SU378403A1 - PA "> & - О ••" .-: •• ^ J.M. Cl. From Yute 1.'28С 08f 3 / 64УДК 678.744.32 (088.8) - Google Patents

Description

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The invention relates to the preparation of acrylic polymers that can be used as Additives to oils.

A method of producing acrylic polymers by radical polymerization of acrylic monomers (methyl methacrylate, butyl methacrylate) by heating is known.

In order to obtain effective ashless additives. For oils, it is proposed to use acrylic or methacrylic acid esters and mixtures of synthetic alcohols of normal structure with carbon numbers 7-20 containing 20-30% of isostructures as starting monomers, and the polymerization process is carried out in the presence of organic solvent in the amount of 120-350% by weight of the monomer.

The proposed method allows to obtain polymers that can be used as effective ashless additives to oils. The use of these risks allows you to create high-index low-caking oils.

The starting monomers are prepared using alcohols with a carbon number of 7-20, produced, for example, by catalytic hydrogenation of fatty acid methyl esters (from paraffin oxidation) or by catalytic hydrogenation of these acids.

Light boilers and solvents used in the process of producing monomers (for example, toluene, xylene, benzene, gasoline, galoshes, etc.) are not distilled off from the resulting esters, since the polymerization of the latter proceeds in the same solvent.

Carrying out the polymerization in the presence of an excess of solvent (120-350% taking into account the amount of solvent contained in the monomer) avoids the formation of an insoluble polymer form and regulates the molecular weight of the resulting products.

At the end of the polymerization, after filtration, the polymerizate is mixed with a low viscosity sulfur oil in an amount that provides a content of 30-70% of the polymer in the additive after the solvent and monomers that have not reacted are distilled off. The solvent is distilled off continuously on a film rotary evaporator.

Example 1. In the polymerizer load 421.2 kg of ether (a mixture of 231 kg of methacrylic esters of a mixture of alcohols and 190.2 kg of toluene) and 176.8 kg of pure toluene. The total amount of toluene loaded is 367 kg or 160% for the polymerized ether.

At a liquid temperature of 85 ° C, a solution of benzoid peroxide (0.46-0.2%, calculated on ether) in toluene is gradually poured. The actual polymerization takes place at atmospheric pressure, with continuous stirring and at a temperature of 90-95 ° C for 5-6 hours. Then, after filtering, 371.5 kg of JS-12 oil are added to the polymerized polymer, the sulfur compounds of which prevent further polymerization during the distillation of the solvent additive and esters. unreacted polymerization. These products are distilled at a film pressure of 80 with an evaporator with a residual 100 mm Hg. Art. After distillation and filtration, 575.5 kg of the expected product are obtained, including 204 kg of polymethacrylate, the yield of which is 3-89%, calculated on the ester taken for polymerization. The finished product (additive) is a mixture of 35% polyacrylates and 65% IC-12 oil. Example 2. In the polymerizer load 421.2 kg of ether (231 kg of ether of alcohols and 190.2 kg of toluene) and 87 kg of pure toluene. Obs, its amount of toluene is 277.5 kg, which is 120%, calculated on the taken ester for polymerization. At 85 ° C, a solution of benzoyl peroxide (0.46 kg) is gradually poured under the conditions given in Example 1. After filtering the imerizate, 394 kg of IC-12 oil are added to it. The solvent and unreacted monomers are distilled off on a film simulator under the conditions specified in Example 1. The yield of polymethacrylate, considering the polymerized ester, is 92% (212.5 kg). Total. Get 606.5 kg of additive. The content of polymethacrylate in the additive is 35 wt. % The polymethacrylates of examples 1 and 2 have the ability to increase the viscosity and viscosity index of oils. Thus, adding polymethacrylate with 12,400 mol. .at. in the amount of 37 ° to the IS-12 oil, its viscosity at 50 ° С rises from 14 to 27 eats, and the viscosity index from 90 to 145, i.e., by 55 units. The addition of 8% full methacrylate of the same molecular weight to the IS-12 oil dramatically increases its viscosity at 50 ° C from 14 to 64 eats, but the viscosity index increases from 14 to 153 units, i.e. by 63 units . Example 3. In the polymerizer load 421.2 kg of ether (a mixture of 231 kg of methacrylic ether fraction of alcohols and 190.2 kg of toluene) and 387.5 kg of toluene. The total amount of toluene loaded is 577.5 kg or 250%, calculated on the ester, taken for polymerization. After heating the batch to 90-95 ° C, a solution of benzoyl peroxide (2.3 kg) in toluene is added to it. The actual polymerization is carried out at a temperature of 100-105 ° C, atmospheric pressure, continuous stirring for 8 hours. After filtration of the polymerizate, 134 kg of MC-10 oil are added to it, after which toluene and unconverted MOIIOmers are distilled off from the desired product - the additive. You polymethacrylate flow, calculated on the loaded ether, is 86.2% (199 kg. A total of 333 kg of additive is obtained. The content of polymethacrylate in the finished additive is 60% by weight. Example 4. The reactor is charged with 421.2 kg of ethereserate, which contains 231 kg of methacrylic esters of alcohols and 190.2 kg of toluene, and 502.8 kg of pure toluene. Total load 693 kg of toluene (300%, calculated on the air). Then, at 90-95 ° C, the peroxide solution is poured into it benzoyl (2.3 kg) in a solution of toluene. Under the conditions specified in Example 3, the actual polymerization proceeds, after which the 125 kg of MC-10 oil, toluene and monomers are distilled off from the finished product. The yield of polymethacrylate, calculated as ether, is 81% (187.1 kg). 312.1 kg of the finished product is obtained. an additive of 60% by weight. These polymethacrylates have the ability to increase the viscosity and viscosity index of oils. Thus, adding 3% of polymethacrylates to IC-12 oil increases its viscosity at 50 ° С from 14 to 20 eats, and the viscosity index with 90 to 135 units These polymethacrylates have low polydispersity, as a result of which they are almost not subject to degradation and the viscosity of the oil thickened by these polymethacrylates is stable when used in high-loaded mechanisms. Example 5. To the reactor load 482.9 kg of ether (276.5 kg of methacrylic esters of a mixture of alcohols Ci2-Cie and 206.4 kg of toluene) and 401.9 kg of pure toluene. The total amount of toluene loaded is 608.3 kg (220%, based on ether). After heating the mass to 90 ° C, a solution of benzoyl peroxide (0.8 kg) in toluene is gradually added. The duration of the polymerization is 5-6 hours / her ori continuous stirring, atmospheric pressure and temperature 98-105 ° C. After filtering the limerization products and adding to them 593.6 kg of IS-20 oil, the solvent and non-polymerized esters are distilled off from the additive (a mixture of polymethacrylates and IS-20 oil) under the conditions specified in Example 1. 848 kg of the finished additive are obtained, including including 254.4 kg of polymethacrylate. The yield of polymethacrylates, considered polymerizable ester, is 92%. The content of polymethacrylate in the additive is 30%. Polymethacrylate has the ability to lower the freezing point of petroleum oils and increase their viscosity and viscosity index. The table shows data on the effectiveness of the action of these polymethacrylates in oils of various viscosity levels.

Subject invention

The method of producing acrylic polymers by radical polymerization of acrylic monomers under heating, characterized in that, in order to obtain effective ashless oil additives, ethers are used as starting monomers

acrylic or methacrylic acid and a mixture of synthetic alcohols of normal structure with a carbon number of 7-20, containing 20-30% of the alcohols, and the polymerization process 1Conducted in the presence of an organic solvent in an amount of 120-350% by weight of the monomer.