CN1079230A - The preparation of polymkeric substance - Google Patents
The preparation of polymkeric substance Download PDFInfo
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- CN1079230A CN1079230A CN93106232A CN93106232A CN1079230A CN 1079230 A CN1079230 A CN 1079230A CN 93106232 A CN93106232 A CN 93106232A CN 93106232 A CN93106232 A CN 93106232A CN 1079230 A CN1079230 A CN 1079230A
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- acid
- catalyst system
- promotor
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- 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
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Abstract
A kind of method for preparing multipolymer, comprising making carbon monoxide and the copolymerization in gas phase under polymerizing condition of one or more alefinically unsaturated compounds, be aggregated under the catalyst system existence and carried out, contain a) a kind of metal of periodictable VIII family in the catalyst system, b) a kind of carrier, and c) a kind of promotor, wherein the consumption of promotor is less than 30 moles on every grammeatom VIII family metal.
Description
The present invention relates to a kind of preparation method of multipolymer, be used to prepare carbon monoxide and one or more contain the multipolymer of ethylenic unsaturated bond compound.
The multipolymer of carbon monoxide and one or more alefinically unsaturated compounds, the unit that wherein derives from carbon monoxide is alternately distributed basically with the unit that derives from alefinically unsaturated compounds, can be by under the polymerizing condition that has the appropriate catalyst system, monomer reaction being made, normally with the catalyst system that contains the group VIII metal.
The preparation of these multipolymers can be carried out in liquid phase, that is, external phase is made of liquid diluent, its normally a kind of catalyst dissolution therein but formed multipolymer is gone up insoluble not polymerisable liquid substantially.The recovery of product and purifying need filter or step with centrifugal separation usually.In addition, usually to reclaim pure thinner with distilation steps.
The preparation of multipolymer also can be carried out in gas phase, and this moment, external phase was made of gasiform carbon monoxide and one or more possible other monomers, if these monomers are being to be present among the gas phase under the main polymerizing condition.The vapor phase production of multipolymer has superiority, and is simpler than liquid phase method because its product reclaims.Can omitting, inherent separates and purification step in the liquid phase method, and these steps are expensive on industrial scale, have so just improved the economy of method.
For the gas phase and the liquid phase embodiment of this method, all made the activity that a large amount of effort increases catalyst system, by changing the component that exists in reaction conditions or the change catalyzer, obtained some improvement.
According to United States Patent (USP) 4,831,113, utilization is mixed quinone and has been improved catalytic activity in catalyst system.The preferable amount of pointing out is every grammeatom palladium 1-10000 mole, particularly 10-5000 mole.According to embodiment, in fact this method is carried out in liquid phase, and the consumption of ester is 10 moles of every grammeatom palladiums, perhaps preferably 100 moles.
But nearest work shows, uses that to contain the quinone amount be that the catalyst body of 100 moles on every grammeatom VIII family metal ties up to that to implement this method in the gas phase not really satisfactory.Though increasing of expection compared in the similar experiment that no quinone exists in activity of such catalysts and the catalyst system, activity can decay to the unacceptable level of scale operation.
Find now unexpectedly, in gas phase operation, use a kind of catalyst system that contains minor amounts of promoters, it is identical that the increase of catalyst activity obtains during at least with a large amount of promotor of previous usefulness, and this in addition high activity level can keep considerable time.
The present invention can be defined as and relate to the method for preparing multipolymer, and this method comprises the copolymerization in the presence of catalyst system in gas phase with carbon monoxide and one or more alefinically unsaturated compounds, contains in the catalyst system:
A) a kind of metal of periodictable group VIII,
B) a kind of carrier and
C) a kind of promotor,
Wherein the quantity of promotor is less than 30 moles on every grammeatom group VIII metal.
Promotor quantity in the catalyst system is advisable to be chosen in every grammeatom group VIII metal 1-10 mole, preferably is chosen in the scope of 2-5 mole.
Suitable promotor comprises the compound that contains one or more electron-withdrawing groups (for example oxygen, alkylsulfonyl, nitroso-group or nitro).Preferably aromatic portion is dominant as compound that promotor uses, or contains the conjugated double bond part in its molecule.
Preferred promotor is selected from and replaces or unsubstituted 1,2-quinone, 1,4-quinone and nitroaromatic.Preferably use 1,4-quinone, for example 2,3-dimethyl-1,4-benzoquinones, 2,6-dimethyl-1,4-benzoquinones, monomethyl-1,4-benzoquinones, 2,3,5,6-tetramethyl--1,4-benzoquinones, 2,5-di-t-butyl-1,4-benzoquinones, 3,5-di-t-butyl-1,4-benzoquinones, 1, a 4-naphthoquinones and a nitro-1,4-benzoquinones.1, the 4-naphthoquinones is preferred especially.
Suitable nitrous acid ester comprises alkyl nitrous acid ester, for example butyl nitrite.The suitable promotor that contains nitro comprises nitro-paraffin, for example 1-nitropropane and better nitroaromatic, for example 1-nitro-naphthalene, 2-nitro-naphthalene, 4-sec.-propyl oil of mirbane, 3-(trifluoromethyl)-oil of mirbane, 2-nitrotoluene and 1, the 3-dinitrobenzene.
The VIII metal comprises noble ruthenium, rhodium, palladium, osmium, iridium and platinum, and iron family metal iron, cobalt and nickel.If be ready, can use the mixture of VIII family metal.Among the group VIII metal, be good with palladium, rhodium and nickel, palladium particularly.
For the group VIII metal is mixed in the catalyst system, usually use a kind of metal-salt, preferably the metal-salt of carboxylic acid, for example acetate.
Except that the group VIII metal, catalyst system of the present invention preferably contains a kind of negatively charged ion of acid constituents, the particularly pKa negatively charged ion less than a kind of acid of 6, and condition is that this acid is not haloid acid.
Catalyst system preferably contains the negatively charged ion of pK less than a kind of acid of 2.
The example of suitable acid is sulfuric acid, perchloric acid, sulfonic acid (for example methylsulfonic acid, trifluoromethanesulfonic acid, tosic acid), Tetrafluoroboric acid, hexafluoro metatitanic acid, phosphofluoric acid, hexafluoro-antimonic acid and carboxylic acid (for example trifluoroacetic acid and trichoroacetic acid(TCA)).Suitable acid also has Lewis acid, for example boron trifluoride, aluminum trifluoride and antimony trifluoride, preferably with a spot of low-level chain triacontanol and so on to contain proton (protic) compound (for example methyl alcohol) combined.
Preferential one or more sour negatively charged ion of selecting in Tetrafluoroboric acid, hexafluoro metatitanic acid, phosphofluoric acid and the hexafluoro-antimonic acid.
The preferably every grammeatom VIII of the quantity of the anionic group in the catalyst system metal 0.5-200 of family mole, particularly 1-100 mole.
If be ready, anionic group can mix simultaneously with the group VIII metal, for example mixes with the form of metal and sour complex compound of participating.One of example is complex compound Pd (CH
3CN)
2(O
3S-C
6H
4-CH
3)
2, it can be by silver salt prepared in reaction in as the acetonitrile of solvent of Palladous chloride and tosic acid.
Except group VIII metal, carrier, promotor and a kind of in case of necessity acid constituents, catalyst system of the present invention preferably also contain one or more can with the ligand of group VIII metal complex.
Suitable ligand comprises monodentate, bidentate and multidentate ligand.
By two atoms of ligand and the bidentate ligands of VIII family metal complex is preferred ligand, and described atom is selected from phosphorus, arsenic, antimony, sulphur and nitrogen-atoms.
The example of suitable bidentate ligands is the bidentate ligands of nitrogen, sulphur and phosphorus.
Preferred nitrogen bidentate ligands is the following compound of general formula
Wherein X and Y representative contains the organic abutment of three or four bridged bond atoms, and two in the bridged bond atom is carbon atom, for example 2,2 '-dipyridyl and 1, the 10-phenanthroline.
Preferred sulphur bidentate ligands is that general formula is R
1-S-R-S-R
2Compound, wherein R representative contains the divalent organic bridge base of at least two carbon atoms, R in bridge
1And R
2Represent a commutable in case of necessity alkyl independently of one another, for example 1,2-two (ethylmercapto group) ethane and suitable-1,2-two (benzylthio-) ethene.
Particularly preferably be the following phosphorus bidentate ligand R of general formula
1R
2P-R-PR
3R
4(II) wherein the meaning of R as above, R
1, R
2, R
3And R
4Represent a replacement or unsubstituted alkyl independently of one another.
R
1, R
2, R
3And R
4Can represent identical or different, commutable fat base, cycloaliphatic radical or aryl in case of necessity.The aryl that preferential selection is replaced by one or more polar groups.Particularly preferably be formula (II) compound, wherein each R
1, R
2, R
3And R
4Represent a phenyl, this phenyl contains alkoxyl group on one or two ortho position of coupled phosphorus atom.
The example of suitable phosphorous bidentate ligand is 1,2-two (diphenylphosphino) ethane, 1,3-two (two (2-methoxyphenyl)-phosphino-s) propane and 1,3-two (two (2, the 6-dimethoxy phenyl) phosphino-)-propane.
Be advisable preferably 1 to 50 mole in the scope of the quantity of the bidentate ligand in the catalyst system with 0.5 to 100 mole on every grammeatom VIII family metal.If catalyst system contains the phosphorus bidentate ligands of formula (II), its quantity is preferably in the scope of 0.75 to 1.5 mole on every grammeatom VIII family metal.
The carrier that participates in catalyst system of the present invention can be an inorganics, for example silicon-dioxide, aluminum oxide, talcum or carbon, or organism, for example Mierocrystalline cellulose, dextrose or dextrane gel.Preferentially selecting for use is the carrier of porous carrier materials basically, and particularly the pore volume that records with the mercury porosimeter is at least the solid support material of 0.01 cubic centimetre of every gram.
Very suitable carriers is such as polymer materialss such as polyethylene, polypropylene, polyoxymethylene and polystyrene.If be ready, can use mixing materials such as silicon-dioxide such as impregnated polymer.
A kind of preferred solid support material identical substantially multipolymer of multipolymer that to be structure will prepare with composition and the inventive method.
The preparation of catalyst system can be carried out in the independent step before the inventive method easily, for example, the solution or the suspension of catalyst component or its precursor is flooded with solid support material.In this mode, various catalyst components can add or join in the solid support material respectively together.
Promotor can be added in the catalyst system equally in advance, also can be added in the reactor under polymerizing condition, thereby original position forms catalyst system of the present invention.
The alefinically unsaturated compounds that is adapted at being used as in the copolymerization process of the present invention raw material comprises the compound of a carbon containing and hydrogen and also contains one or more heteroatomic compound, for example unsaturated ester in addition.
Undersaturated hydrocarbon is preferred alefinically unsaturated compounds.Suitable example is a light alkene, for example ethene, propylene and 1-butylene, ring compound, for example cyclopentenes, and aromatic substance, for example vinylbenzene and alpha-methyl styrene.Preferentially select the mixture of ethene, propylene or ethene and propylene for use.
Mol ratio between the monomer, that is, the mol ratio of carbon monoxide and alefinically unsaturated compounds is typically chosen in the scope between 5: 1 to 1: 5.This mol ratio preferably is chosen in 2: 1 to 1: 2 the scope, for example uses equimolar basically monomer.
Preferably add a small amount of volatile protic liquid (for example lower aliphatic alcohols) and/or hydrogen of containing when carrying out vapour phase polymerization.The amount of this liquid is selected very for a short time, so that liquid is in the gas phase basically under polymerizing condition.Suitable quantity is the 40-60% weight that is enough to the amount of saturated pneumatic jack under polymerizing condition.
The preparation of multipolymer is preferably in 20-200 ℃ the temperature range to be carried out, but does not get rid of the temperature of reaction outside this scope of use.Preferably temperature of reaction is chosen in 25-150 ℃ the scope.
Usually in the scope of 1-200 crust, still preferably 2-150 clings to suitable pressure.
The multipolymer that obtains according to the present invention can be processed into moulded products, film, sheet, fiber etc.They demonstrate the favorable mechanical performance, therefore are suitable for many application that commercial value is arranged, and for example are used in the automotive industry, make wrapping material and various daily necessities that food and drink are used.
The present invention will be further described with following embodiment.Embodiment 1
A kind of carbon monoxide/ethylene copolymer is prepared as follows: a) preparation of catalyst system
With a kind of solution impregnation 5 gram carbon monoxide/ethene linear alternated copolymers, contain in this solution
0.0047 mmole acid chloride
0.024 mmole 1, the 4-naphthoquinones
0.005 mmole 1,3 two (two (2-methoxyphenyl) phosphino-) propane
0.012 mmole Tetrafluoroboric acid (5 water)
0.2 milliliter tetrahydrofuran (THF)
2 ml methanol b) preparation of multipolymer:
To be incorporated in 300 milliliters of autoclaves that agitator is housed according to the catalyst composition that a) obtains.With nitrogen pressurization and relief pressure, repeat this step secondary again, the air that exists in the autoclave is emitted.Then add the carbon monoxide of 1: 1 mol ratio and the mixture of ethene under pressure, meanwhile with the content heating, reach 85 ℃ up to temperature, pressure is 50 crust.Between polymerization period, utilize carbon monoxide/mixture of ethylene of further introducing 1: 1 mol ratio to keep-up pressure.Determine by analysis, utilize these steps to remove most of methyl alcohol as the use of catalyst body series solvent.But in polyblend, stayed 0.5 mole, of methanol of number of iterations.After 1 hour, polymerization velocity is per hour 16.1 kilograms of multipolymers (kg/ (g Pd.h)) of every gram palladium.4 hours post polymerization speed no changes.By cool to room temperature and relief pressure polymerization is stopped after 8 hours.Output is 50.2 grams, is equivalent to average polymerization speed and is 11.3 kilograms/gram palladium hour.Embodiment 2
Basically preparing carbon monoxide/ethylene copolymer described in embodiment 1, is that used catalyst composition contains 0.022 mmole 1, and the 4-benzoquinones replaces naphthoquinones.
1 hour post polymerization speed is 19.8 kilograms/gram palladium hour.Speed still has 17.1 kilograms/gram palladium hour after 4 hours.
Stop polymerization after 8 hours.Output is 65.4 grams, is 15.1 kilograms/gram palladium hour corresponding to average polymerization speed.Embodiment 3
Basically prepare carbon monoxide/ethylene copolymer described in embodiment 1, but used catalyst composition contains 0.018 mmole tetramethyl--1, the 4-benzoquinones replaces naphthoquinones.
1 hour post polymerization speed is 17.7 kilograms/gram palladium hour.Speed still has 16.6 kilograms/gram palladium hour after 4 hours.
Stop polymerization after 7 hours.Output is 57.2 grams, is equivalent to average polymerization speed and is 14.9 kilograms/gram palladium hour.Embodiment 4
Basically described in embodiment 1, prepare carbon monoxide/ethylene copolymer, but used catalyst composition contains 2 of 0.023 mmole, 5-di-t-butyl-1, the 4-benzoquinones replaces naphthoquinones.
1 hour post polymerization speed is 15.6 kilograms/gram palladium hour.Speed still has 13.0 kilograms/gram palladium hour after 4 hours.
Stop polymerization after 7 hours.Output is 52.3 grams, is equivalent to average polymerization speed and is 13.5 kilograms/gram palladium hour.Embodiment A (only for comparing)
Basically described in embodiment 1, prepare carbon monoxide/ethylene copolymer, but be to use the catalyst composition that does not contain naphthoquinones.
1 hour post polymerization speed is 16.0 kilograms/gram palladium hour; Speed is reduced to 11.1 kilograms/gram palladium hour after 4 hours.
Stop polymerization after 21 hours.Output is 62.8 grams, is equivalent to average polymerization speed and only is 5.5 kilograms/gram palladium hour.Embodiment 5
Basically press embodiment 1 described preparation carbon monoxide/ethylene copolymer, replace naphthoquinones but used catalyst composition contains 0.024 mmole oil of mirbane.
1 hour post polymerization speed is 19.0 kilograms/gram palladium hour.Speed still is 15.1 kilograms/gram palladium hour after 4 hours.
Termination reaction after 8 hours.Output is 63.8 grams, is equivalent to average polymerization speed and is about 14.7 kilograms/gram palladium hour.Embodiment B (only for comparing)
Basically press embodiment 5 described preparation carbon monoxide/ethylene copolymers, but the catalyst composition that is to use contains the oil of mirbane rather than 0.024 mmole of 0.5 mmole.
Polymerization velocity after 1 hour is 5.1 a kilograms/gram palladium hour.Speed drops to 3.0 kilograms/gram palladium hour after 4 hours.
Stop polymerization after 22 hours.Output is 38.0 grams, is equivalent to average polymerization speed and is 3.0 kilograms/gram palladium hour.Embodiment 6
Basically press embodiment 1 described preparation carbon monoxide/ethylene copolymer, but following difference is arranged: a) solution with catalyst component floods with a kind of different carbon monoxide/ethene linear alternated copolymer.B) use contains 0.1 mmole but not 0.024 mmole 1, the catalyst composition of 4-naphthoquinones.
1 hour post polymerization speed is 15.8 kilograms/gram palladium hour.Speed still is 12.5 kilograms/gram palladium hour after 4 hours.
Stop polyreaction after 12 hours.Output is 60.2 grams, is equivalent to average polymerization speed and is 9.2 kilograms/gram palladium hour.Embodiment 7
Basically press embodiment 6 described preparation carbon monoxide/ethylene copolymers, but the catalyzer that is to use contains 0.01 mmole 1 of 0.1 mmole, the 4-naphthoquinones.
1 hour post polymerization speed is 15.1 thousand fair/gram palladiums hour.Speed still has 11.6 kilograms/gram palladium hour after 4 hours.
Stop after being aggregated in 12 hours.Output 58.4 gram is equivalent to average polymerization speed and is 8.9 kilograms/gram palladium hour.Embodiment C (only for comparing)
Basically described in embodiment 6, prepare carbon monoxide/ethylene copolymer, but be to use the catalyst composition that does not contain naphthoquinones.
1 hour post polymerization speed is 12.5 kilograms/gram palladium hour.Speed is reduced to 10.1 kilograms/gram palladium hour after 4 hours.
Stop polymerization after 12 hours.Output is 38.5 grams, is equivalent to average polymerization speed and is 5.6 kilograms/gram palladium hour.Embodiment 8
Basically press embodiment 1 described preparation carbon monoxide/ethylene copolymer, but following difference is arranged:, use 5 gram polypropylene instead and in catalyst component solution, flood a) without carbon monoxide/ethene linear alternated copolymer.B) catalyst composition of Shi Yonging contains 0.012 mmole but not the naphthoquinones of 0.024 mmole.
1 hour post polymerization speed is 12.4 kilograms/gram palladium hour.Speed still has 10.7 kilograms/gram palladium hour after 4 hours.
Stop polymerization after 8 hours.Output is 47.4 grams, is equivalent to average polymerization speed and is 10.6 kilograms/gram palladium hour.
Embodiment D (only for comparing)
Basically described in embodiment 8, prepare carbon monoxide/ethylene copolymer, but be to use the catalyst composition that does not contain naphthoquinones.
1 hour post polymerization speed is 10.6 kilograms/gram palladium hour.Speed has been reduced to 8.5 kilograms/gram palladium hour after 4 hours.
Stop polymerization after 4 hours.Output is 25.2 grams, is equivalent to average polymerization speed and is 10.1 kilograms/gram palladium hour.
By above embodiment 1-8 and comparative examples A-D as can be seen, in catalyst composition, there be activity and the stability favourable influence of minor amounts of promoters for catalyst system.
When using a large amount of promotor (100 moles of promotors of every grammeatom palladium, comparative examples B), it is lower to observe catalytic activity.
Use the catalyst composition that does not contain promotor that catalyst activity is decayed fast.
Utilize C
13NMR analyzes and determines, has linear long-chain according to the carbon monoxide/ethylene copolymer of embodiment 1-8 preparation and the multipolymer that obtains in comparative examples A-D, and the unit that wherein derives from carbon monoxide is arranged with the units alternately that derives from ethene.
Claims (10)
1. a method for preparing multipolymer comprises carbon monoxide and the copolymerization in the presence of catalyst system in gas phase of one or more alefinically unsaturated compounds, contains in this catalyst system
A) a kind of metal of periodictable group VIII,
B) a kind of carrier and
C) a kind of promotor, wherein the consumption of promotor is lower than 30 moles of every grammeatom group VIII metals.
2. the described method of claim 1, it is characterized in that, employed catalyst system contains palladium as the group VIII metal, also contain the negatively charged ion of pKa in addition less than a kind of acid of 6, condition is that this acid is not haloid acid, and a kind of bidentate ligands, this ligand is by two atoms that are selected from phosphorus, arsenic, antimony, sulphur and nitrogen-atoms and group VIII metal complex on the ligand.
3. the described method of claim 2 is characterized in that, catalyst system contains the negatively charged ion of a kind of acid in the group that is selected from Tetrafluoroboric acid, hexafluoro metatitanic acid, phosphofluoric acid and hexafluoro-antimonic acid.
4. claim 2 or 3 described methods is characterized in that, it is R that catalyst system contains general formula
1R
2P-R-PR
3R
4A kind of ligand of (formula II), wherein R
1, R
2, R
3And R
4Represent one to replace or unsubstituted alkyl independently of one another, R represents the organic abutment of a divalence, contains at least two carbon atoms in the bridged bond.
5. a kind of method of claim 4 is characterized in that, in the ligand of formula (II), and R
1, R
2, R
3And R
4Represent a phenyl separately, this phenyl contains alkoxyl group on one or two ortho position of the phosphorus atom that is attached thereto.
6. each described method among the claim 1-5 is characterized in that, uses a kind of catalyst system, and carrier wherein is the porous solid support material basically, and this material is identical substantially with the multipolymer that will prepare aspect structure and composition.
7. each described method among the claim 1-6 is characterized in that used catalyst system contains a kind of promotor, be selected from replacement or unsubstituted 1,2-quinone, 1, the group of 4-quinone and nitroaromatic.
8. each described method among the claim 1-7 is characterized in that, the consumption of promotor is chosen in the scope of the every grammeatom VIII metal 1-10 of family mole.
9. the described method of claim 8 is characterized in that, the consumption of promotor is chosen in the scope of the every grammeatom VIII metal 2-5 of family mole.
10. each described method among the claim 1-9, it is characterized in that, the mixture that uses ethene or ethene and propylene is as alefinically unsaturated compounds, be reflected in 25-150 ℃ the temperature range and the pressure of 2-150 crust under carry out, the alefinically unsaturated compounds of use and the mol ratio of carbon monoxide are in 5: 1 to 1: 5 scope.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92201537.5 | 1992-05-27 | ||
| EP92201537 | 1992-05-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1079230A true CN1079230A (en) | 1993-12-08 |
Family
ID=8210635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93106232A Pending CN1079230A (en) | 1992-05-27 | 1993-05-25 | The preparation of polymkeric substance |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPH0632896A (en) |
| KR (1) | KR930023384A (en) |
| CN (1) | CN1079230A (en) |
| AU (1) | AU660255B2 (en) |
| BR (1) | BR9302044A (en) |
| CA (1) | CA2096897A1 (en) |
| MX (1) | MX9303036A (en) |
| PL (1) | PL299055A1 (en) |
| TW (1) | TW285674B (en) |
| ZA (1) | ZA933631B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8909476D0 (en) * | 1989-04-26 | 1989-06-14 | British Petroleum Co Plc | Process for preparing polyketones |
| US5162493A (en) * | 1990-06-22 | 1992-11-10 | Shell Oil Company | Polymerization of co/olefin/functionally substituted olefin with tetra alkyl diphosphine |
| CN1079231A (en) * | 1992-05-27 | 1993-12-08 | 国际壳牌研究有限公司 | The preparation method of the multipolymer of carbon monoxide and alefinically unsaturated compounds |
-
1993
- 1993-05-01 TW TW082103414A patent/TW285674B/zh active
- 1993-05-24 KR KR1019930008957A patent/KR930023384A/en not_active Application Discontinuation
- 1993-05-24 BR BR9302044A patent/BR9302044A/en not_active Application Discontinuation
- 1993-05-25 MX MX9303036A patent/MX9303036A/en unknown
- 1993-05-25 JP JP5122849A patent/JPH0632896A/en active Pending
- 1993-05-25 CN CN93106232A patent/CN1079230A/en active Pending
- 1993-05-25 ZA ZA933631A patent/ZA933631B/en unknown
- 1993-05-25 PL PL29905593A patent/PL299055A1/en unknown
- 1993-05-25 AU AU38796/93A patent/AU660255B2/en not_active Ceased
- 1993-05-25 CA CA002096897A patent/CA2096897A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0632896A (en) | 1994-02-08 |
| ZA933631B (en) | 1993-12-20 |
| PL299055A1 (en) | 1993-11-29 |
| TW285674B (en) | 1996-09-11 |
| CA2096897A1 (en) | 1993-11-28 |
| AU3879693A (en) | 1993-12-02 |
| BR9302044A (en) | 1993-11-30 |
| AU660255B2 (en) | 1995-06-15 |
| KR930023384A (en) | 1993-12-18 |
| MX9303036A (en) | 1994-06-30 |
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