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    • 专利摘要:
    Graft copolymers wherein the backbone polymer is a rubbery, oil soluble ethylene-propylene copolymer or ethylene-propylene diene modified terpolymer and the graft monomer is a C-vinylpyridine or N-vinylpyrrolidone impart dispersant properties to hydrocarbon fuels and combined viscosity index improvement and dispersant properties to lubricating oils for internal combustion engines. The graft copolymers are prepared by intimate admixture of backbone polymer, graft monomer and free radical initiator at a temperature below initiation temperature, followed by a temperature increase to or above initiation temperature, thus providing a product containing little or no byproduct.
    公开号:SU969167A3
    申请号:SU772503853
    申请日:1977-07-21
    公开日:1982-10-23
    发明作者:Ли Стэмбог Роберт；Адриан Галлучио Ричард
    申请人:Ром Энд Хаас Компани (Фирма)；
    IPC主号:
    专利说明:

    when heated, as azotsoder zhaschego vinyl monomer is 2-vinylpyridine, 2-methyl-5-vinilpyridin, N-vinyl pyrrolidone or dimethylaminoethyl methacrylate, and as the hydrocarbon polymer is an ethylene-propylene copolymer etilenpropilondienovy copolymer or low density polyethylene, wherein the hydrocarbon polymer rastvrr dissolved in an organic solvent, then a nitrogen-containing vinyl monomer, a free radical initiator at a temperature of 25 ° C below its decomposition temperature, is added to the resulting solution, with es homo geniziruyut and raise the temperature to the decomposition temperature of the initiator. The method is carried out as follows. The original carbon; the hydrogen copolymer is first dissolved in an organic solvent (for example, dichlorobenzene) at 90-150 ° C until a homogeneous mixture or solution is obtained with continuous stirring. The temperature of the homogeneous solution or mixture afterwards is reduced to about 80 ° C and the graftable monomer is added to the mixture. Then, the initiation agent acting at high temperature (tert-butyl perbenzoate) is introduced at (at this temperature its decomposition does not occur). Thereafter, the monomer, initiation agent and rubber material (hydrocarbon copolymer) are mixed until a homogeneous solution of all components is obtained. In the particular case of ethylene polypropylene copolymer or rubber is introduced in a concentration of about 20 to 30 weight. (based on the solvent), Monomer (for example, 2-vinylpyridine) is administered at a concentration of 1-15 wt. %, prior to about 10 weight. %, based on the hydrocarbon copolymer. The initiation agent is introduced in a concentration of 0.5 to 2 wt.%, More preferably 1 based on the weight of the ethylene-propylene copolymer. During mixing, the temperature is gradually increased to 120-U ° C, preferably 80-150 in order to activate the initiation agent or catalyst, and keep it between these points for about 1-2 hours during this time period the reaction is essentially complete. The finished polyolefin graft copolymer typically contains about 1-10 by weight of nitrogen-containing monomer (preferably 2-6, more precisely 3%}, such as 2-vinylpyridine. The formation of an intimate mixture of reagents prior to initiation is a key aspect of the invention. During the grafting reaction described the method eliminates the formation of a highly undesirable by-product of most grafting reactions. The grafting efficiency, i.e. the percentage of olefin copolymer into which the polar monomer is incorporated, is reduced to max. The ethylene-propylene copolymers can have very different ratios between ethylene and propylene. When the ethylene content is above about 80, the copolymers are partially crystalline, lose their oil solubility and usefulness as substrates, Preferably the ethylene-propylene substrates contain about 50-70 mol. Ethylene, have a viscosity average molecular weight of 10,000-200,000 and a ratio between weight average molecular weight and average numerical molecular weight less than l. With a lower propylene content, higher molecular weights and a wider molecular weight distribution, copolymers are formed that are suitable for the proposed method, but less effective as agents for improving the viscosity index. Ethylene propylene thermopolymers contain a small amount (preferably less than 10 wt.%) Of a non-conjugated diene, such as 1, -hexadiene, dicyclopentadien or ethylidene norbornene. The maximum ethylene content is determined, on the basis of crystallinity (solubility), and the preferred range is 5-6 $ mol of ethylene. A molecular weight of 10,000–20000, recommended by a viscosity average, with a ratio between weight average molecular weight and number average molecular weight is less than 8. Substrates that fall outside the specified interval can be used, but their properties from the point of view of improving the viscosity index (VI) worsened. . 5 The recommended temperature interval for grafting is about 80-150 seconds, however, the reaction temperature depends on the selected initiating agent. The reaction can take place over a wide temperature range (for example, 60-250 ° C, since the selection of the initiating agent is carried out with caution). The choice of the initiating agent and the temperature must be made so that the radicals do not form during the formation of an intimate mixture of reagents and that the process of their formation begins only after the temperature of the reaction mixture rises. During the grafting reaction, any aliphatic or aromatic hydrocarbon may be selected as the dissolving medium, including mineral oil; In this medium, a graft copolymer is obtained, since all the components are soluble in the dissolving medium. Recommended solvents are halogenated aromatic hydrocarbons, such as chlorobenzene and dichlorobenzene (flax dichlorobenzene is most preferred). The reaction can be carried out in the absence of a solvent if the substrates are of sufficiently low melt viscosity at the grafting temperature. When agents of improved viscosity index are subjected to strong mechanical stresses, the source of which is mechanical equipment, the polymers may undergo destruction, and this will reduce the beneficial effect that these additives have on the viscosity and temperature properties of the lubricant. material. This tendency of polymers to mechanically degrade under operating conditions is characterized as shear strength -. The ability of agents to improve viscosity index to resist mechanical displacement when used depends on a number of factors, but molecular weight is of primary importance. The polymer of a very high molecular weight, although it initially creates the entire .my effective regulation in C-temperature properties, is very STRONGLY degraded under working conditions and therefore most of its influence (or its influence completely) disappears. 6 The graft copolymers obtained by the inventive method have a molecular weight too high to be suitable as viscosity improving agents, i.e. they have low shear strength. This is partly due to the technology and production conditions used in the rubber industry, in particular by manufacturers of ethylene-propylene copolymers and thermopolymers. Such polymers are usually prepared with a high molecular weight so that the products are relatively rigid materials. In the case / when these rubbers are prepared with a molecular weight suitable for their use as agents for improving the viscosity index, the polymers are sticky solid materials that flow or creep even at ambient temperature. This requires a slower processing and, consequently, higher costs. Therefore, when used with the proposed method, the usual these. Lenpropylene copolymers products have a molecular weight that is too high to create acceptable shear strength. During the grafting reaction, a significant thickening occurs and, in the evaluation of the graft copolymer, there are signs of deterioration in durability and shear. This leads to the fact that part of the reaction is the process of crosslinking. Although crosslinking can be eliminated, the products thus obtained are usually worse dispersing agents than those prepared by the proposed method in which the degree of crosslinking is acceptable and controllable. Therefore, to some extent this is inherent in the grafting process, and in order to obtain maximum dispersibility it is necessary to make some compromise on shear strength. Currently, there are ways to reduce the molecular weight to the desired interval, i.e. to the point where shear strength becomes acceptable. For this purpose, only mechanical or thermal destruction of the product is required, carried out after the grafting reaction to establish the molecular weight in the recommended range. It has been found that although the grafting reaction products can have a molecular weight of about 30,000 ° C, the desired interval for the final dispersing agent and an improvement in the viscosity index of about 30,000-80000. Any method of degradation can be used, for example, lithing a gear pump or a machine for continuous extrusion, but homogenization is preferred. With this method, the floor is forced under high pressure through a homogenizing device, which uses throttling valves of various designs and narrow openings. In such a device, shifts in the order of 5,000 can be created, preferably about 10,000 to 10,000,000 s. The homogenization process can be carried out periodically or continuously, depending on the degree of destruction desired. The advantage of applying the homogenization process is also that the products obtained by the proposed method become even more effective thickeners than the ethylene-propylene copolymers produced that do not have dispersing properties. Thus, these products, when used in the homogenization step, have not only excellent dispersing performance, but also an excellent balance between thickening and shear strength. They can be used in a wide variety of fuels and lubricants. Their main purpose is additives to lubricants. in this case, their dispersibility and their influence on the viscosity and temperature characteristics is of great importance. Primary materials for the manufacture of lubricating oils include oils of both mineral (petroleum) and synthetic origin. The viscosity of the oils may vary in the invert from the spun oil to the crankcase and lubricating oil for the gearbox. Suitable synthetic fluids include esters such as dialkyl alipinate, dialkyl sebacate, OR dialkylase, triethyl ethers of methylolpropane, Erythritic pentaether ethers, polyalkylene glycol esters, esters-phosphates I1; Typical applications include hydraulic fluids, automotive gear oils, crankcase oils, gearbox lubricants and. fats. Products obtained by the proposed method can be introduced into lubricants in an amount of about 0.3-2.0 weight. (typically approx. 0.6-1.5 weight D. Because these products are rubbery solids, they are processed in the usual way in the form of viscous concentrates containing approximately 7-15% by weight of solid substances in the oil, and the consumer must use such an amount of concentrate to obtain the specified range of the content of the polymer ingredient. Lubricants containing the proposed products may also include other additives to create additional dispersing ability, viscous temperature control, reduction of the freezing point, resistance to high temperatures, inhibition of rust, atmospheric agents, antioxidants, agents that resist extreme pressure, friction modifiers, anti-foaming agents or dyes, dispersion properties of the characteristics. Thus, these products when applied, the stages of homogenization not only have the characteristics of dispersing ability, but also an excellent balance between the ability to thicken and the strength th shear. They can be used in a wide variety of fuels and lubricants; The main purpose is additives to lubricants; in this case, their dispersibility and their effect on the viscosity and temperature characteristics is of great importance. Primary materials for the manufacture of lubricating oils include oils as minerals (petroleum). So also of synthetic origin. The viscosity of the oils may vary from spindle oil to chartered and lubricating oil for gearboxes. Suitable synthetic fluids include esters such as dialkyl adipate, d alkylsebacate or dialklaselainate, trimethylolpropane tetraethers, tetraethers, polyester alkylatane, tetraether, and tetraetherylate, polymethylolpropane, tetraether, and tetraether, in the form of a tritaether, in a solvent, and in the form of a tent, in the form of a tent, in a triterol, in a polyester lithium teaster, a tetraether, a polyester, a tetraether, a tetraester, a polyester, a tetraether, a tetraether, a tetraether, a tetraether, a polyester, a tetraether, a tetraether, a tetraether, a tetraether, a tearatere, a polyester, a polyester, a tetraether, a tetraether, a tetraether, a tetraester, a polyester, a tetraether and a tetraether. (t, phosphate esters or synthesized hydrocarbons of the type p-alpha-olefins or alkylbenzene. K; the number of typical applications from hydraulic fluids, transmission oils for automobiles, crankcase oils, gear lubricants and fats. Products produced by the proposed method can be added to lubricants in an amount of 0, -2,0 wt.%, typically about 0.6-1.5. weight .. Since these products are rubbery three-fold substances, they are processed in the usual way in the form of viscous concentrates with an approximate content of 7-15 by weight, solids in oil, and the consumer must use such an amount of concentrate to obtain a specified content interval polymer ingredient . Lubricants containing the products offered may also include other additives to create additional dispersing - capacity, viscosity and temperature control, lowering the point of melting, resistance to high temperatures, rust inhibition, weather resistant agents, antioxidants, agents that promote extreme resistance. pressure, friction modifiers, backwash foaming agents or dyes. When these products are used in fuels, where dispersing ability is usually important, they use smaller amounts (about 0.001-0.1 wt.%). These fuels may also contain other additives, such as antioxidants, deactivators. metals, stabilizers, anti-rust agents, nozzle detergents, additives that control deposits in the feed system, or other detergents for carburetors.
    for evaluating crankcase oil in terms of sludge formation and varnish deposition resulting from engine operation at low and moderate temperatures. This test indicates the ability of the oil to support positive ventilation of the valves of the cardoa, to keep them in asphalt asphaltenes. The method for determining the dispersing ability of any given polymer is based on the ability of a polymer to disperse asphaltenes in typical mineral oil. Asphaltenes are obtained by oxidizing naphthenic oil with air in the presence of trace amounts of iron oxide as a catalyst (ferric naphthenate). The oxidation is typically carried out at 175 ° C for about 72 hours by blowing air through naphthenic oil to obtain a slurry, which can be separated by centrifugation. The slurry is removed from the oil (extraction with pentane), dissolved in chloroform, and the resulting solution is brought to a solids content of about 2. (bree / volume). If it is necessary to determine the dispersing ability of the polymer, it is dissolved in standard oil, (neutral solvent extracted by solvent 100). It is possible to obtain mixtures containing different amounts of polymer in the oil, approximately 2-0.01 wt. % or less. 10 ml of the mixture treats 2 ml of a standard solution of asphaltenes in chloroform, the sample and the reagent are thoroughly mixed in a test tube, which is then placed in an oven with forced 1 ventilation with a temperature of 90 or 150 and 2 m to remove volatile substances. After that, the test tube is allowed to cool and observe the appearance of the sample. In that case, if the polymer has a dispersing activity, the oil appears transparent, although colored. If the polymer does not have dispersing activity, then at a concentration below about 2% it will not improve the purity of the engine parts when tested on engine parts. B. U-C Sequence Test The Y-C sequence characterizes the method / testing of the tote engines and ensures that they are properly maintained. Test Results. The test engine was completely disassembled, cleaned, and reassembled in a special way. After that, it was installed on a test bench on a dynamometer with appropriate devices for controlling the speed, load and other conditions. The engine worked on standard MS-08 fuel in three stages. During the first stage, the engine operated for 120 minutes at high power, with moderate oil temperatures and s with a high air-fuel ratio (fuel-poor mixture) (A / D). At the second stage, the engine worked for 75 additional minutes at higher temperatures of oil and water, at the third stage - for 45 minutes at low revolutions per minute, at low temperatures of oil and water, and with a low ratio between air and top LIVOM (rich in fuel mixture). Four cycles, each of which lasted for hours, were carried out with dust, and these cycles were performed every day until 8 cycles were carried out (192 working hours of the engine). The engine was then completely disassembled to determine the degree of wear, the presence of sludge, varnish and deposits on the valves. In addition, the blockage of the RUS valve, oil rings and oil sieve was determined. In this test, the ability to disperse the sludge is evaluated, since the lubricant must operate at both low and moderate temperatures. Example. A. Grafting 2-vinylpyridine to ethylene-propylene-ortho-dichlorobenzene copolymer, 657 g added to a clean, nitrogen-flushed, 5-liter flask and; heated to 100 ° C in an atmosphere of azr; ta. Sample from the BO / AO mol. The% copolymer of 31 polyethylene propylene is cut into small pieces and added to the solvent. A total of 225 g of hydrocarbon copolymer is added to dichlorobenzene. After obtaining a homogeneous solution, the contents of the flask are cooled to Btf C and 22.5 g of 2-vinylpyridine produced is introduced into the flask. After “stirring”, 1.32 g of 85% tert-butyl perbenzoate is added to the flask and the temperature is maintained for 0.5 h to complete the stirring, and then the temperature is raised to and within 0.5 h. After holding for kQ a further 1.32 g of tert-butyl perbenzoate is added at this temperature. The solution is kept at YO C for 1 hour and then 1720 g of neutral solvent 100, which is refined mineral oil, is added. The product solution is then stripped in vacuo from the solvent and unreacted monomer at a final pressure of 0.5 mm Hg. Art. and, keeping in these conditions for 1 hour. Then the product is further diluted with 305 g of neutral oil 100 and a concentrate is obtained / containing 10, wt. graft copolymer. A sample of the graft copolymer is isolated (isolated) by dialysis; it contains 0.41 wt. nitrogen, as determined by the Kjeldahl method. The content of titrated nitrogen .0,40 weight .. V. Data characterizing the mixture. The mixture of crankcase oil was prepared according to the following recipe. Formulation B: 8.10 wt. a concentrate in the oil of a product graft copolymer, the preparation of which is described in A; 0.50 wt. Of agent for suppressing the freezing point of i 2.00 wt. an ashless dispersing agent, polybutene succinimide; 2.00 weight. basic magnesium sulfonate (400 TBN); IvSO dB dialkyldithiophosphate, zinc; , 38, b5 6es.% Mineral oil; 47.24 weight. % neutral oil 0.01 wt. % defoaming silicone solution. Viscometric characteristics of the above mixture compared-. The properties are based on the properties of an additive-treated oil that does not contain an agent for improving the viscosity index (VI). It was found that the graft copolymer (A) can be used for the preparation of the crankcase mass, and the W 40 grade (Table 1).
    13
    969167
    1 Table 1,
    C.- Determination of dispersing ability. .
    1. Asphaltene test. In the standard asphaltene test, 0.0–25 wt.% Of the graft copolymer (D) dispersed in Q, k% asphaltenes is used at. The initial ethylene-propylene copolymer does not disperse asphaltenes, even at a copolymer concentration of 2.0%.
    2. Testing for the sequence Y-C (Table 2), 192 h.
    The U-C sequence test was also carried out with formulation B. The test results are given along with the technical conditions that must be met in order to satisfy the working. SE classification of the American Petroleum Institute. Also given. test results using
    , 2 9.3 8.4 7.8 8.2 7.5
    graft copolymer of ethylene propylene with a low content of 2-vinylpyridine used in the same combination as in paragraph B (column 2). This copolymer, obtained during the unsuccessful inoculation experiment, contained only 0.08% by weight of nitrogen, determined by the K'ydal method, and could be considered as the main case. The third column shows the results obtained using a widely used dispersing agent, a methacrylate copolymer. The dispersing activity of the graft copolymer (A) used in formulation B is significantly superior to the market polymethyl methacrylate activity even when the graft copolymer (A) is used in only 25% of the level used in the use of the market product.
    I, Table2.
    8.5 min 8.0 min 7.9 min
    five
    ten
    clean PRI me R 2. The concentrate in copolymer A oil from Example 1 is homogenized under a pressure of 5 W / kg / m of the Menthol-Gaulin laboratory homogenizer, model 15M-8TA. Part of the graft copolymer A is removed after one run (the product is designated as PA), while as the rest is recycled for two additional runs. The ability of the copolymer does not change during homogenization. An evaluation of the shear strength of these products was carried out with typical 10 W “O. recipes. Base oil with a viscosity of 6.0 g / s ы for the effectiveness of graft copolymers as a thickener resio excellent 96916
    .16 Continued table. 2
    walks that of market polymethacrylates. P-A product cooked thickened to viscosity 15, O10 m / s at 98 ,. Lubricants were subjected to destruction in an ultrasonic oscillator according to the AS D-2603 method. Based on the results obtained, it is possible to predict that the change in viscosity will occur after a run of 000 m in the conditions of the operation of the crankcase. Comparison of the shear strength of these homogenized products and the market polymethyl methacrylate, as well as the market, not covering the dispersing ability of ethylene propylene cycpimer, is given in Table. 3. Table 3
    However, homogenization requires about 30% less polymer to achieve an equivalent ratio between agglomeration and shear strength than the market non-dispersing ethylene propylene copolymer.
    Since ethylene-propylene copolymers do not lower the solidification point, - All oils contain 1.1 wt. tf-B, which corresponds to the content. These data can be considered quite acceptable for lubricants 10 W50 car crankcases. .PrimerZ. A 500-mm flask equipped with a thermometer with a c-type stirrer, a reflux condenser, and a nitrogen supply tube was injected with 120 g of benzene. The benzene is heated to 8 ° C and 30.0 g of 60/40 mol. Copolymer is added. % ethylene propylene in the form of small pieces. Heating and stirring are carried out until the copolymer is dissolved (approximately 6 hours), then 2-vinylpyridine is added and the temperature of the solution is reduced to. At this point, the first portion of the initiating agent solution (dicyclohexyl peroxide sidicarbonate) is added 0.30 g of benzene dissolved in 0.70 g of benzene, the residue of the initiating agent solution in portions of 0.20 g each is added at 15-minute intervals some polymethacrylates do this, and in some cases interfere with the action of auxiliary agents lowering the pour point, commercial interests indicate the need to demonstrate the low-temperature properties that can be imparted to the products. The results are given in table. .
    Table 4. Calculation of the polymers of the product of the olimer in the formulation 10W50, the torus is introduced in portions for 1 hour. The reaction mixture is heated for another hour, then oil 100 N is added and the benzene is removed by distillation at atmospheric pressure. Unreacted monomer And other volatiles are removed by distillation in vacuo under a pressure of 0.5 mm Hg. Art. at a cube temperature of 135 ° C. The resulting graft copolymer can disperse 0, t wt.% Asphaltenes at 150 C when used at a concentration of 0.0625%. The nitrogen content in the pure copolymer is 0.27 wt.%. PRI me R l. A five-liter three-liter flask is equipped with a thermometer introduced through a flexible rubber tube attached to a glass-type c-type adapter, mounted in. a glass adapter using a Teflon inlet and a Y-shaped tube into which a dropping funnel with equalized pressure was introduced (LENieM and chilled water in the head. An inlet tube was placed at the top of the refrigerator to create a nitrogen atmosphere throughout the reaction. As a heat source, used. A heating jacket is used that is controlled by a laboratory autotransformer. A 337.5 ru "blend of refined neutral oil 100 is introduced into the reaction flask. The oil is heated with stirring until then gradually adding 225.0 g of an ethylene-propylene terpolymer with 60 mol.% of ethylene and 0 mol. of propylene-diene containing a small amount of diene (1-10, in this case 1-5) are added. The mixture is heated for 5 hours. -TbO P. After completion; dissolving the ter-i polymer, the temperature is lowered for about 1.3 hours and then 1.31 g of market tert-butyl perbenzoate is injected into the reaction mixture. The solution is stirred for approximately 30 minutes at Jero mixes rather quickly heat up. Then another 1.31 g of t-butyl perbenzoate is added. The solution becomes more viscous with continued stirring for 50 minutes at 140 ° C. With this solution, the solution is diluted to approximately 25% solids per polymer substrate and stirred for 3.3 hours at 120-1 ° C. The solution is stripped from unreacted 2-vinylpyridine under pressure, 1.5 mm pTi for 30 minutes. Add oil for dilution so that the final solids content is 10.8% D (according to dialysis data). The grafted polymer product (the grafted terpolymer is analyzed to determine the nitrogen content by the Kjeldahl method and titration with chloric (acetic) acid and a value of 0.53 and O is obtained, 57, wh, corresponds to J, O, and 4.3 wt.% 2-Vinylpyridine in a polymer. The solution co: holding 0.0–25 wtD of the grafted thermal product fully disperses 0.4 wt D of asphaltenes at IStfC. Base oil containing essentially the same additives that were used in the B formula with viscosity 6 , 2110Ric at 98.89 ° C and | 38.841SG / s at 37, required the introduction of 1.46 wt.% Chiyt The 7th of the grafted polymer product so that its viscosity is 14.99-, 10 MVC at 98.89 s and 107.2 PO at 37.78 ° C. Example 5. 250 are introduced into the reaction vessel described in Example 4. g of ethylene-propylene copolymer (ml.%) and 400 g of solvent refined neutral oil 100. The solution is heated with stirring at 175-200 ° C in order for the polymer to dissolve in oil. Complete dissolution requires 3 hours. The temperature is reduced to 76 ° C and within 10 min. 22.5 g of 2-vinylpyridine are introduced. The solution was stirred for 1 hour to interlock 2-vinylpyridine. At the end of the hour, 1.45 g of tert-butyl perbenzoate was added and the solution was stirred at 80-90 0. After 20 minutes, the heat supply was set so that the temperature rose to. After 45 minutes, 125 liters of neutral oil 100 were added to the solution. With a total reaction time of 2.5 hours, counting from the first addition of 2-vinylpyridine, another 1.45 g of tert-butyl perbenzoate was added. After 3 minutes, 135 ml of 100 ml neutral oil was added to reduce the viscosity of the solution. Further injections of neutral oil 100 are made after 3 hours (380 ml) and 3 hours and 15 minutes (500 ml). The solution is heated to and maintained at this temperature for 0.5 h, after which the unreacted monomer is distilled from the solution at a final pressure of 1.5 mm. Hg and 159 ° C; these conditions are maintained for 0.5 hours. After distillation, the solution is diluted with a neutral oil of 100 for the final solids content: 8.5% by weight. Graft copolymer, isolated by; dialysis was analyzed to determine nitrogen by titration with perchloric acid (acetic; acid) and a value of 0.45 was obtained. This corresponds to the introduction of 3.4% by weight of 2-vinylpyridine into the polymer. A solution containing 0.025% by weight of the graft copolymer , completely dispersed 0.4% by weight of asphaltenes at. Adding 0.90% by weight of pure graft copolymer to the base weight of Example 4 resulted in a solution whose viscosity was 1.92% at 98.89 ° E 103.9-1o4, Vc at H / .. EXAMPLE 6. In a five-liter, three-neck flask equipped with a stirrer, a thermometer , a dropping funnel and an adder attached cooler, to maintain a nitrogen atmosphere, load 250 g of a market terpolymer of ethylene propylene diene with a suitable molecular weight to be used as an agent for improving the viscosity index of motor oil. 297 g of dichlorobenzene and g of solvent are added - neutral refined oil 100. The mixture is heated to and stirred for an hour, during this period of time the rubbery terpolymer dissolves and the mixture becomes homogeneous. The mixture is cooled to 8090PC and 25 g of 2-vinylpyridine are added. Stirring is continued for another 30 minutes to obtain a homogeneous mixture. A solution of 1.46 g of marketed 85% tert-butyl perbenzoate in 13.1 g of neutral oil is introduced through an addition funnel into this addition for 13 minutes and the stirring is continued in those mixtures. Then the mixture is heated for another half hour. soak up to within half an hour and kept at this temperature for another 30. min. Another solution of 1.6 g of tert-butyl perbenzoate in 13.1 g of neutral oil 100 is introduced through a dropping funnel for 10 minutes and after that the stirred mixture is kept for an additional 45 minutes. 1250 g of neutral oil 100 is added and the mixture is stirred at 14 ° C until it is completely homogeneous. The refrigerator is rotated so that the distillation can be carried out in a vacuum, and the pressure is slowly reduced by 1-2 mm Hg. and under these conditions, the reaction mixture is kept for 0.5 hours. During this period, 312 g of a mixture of chlorobenzene and unreacted 2-vinylpyridine excess is distilled from the flask. An additional 833 grams of neutral oil 100 is added to reduce the solids content to about 10 wt. After that, the mixture is stirred to homogeneity. The product polymer solution (v. Oil) weighs 2510 g and contains 10.6 wt.% Solids (according to the data of dialysis). The dialyzed sample is analyzed by titration and it is determined that the nitrogen content is Q, 3% by weight, which corresponds to 2.6% by weight of 2-vinylpyridine grafted to the substrate. When conducting the asphaltene test, it was found that 0.0–25 wt% of the pure graft copolymer was dispersed, 0 wt.% Asphaltenes at. When treating the base oil from Example 4 of a 1.3% solution, a product polymer (about 10, solution in oil), the preparation of which was described in this example, a liquid is obtained, the viscosity of which is 15.08 "10-1% with 98.8ES and. 109.571 (at 37.78С. PRI me R 7. Vinylpyridine was grafted to ethylene propylene diene thermopolymer containing 60 mol.% Of ethylene, 4O mol.% Of propylene diene, with a small amount of diene, as in Example 1. The product is then homogenized to create a lower molecular weight, as in Example 2. To obtain an agent for improving the viscosity index, which, when added to a polymer concentration of 1.40 to the base oil containing additives, as in the example, resulted in the formation of a complete oil, its viscosity at 98.89 and 37.78C amounted to Responsibly 15, 117, 651 h. The pure grafted terpolymer contained 0, by weight of nitrogen (according to anal data, 1 by the Kjeldahl method) and 0.0 by 25% by weight of this material was dispersed with 0.4% by weight of asphaltenes at 150 C. Sequence Y - From tests, in an engine of an oil prepared in this way, containing 1.40% by weight of a grafted terpolymer and only 1.0% by weight of polybutenesuccinimide, which is a benzene dispersing agent, gave the following results after 192 hours of operation: Average amount of sludge 8 , 1 Average amount of lacquer 7.8 Corking. Oil rings, 3 Zak oil spreading of the sieve, P / Lu Comparison of these data with the data of table 1 shows that the product obtained in the described manner has a high dispersibility. , PRI me R 8. Analogs are carried out in Example 1, but 2-vinylpyridine is replaced by 2-methyl-5 vinylpyridine. The polymer product, isolated by dialysis, contained 0, and weight of nitrogen, determined by titration with perchloric acid in an acetic acid / toluene medium, which served as a mixed solvent. In this case, 0.0–25 wt.% Of the pure graft copolymer was dispersed with Q.k wt.% Asphaltenes at 150 ° C. When the base oil from the example j was added to the search engine, it was 0.75 wt%, this grafted opatimer produced a liquid, which is 15, at 98.89 ° C and 118, at 37.78 ° C Example 9. 75 g of chlorobenzene are heated to 130 ° C in a three-necked .500 mm flask equipped with a stirrer, a refrigerator, a thermometer, and tubes for introducing and discharging nitrogen. Ethylene propylene copolymer (6Q / kO mol%) in an amount of 25 g is added to monochlorobenzene. After the solution becomes homogeneous, the temperature is brought to and it is maintained at this temperature. 0.25 g of t-butyl peroctoate dissolved in i ml of chlorobenzene is added. 1 ml of this solution is added to the polymer- solution. After 6 minutes, 2.5 g of N-vinylpyrrolidinone are introduced over a period of 2 minutes. Three additional portions of the initiating agent were introduced at intervals of 20 minutes. After 3 hours after the initial initiation of the initiation agent, 225 g of neutral refined mineral oil 100 was added to the flask. After that, the product was stripped with monomial from the solvent and the residual mixture; pressure mm Hg and these conditions are maintained for 30 minutes. The base oil of the example is thickened with a viscosity of 15,010 at 98.89 ° C, adding 1.0 wt. this polymer 0.25 wt.% the graft copolymer is dispersed 0.4 weight. % asphaltenes at. Example 10.100 g of ortho-dichlorobenzene was introduced into the apparatus described in Example 9, together with 33 g of ethylene-propylene copolymer (mol%). The mixture is heated at room temperature and stirred to obtain a homogeneous raster, 0.33 g of tert-butyl perocto-Tate is dissolved in k ml of ortho-dichlorobenzene. The polymer solution is heated to and maintained at this temperature, after which 1 ml of the initiating agent solution is added to the polymer solution. After 5 minutes, 3.3 g of M, N-dimethylaminoethyl methacrylate was added to the solution. At intervals of 20 minutes, three more portions of the initiation agent are added. After 3 hours from the initial introduction of the initiation agent, 200 g of mineral oil was added to the flask. The product is stripped from the solvent and the residual monomer, with final conditions corresponding to a pressure of 1 mm Hg, these conditions are maintained for 30 minutes. Another 97 g of oil is added to the solution to bring the final solids content to 10% by weight. With the addition of 8, a solution of the product to the base oil of example k, a prepared oil is obtained, the viscosity of which is 15.15. / s at 98.89 ° C and 111.8-10 m / s at 37 ,. When tested on the ability to disperse asphalt, it was found that 0.125 weight. .. pure grafted copolymer, isolated by dialysis, dispersed 0, wt. asphaltenes at 90 ° C. Example 11. 750 g of ortho-dichloro-benzene were introduced into a clean, nitrogen-flushed five-liter flask and heated to nitrogen. In total, 500 g of a market molecular weight hydrogenated styrene butadiene suitable for use as an agent for improving the viscosity index is added to dichlorobenzene. The mixture is stirred until a homogeneous solution is obtained. The contents of the flask are cooled to 80 ° C and an 8.0 flask is injected with 50.0 g of 2-vinylpyridine. After the completion of mixing, 2.9 g of marketed tert-butyl perbenzoate was introduced into the flask. The temperature was maintained at 8 ° C for 1.5 hours. After holding for another 40 minutes, another 2.95 g of initiation agent was added. The solution is then kept for the last 1 hour, the last portion of the solution of the initiating agent and 1683 g of neutral oil 100 are injected. The product solution is then stripped in vacuo from volatile substances and the final conditions correspond to a pressure of 5 mm Hg. Art. and temperature, maintained for 1 h. The product is then diluted with another 1150 g of oil and stirred to obtain a homogeneous mixture. A sample of pure grafted jpa copolymer is separated by dialysis, and the copolymer was found to contain 0.61 ppm of nitrogen according to the Kjeldahl method. I When adding 2.61 wt. The% of this graft copolymer to the base oil from example k is obtained with a solution whose viscosity is AND, 96 10V / C at 98, C and 101.1040 m7 at 37 ,. In the asphaltene test, it was found that 0.0–25% by weight of the pure graft copolymer. 0 weight was dispersed. asphaltenes at 150 ° C. Example 12: Analogs to example 10 are carried out; however, instead of ethylene I propylene copolymer, I sample amorphous propylene is used, and 2-ri,. nilpyridine replaced by N, M-dimethylamino ethyl methacrylate. The pure dialysis product contained 0.31 wt. % of nitrogen. It was found that 0.0b25% by weight of this graft copolymer was dispersed to 0, D weight. asphaltenes at 150 ° C. Example 13-Analogs to Example 1 are carried out, but di-tert-butyl peroxide is replaced by tert-butyl perbenzoate and two portions are added at 135 and instead of 80 and respectively. Thus, the primary mixing is carried out at 135 ° C as well. initiation of the reaction at. The polymer product isolated by dialysis contained 0.69% by weight of nitrogen, which was determined by titration with perchloric acid in a mixed solvent of acetic acid / toluene. Again, 0.0–25 wt. I of the graft copolymer disperses 0, i wt.% Of asphaltenes at 150 ° С. The main raw material containing .. additives similar to those used in the formulation B of example 1, having a viscosity of 5.5b1 and at 98, required the addition of: 0.93% by weight of graft polymer in order to: have a viscosity of 15 , 0610 mts at 98.89 ° C. EXAMPLE T. Example 13 is repeated, but the temperature of dissolution and the first addition of initiator is 0 instead. Initiation of re 7 shares is carried out at. The dialysis-treated polymer product contained 0.61% w / w nitrogen, which was determined by titration, and again. 0,0b25 weight. the graft copolymer disperses O, weight asphaltenes at. Example 15: A 5 gallon stainless steel reactor equipped with a double helix stirrer, an inlet aperture, thermocouples for measuring wall temperature and cutting mass and a connecting device to create a nitrogen atmosphere, loads 630 g of an industrial ethylene / propylene copolymer; having an appropriate molecular weight to use. it as a substance that improves the viscosity index of motor oil. 1878 g of o-dichlorobeneol are added, the mixture is heated to 115 ° C and stirred for 6 hours, during which the rubber dissolves. . 31% 5 g M-vinyl pyrrolidinone is added and stirring is continued for 30 minutes to obtain a homogeneous mixture. A solution of 1.2b g of dicumyl peroxide of 12 g of o-dichlorobenzene is added over 15 minutes and the mixture is stirred for another 0.5 hour until complete homogeneity. The resulting mixture is heated to 1.5 hours and stirred at 160 ° C for 1 hour. 00 g of the product is mixed with 1011 g of neutral oil 100 in a five-liter flask and stirring is carried out until a homogeneous mixture is formed. The flask is attached to a vacuum and the pressure is reduced to 12 mm Nd and maintained at that value for 1 hour, during which time o-dichlorobenzene and N-vinylpyrrolidinone are distilled off. The solution of the polymeric product in the oil contained 9.01% by weight of solids, as measured by dialysis, and the polymer product separated by dialysis contained O, 39% by weight I nitrogen, as determined by the Kjeldahl method. Again 0,0b25 weight. the graft copolymer dispersed O, wt.% asphaltenes at the Main raw materials, containing the same at | Cels, as in the formulation in example 1, had a viscosity of 5.5610 m / s at 98 ,, and it was required-0.83 weight . graft copolymer to obtain a viscosity of 15, (at 98,. Comparative experiments. Graft copolymers are prepared as described in the known method. Reduction of 2-Bp means 2-vinylpyridine. A copolymer with a highly unsaturated isoolefin-polyolefin backbone of the macromolecule ow Isobutyleneisoprene polymer.Two samples of half-measure (A and B) were prepared, they were compared with the sample of polymer (C) prepared by the proposed method in the example of producing a caumucous-like copolymer based on approximately 50/50 ethylenpropylene , mostly free of unsaturated i bonds. The results are shown in Table 5, the test procedure is the same as described above. The data in Table 5 show the following advantages of polymers and the way they are obtained as additives to engine lubricants compared to polymers according to a known method:
    Unsaturation, mol.%
    The nitrogen content in the polymer, wt.% (According Kveldalu)
    Download 2-QP,% Introduction 2-BP,%
    Dispersing asphaltenes%
    Columnar fractionation data:
    grafted polyme. : weight,
    active polymer, wt.%
    0.33 10.0 2, k6
    0.0625
    82.3
    71, 7. a) at least 302; greater nitrogen intake, although the amount of 2-vinylpyridine loaded is about half as much (10 versus 20% for preparing polymer samples A and B); b) at least 75% greater administration of 2-vinylpyridine, although its loading amount is half as much; c) only about 1/10 of sample 6 (0,0b25) is required to achieve the same degree of dispersion (asphaltenes), which is achieved using samples A and B; d) data of columnar fractionation show that the amount of copolymer grafted by the proposed method is 2–3 times greater than upon receipt of samples A or B; - e) the data obtained for the mixture confirm the higher thickening ability of sample C, since less than half the amount of polymer provides an equivalent level of viscosity while maintaining good shear strength (% LDTP).
    Mixing data, the content of the polymer, which has a viscosity of 15.0-10 m / s
    权利要求:
    Claims (1)
    [1]
    Claim
    A method of producing grafted copolymers by copolymerization of a nitrogen-containing vinyl monomer with a hydrocarbon polymer in an organic solvent in the presence of a radical initiator when heated, characterized in that, in order to increase the efficiency of the grafted copolymers when used as target additives to oils, as nitrogen-containing vinyl
    类似技术:
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    同族专利:
    公开号 | 公开日
    JPS5218705A|1977-02-12|
    FR2319654A1|1977-02-25|
    YU171876A|1982-05-31|
    BE844761A|1977-01-31|
    DK342776A|1977-02-01|
    SE437671B|1985-03-11|
    SE8401998D0|1984-04-10|
    US4146489B1|1983-11-08|
    IL50167D0|1976-09-30|
    ES450834A1|1977-08-16|
    SE460607B|1989-10-30|
    SE7607952L|1977-02-01|
    RO69516A|1981-08-30|
    DE2634033C2|1988-01-21|
    JPS5947686B2|1984-11-21|
    NL190610B|1993-12-16|
    DE2634033A1|1977-02-10|
    FR2319654B1|1980-05-30|
    GB1558991A|1980-01-09|
    SE8401998L|1984-04-10|
    IT1070321B|1985-03-29|
    SU843767A3|1981-06-30|
    JPS54145787A|1979-11-14|
    CA1088694A|1980-10-28|
    AU1645276A|1978-02-02|
    NL190610C|1994-05-16|
    ZA764290B|1977-08-31|
    NL7608543A|1977-02-02|
    US4146489A|1979-03-27|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US60065275A| true| 1975-07-31|1975-07-31|
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