Salicylic acid alkylation method

FIELD: chemistry.

SUBSTANCE: invention pertains to perfection of the method of obtaining alkylsalicylic acids. The method involves reaction of salicylic acid with an olefin, containing at least four carbon atoms, at high temperature in the presence of alkylsulfonic acid as a catalyst. The invention also pertains to a composition for obtaining additives to lubrication oils, containing alkylsalicylic acid obtained using the above mentioned method. The obtained product has low content of alkylphenols and good colour. Its acid number is 60-95% of the theoretical value. The values of the results of PDSC testing (pressure differential scanning calorimetry) and "panel coker" test are comparable with or surpass the corresponding values for the control salicylic detergents produced in the industries.

EFFECT: obtaining a product of alkylation of salicylic acid with low content of alkylphenols and good colour.

20 cl, 12 ex

 

The level of technology

1. The technical field to which the invention relates

This invention relates to the alkylation of salicylic acid with olefins long chain. Received alkylsalicylate acid can be treated with excess amount of alkali and get useful additives for lubricating oils.

2. Description of the prior art

Know the use of salts of alkaline-earth metals organic carboxylic acids as additives to compositions of lubricating oils. Mentioned salts possess dispersing ability, which helps to ensure the purity of the internal parts of the engine and prevents the deposition of carbon products on the pistons and on the grooves of the pistons, thereby preventing sticking of the piston and rings.

Known also getting alkaline or strongly alkaline) salts of such acids and alkaline-earth metals. Excessive alkalization provides a supply of alkali, which when used in lubricating compositions react with acidic compounds to neutralize acidic compounds formed during operation of the engine in which the use of this composition. As a result, any contamination that may occur dispersed due to the dispersing effect of salt and acid, which would enhance formed the e pollution, neutralized.

High-alkaline salicylates obtained by excessive alkalizing corresponding alkyl salicylic acids. The alkyl group typically represents an alkyl group with a long chain containing more than 14 carbon atoms, which gives the acid solubility in oil. Alkylated salicylic acid is usually obtained by alkylation of phenol with the formation of alkylphenol and subsequent carboxylation of alkylphenol by the reaction of the Kolbe-Schmitt, which gives alkilirovanny salicylic acid. In addition to adverse economic factors associated with the use of high temperatures and/or pressures, the way to get alkyl salicylic acids by the reaction of the Kolbe-Schmitt is complicated by the fact that not all APS with long chain easily carboxydismutase at alkylation mostly linear connections. Specifically, conventional alkylation of phenol linear alkylating agent to give a mixture (about 50:50) ortho-alkylphenol and para-alkylphenol. Received a para-alkyl phenol with long chain easily carboxylases by the reaction of the Kolbe-Schmitt, whereas ortho-alkylphenol with long chain less reactive, and only about 70% of the total number of alkylphenol derived from essentially linear alkylating agent, usually turns into alkilirovanny sa is illovo acid during this reaction.

One way to get around this problem is to alkilirovanii alkylsalicylate (e.g., methyl salicylate) and then to hydrolyze received alkilirovanny alkylsalicylate in order to get alkilirovanny salicylic acid. Methods of alkylation alkylsalicylate described in U.S. patent No. 5434293.

In applications DD-A-269619 and DD-A-293108 described direct alkylation of salicylic acid-olefin using a catalyst acidic ion-exchange resin or polyphosphoric acid, respectively. In both applications indicate that the use of sulfuric acid as a catalyst (in the methods of the prior art, does not include alkylation acid-olefin) is not desirable, as it has many disadvantages, such as problems of corrosion and adverse reactions.

In German patent No. 689600 described the use perchloro acid as a catalyst.

In U.S. patent No. 1998750 described condensation of salicylic acid with any non-aromatic monohydroxy alcohol containing from 5 to 7 carbon atoms, or compounds capable of providing amyl-, hexyl-, cyclohexyl-, or gathergroup, in the presence of sulfuric acid.

In U.S. patent No. 4810398 described the basic salt of the alkali-earth metal and a mixture of organic carboxylic acid, which is obtained (a) by mixing the underwater equivalent of a mixture of organic carboxylic acids and more than one equivalent of hydroxide and/or oxide of alkaline-earth metal in a hydrocarbon solvent; (b) the introduction of carbon dioxide in the mixture in amounts of at least 0.5 equivalent of carbon dioxide equivalent excess alkaline-earth metal; and (c) removing residual solids, if any, and the aqueous layer, if present; in accordance with what a mixture of organic carboxylic acid contains C8-30alkylsalicylate acid and one or more alkenylboronic acids in which the alkyl residue is branched and contains from 4 to 40 carbon atoms. This salt has dispersing properties and is claimed to be suitable for use in the compositions of lubricating oils and fuels.

In U.S. patent No. 4869837 describes how to obtain basic salts of alkaline-earth metal with a mixture of organic carboxylic acids, which comprises (a) mixing one equivalent of a mixture of organic carboxylic acids and more than one equivalent of hydroxide and/or oxide of alkaline-earth metal in a hydrocarbon solvent; (b) introducing carbon dioxide into the resulting mixture in an amount of at least 0.5 equivalent of carbon dioxide equivalent excess alkaline-earth metal and (c) removing residual solids, if any, and the aqueous layer, if present, in accordance with than a mixture of organic carboxylic acid contains soluble in oil is alkylsalicylate acid and one or more uglevodorodnykh succinic acids or anhydrides, in which the average molecular weight hydrocarbon radical is from 120 to 5000.

In U.S. patent No. 4876020 described lubricant composition comprising a lubricating base oil, one or more alkali salts of alkaline-earth metals aromatic carboxylic acid and a stabilizer selected from polyalkoxysiloxanes alcohol, molecular weight which ranges from 150 to 1500.

In U.S. patent No. 5049685 described substituted in the nucleus salicylic acid represented by the following General formula:

in which R1means methyl group, isopropyl group, tert-boutelou group, tert-amylou group, tert-hexoloy group, tert-aktiline group α,α-dialkylamino group or substituted in the nucleus α,α-dialkylamino group; and R2means tert-boutelou group, tert-amylou group, tert-hexoloy group, tert-aktiline group α,α-dialkylamino group or substituted in the nucleus α,α-dialkylamino group and its salt. Substituted in the nucleus of salicylic acid and its salts, as claimed, have good solubility in water, organic solvents or organic polymeric compounds, and they are used as bactericides and germicides, polymer stabilizers connect the deposits or color developers for registration materials.

In U.S. patent No. 5415792 described strongly alkaline alkylalkoxysilane, which are considered to be useful additives for compositions of lubricating oils. Specifically, the composition of additives give ability and dispersibility of the composition of lubricating oils, as well as provide reserve alkalinity.

In U.S. patent No. 5434293 described by way of alkylation alkylsalicylate, which use acid alkylation catalyst and an approximately equimolar amount of alkylsalicylate and alkylating raw materials.

In U.S. patent No. 5451331 described method of production of concentrate additives to lubricating oils with a TBN greater than 300, which includes the interaction at a high temperature component (A) is a derivative of salicylic acid, component (B) is the Foundation of the alkaline-earth metal to be added or a single portion or multiple portions by adding at intermediate points during the reaction, the component (C) at least one compound which is a (i) water, (ii) a polyhydric alcohol containing 2-4 carbon atoms, (iii) di(C3or C4)glycol, (iv) three(C2-C4)glycol, (iv) simple alkilany ether mono - or polyalkyleneglycol formula (I) R(OR1)xOR2(I), where R is C1-C6alkyl group, R1means alkylenes group, R2 means hydrogen or C1-C6alkyl group and x represents an integer from 1 to 6, (vi) C1-C20monohydroxy alcohol, (vii) C1-C20ketone, (viii) C1-C10ester of carboxylic acid or (ix) C1-C20a simple ether, component (D) lubricating oil, component (E) carbon dioxide added after adding the component (C) or after each addition of component (F) is specified carboxylic acid or its derivative, component (G) at least one connection, which is (i) an inorganic halide (ii) of alkanoate ammonium or formate or alkanoate mono-, di-, tri - or tetraalkylammonium, provided that when component (G) is a (ii), component (F) is not an acid chloride of the acid, and the ratio of the masses of all components is such as to obtain a concentrate with a TBN greater than 300.

In U.S. patent No. 5734078 described method of manufacturing alkylsalicylate acid in which the alkyl substituent contains at least 6 carbon atoms, including interaction of salicylic acid with an olefin containing at least 6 carbon atoms, at an elevated temperature in the presence of sulfuric acid as a catalyst. Described as additives to lubricating oils containing metal salt such alkyl salicylic sour and method of their manufacture.

In U.S. patent No. 5792735 described composition of lubricating oils, which is claimed to be suitable for use in low-speed or medium-speed diesel engines and contains fuel oil with a residual oil content of,characterized in that the composition of the lubricant additionally contains a concentrate hidrocarbonetos pinata with a TBN greater than 300 and at least one product from hidrocarbonetos musk and hidrocarbonetos sulfonate. Gidrokarbonatnyj feat preferably is Fantom modified by incorporating carboxylic acid of the formula RCH(R1)CO2H, where R is C10-C24alkyl group, and R1means hydrogen or C1-C4alkyl group, for example, stearic acid.

In U.S. patent No. 6034039 described complex detergents, which are said to provide better control of deposition and corrosion protection, lubrication for the crankcase (engine).

Descriptions of the above-mentioned patents are included in this application as references in its entirety.

The invention

This invention relates to the production of alkyl salicylic acid from salicylic acid and branched internal and α-olefins using a catalyst performancelevel acid, alkylsulfonic the Oh of the acid or acid clay, such as Fulcat® 22B or Filtrol® 20X. Preferably, if the alkyl groups of sulfonic acids contain from 1 to about 30 carbon atoms. Anhydrous methansulfonate acid is particularly preferred (10-30% mole. from the number of moles of salicylic acid). Conditions are such that the suspension of salicylic acid in the olefin can interact at elevated temperatures, preferably from about 120°C to about 160°With excess olefin constituting approximately 20% (mole.) regarding salicylic acid. The products are a mixture ofortho- andpair-monoalkylamines salicylic acid with some dialkylamines and trialkylamines salicylic acids. The content of the alkylphenol is very low and the color of the product is excellent compared to the product obtained by synthesis of the Kolbe-Schmitt. Acid number of alkyl salicylic acids constitute approximately 60-95% of their theoretical values. Values of the test results PDSC (differential scanning calorimetry under pressure) and test panel coker" appropriate high-alkaline calcium salts of salicylic acid is comparable with values for control manufactured salicylate detergents or surpass them.

In the preferred case, where the catalyst is used metasolv the OIC acid, the catalyst can be easily removed and reused by adding a light naphtha, which brings the catalyst to the final reaction product in an amount of from about 10 to about 50 wt.% relative to the reaction mass. If the catalyst is no longer used, methansulfonate acid can be removed by washing with water. The solution alkylsalicylate acid can be applied directly to obtain high-alkaline salicylates of alkaline and alkaline-earth metals.

More specifically, this invention relates to a method of manufacturing alkylsalicylate acids, including the interaction of salicylic acid with an olefin containing at least four carbon atoms, at an elevated temperature in the presence of performancelevel acid, alkylsulfonic acid or acidic clay as a catalyst.

Another object of the present invention relates to compositions containing alkylsalicylate acid obtained by the method including the interaction of salicylic acid with an olefin containing at least four carbon atoms, at an elevated temperature in the presence of performancelevel acid, alkylsulfonic acid or acidic clay as a catalyst.

Description of the preferred embodiments of the invention

The method according to this image is the shadow can be represented by the following equation:

in which

R is selected from the group consisting of hydrogen, linear alkyl groups containing from 4 to 30 carbon atoms, branched alkyl groups containing from 4 to 30 carbon atoms and

R' is selected from the group consisting of linear alkyl groups containing from 4 to 30 carbon atoms and branched alkyl groups containing from 4 to 30 carbon atoms.

In the practical implementation of this invention can be used as the olefin with a linear chain, and olefins, branched-chain, preferably α-olefins. Preferably, when the olefin contains from 4 to 50, more preferably from 8 to 35 and most preferably from 8 to 25 carbon atoms. Suitable olefins include, but are not limited to, isobutylene, propylene trimer, a tetramer of propylene, 1-hexene, 1-octene, 1-mission 1-dodecene, 1-tetradecene, 1-hexadecene, 1 octadecene, 1 achozen, 1 dokusen, 1 tetracosane, mixtures of the above olefins, and the like.

Industrially produced salicylic acid can be used without additional purification.

The conditions of the reaction depend on the nature of the olefin. The conditions described below, used for the reaction with 2-methyl-1-undecanol, an example of a branched 1-olefin with a long carbon chain. Experts in the art dominionist, what other olefins can be and most likely other desirable optimum reaction conditions.

The temperature at which conduct the interaction between salicylic acid and olefin is preferably about 50°With or above and could therefore be in the range from about 50°to 200°C. the Optimum temperature in this interval depends on the length of the carbon chain of the olefin. Usually for olefin C14the optimum temperature is from about 100°C to about 170°C, preferably from about 120°C to about 160°C.

Duration of response is usually not essential. The reaction time is from about 2 to about 36 hours is usually satisfactory.

The reaction can be carried out in a solvent, if necessary, but usually the solvent is not used.

Alkylsalicylate acid may be extracted from the reaction mixture by methods known in the art. For (C12or above) alkylsalicylate acids commonly used extraction solvent, preferably a light naphtha.

Alkylated salicylic acid, obtained by the method according to this invention, used as intermediates in obtaining lubricating oil additives. The way to implement this application involves the stages of education (C4or above) is alkylsalicylate acid, as described above, and its subsequent interaction with the formed metal base in the presence of a solvent at elevated temperature.

The reaction is carried out in the presence of carbon dioxide and, optionally, catalyst carboxylation. The base may be a base formed of an alkaline metal or alkaline-earth metal, or a mixture of them both. The basis of the alkaline-earth metal is preferred. Of the alkaline earth metals are preferred calcium, magnesium and barium, particularly preferred is calcium. The base can be in the form of oxide or hydroxide, such as slaked lime, which is mainly calcium hydroxide.

The amount of added base should be sufficient to obtain high-alkaline salts, i.e. salts in which the ratio of the number of equivalents of the rest of the metal to the number of equivalents balance alkylsalicylate acid is usually greater than about 1.2, and may be 4.5 or higher.

The base can add or at a time or add multiple intermediate points during the reaction.

In addition, high-alkaline reaction mixture in a suitable case contains an activator, preferably oxygen-containing organic solvent and, optionally, water. Suitable asset of the Torah include C 1-6alcohols, polyhydric alcohols, such as glycol, propylene glycol, glycerin or 1,3-dihydroxypropane, ethers, such as simple C1-4monoether glycol or propylene glycol, simple diisopropyl ether, 1,3 - or 1,4-dioxane or 1,3-dioxolane. Preferably, when the activator is a C1-6alcohol, in particular methanol.

The solvent for the reaction alkylsalicylate acid with a base formed by the metal, may be

(1) a polyhydric alcohol containing 2-4 carbon atoms;

(2) di(C2-C4)glycol;

(3) three(C2-C4)glycol;

(4) simple alkilany ether mono - or polyalkyleneglycol formula

R1(OR2)xOR3,

in which R1means C1-C6alkyl group, R2means alkylenes group, R3means hydrogen or C1-C6alkyl group, and x is an integer from 1 to 6;

(5) monohydroxy alcohol containing up to 20 carbon atoms;

(6) a ketone containing up to 20 carbon atoms;

(7) an ester of carboxylic acid containing up to 10 carbon atoms;

(8) volatile liquid hydrocarbon or

(9) a simple ether containing up to 20 carbon atoms.

The preferred solvent is an inert hydrocarbon, which may be either aliphatic or aromatic. Suitable examples include olwal, xylene, naphtha and aliphatic paraffins such as hexane and cycloaliphatic paraffins.

The combination of methanol, which acts as an activator of the reaction, and naphtha is especially preferred.

Taking into account the proposed application of high alkaline products as additives to lubricating oils, preferably as an additional diluent base oil. The base oil may be an animal oil, vegetable or mineral oil. Preferably, when it is a lubricating oil obtained from petroleum, such as naphthenic base, paraffin base or mixed base oil. Alternatively, the lubricating oil may be a synthetic oil, such as synthetic ether complex or polymeric hydrocarbon lubricating oil.

Carbon dioxide used in the manufacture of alkali metal salts in the form of gas or solids, preferably in the form of gas, which can be bubbled through the reaction mixture. Carbon dioxide is usually added after addition of the base.

To obtain the alkali metal salt can be applied carboxylation catalyst. The specified catalyst may represent or inorganic or organic compound, preferably an inorganic compound. Suitable neorg the organic compounds include the halides of hydrogen, the halides of the metals, halides of ammonium, alkanoate metals, alkanoate ammonium or formate or alkanoate di-, tri - or tetraalkylammonium. Examples of suitable catalysts include calcium chloride, ammonium chloride, calcium acetate, ammonium acetate, zinc acetate and the acetate of Tetramethylammonium. The catalyst is usually used in an amount of about 2 wt.%. A more complete description of the production of high-alkaline alkylsalicylate metals can be found in EP-A-0351052.

In an appropriate case, a higher temperature is used in the above reaction may be from about 100 to about 500°F (about 38° up to about 260°).

Concentrate metal salt in the solvent can be removed by conventional means, such as distillation light ends. Finally, the concentrate can be filtered, if necessary.

The amount of concentrate of the additive contained in the finished lubricating oil will depend on the nature of the end use. For application of lubricants in marine conditions is usually sufficient to provide a TBN of from 9 to 100; in lubricating oils for automotive engines is sufficient to provide a TBN of from 4 to 20.

The term "Total base number" "Total Base Number" or "TBN" is used in this application to denote the amount of base equivalent to the number of milligrams of KOH in 1 gram of the additive. Thus, higher numbers BN reflect a more alkaline foods and therefore, a larger supply of alkalinity. Total base number for the additive composition can easily be determined by test method D2896 ASTM or other equivalent methods.

The finished lubricating oil may also contain effective amounts of one or more other conventional lubricating oil additives, for example additives which increase the coefficient of viscosity, antioxidants, dispersing agents, corrosion inhibitors, substances that lower the freezing temperature and the like.

Benefits and significant features of this invention will become more apparent from the following examples.

EXAMPLES

Example 1

The alkylation of salicylic acid

Salicylic acid (215,0 g) is placed in a glass vessel with a volume of 3 l equipped with a stirrer, thermometer and a heating jacket.Add a mixture of C14-C18olefins (367,7 g), followed by alkylation catalyst, preferably 45,1 g methanesulfonic acid. The mixture is heated to 120°C and maintained at this temperature for 24 hours Then injected light naphtha, such as white spirit (582,6 g), and transparent solution is allowed to settle to remove the spent catalyst. The extracted product is salicylic acid, diluted transparent yellowish white spirit, suitable for n is mediocre handling excessive amounts of alkali or interaction with pre-treated with excess alkali detergent.

Example 2

Salicylic acid, monoalkylamines mixture C14C16C18α-olefins (16,4:47,9:35,6% wt./wt.)

In a plastic reactor (volume 3 l) load powder salicylic acid (828,96 g, 6.0 mol). The reactor is equipped with a cover with five holes, mechanical stirrer bearing PTFE, smooth glass shaft, axial and radial impeller PTFE), reflux condenser (connected to the line and nitrogen bubbler with mineral oil to create excess pressure) and the shell Therm-O-Watch®with thermocouple. Charged to the reactor commercially available mixture of C14/C16/C18α-olefins (1414,12 g, 6,30 mol, assuming that the average molecular weight of the mixture of alkenes, comprising 16.4% of 1-tetradecene, 47,9% 1-hexadecene and 35.6% 1 octadecene (% mass.), equal 228,11) and then begin stirring at a rate of approximately 250-300 rpm To the resulting white suspension is added all at once anhydrous methansulfonate acid (173,47 g, 1.8 mol, 30 mole.% regarding salicylic acid). Then the suspension is heated under nitrogen atmosphere to the desired temperature 120°and mix.

As the reaction suspension disappears, and the mixture becomes dark, reddish-orange color. The crystals, which, as suggested, are sublimated salicylic Ki is lotay, appear on the cold surfaces of the apparatus for the reaction. After a full 25 hours at 120°heating stopped and the reaction mixture is allowed to cool. To transfer the reaction product from the reactor into a separating funnel using light naphtha (1.5 l), the phases are separated and get a great upper phase and a dark colored bottom phase of the spent catalyst. From the upper phase is removed the solvent in vacuo (rotary evaporator at 90°With water bath and pressure of <10 mbar) for about 2 hours Getting brownish oil (2189,77 g) (97,6% (based on the total weight of alkene and salicylic acid). The specimen is obtained, as shown, has an acid number, which is 92% of theoretical values, 153,20 mixture monoalkylamines salicylic acid (16,4:47,9:35,6% wt./wt.).

Example a

Comparative example

Salicylic acid, monoalkylamines the tetramer of propylene in the presence of 80% vol./about. aqueous sulfuric acid

In plastica reactor (volume 2 liter) download salicylic acid (138,39 g, 1.00 mol) and 890 ml (25.6 mol) of an aqueous solution of 80% (vol./about.) of sulfuric acid. The suspension is stirred with excess nitrogen pressure and a temperature of 43°and then added dropwise propylene tetramer (185,24 g, 1.1 mol) for about 0.5 hours while adding the reaction temperature when egka reduced to 41° C. Then the reaction mixture is heated to the desired temperature 60°With; however, it is exothermic reaction, and the mixture is heated to 75°C. the Reaction mixture was kept at 60°With a total of over 3 hour Product intense reddish color diluted with 600 ml of water is exothermic and the reaction of dilute sulfuric acid. The diluted product separated into two phases, treated with 200 ml ofn-heptane in a separating funnel. The upper organic phase is preserved, and the lower aqueous phase is extracted twice withn-heptane (100 ml). All the combined organic phases, twice washed with water (300 ml) and then twice with a saturated aqueous solution of sodium chloride (200 ml). The organic phase is dried over anhydrous sodium sulfate. Then, the drying agent is filtered off on a Buchner funnel with suction, the filtrate is evaporated in vacuo (90°C, water bath, vacuum <20 mbar) and get 252,53 g of a viscous dark red oil (78,0%, based on the total weight of alkene and salicylic acid). The product has a sulfur smell, and its acid number is 136,0 (74.2% of theoretical value equal to 183,1).

Example 3

Salicylic acid, monoalkylamines the tetramer of propylene and methanesulfonic acid

Repeat example 2 in a plastic reactor with a volume of 2 l with 414,99 g salicylic is th acid (3.0 mol), 530,61 g of propylene tetramer (3,15 mol) and 86,52 g methanesulfonic acid (0.90 mol). The mixture is stirred and heated in nitrogen atmosphere at 120°C for 26 hours the reaction Product is diluted with water (500 ml) andnheptane (500 ml) and the organic phase is twice washed with water (portions of 500 ml). The aqueous phase is then combined and extracted with 200 ml ofnheptane. All organic extracts are combined and then evaporated under vacuum (90°C, water bath, vacuum <20 mbar), receiving 868,05 g dark colored viscous oil (92,8% (based on total weight of propylene tetramer and salicylic acid). Acid number of the resulting product is 163,2 (89,1% of theoretical value equal to 183,1).

Example 4

Salicylic acid, monoalkylamines mixture C14C16C18α-olefins (10:10:80% wt.)

In a plastic reactor (volume 2 liter), as in example 2, is placed salicylic acid (414,34 g, 3.00 mol), 1-tetradecene (87,32 g, 0,445 mol), 1-hexadecene (87,34 g, 0,389 mol), 1-octadecene (698,70 g, 2,73 mol) and methanesulfonyl acid (86,61 g, 0.90 mol). The suspension is heated at 120°With over 26,5 hours, the Cooled reaction product is diluted with 600 ml of light naphtha and filtered with suction through a glass funnel for filtering with a coarse glass Frit. Layer on the filter is washed with 300 ml light if the Roin. The filtrate separated in the separating funnel and the lower dark layer is separated. The upper organic phase is evaporated under vacuum (90°C, water bath, vacuum <15 mbar), receiving 1119,11 g yellowish oil (86,9% (based on the total weight of alkene and salicylic acid). Acid number of the product of alkylation is 133,8 (87.3 per cent of theoretical value equal to 147,40).

Example 5

Salicylic acid, monoalkylamines a mixture of 1-tetradecene, 1-hexadecene and 1 octadecene (10:10:80(% wt.)

Similar to that described in example 2 in a plastic reactor (volume 3 l) placed salicylic acid (829,04 g, 6.0 mol), 1-tetradecene (152,89 g, 0,7783 mol), 1-hexadecene (152,81 g, 0,689 mol), 1-octadecene (1222,60 g, 5,447 mol) and methanesulfonyl acid (173,02 g of 1.80 mol). The suspension is heated to 130°C in an atmosphere of nitrogen with stirring and maintained at 130°With a total of eight hours. The cooled reaction mixture is diluted with 500 ml ofnheptane and the solution is filtered through a glass funnel for filtering with a coarse glass Frit.

Example 6

Salicylic acid, monoalkylamines 1-tetradecanol

Repeat example 2 in a plastic reactor with a volume of 2 l with 388,84 g (2,815 mol) of salicylic acid, 580,49 g (2,956 mol) of 1-tetradecene and 57,81 g (of 0.60 mol) of anhydrous methanesulfonic acid. The suspension is heated and stirred in the atmosphere of nitrogen for 24 h at 120° C. the Catalyst is removed by washing the product 1 l of water, followed by evaporation at 90°and reduced pressure. Get dark red-brown oil (910,66 g, 93.9 per cent calculated on the total weight of alkene and salicylic acid). Acid number of the resulting product is 112,0 (66.8% of theoretical value equal to 167,7).

Example 7

Salicylic acid, monoalkylamines 1-mission

Repeat example 2 with 414,72 g of salicylic acid (3.0 mol), 441,91 g 1-mission (3,15 mol) and 86,55 g methanesulfonic acid (0.90 mol). The mixture is heated at 120°C in nitrogen atmosphere for 24 hours resulting product is diluted with 200 ml of light naphtha and then lower the dark phase is removed in a separating funnel. From the upper phase is removed the solvent in vacuo (90°C, water bath, vacuum <10 mbar) and get 856,6 g of a dark oil (99,9% (based on the total weight of alkene and salicylic acid). Acid number of the product is 189,8 (94,1% of theoretical value equal to 201,5).

Example 8

Salicylic acid, monoalkylamines 1-octene

Salicylic acid (414,89 g, 3.0 mol), 1-octene (353,5 g and 3.15 mol) and methanesulfonyl acid (57,63 g to 0.60 mol) are combined as in example 2, in a reactor with a volume of 2 liters and heated to the desired temperature 120°when excess nitrogen pressure. The reaction mixture is heated and stirred at 120°in General the th complexity of 24.5 hours To the reaction product add light naphtha (200 ml) and then filtered with suction through a glass funnel with a coarse glass Frit. The filtrate is divided into a large upper phase and the lower darker phase containing the catalyst. The upper phase is evaporated in vacuum (90°C, water bath, vacuum <10 mbar), receiving 755,7 g alkilirovanny salicylic acid as a brown oil (98,4% (based on the total weight of alkene and salicylic acid). Acid number of the product is 211,2 (94.2% of theoretical average of 224,1).

Example 9

Salicylic acid, monoalkylamines mixture C20C22and C24α-olefins

Salicylic acid (414,76 g, 3.0 mol), a mixture of C20C22and C24α-olefins (908,82 g and 3.15 mol) and methanesulfonyl acid (86,82 g, 0.90 mol) are combined in a reactor with a volume of 2 l, as in example 2. As α-olefin is a waxy solid, the mixture is heated to the desired temperature 120°C in nitrogen atmosphere without stirring up until olefin is melted, then start mixing. The reaction mixture is heated at 120°With a total of 22.4 hours the reaction Product was diluted with 500 ml of water and 200 ml ofnheptane and the phases are separated in a separating funnel. The upper organic phase is washed three times with water (on the operations 300 ml). Then the organic phase is evaporated under vacuum (90°C, water bath, vacuum <10 mbar), receiving 1295,85 g of a dark oil (97,9%, based on the total weight of alkene and salicylic acid). The resulting substance hardens over night, turning in a solid cream color, an acid number of which is equal 97,0 (77,6% of theoretical average of 125,0).

Example 10

Salicylic acid, monoalkylamines propylene trimer (nodename)

Analogously to example 2, in a plastic reactor of 2 l of mixed 414,50 g (3.00 mol) of salicylic acid, 398,32 g (3,15 mol) of propylene trimer (noneno) and 86,67 g (0.90 mol) methanesulfonic acid. The suspension is stirred and heated at 120°C for 23 h at a pressure of nitrogen. The reaction product is allowed to cool and diluted with 300 ml of light naphtha. Then the contents of the reactor are filtered through a Buechner funnel with a coarse glass Frit and the filtrate is diluted with 500 ml of light naphtha and 200 ml of water in a separating funnel. The upper organic phase is then evaporated under vacuum (90°C, water bath, vacuum <10 mbar), receiving 774,88 g of a dark viscous oil (95,3%, based on the total weight of alkene and salicylic acid). The final alkylation product has an acid number 230,4 (87,4% of theoretical average of 263,6).

Example 11

Salicylic to the slot, monoalkylamines pentameron propylene

Salicylic acid (414,41 g, 3.00 mol), pentamer propylene (662,96 g and 3.15 mol) and methanesulfonyl acid (86,48 g, 0.90 mol) are combined in a plastic reactor with a volume of 2 l, as described in example 2. The suspension is heated at 120°C in an atmosphere of nitrogen in total for 23 hours a Chilled dark reaction product was diluted with 500 ml ofn-heptane and then filtered through a Buechner funnel with coarse glass Frit with suction. The filtrate is a two-phase system. The lower phase containing the catalyst is separated and the upper organic phase is evaporated under vacuum (90°C, water bath, vacuum of about 30 mbar), receiving 1065,74 g of a viscous dark oil (yield 98.9 per cent calculated on the total weight of alkene and salicylic acid). Acid number of the product of alkylation is 158,6 (98.5% of theoretical average of 161,0).

Whereas numerous changes and modifications can be made without deviation from the principles underlying this invention, reference should be made to the accompanying claims for an understanding of the scope of protection provided by this invention.

1. The method of obtaining alkylsalicylate acids, including the interaction of salicylic acid with an olefin containing at least four carbon atoms,at an elevated temperature in the presence of alkylsulfonic acid as a catalyst.

2. The method according to claim 1, in which the catalyst is anhydrous methansulfonate acid.

3. The method according to claim 1 in which the olefin is chosen from the group consisting of isobutylene, propylene trimer, tetramer of propylene, 1-hexene, 1-octene, 1-mission 1-dodecene, 1-tetradecene, 1-hexadecene, 1 octadecene, 1 eicosene, 1 docosane, 1 tetracosane and mixtures thereof.

4. The method according to claim 2, in which the olefin is chosen from the group consisting of isobutylene, propylene trimer, tetramer of propylene, 1-hexene, 1-octene, 1-mission 1-dodecene, 1-tetradecene, 1-hexadecene, 1 octadecene, 1 eicosene, 1 docosane, 1 tetracosane and mixtures thereof.

5. The method according to claim 1, in which the specified elevated temperature is at least 50°C.

6. The method according to claim 1, in which the specified elevated temperature is from 120°160°C.

7. Composition to obtain a lubricating oil additives containing alkylsalicylate acid obtained by the method according to claim 1.

8. The composition according to claim 7, where the catalyst is anhydrous methansulfonate acid.

9. The composition according to claim 7, where the olefin is selected from the group consisting of isobutylene, propylene trimer, tetramer of propylene, 1-hexene, 1-octene, 1-mission 1-dodecene, 1-tetradecene, 1-hexadecene, 1 octadecene, 1 eicosene, 1 docosane, 1 tetracosane and mixtures thereof.

10. The composition of claim 8, where the olefin is selected from the group consisting of the of isobutylene, of propylene trimer, tetramer of propylene, 1-hexene, 1-octene, 1-mission 1-dodecene, 1-tetradecene, 1-hexadecene, 1 octadecene, 1 eicosene, 1 docosane, 1 tetracosane and mixtures thereof.

11. The composition according to claim 7, where the specified elevated temperature is at least 50°C.

12. The composition according to claim 11, where the specified elevated temperature is from 120°160°C.

13. The method according to claim 1, wherein the olefin comprises a mixture of α-olefins C14-C18.

14. The method according to claim 1, wherein the olefin comprises a mixture of α-olefins With20With22and C24.

15. The method according to claim 1 in which the olefin contains pentamer propylene.

16. The method according to claim 1 in which the olefin contains 2-methyl-1-undecen.

17. The composition according to claim 1 in which the olefin comprises a mixture of α-olefins With14-C18.

18. The composition according to claim 7, in which the olefin comprises a mixture of α-olefins With20With22and C24.

19. The composition according to claim 7, in which the olefin contains pentamer propylene.

20. The composition according to claim 7, in which the olefin contains 2-methyl-1-undecen.



 

Same patents:

FIELD: construction; chemistry.

SUBSTANCE: invention can be used when making single-layer polymer coating driveways of bridge floors of metallic and concrete bridges, and more specifically to polymer compositions of obtaining and using the coating. The composition contains liquid thiocol (polysulfide oligomer), manganese dioxide, dibytyl phthalate, diphenylguanidine, indene-cumaron resin, polymeric petroleum resin, sodium bichromate, oligoester acrylate, oleic acid, cement, textile cord, carbon black, granite and rubber crumps, acetone and toluene. The composition is packed in two-components, and before depositing the two parts (component A and component B) it is mixed, formed and used. The prepared surface is initially coated with an adhesive layer of mastic based on polychloroprene caoutchouc or sealing composition based on thiocol-polysulfide oligomer, and then the polymer composition described here above and the coating are solidified at positive ambient air temperature.

EFFECT: obtained coating has high water-proof properties, abrasion resistance and longevity.

2 cl, 3 tbl

FIELD: material for increase of friction coefficient of vehicle wheels.

SUBSTANCE: material is described for provision of vehicle movement start on slippery snow or ice surface, which consists of disperse loose material composition in the form of wooden chips with size from 1 mm to 10 mm and antiseptic - boric acid that is contained in the material in amount from 1 to 2 % weight.

EFFECT: increase of friction coefficient between vehicle wheel and iced surface.

2 tbl, 1 ex

FIELD: heat-curable sealing compositions.

SUBSTANCE: composition is proposed, containing the following mass components: 100 (meth)acrylic monomer or its mixture with an allyic monomer, 0.5-2.5 initiator, 0.01-0.32 hydroquinone, 0.01-0.13 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl, 0.004-0.05 disodium salt of ethylenediaminetetraacetic acid, 20-125 filler and 5-30 functional additives. The proposed composition has polymerising activity at 100-250°C for 3-8 minutes and breaking stress of 605-15.5 MPa. This adhesive strength is sufficient for withstanding steam pressure of up to 4 MPa. Use of the proposed composition allows for repairing steam pipes with constant supply of steam.

EFFECT: design of a heat-curable sealing composition for repairing steam pipes without interruption of steam supply.

1 cl, 1 tbl, 5 ex

FIELD: polymer chemistry.

SUBSTANCE: polymer composition consists of polysulphide oligomer - liquid thiocols with average molecular weight of 1700-5500 and viscosity of 7.5-50 Pa.s at 25°C, filler - hydrophobic chalk, plasticiser, manganese dioxide and accelerator 2,4,6 - tris(dimethyl aminomethyl)-phenol and an extra adhesive additive - silylated amine chosen from N,N - bis(trimethylsilyl)-N,N -dimethylethylenediamine, N,N - bis(trimethylsilyl) -N,N ,N - triethyldiethylenetriamine and 1,3 -dibutyl-2-methyl-2-vinyl-1,3-diaza-2-silacyclopentane.

EFFECT: higher adhesive, physical and mechanical properties and waterproofing characteristics of the coating.

10 ex, 2 tbl

FIELD: construction.

SUBSTANCE: invention concerns hydraulic engineering and hydromeliorative construction, in particular to compositions for weatherproofing of joints of hydraulic engineering constructions and repairing of concrete and reinforced-concrete constructions of hydro-economic objects, for example, for the purpose of sealing the destroyed joints and the slots formed during maintenance in grout facings of channels and ponds. An invention aim is creation of composition with high physic-mechanical properties for weatherproofing of joints of hydraulic engineering constructions, mainly grout facings of channels and ponds. The pointed aim is achieved due to that composition includes cement, plaster with the crystallising water 7.5-19.0 mass %, calcium hydrocarbonaluminate and the calcium hydro-pomegranate, and in addition contains a sanding dust - a manufacture withdrawal asbestos-technical products.

EFFECT: increase of adhesive durability of sealing composition to concrete of abutting members and decrease in its water absorption.

2 tbl

FIELD: chemistry.

SUBSTANCE: polymeric composition can be used for elastomeric sealing and damp-proof materials of roof and anticorrosion coatings, run track covers and gym flooring systems and contains polysulfide oligomer - liquid thiocol with average molecular weight 1700-5500 and viscosity 7.5 - 50 Pa·c at 25°C temperature, the filler - hydrophobizsated calcium carbonate, plasticiser, manganese dioxide and booster compound 2,4,6 - tris-(dimethylaminomethyl)-phenol and additionally filling agent - carbon P-803.

EFFECT: enhanced physical and mechanical, dump-proof properties on the basis of the composition.

1 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: polymeric composition can be used for elastomeric sealing and damp-proof materials of roof and anticorrosion coatings, run track covers and gym flooring systems and contains polysulfide oligomer - liquid thiocol with average molecular weight 1700-5500 and viscosity 7.5 - 50 Pa·c at 25°C temperature, the filler - hydrophobisated calcium carbonate, the plasticizer, manganese dioxide and booster compound 2,4,6 - tris-(dimethylaminomethyl)-phenol and triethanolamine at mass ratio 2:1 and additionally filling agents - carbon P-803 and hydroxylated comminuted rubber with the concentration of hydroxyl group 2.4-6.7.

EFFECT: improvement of the coating characteristics.

2 tbl

FIELD: chemistry.

SUBSTANCE: invention pertains to the composition for making a surface layer of ice for speed skating competitions and training, used for machine lining and freezing-out of at least one layer of ice on the formed ice block, consisting of the following percentage mass components: 0.000025-0.000625 % polyvinylpyrolidone; 0.00125-0.0125% glycerine; purified water constituting the remaining percentage.

EFFECT: making a surface layer of ice block for speed skating with maximum glide.

3 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to the composition for making a surface layer of ice for speed skating competitions and training, used for machine lining and freezing-out of at least one layer of ice on the formed ice block, consisting of the following percentage mass components: 0.000075-0.00015% polyvinyl spirit; 0.003-0.0075% glycerine and purified water constituting the remaining percentage.

EFFECT: making a surface layer of ice for speed skating, with maximum glide.

3 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention pertains to a defrosting composition, which consists of spirit or a mixture of spirits, a lubrication component, soluble in polar solvents of anticorrosive agents and an extra dispersed powder of polytetrafluoroethylene, nonionogenic surfactant and a hydrate an alkaline metal. The lubrication component used is in the form of liquid copolymers (C14-C16) of alpha-olefins, and alpha, beta saturated 1,4-dicarboxlylic acid, etherified short or medium chain spirits with molar mass from 600 to 7000. The percentage mass components of the composition are as follows: 0.5-3.5 % liquid polymers; 0.01-0.1 % anticorrosive agent; 0.5-3.5 % polytetrafluoroethylene; 0.001-0.015 % nonionogenic surfactant; 0.006-0.04 % hydrate of alkaline metal; spirit or a mixture of spirits constitute the remaining percentage.

EFFECT: composition with higher penetration capacity to the processed surface during defrosting, higher lubricating capacity and prolonged defrosting effect on metallic surfaces.

8 cl, 3 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of fluorinated ester. The process involves the re-esterification step wherein compound of the formula: RAF-COOCF2-RAF and compound of the formula: RA-CH2OH are subjected for the re-esterification reaction in the molar ratio = 1:(1-2) to yield RAF-COOCH2-RA, and the fluorination step wherein the synthesized compound is fluorinated with yielding the reaction product in the amount exceeding the mole amount before the re-esterification reaction and comprising compound of the formula: RAF-COOCF2-RAF wherein RA means a monovalent (C1-C20)-hydrocarbon group, monovalent halogen-containing (C1-C20)-hydroarbon group, monovalent heteroatom-containing (C1-C20)-hydrocarbon group or monovalent (C1-C20)-hydrocarbon group containing halogen atom and heteroatom, and RAF means the same group as RA group or monovalent hydrocarbon group prepared by fluorination of RA group.

EFFECT: improved method of synthesis.

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for synthesis of ester perfluorinated derivative by using a chemical reaction. This reaction represents the fluorination reaction of the parent compound as a raw, the reaction of chemical conversion of fragment of ester perfluorinated derivative to yield another ester perfluorinated derivative or the interaction reaction of carboxylic acid with alcohol under condition that at least one or reagent, i. e. carboxylic acid or alcohol, represents a perfluorinated compound wherein indicated perfluorinated derivative of ester represents a compound comprising a fragment of the formula (1):

with a boiling point 400°C, not above. The reaction time for carrying out abovementioned chemical reaction is sufficient to provide the required yield of ester perfluorinated derivative and wherein this yield of ester perfluorinated compound is determined by the gas chromatography method by using a nonpolar column. Also, invention relates to a method for pyrolysis of ester perfluorinated derivative with a boiling point 400°C, not above, to yield the dissociation product wherein this product represents a derivative of acyl fluoride or ketone and wherein pyrolysis time is sufficient to provide the required degree of conversion of ester perfluorinated derivative and wherein the indicated conversion degree of ester perfluorinated derivative is determined by gas chromatography method by using a nonpolar column. Also, invention relates to a method for analysis of ester perfluorinated derivative with a boiling point 400°C, not above, that involves analysis of ester perfluorinated derivative in a sample containing ester perfluorinated derivative by gas chromatography method by using a nonpolar column wherein ester perfluorinated derivative represents compound comprising a fragment of above given formula (1).

EFFECT: improved method of synthesis.

8 cl, 1 dwg, 2 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to industrially useful fluorine-containing compounds such as fluorinated ester compounds and acyl fluoride compounds. Invention, in particular, provides ester compound wherein all C-H groups are fluorinated and which is depicted by general formula RAFCFR1FOCORBF (4), where RAF, CFR1, and RBF are specified elsewhere. Preparation of the ester compound comprises fluorination of ester (4), which has hydroxyl group(s), acyl fluoride group(s) and which has a structure allowing compound to be fluorinated in liquid phase, fluorination being effected in mixture of ester compound and compound having acyl fluoride group(s). Method does not involve environmentally unfriendly solvent such as, for instance, R-113.

EFFECT: enabled fluorination requiring no specific solvent for each reaction and which can be carried out without separation of solvent before next stage.

9 cl, 8 ex

FIELD: organic chemistry, in particular polymers.

SUBSTANCE: invention relates to new method for production of vic-dichlorofluoroanhydride useful as intermediate of starting monomer for fluorinated polymers with good yield from available raw material. Claimed method includes fluorination of starting material (I): (RH1-EH1-)CRH2RH3CH2-0CORHB in liquid phase to form compound of formula (II): (CF2ClCFCl-EF1-)CRF2RF3CF2-OCORFB; ester bond splitting of formula (II) in gaseous phase under solvent absence to form compound of formula (III): (CF2ClCFCl-EF1-)CRF2RF3COF or compound of formula (III) and compound of formula (IV): FCORFB, wherein RH1 is CX1X2ClCX3Cl- or CClX4=CCl, wherein each X1-X4 independently is hydrogen; RH2 and RH3 independently are hydrogen or linear or branched alkyl, optionally substituted with one or more oxygen; EH1 is alkylene, optionally substituted with one or more oxygen; EF1 = EH1 wherein perfluoroalkylene group is optionally substituted with one or more oxygen; RHB = RFB and are linear or branched perfluoroalkyl group, optionally substituted with chlorine one or more oxygen; RF2 is fluorinated RH2; RF3 is fluorinated RH3; with the proviso, that RF2 is fluorinated RH2; RF3 is fluorinated RH3, i.e. RF2 and RF3 represent RH2 or RH3 with at least one fluorinated hydrogen. Also disclosed are new compounds, represented in claims of invention.

EFFECT: new intermediates useful in polymer fluorination.

11 cl, 7 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention provides improved process for production of a fluorine-containing compound useful as starting material for manufacture of a variety of fluoropolymers with high output when performing short process and using inexpensive and easily accessible chemicals. Process comprises: (i) interaction of indicated below compound 1 with indicated below compound 2 to form indicated below desired compound 3, which is a compound, wherein content of fluorine is at least 30 wt % and which has hydrogen atom or multiple bond capable of being fluorinated; and (ii) liquid-phase fluorination of compound 3 to give indicated below compound 4 followed by (iii) cleaving group EF in compound 4 to produce compound 5 and compound 6: E1-RA-E1 (1), E2-RB (2), RB-E-RA-E-RB (3),

RBF-EF-RAF-EF-RBF (4), EF1-RAF-EF1 (5),

and RBF-EF2 (6), where RAF represents fluorine-containing bivalent saturated, linear or branched hydrocarbon group optionally containing halogen atom other than fluorine and optionally containing one or several ether oxygen atoms; RA represents group, which is the same as group RAF or bivalent organic group capable of being converted into group RAF using fluorination reaction; RBF represents fluorine-containing polyvalent saturated, linear or branched hydrocarbon group optionally containing halogen atom other than fluorine and optionally containing one or several ether or carbonyl oxygen atoms; RB represents group, which is the same as group RBF or polyvalent organic group capable of being converted into group RBF using fluorination reaction; E1 and E2 are such that, when group E1 is -CH2OH or Q1-CH2OH group, then group E2 is -COX or -SO2X group and, when group E2 is -CH2OH or -Q2-CH2OH group, then group E1 is -COX or -SO2X group, where X is halogen atom and Q1 and Q2 may be identical or different and represent -CH(CH3)- or -CH2CH2- group; E represents group -CH2OCO-, -CH2OSO2-, -Q1-CH2OCO-, -Q2-CH2OCO-, -Q1-CH2OSO2-, or -Q2-CH2OSO2-; EF represents group, which is the same as group E or group obtained by fluorination if group E on conditions that at least one group RAF, RBF, or EF is a group formed by fluorination reaction and groups EF1 and EF2 are groups formed by cleaving group EF. Invention also relates to novel fluorine-containing compounds of formulas 3-12, 3-13, 3-14, 3-15, 3-16, 4-12, 4-13, 4-14, 4-15, 4-16, 5-16, which are indicated in description.

EFFECT: increased resource of raw materials for production of fluoropolymers.

8 cl, 23 ex

The invention relates to the production of fluorine-containing compounds, such as industrial useful derived foramerica acid

The invention relates to new liquid under normal conditions of omega-hygrophoraceae esters, which have the properties of surfactants and can be used to displace water from the surface, in compositions for the removal of pollutant products, compositions for fire extinguishing, foam fabrication, when soldering in the vapor phase

The invention relates to ester compounds, method of their production and their use as a means for spooling the fiber

The invention relates to the field of organic chemistry, namely to new chemical compound gross formula

< / BR>
where x= CF2or bond, the sum n + m + C 3 10

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to chemistry of adamantane derivatives, namely, to a novel method for synthesis of 3-halogen-1-(ethoxycarbonyl)-alkyladamantanes of the general formula: wherein Hal means bromine atom (Br); R means hydrogen atom (H), -CH3, -C2H5, -C3H7; Hal means Br; R means -CH3; R1 means -CH3; Hal means chlorine atom (Cl); R means Cl; R1 means Cl that can be used as intermediate compounds used for synthesis of some biologically active substances. Method involves interaction of 1,3-dehydroadamantane with α-halogenalkane carboxylic acids ethyl esters chosen from the following group: ethyl-2-bromoacetate, ethyl-2-bromopropionate, ethyl-2-bromobutyrate, ethyl-2-bromovalerate, ethyl-2-bromo-2-methylpropionate and ethyl-2,2,2-trichloroacetate taken in the mole ratio = 1:(3-5), respectively, in the parent α-halogenalkane carboxylic acid ethyl esters medium, at temperature 50-60°C for 4-6 h. Invention provides expanding assortment of chemical compounds, in particular, synthesis of novel 3-halogen-1-(ethoxycarbonyl)-alkyladamantanes with the high yield.

EFFECT: improved method of synthesis.

6 ex

Up!