• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Oil soluble ethylene polymers or copolymers having a Mn less 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:SU784794A3
    申请号:SU762338657
    申请日:1976-03-26
    公开日:1980-11-30
    发明作者:Дж. Висотски Макс
    申请人:Эксон Рисерч Энд Инджиниринг Компани (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to fuel compositions based on hydrocarbon fuels with the addition of flowability improvers. A fuel composition based on distillate fuels with the addition of an additive improving their flow is known - a product of the interaction of alcohol C, (j-C25 with an unsaturated dicarboxylic acid copolymer of iobalkene C9d-C, le i or more closely related to the fuel composition proposed by essence and the achieved result on the basis of middle distillate fractions with the addition of a mixture of two copolymer additives — a polymer or 7 / CiQL copolymer of alkyl esters of unsaturated carboxylic acids, for example, alkyl acrylates, alkyl methacrylates, etc., with a copolymer ethylene and monomer, for example, a copolymer of ethylene with acrylic, methacrylic fumaric acid C2. A common drawback of the known compositions is the relatively low improvement in their flowability. The purpose of this invention is to improve the flowability of the hydrocarbon composition. The goal is achieved due to the fact that additive mixtures composition based on middle distillate fuel with a boiling range of 120-480 ° C contains 0.011.0% by weight of a mixture of a copolymer of molecular weight 1000-4000 consisting of 3-40 molar parts of ethylene per mole Part C / - C alkyl ester of acrylic acid or .metakrilovoy and polyester -Cjoalkilakrilata Cu and / or alkyl methacrylate at a mixing ratio of 1: 0.1 to 1:20. . The ethylene polymers can have polymethylamine: o main chain, which is divided into parts by hydrogen, halogen, or side oxyhydrocarbon chains. The polymers can be simple ethylene homopolymers, usually obtained by free radical polymerization, which leads to some branching of the chain. Unsaturated monomers capable of copolymerizing with ethylene include unsaturated complex P mono and diesters of the general Formula
    which RI is hydrogen or an alkyl group, for example, methyl, Ri2 is a COOR group, where Ri is E: Hydrogen or C /, / a is preferably, for example, Cj is C alkyl group, with a straight or branched chain, and Rn, hydrogen or - COOR. When RI is -COOR j and Ri.- are hydrogen, such esters include methyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, lauryl acrylate, C; t, oxo-alcohol esters of methacrylic acid; etc. The monomer gpimers in which R is hydrogen and Rij and R.7 are -C00RJ groups are mono- and di-esters of unsaturated dicarboxylic acids, such as monoC, o, oxy-fumarate, di-C, -oxofumarate, diisopropylmaleate, dilauryl fumarate, ethyl methyl fumarate, etc.
    Another class of monomers that can be copolymerized with ethylene are,., -Monoolefins, which can be branched or not. This includes propylene, isobutene, p-octene-1, isooctane-1, P-decene-1, dodecene-1, etc.
     At the same Brem, other monomers can include vinyl chloride, although practically the same results can be obtained using chlorinated ethylene, for example, with a chlorine content of 10 to 35 weight, but as noted earlier, branched polyethylene can be used by itself as a polymer These low molecular weight ethylene polymers are obtained using a free radical polymerization catalyst, or in some cases they can be obtained by thermopolymerization, or in the case of ethylene with other ol In the end, they can be obtained using Ziegler catalysts, for example, they can be obtained as follows. From 0 up to 50% by weight of solvent to the total amount of ethylene monomer, for example, ester monomer, is loaded into the tank, and then this mixture is transferred to a non-stainless steel reactor, adapted for working under pressure and equipped with a stirrer. The temperature in the autoclave is raised to a temperature which is unreleasable for the reaction, for example, up to 7O-250 ° C and the pressure is raised to the desired, for example, from 700 to 25,000 psi (4921758 kg / cm), usually from 900 to 7000 pounds / inch (63.3 -492 kg / cm}. Preferably, the temperature is in the range from 70 to. The catalyst, which is usually dissolved in a solvent so that
    it was possible to switch over / tick, and additional quantities of the second monomer, for example, one unsaturated ester, can be supplied to the reactor continuously or intermittently throughout the reaction time, and a similar continuous or intermittent feed gives a more homogeneous copolymer product than loading the total amount of unsaturated at the very beginning of the reaction. Additions of ethylene can be fed throughout the polymerization through the control pressure regulator, so as to be maintained throughout the whole period, the damage is almost constant. After a reaction time, which is usually between 1/4 and 10 hours, the liquid phase from the reactor is dis-1: 1: -from to remove the solvent, resulting in a polymer residue. Usually, for ease of handling and subsequent displacement with oil, the polymer is dissolved in a light mineral oil in concentrations from 10 to 60% by weight.
    Usually, upon receipt of the polymer per 100 weight.h. from 50 to 1200, and preferably from 100 to 600 parts by weight, of a solvent (usually a hydrocarbon solvent such as benzene, hexane, cyclohexane, etc.) and from 1 to 2 weight. h. catalyst.
    The catalyst can be any of the known catalysts for free radical polymerization, such as azo or peroxide, including branched and non-branched acyl peroxides, carbocytes, as well as other conventional catalysts, for example dibenzoyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl peroctoate, tert-butyl hydroperoxide, c, o-azo-diisobutyl nitrile, dilauro peroxide, etc. Dilauroyl peroxide is preferred when preparing the polymer at low temperatures (e.g. 70 to), while at higher TRi polymerization temperatures it is preferable to use di-tert-butyl peroxide.
    Oil-soluble polyesters, which in their preferred form are polymers of acrylates (including homologues of acrylates) in general, can have a molecular weight Mp from 1,000 to 200,000, and preferably from 2,000 to 100,000,
    Distillates of hydrocarbon oils, which are treated with additives according to the invention, include cracked distillate fractions and natural distillates, boiling in a wide range from 120 to, usually from 1
    up to 400 ° C, such as heating oil and diesel fuel oil.
    The diesel fuel of the present invention may be a mixture in any proportion of direct race distillates and thermal and / or catalytic cracking distillates, or a mixture of middle distillates and heavy distillates, etc. The invention is particularly applicable and effective for treating cold flow of fuels with a high final boiling point, namely fuels in which at least 5 wt.% Boils at a temperature higher than about 350 ° C.
    The inventive compositions can be used either individually or in combination with other oil additives, for example, corrosion inhibitors, antioxidants, precipitation inhibitors, etc.
    Polymer 1. Polymer 1 is a copolymer of ethylene and isobutyl acrylate. This copolymer is prepared according to the following procedure. 500 ml of benzene as a solvent is charged into a three-liter auto-slav with stirring. Then the autoclave is flushed with nitrogen, then with ethylene. After that, the autoclave is heated to EO-C, while the pressure of ethylene in the autoclave is increased (211 kg / cm, continuously pumped into the autoclave 40 ml / h of isobutyl acrylate and 70 ml / h of a solution containing 11.5 wt.% Dilaurope peroxide dissolved in benzene. A total of 100 ml of isobutyl acrylate is injected for 2.4 hours, while 184 ml of peroxide solution is injected into the reactor for 2.6 hours after the start of injection. After the complete injection of peroxide, the mixture is kept for another 10 minutes. the contents of the reactor up to about a reset the pressure in the reactor is discharged and the contents of the autoclave are discharged. Then the solvent and unreacted monomers are removed from the product in a water bath overnight by blowing nitrogen through the product. The final stripped product contains 260 g of ethylene-isobutylacetate copolymer having an average molecular weight of 3545 (measured osmometry) and the ester content is 29 wt.%.
    Polymer A. It is a polyacrylmethacrylate, known as Acryloid 150. This polymer has the following distribution of alkyl groups by the number of carbon atoms, wt.%:
    - 19.5;
    3,4) C „- 37,
    ,five.
    14
    and number average molecular; weight 798800.
    Polymer B. Also is polyacrylmethacrylate. Acryloid 152. This polymer had the following distribution of the content of alkyl groups according to the number of carbon atoms, wt.%:
    With t
    Cfi 6.3;
     - 10.2; . 0 - oh j
     - 12.6)
    C, 5-9.4, s, 5-9HJ
    Cf - 6.6;
    s, d- 11, s; Ci9- 4.3-,
    5.4.
    0
    With a average molecular weight of 17,100 and a weight average molecular Besus of 39,000 (determined by gel permeation chromatography).
    Polymer B. Is a homopolymer
    5 N-tetradecyl acrylate. The monomer was obtained as follows.
    In a round bottom flask with a volume of 100 ml equipped with a stirrer, heating jacket, and refrigerator
    0 and a Dean-Stark trap are charged with 107 g of H-.tradecanol, 40 g of acrylic acid, 1 g of hydroquinone, 3 g of P-toluenesulfonic acid, and 150 ml of reactive heptane. The solution is boiled under reflux for 3 hours, and
    As a result, collect 11 ml of water in a Dean-Stark trap. Then the solution is washed with 75 MP water, 75 ml of 2% sodium hydroxide solution and again with water until neutral.
    0 The solution is dried over magnesium sulfate, filtered and evaporated, yielding 125 g of tetradecyl acrylate.
    The tetradecyl acrylate homopolymer is prepared as follows.
    five
    6 g of previously obtained tetradecyl acrylate, 6 g of hepatan, and 0.6 g of benzoyl peroxide are loaded into a round-bottom microcolumn equipped with a stirrer, a refrigerator, a heating jacket and the introduction of nitrogen. Nitrogen was bubbled through the solution, then heated by peremeshivanii to about 85 with just 45 minutes 0.1 g of hydroquinone is then added and the solvent is evaporated, yielding
    5 5.8 g of polymer with Mn 6196.
    Polymer G. It is a copolymer of n-hexadecyl acrylate and methyl methacrylate, having Hn 2817. Hexadecyl acrylate is also obtained
    0 as tetradecyl acrylate polymer C, with the exception that 122 g of p-hexadecyl alcohol are used in the preparation of acrylic ester. The copolymerization is carried out as
    5 and upon receipt of polymer C, with the exception that a mixture of 7.2 g of hexadecyl acrylate and 1.3 g of methyl methacrylate is used.
    Distillate fuel properties
    0 processed oils are presented below:
    Properties
    Fuel
    Density at 16s
    0.8265 Point noMiTHeHHH, C t-1
    权利要求:
    Claims (1)
    [1]
    Claim
    A fuel composition based on medium distillate petroleum fuel with a boiling range of 120-480 ° C with the addition of a mixture of two copolymer additives, characterized in that, in order to improve the fluidity of the compositions, it contains 0.011.0 wt.% Molecular weight copolymer mixture as an additive mixture 1000-4000, consisting of 3-40 mol.h. ethylene per mole portion of C 1 -Cd alkyl ester or methacrylic acid, and Ciq-C ^ q polyester of alkyl acrylate and / or alkyl methacrylate with a mixture ratio of 1: 0.1 to 1:20.
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    同族专利:
    公开号 | 公开日
    DE2612232A1|1976-10-14|
    US4153424A|1979-05-08|
    FR2305493B1|1982-11-12|
    JPS51117710A|1976-10-16|
    FR2305493A1|1976-10-22|
    GB1542294A|1979-03-14|
    BE839916A|1976-09-23|
    CA1071865A|1980-02-19|
    IT1058439B|1982-04-10|
    NL7603127A|1976-09-30|
    JPS602353B2|1985-01-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE1137261B|1961-03-02|1962-09-27|Roehm & Haas Gmbh|Improvement of the filter point of diesel fuels and heating oils|
    US3275427A|1963-12-17|1966-09-27|Exxon Research Engineering Co|Middle distillate fuel composition|
    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|
    DE2102469C2|1971-01-20|1989-06-29|Basf Ag, 6700 Ludwigshafen|Use of ethylene copolymers as an additive to petroleum and petroleum fractions|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|
    JPS55137193A|1979-04-11|1980-10-25|Toho Chem Ind Co Ltd|Fuel oil having low-temperature fluidity|
    JPS5839472B2|1980-05-30|1983-08-30|Sanyo Chemical Ind Ltd|
    JPS6241558B2|1981-09-03|1987-09-03|Sumitomo Chemical Co|
    GB8404518D0|1984-02-21|1984-03-28|Exxon Production Research Co|Middle distillate compositions|
    CA1282240C|1984-02-21|1991-04-02|Albert Rossi|Fuel oil with added polymer of alkyl ester|
    EP0155807A3|1984-03-22|1985-11-27|Exxon Research And Engineering Company|Middle distillate compositions with improved low temperature properties|
    GB8521393D0|1985-08-28|1985-10-02|Exxon Chemical Patents Inc|Middle distillate compositions|
    GB8522185D0|1985-09-06|1985-10-09|Exxon Chemical Patents Inc|Oil & fuel compositions|
    DE3607444A1|1986-03-07|1987-09-10|Roehm Gmbh|ADDITIVES FOR MINERAL OILS WITH IMPROVEMENT EFFECT|
    US4963279A|1989-02-28|1990-10-16|Exxon Chemical Patents Inc.|C14-carboxylate polymer and viscosity index improver containing oleaginous compositions|
    US5112510A|1989-02-28|1992-05-12|Exxon Chemical Patents Inc.|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|
    US5939365A|1996-12-20|1999-08-17|Exxon Chemical Patents Inc.|Lubricant with a higher molecular weight copolymer lube oil flow improver|
    US6846338B2|1997-07-08|2005-01-25|Clariant Gmbh|Fuel oils based on middle distillates and copolymers of ethylene and unsaturated carboxylic esters|
    GB9930596D0|1999-12-23|2000-02-16|Bp Chem Int Ltd|Compounds|
    DE10349851B4|2003-10-25|2008-06-19|Clariant ProdukteGmbh|Cold flow improver for fuel oils of vegetable or animal origin|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US56307775A| true| 1975-03-28|1975-03-28|
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