EP0226637A1 - Chain-extended poly(aryl ether ketones) - Google Patents
Chain-extended poly(aryl ether ketones)Info
- Publication number
- EP0226637A1 EP0226637A1 EP19860904997 EP86904997A EP0226637A1 EP 0226637 A1 EP0226637 A1 EP 0226637A1 EP 19860904997 EP19860904997 EP 19860904997 EP 86904997 A EP86904997 A EP 86904997A EP 0226637 A1 EP0226637 A1 EP 0226637A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbonate
- bicarbonate
- aryl ether
- chain
- bis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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
- 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
- C08G65/48—Polymers modified by chemical after-treatment
-
- 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
Definitions
- PAEK is the acronym of poly(aryl ether ketone)
- PEEK is the acronym of poly(ether ether ketone) in which the 1,4-phenylene units in the structure are assumed.
- PAEK's may be produced by the Frledel-Crafts catalyzed reaction of aromatic diacylhalldes with unsubstltuted aromatic compounds such as dlphenyl ether as described in, for example, U.S. Patent No. 3,065,205. These processes are generally inexpensive processes; however, the polymers produced by these processes have been stated by Dahl et al., supra, to be brittle and thermally unstable. The Dahl patents, supra, allegedly depict more expensive processes for making superior PAEK's by Frledel-Crafts catalysis. In contrast, PAEK's such as PEEK made by nucleophlllc aromatic substitution reactions generally display good toughness and acceptable mechanical properties.
- the present invention is directed to chain extended poly(aryl ether ketone) polymers. Both the preparation of the starting poly(aryl ether ketone) segments and their subsequent coupling with a diphenol are performed via the nucleophlllc route, i.e. using a base and an aprotic solvent. Products having superior toughness, good fabricabillty, and excellent solvent and temperature resistance are obtained.
- Fluorine and chlorine substituted benzenold reactants are preferred; the fluorine compounds for fast reactivity and the chlorine compounds for their inexpenslveness. Fluorine substituted benzenold compounds are most preferred, particularly when there is a trace of water present in the polymerization reaction system. However, this water content should be maintained below about 11 and preferably below 0.5% for best results.
- Examples of specific dihydric polynuclear phenols include among others the bis-(hydroxyphenyl) alkanes such as 2,2-bis-(4-hydroxyphenyl)propane, 2,4'-dihydroxydiphenylmethane, bis-(2-hydroxypheny1)methane, bis-(4-hydroxyphenyl)methane, bis(4-hydroxy-2,6-dlmethyl-3-methoxyphenyl)methane, 1,1-bls-(4-hydroxyphenyl)ethane, 1,2-bis-(4-hydroxyphenyl)ethane, 1,1-bis-(4-hydroxy-2-chloro ⁇ henyl)ethane, 1,1-bis-(3-methyl-4-hydroxyphenyl)propane, 1,3-bis-(3-methyl-4-hydroxyphenyl)pro ⁇ ane, 2,2-bis-(3-phenyl-4-hydroxyphenyl) ⁇ ro ⁇ ane, 2,2-bis-(3-isopro ⁇ yl-4-hydroxyphen
- the polymerization reaction may be terminated by mixing a suitable end capping reagent, e.g. a mono or polyfunctional halide such as methyl chloride, t-butyl chloride or
- the sodium carbonate or bicarbonate and potassium fluoride are used such that the ratio of potassium to sodium therein is from about 0.001 to about 0.5, preferably from about 0.01 to about 0.25, and most preferably from about 0.02 to about 0.20.
- An excess of total alkali metal may be employed. Hence there may be about 1 to about 1.7 atoms of alkali metal per phenol group. While the use of a large excess of alkali metal may give rise to faster reactions, there is the attendant risk of cleavage of the resulting polymer, particularly when using high temperatures and/or the more active alkali metal salts.
- cesium is a more active metal and potassium is a less active metal so that less cesium and more potassium are used.
- the chioride salts are less active than the fluoride salts so that more chloride and less fluoride is used.
- the polymers 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 oligomer was prepared essentially as in Example 1 except that less potassium fluoride (0.01465 moles, 0.85 gm) was used and the reaction mixture was heated at 200°C for 30 minutes, at 250°C for 1 hour, and then at 290°C for 2 hours.
- the isolated oligomer had a reduced viscosity of 0.51 dl/gm (concentrated sulfuric acid, lgm/100 ml at 25°C).
- Example 2 The reaction of Example 2 was repeated using twice the amounts of all ingredients (500 ml flask). After heating at 290°C for 2 hours,
- the polymer had a reduced viscosity of 1.02 as measured in concentrated sulfuric acid at 25°C at 1% concentration.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyethers (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US74395785A | 1985-06-12 | 1985-06-12 | |
US743957 | 1991-08-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0226637A1 true EP0226637A1 (en) | 1987-07-01 |
Family
ID=24990857
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19860904997 Withdrawn EP0226637A1 (en) | 1985-06-12 | 1986-05-01 | Chain-extended poly(aryl ether ketones) |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0226637A1 (ja) |
JP (1) | JPS63500871A (ja) |
CA (1) | CA1270993A (ja) |
WO (1) | WO1986007368A1 (ja) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4829143A (en) * | 1986-10-28 | 1989-05-09 | Amoco Corporation | Modified poly(aryl ether ketones) derived from biphenol |
DE3700808A1 (de) * | 1987-01-14 | 1988-07-28 | Basf Ag | Verfahren zur herstellung von polyaryletherketonen |
US4777235A (en) * | 1987-07-01 | 1988-10-11 | Amoco Corporation | Production of polyarylene ether from activated dihalo benzenoid monomer, dihydroxy benzenoid monomer and Bis(hydroxyphenyl) monomer |
GB2237810A (en) * | 1989-11-06 | 1991-05-15 | Ici Plc | Aromatic polyetherketones |
GB0020620D0 (en) | 2000-08-22 | 2000-10-11 | Cytec Tech Corp | Compostions adapted for chain linking |
CN100389138C (zh) * | 2006-03-28 | 2008-05-21 | 吴忠文 | 以环丁砜为溶剂合成聚醚醚酮树脂的方法 |
CN100374483C (zh) * | 2006-03-29 | 2008-03-12 | 长春吉大高科技股份有限公司 | 聚醚醚砜和聚醚醚酮三元共聚物的制备方法 |
RU2494118C1 (ru) * | 2012-03-20 | 2013-09-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования Кабардино-Балкарский государственный университет им. Х.М. Бербекова | Способ получения полиэфиркетонов |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1504194A (en) * | 1975-03-25 | 1978-03-15 | Ici Ltd | Aromatic polymer manufacture |
EP0001879B2 (en) * | 1977-09-07 | 1989-11-23 | Imperial Chemical Industries Plc | Thermoplastic aromatic polyetherketones, a method for their preparation and their application as electrical insulants |
US4275186A (en) * | 1978-07-27 | 1981-06-23 | Union Carbide Corporation | Oligomer extended polyarylethers |
US4339568A (en) * | 1979-12-03 | 1982-07-13 | Union Carbide Corporation | Aromatic polymers containing ketone groups |
DE3014230A1 (de) * | 1980-04-14 | 1981-10-22 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von ketogruppenhaltigen polyaethern |
DE3466401D1 (en) * | 1983-05-12 | 1987-10-29 | Ici Plc | Method of increasing molecular weight of poly(aryl ethers) |
-
1986
- 1986-05-01 WO PCT/US1986/000904 patent/WO1986007368A1/en not_active Application Discontinuation
- 1986-05-01 EP EP19860904997 patent/EP0226637A1/en not_active Withdrawn
- 1986-05-01 JP JP50432886A patent/JPS63500871A/ja active Pending
- 1986-05-02 CA CA000508293A patent/CA1270993A/en not_active Expired
Non-Patent Citations (1)
Title |
---|
See references of WO8607368A1 * |
Also Published As
Publication number | Publication date |
---|---|
JPS63500871A (ja) | 1988-03-31 |
CA1270993A (en) | 1990-06-26 |
WO1986007368A1 (en) | 1986-12-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0195448B1 (en) | Process for preparing poly (aryl ether ketone)s | |
US4891167A (en) | Block polymers containing a poly(aryl ether ketone) and methods for their production | |
US4731429A (en) | Novel poly(aryl ether ketones) | |
US4774314A (en) | Preparing poly(aryl ethers) using alkaline earth metal carbonates, organic acid salts, and optionally copper compounds, as catalysts | |
US4767838A (en) | Chain-extended poly(aryl ether ketones) | |
US4774296A (en) | Block polymers containing a poly(aryl ether ketone) and methods for their production | |
EP0275295A1 (en) | Blends containing liquid crystalline polyesters | |
US4820790A (en) | Chain-extended poly(aryl ether ketones) | |
EP0226637A1 (en) | Chain-extended poly(aryl ether ketones) | |
US4748227A (en) | Process for preparing poly(aryl ether)ketones using a sodium carbonate/organic acid salt catalyst | |
EP0211693A1 (en) | Preparation of poly(aryl ether ketones) | |
US5077351A (en) | Process for the preparation of polycarbonate and/or polyarylate block copolymers with poly(aryl ethers) | |
US4687833A (en) | Chain-extended poly(aryl ether ketones) | |
US4642327A (en) | Novel polyetherimides | |
EP0233192B1 (en) | Chain-extended poly (aryl ether ketones) | |
US5084530A (en) | Poly(aryl ether sulfone)-poly(aryl ether ketone) block copolymers | |
US4786694A (en) | Poly(aryl ether ketone) block copolymers | |
EP0231198A1 (en) | Chain-extended poly(aryl ether ketones) | |
US4968758A (en) | Poly(aryl ether sulfone)-poly(aryl ether ketone) block copolymers block copolymers | |
US5120818A (en) | Chain-extended poly(aryl ether ketones) | |
US5159028A (en) | Process for the preparation of polycarbonate and/or polyarylate block copolymers with poly(aryl ethers) | |
JPS62141024A (ja) | 熱可塑性芳香族ポリエ−テルアントラキノンおよびその製造方法 | |
JPS62151421A (ja) | 熱可塑性芳香族ポリエ−テルケトン共重合体およびその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19870130 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE FR GB |
|
17Q | First examination report despatched |
Effective date: 19881205 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
18W | Application withdrawn |
Withdrawal date: 19910523 |
|
R18W | Application withdrawn (corrected) |
Effective date: 19910523 |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: KWIATKOWSKI, GEORGE, THOMAS Inventor name: CLENDINNING, ROBERT, ANDREW |