propan-2-ol following decolourisation by activated carbon.
Example 3 1,4-bis(4-(4-fluorobenzoyl)-2,3,5,6-tetramethylbenzoyl)benzene (1.56g, 21.6Z yield), ie:
having a melting point of 327-3290C was prepared and identified in accordance with the method described in Example 1, the reactants being aluminium chloride (8.96g, 0.067mole), 4-fluorobenzoyl chloride (17.68g, O.lllmole) and 1,4-bis(2,3,5,6-tetramethylbenzoyl)benzene (4.50g, O.Ollmole).
Example 4
Isophthaloyl chloride (5.0g, 0.0246mole) and durene (12.9g, 0.0963mole) were dissolved in carbon disulphide (SOml) and then added dropwise to a suspension of aluminium chloride (9.3g, 0.0697mole) in carbon disulphide (20ml). The bright orange reaction mixture was refluxed for 3 hours. The carbon disulphide was then distilled off and the remaining solid was added to crushed ice and subsequently worked up in accordance with the method described in Example 1.
The final product was identified by elemental analysis and nmr to be 1,3-bis(2,3,5,6-tetramethylbenzoylZbenzene (6.58g, 66.1Z yield), ie:
having a melting point of 168-1690C.
In Examples 5 to 14 below, the following general method was used:a) polymers were prepared by: charging a flask with dihalide and diol
monomers together with diphenyl sulphone under nitrogen; stirring
the mixture; raising the temperature of the mixture to 18O0C and
maintaining it for s hour; adding anhydrous sodium carbonate or
anhydrous potassium carbonate or a mixture of the two; slowly
raising the temperature of the mixture over an hour to 2600C and
then more slowly raising the temperature to maintain the forming
polymer in solution, the temperature being limited to a maximum of
3200C to minimise the degree of oxidative degradation of the
pendant methyl groups.
b) when the mixture became too viscous to be stirred, it was allowed
to cool to room temperature. The flask was then broken and the
extracted crude product, broken into large lumps ( < 20mm), was oven
dried and then milled into a powder. The powder was then
extracted in a Soxhlet extractor over 24 hour periods with:
i) an 8:2 mixture of methanol and water;
ii) a 9:1 mixture of acetone and glacial acetic acid; and
iii) an 8:2 mixture of methanol and acetone.
The reduced viscosity of the polymers was determined using a 1Z
solution of the polymer in concentrated sulphuric acid (98Z) at 250C and the Tg, Tm and heat of fusion (H) of the polymers was determined using a differential scanning calorimeter.
Example 5
The following quantities of reagents were used:bis(4-fluorobenzoyl)durene 110.85 g (0.293 mole) 4,4'-dihydroxybenzophenone 62.14 g (0.290 mole)
diphenyl sulphone 236.48 g (1.08 mole)
sodium carbonate 30.75 g (0.290 mole) potassium carbonate 0.80 g (0.006 mole).
The reaction mixture was slowly raised from 2600C to 3100C over 1.5 hours before it became very viscous.
The refined product (151.6g, 94.7Z yield) was light brown in appearance and had the following properties:reduced viscosity 2.688
Tg 2120C
Tm 2690C 22 22 JlsOC.
Nmr spectroscopy on polymers made in accordance with Example 5 confirmed the structure as having repeat units of the following formula: -
Example 6
The following quantities of reagents were used:bis(4-fluorobenzoyl)durene 122.17 g (0.323 mole) 4,4'-dihydroxdiphenyl sulphone 80.00 g (0.320 mole) diphenyl sulphone 303.30 g (1.39 mole) sodium carbonate 33.92 g (0.320 mole) potassium carbonate 0.88 g (0.006 mole).
The reaction mixture was slowly raised from 2800C to 3100C over 1.75 hours before it became very viscous.
The refined product (181.8g, 96.6Z yield) was light brown in appearance and had the following properties:reduced viscosity 2.306
Tg 2370C
Tm dH
Nmr spectroscopy of the product confirmed the structure as having repeat units of the following formula:
Examole 7
The following quantities of reagents were used:
bis(4-chlorobenzoyl)durene 41.10 g (0.100 mole)
hydroquinone 11.00 g (0.100 mole)
diphenyl sulphone 45.00 g (0.206 mole)
sodium carbonate 10.80 g (0.102 mole).
The reaction mixture was was held at 3150C for two hours and was
then discharged into hot water.
The refined product (31.9g, 71Z yield) was brown in appearance and
had the following properties:
reduced viscosity 0.40
Tg 2030C
Tm 2680C AH 7.6 J/s C Nmr spectroscopy of the product confirmed the structure as having
repeat units of the following formula:
Examole 8
The following quantities of reagents were used:bis(4-fluorobenzoyl)durene 15.12 g (0.040 mole) hydroquinone 4.40 g (0.040 mole) diphenyl sulphone 18.00 g (0.082 mole) sodium carbonate 4.32 g (0.0408 mole).
The reaction mixture was was held at 3150C for two hours before it solidified.
The refined product (12.8g, 72D yield) was brown in appearance and had the following properties:reduced viscosity 0.99
Tg 234OC Tm 2990C 4H 0.5 JlsOC.
Nmr spectroscopy of the product confirmed the structure as having repeat units of the following formula:
Example 9
The following quantities of reagents were used:bis(4-chlorobenzoyl)durene 16.60 g (0.040 mole) 4,4'-dihydroxybenzophenone 8.56 g (0.040 mole) diphenyl sulphone 35.80 g (0.164 mole) sodium carbonate 4.24 g (0.040 mole) potassium carbonate 0.11 g (0.0008 mole).
The reaction mixture was slowly raised from 2750C to 300OC before it became very viscous.
The refined product (20.8g, 62X yield) was brown in appearance and had the following properties:reduced viscosity 0.844
Tg 1850C
Tm
Nmr spectroscopy of the product confirmed the structure as having repeat units of the following formula:
Examnle 10
The following quantities of reagents were used: bis (4-fluorobenzoyl)durene 15.12 g (0.040 mole) 4,4'-dihydroxybenzophenone 4.28 g (0.020 mole) hydroquinone 2.20 g (0.020 mole) diphenyl sulphone 18.00 g (0.082 mole) sodium carbonate 4.32 g (0.0408 mole).
The reaction mixture was held at 3150C for 6 hours before it became very viscous.
The refined product (14.6g, 73t yield) was brown in appearance and had the following properties:reduced viscosity 0.545
Tg 2260C
Tm 2650C H 1.5 JlsOC.
Nmr spectroscopy of the product confirmed the structure as having repeat units of the following formulae:
Example 11
The following quantities of reagents were used:bis(4-fluorobenzoyl)durene 15.27 g (0.0403 mole) 4,4'-biphenol 3.56 g (0.020 mole) 4,4'-dihydroxydiphenyl sulphone 5.02 g (0.020 mole) diphenyl sulphone 35.80 g (0.164 mole)
sodium carbonate 4.24 g (0.040 mole)
potassium carbonate 0.11 g (0.0008 mole).
The reaction mixture was slowly raised from 2800C to 3000C over 3 hours and it was then discharged into water.
The refined product (22.lg, 36Z yield) was brown in appearance and had the following properties:
reduced viscosity 0.555
Tg 2220C
Tm 4H
Nmr spectroscopy of the product confirmed the structure As having
repeat units of the following formulae:
Example 12
The following quantities of reagents were used:bis(4-fluorobenzoyl)durene 7.56 g (0.020 mole) 4,4'-difluorobenzophenone 4.36 g (0.020 mole) 4,4'-dihydroxybenzophenone 8.56 g (0.040 mole) diphenyl sulphone 18.00 g (0.082 mole) sodium carbonate 4.32 g (0.0408 mole).
The reaction mixture was slowly raised from 2800C to 3100C over 3.5 hours before it became very viscous.
The refined product (15.95g, 84.4D yield) was light brown in appearance and had the following properties: reduced viscosity 1.32
Tg 1780C Tm 2470C 30 30 JlsOC.
Nmr spectroscopy of the product confirmed the structure as having repeat units of the following formulae:
Example 13
The following quantities of reagents were used:bis(4-fluorobenzoyl)durene 7.56 g (0.020 mole)
4,4'-difluorodiphenyl sulphone 5.09 g (0.020 mole) 4,4'-dihydroxybenzophenone 8.56 g (0.040 mole) diphenyl sulphone 18.00 g (0.082 mole)
sodium carbonate 4.32 g (0.0408 mole).
The reaction mixture was held at 3000C for 2 hours before it became very viscous.
The refined product (9.94g, 50.7Z yield) was light brown in appearance and had the following properties:reduced viscosity 1.83
Tg 1970C
Tm dH
Nmr spectroscopy of the product confirmed the structure as having repeat units of the following formulae:
Example 14
The following quantities of reagents were used:bis(4-fluorobenzoyl)durene 15.12 g (0.040 mole) 4,4'-thiodiphenol 8.72 g (0.040 mole) diphenyl sulphone 18.00 g (0.082 mole) sodium carbonate 4.32 g (0.0408 mole).
The reaction mixture was held at 26O0C for 10 hours before it became very viscous.
The refined product (15.31g, 68.6D yield) was brown in appearance and had the following properties:reduced viscosity 0.347
Tg 1740C
Tm 2330C ash 0.1 JlsOC.
Nmr spectroscopy of the product confirmed the structure as having repeat units of the following formula:
Claims (10)
- CLAIMS 1. An aromatic compound of formula I:wherein: - A and A1 are SO, S02 or CO and may or may not be the same; Ar and Arl are divalent aromatic groups and may or may not be the same; and X and X1 are halogen, OH or SH, preferably C1 or F.
- 2. A process for making a compound of formula I:wherein: - A and A1 are SO, S02 or CO and may or may not be the same; Ar and Arl are- divalent aromatic groups and may or may not be the same; and X and X1 are halogen, OH or SH, pyeferably.Cl or F, comprises reacting: a) durene with a compound of formula IIA and/or IIB: YAArX IIA YA1ArlX1 IIB wherein A, A1, Ar, Arl, X and X1 are as hereinbefore defined and Y is halogen; or b) durene with a polyoxybenzoyl and/or a polyoxybenzenesulphonyl.whereby a product monomer of formula I in which X - X1 - OH is obtained reactions a) and b) each being carried out in the presence of an acid capable of activating the reaction.
- 3. An aromatic compound of formula III:wherein A and A1 are SO, S02 or CO and may or may not be the same when A is ortho or meta to A1 and wherein A and Al are SO or S02 and may or may not be the same when A is para to A1.
- 4. A process for making a compound of formula III:wherein A and A1 are SO, S02 or CO and may or may not be the same when A is ortho or meta to A1 and wherein A and A1 are SO or S02 and may or may not be the same when A is para to A1, comprises reacting durene with a compound of formula IV:wherein A and A1 are as hereinbefore defined and B is halogen, in the presence of an acid capable of activating the reaction.
- 5. A polyarylether is characterised by containing the unit V: - Ar A D Al Arl - V connected by ether and/or thioether linkages to itself and/or to other units, wherein: A and A1 are SO, S02 or CO and may or may not be the same; Ar and Arl are divalent aromatic groups and may or may not be the same; and D is a residue of durene or of a monomer terminating with durene units.
- 6. A polyarylether according to claim 5, in which groups Ar and Ar have the general formula: Ar2 (A2Ar3)n wherein: - Ar2 and Ar3 are arylene and may be the same or different; A2 is a direct link or SO2, SO, CO, O, S or CR2 where R is hydrogen, C1 to C4 alkyl, phenyl or the two groups R (which otherwise may be the same or different) are joined externally to form a cycloaliphatic ring; and n - O to 3.
- 7. A polyarylether according to claim 5 or claim 6, in which Ar and Arl are 1,4-phenylene.
- 8. A polyarylether according to any one of claims 5 to 7, in which said other units are selected from 2,2-bis(4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl sulphone, hydroquinone, resorcinol, 4,4, -dihydroxybenzophenone, thiophenols, 4,4, -difluorodiphenyl sulphone, 4,4, -dichlorodiphenyl sulphone, 4,4'-difluorobenzophenone and 4,4'-dichlorobenzophenone and the proportion of such units to unit I is in the ranges 10:90 to 90:10, especially 40:60 to 60:40.
- 9. A process for making a polyarylether according to claim 5 comprising reacting a monomer of formula I:wherein: A and A1 are SO, S02 or CO and may or may not be the same; Ar and Arl are divalent aromatic groups and may or may not be the same; and X and X1 are halogen, OH or SH, with itself and/or with one or more other compounds represented by that formula and/or with one or more other nucleophilic reactants, in the presence of a base, the halogen and total amount of OH and SH combined are selected to be in approximate molar equivalence, the reaction proceeding by a nucleophilic substitution mechanism.
- 10. A process for making a polyarylether according to claim 5 comprising reacting durene, or a monomer terminating with durene units, with at least one compound of formula VI: Y - A - Ar - Z - Arl - A1 - yl VI wherein: - A and A1 are SO, S02 or CO and may or may not be the same; Ar and Arl are divalent aromatic groups and may or may not be the samet Y and yl is halogen, OH or SH; and Z is O or S; in presence of an acid capable of activating the reaction, the reaction proceeding by an electrophilic substitution mechanism.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB898904027A GB8904027D0 (en) | 1989-02-22 | 1989-02-22 | Aromatic compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9002640D0 GB9002640D0 (en) | 1990-04-04 |
| GB2235195A true GB2235195A (en) | 1991-02-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB898904027A Pending GB8904027D0 (en) | 1989-02-22 | 1989-02-22 | Aromatic compounds |
| GB9002640A Withdrawn GB2235195A (en) | 1989-02-22 | 1990-02-06 | Durene derivatives |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB898904027A Pending GB8904027D0 (en) | 1989-02-22 | 1989-02-22 | Aromatic compounds |
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| Country | Link |
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| GB (2) | GB8904027D0 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2247679A (en) * | 1990-09-10 | 1992-03-11 | Ici Plc | Aromatic compounds |
| EP0601438A1 (en) * | 1992-12-05 | 1994-06-15 | BASF Aktiengesellschaft | Process for the preparation of polyacylated aromatics |
-
1989
- 1989-02-22 GB GB898904027A patent/GB8904027D0/en active Pending
-
1990
- 1990-02-06 GB GB9002640A patent/GB2235195A/en not_active Withdrawn
Non-Patent Citations (1)
| Title |
|---|
| CAS Registry No. 21335-49-9 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2247679A (en) * | 1990-09-10 | 1992-03-11 | Ici Plc | Aromatic compounds |
| EP0601438A1 (en) * | 1992-12-05 | 1994-06-15 | BASF Aktiengesellschaft | Process for the preparation of polyacylated aromatics |
| US5395975A (en) * | 1992-12-05 | 1995-03-07 | Basf Aktiengesellschaft | Preparation of polyacylated aromatric compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9002640D0 (en) | 1990-04-04 |
| GB8904027D0 (en) | 1989-04-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |