Classifications

• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
  • C10L1/2462—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds
  • C10L1/2468—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds obtained by reactions involving only carbon to carbon unsaturated bonds; derivatives thereof
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  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
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  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
  • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
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  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/165—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aromatic monomers
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/1658—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing conjugated dienes
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/1666—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing non-conjugated dienes
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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
  • C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds 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 an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

• the present invention relates to additives for liquid hydrocarbon compositions, for example gas oils, generally known as middle distillates.
• middle distillates contain alkanes which at low temperatures tend to precipitate under the form of waxes. In this way gelled structures are formed which cause the middle distillate fluidity loss. Therefore there are problems of middle distillate storage, transfer and feeding through pipes, pumps and besides plugging phenomena of the line filters and of those of the propulsor feeding ducts take place.
• middle distillates are characterized from the physical point of view by the following features determined with various standardized methods: Cloud Point (C.P.), Pour Point (P.P.), Cold Filter Plugging Point (C.F.P.P.), Wax Antisettling (W.A.S.), etc.
• Cloud Point C.P.
• Pour Point P.P.
• Cold Filter Plugging Point C.F.P.P.
• Wax Antisettling W.A.S.
• additives also commercial, are known in the art, having selective and/or multifunctional uses able to improve the above mentioned middle distillate cold features.
• the additives have the purpose to modify the wax crystals formed at low temperatures both reducing the size and modifying the shape thereof . Indeed the crystals having reduced sizes give less problems of filter plugging.
• Another property required to the additives is that to maintain in suspension the formed crystals, i.e. to obtain the result to have a reduced settling rate. Also this effect concurs to the non filters plugging at low temperatures and specifically to reduce wax accumulation on the storage tanks bottom of middle distillates.
• the additives known in the art to overcome said drawbacks are generally polymeric products of various kinds.
• the obtained ethylene/alpha-olefin co- polymers have the essential characteristic to have at least 30% of the polymeric chains with ethenylidene or ethylene terminal unsaturations .
• These copolyemrs can be be combined with one or more additives known in the art having the feature to improve the middle distillate characteristics at low temperatures.
• Ethylene/alpha-olefin (co)polymers used for the same purpose are also known in the prior art, see USP 5,097,084. They are characterized by the substantial absence of inversions of the propylene linking, as indicated by the X 2 and/or X 4 parameters lower than or equal to about 0.02, determined by 13 C NMR according to the method described by J.C. Randal in "Macro- molecules" 11, 33 (1978). The ethylene/propylene copolymers having said value of the mentioned parameters show clearly better CFPP values than the copolymers wherein said values are not satisfied, for example in comparison with the vanadium- based catalysts.
• Ethylene or alpha-olefins, or unsaturated esters for example vinylacetates , copolymers with maleic or fumaric acid, or unsaturated monocarboxylic acid esters , for example acrylates .
• Ethylene/ vinylacetate (EVA), fumarates , propionates , etc. can be mentioned. See for example USP 3,661,541, USP 4,211,534, EP 153,176, EP 153,177.
• various combinations of the described copolymers, optionally in combination with a nitrogen polar compound are mentioned.
• An object of the present invention are ethylene polymers with one or more monomers C6 containing at least two unsaturations, at least one being active to give homopolymers in the polymerization with the use of metallocene catalysts; or ethylene polymers with one or more alpha-olefins Ccr from 3 to 20 carbon atoms, and with one or more monomers C ⁇ containing at least two unsaturations , wherein at least one unsaturation being active to give homopolymers in the polymerization with the use of metallocene catalysts, usable as additives to increase the middle distillate properties at low temperatures, obtainable by polymerization of the monomers in the presence of catalysts comprising the reaction product among: 1) a bis-cyclopentadienyl derivative of general formula:
• C pl C p2 M-(L 2 L 3 ) containing groups with oxygen bound to the transition metal , in which M is a metal from the Illb group to the Vb group or of the lanthanide series of the Element Periodic Table;
• Cp x and Cp 2 equal to or different from each other, represent the following groups bound to M with delocalized ⁇ bonds, specifically with an eta 5 bond when the groups are selected from cyclopentadiene , indene, fluorene, or derivatives thereof substituted in the indene and fluorene case also with the hydrogenated phenyl ring (rings) and with substituents both in the phenyl and cyclopentadienyl rings , also with heteroatoms ; or with ⁇ bonds for example in the cyclooctatriene case; or said Cp x Cp 2 groups constrained with M through a bivalent linking bridge, for example -R- type, wherein R is an alkylene,
• R a is an aryl group, optionally the ring carbon atoms being jub ⁇ tituted ⁇ .lso with heteroatoms, and optionally containing substituents for example of alkyl type from 1 to 10 carbon atoms with 2) a co-catalyst selected from the compounds represented by the following formulae: 2a) alumoxane, of general formula:
• R b is an alkyl group from 1 to 5 C atoms, preferably methyl , m is an integer from 1 to 30, preferably from 4 to 20; m' is an integer from 3 to 20, preferably from 4 to 20. 2b) (Li-H) " *- (A) " wherein (A) " is a compatible non coordinating anion, preferably is
• B is an element of the group from Ilia to Via of the Element Periodic Table with metalloid characteristics, preferably boron, phosphorus or arsenic with valence 3 or 5, silicon, more preferably boron with valence 3;
• Q equal to or different from each other, are selected from the following groups: hydrides, halides, alkyls, optionally substituted aryls , for example with halogens, preferably F, alkoxides , aryloxides , dialkylamido , or R 0 COO " wherein R 0 ranges from 1 to 20 carbon atoms, with the proviso that Q is equal to halide only once;
• q is an integer equal to the B valence plus 1.
• the preferred co-catalyst component 2) is 2b).
• the 2a) alumoxane compound of the catalytic system is preferably prepared by reaction of aluminum trimethyl and water, obtaining a mixture of linear and cyclic compounds. They are generally prepared by contacting an aluminum trialkyl solution with water in suitable organic solvents, for example aliphatic hydrocarbons.
• alumoxanes are compounds containing Al-O-Al bonds, having a variable O/Al molar ratiol, obtainable in the art by reaction, under controlled conditions, of an aluminum alkyl, or aluminum alkyl halide, with water and, in the case of aluminum trimethyl, also with an hydrate salt, as hexahydrate aluminum sulphate, pentahydrate copper sulphate and pentahydrate iron sulphate .
• the molar ratio between Al of the 2a) alumoxane component with respect to the component 1) metal amount (metallocene) is in the range 10,000:1-100:1, preferably 5,000:1-500:1.
• metal amount metal amount (metallocene)
• the ratio is in the range (0.1- 4):1 and preferably (0.5-2.0) :1.
• _ can be NH 3 , aniline, pyridine, quinoline, alkylamines , dialkylamines , trialkylamines with the alkyl from 1 to 8 C atoms, preferably from 1 to 4, phenylamines , etc . All these compounds can respectively form quaternary ammonium salts, pyridinium salts, quinolinium salts which represent (L-_-H) + .
• Exemplifying compounds which can be mentioned are the following: substituted trialkyl ammonium salts, for example triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tris (n-butyl ) ammonium tetraphenylborate, trimethylammonium tetrakis(p- tolyl )borate, tributylammonium tetrakis (pentafluorophenyl )borate, tripropylammonium tetrakis( 2 ,4-dimethylphenyl)borate, tributylammonium tetrakis (3,5 -dimethylphenyl ) borate , triethylammonium tetrakis ( 3 , 5 -ditrifluoromethylphenyl )borate, etc.
• substituted trialkyl ammonium salts for example triethylam
• N,N-dialkyl anilinium salts can also be used, such as for example N,N-dimethyl anilinium tetraphenylborate, N,N-die- thyl anilinium tetraphenylborate, N,N-2 , 4 , 6 -pentamethylani - linium tetraphenylborate, etc.
• dialkyl ammonium salts such as di- ( i-propyl )ammoniumtetrakis (pentafluorophenyl ) borate, dicyclohexylammonium tetraphenylborate, etc.
• triaryl phosphonium salts such as triphenylphosphfonium tetraphenylbo- rate, t r i ( me t hy 1 phenyl ) pho s phon i urn tetrakis pentafluorophenylborate , tri (dimethylphenyl ) p o ⁇ phonium tetraphenylborate , etc ..
• Non limiting examples of the 1) compound which can be used to prepare the cation complex are titanium, zirconium, vanadium, hafnium (Hf), chromium, lanthanium derivatives , etc., the titanium or Zr compounds are preferred. Examples which can be mentioned are: bis (eta 5 cyclopentadienyl ) Zr diphenate; bis (eta 5 cyclopentadienyl) Zr of 2 , 3 , 6 - trimethylphenate , bis (eta 5 cyclopentadienyl) Hf diphenate, bis tetra ethylcyclopen- tadienyl Zr diphenate , etc .
• the catalysts of the present invention are obtained for example by direct reaction of bis -cyclopentadienyl metal di- alkyl , preferably dimethyl , with the corresponding phenols .
• the polymerization to obtain the invention copolymers can be carried out in suspension, in solution, or in gas phase, at temperatures generally in the range 0°C-150°C at a pressure generally in the range 1-300 bar, optionally using a molecular weight regulator, for example hydrogen.
• a molecular weight regulator for example hydrogen.
• the invention catalysts are generally used in the ethylene and alpha-olefin copolymerization processes.
• the invention polymers surprisingly show improved activities as CFPP additives with respect to the ethylene/propylene copolymer-3 kncvn in the prior art.
• monomers containing more than one unsaturation C ⁇ we mean preferably one or more dienes, conjugated or not, selected from:
• the cyclic dienes are selected from vinylcycloalkenes or di-cyclo- pentadienes , such as vinylcyclohexene or di- cyclopentadiene-ethyliden-norbornene ;
• - vinylaromatic monomers such as styrene, 2,4 vinylsty- rene, optionally one or more hydrogen atoms of the ring(s) of the cyclic or aromatic monomers being substituted by saturated alkyl groups from 1 to 12 carbon atoms or by unsaturated alkyl groups from 2 to 12 carbon atoms , optionally one or more carbon atoms of the ring being substituted by heteroatoms, preferably nitrogen, oxygen, sulphur.
• the diene (C6) amount is in the range 0.1-50% by moles, preferably 1-25% by moles.
• the Q'-olefins mentioned with Car are preferably: propylene
• the Cor olefin total amount is in the range 5-25% by moles.
• the conjugated dienes for example butadiene, isoprene, piperylene , 1 , 3 -hexadiene, 1 , 3 -octadiene, 2 , 4 -decadiene, di-cyclopentadiene; non conjugated dienes such as 1 , 4 -hexadiene, 7-methyl- 1 , 6 -octadiene; cyclic non conjugated dienes such as norbonene, ethylidennorbonene (ENB), 4 -vinylcyclohexene and vinylaromatic monomers such as styrene, 2, 4 -vinylstyrene, etc., can be mentioned.
• copolymers ethylene/C6 are: ethylene/ethylidennorbornene (also indicated ethylene/ 5- ethylidene- 2 -norbornene) (C2/ENB) ; ethylene/styrene ; ethylene/4 vinyl- eyelohexene, etc.
• copolymers ethylene/Cor/ C ⁇ are: ethylene/propylene/ethylidennoxbornene (C2/C3/ENB) ; ethylene- /butene/ethylidennorbornene (C2/C4/ENB); ethylene/octene/ethy- lidennorbornene (C2/C8/ENB); ethylene/propylene/butadiene; ethylene/propylene/octene/ethylidennorbornene (C2/C3/C8/ENB) ; ethylene/butene/octene/ENB/4 vinyl- eyelohexene, etc.
• Preferably said polymers are obtained by using as catalyst the component 1) in combination with the component 2b).
• the physical characteristics measurements of the middle distillates are carried out by determining the following parameters: Cloud Point (C.P.), Pour Point (P.P.) and Cold Filter Plugging Point (C.F.P.P.) as respectively defined in the ASTM D2500-81; ASTM D97-66 and IP 309/83 methods.
• Cloud Point C.P.
• Pour Point P.P.
• Cold Filter Plugging Point C.F.P.P.
• the intrinsic viscosity (dl/g) is determined according to known methods, for example in tetraline at 135°C.
• the Mv viseometrie molecular weight can also be determined by using intrinsic viscosity methods well known in the prior art. See for example: L.H. Tung, "Fractionation of Synthetic Polymers” Ed. Marcel Dekkers Inc. N.Y. 1977, J. Polymer Sci 20 , 495-506, 1956; G. Moraglio, Chim. Ind. (Milano) 10 984, 1959.
• the preferred number average (Mn) molecular weights of the invention are in the range 300-25,000, preferably 700-20,000, still more preferably 1,000-15,000.
• the molecular weight distribution is generally in the range 1.5-5, usually 1.5-3.5.
• the invention polymers can have a terminal unsaturation content as above defined in the range 0-90%, preferably 10-70%, still more preferably between 10 and -30%.
• the comonomer total amount, ethylene excluded, in the invention polymers is in the range 1-50% by moles, preferably 5-25% by moles .
• the invention polymers can optionally be combined with other cold flow improvers (CFI) known in the prior art to obtain synergic effects both as regards CFPP and filterability, and the WAS effect.
• CFI cold flow improvers
• ethylvinylacetates , fumarates , acrylates , propio- nates are preferably used.
• the invention polymers are combined with the above mentioned CFIs and furthermore also with a third CFI selected from the nitrogen polar compounds.
• J H, R 2 t , R 2 t COOR t , or an aryl or heterocyclic group
• K H, COOR 2 t , OCOR t 2 , or OR 2 t or COOH
• L H, R 2 t , COOR 2 t , OCOR 2 t , COOH, or aryl
• R t ⁇ C 10 R 2 t ⁇ C l f and m 2 and n 2 represent the molar ratios , m in the range 1-0.4, and n 2 in the range 0-0.6.
• the known CFIs can contain also units deriving from other monomers .
• These polymers can be copolymers of maleic anhydride or maleic acid, or of fumaric acid and of another ethylenical- ly unsaturated monomer, for example an alpha-olefin or an unsaturated ester, for example vinyl acetate. Molar ratios between com ⁇ nomers in the range 2:1-1:2 can be used .
• Examples of olefins which can be copolymerized for example with maleic anhydride comprise 1-decene, 1-dodecene, 1 tetradecene, 1- hexadecene and 1-octadecene.
• the copolymer can be esterified with any suitable method and although it is preferred, it is not essential that the maleic anhydride or the fumaric acid are at least esterified T OT 50%.
• Examples of alcohols wnich can be used comprise n-decan- l-ol , n-dodecan- l-ol , n- tetradecan- 1- ol, n-hexadecan-1-ol, and n-octadecan- l-ol .
• the alcohols can also contain up to one methyl substituent for chain, for example, 1-methylpentadecan- l-ol , 2 -methyltridecan- 1 -ol .
• the alcohol can be a mixture of normal and branched alcohols with a single methyl. Each alcohol can be used to esterify maleic anhydride copolymers with any olefin.
• R 2 refers to the average number of carbon atoms in the alkyl group, if the alcohols containing a branched group in the first or in the second position are used, R 2 refers to the branched segment of the alcohol linear chain.
• R 2 + 2 value When mixtures are used, it is important that no more than 15-% of the R 2 groups have the R 2 + 2 value.
• the alcohol selection clearly depends on the selection of the olefin copolymerized with maleic anhydride, so that R + R 2 is in the range 18-38.
• the preferred R + R 2 value can be in connection with the boiling characteristics of the fuel in which the additive is to be used.
• polymers can also be fumarate polymers and copolymers for example as those described in the European patent applications 153,176 and 153,177.
• suitable polymers are alpha-olefin polymers and copolymers and esterified styrene and maleic anhydride copolymers, and esterified styrene and fumaric acid copolymers.
• Other ( co)polymers which can be used are ethylene -unsaturated monocarboxylic acid ester copolymers .
• the ester can be an ester of an unsaturated carboxylic acid with a saturated alcohol or, which is preferred, an ester of a saturated carboxylic acid with an unsatured alcohol .
• the copolymer is an ethylene vinyl acetate copolymer.
• the copolymer advantageously contains from 10 to 50%, preferably advantageously at least 25% by weight of the ester.
• the number average molecular weight of the unsaturated ethylene ester copolymer is advantageously at least 7,500, and more advantageously in the range 850-4,000, preferably 1,250-3,500 and more preferably about 3,000 as measured by osmometry in vapour phase.
• Linear polymers derived from alkylene, for example ethylene, oxides, for example polyethylen glycol , and their amino derivatives can also be used.
• the third CFI additive, the above mentioned nitrogen polar compound, which is preferable to use in combination with the above mentioned CFIs and the invention polymers, and generally the nitrogen polar compounds are generally aminic salts and/or amides formed by reaction of at least a molar part of a substituted hydrocarbide with a molar ratio of hydrocarbon acid having from 1 to 4 groups of carboxylic acid and an anhydride thereof; esters/amides containing from 30 to 300, preferably from 50 to 150 total carbon atoms can also be used.
• These nitrogen compounds are described in US 4,211,534.
• Suitable amines are usually long chain C 12 -C 40 primary, secondary, tertiary or quaternary amines or mixtures thereof , but shorter chains can be used if the resulting nitrogen polar compound is soluble in oil; it will usually contain from about 30 to 300 total carbon atoms.
• the nitrogen polar compound preferably contains at least an alkyl segment of C 8 -C 24 linear chain.
• Suitable amines comprise primary, secondary and tertiary amines, preferably secondary amines, or quaternary ammonium salts .
• Examples of primary amines comprise tetradecyl amine , cocoamine, and hydrogenated tallow amine.
• Examples of secondary amines comprise dioctadecyl amine and methyl phenyl amine. Amine mixtures are also suitable and many amines derived from natural materials are mixtures .
• a preferred amine is a secondary hydrogenated tallow amine of the HNR 3 R 4 formula wherein R 3 and R 4 are alkyl groups derived from hydrogenated tallow greases composed of approximately 4% of C 14 , 31% of C 16 , 59% of C 18 .
• Examples of carboxylic acids (and anhydrides thereof) suitable for preparing these nitrogenous compounds comprise cy- clopentane- 1 , 2 acid dicarboxylic acid and naphthalendicarbox- ylic acids. Generally, these acids will have about 5-13 carbon atoms in the cyclic fraction.
• Preferred acids are benzen dicarboxylic acids such as hthalic, isop thaiie nd tere- phthalic acid.
• the phthalic acid or its anhydride is particularly preferred.
• the particularly preferred compound is the amido-amine salt formed by letting react a molar part of phthalic anhydride with two molar parts of dehydrogenated tallow amine.
• Another preferred compound is the diamide formed by the dehydration of this amide amine salt.
• the known CFI formulations can optionally comprise other additives of fuel oils, many of which are used in the prior art or are known in the literature.
• the additive concentration of the present invention ranges from 10 ppm to 5,000 ppm, preferably from 50 ppm to 900 ppm, more preferably from 100-200 ppm.
• the weight ratios between the invention copolymer, the known CFI (for example EVA, fumarates , propionates , acry- lates ) and the nitrogen polar compound is the following: 10/1:10/1:10, preferably 10/1:5/1:5.
• the molecular weight determination (both number average Mn and weight average Mw) is carried out by gel permeation chromatography (GPC - Gel Permeation Chromatography) which gives also the molecular weight distribution (MWD) .
• GPC gel permeation chromatography
• MWD molecular weight distribution
• the intrinsic viscosity (dl/g) is determined according to known methods, for example in tetraline at 135°C.
• the Mv viseometrie molecular weight can also be determined by using intrinsic viscosity methods well known in the prior art. See for example: L.H. Tung, "Fractionation of Synthetic Polymers” Ed. Marcel Dekkers Inc. N.Y. 1977, J. Polymer Sci 20, 495-506, 1956; G. Moraglio, Chim. Ind. (Milano) 10 984, 1959.
• the used reactor is a steel AISI 316 autoclave (5 1 volume) equipped with stirrer anchor shaped and able to work at a pressure ⁇ 150 bar.
• the autoclave is equipped with 4 feeding inlets, an outlet and a water circulation cooling system.
• the reactor is purged many times with anhydrous and hot nitrogen and maintained under pressure at 120°C for 24 hours.
• the autoclave is cooled to 25°C maintaining the nitrogen pressure at 1 bar.
• Example 2 The mixture is heated to 90°C and when this temperature is reached, 7 bar of ethylene are added. Afterwards 20 mg of Cp 2 Zr (bisphenoxide) solution of Example 1 and 39.3 mg of the cocatalyst of Example 2 are added in 50 ml of toluene under an overpressure of anhydrous nitrogen.
• the polymerization is carried out for 3 minutes maintaining the pressure constant by continuous feeding of ethylene.
• the polymerization is quickly stopped by venting and cooling the autoclave to 25°C.
• the produced polymer is precipitated using ethanol/acetone acidified with hydrochloric acid, washed many times with ethanol/acetone and anhydrified under vacuum.
• the polymer of Example 3 has been used as CFPP additive for the A and B middle distillates having the above mentioned characteristics.
• the CFPP value has been determined by using 50 ppm of polymer .
• Example 3 is repeated with the following variations: instead of 30 g, 40 g of ENB are used.
• the polymer of Example 5 has been used as CFPP additive for the A and B middle distillates having the above mentioned characteristics.
• the CFPP value has been determined by using 50 ppm of polymer.
• Example 3 is repeated with the following variations : instead of 30 g, 20 g of ENB and 15 bar of ethylene are used.
• Example 7 The viseometrie Mv molecular weight is 15,000.
• the CFPP value has been determined by using 50 ppm of polymer.
• Example 3 is repeated with the following variations: 2.5 g of ENB and 60 g of propylene with 10 bar of ethylene and 2 bar of hydrogen as molecular weight regulator are used.
• Example 9 polymer has been used as CFPP additive for the A and B middle distillates having the above mentioned characteristics .
• the CFPP value has been determined by using 50 ppm of polymer.
• Example 3 is repeated with the following variations: 2.5 g of ENB and 60 g of propylene with 7 bar of ethylene are used.
• Example 11 polymer has been used as CFPP additive for the A and B middle distillates having the above mentioned characteristics .
• the CFPP value has been determined by using 50 ppm of polymer.
• Example 3 is repeated with the following variations: 5 g of ENB and 50. g of propylene and 7 bar of ethylene are used.
• Example 13 polymer has been used as CFPP additive for the A and B middle distillates having the above mentioned characteristics .
• the CFPP value has been determined by using 50 ppm of polymer.
• the used reactor is a steel AISI 316 autoclave (5 1 volume) equipped with stirrer anchor shaped and able to work at a pressure ⁇ 150 bar.
• the autoclave is equipped with 4 feeding inlets, an outlet and a water circulation coo.V.ng system.
• the reactor is purged many times with anhydrous and hot nitrogen and maintained under pressure at 120°C for 24 hours.
• the a ⁇ toclave is cooled to 25°C maintaining the nitrogen pressure at 1 bar.
• Example 2 The mixture is heated to 70°C and when this temperature is reached , 6.5 bar of ethylene and 2 bar of hydrogen are added . Then 20 mg of Cp 2 Zr(bisphenoxide ) solution of Example 1 and 39.3 mg of the cocatalyst of Example 2 are added in 50 ml of toluene under an overpressure of anhydrous nitrogen.
• the polymerization is carried out for 6 minutes maintaining the pressure constant by continuous ethylene feeding.
• the polymerization is quickly stopped by venting and cooling the autoclave to 25°C.
• the produced polymer is precipitated using ethanol/acetone acidified with hydrochloric acid, washed many times with ethanol/acetone and anhydrified under vacuum.
• the obtained polymer has been used as CFPP additive for the A and B middle distillates having the above mentioned characteristics.
• the CFPP value has been determined by using 50 ppm of polymer .

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• 1999
  • 1999-03-23 IT IT1999MI000590 patent/IT1311975B1/it active
• 2000
  • 2000-03-15 AU AU32896/00A patent/AU3289600A/en not_active Abandoned
  • 2000-03-15 WO PCT/EP2000/002265 patent/WO2000056789A1/en not_active Ceased

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