SE425909B - DISPOSE OF DISPOSAL OF VINYL CHLORIDE FROM A WATER SLAY OR LATEX OF VINYL CHLORIDE POLYMES - Google Patents
DISPOSE OF DISPOSAL OF VINYL CHLORIDE FROM A WATER SLAY OR LATEX OF VINYL CHLORIDE POLYMESInfo
- Publication number
- SE425909B SE425909B SE7902777A SE7902777A SE425909B SE 425909 B SE425909 B SE 425909B SE 7902777 A SE7902777 A SE 7902777A SE 7902777 A SE7902777 A SE 7902777A SE 425909 B SE425909 B SE 425909B
- Authority
- SE
- Sweden
- Prior art keywords
- vinyl chloride
- latex
- slurry
- weight
- content
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- 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
- C08F6/001—Removal of residual monomers by physical means
- C08F6/003—Removal of residual monomers by physical means from polymer solutions, suspensions, dispersions or emulsions without recovery of the polymer therefrom
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- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (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)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
15 20 25 30 35 40 7902777-7 Vattenuppslamningar med det mycket låga VCM-innehållet som be- skrives häri, är unika och har icke tidigare krävts vid konven- tionella PVC-processer för framställning av PVC-plast. Den gans- ka nyligen upptäckta, potentiella carcinogeniteten hos vinyl- klorid visar nu behovet av uppslamningar med mycket lågt monomer- innehåll, varur torkad PVC-plast med väsentligt minskat VCM- innehåll ner till den punkt där ingen VCM kan spåras med gaskro- matografi, kan framställas. 15 20 25 30 35 40 7902777-7 Water slurries with the very low VCM content described herein are unique and have not previously been required in conventional PVC processes for the production of PVC plastic. The rather recently discovered potential carcinogenicity of vinyl chloride now shows the need for slurries with a very low monomer content, of which dried PVC plastic with significantly reduced VCM content down to the point where no VCM can be detected by gas chromatography, can be produced.
Fördelen med en uppslamning och latex enligt uppfinningen är, att vid vidare avvattning och torkning på vanligt sätt inom PVC-in- dustrin, avger en dylik uppslamning eller latex markant mindre mängd vinylklorid i arbetslokalerna.The advantage of a slurry and latex according to the invention is that during further dewatering and drying in the usual way in the PVC industry, such a slurry or latex emits significantly less vinyl chloride in the work premises.
Den vattenuppslamning eller latex som behandlas enligt förelig- gande uppfinning framställes genom konventionell suspensions- eller emulsionspolymerisation. Vid suspensionspolymerisation eller pärlpolymerisation suspenderas vinylklorid eller en bland- ning av vinylklorid med minst en sammonomer i vatten med använd- ning av dispergeringsmedel och under omröring. Polymerisationen startas med en friradikalalstrande polymerisationsinitiator så- som lauroylperoxid, bensoylperoxid, diisopropylperoxidikarbonat, tertiärt butylperoxipivalat, azo-bis-isobutyronitril, azo-bis- -2,4-dimetylvaleronitril, kombinationer av dialkylperoxidikarbo- nat och lauroylperoxid, sulfonylperoxider och liknande. Disper- geringsmedel såsom metylcellulosa, hydroximetylcellulosa, hydr- oxietylcellulosa, hydroxipropylmetylcellulosa, hydrolyserat po- lyvinylacetat, gelatin, sampolymerer av metylvinyleter och ma- leinsyraanhydrid och kombinationer av de ovanstående ämnena tillsättes även till reaktionsblandningen.The aqueous slurry or latex treated according to the present invention is prepared by conventional suspension or emulsion polymerization. In suspension polymerization or bead polymerization, vinyl chloride or a mixture of vinyl chloride is suspended with at least one comonomer in water using dispersants and with stirring. The polymerization is started with a free radical generating polymerization initiator such as lauroyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, tertiary butyl peroxy pivalate, azo-bis-isobutyronitrile, azo-bis--2,4-dimethylvaleronitrile peroxide and lauryls. Dispersants such as methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, hydrolyzed polyvinyl acetate, gelatin, copolymers of methylvinyl ether and maleic anhydride and combinations of the above substances are also added to the reaction mixture.
Vid emulsionspolymerisation framställes vinylkloridhomopolymerer och sampolymerer med konventionell emulsionspolymerisationstek- nik. Initiatorer för fria radikaler, såsom väteperoxid, orga- niska peroxider, persulfater och redoxsystem användes. Ytaktiva medel som alkylsulfater, alkansulfonater, alkylarylsulfonater och fettsyratvâlar användes för att emulgera vinylkloridmonome- ren och eventuella sammonomerer. En alternativ dispergeringsme- tod beskrives i den amerikanska patentskriften 2 981 722. 10 15 20 25 30 35 40 7902777-7 När sampolymerer framställes polymeriseras vinylklorid med en sampolymeriserbar monomer till en produkt med upp till 30 vikt-% av sammonomeren. Bland de monomerer som kan sampolymeriseras med vinylklorid är akrylsyra, akrylnitril, n-butylakrylat, di- allylmaleat, dibutylmaleat, dietylfumarat, dimetylitakonat, etylakrylat, eten, isobuten, maleinsyraanhydrid, metakrylsyra, metakrylnitril, metylakrylat, metylvinyleter, 2-etylhexylakrylat, propen, triallylcyanurat, triallylisocyanurat, trimetylolpropan, trimetakrylat, vinylacetat, N-vinylkarbazol, vinylidenklorid, vinylisobutyleter, N-vinylpyrrolidon och blandningar därav.In emulsion polymerization, vinyl chloride homopolymers and copolymers are prepared by conventional emulsion polymerization techniques. Free radical initiators such as hydrogen peroxide, organic peroxides, persulfates and redox systems were used. Surfactants such as alkyl sulfates, alkane sulfonates, alkyl aryl sulfonates and fatty acid soaps were used to emulsify the vinyl chloride monomer and any comonomers. An alternative dispersion method is described in U.S. Patent No. 2,981,722. When copolymers are prepared, vinyl chloride is polymerized with a copolymerizable monomer to a product having up to 30% by weight of the comonomer. Among the monomers which can be copolymerized with vinyl chloride are acrylic acid, acrylonitrile, n-butyl acrylate, dialyl maleate, dibutyl maleate, diethyl fumarate, dimethylitaconate, ethyl acrylate, ethylene, isobutylene, maleic anhydride, methacrylic acid, methacrylonitrile, methacrylonitrile , triallyl isocyanurate, trimethylolpropane, trimethacrylate, vinyl acetate, N-vinylcarbazole, vinylidene chloride, vinyl isobutyl ether, N-vinylpyrrolidone and mixtures thereof.
Ytterligare detaljer om framställningen av vinylkloridhomopoly- merer och sampolymerer med pärlpolymerisation och emulsionspoly- merisation angives i Kirk-Othmer “Encyclopedia of Chemical Tech- nology", Second Edition, vol. 21, sid. 373-379.Further details on the preparation of vinyl chloride homopolymers and copolymers with bead polymerization and emulsion polymerization are given in Kirk-Othmer's "Encyclopedia of Chemical Technology", Second Edition, Vol. 21, pp. 373-379.
Uppfinningen kännetecknas av, att en uppslamning eller latex med 5-50 vikt-% av en vinylkloridpolymer och 1000 - 15 000 ppm vinylklorid upphettas vid en temperatur på 70-125°C, företrädes- vis 85-125°C, vid atmosfärstryck för att avlägsna vinylkloridànga tills vinylkloridinnehållet däri är högst 10 ppm räknat på vik- ten polymer i uppslamningen eller latexen. Den torkade polymeren framställes genom avvattning av slurryn eller latexen och har mycket låg vinylkloridhalt, samt kan vidare bearbetas utan att medföra hälsorisker i arbetslokalerna.The invention is characterized in that a slurry or latex with 5-50% by weight of a vinyl chloride polymer and 1000-15,000 ppm vinyl chloride is heated at a temperature of 70-125 ° C, preferably 85-125 ° C, at atmospheric pressure to remove vinyl chloride vapor until the vinyl chloride content therein is not more than 10 ppm by weight of polymer in the slurry or latex. The dried polymer is produced by dewatering the slurry or latex and has a very low vinyl chloride content, and can be further processed without posing health risks in the work premises.
Behandlingen av vinylkloridpolymerer vid förhöjdatemperaturer för att sänka deras monomerinnehåll står i motsats till fackkun- skapen på området, då denna hävdar att dylik upphettning sönder- delas polymererna.The treatment of vinyl chloride polymers at elevated temperatures to lower their monomer content is in contrast to the expertise in the art, as this claims that such heating decomposes the polymers.
Uppfinningen illustreras ytterligare av de följande exemplen.The invention is further illustrated by the following examples.
Exempel 1 - 11 I vart och ett av exemplen 1-11, tabell I, upphettades en vat- tenuppslamning med ca 30 vikt-% polyvinylklorid och omrördes vid den temperatur och ett tryck under den tid som angives för att den ifrågavarande vinylkloridmonomeren skall avlägsnas. 10 15 20 7902777-7 Plasterna B och C framställdes med användning av en blandning av lauroylperoxid och di-2-etylhexyl-peroxidikarbonat som ini- tiator och metylcellulosa som dispergeringsmedel. Plast D fram- ställdes med samma initiator som användes för plast B, hydroxi- propyl-metylcellulosa som suspensionsmedel och trikloreten som kedjeöverföringsmedel. Plasten E framställdes med samma initia- tor och samma suspensionsmedel som plast D.Examples 1 to 11 In each of Examples 1-11, Table I, a water slurry was heated with about 30% by weight of polyvinyl chloride and stirred at the temperature and pressure for the time indicated to remove the vinyl chloride monomer in question. Plastics B and C were prepared using a mixture of lauroyl peroxide and di-2-ethylhexyl peroxydicarbonate as initiator and methylcellulose as dispersant. Plastic D was prepared with the same initiator used for plastic B, hydroxypropyl methylcellulose as suspending agent and trichlorethylene as chain transfer agent. Plastic E was prepared with the same initiator and the same suspending agent as plastic D.
I tabell I hänför sig alla exemplen med undantag av exempel 6 till en laboratoriebehandling, där uppslamningsproverna som be- handlades var mellan 500 och 1000 gram. Exempel 6 avser en halvstor körning med behandling av ca 115 liter uppslamning.In Table I, all the examples with the exception of Example 6 refer to a laboratory treatment, where the slurry samples treated were between 500 and 1000 grams. Example 6 relates to a half-sized run with treatment of about 115 liters of slurry.
I alla exemplen med undantag av exempel 6 och 11, var uppslam- ningen en kommersiell uppslamning framställd genom konventionell låg-temperatur- och vakuumbehandling för att avlägsna oreagerad vinylkloridmonomer, VCM.In all examples except Examples 6 and 11, the slurry was a commercial slurry prepared by conventional low temperature and vacuum treatment to remove unreacted vinyl chloride monomer, VCM.
I tabell I är VCM-koncentrationerna angivna i ppm räknat på plastens vikt.In Table I, the VCM concentrations are given in ppm based on the weight of the plastic.
Genom.jämförelse av de erhållna resultaten framgår föreliggan- de uppfinnings fördelar. 7902777-7 umflumä wxofl n .Q.z .Q.Z .ñud oo? ßw m PP mr om ow .Eu< mm omvw Q ow mw oß ovf .End mß omwm D m om» com mßw .End mm omvw Q w .Q.Z .End oofi mmßmw U ß .Q-Z .Eufl Oof mvm U w mw om mß» .Eu< mm mmmæ U m oßfi mmm mom .Eu< mß mmmæ O w .Q.z m m~ .End mm mmwfi m m .Q.z of om .EQQ mß mmvf m N mm om mm .Eu< mm mmwfi m P _ mm wmšwx Q m Emm ¶Q%Humnvmm%cOx|EH>m Muæuß .mE%¶ .0QOfi%%Hw%%%v%w u am H m H flflwßmä 10 15 20 7902777-7 Exempel 12 - 15 I alla exemplen 12-15 upphettades och omrördes en vattenuppslam- ning av en sampolymer av vinylklorid och vinylacetat, med vi- nylacetathalten omkring 8-16 vikt-% vid de angivna temperaturer- na och trycken för de angivna tiderna för att avlägsna den ifrå- gavarande vinylmonomeren. Uppslamningen innehöll omkring 30 vikt-% av sampolymeren.A comparison of the results obtained shows the advantages of the present invention. 7902777-7 um fl umä wxo fl n .Q.z .Q.Z .ñud oo? ßw m PP mr om ow .Eu <mm omvw Q ow mw oß ovf .End mß omwm D m om »com mßw .End mm omkw Q w .QZ .End oo fi mmßmw U ß .QZ .Eu fl Oof mvm U w mw om mß ».Eu <mm mmmæ U m oß fi mmm mom .Eu <mß mmmæ O w .Qz mm ~ .End mm mmw fi mm .Qz of om .EQQ mß mmvf m N mm om mm .Eu <mm mmw fi m P _ mm wmšwx Q m Emm ¶Q% Humnvmm% cOx | EH> m Muæuß .mE% ¶ .0QO fi %% Hw %%% v% wu am H m H flfl wßmä 10 15 20 7902777-7 Example 12 - 15 In all examples 12- A water slurry of a copolymer of vinyl chloride and vinyl acetate was heated and stirred, with the vinyl acetate content being about 8-16% by weight at the indicated temperatures and pressures for the indicated times to remove the vinyl monomer in question. The slurry contained about 30% by weight of the copolymer.
Plasten F framställdes med en blandning av lauroylperoxid och di-2-etylhexylperoxidikarbonat som initiator och hydroxipropyl- metylcellulosa som dispergeringsmedel. Plast G framställdes med lauroylperoxid som initiator, gelatin som dispergeringsmedel och trikloreten som kedjeöverföringsmedel.Plastic F was prepared with a mixture of lauroyl peroxide and di-2-ethylhexyl peroxydicarbonate as initiator and hydroxypropylmethylcellulose as dispersant. Plastic G was prepared with lauroyl peroxide as initiator, gelatin as dispersant and trichlorethylene as chain transfer agent.
Exemplen 12-15 var laboratorieförsök där den behandlade mängden uppslamning var mellan 500 och 1000 gram. I alla exemplen be- handlades en kommersiell uppslamning framställd med konventionell lågtemperatur- och vakuumbehandling för att avlägsna vinylklorid.Examples 12-15 were laboratory experiments where the treated amount of slurry was between 500 and 1000 grams. In all the examples, a commercial slurry prepared by conventional low temperature and vacuum treatment was treated to remove vinyl chloride.
I tabell II angives VCM-koncentrationerna som vinylklorid i ppm räknat på plastens vikt. 7902777-7 w w of .EQ4 mß fmm U m~ mfi ær ON .E94 mw rwm U wr ßp mm wm .Euá mn vwm m mr mw mm vw .End mw www m Nr z m n N s P VHECE. uo .RE šu> »mmÉ Hwmawxm Emm .c0fiumHufimUnOx|2U> .mämß >m .ufloxmmfiwflcæmom HH HHQQMB 10 15 20 25 30 35 40 7902777-7 Exempel 16 200 gram av en uppslamning med 35 vikt-% polyvinylklorid och 9000 ppm vinylklorid uppvärmdes och omrördes vid 80°C i 3 tim- mar. Prov efter 1, 2 och 3 timmar torkades över natten vid SOOC.Table II lists the VCM concentrations as vinyl chloride in ppm based on the weight of the plastic. 7902777-7 w w of .EQ4 mß fmm U m ~ m fi ær ON .E94 mw rwm U wr ßp mm wm .Euá mn vwm m mr mw mm vw .End mw www m Nr z m n N s P VHECE. uo .RE šu> »mmÉ Hwmawxm Emm .c0 fi umHu fi mUnOx | 2U> .mämß> m .u fl oxmm fi w fl cæmom HH HHQQMB 10 15 20 25 30 35 40 7902777-7 Example 16 200 grams of a slurry with 35% by weight of vinyl and 9% of polyvinyl. and stirred at 80 ° C for 3 hours. Samples after 1, 2 and 3 hours were dried overnight at SOOC.
Dessa torkade prover innehöll resp. 13 ppm, 7 ppm och mindre än 5 ppm vinylklorid.These dried samples contained resp. 13 ppm, 7 ppm and less than 5 ppm vinyl chloride.
Exempel 17 En vattenuppslamning med 30 vikt-% kommersiell vinylklorid-ho- mopolymer framställdes genom pärlpolymerisation med en bland- ning av lauroylperoxid och di-2-etylhexylperoxidikarbonat som initiator, hydroxipropylmetylcellulosa som dispergeringsmedel och trikloreten som kedjeöverföringsmedel. Uppslamningen inne- höll 1212 ppm vinylklorid räknat på homopolymerens vikt.Example 17 A water slurry with 30% by weight of commercial vinyl chloride homopolymer was prepared by bead polymerization with a mixture of lauroyl peroxide and di-2-ethylhexyl peroxydicarbonate as initiator, hydroxypropyl methylcellulose as dispersant and trichloroethene as chain transfer agent. The slurry contained 1212 ppm vinyl chloride based on the weight of the homopolymer.
Ett prov av uppslamningen uppvärmdes och omrördes vid 85°C i 4 timmar i en enliters rundkolv försedd med luftkylare. Uppslam- ningen filtrerades sedan och torkades över natten i 50°C. Det torkade hartset hade en VCM-halt pâ 8 ppm.A sample of the slurry was heated and stirred at 85 ° C for 4 hours in a one liter round flask equipped with an air cooler. The slurry was then filtered and dried overnight at 50 ° C. The dried resin had a VCM content of 8 ppm.
Exempel 18 Exempel 17 upprepades men med temperaturen 75oC istället för 85oC och med homopolymeren framställd med en kombination av lauroylperoxid och di-2-etylhexylperoxidikarbonat som initia- tor och hydroximetylcellulosa som dispergeringsmedel. Prov ef- ter 1, 2, 3 och 4 timmar hade efter torkning över natten vid 50°C VCM-innehåll på resp. 9 ppm, 7 ppm, ej mätbart och ej mät- bart.Example 18 Example 17 was repeated but with the temperature 75 ° C instead of 85 ° C and with the homopolymer prepared with a combination of lauroyl peroxide and di-2-ethylhexyl peroxydicarbonate as initiator and hydroxymethylcellulose as dispersant. Samples after 1, 2, 3 and 4 hours, after drying overnight at 50 ° C, had VCM content of resp. 9 ppm, 7 ppm, not measurable and not measurable.
När uppslamningen upphettades och omrördes vid 8500, hade pro- ver efter 1 och 2 timmar VCM-halter på resp. 7 och 3 ppm efter torkning vid 50°C under natten.When the slurry was heated and stirred at 8500, samples after 1 and 2 hours had VCM levels of resp. 7 and 3 ppm after drying at 50 ° C overnight.
Exempel 19 Till 2000 gram av en polyvinylkloriddispersion-plastlatex med ett plastinnehâll på omkring 40 vikt-%, som hade en vinylklorid- halt på 12 955 ppm räknat på plastens vikt och framställd en- ligt den amerikanska patentskriften 2 981 722, tillsattes 300 ml av en 1 vikt%-ig magnesiumsulfatlösning i vatten. SatsenExample 19 To 2000 grams of a polyvinyl chloride dispersion-plastic latex having a plastic content of about 40% by weight, having a vinyl chloride content of 12,955 ppm by weight of the plastic and prepared according to U.S. Pat. No. 2,981,722, was added 300 ml of a 1% by weight magnesium sulfate solution in water. The rate
Claims (3)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US48211374A | 1974-06-24 | 1974-06-24 | |
US48211274A | 1974-06-24 | 1974-06-24 | |
US05/482,115 US4015064A (en) | 1974-06-24 | 1974-06-24 | Manufacture of polyvinyl chloride of low vinyl chloride monomer content |
Publications (2)
Publication Number | Publication Date |
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SE7902777L SE7902777L (en) | 1979-03-28 |
SE425909B true SE425909B (en) | 1982-11-22 |
Family
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Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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SE7507163A SE419650B (en) | 1974-06-24 | 1975-06-23 | DISPOSE OF DISPOSAL OF VINYL CHLORIDE FROM A WATER SLAY OR LATEX OF VINYL CHLORIDE POLYMES |
SE7902777A SE425909B (en) | 1974-06-24 | 1979-03-28 | DISPOSE OF DISPOSAL OF VINYL CHLORIDE FROM A WATER SLAY OR LATEX OF VINYL CHLORIDE POLYMES |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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SE7507163A SE419650B (en) | 1974-06-24 | 1975-06-23 | DISPOSE OF DISPOSAL OF VINYL CHLORIDE FROM A WATER SLAY OR LATEX OF VINYL CHLORIDE POLYMES |
Country Status (11)
Country | Link |
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JP (1) | JPS6037125B2 (en) |
AU (1) | AU497851B2 (en) |
BR (1) | BR7503870A (en) |
CA (1) | CA1280532C (en) |
DE (1) | DE2527583A1 (en) |
FR (1) | FR2276324A1 (en) |
IL (1) | IL47420A (en) |
IT (1) | IT1040659B (en) |
NL (1) | NL7507527A (en) |
NO (1) | NO148781C (en) |
SE (2) | SE419650B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US4220754A (en) * | 1976-05-25 | 1980-09-02 | Tenneco Chemicals, Inc. | Process for the purification of polyvinyl chloride with oxidizing agents |
US4228273A (en) * | 1978-09-05 | 1980-10-14 | Tenneco Chemicals, Inc. | Process for the removal of vinyl chloride from aqueous dispersions of vinyl chloride resins |
JPS6234717U (en) * | 1985-08-19 | 1987-02-28 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US2662867A (en) * | 1951-03-29 | 1953-12-15 | Goodrich Co B F | Method of stabilizing aqueous dispersions of haloethylene polymers |
NL99391C (en) * | 1956-10-09 | |||
BE579094A (en) * | 1958-05-30 | |||
BE668137A (en) * | 1965-08-11 | 1966-02-11 | ||
IT989178B (en) * | 1972-07-19 | 1975-05-20 | Solvay | PROCEDURE TO ELIMINATE RESIDUAL VINYL CHLORIDE PRESENT IN POLI MERI |
DE2429777C3 (en) * | 1974-06-21 | 1988-09-08 | Hoechst Ag, 6230 Frankfurt | Process for removing unreacted residual vinyl chloride from aqueous dispersions of vinyl chloride polymers |
-
1975
- 1975-06-03 IL IL47420A patent/IL47420A/en unknown
- 1975-06-19 IT IT50131/75A patent/IT1040659B/en active
- 1975-06-20 BR BR4977/75D patent/BR7503870A/en unknown
- 1975-06-20 DE DE19752527583 patent/DE2527583A1/en active Granted
- 1975-06-23 SE SE7507163A patent/SE419650B/en unknown
- 1975-06-23 CA CA000229921A patent/CA1280532C/en not_active Expired - Lifetime
- 1975-06-23 JP JP50075805A patent/JPS6037125B2/en not_active Expired
- 1975-06-23 FR FR7519560A patent/FR2276324A1/en active Granted
- 1975-06-23 AU AU82346/75A patent/AU497851B2/en not_active Ceased
- 1975-06-24 NL NL7507527A patent/NL7507527A/en not_active Application Discontinuation
- 1975-06-24 NO NO752251A patent/NO148781C/en unknown
-
1979
- 1979-03-28 SE SE7902777A patent/SE425909B/en unknown
Also Published As
Publication number | Publication date |
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AU497851B2 (en) | 1979-01-18 |
DE2527583C2 (en) | 1989-05-24 |
JPS5117288A (en) | 1976-02-12 |
BR7503870A (en) | 1976-07-06 |
AU8234675A (en) | 1977-01-06 |
SE7507163L (en) | 1975-12-29 |
NO148781B (en) | 1983-09-05 |
NL7507527A (en) | 1975-12-30 |
CA1280532C (en) | 1991-02-19 |
FR2276324B1 (en) | 1979-04-13 |
SE419650B (en) | 1981-08-17 |
SE7902777L (en) | 1979-03-28 |
IT1040659B (en) | 1979-12-20 |
NO752251L (en) | 1975-12-30 |
NO148781C (en) | 1983-12-14 |
IL47420A (en) | 1978-07-31 |
DE2527583A1 (en) | 1976-01-15 |
JPS6037125B2 (en) | 1985-08-24 |
IL47420A0 (en) | 1975-08-31 |
FR2276324A1 (en) | 1976-01-23 |
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