NO152010B - PROCEDURE FOR THE PREPARATION OF VINYL CHLORIDE POLYMERIZATES - Google Patents
PROCEDURE FOR THE PREPARATION OF VINYL CHLORIDE POLYMERIZATES Download PDFInfo
- Publication number
- NO152010B NO152010B NO780170A NO780170A NO152010B NO 152010 B NO152010 B NO 152010B NO 780170 A NO780170 A NO 780170A NO 780170 A NO780170 A NO 780170A NO 152010 B NO152010 B NO 152010B
- Authority
- NO
- Norway
- Prior art keywords
- vinyl chloride
- mol
- polyvinyl acetate
- partially hydrolyzed
- degree
- Prior art date
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 12
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 230000007062 hydrolysis Effects 0.000 claims description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 239000011118 polyvinyl acetate Substances 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000003381 stabilizer Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 4
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 claims 2
- 229920000642 polymer Polymers 0.000 description 15
- 239000003995 emulsifying agent Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 206010039509 Scab Diseases 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- -1 alkyl phosphates Chemical class 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000003568 Sodium, potassium and calcium salts of fatty acids Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- VARWGDYJBNFXQU-UHFFFAOYSA-N carboxyoxy hexadecyl carbonate Chemical compound CCCCCCCCCCCCCCCCOC(=O)OOC(O)=O VARWGDYJBNFXQU-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- 235000013875 sodium salts of fatty acid Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Foreliggende oppfinnelse vedrører forbedringer ved polymerisasjon eller kopolymerisasjon av vinylklorid i vandig suspensjon . The present invention relates to improvements in the polymerization or copolymerization of vinyl chloride in aqueous suspension.
Fremgangsmåter for polymerisasjon av etylenisk umettede for-bindelser i vandige suspensjoner er kjente. Suspensjons-midler og eventuelle emulgeringsmidler sammen med initiatorer av fri-radikaltypen benyttes ved fremgangsmåtene. De erholdte produkter foreligger i form av partikler. Virkningen av sus-pens jonsstabilisatoren er å holde den polymeriserte monomer Methods for the polymerization of ethylenically unsaturated compounds in aqueous suspensions are known. Suspension agents and any emulsifiers together with initiators of the free radical type are used in the methods. The products obtained are in the form of particles. The effect of the suspension ion stabilizer is to hold the polymerized monomer
i suspensjon og forhindre eller redusere tilbøyeligheter til agglomerering. Virkningen av emulgeringsmidlet er å in suspension and prevent or reduce tendencies to agglomeration. The effect of the emulsifier is to
senke overflatespenningen mellom vannet og monomeren og der-ved redusere dråpestørrelsen til monomerdispersjonen. Emulgeringsmidlet brukes primært når en porøs og lett gelati-ner bar harpiks er ønsket. videre reduseres mengden av fiske-øyne, kompakte polymere korn som ikke har evne til å absorbere- plastif iseringsmidler, i den fremstilte harpiks når et emulgeringsmiddel anvendes. lower the surface tension between the water and the monomer and thereby reduce the droplet size of the monomer dispersion. The emulsifier is primarily used when a porous and light gelatinous resin is desired. furthermore, the amount of fish-eyes, compact polymeric grains that do not have the ability to absorb plasticizers, in the produced resin is reduced when an emulsifier is used.
Generelt anvendes emulgeringsmidler med anion-karakter som lang-kjedede alkylsulfater og sulfonater, metallalkylfos-fater eller ammonium-og natriumsalter av fettsyrer. Ikke-ioniske emulgeringsmidler brukes også hyppig for suspensjonspolymerisasjon. In general, emulsifiers with an anionic character such as long-chain alkyl sulfates and sulfonates, metal alkyl phosphates or ammonium and sodium salts of fatty acids are used. Nonionic emulsifiers are also frequently used for suspension polymerization.
Ved valg av en metode for suspensjonspolymerisasjon av vinylklorid er det viktig å oppnå et vinylkloridpolymerisat som har god evne til å absorbere plastifiseringsmidler og som gir gode gelatineringsegenskaper. Videre er en lav grad av polymer oppbygning viktig for å fullføre polymerisasjonen. Dette er ofte vanskelig å oppnå når emulgeringsmidler anvendes. En videre ulempe ved anvendelse av emulgeringsmidler er at rester av disse blir tilbake i den dannede polymeren. Dette betyr at polymerisatets elektriske egenskaper blir dårlige og at det er en fare for at emulgeringsmiddelet vil komme ut av de ferdige produkter. For å unngå disse bivirkningene må polymerisatet omhyggelig vaskes, hvilket gjør fremgangsmåten dyrere. When choosing a method for suspension polymerization of vinyl chloride, it is important to obtain a vinyl chloride polymer that has a good ability to absorb plasticizers and that provides good gelatinization properties. Furthermore, a low degree of polymer build-up is important to complete the polymerisation. This is often difficult to achieve when emulsifiers are used. A further disadvantage of using emulsifiers is that residues of these remain in the formed polymer. This means that the polymer's electrical properties become poor and that there is a danger that the emulsifier will come out of the finished products. To avoid these side effects, the polymer must be carefully washed, which makes the process more expensive.
Ett formål ved foreliggende oppfinnelse er å finne frem til en metode for suspensjnospolymerisasjon av vinylklorid eller kopolymerisasjon av monomerer som inneholder vinylklorid ved anvendelse av spesielle suspensjonsstabilisa-torer som gir polymerisater med bedre egenskaper uten at det er nødvendig å bruke emulgeringsmidler. One object of the present invention is to find a method for suspension polymerization of vinyl chloride or copolymerization of monomers containing vinyl chloride using special suspension stabilizers which give polymers with better properties without the need to use emulsifiers.
De oppnådde polymerisater har meget gode egenskaper med hensyn til jevn partikkelstørrelsesfordeling, absorpsjons-kapasitet for plastifiseringsmidler og bearbeidelsesegen-skaper. Bilder av skårne snitt av polymerisatet viser en god indre struktur og i det vesentlige å være fri for skall. The polymers obtained have very good properties with regard to uniform particle size distribution, absorption capacity for plasticizers and processing properties. Images of cut sections of the polymer show a good internal structure and essentially being free of shell.
Det prioritetseldre norske utlegningsskrift nr. 147.486 beskriver bruken av en suspensjonsstabilisatorblanding bestående av et polyvinylacetat med en hydrolysegrad mellpm 40-55 mol-% og en vannløselig polyvinylalkohol med en hydrolysegrad mellom 70-90 mol-%. The older priority Norwegian explanatory document no. 147,486 describes the use of a suspension stabilizer mixture consisting of a polyvinyl acetate with a degree of hydrolysis between 40-55 mol-% and a water-soluble polyvinyl alcohol with a degree of hydrolysis between 70-90 mol-%.
I motsetning til nevnte kjente fremgangsmåte vedrører foreliggende oppfinnelse en fremgangsmåte for suspensjonspolymerisasjon av vinylklorid eller vinylklorid med opp til 20 vekt-% kopolymeriserbare etylenisk umettede monomerer, basert på vekten av vinyl kloridet, ved dispergering av monomeren eller monomerblandingen i vann ved bruk av sus-pens jonsstabilisatorblandinger bestående av to delvis hydrolyserte polyvinylacetater og monomeroppløselig fri-radikaldannende initiatorer slik at det anvendes suspensjonsstabilisatorblandinger bestående av: In contrast to the aforementioned known method, the present invention relates to a method for the suspension polymerization of vinyl chloride or vinyl chloride with up to 20% by weight copolymerizable ethylenically unsaturated monomers, based on the weight of the vinyl chloride, by dispersing the monomer or monomer mixture in water using suspension ion stabilizer mixtures consisting of two partially hydrolyzed polyvinyl acetates and monomer-soluble free-radical-forming initiators so that suspension stabilizer mixtures consisting of:
a) et delvis hydrolysert polyvinylacetat med en hydrolysegrad innenfor et området av 30-60 mol% og b) et delvis hydrolysert polyvinylacetat med en hydrolysegrad innenfor et område av 61-80 mol-%, a) a partially hydrolyzed polyvinyl acetate with a degree of hydrolysis within a range of 30-60 mol% and b) a partially hydrolyzed polyvinyl acetate with a degree of hydrolysis within a range of 61-80 mol-%,
hvorved blandingen bestående av whereby the mixture consisting of
a) et delvis hydrolysert "polyvinylacetat med en hydrolysegrad innenfor et område av 40-55 mol-%, og b) et delvis hydrolysert polyvinylacetat med en hydrolysegrad innenfor et området av 70-80 mol-%, unntas, a) a partially hydrolyzed "polyvinyl acetate with a degree of hydrolysis within a range of 40-55 mol-%, and b) a partially hydrolyzed polyvinyl acetate with a degree of hydrolysis within a range of 70-80 mol-%, excepted,
og at det for slike blandinger benyttes et vektforhold mellom a) og b) innenfor blandingsforholdene 10:1-1:1. and that for such mixtures a weight ratio between a) and b) within the mixing ratio of 10:1-1:1 is used.
Mengden av det ovenfor nevnte suspensjonsstabiliserende system bør ligge i området fra 0,01-0,5 vekt-%, fortrinnsvis 0,03-0,2 vekt-% basert på monomeren eller blandingen av monomerer. Vektforholdet av polyvinylacetat med en hydrolysegrad i området 30-40 mol-% og 55-60 mol-% til polyvinylacetat med en hydrolysegrad i området 61-70 mol-% skal være innenfor 1:10-1:1 og fortrinnsvis ligge mellom 1:5- The amount of the above-mentioned suspension stabilizing system should be in the range of 0.01-0.5% by weight, preferably 0.03-0.2% by weight based on the monomer or mixture of monomers. The weight ratio of polyvinyl acetate with a degree of hydrolysis in the range 30-40 mol-% and 55-60 mol-% to polyvinyl acetate with a degree of hydrolysis in the range 61-70 mol-% must be within 1:10-1:1 and preferably lie between 1: 5-
9:1. Spesielt skal nevnes at forholdet 1:5-2:1 er særskilt gunstig for den gode virkning av fremgangsmåten i henhold til oppfinnelsen. 9:1. In particular, it should be mentioned that the ratio 1:5-2:1 is particularly favorable for the good effect of the method according to the invention.
De erholdte polymerisater er porøse og har eksellente egenskaper for bearbeidelse, som god plastifiseringsabsorpsjon og god gelatineringsevne. Polymerisatene har en jevn partikkel-størrelsesfordeling og de inneholder ingen glassaktige partikler. Suspensjonsstabiliseringssystemet gir en meget lav grad av polymer "build-up" eller overhodet ingen. The polymers obtained are porous and have excellent properties for processing, such as good plasticization absorption and good gelatinizing ability. The polymers have a uniform particle size distribution and they contain no glassy particles. The suspension stabilization system provides a very low degree of polymer "build-up" or none at all.
Ved polymerisering under anvendelse av suspensjonsstabiliserende systemet kan kjente metoder brukes. Vektforholdet av monomer til vann bør ligge i området fra 1:1 til 1:2,5 og polymerisasjonen utføres hensiktsmessig ved en temperatur på 20 - 80°C, fortrinnsvis 40 - 70°C ved et trykk som svarer til metningstrykket for vinylkloridet eller monomerblandingen. Kjente monomerløselige fri-radikale som dan-ner initiatorer slik som acylperoksyder, dialkylperoksydi-karbonater, eller blandinger av disse kan anvendes. Som eksempler på egnede komonomerer som brukes i mengder opp til 20 vekt-% basert på vinylkloridet kan nevnes: alkener, vinyl-acetat, vinylidenklorid, akryl- og metakrylsyrer eller deres estere og nitriller, vinylestere og malein- eller fumarsyre. For polymerization using the suspension stabilizing system, known methods can be used. The weight ratio of monomer to water should be in the range from 1:1 to 1:2.5 and the polymerization is suitably carried out at a temperature of 20 - 80°C, preferably 40 - 70°C at a pressure corresponding to the saturation pressure of the vinyl chloride or monomer mixture . Known monomer-soluble free radicals which form initiators such as acyl peroxides, dialkyl peroxydicarbonates, or mixtures thereof can be used. As examples of suitable comonomers used in amounts of up to 20% by weight based on the vinyl chloride can be mentioned: alkenes, vinyl acetate, vinylidene chloride, acrylic and methacrylic acids or their esters and nitriles, vinyl esters and maleic or fumaric acid.
Oppfinnelsen beskrives mer detaljert i de følgende eksempler som imidlertid ikke har til hensikt å begrense denne. I eksemplene gjelder deler og % vektdeler eller vekt-% hvis ikke annet er nevnt. The invention is described in more detail in the following examples, which, however, are not intended to limit this. In the examples, parts and % by weight apply to parts or % by weight unless otherwise stated.
Eksempel I Example I
I en 15 1 stålreaktor utstyrt med en propellrører fylles In a 15 1 steel reactor equipped with a propeller stirrer is filled
130 deler mineralfritt vann 130 parts mineral-free water
0,08 deler polyvinylacetat med en hydrolysegrad på 72 mol-% 0,04 deler av et polyvinylacetat med en hydrolysegrad på 47 0.08 parts polyvinyl acetate with a degree of hydrolysis of 72 mol% 0.04 parts of a polyvinyl acetate with a degree of hydrolysis of 47
mol-% (foreliggende som en 25% oppløsning i metanol) 0,06 deler cetyl-peroksydikarbonat mole % (present as a 25% solution in methanol) 0.06 parts cetyl peroxydicarbonate
Etter evakuering ved 40°C i 15 min. fylles 100 deler vinylklorid i. After evacuation at 40°C for 15 min. 100 parts of vinyl chloride are filled in.
1) gjerne 30 - 55 mol-% og fortrinnsvis 1) preferably 30 - 55 mol% and preferably
2) gjerne 1:5 - 9:1 og fortrinnsvis 1:5 - 2:1 mol-%. 2) preferably 1:5 - 9:1 and preferably 1:5 - 2:1 mol%.
Blandingen ble polymerisert ved 5 5°C. Når trykket var falt til 6 atmosfærer ble polymerisasjonen avbrutt. Det erholdte polymerisatet ble befridd for vann på et filter og vasket med mineralfritt vann. Ingen skorpedannelse ble oppnådd i reaktoren. The mixture was polymerized at 55°C. When the pressure had dropped to 6 atmospheres, the polymerization was interrupted. The resulting polymer was freed from water on a filter and washed with mineral-free water. No crust formation was achieved in the reactor.
Eksempel 2 Example 2
Polymerisasjonen fra eksempel 1 ble gjentatt med den forskjell at forholdet mellom forskjellige polyvinylacetater ble variert som følger: The polymerization from Example 1 was repeated with the difference that the ratio between different polyvinyl acetates was varied as follows:
Eksemplene f) og g) er kombinasjoner av polyvinylacetatene i foreliggende blanding med polyvinylacetat med en høy hydrolysegrad (88 mol-%) som er en vanlig suspensjonsstabilisator ved polymerisasjon av vinylklorid. Eksempel j) viser resultatet ved bruk av polyvinylacetatene med lav eller middels hydrolysegrad henholdsvis som eneste suspensjonsstabilisator. Examples f) and g) are combinations of the polyvinyl acetates in the present mixture with polyvinyl acetate with a high degree of hydrolysis (88 mol %) which is a common suspension stabilizer in the polymerization of vinyl chloride. Example j) shows the result when using the polyvinyl acetates with a low or medium degree of hydrolysis respectively as the only suspension stabilizer.
Som det fremgår av tabellen fremkommer polymerisater erholdt uten bruk av foreliggende oppfinnelse enten i form av skorper eller i form av agglomerater med bred partikkelstørrelsesfor-deling som ikke er brukelige. As can be seen from the table, polymers obtained without the use of the present invention appear either in the form of crusts or in the form of agglomerates with a wide particle size distribution which are not usable.
Polymerisater erholdt ifølge foreliggende oppfinnelse ble ana-lysert med hensyn til bulkdensiteten og partikkelstørrelses-fordelingen ble bestemt ved siktanalyse. Polymers obtained according to the present invention were analyzed with regard to the bulk density and the particle size distribution was determined by sieve analysis.
Resultatene er vist i tabell II. The results are shown in Table II.
Som det fremgår av tabellen oppnås et polymerisat med en snever partikkelstørrelsesfordeling ved polymerisasjon i henhold til foreliggende fremgangsmåte. Videre oppstår ingen problemer med skorpedannelse under polymerisasjonen. As can be seen from the table, a polymer with a narrow particle size distribution is obtained by polymerization according to the present method. Furthermore, no problems with crust formation occur during polymerization.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE7700488A SE431221B (en) | 1977-01-18 | 1977-01-18 | VIEW SUSPENSION POLYMERIZATION OF VINYL CHLORIDE AND EVENT SOMONOMES IN THE PRESENCE OF A SUSPENSION STABILIZER INCLUDING A MIXTURE OF TWO PARTIAL HYDROOLIZED POLYVINYL ACETATE WITH DIFFERENT HYDROLYGRADY |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO780170L NO780170L (en) | 1978-07-19 |
| NO152010B true NO152010B (en) | 1985-04-09 |
| NO152010C NO152010C (en) | 1985-07-17 |
Family
ID=20330202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO780170A NO152010C (en) | 1977-01-18 | 1978-01-17 | PROCEDURE FOR THE PREPARATION OF VINYL CHLORIDE POLYMERIZATES |
Country Status (6)
| Country | Link |
|---|---|
| DE (1) | DE2802063C2 (en) |
| DK (1) | DK154302C (en) |
| FI (1) | FI63766C (en) |
| GB (1) | GB1592012A (en) |
| NO (1) | NO152010C (en) |
| SE (1) | SE431221B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1160355B (en) * | 1978-12-15 | 1987-03-11 | Sigma Italiana Prod Chimici | PROCESS PERFECTED FOR THE PRODUCTION OF POLYVINYL CHLORIDE |
| IN171200B (en) * | 1986-09-05 | 1992-08-15 | Goodrich Co B F | |
| EP0264861A3 (en) * | 1986-10-24 | 1988-11-02 | Air Products And Chemicals, Inc. | Process for producing suspension polyvinyl chloride for powder coating applications |
| DE60205836T2 (en) | 2001-10-05 | 2006-05-18 | Kuraray Co., Ltd., Kurashiki | Dispersion stabilizer for the suspension polymerization of a vinyl compound |
| DE102005041593A1 (en) | 2005-09-01 | 2007-03-08 | Wacker Polymer Systems Gmbh & Co. Kg | Process for the preparation of vinyl chloride-vinyl acetate copolymers in the form of their solid resins |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2812318A (en) * | 1955-10-06 | 1957-11-05 | Goodrich Co B F | Method for granular polymerization of vinyl chloride |
| JPS5121671B2 (en) * | 1972-11-21 | 1976-07-03 | ||
| JPS51115587A (en) * | 1975-03-24 | 1976-10-12 | Kuraray Co Ltd | Method of producing polyvinylchloride resins |
| DE2629880B2 (en) * | 1976-07-02 | 1980-10-16 | Wacker-Chemie Gmbh, 8000 Muenchen | Process for the production of polyvinyl chloride by the suspension process |
-
1977
- 1977-01-18 SE SE7700488A patent/SE431221B/en not_active IP Right Cessation
-
1978
- 1978-01-09 GB GB627/78A patent/GB1592012A/en not_active Expired
- 1978-01-12 FI FI780094A patent/FI63766C/en not_active IP Right Cessation
- 1978-01-17 DK DK023278A patent/DK154302C/en not_active IP Right Cessation
- 1978-01-17 NO NO780170A patent/NO152010C/en unknown
- 1978-01-18 DE DE2802063A patent/DE2802063C2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FI63766C (en) | 1983-08-10 |
| DE2802063A1 (en) | 1978-07-20 |
| DE2802063C2 (en) | 1982-12-23 |
| FI780094A (en) | 1978-07-19 |
| SE7700488L (en) | 1978-07-19 |
| DK154302C (en) | 1989-04-10 |
| DK23278A (en) | 1978-07-19 |
| FI63766B (en) | 1983-04-29 |
| SE431221B (en) | 1984-01-23 |
| DK154302B (en) | 1988-10-31 |
| NO152010C (en) | 1985-07-17 |
| GB1592012A (en) | 1981-07-01 |
| NO780170L (en) | 1978-07-19 |
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