TW201116617A - Ethylene/vinyl acetate/unsaturated esters terpolymer as an additive improving cold resistance of liquid hydrocarbons such as middle distillates and fuels or combustible materials - Google Patents

Abstract

The invention relates to the use as an additive improving cold resistance and filterability of fuels, of at least one copolymer comprising from 81 to 87 % by moles of at least one α -olefin, preferably at least ethylene, from 10.5 to less than 12 % by moles of at least one vinyl ester, preferably at least vinyl acetate, from 1 to 8 % by moles of at least one unsaturated α , β -mono-carboxylic acid ester, preferably at least ethyl-2-hexyl acrylate.

Description

201116617 VI. Description of the Invention: [Technical Field] The present invention relates to the use of a copolymer of an α-olefin, a vinyl ester and an unsaturated α, 々·carboxylate as an additive for improving the cold resistance of a fuel and a lubricant. And fuel oils and packages containing these copolymers. [Prior Art] At low temperatures, hydrocarbon compositions, particularly those containing a middle distillate type of paraffinic wax, such as diesel fuel and heating oil, are in terms of their flow properties. obviously decased. It is well known that the crystallization of paraffin is a limiting factor in the use of middle distillates. Also, it is important to prepare a diesel fuel that is suitable for the temperature to be used in a vehicle', that is, to adapt to the surrounding climate. In general, the cold handling of fuels at -1 〇 is sufficient in many tropical or temperate countries. However, in countries with cold climates such as Scandinavia, Canada and North Asia, temperatures up to -2 °C can be reached. This also applies to household oils stored outside buildings (houses, apartment blocks). The cold workability of the middle distillate type fuel is important, especially for cold starters of engines. If the paraffin crystallizes at the bottom of the tank, it can be driven into the fuel line at startup and significantly block the filter and pre-filter located upstream of the injection system (pump and ejector). Also, when storing household oils, paraffin precipitates to the bottom of the tank and can be driven and blocks the upstream line of the pump and the upstream line of the supply system of the boiler (nozzle and filter). Obviously, the presence of solids (e.g., paraffin crystals) hinders the normal circulation of the middle distillate. -5- 201116617 Several forms of additives have been developed to improve the fluidity in or towards the boiler. In the first phase, the gasoline industry is committed to the development of so-called cold flow additives (cold flow improvers or C FI ) which promote the dispersion of paraffin crystals and thereby prevent the crystals from automatically organizing into large-volume lattices that can cause filter pore blockage. . These additives essentially have an effect on limiting the filtration temperature (LFT) and on the pour point, but do not improve the turbidity point. A number of CFI additives have been described in the prior art (see, for example, US 3,048,479, US 3,627,838, US 3,790,359, US 3,961,961, EP 261 957), typically copolymers of ethylene and unsaturated esters, such as B/Acetate B Ethylene/vinyl acetate (EVA), ethylene/vinyl propionate (EVP), ethylene/vinyl ethanoate (EVE), ethylene/methyl methacrylate (EMMA), and ethylene/ A copolymer of alkyl fumarate.

In order to improve the properties of standard CFIs, the prior art also suggests common CFI additives and lubricants of ethylene/unsaturated ester type (mono or polycarboxylates of mono or polyhydric alcohols, see for example EP 721 492), and anti-precipitation Mixtures (see, for example, FR 2 490 669) with ethers (see for example US 3,999,960, EP 187 488). Improved CFI additives have also been discovered which are terpolymers or copolymers derived from more than three different monomers. For example, 'US 6,509,424 describes a terpolymer in the preparation of ethylene and at least two compounds containing ethylene unsaturation, such as vinyl esters, (meth) acrylates, alkyl vinyl ethers, in a tubular reactor. -6- 201116617 method. These terpolymers can be used as additives to improve the cold flow of petroleum and petroleum distillates. No. 3,642,459 describes the inclusion of 40 to 89% by weight of ethylene, 10 to 40% by weight of a vinyl ester derived from a short chain (C 2 -C 4 )carboxylic acid (such as vinyl acetate), and having a C, 〇-C22 alkyl group. Chain-unsaturated monoester terpolymers; these terpolymers are used as additives to lower the pour point of petroleum distillates and as anti-wax agents and to improve their filterability. US 4,1,56734 describes ethylene, vinyl acetate and terpolymers derived from acrylates of C|2_ CM alcohols which reduce the pour point of fuels incorporating the terpolymers' but do not mention these The additive has an improved cold filterability. WO 2 005/0543 1 4 describes terpolymers of α-olefins, vinyl esters and unsaturated monocarboxylic acid esters which can be used. The preferred ones exemplified by the applicant in the terpolymer contain more than 80% by mole of ethylene and less than 9% by mole of vinyl acetate. Now, these terpolymers containing less than 9 mol% of vinyl acetate have an effect on the reduction of LFT of a middle distillate containing more than 18% of paraffin wax, but on the one hand, in terms of solubility, On the other hand, the blocking tendency (or room temperature filterability) is unsatisfactory: the disruptable filter plugging is indicated. ΕΡ 1 3 9 1 49 8 describes an additive for improving the low temperature fluidity of a middle distillate, which is a vinyl polymer (A), preferably an ethylene-vinyl ester copolymer, which is a material insoluble in hexane. The amount is more than 60% by weight at -20 ° C and less than 30% by weight at 10 ° C; the example of EP 1 3 9 1 4 9 8 clearly shows: copolymer and terpolymer (used The filtration temperature of the 201116617 material insoluble in hexane over 6% at -20 ° C and less than 30% by weight at 10 ° C) (cold filter plugging point (c ο 1 dfi 11 er ρ 1 Ugp 〇int, CFPP )), is reduced in proportion to the same repeating unit in the same proportions, but the amount of material insoluble in hexane used is less than the desired range of copolymer or terpolymer; The copolymers exemplified are EVA copolymers and ethylene-(vinyl acetate)-(vinyl neodecanoate or vinyl 2-ethylhexanoate) terpolymer. There is still an unresolved need for additives to improve the cold resistance (LFT and pour point) of the fuel while reducing or even eliminating the risk of clogging to avoid clogging of the filter of the engine or boiler supply system (injection system and tank) . SUMMARY OF THE INVENTION The present invention relates to the use of copolymers as additives to improve cold resistance (CFI additives) for fuels; these copolymers contain derivatives derived from at least one alpha-olefin, at least one vinyl ester, and at least one unsaturated alpha beta-single a unit of a carboxylate, and preferably a terpolymer of ethylene, vinyl acetate and ethyl-2-hexyl acrylate. The copolymer which can be used as a CFI additive according to the present invention comprises from 81 to 87 mol% of at least one α-olefin, preferably at least ethylene, • 1 〇. 5 to less than 12 mol% of at least one ethylene. The ester, preferably at least vinyl acetate, • 1 to 8.5 mol% of at least the unsaturated α-mono-carboxylic acid 201116617 ester' is preferably at least ethyl acrylate 2-ethyl vinegar. Preferably, the copolymer which can be used as a gastric CFI additive is recorded as a quadrilateral ABCD where A, B, C and D represent the apex of the quadrilateral and correspond to at least the vinyl ester and at least the unsaturated alpha,3 -mono-carboxylic acid Mole of ester %: Α: 12; 1 Β: 12; 6 C: 10.5; 4 D: 10.5; 8.5. Advantageously, the copolymer which is a CFI additive is recorded as a quadrilateral AiBC^D, wherein Al, B, C, and D represent the apex of the quadrilateral and correspond to at least the vinyl ester and at least the unsaturated alpha, uni-mono-carboxylic acid Mole % of the ester: Α, : 12; 2 Β : 1 2 ; 6 Ci: 10.5; 5 D: 10.5; 8.5. [Embodiment] The copolymer according to the present invention is a random copolymer having a weight average molecular weight (Mw) of 3,000 to 30,000 as measured by GPC and a measurement of 1 at 1 by GPC. The number average molecular weight (Μη) to 15,000. These copolymers can be prepared by any polymerization method in a known manner (see, for example, Ullmann's Encyclopedia of Industrial -9-201116617).

Chemistry, 5lh Edition, "Waxes,,, Vol. A 28, ρ. 146; US 3,627, 838, EP 7 590), in particular by free radical polymerization, preferably under high pressure, typically between 1,000 and 3, The degree of 000 bar (100 to 300 MPa) is preferably 1,500 to 2,000 bar (150 to 200 MPa), the reaction temperature is usually 160 to 320 ° C, preferably 200 to 2801, and at least one is selected. In the presence of an organic peroxide and/or a free radical initiator of an oxygen-containing or nitrogen-containing compound and a molecular weight regulator (aliphatic ketone or aldehyde, ...). The copolymer may, for example, be in a tubular reactor in accordance with US 6,509,424 Prepared by the method described above. The hydrocarbon-based composition incorporated by the copolymer of the present invention is selected from the group consisting of oils or fuels, such as diesel fuel, household oils (DOF) for heating equipment, Kerosene, aviation fuel, heavy fuel, etc. Typically, the hydrocarbon composition has a sulfur content of less than 5,000 ppm, preferably less than 500 ppm, and more preferably less than 50 ppm, or even less than 10 ppm and Advantageously, it does not contain any sulfur. The hydrocarbon-based composition contains from 1 to 0 to 500. a middle distillate having a boiling temperature in the range of C; its initial crystallization temperature T cc is often greater than or equal to -20 ° C, usually between -15 t and +10 ° C. These distillates may, for example, be selected from Distillate obtained by direct distillation of crude hydrocarbons, vacuum distillate, hydrotreated distillate, catalytic cracking from vacuum distillate and/or hydrocracking from vacuum distillate a distillate, a distillate obtained by an ARDS (atmospheric pressure residue desulfurization) type conversion method and/or a viscosity reduction method, and a distillate obtained by upgrading a Fischer Tropsch fraction, from plants and/or Distillates obtained from the conversion of BTL (biomass to liquid) of animal biomass (alone-10-201116617 or in combination), and/or esters of plant and animal oils or mixtures thereof. The hydrocarbon composition may also contain distillates resulting from a refinery operation that is more complex than direct distillation from hydrocarbons, such as may be derived from cracking, hydrocracking, and/or catalytic cracking processes and viscosity reduction processes. They can also contain novel distillates Sources, among which may be mentioned in particular: a synthetic heavy distillate which is concentrated in heavy paraffin and contains more than 18 carbon atoms, a synthetic distillate obtained by gas conversion, obtained by a cracking and viscosity reduction method, Such as those obtained by the Fischer Tropsch process, a synthetic distillate obtained from the treatment of biomass from plants and/or animals, in particular such as NexBTL, - and oils and / or plant and / or animal oils Esters' - or otherwise derived from animal and/or plant-derived biodiesel fuels. These novel fuel bases can be used alone or in intermediate distillation with standard petroleum as a fuel base or as a domestic oil base. A mixture of the materials is used; a chain of long paraffin waxes usually containing 1 or more carbon atoms and preferentially C14 to C30. When having a Mw between 5,000 and 27,000 and a Μ between 1,500 and 22,000 as defined earlier, it is preferred to have a Mw between 5,000 and 25,000 and a copolymerization of Μ between 1,500 and 20,000 - 11 - 201116617 The material is degraded into light middle distillates and / or has a low sulfur content (typically below 50 ppm) and / or has a low initial crystallization temperature (which can typically be as low as -20 ° C) Time is especially effective. By light middle distillate, it is meant that the orthoquinone content having 24 or more carbon atoms is from less than about 0.7% by weight of the total fuel composition; and the C18-C23 normal paraffin is the total weight of the fuel. A distillate having a mass ratio of from about 3 to about 5% and a C18-C23 normal paraffin to C24 and higher sarcophagus, usually in the range of from 1 Torr to 35. When having a Mw between 5,000 and 10,000 and a Μ between 1,500 and 8,000, preferably having a Mw between '5,000 and 8,000 and between 1,500 and 5,000 The copolymer of Μη is particularly effective when it is cleaved into the heavy middle distillate and/or has a relatively high initial crystallization temperature (typically in the range of 0 to 15 °C). Heavy middle distillate means that the orthoquinone content having 24 or more carbon atoms is from about 0.7 to about 2% by weight of the total fuel composition; and the C18-C23 normal paraffin is about the total weight of the fuel. A distillate of from 1 to about 10% and having a mass ratio of C18-C23 normal paraffin to C24 + paraffin, usually in the range of 1 to 1 Torr. The copolymer itself may be added to the hydrocarbon composition or preferentially in the form of a concentrated solution, in particular in a solvent, such as an aliphatic or aromatic hydrocarbon in the form of a mixture or a mixture of naphtha, kerosene, hydrocarbon A solution containing a copolymer of 50 to 80% by weight, preferably 60 to 70% by weight, such as S ο 1 vess 〇 solvent, paraffinic hydrocarbon such as pentane or hexane, is added. According to a preferred embodiment of the invention, the hydrocarbon composition comprises from 10 to 50,000 ppm by weight, optionally from 100 to 1,000 ppm by weight from 12 to 201116617, and advantageously from 150 to 500 ppm by weight. At least - a copolymer as described above. In addition to the above-mentioned c FI additive or cold-resistant additive, the hydrocarbon composition may also contain one or more other additives different from the copolymer of the present invention, which are selected from the group consisting of detergents, corrosion inhibitors, dispersants, emulsifiers, and elimination agents. Foaming agents, biocides, reodorants, proceane additives 'friction modifiers, lubricity additives or oil-slip additives (unctu 〇usnessadditive), combustion aids (combustion and soot catalyst promoters), Improves turbidity point, pour point, filter limit temperature improver, anti-precipitant 'anti-wear agent and / or conductivity improver. Among these additives, mention may in particular be made of: a) diesel additives, in particular (but not limited to) selected from alkyl nitrates (preferably 2-ethylhexyl nitrate), arylsulfonyl peroxides ( Preferred is a benzyl peroxide) and an alkyl peroxide (preferably a third butyl peroxide); b) an antifoaming additive, particularly but not limited to, selected from the group consisting of polyoxyalkylenes, oxygen Alkylated polyoxyalkylenes, and fatty acid guanamines derived from vegetable or animal oils. Examples of such additives are given in EP 861 882, EP 663 000 and EP 736 590; c) detergents and/or anti-corrosion uranium additives, in particular (but not limited to) selected from the group consisting of amines, succinimides A group formed by alkenyl butyl quinone imines, polyalkylamines, polyalkyl polyamines, and polyether amines. An example of such an additive is given in EP 9 3 8 5 3 5. d) a lubricity additive or anti-wear agent, in particular (but not limited to) -13- 201116617 selected from the group consisting of fatty acids and their esters or guanamine derivatives, in particular glycerol monooleate, and Ring and polycyclic carboxylic acid derivatives. Examples of such additives are given in the following documents: EP 680 506, EP 860 494, WO 9 8/046 5 6 , EP 9 1 5 944, FR 2 772 7 8 3, FR 2 772 7 84 e ) turbid point additives , particularly but not limited to, selected from the group consisting of long chain olefins / (meth) acrylate / maleimide terpolymers, and maleic acid / fumarate polymers In the group formed. In EP 71 513, EP 1 00 248, FR 2 528 051, FR 2 5 2 8 051, FR 2 528 423 'EP 1 12 195, EP 1 727 5 8 , EP 27 1 3 8 5, EP 29 1 3 07 An example of giving such a force application agent;

f) an anti-precipitation additive and/or a paraffin dispersant, in particular, but not limited to, an alkyl (meth)acrylate copolymer selected from (meth)acrylic acid/polyamine, polyamine alkenyl bismuth a group formed by an imine, a derivative of valine and a derivative of a double-chain fatty amine; or an alkylphenol resin. EP 26 1 95 9 , EP 5 9 3 3 3 1 , EP 674 689, EP 3 27 42 3, EP 5 1 2 889, EP 832 1 72, US 2 0 0 5 / 0 2 2 3 6 3 1 , US 5 , 99 8, 5 3 0, WO 93/ 1 4 1 7 8 examples of such additives; g) cold-operating multifunctional additives selected from polymers based on olefins and nitrate esters Among the groups formed, as described in EP 573 490; h) other C FI additives that improve cold resistance and filterability, such as EVA and/or EVP copolymers. -14 - 201116617 These other additives are usually added in amounts of 100 to 1, 〇〇〇 ppm. The improved cold resistance additive according to the present invention may be added to the hydrocarbon composition inside the refiner and/or to the downstream of the refiner, optionally in the form of a mixture with other additives, or as an additive package. Or in the form of a bag. [Examples] In a tubular reactor, a terpolymer of ethylene, vinyl acetate and ethyl-2-hexyl acrylate was used at a high pressure of 1,400 to 2,500 bar (140 to 250 MPa). And synthesis by radical polymerization at a polymerization temperature of 200 to 28 (TC). This synthesis is carried out by using an aliphatic aldehyde (propionaldehyde) to control molecular mass and by using a peroxide as a polymerization initiator. The Μη and Mw of the synthesized terpolymer and the percentage of the monomer thereof are shown in Table I below. Table 1·. Characteristics of the synthetic polymer Copolymer [vinyl acetate] [Ethyl-2-hexyl acrylate] Μη Mw Thunder % Mohr % Weight % Mohr % 6 (ratio! m) 13.3 6.6 22.1 5.1 12,627 14,610 7(tb m) 13.1 6.5 22.4 5.2 8,842 10,460 irmmm) 27.6 13.7 20.7 4.8 1U80 13,255 UtEEWM) 28.4 14.1 20.4 4.7 12,100 14.372 16 (for comparison) 19.3 9.6 21.5 5 4,498 8.443 18 (ratio) 36.7 17 3.5 0.8 10,000 11,000 17 19 10.4 30.8 7.9 12,000 15,000 19( :h 5) 28 11 0 0 3,000 8,000 20 ( :hi) 30.5 12 0 0 4,000 9.000 Improved cold resistance of these terpolymers The ability is evaluated by combining the two distillates of the motor gasoil type (called GOM 1 and GOM 2 ), which are distilled in Table 2 below - 15 - 201116617 Object feature grouping. Table 2: Fuel characteristic distillation GOMl GOM 2 T90-T20 (°C) 129.6 100.4 PF-T90 (°C) 19.5 24.9 T95 (°C) 353.5 362.4 Cloud point (°C) NF ΕΝ 23015 -6 -4 LFT (° C) ΕΝ 116 - 6 -7 Pour point (°C) NFT 60105 -15 •10 Dead weight (%) chromatography 14.72 14.68 TCC (°C) IP 389 -6.2 -6,3 Sulfur content (ppm EN ISO 20846 18.6 38 400 ppm by weight of each copolymer is decomposed into a motor gas-oil distillate called g〇M 1 and then blocked index FBT (Filter Blocking Tendency) according to IP 387 measuring. G Ο Μ 1 without any additives has an F B T blocking index of 1.0. As a result, it can be seen that in the case of the terpolymer 17 according to the present invention, the blocking tendency of G〇M 1 does not deteriorate, that is, the GOM 1 of the 4000 ppm terpolymer is less than 1.41. FBT. The results are shown in Table 3 below. Table 3: Addition force □ 400 ppm of different terpolymers GOM 1 blocking tendency (IP3 8 7 ). Additive Blocking Index (IP 387) 6 (for comparison) " 6Ό8 ' 7 (for comparison) 6.08 12 (for comparison) ----1.01 ^ --- Γ03 ' 16 (for comparison) - 51 ^ 17 1.0 18 (for comparison) 1.24 19 (for comparison) 5.1 20 (thfeW) 1.9

The cold resistance L F T efficiency of the terpolymers in the G Ο 及 1 and G Ο Μ 2 was measured at a concentration of 2 10 p p m; the results are grouped in Table 4. -16- 201116617 Table 4: Additives for the FLT efficiency test of two low sulfur content gas oils TLF measurement ΓΟΕΝ116 GOM 1 GOM 2 210 ppm 210 ppm ~~ does not contain any additives ~~ -6 -5 6 • 15 7 -16 •15 12 -7 -4 13 -7 -5 17 -19 - 18 -7 - 19 -15 . 20 -16 - Results are seen: the terpolymer of the invention is 7 for gas oil G Ο Μ 1 is the most efficient. Further, from the results obtained in Table 3, it was found that the terpolymer 17 added to GOM 1 in an amount of 400 ppm did not deteriorate the blocking tendency. This is not the case in the case of the comparison of WO 2005/0 54314 with terpolymers 6; 7; 16 and 18 which strongly influence the blocking tendency measured according to IP 3 8 7 It deteriorates and does not have the LFT efficiency as the additive of the present invention. -17-

Claims (1)

201116617 VII. Patent application scope: 1. The use of at least one copolymer as an additive for improving cold resistance and filterability of a fuel, the copolymer comprising: 81 to 87 mol% of at least one α-olefin, preferably At least one vinyl ester of ethylene at least 10.5 to less than 12 mol%, preferably at least vinyl acetate, from 1 to 8.5 mol% of at least one unsaturated alpha, yj-mono-carboxylate, preferably It is at least ethyl-2-hexyl acrylate. 2) The use of at least one copolymer as an additive for improving the cold resistance and filterability of a fuel as claimed in claim 1 which is recorded as a quadrilateral ABCD, wherein a, B, C and D represent the apex of the quadrilateral and Corresponding to at least the vinyl ester and at least the molar % of the unsaturated alpha, A-mono-carboxylate: A: 12; 1 B: 12; 6 C: 10.5; 4 D: 10.5; 3. The use of at least one copolymer for improving the cold resistance and filterability of a fuel as disclosed in claim 1 or 2, the copolymer being recorded as a quadrilateral AiBC^D, wherein A, B, < And D represents the apex of the quadrilateral and corresponds to at least the vinyl ester and at least the molar % of the unsaturated α, A-mono-carboxylate: A, 12; 2 -18- 201116617 B: 12; 6 C , : 1 0.5 ; 5 D: 10.5; 8.5. 4. Use of at least one terpolymer according to any one of claims 1 to 3, wherein the terpolymer comprises units derived from ethylene, units derived from vinyl acetate, and derived from ethyl acrylate Unit of -2-hexyl ester. 5. The use of at least one copolymer of any one of claims 1 to 4, wherein the copolymer has a weight average molecular weight (Mw) measured by GPC of between 3,000 and 30,000, preferably The number average molecular weight (?n) between 3,000 and 20,000 and measured by GPC is usually between 1,000 and 20,000, preferably between 1,500 and 15,000. 6. The use of at least one copolymer as an additive for improving cold resistance and filterability of a fuel according to any one of claims 1 to 5, which does not use a middle distillate such as diesel or heating equipment. Household oils (D 0 F), kerosene, and aviation fuels have a poor tendency to block heavy fuels. 7. The use of at least one copolymer for improving the cold resistance and filterability of a fuel as disclosed in any one of claims 1 to 6, wherein the fuel has a sulfur content of less than 5,000 ppm. Preferably less than 500 ppm, more preferably less than 50 ppm, or even less than 1 ppm, and advantageously no sulfur. 8. A hydrocarbon composition comprising a major amount of a middle distillate having a boiling temperature in the range of from 丨〇〇 to 500 ° C and a minor amount as in the application -19-201116617 range 1 to 7 At least one of the items defined in any one of the items, wherein the weight % of the composition of claim 8 is derived from biomass and diesel of animals and/or plants. 1 0. For the composition of the 8th or 9th patent scope of the patent application, household oil (DOF) for diesel and heating equipment, coal, heavy fuel. 1 1. The weight of any of the claims 8 to 1 includes 10 to 5,000 ppm by weight, preferably 100% by weight, and advantageously 150 to 500 ppm by weight as defined in the items 1 to 5. At least one copolymer. 1 2 . The additive, corrosion inhibitor, dispersant, emulsifier, antibacterial, odor modifier (reodorant) comprising one or more of the copolymers of the present invention, as defined in any one of claims 8 to 11 ), diesel added additive), friction modifier, luturousness additive, combustion aid (burning accelerator), improved turbidity point, pour point, filter limit, anti-precipitant, anti-wear agent and / or Conductivity improver. a copolymer. Containing 〇 to 100, which is selected from the group consisting of oil and aviation fuels, up to 1,000 ppm. The composition of the scope of the patent scope is selected from the group consisting of foaming agents and biocides (procetane slick additive). Asbestos catalyzed temperature modifier -20- 201116617 IV. Designated representative map: (1) The representative representative of the case is: No. (2) The symbol of the representative figure is simple: No 201116617 If there is a chemical formula in the case, please reveal The chemical formula that best shows the characteristics of the invention: none