EP0486836B1 - Petroleum middle distillate with improved cold flow characteristics - Google Patents
Petroleum middle distillate with improved cold flow characteristics Download PDFInfo
- Publication number
- EP0486836B1 EP0486836B1 EP91118118A EP91118118A EP0486836B1 EP 0486836 B1 EP0486836 B1 EP 0486836B1 EP 91118118 A EP91118118 A EP 91118118A EP 91118118 A EP91118118 A EP 91118118A EP 0486836 B1 EP0486836 B1 EP 0486836B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- copolymers
- monomers
- middle distillate
- weight
- mineral oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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- 239000000178 monomer Substances 0.000 claims abstract description 38
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 10
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- 239000002480 mineral oil Substances 0.000 claims 7
- 235000010446 mineral oil Nutrition 0.000 claims 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
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- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
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- 239000003112 inhibitor Substances 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DJDSLBVSSOQSLW-UHFFFAOYSA-N mono(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(O)=O DJDSLBVSSOQSLW-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004209 oxidized polyethylene wax Substances 0.000 description 1
- 235000013873 oxidized polyethylene wax Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- YZBOVSFWWNVKRJ-UHFFFAOYSA-N phthalic acid monobutyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(O)=O YZBOVSFWWNVKRJ-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
- C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
- C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
- C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
- C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
- C10L1/2366—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amine groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
- C10L1/2368—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing heterocyclic compounds containing nitrogen in the ring
Definitions
- the present invention relates to petroleum middle distillates which contain small amounts of a conventional flow improver based on ethylene and copolymers of ethylenically unsaturated carboxylic acid esters of long-chain n-alkanols with long-chain alkyl vinyl ethers and are distinguished by improved flow properties in the cold.
- Middle distillates such as gas oils, diesel oils or heating oils, which are obtained from petroleum by distillation, have different levels of paraffins depending on the origin of the crude oil and depending on the processing method in the refinery.
- the proportion of long-chain n-paraffins in particular determines the cold flow behavior of such distillates.
- the n-paraffins separate out as platelet-shaped interlocking crystals that build up a three-dimensional network (house of cards structure), in which large quantities of still liquid distillate are enclosed and immobilized.
- the crystallization of the n-paraffins is accompanied by a decrease in fluidity and an increase in viscosity. This makes it difficult to supply middle distillates to the combustion units, the failed paraffins clog upstream filters, so that in extreme cases the supply can completely stop.
- ethylene copolymers especially copolymers of ethylene and unsaturated esters, such as those e.g. are described in DE-A-21 02 469 or EP-A-84 148.
- DE-A-16 45 785 discloses the use of polymers with unbranched, saturated side chains with at least 18 carbon atoms to reduce the pour point of heating oil containing wax. These are e.g. Homo- or copolymers of alkyl esters of unsaturated mono- or dicarboxylic acids as well as homo- or copolymers of various alkyl vinyl ethers.
- DE-A-20 47 448 describes the addition of a mixture consisting of polyvinyl ethers and ethylene-vinyl acetate copolymers to paraffin-based crude oils.
- EP-A-360 419 describes middle distillates which contain polymers of vinyl ethers with hydrocarbon radicals of 1 to 17 carbon atoms.
- the following are among the comonomers: Called alkyl acrylates or methacrylates. In the examples, however, only polymers from alkyl vinyl ethers with up to 4 carbon atoms in the side chain are described.
- These C1 to C4 vinyl ethers are copolymerized with maleic or fumaric acid derivatives. Examples of copolymers with acrylic acid derivatives are not given.
- the claimed additives can be used together with other flow improvers.
- the weight ratio of monomers according to formula I to monomers according to formula II is between 10:90 and 95: 5, preferably between 40:60 and 95: 5 and particularly preferably between 60:40 and 90:10 and the ratio of flow improver A to copolymer B is between 40:60 and 95: 5, preferably between 60:40 and 95: 5 and particularly preferably between 70:30 and 90:10.
- the alkyl radicals R2 and R3 are preferably straight-chain and unbranched. However, up to 20% by weight of cyclic and / or branched portions can also be present.
- Examples of monomers according to formula I are n-octyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-hexadecyl (meth) acrylate and n-octadecyl (meth) acrylate and mixtures thereof.
- Examples of monomers according to formula II are n-octadecyl vinyl ether, n-eicosyl vinyl ether, n-docosyl vinyl ether, n-tetracosyl vinyl ether, n-hexacosyl vinyl ether and n-octacosyl vinyl ether and mixtures thereof.
- the copolymers B consist of at least 70% by weight of monomers of the formulas I and II.
- other ethylenically unsaturated monomers can be present, such as, for example, styrene, alkylstyrenes, straight-chain or branched olefins with 2 to 16 Carbon atoms, vinyl esters of C1- to C5-carboxylic acids, acrylonitrile, N-alkyl-substituted acrylamides, N-containing, ethylenically unsaturated heterocycles such as vinylpyrrolidone, vinylimidazole or vinylpyridine, hydroxyl- or amino group-containing monomers such as butanediol monoacrylate, hexanediol monoacrylate, dimethylethylaminoethylamate, and ) acrylic acid esters from C1 to C8 alkanols such as methyl methacrylate, ethyl acrylate
- Examples of flow improvers A are the polymers already mentioned, described in DE-A-21 02 469 and EP-A-84 148, such as copolymers of ethylene with vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate or with esters of (meth) acrylic acid, which are derived from alkanols with 1 to 12 carbon atoms.
- copolymers B together with flow improvers, have synergistic effects. Although the copolymers B alone show little or no flow-improving effect, the combination of A and B far exceeds the individual efficacies.
- the monomers according to formula I are easily accessible. They can be obtained by the known esterification processes. For example, a solution of (meth) acrylic acid and an alkanol or a mixture of different alkanols is heated in an organic solvent with the addition of the usual polymerization inhibitors, e.g. Hydroquinone derivatives and esterification catalysts such as sulfuric acid, p-toluenesulfonic acid or acidic ion exchangers at the boil and remove the water of reaction formed by azeotropic distillation.
- the usual polymerization inhibitors e.g. Hydroquinone derivatives and esterification catalysts such as sulfuric acid, p-toluenesulfonic acid or acidic ion exchangers
- vinyl ethers can polymerize cationically under acidic conditions or decompose in the presence of water and acid to form acetaldehyde, which interferes with the radical polymerization, the neutralization of the catalyst acid and excess (meth) acrylic acid with e.g. Amines or their removal indicated by washing the ester solution with alkaline agents and water to prepare the copolymers B.
- Particularly pure esters can be obtained by distillation of the pre-cleaned ester solution.
- the vinyl ethers of the formula II can be obtained by known processes by reacting alkanols with acetaldehyde and subsequent elimination of water or by catalytic addition of acetylene to alkanols. Particularly pure monomers can also be obtained here by distillation. With vinyl ethers with more than 20 to 22 carbon atoms in the alkyl part, the undecomposed distillation is technically difficult to carry out. In these cases, cleaning by filtration, extraction or recrystallization to remove the catalysts is recommended.
- the copolymers B are prepared by known batch or continuous polymerization processes such as bulk, suspension, precipitation or solution polymerization and initiation with customary radical donors such as acetylcyclohexanesulfonyl peroxide, diacetyl peroxidicarbonate, dicyclohexylproxidicarbonate, di-2-ethylhexyl peroxidate carbonate, tert.
- customary radical donors such as acetylcyclohexanesulfonyl peroxide, diacetyl peroxidicarbonate, dicyclohexylproxidicarbonate, di-2-ethylhexyl peroxidate carbonate, tert.
- -Azobis (4-methoxy-2,4-dimethylvaleronitrile), tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, tert-butyl permaleinate, 2,2'-azobis (isobutyronitrile), bis (tert-butyl peroxide ) cyclohexane, tert-butyl peroxyisopropyl carbonate, tert-butyl peracetate, dicumyl peroxide, di-tert-amyl peroxide, di-tert-butyl peroxide, p-menthane hydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide and mixtures with one another.
- these initiators are used in amounts of 0.1 to 20% by weight, preferably 0.2 to 15% by weight, based on the monomers.
- the polymerization is generally carried out at temperatures of 40 to 400 ° C., preferably 70 to 300 ° C., the use of solvents with boiling temperatures below the polymerization temperature advantageously being carried out under pressure.
- the polymerization is expediently carried out in the absence of air, ie if it is not possible to work under boiling conditions, for example under nitrogen or carbon dioxide, since oxygen delays the polymerization.
- the reaction can be accelerated by using redox coinitiators such as benzoin, dimethylaniline, ascorbic acid and organically soluble complexes of heavy metals such as copper, cobalt, manganese, iron, nickel and chromium.
- the amounts usually used are 0.1 to 2000 ppm by weight, preferably 0.1 to 1000 ppm by weight.
- regulators are, for example, allyl alcohols, such as 1-buten-3-ol, organic mercapto compounds such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, tert-butyl mercaptan, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and tert.- Dodecyl mercaptan, which are generally used in amounts of 0.1 to 10 wt .-%.
- Equipment suitable for the polymerization is e.g. Conventional stirred kettles with, for example, anchor, blade, impeller or multi-stage impulse countercurrent stirrers and for the continuous production of stirred kettle cascades, tubular reactors and static mixers.
- the simplest method of polymerization is bulk polymerization.
- the monomers are polymerized in the presence of an initiator and in the absence of solvents.
- all monomers are mixed in the desired composition and a small part, e.g. about 5 to 10%, in the reactor before, heated to the desired polymerization temperature with stirring and metered in the remaining monomer mixture and the initiator and optionally coinitiator and regulator evenly within 1 to 10 hours, preferably 2 to 5 hours. It is expedient to meter in the initiator and the coinitiator separately in the form of solutions in a small amount of a suitable solvent.
- the copolymer can then be added directly to the middle distillate as a solidified melt or after being taken up in a suitable solvent together with the flow improver.
- a copolymer of (meth) acrylic acid esters and vinyl ethers can be prepared, for example, by continuously feeding the monomers and a suitable initiator to a reactor or two reaction zones connected in series, for example a reactor cascade, and the reaction product after a residence time of 2 to 60, preferably of 5 to 30 minutes, at temperatures between 200 and 400 ° C continuously discharged from the reaction zone.
- the polymerization is expediently carried out at pressures of more than 1 bar, preferably between 1 and 200 bar.
- the copolymers obtained have solids contents of over 99% and can be added to the middle distillate without further treatment.
- Another simple method for producing the copolymers B is solution polymerization. It is carried out in solvents in which the monomers and the copolymers formed are soluble. All solvents which fulfill this requirement and which do not react with the monomers are suitable for this. For example, these are toluene, xylene, ethylbenzene, cumene, high-boiling aromatic mixtures such as Solvesso® 100, 150 and 200, aliphatic and cycloaliphatic hydrocarbons such as n-hexane, cyclohexane, methylcyclohexane, n-octane, iso-octane, paraffin oils, Shellsol® TD , T and K, as well as tetrahydrofuran and dioxane, tetrahydrofuran and dioxane being particularly suitable for achieving low molecular weight copolymers.
- the solution polymerization it is expedient to initially introduce solvent and part of the monomer mixture (for example about 5 to 20%) and to meter in the rest of the monomer mixture with the initiator and, if appropriate, coinitiator, regulator and solvent.
- the monomers can also be metered in individually at different rates. This is advisable for monomers with very different reactivities, as is the case with (meth) acrylates and vinyl ethers and when a particularly uniform distribution of the less reactive vinyl ether is desired.
- the less reactive monomer is metered in faster and the more reactive monomer more slowly. It is also possible to introduce the entire amount of a monomer, preferably the less reactive vinyl ether, and to meter in only the (meth) acrylate.
- polymers A and B should be present together in the form of a concentrate, since the use of 2 concentrates - one each for polymer A and polymer B - makes handling more difficult. Due to the possible incompatibility of polymers A and B, phase separation can occur when the two polymers are mixed in a common solvent. This can optionally be suppressed by suitable solvents and / or additives. Suitable are e.g.
- Alkanols such as iso-butanol, n-hexanol, 2-ethylhexanol, iso-decanol and their adducts with ethylene oxide, propylene oxide and / or butylene oxide, alkylphenols and their adducts with ethylene oxide, propylene oxide and / or butylene oxide as well as half esters or diesters of dicarboxylic acids with alkanols or (Oligo) alkylene oxide half ethers such as mono- or dibutyl phthalate, mono- or di-2-ethylhexyl phthalate or di- (2-methoxyethyl) phthalate.
- Another method of avoiding possible phase separation is to graft copolymer B at least in part onto the flow improver.
- Bulk or solution polymerization is preferably used for the grafting.
- the polymerization can be carried out according to the "batch" or feed procedure.
- the total amount of flow improver A to be grafted is initially introduced together with the monomers and initiator and, if appropriate, coinitiator and regulator are metered in.
- the total amount of flow improver A to be grafted is optionally introduced together with some of the monomers and the rest of the monomers, initiator and, if appropriate, coinitiator and regulator are metered in.
- the copolymer B As already mentioned, it is not necessary to graft the copolymer B onto the entire proportion of the flow improver A. For example, at a ratio A: B of 90:10, for reasons of space-time yield, the copolymer B will only be grafted to a proportion of 2 to 20% by weight of the total amount of A. With a ratio of A: B of 40:60, however, to a proportion of 30 to 100% by weight of the total amount of A.
- copolymer B may also be present in the concentrates described.
- the K values (according to H. Fikentscher, Cellulosechemie, Volume 13, pages 58 to 64 and 71 to 74 (1932)), determined in a 2% (w / v) xylene solution of the copolymers B, are between 10 and 50 , preferably between 10 and 40 and particularly preferably between 13 and 30.
- the particularly preferred range corresponds to molecular weights between approximately 5000 and 25,000 g / mol (number average values, determined by gel permeation chromatography against polystyrene standards).
- the additives A and B according to the invention are added to the petroleum middle distillates together in amounts of 50 to 5000 ppm, preferably 100 to 2000 ppm.
- the middle distillates according to the invention containing small amounts of a flow improver A and a copolymer B, can, depending on the intended use, other additives or additives such as dispersants, anti-foam additives, corrosion inhibitors, antioxidants, dyes and others. contain.
- Examples 4 to 18 were prepared by a procedure analogous to that in Example 3.
- Examples 17 to 20 are comparative examples and do not form part of the present invention.
- the flow improvers FI (A), FI (B) and FI (C) are commercially available products, e.g. the Keroflux® brands from BASF.
- Middle distillate I Heating oils and diesel fuels in commercial West German refinery quality were used as middle distillates. They are referred to as middle distillate I, II, III and IV. Middle distillate I. II III IV Cloud point (° C) + 6 + 4th + 4th + 5 CFPP (° C) 0 - 2nd - 1 - 2nd Initial boiling point (° C) 155 131 169 174 20% boiling point (° C) 232 216 222 219 50% boiling point (° C) 280 262 262 272 90% boiling point (° C) 352 346 351 365 End of boiling point (° C) 382 375 381 385
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Abstract
Description
Die vorliegende Erfindung betrifft Erdölmitteldestillate, die geringe Mengen eines herkömmlichen Fließverbesserers auf Ethylenbasis und Copolymere aus ethylenisch ungesättigten Carbonsäureestern langkettiger n-Alkanole mit langkettigen Alkylvinylethern enthalten und sich durch verbesserte Fließeigenschaften in der Kälte auszeichnen.The present invention relates to petroleum middle distillates which contain small amounts of a conventional flow improver based on ethylene and copolymers of ethylenically unsaturated carboxylic acid esters of long-chain n-alkanols with long-chain alkyl vinyl ethers and are distinguished by improved flow properties in the cold.
Mitteldestillate wie Gasöle, Dieselöle oder Heizöle, die durch Destillation aus Erdölen gewonnen werden, haben je nach Herkunft des Rohöls und in Abhängigkeit von der Verarbeitungsweise in der Raffinerie unterschiedliche Gehalte an Paraffinen. Insbesondere der Anteil an langkettigen n-Paraffinen bestimmt das Kältefließverhalten derartiger Destillate. Beim Abkühlen scheiden sich die n-Paraffine als plättchenförmige miteinander verzahnte Kristalle aus, die ein dreidimensionales Netzwerk aufbauen (Kartenhausstruktur), worin große Mengen noch flüssigen Destillats eingeschlossen und immobilisiert werden. Der Kristallisation der n-Paraffine geht eine Abnahme der Fließfähigkeit und Zunahme der Viskosität parallel. Dadurch wird die Zufuhr von Mitteldestillaten zu den Verbrennungsaggregaten erschwert, die ausgefallenen Paraffine verstopfen vorgeschaltete Filter, so daß es im Extremfall zum völligen Erliegen der Zufuhr kommen kann.Middle distillates such as gas oils, diesel oils or heating oils, which are obtained from petroleum by distillation, have different levels of paraffins depending on the origin of the crude oil and depending on the processing method in the refinery. The proportion of long-chain n-paraffins in particular determines the cold flow behavior of such distillates. Upon cooling, the n-paraffins separate out as platelet-shaped interlocking crystals that build up a three-dimensional network (house of cards structure), in which large quantities of still liquid distillate are enclosed and immobilized. The crystallization of the n-paraffins is accompanied by a decrease in fluidity and an increase in viscosity. This makes it difficult to supply middle distillates to the combustion units, the failed paraffins clog upstream filters, so that in extreme cases the supply can completely stop.
Es ist seit langem bekannt, daß durch Zusatz sogenannter Fließverbesserer dem Verstopfen der Filter bei tiefen Temperaturen begegnet werden kann. Die Additive sorgen durch Keimbildung für die Ausbildung vieler kleiner anstelle weniger großer Paraffinkristalle. Gleichzeitig ändern sie deren Kristallmodifikation, so daß es nicht zur Ausbildung der oben beschriebenen Plättchen kommt. Die bei Anwesenheit von Fließverbesserern gebildeten Paraffinkristalle sind so klein, daß sie die Filter passieren können oder sie bauen einen Filterkuchen auf, der für den noch flüssigen Anteil des Mitteldestillats durchlässig ist, so daß auch bei tiefen Temperaturen ein störungsfreier Betrieb sichergestellt wird.It has long been known that by adding so-called flow improvers, the clogging of the filters can be counteracted at low temperatures. The additives nucleate the formation of many small instead of less large paraffin crystals. At the same time they change their crystal modification so that the platelets described above do not form. The paraffin crystals formed in the presence of flow improvers are so small that they can pass through the filters or they build up a filter cake which is permeable to the still liquid portion of the middle distillate, so that trouble-free operation is ensured even at low temperatures.
In zunehmendem Maße treten in den Raffinerien Mitteldestillat-Schnitte auf, bei denen die Standard-Fließverbesserer ungenügend wirken oder sogar ganz versagen. Dies trifft besonders bei sogenannten hochgeschnittenen Ölen also Fraktionen mit hohem Siedeende (S.E. > 370°C) zu. Das Siedeverhalten ist jedoch nicht das einzige Kriterium. So kommt es vor, daß bei zwei Fraktionen mit ähnlicher Siedekurve aber unterschiedlicher Provinienz des Basis-Rohöls der Standard-Fließverbesserer in einem öl gut anspricht, im anderen Öl jedoch nicht. Die Wirksamkeit der Fließverbesserer wird nach DIN 51 428 indirekt durch Messung des "Cold Filter Plugging Points" (CFPP) ausgedrückt.Middle distillate cuts are increasingly appearing in refineries where the standard flow improvers are insufficient or even fail completely. This applies particularly to so-called high-cut oils, i.e. fractions with a high boiling point (SE> 370 ° C). However, boiling behavior is not the only criterion. So it happens that with two fractions with a similar boiling curve but different provinces of the base crude the standard flow improver responds well in one oil, but not in the other oil. The effectiveness of the flow improver is expressed indirectly according to DIN 51 428 by measuring the "Cold Filter Plugging Point" (CFPP).
Als Standard-Kältefließverbesserer werden an sich bekannte Ethylencopolymere, vor allem Copolymere aus Ethylen und ungesättigten Estern, wie sie z.B. in der DE-A-21 02 469 oder der EP-A-84 148 beschrieben werden, verwendet.Known per se as standard cold flow improvers are ethylene copolymers, especially copolymers of ethylene and unsaturated esters, such as those e.g. are described in DE-A-21 02 469 or EP-A-84 148.
In der Technik werden jedoch neue Fließverbesserer oder Kombinationen benötigt, die auch bei den oben beschriebenen kritischen Ölen gute Wirksamkeit zeigen.In the art, however, new flow improvers or combinations are required which also show good effectiveness with the critical oils described above.
Aus der DE-A-16 45 785 ist die Verwendung von Polymeren mit unverzweigten, gesättigten Seitenketten mit mindestens 18 Kohlenstoffatomen zum Herabsetzen des Fließpunktes von wachshaltigem Heizöl bekannt. Dies sind z.B. Homo- oder Copolymere von Alkylestern ungesättigter Mono- oder Dicarbonsäuren sowie Homo- oder Copolymere verschiedener Alkylvinylether.DE-A-16 45 785 discloses the use of polymers with unbranched, saturated side chains with at least 18 carbon atoms to reduce the pour point of heating oil containing wax. These are e.g. Homo- or copolymers of alkyl esters of unsaturated mono- or dicarboxylic acids as well as homo- or copolymers of various alkyl vinyl ethers.
Die DE-A-20 47 448 beschreibt den Zusatz einer Mischung, bestehend aus Polyvinylethern und Ethylen-Vinylacetat-Copolymeren, zu paraffinbasischen Rohölen.DE-A-20 47 448 describes the addition of a mixture consisting of polyvinyl ethers and ethylene-vinyl acetate copolymers to paraffin-based crude oils.
In der EP-A-360 419 werden Mitteldestillate beschrieben, die Polymere aus Vinylethern mit Kohlenwasserstoffresten von 1 bis 17 Kohlenstoffatomen enthalten. Als Comonomere sind u.a. Alkylacrylate bzw. -methacrylate genannt. In den Beispielen werden jedoch nur Polymere aus Alkylvinylethern mit bis zu 4 Kohlenstoffatomen in der Seitenkette beschrieben. Diese C₁- bis C₄-Vinylether sind mit Malein- bzw. Fumarsäurederivaten copolymerisiert. Beispiele für Copolymere mit Acrylsäurederivaten werden nicht angegeben. Die beanspruchten Additive können zusammen mit anderen Fließverbesserern eingesetzt werden.EP-A-360 419 describes middle distillates which contain polymers of vinyl ethers with hydrocarbon radicals of 1 to 17 carbon atoms. The following are among the comonomers: Called alkyl acrylates or methacrylates. In the examples, however, only polymers from alkyl vinyl ethers with up to 4 carbon atoms in the side chain are described. These C₁ to C₄ vinyl ethers are copolymerized with maleic or fumaric acid derivatives. Examples of copolymers with acrylic acid derivatives are not given. The claimed additives can be used together with other flow improvers.
Bezüglich ihrer Wirksamkeit als Kältefließverbesserer in Mitteldestillaten lassen diese Polymeren jedoch noch zu wünschen übrig.With regard to their effectiveness as a cold flow improver in middle distillates, however, these polymers still leave something to be desired.
Es bestand deshalb die Aufgabe, Zusätze zu Mitteldestillaten zu finden, die eine bessere Wirksamkeit als Kältefließverbesserer besitzen.It was therefore the task of finding additives for middle distillates which have a better activity than cold flow improvers.
Demgemäß wurde nun gefunden, daß Erdölmitteldestillate, enthaltend geringe Mengen von A bekannten Fließverbesserern auf Ethylenbasis und B Copolymeren, die zu mindestens 70 Gew.-% aus einem oder mehreren Monomeren sowohl der Formel I als auch II bestehen,
wobei
- R¹
- Wasserstoff oder Methyl,
- R²
- C₈- bis C₁₈-Alkyl und
- R³
- C₁₈- bis C₂₈-Alkyl bedeuten,
in which
- R¹
- Hydrogen or methyl,
- R²
- C₈ to C₁₈ alkyl and
- R³
- Are C₁₈ to C₂₈ alkyl,
Das Gewichtsverhältnis von Monomeren gemäß Formel I zu Monomeren gemäß Formel II liegt zwischen 10:90 und 95:5, bevorzugt zwischen 40:60 und 95:5 und besonders bevorzugt zwischen 60:40 und 90:10 und das Verhältnis von Fließverbesserer A zu Copolymer B liegt zwischen 40:60 und 95:5, bevorzugt zwischen 60:40 und 95:5 und besonders bevorzugt zwischen 70:30 und 90:10.The weight ratio of monomers according to formula I to monomers according to formula II is between 10:90 and 95: 5, preferably between 40:60 and 95: 5 and particularly preferably between 60:40 and 90:10 and the ratio of flow improver A to copolymer B is between 40:60 and 95: 5, preferably between 60:40 and 95: 5 and particularly preferably between 70:30 and 90:10.
Die Alkylreste R² und R³ sind bevorzugt geradkettig und unverzweigt. Es können jedoch auch bis zu 20 Gew.-% cyclische und/oder verzweigte Anteile enthalten sein.The alkyl radicals R² and R³ are preferably straight-chain and unbranched. However, up to 20% by weight of cyclic and / or branched portions can also be present.
Beispiele für Monomere gemäß Formel I sind n-Octyl(meth)acrylat, n-Decyl(meth)acrylat, n-Dodecyl(meth)acrylat, n-Tetradecyl(meth)acrylat, n-Hexadecyl(meth)acrylat und n-Octadecyl(meth)acrylat sowie Mischungen davon.Examples of monomers according to formula I are n-octyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-hexadecyl (meth) acrylate and n-octadecyl (meth) acrylate and mixtures thereof.
Beispiele für Monomere gemäß Formel II sind n-Octadecylvinylether, n-Eicosylvinylether, n-Docosylvinylether, n-Tetracosylvinylether, n-Hexacosylvinylether und n-Octacosylvinylether sowie Mischungen davon.Examples of monomers according to formula II are n-octadecyl vinyl ether, n-eicosyl vinyl ether, n-docosyl vinyl ether, n-tetracosyl vinyl ether, n-hexacosyl vinyl ether and n-octacosyl vinyl ether and mixtures thereof.
Die Copolymeren B bestehen zu mindestens 70 Gew.-% aus Monomeren gemäß Formeln I und II. Zusätzlich können noch bis zu 30 Gew.-% andere ethylenisch ungesättigte Monomere enthalten sein, wie z.B. Styrol, Alkylstyrole, geradkettige oder verzweigte Olefine mit 2 bis 16 Kohlenstoffatomen, Vinylester von C₁- bis C₅-Carbonsäuren, Acrylnitril, N-Alkyl-substituierte Acrylamide, N-haltige, ethylenisch ungesättigte Heterocyclen wie Vinylpyrrolidon, Vinylimidazol oder Vinylpyridin, hydroxyl- oder aminogruppenhaltige Monomere wie Butandiolmonoacrylat, Hexandiolmonoacrylat, Dimethylaminoethylacrylat, Diethylaminoethylacrylat sowie (Meth)acrylsäureester aus C₁- bis C₈-Alkanolen wie Methylmethacrylat, Ethylacrylat, Isobutylacrylat u.a., sowie Maleinsäure-, Fumarsäure- und Itaconsäureester aus C₁- bis C₂₈-Alkanolen.The copolymers B consist of at least 70% by weight of monomers of the formulas I and II. In addition, up to 30% by weight of other ethylenically unsaturated monomers can be present, such as, for example, styrene, alkylstyrenes, straight-chain or branched olefins with 2 to 16 Carbon atoms, vinyl esters of C₁- to C₅-carboxylic acids, acrylonitrile, N-alkyl-substituted acrylamides, N-containing, ethylenically unsaturated heterocycles such as vinylpyrrolidone, vinylimidazole or vinylpyridine, hydroxyl- or amino group-containing monomers such as butanediol monoacrylate, hexanediol monoacrylate, dimethylethylaminoethylamate, and ) acrylic acid esters from C₁ to C₈ alkanols such as methyl methacrylate, ethyl acrylate, isobutylacrylate and others, and maleic, fumaric and itaconic esters from C₁ to C₂₈ alkanols.
Beispiele für die Fließverbesserer A sind die bereits erwähnten, in DE-A-21 02 469 und EP-A-84 148 beschriebenen Polymeren, wie Copolymere aus Ethylen mit Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinylpivalat bzw. mit Estern der (Meth)acrylsäure, die sich von Alkanolen mit 1 bis 12 Kohlenstoffatomen ableiten. Ebenfalls geeignet sind Mischungen mehrerer Copolymerer aus Ethylen und Vinylacetat (EP-A-261 951, Additiv A), Copolymere aus Ethylen mit α-Olefinen (EP-A-261 957, Additiv D) sowie die in der DE-A-36 24 147 angegebenen Mischungen aus Terpolymeren aus Ethylen, Vinylacetat und Diisobuten mit oxidiertem Polyethylenwachs. Besonders bevorzugt sind Copolymere aus Ethylen mit Vinylacetat oder Vinylpropionat oder Ethylhexylacrylat.Examples of flow improvers A are the polymers already mentioned, described in DE-A-21 02 469 and EP-A-84 148, such as copolymers of ethylene with vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate or with esters of (meth) acrylic acid, which are derived from alkanols with 1 to 12 carbon atoms. Mixtures of several copolymers of ethylene and vinyl acetate (EP-A-261 951, additive A), copolymers of ethylene with α-olefins (EP-A-261 957, additive D) and those in DE-A-36 24 are also suitable 147 specified mixtures of terpolymers of ethylene, vinyl acetate and diisobutene with oxidized polyethylene wax. Copolymers of ethylene with vinyl acetate or vinyl propionate or ethylhexyl acrylate are particularly preferred.
Die Copolymeren B zeigen zusammen mit Fließverbesserern synergistische Wirkungen. Obwohl die Copolymeren B alleine keine oder nur geringe fließverbessernde Wirkung zeigen, übertrifft die Kombination von A und B die Einzelwirksamkeiten bei weitem.The copolymers B, together with flow improvers, have synergistic effects. Although the copolymers B alone show little or no flow-improving effect, the combination of A and B far exceeds the individual efficacies.
Die Monomeren gemäß Formel I sind leicht zugänglich. Sie können nach den bekannten Verfahren der Veresterung erhalten werden. Beispielsweise erhitzt man eine Lösung aus (Meth)acrylsäure und einem Alkanol oder einer Mischung verschiedener Alkanole in einem organischen Lösungsmittel unter Zusatz der üblichen Polymerisationsinhibitoren, z.B. Hydrochinonderivaten und Veresterungskatalysatoren wie Schwefelsäure, p-Toluolsulfonsäure oder sauren Ionenaustauschern zum Sieden und entfernt das gebildete Reaktionswasser durch azeotrope Destillation. Da Vinylether unter sauren Bedingungen kationisch polymerisieren können bzw. sich bei Anwesenheit von Wasser und Säure unter Bildung von Acetaldehyd zersetzen, der die radikalische Polymerisation stört, ist die Neutralisation der Katalysatorsäure sowie überschüssiger (Meth)acrylsäure mit z.B. Aminen oder deren Entfernung durch Waschen der Esterlösung mit alkalischen Mitteln und Wasser zur Herstellung der Copolymeren B angezeigt. Besonders reine Ester können durch Destillation der vorgereinigten Esterlösung erhalten werden.The monomers according to formula I are easily accessible. They can be obtained by the known esterification processes. For example, a solution of (meth) acrylic acid and an alkanol or a mixture of different alkanols is heated in an organic solvent with the addition of the usual polymerization inhibitors, e.g. Hydroquinone derivatives and esterification catalysts such as sulfuric acid, p-toluenesulfonic acid or acidic ion exchangers at the boil and remove the water of reaction formed by azeotropic distillation. Since vinyl ethers can polymerize cationically under acidic conditions or decompose in the presence of water and acid to form acetaldehyde, which interferes with the radical polymerization, the neutralization of the catalyst acid and excess (meth) acrylic acid with e.g. Amines or their removal indicated by washing the ester solution with alkaline agents and water to prepare the copolymers B. Particularly pure esters can be obtained by distillation of the pre-cleaned ester solution.
Weitere Möglichkeiten zur Herstellung der Monomeren gemäß Formel I ist die Umsetzung von (Meth)acrylsäurechlorid oder -anhydrid mit den entsprechenden Alkanolen sowie die als Umesterung bekannte Umsetzung von niederen (Meth)acrylsäureestern mit den entsprechenden C₈- bis C₁₈-Alkanolen unter Zusatz saurer oder basischer Katalysatoren und destillativer Entfernung des niederen Alkanols. Auch bei diesen Herstellverfahren sollte der Ester soweit aufgearbeitet werden, daß keine Säure mehr vorhanden ist.Further possibilities for the preparation of the monomers according to formula I are the reaction of (meth) acrylic acid chloride or anhydride with the corresponding alkanols and the known reaction as transesterification of lower (meth) acrylic acid esters with the corresponding C₈ to C₁₈ alkanols with the addition of acidic or basic Catalysts and distillative removal of the lower alkanol. In these production processes, too, the ester should be worked up to such an extent that no acid is present.
Die Vinylether gemäß Formel II sind nach bekannten Verfahren durch Umsetzung von Alkanolen mit Acetaldehyd und anschließender Wasserabspaltung bzw. durch katalytische Addition von Acetylen an Alkanole erhältlich. Besonders reine Monomere können auch hier durch Destillation erhalten werden. Bei Vinylethern mit mehr als 20 bis 22 Kohlenstoffatomen im Alkylteil ist die unzersetzte Destillation technisch schwierig durchzuführen. In diesen Fällen ist eine Reinigung durch Filtration, Extraktion oder Umkristallisieren zur Entfernung der Katalysatoren empfehlenswert.The vinyl ethers of the formula II can be obtained by known processes by reacting alkanols with acetaldehyde and subsequent elimination of water or by catalytic addition of acetylene to alkanols. Particularly pure monomers can also be obtained here by distillation. With vinyl ethers with more than 20 to 22 carbon atoms in the alkyl part, the undecomposed distillation is technically difficult to carry out. In these cases, cleaning by filtration, extraction or recrystallization to remove the catalysts is recommended.
Die Herstellung der Copolymeren B erfolgt nach bekannten diskontinuierlichen oder kontinuierlichen Polymerisationsverfahren wie Masse-, Suspensions-, Fällungs- oder Lösungspolymerisation und Initiierung mit üblichen Radikalspendern wie Acetylcyclohexansulfonylperoxid, Diacetylperoxidicarbonat, Dicyclohexylproxidicarbonat, Di-2-ethylhexylperoxidicarbonat, tert.-Butylperneodecanoat, 2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitril), tert.-Butylperpivalat, tert.-Butylper-2-ethylhexanoat, tert.-Butylpermaleinat, 2,2'-Azobis(isobutyronitril), Bis-(tert.-butylperoxid)cyclohexan, tert.-Butylperoxiisopropylcarbonat, tert.-Butylperacetat, Dicumylperoxid, Di-tert.-amylperoxid, Di-tert.-butylperoxid, p-Menthanhydroperoxid, Cumolhydroperoxid oder tert.-Butylhydroperoxid und Mischungen untereinander. Im allgemeinen werden diese Initiatoren in Mengen von 0,1 bis 20 Gew.-%, vorzugsweise 0,2 bis 15 Gew.-% berechnet auf die Monomeren, eingesetzt.The copolymers B are prepared by known batch or continuous polymerization processes such as bulk, suspension, precipitation or solution polymerization and initiation with customary radical donors such as acetylcyclohexanesulfonyl peroxide, diacetyl peroxidicarbonate, dicyclohexylproxidicarbonate, di-2-ethylhexyl peroxidate carbonate, tert. -Azobis (4-methoxy-2,4-dimethylvaleronitrile), tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, tert-butyl permaleinate, 2,2'-azobis (isobutyronitrile), bis (tert-butyl peroxide ) cyclohexane, tert-butyl peroxyisopropyl carbonate, tert-butyl peracetate, dicumyl peroxide, di-tert-amyl peroxide, di-tert-butyl peroxide, p-menthane hydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide and mixtures with one another. In general, these initiators are used in amounts of 0.1 to 20% by weight, preferably 0.2 to 15% by weight, based on the monomers.
Die Polymerisation erfolgt in der Regel bei Temperaturen von 40 bis 400°C, vorzugsweise 70 bis 300°C, wobei die Verwendung von Lösungsmitteln mit Siedetemperaturen unterhalb der Polymerisationstemperatur zweckmäßig unter Druck gearbeitet wird. Die Polymerisation wird zweckmäßig unter Luftausschluß, d.h. wenn nicht unter Siedebedingungen gearbeitet werden kann, z.B. unter Stickstoff oder Kohlendioxid durchgeführt, da Sauerstoff die Polymerisation verzögert. Durch Mitverwendung von Redox-Coinititiatoren wie Benzoin, Dimethylanilin, Ascorbinsäure sowie organisch löslichen Komplexen von Schwermetallen wie Kupfer, Kobalt, Mangan, Eisen, Nickel und Chrom kann die Reaktion beschleunigt werden. Die üblicherweise eingesetzten Mengen liegen bei 0,1 bis 2000 Gew.-ppm, vorzugsweise 0,1 bis 1000 Gew.-ppm. Bei der Wahl des Initiators bzw. Initiatorsystems ist es zweckmäßig, bei der gewählten Polymerisationstemperatur darauf zu achten, daß die Halbwertszeit des Initiators oder Initiatorsystems weniger als 4 Stunden beträgt.The polymerization is generally carried out at temperatures of 40 to 400 ° C., preferably 70 to 300 ° C., the use of solvents with boiling temperatures below the polymerization temperature advantageously being carried out under pressure. The polymerization is expediently carried out in the absence of air, ie if it is not possible to work under boiling conditions, for example under nitrogen or carbon dioxide, since oxygen delays the polymerization. The reaction can be accelerated by using redox coinitiators such as benzoin, dimethylaniline, ascorbic acid and organically soluble complexes of heavy metals such as copper, cobalt, manganese, iron, nickel and chromium. The amounts usually used are 0.1 to 2000 ppm by weight, preferably 0.1 to 1000 ppm by weight. When choosing the initiator or initiator system, it is advisable to ensure at the chosen polymerization temperature that the half-life of the initiator or initiator system is less than 4 hours.
Zur Erzielung niedermolekularer Copolymerer ist es oftmals zweckmäßig, in Gegenwart von Reglern zu arbeiten. Geeignete Regler sind beispielsweise Allylalkohole, wie 1-Buten-3-ol, organische Mercaptoverbindungen wie 2-Mercaptoethanol, 2-Mercaptopropanol, Mercaptoessigsäure, Mercaptopropionsäure, tert.-Butylmercaptan, n-Butylmercaptan, n-Octylmercaptan, n-Dodecylmercaptan und tert.-Dodecylmercaptan, die im allgemeinen in Mengen von 0,1 bis 10 Gew.-% eingesetzt werden.To achieve low molecular weight copolymers it is often advisable to work in the presence of regulators. Suitable regulators are, for example, allyl alcohols, such as 1-buten-3-ol, organic mercapto compounds such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, tert-butyl mercaptan, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and tert.- Dodecyl mercaptan, which are generally used in amounts of 0.1 to 10 wt .-%.
Für die Polymerisation geeignete Apparaturen sind z.B. übliche Rührkessel mit beispielsweise Anker-, Blatt-, Impeller- oder Mehrstufenimpuls-Gegenstrom-Rührer und für die kontinuierliche Herstellung Rührkesselkaskaden, Rohrreaktoren und statische Mischer.Equipment suitable for the polymerization is e.g. Conventional stirred kettles with, for example, anchor, blade, impeller or multi-stage impulse countercurrent stirrers and for the continuous production of stirred kettle cascades, tubular reactors and static mixers.
Die einfachste Polymerisationsmethode ist die Massepolymerisation. Dabei werden die Monomeren in Gegenwart eines Initiators und in Abwesenheit von Lösungsmitteln polymerisiert. Zweckmäßigerweise mischt man alle Monomeren in der gewünschten Zusammensetzung und legt einen kleinen Teil, z.B. ca. 5 bis 10 %, im Reaktor vor, erhitzt unter Rühren auf die gewünschte Polymerisationstemperatur und dosiert die restliche Monomerenmischung und den Initiator und gegebenenfalls Coinitiator sowie Regler innerhalb von 1 bis 10 Stunden, vorzugsweise 2 bis 5 Stunden, gleichmäßig zu. Es ist dabei zweckmäßig, den Initiator sowie den Coinitiator getrennt in Form von Lösungen in einer kleinen Menge eines geeigneten Lösungsmittels zuzudosieren. Das Copolymere läßt sich dann direkt als erstarrte Schmelze oder nach Aufnahme in einem geeigneten Lösungsmittel dem Mitteldestillat zusammen mit dem Fließverbesserer zugeben.The simplest method of polymerization is bulk polymerization. The monomers are polymerized in the presence of an initiator and in the absence of solvents. Advantageously, all monomers are mixed in the desired composition and a small part, e.g. about 5 to 10%, in the reactor before, heated to the desired polymerization temperature with stirring and metered in the remaining monomer mixture and the initiator and optionally coinitiator and regulator evenly within 1 to 10 hours, preferably 2 to 5 hours. It is expedient to meter in the initiator and the coinitiator separately in the form of solutions in a small amount of a suitable solvent. The copolymer can then be added directly to the middle distillate as a solidified melt or after being taken up in a suitable solvent together with the flow improver.
Geeignet zur Herstellung der gewünschten Copolymeren ist auch ein kontinuierliches Hochdruckverfahren, das Raum-Zeit-Ausbeuten von 1 bis 50 kg Polymer pro Liter Reaktor und Stunde zuläßt. Als Polymerisationsapparatur kann z.B. ein Druckkessel, eine Druckkesselkaskade, ein Druckrohr oder auch ein Druckkessel mit einem nachgeschalteten Reaktionsrohr, das mit einem statischen Mischer versehen ist, verwendet werden. Vorzugsweise polymerisiert man die Monomeren aus (Meth)acrylsäureestern und Vinylethern in mindestens zwei hintereinander geschalteten Polymerisationszonen. Dabei kann die eine Reaktionszone aus einem druckdichten Kessel, die andere aus einem heizbaren statischen Mischer bestehen. Man erhält dabei Umsätze von mehr als 99 %. Ein Copolymer aus (Meth)acrylsäureestern und Vinylethern kann beispielsweise dadurch hergestellt werden, daß man die Monomeren und einen geeigneten Initiator einem Reaktor oder zwei hintereinander geschalteten Reaktionszonen, beispielsweise eine Reaktorkaskade, kontinuierlich zuführt und das Reaktionsprodukt nach einer Verweilzeit von 2 bis 60, vorzugsweise von 5 bis 30 Minuten, bei Tempeaturen zwischen 200 und 400°C kontinuierlich aus der Reaktionszone ausschleust. Die Polymerisation wird zweckmäßig bei Drücken von mehr als 1 bar, vorzugsweise zwischen 1 und 200 bar durchgeführt. Die erhaltenen Copolymeren weisen Feststoffgehalte von über 99 % auf und können ohne weitere Behandlung dem Mitteldestillat zugeführt werden.A continuous high-pressure process which permits space-time yields of 1 to 50 kg of polymer per liter of reactor and hour is also suitable for producing the desired copolymers. For example, a pressure vessel, a pressure vessel cascade, a pressure tube or a pressure vessel with a downstream reaction tube, which is provided with a static mixer, can be used as the polymerization apparatus. The monomers of (meth) acrylic acid esters and vinyl ethers are preferably polymerized in at least two polymerization zones connected in series. One reaction zone can consist of a pressure-tight vessel, the other of a heatable static mixer. You get sales of more than 99%. A copolymer of (meth) acrylic acid esters and vinyl ethers can be prepared, for example, by continuously feeding the monomers and a suitable initiator to a reactor or two reaction zones connected in series, for example a reactor cascade, and the reaction product after a residence time of 2 to 60, preferably of 5 to 30 minutes, at temperatures between 200 and 400 ° C continuously discharged from the reaction zone. The polymerization is expediently carried out at pressures of more than 1 bar, preferably between 1 and 200 bar. The copolymers obtained have solids contents of over 99% and can be added to the middle distillate without further treatment.
Eine weitere einfache Methode zur Herstellung der Copolymeren B ist die Lösungspolymerisation. Sie wird durchgeführt in Lösungsmitteln, in denen die Monomeren und die gebildeten Copolymeren löslich sind. Es sind hierfür alle Lösunsmittel geeignet, die diese Vogabe erfüllen und die mit den Monomeren keine Reaktion eingehen. Beispielsweise sind dies Toluol, Xylol, Ethylbenzol, Cumol, hochsiedende Aromatengemische wie z.B. Solvesso® 100, 150 und 200, aliphatische und cycloaliphatische Kohlenwasserstoffe wie z.B. n-Hexan, Cyclohexan, Methylcyclohexan, n-Octan, iso-Octan, Paraffinöle, Shellsol® TD, T und K sowie Tetrahydrofuran und Dioxan, wobei zur Erzielung niedermolekularer Copolymerer Tetrahydrofuran und Dioxan besonders gut geeignet sind. Bei der Durchführung der Lösungspolymerisation ist es zweckmäßig, Lösungsmittel und einen Teil der Monomerenmischung (z.B. ca. 5 bis 20 %) vorzulegen und den Rest der Monomerenmischung mit dem Initiator und gegebenenfalls Coinitiator, Regler und Lösungsmittel zuzudosieren. Die Monomeren können auch einzeln, mit unterschiedlicher Geschwindigkeit, zudosiert werden. Dies empfiehlt sich bei Monomeren mit stark unterschiedlicher Reaktivität, wie dies bei (Meth)acrylaten und Vinylethern der Fall ist und wenn eine besonders gleichmäßige Verteilung des weniger reaktiven Vinylethers gewünscht wird. Dabei wird das weniger reaktive Monomer schneller und das reaktivere Monomer langsamer zudosiert. Es ist auch möglich die gesamte Menge eines Monomeren, vorzugsweise des weniger reaktiven Vinylethers, vorzulegen und nur das (Meth)acrylat zuzudosieren. Schließlich ist es auch möglich die gesamten Monomeren und das Lösungsmittel vorzulegen und nur den Initiator und gegebenenfalls Coinitiator und Regler zuzudosieren ("Batch"-Fahrweise). Bei der Durchführung dieser Fahrweise in größerem Maßstab können jedoch Probleme mit der Wärmeabführung auftreten, so daß diese Fahrweise nur bei geringen Konzentrationen der zu polymerisierenden Monomeren angewendet werden. sollte. Die Konzentrationen der zu polymerisierenden Monomeren liegen zwischen 20 und 80 Gew.-%, bevorzugt 30 und 70 Gew.-%. Das feste Copolymer kann problemlos durch Verdampfen des Lösungsmittels gewonnen werden. Es ist jedoch zweckmäßig, ein Lösungsmittel zur Polymerisation zu wählen, welches mit dem Mitteldestillat verträglich ist, so daß die Polymerisatlösung dem Mitteldestillat direkt zugesetzt werden kann. Die Lösungspolymerisation ist die bevorzugte Herstellungsform für die Copolymeren aus (Meth)acrylaten und Vinylethern.Another simple method for producing the copolymers B is solution polymerization. It is carried out in solvents in which the monomers and the copolymers formed are soluble. All solvents which fulfill this requirement and which do not react with the monomers are suitable for this. For example, these are toluene, xylene, ethylbenzene, cumene, high-boiling aromatic mixtures such as Solvesso® 100, 150 and 200, aliphatic and cycloaliphatic hydrocarbons such as n-hexane, cyclohexane, methylcyclohexane, n-octane, iso-octane, paraffin oils, Shellsol® TD , T and K, as well as tetrahydrofuran and dioxane, tetrahydrofuran and dioxane being particularly suitable for achieving low molecular weight copolymers. When carrying out the solution polymerization, it is expedient to initially introduce solvent and part of the monomer mixture (for example about 5 to 20%) and to meter in the rest of the monomer mixture with the initiator and, if appropriate, coinitiator, regulator and solvent. The monomers can also be metered in individually at different rates. This is advisable for monomers with very different reactivities, as is the case with (meth) acrylates and vinyl ethers and when a particularly uniform distribution of the less reactive vinyl ether is desired. The less reactive monomer is metered in faster and the more reactive monomer more slowly. It is also possible to introduce the entire amount of a monomer, preferably the less reactive vinyl ether, and to meter in only the (meth) acrylate. Finally, it is also possible to initially charge all of the monomers and the solvent and to meter in only the initiator and, if appropriate, coinitiator and regulator ("batch" procedure). When carrying out this procedure on a larger scale, problems with heat dissipation can occur, so that this procedure is only used at low concentrations of the monomers to be polymerized. should. The concentrations of the monomers to be polymerized are between 20 and 80% by weight, preferably 30 and 70% by weight. The solid copolymer can easily be obtained by evaporating the solvent. However, it is expedient to choose a solvent for the polymerization which is compatible with the middle distillate, so that the polymer solution can be added directly to the middle distillate. Solution polymerization is the preferred form of preparation for the copolymers of (meth) acrylates and vinyl ethers.
In der Technik besteht die Notwendigkeit, die erfindungsgemäßen Additive, bestehend aus einem Fließverbesserer A und einem Copolymeren B, in leicht handhabbarer Form bereitzustellen. Dazu sollten die Polymeren A und B zusammen in Form eines Konzentrats vorliegen, da die Verwendung von 2 Konzentraten - je eins für Polymer A und Polymer B - die Handhabung erschwert. Aufgrund der möglichen Unverträglichkeit der Polymeren A und B, kann es bei der reinen Abmischung der beiden Polymeren in einem gemeinsamen Lösungsmittel zur Phasenseparation kommen. Diese kann gegebenenfalls durch geeignete Lösungsmittel und/oder Zusatzstoffe unterdrückt werden. Geeignet sind z.B. Alkanole wie iso-Butanol, n-Hexanol, 2-Ethylhexanol, iso-Decanol und deren Addukte mit Ethylenoxid, Propylenoxid und/oder Butylenoxid, Alkylphenole und deren Addukte mit Ethylenoxid, Propylenoxid und/oder Butylenoxid sowie Halbester oder Dieester von Dicarbonsäuren mit Alkanolen oder (Oligo)alkylenoxidhalbethern wie Mono- oder Dibutylphthalat, Mono- oder Di-2-ethylhexylphthalat oder Di-(2-methoxyethyl)phthalat.There is a need in industry to provide the additives according to the invention, consisting of a flow improver A and a copolymer B, in an easily manageable form. For this purpose, polymers A and B should be present together in the form of a concentrate, since the use of 2 concentrates - one each for polymer A and polymer B - makes handling more difficult. Due to the possible incompatibility of polymers A and B, phase separation can occur when the two polymers are mixed in a common solvent. This can optionally be suppressed by suitable solvents and / or additives. Suitable are e.g. Alkanols such as iso-butanol, n-hexanol, 2-ethylhexanol, iso-decanol and their adducts with ethylene oxide, propylene oxide and / or butylene oxide, alkylphenols and their adducts with ethylene oxide, propylene oxide and / or butylene oxide as well as half esters or diesters of dicarboxylic acids with alkanols or (Oligo) alkylene oxide half ethers such as mono- or dibutyl phthalate, mono- or di-2-ethylhexyl phthalate or di- (2-methoxyethyl) phthalate.
Eine weitere Methode, eine eventuelle Phasenseparation zu vermeiden, besteht darin, das Copolymer B zumindest zum Teil auf den Fließverbesserer zu pfropfen. Zur Pfropfung wird vorzugsweise die Masse- oder Lösungspolymerisation verwendet. Die Polymerisation kann nach der "Batch"- oder Zulauffahrweise erfolgen. Bei der "Batch"-Fahrweise wird die gesamte Menge an Fließverbesserer A, auf die gepfropft werden soll, zusammen mit den Monomeren vorgelegt und Initiator sowie gegebenenfalls Coinitiator und Regler zudosiert. Bei der Zulauffahrweise wird die gesamte Menge an Fließverbesserer A, auf die gepfropft werden soll, gegebenenfalls zusammen mit einem Teil der Monomeren vorgelegt und der Rest der Monomeren, Initiator sowie gegebenenfalls Coinitiator und Regler zudosiert.Another method of avoiding possible phase separation is to graft copolymer B at least in part onto the flow improver. Bulk or solution polymerization is preferably used for the grafting. The polymerization can be carried out according to the "batch" or feed procedure. In the "batch" procedure, the total amount of flow improver A to be grafted is initially introduced together with the monomers and initiator and, if appropriate, coinitiator and regulator are metered in. In the feed procedure, the total amount of flow improver A to be grafted is optionally introduced together with some of the monomers and the rest of the monomers, initiator and, if appropriate, coinitiator and regulator are metered in.
Wie bereits erwähnt, ist es nicht nötig das Copolymer B auf den gesamten Anteil des Fließverbesserers A zu pfropfen. Beispielsweise wird man bei einem Verhältnis A:B von 90:10 aus Gründen der Raum-Zeit-Ausbeute das Copolymer B nur auf einen Anteil von 2 bis 20 Gew.-% der Gesamtmenge von A pfropfen. Bei einem Verhälntis von A:B von 40:60 jedoch auf einen Anteil von 30 bis 100 Gew.-% der Gesamtmenge von A.As already mentioned, it is not necessary to graft the copolymer B onto the entire proportion of the flow improver A. For example, at a ratio A: B of 90:10, for reasons of space-time yield, the copolymer B will only be grafted to a proportion of 2 to 20% by weight of the total amount of A. With a ratio of A: B of 40:60, however, to a proportion of 30 to 100% by weight of the total amount of A.
Auch ist es nicht nötig, das Copolymer B vollständig auf einen Teil des Fließverbesserers A zu pfropfen. Dies ist ohnehin schwierig, da die Pfropfausbeute im allgemeinen 100 % nicht erreicht, so daß in den beschriebenen Konzentraten neben Pfropfcopolymerisaten und unumgesetztem oder zugemischtem Fließverbesserer A auch nicht gepfropftes Copolymer B vorliegen kann.It is also not necessary to graft the copolymer B completely onto part of the flow improver A. This is difficult anyway, since the grafting yield generally does not reach 100%, so that in addition to graft copolymers and unconverted or admixed flow improver A, copolymer B may also be present in the concentrates described.
Die K-Werte (nach H. Fikentscher, Cellulosechemie, Band 13, Seiten 58 bis 64 und 71 bis 74 (1932)), bestimmt in 2 %iger (Gew./Vol.) xylolischer Lösung der Copolymerisate B liegen zwischen 10 und 50, vorzugsweise zwischen 10 und 40 und besonders bevorzugt zwischen 13 und 30. Der besonders bevorzugte Bereich entspricht Molekulargewichten zwischen ca. 5000 und 25.000 g/mol (Zahlenmittelwerte, bestimmt durch Gelpermeationschromatographie gegen Polystyrol-Standards).The K values (according to H. Fikentscher, Cellulosechemie, Volume 13, pages 58 to 64 and 71 to 74 (1932)), determined in a 2% (w / v) xylene solution of the copolymers B, are between 10 and 50 , preferably between 10 and 40 and particularly preferably between 13 and 30. The particularly preferred range corresponds to molecular weights between approximately 5000 and 25,000 g / mol (number average values, determined by gel permeation chromatography against polystyrene standards).
Die erfindungsgemäßen Additive A und B werden den Erdölmitteldestillaten zusammen in Mengen von 50 bis 5000 ppm, bevorzugt 100 bis 2000 ppm, zugesetzt.The additives A and B according to the invention are added to the petroleum middle distillates together in amounts of 50 to 5000 ppm, preferably 100 to 2000 ppm.
Die erfindungsgemäßen Mitteldestillate, enthaltend geringe Mengen eines Fließverbesserers A und eines Copolymeren B, können, je nach Verwendungszweck, noch andere Additive oder Zusatzstoffe wie Dispergatoren, Anti-Schaum-Additive, Korrosionsschutzmittel, Antioxidantien, Farbstoffe u.a. enthalten.The middle distillates according to the invention, containing small amounts of a flow improver A and a copolymer B, can, depending on the intended use, other additives or additives such as dispersants, anti-foam additives, corrosion inhibitors, antioxidants, dyes and others. contain.
Die Erfindung wird durch die folgenden Beispiele erläutert:The invention is illustrated by the following examples:
In einem Reaktor, der versehen war mit Rührer, Heizung und Zulaufvorrichtung wurden 144 g Laurylacrylat, 16 g n-Octadecylvinylether, 0,16 g 2-Mercaptoethanol, 65 mg Triethylamin und 69 g Toluol im schwachen Stickstoffstrom unter Rühren auf 100°C erhitzt und innerhalb von 4 Stunden eine Lösung von 0,64 g tert.-Butylper-2-ethylhexanoat in 38,2 g Toluol gleichmäßig zudosiert. Anschließend wurde noch eine Stunde bei 100°C nacherhitzt und mit ca. 54 g Toluol verdünnt. Man erhielt eine klare, gelbliche ca. 50 gew.-%ige Lösung. Der K-Wert des Polymeren betrug 24,8.In a reactor which was provided with a stirrer, heating and feed device, 144 g of lauryl acrylate, 16 g of n-octadecyl vinyl ether, 0.16 g of 2-mercaptoethanol, 65 mg of triethylamine and 69 g of toluene were heated to 100 ° C. in a gentle stream of nitrogen with stirring and A solution of 0.64 g of tert-butyl per-2-ethylhexanoate in 38.2 g of toluene was metered in uniformly within 4 hours. The mixture was then heated at 100 ° C for one hour and diluted with about 54 g of toluene. A clear, yellowish, approximately 50% by weight solution was obtained. The K value of the polymer was 24.8.
In einem Reaktor gemäß Beispiel 1 wurden 144 g Laurylacrylat, 16 g n-Octadecylvinylether und 68,6 g Solvesso® 150 (hochsiedendes Aromatengemisch der Fa. Esso) im schwachen Stickstoffstrom unter Rühren auf 80°C erhitzt und innerhalb von 4 Stunden eine Lösung von 0,48 g Azoisobutyronnitril in 30 g Solvesso® 150 gleichmäßig zudosiert. Anschließend wurde eine Lösung von 0,16 g Azoisobutyronitril in 8,5 g Solvesso® 150 zugegeben, zwei Stunden bei 80°C nacherhitzt und mit 53,5 g Solvesso® 150 verdünnt. Es wurde eine klare, farblose, viskose, ca. 50 gew.-%ige Polymerlösung erhalten. Der K-Wert des Polymeren betrug 28,3.In a reactor according to Example 1, 144 g of lauryl acrylate, 16 g of n-octadecyl vinyl ether and 68.6 g of Solvesso® 150 (high-boiling aromatic mixture from Esso) were heated to 80 ° C. in a slow stream of nitrogen with stirring and a solution of Evenly add 0.48 g azoisobutyronitrile in 30 g Solvesso® 150. A solution of 0.16 g of azoisobutyronitrile in 8.5 g of Solvesso® 150 was then added, the mixture was reheated at 80 ° C. for two hours and diluted with 53.5 g of Solvesso® 150. A clear, colorless, viscous, approximately 50% by weight polymer solution was obtained. The K value of the polymer was 28.3.
In einem Reaktor gemäß Beispiel 1 wurden 29,2 g Laurylacrylat, 7,3 g n-Octadecylvinylether und 55,4 g Shellsol® K (hochsiedendes n- und iso-Paraffingemisch der Fa. Shell) im schwachen Stickstoffstrom unter Rühren auf 100°C erhitzt und innerhalb von 2 Stunden eine Lösung von 102,1 g Laurylacrylat, 26,0 g n-Vinyloctadecylether und 14,6 g Shellsol® K sowie innerhalb von 4 Stunden eine Lösung von 0,5 g tert.-Butylper-2-ethylhexanoat in 25 g Shellsol® K gleichmäßig zudosiert. Anschließend wurde eine Lösung von 0,17 g tert.-Butylper-2-ethylhexanoat in 4,2 g Shellsol® K zugegeben, eine Stunde bei 100°C nacherhitzt und mit 67,5 g Shellsol® K verdünnt. Es wurde eine klare, farblose, schwach viskose Polymerlösung erhalten. Der K-Wert des Polymeren betrug 19,6.In a reactor according to Example 1, 29.2 g of lauryl acrylate, 7.3 g of n-octadecyl vinyl ether and 55.4 g of Shellsol® K (high-boiling n- and iso-paraffin mixture from Shell) were stirred at 100 ° C. in a slow stream of nitrogen heated and within 2 hours a solution of 102.1 g lauryl acrylate, 26.0 g n-vinyl octadecyl ether and 14.6 g Shellsol® K and within 4 hours a solution of 0.5 g tert-butyl per-2-ethylhexanoate evenly dosed in 25 g Shellsol® K. A solution of 0.17 g of tert-butyl per-2-ethylhexanoate in 4.2 g of Shellsol® K was then added, the mixture was reheated at 100 ° C. for one hour and diluted with 67.5 g of Shellsol® K. A clear, colorless, slightly viscous polymer solution was obtained. The K value of the polymer was 19.6.
Nach analogem Verfahren wie in Beispiel 3 wurden die Beispiele 4 bis 18 hergestellt.
In einem Reaktor gemäß Beispiel 1 wurden 51,4 g (ca. 0,1 Mol) Di-n-Tetradecylfumarat und 10,0 g (0,1 Mol) n-Butylvinylether mit schwachen Stickstoffstrom und Rühren auf 90°C erhitzt. Dann wurden 0,4 g AIBN zugegeben und 6 Stunden polymerisiert, wobei jede Stunde weitere 0,1 g AIBN zugesetzt wurden. Es wurde eine viskose, 99 gew.-%ige Polymerlösung vom K-Wert 11,5 erhalten.In a reactor according to Example 1, 51.4 g (approx. 0.1 mol) of di-n-tetradecyl fumarate and 10.0 g (0.1 mol) of n-butyl vinyl ether were heated to 90 ° C. with a gentle stream of nitrogen and stirring. Then 0.4 g of AIBN was added and polymerized for 6 hours, with an additional 0.1 g of AIBN being added every hour. A viscous, 99% by weight polymer solution with a K value of 11.5 was obtained.
In einem Reaktor gemäß Beispiel 1 wurden 1,5 g Bortrifluorid-etherat in 187,5 g Toluol vorgelegt und bei 30°C eine Lösung von 90 g n-Octadecylvinylether in 22,5 g Toluol gleichmäßig innerhalb einer Stunde zudosiert, weitere 10 Minuten gerührt und die Polymerisation durch Zugabe von 5 ml Methanol beendet. Die Polymerlösung wurde in Aceton gefällt und im Vakuum getrocknet. Der K-Wert betrug 15,4.1.5 g of boron trifluoride etherate in 187.5 g of toluene were placed in a reactor according to Example 1, and a solution of 90 g of n-octadecyl vinyl ether in 22.5 g of toluene was metered in uniformly at 30 ° C. over the course of one hour and the mixture was stirred for a further 10 minutes and the polymerization was terminated by adding 5 ml of methanol. The polymer solution was precipitated in acetone and dried in vacuo. The K value was 15.4.
Die Beispiele 17 bis 20 sind Vergleichsbeispiele und nicht Bestandteil der vorliegenden Erfindung.Examples 17 to 20 are comparative examples and do not form part of the present invention.
Pfropfung von Laurylacrylat und n-Octadecylvinylether auf einen Fließverbesserer, bestehend aus 60 Gew.-% Ethylen und 40 Gew.-% Vinylpropionat mit einem mittleren Molekulargewicht von ca. 2500 (bestimmt durch Dampfdruckosmometrie) = FI(A).Grafting of lauryl acrylate and n-octadecyl vinyl ether onto a flow improver, consisting of 60% by weight of ethylene and 40% by weight of vinyl propionate with an average molecular weight of approx. 2500 (determined by vapor pressure osmometry) = FI (A).
In einem Reaktor gemäß Beispiel 1 wurden 215 g des Fließverbesserers FI(A) und 86 g Shellsol® K im schwachen Stickstoffstrom und Rühren auf 100°C erhitzt. Dazu wurden 86 g einer Mischung aus 516 g Laurylacrylat, 129 g n-Octadecylvinyleher und 73,1 g Shellsol® K gegeben und der Rest der Mischung in 2 Stunden gleichmäßig zudosiert. Gleichzeitig wurden 1,94 g tert.Butylper-2-ethylhexanoat, gelöst in 64,5 g Shellsol® K innerhalb von 4 Stunden gleichmäßig zudosiert. Anschließend wurde eine Lösung von 0,65 g tert.-Butylper-2-ethylhexanoat in 21,5 g Shellsol® K zugegeben, eine Stunde nachgeheizt und mit 615 g Solvesso® 150 (hochsiedendes Aromatengemisch der Fa. Esso) verdünnt. Es wurde eine ca. 50 gew.-%ige schwach trübe Polymerlösung vom K-Wert 25,2 erhalten. Davon wurden 80 g mit 110 g FI(A) und 110 g Solvesso® 150 bei 60°C gemischt. Es wurde eine bei Raumtemperatur trübe Mischung erhalten, die aus insgesamt ca. 80 Teilen Fließverbesserer FI(A) und 20 Teilen Copolymer B besteht. Die Mischung ist mehr als 10 Wochen bei Raumtemperatur stabil.In a reactor according to Example 1, 215 g of the flow improver FI (A) and 86 g of Shellsol® K were heated to 100 ° C. in a gentle stream of nitrogen and with stirring. 86 g of a mixture of 516 g of lauryl acrylate, 129 g of n-octadecylvinylyl ether and 73.1 g of Shellsol® K were added and the rest of the mixture was metered in uniformly in 2 hours. At the same time, 1.94 g of tert-butyl per-2-ethylhexanoate, dissolved in 64.5 g of Shellsol® K, were metered in uniformly over the course of 4 hours. A solution of 0.65 g of tert-butyl per-2-ethylhexanoate in 21.5 g of Shellsol® K was then added, the mixture was heated for one hour and diluted with 615 g of Solvesso® 150 (high-boiling aromatic mixture from Esso). An approximately 50% by weight slightly cloudy polymer solution with a K value of 25.2 was obtained. 80 g of these were mixed with 110 g FI (A) and 110 g Solvesso® 150 at 60 ° C. A mixture which was cloudy at room temperature and was composed of a total of about 80 parts of flow improver FI (A) and 20 parts of copolymer B was obtained. The mixture is stable for more than 10 weeks at room temperature.
Im folgenden bedeuten:
FI = Fließverbesserer, im besonderen
- FI(A)
- Ethylen/Vinylpropionat (mit ca. 40 Gew.-% Vinylpropionat) mit einem mittleren Molekulargewicht von ca. 2500 (bestimmt durch Dampfdruckosmometrie)
- FI(B)
- Ethylen/Vinylpropionat (mit ca. 30 Gew.-% Vinylpropionat mit einem mittleren Molekulargewicht von ca. 2500
- FI(C)
- Ethylen/Vinylacetat (mit ca 30 Gew.-% Vinylacetal) mit einem mittleren Molekulargewicht von ca. 2500.
FI = flow improver, in particular
- FI (A)
- Ethylene / vinyl propionate (with approx. 40% by weight vinyl propionate) with an average molecular weight of approx. 2500 (determined by vapor pressure osmometry)
- FI (B)
- Ethylene / vinyl propionate (with approx. 30% by weight vinyl propionate with an average molecular weight of approx. 2500
- FI (C)
- Ethylene / vinyl acetate (with approx. 30% by weight vinyl acetal) with an average molecular weight of approx. 2500.
Bei den Fließverbesserern FI(A), FI(B) und FI(C) handelt es sich um handelsübliche Produkte, z.B. die Keroflux® Marken der Fa. BASF.The flow improvers FI (A), FI (B) and FI (C) are commercially available products, e.g. the Keroflux® brands from BASF.
Als Mitteldestillate wurden Heizöle und Dieselkraftstoffe in handelsüblicher westdeutscher Raffineriequalität verwendet. Sie sind als Mitteldestillat I, II, III und IV bezeichnet.
Geprüft wurde der "Cold Filter Plugging Point" (CFPP) nach DIN 51428. Die Ergebnisse sind in der folgenden Tabelle zusammengefaßt.
Wie die obigen Beispiele zeigen, wirken die herkömmlichen Fließverbesserer FI(A), FI(B) und FI(C) in den Mitteldestillaten nur ungenügend. Alleiniger Zusatz der erfindungsgemäßen Copolymere verschlechtert den CFPP der Mitteldestillate eher noch. Die synergistische Wirkung von Fließverbesserer und erfindungsgemäßen Copolymeren wird durch die Beispiele 7 bis 40 verdeutlicht.As the above examples show, the conventional flow improvers FI (A), FI (B) and FI (C) only work insufficiently in the middle distillates. The sole addition of the copolymers according to the invention rather worsens the CFPP of the middle distillates. The synergistic effect of flow improvers and copolymers according to the invention is illustrated by Examples 7 to 40.
Wie die Vergleichsbeispiele zeigen, bewirkt weder das Polyacrylat (Beispiel 42) noch der Polyvinylether (Beispiel 45) zusammen mit den herkömmlichen Fließverbesserern eine befriedigende CFPP-Erniedrigung Auch die in EP-A-360 419 beschriebenen Copolymere mit kurzkettigen Vinylethern (Beispiele 43 und 44) erweisen sich in obigen Ölen als unwirksam, während die erfindungsgemäßen Copolymerisate aus Alkylacrylaten, langkettigen Vinylethern und gegebenenfalls einem weiteren Monomeren in Kombination mit FI(A), FI(B) oder FI(C) bei geringer Dosierung den CFPP deutlich absenken.As the comparative examples show, neither the polyacrylate (example 42) nor the polyvinyl ether (example 45) together with the conventional flow improvers brings about a satisfactory reduction in CFPP. The copolymers described in EP-A-360 419 with short-chain vinyl ethers (examples 43 and 44) have been found to be ineffective in the above oils, while the copolymers of alkyl acrylates, long-chain vinyl ethers and, if appropriate, a further monomer in combination with FI (A), FI (B) or FI (C) according to the invention significantly reduce the CFPP at low dosage.
Claims (7)
- A mineral oil middle distillate having improved cold flow properties, containing small amounts ofA) conventional ethylene-based flow improvers andB) copolymers which contain at least 70% by weight of one or more monomers of both the formula I and the formula IIwhere R¹ is hydrogen or methyl, R² is C₈-C₁₈-alkyl and R³ is C₁₈-C₂₈-alkyl and the weight ratio of A to B is from 40:60 to 95:5.
- A mineral oil middle distillate as claimed in claim 1, wherein the ratio of the monomers of the formula I to monomers of the formula II in the copolymers B is from 10:90 to 95:5.
- A mineral oil middle distillate as claimed in claim 1, wherein the alkyl substituents in the copolymers B are straight-chain and not branched.
- A mineral oil middle distillate as claimed in claim 1, wherein the copolymers may contain up to 30% by weight of other ethylenically unsaturated monomers.
- A mineral oil middle distillate as claimed in claim 1, wherein the conventional flow improvers used are copolymers of ethylene with vinyl acetate, vinyl propionate or ethylhexyl acrylate.
- A mineral oil middle distillate as claimed in claim 1, wherein from 0 to 100% of the copolymers are grafted onto the conventional flow improvers.
- A mineral oil middle distillate as claimed in claim 1, which contains the flow improvers A and the copolymers B together in amounts of from 50 to 5000 ppm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4036227A DE4036227A1 (en) | 1990-11-14 | 1990-11-14 | PETROLEUM DISTILLATES WITH IMPROVED FLOW PROPERTIES IN THE COLD |
| DE4036227 | 1990-11-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0486836A1 EP0486836A1 (en) | 1992-05-27 |
| EP0486836B1 true EP0486836B1 (en) | 1995-02-15 |
Family
ID=6418231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91118118A Expired - Lifetime EP0486836B1 (en) | 1990-11-14 | 1991-10-24 | Petroleum middle distillate with improved cold flow characteristics |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0486836B1 (en) |
| AT (1) | ATE118529T1 (en) |
| CA (1) | CA2055418A1 (en) |
| DE (2) | DE4036227A1 (en) |
| ES (1) | ES2068464T3 (en) |
| FI (1) | FI105824B (en) |
| NO (1) | NO304077B1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2710652B1 (en) * | 1993-09-30 | 1995-12-01 | Elf Antar France | Composition of cold operability additives for middle distillates. |
| WO2005040315A1 (en) * | 2003-10-22 | 2005-05-06 | Leuna Polymer Gmbh | Additive mixture as component of a mineral oil composition |
| ATE547472T1 (en) | 2009-09-25 | 2012-03-15 | Evonik Rohmax Additives Gmbh | COMPOSITION FOR IMPROVING THE COLD FLOW PROPERTIES OF FUEL OILS |
| WO2014095408A1 (en) | 2012-12-18 | 2014-06-26 | Basf Se | Polymer formulations in solvents with a high flash point, method for the production thereof and use thereof as pour-point depressants for crude oils, mineral oils or mineral oil products |
| CN104837872B (en) | 2012-12-18 | 2017-08-08 | 巴斯夫欧洲公司 | The purposes of the polymer composition that ethylene vinyl ester copolymers and (methyl) alkyl acrylate are constituted, its preparation method and its pour-point depressant as crude oil, mineral oil or mineral oil product |
| US9574146B2 (en) | 2012-12-18 | 2017-02-21 | Basf Se | Polymeric compositions composed of ethylene-vinyl ester copolymers alkyl (meth)acrylates, processes for production thereof and use thereof as pour point depressants for crude oils, mineral oils or mineral oil products |
| AR100387A1 (en) | 2014-02-18 | 2016-10-05 | Basf Se | COPOLYMERS UNDERSTANDING ETHYLENE, VINYL ESTERS AND ACRYLIC ACID (MET) ESTERS, THEIR FORMULATIONS AND USES AS A FLUIDITY POINT DEPRESSOR, WAX INHIBITOR AND FLOW OIL POTENTIATOR |
| MX2017004771A (en) | 2014-10-13 | 2017-10-12 | Avery Dennison Corp | Vinyl acetate-ethylene / acrylic polymer emulsions and products and methods relating thereto. |
| DE102015226635A1 (en) | 2015-12-23 | 2017-06-29 | Clariant International Ltd | Polymer compositions with improved handleability |
| US20210017341A1 (en) | 2018-03-26 | 2021-01-21 | Basf Se | Hyperbranched polyethers and their use, especially as pour point depressant and wax inhibitors |
| EP3798261A1 (en) | 2019-09-26 | 2021-03-31 | Clariant International Ltd | Polymer compositions and their use as pour point depressant in paraffin-containing hydrocarbon oils |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL148099B (en) * | 1966-03-17 | 1975-12-15 | Shell Int Research | PROCEDURE FOR REDUCING THE FLOOD POINT OF A FUEL MIXTURE. |
| NL6709453A (en) * | 1967-07-07 | 1969-01-09 | ||
| US3961915A (en) * | 1974-12-27 | 1976-06-08 | Exxon Research And Engineering Company | Synergistic additive in petroleum middle distillate fuel |
| FR2572410B1 (en) * | 1984-10-25 | 1987-09-04 | Elf Aquitaine | ETHYLENE GRAFT COPOLYMERS USED IN PARTICULAR AS ADDITIVES FOR THE INHIBITION OF PARAFFIN DEPOSITION IN CRUDE OILS AND COMPOSITIONS CONTAINING THE OILS AND ADDITIVES |
| FR2592658B1 (en) * | 1986-01-09 | 1988-11-04 | Inst Francais Du Petrole | ADDITIVE COMPOSITIONS IN PARTICULAR FOR IMPROVING THE COLD FILTRABILITY PROPERTIES OF MEDIUM OIL DISTILLATES. |
| GB8820071D0 (en) * | 1988-08-24 | 1988-09-28 | Exxon Chemical Patents Inc | Fuel compositions |
| DE3905681A1 (en) * | 1989-02-24 | 1990-08-30 | Basf Ag | CONCENTRATED MIXTURES OF GAPPOPOLYMERISATS FROM ESTERS OF UNSATURATED ACIDS AND ETHYLENE-VINYLESTER COPOLYMERISATS |
-
1990
- 1990-11-14 DE DE4036227A patent/DE4036227A1/en not_active Withdrawn
-
1991
- 1991-10-24 EP EP91118118A patent/EP0486836B1/en not_active Expired - Lifetime
- 1991-10-24 AT AT91118118T patent/ATE118529T1/en not_active IP Right Cessation
- 1991-10-24 DE DE59104601T patent/DE59104601D1/en not_active Expired - Lifetime
- 1991-10-24 ES ES91118118T patent/ES2068464T3/en not_active Expired - Lifetime
- 1991-10-30 FI FI915126A patent/FI105824B/en active
- 1991-11-13 CA CA002055418A patent/CA2055418A1/en not_active Abandoned
- 1991-11-13 NO NO914443A patent/NO304077B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ES2068464T3 (en) | 1995-04-16 |
| DE59104601D1 (en) | 1995-03-23 |
| FI915126A0 (en) | 1991-10-30 |
| EP0486836A1 (en) | 1992-05-27 |
| NO914443D0 (en) | 1991-11-13 |
| ATE118529T1 (en) | 1995-03-15 |
| FI105824B (en) | 2000-10-13 |
| NO304077B1 (en) | 1998-10-19 |
| NO914443L (en) | 1992-05-15 |
| DE4036227A1 (en) | 1992-05-21 |
| FI915126A (en) | 1992-05-15 |
| CA2055418A1 (en) | 1992-05-15 |
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