CA1146976A - Stabilized halogenated hydrocarbons - Google Patents
Stabilized halogenated hydrocarbonsInfo
- Publication number
- CA1146976A CA1146976A CA000353144A CA353144A CA1146976A CA 1146976 A CA1146976 A CA 1146976A CA 000353144 A CA000353144 A CA 000353144A CA 353144 A CA353144 A CA 353144A CA 1146976 A CA1146976 A CA 1146976A
- Authority
- CA
- Canada
- Prior art keywords
- halogenated hydrocarbon
- trichloroethane
- weight
- tertiary amine
- methylene chloride
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/30—Materials not provided for elsewhere for aerosols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/42—Use of additives, e.g. for stabilisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Detergent Compositions (AREA)
- Containers And Packaging Bodies Having A Special Means To Remove Contents (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fire-Extinguishing Compositions (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Abstract of the disclosure:
Many halogenated hydrocarbons, such as methylene chloride or fluorotrichloromethene, are slowly hydrolyzed even in the presence of small amounts of water. It has been found that they can be stabilized by adding thereto from 0,001 to 10 % by weight of a tertiary amine of the formula RR1R2N wherein R and R1, independent from each other, represent alkyl groups with from 1 to 10 carbon atoms and R2 represents an isopropyl, butyl (2), tertiary butyl or cyclohexyl group.
Many halogenated hydrocarbons, such as methylene chloride or fluorotrichloromethene, are slowly hydrolyzed even in the presence of small amounts of water. It has been found that they can be stabilized by adding thereto from 0,001 to 10 % by weight of a tertiary amine of the formula RR1R2N wherein R and R1, independent from each other, represent alkyl groups with from 1 to 10 carbon atoms and R2 represents an isopropyl, butyl (2), tertiary butyl or cyclohexyl group.
Description
- 2 - HOE 79/F 137 The present invention relates to the stabilization of halogenated hydrocarbons, especially those, which are liquid at room temperature, against decomposition in the presence of water. Halogenated hydrocarbons are used, inter alia, for extracting, degreasing or purify-ing metals and as solvents for other active ingredients.
In many application fields the halogenated hydro-carbon is contacted with water which may cause a rapid or slow decomposition, with hydrogen halogenide being 1~ formed. Thus, present metals, for example tin plate, are corroded in many cases.
Hydrogenated hydrocarbons, preferably methylene chloride and 1 r 1 ~1-trichloroethane, but also fluoro-trichloromethane, are used as solvents for a ~ariety of active ingredients, even for aerosol sprays. In most cases, the halogenated hydrocarbon, for example methylene chloride, is blended with other organic solvents, such as alcohols or aliphatic hydrocarbons.
In general, a stabilization of the halogenated hydro-carbon in the absence of water, is easy or unnecessary.Insecticides or hair sprays, which contain methylene chloride, for example, are in general anhydrous.
An important advantage of the abovementioned halogenated hydrocarbons, besides their high dissolving power for many substances, is that they are classified as non-combustible, according to the legal regulations for compressed gas bottles that are binding within the EC zone. When using said halogenated hydrocarbons in spray formulations, especially in the presence of other combustible components, the safety requirements imposed on products which do not carry the sign "combustible", can be met tthe declaration of combusti-bility is obligatory in some countries if the proportion by weight of combustible components, calculated the total spray, is 45 % or more).
A disadvantage of the abovementioned chlorocarbon solvents is their noticeable sensitivity to water. This also applies to many other halogenated hydrocarbons, .';.,.: ' ~
.
-
In many application fields the halogenated hydro-carbon is contacted with water which may cause a rapid or slow decomposition, with hydrogen halogenide being 1~ formed. Thus, present metals, for example tin plate, are corroded in many cases.
Hydrogenated hydrocarbons, preferably methylene chloride and 1 r 1 ~1-trichloroethane, but also fluoro-trichloromethane, are used as solvents for a ~ariety of active ingredients, even for aerosol sprays. In most cases, the halogenated hydrocarbon, for example methylene chloride, is blended with other organic solvents, such as alcohols or aliphatic hydrocarbons.
In general, a stabilization of the halogenated hydro-carbon in the absence of water, is easy or unnecessary.Insecticides or hair sprays, which contain methylene chloride, for example, are in general anhydrous.
An important advantage of the abovementioned halogenated hydrocarbons, besides their high dissolving power for many substances, is that they are classified as non-combustible, according to the legal regulations for compressed gas bottles that are binding within the EC zone. When using said halogenated hydrocarbons in spray formulations, especially in the presence of other combustible components, the safety requirements imposed on products which do not carry the sign "combustible", can be met tthe declaration of combusti-bility is obligatory in some countries if the proportion by weight of combustible components, calculated the total spray, is 45 % or more).
A disadvantage of the abovementioned chlorocarbon solvents is their noticeable sensitivity to water. This also applies to many other halogenated hydrocarbons, .';.,.: ' ~
.
-
- 3 - HOE 79/F 137 especially to those which have only a low halogenation degree and contain less than 4 fluorine atoms in the molecule~
Even in the presence of small portions of water in an aerosol spray, pure methylene chloride, for examrle, especially on contact with metals, is hydrolized in a relatively short time (~ to 8 weeks) to such a degree that the metallic compressed gas bottle underyoes corrosion by the hydrogen chloride split off. ~
~0 sufficient high portion of water may be introduced into the spray formula by blending the chlorohydro-carbon with ethanole having a strength of 96 ~ by volume.
In most cases the content is also chemically attacked by the hydrochloric acid formed, thus making the whole content of the bottle unuseable.
Therefore many experiments have been ~arried out to stabilize halogenated hydrocarbons, especially the compounds methylene chloride and 1,~ trichloroe~thane, which are of special importance for the manufacture of aerosols, against hydrolysis by addition of inhibi~
tors. Epoxides and/or secondary amines, or e~ample, have been added to halogenated hydrocarbons, especially methylene chloride. From the toxicological point of view, however, epoxides have to be considered as unacceptable.
2S Secondary arnines, in the presence of nitrites, can lead to the formation of nitrosamines which may be cancerogenic. Another disadvantage is that the effect of the abovementioned stabilizers is slowly reduced and temporally limited because the stabilizers either react 3~ with the halogenated hydrocarbon or with the hydrogen halide formed therefrom. There have also been used N-methylpyrrole and N-alkylmorpholine in order to protect methylene chloride (in the absence of water~
against decomposition by metals or metal salts (GB-PS
932~38). This is also valid for the known tertiary amines r such as triethylamine ~IS-patent application 370~309).
Therefore it was necessary to stabilize halogenated .
.
., . . ~ , 97~
hydrocarbons against hydrolysis by toxicologically unobjectionable compounds in such a way that their effectiveness is guaranteed for a long time.
Now it has been found that halogenated hydrocarbons selected from the group consisting of methylene chloride, 1~
trichloroethane, fluorotrichloromethane, and 1,1,2-trifluoro-1,2,2-trichloroethane can be stabilized against decomposition by water, by adding thereto from 0.001 to 10 % by weight of a kertiary amine of the formula RR R N (I) wherein R and Rl, independently from one another stand for alkyl groups with from 1 to 10 carbon atoms and R2 means isopropyl, bwtyl-(2)~ tertiary butyl or cyclohexyl. The alkyl radicals may be linear, branched or cyclic.
Preferred stabilizers are tertiary amines oE the formula R2N-C(C~I3)3 (II~
with R having the abovementioned meaning.
Very efective stabilizers are also tertiary amines of the formula 1 2 RR R N (III) with R standing for alkyl with from 1 to 10 carbon atoms and Rl and R2 independently meaning isopropyl, butyl-(2), tertiary butyl or cyclohexyl.
R is preferably alkyl with 1 to 4 carbon atoms, especially the methyl or ethyl radical. Tertiary amines of the formula ~II, with Rl being identical with R2 are preferred because they can be manufactured more easily.
Preferred concentration ranges for the tertiary amine, employed according to the invention, are 0.005
Even in the presence of small portions of water in an aerosol spray, pure methylene chloride, for examrle, especially on contact with metals, is hydrolized in a relatively short time (~ to 8 weeks) to such a degree that the metallic compressed gas bottle underyoes corrosion by the hydrogen chloride split off. ~
~0 sufficient high portion of water may be introduced into the spray formula by blending the chlorohydro-carbon with ethanole having a strength of 96 ~ by volume.
In most cases the content is also chemically attacked by the hydrochloric acid formed, thus making the whole content of the bottle unuseable.
Therefore many experiments have been ~arried out to stabilize halogenated hydrocarbons, especially the compounds methylene chloride and 1,~ trichloroe~thane, which are of special importance for the manufacture of aerosols, against hydrolysis by addition of inhibi~
tors. Epoxides and/or secondary amines, or e~ample, have been added to halogenated hydrocarbons, especially methylene chloride. From the toxicological point of view, however, epoxides have to be considered as unacceptable.
2S Secondary arnines, in the presence of nitrites, can lead to the formation of nitrosamines which may be cancerogenic. Another disadvantage is that the effect of the abovementioned stabilizers is slowly reduced and temporally limited because the stabilizers either react 3~ with the halogenated hydrocarbon or with the hydrogen halide formed therefrom. There have also been used N-methylpyrrole and N-alkylmorpholine in order to protect methylene chloride (in the absence of water~
against decomposition by metals or metal salts (GB-PS
932~38). This is also valid for the known tertiary amines r such as triethylamine ~IS-patent application 370~309).
Therefore it was necessary to stabilize halogenated .
.
., . . ~ , 97~
hydrocarbons against hydrolysis by toxicologically unobjectionable compounds in such a way that their effectiveness is guaranteed for a long time.
Now it has been found that halogenated hydrocarbons selected from the group consisting of methylene chloride, 1~
trichloroethane, fluorotrichloromethane, and 1,1,2-trifluoro-1,2,2-trichloroethane can be stabilized against decomposition by water, by adding thereto from 0.001 to 10 % by weight of a kertiary amine of the formula RR R N (I) wherein R and Rl, independently from one another stand for alkyl groups with from 1 to 10 carbon atoms and R2 means isopropyl, bwtyl-(2)~ tertiary butyl or cyclohexyl. The alkyl radicals may be linear, branched or cyclic.
Preferred stabilizers are tertiary amines oE the formula R2N-C(C~I3)3 (II~
with R having the abovementioned meaning.
Very efective stabilizers are also tertiary amines of the formula 1 2 RR R N (III) with R standing for alkyl with from 1 to 10 carbon atoms and Rl and R2 independently meaning isopropyl, butyl-(2), tertiary butyl or cyclohexyl.
R is preferably alkyl with 1 to 4 carbon atoms, especially the methyl or ethyl radical. Tertiary amines of the formula ~II, with Rl being identical with R2 are preferred because they can be manufactured more easily.
Preferred concentration ranges for the tertiary amine, employed according to the invention, are 0.005
-4-: ' :
., ~ ' ~ 3
., ~ ' ~ 3
- 5 - HOE 79/F 137 to 5 ~ by weight, specially 0.01 to 1 % by weight.
Furthermore, it has ~een found that the stabilizing e~fect of the tert;ary amine is increased in the presence of an ether. As ethers there are preferably employed those compounds which only consist of C, H and O and which have no other reactive groups. Specially preferred are low molecular weight alkyl ethers or cy~loalkyl ethers whose alkyl radicals contain from 1 to 6 C-atoms.
Ether contents of more than 1 % by weight proved to be especially effective. Very favorable reactions showed 5- or 6-membered heterocyclic compounds, for example tetrahydrofuran, or unbranched dialkyl ethers with 2 tQ 6 carbon atoms, such as diethyl ether, dimethyl ether or methylethyl ether.
Subjec-t of the invention are, furthermore, aerosol packages which contain a mixture of at least one halogenated hydrocarbon, liquid at room temperature and normal pressure, at least one liquefied aerosol propellant, which is gaseous at room temperature and normal pressure, as well as water. These packages may also contain other organic solvents and active ingredients.
By the term "active ingredient'l in the presen~ appli-cation there are to be understood substances which cannot be considered as liquid halogenated hydro-carbons, organic solvents or propellants, which, however,are important for the use of aerosol formulation.
Examples hereof are perfumes, dyestuffs and binding agents (in lacquer sprays) and bactericides. These active ingredients, in general, have only a small influence on the hydrolysis of the halogenated hydrocarbons presen-t. In sprays for producing low temperatures or in paint removers based on methylene chloride, for example, they are not necessary.
Of special interest are aerosol packages containing 35~rom 10-89.5 ~ by weight of liquid halogenated hydro-carbon 0-75 ~ by weight of other organic solvents, 0.5-25 ~ by weight of water, .
: : .
- ' :
~ 6 - HO~ 79/F 137 0 - 35 % by weight of active ingredients and 10 - 70 ~ by weight of liquefied aerosol propellant gas, the content being stabilized by an amount of a tertiary amine of the formulae ~, II or III in the range from ~.OOQ01 to 0.1 part by weight per part by weight of liquid halogenated hydrocarbon.
The stabilization according to t:he invention is of special importance~ if the aerosol formulations mentioned above are dispensed to aerosol packages made from metal. In this case, the corrosive attack on the metal (for example tin plate) may be substantially suppressed ior a long time.
The following examples illustrate the invention:
E x a m p l e 5 Test mixtures were dispensed to welded tin plate aerosol bottles (18 oz) without interior lacquer protection. The bottles were closed by normal aerosol valves provided with blank tin plate disks and after being char~ed with the propellant, they were stored at 40C in a vertical position. When the intended storage time of, in general, 4, 8 and 12 weeks had passed, the bottles still charged were cooled to temperature lower than the boiling point of the propel-lants employed, they were perforated at the dome by means of a thorn and left to stand under a hood until they had reached again room temperature, with the portions of propellant evaporating gradually. The remaining contents were poured into beakers and the cleared bottles were opend by sawing~ The remaining mixture (without propellant) as well as the opened tin plate bottles were examined optically for signs of corrosion. The statement "without result of an exami-nation" means that the charge or the material of the bottle were uncharged, as compared with the original charge.
The following tables show the relation between stabilizator for water-containing methylene chloride, duration of storing and the corrosion of the aerosol ,-~7'1~
bottles. Experiments 1 to 4 are comparative experiments.
Experiments 5 to 7 are in accordance with the invention.
.
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Furthermore, it has ~een found that the stabilizing e~fect of the tert;ary amine is increased in the presence of an ether. As ethers there are preferably employed those compounds which only consist of C, H and O and which have no other reactive groups. Specially preferred are low molecular weight alkyl ethers or cy~loalkyl ethers whose alkyl radicals contain from 1 to 6 C-atoms.
Ether contents of more than 1 % by weight proved to be especially effective. Very favorable reactions showed 5- or 6-membered heterocyclic compounds, for example tetrahydrofuran, or unbranched dialkyl ethers with 2 tQ 6 carbon atoms, such as diethyl ether, dimethyl ether or methylethyl ether.
Subjec-t of the invention are, furthermore, aerosol packages which contain a mixture of at least one halogenated hydrocarbon, liquid at room temperature and normal pressure, at least one liquefied aerosol propellant, which is gaseous at room temperature and normal pressure, as well as water. These packages may also contain other organic solvents and active ingredients.
By the term "active ingredient'l in the presen~ appli-cation there are to be understood substances which cannot be considered as liquid halogenated hydro-carbons, organic solvents or propellants, which, however,are important for the use of aerosol formulation.
Examples hereof are perfumes, dyestuffs and binding agents (in lacquer sprays) and bactericides. These active ingredients, in general, have only a small influence on the hydrolysis of the halogenated hydrocarbons presen-t. In sprays for producing low temperatures or in paint removers based on methylene chloride, for example, they are not necessary.
Of special interest are aerosol packages containing 35~rom 10-89.5 ~ by weight of liquid halogenated hydro-carbon 0-75 ~ by weight of other organic solvents, 0.5-25 ~ by weight of water, .
: : .
- ' :
~ 6 - HO~ 79/F 137 0 - 35 % by weight of active ingredients and 10 - 70 ~ by weight of liquefied aerosol propellant gas, the content being stabilized by an amount of a tertiary amine of the formulae ~, II or III in the range from ~.OOQ01 to 0.1 part by weight per part by weight of liquid halogenated hydrocarbon.
The stabilization according to t:he invention is of special importance~ if the aerosol formulations mentioned above are dispensed to aerosol packages made from metal. In this case, the corrosive attack on the metal (for example tin plate) may be substantially suppressed ior a long time.
The following examples illustrate the invention:
E x a m p l e 5 Test mixtures were dispensed to welded tin plate aerosol bottles (18 oz) without interior lacquer protection. The bottles were closed by normal aerosol valves provided with blank tin plate disks and after being char~ed with the propellant, they were stored at 40C in a vertical position. When the intended storage time of, in general, 4, 8 and 12 weeks had passed, the bottles still charged were cooled to temperature lower than the boiling point of the propel-lants employed, they were perforated at the dome by means of a thorn and left to stand under a hood until they had reached again room temperature, with the portions of propellant evaporating gradually. The remaining contents were poured into beakers and the cleared bottles were opend by sawing~ The remaining mixture (without propellant) as well as the opened tin plate bottles were examined optically for signs of corrosion. The statement "without result of an exami-nation" means that the charge or the material of the bottle were uncharged, as compared with the original charge.
The following tables show the relation between stabilizator for water-containing methylene chloride, duration of storing and the corrosion of the aerosol ,-~7'1~
bottles. Experiments 1 to 4 are comparative experiments.
Experiments 5 to 7 are in accordance with the invention.
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Claims (21)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A halogenated hydrocarbon selected from the group consisting of methylene chloride, 1,1,1-trichloroethane, fluorotri-chloromethane, and 1,1,2-trifluoro-1,2,2,-trichloroethane, stabilized against decomposition by water, which comprises as stabilizer from 0.001 to 10 % by weight of a tertiary amine of the formula RR1R2N (I) with R and and R1 independent from one another being alkyl with 1 to 10 carbon atoms and with R2 meaning isopropyl, butyl-(2), tertiary butyl or cyclohexyl.
2. Halogenated hydrocarbon according to claim 1, comprising the tertiary amine of the formula R2NC(CH3)3 (II)
3. Halogenated hydrocarbon according to claim 1, comprising as stabilizer a tertiary amine of the formula RR1R2N (III) with R being alkyl with 1 to 10 carbons and R1 and R2, independent from one another, being isopropyl, butyl-(2), tertiary butyl or cyclohexyl.
4. Halogenated hydrocarbon according to claim 3, comprising the tertiary amine of the formula RR?N (IV)
5. Halogenated hydrocarbon according to claim 3, wherein R is an alkyl with 1 to 4 carbon atoms.
6. Halogenated hydrocarbon according to claim 1, 2 or 3, comprising as stabilizer from 0.01 to 1 % by weight of the tertiary amine.
7. Halogenated hydrocarbon/ether mixture with a weight ratio of halogenated hydrocarbon/ether of from 1:2 to 100:1, comprising as stabilizer for the mixture from 0.001 to 10 % by weight of a tertiary amine as defined in claim 1, wherein the halogenated hydrocarbon is selected from the group consisting of methylene chloride, 1,1,1-trichloroethane, fluorotrichloromethane and 1,1,2-trifluoro-1,2,2-trichloroethane.
8. Mixture according to claim 7, wherein the ether consists only of carbon, hydrogen and oxygen and is free from other functional groups.
9. Mixture according to claim 8, wherein the ether is an aliphatic linear ether with a total of 2 to 6 C-atoms.
10. A process for stabilizing halogenated hydrocarbons selected from the group consisting of methylene chloride, 1,1,1-trichloroethane, fluorotrichloromethane, and 1,1,2-trifluoro-1,2,2-trichloroethane against decomposition by water, which comprises incorporating therein, as stabilizer, from 0.001 to 10 by weight of a tertiary amine of the formula RR1R1N (I) with R and R1 independent from one another being alkyl with 1 to 10 carbon atoms and with R2 meaning isopropyl, butyl-(2), tertiary butyl or cyclohexyl.
11. A process for stabilizing a halogenated hydrocarbon/ether mixture as defined in claim 7, against decomposition by water, which comprises incorporating therein, as stabilizer, from 0.001 to 10 % by weight of a tertiary amine as defined in claim 1, wherein the halogenated hydrocarbon is selected from the group consisting of methylene chloride, 1,1,1-trichloroethane, fluorotrichloromethane, and 1,1,2-trifluoro-1,2,2-trichloroethane.
12. Aerosol bottle containing a charge consisting of 10 - 89.5 % by weight of halogenated hydrocarbon, selected from the group consisting of methylene chloride, 1,1,1-trichloroethane, fluorotriehloromethane, and 1,1,2-trifluoro-1,2,2-trichloroethane, 0 - 75 % by weight of other organic solvents, 0.5 - 25 % by weight of water, 0 - 35 % by weight of active ingredients and 10 - 70 % by weight of liquefied aerosol propellant, wherein the charge contains from 0.00001 to 0.1 part by weight of a tertiary amine of claim 1 per part by weight of halogenated hydrocarbon.
13. Aerosol bottle according to claim 12, wherein the bottle is made from metal.
14. Stabilized methylene chloride, according to claim 1, 2 or 4.
15. Stabilized 1,1,1-trichloroethane, according to claim 1, 2 or 4.
16. Stabilized fluorotrichloromethane, according to claim 1, 2 or 4.
17. Stabilized 1,1,2-trifluoro-1,2,2-trichloroethane, according to claim l, 2 or 4.
18. A mixture according to claim 7, 8 or 9 wherein the halogenated hydrocarbon is methylene chloride.
19. A mixture according to claim 7, 8 or 9 wherein the halogenated hydrocarbon is 1,1,1-trichloroethane.
20. A mixture according to claim 7, 8 or 9 wherein the halogenated hydrocarbon is fluorotrichloromethane.
21. A mixture according to claim 7, 8 or 9 wherein the halogenated hydrocarbon is 1,1,2-trifluoro-1,2,2-trichloroethane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2922700.7 | 1979-06-02 | ||
| DE19792922700 DE2922700A1 (en) | 1979-06-02 | 1979-06-02 | STABILIZED HALOGEN HYDROCARBONS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1146976A true CA1146976A (en) | 1983-05-24 |
Family
ID=6072459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000353144A Expired CA1146976A (en) | 1979-06-02 | 1980-05-30 | Stabilized halogenated hydrocarbons |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0023540B1 (en) |
| JP (1) | JPS55164633A (en) |
| AT (1) | ATE5712T1 (en) |
| AU (1) | AU532886B2 (en) |
| CA (1) | CA1146976A (en) |
| DE (2) | DE2922700A1 (en) |
| DK (1) | DK231780A (en) |
| ES (1) | ES8100793A1 (en) |
| FI (1) | FI70203C (en) |
| IE (1) | IE49832B1 (en) |
| NO (2) | NO154228C (en) |
| ZA (1) | ZA803267B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3230048A1 (en) * | 1982-08-12 | 1984-02-16 | Wacker-Chemie GmbH, 8000 München | METHOD FOR STABILIZING CHLORINE HYDROCARBONS, METHOD STABILIZED CHLORINE HYDROCARBONS AND THEIR USE |
| CA1318086C (en) * | 1987-05-20 | 1993-05-25 | Stephen M. Campbell | Process and composition for stabilization of ar-brominated styrenic monomers against premature polymerization |
| DE3936731A1 (en) * | 1989-11-04 | 1991-05-08 | Hoechst Ag | METHOD FOR STABILIZING CHLORINE PARAFFINS |
| EP1382655A3 (en) * | 1990-09-03 | 2004-03-10 | Connetics Australia Pty Limited | A concentrated aerosol space spray |
| US5935554A (en) * | 1990-09-03 | 1999-08-10 | Soltec Research Pty. Ltd. | Concentrated aerosol space spray that is not an emulsion |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2476554A (en) * | 1941-03-20 | 1949-07-19 | Continental Oil Co | Method of inhibiting deterioration of organic compounds |
| DE1768613A1 (en) * | 1968-06-06 | 1972-02-17 | Dynamit Nobel Ag | Stabilization of trichlorethylene |
-
1979
- 1979-06-02 DE DE19792922700 patent/DE2922700A1/en not_active Withdrawn
-
1980
- 1980-05-23 DE DE8080102878T patent/DE3065984D1/en not_active Expired
- 1980-05-23 EP EP80102878A patent/EP0023540B1/en not_active Expired
- 1980-05-23 AT AT80102878T patent/ATE5712T1/en not_active IP Right Cessation
- 1980-05-27 ES ES491893A patent/ES8100793A1/en not_active Expired
- 1980-05-29 FI FI801745A patent/FI70203C/en not_active IP Right Cessation
- 1980-05-29 DK DK231780A patent/DK231780A/en not_active Application Discontinuation
- 1980-05-30 IE IE1138/80A patent/IE49832B1/en unknown
- 1980-05-30 CA CA000353144A patent/CA1146976A/en not_active Expired
- 1980-05-30 NO NO801615A patent/NO154228C/en unknown
- 1980-05-30 JP JP7159680A patent/JPS55164633A/en active Pending
- 1980-06-02 AU AU58959/80A patent/AU532886B2/en not_active Ceased
- 1980-06-02 ZA ZA00803267A patent/ZA803267B/en unknown
-
1984
- 1984-04-30 NO NO841727A patent/NO841727L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU5895980A (en) | 1980-12-11 |
| DK231780A (en) | 1980-12-03 |
| NO154228B (en) | 1986-05-05 |
| DE3065984D1 (en) | 1984-02-02 |
| EP0023540A3 (en) | 1981-04-22 |
| ZA803267B (en) | 1981-06-24 |
| IE801138L (en) | 1980-12-02 |
| FI801745A (en) | 1980-12-03 |
| NO154228C (en) | 1986-08-13 |
| EP0023540A2 (en) | 1981-02-11 |
| ATE5712T1 (en) | 1984-01-15 |
| ES491893A0 (en) | 1980-12-16 |
| ES8100793A1 (en) | 1980-12-16 |
| AU532886B2 (en) | 1983-10-20 |
| DE2922700A1 (en) | 1980-12-11 |
| JPS55164633A (en) | 1980-12-22 |
| FI70203B (en) | 1986-02-28 |
| FI70203C (en) | 1986-09-15 |
| EP0023540B1 (en) | 1983-12-28 |
| NO801615L (en) | 1980-12-03 |
| IE49832B1 (en) | 1985-12-25 |
| NO841727L (en) | 1980-12-03 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |