NO120009B - - Google Patents
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- Publication number
- NO120009B NO120009B NO156718A NO15671865A NO120009B NO 120009 B NO120009 B NO 120009B NO 156718 A NO156718 A NO 156718A NO 15671865 A NO15671865 A NO 15671865A NO 120009 B NO120009 B NO 120009B
- Authority
- NO
- Norway
- Prior art keywords
- polyethylene terephthalate
- methanol
- terephthalic acid
- weight
- boiling organic
- Prior art date
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- -1 polyethylene terephthalate Polymers 0.000 claims description 14
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 11
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- 238000005809 transesterification reaction Methods 0.000 claims description 6
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011012 grey crystal Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
- G03C1/496—Binder-free compositions, e.g. evaporated
- G03C1/4965—Binder-free compositions, e.g. evaporated evaporated
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
- G03C1/725—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing inorganic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
- G03C1/725—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing inorganic compounds
- G03C1/7253—Lead salts
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
- G03C2001/091—Gold
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
- G03C2001/095—Disulfide or dichalcogenide compound
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
- G03C2001/097—Selenium
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Fremgangsmåte til avbygging av polyetylentereftalat til tereftalsyredimetylester. Process for breaking down polyethylene terephthalate into terephthalic acid dimethyl ester.
Oppfinnelsen angår en fremgangsmåte til avbygging av polyetylentereftalat til tereftalsyredimetylester under trykk og ved temperaturer opp til 210° C i nærvær av metanol samt høytkokende organiske forbindelser og omestreringskatalysatorer. The invention relates to a method for breaking down polyethylene terephthalate to terephthalic acid dimethyl ester under pressure and at temperatures up to 210° C in the presence of methanol as well as high-boiling organic compounds and transesterification catalysts.
Avbygging av polyetylentereftalat fore-tas når misfarget og forurenset avfall i Decomposition of polyethylene terephthalate is carried out when discolored and contaminated waste i
form av tråder, fibre eller bånd- eller også kompakte masser skal anvendes om igjen av økonomiske grunner. Man har foreslått å avbyggge disse avfall ved omsetning med kokende glykol. De derved erholdte teref-talsyrediglykolestere er sterkt forurenset in the form of threads, fibers or ribbons or compact masses must be reused for economic reasons. It has been proposed to break down these wastes by treatment with boiling glycol. The terephthalic acid diglycol esters thus obtained are heavily contaminated
og lar seg erfaringsmessig bare meget vans-kelig rense. Det er videre blitt foreslått å avbygge polyetylentereftalat med konsen-trerte syrer til det dannes tereftalsyre. Denne omstendige fremgangsmåte betyr ikke noe særlig fremskritt fordi tereftal-syren likeledes fåes i forurenset tilstand, og først må forestres hvis man skal an-vende den til en ny polykondensasjon. Etter et annet forslag lykkes avbygging av polyetylentereftalat hvis man oppheter polyesteren i nærvær av katalysatorer som f. eks. metafosforsyre og i nærvær av over-hetet metanoldamp uten anvendelse av trykk til 220—245° C. and, according to experience, is only very difficult to clean. It has also been proposed to break down polyethylene terephthalate with concentrated acids until terephthalic acid is formed. This elaborate procedure does not mean any particular progress because the terephthalic acid is likewise obtained in a contaminated state, and must first be esterified if it is to be used for a new polycondensation. According to another proposal, the decomposition of polyethylene terephthalate is successful if the polyester is heated in the presence of catalysts such as e.g. metaphosphoric acid and in the presence of superheated methanol steam without the application of pressure to 220-245° C.
Oppfinnerne har funnet at avbygging av polyetylentereftalat til tereftalsyredimetylester oppnås med meget godt utbytte og meget rent produkt hvis man oppheter polyesteren i nærvær av metanol samt av høytkokende organiske forbindelser som difenyl, difenyloksyd, difenylmetan, a- og The inventors have found that the breakdown of polyethylene terephthalate to terephthalic acid dimethyl ester is achieved with a very good yield and a very pure product if the polyester is heated in the presence of methanol and of high-boiling organic compounds such as diphenyl, diphenyl oxide, diphenylmethane, a- and
p-metylnaftalin og omestringskatalysa- p-methylnaphthalene and transesterification catalysis
torer under trykk til høyst 210° C. Som omestringskatalysatorer kan det herunder anvendes alle hertil kjente katalysatorer. Særlig virksomme er sink, sinkoksyd, sink-acetat, blyoksyd, blyacetat, magnesium, magnesiumoksyd og jern. Det anvendte trykk kan utgjøre ca. 10 til 19 ato. For avbygging kommer særlig slike polyestere på tale i form av tråder, børster eller fargede og forurensede tekstilprodukter skal anvendes om igjen. Det er overraskende at den ved fremgangsmåten i henhold til oppfinnelsen erholdte dimetylester fås med godt utbytte og stor renhet ennskjønt man går ut fra misfarget avfall. De høytkok-ende organiske forbindelser anvendes i en mengde av 1—10 vektsprosent beregnet på vekten av polyesteren. Den for utførelsen av fremgangsmåten gunstige temperatur utgjør når det samtidig anvendes trykk 140—160° C. Ved disse temperaturer be-virker de nevnte høytkokende forbindelser at polyesteren begynner å svelle, resp. løse seg opp, hvoretter den i nærvær av metanol og omestringskatalysator avbygges til den ønskede tereftalsyredimetylester. tor under pressure to a maximum of 210° C. All known catalysts can be used below as transesterification catalysts. Particularly effective are zinc, zinc oxide, zinc acetate, lead oxide, lead acetate, magnesium, magnesium oxide and iron. The applied pressure can amount to approx. 10 to 19 ato. For decommissioning, such polyesters in particular come into question in the form of threads, brushes or colored and contaminated textile products that must be reused. It is surprising that the dimethyl ester obtained by the method according to the invention is obtained with a good yield and great purity, even though the starting point is discolored waste. The high-boiling organic compounds are used in an amount of 1-10 percent by weight calculated on the weight of the polyester. The temperature favorable for carrying out the method is, when pressure is used at the same time, 140-160° C. At these temperatures, the aforementioned high-boiling compounds cause the polyester to begin to swell, resp. dissolve, after which it is broken down in the presence of methanol and transesterification catalyst to the desired terephthalic acid dimethyl ester.
Ved et sammenligningsforsøk kunne man fastslå at en avbygging av polyesteren under de samme forsøksbetingelser men uten tilsetning av de nevnte høytkokende organiske forbindelser bare foregår ufull-stendig. Det oppnås herved bare en ufull-stendig avbygging spesielt betinget av dannelsen av en blandingsester av tereftalsyre, metanol og etylenglykol. I nærvær av de nevnte høytkokende organiske forbindelser derimot foregår det en fullstendig avbygging av reaksjonsproduktet, hvorved det dannes over 90 pst. av den ønskede dimetylester. De for utførelsen av reaksjonen nødvendige omestringskatalysatorer befin-ner seg i reaksjonsblandingen i fast form og kan lett fjernes ved filtrering. In a comparison test, it could be determined that a breakdown of the polyester under the same test conditions but without the addition of the aforementioned high-boiling organic compounds only takes place incompletely. Hereby only an incomplete decomposition is achieved, particularly due to the formation of a mixed ester of terephthalic acid, methanol and ethylene glycol. In the presence of the aforementioned high-boiling organic compounds, on the other hand, a complete breakdown of the reaction product takes place, whereby more than 90 per cent of the desired dimethyl ester is formed. The transesterification catalysts required for carrying out the reaction are in the reaction mixture in solid form and can be easily removed by filtration.
Eksempel 1. Example 1.
I en autoklav innfører man 4 kg polyetylentereftalatavfall i form av fibre resp. tråder og tilsetter 4,8 liter metanol samt 400 gr a-metylnaftalin og 40 gr sinkstøv. Under opprettholdelse av et trykk på 18 ato opphetes autoklaven ved 130—140° C i 4 timer. I dette tidsrom blir reaksjons-mas.sen stadig omrørt. Etter avkjøling får man råesteren i form av en kompakt hvitgrå krystallmasse som utrøres med 1,5 liter metanol for å muliggjøre en bedre filtrering. Råesteren blir deretter ved avsuging befridd for glykol og a-metylnaftalin og fås deretter ved omkrystallisering fra metanol, under samtidig utskillelse av kata-lysatoren sink, i ren form og med et utbytte på 90 pst. 4 kg of polyethylene terephthalate waste in the form of fibers or threads and add 4.8 liters of methanol as well as 400 gr a-methylnaphthalene and 40 gr zinc dust. While maintaining a pressure of 18 ato, the autoclave is heated at 130-140° C for 4 hours. During this time, the reaction mass is constantly stirred. After cooling, the crude ester is obtained in the form of a compact white-grey crystal mass which is stirred with 1.5 liters of methanol to enable better filtration. The crude ester is then freed from glycol and α-methylnaphthalene by suction and is then obtained by recrystallization from methanol, with simultaneous separation of the catalyst zinc, in pure form and with a yield of 90 per cent.
Eksem- pel 2. Example 2.
4 kg polyetylentereftalatavfall i form av fargede og forurensede kompakte masser anbringes i en autoklav og det tilsettes 420 gr difenyloksyd og 30 gr magnesium samt 5 liter metanol. Under opprettholdelse av et trykk av 16 ato holdes autoklaven på en temperatur av 135° C i 4 timer. Her- 4 kg of polyethylene terephthalate waste in the form of colored and contaminated compact masses is placed in an autoclave and 420 gr of diphenyl oxide and 30 gr of magnesium and 5 liters of methanol are added. While maintaining a pressure of 16 ato, the autoclave is kept at a temperature of 135° C. for 4 hours. Here-
under blir reaksjonsmassen omrørt. Etter avkjøling får man råesteren i form av en kompakt hvitgrå krystallmasse som tilsettes 1,5 liter metanol for å oppnå bedre filtrering. Den ved avsuging rensede rå-ester gir deretter ved omkrystallisering fra metanol tereftalsyredimetylester i ren form og med et utbytte på 91 pst. during which the reaction mass is stirred. After cooling, the crude ester is obtained in the form of a compact white-grey crystal mass to which 1.5 liters of methanol is added to achieve better filtration. The crude ester purified by suction then gives, by recrystallization from methanol, terephthalic acid dimethyl ester in pure form and with a yield of 91 per cent.
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US34345664A | 1964-02-10 | 1964-02-10 | |
| US468972A US3297446A (en) | 1964-02-10 | 1965-07-01 | Synergistic sensitization of photographic systems with labile selenium and a noble metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO120009B true NO120009B (en) | 1970-08-10 |
Family
ID=26993479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO156718A NO120009B (en) | 1964-02-10 | 1965-02-10 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US3297446A (en) |
| BE (1) | BE659479A (en) |
| CH (1) | CH441997A (en) |
| DE (1) | DE1472818A1 (en) |
| DK (1) | DK130897B (en) |
| GB (2) | GB1098466A (en) |
| NL (1) | NL144403B (en) |
| NO (1) | NO120009B (en) |
| SE (1) | SE333096B (en) |
Families Citing this family (53)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3442653A (en) * | 1964-02-10 | 1969-05-06 | Eastman Kodak Co | Sensitized silver halide systems with activated nonlabile selenium compounds |
| US3396028A (en) * | 1964-11-25 | 1968-08-06 | Eastman Kodak Co | Silver halide emulsions containing hydroxy carboxylic acid derivatives as fog inhibitors |
| US3408197A (en) * | 1967-01-03 | 1968-10-29 | Eastman Kodak Co | Synergistic sensitization of silver halide emulsions with labile selenium formed in situ |
| US3408196A (en) * | 1967-01-03 | 1968-10-29 | Eastman Kodak Co | Sensitization of silver halide emulsion with labile selenium formed in situ |
| US3655407A (en) * | 1969-03-10 | 1972-04-11 | Eastman Kodak Co | Method of coating dilute aqueous emulsions |
| JPS5033847B2 (en) * | 1971-09-27 | 1975-11-04 | ||
| US3976489A (en) * | 1972-03-24 | 1976-08-24 | Polaroid Corporation | Silver halide photographic products with semiconductor sensitizers |
| US3769017A (en) * | 1972-03-29 | 1973-10-30 | Konishiroku Photo Ind | Photosensitive silver halide element containing a thiosugar antifoggant |
| US4003746A (en) * | 1975-07-01 | 1977-01-18 | E. I. Du Pont De Nemours And Company | Organic heterocyclic and thioaryl phosphines in silver halide emulsions and developers therefor |
| CH597627A5 (en) * | 1975-11-17 | 1978-04-14 | Ciba Geigy Ag | |
| GB1545975A (en) * | 1975-12-16 | 1979-05-16 | Asahi Chemical Ind | Dry image forming material |
| US4411985A (en) * | 1981-09-17 | 1983-10-25 | Eastman Kodak Company | Heat stabilizable photographic silver halide material and process |
| JPS59180536A (en) * | 1983-03-30 | 1984-10-13 | Konishiroku Photo Ind Co Ltd | Silver halide photographic emulsion |
| JP2664247B2 (en) * | 1989-05-31 | 1997-10-15 | 富士写真フイルム株式会社 | Silver halide photographic emulsion |
| US5166045A (en) * | 1989-06-19 | 1992-11-24 | Eastman Kodak Company | Doping of silver halide emulsions with group VIB compounds to form improved photoactive grains |
| JP3049335B2 (en) * | 1990-05-21 | 2000-06-05 | 富士写真フイルム株式会社 | Silver halide photographic material |
| JPH0432831A (en) * | 1990-05-29 | 1992-02-04 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material |
| JP2840877B2 (en) | 1990-08-30 | 1998-12-24 | 富士写真フイルム株式会社 | Silver halide photographic material |
| EP0514675B1 (en) | 1991-04-22 | 1999-12-08 | Fuji Photo Film Co., Ltd. | Silver halide photographic materials and method for processing the same |
| DE69206871T2 (en) * | 1991-05-10 | 1996-06-13 | Fuji Photo Film Co Ltd | Silver halide photographic material |
| US5210002A (en) * | 1991-07-25 | 1993-05-11 | Eastman Kodak Company | Nucleated high contrast photographic elements containing urea compounds which enhance speed and increase contrast |
| US5213944A (en) * | 1991-10-17 | 1993-05-25 | Eastman Kodak Company | Nucleated high contrast photographic elements containing substituted thioureas which enhance speed and increase contrast |
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| JP2777949B2 (en) | 1992-04-03 | 1998-07-23 | 富士写真フイルム株式会社 | Silver halide color photographic materials |
| JPH06110149A (en) * | 1992-09-30 | 1994-04-22 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material |
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| DE69325897T2 (en) * | 1993-05-26 | 2000-04-20 | Agfa-Gevaert N.V. | Red silver halide photographic material |
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| US5492804A (en) * | 1994-06-30 | 1996-02-20 | Minnesota Mining And Manufacturing Company | Chromogenic leuco redox-dye-releasing compounds for photothermographic elements |
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| DE69516054T2 (en) * | 1994-07-18 | 2000-10-26 | Konica Corp., Tokio/Tokyo | Silver halide photographic element and its processing method |
| US5616446A (en) * | 1994-09-29 | 1997-04-01 | Konica Corporation | Silver halide photographic light-sensitive material |
| US5928857A (en) * | 1994-11-16 | 1999-07-27 | Minnesota Mining And Manufacturing Company | Photothermographic element with improved adherence between layers |
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| US5763154A (en) * | 1996-08-07 | 1998-06-09 | Eastman Kodak Company | Palladium chemical sensitizers for silver halides |
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| US6100021A (en) * | 1998-12-15 | 2000-08-08 | Agfa-Gevaert N.V. | Sensitization of silver halide |
| EP1726990A4 (en) * | 2004-03-11 | 2008-03-19 | Fujifilm Corp | Photosensitive material for silver halide color photograph |
| US7241564B2 (en) | 2004-08-02 | 2007-07-10 | Fujifilm Corporation | Silver halide holographic sensitive material and system for taking holographic images by using the same |
| JP2006106022A (en) * | 2004-09-30 | 2006-04-20 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
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| JP2006308873A (en) * | 2005-04-28 | 2006-11-09 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
| JP4887201B2 (en) | 2007-04-13 | 2012-02-29 | 富士フイルム株式会社 | Silver halide photographic light-sensitive material and image forming method using the same |
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| US7524621B2 (en) * | 2007-09-21 | 2009-04-28 | Carestream Health, Inc. | Method of preparing silver carboxylate soaps |
| US7622247B2 (en) * | 2008-01-14 | 2009-11-24 | Carestream Health, Inc. | Protective overcoats for thermally developable materials |
| WO2017123444A1 (en) | 2016-01-15 | 2017-07-20 | Carestream Health, Inc. | Method of preparing silver carboxylate soaps |
| CN110093507B (en) * | 2019-04-17 | 2020-09-22 | 华南理工大学 | Method for enriching and recovering gold ions in solution by polyselenurone |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1574943A (en) * | 1924-06-06 | 1926-03-02 | Eastman Kodak Co | Art of light-sensitive photographic materials |
| US3128184A (en) * | 1960-01-25 | 1964-04-07 | Eastman Kodak Co | Antifoggants for gold sensitized emulsions in the presence of reduction sensitizers |
| BE624013A (en) * | 1961-10-26 |
-
1965
- 1965-02-09 NL NL656501562A patent/NL144403B/en unknown
- 1965-02-09 DK DK64865AA patent/DK130897B/en unknown
- 1965-02-09 DE DE19651472818 patent/DE1472818A1/en active Pending
- 1965-02-09 BE BE659479A patent/BE659479A/xx unknown
- 1965-02-10 GB GB5713/65A patent/GB1098466A/en not_active Expired
- 1965-02-10 CH CH176765A patent/CH441997A/en unknown
- 1965-02-10 SE SE01685/65A patent/SE333096B/xx unknown
- 1965-02-10 NO NO156718A patent/NO120009B/no unknown
- 1965-07-01 US US468972A patent/US3297446A/en not_active Expired - Lifetime
-
1966
- 1966-06-30 GB GB29373/66A patent/GB1150573A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| US3297446A (en) | 1967-01-10 |
| GB1150573A (en) | 1969-04-30 |
| DE1472818A1 (en) | 1969-12-04 |
| DK130897B (en) | 1975-04-28 |
| NL144403B (en) | 1974-12-16 |
| GB1098466A (en) | 1968-01-10 |
| NL6501562A (en) | 1965-08-11 |
| BE659479A (en) | 1965-05-28 |
| SE333096B (en) | 1971-03-01 |
| CH441997A (en) | 1967-08-15 |
| DK130897C (en) | 1975-09-29 |
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