DE2324154C2 - - Google Patents
Info
- Publication number
- DE2324154C2 DE2324154C2 DE2324154A DE2324154A DE2324154C2 DE 2324154 C2 DE2324154 C2 DE 2324154C2 DE 2324154 A DE2324154 A DE 2324154A DE 2324154 A DE2324154 A DE 2324154A DE 2324154 C2 DE2324154 C2 DE 2324154C2
- Authority
- DE
- Germany
- Prior art keywords
- column
- monomer
- polymerization
- droplets
- aqueous
- 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 - Lifetime
Links
- 239000000178 monomer Substances 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 25
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 239000011324 bead Substances 0.000 claims description 22
- 239000012736 aqueous medium Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 13
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000003381 stabilizer Substances 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 239000008346 aqueous phase Substances 0.000 claims description 8
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- 239000002609 medium Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000003505 polymerization initiator Substances 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 230000000087 stabilizing effect Effects 0.000 claims description 4
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 3
- GCNKJQRMNYNDBI-UHFFFAOYSA-N [2-(hydroxymethyl)-2-(2-methylprop-2-enoyloxymethyl)butyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(CC)COC(=O)C(C)=C GCNKJQRMNYNDBI-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 claims 1
- GQPVFBDWIUVLHG-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(CO)COC(=O)C(C)=C GQPVFBDWIUVLHG-UHFFFAOYSA-N 0.000 claims 1
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 claims 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims 1
- 235000021120 animal protein Nutrition 0.000 claims 1
- 229910021538 borax Inorganic materials 0.000 claims 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 claims 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 235000010339 sodium tetraborate Nutrition 0.000 claims 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 239000011049 pearl Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007900 aqueous suspension Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- -1 styrene Chemical class 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229940092782 bentonite Drugs 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- 235000012216 bentonite Nutrition 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- 238000009739 binding Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012737 fresh medium Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012022 methylating agents Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000008252 pharmaceutical gel Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/04—Fractionation
-
- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/24—Polymer with special particle form or size
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US25463372A | 1972-05-15 | 1972-05-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2324154C2 true DE2324154C2 (en, 2012) | 1990-08-23 |
Family
ID=22965019
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2324154A Granted DE2324154A1 (de) | 1972-05-15 | 1973-05-12 | Verfahren zur herstellung von gleichfoermigen teilchen aus polymerkuegelchen |
| DE2324154A Expired - Lifetime DE2324154C2 (en, 2012) | 1972-05-15 | 1973-05-12 |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2324154A Granted DE2324154A1 (de) | 1972-05-15 | 1973-05-12 | Verfahren zur herstellung von gleichfoermigen teilchen aus polymerkuegelchen |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5336510B2 (en, 2012) |
| KR (1) | KR780000275B1 (en, 2012) |
| AR (1) | AR195003A1 (en, 2012) |
| AU (1) | AU476028B2 (en, 2012) |
| CA (1) | CA1027724A (en, 2012) |
| DE (2) | DE2324154A1 (en, 2012) |
| ES (1) | ES414758A1 (en, 2012) |
| FR (1) | FR2184846B1 (en, 2012) |
| GB (1) | GB1436167A (en, 2012) |
| IT (1) | IT987451B (en, 2012) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2484421A1 (fr) * | 1980-06-13 | 1981-12-18 | Dia Prosim Sa France | Procede continu de polymerisation en lit fluidise |
| JPS57205402A (en) * | 1981-06-12 | 1982-12-16 | Kanegafuchi Chem Ind Co Ltd | Continuous suspension polymerization |
| JPS5891701A (ja) * | 1981-11-27 | 1983-05-31 | Kanegafuchi Chem Ind Co Ltd | 連続懸濁重合方法 |
| JPS60190402A (ja) * | 1984-03-12 | 1985-09-27 | Hitachi Chem Co Ltd | ビニル重合体の製造法 |
| JPH03249931A (ja) * | 1989-11-16 | 1991-11-07 | Mitsubishi Kasei Corp | 水中油型均一液滴分散液の製造法及び均一粒径ポリマービーズの重合方法 |
| DE69109706T3 (de) * | 1990-02-23 | 2002-12-05 | Tomoegawa Paper Co., Ltd. | Verfahren und Apparat zur Suspensionspolymerisation. |
| US6277933B1 (en) | 1998-04-03 | 2001-08-21 | Solutia Inc. | Polyacrylonitrile particles by surfmer polymerization and sodium removal by chemical exchange |
| US6143835A (en) * | 1998-04-03 | 2000-11-07 | Solutia Inc. | Polyacrylonitrile polymer treatment |
| KR20040007742A (ko) | 2001-06-22 | 2004-01-24 | 세키스이가가쿠 고교가부시키가이샤 | 수지 미립자의 제조 방법, 수지 미립자 및 수지 미립자의제조 장치 |
| DE102005044035A1 (de) * | 2005-09-14 | 2007-03-15 | Basf Ag | Verfahren zum Vertropfen von Flüssigkeiten |
| JP5231189B2 (ja) * | 2008-01-09 | 2013-07-10 | ローム アンド ハース カンパニー | 均一なサイズのポリマービーズを製造する方法 |
| US9228028B2 (en) | 2010-03-20 | 2016-01-05 | Relypsa, Inc. | Continuous process for preparing polyfluoroacrylate particles |
| US8816026B2 (en) * | 2012-09-20 | 2014-08-26 | Thermax Limited | Method and apparatus for preparing polymer beads of uniform particle size by suspension polymerisation |
| CN105924547A (zh) * | 2016-07-07 | 2016-09-07 | 宁波争光树脂有限公司 | 一种用于悬浮聚合的喷淋反应装置 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3172878A (en) * | 1965-03-09 | Suspension polymerization process using additive mixtures of polyacrylamide and natural gums | ||
| DE1116900B (de) * | 1955-03-28 | 1961-11-09 | Dow Chemical Co | Verfahren zur kontinuierlichen Suspensionspolymerisation |
| FR1297689A (fr) * | 1960-09-23 | 1962-06-29 | Koppers Co Inc | Perfectionnements apportés aux procédés pour la polymérisation en suspension aboutissant à l'obtention de particules de dimensions déterminées |
| FR1559139A (en, 2012) * | 1967-02-09 | 1969-03-07 |
-
1973
- 1973-04-28 JP JP4834373A patent/JPS5336510B2/ja not_active Expired
- 1973-05-12 DE DE2324154A patent/DE2324154A1/de active Granted
- 1973-05-12 DE DE2324154A patent/DE2324154C2/de not_active Expired - Lifetime
- 1973-05-14 ES ES414758A patent/ES414758A1/es not_active Expired
- 1973-05-14 CA CA171,288A patent/CA1027724A/en not_active Expired
- 1973-05-15 KR KR7300787A patent/KR780000275B1/ko not_active Expired
- 1973-05-15 IT IT24103/73A patent/IT987451B/it active
- 1973-05-15 AR AR248026A patent/AR195003A1/es active
- 1973-05-15 GB GB2306173A patent/GB1436167A/en not_active Expired
- 1973-05-15 FR FR7317495A patent/FR2184846B1/fr not_active Expired
- 1973-05-15 AU AU55720/73A patent/AU476028B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| AU5572073A (en) | 1974-11-21 |
| KR780000275B1 (en) | 1978-07-24 |
| IT987451B (it) | 1975-02-20 |
| JPS4955782A (en, 2012) | 1974-05-30 |
| ES414758A1 (es) | 1976-06-16 |
| DE2324154A1 (de) | 1973-11-29 |
| AR195003A1 (es) | 1973-08-30 |
| JPS5336510B2 (en, 2012) | 1978-10-03 |
| GB1436167A (en) | 1976-05-19 |
| CA1027724A (en) | 1978-03-14 |
| AU476028B2 (en) | 1976-09-09 |
| FR2184846A1 (en, 2012) | 1973-12-28 |
| FR2184846B1 (en, 2012) | 1977-02-11 |
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