SU633487A3 - Method of obtaining additives to lubricating oils - Google Patents

Description

An oxidized copolymer of ethylene and propylene or ethylene, propylene, and a Cr – Sy – a – olefin with an average molecular weight of 10,000–1BC) 0 (X) is used in the olfinic polymer. having 140-400 methyl groups per 1000 carbon atoms of the main chain at a molar ratio of copolymer: formaldehyde; polyalkylene polyamine-1: 2: 2 - 1:20; : 20 respectively. The method consists in obtaining additives to lubricating oils by treating the oxidized olefinic polymer with formaldehyde and polyalkylenepolyamine at 120-170 ° C, the oxidized copolymer of ethylene and propylene or ethylene, propylene and Ca-Cgo-a-olefin with an average of molecules being used as the oxidized olefinic polymer. with a weight of 10,000-100,000, having 140-400 methyl. groups per 100 carbon atoms of the main chain, with a molar ratio in molar proportions of copolymer: formaldehyde: polyalkylene polyamine-1: 2: 2 - 1:20:20, respectively. The preparation of the additive is preferably carried out in the presence of an inactive organic solvent or diluent, for example, an aromatic hydrocarbon — benzene, xylene, toluene, or an aliphatic hydrocarbon solvent, for example hexaa. Most suitable for use as a solvent or diluent is a low viscosity hydrocarbon oil, such as mineral oil, obtained from a solvent. The use of a solvent or diluent is especially important because it facilitates the displacement of agents and the control of the reaction temperature. The copolymer refers to amorphous copolymers consisting of ethylene and propylene; however, such copolymers may contain a small amount of polymers (do) obtained from other olefin monomers, which corresponds to the molar ratios of monomeric units of ethylene and propylene in the copolymer. Such olefin monomers include monomers of the general formula RCH CHa, where R is an aliphatic or cycloaliphatic radical with a carbon number of 2-20, for example, butene-1, hexene-1, 4-methyl-pentene, decene-1; Ainylidene norbornene, 5-methylene-2-norborene. Other olefin monomers having many double bonds can also be used, in particular diolefins containing 4-25 carbon atoms, i.e. 1,4-butadiene, 1,3-hexadiene, 1.4-pentadiene, 2-methyl-1,5-hexadiene, 1.7-octadiene. Suitable ethylene-propylene copolymers are copolymers containing 30-65, preferably 35-45 / o. Propylene molecules, having an average molecular weight of 20 (SO, i.e., 10,000-1.COOO, preferably 28,000-40000, containing at least 150 methyl groups per 1000 carbon atoms of the main chain. The most appropriate ethylene-propylene copolymer is a copolymer having the following characteristics: Average molecular weight 25000-35000 Amount of propylene monomer, mol. ° / o38 --- 42 Number of side methyl groups per 1000 carbon atoms primary center EPi160-170 Intrinsic viscosity g / cm 1.7-2-2 Oxidation of the copolymer is carried out by the usual known methods. Suitable amines are, for example, methylamine, dibutylamine, cyclohexylamine, propylamine, decylamine, ethylene diamine, cyclohexylamine, propylamine, decylamine, ethylene diamine, diethylenetriamine, triethylene tetramine, tetrapropylenepentamine, tripropylenetetramine, tetrapropylenepentamine, and other polyalkylene polyamines in which alkylene groups contain about 10 carbon atoms. Aldehydes Ow. for example, formaldehyde, acetaldehyde, oxydehyde. It is preferred to use formaldehyde or formaldehyde which produces compounds such as formaldehyde and formalin. Example I. An amorphous copolymer of ethylene and propylene is prepared in the presence of a Ziegler-Natta type catalyst, a vanadium oxytrichloride solution in combination with ethylamine pentochloride solution. Dry heptane (1200 ml) is saturated at 30 ° C in a gas mixture containing 50 mol. ° / o ethylene, 35 mol. ° / about propylene and 15 mol.% Hydrogen. This gas mixture is introduced at a rate of 00 l / h, passed through heptane and then removed from the system. The catalyst components are then added. A vanadium hydroxitric chloride solution {L, 37 ° / o from the weight of the mixture at a rate of 13 ml / h) and ethnlamine perchloride solution (0.459% by weight of the mixture with a speed of 60 ml / molar ratio, 66 are introduced into the olefinic mixture. 66 and ethylene is adjusted so as to compensate for the higher reactivity of the latter. The average propylene: ethylene ratio is 2.3 (as determined periodically with gas chromatographic analyzes). After 1.25 hours, polymerization is stopped by separating the azo gas mixture ohm. Then, the reaction mixture was twice ppomyvak t methanol in order to remove the catalyst and dezaktivnzirovat. When nspolzovanin

The specified amount of a vanadium-based catalyst was obtained in 1680 g of polymer per I hOCOS.

The reduced copolymer has an average molecular weight (Mn) of 28,000, which is determined by measuring the osmotic vapor pressure, 159 side methyl groups per 1000 carbon atoms of the main chain, as determined by infrared spectroscopy, and an intrinsic viscosity of 2.28 g / cm measured in 100 ml of decalin at 139 ° C.

A solution of 70 g of the obtained copolymer is heated to 4 ° C in 1000 g of heptane, while purging with nitrogen to remove heptane. Once the heptane is removed, a gradual addition of 280 g of mineral oil is started and the viscous oil-copolymer mixture is heated to 221 ° C with vigorous stirring. At this point, the nitrogen flushing is stopped and the vessel in which the reaction is carried out is connected to the atmosphere. After half an hour, the viscosity of the mixture decreases to such an extent that it is possible to carry out vigorous stirring at an optimum oxidation temperature of 154 ° C. With this temperature and stirring, heating is continued for 2.5 hours. The chemical conversion, measured by silica gel chromatography, was 100%.

900 g of benzene are added to 655 g of an oil solution of the oxidized copolymer (20 / o active oxidized copolymer) and the solution is heated to lo 49 ° C. Then, 0.69 g of solid paraformaldeside (0.52% by weight of the oxidized copolymer) is added and the mixture is heated to 49 ° C for 0.5 h. Then, 2.66 g of hexamethylenediamine (2% by weight of the oxidized copolymer) is added and the solution is heated at for 3 h

The resulting product is heated to 149 ° C, then at the same temperature. Purged with nitrogen for 1 h to remove the benzene solvent. The activity of the product without a solvent in the addition of oil reaches 13%. A crystalline product with a colorimetric characteristic of 6.70 (ASTM scale) and a content of 0.06% nitrogen and 0.1% oxygen is obtained.

Example 2. A solution of 70 g of the copolymer described in Example 1 is heated to 65 ° C in 1000 g of heptane while purging with nitrogen to remove heptane. After removal of 1.heptane, 650 g of mineral oil extracted from the solvent is gradually added, and the viscous oil – polymer mixture is heated to 182 ° C with vigorous stirring and purging with nitrogen. This is continued for 0.5 hour to remove the last residual heptane solvent. According to the measurement of silica gel chromatography, the chemical conversion is. Measurements made with a 5.8 µm wide tape that absorbs red THH light are gtpcchzali. that the carbide content in the oxidized product was 7.5 units (element thickness 0.002 inches). The oxygen content in the product was 0.89%.

200 g of the oxidized copolymer (0 ° / o of the active oxidized copolymer in mineral oil is heated to 160 ° C under a layer of nitrogen. Then 0.38 g of solid paraformaldehyde (1.9% by weight of the oxidized 0 copolymer) and 1.5 g liquid anhydrous hexamethylenediamine (75% by weight of the oxidized copolymer). Stirring and heating g / ri at this temperature is continued for 2 h, then the resulting product is purged with a TOM for 0.5 h to remove residual volatile products. The product of the filtrate gives a clear crystalline product with follow their parameters:

The amount of the obtained product,% 10.0

Number and grade of a cat,% 0.185

The amount of oxygen,% 0.45

Colorimetric characteristic (according to ASTM scale) 7.0 Viscosity by viscometer “Saybolt-Universal at 444 ° С, s 3200

Example A solution of 115 g of the copolymer described in Example I is heated to 121 ° C in 1745 g of heptane in a stream of nitrogen to remove 0 heptane. As the nitrogen is removed, the mineral oil extracted from the solvent (770 g) is gradually added. After complete removal of heptane at 177 ° C in a stream of nitrogen, 885 g of an oil of a nasol polymer solution containing 13% of the copolymer are obtained.

five

The copolymer is oxidized by heating this mixture to 20 ° C by combining the reaction vessel with the atmosphere. At the same time, the mixing is intensified to such an extent that

make sufficient dispersion of this viscous fluid, ensuring close contact with air. After 0.5 h after the start of the reaction, the oxidation of the copolymer begins, resulting in a decrease in viscosity. Stirring and reaction temperature are gradually reduced to 154 ° C n after 2.5 h according to silica gel chromatography, the recovered product contains 17% of active oxidized products, which corresponds to the calculated chemical conversion of the copolymer into oxygen-containing products (at O-5% oxidation of oil diluent).

900 g of benzene are added to 885 g of the oxidized srpolnmer product, heated to 5 49 ° C in a stream of nitrogen, then 0.62 g (0, CS07 mol) of powdered anhydrous para reformed ice is added at one time and the temperature is raised to 60 ° C within 0.5 hours. Then, at one time, 2.4 g are added

(0.0207 mol) of liquid anhydrous hexamethylenediamine, and the resulting mixture was adjusted to 80 ° C. The molar ratio of the pea gene and the young were respectively equal. 1: 4: 4. After one hour at an average rate of distillation, complete separation of water occurs. Residual benzene is removed by heating the reaction mixture to 100 ° C in a stream of nitrogen. Heating and flushing with nitrogen continue for more than 1 hour to remove residual volatile impurities. Obtain 800 g of pure product (output 39,4 ° / OH with the following indicators: Activity,% 13

Nitrogen content, found,% 0.058 calculated, / o 0.063 Viscosity measured in a Seibolt-univercé Viscometer at 99 ° C, c2 | (U

Example 4. 1625 g of a solution consisting of 130 g of an oxidized ethylene propylene copolymer described in Example 3 and 1495 g of mineral oil extracted from the solvent are mixed with 1200 cm of benzene and prepared for oxidation as in Example 3. Anako oxidized copolymer paraformaldehyde and hexamethyl diamine are used in a molar ratio of 1: 8.6: 8.6, respectively, based on (as in example 3) an oxidized copolymer having an average molecular weight of 22,200. The reaction conditions and the procedure are the same as in example 3 Get a clean product with 99.5% yield, having the following characteristics:

Activity% .8,0

Amount of nitrogen. found % 0.084 calculated,% 0.086 Viscosity, measured on a Saybolt station wagon viscometer at 99 ° C, s1125

Example 5. A copolymer obtained from 55 mol.% Of ethylene, 35 mol. / O of propylene and 10 mol.% / O-decene is prepared and then oxidized as described in example I. Then the oxidized copolymer is treated with paraformaldehyde and hexamethylene diamium under the condition x of example 1, and these reagents are used in a molar ratio of 1: 4: 4, respectively. The recovered product has an activity of 13% and contains 0, nitrogen.

Example 6. A copolymer of ethylene and propylene with a molecular weight of 12,000, containing 140 methyl groups per 1000 carbon atoms of the main chain, is dissolved in heptane at a temperature of 95 ° C, mixing them. Mineral oil is added to the hot mixed solution at the rate of 400 g of oil per 0.005 mol of co-chohlimer, and the solution is heated to separate heptane, which is added by introducing nitrogen B {) into the newly formed solution. After removing heptaia, 460 g of the solution contains 0.005 maa

or 13 ./o copolymer. This solution is vigorously stirred at lUFC. Then the solution is heated to 150 ° C and air is introduced into it at the indicated temperature, while in

As a result of infrared absorption, no 1 ketocarbonyl group is formed per molecule. The solution of the oxidized copolymer contains about 0.005 mol of the oxidized copolymer and 400 g of oil diluent. 450 g of such a solution containing

OD) 05 mol of the oxidized copolymer, stirred and kept under nitrogen at 120 ° C, at the same time adding formalin {37% CHjO) to obtain 0.02 mol of formaldehyde and 0.01 mol of molten hexamethyldiamide. The temperature of the resulting solution increases, as a result of the heat of reaction, 7 and under the influence of the molten diamine. After that, the reaction mixture is heated to 170 ° C, maintained at this temperature

0 for 30 minutes, nitrogen is introduced into it and then the reaction flask is emptied into a water-cooled vessel. Stirring, heating to 170 ° C and introducing nitrogen continue until the formation of water condensate has ceased.

The resulting solution contains 11.14% of the oxidized copolymer, formaldehyde and diamine with the corresponding molar ratio of reagents 1: 2: 2. The nitrogen content in the solution is 0.062, and the oxygen content is 0 0.017 wt.%.

Example 7. A solution containing 0.005 mol of ethylene, propylene and 1,4-butadiene is a terpolymer with a molecular weight of 100,000 and containing 400 methyl groups and 1000 carbon atoms of the main chain, for 4500 g of oil is prepared at 170 ° C. The solution is shaken and oxidized with a gas mixture consisting of 50% oxygen and 50% nitrogen by volume at a temperature of 180 ° C until

0 the oxygen content in the oxidized polymer, determined by infrared absorption, does not constitute one ketocarbonyl group per molecule. The solution obtained for this purpose contains, for every 4500 g of oil, 0.005 mol of an oxidized polymer with a molecular weight of 72000.

A sample of such a solution weighing 4860 g (0.005 mol of oxidized polymer) is diluted with benzene, so that the diluted solution can be easily moved at a temperature of 140 ° C. Melted hexamethylene diamine (0.04 mol) —and molten formaldehyde vapor are added to a hot solution of the sequence; gg io to obtain 0.04 mol CHj O. The resulting reaction mixture 55 is heated by the heat of reaction and the temperature of the reagents is maintained at 180 ° C for 60 minutes, after which the rheu |: cyoin vessel is refluxed to distill off benzene and with a fridge with

side output to allow water condensate to drain, is a byproduct. Nitrogen is then introduced into the hot diluent until all benzene and all the co-product is swept away. The resulting solution, weighing 4865 g, contains 0.005 mol of condensate product containing 1: 8: 8 individual components. The solution contains 0.023% nitrogen and 0.0016% oxygen by weight.

Example 8. An oily solution of a copolymer with a molecular weight of 55,000 ethylene and propylene, containing 175 methyl groups per 1000 carbon atoms of the main chain, is oxidized as described above. The resulting solution contains an oxidized copolymer with a molecular weight of 43,000 with one ketocarbonyl group per molecule.

According to the invention, 0.0 mol of oxidized copolymer, 0.153 mol of hexamethylenediamine, and 0.153 mol of formaldehyde, obtained by JO from paraformaldehyde, react with 5.973 g of mineral oil diluted with 1500 g of benzene at a temperature of 80 ° C. Ben

30/1 is used as a diluent so that the reaction mixture can be shaken more easily and to facilitate the removal of water, which is a side reaction product, as described in the previous section. The patch solution of the product (molar ratio of reagents 1: 15.3: 15.3) contains about 7% by weight of the product with a nitrogen content of 0.06% by weight.

The viscosity indices of the product are given in abl. 1, in which the following oil samples are used:

Sample A - oil grade 150 on a neutral basis;

Sample B — AHfazan A plus 1.1% pure (i.e., undiluted) product obtained in Example 1;

Sample C — Sample A plus 1.5% pure oxidized polynzobutylene (average molecular weight 1500);

Sample D — Sample A plus 1.5% pure oxidized ethylene propylene copolymer (average molecular weight 2000)

T a 6 l and a

The effectiveness of the Additives according to the invention is tested by the method of petna. In this test, a certain amount of the test additive is mixed with a certain amount of lubricating oil for cm; crankcase, the composition of which is used in an engine test program lasting 192 hours (this time is three times longer than the normal test time). This composition is heated and stirred at 149 ° C for 16 hours, and a portion is transferred onto blotting paper. At the same time, another oil used in the 192-hour engine test program is tested by mixing and heating 149 ° C for 16 hours and depositing one aliquot on blotting paper. At the same time, for comparison, the readily available commercial bisazole dispersing agent is mixed in the manner described above. Deposits on blotting paper are altered to obtain the average diameter of the outer oil circle (D)) and the average diameter of the inner circle of the sediment (Da). The ratio is an indication of the detergent dispersant properties of the additive agent.

In tab. 2 shows the density of such an additive in comparison with the trademark of a dispersant additive. In the test using the following samples:

A - control oil without dispersing agent;

B - control oil plus 1.0% of the product from example 3.

C - control oil plus 1.0% of commercial dispersant priGPVKI. Table 2 Progress Dispersion of Surge Argues From the data presented, it follows that the proposed products are effective dispersing agents and are superior in terms of their properties to the best commercially available dispersing agents. Lubricating oil compositions containing the products supplied are tested. The following oils are used in the test. Sample A, composition,% by volume: Oil extracted from solvent 49.8 Oil extracted from solvent 36.8 Zinc bottled dithiophosphate1, 2 High base magnesium sulfonate .1.2 Product, Example 3 (13 ° active / o ingredient 1.4 o6.% 11.0

The data given in table. I, 2, and 3, showing: that the proposed product gives a composition with a high level of dispersibility and good viscosity index properties.

Claims (2)

Invention Formula The method of producing additives for lubricating oils of oxidized olefinic polymer processing with formaldehyde n polyalklen-polyamine at 120 170 ° C, characterized in that, in order to increase the dispersion of table 3 Bridges of additives in oil H improve the viscosity of the latter, as an oxidized olefinic polymer, an oxidized copolymer of ethylene n propylene or ethylene, propylene and C-Su-a-olefin with an average molecular weight of fOOOO - 100000, having 140-400 methyl groups on 1 (HU carbon atoms of the main chain in a molar ratio of copolymer: formaldegnd.-polnalkylenopolynamn g 1: 2: 2 - 1:20:20, respectively. Sample B, composition, o6.%; Oil extracted from solvent 25, 1 Oil, extracted from dissolve, 80.0 Zinc bottled ditnofosfat1 .2 C high base magnesium ulfonate1.2 Depressant additive, persisting oil hardening temperature 0.5 Product described in Examples Zi 4 (activity 0 ° / o, active ingredient 1.2% r.) 12.0 Sample C: Oil extracted from solution 30, 0 Oil extracted from solvent 56, 93 Zinc dialkyl dithiophosphate1, 1 Magnesium sulfonate with a high base2.0 Commercial additive that improves the properties of oils 5.2 Silicone protrusion agent 0.05 Commercial ashless dispersing agent (active 42%, active ingredient 2 .%), 4.77 Data received nnye in these tests, is led) in the Table. 3 13f.:VV187Н Sources of information taken from 2. US patent number 3316177. cl. 252 51.5. mania during examination: 1967. I. US Patent No. 3368972. CL 252 47.5.3 US Patent No. 3544520. CL. 260- 72. 1968.197P.