WO2001038422A1 - Method for isolating dihydroxybiphenyl polyethersulfones - Google Patents
Method for isolating dihydroxybiphenyl polyethersulfones Download PDFInfo
- Publication number
- WO2001038422A1 WO2001038422A1 PCT/US2000/030266 US0030266W WO0138422A1 WO 2001038422 A1 WO2001038422 A1 WO 2001038422A1 US 0030266 W US0030266 W US 0030266W WO 0138422 A1 WO0138422 A1 WO 0138422A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyethersulfone
- dihydroxybiphenyl
- solvent
- range
- water
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
Definitions
- This invention relates to polyethersulfones, and more particularly to an improved method for preparing dihydroxybiphenyl- and dihydroxybenzene-derived polyethersulfones.
- Dihydroxybiphenyl-derived polyethersulfones are known in the art.
- a common example is the polyethersulfone derived from 4,4 -dihydroxybiphenyl ana bis(4- chlorophenyl) sulfone (hereinafter sometimes "DDS"), which comprises structural units of the formula I :
- the polyethersulfone of formula I is typically an amorphous, injection mold-ible resin with high solvent resistance and other desirable properties. It is most often prepared by a reaction of the DDS with an alkali metal salt of the dihydroxybiphenyl (hereinafter sometimes "biphenyl salt") at high temperature (typically at least 140°C) in solution in a dipolar aprotic solvent, as illustrated by dimethyl suifoxide and sulfolane, which may be combined with chlorobenzene, as described, for example, in Johnson et al., J. Poly. ScL, Part A-l, 5, 2375-2398 (1967).
- the present invention is based on the discovery that polyethersulfones can be prepared by any method known in the art and subsequently rendered crystalline.
- the crystalline polymer is of a particle size which renders it easily separable in the solid state from the reaction mixture in which it was prepared, along with by-product salt which can subsequently be easily removed by extraction with water.
- the invention in one of its aspects, therefore, is a method for isolating a dihydroxybiphenyl- or dihydroxyphenyl-derived polyethersulfone which comprises:
- Another aspect of the invention is crystalline dihydroxybiphenyl- or dihydroxyphenyl-derived polyethersulfones having an average particle size in the range of about 5-100 microns.
- the polyethersulfones which are the subject of the present invention are typically prepared from at least one monomer unit reagent comprising an alkali metal salt of a dihydroxybenzene such as resorcinol or hydroquinone or a dihydroxybiphenyl such as 3,3 - or 4,4 -dihydroxybiphenyl, with 4,4 -dihydroxybiphenyl being preferred.
- the salt is typically a sodium or potassium salt. Sodium salts are frequently preferred by reason of their availability and relatively low cost.
- the other reagent is at least one monomer unit comprising a bis(halophenyl) sulfone such as bis(3-bromophenyl) sulfone or DDS, the latter being preferred. Equimolar proportions of these two reagents are preferably employed. It is also contemplated to employ polyethersulfones containing minor proportions, generally up to about 25 mole percent, of structural units derived from other monomers.
- the condensation reaction between these two reagents is conducted under strictly anhydrous conditions. It may be conducted in a dipolar aprotic solvent, in a water-immiscible solvent or in a mixture of the two. Preparation in a solvent system that includes a dipolar aprotic solvent is generally at a temperature in the range of ibout 150-300°C, as described hereinabove.
- a solvent system consisting of at least one water- immiscible aromatic solvent such as chlorobenzene, o-dichlorobenzene, trichlorobenzene, chlorotoluene, anisole, phenetole, diphenyl ether or another aromatic compound having a polarity no higher than those, in combination with a phase transfer catalyst and at a temperature in the range of about 125-250°C.
- Phase transfer catalysts with high thermal stability i.e., those that are stable in the range of about 125-250°C
- phase transfer catalysts have this property. They include quaternary phosphonium salts of the type disclosed in U.S. Patent 4,273,712, N-alkyl-4-dialkylaminopyridinium salts of the type disclosed in U.S. Patents 4,460,778 and 4,595,760, and guanidinium salts of the type disclosed in the aforementioned US Patent 5,229,482. Said patents are incorporated by reference herein.
- phase transfer catalysts by reason of their exceptional stability at high temperatures and their effectiveness to produce high molecular weight polyethersulfones in high yield, are the hexaalkylguanidinium and ⁇ , ⁇ >-bis(pentaalkylguanidinium)alkane salts. Proportions of catalyst, when employed, are most often in the range of about 1-10 mole percent based on sulfone.
- step A of the method of the invention the solution of the polyethersulfone is treated to effect crystallization of said polyethersulfone.
- Such treatment may be by merely cooling a solution in a water-immiscible solvent, preferably the solution in which the polyethersulfone was prepared, from the reaction temperature to one in the range of about 20-100°C, and typically to ambient temperature. Slow cooling, over a period of at least about 2 hours, is often particularly effective for crystallization. It is also within the scope of the invention to contact the solution before or during cooling with a crystallization aid.
- the preferred crystallization aid is preformed polyethersulfone in its crystalline form. It is also contemplated to employ inorganic nucleating agents such as titanium dioxide and talc as crystallization aids.
- the average particle size of the crystalline polyethersulfone obtained as described above is typically in the range of about 5-500 microns, most often about 20-200 microns and preferably about 50-100 microns. Frequently, at least 90% of the crystalline polyethersulfone particles thus produced have a particle size of at least 15 microns, preferably at least 20 microns. Particle sizes for the purposes of this invention were determined by laser diffraction using a Coulter LS-100 apparatus.
- particle sizes outside the above- noted typical range, and particularly larger particle sizes may be desired for certain applications; for example, for blending with additives such as pigments, stabilizers and fire retardants and with other polymers. Particles which are too fine may cause dust problems which can lead to powder explosions and other health hazards.
- finer particles may be required for powder coating purposes and aqueous suspensions, e.g., for composite fiber impregnation. Modifications to achieve other particle sizes may be include control of polymer concentration, changes in solvent composition, use of different cooling temperatures, alteration in rate of cooling, use and amount of crystallization nucleating agents and the like.
- step B the crystallized polyethersulfone particles are separated from the solvent and remainder of the reaction mixture. This is typically done by filtration, whereupon by-product alkali metal halide salt is recovered in admixture with the polyethersulfone. Conventional washing steps employing organic solvents such as toluene and methanol may also be employed; they are typically effective to remove phase transfer catalyst from the polyethersulfone.
- step C the by-product salt is removed from the polyethersulfone. This is typically achieved by simple extraction with water, most often at a temperature in the range of about 60-90°C for efficient salt dissolution.
- the crystalline polyethersulfones of this invention often have advantages over the amorphous form of the same polymers, particularly from the standpoint of handling, since they do not agglomerate.
- the mixture was heated to reflux, with stirring, whereupon most of the water was removed as an azeotrope with the cyclohexane; 150 ml of toluene was then added over 1.5 hours and distillation was continued to remove all water and cyclohexane.
- o-Dichlorobenzene 100 ml was added and the Dean-Stark trap was replaced y a recirculating trap containing calcium hydride as a drying agent.
- the c dichlorobenzene was refluxed through the trap for 2 hours, after which the solution was cooled and 17.826 g (62.08 mmol) of DDS, 1.310 g (4.97 mmol) of hexaethylguanidinium chloride and 25 ml of dry o-dichlorobenzene were added.
- the mix t ure was heated under reflux for 7 hours and the resulting viscous solution was diluted with 150 ml of o-dichlorobenzene and allowed to cool to room temperature over three hours, whereupon the product polyethersulfone precipitated as fine solid particles.
- the resulting thick slurry was filtered and the filtration residue was washed with 100 ml of toluene, followed by 100 ml of methanol and two portions of hot water. Finally, the purified polyethersulfone was dried in a vacuum oven at 100°C. The yield was 95.3% of the theoretical amount of a product having a sodium content of 58 parts per million (ppm). Its average particle size was 63 microns and 90% of the particles had a size of at least 25 microns.
- the glass transition temperature (Tg) and melting temperature (Tm) values were 226° and 264°C, respectively.
- Example 1 A 500 ml three-necked flask set up as in Example 1 was charged in a nitrogen atmosphere with 10.01 1 g (125.48 mmol) of 50.14% aqueous sodium hydroxide solution, 1 1.683 g (62.74 mmol) of 4, 4 -dihydroxybiphenyl, 50 ml of water and 160 ml of cyclohexane. The mixture was dehydrated as in Example 1 and anisole, 100 ml, was added and refluxed through the calcium hydride trap for 1.5 hours, after which the solution was cooled and 18.017 g (62.74 mmol) of DDS and 25 ml of dry anisole were added.
- the mixture was reheated to 145°C, 1.32 g (5.02 mmol) of hexaethylguanidinium chloride was added and the mixture was heated under reflux (155°C) for 8 hours.
- the resulting viscous solution was diluted with 150 ml of o-dichlorobenzene and allowed to cool to room temperature, whereupon the product polyethersulfone precipitated as fine solid particles.
- the resulting thick slurry was filtered and the filtration residue was washed with 200 ml of methanol and two portions of hot water. Finally, the purified polyethersulfone was dried in a vacuum oven at 100°C.
- the yield was 95.4% of the theoretical amount of a product having a sodium con ent of 32 ppm. Its average particle size was 177 microns and 90% of the particles had a size of at least 38 microns. The molecular weight was 48,400.
- Example 2 The procedure of Example 2 was repeated, employing 9.919 g ( 124.33 mmol) of aqueous sodium hydroxide, 11.576 g (62.17 mmol) of 4, 4 -dihydroxybiphenyl, 17.852 g (62.17 mmol) of DDS and 1.73 g (4.97 mmol) of hexa-n-propylguanidinium chloride.
- 150 ml of anisole was added and the mixture was cooled to 85°C and spiked with 50 milligrams (mg) of preformed crystalline polyethersulfone.
- the polyethersulfone product obtained in 95.1% yield, had a sodium content of 29 ppm and an average particle size of 119 microns; 90% of the particles had a size of at least 20 microns.
- the molecular weight was 53,700.
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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)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00976859A EP1242503B1 (en) | 1999-11-29 | 2000-11-02 | Method for isolating dihydroxybiphenyl polyethersulfones |
JP2001540182A JP2003514969A (en) | 1999-11-29 | 2000-11-02 | Method for isolating dihydroxybiphenyl polyether sulfone |
DE60027321T DE60027321T2 (en) | 1999-11-29 | 2000-11-02 | METHOD OF ISOLATING DIHYDROXYBIPHENYLPOLYETHERSULFONES |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/451,229 US6197924B1 (en) | 1999-11-29 | 1999-11-29 | Method for isolating dihydroxybiphenyl polyethersulfones |
US09/451,229 | 1999-11-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001038422A1 true WO2001038422A1 (en) | 2001-05-31 |
Family
ID=23791351
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2000/030266 WO2001038422A1 (en) | 1999-11-29 | 2000-11-02 | Method for isolating dihydroxybiphenyl polyethersulfones |
Country Status (6)
Country | Link |
---|---|
US (1) | US6197924B1 (en) |
EP (1) | EP1242503B1 (en) |
JP (1) | JP2003514969A (en) |
AT (1) | ATE323120T1 (en) |
DE (1) | DE60027321T2 (en) |
WO (1) | WO2001038422A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US9040651B2 (en) | 2011-10-31 | 2015-05-26 | Sabic Global Technologies B.V. | Poly(aryl ether sulfone) composition, and method of making |
EP3222651A1 (en) * | 2016-03-21 | 2017-09-27 | Basf Se | Desalination of polyaryl ethers by means of melt extraction |
EP3587470B1 (en) | 2018-06-27 | 2023-12-06 | SHPP Global Technologies B.V. | Semicrystalline polyphenylsulfone and associated method of making and method of additive manufacturing |
JP2022520769A (en) * | 2019-02-08 | 2022-04-01 | ビーエーエスエフ ソシエタス・ヨーロピア | Crystal composition (CC) containing 4,4'-dichlorodiphenyl sulfoxide crystal (C) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3795660A (en) * | 1971-01-05 | 1974-03-05 | Ici Ltd | Method of isolating aromatic polysulphones |
US4945154A (en) * | 1989-07-07 | 1990-07-31 | Hexcel Corporation | Densified polyethersulfone |
JPH06242430A (en) * | 1993-02-19 | 1994-09-02 | Ube Ind Ltd | Liquid crystal element |
US5910558A (en) * | 1993-01-08 | 1999-06-08 | Basf Aktiengesellschaft | Micropowders |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3850384T2 (en) | 1987-09-28 | 1995-02-23 | Asahi Chemical Ind | METHOD FOR PRODUCING CRYSTALLINE AROMATIC POLYCARBONATE AND AROMATIC POLYCARBONATE PRODUCED IN THIS PRODUCT. |
US5229482A (en) | 1991-02-28 | 1993-07-20 | General Electric Company | Phase transfer catalyzed preparation of aromatic polyether polymers |
US5830974A (en) | 1997-02-13 | 1998-11-03 | General Electric Company | Method for preparing aromatic polyether polymers |
-
1999
- 1999-11-29 US US09/451,229 patent/US6197924B1/en not_active Expired - Lifetime
-
2000
- 2000-11-02 DE DE60027321T patent/DE60027321T2/en not_active Expired - Lifetime
- 2000-11-02 AT AT00976859T patent/ATE323120T1/en not_active IP Right Cessation
- 2000-11-02 JP JP2001540182A patent/JP2003514969A/en not_active Withdrawn
- 2000-11-02 WO PCT/US2000/030266 patent/WO2001038422A1/en active IP Right Grant
- 2000-11-02 EP EP00976859A patent/EP1242503B1/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3795660A (en) * | 1971-01-05 | 1974-03-05 | Ici Ltd | Method of isolating aromatic polysulphones |
US4945154A (en) * | 1989-07-07 | 1990-07-31 | Hexcel Corporation | Densified polyethersulfone |
US5910558A (en) * | 1993-01-08 | 1999-06-08 | Basf Aktiengesellschaft | Micropowders |
JPH06242430A (en) * | 1993-02-19 | 1994-09-02 | Ube Ind Ltd | Liquid crystal element |
Non-Patent Citations (2)
Title |
---|
CHEMICAL ABSTRACTS, vol. 89, no. 8, August 1979, Columbus, Ohio, US; abstract no. 60488n, AOYAGI T. ET AL: "Purification of 4,4'-dichlorodiphenyl-4,4'-dihydroxydiphenylsulphone copolymers" page 31; XP002157776 * |
DATABASE WPI Section Ch Week 199440, Derwent World Patents Index; Class A26, AN 1994-319406, XP002157777 * |
Also Published As
Publication number | Publication date |
---|---|
EP1242503A1 (en) | 2002-09-25 |
ATE323120T1 (en) | 2006-04-15 |
US6197924B1 (en) | 2001-03-06 |
DE60027321T2 (en) | 2007-03-15 |
JP2003514969A (en) | 2003-04-22 |
EP1242503B1 (en) | 2006-04-12 |
DE60027321D1 (en) | 2006-05-24 |
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