WO2000056843A1 - Polymères d'éthylène - Google Patents

Polymères d'éthylène Download PDF

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Publication number
WO2000056843A1
WO2000056843A1 PCT/EP2000/002264 EP0002264W WO0056843A1 WO 2000056843 A1 WO2000056843 A1 WO 2000056843A1 EP 0002264 W EP0002264 W EP 0002264W WO 0056843 A1 WO0056843 A1 WO 0056843A1
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Prior art keywords
ethylene
carbon atoms
moles
mixtures according
copolymers
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PCT/EP2000/002264
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English (en)
Inventor
Federico Milani
Paolo Falchi
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Societa' Italiana Additivi Per Carburanti S.R.L.
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Application filed by Societa' Italiana Additivi Per Carburanti S.R.L. filed Critical Societa' Italiana Additivi Per Carburanti S.R.L.
Priority to AU32895/00A priority Critical patent/AU3289500A/en
Publication of WO2000056843A1 publication Critical patent/WO2000056843A1/fr

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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
    • C10L1/16—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
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • 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
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • 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
    • C10L1/16—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, 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
    • C10L1/16—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, 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
    • C10L1/16—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

Definitions

  • the present invention relates to additives for liquid hydrocarbon compositions, for example gas oils, generally known as middle distillates which show improved CFPP values as defined hereinunder.
  • middle distillates contain alkanes which at low temperatures tend to precipitate under the form of waxes, which are linear chain paraffins having a limited solubility and which tend to crystallize as the temperature decreases. 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.
  • CFI additives
  • the additives have the purpose to modify the wax crystals formed at low temperatures both reducing the sizes 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 filter plugging at low temperatures and specifically to reduce wax accumulation on the storage tanks bottom of middle distillates.
  • ethylene copolymers with unsaturated esters for example vinylacetates , maleic or fumaric acid, or unsaturated monocarboxylic acid esters, for example acrylates
  • unsaturated esters for example vinylacetates , maleic or fumaric acid, or unsaturated monocarboxylic acid esters, for example acrylates
  • the 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.
  • Ethylene/alpha-olefins (co) polymers suitable to the same purpose are also known in the prior art, see USP 5,097,084, which are characterized by the substantial absence of inversions of the alpha-olefin linking, for example, propylene, as indicated by the X 2 and/or X 4 parameters lower than or equal to about 0.02, determined by ⁇ 3 C NMR according to the method described by J.C. Randal in "Macromolecules" 11, 33 (1978).
  • the ethylene/propylene copolymers having said value of the mentioned parameters show improved CFPP values than the copolymers wherein said values are not satisfied, for example in comparison with those obtained by using vanadium-based catalysts .
  • the patent application WO 91/11488 describes as additives ethylene (co) olymers with alpha-olefins, in particular ethylene/propylene copolymers obtained by polymerization of ethylene with alpha-olefins in the presence of catalysts based on a) coordination organometallic compounds which are cyclopentadienyl derivatives of a metal of the Group 4b of the Periodic Table and they can be mono-, di- and tri -cyclopenta- dienes and derivatives thereof of the transition metal, with b) alumoxanes , which are the reaction products of aluminum trialkyls with water and specifically methylalumoxane .
  • the obtained ethylene/alpha-olefin copolymers have the essential characteristic to have at least 30% of the polymeric chains with ethylene and ethylidene terminal unsaturations .
  • These copolymers can be combined with one or more additives known in the art as CFI such as vinylacetates, fumarates , acrylates, propionates and polar compounds, for example tallowa ines .
  • Ethylene copolymers with alpha-olefins usable as additives to increase the properties at low temperatures of the midle distillate obtainable by reaction of a bis-cyclopentadienyl derivative, characterized by having two phenoxide groups linked to the transition metal, are also known. See for example EP 848,020.
  • An object of the present invention are mixtures comprising the following components: a) ethylene copolymers (C 2 ) with one or more of the following comonomers :
  • - C one or more linear or branched alpha-olefins, from 3 to 20 carbon atoms, and/or
  • - CS 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 vinylstyrene , 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 comonomer total amount being in the range 1-50% by moles, preferably 5-25% by moles, the average molecular weight by number being in the range 300-25,000, preferably 700-15,000; and b) ethylene copolymers with one or more comonomers mentioned in a) , the comonomer total amount being in the range 1-50% by moles, preferably 5-25% by moles, the average molecular weight by number being in the range 700-15,000; the composition difference in terms of total sum of the comono
  • composition difference in terms of total sum of the comonomers of a) and b) is at most 10-15% by moles.
  • the ⁇ r-olefins mentioned with Car are preferably: propylene (C3), 1-butene (C4), 1-hexene (C6), 1-octene (C8), 1-decene (CIO), 1-dodecene (C12), 4-metl- 1-pentene.
  • the Ca 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 norbornene, ethylidennorbornene (ENB), 4 -vinyl - cyclohexene and vinylaromatic monomers such as styrene, 2,4-vi- nylstyrene, etc., can be mentioned.
  • non conjugated dienes such as 1 , 4 -hexadiene , 7 -methyl- 1 , 6 -octadiene
  • cyclic non conjugated dienes such as norbornene, ethylidennorbornene
  • the C ⁇ diene amount is in the range 0-25% by moles, preferably 1-5% by moles.
  • copolymers examples include C 2 /C ⁇ r (II); C 2 /C ⁇ (III); C 2 /C ⁇ ./C ⁇ (IV).
  • copolymers (II) are: ethylene/propylene (C2/C3); ethylene/propylene/butene (C2/C3/- C4 ) ; ethylene/butene/hexene (C2/C4/C6); ethylene/butene/octene (C2/C4/C8), etc.
  • copolymers (III) are: ethylene/ethylidennorbornene (also indicated ethylene/ 5- ethylidene- 2 -norbornene) (C2/ENB); ethylene/styrene; ethylene/ /ENB/4 vinyl -cyclohexene, etc.
  • copolymers (IV) are: ethylene/propylene/ethylidennorbornene ( 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 - cyclohexene , etc.
  • the a) and b) (co) polymers are obtainable by polymerization of the monomers in the presence of catalysts comprising the reaction product between:
  • D is an element of the group from Ilia to Via of the
  • Element Periodic Table with metalloidic characteristics preferably boron, phosphorus or arsenic with valence 3 or
  • Q are selected from the following groups: hydrides, halides , alkyls, aryls optionally substituted, for example with halogens, preferably F, alkoxides, aryloxides , dialkylamido, or R Q 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 D valence plus 1.
  • the metallocene compound 1) is preferably a bis-cyclopentadienyl derivative of general formula:
  • M is a metal from the lllb group to the IVb 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 phenilic hydrogenated ring (rings) and with substituents both in the phenil and cyclopentadienyl rings, also with hetero- atoms; or with ⁇ bonds for example in the cyclooctatriene case; or said Cp 1 Cp 2 groups constrained with M through a bivalent linking bridge, for example -R- type, wherein R is an alkylene, preferably from 1 to 4 carbon atoms, -Si(R') 2 " wherein R' is an alkyl from 1 to 10 C
  • metallocene compounds of patent application WO 91/11488 wherein L 2 and L 3 are for example halogens or alkyl groups or hydrogen can be used.
  • L 2 and L 3 are for example halogens or alkyl groups or hydrogen
  • the co-catalyst alumoxane has the 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.
  • the structure of invention (co)polymers was characterized by DSC (Differential Scanning Calorimetry) and 13 C NMR in order to determine the % of cristalline material, the length of ethylene sequences and the amount of comonomer inversions.
  • the 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 putting into contact 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 molar ratio O/Al , obtainable in the art by reaction, under controlled conditions, of an aluminum alkyl, or an aluminum alkyl halide, with water and, in the case of aluminum trimethyl, also with an hydrate salt, as aluminum hexahydrate sulphate, copper pentahydrate sulphate and iron pentahydrate sulphate .
  • the molar ratio between Al of the 2) component alumoxane with respect to the metal amount of component 1) (metallocene) is in the range 10,000:1-100:1, preferably 5,000:1-500:1. In the case of the boron compound the ratio is in the range 0.1- 4.0:1 and preferably 0.5-2.0:1.
  • L 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 1 -H) ⁇ .
  • Exemplifying compounds which can be mentioned are the following: substituted trialkyl ammonium salts, for example triethylammo- nium tetraph ⁇ nylborate , tripropylammoniu tetraphenylborate , tris (n-butyl ) ammonium tetraphenylborate, trimethylammoniu te- trakis (p- tolyl )borate , tributylammonium tetrakis ( pentafluoro- phenyl ) borate , tripropylammonium tetrakis ( 2 , 4 -dime - thylphenyl )borate , tributylammonium tetrakis ( 3 , 5 -di ethylphe- nyl)borate, triethylammonium tetrakis ( 3 , 5 -ditrifluoromethyl
  • 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 , dieyelohexylammonium tetraphenylborate, etc.
  • triaryl phosphonium salts such as triphenylphosphfonium tetraphenylborate, t r i ( me t hy 1 ph eny 1 ) pho s phon i um tetrakis pentafluorophenylborate , tri (dimethylphenyl ) phosphonium tetraphenylborate, etc...
  • Preferred non limiting examples of the 1) compound which can be used to prepare the cation complex are titanium, zirconium, vanadium, hafnium (Hf), chromium, lanthanium deri- vatives, ecc . , the titanium or Zr compounds are preferred. Examples which can be mentioned are: bis (eta 5 cyclopentadie- nyl ) Zr diphenate; bis (eta 5 cyclopentadienyl ) Zr of 2,3,6- trimethylphenate , bis (eta 5 cyclopentadienyl) Hf diphenate, bis tetramethylcyclopentadienyl Zr diphenate, etc.
  • metallocene catalysts which can be used are well known in the prior art, for example in EP 129,368, EP 128,046, EP 260,299, these three patents are herein incorporated by reference .
  • the preferred catalysts of the present invention are obtained for example by direct reaction of bis-cyclopentadienyl metal dialkyl , preferably dimethyl, with the corresponding phenols. See the European patent application 848,020.
  • the polymerization to obtain the invention copolymers can be carried out by operating 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 (co)polymer mixtures as above defined surprisingly show improved activities as CFPP additives with respect to the single copolymers .
  • the (co- ) olymers obtained by using as catalyst the preferred 1) component in combination with the preferred 2) cocatalyst, for example boranes and/or borates as above mentioned, are pre- f erred .
  • 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 defined in the ASTM D2500- 81; ASTM D97-66 and IP 309/83 methods, respectively.
  • Cloud Point C.P.
  • Pour Point P.P.
  • Cold Filter Plugging Point C.F.P.P.
  • the invention (co) polymers can be combined with other cold flow improvers (CFI) known in the prior art to obtain synergic effects both as regards CFPP and the filterability, and the WAS effect.
  • CFI cold flow improvers
  • ethylvinylacetates fumarates, acrylates, propionates 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.
  • a nitrogen polar compound is generally selected from aminic salts and/or amides formed by reaction of at least a molar part of a substituted hydrocarbide with a molar part of hydrocarbon acid having from 1 to 4 carboxylic acid groups and an anhydride thereof; esters/amides containing from 30 to 300, preferably from 50 to 150 total carbon atoms, can also be used.
  • aminic salts and/or amides formed by reaction of at least a molar part of a substituted hydrocarbide with a molar part of hydrocarbon acid having from 1 to 4 carboxylic acid groups and an anhydride thereof; esters/amides containing from 30 to 300, preferably from 50 to 150 total carbon atoms, can also be used.
  • Suitable amines are usually long chain C 12 -C 4g 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 linear C 8 -C 2 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.
  • 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 formula wherein R 3 and R 4 are alkyl groups derived from hydrogenated tallow greases composed of approximately 4% of C 1 , 31% of C 16 , 59 % of C 18 .
  • Examples of carb ⁇ xylic acids (and anhydrides thereof) suitable for preparing these nitrogen compounds comprise cyclo- pentane-1,2 acid dicarboxylic acid and naphthalendicarboxylic acids. Generally, these acids have about 5-13 carbon atoms in the cyclic fraction.
  • Preferred acids are benzen dicarboxylic acids such as phthalic, isophthalic and terephthalic 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 500 ppm, more preferably from 100 to 200 ppm.
  • the weight ratios between the invention copolymer, the known CFI (for example EVA, fumarates , propionates, acrylates) 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 viscometric 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 molecular weight distribution is generally in the range 1.5-5, preferably 1.5-3.5.
  • the A and B gas oils (middle distillates) free from additives used in the tests have the following characteristics : type A type B density (IP 160) ( 15°C/gxcm "3 ) 0.8397 0.83
  • 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 at 25°C maintaining the nitrogen pressure at 1 bar.
  • the polymerization is carried out for 6 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 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.
  • Example 3 is repeated with the following variations: instead of propylene 100 g of octene and 5 bar of ethylene are used without employing hydrogen as molecular weight regulator and using a polymerization temperature of 80°C.
  • the viscometric Mv molecular weight is 10,200.
  • the number average Mn molecular weight is 5,000.
  • the obtained polymer has been used as CFPP additive for the B middle distillate having the above mentioned characteristics.
  • the CFPP value has been determined by using 50 ppm of polymer .
  • the CFPP has been determined in the B middle distillate by using a mixture of the polymers of Example 3 and Example 4 in a weight ratio between the two of 1:1 according to the present invention.
  • the CFPP value has been determined by using 50 ppm of the mixture of the two above mentioned polymers.
  • Example 4 is repeated with the following variations: instead of 100 g, 80 g of octene are used.
  • the viscometric Mv molecular weight is 13,800.
  • the number average Mn molecular weight is 6,800.
  • the obtained polymer has been used as CFPP additive for the B middle distillate 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: 50 g of octene together with propylene, in an amount of 50 g, are also added; the polymerization temperature was of 70°C and 5 bar of ethylene without hydrogen as molecular weight regulator; 15 mg of Cp 2 Zr(bisphenoxide) solution of Example 1 and 29.5 mg of the cocatalyst of Example 2 in 50 ml of toluene are added under an overpressure of anhydrous nitrogen.
  • the polymerization is carried out for 5 minutes maintaining the pressure constant by continuous ethylene feeding.
  • 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 .
  • the CFPP has been determined in the B middle distillate by using a mixture of the polymers of Examples 6 and 7 in a 1:1 ratio by weight.
  • the CFPP value has been determined by using 50 ppm of the mixture of the two above mentioned products.
  • Example 7 is repeated with the following variations: propylene in an amount of 50 g, octene 50 g.
  • the polymerization is carried out for 4 minutes maintaining the pressure constant by continuous ethylene feeding .
  • the viscometric Mv molecular weight is 14,000.
  • the number average Mn molecular weight is 7,200.
  • the obtained polymer has been used as CFPP additive for the B middle distillate having the above mentioned characteristics .
  • the CFPP value has been determined by using 50 ppm of polymer .
  • the CFPP has been determined in the B middle distillate by using a mixture of the polymers of Examples 7 and 9 in a 1:1 ratio by weight.
  • the CFPP value has been determined by using 50 ppm of the mixture of the two above mentioned polymers.
  • Example 3 is repeated with the following variations: instead of propylene, 100 g of octene are added; 5 bar of ethylene without using hydrogen as molecular weight regulator; 15 mg of Cp 2 Zr (bisphenoxide) solution of Example 1 and 29.5 mg of the cocatalyst of Example 2 in 50 ml of toluene under an overpressure of anhydrous nitrogen, are introduced.
  • the polymerization is carried out for 4 minutes maintaining the pressure constant by continuous ethylene feeding.
  • the obtained polymer has been used as CFPP additive for the A middle distillate having the above mentioned characteristics .
  • the CFPP value has been determined by using 50 ppm of polymer.
  • EXAMPLE 12 The CFPP has been determined in the A middle distillate by using a mixture of the polymers of Examples 3 and 11 in a ratio by weight between the two respectively of 3:1.
  • the CFPP value has been determined by using 50 ppm of the mixture of the two above mentioned polymers.
  • the CFPP has been determined in the A middle distillate by using a mixture of the polymers of Examples 3 and 7 in a ratio by weight between the two respectively of 3:1.
  • the CFPP value has been determined by using 50 ppm of the mixture of the two above mentioned polymers.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention concerne des mélanges comprenant les composants suivants: a) des copolymères d'éthylène (C2) comprenant un des comonomères suivants: Cα: une ou plusieurs alpha-oléfines linéaires ou ramifiées comprenant entre 3 et 20 atomes de carbone, et/ou Cβ: un ou plusieurs diènes, éventuellement conjugués, la quantité totale de comonomères étant comprise entre 1 et 50 % en moles; b) des copolymères d'éthylène comprenant un ou plusieurs comonomères mentionnés dans a), la quantité totale de comonomères étant comprise entre 1 et 50 % en moles. La différence de composition en termes de somme totale des comonomères de a) et b) s'élève à au moins 1 % en moles, de préférence au moins 5 % en moles. Les rapports a):b) en poids sont compris entre 5:1 et 1:5.
PCT/EP2000/002264 1999-03-23 2000-03-15 Polymères d'éthylène WO2000056843A1 (fr)

Priority Applications (1)

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AU32895/00A AU3289500A (en) 1999-03-23 2000-03-15 Ethylene polymers

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IT1999MI000589 IT1311974B1 (it) 1999-03-23 1999-03-23 Polimeri dell'etilene.
ITMI99A000589 1999-03-23

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WO2000056843A1 true WO2000056843A1 (fr) 2000-09-28

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103570853A (zh) * 2013-10-21 2014-02-12 虞海盈 一种官能化聚烯烃材料的制造方法
CN103570854A (zh) * 2013-10-21 2014-02-12 虞海盈 一种官能化聚烯烃材料

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0350072A1 (fr) * 1988-07-08 1990-01-10 SOCIETA' ITALIANA ADDITIVI PER CARBURANTI S.r.l. Compositions d'hydrocarbures de raffinage ayant une fluidité modifiée à basses températures
WO1991011488A1 (fr) * 1990-01-31 1991-08-08 Exxon Chemical Patents Inc. Additifs et compositions de mazout
EP0572034A2 (fr) * 1992-05-29 1993-12-01 Idemitsu Kosan Company Limited Copolymère éthylénique et composition de copolymères éthyléniques
US5272236A (en) * 1991-10-15 1993-12-21 The Dow Chemical Company Elastic substantially linear olefin polymers
WO1997032946A1 (fr) * 1996-03-08 1997-09-12 Dupont Dow Elastomers L.L.C. Polymeres ethylene/alpha-olefines sensiblement lineaires servant d'agents elevant l'indice de viscosite ou d'agents gelifiants
EP0848020A1 (fr) * 1996-12-12 1998-06-17 SOCIETA' ITALIANA ADDITIVI PER CARBURANTI S.r.l. Copolymères éthylène/alphaoléfines

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0350072A1 (fr) * 1988-07-08 1990-01-10 SOCIETA' ITALIANA ADDITIVI PER CARBURANTI S.r.l. Compositions d'hydrocarbures de raffinage ayant une fluidité modifiée à basses températures
WO1991011488A1 (fr) * 1990-01-31 1991-08-08 Exxon Chemical Patents Inc. Additifs et compositions de mazout
US5272236A (en) * 1991-10-15 1993-12-21 The Dow Chemical Company Elastic substantially linear olefin polymers
EP0572034A2 (fr) * 1992-05-29 1993-12-01 Idemitsu Kosan Company Limited Copolymère éthylénique et composition de copolymères éthyléniques
WO1997032946A1 (fr) * 1996-03-08 1997-09-12 Dupont Dow Elastomers L.L.C. Polymeres ethylene/alpha-olefines sensiblement lineaires servant d'agents elevant l'indice de viscosite ou d'agents gelifiants
EP0848020A1 (fr) * 1996-12-12 1998-06-17 SOCIETA' ITALIANA ADDITIVI PER CARBURANTI S.r.l. Copolymères éthylène/alphaoléfines

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103570853A (zh) * 2013-10-21 2014-02-12 虞海盈 一种官能化聚烯烃材料的制造方法
CN103570854A (zh) * 2013-10-21 2014-02-12 虞海盈 一种官能化聚烯烃材料

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ITMI990589A1 (it) 2000-09-23
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