US2288799A - Process of recovering water-insoluble lower fatty acid esters of cellulose - Google Patents
Process of recovering water-insoluble lower fatty acid esters of cellulose Download PDFInfo
- Publication number
- US2288799A US2288799A US26110139A US2288799A US 2288799 A US2288799 A US 2288799A US 26110139 A US26110139 A US 26110139A US 2288799 A US2288799 A US 2288799A
- Authority
- US
- United States
- Prior art keywords
- scrap
- water
- film
- cellulose
- base
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920002678 cellulose Polymers 0.000 title description 26
- 239000001913 cellulose Substances 0.000 title description 21
- 238000000034 method Methods 0.000 title description 19
- -1 fatty acid esters Chemical class 0.000 title description 12
- 235000014113 dietary fatty acids Nutrition 0.000 title description 10
- 239000000194 fatty acid Substances 0.000 title description 10
- 229930195729 fatty acid Natural products 0.000 title description 10
- 239000002585 base Substances 0.000 description 32
- 239000003599 detergent Substances 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 238000011282 treatment Methods 0.000 description 22
- 150000001768 cations Chemical class 0.000 description 21
- 239000007788 liquid Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000020 Nitrocellulose Substances 0.000 description 10
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 229920000159 gelatin Polymers 0.000 description 10
- 239000008273 gelatin Substances 0.000 description 10
- 229920001220 nitrocellulos Polymers 0.000 description 10
- 108010010803 Gelatin Proteins 0.000 description 9
- 235000019322 gelatine Nutrition 0.000 description 9
- 235000011852 gelatine desserts Nutrition 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- SXPWTBGAZSPLHA-UHFFFAOYSA-M cetalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SXPWTBGAZSPLHA-UHFFFAOYSA-M 0.000 description 6
- 229960000228 cetalkonium chloride Drugs 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KCEQOESJQVRUBO-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.CCCCCCCCCCCC[N+]1=CC=CC=C1 KCEQOESJQVRUBO-UHFFFAOYSA-M 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 1
- 229920002201 Oxidized cellulose Polymers 0.000 description 1
- 102000018210 Recoverin Human genes 0.000 description 1
- 108010076570 Recoverin Proteins 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229940107304 oxidized cellulose Drugs 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/10—Esters of organic acids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- This invention has to do with the.recovery of filmscrap, having a cellulose derivativebase, in which the scrap is, treated at an elevated temperature with water containing a cation. active detergent.
- photographic film comprises a base of; a cellulose derivative, preferably a cellulose ester, such as cellulose nitrate, cellulose acetate or a mixed ester of cellulose, such as cellulose acetate propionate. or cellulose acetate butyrate, overcoated with a gelatin layer containing a silver halide.
- a gelatin layer containing a silver halide.
- the scrap In carrying out our invention, it is preferred to first comminute the scrap, such as by chopping, although in some cases, such as with wide rolls of scrap film, it might be desirable to run a continuous process, by passing the sheeting through the recovery bath.
- the comminuted film In the case of the comminuted film, it is stirred with one or more changes of a solution of. a cation active detergent in water at an elevated. temperature after which the recovered film, base is rinsed and dried.
- the resulting product forms a, smooth, clear solution incoating solvents, which is a satisfactory indication of the, completeness of removal of the overcoatings, such as the gelatin layers and the subbing layers. which are present.
- the subbing layers which are susceptible to removalfrom the film in accordance with our invention, are any of the usual types of layers which are used to cause the gelatin layer to adhere to the film base. If the subbing layer is so moisture resistant that it will not be efiected by the solution of a cation active detergent at elevated temperature, it is not suitable to bond withthe gelatin layer.
- the preferred temperature of operation is 180-210" F. This temperature permits the use of the greatest amount of heat under normal pressure conditions. If, however, elevated pressures are not objectionable, the temperature may be raised above the boiling temperature of the water, the maximum temperature permissible being governed by the temperature which the film will stand without decomposing or being effected detrimentally.
- 180 F. isv preferred, as the lower limit, as only a short time is necessary for treating the film scrap, nevertheless, lower temperatures, such as from 180 down to 120 F., might be employed if sufiicient time is given for the treatment.
- a time of five minutes for each treatment is sufficient for a temperature of 210 and for the preferred temperature of 180-210 5-20 minutes is satisfactory for each treatment, especially where a plurality of treatments is given as is usually the case.
- a. total treatment time of 24 hours is desirable to give a substantially complete removal of the foreign material. 7
- the cation active detergent may be present in the water from .01% up to 25% or more, the higher limit being set only by the proportion of detergent which can be incorporated. In other words, very low concentrations of the detergent have been found to be effective and yet high concentrations have also given satisfactory results. However, in order to assure reuse of the liquid and economy of operation, it is preferred that the detergent be present in a proportion of .05%2%. In reusing the liquid, especially in cases of extended reuse, the liquid should be fortified at intervals by the further addition of small amounts of detergent. As pointed out previously, it is desirable, especially in case of comminuted scrap, to employ stirring as this uniformly exposes the particles of scrap to the action of the liquid and thereby gives a better treatment than would be possible where stirring is not employed.
- one treatment is sufficient to recover the ester employed as the film base.
- one treatment substantially removes all the foreign materials, but to obtain an excellent recovered product it is desirable to use more than one treatment. Twotreatments give a fairly satisfactory product and three are ordinarily sufficient to give a product of high quality. Further treatments may be given if desired but are ordinarily unnecessary.
- subbing layers which might be present and which are removable by our process are gelatin layers, whether hardened or not, layers of polyvinyl acetate (common known as Gelva resin), nitrate subbing layers, layers of resins, such as glyptal resins or mixtures of materials such as cellulose nitrate-gelatin or gelatin-oxidized cellulose acetate sub.
- Gelva resin polyvinyl acetate
- resins such as glyptal resins or mixtures of materials such as cellulose nitrate-gelatin or gelatin-oxidized cellulose acetate sub.
- the subbing layer except in the case of gelatin, is exceedingly thin, not exceeding one tenthousandth of an inch.
- the cation active detergents which are suitable for use in our process, are those of a watersoluble variety which have been previously mentioned in the prior art.
- the watersoluble cation active detergents disclosed in U. S. Patent No. 2,125,031 of Polak et al., are admirably suited for the purposes of our invention.
- Some of the compounds of this type, which give a good product when used in accordance with our invention, are triethyllaurylammonium bromide, triethyllaurylammonium perchlorate, lauryl pyridinium p-toluene-sulfonate, and dimethylbenzylcetylammonium chloride.
- the salts of other acids giving water-soluble products, such as the sulfates, may be employed.
- An example of compounds, which are valuable in our process are the quaternary ammonium salts having the following formula:
- R3-NX in which R represents aliphatic or aralkyl radicals, R represents aliphatic radicals, having 8 or more carbon atoms, and X represents an acid radical, giving water-soluble salts with the quaternary ammonium base.
- Example I 30 parts of film scrap, having a base of a lower fatty acid ester of cellulose, were chopped up and then boiled for one hour with 600 parts of a 0.5% solution of dimethyl benzyl cetyl ammonium chloride in water withoccasional agitation. The mother liquor was removed and the treatments were repeated twice, making a total of three treatments. The scrap was rinsed by boiling 6-8 times for fifteen minutes, each time with 600 parts of distilled water, and dried. The product gave a smooth, clear, brilliant solution in coating solvents, indicating complete removal of foreign materials known to be present in the untreated film scrap.
- Example II 40 parts of chopped processed film was boiled for three periods of one hour each with 600 parts of a 0.25% solution of dimethyl benzyl cetyl ammonium chloride. The scrap was rinsed, as in Example I, and dried. A solution of it in coating solvents was smooth and clear.
- Example III 30 parts of chopped film scrap was given 3 one hour boils with 600 parts of a 0.05% solution of dimethyl benzyl cetyl ammonium chloride in distilled water, rinsed, as in Example I, and dried. The product formed a grain-free solution in coating solvents.
- Example IV 30 parts of chopped film scrap was boiled with three successive portions of 600 parts each of a 1% solution of triethyllaurylammonium perchlorate in distilled water. The product was rinsed, as in Example I, and dried. It formed a smooth solution in coating solvents.
- a purified water be employed, as we have found that certain impurities in some types of water used in the boiling operations either decrease or completely destroy the effectiveness of our treatment. Therefore, it is essential in our process that a purified water, such as distilled or softened water, be used, or that the solution have a pH sufficiently acid to neutralize the effect of the water.
- the cellulose esters, recovered by our process, may be dissolved up in suitable coating solvents and used to form sheeting, or coatings, or any other purpose for which the use of a clear solution of a cellulose ester is desirable.
- a method of renovating film scrap having a base of a water-insoluble cellulose compound which comprises treating the scrap with a plurality of 0.5% solutions of dimethyl benzyl cetyl ammonium chloride in water, at a temperature above 120 F. but below the decomposition temperature of the film base until a surface coating is removed therefrom.
- a method of renovating film scrap having a base of a water-insoluble cellulose compound which comprises treating the scrap with a plurality of 1% solutions of triethyllaurylammonium perchlorate at a temperature above 120 F. but below the decomposition temperature of the film base until a surface coating is removed therefrom.
- a method of removing a thin layer of nitrocellulose from a base of a water-insoluble lower fatty acid ester of cellulose to which the layer is attached which comprises treating the cellulose ester material with a bath substantially free of alkali essentially consisting of a water solution of a water-soluble cation active detergent in which a negative substituent is linked directely to nitrogen, the cation portion of the detergent containing an alkyl substituent having at least 8 carbon atoms, at a temperature above 120 F. but below the decomposition temperature of the fatty acid ester of cellulose until the thin nitrocellulose layer is removed therefrom.
- a method of removing a thin layer of nitrocellulose from a base of a water-insoluble lower fatty acid ester of cellulose to which the layer is attached which comprises treating the cellulose ester material with a bath substantially free of alkali essentially consisting of water containing 0.05 to 2% of a cation active detergent in which a negative substituent is linked directly to nitrogen, the cation portion of the detergent containing an alkyl substituent having at least 8 carbon atoms, at a temperature of 180-210 F. until the thin nitrocellulose layer is removed from the base material.
- a method of renovating film scrap having a base of a water-insoluble lower fatty acid ester of cellulose and a subbing layer of nitrocellulose thereon, which comprises treating the scrap With a bath substantially free of alkali essentially consisting of a water solution of a water-soluble cation active detergent in which the negative substituent is linked directly to nitrogen, the cation portion of the detergent containing an alkyl substituent having at least 8 carbon atoms, at a temperature above F. but below the decomposition temperature of the film base until the nitrate subbing layer is removed therefrom.
- a method of renovating film scrap having a base of a water-insoluble lower fatty acid ester of cellulose and a nitrocellulose subbing layer thereon which comprises treating the scrap with a plurality of water solutions of a cation active detergent in water, at a temperature above 120 F. but below the decomposition temperature of the film base until the nitrate subbing layer is removed therefrom, the cation active detergent employed having a negative substituent linked directly to nitrogen and the cation portion of the detergent containing an alkyl substituent of at least 8 carbon atoms.
- a method of renovating film scrap having a base of a water-insoluble mixed ester of cellulose the acyl of which consists of fatty acid groups of 2-4 carbon atoms to Which is attached a thin layer of nitrocellulose which comprises treating the scrap with an alkali-free bath essentially consisting of a water solution of a water-soluble cation active detergent in which the negative substituent is linked directly to nitrogen, the cation portion of the detergent containing an alkyl substituent having at least 8 carbon atoms, at a temperature above 120 F. but below the decomposi tion temperature of the film base until the nitrate subbing layer is removed therefrom.
- a method of renovating film scrap having a base of a water-insoluble lower fatty acid ester of cellulose and a thin layer of nitrocellulose thereon which comprises treating the scrap with a 0.5% solution of dimethyl benzyl cetyl ammonium chloride in water, at a temperature above 120 F. but below the decomposition temperature of the film base until the thin nitrate layer is removed therefrom.
- a method of renovating film scrap having a base of a water-insoluble lower fatty acid ester of cellulose and a thin layer of nitrocellulose thereon which comprises treating the scrap with a 1% solution of triethyllaurylammonium perchlorate, at a temperature above 120 F. but below the decomposition temperature of the film base until the thin nitrate layer is removed therefrom.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR956720D FR956720A (enrdf_load_html_response) | 1939-03-10 | ||
US26110139 US2288799A (en) | 1939-03-10 | 1939-03-10 | Process of recovering water-insoluble lower fatty acid esters of cellulose |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US26110139 US2288799A (en) | 1939-03-10 | 1939-03-10 | Process of recovering water-insoluble lower fatty acid esters of cellulose |
Publications (1)
Publication Number | Publication Date |
---|---|
US2288799A true US2288799A (en) | 1942-07-07 |
Family
ID=22991961
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US26110139 Expired - Lifetime US2288799A (en) | 1939-03-10 | 1939-03-10 | Process of recovering water-insoluble lower fatty acid esters of cellulose |
Country Status (2)
Country | Link |
---|---|
US (1) | US2288799A (enrdf_load_html_response) |
FR (1) | FR956720A (enrdf_load_html_response) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2554179A (en) * | 1946-03-14 | 1951-05-22 | Ici Ltd | Process of producing nitrocellulose and a blasting explosive containing same |
US3865808A (en) * | 1972-07-18 | 1975-02-11 | Poudres & Explosifs Ste Nale | Recovery of nitrocellulose from the filtrate obtained after the nitration of cellulose |
-
0
- FR FR956720D patent/FR956720A/fr not_active Expired
-
1939
- 1939-03-10 US US26110139 patent/US2288799A/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2554179A (en) * | 1946-03-14 | 1951-05-22 | Ici Ltd | Process of producing nitrocellulose and a blasting explosive containing same |
US3865808A (en) * | 1972-07-18 | 1975-02-11 | Poudres & Explosifs Ste Nale | Recovery of nitrocellulose from the filtrate obtained after the nitration of cellulose |
Also Published As
Publication number | Publication date |
---|---|
FR956720A (enrdf_load_html_response) | 1950-02-06 |
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