SE445212B - 1,1,1-TRICLORETHANE STABILIZED BY AN EPOXIAL COOLESTER - Google Patents

Description

7901448-6 By the term "epoxyalkyl ester" is meant herein context such compounds in which an epoxy group is introduced in the alkyl group of the alcohol and / or in the alkyl group of it carboxylic acid from which the ester is obtained.

The alkyl ester as such (into which the epoxy group is introduced) can be obtained from a carboxylic acid, containing an n-alkyl-, isoalkyl or cycloalkyl group, and from an alcohol containing holds an n-alkyl-7 isoalkyl, alkenyl or cycloalkyl group, or which is a polyol. * Examples of epoxy alkyl esters include e.g. oktylep- oxystearate and butylepoxystearate. An example of an epoxy cooling ester is epoxy-2-ethylhexyl stearate. An example of an epoxy cycloalkyl ester is epoxycyclohexyl stearate. Mixtures of epoxy alkyl esters can also be used. _ A mixture of epoxy alkyl esters, obtained from chain fatty acids and glycerol, are very useful accordingly with the invention as a stabilizer for 1,1,1-trichloroethane. Special Particularly valuable stabilizers are epoxidized vegetable oils, e.g. epoxidized soybean oil and epoxidized linseed oil, which contains such epoxy alkyl esters.

The epicylkyl esters can be prepared in known manner, e.g. by epoxidation of the corresponding esters, containing ethylene unsaturation in the acid and / or alcohol components.

Very small amounts by weight of the epoxyalkyl esters, e.g. of the epoxidized vegetable oil, are useful accordingly with the invention. So e.g. has 0.025% by weight or more smaller amount of the epoxy alkyl esters in question, based on the a stabilizing effect on 1,1,1-trichloroethane.

Usually the amount of the epoxy alkyl ester is greater than 0.05%. but not more than 5% by weight of the solvent. šâ t.d. very good results can be achieved when the amount of epoxy the alkyl ester is in the range of 0.1-2% by weight of the medlet.

In One or more conventional stabilizers for 1,1,1- trichloroethane can also be associated with the present new stabilizer. sator. So e.g. valuable results can then be obtained in 1,1,1-tri- The chloroethane is also incorporated in a stabilizing amount of one or several of the following conventional stabilizing compounds, namely 7901448-6 organic nitrates, nitriles, nitroalkanes, cyclic ethers with 3- to 6-membered rings, amines, alcohols, alkyl esters and ketones. Any of these known stabilizers are usually present in an amount not exceeding 4% by weight, calculated on the solvent. In fact, significantly smaller amounts of conventional stabilizers can be used if desired. kas.

In accordance with the present invention, there is also provided so concentrated solutions of the epoxyalkyl ester in 1,1,1-trichloro- ethane, in which the amounts by weight of the epoxyalkyl ester are very re than the previously mentioned 5% by weight. These solutions can contain 20-70% by weight of epoxyalkyl esters, e.g. epoxybutyl- stearate and epoxidized vegetable oil, based on solvents let. By adding such a concentrate to pure solution or to solvents depleted in said epoxy cooling ester, can be obtained 1,1,1-trichloroethane containing the desired smaller amounts of the epoxyalkyl ester, which can then be used directly for cleaning metals or for other purposes. Equal- so concentrate can be used which contains not only one large weight of epoxy alkyl ester but also a large amount of one or several conventional stabilizers.

The invention is further elucidated with the aid of the following embodiments, where all the percentages given refer to the percent.

Example The apparatus comprising a pear-shaped glass flask having a space of 100 ml, placed umkm a vertical glass tube that led to a water-cooled reflux condenser. The pipe was also fitted with a horizontal glass side tube, which was adjacent to another horizontal glass tube. The ends of the two horizontal pipes were shaped in such a way that by applying a spring clip in accordance with what follows, a desired amount of solvent part could be removed from the end of the other glass tube. This last said adjacent to a third glass tube which was bent at right angles to communicate with a mild carbon steel tube with a length of 15 cm and a diameter of 0.64 cm. Heat from a Meker- burner was fed through a jacketed tube to the center of (3 cm length) the vertical tube of nüukt carbon steel. A glass tube connection the steel tube via two right angles with the glass flask. 7901448-6 50 ml of 1,1,1-trichloroethane were introduced into the glass flask. Through heating of the mild carbon steel tube passed 1,1,1-trichloroethane through the glass side arms and the tube of mild carbon steel, which thus served as a thermosiphon. The circulating 1,1,1-trichloro- the ethane was thus subjected to an accelerated stability test in the presence of mild carbon steel.

Different amounts of epoxy alkyl esters with and without conventional stabilizers were incorporated into the 1,1,1-trichloroethane and the accelerated stability test was subjected for a period of time of 120 minutes. Occurrence of acidity, measured to pH 4, in the steam (in the condenser) and in the stabilized solvent were determined in 'where applicable with universal indicator paper. Similar attempts was also carried out with an epoxy alkyl ester which also contained conventional stabilizers.

The results obtained are summarized in Table 1 below.

Table 1 ONOC Stabilizer Time for steam to get angry Time for the liquid to get angry 0.2% epoxidized soybean oil (I), known under the trade name Para- plex G 62 and commercially available from Röhm & Haas .5% epoxidized soybean lja (I) plus % isopropyl nitrate % nitromethane ONOO IN .5% epoxidized soybean lja (I) plus % t-butanol .5% nitromethane 0.5% epoxidized soybean oil (I) plus 2% t-amyl alcohol 0.5% nitromethane 0.5% epoxidized soybean oil (I) plus 2% methyl ethyl ketone 0.5 9 nitromethane no characters on acidity after 120 min. ditto .ditto ditto ditto no characters on acicity after 120 min. ditto_ ditto ditto ditto Table 1 (continued) 7901448-6 Stabilizer Time for steam to get angry Time for the liquid to get angry 0.5 ß epoxidized soybean oil (I) plus 55 W 1,4-åi0X & n 0.5% nitromethane 0.5% oxidized soybean oil (I plus % isobutyl acetate % nitromethane \ oxidized soybean , 5% e lga (I plus ß š-methyl-5-butyn-2- Q ° nitromethane , 5% e oxidized soybean lja (I plus ß l, §-dioxolone .5% nitromethane o, o5 '26 acetamenya- dimethylhydrazone Q 2 O O 0 2 0 » 0 0 2 Û 0.2% epoxidized linol (II), known under the name Edenol® B no characters on aoidity after 120 min ditto ditto ol ditto yes 515 ditto and available commercial from Henkel & C 0.5% epoxidized lin- oil (II) plus 2% isopropyl nitrate 0,% nitromethane 0 ditto no characters on acidity after 120 min ditto ditto ditto ditto ditto , 5% epoxidized lin ~ lja (I) plus % tfbutanol .5% nitromethane OO OUJOO ,% epoxidized lin- lja (II) plus t-amyl alcohol .5% nitromethane ïå 1 .5% epoxidized lin- läa (I) plus 0 methyl ethyl ketone .5% nitromethane OIUOO ON ditto ditto ditto ditto ditto ditto 79Û1448 ° 6 6 Table 1 (continued) Stabilizer Time for steam to get angry Time for the liquid to get angry 0.5% epoxidized lin- oil (II) plus , 5% 1,4-dioxane 0.5% nitromethane 'epoxidized lin ~ 'a (II) plus 2% isobutyl acetate 0.5% nitromethane O O š fi l .5% epoxidized lin- lja (II) plus % -methyl-5 = butyn-2-ol % nitromethane , 5% »epoxy-coated lin ~ and (II) plus % 1, α-aioxoian .5% nitromethane , O5% acetaläehyä- amethylhydrazone no characters on acidity after 120 min ditto ditto ditto no characters acidity after 120 min ditto ditto äito 0.25% e oxiaeraa 11.11- oil (II plus , 5 Él, 4 ~ dioxane 0.5% nitromethane 0.2% 1,2-butenoxy ditto ditto % e oxiäeraä lin- 3a (II§ plus O% 'methyl ethyl ketone 0% nitromethane % 1,2-butene oxide ditto ditto 0.2% epoxy octyl stearate ditto ditto 2% epoxy octyl stearate u 2/5 lgß-aioxane In nitromethane 0.5% epoxy-2-ethyl- hexystearate (III) known under the trade name . -Eaenoi ® ß 74 .and till- .available commercially from Henkel & Co ditto ditto ditto ditto 7 _ 7901448-6 Table 1 (continued) Stabilizer Time for steam to get angry Time for the liquid to get angry S% (III) plus W isopropyl nitrate , 5 t nitromethane f (III) plus I-butanol 'nitromethane Ä (III) plus -amyl alcohol nitromethane .n _ Us \\ Q .. f ~ n Q E * d ' IN. šäd ' _. 1 u % (III) plus w methyl ethyl ketone 3 in nitromethane CNC ONO OIUO ODJO Uävï M1 š \ no characters on acidity after 120 min ditto ditto ditto .no characters on acidity after 120 min ditto ditto ditto ditto ditto % (III) plus % isobutyl acetate % nitromethane % (III) plus 2-methyl-5-butynphâ-ol % nitromethane 9. \ n ëêm O 7% (III) plus 2 in 1,5-dioxolane 0.5% nitromethane 0 5 \)'IN I. x ,% acetaldehyde- dimethylhydrazone 0.5% epoxycyclohexyl- stearate (IV), known as the trade name Edenol HS 255 and available commercially from Henkel Go 0, §% (IV) plus 2 w isopropyl nitrate nitromethane u V1 Q .ditto ditto ditto ditto ditto ditto ditto ditto ditto ditto ditto ditto 7901448-6, 8 Table 1 (continued) seabiiisator mia gets the steam mia for the liquid to get angry to get angry 0.5 '54 (IV) plus no characters enter. sign 2% t-mlaikonol on aciaieet on aciaitet 0.5% nitromethane after 120 min after 120 min 0.5% (Iv) plus 2 ° / ø methyl ethyl ketone ditto ditto 0.5 "ß nitromethane ' 0.5 913 (Iv) plus 3.5% 1A-dioxane ditto ditto 0.5% nitromethane 0.5% (IV) plus s 2% isobutylacetate ditto ditto 0.5 "fw nitromethane 0.5% (IV) plus i 2 95 B-methyl-š-butyn-Z-ol ditto ditto 0.5% nitromethane 0.5% (iv) plus 2 96 lJ-dioxolan ditto ditto 0.5 ”ß nitromethane 0, 05 Sá acetaldehyde- dimethylhydrazone It is clear from these attempts that someone occurrence of aeidity did not occur in the vapor or in the liquid after the stipulated time period of 120 minutes, not even after Several hours. So tex. lnmde, with a stabilizing mixture, consisting of 0.5 in Edenol® B 516 plus 2,74 isopropyl nitrate and 0.5% nitromethane has no acidity occurring in the steam or in the liquid is not detected even after 14 hours. - f Comparative experiments For the sake of comparison, the above described, accelerated the heat stability test as well. for determination of. the time it took before acidity arose, determined. with -universal- indicator paper to pH 4, with lï, l'f, lli-trichloroethane, stabilized with stabilizing materials outside the scope of the invention.

Deer-held results are reported in the following bell 2. » 7901448-6 9 Table 2 Stabilizer Time for the steam Time for the liquid to get angry to get angry 0.2 26 l fi-butene oxide 5 min 25 min 2% isopropyl nitrate 0.5 ° / v nitromethane 4 min Ll- min 2,945 t-amyl alcohol 0.5% nitromethane 1.5 min 19 min 2% methyl ethyl ketone % nitromethane 20 min 20 min , 5 “ïá IA-dioxane 0.5% nitromethane 15 min _6 min % isobutyl acetate 0.5% nitromethane 2 min 5 min 2 96 2β-methyl-5-butyn-2-ol 0.5 90 nitromethane 5 min 20 min 2% β-dioxolane O, 5 ”Is nitromethane 0.05% acetaldehyde- 5 min 40 min dimethylhydrazone ä% isoprošylnitrnt 2% 1J-dioxolane g, 96 lß-butene oxide 5 min 10 min 95 nitromethane »5

Claims (9)

79n144s-6 m Claims 1, 1, 1, 1, 1-trichloroethane, characterized in that the red is stabilized by means of an epoxy-ester, obtained from a carboxylic acid, containing 12-20 carbon atoms, and from an alcohol containing 5-12 carbon atoms. 1,1,1,1-Trichloroethane according to claim 1, characterized in that the alcohol component from which the ester is obtained contains 3-8 carbon atoms. 1,1,1,1-Trichloroethane according to claim 1 and / or claim 2, characterized in that the epoxy ester is obtained from a carboxylic acid, containing an n-alkylalkylalkyb, alkenyl or cycloallcyl group and an alcohol, containing an n-alkyl fi isoallqfl fi alkenyl or cycloallcyl group, or a polyol. 1,1,1,1-Trichloroethane according to claim 5, characterized in that the epoxyalkyl ester is octyl epoxy stearate. A 1,1,1-trichloroethane according to claim 5, characterized in that the epoxyalkyl ester is butyl epoxy stearate. The 1,1,1-trichloroethane according to claim 3, characterized in that the epoxyisoalkyl ester is epoxy-α-ethylhexyl stearate. 1,1,1,1-Trichloroethane according to claim 5, characterized in that the epoxycycloalkyl ester is an epoxycycloheecyl stearate. 1,1,1,1-Trichloroethane according to claim 3, characterized in that the stabilizer: for 1,1,1,1-trichloroethane is a mixture of epoxyalkyl esters, obtained from long chain fatty acid or glycerol. The 1,1,1,1-trichloroethane according to claim 8, characterized in that the stabilizer is an epoxidized vegetable oil. 'lO. 1, 1,1-Trichloroethane according to claim 8, characterized in that the stabilizer is an epoxidized soybean oil. ll. The 1,1,1-trichloroethane according to claim 8, wherein the stabilizer is an epoxidized linseed oil. 12. N-tri-triioretane according to one of the preceding claims, characterized in that it also contains a stabilizing amount of one or more of the following conventional stabilizers, namely organic nitrates, -scuupuuav-p -í -------- -. -..___ 1, 7901448-6 nitriles, nitroallzanes, cyclic ether ethers having 5- to 6-membered rings, amines, alcohols, alkyl esters and acetones.