CA2148596A1 - Process for polymerizing alpha-olefin - Google Patents
Process for polymerizing alpha-olefinInfo
- Publication number
- CA2148596A1 CA2148596A1 CA002148596A CA2148596A CA2148596A1 CA 2148596 A1 CA2148596 A1 CA 2148596A1 CA 002148596 A CA002148596 A CA 002148596A CA 2148596 A CA2148596 A CA 2148596A CA 2148596 A1 CA2148596 A1 CA 2148596A1
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- Prior art keywords
- carbon atoms
- group
- magnesium
- process according
- compound
- Prior art date
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- 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
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/656—Pretreating with metals or metal-containing compounds with silicon or compounds thereof
- C08F4/6562—Pretreating with metals or metal-containing compounds with silicon or compounds thereof and metals of C08F4/64 or compounds thereof
-
- 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
- C08F10/00—Homopolymers and 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- 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
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
- C08F4/6543—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A process for polymerizing one or more .alpha.-olefins of up to 20 carbon atoms which comprises contacting the one or more .alpha.-olefins under polymerization conditions with a catalyst system comprising: (a) a titanium halide-containing, magnesium-containing pro-catalyst component wherein the component is obtained by contacting a magnesium compound of the formula MgR'R", wherein R' and R"
are, independently, alkoxide group, aryloxide group or halogen, with a halogenated tetravalent titanium compound in the presence of a polycarboxylic acid ester electron donor with or without a halohydrocarbon, (b) an organo-aluminium cocatalyst component, and (c) an organosilane selectivity control agent represented by general formula (i), wherein R1 is alkyl group of 13 to 30 carbon atoms, alkaryl group of 16 to 36 carbon atoms or aralkyl group of 16 to 36 carbon atoms; R2 and R3 are, independently, methyl or alkyl group of 13 to 30 carbon atoms or hydrocarbyloxy group of 1 to 6 carbon atoms; and R4 is a hydrocarbyloxy group of 1 to 6 carbon atoms. The process affords high catalyst productivity and produces polymer products that have broad molecular weight distribution while retaining low oligomer content properties.
are, independently, alkoxide group, aryloxide group or halogen, with a halogenated tetravalent titanium compound in the presence of a polycarboxylic acid ester electron donor with or without a halohydrocarbon, (b) an organo-aluminium cocatalyst component, and (c) an organosilane selectivity control agent represented by general formula (i), wherein R1 is alkyl group of 13 to 30 carbon atoms, alkaryl group of 16 to 36 carbon atoms or aralkyl group of 16 to 36 carbon atoms; R2 and R3 are, independently, methyl or alkyl group of 13 to 30 carbon atoms or hydrocarbyloxy group of 1 to 6 carbon atoms; and R4 is a hydrocarbyloxy group of 1 to 6 carbon atoms. The process affords high catalyst productivity and produces polymer products that have broad molecular weight distribution while retaining low oligomer content properties.
Description
~14~59 6 ) T - 3 1l7 .~* . j - ~ DESCRIPTION -~
PROCESS FOR POLY~ERI~ING ALP~A-OLEFIN
Technical Field. .
This invention relates ~o a process for producing ~-olefin polymers. More particularly, the invention-relates to a process -~at utilizes a novel high activity s~ereoregular ~olyme~ization catalyst system to produce ~-ole~in pol~Imers having imprcved polymer properties.
ackqround Art The use o~ a solid, transition metal based, olefin polymerization catalyst systèm including a titanium~containing, magnesium halide-~ased catalyst component to produce a polymer of an ~-ole~in such as ethyl`ene, propylene, and butene-1, is well known in the art. SUch polymerization catalyst systems are typically obtained by the combination of a magnesium halide-based catalyst component, an organoaluminum compound and one or more electron donors. For..convenience of reference, the soIid titanium-containing catal~st component is referred to herein as "procatalyst"~.. the arganoaluminum compound, as ~ ."cocatalyst", and an electron dono~ sompoundJ wh~-ch is typically used separately, or used ~artially or totally complexed with the organoaluminum compound, as l'selestivi~y control agent" ~SC~) J It is also known~to incorporate electron donor compounds into the pro catalyst. The electron donor which is incorporated with the titanium-containing compounds sexves a different purpose than the electron donor referred to as the selectiv.i~y control agent. The compounds which are used as the electron donor are the same as or dif~erent from compounds which are used as ~hë selectivity control agent~ The abo~e-described stereoregular high acti~ity catalysts ~are broadly con~en~ional and are described i~ n~merous ~atents and other references including EP~A-02g7l63, US-A-4,728/7Q5 and GB-A-2143834.
: Although a ~road range o~ compounds are known generally as ~electivity control~agents, a particular catalyst 3S component may have a specific compound or groups of compounds with whl.-~ it is s?ecially compati~le~ For anv given ~ F ~J r~ r~ F ~T
-`, 214~536 ,~
procatalyst andjor cocatalyst, discovery of an appropriate type of selectivity control agent can lead to signif~cant increases in catalyst efficiency, hydrogen utilization efficiency as well as an improvement in polymer product properties.
Many classes o~ selectivity control agents have been disclosed for possible use in polymerization catalysts. One clas~ ar such selectivity control agents is the class of organo silanes. ~ For example, Hoppin et al, U.S. Patent - 4,990,478, describe branched C3 C10 alkyl-t-butoxydimethoxysilanes. Other aliphatic silanes are descri~ed in Hoppin et al, U.Si Patent 4,829,03$. Kioka et al, U.S.
Patent 5,028,671, describe a catalyst syste~ which incorporates various alkylalkoxysilanes, such as di-n-octadecyldimethoxysilane and di-n-octadecyldiethoxysilane as selectivity control agents.
Although many methods are known for producing highly stereoregu~ar ~-olefin polymers, it is still desired to improve the acti~ity of the catalyst and produce polymers or copolymers that exhibit improved properties such as high ~ w and broad molecular weight distribu~ion.-;~urther, it ls desired to produce polymers or copolymers tha~ exhiblt a reduction in the `. amount of ~olatiles.
Disclosure of the Invention The invention relates to an improved process for the production of homopolymers or copolymers of ~-oIe~ins that ha~e improved polymer properties.
More particularly, thë present inYention is a process for the production of polymers using a high activity olefin polymerization catalyst system which comprises (a) a titanium l~halide-containing procatalyst component ~tained by , halogenating a magnesium compound of the formula MgR'RJ', ; wherein R' is~an a~koxide group, aryloxy group or a hydrocarbyl carbonate group and R'' is an alkoxide group, an ar~Ioxy group, a hydrocarbyl group or a halogen, especially an alkoxide group containing from 1 to 10 carbon a~oms with a halogenated tetra~alent titanium compound containing 2 to 4 halogen atoms in th~: preserlce of an electron donor, and a ~: ~
AME!IDE3 ^`~EET
21~596 -., ; 1. . .
.
- 2a -.~ ,. ~, :`
halohydrocarbon, (b)~.an organoaluminum cocatalyst component, :~`
and tc) an organosilane selectivity control agent having the ~"
qeneral formula:
- .:
. ~
, ~ ' : .
.. - . ::
-.
: ::: :
:: .: : ' : : i :
A~\AEl~cD SHE~
- 21~8~9~ .
`
_.... , -,`
Rl / R
` \si R2 ~ ~?.4 .," ~ ' ''.
~
- .
wherein R~ is a preferably linear, alkyl group of 13 to 30 carbon atoms, an alkaryl group of 1~ to 36 carbon atoms or aralkyl group of 16 to 36 carbon atomsi R2 and R3 are, independently, methyl or alkyl groups of 13 to 30 carbon atoms, or hydrocarboxyloxy group of 1 to 6 car~on atoms; and R~ is hydrocarbyloxy group of 1 to 6 carbon atoms.
Descri~tion of the Invention EP-A 0455313 discloses a catalyst system derived 15- ~rom component (b) above, an organosilicon which can be one defined for component (c) and a solid titanium catalyst which is not obtained using a halohydrocarbon~
The magneslum compound employed in the preparation of the solid catalyst component contains 20 alkcxide, aryloxide, hydrocar~yl carbonate or halogen. The ;
alkoxide, when present, usually ~ontains from 1 to 10 carbo~ :
atoms. Alkoxides containing from 1 to 8 carbon atoms are preferable, with alkoxides of 2 to 4 carbon atoms being more preferable. The aryloxide, when present, generally contains from 6 to 10 carbon atoms, with 6 to 8 carbon atoms being preferred. The hydro~arbyl car~onate, when present, generally contains 1 to 10 carbon atoms. When halogèn is present, i~ can~be present as bromine, fluorine, `iodine or r.,.
chlorine, with chlorine being preferred.
Suitable magnesium compounds are magneslum chloride, magnesium bromid~, magnesium ~luoride, ethoxy magnesiu~
~romide, isobuto~y~ magnesium chloride, phenoxy magnesium iodide, cumyloxy magnesium ~romide, magnesium diethoxidep magnes um isopropoxide, magnesium ethyl carbonate, ethoxy magnesium, magnesi ~ steara~e, magnesium laura~e, and naphthoxy ~agnesium chloride. Especially preferred as ~he magnesium n ~ F ~T
~ 214859~ ~ `
compounds are magnesium dialkoxides. Preferred magnesium compound is magnesium diethoxide.
Ha ~ ~ ~ ion of the magnesium compound with the halogenated tetravalent titanium compound is generally effected by using an excess of the titanium compound. At least 2 moles of the titanium compoun~ are normally used per mole of the magnesium compound. Preferably from 4 moles to 100 moles of the titanium compound are used per mole of the magnesium compoundj and most preferably from 4 moles to 20 moles of the titanium compound are used per mole of the magnesium compound.
Halogenation of the magnesium compound with the halogenated tetravalent titanium compound is usually effected by contacting the compounds at an elevated temperature in the range from about 60C to about 150C, preferably from about 70C to about 120C. Usually the reac~ion is allowed to proceed over a period of 0.1 to 6 hours/ preferably from about 0.6 to about 3.5 hours. The halogenated product is solid material which is isolated fro~ the liquid reaction medium by a ~ suitable separation meth~, such as conventional filtration.
; The halogenated tetravalent compound employed to halogenate the magnesium compound contalns at least two halogen-at~ms, and preferably contains ~our halogen atoms. The halogen ~atoms are chlorine atoms, bromine atoms/ iodinè ~to~s or fluorine atoms. The halogenated tetravalent titanium compo~nd has up to two alkoxy or aryloxy groups. Examples of suitable halogenated tetravalent titanium compounds include diethoxytitanium dibromide, isopropoxytitanium triiodide, dihexoxytitaniu~dichloride, phenoxytitanium trichloride, titanium tetrachloride and titanium-tetrabromide. The preferred halo~enated tetravalent ti~anium compound is titanium tetrachloride.
Halogenation~of the magneslum compound with the ~halogenated~tetravalent titanium compound, as notad, is conducted in the presence of a~halohydrocarbon and an electron donor. I~ desi~red, an iner~t~hydrocarbon diluent or solvent may ~ ; also be present.
:~; :
:~ ~
AMEN9E~ Sl',EET
` 214~59~
.
Suitable halohydrocarbons include aromatic or aliphatic, including cyclic and alicyclic compounds.
Preferably the halohydrocarbon contains 1 or 2 halogen atoms, although more may be p~esent if desired. It is prefarred that the halogen is, independently, chlorine, bromine or ~luorine.
Exemplary of suitable aromatic halohydrocarbons are chlorobenzene, bromobenzene, dichlorobenzene, dichlorodihromobenzene, o-chlorotoluene, chlorotoluene, dichlorotoluene, chloronaphthalene Chlorobenzene, o-chlorotoluene and dichlorobenzene are the preferredhalohvdrocarbons, with chlorobenzene and o-chlorotoluene being more preferred.
' The ~'iphatic halohydrocarbons which can be employed suitably have 1 to 12 carbon atoms. Preferably such halohydrocarbons have 1 to 9 carbon atoms and at least 2 halogen atoms. Most preferably the halogen is present as chlorine. Suitable aliphatic halohydrocarbons include dibromomethane, trichloromethane, 1,2-dichloroethane, ..,.; ., trichloroethane, dichloro~luoroethane, hexachloroethane, trichloropropane, chlorobutane, dichlorobutane, ehloropentane, trichlorofluorooctane, tetrachloroisooctane, dibromodi~
fluorodecane. The pre~erred aliphatic halohydrocar~ons are carbon tetrachloride and trichloroethane.
Aromatic halohydrocarbons arepreferred, ~articularly those Qf 6 to 12 carbon atoms, and especial~y those of 6 to lQ
carbon atoms.
~ ypical electron d~nors that are incorpoxated within the procatalyst include esters, particularly axomatic estexs, ; ethers, particularly aromatic ethers, ketones, phenols, amines, am~des, imines, nitriles, phosphines, p~osphites, stibines, arsines, phosphoramides and aleoholates. Esters of polycarboxylic acids are ~he pre~erred electron donors~
Particularly preferred ~are alkyl as~ers of aromatic polycar~oxyli~ acid Tllustrati~e of suitable esters of polycarboxylic acid electron donQrs are die~hyl phthalate, diisoamyl phthalate, ethyl p-ethoxybenzoate, methyl p-ethoxybenzoate, diisobutyl phthalate, dimethyl S
E~!J
8~ ~i 16 - .
`````!
-6~
napthalenedicarboxylate, diisobutyl maleate., diisopropyl terephthalate, a~d diisoamyl phyhalate. Diisobutyl phthalate and ethyi-p-ethoxybenzoate are the preferred alkyl ester of an aromatic carboxylic acid.
After the solid halogenated product has been separated from the liquid reaction medium, it can be treated one or more ., tlmes with a~ditional halogenated tetravalen~ titanium compound. Preferably, the halogenated product is trPated multiple times with separate portions of the halogenated tetravalent titanium compound. ~e~ter results are obtained i~
the halogenated product is treated twice with separate portions of the halogenated tetravalent titanium compound. If desired, the solid halogenated.product is treated one or more times with a mixture of halogenated tetravalent titanium compound and a halohydrocarbon. As In the initial halogenation,.,at least 2 moles of the titanium compound are generally.employed per mole .
of the magnesium compound, and preferably from 4 moles to 100 moles of the titanium compound are employed per'mole of the ~, magne~ium compound. Most preferably from 4 moles to 2Q..moles of the titanium compound 'per mole of magnesium"compound.
':'`~^. . Optionally, the solid~halogenated product is treated at least once w~th one or more acid chlorides during~the ', ad~itional treatments with the halogenated tetravalent titanium compound. Suitable acid chlorides include benzoyl chloride and phthaloyl chloride. The preferred acid chlorid,e is phtyaloyl : chloride.
After the solid halogenated product has been treated one ~r more times with additional~halo'genated tetravalent titanium compound, it is desirably separated from the liquid,,l relacti`on medium,;washed 'at least once'with~an iner~ hydlroca~bon of up to 10 carbon atoms to remove unreacted titanium compounds, and dried. Exemplary of the iner~ hydrocarbons that are suitable f~or the invent'ion are,isopentane, isooctane, hexane, heptane and cyclohexane.
~ Preferred final washed~products have a titanium content of from 0.5 percent by weight to 6,0 percent by weight.
A more preferred~final wash product has from 1.5 percent by .
; :
21~859~
` ' ' ' '-;'' weight to 4.0 percent by weight. The a~omic ratio of titanium to magnesium in the final product is between 0.01:1 and 0.2:1.
A praferred final product has an atomic ratio of titanium to magnesium from about o.02:1 to o.15:1.
The cocatalyst is an organoaluminum compound which is typically an alkyIaluminum compound. Suitable al~ylaluminum compounds include trialkylaluminum compounds, such as triethyl-aluminum or triisobutylaluminum; dialkylaluminum halides such as diethylaluminum chloride and dipropylaluminum chloride; and dialkylaluminum alkoxides such as~diethylaluminum ethoxide.
Trialkylaluminum compounds axe preferred, with triethylaluminum being the preferred trialkylaluminum compound.
The organosilane selectivity control agents in the cat~lyst system contain at least one silicon-oxygen-carbon li.nkage. Suitable organosilane compounds include co,mpounds having the following general formula~
E~ R3 4 ~ ` \ Si ' ''~
R2 / ~4 ..
wherein ~1 is a linear àlkyl-~roup of 13 to 30 carbon a~oms, . alkary.l group of 16 to 36 carbon atoms or aralkyl g~oup of 16 to 36 carbon akoms. It is pre~erred~tha~ Rl is alkyl ~roup o~
16 to 3Q carbon at~ms, al~aryl group of 19 to 3Q carbon atoms or aralkyl group of ~9 to 30 carbon atoms. It is further . 2S pre~erred that Rl is alkyl ~roup.of 1.8 to 28 carbo~ atoms. R2 and R3 are, independently, methyl or alkyl group o~ 13 to 30 carbon atoms, or hydrocarbylo ~ groups of 1 to 6 carbon atoms.
:It is preferred that R2 and R3 arej independently, methyl or alkyl group o~ 16 to 30 ca~bon atoms or alkoxy group o~ 1 to 4 ca~bon a~oms. It~:is further prefe~red that R2 is methyl or alkyl ,group of 18 to 28:c~rbon atoms or al~oxy ~roup of 1 to 4 carbon atoms and R3.is al~oxy gro~p o~ 1 to 4 carbon a~ms~ Tt is preferred that R~ is alkoxy group o~ 1 to 4 ~ax~on at~ms.
R4 is hydrocarbyloxy group of 1 ~o 6 carbon atoms. It is : 35 further preferred that R2, R3 a~d ~ are ethoxy or me~hoxy groups. Examples o~ suitable organosilane selectivity control agents inc~ude n-o~tadecyltriethoxysilane, n-triacontyl-AME~DEDSkEE~
214859fi ` ! - 8-triethoxysilane, methyl-n-octadecyldimethoxysilane, methyl-n-octadecyldiethoxysil~ne, n-octadecyltrimethoxysilane, n-triacontyltrimethoxysilanè and mixtures thereof. The preferred organosilan~a selectivity control.agents are n-.^.
octadecyltriethoxysilane, n-methyloctadecyldimethoxysilane and n-octadecyltrimethoxysilane. The in~ention also contemplates the use of mixtures of two or more selectivity control agents.
The selectivi~y co~trol agent is suitably provided in a quantity such that the molar ratio of the selecti~ity control agent to the titanium present in the procatalyst is fxom about 0.5 to..about 80. ~olar ratios from about 2 to about 60 are preferred, with molar ratios from about 5 to about 40 being more preferred.
The high acti~ity stereoregular polymerization catalyst is utilized to effect polymerization by contacting at least one -olefin under. polymerization conditions. In accordance with ~he invention, the procatalyst component, .
organoaluminum cocatalyst, and selectivity control agent are intxoduced into the polymerization reactor.~eparately or, if desîred, two or. all of the components are partialIy or completely mixed with each other ~efore they are introduced into the reactor.
The partîcular type.. of polymerizatîon process utîlized is not crîtîcal to the operation af the present inventîon and the polymerization processes now regarded as con~entional are suitable în the process of ~he inventîon. The ;~
polymerization is conducted under pol~merîzation condi~ions as a liguid phase or a: gas-phase process employing a fluidized catalyst bed.
The polymerizatîon conducted în ~he~ lîquîd~phas~
employs as reactîon diluent an added înert lî~uid diluent or alternatively a li~uid dîluent which comprises the olefint such as propylene or 1-butene, undergoing polymeriza~ion. If a ¢opolymer i~ prepared wherein ethyl~e îs one of th~ monomers, e~hylene is întroduced by conventional means to a diluent.
~ îcal polymerization conditîons înclude a reactîon temperature ~rom about 25C to about 125C, with temperatures from about 3~C to about 90C beîng preferred, and a pressure '!
AMENGED ~!EET
_J :, ,, , . ~llL85~
.. !
sufficient to maintain the reaction mixture in a li~uid phase.
Such pressures are from about 150 psi to about 1200 psi, with pressures from about 250 p~i to about 900 psi are preferred~
The liquid phase reaction is operated in a batchwise manner or .. ~ as a continuous or semi-continuous process. Subsequent to reaction, the polymer product is recovered by cGnventional procedures. The precise controls of the polymerization conditions and reaction parameters of the liquid phase process :~
are within the skill of the art.
As an alternate embodiment of the invention, the -~
polymerization is conducted in a gas phase process in the presence of a fluidized catalyst bed. One such gas phase process polymerization process is described in U.S. Patent 4,379,7S9. The gas phase process typically involves charging to reactor an amount of preformed polymer particles, gaseous monomer and separately charge a lesser amount of each catalyst component. G~seous monomer, such as propylene, ls passed through the bed of solid particles at a high rate under condit.Lons of temperature and pressure sufficient to initiate
PROCESS FOR POLY~ERI~ING ALP~A-OLEFIN
Technical Field. .
This invention relates ~o a process for producing ~-olefin polymers. More particularly, the invention-relates to a process -~at utilizes a novel high activity s~ereoregular ~olyme~ization catalyst system to produce ~-ole~in pol~Imers having imprcved polymer properties.
ackqround Art The use o~ a solid, transition metal based, olefin polymerization catalyst systèm including a titanium~containing, magnesium halide-~ased catalyst component to produce a polymer of an ~-ole~in such as ethyl`ene, propylene, and butene-1, is well known in the art. SUch polymerization catalyst systems are typically obtained by the combination of a magnesium halide-based catalyst component, an organoaluminum compound and one or more electron donors. For..convenience of reference, the soIid titanium-containing catal~st component is referred to herein as "procatalyst"~.. the arganoaluminum compound, as ~ ."cocatalyst", and an electron dono~ sompoundJ wh~-ch is typically used separately, or used ~artially or totally complexed with the organoaluminum compound, as l'selestivi~y control agent" ~SC~) J It is also known~to incorporate electron donor compounds into the pro catalyst. The electron donor which is incorporated with the titanium-containing compounds sexves a different purpose than the electron donor referred to as the selectiv.i~y control agent. The compounds which are used as the electron donor are the same as or dif~erent from compounds which are used as ~hë selectivity control agent~ The abo~e-described stereoregular high acti~ity catalysts ~are broadly con~en~ional and are described i~ n~merous ~atents and other references including EP~A-02g7l63, US-A-4,728/7Q5 and GB-A-2143834.
: Although a ~road range o~ compounds are known generally as ~electivity control~agents, a particular catalyst 3S component may have a specific compound or groups of compounds with whl.-~ it is s?ecially compati~le~ For anv given ~ F ~J r~ r~ F ~T
-`, 214~536 ,~
procatalyst andjor cocatalyst, discovery of an appropriate type of selectivity control agent can lead to signif~cant increases in catalyst efficiency, hydrogen utilization efficiency as well as an improvement in polymer product properties.
Many classes o~ selectivity control agents have been disclosed for possible use in polymerization catalysts. One clas~ ar such selectivity control agents is the class of organo silanes. ~ For example, Hoppin et al, U.S. Patent - 4,990,478, describe branched C3 C10 alkyl-t-butoxydimethoxysilanes. Other aliphatic silanes are descri~ed in Hoppin et al, U.Si Patent 4,829,03$. Kioka et al, U.S.
Patent 5,028,671, describe a catalyst syste~ which incorporates various alkylalkoxysilanes, such as di-n-octadecyldimethoxysilane and di-n-octadecyldiethoxysilane as selectivity control agents.
Although many methods are known for producing highly stereoregu~ar ~-olefin polymers, it is still desired to improve the acti~ity of the catalyst and produce polymers or copolymers that exhibit improved properties such as high ~ w and broad molecular weight distribu~ion.-;~urther, it ls desired to produce polymers or copolymers tha~ exhiblt a reduction in the `. amount of ~olatiles.
Disclosure of the Invention The invention relates to an improved process for the production of homopolymers or copolymers of ~-oIe~ins that ha~e improved polymer properties.
More particularly, thë present inYention is a process for the production of polymers using a high activity olefin polymerization catalyst system which comprises (a) a titanium l~halide-containing procatalyst component ~tained by , halogenating a magnesium compound of the formula MgR'RJ', ; wherein R' is~an a~koxide group, aryloxy group or a hydrocarbyl carbonate group and R'' is an alkoxide group, an ar~Ioxy group, a hydrocarbyl group or a halogen, especially an alkoxide group containing from 1 to 10 carbon a~oms with a halogenated tetra~alent titanium compound containing 2 to 4 halogen atoms in th~: preserlce of an electron donor, and a ~: ~
AME!IDE3 ^`~EET
21~596 -., ; 1. . .
.
- 2a -.~ ,. ~, :`
halohydrocarbon, (b)~.an organoaluminum cocatalyst component, :~`
and tc) an organosilane selectivity control agent having the ~"
qeneral formula:
- .:
. ~
, ~ ' : .
.. - . ::
-.
: ::: :
:: .: : ' : : i :
A~\AEl~cD SHE~
- 21~8~9~ .
`
_.... , -,`
Rl / R
` \si R2 ~ ~?.4 .," ~ ' ''.
~
- .
wherein R~ is a preferably linear, alkyl group of 13 to 30 carbon atoms, an alkaryl group of 1~ to 36 carbon atoms or aralkyl group of 16 to 36 carbon atomsi R2 and R3 are, independently, methyl or alkyl groups of 13 to 30 carbon atoms, or hydrocarboxyloxy group of 1 to 6 car~on atoms; and R~ is hydrocarbyloxy group of 1 to 6 carbon atoms.
Descri~tion of the Invention EP-A 0455313 discloses a catalyst system derived 15- ~rom component (b) above, an organosilicon which can be one defined for component (c) and a solid titanium catalyst which is not obtained using a halohydrocarbon~
The magneslum compound employed in the preparation of the solid catalyst component contains 20 alkcxide, aryloxide, hydrocar~yl carbonate or halogen. The ;
alkoxide, when present, usually ~ontains from 1 to 10 carbo~ :
atoms. Alkoxides containing from 1 to 8 carbon atoms are preferable, with alkoxides of 2 to 4 carbon atoms being more preferable. The aryloxide, when present, generally contains from 6 to 10 carbon atoms, with 6 to 8 carbon atoms being preferred. The hydro~arbyl car~onate, when present, generally contains 1 to 10 carbon atoms. When halogèn is present, i~ can~be present as bromine, fluorine, `iodine or r.,.
chlorine, with chlorine being preferred.
Suitable magnesium compounds are magneslum chloride, magnesium bromid~, magnesium ~luoride, ethoxy magnesiu~
~romide, isobuto~y~ magnesium chloride, phenoxy magnesium iodide, cumyloxy magnesium ~romide, magnesium diethoxidep magnes um isopropoxide, magnesium ethyl carbonate, ethoxy magnesium, magnesi ~ steara~e, magnesium laura~e, and naphthoxy ~agnesium chloride. Especially preferred as ~he magnesium n ~ F ~T
~ 214859~ ~ `
compounds are magnesium dialkoxides. Preferred magnesium compound is magnesium diethoxide.
Ha ~ ~ ~ ion of the magnesium compound with the halogenated tetravalent titanium compound is generally effected by using an excess of the titanium compound. At least 2 moles of the titanium compoun~ are normally used per mole of the magnesium compound. Preferably from 4 moles to 100 moles of the titanium compound are used per mole of the magnesium compoundj and most preferably from 4 moles to 20 moles of the titanium compound are used per mole of the magnesium compound.
Halogenation of the magnesium compound with the halogenated tetravalent titanium compound is usually effected by contacting the compounds at an elevated temperature in the range from about 60C to about 150C, preferably from about 70C to about 120C. Usually the reac~ion is allowed to proceed over a period of 0.1 to 6 hours/ preferably from about 0.6 to about 3.5 hours. The halogenated product is solid material which is isolated fro~ the liquid reaction medium by a ~ suitable separation meth~, such as conventional filtration.
; The halogenated tetravalent compound employed to halogenate the magnesium compound contalns at least two halogen-at~ms, and preferably contains ~our halogen atoms. The halogen ~atoms are chlorine atoms, bromine atoms/ iodinè ~to~s or fluorine atoms. The halogenated tetravalent titanium compo~nd has up to two alkoxy or aryloxy groups. Examples of suitable halogenated tetravalent titanium compounds include diethoxytitanium dibromide, isopropoxytitanium triiodide, dihexoxytitaniu~dichloride, phenoxytitanium trichloride, titanium tetrachloride and titanium-tetrabromide. The preferred halo~enated tetravalent ti~anium compound is titanium tetrachloride.
Halogenation~of the magneslum compound with the ~halogenated~tetravalent titanium compound, as notad, is conducted in the presence of a~halohydrocarbon and an electron donor. I~ desi~red, an iner~t~hydrocarbon diluent or solvent may ~ ; also be present.
:~; :
:~ ~
AMEN9E~ Sl',EET
` 214~59~
.
Suitable halohydrocarbons include aromatic or aliphatic, including cyclic and alicyclic compounds.
Preferably the halohydrocarbon contains 1 or 2 halogen atoms, although more may be p~esent if desired. It is prefarred that the halogen is, independently, chlorine, bromine or ~luorine.
Exemplary of suitable aromatic halohydrocarbons are chlorobenzene, bromobenzene, dichlorobenzene, dichlorodihromobenzene, o-chlorotoluene, chlorotoluene, dichlorotoluene, chloronaphthalene Chlorobenzene, o-chlorotoluene and dichlorobenzene are the preferredhalohvdrocarbons, with chlorobenzene and o-chlorotoluene being more preferred.
' The ~'iphatic halohydrocarbons which can be employed suitably have 1 to 12 carbon atoms. Preferably such halohydrocarbons have 1 to 9 carbon atoms and at least 2 halogen atoms. Most preferably the halogen is present as chlorine. Suitable aliphatic halohydrocarbons include dibromomethane, trichloromethane, 1,2-dichloroethane, ..,.; ., trichloroethane, dichloro~luoroethane, hexachloroethane, trichloropropane, chlorobutane, dichlorobutane, ehloropentane, trichlorofluorooctane, tetrachloroisooctane, dibromodi~
fluorodecane. The pre~erred aliphatic halohydrocar~ons are carbon tetrachloride and trichloroethane.
Aromatic halohydrocarbons arepreferred, ~articularly those Qf 6 to 12 carbon atoms, and especial~y those of 6 to lQ
carbon atoms.
~ ypical electron d~nors that are incorpoxated within the procatalyst include esters, particularly axomatic estexs, ; ethers, particularly aromatic ethers, ketones, phenols, amines, am~des, imines, nitriles, phosphines, p~osphites, stibines, arsines, phosphoramides and aleoholates. Esters of polycarboxylic acids are ~he pre~erred electron donors~
Particularly preferred ~are alkyl as~ers of aromatic polycar~oxyli~ acid Tllustrati~e of suitable esters of polycarboxylic acid electron donQrs are die~hyl phthalate, diisoamyl phthalate, ethyl p-ethoxybenzoate, methyl p-ethoxybenzoate, diisobutyl phthalate, dimethyl S
E~!J
8~ ~i 16 - .
`````!
-6~
napthalenedicarboxylate, diisobutyl maleate., diisopropyl terephthalate, a~d diisoamyl phyhalate. Diisobutyl phthalate and ethyi-p-ethoxybenzoate are the preferred alkyl ester of an aromatic carboxylic acid.
After the solid halogenated product has been separated from the liquid reaction medium, it can be treated one or more ., tlmes with a~ditional halogenated tetravalen~ titanium compound. Preferably, the halogenated product is trPated multiple times with separate portions of the halogenated tetravalent titanium compound. ~e~ter results are obtained i~
the halogenated product is treated twice with separate portions of the halogenated tetravalent titanium compound. If desired, the solid halogenated.product is treated one or more times with a mixture of halogenated tetravalent titanium compound and a halohydrocarbon. As In the initial halogenation,.,at least 2 moles of the titanium compound are generally.employed per mole .
of the magnesium compound, and preferably from 4 moles to 100 moles of the titanium compound are employed per'mole of the ~, magne~ium compound. Most preferably from 4 moles to 2Q..moles of the titanium compound 'per mole of magnesium"compound.
':'`~^. . Optionally, the solid~halogenated product is treated at least once w~th one or more acid chlorides during~the ', ad~itional treatments with the halogenated tetravalent titanium compound. Suitable acid chlorides include benzoyl chloride and phthaloyl chloride. The preferred acid chlorid,e is phtyaloyl : chloride.
After the solid halogenated product has been treated one ~r more times with additional~halo'genated tetravalent titanium compound, it is desirably separated from the liquid,,l relacti`on medium,;washed 'at least once'with~an iner~ hydlroca~bon of up to 10 carbon atoms to remove unreacted titanium compounds, and dried. Exemplary of the iner~ hydrocarbons that are suitable f~or the invent'ion are,isopentane, isooctane, hexane, heptane and cyclohexane.
~ Preferred final washed~products have a titanium content of from 0.5 percent by weight to 6,0 percent by weight.
A more preferred~final wash product has from 1.5 percent by .
; :
21~859~
` ' ' ' '-;'' weight to 4.0 percent by weight. The a~omic ratio of titanium to magnesium in the final product is between 0.01:1 and 0.2:1.
A praferred final product has an atomic ratio of titanium to magnesium from about o.02:1 to o.15:1.
The cocatalyst is an organoaluminum compound which is typically an alkyIaluminum compound. Suitable al~ylaluminum compounds include trialkylaluminum compounds, such as triethyl-aluminum or triisobutylaluminum; dialkylaluminum halides such as diethylaluminum chloride and dipropylaluminum chloride; and dialkylaluminum alkoxides such as~diethylaluminum ethoxide.
Trialkylaluminum compounds axe preferred, with triethylaluminum being the preferred trialkylaluminum compound.
The organosilane selectivity control agents in the cat~lyst system contain at least one silicon-oxygen-carbon li.nkage. Suitable organosilane compounds include co,mpounds having the following general formula~
E~ R3 4 ~ ` \ Si ' ''~
R2 / ~4 ..
wherein ~1 is a linear àlkyl-~roup of 13 to 30 carbon a~oms, . alkary.l group of 16 to 36 carbon atoms or aralkyl g~oup of 16 to 36 carbon akoms. It is pre~erred~tha~ Rl is alkyl ~roup o~
16 to 3Q carbon at~ms, al~aryl group of 19 to 3Q carbon atoms or aralkyl group of ~9 to 30 carbon atoms. It is further . 2S pre~erred that Rl is alkyl ~roup.of 1.8 to 28 carbo~ atoms. R2 and R3 are, independently, methyl or alkyl group o~ 13 to 30 carbon atoms, or hydrocarbylo ~ groups of 1 to 6 carbon atoms.
:It is preferred that R2 and R3 arej independently, methyl or alkyl group o~ 16 to 30 ca~bon atoms or alkoxy group o~ 1 to 4 ca~bon a~oms. It~:is further prefe~red that R2 is methyl or alkyl ,group of 18 to 28:c~rbon atoms or al~oxy ~roup of 1 to 4 carbon atoms and R3.is al~oxy gro~p o~ 1 to 4 carbon a~ms~ Tt is preferred that R~ is alkoxy group o~ 1 to 4 ~ax~on at~ms.
R4 is hydrocarbyloxy group of 1 ~o 6 carbon atoms. It is : 35 further preferred that R2, R3 a~d ~ are ethoxy or me~hoxy groups. Examples o~ suitable organosilane selectivity control agents inc~ude n-o~tadecyltriethoxysilane, n-triacontyl-AME~DEDSkEE~
214859fi ` ! - 8-triethoxysilane, methyl-n-octadecyldimethoxysilane, methyl-n-octadecyldiethoxysil~ne, n-octadecyltrimethoxysilane, n-triacontyltrimethoxysilanè and mixtures thereof. The preferred organosilan~a selectivity control.agents are n-.^.
octadecyltriethoxysilane, n-methyloctadecyldimethoxysilane and n-octadecyltrimethoxysilane. The in~ention also contemplates the use of mixtures of two or more selectivity control agents.
The selectivi~y co~trol agent is suitably provided in a quantity such that the molar ratio of the selecti~ity control agent to the titanium present in the procatalyst is fxom about 0.5 to..about 80. ~olar ratios from about 2 to about 60 are preferred, with molar ratios from about 5 to about 40 being more preferred.
The high acti~ity stereoregular polymerization catalyst is utilized to effect polymerization by contacting at least one -olefin under. polymerization conditions. In accordance with ~he invention, the procatalyst component, .
organoaluminum cocatalyst, and selectivity control agent are intxoduced into the polymerization reactor.~eparately or, if desîred, two or. all of the components are partialIy or completely mixed with each other ~efore they are introduced into the reactor.
The partîcular type.. of polymerizatîon process utîlized is not crîtîcal to the operation af the present inventîon and the polymerization processes now regarded as con~entional are suitable în the process of ~he inventîon. The ;~
polymerization is conducted under pol~merîzation condi~ions as a liguid phase or a: gas-phase process employing a fluidized catalyst bed.
The polymerizatîon conducted în ~he~ lîquîd~phas~
employs as reactîon diluent an added înert lî~uid diluent or alternatively a li~uid dîluent which comprises the olefint such as propylene or 1-butene, undergoing polymeriza~ion. If a ¢opolymer i~ prepared wherein ethyl~e îs one of th~ monomers, e~hylene is întroduced by conventional means to a diluent.
~ îcal polymerization conditîons înclude a reactîon temperature ~rom about 25C to about 125C, with temperatures from about 3~C to about 90C beîng preferred, and a pressure '!
AMENGED ~!EET
_J :, ,, , . ~llL85~
.. !
sufficient to maintain the reaction mixture in a li~uid phase.
Such pressures are from about 150 psi to about 1200 psi, with pressures from about 250 p~i to about 900 psi are preferred~
The liquid phase reaction is operated in a batchwise manner or .. ~ as a continuous or semi-continuous process. Subsequent to reaction, the polymer product is recovered by cGnventional procedures. The precise controls of the polymerization conditions and reaction parameters of the liquid phase process :~
are within the skill of the art.
As an alternate embodiment of the invention, the -~
polymerization is conducted in a gas phase process in the presence of a fluidized catalyst bed. One such gas phase process polymerization process is described in U.S. Patent 4,379,7S9. The gas phase process typically involves charging to reactor an amount of preformed polymer particles, gaseous monomer and separately charge a lesser amount of each catalyst component. G~seous monomer, such as propylene, ls passed through the bed of solid particles at a high rate under condit.Lons of temperature and pressure sufficient to initiate
2~ .and maintain polymerization. Unreacted olefin is separated and recovered and polymerized olefin particles are separated at a ~ rate substantially equivalent to its produ~tion. The process is conducted in a batchwise manner or a continuous or semi- ~ -continuous process wit~ constant or intermittent addition of 2S the catalyst components and/or ~-olefin to the polymerization ~` reactor. Typical~.. polymerizati~n temperatures for a g~s phase process are from about 30C to about 120C and typical pressures are up to about ~70 kg/cm2 (1000 psi), with pressures from about 7 kg/cm~ (100 psi) to about 35 kg/cm2 (500 psi) being preferred~
In;both the liquid phase and the gas-phase poly-merization processes, molesular hydrogen is added to the reaction mixture as a chain transfer agent to re~ulate the moIecular weight ~of ~hè polymeric produc~. Hy~rogen is S typically employed for this pu~pose in a manner well known ~o persons skilled in t~e artO The precise control of reaction `, 2 1 4 8 ~
. .
C
conditions, the rate of addition o~ feed component and molecular hydrogen is ~roadly within the skill of the art.
The preseIlt invention is useful in the polymerization of ~-olefins of up to 20.carbon atoms! such as ethylene, propylene, dodecane, including mixtures thereof. ~t is pre~erred that ~-ole~ins of 3 carbon atoms to 8 carbon atoms, such as propylene, buteneT1 and pentene-l and hexane-l, are polymerized.
The polymers produced according to this invention are predominantly isotactic. Polymer yields are high relative to the amount of catalyst employed. The process af the invention produce homopolymers and copolymers includ~ng both ràndom and impact copol~mers havin~ a relativel~ high stiffness while having a broad molecular weight distribution and maintaining an :~
15 ; o~igomers content (determined by the weight fraction of~
oligomer) of less than 300 ppm if a homopolymer and ~ess than 600 ppm if a copolymer.: The preferred homopolymers o~ the~
inventi~n ha~e an oliyomers content of less than lSO ppm is preferred. More preferred`homopolxmers haYe:oligomers con~ent 20 of less than 80 ppm~ A reduction in oligomers conte~t is ;:
.indicati~e of a reduction in volatiles, e.g. smoke and/or oil, ~: liberated d~rin~ subsequent processing, e.g. extrus~on Other eatures, ad~antages and embodi~ents of the ~i:nvention disclosed herein will~be readily apparent to those ; 25 exercising ordinary ~.skill after reading the foregoing ~:
disclosure. In ~his regard, while specific e~ odiments o~ ~he invention have~ ~een described in :detail, ~ariations - and modifica~ions of~:~these~embodiments can be effected without departing from the spirit and scope of the invention as:
descr~bed and~dlaimed.
The inve~tion described herein is illustratedl bu~
not~ limited by ~he :~fol~owing~Illustrative~ Emb~diments and Comparative EY~mple. :The ~ollowinq te~ms are;~sed t~roughout the Illustrative Embodiments and Comparative Example:
35 : ODTM5~ (n-octadecyltrimethoxysilane) ODTES (n-octa~ecyltriethoxysilane~
DNDDMS tdi-n-decyldimethoxysilane) DDTMS (n-dodec::yltrimethoxysilane~
CTMS~(n-triacontyltrimethoxysilane~
AMEND~D SHEE~
~ 1 4 ~
MNDD~S (methyl~n-decyldimethoxysilane) MODD~S ~methyl-n-octadecyldiethoxysilane) PEEB tethyl-p-ethoxybenzoate) NP~MS (n-propyl~rimethoxysilane) S DIBDES (diisobutyldiethoxysilane) .
DIBDMS (diisobutyldimethoxysilane).
ILLUSTRATIVE EMBODXMENT I
(a) Preparation of Procatalyst Component The procatalyst ~as prep~red by adding magnesium diethoxide (2.17 gl 19 mmol) to 5S ml of a 50/50 (vol/vol) mixture of TiCl4/chlorobenzene. A~ter adding diisobutyl " .. . . .. .
phthalate (0.74 ml, 2.75 mmol), the mixture was heated in an oil bath and stirred at 110C.for 60 minutes. The mixture was filtered hot and the solid portion was slurried in 55 ml o~- a 50/SO (vol/vol) mixture of TiCl~/chlorobenzene~ In the preparation of some o~ the procatalyst, phthaloyl chloride :
(0.13 ml, O.90 mmol) was added to the slurry at room ;
temperature. The resulting slurry was stirred at 110C for 60 - minutes, filtered, and~the solvent obtained was slurried again . 20 in a fre~h ~ 50 mixtur~. of TiCl4/chlorobenzene. Af~er : stirring at 110~ for 30 minutes, th~ mixture was filtered and allowed to cool to.room temperature. The procatalyst slurry -, was washed 6 times with 125 ml portions of isooctane and ~hen dried for 120 minu~es, at 25'C, under nitrogen.
2S ~ ) Polymerization of Propylene .` ~`
: Various catalysts were produced using several organosilanes as the selecti~ity control agent, some of which axe withln the scope of the invention (TCTMS, ODTES, ODTMS, and MODDES) :and other hat are not within the scope o~ the .3Q i~vention (NPT~S~ DNDDMS, DIBDES, DDTMS, MNDD~S and DIBDMS)..
Propylene (2iooc~) and molecular hydrogen were introduced lnto a 1 gallon autocla~e.~ The temperature~ o~ the propylene and . molecular hydrogen was raised~ to 67Co ~n organosilane selectivity con~roi agent, triethylaluminum, and the :
35 ~ pro~atalyst clurry producPd above we~e:premixed for about 20 minutes and then the mixture was introduced into the autoc~aYe.
: The amount of silane utilized~ in ~he polymerization also va~_ed. The amount of triethylaluminum (0.70 mmoles) and the amount of the~ procatalyst slurry (sufficient quantity of .
A~Vlr~lG~3 S`-IEET
: ~ - 214~5g6 `. ~
procatalyst to provide o~Ol mmoles of titanium) remained constant. The autocla~e was then heated to about 67C and the polymerization was continued at 67C for one hour. The polypropylene product was recovered from the resulting mixture S by conventional methods~a~d the weight of the product was used to calculate the reaction yield in millions of grams of poIymer product per gram (MMg/g3 of titanium in the procatal~st. The term IIQI~ was calcu7 ated as the quotient of the weight average molecular ~eight ~Mw) and the number a~erage molecular weight (~), determined by gel permeation chromatography. The term "~" as defined in "Encyclopedia of Polymer Science and Engineering, 2nd Edition", Vol. lO, pp. 1-19 (1987~, incorporated herein by reference, is the z-average molecula~
weight. The term "X" was calculated as the quotient of ~ and Mw~ "Melt Flow" is determined according to ASTM D-1238-73, condition L. "Viscosity Ratio"~was determined ~by cone and plate rheome~ry ~dynamic viscosity me~s~rements) as a ratio of ... . . .
the viscosi~y of the pr~oduct at;a~frequency of 0.1 H~ divided by the. viscosity o~ th~e product at a frequency of 1.0 Hz. As q 20 the viscosity ratio of~polymer product in~reases, the molecular weight distribution increases.
The results of a series of polymerizations are shown in T~BLE
I `' ~
:
t :
... ... .. .. . .. . ..
~ 2 ~L 4 ~ 5 9 ~ O ul ~, n ~ 3 , 3 ~ ~ ~ w w , 3 I' I~ r~ ~ ~n o t-t Xl ~ O O O O o ~ O O O O Q O O O O O
1~ o o ~ J o t~ o o ~ t~ ~--Ul ~ ~ ~U~ ,p Ul ~ U~ Ul C~ ~1 ~ -CO W Ul O :.-P.~ P) 11 0 It It ~ '' tD tD -`~ '-~ ~ ,............ ~
`' Y ~ ~ ~ )-' '~ 1~ 1' ~ W N ~ t`~ ~ ~ W 1 . o ~ 1 `J ~ ~ W ~i W W W ~ ~1 ~D '.
o ~ . . U~, ,' '.
~ ~ ~ . . ~
O Op~ ' O o ~, r o t~ ) w ~ ~~ w )~ 1 3 ~
o ~ 3 't O ~ ~ :
W o W~ ~~ W' CO ~ ~ VS l~l ~, : H
` ~D ,.
W ~ ~ Co ~' ~ ~ O ~ ~ O ~ ~ ~ W ~ W ~ g ,~
~ ' ~ , .~..... .
t~ O C~ D ~ wG~ Ul ~ O Ul -C:) OOOOOO~OOOOOOOOOO O , -:
o ~ ~ o ~ ~ ~ ~ ~ ~ ~ ~~ `~ ~ ~ ~ ~ 10 ,p D ~ ~ O ~ I~ '~ n ~ w o ~ ~
c ~ o O O ~ ~t A ~ r n c~ u r ~T
-~ 214~59~- :
ComParative ExamPle (a) Preparation of Procatalyst Component The procatalyst was prepared by adding magnesium diethoxide (50 mmo~) to 150 ml of a 50/50 ~vol/vol) mixture of chlorobenzene/TiCl4. After addiIlg ethyl benzoate ~16.7 mmol), the mixture was heated in an oil ~ath and stirred at llQC for approximately 60 minutes... The resulting slurry was filtered i and slurried twice with 150 ml of a fresh 50/50 (vol/vol).
Benzoyl chlor-de (0.:4 mlj was added to the ~inal slurry. After stirring at 110C for approximately 30 minutes, the mixture was filtered. The slurry was washed six times with 150 ml portions of isopentane and then dried for~ 90 minutes, at 30C, under nitrogen.
(b) Polymerization -.
Using the above-described procatalyst (section a), propylene was polymerized as described in Illustrative Embodiment I, section (b), except the selectivity control agent was PEEB.
~- Illus~rative Embodiment II
20 ~ To illustrate a further advantage of ~he~catalyst system of the invention, polymer products havi~g a melt flow of ~; a~'~ut 3.0 dg/min were produced according to the procedures described in Illustrative Embodiment I and the Comparative Example. In particuIar r the polymer products were~ produced 2S using 0.2 mmol of the speci~ied selectivity control agent ("SCA'I) and sufficient hydrogen necessary to produce a polymer having a melt flow of about.3.0 dg/min. The values are shown . in:T~BLE II. ~ . ;
-:~ :
. . !
, ,;
' 14 `:
' :
~ ~ .
A~.i;E;11'3~E.T ~-~:``!; 2148~6 . .
TABLE II
SCAI mmol of H2 Required4 T~ 2 TCTMS ~ ~8 ODTMS : : ~20 DDTMS 22 `
DNDDMS 29 ~`
0.2 ~mol of each selectivity control agent was used.
~ For comparison 15 . : 3 Comparative Example : . ................................... ` :
- 4 mmol of H2 required to make a polymer product having a melt flow of about 3 dg/min .
: As noted, the catalyst systems of the invention .
exhibit increased hydrogen utilization e~ficiency.
Illustrativ~ Embodiment III ~ :
Viscosity ratio values were~taken for the pol~mers ~ having a melt flow~o~ about 3 dg/min.~ The values are shown in `; ~ TABLE`I I. : : :
~ : Table III
: 25 ~CA . ~_iscosit~ ~atio MODDES ~ .85~
` . :TCrMS : `-- . 1.80`.
: :~ :ODTES ~ : ' 10 7 ~ -: ` : ODZ~MS ~ ~ 1.60 ... 30~ DNDDMS : ~ ~ 1.62 MN~ ,60 NP~MSI ~ 1.58 For comparison It is seen f ~om: TABLE III ~hat th~ catalyst sys~ems ~of;the inventlon exhi~it a higher viscosity ratio and therefore 2 1~ 8 ~ ~ ~
a broader molecular weight distribution than conventional cat~lyst systems using NPTMS as the selectivity control agent.
, . ~ ,.
-;
~t :`' ., ~ ' ~ .. . , . j,,~, .s.
`~
`
:
.,-.,' A ~ U ~ ~T
In;both the liquid phase and the gas-phase poly-merization processes, molesular hydrogen is added to the reaction mixture as a chain transfer agent to re~ulate the moIecular weight ~of ~hè polymeric produc~. Hy~rogen is S typically employed for this pu~pose in a manner well known ~o persons skilled in t~e artO The precise control of reaction `, 2 1 4 8 ~
. .
C
conditions, the rate of addition o~ feed component and molecular hydrogen is ~roadly within the skill of the art.
The preseIlt invention is useful in the polymerization of ~-olefins of up to 20.carbon atoms! such as ethylene, propylene, dodecane, including mixtures thereof. ~t is pre~erred that ~-ole~ins of 3 carbon atoms to 8 carbon atoms, such as propylene, buteneT1 and pentene-l and hexane-l, are polymerized.
The polymers produced according to this invention are predominantly isotactic. Polymer yields are high relative to the amount of catalyst employed. The process af the invention produce homopolymers and copolymers includ~ng both ràndom and impact copol~mers havin~ a relativel~ high stiffness while having a broad molecular weight distribution and maintaining an :~
15 ; o~igomers content (determined by the weight fraction of~
oligomer) of less than 300 ppm if a homopolymer and ~ess than 600 ppm if a copolymer.: The preferred homopolymers o~ the~
inventi~n ha~e an oliyomers content of less than lSO ppm is preferred. More preferred`homopolxmers haYe:oligomers con~ent 20 of less than 80 ppm~ A reduction in oligomers conte~t is ;:
.indicati~e of a reduction in volatiles, e.g. smoke and/or oil, ~: liberated d~rin~ subsequent processing, e.g. extrus~on Other eatures, ad~antages and embodi~ents of the ~i:nvention disclosed herein will~be readily apparent to those ; 25 exercising ordinary ~.skill after reading the foregoing ~:
disclosure. In ~his regard, while specific e~ odiments o~ ~he invention have~ ~een described in :detail, ~ariations - and modifica~ions of~:~these~embodiments can be effected without departing from the spirit and scope of the invention as:
descr~bed and~dlaimed.
The inve~tion described herein is illustratedl bu~
not~ limited by ~he :~fol~owing~Illustrative~ Emb~diments and Comparative EY~mple. :The ~ollowinq te~ms are;~sed t~roughout the Illustrative Embodiments and Comparative Example:
35 : ODTM5~ (n-octadecyltrimethoxysilane) ODTES (n-octa~ecyltriethoxysilane~
DNDDMS tdi-n-decyldimethoxysilane) DDTMS (n-dodec::yltrimethoxysilane~
CTMS~(n-triacontyltrimethoxysilane~
AMEND~D SHEE~
~ 1 4 ~
MNDD~S (methyl~n-decyldimethoxysilane) MODD~S ~methyl-n-octadecyldiethoxysilane) PEEB tethyl-p-ethoxybenzoate) NP~MS (n-propyl~rimethoxysilane) S DIBDES (diisobutyldiethoxysilane) .
DIBDMS (diisobutyldimethoxysilane).
ILLUSTRATIVE EMBODXMENT I
(a) Preparation of Procatalyst Component The procatalyst ~as prep~red by adding magnesium diethoxide (2.17 gl 19 mmol) to 5S ml of a 50/50 (vol/vol) mixture of TiCl4/chlorobenzene. A~ter adding diisobutyl " .. . . .. .
phthalate (0.74 ml, 2.75 mmol), the mixture was heated in an oil bath and stirred at 110C.for 60 minutes. The mixture was filtered hot and the solid portion was slurried in 55 ml o~- a 50/SO (vol/vol) mixture of TiCl~/chlorobenzene~ In the preparation of some o~ the procatalyst, phthaloyl chloride :
(0.13 ml, O.90 mmol) was added to the slurry at room ;
temperature. The resulting slurry was stirred at 110C for 60 - minutes, filtered, and~the solvent obtained was slurried again . 20 in a fre~h ~ 50 mixtur~. of TiCl4/chlorobenzene. Af~er : stirring at 110~ for 30 minutes, th~ mixture was filtered and allowed to cool to.room temperature. The procatalyst slurry -, was washed 6 times with 125 ml portions of isooctane and ~hen dried for 120 minu~es, at 25'C, under nitrogen.
2S ~ ) Polymerization of Propylene .` ~`
: Various catalysts were produced using several organosilanes as the selecti~ity control agent, some of which axe withln the scope of the invention (TCTMS, ODTES, ODTMS, and MODDES) :and other hat are not within the scope o~ the .3Q i~vention (NPT~S~ DNDDMS, DIBDES, DDTMS, MNDD~S and DIBDMS)..
Propylene (2iooc~) and molecular hydrogen were introduced lnto a 1 gallon autocla~e.~ The temperature~ o~ the propylene and . molecular hydrogen was raised~ to 67Co ~n organosilane selectivity con~roi agent, triethylaluminum, and the :
35 ~ pro~atalyst clurry producPd above we~e:premixed for about 20 minutes and then the mixture was introduced into the autoc~aYe.
: The amount of silane utilized~ in ~he polymerization also va~_ed. The amount of triethylaluminum (0.70 mmoles) and the amount of the~ procatalyst slurry (sufficient quantity of .
A~Vlr~lG~3 S`-IEET
: ~ - 214~5g6 `. ~
procatalyst to provide o~Ol mmoles of titanium) remained constant. The autocla~e was then heated to about 67C and the polymerization was continued at 67C for one hour. The polypropylene product was recovered from the resulting mixture S by conventional methods~a~d the weight of the product was used to calculate the reaction yield in millions of grams of poIymer product per gram (MMg/g3 of titanium in the procatal~st. The term IIQI~ was calcu7 ated as the quotient of the weight average molecular ~eight ~Mw) and the number a~erage molecular weight (~), determined by gel permeation chromatography. The term "~" as defined in "Encyclopedia of Polymer Science and Engineering, 2nd Edition", Vol. lO, pp. 1-19 (1987~, incorporated herein by reference, is the z-average molecula~
weight. The term "X" was calculated as the quotient of ~ and Mw~ "Melt Flow" is determined according to ASTM D-1238-73, condition L. "Viscosity Ratio"~was determined ~by cone and plate rheome~ry ~dynamic viscosity me~s~rements) as a ratio of ... . . .
the viscosi~y of the pr~oduct at;a~frequency of 0.1 H~ divided by the. viscosity o~ th~e product at a frequency of 1.0 Hz. As q 20 the viscosity ratio of~polymer product in~reases, the molecular weight distribution increases.
The results of a series of polymerizations are shown in T~BLE
I `' ~
:
t :
... ... .. .. . .. . ..
~ 2 ~L 4 ~ 5 9 ~ O ul ~, n ~ 3 , 3 ~ ~ ~ w w , 3 I' I~ r~ ~ ~n o t-t Xl ~ O O O O o ~ O O O O Q O O O O O
1~ o o ~ J o t~ o o ~ t~ ~--Ul ~ ~ ~U~ ,p Ul ~ U~ Ul C~ ~1 ~ -CO W Ul O :.-P.~ P) 11 0 It It ~ '' tD tD -`~ '-~ ~ ,............ ~
`' Y ~ ~ ~ )-' '~ 1~ 1' ~ W N ~ t`~ ~ ~ W 1 . o ~ 1 `J ~ ~ W ~i W W W ~ ~1 ~D '.
o ~ . . U~, ,' '.
~ ~ ~ . . ~
O Op~ ' O o ~, r o t~ ) w ~ ~~ w )~ 1 3 ~
o ~ 3 't O ~ ~ :
W o W~ ~~ W' CO ~ ~ VS l~l ~, : H
` ~D ,.
W ~ ~ Co ~' ~ ~ O ~ ~ O ~ ~ ~ W ~ W ~ g ,~
~ ' ~ , .~..... .
t~ O C~ D ~ wG~ Ul ~ O Ul -C:) OOOOOO~OOOOOOOOOO O , -:
o ~ ~ o ~ ~ ~ ~ ~ ~ ~ ~~ `~ ~ ~ ~ ~ 10 ,p D ~ ~ O ~ I~ '~ n ~ w o ~ ~
c ~ o O O ~ ~t A ~ r n c~ u r ~T
-~ 214~59~- :
ComParative ExamPle (a) Preparation of Procatalyst Component The procatalyst was prepared by adding magnesium diethoxide (50 mmo~) to 150 ml of a 50/50 ~vol/vol) mixture of chlorobenzene/TiCl4. After addiIlg ethyl benzoate ~16.7 mmol), the mixture was heated in an oil ~ath and stirred at llQC for approximately 60 minutes... The resulting slurry was filtered i and slurried twice with 150 ml of a fresh 50/50 (vol/vol).
Benzoyl chlor-de (0.:4 mlj was added to the ~inal slurry. After stirring at 110C for approximately 30 minutes, the mixture was filtered. The slurry was washed six times with 150 ml portions of isopentane and then dried for~ 90 minutes, at 30C, under nitrogen.
(b) Polymerization -.
Using the above-described procatalyst (section a), propylene was polymerized as described in Illustrative Embodiment I, section (b), except the selectivity control agent was PEEB.
~- Illus~rative Embodiment II
20 ~ To illustrate a further advantage of ~he~catalyst system of the invention, polymer products havi~g a melt flow of ~; a~'~ut 3.0 dg/min were produced according to the procedures described in Illustrative Embodiment I and the Comparative Example. In particuIar r the polymer products were~ produced 2S using 0.2 mmol of the speci~ied selectivity control agent ("SCA'I) and sufficient hydrogen necessary to produce a polymer having a melt flow of about.3.0 dg/min. The values are shown . in:T~BLE II. ~ . ;
-:~ :
. . !
, ,;
' 14 `:
' :
~ ~ .
A~.i;E;11'3~E.T ~-~:``!; 2148~6 . .
TABLE II
SCAI mmol of H2 Required4 T~ 2 TCTMS ~ ~8 ODTMS : : ~20 DDTMS 22 `
DNDDMS 29 ~`
0.2 ~mol of each selectivity control agent was used.
~ For comparison 15 . : 3 Comparative Example : . ................................... ` :
- 4 mmol of H2 required to make a polymer product having a melt flow of about 3 dg/min .
: As noted, the catalyst systems of the invention .
exhibit increased hydrogen utilization e~ficiency.
Illustrativ~ Embodiment III ~ :
Viscosity ratio values were~taken for the pol~mers ~ having a melt flow~o~ about 3 dg/min.~ The values are shown in `; ~ TABLE`I I. : : :
~ : Table III
: 25 ~CA . ~_iscosit~ ~atio MODDES ~ .85~
` . :TCrMS : `-- . 1.80`.
: :~ :ODTES ~ : ' 10 7 ~ -: ` : ODZ~MS ~ ~ 1.60 ... 30~ DNDDMS : ~ ~ 1.62 MN~ ,60 NP~MSI ~ 1.58 For comparison It is seen f ~om: TABLE III ~hat th~ catalyst sys~ems ~of;the inventlon exhi~it a higher viscosity ratio and therefore 2 1~ 8 ~ ~ ~
a broader molecular weight distribution than conventional cat~lyst systems using NPTMS as the selectivity control agent.
, . ~ ,.
-;
~t :`' ., ~ ' ~ .. . , . j,,~, .s.
`~
`
:
.,-.,' A ~ U ~ ~T
Claims (17)
1. A process for polymerizing one or more .alpha.-olefins of up to 20 carbon atoms which comprises contacting the one or more .alpha.-olefins under polymerization conditions with a catalyst system comprising:
(a) a magnesium halide-containing procatalyst component containing magnesium, titanium and halide, said procatalyst component being obtained by halogenating a magnesium compound of the formula MgR'R'', wherein R' is an alkoxide group aryloxy group or a hydrocarbyl carbonate group and R'' is an alkoxide group, an aryloxy group, a hydrocarbyl carbonate group or a halogen with a halogenated tetravalent titanium compound containing 2 to 4 halogen atoms, in the presence of a halohydrocarbon and an electron donor;
(b) an organoaluminum cocatalyst component; and (c) an organosilane selectivity control agent having the formula:
wherein R1 is an alkyl group of 13 to 30 carbon atoms, alkaryl group of 16 to 36 atoms; R2 and R3 are, independently, methyl or alkyl group of 13 to 30 carbon atoms or hydrocarbyloxy group of 1 to 6 carbon atoms; and R4 is a hydrocarbyloxy group of 1 to 6 carbon atoms.
(a) a magnesium halide-containing procatalyst component containing magnesium, titanium and halide, said procatalyst component being obtained by halogenating a magnesium compound of the formula MgR'R'', wherein R' is an alkoxide group aryloxy group or a hydrocarbyl carbonate group and R'' is an alkoxide group, an aryloxy group, a hydrocarbyl carbonate group or a halogen with a halogenated tetravalent titanium compound containing 2 to 4 halogen atoms, in the presence of a halohydrocarbon and an electron donor;
(b) an organoaluminum cocatalyst component; and (c) an organosilane selectivity control agent having the formula:
wherein R1 is an alkyl group of 13 to 30 carbon atoms, alkaryl group of 16 to 36 atoms; R2 and R3 are, independently, methyl or alkyl group of 13 to 30 carbon atoms or hydrocarbyloxy group of 1 to 6 carbon atoms; and R4 is a hydrocarbyloxy group of 1 to 6 carbon atoms.
2. A process according to claim 1, wherein said organosilane selectivity control agent is present in a quantity such that the molar ratio of the selectivity control agent to titanium present in the procatalyst component is from about 0.5 to about 80.
3. A process according to claim 1 or 2 wherein R1 is an alkyl group of 16 to 30 carbon atoms, an alkaryl group of 19 to 30 carbon atoms or an aralkyl group of 19 to 30 carbon atoms; R2 and R3 are, independently, methyl or alkyl group of 16 to 30 carbon atoms or alkoxy group of 1 to 4 carbon atoms, and R4 is alkoxy group of 1 to 4 carbon atoms.
4. A process according to claim 3 wherein R3 and R4 are alkoxy groups of 1 or 2 carbon atoms.
5. A process according to any one of claims 1 to 4, wherein the organosilane selectivity control agent is n-octadecyltriethoxysilane, n-octadecyltrimethoxysilane, n-triacontyltrimethoxysilane, n-tricontyltriethoxysilane, methyl-n-octadecyldimethoxysilane, methyl-n-octadecyldiethoxysilane or a mixture thereof.
6. A process according to any one of claims 1 to 5 wherein the organosilane is n-octadecyltrimethyoxysilane, n-octadecyltriethoxysilane, methyl-n-octadecyldiethoxysilane or methyl-n-octadecyldimethoxysilane.
7. A process according to any one of claims 1 to 6, wherein the halogenated tetravalent titanium compound is titanium tetrachloride.
8. A process according to any one of claims 1 to 7 wherein R' and R'' are alkoxy groups of 1 to 10 carbon atoms.
9. A process according to claim 8, wherein the magnesium compound is magnesium diethoxide.
10. A process according to any one of claims 1 to 9 wherein the electron donor is an ester or ether.
11. A process according to claim 10 wherein the electron donor is a polycarboxylic acid ester.
12. A process according to claim 11 wherein the polycarboxylic acid ester electron donor is diisobutyl phthalate.
13. A process according to any one of claims 1 to 12, wherein the .alpha.-olefln is propylene and/or ethylene.
14. An olefin polymerization catalyst system comprising:
(a) a magnesium halide-containing procatalyst component obtained by halogenating a magnesium compound of formula MyR'R'' as defined in claim 1 with a halogenated tetravalent titanium compound, in the presence of an electron donor and a halogenated hydrocarbon, (b) an organoaluminum cocatalyst component, and (c) an organosilane selectivity control agent having the formula as defined in claim 1.
(a) a magnesium halide-containing procatalyst component obtained by halogenating a magnesium compound of formula MyR'R'' as defined in claim 1 with a halogenated tetravalent titanium compound, in the presence of an electron donor and a halogenated hydrocarbon, (b) an organoaluminum cocatalyst component, and (c) an organosilane selectivity control agent having the formula as defined in claim 1.
15. An olefin polymerization catalyst system according to claim 14, wherein the molar ratio of the selectivity control agent to the titanium present in the procatalyst is from about 0.5 to about 80.
16. An olefin polymerization catalyst system according to claim 14 or 15, wherein the magnesium compound is magnesium alkoxide, the halogenated tetravalent titanium compound contains four halogen atoms and the organoaluminum cocatalyst is a trialkylaluminum compound.
17. An olefin polymerization catalyst system according to claim 14 or 15, wherein the magnesium compound is magnesium diethoxide, the electron donor is diisobutyl phthalate, and the halohydrocarbon is chlorobenzene or o-chlorotoluene.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US97240292A | 1992-11-06 | 1992-11-06 | |
| US972,402 | 1992-11-06 | ||
| PCT/US1993/010653 WO1994011409A1 (en) | 1992-11-06 | 1993-11-05 | Process for polymerizing alpha-olefin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2148596A1 true CA2148596A1 (en) | 1994-05-26 |
Family
ID=25519617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002148596A Abandoned CA2148596A1 (en) | 1992-11-06 | 1993-11-05 | Process for polymerizing alpha-olefin |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0667875A1 (en) |
| KR (1) | KR950704372A (en) |
| CN (1) | CN1092431A (en) |
| AU (1) | AU5458394A (en) |
| BR (1) | BR9307390A (en) |
| CA (1) | CA2148596A1 (en) |
| MX (1) | MX9306919A (en) |
| WO (1) | WO1994011409A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU706739B2 (en) * | 1994-05-12 | 1999-06-24 | Showa Denko Kabushiki Kaisha | A method for the production of propylene-based polymers, catalyst component or polymerization and method for its production |
| KR100502370B1 (en) * | 2000-09-29 | 2005-07-19 | 도호 티타늄 가부시키가이샤 | Catalyst for olefin polymerization |
| DE60335459D1 (en) | 2002-04-24 | 2011-02-03 | Symyx Solutions Inc | BROKEN BI-AROMATIC LIGANDS, COMPLEXES, CATALYSTS, POLYMERIZATION METHODS, AND POLYMERS |
| US7091292B2 (en) | 2002-04-24 | 2006-08-15 | Symyx Technologies, Inc. | Bridged bi-aromatic catalysts, complexes, and methods of using the same |
| US7060848B2 (en) | 2002-04-24 | 2006-06-13 | Symyx Technologies, Inc. | Bridged bi-aromatic catalysts, complexes, and methods of using the same |
| CN1955195B (en) * | 2005-10-26 | 2010-06-16 | 中国石油化工股份有限公司 | Catalyst, preparation method and application for olefin polymerization or copolymerization |
| US20100121010A1 (en) * | 2007-05-22 | 2010-05-13 | Borealis Technology Oy | Catalyst system for polypropylene copolymers |
| BR112012009515A2 (en) * | 2009-10-22 | 2017-02-21 | Basell Polyolefine Gmbh | "catalytic components for the polymerization of olefins and catalysts obtained therefrom" |
| CN102898558B (en) * | 2011-07-26 | 2015-06-17 | 中国石油化工股份有限公司 | Application of catalyst component in olefin polymerization |
| CN102898557B (en) * | 2011-07-26 | 2015-06-17 | 中国石油化工股份有限公司 | Application of catalyst component in olefin polymerization |
| CN102898555B (en) * | 2011-07-26 | 2015-06-17 | 中国石油化工股份有限公司 | Application of catalyst component in olefin polymerization |
| CN102898556B (en) * | 2011-07-26 | 2015-06-17 | 中国石油化工股份有限公司 | Application of catalyst component in olefin polymerization |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2143834B (en) * | 1983-07-20 | 1987-06-03 | Toho Titanium Co Ltd | Polymerization catalyst |
| JPH06104693B2 (en) * | 1986-01-06 | 1994-12-21 | 東邦チタニウム株式会社 | Catalyst for olefin polymerization |
| CA1310955C (en) * | 1987-03-13 | 1992-12-01 | Mamoru Kioka | Process for polymerization of olefins and polymerization catalyst |
-
1993
- 1993-11-05 BR BR9307390-9A patent/BR9307390A/en not_active Application Discontinuation
- 1993-11-05 KR KR1019950701794A patent/KR950704372A/en not_active Application Discontinuation
- 1993-11-05 EP EP93925170A patent/EP0667875A1/en not_active Ceased
- 1993-11-05 CA CA002148596A patent/CA2148596A1/en not_active Abandoned
- 1993-11-05 MX MX9306919A patent/MX9306919A/en unknown
- 1993-11-05 WO PCT/US1993/010653 patent/WO1994011409A1/en not_active Application Discontinuation
- 1993-11-05 AU AU54583/94A patent/AU5458394A/en not_active Abandoned
- 1993-11-06 CN CN93112706A patent/CN1092431A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN1092431A (en) | 1994-09-21 |
| WO1994011409A1 (en) | 1994-05-26 |
| MX9306919A (en) | 1995-01-31 |
| KR950704372A (en) | 1995-11-20 |
| AU5458394A (en) | 1994-06-08 |
| EP0667875A1 (en) | 1995-08-23 |
| BR9307390A (en) | 1999-08-31 |
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