CA1068048A - Ethylene polymerization catalysts - Google Patents
Ethylene polymerization catalystsInfo
- Publication number
- CA1068048A CA1068048A CA259,845A CA259845A CA1068048A CA 1068048 A CA1068048 A CA 1068048A CA 259845 A CA259845 A CA 259845A CA 1068048 A CA1068048 A CA 1068048A
- Authority
- CA
- Canada
- Prior art keywords
- precipitate
- chromium
- ethylene
- aluminum
- polymer
- 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.)
- Expired
Links
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000005977 Ethylene Substances 0.000 title claims abstract description 25
- 239000002685 polymerization catalyst Substances 0.000 title claims description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 100
- 229920000573 polyethylene Polymers 0.000 claims abstract description 76
- 239000002244 precipitate Substances 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 53
- 230000008569 process Effects 0.000 claims abstract description 37
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 35
- 239000011651 chromium Substances 0.000 claims abstract description 30
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 14
- 150000001336 alkenes Chemical class 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims description 37
- 239000003929 acidic solution Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 17
- 239000000499 gel Substances 0.000 claims description 16
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 15
- -1 Al+++ cations Chemical class 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 4
- 229910001430 chromium ion Inorganic materials 0.000 claims 1
- 229910010272 inorganic material Inorganic materials 0.000 claims 1
- 239000011147 inorganic material Substances 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 abstract description 21
- 238000009826 distribution Methods 0.000 abstract description 9
- 230000006698 induction Effects 0.000 abstract description 8
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 25
- 239000012153 distilled water Substances 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 235000010210 aluminium Nutrition 0.000 description 17
- 229940009859 aluminum phosphate Drugs 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 15
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 230000004913 activation Effects 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- 239000000908 ammonium hydroxide Substances 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000000155 melt Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 229910017974 NH40H Inorganic materials 0.000 description 7
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 7
- 239000001282 iso-butane Substances 0.000 description 7
- 239000002609 medium Substances 0.000 description 7
- 235000011007 phosphoric acid Nutrition 0.000 description 7
- 239000000969 carrier Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910000423 chromium oxide Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 235000012501 ammonium carbonate Nutrition 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000009850 completed effect Effects 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NOBPYVGMURQTKS-UHFFFAOYSA-M O[Cr](O[Si](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)(=O)=O Chemical compound O[Cr](O[Si](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)(=O)=O NOBPYVGMURQTKS-UHFFFAOYSA-M 0.000 description 1
- 102000016462 Phosphate Transport Proteins Human genes 0.000 description 1
- 108091007643 Phosphate carriers Proteins 0.000 description 1
- 208000036366 Sensation of pressure Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- TYYBBNOTQFVVKN-UHFFFAOYSA-N chromium(2+);cyclopenta-1,3-diene Chemical compound [Cr+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 TYYBBNOTQFVVKN-UHFFFAOYSA-N 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000332 continued effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010412 oxide-supported catalyst Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000037048 polymerization activity Effects 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
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US61225275A | 1975-09-10 | 1975-09-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1068048A true CA1068048A (en) | 1979-12-11 |
Family
ID=24452382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA259,845A Expired CA1068048A (en) | 1975-09-10 | 1976-08-25 | Ethylene polymerization catalysts |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5248583A (enExample) |
| BE (1) | BE845754A (enExample) |
| CA (1) | CA1068048A (enExample) |
| DE (1) | DE2640100A1 (enExample) |
| FR (1) | FR2323702A1 (enExample) |
| GB (1) | GB1561756A (enExample) |
| IT (1) | IT1069569B (enExample) |
| NL (1) | NL7610099A (enExample) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4364839A (en) | 1980-12-31 | 1982-12-21 | Phillips Petroleum Company | Catalyst comprising chromium on silica/phosphate support |
| US4444965A (en) * | 1980-12-31 | 1984-04-24 | Phillips Petroleum Company | Olefin polymerization using chromium on an aluminum phosphate produced from a concentrated mass |
| CA1168833A (en) * | 1980-12-31 | 1984-06-12 | Max P. Mcdaniel | Production of aluminum phosphate from concentrated mass |
| US4364841A (en) | 1980-12-31 | 1982-12-21 | Phillips Petroleum Company | Phosphate containing support with zerovalent chromium |
| US4444964A (en) * | 1980-12-31 | 1984-04-24 | Phillips Petroleum Company | Polymerization process using phosphate supported chromium catalyst |
| US4444968A (en) * | 1980-12-31 | 1984-04-24 | Phillips Petroleum Company | Olefin polymerization with phosphate supported zerovalent chromium |
| US4397765A (en) | 1980-12-31 | 1983-08-09 | Phillips Petroleum Company | Phosphated alumina or aluminum phosphate chromium catalyst |
| US4364855A (en) | 1980-12-31 | 1982-12-21 | Phillips Petroleum Company | Production of aluminum phosphate from concentrated mass |
| US4444966A (en) * | 1982-05-05 | 1984-04-24 | Phillips Petroleum Company | Polymerization using phosphated alumina or aluminum phosphate chromium catalyst |
| EP0215336B1 (en) * | 1985-08-29 | 1992-02-05 | W.R. Grace & Co.-Conn. | High pore volume aluminum phosphate |
| US6461415B1 (en) * | 2000-08-23 | 2002-10-08 | Applied Thin Films, Inc. | High temperature amorphous composition based on aluminum phosphate |
-
1976
- 1976-08-25 CA CA259,845A patent/CA1068048A/en not_active Expired
- 1976-08-25 GB GB3528576A patent/GB1561756A/en not_active Expired
- 1976-09-01 BE BE170276A patent/BE845754A/xx unknown
- 1976-09-07 DE DE19762640100 patent/DE2640100A1/de not_active Withdrawn
- 1976-09-09 IT IT5120076A patent/IT1069569B/it active
- 1976-09-09 FR FR7627077A patent/FR2323702A1/fr active Granted
- 1976-09-10 NL NL7610099A patent/NL7610099A/xx not_active Application Discontinuation
- 1976-09-10 JP JP10795576A patent/JPS5248583A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| FR2323702B1 (enExample) | 1980-07-18 |
| JPS5248583A (en) | 1977-04-18 |
| GB1561756A (en) | 1980-02-27 |
| DE2640100A1 (de) | 1977-03-31 |
| BE845754A (fr) | 1977-03-01 |
| FR2323702A1 (fr) | 1977-04-08 |
| IT1069569B (it) | 1985-03-25 |
| NL7610099A (nl) | 1977-03-14 |
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