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    • 专利摘要:
    Oil soluble ethylene polymers or copolymers having a Mn greater than about 4000 in combination with an oil soluble polyester material such as a homopolymer or copolymer, comprising at least 10% by weight C4 to C16 substantially straight-chain alkyl esters of acrylic or methacrylic acid, are useful in improving the cold flow properties of distillate hydrocarbon oils.
    公开号:SU718017A3
    申请号:SU762338656
    申请日:1976-03-26
    公开日:1980-02-25
    发明作者:Дж.Висотски Макс
    申请人:Эксон Рисерч Энд Инджиниринг Компани (Фирма)；
    IPC主号:
    专利说明:

    Atrial alkyl esters of acryloic or methacrylic acid.
    Ethylene polymers typically have a base metal base chain that is divided into segments by carbon and hydrogen, halide, or hydrogen and hydrogen side chains. The polymers can simply be homopolymers of ethylene, usually irradiating with free radical polymerization, which usually leads to some branching
    Examples of esters can be vinyl acetate, vinyl laurate vinyl laurate, vinyl myristate, vinyl palmitate, etc. When R is COOR.
    and in vivo, such esters include methyl acrylate, isobutyl acrylate, 2-ethyl hexyl acrylate, methyl methacrylate, lauryl acrylate, C, oxo-alcohol esters of methacrylic acid, etc. examples of monomers where RI is hydrogen, and RS. and ReCOOR groups include mono- and di-esters of unsaturated dicarboxylic acids, such as C-oxofumarate, di-C-oxofumarate, diisopropyl maleate, dalauryl fumarate, ethyl methyl fumarate, etc.
    Another class of monomers that can be. subjected to copolymerisy and hl with ethylene, includes C j-C rf-ole Fina, which can be either branched or unbranched, such as propylene, isobutylene, okten-1, iebbten-1, decen-1, before dozeni etc. .
    In addition, other monomers include vinyl chloride, although essentially the same result can be obtained with chlorinated polyethylene, for example, with a chlorine content of about 10 to 35 wt. % sludge branched polyethylene can be used as a polymer.
    These oil-vnjc; Reagents from ethyl polymer, which decrease the freezing temperature of the 5FU, are usually formed by using a free radical promoter, or in some cases, they can be obtained by thermal polymerization, or they can be obtained with cycler catalysts in the case of ethylene copolymerization with other olefins. The polymers produced by the radial mechanism appear to be more important and can be obtained as follows. The solvent and from 0 to 50 weight,% of the total amount of monomer other than ethylene, for example, ester monomer used in a one-time loading, is loaded into a stainless steel autoclave and equipped with a stirrer. The temperature of the autoclave is then adjusted to 70-250 ° C, 11 is pressurized with / ethylene, for example, to 49.221, 758 kg / cm. Temperatures ranging from 70 to 160 ° C are preferred. The promoter, usually dissolved in a solvent so that it can be pumped, and additional quantities of the second monomer, for example, an unsaturated ester, can be added to the autoclave continuously or less, intermittently, over the course of the reaction, the continuous or intermittent addition of which leads to a more homogeneous copolymer product, as compared with the addition of the total amount of unsaturated ester at the beginning of the reactions. In addition, as ethylene is consumed in the polymerization reaction, an additional amount of ethylene can be supplied through a pressure control regulator, in order to maintain the desired reaction pressure constant throughout the reaction time. The total reaction time is from 1/4 to 10 hours. The liquid phase from the contents of the autoclave is distilled to remove the solvent and other volatile constituents of the reaction mixture; a polymer is obtained as a residue. Typically, to speed up processing and blending of the oil, the polymer is dissolved in a light mineral oil to form a concentrate, usually containing from 10 to 60% by weight of polymer.
    Usually, based on 100 weight. including polymer, which is obtained, use from 50 to 1200, preferably from 100 to 600 weight. including a solvent, typically a hydrocarbon, such as benzene, hexane, cyclohexane, etc., and about 1 to 20 parts by weight of a promoter. The promoter can be any of. conventional free radical promoters, such as peroxide promoters and azo-type promoters, including acyl peroxides of branched, branched or unbranched carboxylic acids, as well as other conventional promoters.
    As a polyalkyl ester, esters of acrylic acid, e 1 -alkyl-y or L-aryl-, or ea-chloro, or cC-aza-iLi with c-oxohomologs and monohydric alcohols containing more than three atoms can be used. carbon, such as hexyl, octyl, decyl, lauric, myristyl, cetyl, etc. esters of acrylic acid, f-methacrylic acid, atropic acid, cinnamic acid, crotonic acid, acrylic acid, cC-chloroacrylic acid, and other known cC or / 3-homologues of acrylic acid. These elephant esters are preferably normal, primary saturated aliphatic alcohols, however
    can also be used analogous esters of the corresponding secondary, or branched spirtohz. In addition, esters of the above acrylic acid with monosubstituted aromatic, hydroaromatic or ether alcohols, such as benzyl, cyclohexyl, amylphenyl, butyloxyethyl esters, can be used. acids. Vinyl esters of valeric, heptane, lauric, palmitic, amylbenzoic, naphthenic, cyclohexanoic, or i-butyloxybutyric acid can also be used.
    The most effective polymers are polymerized esters of acrylic acid or oC-methacrylic acid and monohydric, saturated, primary aliphatic alcohols containing from 4 to 16 carbon atoms in the molecule. Oil-soluble polyesters include Cd-C (alkyl esters of acrylic acid slots, homologues of acrylic acid and analogs of acrylic acid, mean poly (Cf-C f, alkyl acrylates). The oil-soluble polymer or copolymer has a solubility in fuel, about 0.001 wt.% At .20 ° C. Optimal polyesters with higher solubility and stability in fuels are polyesters that are derived from linear, monoatomic primary saturated aliphatic alcohols containing from 8 to 16 carbon atoms, such as rmalnye octyl, lauryl, cetyl acid esters. These esters are prepared from mixtures of higher aliphatic alcohols, such as those obtained by catalytic hydrogenation of saturated acids or esters thereof.
    Mixtures can be simple mixtures of polymers or copolymers, which can be obtained by polymerizing a mixture of two or more esters.
    The monomers described - monocarboxylic esters - can be copolymerized in various quantities, for example, up to 25 wt. % of other unsaturated esters or olefins.
    Distillate hydrocarbon fuels that are treated with combination additives include cracked fuels and direct fuels that boil at a wide temperature range from 120 ° C to and from to, such as heating oil and diesel heavy fuel oil.
    The distillate fuel may include a mixture in any proportion of direct-distillate distillates and thermally and / or catalytically cracked
    distillates, or mixtures of medium leaflets and heavy distillates, etc. The proposed composition is effective as an additive for high boiling point fuels, 5 i.e. fuels that boil at least about 5 wt.% at a temperature higher.
    A copolymer of ethylene and vinyl acetate with number average mol. at. about
    Q 8000 (1) contains about 28 wt.% Vinyl acetate. The ethylene copolymer can be prepared by the free and radical polymerization of ethylene and vinyl ester of the lower saturated monobasic aliphatic carboxylic acid.
    Example 2. A copolymer of ethylene and isobutyl acrylate with sredneklo-. vym mol.v. about 7., 350 (P) contains about 20 weight. % izbut11lakryla0 ta. This copolymer has a melt index of 116-127 C.
    Example 3. A copolymer of ethylene and 2-ethylhexyl acrylate was prepared as follows. In a three-liter autoclave with a stirrer load 1200 ml of benzene. The autoclave is flushed with nitrogen and then with ethylene. The autoclave is heated until the pressure is reduced to ethylene in the autoclave until the pressure rises to 421.9 kg / cm.
    Then, maintaining the temperature at 110 ° C and the indicated pressure, the pump is continuously fed into the autoclave at a rate of 20 g / h of 2-ethyl hexyl acrylate and a solution containing 0.5% by weight of peroxide
     dilauroyl dissolved in benzene. In general, 40 g of 2-ethylhexyl acrylate are introduced in 2 hours, while 0.4 tons of peroxide solution are fed to the reactor 2 hours from the start of the input. Mixture
    0 maintained at 110 ° C for 1.5 minutes Then the temperature of the reaction
    the mixture is reduced to 60 ° C, the pressure in the reactor is reduced, and the contents are discharged from the autoclave. Empty reactor
    5 is washed with 1 liter of warm benzene (about 50 ° C, which is added to the product. The product is freed from solvent and unreacted monomers on the steam bath by blowing nitrogen through the product. The product, free from volatile, consists of 120 g of a copolymer of ethylene and 2-ethylhexyl acrylate having a number average mol.v. 6120 and 31.9 wt.% of ester.
    Example4. Polyalkyl methacrylate (IV) has the following distribution of alkyls, wt. %: - 3.4;
    - 37.8; C - 19.5, - C - 8.8 and
    M2
     - 10.5. Number average mol. weight 0 82500 and srednevesovoy mol. weight
    798800 (measured using gel permeation chromatography).
    Example 5. The polyalkyl methacrylate (U) has the following distribution of alkyls,%: 6, -; Cf.-8.3;
    12,
    C44-10.2; 9.4; WITH
    (b
    C, - 6.6; 11.3; 4.3; and
    S-H 4 th e, h. - - -. - Number average mol. at. 17100 and among the Evese mol. at. 39,000 (by gel permeation chromatography).
    PRI me R 6. Homopolymer tetralecylacrylate (VjL). The monomer is obtained in the following manner. In a 50 ml ml round bottom flask equipped with a stirrer, a heating jacket, a Dean-Stark condenser and a receiver, 107 g of tetradecanol and 40 g of acrylbvoic acid, 1 g of hydrokinone, 3 g of p-toluenesulfonic acid and 150 ml of heptane are added. The solution is refluxed, during which time 11 and " 1 of water are collected in a Dean-Stark receiver. The solution was washed with 75 Mil water, 75 ml of a 2% aqueous solution of sodium hydroxide and once more with water until the wash water became neutral. The solution was dried over magnesium sulphate, filtered and evaporated, 125 g of tetradecyl acrylate were obtained.
    Gokeypolymer tetradecyl acrylate get the following way. In a round bottom flask equipped with a stirrer, a condenser, a heating jacket and a nitrogen inlet tube, b g of tetradecyl acrylate, 6 g of heptane and 0.06 g of peroxide b | nzoyl are added. The solution is purged with nitrogen, heated with stirring for 45 minutes. Then, 0.1 g of hydroquinone is added and the solvent is evaporated, yielding g of polymer with a mol. at. 6.196. ....
    p PRI me R 7. Copolymer of hexadecyl acrylate and methyl methacrylate (Vll) mol, c. 2,817.
    Hexadecyl acrylate also obtained uac to tetradecyl acrylate, except that 122 g of hexadecyl alcohol is used in the preparation of acrylic acid ester. The copolymerization is carried out by analogs: example 6, except that a mixture of 7.2 g of hexadecyl acrylate and 1.3 g of methyl methacrylate is used.
    In t / abl. 1 shows the properties of distillate liquid fuel subjected to the test. . Table 1
    Magnitude
    Indicator unit 1 measure
    Density at 16 C
    Temperature-: turbid1 and, s
    Aniline point, C
    Continuation of table 1
    Magnitude
    Indicator, unit
    Distillation, C
    Start point
    boil
    20%
    50%
    80%
    95%
    End point
    boil
    Paraffin Limits
      -
    measurements by the AZTMD-D-1160 method,
    Various polymer blends 1-111 are prepared with fy-ViJ polymers. in the fuel by simple dissolving and in the liquid fuel. The fuel and polymer are heated approximately to, the polymer is added separately, and the mixture is stirred. In other cases, the polymer is added with stirring to the fuel to form a fuel concentrate, which typically has about 60 wt. % polymer dissolved in light mineral oil .- -; .,. -.
    The cold-flow properties of the mixture are determined by monitoring the chill-point: 6d filter (CTFCP). The control of the cold filter plugging point is carried out using 45 ml of a sample of fuel that has been subjected to the test. The fuel is cooled in a bath, the temperature of which is maintained at approximately -3 ° C. In one degree, starting at a higher cloud point. The fuel is tested on a test instrument consisting of a pipette, the lower end of which is connected with an inverted funnel .. The expanded across the mouth of the funnel is a 350 mesh sieve with a mesh of 2.90 cm. Approximately 7 vacuum is applied to the upper end of the pipette. mm od.st., immersing a sieve in the fuel sample. Due to the vacuum, the fuel nt will flow through a sieve in the upper part of the pipette to the mark showing the volume of fuel 20 ml The test is repeated after each decrease in temperature of one degree until the filling of the pipette to the above mark is disturbed due to
    sieve blockage with paraffin crystals,
    The test results and the mixture obtained are presented in Table 2.
    Table 2
    KTZHF, C
    Polymer
    Missing
    0.04% polymer
    0.01% polymer
    0.01% polymer
    0.04% polymer
    0.02% polymer
    0.02% polymer
    0.02% polymer
    0.02% polymer
    0.02% polymer
    0.005% polymer 0.01% polymer
    0.005% polymer 0.01% polymer
    0.005% polymer 0.01% polymer
    0.01% polymer 0.01% polymer
    0.01% polymer 0.01% polymer
    权利要求:
    Claims (3)
    [1]
    Formula invented
    1, fuel composition based on a hydrocarbon distillate fuels in the range vykipakvdego 120-480s with addition of a mixture of additives consisting of a copolymer of ethylene with nenasyygennym carboxylic acid ester and an oil-soluble polialKyDbyYgO ester of acrylic or methacrylic acid, characterized in that, in order improving the low-temperature properties of the composition, it contains a copolymer of ethylene with an unsaturated carboxylic ester .E. 40060000 when the content of the mixture of additives in the amount of 0.001-1.0 weight. %
    and The mixture of additives contains 5-90 weight. the specified copolymer.
    [2]
    2, The fuel composition according to claim 1, characterized in that it contains a copolymer of 3-40 moles of ethylene per 1 mole of alkyl ester of the general formula
    five
    9 C
    g R 3 or CH j where R is HRg-OOCR or. C. UN
    OR COOH
    Rj-
    or alkyl With
    [3]
    3. The fuel composition according to claim 1, wherein it contains polyalkyl ester, consisting of 25-100% Cg-C unbranched alkyl esters of acrylic or methacrylic acid.
    Sources of information taken into account in the examination
    1 Patent of Great Britain 1303074, cl. With 5 G, pub. 1973
    2. US patent No. 3275427, CL 44-62, published. 1966 (traces)
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    同族专利:
    公开号 | 公开日
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    GB1542293A|1979-03-14|
    FR2305492B1|1980-04-30|
    DE2612248C2|1989-10-19|
    CA1071866A|1980-02-19|
    JPS51119705A|1976-10-20|
    FR2305492A1|1976-10-22|
    NL7602922A|1976-09-30|
    US4153423A|1979-05-08|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
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    US3275427A|1963-12-17|1966-09-27|Exxon Research Engineering Co|Middle distillate fuel composition|
    US3792983A|1968-04-01|1974-02-19|Exxon Research Engineering Co|Ethylene and acrylate esters, their preparation and their use as wax crystal modifiers|
    US3832150A|1968-09-17|1974-08-27|Exxon Research Engineering Co|Fuel oil with improved low temperature flowability|
    US3620696A|1968-09-17|1971-11-16|Exxon Research Engineering Co|Fuel oil with improved flow properties|
    US3661541A|1969-04-22|1972-05-09|Exxon Research Engineering Co|Fuel oil compositions containing a mixture of polymers to improve the pour point and flow properties|
    US4010006A|1969-05-09|1977-03-01|Exxon Research And Engineering Company|Flow improvers|
    GB1285087A|1969-12-18|1972-08-09|Shell Int Research|Oil compositions|US4261703A|1978-05-25|1981-04-14|Exxon Research & Engineering Co.|Additive combinations and fuels containing them|
    US4211534A|1978-05-25|1980-07-08|Exxon Research & Engineering Co.|Combination of ethylene polymer, polymer having alkyl side chains, and nitrogen containing compound to improve cold flow properties of distillate fuel oils|
    JPS6244037B2|1982-02-10|1987-09-17|Nippon Oils & Fats Co Ltd|
    JPH0247518B2|1982-07-06|1990-10-19|Kao Corp|
    US4613342A|1982-08-09|1986-09-23|The Lubrizol Corporation|Hydrocarbyl substituted carboxylic acylating agent derivative containing combinations, and fuels containing same|
    US4575526A|1982-08-09|1986-03-11|The Lubrizol Corporation|Hydrocarbyl substituted carboxylic acylaging agent derivative containing combinations, and fuels containing same|
    US4564460A|1982-08-09|1986-01-14|The Lubrizol Corporation|Hydrocarbyl-substituted carboxylic acylating agent derivative containing combinations, and fuels containing same|
    US4623684A|1982-08-09|1986-11-18|The Lubrizol Corporation|Hydrocarbyl substituted carboxylic acylating agent derivative containing combinations, and fuels containing same|
    US4439308A|1982-09-29|1984-03-27|Exxon Research And Engineering Co.|Solvent dewaxing waxy bright stock using a combination polydialkylfumarate-vinyl acetate copolymer and wax-naphthalene condensate dewaxing aid|
    US4461698A|1982-09-29|1984-07-24|Exxon Research And Engineering Co.|Solvent dewaxing waxy hydrocarbon distillate oils using a combination wax-naphthalene condensate and poly-dialkylfumarate/vinyl acetate copolymer dewaxing aid|
    US4451353A|1982-09-29|1984-05-29|Exxon Research And Engineering Co.|Solvent dewaxing waxy hydrocarbon distillates using a combination poly acrylate polymer and polymethacrylate polymer dewaxing aid|
    US4406771A|1982-09-29|1983-09-27|Exxon Research And Engineering Co.|Solvent dewaxing waxy hydrocarbon oil distillates using a combination poly di-alkyl fumarate-vinyl acetate copolymer having pendent carbon side chain length of predominantly C22 and polyalkylacrylate polymer dewaxing aid|
    US4460453A|1982-09-29|1984-07-17|Exxon Research And Engineering Co.|Solvent dewaxing waxy bright stock using a combination polydialkyl fumarate-vinyl acetate copolymer and polyalkylacrylate polymer dewaxing aid|
    CA1282240C|1984-02-21|1991-04-02|Albert Rossi|Fuel oil with added polymer of alkyl ester|
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    GB2172302A|1985-01-21|1986-09-17|Fuels Energy Systems Limited|Fuel additive|
    GB8522185D0|1985-09-06|1985-10-09|Exxon Chemical Patents Inc|Oil & fuel compositions|
    JPS6284337U|1985-11-15|1987-05-29|
    GB8609293D0|1986-03-18|1986-05-21|Exxon Chemical Patents Inc|Liquid fuel compositions|
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    US5112510A|1989-02-28|1992-05-12|Exxon Chemical Patents Inc.|Carboxylate polymer and viscosity index improver containing oleaginous compositions|
    US4963279A|1989-02-28|1990-10-16|Exxon Chemical Patents Inc.|C14-carboxylate polymer and viscosity index improver containing oleaginous compositions|
    WO1991016407A1|1990-04-19|1991-10-31|Exxon Chemical Patents Inc.|Additives for distillate fuels and distillate fuels containing them|
    FR2710652B1|1993-09-30|1995-12-01|Elf Antar France|Composition of cold operability additives for middle distillates.|
    GB9930596D0|1999-12-23|2000-02-16|Bp Chem Int Ltd|Compounds|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/562,892|US4153423A|1975-03-28|1975-03-28|Polymer combinations useful in distillate hydrocarbon oils to improve cold flow properties|
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