CA2118711A1 - Preparation of polypropylene under high pressure - Google Patents
Preparation of polypropylene under high pressureInfo
- Publication number
- CA2118711A1 CA2118711A1 CA002118711A CA2118711A CA2118711A1 CA 2118711 A1 CA2118711 A1 CA 2118711A1 CA 002118711 A CA002118711 A CA 002118711A CA 2118711 A CA2118711 A CA 2118711A CA 2118711 A1 CA2118711 A1 CA 2118711A1
- Authority
- CA
- Canada
- Prior art keywords
- alkyl
- aryl
- cycloalkyl
- propylene
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- 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
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—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
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
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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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A process is disclosed for producing homopolymers of propylene or copolymers of propylene with other olefins or their mixtures.
Polymerisation is carried out under pressures from 100 to 3000 bars and at temperatures from 100 to 330· C, using as catalyst a metallocene catalyst system.
Polymerisation is carried out under pressures from 100 to 3000 bars and at temperatures from 100 to 330· C, using as catalyst a metallocene catalyst system.
Description
2 1 1 S 7 1 1 o.z. 0050/42666 --Preparation of polypropylene under hiqh pressure The present invention relates to a process for the preparation of homopolymers of propylene or copoly-mers of propylene with other olefins or mixtures thereof.
s Processes for the preparation of homo- and/or copolymers of propylene at low pressures and with the use of Ziegler catalyst systems are disclosed in, for ex-ample, EP-A 351 392 and EP-A 321 852. However, hetero-geneous systems are present, the productivities are unsatisfactory and the choice of comonomers is lLmited.
It is an object of the present invention to proYide a process for the preparation of homo- and/or copolymers of propylene which does not have the stated disadvantages.
We have found that this o~ject is achieved by a process for the preparation of homopolymers of propylene or copolymers of propylene with other olefins or mixture~
thereof, wherein polymerization is carried out at from 100 to 3000 bar and at from 100 to 330C and the catalyst used is a metallocene catalyst system.
These processes gi~e linear homopolymers with propylene or linear copolymers which have short chain branche~
Cyclic olefins of 3 to 12, preferably 4 to 8, carbon atom~, dienes, in particular ~ dienes of 4 to 10 carbon atoms, 3uch as hexa-1,5-diene, and olefins of 2 to 10 carbon atom~, preferably ethylene, butenes and hexenes~ have proven suitable as olsfins which can be copolymerized with propylene, the ~-olefins being par-ticularly preferred. These olefins may also have aryl or hetero element substituents, such as styrene or un-saturated substituted silanes.
As a rule, these comonomers are used in amounts of from 0.1 to 99.9~ preferably from 1 to 99 t ~ by weight, based on the amount of propylene.
The catalysts used are metallocene catalyst systems which contain, among the actiYe components, a 21~8~11 - 2 - o.Z. 0050/42666 complex of metals of subgroups IV and V of the Periodic Table, in particular of titanium, zirconium, hafnium, vanadium, niobium or tantalum. Preferably used complexes are those in which the metal atom is bonded via ~ ~onds to unsaturated cyclic hydrocarbon atoms, for example cyclopentadienyl, fluorenyl or indenyl group3. Further-more, in the preferably used complexes, the metal atom may also be bonded to further ligand~, in particular to fluorine, chlorine, bromine and iodine or to Cl-C1O-alkyl, for example methyl, ethyl, propyl or butyl. Particularly suitable complexes contain in particular chlorine.
Preferred metallocene catalyst systems contain, as active components, a) a metallocene complex of the general formula I
~4 ~
z where M is titanium, zirconium, hafnium, vanadium, niobium or tantalum, X i~ fluorinQ, chlorine, bromine, iodin~, hydrogen, C1-C1O-alkyl, C6-Cl5-aryl or -oR6, R6 is Cl-C1O-alkyl, C6-Cls-aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl, each having from 1 to lO
car~on atoms in the al~yl radical and 6 to 20 carbon atoms in the aryl radical, Rl to R5 are each hydrogen, Cl-C1O-alkyl, 5-membered to 7-membered cycloalkyl which in turn may carry a Cl-C6-alkyl radical as a substituent, C6-Cl5-aryl or arylalkyl, where two ad~acent radicals together may furthermore form unsaturated cyclic groups of 4 to 15 carbon atoms, or Si(R7)3, R7 is Cl-C~-alkyl, C6-Cl5-aryl or C3-C10-cycloalkyl, :, 21~711
s Processes for the preparation of homo- and/or copolymers of propylene at low pressures and with the use of Ziegler catalyst systems are disclosed in, for ex-ample, EP-A 351 392 and EP-A 321 852. However, hetero-geneous systems are present, the productivities are unsatisfactory and the choice of comonomers is lLmited.
It is an object of the present invention to proYide a process for the preparation of homo- and/or copolymers of propylene which does not have the stated disadvantages.
We have found that this o~ject is achieved by a process for the preparation of homopolymers of propylene or copolymers of propylene with other olefins or mixture~
thereof, wherein polymerization is carried out at from 100 to 3000 bar and at from 100 to 330C and the catalyst used is a metallocene catalyst system.
These processes gi~e linear homopolymers with propylene or linear copolymers which have short chain branche~
Cyclic olefins of 3 to 12, preferably 4 to 8, carbon atom~, dienes, in particular ~ dienes of 4 to 10 carbon atoms, 3uch as hexa-1,5-diene, and olefins of 2 to 10 carbon atom~, preferably ethylene, butenes and hexenes~ have proven suitable as olsfins which can be copolymerized with propylene, the ~-olefins being par-ticularly preferred. These olefins may also have aryl or hetero element substituents, such as styrene or un-saturated substituted silanes.
As a rule, these comonomers are used in amounts of from 0.1 to 99.9~ preferably from 1 to 99 t ~ by weight, based on the amount of propylene.
The catalysts used are metallocene catalyst systems which contain, among the actiYe components, a 21~8~11 - 2 - o.Z. 0050/42666 complex of metals of subgroups IV and V of the Periodic Table, in particular of titanium, zirconium, hafnium, vanadium, niobium or tantalum. Preferably used complexes are those in which the metal atom is bonded via ~ ~onds to unsaturated cyclic hydrocarbon atoms, for example cyclopentadienyl, fluorenyl or indenyl group3. Further-more, in the preferably used complexes, the metal atom may also be bonded to further ligand~, in particular to fluorine, chlorine, bromine and iodine or to Cl-C1O-alkyl, for example methyl, ethyl, propyl or butyl. Particularly suitable complexes contain in particular chlorine.
Preferred metallocene catalyst systems contain, as active components, a) a metallocene complex of the general formula I
~4 ~
z where M is titanium, zirconium, hafnium, vanadium, niobium or tantalum, X i~ fluorinQ, chlorine, bromine, iodin~, hydrogen, C1-C1O-alkyl, C6-Cl5-aryl or -oR6, R6 is Cl-C1O-alkyl, C6-Cls-aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl, each having from 1 to lO
car~on atoms in the al~yl radical and 6 to 20 carbon atoms in the aryl radical, Rl to R5 are each hydrogen, Cl-C1O-alkyl, 5-membered to 7-membered cycloalkyl which in turn may carry a Cl-C6-alkyl radical as a substituent, C6-Cl5-aryl or arylalkyl, where two ad~acent radicals together may furthermore form unsaturated cyclic groups of 4 to 15 carbon atoms, or Si(R7)3, R7 is Cl-C~-alkyl, C6-Cl5-aryl or C3-C10-cycloalkyl, :, 21~711
- 3 - O.Z. 0050/42666 _-- R12 ::
Z is X or R11 ~ R~ ~
Rlo R9 .:
Ra to Rl2 are each hydrogen, Cl-C1O-alkyl, 5-membered to 7-membered cycloalkyl which in turn may carry a Cl-C1O-alkyl radical as a substituent, C6-Cl5-aryl or arylalkyl, and two adjacent radicals together may form cyclic groups of --
Z is X or R11 ~ R~ ~
Rlo R9 .:
Ra to Rl2 are each hydrogen, Cl-C1O-alkyl, 5-membered to 7-membered cycloalkyl which in turn may carry a Cl-C1O-alkyl radical as a substituent, C6-Cl5-aryl or arylalkyl, and two adjacent radicals together may form cyclic groups of --
4 to 15 carbon atoms, or Si(R13) 3 Rl3 is Cl-C1O-alkyl, C6-Cls-aryl or C3-C10-cycloalkyl, ;~
or R4 and Z together form a group -tY(Rl4) 2 ] n~E~ ~ -Y is silicon, germanium, tin or carbon, Rl4 is Cl-C1O-alkyl, C3-C10-cycloalkyl or C6-C1O-cycloalkyl, n is 1, 2, 3 or 4, `~
R12 ~ ~, E is ~ ~ ~ R3 or A, ~=
~ ''".
Rlo R9 A is -O-, -S-, NR15 or PR15 ~ ~ :. ., Rl5is Cl-C1O-alkyl, Cs-C1s-aryl, C3-C10-cycloalkyl, alkylaryl ``~
lS or Si(Rl6)3 and Rl6 i8 Cl-C1O-alkyl, C6-Cl5-aryl, C3-C10-cycloalkyl or -alkylaryl, and b) an open-chain or cyclic alumoxane compound of the general formula II or III
Rl7~ "~:
AltO--Al ] Rl7 ~:
R17~ I m II :
Rl7 v . . _ . I I I I
''"
O--Al ] .;:
m .
:`. `-`
: ' 2118711 ~ ~
_ 4 - O.Z. 0050/42666 where Rl7 is C1-C~-alkyl and m is an integer of from 5 to 30.
Among the metallocene complexes of the general formula I, R4~ Ia M~3 R3 R2 ~:
R4~
s R5 ~:
MX2 Ib R12 / `' R~ R8 ~.
Rl~ R9 :~
R3 ~ ~2 /~Rl R~ \ :
~R14)2Y R12 MX2 Ic and `~
Rl R9 52I18711 o z. 0050/42666 I d [ (R14) `Yl ~ A / X2 are preferred.
Paticularly preferred compounds of the formula ~a are those in which M i~ titanium, zirconium or hafnium~
X ic chlorine and Rl to Rs are each hydrogen OI' Cl-C4-alkyl.
Particularly pref~rred compound~ of the formula Ib are tho~e in which M i~ zirconium or hafnium, X is chlorine, Rl to Rs are each hydrogen, C1-C4-alkyl or Si~R7)3 and R6 to Rl are each hydrogen, Cl-C~-alkyl `or Si(R )3r Particularly suitabl~ compound~ of the formula Ib are those in which ~he cyclop n~adi.enyl radicals are identical, the un3ubstituted cyclopentadienyl radicals being preferred.
Particularly suit~le compound~ of the formula Ic are those in which Rl and R8 are iden~ic~l and are each hydrog~n or Cl-C1O alkyl~ R5 and Rl2 are iden~ical and are each hydrogen, methyl, ethyl, i~opropyl or ter~-butyl, R3 and Rl are C1 C4-alkylt R2 and R9 are each hydrogen, or two ad~acent radicals R2 and R3t and R9 and R10, togeth~r orm un~aturat~d cyclic group of 4 to 12 carbon atoms, Rl4 is Cl-Ca-alkyl, M is zirconium or hafnium, Y is sili-con, germanium, tin or carbon and X i5 chloxine.
Examples of particularly suitable complexes include dimethylsilanediylbis-(3-tert-butyl-5 methylcyclopenta-dienyl)zirconium dichlorid~
2I1~711 - 6 - o.z. 0050/~2666 ~ diethylsilanediylbis-(3-tert-butyl-S-methylcyclopenta-dienyl)zirconium dichloride, methylethylsilanediylbis-(3-tert-butyl-5-methylcyclo-pentadienyl)zirconium dichloride, S dimethylsilanediylbis-(3-tert-butyl-5-ethylcyclopenta-dienyl)zirconium dichloride, dimethylsilanediylbis-(3-tert-butyl-5-methylcyclopenta- ~::
dienyl)dimethylzirconium~ ~
dimethylsilanediylbis-(2-methylindenyl)zirconium :
dichloride, ::
diethylsilanediylbis-(2-methylindenyl)zirconium dichloride, ~:
dimethylsilanediylbis-(2-ethylindenyl)zirconium dichloride, ::
lS dimethylsilanediylbis-(2-isopropylindenyl)zirconium dichloride, . ` `~
dimethylsilanediylbis-(2-tert-butylindenyl)zirconium ;`
: dlchloride, ~:
diethylsilanediylbis-(2-methylindenyl)zirconium ~
~dibromide, ~.
dimethylsulfidebis-(2-methylindenyl)zirconium dichloride, ~;~
dimethylsilanediylbis-(2-methyl-5-methylcyclopenta- ;~
dienyl)zirconium dichloride, : :dim~thylsilanediylbis-(2-methyl-5-ethylcyclopenta~
dienyl)zirconium dichloride, ~;`
dimethylsilanediylbis-~2-ethyl-5-isopropylcyclopenta- `~
dienyl)zirconium dichloride, .
dimethyl~ilanediylbis (2-me~hylindenyl~zirconium dichloride, : 30 dimethyl~ilanediylbi~-(2-methylbenzindenyl)zirconium dichloride and dimetlhylsilanediylbi~-(2-m~thylindenyl)hafnium dichloride.
In the compounds of the general formula Id, particularly suitable ones are those in which M is : zirconium or hafnium, X is chlorine or Cl-C10-alkyl, Y is - silicon or carbon when:n is 1 or carbon when n is 2, R~4 2l~s~
- 7 - O.z. 0050/42666 i~ Cl-C~-alkyl~ C5- or C6-cycloalkyl or C6-C1O-~ryl, A is -O-, -S- or NRl5 and Rl to R3 and R5 are each hydroqen, Cl-C1O-alkyl, C~-C10-cycloalkyl, C6-C~s-aryl or Si(R7) 3 .
Complexes of this type can be synthesized by conventional methods, the reaction of ~h~ correspondingly substituted, cyclic hydrocarbon anions with halides of titanium, zirconium, hafnium, vanadium, niobium or tantalum being preferred. Examples of corresponding preparation processes are described in, inter alia, Journal of Organometallic Chemistry 369 (1989) r 359~370 .
The metallocene co~plexe-~ may also be present in cationic form, a~ described in EP-A 277 003 and EP-A 277 ~:
004. `:
In addition to the complexes, the metallocene catalyst sy~tem~ g~nerally al~o contain oligomeric alumoxane compounds of th~ general formula II or III, :~
where R17 is preferably methyl or ethyl and m is from~10 to 25.
20 ~ The preparation of these oligomeric alumoxane compounds is usually carried out by reacting a solution ~-of trialkylaluminum with water and i~ described in, inter alia, EP-A 284 708 and US-A 4,794,096. ::
As a rule, the oligomeric alumoxane compounds obtained are in the form of mix~ur~s of both linear and cyclic chain moleculec of different lengths, ~o that m i~
to be regarded as an average value. The alumoxane co~pounds may also b~ present a~ a mixture with other m~t~l alkyls, preferably with alkylaluminum~
In the novel proce~, it has proven advantageous to use the complex of metal~ of subgxoups IV and V of the Periodic Tabl~ and the oligomeric alumoxane compounds in amounts such that the atomic ratio of aluminum from the oligomeric alumoxane compound to the transition metal from the complex of metals of subgroups IV and V of the Periodic Table is from lO : 1 to lO~ : 1, in particular 21 ~ ~' 71 i - 8 - O.Z. 0050/42666 from 10 : l to lO~
For the novel process, the catalysts are general-ly used in an amount of from 10~1 to 10-9, preferably from 10-2 to lO-s, mol/l of metal.
The process can be carried out in the reactors usually used for high pressure polymerization, for example in stirred autoclaves.
It has proven advantageous first to mix the complex of metals of subgroups IV and V of the Periodic Table with the oligomeric alumoxane compound before the polymerization, with the result that an activated catal yst sy~tem is formed. The duration of the activation step i~ u~ually from 1 to 120 minutes, preferably from 10 to 100 minutes. Mixing is preferably carried out in such a way that the complex is brought into contact with the solution of the oligom~ric alumoxane compound in an inert solven~`, for example in benzene, toluene, hexane, h~ptane or a mixture thereof, at from 0 to 50C. `~
The novel process can b~ carried out by a method in which the solution of complexes and oligomeric alumoxane compounds are mixed upstream of the reactor and/or are fed .into the reactor at a plu2ality sf points.
The polymerization can be carried out batchw.ise or continuou ly. Pressures of from 100 to 3,500 bar, preferably from 500 to 3,000, in particular from 1,800 to 3,000, bar and temperatures of from 100 ~o 330C, prefer-ably from 120 to 300C, in parti ular from 120 to 2509C, ar~ employed. Th~ residence tLme~ are from 20 to 240, preferably from 30 to 120, seconds.
Th~ e~ential advantage~ of ~he novel process are that high productivities are achieved~ the choice of comonomer~ i~ very large and high conversions arQ reached in con~unction with short residence tLmes and high .
molecular w~ights.
2~ 711 - 9 - O.z. 0050/42666 .
EXAMPLES
Preparation of a propylene homopolymer (PP) 400 mg (~ 1 mmol) of 5H3C\ ~ Ic~
C \ zrC12 '. ~:
H~C
were di~solved in a mixture of 50 ml (36 g, 0.5 mol) of .. .. ~ .
trLmethylaluminum and 290 g of a 1.53 molar solution of :~
methylalumoxane (0.5 mol) in 10 1 of toluene. 10 m3 of propylena/h and the solution desçribed above were metered ~-into a continuou~ high pressure stirred autoclave in the -~
ab~ence of air and moisture.
Table 1 shews the experLmental condition~ and the re3ult~. `:
The weight averag~ molecular weight Mw was deter- :`5 mined by gel permeation chromatography.
Temperature Pressure g Ic ' ~h Residence Productivity MW
[ C] ~bar] time __ _ [min] Ic' h]
149 L, 510 0 .17 1. S 8, 380 2, 000 2 5 EXA~LE 2 Preparation of a propylenete~hyl~nQ copolym~r The procedure described in Example 1 was follow- -~
ed, except that a mixtura of propylene and ethylene was lo21 ~ ~ 71 1 o. Z . ooso/4~666 polymerized. ;
Table ~ shows the experimental conditions and the results.
TA~,LE 2 __ . - . .
Temperature Pressure g Ic'/h X by wt. of Productivity _ [C] [bar] propylene to X by wt. of [g polymer~
ethylene in g Ic'-h]
the gas mix-lgO 1, 508 0 . 078 77/23 24, 358 10, 000 :
or R4 and Z together form a group -tY(Rl4) 2 ] n~E~ ~ -Y is silicon, germanium, tin or carbon, Rl4 is Cl-C1O-alkyl, C3-C10-cycloalkyl or C6-C1O-cycloalkyl, n is 1, 2, 3 or 4, `~
R12 ~ ~, E is ~ ~ ~ R3 or A, ~=
~ ''".
Rlo R9 A is -O-, -S-, NR15 or PR15 ~ ~ :. ., Rl5is Cl-C1O-alkyl, Cs-C1s-aryl, C3-C10-cycloalkyl, alkylaryl ``~
lS or Si(Rl6)3 and Rl6 i8 Cl-C1O-alkyl, C6-Cl5-aryl, C3-C10-cycloalkyl or -alkylaryl, and b) an open-chain or cyclic alumoxane compound of the general formula II or III
Rl7~ "~:
AltO--Al ] Rl7 ~:
R17~ I m II :
Rl7 v . . _ . I I I I
''"
O--Al ] .;:
m .
:`. `-`
: ' 2118711 ~ ~
_ 4 - O.Z. 0050/42666 where Rl7 is C1-C~-alkyl and m is an integer of from 5 to 30.
Among the metallocene complexes of the general formula I, R4~ Ia M~3 R3 R2 ~:
R4~
s R5 ~:
MX2 Ib R12 / `' R~ R8 ~.
Rl~ R9 :~
R3 ~ ~2 /~Rl R~ \ :
~R14)2Y R12 MX2 Ic and `~
Rl R9 52I18711 o z. 0050/42666 I d [ (R14) `Yl ~ A / X2 are preferred.
Paticularly preferred compounds of the formula ~a are those in which M i~ titanium, zirconium or hafnium~
X ic chlorine and Rl to Rs are each hydrogen OI' Cl-C4-alkyl.
Particularly pref~rred compound~ of the formula Ib are tho~e in which M i~ zirconium or hafnium, X is chlorine, Rl to Rs are each hydrogen, C1-C4-alkyl or Si~R7)3 and R6 to Rl are each hydrogen, Cl-C~-alkyl `or Si(R )3r Particularly suitabl~ compound~ of the formula Ib are those in which ~he cyclop n~adi.enyl radicals are identical, the un3ubstituted cyclopentadienyl radicals being preferred.
Particularly suit~le compound~ of the formula Ic are those in which Rl and R8 are iden~ic~l and are each hydrog~n or Cl-C1O alkyl~ R5 and Rl2 are iden~ical and are each hydrogen, methyl, ethyl, i~opropyl or ter~-butyl, R3 and Rl are C1 C4-alkylt R2 and R9 are each hydrogen, or two ad~acent radicals R2 and R3t and R9 and R10, togeth~r orm un~aturat~d cyclic group of 4 to 12 carbon atoms, Rl4 is Cl-Ca-alkyl, M is zirconium or hafnium, Y is sili-con, germanium, tin or carbon and X i5 chloxine.
Examples of particularly suitable complexes include dimethylsilanediylbis-(3-tert-butyl-5 methylcyclopenta-dienyl)zirconium dichlorid~
2I1~711 - 6 - o.z. 0050/~2666 ~ diethylsilanediylbis-(3-tert-butyl-S-methylcyclopenta-dienyl)zirconium dichloride, methylethylsilanediylbis-(3-tert-butyl-5-methylcyclo-pentadienyl)zirconium dichloride, S dimethylsilanediylbis-(3-tert-butyl-5-ethylcyclopenta-dienyl)zirconium dichloride, dimethylsilanediylbis-(3-tert-butyl-5-methylcyclopenta- ~::
dienyl)dimethylzirconium~ ~
dimethylsilanediylbis-(2-methylindenyl)zirconium :
dichloride, ::
diethylsilanediylbis-(2-methylindenyl)zirconium dichloride, ~:
dimethylsilanediylbis-(2-ethylindenyl)zirconium dichloride, ::
lS dimethylsilanediylbis-(2-isopropylindenyl)zirconium dichloride, . ` `~
dimethylsilanediylbis-(2-tert-butylindenyl)zirconium ;`
: dlchloride, ~:
diethylsilanediylbis-(2-methylindenyl)zirconium ~
~dibromide, ~.
dimethylsulfidebis-(2-methylindenyl)zirconium dichloride, ~;~
dimethylsilanediylbis-(2-methyl-5-methylcyclopenta- ;~
dienyl)zirconium dichloride, : :dim~thylsilanediylbis-(2-methyl-5-ethylcyclopenta~
dienyl)zirconium dichloride, ~;`
dimethylsilanediylbis-~2-ethyl-5-isopropylcyclopenta- `~
dienyl)zirconium dichloride, .
dimethyl~ilanediylbis (2-me~hylindenyl~zirconium dichloride, : 30 dimethyl~ilanediylbi~-(2-methylbenzindenyl)zirconium dichloride and dimetlhylsilanediylbi~-(2-m~thylindenyl)hafnium dichloride.
In the compounds of the general formula Id, particularly suitable ones are those in which M is : zirconium or hafnium, X is chlorine or Cl-C10-alkyl, Y is - silicon or carbon when:n is 1 or carbon when n is 2, R~4 2l~s~
- 7 - O.z. 0050/42666 i~ Cl-C~-alkyl~ C5- or C6-cycloalkyl or C6-C1O-~ryl, A is -O-, -S- or NRl5 and Rl to R3 and R5 are each hydroqen, Cl-C1O-alkyl, C~-C10-cycloalkyl, C6-C~s-aryl or Si(R7) 3 .
Complexes of this type can be synthesized by conventional methods, the reaction of ~h~ correspondingly substituted, cyclic hydrocarbon anions with halides of titanium, zirconium, hafnium, vanadium, niobium or tantalum being preferred. Examples of corresponding preparation processes are described in, inter alia, Journal of Organometallic Chemistry 369 (1989) r 359~370 .
The metallocene co~plexe-~ may also be present in cationic form, a~ described in EP-A 277 003 and EP-A 277 ~:
004. `:
In addition to the complexes, the metallocene catalyst sy~tem~ g~nerally al~o contain oligomeric alumoxane compounds of th~ general formula II or III, :~
where R17 is preferably methyl or ethyl and m is from~10 to 25.
20 ~ The preparation of these oligomeric alumoxane compounds is usually carried out by reacting a solution ~-of trialkylaluminum with water and i~ described in, inter alia, EP-A 284 708 and US-A 4,794,096. ::
As a rule, the oligomeric alumoxane compounds obtained are in the form of mix~ur~s of both linear and cyclic chain moleculec of different lengths, ~o that m i~
to be regarded as an average value. The alumoxane co~pounds may also b~ present a~ a mixture with other m~t~l alkyls, preferably with alkylaluminum~
In the novel proce~, it has proven advantageous to use the complex of metal~ of subgxoups IV and V of the Periodic Tabl~ and the oligomeric alumoxane compounds in amounts such that the atomic ratio of aluminum from the oligomeric alumoxane compound to the transition metal from the complex of metals of subgroups IV and V of the Periodic Table is from lO : 1 to lO~ : 1, in particular 21 ~ ~' 71 i - 8 - O.Z. 0050/42666 from 10 : l to lO~
For the novel process, the catalysts are general-ly used in an amount of from 10~1 to 10-9, preferably from 10-2 to lO-s, mol/l of metal.
The process can be carried out in the reactors usually used for high pressure polymerization, for example in stirred autoclaves.
It has proven advantageous first to mix the complex of metals of subgroups IV and V of the Periodic Table with the oligomeric alumoxane compound before the polymerization, with the result that an activated catal yst sy~tem is formed. The duration of the activation step i~ u~ually from 1 to 120 minutes, preferably from 10 to 100 minutes. Mixing is preferably carried out in such a way that the complex is brought into contact with the solution of the oligom~ric alumoxane compound in an inert solven~`, for example in benzene, toluene, hexane, h~ptane or a mixture thereof, at from 0 to 50C. `~
The novel process can b~ carried out by a method in which the solution of complexes and oligomeric alumoxane compounds are mixed upstream of the reactor and/or are fed .into the reactor at a plu2ality sf points.
The polymerization can be carried out batchw.ise or continuou ly. Pressures of from 100 to 3,500 bar, preferably from 500 to 3,000, in particular from 1,800 to 3,000, bar and temperatures of from 100 ~o 330C, prefer-ably from 120 to 300C, in parti ular from 120 to 2509C, ar~ employed. Th~ residence tLme~ are from 20 to 240, preferably from 30 to 120, seconds.
Th~ e~ential advantage~ of ~he novel process are that high productivities are achieved~ the choice of comonomer~ i~ very large and high conversions arQ reached in con~unction with short residence tLmes and high .
molecular w~ights.
2~ 711 - 9 - O.z. 0050/42666 .
EXAMPLES
Preparation of a propylene homopolymer (PP) 400 mg (~ 1 mmol) of 5H3C\ ~ Ic~
C \ zrC12 '. ~:
H~C
were di~solved in a mixture of 50 ml (36 g, 0.5 mol) of .. .. ~ .
trLmethylaluminum and 290 g of a 1.53 molar solution of :~
methylalumoxane (0.5 mol) in 10 1 of toluene. 10 m3 of propylena/h and the solution desçribed above were metered ~-into a continuou~ high pressure stirred autoclave in the -~
ab~ence of air and moisture.
Table 1 shews the experLmental condition~ and the re3ult~. `:
The weight averag~ molecular weight Mw was deter- :`5 mined by gel permeation chromatography.
Temperature Pressure g Ic ' ~h Residence Productivity MW
[ C] ~bar] time __ _ [min] Ic' h]
149 L, 510 0 .17 1. S 8, 380 2, 000 2 5 EXA~LE 2 Preparation of a propylenete~hyl~nQ copolym~r The procedure described in Example 1 was follow- -~
ed, except that a mixtura of propylene and ethylene was lo21 ~ ~ 71 1 o. Z . ooso/4~666 polymerized. ;
Table ~ shows the experimental conditions and the results.
TA~,LE 2 __ . - . .
Temperature Pressure g Ic'/h X by wt. of Productivity _ [C] [bar] propylene to X by wt. of [g polymer~
ethylene in g Ic'-h]
the gas mix-lgO 1, 508 0 . 078 77/23 24, 358 10, 000 :
Claims (2)
1. A process for the preparation of a homopolymer of propylene or of a copolymer of propylene with other olefins or mixtures thereof, wherein polymerization is carried out at from 100 to 3,000 bar and at from 100 to 330°C and the catalyst used is a metallocene catalyst system.
2. A process as claimed in claim 1, wherein a metallocene catalyst system is used which contains, as active components, a) a metallocene complex of the formula I
I
where M is titanium, zirconium, hafnium, vanadium, niobium or tantalum, X is fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C6-C15-aryl or -OR6, R6 is C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl, each having from 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, R1 to R5 are each hydrogen, C1-C10-alkyl, 5-membered to 7-membered cycloalkyl which in turn may carry a C1-C10-alkyl radical as a substituent, C6-C15-aryl or arylalkyl, where two adjacent radicals together may furthermore form cyclic groups of 4 to 15 carbon atoms, or Si(R7)3, R7 is C1-C10-alkyl, C6-C15-aryl or C3-C10-cycloalkyl, Z is X or R8 to R12 are each hydrogen, C1-C10-alkyl, 5-membered to 7-membered cycloalkyl which in turn may carry a C1-C10-alkyl radical as a substituent, C6-C15-aryl or arylalkyl, and two adjacent radicals together may form cyclic groups of 4 to 15 carbon atoms, or Si(R13)3, R13 is C1-C10-alkyl, C6-C15-aryl or C3-C10-cycloalkyl, or R4 and Z together form a group [Y(R14)2]n-E-, Y is silicon, germanium, tin or carbon, R14 is C1-C10-alkyl, C3-C10-cycloalkyl or C6-C15-cycloalkyl, n is 1, 2, 3 or 4, E is or A, A is -O-, -S-, or , R15 is C1-C10-alkyl, C6-C15-aryl, C3-C10-cycloalkyl, alkylaryl or Si(R16)3 and R16 is C1-C10-alkyl, C6-C15-aryl, C3-C10-cycloalkyl or alkylaryl, and b) an open-chain or cyclic alumoxane compound of the formula II or III
III
where R17 is C1-C4-alkyl and m is an integer of from 5 to 30.
I
where M is titanium, zirconium, hafnium, vanadium, niobium or tantalum, X is fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C6-C15-aryl or -OR6, R6 is C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl, each having from 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, R1 to R5 are each hydrogen, C1-C10-alkyl, 5-membered to 7-membered cycloalkyl which in turn may carry a C1-C10-alkyl radical as a substituent, C6-C15-aryl or arylalkyl, where two adjacent radicals together may furthermore form cyclic groups of 4 to 15 carbon atoms, or Si(R7)3, R7 is C1-C10-alkyl, C6-C15-aryl or C3-C10-cycloalkyl, Z is X or R8 to R12 are each hydrogen, C1-C10-alkyl, 5-membered to 7-membered cycloalkyl which in turn may carry a C1-C10-alkyl radical as a substituent, C6-C15-aryl or arylalkyl, and two adjacent radicals together may form cyclic groups of 4 to 15 carbon atoms, or Si(R13)3, R13 is C1-C10-alkyl, C6-C15-aryl or C3-C10-cycloalkyl, or R4 and Z together form a group [Y(R14)2]n-E-, Y is silicon, germanium, tin or carbon, R14 is C1-C10-alkyl, C3-C10-cycloalkyl or C6-C15-cycloalkyl, n is 1, 2, 3 or 4, E is or A, A is -O-, -S-, or , R15 is C1-C10-alkyl, C6-C15-aryl, C3-C10-cycloalkyl, alkylaryl or Si(R16)3 and R16 is C1-C10-alkyl, C6-C15-aryl, C3-C10-cycloalkyl or alkylaryl, and b) an open-chain or cyclic alumoxane compound of the formula II or III
III
where R17 is C1-C4-alkyl and m is an integer of from 5 to 30.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4130299A DE4130299A1 (en) | 1991-09-12 | 1991-09-12 | METHOD FOR PRODUCING HIGH PRESSURE POLYPROPYLENE |
| DEP4130299.0 | 1991-09-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2118711A1 true CA2118711A1 (en) | 1993-03-18 |
Family
ID=6440414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002118711A Abandoned CA2118711A1 (en) | 1991-09-12 | 1992-09-02 | Preparation of polypropylene under high pressure |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0603232B1 (en) |
| JP (1) | JPH06510808A (en) |
| CN (1) | CN1061995C (en) |
| AR (1) | AR248032A1 (en) |
| CA (1) | CA2118711A1 (en) |
| DE (2) | DE4130299A1 (en) |
| ES (1) | ES2085033T3 (en) |
| FI (1) | FI941139A0 (en) |
| HU (1) | HUT66545A (en) |
| NO (1) | NO302075B1 (en) |
| WO (1) | WO1993005082A1 (en) |
| ZA (1) | ZA926925B (en) |
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| US6117962A (en) * | 1997-12-10 | 2000-09-12 | Exxon Chemical Patents Inc. | Vinyl-containing stereospecific polypropylene macromers |
| US6555635B2 (en) | 1997-02-07 | 2003-04-29 | Exxonmobil Chemical Patents Inc. | Preparation of vinyl-containing macromers |
| US6750307B2 (en) | 1997-02-07 | 2004-06-15 | Exxon Mobil Chemical Patents Inc. | Propylene polymers incorporating polyethylene macromers |
| US7279536B2 (en) | 2002-09-20 | 2007-10-09 | Exxonmobil Chemical Patents Inc. | Polymer production at supercritical conditions |
| US7319125B2 (en) | 2002-09-20 | 2008-01-15 | Exxonmobil Chemical Patents Inc. | Supercritical polymerization process and polymers produced therefrom |
| WO2008150572A1 (en) * | 2007-06-04 | 2008-12-11 | Exxonmobil Chemical Patents Inc. | Super-solution homogeneous propylene polymerization |
| US7741420B2 (en) | 2004-07-14 | 2010-06-22 | Exxonmobil Chemical Patents Inc. | Polymer production at supercritical conditions |
| US7910637B2 (en) | 2007-09-13 | 2011-03-22 | Exxonmobil Research And Engineering Company | In-line blending of plasticizers with a base polymer |
| US7910679B2 (en) | 2007-12-20 | 2011-03-22 | Exxonmobil Research And Engineering Company | Bulk homogeneous polymerization process for ethylene propylene copolymers |
| US7928162B2 (en) | 2007-09-13 | 2011-04-19 | Exxonmobil Research And Engineering Company | In-line process for producing plasticized polymers and plasticized polymer blends |
| US7994237B2 (en) | 2007-12-20 | 2011-08-09 | Exxonmobil Research And Engineering Company | In-line process to produce pellet-stable polyolefins |
| US8008412B2 (en) | 2002-09-20 | 2011-08-30 | Exxonmobil Chemical Patents Inc. | Polymer production at supersolution conditions |
| US8022142B2 (en) | 2008-12-15 | 2011-09-20 | Exxonmobil Chemical Patents Inc. | Thermoplastic olefin compositions |
| US8080610B2 (en) | 2007-03-06 | 2011-12-20 | Exxonmobil Research And Engineering Company | Monomer recycle process for fluid phase in-line blending of polymers |
| US8138269B2 (en) | 2007-12-20 | 2012-03-20 | Exxonmobil Research And Engineering Company | Polypropylene ethylene-propylene copolymer blends and in-line process to produce them |
| US8143352B2 (en) | 2006-12-20 | 2012-03-27 | Exxonmobil Research And Engineering Company | Process for fluid phase in-line blending of polymers |
| US8242237B2 (en) | 2006-12-20 | 2012-08-14 | Exxonmobil Chemical Patents Inc. | Phase separator and monomer recycle for supercritical polymerization process |
| US8318875B2 (en) | 2008-01-18 | 2012-11-27 | Exxonmobil Chemical Patents Inc. | Super-solution homogeneous propylene polymerization and polypropylenes made therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5408017A (en) * | 1987-01-30 | 1995-04-18 | Exxon Chemical Patents Inc. | High temperature polymerization process using ionic catalysts to produce polyolefins |
| US5384299A (en) * | 1987-01-30 | 1995-01-24 | Exxon Chemical Patents Inc. | Ionic metallocene catalyst compositions |
| WO1994000500A1 (en) * | 1992-06-26 | 1994-01-06 | Exxon Chemical Patents Inc. | Solution phase polymerization process utilizing metallocene catalyst with production of olefin polymers |
| FI105820B (en) * | 1995-10-10 | 2000-10-13 | Borealis Tech Oy | Process for the preparation of homopolymers or copolymers of propylene |
| ES2142615T3 (en) | 1995-10-10 | 2000-04-16 | Borealis As | PROCEDURE FOR MANUFACTURING HOMOPOLYMERS OR COPOLYMERS OF PROPYLENE. |
| DE19653079A1 (en) * | 1996-12-19 | 1998-06-25 | Basf Ag | Process for the gas phase polymerization of C¶2¶-C¶8¶-Alk-1-enes using Ziegler-Natta or metallocene catalyst systems |
| US6153702A (en) * | 1997-09-12 | 2000-11-28 | Eastman Chemical Company | Polymers, and novel compositions and films therefrom |
| DE19903783A1 (en) * | 1999-02-01 | 2000-08-03 | Elenac Gmbh | Process for the preparation of polyolefins with a broad molecular weight distribution |
| EP1334139A2 (en) | 2000-11-07 | 2003-08-13 | Symyx Technologies, Inc. | Substituted pyridyl amine ligands, complexes and catalysts therefrom. processes for producing polyolefins therewith |
| GB0111020D0 (en) * | 2001-05-04 | 2001-06-27 | Borealis Tech Oy | Process |
| US7807769B2 (en) | 2002-09-20 | 2010-10-05 | Exxonmobil Chemical Patents Inc. | Isotactic polypropylene produced from supercritical polymerization process |
| CH710441A2 (en) | 2014-12-02 | 2016-06-15 | Rowak Ag | Powdered compositions of thermoplastics and use of the compositions. |
| CA3159497A1 (en) * | 2019-12-03 | 2021-06-10 | Dongcheol Shin | Transition metal compound, catalyst composition comprising same, and method for producing olefin polymer using catalyst composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3150270A1 (en) * | 1981-12-18 | 1983-06-30 | EC Erdölchemie GmbH, 5000 Köln | High-pressure polymerisation of ethylene |
| US5055438A (en) * | 1989-09-13 | 1991-10-08 | Exxon Chemical Patents, Inc. | Olefin polymerization catalysts |
| DE3743320A1 (en) * | 1987-12-21 | 1989-06-29 | Hoechst Ag | 1-OLEFIN STEREO BLOCK POLYMER WAX AND METHOD FOR THE PRODUCTION THEREOF |
| DE3929693A1 (en) * | 1989-09-07 | 1991-03-14 | Hoechst Ag | METHOD FOR PRODUCING A POLYOLEFIN WAX |
-
1991
- 1991-09-12 DE DE4130299A patent/DE4130299A1/en not_active Withdrawn
-
1992
- 1992-09-02 WO PCT/EP1992/002017 patent/WO1993005082A1/en active IP Right Grant
- 1992-09-02 EP EP92918593A patent/EP0603232B1/en not_active Expired - Lifetime
- 1992-09-02 CA CA002118711A patent/CA2118711A1/en not_active Abandoned
- 1992-09-02 JP JP5504947A patent/JPH06510808A/en active Pending
- 1992-09-02 HU HU9400744A patent/HUT66545A/en unknown
- 1992-09-02 DE DE59205977T patent/DE59205977D1/en not_active Expired - Fee Related
- 1992-09-02 ES ES92918593T patent/ES2085033T3/en not_active Expired - Lifetime
- 1992-09-09 AR AR92323141A patent/AR248032A1/en active
- 1992-09-11 ZA ZA926925A patent/ZA926925B/en unknown
- 1992-09-11 CN CN92110667A patent/CN1061995C/en not_active Expired - Fee Related
-
1994
- 1994-03-10 FI FI941139A patent/FI941139A0/en unknown
- 1994-03-11 NO NO940873A patent/NO302075B1/en not_active IP Right Cessation
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6555635B2 (en) | 1997-02-07 | 2003-04-29 | Exxonmobil Chemical Patents Inc. | Preparation of vinyl-containing macromers |
| US6750307B2 (en) | 1997-02-07 | 2004-06-15 | Exxon Mobil Chemical Patents Inc. | Propylene polymers incorporating polyethylene macromers |
| US6774191B2 (en) | 1997-02-07 | 2004-08-10 | Exxonmobil Chemical Patents Inc. | Propylene polymers incorporating polyethylene macromers |
| US6117962A (en) * | 1997-12-10 | 2000-09-12 | Exxon Chemical Patents Inc. | Vinyl-containing stereospecific polypropylene macromers |
| US8058371B2 (en) | 2002-09-20 | 2011-11-15 | Exxonmobil Chemical Patents Inc. | Super-solution homogeneous propylene polymerization |
| US7279536B2 (en) | 2002-09-20 | 2007-10-09 | Exxonmobil Chemical Patents Inc. | Polymer production at supercritical conditions |
| US7354979B2 (en) | 2002-09-20 | 2008-04-08 | Exxonmobil Chemical Patents Inc. | Polymer production at supercritical conditions |
| US7319125B2 (en) | 2002-09-20 | 2008-01-15 | Exxonmobil Chemical Patents Inc. | Supercritical polymerization process and polymers produced therefrom |
| US8008412B2 (en) | 2002-09-20 | 2011-08-30 | Exxonmobil Chemical Patents Inc. | Polymer production at supersolution conditions |
| US7741420B2 (en) | 2004-07-14 | 2010-06-22 | Exxonmobil Chemical Patents Inc. | Polymer production at supercritical conditions |
| US8242237B2 (en) | 2006-12-20 | 2012-08-14 | Exxonmobil Chemical Patents Inc. | Phase separator and monomer recycle for supercritical polymerization process |
| US8143352B2 (en) | 2006-12-20 | 2012-03-27 | Exxonmobil Research And Engineering Company | Process for fluid phase in-line blending of polymers |
| US8080610B2 (en) | 2007-03-06 | 2011-12-20 | Exxonmobil Research And Engineering Company | Monomer recycle process for fluid phase in-line blending of polymers |
| WO2008150572A1 (en) * | 2007-06-04 | 2008-12-11 | Exxonmobil Chemical Patents Inc. | Super-solution homogeneous propylene polymerization |
| US7910637B2 (en) | 2007-09-13 | 2011-03-22 | Exxonmobil Research And Engineering Company | In-line blending of plasticizers with a base polymer |
| US7928162B2 (en) | 2007-09-13 | 2011-04-19 | Exxonmobil Research And Engineering Company | In-line process for producing plasticized polymers and plasticized polymer blends |
| US7994237B2 (en) | 2007-12-20 | 2011-08-09 | Exxonmobil Research And Engineering Company | In-line process to produce pellet-stable polyolefins |
| US8138269B2 (en) | 2007-12-20 | 2012-03-20 | Exxonmobil Research And Engineering Company | Polypropylene ethylene-propylene copolymer blends and in-line process to produce them |
| US7910679B2 (en) | 2007-12-20 | 2011-03-22 | Exxonmobil Research And Engineering Company | Bulk homogeneous polymerization process for ethylene propylene copolymers |
| US8318875B2 (en) | 2008-01-18 | 2012-11-27 | Exxonmobil Chemical Patents Inc. | Super-solution homogeneous propylene polymerization and polypropylenes made therefrom |
| US8022142B2 (en) | 2008-12-15 | 2011-09-20 | Exxonmobil Chemical Patents Inc. | Thermoplastic olefin compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| FI941139A (en) | 1994-03-10 |
| ZA926925B (en) | 1994-03-11 |
| CN1061995C (en) | 2001-02-14 |
| WO1993005082A1 (en) | 1993-03-18 |
| JPH06510808A (en) | 1994-12-01 |
| NO940873D0 (en) | 1994-03-11 |
| NO302075B1 (en) | 1998-01-19 |
| EP0603232B1 (en) | 1996-04-10 |
| FI941139A0 (en) | 1994-03-10 |
| DE4130299A1 (en) | 1993-03-18 |
| HUT66545A (en) | 1994-12-28 |
| EP0603232A1 (en) | 1994-06-29 |
| AR248032A1 (en) | 1995-05-31 |
| DE59205977D1 (en) | 1996-05-15 |
| NO940873L (en) | 1994-03-11 |
| HU9400744D0 (en) | 1994-06-28 |
| CN1070654A (en) | 1993-04-07 |
| ES2085033T3 (en) | 1996-05-16 |
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