WO1996015177A1 - Polymerization of carbon monoxide and ethylene using catalyst containing non-coordinating, non-acidic anion - Google Patents
Polymerization of carbon monoxide and ethylene using catalyst containing non-coordinating, non-acidic anion Download PDFInfo
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- WO1996015177A1 WO1996015177A1 PCT/US1995/014833 US9514833W WO9615177A1 WO 1996015177 A1 WO1996015177 A1 WO 1996015177A1 US 9514833 W US9514833 W US 9514833W WO 9615177 A1 WO9615177 A1 WO 9615177A1
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- WIPO (PCT)
- Prior art keywords
- anion
- salt
- tetrasubstituted
- group viii
- viii metal
- Prior art date
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- 150000001450 anions Chemical class 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000005977 Ethylene Substances 0.000 title claims abstract description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 title claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000003839 salts Chemical class 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 229920001470 polyketone Polymers 0.000 claims abstract description 24
- 229910052796 boron Inorganic materials 0.000 claims abstract description 23
- 239000003446 ligand Substances 0.000 claims abstract description 21
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 12
- 239000006227 byproduct Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 150000001768 cations Chemical class 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 13
- -1 monoboron anion Chemical class 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 9
- 150000001638 boron Chemical class 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- YFTIOFHTBMRALM-UHFFFAOYSA-N ethene;formaldehyde Chemical group C=C.O=C YFTIOFHTBMRALM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 1
- 229940005561 1,4-benzoquinone Drugs 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Chemical class 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
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
- C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
- C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
Definitions
- catalysts for polyketone polymer production which are formed from a Group VIII metal, such as palladium, and a bidentate ligand containing a Group V or VI heteroatom, such as phosphorus, coordinating, acidic species, such as those formed from (a) a 2:1 reaction mixture of a substituted salicylic acid and boric acid (U.S. Patent No. 5,187,258 to K.G. Smith), (b) tetrafluoroboric acid (U.S. Patent Nos. 5,216,120 to E. Drent et al. and 5,243,026 to P.A.
- Chien illustrates the use of non-coordinating tetrasubstituted monoboron anions, such as boron tetraphenyl and boron tetra(pentafluorophenyl) in the polymerization of polyketone polymers containing an ⁇ -olefin containing no less than three carbon atoms.
- This patent teaches away from the use of ethylene as a comonomer for the polymerization reaction (See, for example, Col. 6, lines 46-49 and Col. 7, lines 4-15) even though it discloses use of catalyst systems which can be considered to be non-acidic.
- European Patent Publication No. 619,335 to BP Chemicals Ltd. contains a disclosure of using certain boron hydrocarbyl compounds as anions in catalysts for the synthesis of a polyketone polymer.
- the main thrust of this patent disclosure is the use of Lewis acidic, trisubstituted boron compounds of the formula BXYZ, where at least one of X, Y, or Z is a monovalent hydrocarbyl group.
- This patent contains an isolated, inconsistent mention of certain tetrasubstituted boron species at page 3, lines 48-53 without any other disclosure indicating that such species, which would be non-acidic, as defined hereinbelow, rather than acidic, were ever used to make polyketone polymers.
- the disclosure of these tetrasubstituted boron species is inconsistent with the main thrust of the disclosure of using Lewis acid species (e.g., Claim 2).
- the present invention relates, in one embodiment, to a process for the production of a polyketone by the polymerization of carbon monoxide and ethylene in the presence of a catalytically effective amount of a catalyst formed from a Group VIII metal source, such as palladium, a bidentate ligand containing a Group VA or VIA heteroatom, such as phosphorus, and an anion which is a non-coordinating, non-acidic tetrasubstituted anion containing a Group IIIA element, such as boron, with the anion preferably being either an unsubstituted or substituted boron tetraphenyl compound.
- a catalyst formed from a Group VIII metal source such as palladium
- a bidentate ligand containing a Group VA or VIA heteroatom such as phosphorus
- an anion which is a non-coordinating, non-acidic tetrasubstituted anion containing a Group IIIA element, such as boron, with the
- the invention also relates to a facile synthesis procedure for making the catalyst by the exchange reaction of a ligand-conjugated Group VIII metal salt with a salt containing the non-coordinating, non-acidic tetrasubstituted anion containing the Group IIIA element in a solvent medium which causes the separation (due to differing solubilities) of the desired catalyst from the by-product of the reaction which comprises the anion from salt which was used as the Group VIII metal source and the cation from the salt used as the source of the non-coordinating, non-acidic tetrasubstituted anion containing the Group IIIA element.
- non-acidic in defining the nature of the above-described anion is intended to indicate that when a catalyst containing that anion is used to make the carbon monoxide-ethylene polyketone such a polyketone product has a substantially enhanced resistance to thermal degradation, when melt processed, as compared to a comparable polyketone formed using known catalyst systems containing anions derived from such acidic materials as para-toluene sulfonic acid, trifluoroacetic acid, tetrafluoroboric acid, or trihydrocarbyl-substituted boron species.
- acidic materials as para-toluene sulfonic acid, trifluoroacetic acid, tetrafluoroboric acid, or trihydrocarbyl-substituted boron species.
- the present invention relies upon the novel use of certain of the catalyst systems described in the above-referenced Chien patent for use in the formation of a polyketone polymer from carbon monoxide and ethylene, rather than the polyketone polymers synthesized by Chien which utilized, as essential comonomers therein, ⁇ -olefins having a higher carbon content than the ethylene comonomer of the present invention.
- the Chien patent is incorporated herein by reference for its teaching of the general polymerization conditions which may be used for synthesizing polyketones as well as its generalized description of how its catalyst systems can be formed.
- the catalyst system is formed from a Group VIII metal source, a bidentate ligand containing a Group VA or VIA heteroatom, and an anion which is a non-coordinating, non- acidic tetrasubstituted anion containing a Group IIIA element.
- Group VIII metal source is to be construed as covering those conventionally used compounds which have traditionally been employed in making catalysts for the polymerization of carbon monoxide and an olefin.
- the preferred Group VIII metal is palladium and sources of this metal include tetrakis(acetonitrile) palladium tetrafluoroborate.
- a bidentate ligand containing a Group VA or VIA heteroatom is to be construed as covering those bidentate ligands containing nitrogen, phosphorus (as preferred) , arsenic, or antimony heteroatoms which have been traditionally employed in making catalysts for the polymerization of carbon monoxide and an olefin.
- These bidentate ligands have the general formula (R 1 ) 3 -M-R 2 -M- (R 1 ) 2 , where M is one of the aforesaid heteroatoms, R is alkyl, cycloalkyl, or phenyl, with lower alkyl or phenyl being preferred, and R being alkylene, such as propylene.
- This type of ligand may be used in an amount ranging from about 0.5 mole to about 2 moles per mole of Group VIII metal, most preferably 1 mole per mole of metal.
- the anion is a non- coordinating, non-acidic tetrasubstituted anion containing a Group IIIA element, such as boron (which is preferred) or aluminum.
- a Group IIIA element such as boron (which is preferred) or aluminum.
- boron tetraphenyl compounds either by unsubstituted boron tetraphenyl itself or by a substituted compound of that type, such as the fully halogen substituted boron tetra(pentafluorophenyl) .
- the amount of this anion may range from about 1 to about 10 moles per mole of palladium, preferably from about 1 to about 2 moles per mole of palladium.
- the catalyst is advantageously formed by the exchange reaction of a ligand-conjugated Group VIII metal salt with a salt containing the non-coordinating, non-acidic tetrasubstituted anion containing the Group IIIA element in a solvent medium which causes the separation (due to differing solubilities) of the desired catalyst from the by-product of the reaction which comprises the anion from salt which was used as the Group VIII metal source and the cation from the salt used as the source of the non-coordinating, non-acidic tetrasubstituted anion containing the Group IIIA element.
- the process entails the initial dissolving, in an appropriate solvent, such as acetonitrile, of a source of the Group VIII metal. Then, a solution (e.g., in methylene chloride) of the bidentate ligand is added to the previously described solution to form the ligand-conjugated species, also in solution, which forms one of the actual reagents.
- an appropriate solvent such as acetonitrile
- the next step is to react such a reagent species, which is dissolved in the thus produced solution, with a salt reagent (containing, as an anion, the non-coordinating, non- acidic anion comprising the Group IIIA element) forming, via exchange reaction, the desired catalyst and a by-product which each have differing solubilities in the resulting solvent medium so as to separate therefrom.
- a salt reagent containing, as an anion, the non-coordinating, non- acidic anion comprising the Group IIIA element
- the cation used with the salt reagent comprising the anion desired in the final catalyst can be an alkali metal, such as lithium.
- the net result of the entire process is the, for example, the production of a solubilized catalyst species, containing the ligand-Group VIII metal moiety, as cation, and the non-coordinating, non-acidic anion, with the production of a precipitated and removed by-product comprising the cation originally associated with the non-coordinating, non- acidic anion when in the final catalyst and the original anion associated with the ligand-conjugated Group VIII metal-containing cation.
- the organic oxidizing agent component e.g., 1,4-benzoquinone identified at Col. 5, lines 15-26 of U.S. Patent No. 5,216,120 of E. Drent et al. may be added as an optional additive to prolong the life of the instant catalyst at the levels disclosed therein.
- the catalyst described herein for use in the manufacture of a polyketone from carbon monoxide and ethylene can be used in those polymerization procedures known to persons of ordinary skill in the art for making such a polyketone polymer using amounts of the catalyst as conventionally employed and ratios of carbon monoxide to ethylene also as conventionally employed.
- the catalysts used in these Examples was of the formula (Ph a P(CH 2 ) 3 PPh 2 )Pd(CH 3 CN) 2 2B(C ⁇ P 5 ) 4 .
- the method used to prepare this catalyst comprised the following steps: O.llg of Pd(CH 3 CN) 4 2BF 4 was dissolved in 1 ml of acetonitrile, followed by addition of a solution of 0.105g of Ph 3 P(CH 2 ) 3 PPh 2 in 2 ml of methylene chloride, followed by addition of a solution of 0.35g of LiB(C 6 F 5 ) 4 in 2 ml of methylene chloride. The product was a yellow-orange solution. The solvent was removed under vacuum. The residue which remained was dissolved in 6 ml of methylene chloride and, when applicable, O.llg of 1,4 benzoguinone in 2 ml of methylene chloride was added.
- the catalyst used in these Examples was of the formula (Ph 2 P(CHj) 3 PPh 2 )Pd(CH 3 CN) 2 2BPh 4 .
- the catalyst was prepared by dissolving 0.11 g of Pd(CH 3 CN) 4 2BF 4 in a mixture of 4 ml of acetonitrile and 1 ml of methylene chloride followed by the addition of a solution of 0.105g (one equivalent) of Ph 3 P(CH 2 ) 3 PPh 2 in 2 ml of methylene chloride. A solution of 0.17 g of NaBPh 4 in a mixture of 2 ml of acetonitrile and 4 ml of methylene chloride was then added. A white precipitant formed.
- the precipitant that was formed was NaBF 4 , and the compound (Ph 2 P(CH 2 ) 3 PPh 2 )Pd(CH 3 CN) 2 2BPh 4 that was formed remained in solution as shown by X H and 19 F NMR spectroscopy.
- the precipitant was filtered off, and the solution was injected into a 1 liter autoclave containing 600 ml of methanol as a polymerization solvent and pressurized with 1:1 carbon monoxide and ethylene to 360 psig. All reactions were terminated after two hours.
- the test (as described in U.S. Patent Nos. 4,983,649, 4,999,399 and 5,049,630) involves the measurement of the heats of crystallization of the polymer before and after exposure to high temperature for a given period of time.
- the result is a number (C J /C J ) of between 0 and 1.0 with 1.0 indicating a perfect thermal stability.
- the unstabilized product showed values of 0.78, 0.81, and 0.83, respectively, after heating to 285°C for ten minutes.
- the unstabilized sample from Example 9 showed a superior thermal stability of 0.97 when heated to the more severe conditions of 295°C for ten minutes. If the material of this Example were heated at 285°C, the stability value would be in excess of 0.97.
- the polyketone product having a thermal stability values, as described above, of no less than 0.90, preferably no less than about 0.95, are deemed to be novel compositions as well as thermally processed products thereof (e.g., formed articles, fibers, food packaging, etc.) .
- thermally processed products thereof e.g., formed articles, fibers, food packaging, etc.
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Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95941395A EP0792313A4 (en) | 1994-11-14 | 1995-11-13 | Polymerization of carbon monoxide and ethylene using catalyst containing non-coordinating, non-acidic anion |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/339,096 US5494998A (en) | 1994-11-14 | 1994-11-14 | Polymerization of carbon monoxide and ethylene using catalyst containing non-coordinating, non-acidic anion |
US08/339,096 | 1994-11-14 |
Publications (1)
Publication Number | Publication Date |
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WO1996015177A1 true WO1996015177A1 (en) | 1996-05-23 |
Family
ID=23327488
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US1995/014833 WO1996015177A1 (en) | 1994-11-14 | 1995-11-13 | Polymerization of carbon monoxide and ethylene using catalyst containing non-coordinating, non-acidic anion |
Country Status (4)
Country | Link |
---|---|
US (3) | US5494998A (en) |
EP (1) | EP0792313A4 (en) |
CA (1) | CA2205266A1 (en) |
WO (1) | WO1996015177A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US6969714B2 (en) | 2000-09-05 | 2005-11-29 | Astrazeneca Ab | Imidazolo-5-YL-2-anilino-pyrimidines as agents for the inhibition of the cell proliferation |
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---|---|---|---|---|
US5741939A (en) * | 1995-03-22 | 1998-04-21 | Shell Oil Company | Process for the copolymerization of carbon monoxide with an olefinically unsaturated compound |
US5703201A (en) * | 1995-10-10 | 1997-12-30 | Akzo Nobel Nv | Catalyst for polymerization of polyketone formed by treatment with carbon monoxide and olefin |
DE19829519A1 (en) * | 1998-07-02 | 2000-01-05 | Basf Ag | Water soluble transition metal complexes |
US6852662B2 (en) * | 1998-07-02 | 2005-02-08 | Basf Aktiengesellschaft | Catalyst systems based on transition metal complexes for carbon monoxide copolymerization in an aqueous medium |
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US5216120A (en) * | 1991-02-26 | 1993-06-01 | Shell Oil Company | Polymerization of co/olefin with catalyst comprising palladium compound, lewis acid and bronsted acid |
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US5352767A (en) * | 1992-01-08 | 1994-10-04 | University Of Massachusetts - Amherst | Alpha-olefin/carbon monoxide attenuating copolymers and improved catalyst and method for copolymerizing the same |
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GB8907624D0 (en) * | 1989-04-05 | 1989-05-17 | British Petroleum Co Plc | Process for preparing polyketones |
US4983649A (en) * | 1989-05-15 | 1991-01-08 | Shell Oil Company | Stabilized polyketone blend |
NL8901253A (en) * | 1989-05-19 | 1990-12-17 | Stamicarbon | POLYMERIC FILAMENTS, TAPES AND FILMS WITH HIGH MODULUS, HIGH STRENGTH AND HIGH MELTING TEMPERATURE AND A METHOD FOR THE PRODUCTION THEREOF. |
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EP0456306B1 (en) * | 1990-05-09 | 1995-12-13 | Akzo Nobel N.V. | Process for making polyketone fibres |
WO1994000623A1 (en) * | 1992-06-26 | 1994-01-06 | Akzo Nobel N.V. | Polyketone yarn and a method of manufacturing same |
KR940007081A (en) * | 1992-09-29 | 1994-04-26 | 리챠드 데이비드 크락 | How to prepare polyketone |
ES2131636T3 (en) * | 1993-04-06 | 1999-08-01 | Bp Chem Int Ltd | CATALYTIC COMPOSITION. |
EP0702046B1 (en) * | 1994-09-15 | 2000-05-24 | Shell Internationale Researchmaatschappij B.V. | Process for the copolymerization of carbon monoxide with an olefinically unsaturated compound |
EP0702045A3 (en) * | 1994-09-15 | 1996-07-17 | Shell Int Research | Gas phase process for the copolymerization of carbon monoxide and ethylenically unsaturated compounds |
-
1994
- 1994-11-14 US US08/339,096 patent/US5494998A/en not_active Expired - Fee Related
-
1995
- 1995-06-06 US US08/466,321 patent/US5523385A/en not_active Expired - Fee Related
- 1995-06-06 US US08/466,322 patent/US5506338A/en not_active Expired - Fee Related
- 1995-11-13 CA CA002205266A patent/CA2205266A1/en not_active Abandoned
- 1995-11-13 WO PCT/US1995/014833 patent/WO1996015177A1/en not_active Application Discontinuation
- 1995-11-13 EP EP95941395A patent/EP0792313A4/en not_active Withdrawn
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5216120A (en) * | 1991-02-26 | 1993-06-01 | Shell Oil Company | Polymerization of co/olefin with catalyst comprising palladium compound, lewis acid and bronsted acid |
US5245123A (en) * | 1991-02-26 | 1993-09-14 | Shell Oil Company | Vapor phase polymerization of co/olefin with palladium compound, lewis acid and bidentate ligand |
US5243026A (en) * | 1991-09-27 | 1993-09-07 | Shell Oil Company | Continuous gas phase polymerization of co/olefin with palladium and metal fluoride lewis acid catalyst |
US5352767A (en) * | 1992-01-08 | 1994-10-04 | University Of Massachusetts - Amherst | Alpha-olefin/carbon monoxide attenuating copolymers and improved catalyst and method for copolymerizing the same |
Non-Patent Citations (1)
Title |
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See also references of EP0792313A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6969714B2 (en) | 2000-09-05 | 2005-11-29 | Astrazeneca Ab | Imidazolo-5-YL-2-anilino-pyrimidines as agents for the inhibition of the cell proliferation |
Also Published As
Publication number | Publication date |
---|---|
US5523385A (en) | 1996-06-04 |
EP0792313A4 (en) | 1998-02-18 |
US5506338A (en) | 1996-04-09 |
US5494998A (en) | 1996-02-27 |
EP0792313A1 (en) | 1997-09-03 |
CA2205266A1 (en) | 1996-05-23 |
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