NO751555L - - Google Patents
Info
- Publication number
- NO751555L NO751555L NO751555A NO751555A NO751555L NO 751555 L NO751555 L NO 751555L NO 751555 A NO751555 A NO 751555A NO 751555 A NO751555 A NO 751555A NO 751555 L NO751555 L NO 751555L
- Authority
- NO
- Norway
- Prior art keywords
- borate
- approx
- amount
- polymerization
- reactor
- Prior art date
Links
- 238000000034 method Methods 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 10
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 8
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 8
- 229910021538 borax Inorganic materials 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- -1 alkali metal borate Chemical class 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 239000000872 buffer Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- 239000011877 solvent mixture Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 3
- 229910052708 sodium Inorganic materials 0.000 claims 3
- 239000011734 sodium Substances 0.000 claims 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims 2
- 239000004800 polyvinyl chloride Substances 0.000 claims 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical class [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 13
- 239000000203 mixture Substances 0.000 description 9
- 239000002609 medium Substances 0.000 description 7
- 150000001642 boronic acid derivatives Chemical class 0.000 description 5
- 239000004328 sodium tetraborate Substances 0.000 description 5
- JREYOWJEWZVAOR-UHFFFAOYSA-N triazanium;[3-methylbut-3-enoxy(oxido)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].CC(=C)CCOP([O-])(=O)OP([O-])([O-])=O JREYOWJEWZVAOR-UHFFFAOYSA-N 0.000 description 5
- 239000007900 aqueous suspension Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 229920000609 methyl cellulose Polymers 0.000 description 4
- 239000001923 methylcellulose Substances 0.000 description 4
- 235000010981 methylcellulose Nutrition 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000375 suspending agent Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000012066 reaction slurry Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UKDOTCFNLHHKOF-FGRDZWBJSA-N (z)-1-chloroprop-1-ene;(z)-1,2-dichloroethene Chemical group C\C=C/Cl.Cl\C=C/Cl UKDOTCFNLHHKOF-FGRDZWBJSA-N 0.000 description 1
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 1
- WJUKOGPNGRUXMG-UHFFFAOYSA-N 1,2-dibromo-1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)(Br)C(Cl)(Cl)Br WJUKOGPNGRUXMG-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 description 1
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229920003091 Methocel™ Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- FZQSLXQPHPOTHG-UHFFFAOYSA-N [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 Chemical compound [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 FZQSLXQPHPOTHG-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- XNNQFQFUQLJSQT-UHFFFAOYSA-N bromo(trichloro)methane Chemical compound ClC(Cl)(Cl)Br XNNQFQFUQLJSQT-UHFFFAOYSA-N 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 description 1
- IHUREIPXVFKEDT-UHFFFAOYSA-N dibromo(dichloro)methane Chemical compound ClC(Cl)(Br)Br IHUREIPXVFKEDT-UHFFFAOYSA-N 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 description 1
- RSCACTKJFSTWPV-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 RSCACTKJFSTWPV-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical class COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- GKXZMEXQUWZGJK-UHFFFAOYSA-N tribromo(chloro)methane Chemical compound ClC(Br)(Br)Br GKXZMEXQUWZGJK-UHFFFAOYSA-N 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
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Description
Foreliggende oppfinnelse er en forbedret fremgangsmåte for å redusere mengden av PVC-avsetninger på de indre vegger av reaksjonskaret under suspensjonspolymerisering av vinylklorid-monomerer (VCM). The present invention is an improved method for reducing the amount of PVC deposits on the inner walls of the reaction vessel during suspension polymerization of vinyl chloride monomers (VCM).
Det er blitt foreslått en rekke metoder som forsøk på å oppnå en suspensjonspolymerisering av VCM som.vil gi en redusert mengde med polymeravsetninger på de indre vegger av reaktoren. En generell metode har vært anvendelsen av forskjellige additiver. For eksempel er det i U.S.-patentskrift" rir. 3«488«328 til Koyanagi et al. foreslått en kombinert anvendelse av et ikke-ionisk overflateaktivt middel, som dispergeringsmiddel, et organisk oppløsningsmiddel,. som er inert ved polymeriseringsreaksjonen, og et alkalisk reaksjonsmedium. Den sistnevnte, bestanddel oppnås ved tilsetning av alkalimetall- eller jordalkalimetallsalter, f.eks. hydroksyder, karbonater, acetater, fosfater og alkohol-ater av disse metaller. Anvendelse av et belegg av en polar organisk forbindelse, farved: off og/eller pigment på de indre vegger av reaktoren ble foreslått i U.S.-patentskrift nr. 3.669.946 til Koyanagi et al. Tilsetning av oksyder eller hydroksyder av et alkalimetall for å holde pH-verdien over 8,0 er beskrevet i japansk patentskrift nr. 70/37-988 og belgisk patent-, skrift nr. 78O.418. A number of methods have been proposed as attempts to achieve a suspension polymerization of VCM which will give a reduced amount of polymer deposits on the inner walls of the reactor. A general method has been the use of various additives. For example, in U.S. Patent No. 3,488,328 to Koyanagi et al., there is proposed a combined use of a nonionic surfactant as a dispersant, an organic solvent, which is inert to the polymerization reaction, and an alkaline reaction medium. The latter component is obtained by the addition of alkali metal or alkaline earth metal salts, e.g. hydroxides, carbonates, acetates, phosphates and alcoholates of these metals. Application of a coating of a polar organic compound, colored: off and/or pigment on the inner walls of the reactor was proposed in U.S. Patent No. 3,669,946 to Koyanagi et al. Addition of oxides or hydroxides of an alkali metal to keep the pH above 8.0 is described in Japanese Patent No. 70/ 37-988 and Belgian Patent Document No. 780.418.
Fremgangsmåten i henhold til foreliggende oppfinnelse gir en uventet reduksjon i dannelsen av polymeravsetninger på grunn av anvendelsen av et ammonium- eller alkalimetallborat. The method according to the present invention provides an unexpected reduction in the formation of polymer deposits due to the use of an ammonium or alkali metal borate.
De ammonium- og jordalkalimetallborater som er ment å skulle innbefattes av omfanget av uttrykket "borat" når det be-nyttes her, er: ammoniumborat, NH^HB^O^'3H20; vannfritt boraks, Na2B^0^; boraks-pentahydrat, Na2B^0^•5^0; natriumborat-deka-hydrat, Na2B^0y•lOH^O;0g kaliumtetraborat, K2B^0y-8H20. Boratet kan enten settes til polymerisasjonsmediet eller det kan utvikles in situ ved tilsetning av ekvimolære méngder av borsyre og et ammonium- eller alkalimetallhydroksyd eller -bikarbonat. Nat-riumboratene er de foretrukne borater. The ammonium and alkaline earth metal borates intended to be included within the scope of the term "borate" as used herein are: ammonium borate, NH^HB^O^'3H 2 O; anhydrous borax, Na2B^0^; borax pentahydrate, Na2B^0^•5^0; sodium borate deca-hydrate, Na2B^0y•lOH^O;0g potassium tetraborate, K2B^0y-8H20. The borate can either be added to the polymerization medium or it can be developed in situ by adding equimolar amounts of boric acid and an ammonium or alkali metal hydroxide or bicarbonate. The sodium borates are the preferred borates.
På tross av anvendelse av visse borater, f.eks. boraks, som buffer ved fremstilling av forskjellige andre polymerer, se Encycl. Polymer Sei. Technol., 2:569-570 (I964), 71 Chem. Abstracts 22458y (italiensk patentskrift nr. 809.717) og fransk patentskrift nr. 2.163.967, var det ikke kjent at denne spesi-elle substanstype ville gi en ren reaktor ved benyttelse ved suspensjonspolymerisering av PVC. Den mengde med borat som blir anvendt i polymeriseringsmediet i henhold til foreliggende oppfinnelse, gir en pH-verdi på mellom ca. 7>5og 10 under hele reaksjonsforløpet, fortrinnsvis mellom ca. 8,0 og 9,0, og hindrer i vesentlig grad dannelse av polymeravsetninger på de indre over-flater av reaksjonskaret. Despite the use of certain borates, e.g. borax, as a buffer in the manufacture of various other polymers, see Encycl. Polymer Sei. Technol., 2:569-570 (1964), 71 Chem. Abstracts 22458y (Italian patent document no. 809,717) and French patent document no. 2,163,967, it was not known that this special type of substance would provide a clean reactor when used in the suspension polymerization of PVC. The amount of borate that is used in the polymerization medium according to the present invention gives a pH value of between approx. 7>5 and 10 during the entire course of the reaction, preferably between approx. 8.0 and 9.0, and substantially prevents the formation of polymer deposits on the inner surfaces of the reaction vessel.
Suspensjonspolymerisering av PVC er velkjent i industrien. Suspension polymerization of PVC is well known in the industry.
Noen senere eksempler på. slike, fremgangsmåter er beskrevet i U.S.-patentskrifter nr. 3-488.328 til Koyanagi et al., nr. 3-5H-822 til Kraft et al. og nr. 3.669.946 til Koyanagi et al. Some later examples of. such methods are described in U.S. Patent Nos. 3-488,328 to Koyanagi et al., No. 3-5H-822 to Kraft et al. and No. 3,669,946 to Koyanagi et al.
I bunn og grunn omfatter en slik fremgangsmåte-type som den i henhold tii■foreliggende oppfinnelse, polymerisering av et vandig suspensjonspolymeriseringsmedium med en tilsetning av vinylkloridmonomer på fra ca. 10 til 50 vekt-$, idet nevnte vinylkloridmonomer eventuelt inneholder .0 - 50$ av velkjente monomerer som er kopolymeriserbare med nevnte vinylklorid, såsom . oppført i U.S.-patentskrift nr. 3.488.328, fra ca. 0,02 til 2$ med suspenderingsmiddel, eventuelt fra omkring 0,001 til 5$ med kjedeoverføringsmiddel, fra ca. 0,01 til 0,5 vekt-$ med borat som et buffer-middel, fra ca. 0,01 til 0,3$ med initiator og Basically, such a type of method as the one according to the present invention comprises polymerization of an aqueous suspension polymerization medium with an addition of vinyl chloride monomer of from approx. 10 to 50% by weight, said vinyl chloride monomer possibly containing .0 - 50% of well-known monomers which are copolymerizable with said vinyl chloride, such as . listed in U.S. Patent No. 3,488,328, from approx. 0.02 to 2$ of suspending agent, optionally from about 0.001 to 5$ of chain transfer agent, from about 0.01 to 0.5 wt-$ with borate as a buffering agent, from approx. 0.01 to 0.3$ with initiator and
resten utgjøres av vann, idet de angitte prosenter er basert på den totale vekt av suspensjonen. Suspensjonspolymeriseringen blir fortrinnsvL s utført ved en temperatur på mellom 40 og 75°C the rest is made up of water, the indicated percentages being based on the total weight of the suspension. The suspension polymerization is preferably carried out at a temperature of between 40 and 75°C
Anvendelsen av ovennevnte borater er vesentlig for at foreliggende oppfinnelse skal gi heldig utfall. De må blandes inn i polymeriseringsmediet, enten ved tilsetning av boratet eller ved utvikling av boratet in situ, og i. en mengde som vil gi en pH-verdi på mellom 7,5 og 10 gjennom hele omsetningen, fortrinnsvis mellom ca. 8,0 og 9>0. Mengden av borat i mediet vil vanligvis variere mellom ca. 0,01 og ca.0,5$, fortrinnsvis mellom ca. 0,2 og ca. 0,3$, av den vandige suspensjon som inne- The use of the above-mentioned borates is essential for the present invention to produce a successful outcome. They must be mixed into the polymerization medium, either by adding the borate or by developing the borate in situ, and i. in an amount that will give a pH value of between 7.5 and 10 throughout the reaction, preferably between approx. 8.0 and 9>0. The amount of borate in the medium will usually vary between approx. 0.01 and approx.0.5$, preferably between approx. 0.2 and approx. 0.3$, of the aqueous suspension containing
holder vinylkloridmonomeren. Dersom bdratet ikke blir benyttet, vil pH-verdien falle fra ca. 7 til ca- 4 etter som polymeriseringen skrider fr»em, og det vil foregå tilsmussing av veggene. De ovenfor beskrevne borater gir en uventet øket grad av reaktor-renhet sammenlignet med anvendelse av andre buffere eller alkaliske substanser som frembringer et lignende pH-område i den vandige suspensjon. Anvendelse av disse borater påvirker ikke varmestabiliteten, den relative viskositet eller partikkelstørr-elsen til det resulterende produkt. holding the vinyl chloride monomer. If the bedrate is not used, the pH value will fall from approx. 7 to approx. 4 as the polymerization progresses, and soiling of the walls will occur. The borates described above provide an unexpectedly increased degree of reactor purity compared to the use of other buffers or alkaline substances which produce a similar pH range in the aqueous suspension. Use of these borates does not affect the heat stability, relative viscosity or particle size of the resulting product.
De suspenderingsmidler som kan anvendes ved foreliggende fremgangsmåte, er de syntetiske eller naturlige polymerer som har beskyttende kolloidale egenskaper, så som delvis forsåpet polyvinylacetat, celluloseeter og gelatin. Metylcelluloseeter-derivater som er kommersielt tilgjengelige under handelsbetegn-elsen "Methocel", fra Dow Chemical Company, er foretrukket. The suspending agents which can be used in the present method are the synthetic or natural polymers which have protective colloidal properties, such as partially saponified polyvinyl acetate, cellulose ether and gelatin. Methyl cellulose ether derivatives commercially available under the trade name "Methocel", from the Dow Chemical Company, are preferred.
Initiatorer som er egnet for anvendelse ved denne fremgangsmåte, er også velkjent for fagfolk i industrien. Foretrukne forbindelser er 2,2'-azobisisobutyronitril, a,a'-azobis(a,^ -di-metylvaleronitril), lauroylperoksyd, benzoylperoksyd, diisoprop-ylperoksydikarbonat (IPP), t-butyl-peroksypivalat (TBP) og a,a'-azobis(a,^ -dimetyl-^ -metoksyvaleronitril). Når det blir anvendt katalysatorer med en halveringstid på 10 timer ved temperaturer under omkring 60°C, så som IPP og TBP, enten alene eller sammen med konvensjonelle fri-radikal-initiatorer med et vékt-forhold på 1:3 til 1:6, oppnås ytterligere reaktor-renhet ved å benytte dem når de er tilstede i et oppløsningsmiddel som omfatter et lineært eller forgrenet C^-C-^-mettet hydrokarbon, f. eks. heksan. Selvom det er blitt foreslått å anvende en rekke opp-løsningsmidler som et middel for. å benytte slike initiatorer, Initiators suitable for use in this process are also well known to those skilled in the art. Preferred compounds are 2,2'-azobisisobutyronitrile, a,a'-azobis(a,^-dimethylvaleronitrile), lauroyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate (IPP), t-butyl peroxypivalate (TBP) and a,a' -azobis(α,^-dimethyl-^-methoxyvaleronitrile). When using catalysts with a half-life of 10 hours at temperatures below about 60°C, such as IPP and TBP, either alone or together with conventional free-radical initiators with a weight ratio of 1:3 to 1:6, further reactor purity is achieved by using them when they are present in a solvent comprising a linear or branched C₁-C₂-saturated hydrocarbon, e.g. hexane. Although it has been proposed to use a number of solvents as a means of. to use such initiators,
se U.S. Reissue patent nr. 25.763 og PPG Technical Service Bulletin nr. 350 (4. januar I963), så er det hittil ikke blitt realisert at anvendelse av de CppC-^-mett ede eller forgrenede hydrokarboner, fortrinnsvis heksan eller heptan, ytterligere forbedrer reaktor-renheten ved suspensjonspolymerisering av PVC. Mengden av CcpC-^-hydrokarbon-oppløsningsmiddel som anvendes, vil ligge i området fra omkring 0,1 til ca. 0,4 vekt-%, basert på vekten av vinylklorid-monomerer, fortrinnsvis fra ca. 0,2 til ca. 0,3 vekt-%. see U.S. Reissue Patent No. 25,763 and PPG Technical Service Bulletin No. 350 (January 4, 1963), it has not yet been realized that the use of the CppC-^-saturated or branched hydrocarbons, preferably hexane or heptane, further improves reactor- the purity of suspension polymerization of PVC. The amount of CcpC-^-hydrocarbon solvent used will range from about 0.1 to about 0.4% by weight, based on the weight of vinyl chloride monomers, preferably from approx. 0.2 to approx. 0.3% by weight.
Det foretrekkes å tilsette initiator-oppløsningsmiddel-blandingen til reaktor-mediet bare etter at reaktor-mediet har nådd den ønskede reaksjonstemperatur og etter at agiteringen er begynt. Dette resulterer i forøket reaktor-renhet når disse initiatorer blir anvendt. It is preferred to add the initiator-solvent mixture to the reactor medium only after the reactor medium has reached the desired reaction temperature and after agitation has begun. This results in increased reactor purity when these initiators are used.
De eventuelle kjedeoverføringsmidler innbefatter halogenerte alifatiske hydrokarboner inneholdende fra 1 til 20 karbon-at omer, fortrinnsvis 1-5 karbonatomer, og fra ca. 1 til 30 halogenatomer. De foretrukne halogenatomer er klor og brom. Eksempler på spesielt ønskelige kjedeoverføringsmidler av halogenerte hydrokarboner ved foreliggende oppfinnelse, er karbontetraklorid, kloroform, bromoform, etyltriklorid, perkloretylen, 1,2-diklor-etylen, n-butylbromid, 2-brom-propan, tetrabrometan, 1,2-dibrom-tetrakloretan, trifluor-l-kloretan, tribromklormetan, tetrabrometan, dibromdiklormetan, bromtriklormetan og lignende..Andre The optional chain transfer agents include halogenated aliphatic hydrocarbons containing from 1 to 20 carbon atoms, preferably 1-5 carbon atoms, and from about 1 to 30 halogen atoms. The preferred halogen atoms are chlorine and bromine. Examples of particularly desirable chain transfer agents of halogenated hydrocarbons in the present invention are carbon tetrachloride, chloroform, bromoform, ethyl trichloride, perchlorethylene, 1,2-dichloroethylene, n-butyl bromide, 2-bromo-propane, tetrabromoethane, 1,2-dibromo-tetrachloroethane , trifluoro-l-chloroethane, tribromochloromethane, tetrabromomethane, dibromodichloromethane, bromotrichloromethane and the like..Other
kjedeoverføringsmidler som kan anvendes innbefatter de velkjente chain transfer agents which may be used include those well known
alkylmerkaptan-kjedeoverføringsmidler, f.eks.' n-decyl-merkaptan, t-dodeeyl-merkaptan og lignende. alkyl mercaptan chain transfer agents, e.g.' n-decyl mercaptan, t-dodeeyl mercaptan and the like.
Den vandige suspensjon som skal omsettes, omfatter kata-lysatoren, vinylkloridmonomertilsetningen, boratet, bufferen, suspenderingsmidlet og, om ønskes, kjedeoverføringsmidlet, og omsetningen blir utført i et lukket reaksjonskar eller polyméri-sator under autogent trykk. Karet er forsynt med en agitator, ledeplater, temperaturreguleringsanordninger og har vanligvis kappe, slik at temperaturen kan reguleres bedre. Reaksjonskaret må ha tilstrekkelig overflateareal for kjøling for effektivt å fjerne polymerisasjonsvarmen og dermed gjøre det mulig for opera-tøren å holde temperaturen og følgelig trykket under nøyaktig kontroll. Agitering av blandingen kan utføres med forskjellige midler og kan variere betraktelig. Den må være tilstrekkelig kraftig til å dispergere den flytende vinylkloridmonomer-tilsetning i form av små dråper gjennom hele det vandige medium. The aqueous suspension to be reacted comprises the catalyst, the vinyl chloride monomer addition, the borate, the buffer, the suspending agent and, if desired, the chain transfer agent, and the reaction is carried out in a closed reaction vessel or polymerizer under autogenous pressure. The vessel is equipped with an agitator, guide plates, temperature control devices and usually has a jacket, so that the temperature can be better regulated. The reaction vessel must have sufficient surface area for cooling to effectively remove the heat of polymerization and thus enable the operator to keep the temperature and consequently the pressure under precise control. Agitation of the mixture can be carried out by different means and can vary considerably. It must be sufficiently powerful to disperse the liquid vinyl chloride monomer additive in the form of small droplets throughout the aqueous medium.
Omsetningen blir fortsatt inntil det blir iakttatt et tydelig trykkfall (d.v.s. omkring 70-95$ omdannelse), og ved dette punkt kan satsen overføres til et strippe-apparat for å fjerne uomsatt monomer. Satsene blir så ferdigbehandlet eller tørket for å frembringe en granulær polymer ved anvendelse av metoder som er velkjent for fagfolk i industrien. De etterfølg-ende eksempler vil ytterligere belyse oppfinnelsen. The reaction is continued until a distinct pressure drop is observed (ie about 70-95$ conversion), at which point the batch can be transferred to a stripping apparatus to remove unreacted monomer. The batches are then finished or dried to produce a granular polymer using methods well known to those skilled in the art. The following examples will further illustrate the invention.
EKSEMPEL 1EXAMPLE 1
En rustfri autoklav med en kapasitet på 7»57liter og utstyrt med en rører av skovl-type, ble ved romtemperatur til- satt 4*500 g destillert, avionisert varln, 2,1 g metylcellulose, 5.0 g boraks (Na2B^0y*10 H20) og 2,1 g azobis(isobutyronitril). pH-verdien i denne blanding var 8,5- Autoklaven ble lukket og evakuert med en vakuum-pumpe. Så ble det satt 3*000 g vinylklorid-monomerer til reaktoren. Reaksjonsblandingen ble oppvarmet til 70°C under god agitering (400 o.p.m.). Damp-trykket i reaksjonsblandingen (opprinnelig ca. 11,55 kg/cm 2 ved 70 oC) begynte å falle etter 4 timer med omsetning. Da trykket var 6,30 kg/cm , ble reaksjonsblandingen avkjølt og gjenværende vinylklorid-monomerer ble gjenvunnet. Det ble erholdt omkring 90$ omdannelse. pH-verdien i reaksjonsoppslemningen var omkring 8,0, og reaktoren var svært ren, som vist ved vesentlig ingen avsetning av polymer på vegger, ledeplater og agitator i reaktoren. A stainless autoclave with a capacity of 7.57 liters and equipped with a paddle-type stirrer was added at room temperature to 4*500 g of distilled, deionized varln, 2.1 g of methyl cellulose, 5.0 g of borax (Na2B^0y*10 H 2 O) and 2.1 g of azobis(isobutyronitrile). The pH value in this mixture was 8.5. The autoclave was closed and evacuated with a vacuum pump. Then 3*000 g of vinyl chloride monomers were added to the reactor. The reaction mixture was heated to 70°C with good agitation (400 rpm). The vapor pressure in the reaction mixture (originally approx. 11.55 kg/cm 2 at 70 oC) began to drop after 4 hours of reaction. When the pressure was 6.30 kg/cm 2 , the reaction mixture was cooled and residual vinyl chloride monomers were recovered. About 90$ conversion was obtained. The pH value in the reaction slurry was around 8.0, and the reactor was very clean, as shown by substantially no deposition of polymer on the walls, guide plates and agitator in the reactor.
EKSEMPEL 2EXAMPLE 2
Den samme polymerisering som beskrevet i eksempel 1 ble gjentatt ytterligere tre ganger ved anvendelse av samme reaktor uten rensing med oppløsningsmiddel. Denne reaktor var fortsatt svært ren og kunne uten tvil anvendes til flere polymeriseringer før det var nødvendig med rensing med oppløsningsmiddel. The same polymerization as described in Example 1 was repeated a further three times using the same reactor without solvent cleaning. This reactor was still very clean and could no doubt be used for several polymerizations before solvent cleaning was necessary.
EKSEMPLER' 3- 8EXAMPLES' 3- 8
Til den samme reaktor som ble anvendt i eksemplene 1 og 2, ble det satt.4*500 g destillert, avionisert vann, 2,1 g metylcellulose og 5,0 g boraks. pH-verdien i oppløsningen var 8,5« Blandingen ble oppvarmet t±l! 4.^ >°C og så ble det innført 2.1 g azobis(a,^-dimetylvaleronitril) i reaktoren. Reaktoren To the same reactor that was used in examples 1 and 2, 4*500 g of distilled, deionized water, 2.1 g of methyl cellulose and 5.0 g of borax were added. The pH value of the solution was 8.5" The mixture was heated t±l! 4.^ >°C and then 2.1 g of azobis(a,^-dimethylvaleronitrile) were introduced into the reactor. The reactor
ble lukket og evakuert og det ble innført 3-000 g vinylklorid-monomerer i reaktoren. Blandingen ble oppvarmet til 55°0 og ble holdt ved. denne temperatur inntil det ble iakttatt et trykk-fall på ca. 13,6 kg. Mengden av avsetning på den indre overflate av veggene var ubetydelig. Reaktoren ble anvendt til ytterligere fem fortløpende utførelser uten rensing med oppløs-ningsmiddel. Reaktoren var fortsatt ren nok til flere utførel-ser etter at den sjette gjentatte utførelse var avsluttet. was closed and evacuated and 3000 g of vinyl chloride monomers were introduced into the reactor. The mixture was heated to 55°C and maintained. this temperature until a pressure drop of approx. 13.6 kg. The amount of deposition on the inner surface of the walls was negligible. The reactor was used for a further five consecutive runs without solvent cleaning. The reactor was still clean enough for several runs after the sixth repeat run was finished.
EKSEMPLER q- 11EXAMPLES q- 11
Den generelle fremgangsmåte som ble anvendt i eksemplene 1 og 2, ble gjentatt med fravær av boraks i polymerisasjonsoppskriften. De indre vegger av reaktoren var fullstendig belagt med polymer endog etter tredje sats, og det ble iakttatt en viss avskalling av polymer fra de indre vegger av reaktoren da den The general procedure used in Examples 1 and 2 was repeated with the absence of borax in the polymerization recipe. The inner walls of the reactor were completely coated with polymer even after the third batch, and some peeling of polymer from the inner walls of the reactor was observed when the
fjerde utførelse var fullført.fourth execution was complete.
EKSEMPLER 12- 14-EXAMPLES 12- 14-
Den generelle fremgangsmåte angitt i eksemplene 3_8 ble gjentatt med fravær av boraks i polymerisasjonsoppskriften. Innsiden av reaktoren fremviste igjen et høyt nivå med vegg-tilgroing. The general procedure indicated in Examples 3-8 was repeated with the absence of borax in the polymerization recipe. The inside of the reactor again showed a high level of wall fouling.
EKSEMPEL 15EXAMPLE 15
En blanding av 4-500 g destillert, avionisert vann, 2,1 g metylcellulose og 10 g natrium-tripolyfosfat ble satt til en autoklav av rustfritt stål på 7,57 liter. Til denne blanding ble det ved 30°C satt 4 g diisopropylperoksykarbonat (IPP). pH-verdien i blandingen var 8,4- Autoklaven ble lukket og ble evakuert med en vakuum-pumpe. Så ble det satt 3-000 g vinylklorid-monomerer til reaktoren. Polymeriseringen ble fortsatt ved 50°C inntil det ble et trykkfall på 15,9 kg- Reaksjonsblandingen ble avkjølt og de gjenværende vinylklorid-monomerer . ble gjenvunnet.. Det ble oppnådd en omdannelse på ca. 90%- pH-verdien i reaksjonsoppslemningen var 8,0, og reaktoren fremviste et tynt belegg av polymer-opp.bygning på sin indre overflate. Dette eksempel viser at selv om natrium-tripolyfosfat opprettholder pH-verdien'i området 8-9, så hindrer det ikke tilgroing på veggene. A mixture of 4-500 g of distilled, deionized water, 2.1 g of methylcellulose and 10 g of sodium tripolyphosphate was added to a 7.57 liter stainless steel autoclave. 4 g of diisopropyl peroxycarbonate (IPP) were added to this mixture at 30°C. The pH value in the mixture was 8.4. The autoclave was closed and evacuated with a vacuum pump. Then 3000 g of vinyl chloride monomers were added to the reactor. The polymerization was continued at 50°C until there was a pressure drop of 15.9 kg. The reaction mixture was cooled and the remaining vinyl chloride monomers. was recovered.. A conversion of approx. The 90% pH value of the reaction slurry was 8.0, and the reactor exhibited a thin coating of polymer build-up on its inner surface. This example shows that although sodium tripolyphosphate maintains the pH value in the range 8-9, it does not prevent growth on the walls.
EKSEMPEL 16EXAMPLE 16
Til den samme reaktor som ble anvendt i eksempel 15, ble det satt samme mengde bestanddeler som beskrevet i eksempel 15, og polymeriseringen ble gjentatt. Reaktor-overflaten hadde en mye tykkere oppbygning av polymeravsetning. To the same reactor as used in Example 15, the same amount of ingredients as described in Example 15 was added, and the polymerization was repeated. The reactor surface had a much thicker build-up of polymer deposits.
EKSEMPEL 17EXAMPLE 17
En oppløsning av 2,1 g metylcellulose og 5 g natriumborat i 4-500 g destillert, avionisert vann, ble anbragt i en reaktor av rustfritt stål på 7,57 liter som var forsynt med en rører av skovl-type. Blandingen ble oppvarmet til 40°C, og reaktoren ble evakuert. Vinylklorid-monomer (3-000 g) ble innført og blandingen ble oppvarmet til 50°C under agitering. En initiator-oppløsning (10 g av 25 vektprosents IPP i heksan) ble innført i reaktoren for å gi en tilsetning på ,0,25$ med heksan, basert på vekten av VCM, og polymeriseringen ble fortsatt inntil det ble iakttatt et trykk-fall på 13,6 kg. Den indre overflate av reaktoren var svært ren, og det var nesten ikke noen polymeravsetning. A solution of 2.1 g of methyl cellulose and 5 g of sodium borate in 4-500 g of distilled, deionized water was placed in a 7.57 liter stainless steel reactor fitted with a paddle type stirrer. The mixture was heated to 40°C and the reactor was evacuated. Vinyl chloride monomer (3-000 g) was introduced and the mixture was heated to 50°C with agitation. An initiator solution (10 g of 25% by weight IPP in hexane) was introduced into the reactor to give a 0.25% addition of hexane, based on the weight of VCM, and the polymerization was continued until a pressure drop was observed of 13.6 kg. The inner surface of the reactor was very clean and there was almost no polymer deposition.
EKSEMPEL l8EXAMPLE 18
Den i eksempel 17 anvendte reaktor ble, uten rensing med oppløsningsmiddel, anvendt til ytterligere 4 fortløpende polymeriseringer av vinylklorid, ved å følge fremgangsmåten ovenfor. Reaktoren var fortsatt ren nok til flere utførelser. The reactor used in example 17 was, without cleaning with solvent, used for a further 4 consecutive polymerizations of vinyl chloride, by following the procedure above. The reactor was still clean enough for several runs.
EKSEMPEL 19EXAMPLE 19
Fast IPP ble anvendt som initiator, i fravær av heksan, ved den samme fremgangsmåte som angitt i eksemplene 17 og 18. De indre vegger av reaktoren fremviste betydelige mengder med polymeravsetning etter bare to utførelser. Solid IPP was used as initiator, in the absence of hexane, by the same procedure as in Examples 17 and 18. The inner walls of the reactor showed significant amounts of polymer deposition after only two runs.
Claims (15)
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BE (1) | BE828699A (en) |
BR (1) | BR7502353A (en) |
CA (1) | CA1042143A (en) |
DE (1) | DE2518814A1 (en) |
FR (1) | FR2269546A1 (en) |
GB (1) | GB1498846A (en) |
IL (1) | IL46787A (en) |
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DE2803344C3 (en) * | 1978-01-26 | 1981-09-24 | Sartorius GmbH, 3400 Göttingen | Device for mass transfer between fluids with the interposition of a membrane |
JPS55137108A (en) * | 1979-04-13 | 1980-10-25 | Nissan Chem Ind Ltd | Production of vinyl chloride resin |
DE3505238A1 (en) * | 1985-02-15 | 1986-08-21 | Hoechst Ag, 6230 Frankfurt | Process for the preparation of dry vinyl chloride suspension polymers |
-
1975
- 1975-03-10 IL IL46787A patent/IL46787A/en unknown
- 1975-03-20 NL NL7503330A patent/NL7503330A/en not_active Application Discontinuation
- 1975-03-24 GB GB12095/75A patent/GB1498846A/en not_active Expired
- 1975-04-04 JP JP50041144A patent/JPS50141685A/ja active Pending
- 1975-04-09 FR FR7511030A patent/FR2269546A1/fr not_active Withdrawn
- 1975-04-10 CA CA224,336A patent/CA1042143A/en not_active Expired
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NL7503330A (en) | 1975-11-04 |
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