DE1296643B - Bis- (3-chloro-5-tertiary-butyl-6-hydroxyphenyl) methane and its use as an antioxidant - Google Patents

Description

The invention relates to the new compound bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane of the formula and the use of this compound as an antioxidant for petroleum hydrocarbons, mineral oil lubricants consisting of hydrocarbons and jet fuels consisting of hydrocarbons, which normally tend to decompose in the presence of air, oxygen or ozone and at elevated temperatures, preferably in amounts of 0.001 to 5 percent by weight, especially 0, 01 to 0.1 percent by weight, based on the substance to be protected.

It is known from US Pat. No. 3,043,775 that certain bis (3.5 dialkyl-4-hydroxyphenyl) methanes are suitable as antioxidants. It deals However, these are halogen-free compounds that have a stabilizing effect inferior to the bis (3-chloro-5-tert-butyl-o-hydroxyphenyl) methane of the invention are. U.S. Patent 2,671,813 and the Journal of the American Chemical Society, Vol. 74, 1952, pp. 3410 and 3411 it is mentioned that produced by condensation of certain substituted phenols with formaldehyde Bis (5-halo-6-hydroxyphenyl) methanes are mild antioxidants. The inventive New connection has a different one compared to these known connections Structure and a far superior stabilizing effect.

Most of the time, the new compound according to the invention will normally be substance sensitive to air, oxygen or ozone in an amount from 0.001 to 5 percent by weight, preferably 0.01 to 0.1 percent by weight, added.

Liquid and solid petroleum hydrocarbons are obtained through the addition of the antioxidant according to the invention has a greatly increased shelf life. For example, gasoline, jet fuel, kerosene, heating oil, turbine oils, insulating oils, Motor oils and various waxes have increased stability against oxidation when they are contain the antioxidant according to the invention. Similarly increases the oxidation stability of liquid hydrocarbon fuels with organometallic Additives such as tetraethyl lead and other organometallic as fuel additives compounds used, considerably if they are the new antioxidant according to the invention contain.

The novel bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane according to the invention is generally an excellent stabilizer additive to tetraalkyl lead anti-knock agents, which are added to the fuel. The anti-knock agent mixtures stabilized according to the invention may also contain organic halogen compounds that are effective as detergents, which become volatile with the lead during the combustion process React lead halides. In addition, other ingredients, such as dyes, as a means of identification, metal deactivators or diluents present be. Gasolines with the additives mentioned are used both before and after Addition of anti-knock liquid by the new compound according to the invention is favorable affects and show a prolonged storage stability.

In addition to the increased shelf life, machine oils and Functional fluids, such as automatic transmission and hydraulic fluids based on hydrocarbons, due to the compound according to the invention a high Resistance to oxidation at elevated temperatures. With the invention Antioxidant-added lubricating oils exhibited even at extremely high temperatures no oxidative degradation.

The addition of small amounts of the compound according to the invention to hydraulic, Transformer or other highly purified industrial ells and crankcase lubricating oils and lubricating greases made from these Ulen by the addition of metallic soaps are increased their resistance to degradation in the presence of air, oxygen or ozone is considerable.

In addition, they are used in the manufacture of the lubricating greases Metal soaps for their part are stabilized by using the compounds according to the invention.

The antioxidant according to the invention is also suitable for protection of paraffins and microcrystalline petroleum waxes against oxidative degradation.

The mineral lubricating oils according to the invention against oxidation are those that are made from naturally occurring crude oil Distillation and other refining processes well known in the art will. These Ule include lubricating and industrial oils, such as crankcase oils, Transformer oils, turbine oils, transmission fluids, cutting oils, industrial Ule, mineral white oils, glass tempering oils, with soaps and inorganic thickeners (Fats) thickened Ule and, in general, machine and oil derived from crude oil Industrial oils, which are normally exposed to air and especially at higher temperatures especially in the presence of metal-containing catalysts such as iron, iron oxide, Copper and silver are subject to decomposition.

The stabilized by adding the antioxidant according to the invention Lubricant compositions can effectively contain other known additives, like other inhibitors, surface-active dispersants, pour point depressants, Viscosity index improvers, antifoam agents, rust inhibitors, lubricity improving agents or agents which strengthen the film, as well as dyes, can be added. The inhibitors which can be used together with the additive according to the invention include including sulfurized whale oil, sulfurized terpenes, sulfurized paraffin wax olefins, aromatic sulfides, alkylphenol sulfides, lecithin, neutralized dithiophosphates, Phosphorus pentasulphide terpene reaction products, diphenylamine, phenylnaphthylamine, tS-naphthol and pyrogallol. As examples of the surface-active dispersants be metal soaps of higher molecular acids, such as aluminum naphthenates, calcium phenyl stearates, Calcium alkyl salicylates, alkaline earth petroleum sulfonates, alkaline earth alkylphenol sulfides (e.g. B. barium amylphenol sulfide, calcium octylphenol disulfide) and metal salts with wax-substituted Phenol derivatives listed. As a viscosity index improver and pour point depressants can effectively be polymeric methacrylic acid esters higher fatty alcohols and the corresponding polymeric esters of acrylic acid and higher fatty alcohols can be used.

The compound of the invention is available as an additive to steam turbine oils particularly effective. This is shown when testing according to the standard test procedure ASTM-D-943-54 of the American Society for Testing Materials. Be in this test 300 ml of a suitable test oil was brought into contact with 60 ml of water and the resulting Oil-water mixture kept at 950 C while passing 3 liters of oxygen every hour through it, the oxidation being catalyzed by iron and copper wire. They became regular Measurements of the acid number of the test oil are carried out in the absence of an antioxidant to over 2.0. In contrast, the addition resulted in less, for stabilization sufficient amounts of the compound according to the invention to steam turbine oils noticeable resistance to oxidative degradation.

The novel compound of the present invention is also extremely effective as an antioxidant for natural and synthetic elastomers made from high molecular weight, unsaturated hydrocarbon polymers, e.g. B. natural and synthetic, optionally oil-expanded rubbers vulcanized with sulfur.

Examples of such elastomers are polybutadiene, methyl rubber, Polybutadiene rubber, butyl rubber, SB-R rubber, GR-N rubber, piperylene rubber, Dimethyl butadiene rubber. Generally stabilized against oxidative degradation Hydrocarbon polymers and elastomers, polymers such as polystyrene, polybutadiene, Polyisobutylene, polyethylene, isobutylene-styrene copolymers.

Other polymers that can be stabilized according to the invention are polyvinyl chloride, Polyvinyl acetate, various epoxy resins, polyester resins and polymers including Alkyd resins and monoolefin polymers such as polyethylene and polypropylene.

Bis- (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane is also an effective antioxidant for synthetic lubricants based on organic compounds that contain other elements besides carbon and hydrogen contain. Examples are diester lubricants, silicones, halogenated, organic compounds including fluorocarbons, polyalkylene glycol lubricants and organic phosphoric acid esters suitable as hydraulic fluids and lubricants.

The novel compound of the present invention can be used in a variety of diester oils those described in Industrial and Engineering Chemistry, Vol. 39, 1947, pp. 484-491 Species are added as antioxidants. So it is particularly suitable for Stabilization of diesters produced by esterification of straight-chain, dibasic Acids with 4 to about 16 carbon atoms with saturated, straight-chain or branched ones monohydric alcohols having 1 to 10 carbon atoms can be obtained.

The most common diester lubricants are created by esterification one mole of a dicarboxylic acid of the formula HOOC (CH2) xCOOH in which x is a number of 2 to 8 means with 2 moles of a branched chain alcohol having at least 4 carbon atoms and have molecular weights from about 300 to about 600 and freezing and pour points from around -400C down to around -730C.

Their flashpoints and focal points are between about 150 and about 2600 C and their auto-ignition temperatures between about 35 and 430 "C.

Another class of synthetic lubricants using the invention The silicone lubricants are of increased oxidation stability. For naming more specific Compounds is established by the American Chemical Society Committee on Nomenclature, Spelling and Pronunciation (Chemical Engineering News, 24, 1946, 1233) recommended Notation can be used. This is how compounds with Si-O become Si bonds as siloxanes, derivatives of the silane Sie4, in which one or more water atoms pass through organic groups are replaced as silanes, silicates and silicate ester compounds referred to as silanoxy derivatives, i.e. as alkoxy- or aryloxysilanes.

As base materials for the lubricant compositions stabilized according to the invention Serving silicone oils and fats include polysiloxane oils and fats of the type Polyalkyl, polyaryl, polyalkoxy, polyaryloxysiloxanes, e.g. B. polydimethylsiloxane, Polymethylphenylsiloxane and polymethoxyphenoxysiloxane. Furthermore, silicate ester oils, such as tetraalkyloxy and tetraaryloxysilanes, e.g. B. those from tetra-2-ethylhexyl and tetra-p-tertiary-butylphenyl type as well as the silanes can be used. This also includes the halogen-substituted siloxanes, such as chlorophenylpolysiloxanes.

Polyalkyl-, polyaryl- and polyalkylpolyarylsiloxanes which contain the inventive Containing antioxidants, possess a range over a wide temperature range extensive, high oxidation stability.

The polyalkylsiloxanes, such as dimethylpolysiloxane, are used because of their within a wide temperature range compared to extremely low changes in viscosity the polyaryl and polyalkyl polyarylsiloxanes are generally preferred.

The novel antioxidant according to the invention is suitable for stabilizing certain halogen-containing organic compounds which, due to their physical properties, are especially suitable as lubricants. They usually contain chlorine or fluorine as halogen. Such fluorocarbon lubricants are linear polymers with a repeating group of the formula: Typical examples of chlorinated organic lubricants are chlorodiphenyl, chloronaphthalene, chlorodiphenyloxides and chlorinated paraffin waxes.

Other lubricants stabilized by the compound of the invention are polyalkylene glycol lubricants, usually made by reacting an aliphatic Alcohol with an alkylene oxide, especially ethylene oxide and propylene oxide, are formed.

Depending on the alcohol used and the molecular weight of the connection can Polyalkylene glycol lubricants either be water-insoluble or water-soluble. The molecular weights of these polymers can vary between about 400 and more than 3000. In general, the polyalkylene glycol lubricants are characterized by high viscosity index, low API density and low pour points. They have the general formula R - (-0- CnH2 n) xOH in which n is some low whole Number, x is a number between about 10 and about 100 and R denotes from the aliphatic Alcohol-derived hydrocarbon radical means.

Another class of synthetic substances improved by the antioxidant according to the invention are phosphoric acid esters, which generally have the following formula: in which R, R 'and R "represent hydrogen atoms or organic radicals and at least one of the radicals R is an organic radical. A typical example of these substances is tricresyl phosphate. These phosphoric esters are generally characterized by excellent fire resistance and high lubricity.

For the preparation of the lubricant compositions stabilized according to the invention The fats used can be made into one of the above by adding a soap Ele produced.

Such soaps come from animal or vegetable fats or Fatty acids, wool fat, resin or petroleum acids. Typical examples are lead oleate, Lithium stearate, aluminum tristearate, calcium glycerides and sodium oleate. About that In addition, the polyester fats cannot convert unreacted fat, fatty acid and alkali saponifiable substances such as glycerine and fatty alcohols, resin or wool fat, water and contain certain additives acting as modifiers or peptizers.

Those are particularly suitable for the stabilization according to the invention Fats obtained by mixing lithium soap with polyester oils, because compared to other soaps such as sodium, calcium or lead soaps, mixed fats have a higher resistance to oxidation.

The lubricant mixtures to be stabilized are mixed with a suitable Amount of bis43-chloro-5-tert-butyl-6-hydroxyphenyl) methane mixed. Possibly can previously concentrated solutions of the stabilizer in the base lubricant and then with further lubricant to the desired Concentration can be diluted.

An advantage of the compound according to the invention is that it is easy and rapid miscibility of bis (3-chloro-5-tertiary-butyl-6-hydroxyphenyl) methane and in its relatively low melting point that under normal conditions of use eliminates the risk of the stabilizer separating out of the lubricant. Another advantage of the invention is the extremely good compatibility of Bis- (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane with the often used for reinforcement the Lubricant compositions used common additives such as dispersants, Viscosity index improvers, dyes, rust inhibitors and defoamers.

In addition, the compound of the invention is also useful as an antioxidant for animal or vegetable fats and (: oils, such as butter, lard, beef tallow, Fish oils, such as cod liver oil, castor oil, soybean oil, rapeseed oil, coconut oil, olive oil, Palm oil, wheat oil, sesame oil, peanut oil, babassu oil, citrus oils, cottonseed oil and various compositions containing such materials as nut butters, peanuts and others whole nuts, preparations for salad, margarine and other vegetable shortening as well as certain foods made from animal fats that tend to go rancid and fatty animal feed and fish meal used as animal feed against rancidity usable during storage. The mixtures mentioned are not only anti-oxidative Protected against degradation, the admixture of the compound according to the invention rather has the effect also a prevention of the breakdown of vitamins A, D and E as well as certain B vitamins.

The effectiveness of the compound of the invention as an antioxidant for fats is shown when the Norma-Hoffman-Grease-Oxidation-Stability-Test is carried out according to ASTM test method D-942-50. The presence of small amounts of the invention Compound in conventional fats considerably reduces the oxidative breakdown.

When using the compound of the invention as an antioxidant for non-petroleum based fats and ole can increase the effectiveness the additives according to the invention still use an acidic, synergistic substance, z. B. citric acid, phosphoric acid, ascorbic acid, acidic ethyl phosphate, glucuronolactone, Phytic acid, tartaric acid and aconitic acid.

For the preparation of the new compound bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane 4-chloro-6-tert-butylphenol is used with formaldehyde in the presence of an alkali metal hydroxide and a low molecular weight, aliphatic alcohol, preferably ethanol or Isopropanol, as a solvent.

The reaction is carried out at temperatures between 20 and about 90.degree and takes half an hour to around 40 hours, depending on the temperature used.

The bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane obtained is made by stripping off the solvent and then distilling the reaction residue separated under reduced pressure.

Production of bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane a) In one equipped with a reflux condenser, heater, stirrer and filler neck Reaction vessel were 3142 parts of isopropanol and 66 parts of potassium hydroxide up to complete dissolution of the potassium hydroxide, then stirred with 1846 parts of 4-chloro-6-tert-butylphenol added and the mixture was heated to 45 ° C. At this temperature, 420 parts a 36.30/0 formaldehyde solution was added in portions. The overall mix was kept at 45 ° C. with stirring for 6 hours, then cooled to room temperature and finally acidified with about 200 parts of dilute hydrochloric acid. The acidified Mixture was made with about 5500 parts of petroleum ether are added, the isopropanol extracted with water and the aqueous layer discarded. The organic layer was then distilled through a column filled with spirals and thereby 665 parts Obtained bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane; Bp 0.3: 209 to 213 ° C.

Part of this compound was recrystallized from petroleum ether and here pure bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane of melting point 114 to 14.50C.

C21H26Cl2O2: Calculated ... C 66.1, H 6.8, Cl 18.60 / o; found . C. 64.0, H 6.6, Cl 19.6%.

An infrared spectrum of the compound showed bands of a partial hindered hydroxyl of a bisphenol compound. The ones from the infrared spectrum certain ring substituents gave a 1,2,46 substituted benzene ring. b) 4-chloro-6-tert-butylphenol was in isopropanol as solvent with 37%, aqueous formaldehyde in the presence of potassium hydroxide as a catalyst for 17 hours implemented at reflux temperature. It was worked in the following way: That The reaction vessel was initially filled with 19 parts of potassium hydroxide in about 100 parts of isopropanol charged and then flushed with nitrogen. Then 61 Parts of 4-chloro-6-tert-butylphenol and about 7 parts of formaldehyde in the form of a 37%, aqueous solution added.

After the addition of the formaldehyde, the reaction mixture was under Heated to reflux. After the reaction, the mixture was taken up in n-hexane, washed well with water, dried and the isopropanol at reduced pressure distilled off. A viscous oil remained behind during its fractional distillation 26% of the starting phenol, 5% 6-tert-butyl-4-chloro-2-hydroxymethylphenol (bp 0.5 : 125 to 127 ° C) and 11% bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane with a boiling point of 180 to 220 ° C at 0.5 Torr and a melting point of 109 up to 1100 ° C was obtained. The structure of the compound was determined by infrared analysis confirmed.

The following examples explain the use of bis (3-chloro-5-tertiary-butyl-6-hydroxyphenyl) methane as an antioxidant according to the invention.

The physical properties of those used in the examples Hydrocarbon oils are listed in Table I.

Table I Properties of the petroleum hydrocarbon oils used in the examples Ule ABC API density at 60 "C 30.3 30.5 20.5 Viscosity Saybolt Seconds at 380C. 178.8 373.8 249.4 Seconds at 99 ° C .. 52.0 58.4 45.7 Viscosity index ...... 154.2 107.4 35.8 Pour point. . ........ -30 +10 Flash point ....... 410 465 365 Sulfur content in% .... 0.2 0.3 0.3 EXAMPLE 1 12 parts (0.01 20 / o) of bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane are added to 100,000 parts of CII A with stirring. The CII shows an improved resistance to oxidative degradation.

Example 2 To 100,000 parts of oil B, 2000 parts (2%) of bis (3-chloro-5-tert iär-butyl-6-hydroxyphenyl) methane given. When this mixture is stirred, it arises a homogeneous solution with increased resistance to oxidation.

Example 3 To 100,000 parts of CII C are 5 parts (0.0050 / o) Bis- (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane added. After mixing the oil has an increased resistance to oxidation.

Example 4 To 100,000 parts of di-secondary amyl sebacate with a viscosity of 33.8 Saybolt Universal Seconds (SUS) at 99 ° C, a viscosity index of 133 and a molecular weight of 342.5 are 100 parts (0.1%) of bis (3-chloro-5-tert-butyl-6-hydroxy) methane given. The obtained diester lubricant has significantly increased durability against oxidative degradation.

Example 5 To 100,000 parts of di (2-ethylhexyl) adipate with a viscosity of 34.2 SUS at 99 ° C, a viscosity index of 121 and a molecular weight of 37.6, 5000 parts (5%) are bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane given.

Once mixed, the resulting diester lubricant has a excellent resistance to oxidative degradation.

Example 6 5 parts of bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane are with 2495 parts of diisooctyl azelate with a kinematic viscosity of 3.34 cSt at - 54 ° C (ASTM 445-52 T), an ASTM drop of 0.693 between -40 and + 99 ° C (ASTM D-341-43) and a pour point of -65 ° C (ASTM D-97-47). Its flash point is 218 ° C (ASTM D-92-52), and its specific gravity is 0.9123 25 ° C. The resulting lubricant shows an extremely high oxidation stability.

Example 7 To increase the resistance to oxidation of a fat 3 parts of bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane with 197 parts a fat made of 12.5% lithium stearate, 1 part polybutene (molecular weight 12,000), 2% calcium xylyl stearate and 84.5% di- (2-ethylhexyl) sebactate mixed.

Example 8 To increase the resistance to oxidation of a fat 8 parts of bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane with 920 parts a fat of 12% lithium stearate, 1% polybutene (molecular weight 12,000), 2% calcium xylyl stearate, 34, () $ () di- (2-ethylhexyl) sebacate and 51% di- (2-ethylhexyl) adipate mixed.

Example 9 10 parts of bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane are mixed with 10,000 parts of a fat of 110/0 lithium stearate, 10/0 polybutene (molecular weight 12000), 1% sorbitol monooleate and 86.6% di- [1 [1- (2-methylpropyl) -4-ethylocytl] sebacate mixed.

Example 10 On a siloxane liquid made from a halogen-substituted one Polyphenylpolymethylsiloxane with a viscosity of 71 cSt at 25 "C and 24 cSt at 75''C, a specific gravity of 1.03 at 25 C, a freezing point at -70 ° C and a flash point of 282 ° C is bis (3-chloro-5-tertiary-butyl-6-hydroxyphenyl) methane added in an amount of 1.5%. Due to its content, this oil mixture has Bis- (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane has an extremely high resistance against oxidative degradation.

Example II To a phenylmethylpolysiloxane fluid with a Viscosity from 100 to 150 cSt at 25 ° C, a shell flash point of 302 ° C (ASTM D-92-; 3), a freezing point of -51 ° C and a specific gravity of 1.07 At 25 ° C., 0.1 (1/1 bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane is added.

Example 12 By dissolving bis (3-chloro-5-tertiary-butyl-6-hydroxy-phenyl) -methyan a lubricant is obtained in tribenzyl-n-hexadecylsilane (boiling point 245 to 248 ° C.) with improved resistance to oxidation.

Example 13 A batch with 0.010 / o bis (3-chloro-5-tertiary-butyl-6-hydroxyphenyl) methane is made into a fluorocarbon grease by adding an appropriate amount of this compound with a penetration of 267 mm at 25 ° C, 285 mm at 38 ° C and 300 mm at 52 ° C (ASTM 217-48) and a drop point of at least 204 ° C (ASTM D-566-42).

Example 14 To a polyalkylene glycol oil lubricant having a viscosity index of 148, an ASTM pour point of -48 "C, a flash point of 150 C, a density of 0.979 and a Saybolt viscosity of 135 at 38 "C are 10 /, bis- (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane added, making a highly oxidation resistant polyalkylene glycol lubricant is obtained.

Example 15 A lubricant with increased resistance to oxidation based on a chlorinated, organic compound is made by adding 0.5% bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane to a chlorodiphenyl oil from the boiling range 260 to 325 ° C, a Saybolt viscosity of about 49 at 38 "C, a Pour point of -34 "C and a density of about 1.267 produced.

Example 16 A hydraulic fluid that also acts as a lubricant is effective, with improved resistance to oxidation, adding 20 /, Bis- (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane produced to tricresyl phosphate.

Example 17 Panel coker tests were conducted using a Petroleum hydrocarbon lubricating oil carried out.

In this test, which is in the Aeronautical Standards of the Departments of Navy and Airforce, Spec.

MIL-L-7808C dated November 2, 1955, is resistance to oxidation measured by rushes at elevated temperatures in the presence of air, the ele periodically come into contact with a hot metal surface. In the trials a commercially available di- (2-ethylhexyl) sebacate without additives was used as a diester lubricant used. The test was modified in such a way that the "Panel Coker" device 10 hours at 288 ° C was operated in a cycle by the spray nozzle in each 5 Seconds in operation and then each 55 seconds was out of operation. After this At the end of the experiment, the degree of decomposition was different among these Oils tested for high temperature oxidation conditions by weighing them on the metal plate formed deposits determined. The base oil used consisted of an initial one Additive-free, solvent-refined, commercially available neutral mineral lubricating oil with a viscosity of 200 SUS at 38 "C and a viscosity index of 95. Es it is found that the additive-free CI1 under the above experimental conditions There was 434 mg of deposit on the plate. However, if the oil is 1 percent by weight Bis- (3-chlorop-5-tert-butyl-6-hydroxyphenyl) methane had been treated there was only 82 mg of deposit on the plate.

Example 18 To further demonstrate the effectiveness of bis (3-chloro-5-tertiary-butyl-6-hydroxyphenyl) methane experiments with a highly refined mineral oil were used as an antioxidant a viscosity index of 106.5 and a viscosity of 87.1 SUS at 380 ° C. The CII was in separate samples (with and without addition of the compound according to the invention) placed in a device for measuring the oxidation stability of the oil, which from a 12 ccm glass vessel with a mercury manometer connectable Inlet pipe consists. After filling the DI, the vessel is filled with oxygen at atmospheric pressure rinsed out, then connected to the mercury manometer and then into a The bath was immersed constantly at 150 "C, causing changes in oxygen pressure are displayed on the pressure gauge. The manometer is observed until it is in the vessel a rapid pressure drop occurs, from immersion to the beginning of the Time elapsing pressure drop evaluated as the induction time of the CIls. All Iron (III) hexoate is used as an oxidation catalyst to test the test conditions added, the iron salt concentration, calculated as Fe2O3, being adjusted to 0.05% will. The amount of oil introduced is 1 ml for each test Testing of this type, the base oil has an induction time of 2 to 3 minutes, which is its total Proves that it is not resistant to oxidative degradation at 150 ° C. If on the other hand the oil Contains 0.01 mol of bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane per liter, the induction time is 349 minutes. Thus, the stability of the DI increased by a factor of about 115 to 175 compared to the original value.

Example 19 Further evidence of the effect of the invention The Polyveriform Oxidation Stability Tests provide compound as an antioxidant, in the article "Factors Causing Lubricating Oil Deterioration in Engines" in Industrial and Engineering Chemistry, Analytical Edition, 17, 1945, 309, as well as in the article “A Bearing Corrosion Test for Lubricating Oils and its Correlation with Engine Performance "in Analytical Chemistry, 21, 1949, 737. With this test one can use the mode of action of lubricating oil antioxidants evaluate. The test device, the test method used, and the relationship between the results obtained and the work in the engine are mentioned in the first of these Articles discussed.

The extent of the oxidation taking place in the test is expressed in values the acid number and the increase in viscosity of the OIs were measured. For example, was in a test series according to the first-mentioned reference, but without the one there steel and copper test sample described, an additive-free lubricating oil compared with the same CII, but the additive I weight percent bis- (3-chloro-5-tert-r-butyl-6- hydroxyphenyl) methane.

In order to obtain the most stringent test conditions possible, 20 hours were allowed about 48 liters of air passed through the CIl kept at 150 ° C. every hour for a long time.

The additive-free UI had an acid number of 6.0 and after the end of the test a viscosity increase of 1030/0. In contrast, it was 1 percent by weight Bis- (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane-containing sample has an acid number of only 1.6 and exhibited a viscosity that was only 23% higher.

In addition, that was stabilized with the compound of the invention CII remained sludge-free.

Example 20 To further demonstrate the advantages that can be achieved according to the invention experiments with a diesel oil for electric motors with a viscosity index of 54 and a SUS viscosity of 919 at 38 ° C. This test will the oil is heated to 163 ° C. for 120 hours while stirring, to promote oil decomposition two metal catalysts, namely a silver-plated bolt bearing bush and a copper metal catalyst, were added.

The decomposition is determined by the acid number measured after the end of the experiment and determined by the percentage increase in viscosity at 38 ° C. Also shows the nature of the silver sample indicates poor oil performance. A sample The oil used in this experiment contained a commercially available zinc dithiosulphate in an amount of 0.02 percent by weight based on sulfur. In this test rose the acid number of the CIls to 2.6, and the viscosity increased by 47 ° / 0. However, it was a CII with 4% barium sulfonate and 0.05 percent by weight bis (3-chloro-5th tertiary-butyl-6-hydroxyphenyl) methane Subjected to these test conditions, the final acid number was only 0.5 and the viscosity had only increased by 31%. In addition, the silver sample survived the test essentially unchanged.

Example 21 To 10,000 parts of a 115/145 aviation fuel with 1.18 ml of tetraethyl lead per liter, an initial boiling point of 43 ° C and an end boiling point of 166 "C and an API density of 71.0" are 0.50 / 0 bis (3-chloro-5-tertiary-butyl-6. hydroxyphenyl) methane admitted.

Example 22 1000 parts of melted pork fat are mixed with 1 part (0.1 0 / o) bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane mixed. After this When cooled, the lard can be stored for a long time without becoming rancid.

Example 23 To 10,000 parts of corn oil are added 5 parts with stirring (0.05%) bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane and 2 parts (0.02%) Ascorbic acid added. The resulting corn oil has improved shelf life.

Example 24 100 parts heated to 82 ° C (from a partially hydrogenated, vegetable CII produced) monoglyceride are stirred with stirring Bis- (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane and 4 parts of citric acid were added. 10 parts of the resulting monoglyceride batch become 10,000 parts with stirring added melted pork fat. The lard composition thus formed with a content of 0.0050 / o bis (3-chloro-5-tertiary-butyl-6-hydroxyphenylfmethane and 0.0040 / o citric acid can be stored for a long time at room temperature, without going rancid.

Example 25 To the strong increase in the thermal stability To show application of the method according to the invention, tests were carried out in an as Coordinating Fuel Research (CFR) Jet Fuel Coker known device carried out. Experimental procedure and apparatus are in Petroleum Processing, December 1955, Pp. 1909 to 1911, and described in Coordinating Research Council Manual No. 3. In this device, a jet fuel is pushed through a pressure of 68 kg / cm2 Preheating tube with centrally mounted heating element pressed through to it to a predetermined Bring temperature. The heated fuel is then passed through a hot filter pressed from sintered steel into a second tube. If the fuel is increased at the If the temperature decomposes, the filter becomes clogged and a pressure drop occurs on him, which is measured by a pressure gauge bridging the filter. The following Attempts were continued until the fuel decomposed on the filter a pressure drop of 635 torr occurred, or after 300 in the absence of a pressure drop Minutes canceled. In all experiments, the flow rate of the Fuel to 2.72 kg / hour. held.

Jet fuels stabilized with the compound according to the invention were made by adding bis- (3-chloro-5-tertiary-butyl-6-hydroxyphenyl) methane made to samples of three different commercially available JP-5 fuels, which meet all the requirements of the above-mentioned requirements with the exception of the thermal Satisfied stability properties. In these tests with JP-5, each fuel sample was also examined without the addition of the compound according to the invention. the Test conditions were set so that the preheater temperature was 204 ° C and that of the filter was 2600 ° C. The results of these tests are shown in the table II listed.

Table II JP-5 fuels with and without bis (3-chloro-5-tertiary-butyl-6-hydroxyphenyl) methane Bis (3-chloro-5-tertiary pressure drop Kraft-butyl-6-hydroxy-am filter trial time substance phenyl) methane Concentration kg / m3 torr minutes J 0 635 91 J 0.37 1.5 300 K 0 635 39 K 419 10.7 300 The values listed in Table II show the extraordinary improvements in the thermal stability of both fuels with the addition of 0.37 and

0.19 kg / m3 additive for the fuels examined.

Besides the big improvements in filter clogging reduction there are other advantages.

The fuel J containing no additive decomposed during of the 91 minute test so far that 20% of the surface of the preheater tube were covered with black, dark brown and yellow-brown decomposition products. When adding 0.37 kg of bis (3-chloro-5-tertiary-butyl-6-hydroxyphenyl) methane each Cubic meters of fuel, the deposits went down to a very faint yellow-brown Approach back, improving the nature of the precipitation on the Displayed preheater tubes. Similarly, when studying the fuel K without addition during the 39 minute test, a total of 700 '() of the preheater surfaces covered with dark brown to light yellow brown precipitates. In contrast, decreased when 0.19 kg of the compound according to the invention is added per cubic meter of fuel the total precipitation area after 300 minutes of test duration to 10%, and the Precipitation was light yellow-brown to brown. In both cases, therefore, was through - use of bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane is a great improvement of fuel reached.

Example 26 To further illustrate the effect of the invention Connection to the thermal stability properties of jet fuels was made attempted a commercial J P-4 fuel. In this attempt the preheater temperature was kept at 1500 C and the filter temperature at 205 ° C. The other test conditions were the same as described above. Of the Additive-free fuel showed a pressure drop of 635 at the filter after 109 minutes Torr, and during this time 40% of the preheater surfaces were brown coated to yellow-brown precipitates. When adding 0.1 kg of bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane per cubic meter of fuel there was a total pressure drop of only 2.5 Torr during a trial period of 300 minutes.

In addition, the preheater surfaces were under these conditions perfectly clean. This attempt further proves the extraordinary ability of the compound according to the invention, even in a low additional concentration, the thermal To reduce stability problems of jet fuels.

Comparative experiments The stabilizing effect of bis- (3-chloro-5-tertiary- butyl-6-hydroxyphenyl) methane (compound according to the invention "AN-105") and bis (3,5-di-tertiary-butyl-4-hydroxyphenyl) methane (Compound “AN-2” according to US Pat. No. 3,043,775) to hydrocarbon products examined.

1. Stabilizing effect against hydrocarbon mineral oil lubricants The "Polyveriform test method" described in Example 19 was used.

In each case 100 ml samples of a neutral, solvent-cleaned mineral oil which contained 0.1 percent by weight Fe2O3 as iron (III) (2-ethylhexoate) and 0.05 percent by weight lead bromide were examined. In addition to the samples each protected with a comparison compound, unprotected samples were also examined. The degree of mineral oil decomposition in the individual samples, determined from the increase in acid number and the percentage increase in viscosity, can be seen in Table III below: Table III Concentration viscosity Addition tration acid number increase increase None ~ 5, 6, 5.6 89 AN-105. . . . . . . . 1.0 1.7 4 None .......... - 5.6 130 AN-105. . . . . . . 1.0 1.8 23 None ~ 5,6 5,6 130 AN-2. . . . . . . . . . to 1.0 4.9 92 None ........... - 6.4 92 AN-105. . . . . . . . 0.5 2.7 21 None ........... - 5.86 113 AN-2. . . . . . . . . . 0.5 4.63 82 As can be seen, the compound according to the invention is far superior to the comparative product in its stabilizing effect on hydrocarbon mineral oil lubricants.

2. Stabilizing effect on hydrocarbon jet fuels The properties as an antioxidant for jet fuels at high temperature were determined by the fact that stabilized or unstabilized fuel (Ashland JP-5 fuel) from one Container over a preheater was passed into a liauplheizkammer, where as a result of the heat effect a certain amount of fuel decomposed, which by measuring the on one of the heating chambers downstream filter remaining residue was determined. The temperature in the preheater was 204 "C, in the main heating chamber 2600 C. The pressure change (n P) determined in the fuel when passing through the filter.

The maximum duration of a single experiment was 300 minutes, with the attempt was terminated before a pressure change of # P = 25 Torr was reached and the respective term was noted. The test results are in the following Given in the table.

Table IV Concentration Comparative Additional tration AP in Torr duration up to SP g / l minutes None ............ - 25.0 39 AN-2. . . . . . . . . . 0.11 25.0 79 AN-105 ........... 0.14 4.2 300 Even if the concentration of the compound according to the invention was somewhat higher than in the comparison case, the stabilization result, which is orders of magnitude better, clearly proves the superiority of the compound according to the invention.

In addition, the stabilizing effect of bis (3-chloro-5-tertiary-butyl-6-hydroxyphenyl) methane (compound according to the invention) with the stabilizing effect of bis- (3-tertiary-butyl-5-chloro-6-hydroxyphenyl) - methane according to U.S. Patent 2,671,813. It was again the one already described Polyveriform test method «applied. There were 100 ml samples each of a neutral, solvent-cleaned mineral oil that contains 0.05 percent by weight Fe2O3 as iron (III) -2-ethylhexoate and 0.1 percent by weight of lead bromide.

One of the compounds to be tested was added to each of these samples, while a comparative sample remained free of antioxidants. The samples were subjected to the same temperature and oxidation conditions, whereby the on 149 ° C heated samples for 20 hours air in an amount of 48 liters per hour became. Afterward the acid number and the viscosity of the sample were investigated. The increase in acid number and viscosity is a measure of the degree of oxidation.

The results of this experiment are shown in the following table: Table V Concentration viscosity viscosity acid number tration Additional increase Weight gain @ percent None ...................... - 7.6 136 link according to USA. Patent specification 2671813 1,0 7.1 129 Inventive appropriate Connection .. 1.0 1.6 26 This experiment shows that the compound according to the invention bis- (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane is an extremely effective antioxidant, while the known isomer is poorly effective.

Claims (1)

Claims: 1. Bis- (3-chloro-5-teritarian-butyl-6-hydroxyphenyl) methane of the formula 2. Use of bis (3-chloro-5-tert-butyl-6-hydroxyphenyl) methane as an antioxidant for petroleum hydrocarbons, mineral oil lubricants made of hydrocarbons and jet fuels made of hydrocarbons, which are normally in the presence of air, oxygen or ozone and with Tend to decompose at elevated temperatures, preferably in amounts of 0.001 to 5 percent by weight, especially 0.01 to 0.1 percent by weight, based on the substance to be protected.