CA2111363A1 - Process for the preparation of polyolefin waxes - Google Patents
Process for the preparation of polyolefin waxesInfo
- Publication number
- CA2111363A1 CA2111363A1 CA002111363A CA2111363A CA2111363A1 CA 2111363 A1 CA2111363 A1 CA 2111363A1 CA 002111363 A CA002111363 A CA 002111363A CA 2111363 A CA2111363 A CA 2111363A CA 2111363 A1 CA2111363 A1 CA 2111363A1
- Authority
- CA
- Canada
- Prior art keywords
- group
- metallocene
- different
- alkyl group
- zirconium dichloride
- 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
Links
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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
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63912—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1868—Stationary reactors having moving elements inside resulting in a loop-type movement
- B01J19/1881—Stationary reactors having moving elements inside resulting in a loop-type movement externally, i.e. the mixture leaving the vessel and subsequently re-entering it
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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
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—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
- 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
- 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
- C08F10/08—Butenes
-
- 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
- C08F10/14—Monomers containing five or more carbon atoms
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- 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
- C08F4/02—Carriers therefor
-
- 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
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/6392—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/63922—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/63927—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00121—Controlling the temperature by direct heating or cooling
- B01J2219/00128—Controlling the temperature by direct heating or cooling by evaporation of reactants
-
- 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
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Abstract
Abstract of the Disclosure Process for the preparation of polyolefin waxes By polymerizing olefins in a low-boiling suspending agent, in particular propane, and removing the heat of reaction by evaporative cooling in the presence of a metallocene catalyst, polyolefin waxes are obtained without it being possible for wall deposits to adversely affect the cooling of the reactor.
Description
211~3~3 HOECHST AKTIENGESELLSCHAFT HOE 92/F 407 Dr.DA/-,~., - Process for the preparation of polyolefin waxes :~
The present invention relates to a proceB~ for the preparation of polyolefin waxes having a low residual a3h 5 content. ~
., ' "~ .
Polyolefin waxes, in particular polyethylene waxes, are important for a large number of applications. In par-ticular, highly crystalline waxes are attracting increas-! ing interest for mixing with abrasion-re~istant printing inks, for the matting of paints and for the preparation of emulsifiable waxes for cleaning agents.
Processes for the preparation of polyolefin waxes at temperatures above 100C in solution in a high-boiling hydrocarbon are known (cf. British Patent No. 1,311,013 and U.S. Patent 3,951,935). A suspen~ion polymerization at temperatures below the wax melting point is unsuccess-ful owing to the high solubility and/or the good ~welling capacity of these products.
It was found that waxes are soluble only to a negliqible extent, if at all, in low-boiling hydrocarbon~, in particular propane, and consequently a ~uspension process -is also pos~ible for semicrystalline waxes (cf. German ~-~
Patent Application No. 4,217,378). this suspension polymerization process i8 economically advantageous compared with the solution process, owing to the simpler separation of the suspending agent and the lower viscosity of the system.
.
A major problem in the suspension polymerization, in particular with the u~e of soluble catalyst ~y~tems, is the build-up of wall deposits, which hinders the jacket 30 cooling of the reactors. Particularly when the ratio of ~ -reactor surface area to reactor volume becomes more disadvantageous through the construction of larger reactors, uncontrollable heating of the polymerization ` `` ~1~13~3 ~ system may occur a~ a re~ult of the prevention of heat - tran~fex.
It was therefore the object to find a polymerization process in which polyolefin waxe~ can be prepared without the disadvantages de~cribed, using metallocene catalysts.
~,, It was found that, in the suspension polymerization of ethylene and other olef in8 in propane u~ing metallocene catalyst systems, cooling of the reactor can be carried ollt by condensation of vapor ("evaporative cooling"), and that reactor deposits are avoided as a result.
The invention thus relates to a proces~ for the prepara-tion of a polyolefin wax by polymerization or copolymer-izatin of olefinæ or diolefins at a temperature of -40 to 100C, at a pressure of 0.5 to 120 bar, in 6uspension and in the presence of a catalyst comprising a metallocene and a cocatalyst, wherein the metallocene i6 a compound of the formula I
/~
R 2 R 4 :~
in which M1 i8 a metal of group IVb, Vb or VIb of the Periodic ~able of Elements, 20 R' and R2 are identical or different and are a hydrogen ~ ~-atom, a Cl-C10-alkyl group, a C,-C,0-alkoxy group, a C6-C,0-aryl group, a C6-C,0-aryloxy group, a C2-C,0-alkenyl group, -~
a C,-C40-arylalkyl group, a C7-C40-alkylaryl group, a C~-C,0-arylalkenyl group or a halogen atom and R3 and R4 are identical or different and are a mononuclear or polynuclear hydrocarbon radical which may form a -~
sandwich structure with the central atom Ml, low-boiling hydrocarbons having 3 or 4 carbon atoms or low-boiling halogenated hydrocarbonæ are used aæ
suspending agents and the heat of reaction is removed by evaporative cooling. - ~
--.:
:':
`"'1 ` ~ ~ ', ~
3~3 In the process according to the invention, the monomers used are olefins, diolefins and other un~aturated hydro-carbons having 2 to 18 carbon atom~. Such monomers are -~ cyclic, polycyclic, linear or branched unsaturated hydrocarbons. Examples of these are ethylene, propylene, ;~1 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, ~tyrene or cyclic olefins, such as cyclopentene, cyclohexene, norbornene, 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene (DMON) and their structural derivatives, as well as diolefins, such as norbornadiene, 1,3-butadiene, 1,4-pentadiene, 1,4- or 1,5-hexadiene, 1,7-octadiene or 1,3- or 1,5-cycloocta-diene. The polymerization of ethylene or propylene and the copolymerization of ethylene or propylene with an olefin having 3 to 10 carbon atoms is preferred, and particularly preferred copolymer waxes are ethylene/
propylene, ethylene/l-butene and ethylene/l-hexene polymer waxes and ethylene/propylene/1-butene terpolymer waxes.
. '~
The polymerization is carried out in the presence of a metallocene catalyst system. ~ ;
,,~
Suitable highly active metallocene catalyst systems for the preparation of polyolefin waxes in low boilers ~ `~
comprise a metallocene and a cocatalyst.
, ~.
The metallocene is a compound of the formula I
R1 / R~
\ ~
' / \
R2 R~
in which Ml is a metal of group IVb, Vb or VIb of the Periodic Table of Elements, Rl and R2 are identical or different and are a hydrogen atom, a Cl-ClO-alkyl group, a Cl-ClO-alkoxy group, a C~-Cl0-aryl group, a C6-Cl0-aryloxy group, a C2-Cl0-alkenyl group, a C7-C,O-arylalkyl group, a C,-C,0-alkylaryl group, a ~1113~3 . - 4 -. C5-C40-arylalkenyl group or a halogen atom and R3 and R' are identical or differ~nt and are a mononuclear or polynuclear hydrocarbon radical which may form a san~wich structure with the central atom Ml.
The formula I also embraces compounds of the formula Ia ~ R~
and of the formula Ib :~
( CR ~ ~ R 1 2 )m R13 (Ib) C R ~ ! R ~ 2 ~
~ . ' ."
. .~
In the formulae Ia and Ib, Ml is a metal of group IVb, Vb ;~
or VIb of the Periodic Table of Element~, for example .~ :
titanium, zirconium, hafnium, vanadium, niobium, tan~
10 talum, chromium, molybdenum and tungsten, preferably :
titanium, zirconium and hafnium.
'~
~ 5 - 2~3 63 R' and R2 are identical or different and are a hydrogen atom, a C,-C,0-alkyl group, preferably a C,-C3-alkyl group, a C~-C~0-alkoxy group, preferably a C,-C3-alkoxy group, a C6-C,0-aryl group, preferably a Cc-C8-aryl group, a C6-C,0-aryloxy group, preferably a C6-C8-aryloxy qroup, a C2-C,0-alkenyl group, preferably a C2-C~-alkenyl group, a C7-C40-arylalkyl group, preferably a C~-C~0-arylalkyl group, a C7-C,0-alkylaryl group, preferably a C~-C~2-alkylaryl group, a Ca-C40-arylalkenyl group, preferably a C8-C,2-arylalkenyl group, or a halogen atom, preferably chlorine or methyl.
R3 and R4 are identical or different and are a mononuclear or polynuclear hydrocarbon radical which may form a sandwich structure with the central atom Ml. R3 and R' are preferably cyclopentadienyl, indenyl, tetrahydro-indenyl, benzoindenyl or fluorenyl, it being po~sible forthe parent structures to carry additional substituents or to be bridged with one another.
R5, R6~ R7~ R~ R9 and Rl are identical or different and are a hydrogen atom, a halogen atom, preferably a fluor-ine, chlorine or bromine atom, a Cl-Cl0-alkyl group, preferably a C,-C,-alkyl group, a C6-C~0-aryl group, preferably a C6-C8-aryl group, a C,-C,0-alkoxy group, preferably a C,-C3-alkoxy group, or an -NRl'2, -SRl', -oSiRl43, -SiRl'3 or -PR'~2 radical in which Rl4 i8 a C,-ClO-alkyl group, preferably a Cl-C3-alkyl group, or a Cc-C
aryl group, preferably a C,-C8-aryl group, or, in the ca~e of Si- or P-containing radicals, also a halogen atom, preferably a chlorine atom, or two adjacent radicals R5, R6, R', R8, R9 or Rl each form a ring with the carbon atoms linking them. Particularly preferred ligands are the substituted compounds of the parent structures indenyl, tetrahydroindenyl, benzoindenyl, fluorenyl and cyclopentadienyl.
Rl3 i8 `~!3 :4 .
- 6 _ 2~363 .. ~ , R15 ~5 R15 R15 R15 2__1 2 12_ --M2_ CR172--o_1,J2_o_ l 16l ~ 6 l 16l 16 1 1 G
~.
:
R 15 R 15R ~ S R 15 -I- -o-I2_ 12 o lZ~
1 1 6 R 16 l ~ o I 16 =BR'5, =AlRls, -Ge-, -Sn-, -0-, -S-, ~S0, -S02, ~NR15, ~C0, -PR1s or =P(o)Rl5, in which R'5, Rl6 and R" are identical or different and are a hydrogen atom, a halogen atom, a C,~
C30-alkyl group, preferably a C,-C4-alkyl group, in particular a methyl group, a C1-C10-fluoroalkyl group, preferably a CF3 group, a C6-C10-fluoroaryl group, preferably a pentafluorophenyl group, a C6-C,0-aryl group, preferably a C6-C6-aryl group, a C,-C,0-alkoxy group, preferably a C1-C4-alkoxy group, in paxticular a methoxy group, a C2-C10-alkenyl group, preferably a C2-C4-alkenyl group, a C7-C40-arylalkyl group, preferably a C,-C10-aryl-alkyl qroup, a C8-C40-arylalkenyl group, preferably a Ca~
Cl2-arylalkenyl group, or a C7-C40-alkylaryl group, preferably a C~-C~2-alkylaryl group, or Rls and Rls or Rl5 and Rl', together with the atoms linking them, each form a ring.
. .
M2 is 3ili~0n ~ germanium or tin, preferably sili~on and germanium.
Rl3 iB preferably -CRlsR'6, -SiRlsR16, -GeR'sRl6, -0-, -S-, 20 eS0, -PRls or -P(O)R1s. ~-Rll and Rl2 are identical or different and have the meaning stated for Rls.
m and n are identical or different and are zero, 1 or 2, :~
preferably zero or 1, m plUB n being zero, 1 or 2, : ~
: . . -- -3 ~3 ~ - 7 --;~
. preferably zero or 1.
Examples of preferred metallocene~ are: -bis(cyclopentadienyl)zirconium dichloride, s! bi~(methylcyclopentadienyl)zirconium dichloride, --bis(n-butylcyclopentadienyl)zirconium dichloride, bis(i-butylcyclopentadienyl)zirconium dichloride, bis(alkylcyclopentadienyl)zirconium dichloride, ~ :
bis(l,2-dimethylcyclopentadienyl)zirconium dichloride, bis(l,3-dimethylcyclopentadienyl)zirconium dichloride, bis(l,2,4-trimethylcyclopentadienyl)zirconium dichloride, bis(l,2,3-trimethylcyclopentadienyl)zirconium dichloride, bis(indenyl)zirconium dichloride, bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, --bis(l-methylindenyl)zirconium dichloride, bis(2-methylindenyl)zirconium dichloride, bis(4-methylindenyl)zirconium dichloride, bis(5-methylindenyl)zirconium dichloride, bis(2-methyl-4,6-di-i-propyl-indenyl)zirconium dichloride, bis(alkylindenyl)zirconium dichloride, bis(cyclopentadienyl)zirconiumdimethyl and bis(cyclopentadienyl)zirconiumdibenzyl, - and further preferred metallocenes:
dialkylsilylbis(indenyl)zirconium dichloride, alkylalkylenebis(indenyl)zirconium dichloride, alkylenebis(indenyl)zirconium dichloride, diarylalkenylbis~indenyl)zirconium dichloride, alkylenebis(indenyl)hafnium dichloride, diarylsilylbis~indenyl)zirconium dichloride, (aryl)(alkyl)bis(indenyl)zirconium dichloride, dialkylgermylbis(indenyl)zirconium dichloride, (alkyl)(alkenyl)silylbis(indenyl)zirconium dicbloride, (aryl)(alkenyl)silylbis(indenyl)zirconium dichloride, dimethylsilylbis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dichloride, diphenylsilylbis(indenyl)zirconium dichloride, 3 ~ S~ .
~.i dimethylgermylbis(indenyl~zirconium dichloride, ~ bis(pentamethylcyclopentadienyl)zirconium dichloride, ~-~
~ dimethyl~ilyl-bi6(l-tetrahydroindenyl)zirconium ;~ dichloride, ;~ S ethylene-bis(1-tetrahydroindenyl)zirconium dichloride, -- ~:
dimethylsilyl-bi~-1-(2-methyltetrahydroindenyl)zirconium ~-~
. dichloride, ethylene-bis-1-(2-methyl-tetrahydroindenyl)zirconium dichloride, ~ :
dimethylsilyl-bis-1-(2,3,5-trimethylcyclopentadienyl)~
zirconium dichloride, ~:
dimethylsilyl-bis-1-(2,4-dimethylcyclopentadienyl)-zirconium dichloride, ethylene-bis(l-indenyl)zirconium dichloride, dimethylsilyl-bis(1-indenyl)zirconium dichloride, diphenylsilyl-bis(l-indenyl)zirconium dichloride, dimethylsilyl-bi~ indenyl)zirconiumdimethyl, dimethylsilyl-bis-1-(2-methyl-indenyl)zirconium dichloride, .
phenylmethylsilyl-bis-1-(2-methyl-indenyl)zirconium dichloride, :-~
dimethylsilyl-bis-1-(2-methyl-4-ethylindenyl)zirconium -:
dichloride, dimethylsilyl-bis-1-(2-methyl-4-i-propylindenyl)zirconium -~
dichloride and ethylene-bis-1-(4,7-dimethyl-indenyl)zirconium : -dichloride, and other metallocenes which can be used:
diphenylmethylene(9-fluorenyl)(cyclopentadienyl)zirconium 30 dichloride, :
dimethylsilyl(9-fluorenyl)(cyclopentadienyl)zirconium dichloride, isopropylidene(9-fluorenyl)(cyclopentadienyl)zirconium dichloride and ~ :-isopropylidene(l-indenyl)(cyclopentadienyl)zirconium dichloride. ~ -~
The present invention relates to a proceB~ for the preparation of polyolefin waxes having a low residual a3h 5 content. ~
., ' "~ .
Polyolefin waxes, in particular polyethylene waxes, are important for a large number of applications. In par-ticular, highly crystalline waxes are attracting increas-! ing interest for mixing with abrasion-re~istant printing inks, for the matting of paints and for the preparation of emulsifiable waxes for cleaning agents.
Processes for the preparation of polyolefin waxes at temperatures above 100C in solution in a high-boiling hydrocarbon are known (cf. British Patent No. 1,311,013 and U.S. Patent 3,951,935). A suspen~ion polymerization at temperatures below the wax melting point is unsuccess-ful owing to the high solubility and/or the good ~welling capacity of these products.
It was found that waxes are soluble only to a negliqible extent, if at all, in low-boiling hydrocarbon~, in particular propane, and consequently a ~uspension process -is also pos~ible for semicrystalline waxes (cf. German ~-~
Patent Application No. 4,217,378). this suspension polymerization process i8 economically advantageous compared with the solution process, owing to the simpler separation of the suspending agent and the lower viscosity of the system.
.
A major problem in the suspension polymerization, in particular with the u~e of soluble catalyst ~y~tems, is the build-up of wall deposits, which hinders the jacket 30 cooling of the reactors. Particularly when the ratio of ~ -reactor surface area to reactor volume becomes more disadvantageous through the construction of larger reactors, uncontrollable heating of the polymerization ` `` ~1~13~3 ~ system may occur a~ a re~ult of the prevention of heat - tran~fex.
It was therefore the object to find a polymerization process in which polyolefin waxe~ can be prepared without the disadvantages de~cribed, using metallocene catalysts.
~,, It was found that, in the suspension polymerization of ethylene and other olef in8 in propane u~ing metallocene catalyst systems, cooling of the reactor can be carried ollt by condensation of vapor ("evaporative cooling"), and that reactor deposits are avoided as a result.
The invention thus relates to a proces~ for the prepara-tion of a polyolefin wax by polymerization or copolymer-izatin of olefinæ or diolefins at a temperature of -40 to 100C, at a pressure of 0.5 to 120 bar, in 6uspension and in the presence of a catalyst comprising a metallocene and a cocatalyst, wherein the metallocene i6 a compound of the formula I
/~
R 2 R 4 :~
in which M1 i8 a metal of group IVb, Vb or VIb of the Periodic ~able of Elements, 20 R' and R2 are identical or different and are a hydrogen ~ ~-atom, a Cl-C10-alkyl group, a C,-C,0-alkoxy group, a C6-C,0-aryl group, a C6-C,0-aryloxy group, a C2-C,0-alkenyl group, -~
a C,-C40-arylalkyl group, a C7-C40-alkylaryl group, a C~-C,0-arylalkenyl group or a halogen atom and R3 and R4 are identical or different and are a mononuclear or polynuclear hydrocarbon radical which may form a -~
sandwich structure with the central atom Ml, low-boiling hydrocarbons having 3 or 4 carbon atoms or low-boiling halogenated hydrocarbonæ are used aæ
suspending agents and the heat of reaction is removed by evaporative cooling. - ~
--.:
:':
`"'1 ` ~ ~ ', ~
3~3 In the process according to the invention, the monomers used are olefins, diolefins and other un~aturated hydro-carbons having 2 to 18 carbon atom~. Such monomers are -~ cyclic, polycyclic, linear or branched unsaturated hydrocarbons. Examples of these are ethylene, propylene, ;~1 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, ~tyrene or cyclic olefins, such as cyclopentene, cyclohexene, norbornene, 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene (DMON) and their structural derivatives, as well as diolefins, such as norbornadiene, 1,3-butadiene, 1,4-pentadiene, 1,4- or 1,5-hexadiene, 1,7-octadiene or 1,3- or 1,5-cycloocta-diene. The polymerization of ethylene or propylene and the copolymerization of ethylene or propylene with an olefin having 3 to 10 carbon atoms is preferred, and particularly preferred copolymer waxes are ethylene/
propylene, ethylene/l-butene and ethylene/l-hexene polymer waxes and ethylene/propylene/1-butene terpolymer waxes.
. '~
The polymerization is carried out in the presence of a metallocene catalyst system. ~ ;
,,~
Suitable highly active metallocene catalyst systems for the preparation of polyolefin waxes in low boilers ~ `~
comprise a metallocene and a cocatalyst.
, ~.
The metallocene is a compound of the formula I
R1 / R~
\ ~
' / \
R2 R~
in which Ml is a metal of group IVb, Vb or VIb of the Periodic Table of Elements, Rl and R2 are identical or different and are a hydrogen atom, a Cl-ClO-alkyl group, a Cl-ClO-alkoxy group, a C~-Cl0-aryl group, a C6-Cl0-aryloxy group, a C2-Cl0-alkenyl group, a C7-C,O-arylalkyl group, a C,-C,0-alkylaryl group, a ~1113~3 . - 4 -. C5-C40-arylalkenyl group or a halogen atom and R3 and R' are identical or differ~nt and are a mononuclear or polynuclear hydrocarbon radical which may form a san~wich structure with the central atom Ml.
The formula I also embraces compounds of the formula Ia ~ R~
and of the formula Ib :~
( CR ~ ~ R 1 2 )m R13 (Ib) C R ~ ! R ~ 2 ~
~ . ' ."
. .~
In the formulae Ia and Ib, Ml is a metal of group IVb, Vb ;~
or VIb of the Periodic Table of Element~, for example .~ :
titanium, zirconium, hafnium, vanadium, niobium, tan~
10 talum, chromium, molybdenum and tungsten, preferably :
titanium, zirconium and hafnium.
'~
~ 5 - 2~3 63 R' and R2 are identical or different and are a hydrogen atom, a C,-C,0-alkyl group, preferably a C,-C3-alkyl group, a C~-C~0-alkoxy group, preferably a C,-C3-alkoxy group, a C6-C,0-aryl group, preferably a Cc-C8-aryl group, a C6-C,0-aryloxy group, preferably a C6-C8-aryloxy qroup, a C2-C,0-alkenyl group, preferably a C2-C~-alkenyl group, a C7-C40-arylalkyl group, preferably a C~-C~0-arylalkyl group, a C7-C,0-alkylaryl group, preferably a C~-C~2-alkylaryl group, a Ca-C40-arylalkenyl group, preferably a C8-C,2-arylalkenyl group, or a halogen atom, preferably chlorine or methyl.
R3 and R4 are identical or different and are a mononuclear or polynuclear hydrocarbon radical which may form a sandwich structure with the central atom Ml. R3 and R' are preferably cyclopentadienyl, indenyl, tetrahydro-indenyl, benzoindenyl or fluorenyl, it being po~sible forthe parent structures to carry additional substituents or to be bridged with one another.
R5, R6~ R7~ R~ R9 and Rl are identical or different and are a hydrogen atom, a halogen atom, preferably a fluor-ine, chlorine or bromine atom, a Cl-Cl0-alkyl group, preferably a C,-C,-alkyl group, a C6-C~0-aryl group, preferably a C6-C8-aryl group, a C,-C,0-alkoxy group, preferably a C,-C3-alkoxy group, or an -NRl'2, -SRl', -oSiRl43, -SiRl'3 or -PR'~2 radical in which Rl4 i8 a C,-ClO-alkyl group, preferably a Cl-C3-alkyl group, or a Cc-C
aryl group, preferably a C,-C8-aryl group, or, in the ca~e of Si- or P-containing radicals, also a halogen atom, preferably a chlorine atom, or two adjacent radicals R5, R6, R', R8, R9 or Rl each form a ring with the carbon atoms linking them. Particularly preferred ligands are the substituted compounds of the parent structures indenyl, tetrahydroindenyl, benzoindenyl, fluorenyl and cyclopentadienyl.
Rl3 i8 `~!3 :4 .
- 6 _ 2~363 .. ~ , R15 ~5 R15 R15 R15 2__1 2 12_ --M2_ CR172--o_1,J2_o_ l 16l ~ 6 l 16l 16 1 1 G
~.
:
R 15 R 15R ~ S R 15 -I- -o-I2_ 12 o lZ~
1 1 6 R 16 l ~ o I 16 =BR'5, =AlRls, -Ge-, -Sn-, -0-, -S-, ~S0, -S02, ~NR15, ~C0, -PR1s or =P(o)Rl5, in which R'5, Rl6 and R" are identical or different and are a hydrogen atom, a halogen atom, a C,~
C30-alkyl group, preferably a C,-C4-alkyl group, in particular a methyl group, a C1-C10-fluoroalkyl group, preferably a CF3 group, a C6-C10-fluoroaryl group, preferably a pentafluorophenyl group, a C6-C,0-aryl group, preferably a C6-C6-aryl group, a C,-C,0-alkoxy group, preferably a C1-C4-alkoxy group, in paxticular a methoxy group, a C2-C10-alkenyl group, preferably a C2-C4-alkenyl group, a C7-C40-arylalkyl group, preferably a C,-C10-aryl-alkyl qroup, a C8-C40-arylalkenyl group, preferably a Ca~
Cl2-arylalkenyl group, or a C7-C40-alkylaryl group, preferably a C~-C~2-alkylaryl group, or Rls and Rls or Rl5 and Rl', together with the atoms linking them, each form a ring.
. .
M2 is 3ili~0n ~ germanium or tin, preferably sili~on and germanium.
Rl3 iB preferably -CRlsR'6, -SiRlsR16, -GeR'sRl6, -0-, -S-, 20 eS0, -PRls or -P(O)R1s. ~-Rll and Rl2 are identical or different and have the meaning stated for Rls.
m and n are identical or different and are zero, 1 or 2, :~
preferably zero or 1, m plUB n being zero, 1 or 2, : ~
: . . -- -3 ~3 ~ - 7 --;~
. preferably zero or 1.
Examples of preferred metallocene~ are: -bis(cyclopentadienyl)zirconium dichloride, s! bi~(methylcyclopentadienyl)zirconium dichloride, --bis(n-butylcyclopentadienyl)zirconium dichloride, bis(i-butylcyclopentadienyl)zirconium dichloride, bis(alkylcyclopentadienyl)zirconium dichloride, ~ :
bis(l,2-dimethylcyclopentadienyl)zirconium dichloride, bis(l,3-dimethylcyclopentadienyl)zirconium dichloride, bis(l,2,4-trimethylcyclopentadienyl)zirconium dichloride, bis(l,2,3-trimethylcyclopentadienyl)zirconium dichloride, bis(indenyl)zirconium dichloride, bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, --bis(l-methylindenyl)zirconium dichloride, bis(2-methylindenyl)zirconium dichloride, bis(4-methylindenyl)zirconium dichloride, bis(5-methylindenyl)zirconium dichloride, bis(2-methyl-4,6-di-i-propyl-indenyl)zirconium dichloride, bis(alkylindenyl)zirconium dichloride, bis(cyclopentadienyl)zirconiumdimethyl and bis(cyclopentadienyl)zirconiumdibenzyl, - and further preferred metallocenes:
dialkylsilylbis(indenyl)zirconium dichloride, alkylalkylenebis(indenyl)zirconium dichloride, alkylenebis(indenyl)zirconium dichloride, diarylalkenylbis~indenyl)zirconium dichloride, alkylenebis(indenyl)hafnium dichloride, diarylsilylbis~indenyl)zirconium dichloride, (aryl)(alkyl)bis(indenyl)zirconium dichloride, dialkylgermylbis(indenyl)zirconium dichloride, (alkyl)(alkenyl)silylbis(indenyl)zirconium dicbloride, (aryl)(alkenyl)silylbis(indenyl)zirconium dichloride, dimethylsilylbis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dichloride, diphenylsilylbis(indenyl)zirconium dichloride, 3 ~ S~ .
~.i dimethylgermylbis(indenyl~zirconium dichloride, ~ bis(pentamethylcyclopentadienyl)zirconium dichloride, ~-~
~ dimethyl~ilyl-bi6(l-tetrahydroindenyl)zirconium ;~ dichloride, ;~ S ethylene-bis(1-tetrahydroindenyl)zirconium dichloride, -- ~:
dimethylsilyl-bi~-1-(2-methyltetrahydroindenyl)zirconium ~-~
. dichloride, ethylene-bis-1-(2-methyl-tetrahydroindenyl)zirconium dichloride, ~ :
dimethylsilyl-bis-1-(2,3,5-trimethylcyclopentadienyl)~
zirconium dichloride, ~:
dimethylsilyl-bis-1-(2,4-dimethylcyclopentadienyl)-zirconium dichloride, ethylene-bis(l-indenyl)zirconium dichloride, dimethylsilyl-bis(1-indenyl)zirconium dichloride, diphenylsilyl-bis(l-indenyl)zirconium dichloride, dimethylsilyl-bi~ indenyl)zirconiumdimethyl, dimethylsilyl-bis-1-(2-methyl-indenyl)zirconium dichloride, .
phenylmethylsilyl-bis-1-(2-methyl-indenyl)zirconium dichloride, :-~
dimethylsilyl-bis-1-(2-methyl-4-ethylindenyl)zirconium -:
dichloride, dimethylsilyl-bis-1-(2-methyl-4-i-propylindenyl)zirconium -~
dichloride and ethylene-bis-1-(4,7-dimethyl-indenyl)zirconium : -dichloride, and other metallocenes which can be used:
diphenylmethylene(9-fluorenyl)(cyclopentadienyl)zirconium 30 dichloride, :
dimethylsilyl(9-fluorenyl)(cyclopentadienyl)zirconium dichloride, isopropylidene(9-fluorenyl)(cyclopentadienyl)zirconium dichloride and ~ :-isopropylidene(l-indenyl)(cyclopentadienyl)zirconium dichloride. ~ -~
2~113~3 .,~ g ~ ~, ~Ethylenebis~indenyl)zirconium dichloride, bi6(indenyl)-:-~zirconium dichloride, bis(4,5,6,7-tetrahydroindenyl~-`~,zirconium dichloride, bTts(cyclopentadienyl)zirconium-dimethyl, bi6(methylcyclopentadienyl)zirconium di-chloride, bis~n-butylcyclopentadienyl)zirconium di-chloride and bis(cyclopentadienyl)zirconium dichloride ~ -are particularly preferably used.
In principle, any compound which, owing to it~ Lewis acidity, i8 capable of converting the neutral metallocene into a cation and stabilizing it ("labile coordination") is sllitable as a cocataly~t. In addition, the cocatalyst or the anion formed from it should not undergo any further reactions with the metallocene cation.
The cocatalyst of the catalyst to be used according to the invention is preferably an aluminoxane or another organoaluminum compound. The aluminoxane i8 a compound of the formula IIa for the linear type and/or of the formula IIb for the cyclic type R l ~ l _ ", _ ~ R I ~
A I-- t A I--O ~ A ~ ( I I o ) ~ l l b ) In these formulae, R16' is a C1-C6-alkyl group, preferably 20 methyl, ethyl, n-butyl or isobutyl, in particular methyl -~
or butyl, and p is an integer from 4 to 30, preferably 10 to 20, it being possible for radicals RlB also to be different. Methylaluminoxane and methylbutylalllm;noxane ' ~
: . :
:~ 2~ 13~3 .,"~ .... ..
having a methyl : butyl ratio of 100 : 1 to 1 : 1 are particularly preferred, butyl being intended to mean n-butyl or isobutyl or n-butyl/isobutyl mixtures and the radicals having any distribution, preferably a random distribution.
,~' :
A further possibility is the u~e of ~upported aluminox-anes by, for example, suspending the carrier under inert ;
conditions in a solution of at lea~t one alkylaluminum and reacting this suspen~ion with water.
: : ::
The catalyst to be used according to the invention can be prepared by reacting the transition metal compound with the organoaluminum compound by various methods~
!. 1) The organoaluminum compound is combined, in a suitable solvent, such as, for example, pentane, hexane, heptane, toluene or dichloromethane, with the transition metal compound at a temperature of -20 to +120C, preferably at -10 to 40C, by thorough mlxing, for example by stirring. The molar ratio Al : M1 is 1 : 1 to -~
10,000 : 1, preferably 10 : 1 to 2,000 : 1, and the reaction time is 5 to 120 minutes, preferably 10 to 30 minutes, at an aluminum concentration of more than 0.01 mol/dm3, preferably more than 0.1 mol/dm3, under inert gas.
. .
2) An insoluble or supported aluminoxane, in the form of a suspension having a content of 1 to 40% by weight, preferably 5 to 20% by weight, in an aliphatic, inert suspending agent, such as n-decane, hexane, heptane or diesel oil, is reacted with a finely milled transition metal compound or its ~olution in an inert solvent, ~uch as toluene, hexane, heptane or dichloromethane, in a molar ratio Al : M1 of 1 : 1 to 10,000 : 1, preferably 10 : 1 to 2,000 : 1, at a temperature of -20 to ~120C, preferably -20 to 40C, for a reaction time of 5 to 120 minutes, preferably lQ to 60 minutes, with thorough mixing.
~ :
:J ~
~i~13~3 The catalyst thus prepared i8 either used as a suspension directly for the polymerization or separated off by filtration or decanting and washed with an inert suspend-ing agent, such as toluene, n-decane, hexane, heptane, diesel oil or dichloromethane. After such a wa~h, it can be metered into the polymerization system either as a powder after drying in vacuo or in solvent-moist form after resuspen~ion as a suspension in an inert suspending agent, such as, for example, toluene, hexane, heptane, diesel oil or dichloromethane.
The catalyst prepared according to 1) or 2) may also be 1 used in prepolymerized form, or the metallocene can be ;~ applied to a carrier before being used.
.!, One of the olefins to be polymerized is preferably used for the prepolymerization. Suitable carriers are, for example, silica gel, alumina, solid aluminoxane or other organic or inorganic carriers. A polyolefin carrier is also suitable.
Instead of the organoaluminum compounds, compounds of the formulae Rl9~NH4~BR2" R19~PH, BR20~ R19CBR~0 or BR20 also be used as cocatalysts. In these formulae, x is a number from 1 to 4, the radicals R19 are identical or different, preferably identical, and are C~-C1O-alkyl or C6-Cl~-aryl, or two radicals Rl9, together with the atom linking them, form a ring, and the radicals R20 are identical or different, preferably identical, and are C6-Cl~-aryl which may be substituted by alkyl, haloalkyl or fluorine. In particular, R19 i8 ethyl, propyl, butyl or phenyl and R20 is phenyl, pentafluorophenyl, 3,5-bis-30 trifluoromethylphenyl, mesityl, xylyl or tolyl. -These cocataly6ts are particularly suitable in combina-¦ tion with metallocenes of the formula I when Rl and R' are a Cl-C1O-alkyl group or an aryl or benzyl group, prefer-ably a methyl group. The derivatization to give the metallocenes of the formula I can be carried out by ' ~ ~ ~
: :
2 ~ 3 :::
methods known from the literature, for example by reac- -~
tion with alkylating agents, ~uch a~ methyllithium (cf. -~
~ Organometallic~ 9 ~1990) 1539; J. Am. Chem. Soc. 95 -~, (1973) 6263).
. ~. ., 3 5 When the abovementioned cocatalysts are u~ed, the actual ~-~
(active) polymerization catalygt comprises the reaction ~;, product of metallocene and of one of the stated com- ~ ;~
pounds. This reaction product i8 therefore first prefer-ably prepared outside the polymerization reactor in a 10 separate step using a suitable solvent, such as, for ~17 example, toluene.
The transition metal component is used in a concentration of, based on the transition metal, 10-3 to 10-7, preferably ; -, 10-4 to 10-6~ mol of Ml per dm3 of solvent- The cocataly3t ~
15 is used in a concentration of, based on the content of ~-aluminum, 10-5 to 10-1 mol, preferably 10-4 to 10-2 mol, per dm3 of olvent. In principle, however, higher concentra-tions are also possible.
,~
~ .
The polymer~zation is carried out as a suspension poly- -~
20 merization with evaporative cooling. -~
Suitable suspending agents are low-boiling hydrocarbons, such a~, for example, propane, i~obutane or n-butane, or low-boiling halogenated hydrocarbons, ~uch as, for ~--example, methylene chloride, and their mixtures with one 25 another or with other suspending agents, such as hexane, heptane, octane, diesel oils or toluene, or with olefins, as described above. Furthermore, up to 40% by weight of the suspending agent may be liguid 012fins. A preferred main component of the suspending agent i8 propane.
~.
30 The polymerization is carried out at a temperature of 40-95C, at an olefin partial pressure of 0.5 to 30 bar, at a hydrogen partial pressure of O to 10 bar, with the addition (based on Al) of 0.01 to 10 mmol of cocatalyst/ -dm3 of suspending agent and with a catalyst/cocatalyst æ ~ :~
~ ' ' .', ~ ' ,, t'', ~ , ~ . ' ' " ' ~ :. ' ' ' , , . ' `
~ 1 1 1 3 6 3 ~ ratio of 1 : 1 to 1 : 1,000.
i-~ The total pressure of the ~y~tem i8 not more than 150% of the vapor pressure of the suspending agent at the poly-merization temperature. It i8 preferable to use propane as a suspending agent at 60-80C and a total pressure of 23 to 48 bar, particularly preferably at 70C and 26 to 39 bar.
I
In order to regulate the molar weight, hydrogen is additionally introduced or the polymerization temperature is changed, it also being possible to obtain polymers having a broad molecular weight distribution by periodic '''~? changes or a defined multistage process-For the polymerization, another alkylalllm;num compound, such as, for example, trimethylaluminum, triethyl-aluminum, triisobutylaluminum or isoprenylaluminum, mayadditionally be introduced for rendering the polymeriza-tion system inert, in a concentration of 1 to 0.001 mmol of Al per kg of reactor content, before the addition of the catalyst.
:.
20 In addition, the polymer molecular weight achieved in the ; ~-procesa according to the invention is determined by the type of metallocene used, by the Al/Zr ratio of the ~`
catalyst system and by the addition and type of further alkylaluminums.
The polymerization ;is aarried out batchwise or con-tinuously in one or more stages, and any residence times can be realized owing to the only slight time-dependent decrease in the polymerization activity.
For the suspension process with evaporative cooling, the narrow molecular weight distribution achievable with metallocene catalyst systems is also advantageous since ~-it makes it possible to achieve a lower proportion of volatile oligomers, which may accumulate in the '~'. '- -'' '.
, - 14 ~ 1363 condensers during prolonged operation. :::
~3 The polymerization i8 carried out in an apparatus a~ :
shown schematically in the Figure. ~
~ In the Figure, the meaning~ are as follows: ~ :
`: 5 1 Reactor (if neces3ary with stirrer) ~ 2 Separating column/stillhead ~ ~:
:~ 3 Pipeline 3 4 Condenser '`.~1 ~j 5 Pipeline 10 6 Equilibrating vessel 7 Pipeline 8 Pump ::~
9 Pipeline ~-Valve 15 11 Pipeline : ~ :
12 Valve 13 Feed pipe for monomer~ and hydrogen 14 Feed pipe for suspending agent 15 Feed pipe for cataly~t and cocatalyst :~
20 16 Feed pipe for alkylaluminum or additional cocatalyst ~:
17 Discharge pipe ~:
The polymerization reactor (1) iB equipped with a separa~
ting column (stillhead) (2). From this separating column a pipeline (3) leads to a condenser (4), which however 25 may also be connected directly to the ~eparating column .
(2). A pipeline (5) leads to an equilibrating vessel (6) which is connected via a pipeline .(7), a pump (8) and a pipeline (9) to the reactor (1). Downstream of the pump ~:~
(8), a pipeline (11) leads to the ~eparating column/
stillhead (2). The pipeline (9~ can be ~hut off by a valve (10) and the pipeline (11) by a valve (12). The feed pipes (13) and (14) also lead into the reactor (1), ~c:-the pipe (14) additionally being connected to a feed pipe :~
(15). The reactor (1) can be emptied through the dis~
charge pipe (17). A feed pipe (16) is also connected to the pipeline (7).
.:"~
~1~13~3 The suspending agent present in the reactor (1) i8 aaused $ to boil by the heat of polymerization and flows through -~ the pipeline (3) into the condenser (4), where it is j! condensed. Low molecular weight product~ are retained in the separating column (23. The condensed ~u3pendinq agent i~ fed through the pipeline (5) to the equilibrating vessel (6), from where it i~ removed through the pipeline (7) and is recycled by means of the pump (8) through the pipeline (9) and the valve (10) into i 10 the reactor (1). Additional activator (alkylaluminum or cocatalyst) is fed through the pipeline (16) into the stream of the suspending agent. In the preparation of low molecular weight product~, some of the suspending agents can be fed through the pipe (11) and the valve (12) into the separating column (2) to support there the recycling of entrained products into the reactor (1).
Monomers and hydrogen are fed into the reactor (1) ~-through the feed pipe (13), and fresh su~pending agent through the feed pipe (14). The mixture of cataly~t and cocatalyst is introduced into the stream of the suspending agent through the feed pipe (15). The polymer -wax formed is removed from the reactor (1) through the discharge pipe (17). -~
: ~
In order to increase the yield, or for a two-stage process, a second reactor may be arranged downstream of the suspen3ion discharge (17).
In order to inarease the solids content at the suspension discharge, the latter can be mounted on a sedimentation part in the reactor bottom. This reduces the proportion of monomers dissolved in the suspending agent and the operating costs for recycling the suspending agent and maintaining the cocatalyst level in the reactor.
The catalyst can be metered as a solution or in supported form as a suspension. For preactivation, some of the cocatalyst (30 to 80 mol %, based on Al) i8 mixed with the cataly~t at least 10 minutes before metering into the ~ - 16 - , reactor or is already part of the supported catalyst.
The cataly~t 601ution thus prepared can be metered into the reactor either directly or preferably in dilute form via the feed pipe (14) of the suspending agent.
Y~ 5 In order to regulate the cocatalyst level, the cocatalyst ~l may furthermore be metered separately and together with further alkylaluminums into the reactor or into the condenRate return (7).
.
In general, hydrocarbons, such as toluene, heptane, hexane, pentane, butane or propane, and industrial diesel oils are suitable as solvents or suspending agentR for catalyst or cocatalyst.
::
It i8 in general possible to dispense with stirring of the reactor content since the boiling suspending agent 15 produces good circulation. ~-Further processing of the suRpension of wax and low boilers, conventional methods for wax proce~sing can be used after the pressure has been released.
.--The polyolefin wax prepared according to the invention is separated from the suspending agent and dried.
Polyethylene waxes prepared according to the invention ~-are composed of 100 to 80% by weight, based on the total ~-~
polymer, of ethylene units and 0 to 20% by weight, based ¦ on the total polymer, of units which are derived from ;
another olefin, a diolefin or another unsaturated hydrocarbon, in particular propylene, l-butene, 2-butene, 4-methyl-1-pentene or l-hexene. They have an average molecular weight M~ of about 500 to about 50,000, preferably about 1,000 to about 30,000. The molecular 30 weight distribution (polydispersity) M~/M~ is extremely -~
narrow and is about 1 to 5, preferably 1 to 3. The melting range of the wax can be adjusted as required from about 126 to 132C for a homopolymer down to about 80 to ~1 2~13~3 90C by copolymerization.
Polypropylene waxes prepared according to the invention ~;j are composed of 80 to 100, preferably 90 to 100, % by weight, based on the total polymer, of propylene units and 0 to 20, preferably 0 to 10, % by weight, based on ~:~ the total polymer, of units which are derived from eth-., ylene or one of the other olefins described above. Th~y ,~ have an average molecular weight M~ of 1,000 to 50,000 g/
mol, preferably 8,000 to 45,000 g/mol, a polydi~persity `~ 10 ~,/M~ of 1 to 5, preferably 1 to 3, a melting point of 50 to 160~C, preferably 90 to 160C, a melt viscosity of 100 to 80,000 mPa.s, preferably 120 to 50,000 mPa.s, at 170C
and a random distribution of the comonomer units in the polymer chain.
~ ' The evaporative cooling require~ a8 high a proportion as possible of condensable gases in the vapor space and i~
therefore useful only in the case of catalyst systems which polymerize with very high conversions even at low ethylene pre~sure. Also advantageous for carrying out the evaporative cooling is the low hydrogen parti~
pressure which, owing to the good hydrogen re~ponso characteristics of the metallocene catalysts, i8 required for achieving the polymer molecular weights typical of -~
waxes.
.
A further advantage of the evaporative cooling is the avoidance of a reduction in the cooling capacity of the polymerization reactor through the build-up of wall depo3its. Furthermore, dispensing with wall cooling results in reduced deposit formation. The com~ination of evaporative cooling with back-washing makes it possible to free the upper part of the reactor continuously or discontinuously from product particles, with the result that shutdowns for aleaning the pipelines and condenser to remove entrained particles can be avoided. The introduction of back-washing thus permit~ continuous operation.
-~: ~111363 ~ 18 -A further advantage of this polymerization proc~ss i8 the ;~ high space-time yield which can be realized by the v efficient evaporative cooling, regardle~s o~ the ~ize of the polymerization system.
In principle, any compound which, owing to it~ Lewis acidity, i8 capable of converting the neutral metallocene into a cation and stabilizing it ("labile coordination") is sllitable as a cocataly~t. In addition, the cocatalyst or the anion formed from it should not undergo any further reactions with the metallocene cation.
The cocatalyst of the catalyst to be used according to the invention is preferably an aluminoxane or another organoaluminum compound. The aluminoxane i8 a compound of the formula IIa for the linear type and/or of the formula IIb for the cyclic type R l ~ l _ ", _ ~ R I ~
A I-- t A I--O ~ A ~ ( I I o ) ~ l l b ) In these formulae, R16' is a C1-C6-alkyl group, preferably 20 methyl, ethyl, n-butyl or isobutyl, in particular methyl -~
or butyl, and p is an integer from 4 to 30, preferably 10 to 20, it being possible for radicals RlB also to be different. Methylaluminoxane and methylbutylalllm;noxane ' ~
: . :
:~ 2~ 13~3 .,"~ .... ..
having a methyl : butyl ratio of 100 : 1 to 1 : 1 are particularly preferred, butyl being intended to mean n-butyl or isobutyl or n-butyl/isobutyl mixtures and the radicals having any distribution, preferably a random distribution.
,~' :
A further possibility is the u~e of ~upported aluminox-anes by, for example, suspending the carrier under inert ;
conditions in a solution of at lea~t one alkylaluminum and reacting this suspen~ion with water.
: : ::
The catalyst to be used according to the invention can be prepared by reacting the transition metal compound with the organoaluminum compound by various methods~
!. 1) The organoaluminum compound is combined, in a suitable solvent, such as, for example, pentane, hexane, heptane, toluene or dichloromethane, with the transition metal compound at a temperature of -20 to +120C, preferably at -10 to 40C, by thorough mlxing, for example by stirring. The molar ratio Al : M1 is 1 : 1 to -~
10,000 : 1, preferably 10 : 1 to 2,000 : 1, and the reaction time is 5 to 120 minutes, preferably 10 to 30 minutes, at an aluminum concentration of more than 0.01 mol/dm3, preferably more than 0.1 mol/dm3, under inert gas.
. .
2) An insoluble or supported aluminoxane, in the form of a suspension having a content of 1 to 40% by weight, preferably 5 to 20% by weight, in an aliphatic, inert suspending agent, such as n-decane, hexane, heptane or diesel oil, is reacted with a finely milled transition metal compound or its ~olution in an inert solvent, ~uch as toluene, hexane, heptane or dichloromethane, in a molar ratio Al : M1 of 1 : 1 to 10,000 : 1, preferably 10 : 1 to 2,000 : 1, at a temperature of -20 to ~120C, preferably -20 to 40C, for a reaction time of 5 to 120 minutes, preferably lQ to 60 minutes, with thorough mixing.
~ :
:J ~
~i~13~3 The catalyst thus prepared i8 either used as a suspension directly for the polymerization or separated off by filtration or decanting and washed with an inert suspend-ing agent, such as toluene, n-decane, hexane, heptane, diesel oil or dichloromethane. After such a wa~h, it can be metered into the polymerization system either as a powder after drying in vacuo or in solvent-moist form after resuspen~ion as a suspension in an inert suspending agent, such as, for example, toluene, hexane, heptane, diesel oil or dichloromethane.
The catalyst prepared according to 1) or 2) may also be 1 used in prepolymerized form, or the metallocene can be ;~ applied to a carrier before being used.
.!, One of the olefins to be polymerized is preferably used for the prepolymerization. Suitable carriers are, for example, silica gel, alumina, solid aluminoxane or other organic or inorganic carriers. A polyolefin carrier is also suitable.
Instead of the organoaluminum compounds, compounds of the formulae Rl9~NH4~BR2" R19~PH, BR20~ R19CBR~0 or BR20 also be used as cocatalysts. In these formulae, x is a number from 1 to 4, the radicals R19 are identical or different, preferably identical, and are C~-C1O-alkyl or C6-Cl~-aryl, or two radicals Rl9, together with the atom linking them, form a ring, and the radicals R20 are identical or different, preferably identical, and are C6-Cl~-aryl which may be substituted by alkyl, haloalkyl or fluorine. In particular, R19 i8 ethyl, propyl, butyl or phenyl and R20 is phenyl, pentafluorophenyl, 3,5-bis-30 trifluoromethylphenyl, mesityl, xylyl or tolyl. -These cocataly6ts are particularly suitable in combina-¦ tion with metallocenes of the formula I when Rl and R' are a Cl-C1O-alkyl group or an aryl or benzyl group, prefer-ably a methyl group. The derivatization to give the metallocenes of the formula I can be carried out by ' ~ ~ ~
: :
2 ~ 3 :::
methods known from the literature, for example by reac- -~
tion with alkylating agents, ~uch a~ methyllithium (cf. -~
~ Organometallic~ 9 ~1990) 1539; J. Am. Chem. Soc. 95 -~, (1973) 6263).
. ~. ., 3 5 When the abovementioned cocatalysts are u~ed, the actual ~-~
(active) polymerization catalygt comprises the reaction ~;, product of metallocene and of one of the stated com- ~ ;~
pounds. This reaction product i8 therefore first prefer-ably prepared outside the polymerization reactor in a 10 separate step using a suitable solvent, such as, for ~17 example, toluene.
The transition metal component is used in a concentration of, based on the transition metal, 10-3 to 10-7, preferably ; -, 10-4 to 10-6~ mol of Ml per dm3 of solvent- The cocataly3t ~
15 is used in a concentration of, based on the content of ~-aluminum, 10-5 to 10-1 mol, preferably 10-4 to 10-2 mol, per dm3 of olvent. In principle, however, higher concentra-tions are also possible.
,~
~ .
The polymer~zation is carried out as a suspension poly- -~
20 merization with evaporative cooling. -~
Suitable suspending agents are low-boiling hydrocarbons, such a~, for example, propane, i~obutane or n-butane, or low-boiling halogenated hydrocarbons, ~uch as, for ~--example, methylene chloride, and their mixtures with one 25 another or with other suspending agents, such as hexane, heptane, octane, diesel oils or toluene, or with olefins, as described above. Furthermore, up to 40% by weight of the suspending agent may be liguid 012fins. A preferred main component of the suspending agent i8 propane.
~.
30 The polymerization is carried out at a temperature of 40-95C, at an olefin partial pressure of 0.5 to 30 bar, at a hydrogen partial pressure of O to 10 bar, with the addition (based on Al) of 0.01 to 10 mmol of cocatalyst/ -dm3 of suspending agent and with a catalyst/cocatalyst æ ~ :~
~ ' ' .', ~ ' ,, t'', ~ , ~ . ' ' " ' ~ :. ' ' ' , , . ' `
~ 1 1 1 3 6 3 ~ ratio of 1 : 1 to 1 : 1,000.
i-~ The total pressure of the ~y~tem i8 not more than 150% of the vapor pressure of the suspending agent at the poly-merization temperature. It i8 preferable to use propane as a suspending agent at 60-80C and a total pressure of 23 to 48 bar, particularly preferably at 70C and 26 to 39 bar.
I
In order to regulate the molar weight, hydrogen is additionally introduced or the polymerization temperature is changed, it also being possible to obtain polymers having a broad molecular weight distribution by periodic '''~? changes or a defined multistage process-For the polymerization, another alkylalllm;num compound, such as, for example, trimethylaluminum, triethyl-aluminum, triisobutylaluminum or isoprenylaluminum, mayadditionally be introduced for rendering the polymeriza-tion system inert, in a concentration of 1 to 0.001 mmol of Al per kg of reactor content, before the addition of the catalyst.
:.
20 In addition, the polymer molecular weight achieved in the ; ~-procesa according to the invention is determined by the type of metallocene used, by the Al/Zr ratio of the ~`
catalyst system and by the addition and type of further alkylaluminums.
The polymerization ;is aarried out batchwise or con-tinuously in one or more stages, and any residence times can be realized owing to the only slight time-dependent decrease in the polymerization activity.
For the suspension process with evaporative cooling, the narrow molecular weight distribution achievable with metallocene catalyst systems is also advantageous since ~-it makes it possible to achieve a lower proportion of volatile oligomers, which may accumulate in the '~'. '- -'' '.
, - 14 ~ 1363 condensers during prolonged operation. :::
~3 The polymerization i8 carried out in an apparatus a~ :
shown schematically in the Figure. ~
~ In the Figure, the meaning~ are as follows: ~ :
`: 5 1 Reactor (if neces3ary with stirrer) ~ 2 Separating column/stillhead ~ ~:
:~ 3 Pipeline 3 4 Condenser '`.~1 ~j 5 Pipeline 10 6 Equilibrating vessel 7 Pipeline 8 Pump ::~
9 Pipeline ~-Valve 15 11 Pipeline : ~ :
12 Valve 13 Feed pipe for monomer~ and hydrogen 14 Feed pipe for suspending agent 15 Feed pipe for cataly~t and cocatalyst :~
20 16 Feed pipe for alkylaluminum or additional cocatalyst ~:
17 Discharge pipe ~:
The polymerization reactor (1) iB equipped with a separa~
ting column (stillhead) (2). From this separating column a pipeline (3) leads to a condenser (4), which however 25 may also be connected directly to the ~eparating column .
(2). A pipeline (5) leads to an equilibrating vessel (6) which is connected via a pipeline .(7), a pump (8) and a pipeline (9) to the reactor (1). Downstream of the pump ~:~
(8), a pipeline (11) leads to the ~eparating column/
stillhead (2). The pipeline (9~ can be ~hut off by a valve (10) and the pipeline (11) by a valve (12). The feed pipes (13) and (14) also lead into the reactor (1), ~c:-the pipe (14) additionally being connected to a feed pipe :~
(15). The reactor (1) can be emptied through the dis~
charge pipe (17). A feed pipe (16) is also connected to the pipeline (7).
.:"~
~1~13~3 The suspending agent present in the reactor (1) i8 aaused $ to boil by the heat of polymerization and flows through -~ the pipeline (3) into the condenser (4), where it is j! condensed. Low molecular weight product~ are retained in the separating column (23. The condensed ~u3pendinq agent i~ fed through the pipeline (5) to the equilibrating vessel (6), from where it i~ removed through the pipeline (7) and is recycled by means of the pump (8) through the pipeline (9) and the valve (10) into i 10 the reactor (1). Additional activator (alkylaluminum or cocatalyst) is fed through the pipeline (16) into the stream of the suspending agent. In the preparation of low molecular weight product~, some of the suspending agents can be fed through the pipe (11) and the valve (12) into the separating column (2) to support there the recycling of entrained products into the reactor (1).
Monomers and hydrogen are fed into the reactor (1) ~-through the feed pipe (13), and fresh su~pending agent through the feed pipe (14). The mixture of cataly~t and cocatalyst is introduced into the stream of the suspending agent through the feed pipe (15). The polymer -wax formed is removed from the reactor (1) through the discharge pipe (17). -~
: ~
In order to increase the yield, or for a two-stage process, a second reactor may be arranged downstream of the suspen3ion discharge (17).
In order to inarease the solids content at the suspension discharge, the latter can be mounted on a sedimentation part in the reactor bottom. This reduces the proportion of monomers dissolved in the suspending agent and the operating costs for recycling the suspending agent and maintaining the cocatalyst level in the reactor.
The catalyst can be metered as a solution or in supported form as a suspension. For preactivation, some of the cocatalyst (30 to 80 mol %, based on Al) i8 mixed with the cataly~t at least 10 minutes before metering into the ~ - 16 - , reactor or is already part of the supported catalyst.
The cataly~t 601ution thus prepared can be metered into the reactor either directly or preferably in dilute form via the feed pipe (14) of the suspending agent.
Y~ 5 In order to regulate the cocatalyst level, the cocatalyst ~l may furthermore be metered separately and together with further alkylaluminums into the reactor or into the condenRate return (7).
.
In general, hydrocarbons, such as toluene, heptane, hexane, pentane, butane or propane, and industrial diesel oils are suitable as solvents or suspending agentR for catalyst or cocatalyst.
::
It i8 in general possible to dispense with stirring of the reactor content since the boiling suspending agent 15 produces good circulation. ~-Further processing of the suRpension of wax and low boilers, conventional methods for wax proce~sing can be used after the pressure has been released.
.--The polyolefin wax prepared according to the invention is separated from the suspending agent and dried.
Polyethylene waxes prepared according to the invention ~-are composed of 100 to 80% by weight, based on the total ~-~
polymer, of ethylene units and 0 to 20% by weight, based ¦ on the total polymer, of units which are derived from ;
another olefin, a diolefin or another unsaturated hydrocarbon, in particular propylene, l-butene, 2-butene, 4-methyl-1-pentene or l-hexene. They have an average molecular weight M~ of about 500 to about 50,000, preferably about 1,000 to about 30,000. The molecular 30 weight distribution (polydispersity) M~/M~ is extremely -~
narrow and is about 1 to 5, preferably 1 to 3. The melting range of the wax can be adjusted as required from about 126 to 132C for a homopolymer down to about 80 to ~1 2~13~3 90C by copolymerization.
Polypropylene waxes prepared according to the invention ~;j are composed of 80 to 100, preferably 90 to 100, % by weight, based on the total polymer, of propylene units and 0 to 20, preferably 0 to 10, % by weight, based on ~:~ the total polymer, of units which are derived from eth-., ylene or one of the other olefins described above. Th~y ,~ have an average molecular weight M~ of 1,000 to 50,000 g/
mol, preferably 8,000 to 45,000 g/mol, a polydi~persity `~ 10 ~,/M~ of 1 to 5, preferably 1 to 3, a melting point of 50 to 160~C, preferably 90 to 160C, a melt viscosity of 100 to 80,000 mPa.s, preferably 120 to 50,000 mPa.s, at 170C
and a random distribution of the comonomer units in the polymer chain.
~ ' The evaporative cooling require~ a8 high a proportion as possible of condensable gases in the vapor space and i~
therefore useful only in the case of catalyst systems which polymerize with very high conversions even at low ethylene pre~sure. Also advantageous for carrying out the evaporative cooling is the low hydrogen parti~
pressure which, owing to the good hydrogen re~ponso characteristics of the metallocene catalysts, i8 required for achieving the polymer molecular weights typical of -~
waxes.
.
A further advantage of the evaporative cooling is the avoidance of a reduction in the cooling capacity of the polymerization reactor through the build-up of wall depo3its. Furthermore, dispensing with wall cooling results in reduced deposit formation. The com~ination of evaporative cooling with back-washing makes it possible to free the upper part of the reactor continuously or discontinuously from product particles, with the result that shutdowns for aleaning the pipelines and condenser to remove entrained particles can be avoided. The introduction of back-washing thus permit~ continuous operation.
-~: ~111363 ~ 18 -A further advantage of this polymerization proc~ss i8 the ;~ high space-time yield which can be realized by the v efficient evaporative cooling, regardle~s o~ the ~ize of the polymerization system.
5 The Example~ which follow are intended to illustrate the invention in detail.
The meanings are as follows:
VN - Viscosity number in cm3~g MW 3 Weight average molecular determined by 1 10 weight gel permeation ~ -M~ = Number average molecular ~ ~ chromatography ,; weight ~4, MW/M~ ~ Polydisper~ity J ~ (Numerical data in g/mol) 15 MV e Melt viscosity, determined using -;~
a rotational viscometer at 140C
BD - Bulk density of the polymer powder in g/dm3 Nelting points, crystallization points, the half-widths thereof, the enthalpies of fusion and of cry~tallization 20 and the glass transition temperature~ ~T9) were ;~M~
determined by DSC measurements (10C/min heating/coolinq ~-rate). -. ~
Examples All glass apparatuses were heated in vacuo ~nd flu~hed with argon or nitrogen. All operations were carried out in the absence of moisture and oxygen in Schlenk vss~els.
The solvents u~ed were each freshly distilled over Na/R
alloy under argon and stored in Schlenk vessels.
The stated polymer melting points are taken from a DSC
measurement for the second melting ~10C~min). The i~otactic index was determined from FT-IR spectra without prior extraction of the sample, via the intensity ratio of the bands at 998 cm~l and 972 cm~', according to Dechant, "IR-spectroskopische Untersuchungen von Poly-meren" tIR spectroscopic investigations of polymers], . .
- 19- 21113~3 .~
Akademie Vlg., Berlin 1972.
:: -Methylaluminoxane wa~ obtained commercially as a 10~
strength toluene solution and, according to the all~inum determination, contained 36 mg of Al/cm3. The average degree of oligomerization according to the freezing point - depression in ~enzene was n = 20.
:~, ::
The aluminum determination was carried out by complexo--~ metric titration according to Schwarzenbach, after hydrolysis with water and sulfuric acid.
'. . ~
The polymerizations were carried out in an apparatus similar to that shown in the Figure.
.
Example 1 30 kg of propane and 2.70 kg of propylene and 100 cm3 of ~-a solution of methylaluminoxane in toluene were intro-duced into an apparatus according to the Figure h~ving a 100 dm3 vessel and flushed with nitrogen 0.5 b~r hydrogen and 4 bar ethylene were fed in while stirring at 170 rpm.
At the same time, 35 mg of bis(indenyl)zirconium di-chloride were dissolved in 100 cm3 of the solution of methylaluminoxane in toluene and stirring was carried out ~ -for 15 minutes. -~
~ ' The stirrer in the reactor wa8 switched off and the polymerization was started by pumping in the catalyst solution over 10 minutes. The internal temperature of the reactor increased rapidly and was regulated at 70C
by subseguently feeding in ethylene. The relative concentration of the gases in the vapor space of the reactor was monitored with the aid of a gas chromatograph (GC). Hydrogen and propylene were subsequently metered in at a con~tant ratio to the ethylene according to GC. ;~
A total pressure of 30 bar was achieved at equilibrium.
~ ~1113~3 The valves (10) and (12) were set 80 that the pump (8) delivered 10% by volume of the circulation via pipe ~
~- into the ~tillhead (2) of the reactor (1). After a polymerization tLme of 1 hour, the propane wax ~uspension 5 wa discharged into a proceesing ves~el and the catalyst ; was deactivated by adding isopropanol. After the propanehad been distilled off and the product dried at reduced pressure, 11.2 kg of copolymer wax h~ving a VN of -;
22 cm3/g~ a melting point (DSC) of 112C and a DSC en-~1 10 thalpy of fu~ion of 138 J/g were obtained when the ~' processing vessel was opened. The viscosity of the melt --~i was 1,200 mPa.s at 140C. The propylene content was `i 4.4 mol % according to '3C-NMR. ~ -~
The experiment was repeated four times. The yield 15 remained constant at about 5% by weight. After the 3 reactor was opened, no wall deposits were found, apart `~ from finely divided product residues on the bottom.
Comparative Example A ~--Example 1 was repeated, the double jacket of the reactor being connected to a thermostat ~ystem and pipe t3) and valves (10) and (12) being closed. The polymerization was then continued at 30C by adding the catalyst and thereafter with cooling to an internal reactor temperature of 70C. Ethylene was continuously metered in up to a total pressure of 30 bar, and propylene and hydrogen were added in accordance with the result~ of the GC measurement.
After 1 hour, 10.5 kg of copolymer wax having a VN of 19 ~m3/g and a melt viscosity of 800 mPa.s at 140C
3C resulted.
The experiment was repeated four times. The dif~erence between jacket temperature and internal reactor tempera-ture increa~ed with progressive operating time. After the reactor had been opened, a cohesive wax depo~it C ~ ~ Ob _ ~ ~ f ~
;~111363 ,~ i having a thickness of about 0.5 mm was found on the inner wall of the reactor ; `
.~ Comparative Example B ~;
Example 1 was repeated, the valve (12) remaining closed during operation.
~ . ~
After the processing vessel had been opened, 11.6 kg of copolymer wax having a VN of 20 cm3/g and a melt Vi9 cosity of 910 mPa.s at 140C were obtained. The experi-ment was repeated four times. After the reactor had been opened, no wall deposits were found, as in 2xample 1.
Loose deposits of a fine material were found in the reactor stillhead (2) and partly in the pipe (3). The VN
of 18 cm3/g indicated that the deposits were composed mainly of entrained product and only to a small extent of oligomer~.
, .,~
.' ~
: -
The meanings are as follows:
VN - Viscosity number in cm3~g MW 3 Weight average molecular determined by 1 10 weight gel permeation ~ -M~ = Number average molecular ~ ~ chromatography ,; weight ~4, MW/M~ ~ Polydisper~ity J ~ (Numerical data in g/mol) 15 MV e Melt viscosity, determined using -;~
a rotational viscometer at 140C
BD - Bulk density of the polymer powder in g/dm3 Nelting points, crystallization points, the half-widths thereof, the enthalpies of fusion and of cry~tallization 20 and the glass transition temperature~ ~T9) were ;~M~
determined by DSC measurements (10C/min heating/coolinq ~-rate). -. ~
Examples All glass apparatuses were heated in vacuo ~nd flu~hed with argon or nitrogen. All operations were carried out in the absence of moisture and oxygen in Schlenk vss~els.
The solvents u~ed were each freshly distilled over Na/R
alloy under argon and stored in Schlenk vessels.
The stated polymer melting points are taken from a DSC
measurement for the second melting ~10C~min). The i~otactic index was determined from FT-IR spectra without prior extraction of the sample, via the intensity ratio of the bands at 998 cm~l and 972 cm~', according to Dechant, "IR-spectroskopische Untersuchungen von Poly-meren" tIR spectroscopic investigations of polymers], . .
- 19- 21113~3 .~
Akademie Vlg., Berlin 1972.
:: -Methylaluminoxane wa~ obtained commercially as a 10~
strength toluene solution and, according to the all~inum determination, contained 36 mg of Al/cm3. The average degree of oligomerization according to the freezing point - depression in ~enzene was n = 20.
:~, ::
The aluminum determination was carried out by complexo--~ metric titration according to Schwarzenbach, after hydrolysis with water and sulfuric acid.
'. . ~
The polymerizations were carried out in an apparatus similar to that shown in the Figure.
.
Example 1 30 kg of propane and 2.70 kg of propylene and 100 cm3 of ~-a solution of methylaluminoxane in toluene were intro-duced into an apparatus according to the Figure h~ving a 100 dm3 vessel and flushed with nitrogen 0.5 b~r hydrogen and 4 bar ethylene were fed in while stirring at 170 rpm.
At the same time, 35 mg of bis(indenyl)zirconium di-chloride were dissolved in 100 cm3 of the solution of methylaluminoxane in toluene and stirring was carried out ~ -for 15 minutes. -~
~ ' The stirrer in the reactor wa8 switched off and the polymerization was started by pumping in the catalyst solution over 10 minutes. The internal temperature of the reactor increased rapidly and was regulated at 70C
by subseguently feeding in ethylene. The relative concentration of the gases in the vapor space of the reactor was monitored with the aid of a gas chromatograph (GC). Hydrogen and propylene were subsequently metered in at a con~tant ratio to the ethylene according to GC. ;~
A total pressure of 30 bar was achieved at equilibrium.
~ ~1113~3 The valves (10) and (12) were set 80 that the pump (8) delivered 10% by volume of the circulation via pipe ~
~- into the ~tillhead (2) of the reactor (1). After a polymerization tLme of 1 hour, the propane wax ~uspension 5 wa discharged into a proceesing ves~el and the catalyst ; was deactivated by adding isopropanol. After the propanehad been distilled off and the product dried at reduced pressure, 11.2 kg of copolymer wax h~ving a VN of -;
22 cm3/g~ a melting point (DSC) of 112C and a DSC en-~1 10 thalpy of fu~ion of 138 J/g were obtained when the ~' processing vessel was opened. The viscosity of the melt --~i was 1,200 mPa.s at 140C. The propylene content was `i 4.4 mol % according to '3C-NMR. ~ -~
The experiment was repeated four times. The yield 15 remained constant at about 5% by weight. After the 3 reactor was opened, no wall deposits were found, apart `~ from finely divided product residues on the bottom.
Comparative Example A ~--Example 1 was repeated, the double jacket of the reactor being connected to a thermostat ~ystem and pipe t3) and valves (10) and (12) being closed. The polymerization was then continued at 30C by adding the catalyst and thereafter with cooling to an internal reactor temperature of 70C. Ethylene was continuously metered in up to a total pressure of 30 bar, and propylene and hydrogen were added in accordance with the result~ of the GC measurement.
After 1 hour, 10.5 kg of copolymer wax having a VN of 19 ~m3/g and a melt viscosity of 800 mPa.s at 140C
3C resulted.
The experiment was repeated four times. The dif~erence between jacket temperature and internal reactor tempera-ture increa~ed with progressive operating time. After the reactor had been opened, a cohesive wax depo~it C ~ ~ Ob _ ~ ~ f ~
;~111363 ,~ i having a thickness of about 0.5 mm was found on the inner wall of the reactor ; `
.~ Comparative Example B ~;
Example 1 was repeated, the valve (12) remaining closed during operation.
~ . ~
After the processing vessel had been opened, 11.6 kg of copolymer wax having a VN of 20 cm3/g and a melt Vi9 cosity of 910 mPa.s at 140C were obtained. The experi-ment was repeated four times. After the reactor had been opened, no wall deposits were found, as in 2xample 1.
Loose deposits of a fine material were found in the reactor stillhead (2) and partly in the pipe (3). The VN
of 18 cm3/g indicated that the deposits were composed mainly of entrained product and only to a small extent of oligomer~.
, .,~
.' ~
: -
Claims (9)
1. A process for the preparation of a polyolefin wax by polymerization or copolymerization of olefins or diolefins at a temperature of -40 to 95°C, at a pressure of 0.5 to 120 bar, in suspension and in the presence of a catalyst comprising a metallocene and a cocatalyst, wherein the metallocene is a compound of the formula I
( I ) in which M1 is a metal of group IVb, Vb or VIb of the Periodic Table of Elements, R1 and R2 are identical or different and are a hydrogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C6-C10-aryl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group, a C8-C40-arylalkenyl group or a halogen atom and R3 and R4 are identical or different and are a mononuclear or polynuclear hydrocarbon radical which may form a sandwich structure with the central atom M1, low-boiling hydrocarbons having 3 or 4 carbon atoms or low-boiling halogenated hydrocarbons are used as suspending agents and the heat of reaction is removed by evaporative cooling.
( I ) in which M1 is a metal of group IVb, Vb or VIb of the Periodic Table of Elements, R1 and R2 are identical or different and are a hydrogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C6-C10-aryl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group, a C8-C40-arylalkenyl group or a halogen atom and R3 and R4 are identical or different and are a mononuclear or polynuclear hydrocarbon radical which may form a sandwich structure with the central atom M1, low-boiling hydrocarbons having 3 or 4 carbon atoms or low-boiling halogenated hydrocarbons are used as suspending agents and the heat of reaction is removed by evaporative cooling.
2. The process as claimed in claim 1, wherein the metallocene is a compound of the formula Ia ( I a ) in which R1 and R2 have the meaning stated in claim 1 and R5, R6, R7, R8, R9 and R10 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C6-C10-aryl group, a C1-C10-alkoxy group or an -NR142, -SR14, -OSiR143, -SiR143 or -PR142 radical in which R14 is a C1-C10-alkyl group or C6-C10-aryl group or, in the case of Si- or P-containing radicals, also a halogen atom, or two adjacent radicals R5, R6, R7, R8, R9 or R10 each form a ring with the carbon atoms linking them.
3. The process as claimed in claim 1, wherein the metallocene is a compound of the formula Ib ( I b ) in which R1 and R2 have the meaning stated in claim 1, R5, R6, R8, R9 and R14 have the meaning stated in claim 2 and R13 is , , , , , , =BR15, =AlR15, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, =NR15, =CO, =PR15 or P(O)R15, in which R15, R16 and R17 are identical or different and are a hydrogen atom, a halogen atom, a C1-C30-alkyl group, a C1-C10-fluoro-alkyl group, a C6-C10-fluoroaryl group, a C6-C10-aryl group, a C1-C10-alkoxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C8-C40-arylalkenyl group or a C7-C40-alkylaryl group, or R15 and R16 or R15 and R17, together with the atoms linking them, each form a ring, M2 is silicon, germanium or tin and R11 and R12 are identical or different and have the meaning stated for R15, m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2, preferably zero or 1.
4. The process as claimed in claim 1, wherein the cocatalyst is an aluminoxane of the formula IIa for the linear type and/or of the formula IIb for the cyclic type ( I I a) ( I I b) in which R18 is a C1-C6-alkyl group and p is an integer from 4 to 20.
5. The process as claimed in claim 1, wherein the suspending agent is propane or butane.
6. The process as claimed in claim 1, wherein the suspending agent is propane.
7. The process as claimed in claim 1, wherein a catalyst which is present on a carrier is used.
8. The process as claimed in claim 1, wherein ethylene, propylene, 1-butene, 4-methyl-1-pentene or 1-hexene is polymerized.
9. The process as claimed in claim 1, wherein the evaporative cooling is operated in combination with back-washing.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4242203 | 1992-12-15 | ||
| DEP4242203.5 | 1992-12-15 |
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|---|---|
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|---|---|---|---|
| CA002111363A Abandoned CA2111363A1 (en) | 1992-12-15 | 1993-12-14 | Process for the preparation of polyolefin waxes |
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|---|---|
| EP (1) | EP0602509B1 (en) |
| JP (1) | JPH06293805A (en) |
| KR (1) | KR940014458A (en) |
| AT (1) | ATE150035T1 (en) |
| AU (1) | AU669943B2 (en) |
| BR (1) | BR9305049A (en) |
| CA (1) | CA2111363A1 (en) |
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| DE (1) | DE59305751D1 (en) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6335410B1 (en) | 1996-01-22 | 2002-01-01 | The Dow Chemical Company | Ultra-low molecular weight ethylene polymers |
| US7825186B2 (en) | 2004-10-06 | 2010-11-02 | Clariant Produkte (Deutschland) Gmbh | Use of polyolefin waxes in hot melt road marking compositions |
| CN114832736A (en) * | 2022-05-13 | 2022-08-02 | 中国成达工程有限公司 | Polyethylene elastomer polymerization heat removal method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5466766A (en) * | 1991-05-09 | 1995-11-14 | Phillips Petroleum Company | Metallocenes and processes therefor and therewith |
| FR2729393B1 (en) | 1995-01-18 | 1997-03-21 | Bp Chemicals Snc | OLEFIN POLYMERIZATION PROCESS |
| US5977251A (en) * | 1996-04-01 | 1999-11-02 | The Dow Chemical Company | Non-adiabatic olefin solution polymerization |
| AU714023B2 (en) * | 1996-04-01 | 1999-12-16 | Dow Chemical Company, The | Olefin solution polymerization |
| DE19623707A1 (en) * | 1996-06-14 | 1997-12-18 | Hoechst Ag | Transition metal compound |
| ES2209008T3 (en) | 1997-07-11 | 2004-06-16 | Clariant Gmbh | PROCEDURE FOR OXIDATION OF POLYETHYLENE WAXES. |
| ES2227747T3 (en) * | 1997-07-11 | 2005-04-01 | Clariant Gmbh | USE OF POLYOLEFIN WAXES. |
| DE19729833A1 (en) * | 1997-07-11 | 1999-01-14 | Clariant Gmbh | Polypropylene wax |
| JP3639858B2 (en) * | 1997-09-12 | 2005-04-20 | 日本甜菜製糖株式会社 | Method and apparatus for producing raffinose crystals |
| US6166152A (en) * | 1998-02-26 | 2000-12-26 | Phillips Petroleum Company | Process to produce low density polymer in a loop reactor |
| DE19860174A1 (en) | 1998-12-24 | 2000-06-29 | Clariant Gmbh | Polymer oxidates and their use |
| EP1292644B1 (en) * | 2000-06-20 | 2004-09-15 | Basf Aktiengesellschaft | Pigment concentrates and method for producing them |
| DE50110557D1 (en) | 2000-09-28 | 2006-09-07 | Basell Polyolefine Gmbh | PROCESS FOR PREPARING HIGH-BRANCHED ETHYLENE POLYMERISES |
| CN101616938B (en) | 2007-02-19 | 2012-08-15 | 出光兴产株式会社 | Alpha-olefin polymer and process for producing the same |
| CN103080147B (en) * | 2010-08-31 | 2015-07-29 | 巴塞尔聚烯烃股份有限公司 | The wax deposit improved is utilized to prepare the method for polyolefin polymer |
| JP5588318B2 (en) * | 2010-11-22 | 2014-09-10 | ユシロ化学工業株式会社 | Oil-based plunger lubricant composition |
| KR102381810B1 (en) * | 2019-05-29 | 2022-04-04 | 바젤 폴리올레핀 게엠베하 | Suspension Method for Preparation of Ethylene Polymer comprising Work-up of Suspension Medium |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1256246A (en) * | 1984-04-09 | 1989-06-20 | Thomas J. Pullukat | Copolymerization of ethylene |
| DE3743322A1 (en) * | 1987-12-21 | 1989-06-29 | Hoechst Ag | Polyethylene wax and method for its production |
| DE3743321A1 (en) * | 1987-12-21 | 1989-06-29 | Hoechst Ag | 1-OLEFIN POLYMER WAX AND METHOD FOR THE PRODUCTION THEREOF |
| DE3743320A1 (en) * | 1987-12-21 | 1989-06-29 | Hoechst Ag | 1-OLEFIN STEREO BLOCK POLYMER WAX AND METHOD FOR THE PRODUCTION THEREOF |
-
1993
- 1993-11-20 TW TW082109778A patent/TW322495B/zh active
- 1993-12-07 ES ES93119715T patent/ES2100434T3/en not_active Expired - Lifetime
- 1993-12-07 AT AT93119715T patent/ATE150035T1/en not_active IP Right Cessation
- 1993-12-07 DE DE59305751T patent/DE59305751D1/en not_active Expired - Fee Related
- 1993-12-07 EP EP93119715A patent/EP0602509B1/en not_active Expired - Lifetime
- 1993-12-13 AU AU52367/93A patent/AU669943B2/en not_active Ceased
- 1993-12-14 BR BR9305049A patent/BR9305049A/en not_active Application Discontinuation
- 1993-12-14 KR KR1019930027561A patent/KR940014458A/en not_active Application Discontinuation
- 1993-12-14 CA CA002111363A patent/CA2111363A1/en not_active Abandoned
- 1993-12-14 ZA ZA939361A patent/ZA939361B/en unknown
- 1993-12-14 RU RU93055884A patent/RU2117674C1/en active
- 1993-12-14 JP JP5313633A patent/JPH06293805A/en active Pending
- 1993-12-14 CZ CZ932749A patent/CZ274993A3/en unknown
-
1998
- 1998-06-23 HK HK98106077A patent/HK1006722A1/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6335410B1 (en) | 1996-01-22 | 2002-01-01 | The Dow Chemical Company | Ultra-low molecular weight ethylene polymers |
| US7825186B2 (en) | 2004-10-06 | 2010-11-02 | Clariant Produkte (Deutschland) Gmbh | Use of polyolefin waxes in hot melt road marking compositions |
| CN114832736A (en) * | 2022-05-13 | 2022-08-02 | 中国成达工程有限公司 | Polyethylene elastomer polymerization heat removal method |
Also Published As
| Publication number | Publication date |
|---|---|
| HK1006722A1 (en) | 1999-03-12 |
| EP0602509A3 (en) | 1994-07-06 |
| EP0602509B1 (en) | 1997-03-12 |
| AU669943B2 (en) | 1996-06-27 |
| DE59305751D1 (en) | 1997-04-17 |
| JPH06293805A (en) | 1994-10-21 |
| TW322495B (en) | 1997-12-11 |
| ATE150035T1 (en) | 1997-03-15 |
| AU5236793A (en) | 1994-06-30 |
| BR9305049A (en) | 1994-06-21 |
| CZ274993A3 (en) | 1994-07-13 |
| ES2100434T3 (en) | 1997-06-16 |
| EP0602509A2 (en) | 1994-06-22 |
| KR940014458A (en) | 1994-07-18 |
| ZA939361B (en) | 1994-08-08 |
| RU2117674C1 (en) | 1998-08-20 |
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